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Prelims.qxd 12/22/2006 11:10 AM Page i

Handbook of Electrochemistry
This page intentionally left blank
Prelims.qxd 12/22/2006 11:10 AM Page iii

Handbook of Electrochemistry
Cynthia G. Zoski
New Mexico State University
Department of Chemistry and Biochemistry
Las Cruces, New Mexico, USA

Amsterdam ● Boston ● Heidelberg ● London ● New York ● Oxford

Paris ● San Diego ● San Francisco ● Singapore ● Sydney ● Tokyo
Prelims.qxd 12/22/2006 11:10 AM Page iv

Elsevier
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The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, UK

First edition 2007

Copyright © 2007 Elsevier B.V. All rights reserved

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of the publisher

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can submit your request online by visiting the Elsevier web site at http://elsevier.com/locate/permissions, and select-
ing Obtaining permission to use Elsevier material

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No responsibility is assumed by the publisher for any injury and/or damage to persons or property as a matter of
products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions or
ideas contained in the material herein. Because of rapid advances in the medical sciences, in particular, inde-
pendent verification of diagnoses and drug dosages should be made

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07 08 09 10 11 10 9 8 7 6 5 4 3 2 1
Preface.qxd 12/22/2006 11:10 AM Page v

Preface
Electrochemistry now plays an important role in a vast number of fundamental research
and applied areas. These include, but are not limited to, the exploration of new inorganic
and organic compounds, biochemical and biological systems, corrosion, energy applica-
tions involving fuel cells and solar cells, and nanoscale investigations. There are many
excellent textbooks and monographs, which explain the fundamentals and theory of elec-
trochemistry. This handbook is not a textbook, however, but rather a source of electro-
chemical information, details of experimental considerations, representative calculations,
and illustrations of the possibilities available in electrochemical experimentation. It is
most closely allied with the textbook Electrochemical Methods: Fundamentals and
Applications by Allen J. Bard and Larry R. Faulkner, second edition.
The Handbook of Electrochemistry is divided into five parts: Fundamentals (Chapter 1),
Laboratory Practical (Chapters 2–10), Techniques (Chapters 11–14), Applications (Chapters
15–17), and Data (Chapters 18–20). Chapter 1 covers the fundamentals of electrochemistry
that are essential for everyone working in this field and sets the stage for the following
19 chapters. Thus, Chapter 1 presents an overview of electrochemical conventions, terminol-
ogy, fundamental equations, electrochemical cells, experiments, literature, textbooks, and spe-
cialized books. Laboratory aspects of electrochemistry are emphasized in the following nine
chapters that include Practical Electrochemical Cells (Chapter 2), Solvents and Supporting
Electrolytes (Chapter 3), Reference Electrodes (Chapter 4), Solid Electrode Materials:
Pretreatment and Activation (Chapter 5), Ultramicroelectrodes (Chapter 6), Potentiometric
Ion-Selective Electrodes (Chapter 7), Chemically Modified Electrodes (Chapter 8),
Semiconductor Electrodes (Chapter 9), and Microelectrode Arrays (Chapter 10).
Electrochemical techniques covered in this handbook range from classical experiments
(Chapter 11) to Scanning Electrochemical Microscopy (SECM) (Chapter 12), Electro-
generated Chemiluminesence (Chapter 13), and Spectroelectrochemistry (Chapter 14).
These four chapters also include representative applications based on the method described.
Specific electrochemical applications based on the preceding chapters illustrate the impact
of electrochemistry in exploring diverse topics ranging from electrode kinetic determina-
tions (Chapter 15), unique aspects of metal deposition (Chapter 16) including micro- and
nanostructures, template deposition, and single particle deposition, and electrochemistry in
small places and at novel interfaces (Chapter 17) including biological cells, single molecule
electrochemistry, and electrochemistry at liquid/liquid interfaces. The remaining three
chapters provide useful electrochemical data and information involving electrode potentials
(Chapter 18), diffusion coefficients (Chapter 19), and methods used in measuring liquid-
junction potentials (Chapter 20). The majority of the chapters were supervised by a single
corresponding author. Exceptions to this are Chapters 6, Ultramicroelectrodes; Chapter 16,
Metal Deposition; and Chapter 17, Electrochemistry in Small Places and at Novel
Interfaces, where several authors contributed to different sections in a specific chapter.

v
Preface.qxd 12/22/2006 11:10 AM Page vi

vi Preface

I would like to thank the contributors of this handbook, colleagues in the electrochem-
ical community, and the authors of the many papers, textbooks, and specialized books
whose work is cited in this handbook and has led to the development of electrochemistry,
its expansion into diverse areas, and much of the information presented in this handbook.
I especially want to thank Allen J. Bard, a pioneer in electrochemistry, for his helpful com-
ments, suggestions, advice, and unwavering encouragement during the editing of this
handbook.

Cynthia G. Zoski
Contents.qxd 12/22/2006 11:09 AM Page vii

Contents
Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . v
Corresponding Authors. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xix

I Fundamentals. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 01
1 Fundamentals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 03
1.1 Conventions in Electrochemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 03
1.1.1 Potential conventions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 03
1.1.2 Current conventions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 06
1.2 Terminology. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 06
1.3 Fundamental Equations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 08
1.3.1 Nernst equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 09
1.3.2 Equilibrium constant . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 09
1.3.3 Mass-transfer limited current. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
1.3.4 Cottrell equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
1.3.5 Faraday’s law . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
1.4 Factors Affecting Reaction Rate and Current . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
1.4.1 Current, current density, and rate. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
1.4.2 Reversibility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
1.4.3 Kinetics. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
1.5 Equations Governing Modes of Mass Transfer . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
1.5.1 Nernst–Planck equation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
1.5.2 Fick’s laws of diffusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
1.6 Electrochemical Cells. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
1.7 Cell Resistance; Capacitance; Uncompensated Resistance . . . . . . . . . . . . . . . . . . . 22
1.8 Overview of Electrochemical Experiments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
1.9 Electrochemistry Literature; Textbooks; Specialized Books . . . . . . . . . . . . . . . . . . 25
1.9.1 Electrochemical journals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
1.9.2 Specialized texts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
1.9.3 Review series . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28

II Laboratory Practical . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
2 Practical Electrochemical Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
2.1 Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
2.2 General Cell Designs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
2.2.1 Two-electrode cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
2.2.2 Three-electrode cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35

vii
Contents.qxd 12/22/2006 11:09 AM Page viii

viii Contents

2.3 Electrochemical Cells for Specific Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . 35

2.3.1 Flow-through cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
2.3.2 Thin-layer cells (TLCs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
2.3.3 Spectroelectrochemical cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
2.3.4 Electrochemical cells for molten salts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
2.3.5 Attachment to a vacuum line . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
2.4 Establishing and Maintaining an Inert Atmosphere . . . . . . . . . . . . . . . . . . . . . . . . . 50
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55

3 Solvents and Supporting Electrolytes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57

3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
3.2 Electrolyte Conductivity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
3.3 Cells, Electrodes and Electrolytes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
3.4 Cell Time Constants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
3.5 Solvents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
3.5.1 Protic solvents. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
3.5.2 Nitriles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
3.5.3 Halogenated organics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
3.5.4 Amides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
3.5.5 Sulfoxides and sulfones. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
3.5.6 Ethers, carbonates, lactone . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
3.6 Salts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
3.7 “Exotic” Electrolytes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
3.8 Purification Procedures for some Commonly Used Solvents in Electrochemistry . . . 68
3.8.1 Acetonitrile . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
3.8.2 Butyronitrile . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
3.8.3 Benzonitrile . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
3.8.4 Propylene carbonate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
3.8.5 Dichloromethane. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
3.8.6 Dimethylformamide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
3.9 Purification Procedures for some Commonly Used Salts in Electrochemistry . . . . . 70
3.9.1 Tetraethylammonium tetrafluoroborate . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
3.9.2 Tetraethylammonium tetraphenylborate . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
3.9.3 Tetraethylammonium hexafluorophosphate . . . . . . . . . . . . . . . . . . . . . . . . . 71
3.9.4 Tetrabutylammonium tetrafluoroborate . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
3.9.5 Tetrabutylammonium hexafluorophosphate . . . . . . . . . . . . . . . . . . . . . . . . . 71
3.9.6 Lithium perchlorate. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71

4 Reference Electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
4.1.1 Selecting a reference electrode . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
4.1.2 Converting between aqueous potential scales . . . . . . . . . . . . . . . . . . . . . . . 74
4.2 Basic Components of a Reference Electrode . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
4.2.1 Body material . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
4.2.2 Top seal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
Contents.qxd 12/22/2006 11:09 AM Page ix

Contents ix

4.2.3 Junction (4) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77

4.2.4 Active component of RE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
4.3 Electrode Details and Fabrication . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
4.3.1 Hydrogen electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
4.3.2 Mercury electrodes (24) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
4.3.3 Silver electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
4.3.4 Quasi-reference electrodes (QRE) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
4.4 Junctions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
4.4.1 Filling solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
4.4.2 Salt bridges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
4.4.3 Double-junction reference electrodes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
4.4.4 Reference electrode impedance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
4.5 Reference Electrodes: Nonaqueous Solvents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
4.6 Reference Electrode Calibration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
4.6.1 Versus a second reference electrode. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
4.6.2 Using a well-defined redox couple . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
4.7 Maintenance. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
4.7.1 Storage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
4.7.2 Cleaning junctions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
4.7.3 Replacing filling solutions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
4.7.4 Regenerating the reference electrode . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
4.8 Troubleshooting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
4.8.1 Special notes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108

