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ANALYTICAL ELECTROCHEMISTRY ANALYTICALELECTROCHEMISTRYThird EditionJoseph Wang Copyright © 2006 by John Wiley & Sons, Inc. All rights reserved.Published by John Wiley & Sons, Inc., Hoboken, New Jersey.Published simultaneously in Canada.No part of this publication may be reproduced, stored in a retrieval system, or transmitted inany form or by any means, electronic, mechanical, photocopying, recording, scanning, orotherwise, except as permitted under Section 107 or 108 of the 1976 United States CopyrightAct, without either the prior written permission of the Publisher, or authorization throughpayment of the appropriate per-copy fee to the Copyright Clearance Center, Inc., 222Rosewood Drive, Danvers, MA 01923, (978) 750-8400, fax (978) 750-4470, or on the web atwww.copyright.com. 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Neither the publisher nor author shall be liable for any loss of profit or anyother commercial damages, including but not limited to special, incidental, consequential, orother damages.For general information on our other products and services or for technical support, pleasecontact our Customer Care Department within the United States at (800) 762-2974, outside theUnited States at( 317) 572-3993 or fax (317) 572-4002.Wiley also publishes its books in a variety of electronic formats. Some content that appears inprint may not be available in electronic formats. For more information about Wiley products,visit our web site at www.wiley.com.Library of Congress Cataloging-in-Publication Data:Wang, Joseph, 1948–Analytical electrochemistry / Joseph Wang.—3rd ed.p. cm.ISBN-13 978-0-471-67879-3 (cloth)ISBN-10 0-471-67879-1 (cloth)1. Electrochemical analysis. I. Title.QD115.W33 2006543′.4—dc222005028185Printed in the United States of America.10987654321 Dedicated to the memory of my parents, Elka and Moshe Wang viiCONTENTSPreface xiAbbreviations and Symbols xiii1 Fundamental Concepts 11.1 Why Electroanalysis?, 11.2 Faradaic Processes, 31.2.1 Mass-Transport-Controlled Reactions, 41.2.1.1 Potential-Step Experiment, 71.2.1.2 Potential-Sweep Experiments, 91.2.2 Reactions Controlled by the Rate of Electron Transfer, 121.2.2.1 Activated Complex Theory, 161.3 Electrical Double Layer, 191.4 Electrocapillary Effect, 231.5 Supplementary Reading, 25Problems, 27References, 282 Study of Electrode Reactions and Interfacial Properties 292.1 Cyclic Voltammetry, 292.1.1 Data Interpretation, 322.1.1.1 Reversible Systems, 322.1.1.2 Irreversible and Quasi-reversible Systems, 342.1.2 Study of Reaction Mechanisms, 35 2.1.3 Study of Adsorption Processes, 372.1.4 Quantitative Applications, 412.2 Spectroelectrochemistry, 422.2.1 Experimental Arrangement, 432.2.2 Principles and Applications, 442.2.3 Electrochemiluminescence, 472.2.4 Optical Probing of Electrode–Solution Interfaces, 482.3 Scanning Probe Microscopy, 492.3.1 Scanning Tunneling Microscopy, 502.3.2 Atomic Force Microscopy, 512.3.3 Scanning Electrochemical Microscopy, 532.4 Electrochemical Quartz Crystal Microbalance, 572.5 Impedance Spectroscopy, 58Examples, 61Problems, 63References, 643 Controlled-Potential Techniques 673.1 Chronoamperometry, 673.2 Polarography, 693.3 Pulse Voltammetry, 763.3.1 Normal-Pulse Voltammetry, 763.3.2 Differential-Pulse Voltammetry, 773.3.3 Square-Wave Voltammetry, 803.3.4 Staircase Voltammetry, 823.4 AC Voltammetry, 843.5 Stripping Analysis, 853.5.1 Anodic Stripping Voltammetry, 863.5.2 Potentiometric Stripping Analysis, 893.5.3 Adsorptive Stripping Voltammetry and Potentiometry, 913.5.4 Cathodic Stripping Voltammetry, 943.5.5 Abrasive Stripping Voltammetry, 943.5.6 Applications, 943.6 Flow Analysis, 983.6.1 Principles, 983.6.2 Cell Design, 1003.6.3 Mass Transport and Current Response, 1033.6.4 Detection Modes, 105Examples, 108Problems, 111References, 1124 Practical Considerations 1154.1 Electrochemical Cells, 1154.2 Solvents and Supporting Electrolytes, 117viiiCONTENTS 4.3 Oxygen Removal, 1184.4 Instrumentation, 1194.5 Working Electrodes, 1234.5.1 Mercury Electrodes, 1234.5.2 Solid Electrodes, 1274.5.2.1 Rotating Disk and Rotating Ring Disk Electrodes, 1284.5.2.2 Carbon Electrodes, 1304.5.2.2.1 Glassy Carbon Electrodes, 1314.5.2.2.2 Carbon Paste Electrodes, 1314.5.2.2.3 Carbon Fiber Electrodes, 1334.5.2.2.4 Diamond Electrodes, 1334.5.2.3 Metal Electrodes, 1344.5.3 Chemically