Fundamentals of Electroanalytical Chemistry

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Edition: 1st
Format: Paperback
Pub. Date: 2001-03-30
Publisher(s): WILEY
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Summary

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.

Author Biography

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.

Table of Contents

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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