5 Solid Electrode Materials: Pretreatment and Activation . . . . . . . . . . . . . . . . . . . . . . 111

5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
5.2 Carbon Electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
5.2.1 Highly oriented pyrolytic graphite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
5.2.2 Glassy carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
5.2.3 Pyrolyzed photoresist films (PPF) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126
5.2.4 Carbon fibers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128
5.2.5 Carbon nanotubes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133
5.2.6 Diamond films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135
5.2.7 Tetrahedral amorphous carbon (Ta-C) films. . . . . . . . . . . . . . . . . . . . . . . . . 140
5.3 Metal Electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
5.3.1 Polycrystalline platinum and gold . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 144
5.3.2 Single-crystal platinum and gold . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146
5.4 Semiconductor Electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147
5.4.1 Indium tin oxide (ITO) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147
5.5 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150

6 Ultramicroelectrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
6.1 Behavior Of Ultramicroelectrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
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6.1.1 Electrode response times . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 156

6.1.2 Factors that influence the electrode response time . . . . . . . . . . . . . . . . . . . . 159
6.1.3 Origins of non-ideal responses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 160
6.1.4 Fundamentals of faradaic electrochemistry . . . . . . . . . . . . . . . . . . . . . . . . . 164
6.1.5 Origins of non-ideal faradaic responses . . . . . . . . . . . . . . . . . . . . . . . . . . . . 168
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171
6.2 Microelectrode Applications. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171
6.2.1 Electroanalysis at the micro- and nano-length scale . . . . . . . . . . . . . . . . . . . 172
6.2.2 Spatially heterogeneous systems: biological structures . . . . . . . . . . . . . . . . 175
6.2.3 Low conductivity media . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177
6.2.4 Ultrafast electrochemical techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 180
6.2.5 AC electrokinetics. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 184
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 186
6.3 UME Fabrication/Characterization Basics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
6.3.1 Platinum and gold inlaid disks ⱖ 5 ␮m diameter . . . . . . . . . . . . . . . . . . . . . 189
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197
6.3.2 Platinum and gold inlaid disks ⱖ 5 ␮m diameter . . . . . . . . . . . . . . . . . . . . . 197
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199
6.3.3 Laser-pulled ultramicroelectrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211
6.3.4 Platinum conical ultramicroelectrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 216
6.3.5 Flame-etched carbon nanofibers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221
6.3.6 Electrochemically etched carbon fiber electrodes . . . . . . . . . . . . . . . . . . . . 221
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 226
6.3.7 Gold spherical microelectrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 226
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235
6.3.8 Hg microhemispherical electrodes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
6.3.9 Clarke oxygen microelectrode . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 248
6.3.10 Nitric oxide microsensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 249
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 253
6.3.11 Glass nanopore electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 254
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 260

7 Potentiometric Ion-Selective Electrodes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 261

7.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 261
7.2 Classification and Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263
7.2.1 Phase boundary potential. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263
7.2.2 Ion-exchanger-based ISEs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 264
7.2.3 Neutral-ionophore-based ISEs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 266
7.2.4 Charged-ionophore-based ISEs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 270
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7.3 Equilibrium Potentiometric Responses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 273

7.3.1 The Nikolsky–Eisenman equation and phase boundary potential model. . . . 273
7.3.2 Effect of ionic sites on selectivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 276
7.3.3 Apparently “non-Nernstian” equilibrium responses . . . . . . . . . . . . . . . . . . . 279
7.4 Non-Equilibrium Potentiometric Responses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 282
7.4.1 Mixed ion-transfer potentials. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 282
7.4.2 Elimination of non-equilibrium effects in separate solutions . . . . . . . . . . . . 284
7.4.3 Effects of transmembrane ion flux on detection limit. . . . . . . . . . . . . . . . . . 287
7.4.4 Non-equilibrium responses for polyion detection. . . . . . . . . . . . . . . . . . . . . 290
7.5 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 291
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 292

8 Chemically Modified Electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 295

8.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 295
8.2 Substrate Materials and Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 296
8.3 Modified Electrode Types . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 296
8.3.1 Langmuir-Blodgett . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 297
8.3.2 Self-assembly . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 300
8.3.3 Covalent attachment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 305
8.3.4 Clay modified electrodes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 308
8.3.5 Zeolite modified electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 311
8.3.6 Sol-gel modified electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 314
8.3.7 Polymer modified electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 317
8.3.8 DNA modified electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 322
8.4 Conclusions and Prospects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 322
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 323

9 Semiconductor Electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 329

9.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 329
9.2 Semiconductor Basics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 330
9.2.1 Band theory of solids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 330
9.2.2 Size quantization in semiconductors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 336
9.3 Energetics of a Semiconductor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 340
9.3.1 Semiconductor–electrolyte interface (SEI). . . . . . . . . . . . . . . . . . . . . . . . . . 343
9.4 Semiconductor Electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 346
9.4.1 Electron transfer at semiconductor–electrolyte interface . . . . . . . . . . . . . . . 346
9.4.2 lluminated semiconductor electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 349
9.4.3 Cyclic voltammetry (CV) at semiconductor electrodes . . . . . . . . . . . . . . . . 351
9.4.4 Fermi-level pinning in semiconductor electrodes . . . . . . . . . . . . . . . . . . . . 355
9.4.5 Characterization of the SEI by scanning electrochemical
microscopy (SECM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 358
9.5 Types of Semiconductor Electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 367
9.5.1 Single crystal and epitaxial film electrodes . . . . . . . . . . . . . . . . . . . . . . . . . 367
9.5.2 Polycrystalline electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 369
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9.6 Nanostructured Semiconductor Electrodes (NSSE) . . . . . . . . . . . . . . . . . . . . . . . 374

9.6.1 Epitaxial methods for the preparation of NSSE . . . . . . . . . . . . . . . . . . . 375
9.6.2 Preparation of particulate films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 375
9.6.3 Electrochemistry on nanostructured semiconductors. . . . . . . . . . . . . . . . 377
9.6.4 Electrochemistry on suspended semiconductor nanoparticles . . . . . . . . . 378
9.7 Semiconductor Electrode Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 381
9.7.1 Solar cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 381
9.7.2 Sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 384
Acknowledgments. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 385
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 385

10 Microelectrode Arrays . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 391

10.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 391
10.2 Classification of Microelectrode Arrays . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 392
10.2.1 Microelectrode designs. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 392
10.2.2 Microelectrode array behavior . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 394
10.3 Theory: Diffusion at Microelectrode Arrays . . . . . . . . . . . . . . . . . . . . . . . . . . . . 396
10.3.1 Arrays of electrodes operating at identical potentials . . . . . . . . . . . . . . . 396
10.3.2 Arrays of electrodes operating in generator/collector mode . . . . . . . . . . 400
10.4 Fabrication of Microelectrode Arrays . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 403
10.4.1 Mechanical methods. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 404
10.4.2 Template approaches . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 407
10.4.3 Lithographic techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 411
10.4.4 Etching techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 416
10.5 Electrochemical Characterisation of Microelectrode Arrays . . . . . . . . . . . . . . . . 418
10.5.1 Chronoamperometry and cyclic voltammetry . . . . . . . . . . . . . . . . . . . . . 419
10.5.2 Scanning electrochemical microscopy . . . . . . . . . . . . . . . . . . . . . . . . . . 422
10.5.3 Optical microscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 422
10.6 Conclusion and Prospects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 422
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 423

III Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 429

11 Classical Experiments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 431
11.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 431
11.2 Selected Experimental Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 432
11.2.1 Potential steps . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 432
11.2.2 Potential sweeps. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 438
11.2.3 Combinations of sweeps and steps . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 445
11.2.4 Microelectrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 447
11.2.5 Rotating disc electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 451
11.2.6 Small amplitude perturbations and impedance methods . . . . . . . . . . . . . 454
11.3 Simulations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 458
11.3.1 Electrochemical simulations—a few questions . . . . . . . . . . . . . . . . . . . . 458
11.3.2 Basic principles of an electrochemical simulation. . . . . . . . . . . . . . . . . . 460
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11.4 Troubleshooting Electrochemical Experiments: A Checklist . . . . . . . . . . . . . . . . 464

11.4.1 Checking the results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 464
11.4.2 No current response . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 464
11.4.3 Potential shift . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 465
11.4.4 Currents lower than expected . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 466
11.4.5 Slanted voltammogram . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 466
11.4.6 Noisy current . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 466
11.4.7 Other common problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 466
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 467

12 Scanning Electrochemical Microscopy. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 471

12.1 Introduction and Principles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 471
12.2 Instrumentation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 473
12.2.1 Basic SECM apparatus. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 473
12.2.2 Combining SECM with other techniques . . . . . . . . . . . . . . . . . . . . . . . . 475
12.3 Methods and Operational Modes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 479
12.3.1 Amperometric methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 479
12.3.2 Potentiometric method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 489
12.3.3 Imaging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 497
12.4 Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 501
12.4.1 Heterogeneous kinetics. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 501
12.4.2 Homogeneous chemical reactions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 506
12.4.3 Catalytic activity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 510
12.4.4 Surface reactivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 514
12.4.5 Patterning. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 519
12.4.6 Biological applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 524
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 535