Modified Electrodes, 1364.5.3.1 Self-Assembled Monolayers, 1364.5.3.2 Carbon-Nanotube-Modified Electrodes, 1394.5.3.3 Sol-gel Encapsulation of Reactive Species, 1394.5.3.4 Electrocatalytically Modified Electrodes, 1404.5.3.5 Preconcentrating Electrodes, 1414.5.3.6 Permselective Coatings, 1434.5.3.7 Conducting Polymers, 1464.5.4 Microelectrodes, 1494.5.4.1 Diffusion at Microelectrodes, 1514.5.4.2 Microelectrode Configurations, 1524.5.4.3 Composite Electrodes, 154Examples, 158Problems, 158References, 1595 Potentiometry 1655.1 Principles of Potentiometric Measurements, 1655.2 Ion-Selective Electrodes, 1735.2.1 Glass Electrodes, 1735.2.1.1 pH Electrodes, 1735.2.1.2 Glass Electrodes for Other Cations, 1775.2.2 Liquid Membrane Electrodes, 1775.2.2.1 Ion Exchanger Electrodes, 1795.2.2.2 Neutral Carrier Electrodes, 1825.2.3 Solid-State Electrodes, 1855.2.4 Coated-Wire Electrodes and Solid-State Electrodes Without anInternal Filling Solution, 1885.3 On-line, On-site, and In Vivo Potentiometric Measurements, 190Examples, 194Problems, 196References, 197CONTENTSix 6 Electrochemical Sensors 2016.1 Electrochemical Biosensors, 2026.1.1 Enzyme-Based Electrodes, 2026.1.1.1 Practical and Theoretical Considerations, 2026.1.1.2 Enzyme Electrodes of Analytical Significance, 2086.1.1.2.1 Glucose Sensors, 2086.1.1.2.2 Ethanol Electrodes, 2126.1.1.2.3 Urea Electrodes, 2136.1.1.2.4 Toxin (Enzyme Inhibition) Biosensors, 2156.1.1.3 Tissue and Bacteria Electrodes, 2156.1.2 Affinity Biosensors, 2166.1.2.1 Immunosensors, 2166.1.2.2 DNA Hybridization Biosensors, 2186.1.2.2.1 Background and Principles, 2186.1.2.2.2 Electrical Transduction of DNA Hybridization, 2196.1.2.2.3 Other Electrochemical DNA Biosensors, 2216.1.2.3 Receptor-Based Sensors, 2226.1.2.4 Electrochemical Sensors Based on MolecularlyImprinted Polymers, 2246.2 Gas Sensors, 2246.2.1 Carbon Dioxide Sensors, 2256.2.2 Oxygen Electrodes, 2266.3 Solid-State Devices, 2276.3.1 Ion-Selective Field Effect Transistors, 2276.3.2 Microfabrication of Solid-State Sensor Assemblies, 2296.3.3 Microfabrication Techniques, 2296.3.4 Micromachined Analytical Microsystems, 2326.4 Sensor Arrays, 234Examples, 237Problems, 238References, 239Index 245xCONTENTS xiPREFACEThe goal of this textbook is to cover the full scope of modern electroanalyti-cal techniques and devices. The main emphasis is on electroanalysis, ratherthan physical electrochemistry. The objective is to provide a sound under-standing of the fundamentals of electrode reactions and the principles of elec-trochemical methods, and to demonstrate their potential for solving real-lifeanalytical problems. The high performance, small size, and low cost of elec-trochemical devices has led to many important detection systems. Given theimpressive progress in electroanalytical chemistry and its growing impact onanalytical chemistry, this work offers also an up-to-date, easy-to-read presen-tation of more recent advances, including new methodologies, sensors, detec-tors, and microsystems. The book is suitable for a graduate-level course inelectroanalytical chemistry or as a supplement to a high-level undergraduatecourse in instrumental analysis. It should also be very useful to those consid-ering the use of electroanalysis in their laboratories.The material is presented in six roughly equal chapters. The first chapter isdevoted to fundamental aspects of electrode reactions and the structure of theinterfacial region. Chapter 2 discusses the study of electrode reactions andhigh-resolution surface characterization. Chapter 3 gives an overview of finite-current-controlled potential techniques. Chapter 4 describes the electro-chemical instrumentation and electrode materials (including new and modifiedmicroelectrodes). Chapter 5 deals with the principles of potentiometric meas-urements and various classes of ion-selective electrodes, while Chapter 6 isdevoted to the growing field of chemical sensors (including modern biosen-sors, gas sensors, microchip devices, and sensor arrays). Numerous up-to-datereferences, covering the latest literature, are given at the end of each chapter. By discussing more recent advances, this book attempts to bridge the commongap between research literature and standard textbooks.This third edition of Analytical Electrochemistry is extensively revised andupdated, and reflects the rapid growth of electroanalytical