Fundamentals of Electroanalytical Chemistry

This thoroughly updated open learning text provides an introduction to electroanalytical chemistry, one of today's fastest growing and most exciting frontiers of analytical science. The author discusses electroanalysis in a non-mathematical and informal tutorial style and offers over 250 discussion and self-assessment questions. In addition he includes 50 worked examples that provide excellent material for testing the reader's understanding of the subject matter. The topics covered include the following: * Simple emf measurements with cells * Equilibrium and dynamic measurements * Polarography * Cyclic voltammetry * Rotated disc, ring-disc and wall-jet electrodes * In situ spectroelectrochemistry measurements * Impedance analysis * Preparation of electrodes * Data processing The book also contains a comprehensive bibliography and details of web-based resources. It assumes no prior knowledge of this powerful branch of analytical science and will be an invaluable aid for anyone wanting to perform analytical measurements using electrochemical technqiues. Is approach makes it also ideal for students.

The author, Paul Monk, was brought up in Hastings, on England's south coast, where he attended a local comprehensive school. Despite this education, he achieved entrance to the University of Exeter to read Chemistry. Having obtained a B. Sc. degree and then a doctorate (in 1989) on the electrochemistry of the viologens, he was awarded a fellowship at the University of Aberdeen to study the electrochromism of thin films of tungsten trioxide. He joined the staff of the Department of Chemistry and Materials, Manchester Metropolitan University in 1991 as a lecturer in Physical Chemistry. He was promoted to Senior Lecturer in 1998. He enjoys writing, and is also the author of the books Electrochromism: Fundamentals and Applications and The Viologens, both of these published by John Wiley & Sons. Paul Monk is married, in which state he is instructed to profess great happiness, and is also a Methodist Local Preacher.

Series Preface

xi

Preface

xiii

Acronyms, Abbreviations and Symbols

xv

About the Author

xxi

Explanatory Foreword

1

(10)

Electroanalysis

1

(2)

Nomenclature and Terminology (IUPAC and Non-IUPAC)

3

(6)

This Book

9

(2)

Reference

10

(1)

Introductory Overview and Discussion of Experimental Methodology

11

(14)

Overview of the Differences between Equilibrium and Dynamic Measurements

12

(5)

The Magnitude of the Current: Rates of Electron Transfer, Mass Transport, and their Implications

17

(6)

The Implications of Using Diffusive or Convective Control

23

(2)

Reference

24

(1)

Equilibrium Measurements: `Frustrated' Equilibrium with No Net Electron Transfer

25

(60)

Introduction: What is `Equilibrium'? Concepts of `Frustrated' Equilibrium

26

(3)

Revision: emf, Electrode Potentials and the SHE

29

(7)

Terminology and Symbolisms

29

(4)

Reference Electrodes

33

(3)

The Nernst Equation and its Permutations

36

(8)

Limitations of the Nernst Equation

42

(2)

Differences between Concentration and Activity

44

(13)

Brief Discourse on Ion-Ion Interactions

44

(3)

Activities

47

(1)

Activity Coefficients

48

(2)

Revision of Debye-Huckel Theory

50

(7)

Applications Based on Calculations with the Nernst Equation

57

(14)

pH Determination and the pH Electrode

57

(3)

Ion-Selective Electrodes

60

(9)

Potentiometric Determination of Solubility Constants

69

(2)

Causes and Treatment of Errors

71

(14)

Current Passage through a Cell Causing Internal Compositional Changes

72

(1)

Current Passage through Reference Electrodes

73

(1)

Determination of Concentration when the Mean Ionic Activity Coefficient is Unknown

74

(1)

Cell Design and the Effects of `IR Drop'

74

(1)

Additional Sources of Potential Owing to Ionic Transport and Junction Potentials

75

(10)

Potentiometry: True Equilibrium and Monitoring Systems with Electron Transfer

85

(22)

Introduction to Potentiometry

86

(14)

Redox Titrations: End Points and Shapes of Curves

86

(10)

Determination of Equilibrium Constants and Solubility Constants

96

(4)

Redox Indicators

100

(3)

Treatment of Errors

103

(4)

Routine Errors

103

(1)

Errors Caused by Low Precision of Volume Determination: Use of Gran Plots

103

(2)

Errors Caused by Poor ISE Selectivity

105

(2)

Coulometry

107

(24)

Introduction to Coulometry and Faraday's Laws

108

(14)

Faradaic and Non-Faradaic Charge

115

(2)