13 Electrogenerated Chemiluminescence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 541

13.1 Concepts and History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 541
13.2 Types of Luminescence. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 541
13.3 Fundamental Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 542
13.3.1 Ion annihilation ECL . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 542
13.3.2 Coreactant ECL (123) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 546
13.4 Experimental Setup. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 554
13.4.1 Electrochemical media . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 554
13.4.2 Cell design and electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 556
13.4.3 Light detection and ECL instrumentation . . . . . . . . . . . . . . . . . . . . . . . . 560
13.5 Types of Experiments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 568
13.5.1 Ion annihilation ECL: Ru(bpy)32+ and derivatives. . . . . . . . . . . . . . . . . . 568
13.5.2 Coreactant ECL of Ru(bpy)32+/TPrA system in aqueous solutions. . . . . . 570
13.6 Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 572
13.6.1 Applications of Ru(bpy)32+ ECL: determination of oxalate and
organic acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 573
13.6.2 Applications of Ru(bpy)32+ ECL: determination of amines . . . . . . . . . . . 574
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13.6.3Applications of Ru(bpy)32+ ECL: determination of amino acids . . . . . . . 575

13.6.4Applications of Ru(bpy)32+ ECL: determination of pharmaceuticals . . . . 576
13.6.5Applications of Ru(bpy)32+ ECL: determination of Ru(bpy)32+ . . . . . . . . 577
13.6.6Applications of Ru(bpy)32+ ECL in capillary electrophoresis (CE)
and micro-total analysis (TAS). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 577
13.6.7 Application of Ru(bpy)32+ ECL: determination of clinical analytes . . . . . 578
13.6.8 Applications of Ru(bpy)32+ ECL: analytes associated with
food, water, and biological agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 580
Acknowledgments. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 582
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 582

14 Spectroelectrochemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 591
14.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 591
14.2 Light Transmission and Reflection at an Electrode Surface . . . . . . . . . . . . . . . . . 592
14.3 Electronic Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 593
14.3.1 Transmittance spectroscopy and optically transparent cell
materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 594
14.3.2 Thin layer spectroelectrochemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 595
14.3.3 Spectroelectrochemistry: semi-infinite linear diffusion . . . . . . . . . . . . . . 601
14.3.4 Long optical pathway thin layer cells (LOPTLC) . . . . . . . . . . . . . . . . . . 603
14.3.5 Reflectance spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 605
14.4 Luminiscence Spectroelectrochemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 612
14.4.1 Steady-state luminescence spectroelectrochemistry . . . . . . . . . . . . . . . . 612
14.4.2 Time-resolved luminescence spectroelectrochemistry . . . . . . . . . . . . . . . 615
14.5 Vibrational Spectroelectrochemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 616
14.5.1 IR spectroelectrochemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 618
14.5.2 Raman spectroelectrochemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 623
14.6 Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 632
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 633

IV Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 637
15 Determination of Electrode Kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 639
15.1 Introduction to Kinetic Measurements. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 639
15.2 Heterogeneous Electron Transfer: Transient Methods . . . . . . . . . . . . . . . . . . . . . 641
15.2.1 Linear sweep and cyclic voltammetry. . . . . . . . . . . . . . . . . . . . . . . . . . . 641
15.2.2 Sampled-current voltammetry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 644
15.2.3 Ac voltammetry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 645
15.3 Heterogeneous Electron Transfer: Steady-State Methods. . . . . . . . . . . . . . . . . . . 646
15.3.1 Steady-state voltammetry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 646
15.3.2 Scanning electrochemical microscopy (SECM) . . . . . . . . . . . . . . . . . . . 648
15.4 Processes with Coupled Homogeneous Reactions . . . . . . . . . . . . . . . . . . . . . . . . 651
15.4.1 Linear sweep and cyclic voltammetry. . . . . . . . . . . . . . . . . . . . . . . . . . . 651
15.4.2 Scanning electrochemical microscopy (SECM) . . . . . . . . . . . . . . . . . . . 655
15.4.3 Simulations and curve fitting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 656
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 660
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16 Metal Deposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 661

16.1 Electrodeposition of Nanostructures and Microstructures on Highly
Oriented Pyrolytic Graphite (HOPG) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 661
16.1.1 Introduction and perspective . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 661
16.1.2 HOPG: seeing electrodeposited metal nano- and microparticles . . . . . . . 663
16.1.3 Brownian Dynamics simulations: understanding particle size
distribution broadening . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 664
16.1.4 “Slow-growth” electrodeposition: dimensionally uniform metal
nano- and microparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 667
16.1.5 Electrodeposition of metal nanowires . . . . . . . . . . . . . . . . . . . . . . . . . . . 673
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 676
16.2 Template Deposition of Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 678
16.2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 678
16.2.2 Templating membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 678
16.2.3 Template deposition of metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 686
16.2.4 Morphological and optical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . 695
16.2.5 Electrochemistry with template nanomaterials: nanoelectrode
ensembles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 697
16.2.6 Conclusions and prospects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 704
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 706
16.3 Single Particle Deposition on Nanometer Electrodes. . . . . . . . . . . . . . . . . . . . . . 709
16.3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 709
16.3.2 Electrode selection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 710
16.3.3 Electrodeposition of particles: electrokinetic vs. diffusion control . . . . . 711
16.3.4 Nucleation exclusion zones: modeling particle growth . . . . . . . . . . . . . . 715
16.3.5 Examples of systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 717
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 717

17 Electrochemistry in Small Places and at Novel Interfaces . . . . . . . . . . . . . . . . . . . . 719

17.1 Electrochemistry in and at Single Biological Cells . . . . . . . . . . . . . . . . . . . . . . . 719
17.1.1 Electrochemistry at the cell membrane–solution interface. . . . . . . . . . . . 719
17.1.2 Electrochemistry at lipid bilayer membranes . . . . . . . . . . . . . . . . . . . . . 726
17.1.3 Electrochemistry in small drops and vials. . . . . . . . . . . . . . . . . . . . . . . . 737
17.1.4 Intracellular electrochemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 742
17.1.5 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 744
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 746
17.2 Single Molecule Electrochemistry. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 749
17.2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 749
17.2.2 Special topics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 749
17.2.3 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 783
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 783
17.3 Electrochemistry at Liquid/Liquid Interfaces. . . . . . . . . . . . . . . . . . . . . . . . . . . . 785
17.3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 785
17.3.2 Fundamentals. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 786
17.3.3 Charge transfer reactions at liquid/liquid interfaces . . . . . . . . . . . . . . . . 793
17.3.4 Methodologies and techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 799
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17.3.5 Applications. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 802

17.3.6 Prospects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 806
Acknowledgments. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 806
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 806

V Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 811
18 Electrode Potentials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 813
18.1 Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 813
18.2 Estimated Potential Ranges: Aqueous and Non-aqueous Solutions . . . . . . . . . . . 813
18.3 Standard Electrode Potentials: Aqueous Solutions. . . . . . . . . . . . . . . . . . . . . . . . 813
18.4 Formal Electrode Potentials: Aprotic Solvents. . . . . . . . . . . . . . . . . . . . . . . . . . . 813
18.5 Formal Electrode Potentials: Common Organic Mediators . . . . . . . . . . . . . . . . . 820
18.6 Electrode Potentials: Inorganic One-Electron Complexes . . . . . . . . . . . . . . . . . . 820
18.7 Formal Electrode Potentials: Biological Redox Species. . . . . . . . . . . . . . . . . . . . 821
18.8 Formal Electrode Potentials: Common Vitamins, Drugs, Neurochemicals . . . . . . 821
18.9 Abbreviations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 822
18.10 Chemical Structures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 825
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 827

19 Diffusion Coefficients . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 829

19.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 829
19.2 Fundamental Equations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 829
19.3 General Considerations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 830
19.3.1 Selection of a technique . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 830
19.3.2 Electrode . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 833
19.3.3 Electrochemical system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 835
19.3.4 Instrumentation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 835
19.4 Electrochemical Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 836
19.4.1 Potential step techniques (chronoamperometry) . . . . . . . . . . . . . . . . . . . 836
19.4.2 Rotating disk electrode techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 840
19.4.3 Potential sweep techniques. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 842
19.4.4 Current step techniques (chronopotentiometry). . . . . . . . . . . . . . . . . . . . 843
19.4.5 Scanning electrochemical microscopy (SECM) techniques. . . . . . . . . . . 844
19.5 Tables of Diffusion Coefficients . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 844
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 847

20 Liquid Junction Potentials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 849

20.1 Types of Liquid Junctions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 849
20.1.1 Interfacial potentials without electrolyte transport . . . . . . . . . . . . . . . . . 849
20.1.2 Interfacial potentials with electrolyte transport . . . . . . . . . . . . . . . . . . . . 850
20.2 Transference Numbers and Conductivity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 854
20.2.1 Experimental methods of determining transference number . . . . . . . . . . 854
20.2.2 Sample calculations of ionic transference numbers. . . . . . . . . . . . . . . . . 860
20.2.3 Experimental methods of determining electrolytic conductivity . . . . . . . 863
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20.2.4 Sample calculations relating to electrolytic conductivity. . . . . . . . . . . . . 864

20.2.5 Tabulation of parameters related to electrolyte conductance . . . . . . . . . . 866
20.3 Minimization of Liquid Junction Potentials. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 867
20.3.1 Balancing ionic mobilities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 867
20.3.2 The salt bridge . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 870
20.4 Junctions of Immiscible Liquids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 870
20.4.1 The non-polarisable liquid/liquid interface . . . . . . . . . . . . . . . . . . . . . . . 870
20.4.2 The polarisable liquid/liquid interface . . . . . . . . . . . . . . . . . . . . . . . . . . 872
20.5 Non-Classical Electrolytes: Polymer–Based Electrolytes and Ionic Liquids. . . . . 874
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 876

Subject Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 879

Colour Section to be found at the end of the book

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Corresponding Authors
Shigeru Amemiya University of Pittsburgh, Pittsburgh, PA, USA

Melisa D. Arning Saint Louis University, St. Louis, MO, USA

John E. Baur Illinois State University, Normal, IL, USA

Adam J. Bergren Iowa State University, Ames, IA, USA (present address: The
University of Alberta, Edmonton, Alberta, Canada)
Shaowei Chen University of California, Santa Cruz, CA, USA
Madalina Ciobanu Vanderbilt University, Nashville, TN, USA
David E. Cliffel Vanderbilt University, Nashville, TN, USA
Stephen Creager Clemson University, Clemson, SC, USA
Christophe Demaille Université Paris 7-UMR CNRS 7591, France
Guy Denuault University of Southampton, UK
Robert A.W. Dryfe University of Manchester, Manchester, UK
Grant A. Edwards Iowa State University, Ames, IA, USA (present address: Northern
Kentucky University, Highland Heights, KY, USA)
Andrew G. Ewing Pennsylvania State University, PA, USA
Fu-Ren F. Fan The University of Texas at Austin, Austin, TX, USA
José Fernandez The University of Texas at Austin, Austin, TX, USA
Robert J. Forster Dublin City University, Ireland
Santosh K. Haram University of Pune, Ganeshkhind, Pune, India
Katherine B. Holt The University of Texas at Austin, Austin, TX, USA (present
address: University College London, London, UK)
Tia E. Keyes Dublin City University, Ireland
Anthony Kucernak Imperial College London, London, UK
Youngmi Lee University of Tennessee, Knoxville, TN, USA
Biao Liu The University of Texas at Austin, Austin, TX, USA
Janine Mauzeroll Université Paris 7-UMR CNRS 7591, France (present address:
Université du Québec à Montréal, Montréal, Québec, Canada)

xix
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passed the river with the bulk of his army, and that he had only left
on our side a corps to cover his bridges; but in fact he had only sent
across his cavalry and trains. Between Howard's corps at Paice's
Ferry and the rest of Thomas's army pressing up against this tete-
du-pont, was a space concealed by dense woods, in crossing which I
came near riding into a detachment of the enemy's cavalry; and
later in the same day Colonel Frank Sherman, of Chicago, then on
General Howard's staff, did actually ride straight into the enemy's
camp, supposing that our lines were continuous. He was carried to
Atlanta, and for some time the enemy supposed they were in
possession of the commander-in-chief of the opposing army.
I knew that Johnston would not remain long on the west bank of
the Chattahoochee, for I could easily practise on that ground to
better advantage our former tactics of intrenching a moiety in his
front, and with the rest of our army cross the river and threaten
either his rear or the city of Atlanta itself, which city was of vital
importance to the existence not only of his own army, but of the
Confederacy itself. In my dispatch of July 6th to General Halleck, at
Washington, I state that:
Johnston (in his retreat from Kenesaw) has left two breaks in the
railroad—one above Marietta and one near Mining's Station. The
former is already repaired, and Johnston's army has heard the sound
of our locomotives. The telegraph is finished to Mining's Station, and
the field-wire has just reached my bivouac, and will be ready to
convey this message as soon as it is written and translated into
cipher.
I propose to study the crossings of the Chattahoochee, and, when
all is ready, to move quickly. As a beginning, I will keep the troops
and wagons well back from the river, and only display to the enemy
our picket-line, with a few field-batteries along at random. I have
already shifted Schofield to a point in our left rear, whence he can in
a single move reach the Chattahoochee at a point above the
railroad-bridge, where there is a ford. At present the waters are
turbid and swollen from recent rains; but if the present hot weather
lasts, the water will run down very fast. We have pontoons enough
for four bridges, but, as our crossing will be resisted, we must
manoeuvre some. All the regular crossing-places are covered by
forts, apparently of long construction; but we shall cross in due time,
and, instead of attacking Atlanta direct, or any of its forts, I propose
to make a circuit, destroying all its railroads. This is a delicate
movement, and must be done with caution. Our army is in good
condition and full of confidence; but the weather is intensely hot,
and a good many men have fallen with sunstroke. The country is
high and healthy, and the sanitary condition of the army is good.
At this time Stoneman was very active on our extreme right,
pretending to be searching the river below Turner's Ferry for a
crossing, and was watched closely by the enemy's cavalry on the
other side, McPherson, on the right, was equally demonstrative at
and near Turner's Ferry. Thomas faced substantially the intrenched
tete-du-pont, and had his left on the Chattahoochee River, at Paice's
Ferry. Garrard's cavalry was up at Roswell, and McCook's small
division of cavalry was intermediate, above Soap's Creek. Meantime,
also, the railroad-construction party was hard at work, repairing the
railroad up to our camp at Vining's Station.
Of course, I expected every possible resistance in crossing the
Chattahoochee River, and had made up my mind to feign on the
right, but actually to cross over by the left. We had already secured
a crossing place at Roswell, but one nearer was advisable; General
Schofield had examined the river well, found a place just below the
mouth of Soap's Creek which he deemed advantageous, and was
instructed to effect an early crossing there, and to intrench a good
position on the other side, viz., the east bank. But, preliminary
thereto, I had ordered General Rousseau, at Nashville, to collect, out
of the scattered detachments of cavalry in Tennessee, a force of a
couple of thousand men, to rendezvous at Decatur, Alabama, thence
to make a rapid march for Opelika, to break up the railroad links
between Georgia and Alabama, and then to make junction with me
about Atlanta; or, if forced, to go on to Pensacola, or even to swing
across to some of our posts in Mississippi. General Rousseau asked
leave to command this expedition himself, to which I consented, and
on the 6th of July he reported that he was all ready at Decatur, and I
gave him orders to start. He moved promptly on the 9th, crossed the
Coosa below the "Ten Islands" and the Tallapoosa below "Horseshoe
Bend," having passed through Talladega. He struck the railroad west
of Opelika, tore it up for twenty miles, then turned north and came
to Marietta on the 22d of July, whence he reported to me. This
expedition was in the nature of a raid, and must have disturbed the
enemy somewhat; but, as usual, the cavalry did not work hard, and
their destruction of the railroad was soon repaired. Rousseau, when
he reported to me in person before Atlanta, on the 28d of July,
stated his entire loss to have been only twelve killed and thirty
wounded. He brought in four hundred captured mules and three
hundred horses, and also told me a good story. He said he was far
down in Alabama, below Talladega, one hot, dusty day, when the
blue clothing of his men was gray with dust; he had halted his
column along a road, and he in person, with his staff, had gone to
the house of a planter, who met him kindly on the front-porch. He
asked for water, which was brought, and as the party sat on the
porch in conversation he saw, in a stable-yard across the road, quite
a number of good mules. He remarked to the planter, "My good sir, I
fear I must take some of your mules." The planter remonstrated,
saying he had already contributed liberally to the good cause; that it
was only last week he had given to General Roddy ten mules.
Rousseau replied, "Well, in this war you should be at least neutral—
that is, you should be as liberal to us as to Roddy" (a rebel cavalry
general). "Well, ain't you on our side?" "No," said Rousseau; "I am
General Rousseau, and all these men you see are Yanks." "Great
God! is it possible! Are these Yanks! Who ever supposed they would
come away down here in Alabama?" Of course, Rousseau took his
ten mules.
Schofield effected his crossing at Soap's Creek very handsomely
on the 9th, capturing the small guard that was watching the
crossing. By night he was on the high ground beyond, strongly
intrenched, with two good pontoon-bridges finished, and was
prepared, if necessary, for an assault by the whole Confederate
army. The same day Garrard's cavalry also crossed over at Roswell,
drove away the cavalry-pickets, and held its ground till relieved by
Newton's division of Howard's corps, which was sent up temporarily,
till it in turn was relieved by Dodge's corps (Sixteenth) of the Army
of the Tennessee, which was the advance of the whole of that army.
That night Johnston evacuated his trenches, crossed over the
Chattahoochee, burned the railroad bridge and his pontoon and
trestle bridges, and left us in full possession of the north or west
bank-besides which, we had already secured possession of the two
good crossings at Roswell and Soap's Creek. I have always thought
Johnston neglected his opportunity there, for he had lain
comparatively idle while we got control of both banks of the river
above him.
On the 13th I ordered McPherson, with the Fifteenth Corps, to
move up to Roswell, to cross over, prepare good bridges, and to
make a strong tete-du-pont on the farther side. Stoneman had been
sent down to Campbellton, with orders to cross over and to threaten
the railroad below Atlanta, if he could do so without too much risk;
and General Blair, with the Seventeenth Corps, was to remain at
Turner's Ferry, demonstrating as much as possible, thus keeping up
the feint below while we were actually crossing above. Thomas was
also ordered to prepare his bridges at Powers's and Paice's Ferries.
By crossing the Chattahoochee above the railroad bridge, we were
better placed to cover our railroad and depots than below, though a
movement across the river below the railroad, to the south of
Atlanta, might have been more decisive. But we were already so far
from home, and would be compelled to accept battle whenever
offered, with the Chattahoochee to our rear, that it became
imperative for me to take all prudential measures the case admitted
of, and I therefore determined to pass the river above the railroad-
bridge-McPherson on the left, Schofield in the centre, and Thomas
on the right. On the 13th I reported to General Halleck as follows:
All is well. I have now accumulated stores at Allatoona and
Marietta, both fortified and garrisoned points. Have also three places
at which to cross the Chattahoochee in our possession, and only
await General Stoneman's return from a trip down the river, to cross
the army in force and move on Atlanta.
Stoneman is now out two days, and had orders to be back on the
fourth or fifth day at furthest.
From the 10th to the 15th we were all busy in strengthening the
several points for the proposed passage of the Chattahoochee, in
increasing the number and capacity of the bridges, rearranging the
garrisons to our rear, and in bringing forward supplies. On the 15th
General Stoneman got back to Powder Springs, and was ordered to
replace General Blair at Turner's Ferry, and Blair, with the
Seventeenth Corps, was ordered up to Roswell to join McPherson.
On the 17th we began the general movement against Atlanta,
Thomas crossing the Chattahoochee at Powers's and Paice's, by
pontoon-bridges; Schofield moving out toward Cross Keys, and
McPherson toward Stone Mountain. We encountered but little
opposition except by cavalry. On the 18th all the armies moved on a
general right wheel, Thomas to Buckhead, forming line of battle
facing Peach-Tree Creek; Schofield was on his left, and McPherson
well over toward the railroad between Stone Mountain and Decatur,
which he reached at 2 p.m. of that day, about four miles from Stone
Mountain, and seven miles east of Decatur, and there he turned
toward Atlanta, breaking up the railroad as he progressed, his
advance-guard reaching Ecatur about night, where he came into
communication with Schofield's troops, which had also reached
Decatur. About 10 A.M. of that day (July 18th), when the armies
were all in motion, one of General Thomas's staff-officers brought
me a citizen, one of our spies, who had just come out of Atlanta,
and had brought a newspaper of the same day, or of the day before,
containing Johnston's order relinquishing the command of the
Confederate forces in Atlanta, and Hood's order assuming the
command. I immediately inquired of General Schofield, who was his
classmate at West Point, about Hood, as to his general character,
etc., and learned that he was bold even to rashness, and courageous
in the extreme; I inferred that the change of commanders meant
"fight." Notice of this important change was at once sent to all parts
of the army, and every division commander was cautioned to be
always prepared for battle in any shape. This was just what we
wanted, viz., to fight in open ground, on any thing like equal terms,
instead of being forced to run up against prepared intrenchments;
but, at the same time, the enemy having Atlanta behind him, could
choose the time and place of attack, and could at pleasure mass a
superior force on our weakest points. Therefore, we had to be
constantly ready for sallies.
 Full Size