The Effects of Absorption, Capacitance and the Electrode Double-Layer

117

(5)

Stripping

122

(3)

Microelectrodes

125

(2)

Introduction to Electron Mediation

127

(1)

Treatment of Errors

128

(3)

Analysis by Dynamic Measurement, A: Systems under Diffusion Control

131

(64)

Experimental Introduction to Dynamic Electrochemistry

132

(4)

Chronoamperometry: Current Determined with Time

136

(6)

The Nernst Layer (`Depletion' Layer)

137

(4)

The Cottrell Equation

141

(1)

Polarography at Hg Electrodes

142

(14)

The Polarographic Experiment

143

(1)

Polarography: the Dropping-Mercury Electrode

144

(7)

Treatment of Polarographic Data: Obtaining E1/2 and its Use

151

(2)

Determination of Equilibrium Constants: Shifts in E1/2 on Complexation

153

(3)

Linear-Sweep and Cyclic Voltammetry at Solid Electrodes

156

(20)

The Randles-Sevcik Equation

162

(4)

The Effect of Slow Electron Transfer: Semiconducting Electrodes

166

(2)

Quantification of Diffusion Phenomena

168

(1)

Mechanistic Data from Voltammetry

169

(7)

Improving Sensitivity: Pulse Methods

176

(9)

Normal Pulse Voltammetry

176

(3)

Differential Pulse Voltammetry

179

(3)

Square-Wave Pulse Voltammetry

182

(3)

Stripping Voltammetry

185

(3)

The Glucose Sensor: a Worked Example of Voltammetric Analysis

188

(3)

Causes and Treatment of Errors

191

(4)

Polarographic `Peaks'

191

(1)

IR Drop: the Lugging Capillary

192

(3)

Analysis by Dynamic Measurement, B: Systems under Convection Control

195

(42)

Introduction to Convective Systems

196

(1)

The Rotated Disc Electrode

197

(13)

Discussion of the Experiment

197

(5)

The Levich Equation

202

(8)

Flow Cells, Channel Electrodes and Wall-Jet Electrodes

210

(8)

Flow Cells and Channel Electrodes

210

(5)

The Wall-Jet Electrode

215

(3)

The Rotated Ring-Disc Electrode

218

(5)

Rate Constants of Electron Transfer

223

(11)

The Tafel Approach to Electrode Kinetics

225

(1)

The Butler-Volmer Approach

226

(6)

Koutecky-Levich Plots and Measurement of the Rates of Electron Transfer

232

(2)

Causes and Treatment of Errors

234

(3)

Reference

236

(1)

Additional Methods

237

(38)

Spectroelectrochemistry

238

(15)

Introduction: What is Spectroelectrochemistry?

238

(1)

Electrochemical UV - Visible Spectroscopy

239

(8)

Electrochemical EPR Spectroscopy

247

(6)

Electroanalytical Measurements Involving Impedance

253

(17)

What is Impedance?

253

(9)

Impedances of Real Cells: Quantification of Diffusion Phenomena and the Warburg Impedance

262

(8)

Causes and Treatment of Errors

270

(5)

Discontinuities in an OTE Conductor

270

(1)

Total Internal Reflection in UV - Visible Spectroscopy

270

(1)

Large Absorbances and the Optical Band Edge

271

(2)

Stray EPR Absorptions

273

(1)

Reference

274

(1)

Electrode Preparation

275

(14)

Preparation and Characterization of Solid Electrode Surfaces

276

(10)

Cleaning Electrode Surfaces

276

(4)

Manufacturing Electrodes

280

(4)

Making Reference Electrodes

284

(2)

Microelectrodes

286

(1)

Screen-Printed Electrodes

287

(2)

Reference

288

(1)

Data Processing

289

(16)

Simulation of Electrochemical Data

289

(10)

Sample Programs

293

(6)

Simulation Packages

299

(3)

Web-Based Resources

302

(3)

References

304

(1)

Appendices

305

(6)

1 Named Electroanalysis Equations Used in the Text

305

(1)

2 Writing a Cell Schematic

306

(1)

3 The Electrode Potential Series (against the SHE)

307

(4)

Responses to Self-Assessment Questions

311

(18)

Bibliography

329

(8)

Glossary of Terms

337

(10)

SI Units and Physical Constants

347

(4)

Periodic Table

351

(2)

Index

353

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Fundamentals of Electroanalytical Chemistry

Summary

Author Biography

Table of Contents

Supplemental Materials