On the 19th the three armies were converging toward Atlanta,

meeting such feeble resistance that I really thought the enemy
intended to evacuate the place. McPherson was moving astride of
the railroad, near Decatur; Schofield along a road leading toward
Atlanta, by Colonel Howard's house and the distillery; and Thomas
was crossing "Peach-Tree" in line of battle, building bridges for
nearly every division as deployed. There was quite a gap between
Thomas and Schofield, which I endeavored to close by drawing two
of Howard's divisions nearer Schofield. On the 20th I was with
General Schofield near the centre, and soon after noon heard heavy
firing in front of Thomas's right, which lasted an hour or so, and
then ceased.
I soon learned that the enemy had made a furious sally, the blow
falling on Hooker's corps (the Twentieth), and partially on Johnson's
division of the Fourteenth, and Newton's of the Fourth. The troops
had crossed Peach-Tree Creek, were deployed, but at the time were
resting for noon, when, without notice, the enemy came pouring out
of their trenches down upon them, they became commingled, and
fought in many places hand to hand. General Thomas happened to
be near the rear of Newton's division, and got some field-batteries in
a good position, on the north side of Peach-Tree Creek, from which
he directed a furious fire on a mass of the enemy, which was passing
around Newton's left and exposed flank. After a couple of hours of
hard and close conflict, the enemy retired slowly within his trenches,
leaving his dead and many wounded on the field. Johnson's and
Newton's losses were light, for they had partially covered their fronts
with light parapet; but Hooker's whole corps fought in open ground,
and lost about fifteen hundred men. He reported four hundred rebel
dead left on the ground, and that the rebel wounded would number
four thousand; but this was conjectural, for most of them got back
within their own lines. We had, however, met successfully a bold
sally, had repelled it handsomely, and were also put on our guard;
and the event illustrated the future tactics of our enemy. This sally
came from the Peach-Tree line, which General Johnston had carefully
prepared in advance, from which to fight us outside of Atlanta. We
then advanced our lines in compact order, close up to these finished
intrenchments, overlapping them on our left. From various parts of
our lines the houses inside of Atlanta were plainly visible, though
between us were the strong parapets, with ditch, fraise, chevaux-de-
frise, and abatis, prepared long in advance by Colonel Jeremy F.
Gilmer, formerly of the United States Engineers. McPherson had the
Fifteenth Corps astride the Augusta Railroad, and the Seventeenth
deployed on its left. Schofield was next on his right, then came
Howard's, Hooker's, and Palmer's corps, on the extreme right. Each
corps was deployed with strong reserves, and their trains were
parked to their rear. McPherson's trains were in Decatur, guarded by
a brigade commanded by Colonel Sprague of the Sixty-third Ohio.
The Sixteenth Corps (Dodge's) was crowded out of position on the
right of McPherson's line, by the contraction of the circle of
investment; and, during the previous afternoon, the Seventeenth
Corps (Blair's) had pushed its operations on the farther side of the
Augusta Railroad, so as to secure possession of a hill, known as
Leggett's Hill, which Leggett's and Force's divisions had carried by
assault. Giles A. Smith's division was on Leggett's left, deployed with
a weak left flank "in air," in military phraseology. The evening before
General Gresham, a great favorite, was badly wounded; and there
also Colonel Tom Reynolds, now of Madison, Wisconsin, was shot
through the leg. When the surgeons were debating the propriety of
amputating it in his hearing, he begged them to spare the leg, as it
was very valuable, being an "imported leg." He was of Irish birth,
and this well-timed piece of wit saved his leg, for the surgeons
thought, if he could perpetrate a joke at such a time, they would
trust to his vitality to save his limb.
During the night, I had full reports from all parts of our line, most
of which was partially intrenched as against a sally, and finding that
McPherson was stretching out too much on his left flank, I wrote him
a note early in the morning not to extend so much by his left; for we
had not troops enough to completely invest the place, and I
intended to destroy utterly all parts of the Augusta Railroad to the
east of Atlanta, then to withdraw from the left flank and add to the
right. In that letter I ordered McPherson not to extend any farther to
the left, but to employ General Dodge's corps (Sixteenth), then
forced out of position, to destroy every rail and tie of the railroad,
from Decatur up to his skirmish-line, and I wanted him (McPherson)
to be ready, as soon as General Garrard returned from Covington
(whither I had sent him), to move to the extreme right of Thomas,
so as to reach if possible the railroad below Atlanta, viz., the Macon
road. In the morning we found the strong line of parapet, "Peach-
Tree line," to the front of Schofield and Thomas, abandoned, and
our lines were advanced rapidly close up to Atlanta. For some
moments I supposed the enemy intended to evacuate, and in person
was on horseback at the head of Schofield's troops, who had
advanced in front of the Howard House to some open ground, from
which we could plainly see the whole rebel line of parapets, and I
saw their men dragging up from the intervening valley, by the
distillery, trees and saplings for abatis. Our skirmishers found the
enemy down in this valley, and we could see the rebel main line
strongly manned, with guns in position at intervals. Schofield was
dressing forward his lines, and I could hear Thomas farther to the
right engaged, when General McPherson and his staff rode up. We
went back to the Howard House, a double frame-building with a
porch, and sat on the steps, discussing the chances of battle, and of
Hood's general character. McPherson had also been of the same
class at West Point with Hood, Schofield, and Sheridan. We agreed
that we ought to be unusually cautious and prepared at all times for
sallies and for hard fighting, because Hood, though not deemed
much of a scholar, or of great mental capacity, was undoubtedly a
brave, determined, and rash man; and the change of commanders
at that particular crisis argued the displeasure of the Confederate
Government with the cautious but prudent conduct of General Jos.
Johnston.
 McPherson was in excellent spirits, well pleased at the progress of
events so far, and had come over purposely to see me about the
order I had given him to use Dodge's corps to break up the railroad,
saying that the night before he had gained a position on Leggett's
Hill from which he could look over the rebel parapet, and see the
high smoke-stack of a large foundery in Atlanta; that before
receiving my order he had diverted Dodge's two divisions (then in
motion) from the main road, along a diagonal one that led to his
extreme left flank, then held by Giles A. Smith's division
(Seventeenth Corps), for the purpose of strengthening that flank;
and that he had sent some intrenching-tools there, to erect some
batteries from which he intended to knock down that foundery, and
otherwise to damage the buildings inside of Atlanta. He said he
could put all his pioneers to work, and do with them in the time
indicated all I had proposed to do with General Dodge's two
divisions. Of course I assented at once, and we walked down the
road a short distance, sat down by the foot of a tree where I had my
map, and on it pointed out to him Thomas's position and his own. I
then explained minutely that, after we had sufficiently broken up the
Augusta road, I wanted to shift his whole army around by the rear to
Thomas's extreme right, and hoped thus to reach the other railroad
at East Point. While we sat there we could hear lively skirmishing
going on near us (down about the distillery), and occasionally round-
shot from twelve or twenty-four pound guns came through the trees
in reply to those of Schofield, and we could hear similar sounds all
along down the lines of Thomas to our right, and his own to the left;
but presently the firing appeared a little more brisk (especially over
about Giles G. Smith's division), and then we heard an occasional
gun back toward Decatur. I asked him what it meant. We took my
pocket-compass (which I always carried), and by noting the direction
of the sound, we became satisfied that the firing was too far to our
left rear to be explained by known facts, and he hastily called for his
horse, his staff, and his orderlies.
McPherson was then in his prime (about thirty-four years old),
over six feet high, and a very handsome man in every way, was
universally liked, and had many noble qualities. He had on his boots
outside his pantaloons, gauntlets on his hands, had on his major-
general's uniform, and wore a sword-belt, but no sword. He hastily
gathered his papers (save one, which I now possess) into a pocket-
book, put it in his breast-pocket, and jumped on his horse, saying he
would hurry down his line and send me back word what these
sounds meant. His adjutant-general, Clark, Inspector-General
Strong, and his aides, Captains Steele and Gile, were with him.
Although the sound of musketry on our left grew in volume, I was
not so much disturbed by it as by the sound of artillery back toward
Decatur. I ordered Schofield at once to send a brigade back to
Decatur (some five miles) and was walking up and down the porch
of the Howard House, listening, when one of McPherson's staff, with
his horse covered with sweat, dashed up to the porch, and reported
that General McPherson was either "killed or a prisoner." He
explained that when they had left me a few minutes before, they
had ridden rapidly across to the railroad, the sounds of battle
increasing as they neared the position occupied by General Giles A.
Smith's division, and that McPherson had sent first one, then
another of his staff to bring some of the reserve brigades of the
Fifteenth Corps over to the exposed left flank; that he had reached
the head of Dodge's corps (marching by the flank on the diagonal
road as described), and had ordered it to hurry forward to the same
point; that then, almost if not entirely alone, he had followed this
road leading across the wooded valley behind the Seventeenth
Corps, and had disappeared in these woods, doubtless with a sense
of absolute security. The sound of musketry was there heard, and
McPherson's horse came back, bleeding, wounded, and riderless. I
ordered the staff-officer who brought this message to return at once,
to find General Logan (the senior officer present with the Army of
the Tennessee), to report the same facts to him, and to instruct him
to drive back this supposed small force, which had evidently got
around the Seventeenth Corps through the blind woods in rear of
our left flank. I soon dispatched one of my own staff (McCoy, I
think) to General Logan with similar orders, telling him to refuse his
left flank, and to fight the battle (holding fast to Leggett's Hill) with
the Army of the Tennessee; that I would personally look to Decatur
and to the safety of his rear, and would reenforce him if he needed
it. I dispatched orders to General Thomas on our right, telling him of
this strong sally, and my inference that the lines in his front had
evidently been weakened by reason thereof, and that he ought to
take advantage of the opportunity to make a lodgment in Atlanta, if
possible.
Meantime the sounds of the battle rose on our extreme left more
and more furious, extending to the place where I stood, at the
Howard House. Within an hour an ambulance came in (attended by
Colonels Clark and Strong, and Captains Steele and Gile), bearing
McPherson's body. I had it carried inside of the Howard House, and
laid on a door wrenched from its hinges. Dr. Hewitt, of the army, was
there, and I asked him to examine the wound. He opened the coat
and shirt, saw where the ball had entered and where it came out, or
rather lodged under the skin, and he reported that McPherson must
have died in a few seconds after being hit; that the ball had ranged
upward across his body, and passed near the heart. He was dressed
just as he left me, with gauntlets and boots on, but his pocket-book
was gone. On further inquiry I learned that his body must have been
in possession of the enemy some minutes, during which time it was
rifled of the pocket-book, and I was much concerned lest the letter I
had written him that morning should have fallen into the hands of
some one who could read and understand its meaning. Fortunately
the spot in the woods where McPherson was shot was regained by
our troops in a few minutes, and the pocket-book found in the
haversack of a prisoner of war captured at the time, and it and its
contents were secured by one of McPherson's staff.
While we were examining the body inside the house, the battle
was progressing outside, and many shots struck the building, which
I feared would take fire; so I ordered Captains Steele and Gile to
carry the body to Marietta. They reached that place the same night,
and, on application, I ordered his personal staff to go on and escort
the body to his home, in Clyde, Ohio, where it was received with
great honor, and it is now buried in a small cemetery, close by his
mother's house, which cemetery is composed in part of the family
orchard, in which he used to play when a boy. The foundation is
ready laid for the equestrian monument now in progress, under the
auspices of the Society of the Army of the Tennessee.
The reports that came to me from all parts of the field revealed
clearly what was the game of my antagonist, and the ground
somewhat favored him. The railroad and wagon-road from Decatur
to Atlanta lie along the summit, from which the waters flow, by
short, steep valleys, into the "Peach-Tree" and Chattahoochee, to the
west, and by other valleys, of gentler declivity, toward the east
(Ocmulgee). The ridges and level ground were mostly cleared, and
had been cultivated as corn or cotton fields; but where the valleys
were broken, they were left in a state of nature—wooded, and full of
undergrowth. McPherson's line of battle was across this railroad,
along a general ridge, with a gentle but cleared valley to his front,
between him and the defenses of Atlanta; and another valley, behind
him, was clear of timber in part, but to his left rear the country was
heavily wooded. Hood, during the night of July 21st, had withdrawn
from his Peach-Tree line, had occupied the fortified line of Atlanta,
facing north and east, with Stewart's—formerly Polk's—corps and
part of Hardee's, and with G. W. Smith's division of militia. His own
corps, and part of Hardee's, had marched out to the road leading
from McDonough to Decatur, and had turned so as to strike the left
and, rear of McPherson's line "in air." At the same time he had sent
Wheeler's division of cavalry against the trains parked in Decatur.
Unluckily for us, I had sent away the whole of Garrard's division of
cavalry during the night of the 20th, with orders to proceed to
Covington, thirty miles east, to burn two important bridges across
the Ulcofauhatchee and Yellow Rivers, to tear up the railroad, to
damage it as much as possible from Stone Mountain eastward, and
to be gone four days; so that McPherson had no cavalry in hand to
guard that flank.
The enemy was therefore enabled, under cover or the forest, to
approach quite near before he was discovered; indeed, his skirmish-
line had worked through the timber and got into the field to the rear
of Giles A. Smith's division of the Seventeenth Corps unseen, had
captured Murray's battery of regular artillery, moving through these
woods entirely unguarded, and had got possession of several of the
hospital camps. The right of this rebel line struck Dodge's troops in
motion; but, fortunately, this corps (Sixteenth) had only to halt, face
to the left, and was in line of battle; and this corps not only held in
check the enemy, but drove him back through the woods. About the
same time this same force had struck General Giles A. Smith's left
flank, doubled it back, captured four guns in position and the party
engaged in building the very battery which was the special object of
McPherson's visit to me, and almost enveloped the entire left flank.
The men, however, were skillful and brave, and fought for a time
with their backs to Atlanta. They gradually fell back, compressing
their own line, and gaining strength by making junction with
Leggett's division of the Seventeenth Corps, well and strongly posted
on the hill. One or two brigades of the Fifteenth Corps, ordered by
McPherson, came rapidly across the open field to the rear, from the
direction of the railroad, filled up the gap from Blair's new left to the
head of Dodge's column—now facing to the general left—thus
forming a strong left flank, at right angles to the original line of
battle. The enemy attacked, boldly and repeatedly, the whole of this
flank, but met an equally fierce resistance; and on that ground a
bloody battle raged from little after noon till into the night. A part of
Hood's plan of action was to sally from Atlanta at the same moment;
but this sally was not, for some reason, simultaneous, for the first
attack on our extreme left flank had been checked and repulsed
before the sally came from the direction of Atlanta. Meantime,
Colonel Sprague, in Decatur, had got his teams harnessed up, and
safely conducted his train to the rear of Schofield's position, holding
in check Wheeler's cavalry till he had got off all his trains, with the
exception of three or four wagons. I remained near the Howard
House, receiving reports and sending orders, urging Generals
Thomas and Schofield to take advantage of the absence from their
front of so considerable a body as was evidently engaged on our
left, and, if possible, to make a lodgment in Atlanta itself; but they
reported that the lines to their front, at all accessible points, were
strong, by nature and by art, and were fully manned. About 4 p.m.
the expected, sally came from Atlanta, directed mainly against
Leggett's Hill and along the Decatur road. At Leggett's Hill they were
met and bloodily repulsed. Along the railroad they were more
successful. Sweeping over a small force with two guns, they reached
our main line, broke through it, and got possession of De Gress's
battery of four twenty-pound Parrotts, killing every horse, and
turning the guns against us. General Charles R. Wood's division of
the Fifteenth Corps was on the extreme right of the Army of the
Tennessee, between the railroad and the Howard House, where he
connected with Schofield's troops. He reported to me in person that
the line on his left had been swept back, and that his connection
with General Logan, on Leggett's Hill, was broken. I ordered him to
wheel his brigades to the left, to advance in echelon, and to catch
the enemy in flank. General Schofield brought forward all his
available batteries, to the number of twenty guns, to a position to
the left front of the Howard House, whence we could overlook the
field of action, and directed a heavy fire over the heads of General
Wood's men against the enemy; and we saw Wood's troops advance
and encounter the enemy, who had secured possession of the old
line of parapet which had been held by our men. His right crossed
this parapet, which he swept back, taking it in flank; and, at the
same time, the division which had been driven back along the
railroad was rallied by General Logan in person, and fought for their
former ground. These combined forces drove the enemy into
Atlanta, recovering the twenty pound Parrott guns but one of them
was found "bursted" while in the possession of the enemy. The two
six-pounders farther in advance were, however, lost, and had been
hauled back by the enemy into Atlanta. Poor Captain de Gress came
to me in tears, lamenting the loss of his favorite guns; when they
were regained he had only a few men left, and not a single horse.
He asked an order for a reequipment, but I told him he must beg
and borrow of others till he could restore his battery, now reduced to
three guns. How he did so I do not know, but in a short time he did
get horses, men, and finally another gun, of the same special
pattern, and served them with splendid effect till the very close of
the war. This battery had also been with me from Shiloh till that
time.
The battle of July 22d is usually called the battle of Atlanta. It
extended from the Howard House to General Giles A. Smith's
position, about a mile beyond the Augusta Railroad, and then back
toward Decatur, the whole extent of ground being fully seven miles.
In part the ground was clear and in part densely wooded. I rode
over the whole of it the next day, and it bore the marks of a bloody
conflict. The enemy had retired during the night inside of Atlanta,
and we remained masters of the situation outside. I purposely
allowed the Army of the Tennessee to fight this battle almost
unaided, save by demonstrations on the part of General Schofield
and Thomas against the fortified lines to their immediate fronts, and
by detaching, as described, one of Schofield's brigades to Decatur,
because I knew that the attacking force could only be a part of
Hood's army, and that, if any assistance were rendered by either of
the other armies, the Army of the Tennessee would be jealous.
Nobly did they do their work that day, and terrible was the slaughter
done to our enemy, though at sad cost to ourselves, as shown by
the following reports:

HEADQUARTERS MILITARY DIVISION OF THE

MISSISSIPPI
IN THE FIELD NEAR ATLANTA, July 23,1864.

General HALLECK, Washington, D. C.

Yesterday morning the enemy fell back to the

intrenchments proper of the city of Atlanta, which are
in a general circle, with a radius of one and a half
miles, and we closed in. While we were forming our
lines, and selecting positions for our batteries, the
enemy appeared suddenly out of the dense woods in
heavy masses on our extreme left, and struck the
Seventeenth Corps (General Blair) in flank, and was
forcing it back, when the Sixteenth Corps (General
Dodge) came up and checked the movement, but the
enemy's cavalry got well to our rear, and into Decatur,
and for some hours our left flank was completely
enveloped. The fight that resulted was continuous until
night, with heavy loss on both sides. The enemy took
one of our batteries (Murray's, of the Regular Army)
that was marching in its place in column in the road,
unconscious of danger. About 4 p.m. the enemy sallied
against the division of General Morgan L. Smith, of the
Fifteenth Corps, which occupied an abandoned line of
rifle-trench near the railroad east of the city, and
forced it back some four hundred yards, leaving in his
hands for the time two batteries, but the ground and
batteries were immediately after recovered by the
same troops reenforced. I cannot well approximate our
loss, which fell heavily on the Fifteenth and
Seventeenth Corps, but count it as three thousand; I
know that, being on the defensive, we have inflicted
equally heavy loss on the enemy.

General McPherson, when arranging his troops about

11.00 A.M., and passing from one column to another,
incautiously rode upon an ambuscade without
apprehension, at some distance ahead of his staff and
orderlies, and was shot dead.

W. T. SHERMAN, Major-General commanding.

HEADQUARTERS MILITARY DIVISION OF THE

MISSISSIPPI IN THE FIELD NEAR ATLANTA, July
26,1864.

Major-General HALLECK, Washington, D. C.

GENERAL: I find it difficult to make prompt report of

results, coupled with some data or information,
without occasionally making mistakes. McPherson's
sudden death, and Logan succeeding to the command
as it were in the midst of battle, made some confusion
on our extreme left; but it soon recovered and made
sad havoc with the enemy, who had practised one of
his favorite games of attacking our left when in
motion, and before it had time to cover its weak flank.
After riding over the ground and hearing the varying
statements of the actors, I directed General Logan to
make an official report of the actual result, and I
herewith inclose it.

Though the number of dead rebels seems excessive, I

am disposed to give full credit to the report that our
loss, though only thirty-five hundred and twenty-one
killed, wounded, and missing, the enemy's dead alone
on the field nearly equaled that number, viz., thirty-two
hundred and twenty. Happening at that point of the
line when a flag of truce was sent in to ask permission
for each party to bury its dead, I gave General Logan
authority to permit a temporary truce on that flank
alone, while our labors and fighting proceeded at all
others.

I also send you a copy of General Garrard's report of

the breaking of the railroad toward Augusta. I am now
grouping my command to attack the Macon road, and
with that view will intrench a strong line of
circumvallation with flanks, so as to have as large an
infantry column as possible, with all the cavalry to
swing round to the south and east, to strike that road
at or below East Point.

I have the honor to be, your obedient servant,

W. T. SHERMAN, Major-General commanding.

HEADQUARTERS DEPARTMENT AND ARMY OF THE

TENNESSEE
BEFORE ATLANTA GEORGIA, July 24, 1864

Major-General W. T. SHERMAN, commanding Military

Division of the Mississippi.

GENERAL: I have the honor to report the following

general summary of the result of the attack of the
enemy on this army on the 22d inst.

Total loss, killed, wounded, and missing, thirty-five

hundred and twenty-one, and ten pieces of artillery.

We have buried and delivered to the enemy, under a

flag of truce sent in by them, in front of the Third
Division, Seventeenth Corps, one thousand of their
killed.

The number of their dead in front of the Fourth

Division of the same corps, including those on the
ground not now occupied by our troops, General Blair
reports, will swell the number of their dead on his front
to two thousand.

The number of their dead buried in front of the

Fifteenth Corps, up to this hour, is three hundred and
sixty, and the commanding officer reports that at least
as many more are yet unburied; burying-parties being
still at work.

The number of dead buried in front of the Sixteenth

Corps is four hundred and twenty-two. We have over
one thousand of their wounded in our hands, the
larger number of the wounded being carried off during
the night, after the engagement, by them.

We captured eighteen stands of colors, and have them

now. We also captured five thousand stands of arms.

The attack was made on our lines seven times, and

was seven times repulsed. Hood's and Hardee's corps
and Wheeler's cavalry engaged us.

We have sent to the rear one thousand prisoners,

including thirty-three commissioned officers of high
rank.

We still occupy the field, and the troops are in fine

spirits. A detailed and full report will be furnished as
soon as completed.

Recapitulation.
Our total loss 3,521

Enemy's dead, thus far reported, buried,

and delivered to them 3,220

Total prisoners sent North 1,017

Total prisoners, wounded, in our hands 1,000
 Estimated loss of the enemy, at least 10,000

Very respectfully, your obedient servant,

Joan A. Logan, Major-General.

On the 22d of July General Rousseau reached Marietta, having

returned from his raid on the Alabama road at Opelika, and on the
next day General Garrard also returned from Covington, both having
been measurably successful. The former was about twenty-five
hundred strong, the latter about four thousand, and both reported
that their horses were jaded and tired, needing shoes and rest. But,
about this time, I was advised by General Grant (then investing
Richmond) that the rebel Government had become aroused to the
critical condition of things about Atlanta, and that I must look out for
Hood being greatly reenforced. I therefore was resolved to push
matters, and at once set about the original purpose of transferring
the whole of the Army of the Tennessee to our right flank, leaving
Schofield to stretch out so as to rest his left on the Augusta road,
then torn up for thirty miles eastward; and, as auxiliary thereto, I
ordered all the cavalry to be ready to pass around Atlanta on both
flanks, to break up the Macon road at some point below, so as to cut
off all supplies to the rebel army inside, and thus to force it to
evacuate, or come out and fight us on equal terms.
But it first became necessary to settle the important question of
who should succeed General McPherson? General Logan had taken
command of the Army of the Tennessee by virtue of his seniority,
and had done well; but I did not consider him equal to the command
of three corps. Between him and General Blair there existed a
natural rivalry. Both were men of great courage and talent, but were
politicians by nature and experience, and it may be that for this
reason they were mistrusted by regular officers like Generals
Schofield, Thomas, and myself. It was all-important that there
should exist a perfect understanding among the army commanders,
and at a conference with General George H. Thomas at the
headquarters of General Thomas J. Woods, commanding a division
in the Fourth Corps, he (Thomas) remonstrated warmly against my
recommending that General Logan should be regularly assigned to
the command of the Army of the Tennessee by reason of his
accidental seniority. We discussed fully the merits and qualities of
every officer of high rank in the army, and finally settled on Major-
General O. O. Howard as the best officer who was present and
available for the purpose; on the 24th of July I telegraphed to
General Halleck this preference, and it was promptly ratified by the
President. General Howard's place in command of the Fourth Corps
was filled by General Stanley, one of his division commanders, on
the recommendation of General Thomas. All these promotions
happened to fall upon West-Pointers, and doubtless Logan and Blair
had some reason to believe that we intended to monopolize the
higher honors of the war for the regular officers. I remember well
my own thoughts and feelings at the time, and feel sure that I was
not intentionally partial to any class, I wanted to succeed in taking
Atlanta, and needed commanders who were purely and technically
soldiers, men who would obey orders and execute them promptly
and on time; for I knew that we would have to execute some most
delicate manoeuvres, requiring the utmost skill, nicety, and
precision. I believed that General Howard would do all these
faithfully and well, and I think the result has justified my choice. I
regarded both Generals Logan and Blair as "volunteers," that looked
to personal fame and glory as auxiliary and secondary to their
political ambition, and not as professional soldiers.
As soon as it was known that General Howard had been chosen to
command the Army of the Tennessee; General Hooker applied to
General Thomas to be relieved of the command of the Twentieth
Corps, and General Thomas forwarded his application to me
approved and heartily recommended. I at once telegraphed to
General Halleck, recommending General Slocum (then at Vicksburg)
to be his successor, because Slocum had been displaced from the
command of his corps at the time when the Eleventh and Twelfth
were united and made the Twentieth.
General Hooker was offended because he was not chosen to
succeed McPherson; but his chances were not even considered;
indeed, I had never been satisfied with him since his affair at the
Gulp House, and had been more than once disposed to relieve him
of his corps, because of his repeated attempts to interfere with
Generals McPherson and Schofield. I had known Hooker since 1836,
and was intimately associated with him in California, where we
served together on the staff of General Persifer F. Smith. He had
come to us from the East with a high reputation as a "fighter," which
he had fully justified at Chattanooga and Peach-Tree Creek; at which
latter battle I complimented him on the field for special gallantry,
and afterward in official reports. Still, I did feel a sense of relief
when he left us. We were then two hundred and fifty miles in
advance of our base, dependent on a single line of railroad for our
daily food. We had a bold, determined foe in our immediate front,
strongly intrenched, with communication open to his rear for
supplies and reenforcements, and every soldier realized that we had
plenty of hard fighting ahead, and that all honors had to be fairly
earned.
Until General Slocum joined (in the latter part of August), the
Twentieth Corps was commanded by General A. S. Williams, the
senior division commander present. On the 25th of July the army,
therefore, stood thus: the Army of the Tennessee (General O. O.
Howard commanding) was on the left, pretty much on the same
ground it had occupied during the battle of the 22d, all ready to
move rapidly by the rear to the extreme right beyond Proctor's
Creek; the Army of the Ohio (General Schofield) was next in order,
with its left flank reaching the Augusta Railroad; next in order,
conforming closely with the rebel intrenchments of Atlanta, was
General Thomas's Army of the Cumberland, in the order of—the
Fourth Corps (Stanley's), the Twentieth Corps (Williams's), and the
Fourteenth Corps (Palmer's). Palmer's right division (Jefferson C.
Davis's) was strongly refused along Proctor's Creek. This line was
about five miles long, and was intrenched as against a sally about as
strong as was our enemy. The cavalry was assembled in two strong
divisions; that of McCook (including the brigade of Harrison which
had been brought in from Opelika by General Rousseau) numbered
about thirty-five hundred effective cavalry, and was posted to our
right rear, at Turner's Ferry, where we had a good pontoon-bridge;
and to our left rear, at and about Decatur, were the two cavalry
divisions of Stoneman, twenty-five hundred, and Garrard, four
thousand, united for the time and occasion under the command of
Major-General George Stoneman, a cavalry-officer of high repute. My
plan of action was to move the Army of the Tennessee to the right
rapidly and boldly against the railroad below Atlanta, and at the
same time to send all the cavalry around by the right and left to
make a lodgment on the Macon road about Jonesboro.
All the orders were given, and the morning of the 27th was fixed
for commencing the movement. On the 26th I received from General
Stoneman a note asking permission (after having accomplished his
orders to break up the railroad at Jonesboro) to go on to Macon to
rescue our prisoners of war known to be held there, and then to
push on to Andersonville, where was the great depot of Union
prisoners, in which were penned at one time as many as twenty-
three thousand of our men, badly fed and harshly treated. I wrote
him an answer consenting substantially to his proposition, only
modifying it by requiring him to send back General Garrard's division
to its position on our left flank after he had broken up the railroad at
Jonesboro. Promptly, and on time, all got off, and General Dodge's
corps (the Sixteenth, of the Army of the Tennessee) reached its
position across Proctor's Creek the same evening, and early the next
morning (the 28th) Blair's corps (the Seventeenth) deployed on his
right, both corps covering their front with the usual parapet; the
Fifteenth Corps (General Logan's) came up that morning on the right
of Blair, strongly refused, and began to prepare the usual cover. As
General Jeff. C. Davis's division was, as it were, left out of line, I
ordered it on the evening before to march down toward Turner's
Ferry, and then to take a road laid down on our maps which led from
there toward East Point, ready to engage any enemy that might
attack our general right flank, after the same manner as had been
done to the left flank on the 22d.
Personally on the morning of the 28th I followed the movement,
and rode to the extreme right, where we could hear some
skirmishing and an occasional cannon-shot. As we approached the
ground held by the Fifteenth Corps, a cannon-ball passed over my
shoulder and killed the horse of an orderly behind; and seeing that
this gun enfiladed the road by which we were riding, we turned out
of it and rode down into a valley, where we left our horses and
walked up to the hill held by Morgan L. Smith's division of the
Fifteenth Corps. Near a house I met Generals Howard and Logan,
who explained that there was an intrenched battery to their front,
with the appearance of a strong infantry support. I then walked up
to the ridge, where I found General Morgan L. Smith. His men were
deployed and engaged in rolling logs and fence-rails, preparing a
hasty cover. From this ridge we could overlook the open fields near a
meeting-house known as "Ezra Church," close by the Poor-House.
We could see the fresh earth of a parapet covering some guns (that
fired an occasional shot), and there was also an appearance of
activity beyond. General Smith was in the act of sending forward a
regiment from, his right flank to feel the position of the enemy,
when I explained to him and to Generals Logan and Howard that
they must look out for General Jeff. C. Davis's division, which was
coming up from the direction of Turner's Ferry.
As the skirmish-fire warmed up along the front of Blair's corps, as
well as along the Fifteenth Corps (Logan's), I became convinced that
Hood designed to attack this right flank, to prevent, if possible, the
extension of our line in that direction. I regained my horse, and rode
rapidly back to see that Davis's division had been dispatched as
ordered. I found General Davis in person, who was unwell, and had
sent his division that morning early, under the command of his
senior brigadier, Morgan; but, as I attached great importance to the
movement, he mounted his horse, and rode away to overtake and to
hurry forward the movement, so as to come up on the left rear of
the enemy, during the expected battle.
By this time the sound of cannon and musketry denoted a severe
battle as in progress, which began seriously at 11.30 a.m., and
ended substantially by 4 p.m. It was a fierce attack by the enemy on
our extreme right flank, well posted and partially covered. The most
authentic account of the battle is given by General Logan, who
commanded the Fifteenth Corps, in his official report to the
Adjutant-General of the Army of the Tennessee, thus:

HEADQUARTERS FIFTEENTH ARMY CORPS

BEFORE ATLANTA, GEORGIA, July 29, 1864

Lieutenant-Colonel WILLIAM T. CLARK, Assistant

Adjutant-General, Army of the Tennessee, present.

COLONEL: I have the honor to report that, in

pursuance of orders, I moved my command into
position on the right of the Seventeenth Corps, which
was the extreme right of the army in the field, during
the night of the 27th and morning of the 28th; and,
while advancing in line of battle to a more favorable
position, we were met by the rebel infantry of Hardee's
and Lee's corps, who made a determined and
desperate attack on us at 11 A.M. of the 28th
(yesterday).

My lines were only protected by logs and rails, hastily

thrown up in front of them.

The first onset was received and checked, and the

battle commenced and lasted until about three o'clock
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