chemistry since1999. It contains a number of new topics, including DNA biosensors, imped-ance spectroscopy, detection for capillary electrophoresis, diamond electrodes,carbon-nanotube- and nanoparticle-based assays and devices, large-amplitudeAC voltammetry, microfluidic (“lab on a chip”) devices, or molecularly-imprinted polymeric sensors. Other topics, such as the principles of potentio-metric measurements, spectroelectrochemistry, electrochemiluminescence,modified and microelectrodes, scanning electrochemical and atomic forcemicroscopies, electrical communication between redox enzymes and elec-trodes, explosive detection, or enzyme and immunoelectrodes, have beengreatly expanded. The entire text has been updated to cover the very latest(as of August 2005) developments in electroanalytical chemistry. Numerousnew illustrations, worked-out examples and end-of-chapter problems havebeen added to this edition. Existing figures have been redrawn and improved.In the 5 years since the second edition I have received numerous suggestions,many of which have been incorporated in the second edition.Finally, I wish to thank my wife, Ruth, and my daughter, Sharon, for theirlove and patience; Vairavan Subramanian and Daphne Hui for their technicalassistance; the editorial and production staff of John Wiley & Sons, Inc. fortheir help and support; Professor Erno Pretsch (ETH, Zurich) for extremelyuseful suggestions; and the numerous electrochemists across the globe who ledto the advances reported in this textbook. Thank you all!Joseph WangTempe, AZxiiPREFACE [...]... papers and reviews covering innovations and trends in the field of electroanalytical chemistry: Bioelectrochemistry and Bioenergetics Biosensors and Bioelectronics Electroanalysis Electrochemistry Communications Electrochimica Acta Journal of Applied Electrochemistry Journal of Electroanalytical and Interfacial Electrochemistry SUPPLEMENTARY READING 25 420 380 340 300 260 0.8 0.4 0 –0.4 E–E z (V) –0.8 –1.2 Interfacial... York, 1996. Janata, J., Principles of Chemical Sensors, Plenum Press, New York, 1989. Koryta, J.; Dvorak, J., Principles of Electrochemistry, Wiley, Chichester, UK, 1987. Rieger, P., Electrochemistry, Prentice-Hall, Englewood Cliffs, NJ, 1987. Sawyer, D.; Roberts, J., Experimental Electrochemistry for Chemists, Wiley, New York, 1974. Smyth, M.; Vos, J., Analytical Voltammetry, Elsevier, Amsterdam, 1992. Turner,... not be available in electronic formats. For more information about Wiley products, visit our web site at www.wiley.com. Library of Congress Cataloging-in-Publication Data: Wang, Joseph, 1948– Analytical electrochemistry / Joseph Wang.—3rd ed. p. cm. ISBN-13 978-0-471-67879-3 (cloth) ISBN-10 0-471-67879-1 (cloth) 1. Electrochemical analysis. I. Title. QD115.W33 2006 543′.4—dc22 2005028185 Printed in the... nFE c c, ‡‡ =+ 0 α 18 FUNDAMENTAL CONCEPTS By discussing more recent advances, this book attempts to bridge the common gap between research literature and standard textbooks. This third edition of Analytical Electrochemistry is extensively revised and updated, and reflects the rapid growth of electroanalytical chemistry since 1999. It contains a number of new topics, including DNA biosensors, imped- ance spectroscopy,... of electroactive substance t 1 C b C 0 t 2 t 3 t 3 > t 2 > t 1 Figure 1.2 Concentration profiles for different times after the start of a potential-step experiment. Brett, C.; Oliveira Brett, A. M., Electrochemistry: Principles, Methods and Applications, Oxford Univ. Press, Oxford, UK, 1993. Diamond, D., Chemical and Biological Sensors, Wiley, New York, 1998. Gileadi, E., Electrode Kinetics, VCH Publishers,... devices, large-amplitude AC voltammetry, microfluidic (“lab on a chip”) devices, or molecularly- imprinted polymeric sensors. Other topics, such as the principles of potentio- metric measurements, spectroelectrochemistry, electrochemiluminescence, modified and microelectrodes, scanning electrochemical and atomic force microscopies, electrical communication between redox enzymes and elec- trodes, explosive... conditions results in a time-dependent concentration profile: (1.9) Cxt C x Dt OO O , b erf () = () − () [] {} 14 12 ∂ ∂ = ∂ ∂ + ∂ ∂ C t C r 2 r C r D 2 2 FARADAIC PROCESSES 7 1 Analytical Electrochemistry, Third Edition, by Joseph Wang Copyright © 2006 John Wiley & Sons, Inc. 1 FUNDAMENTAL CONCEPTS 1.1 WHY ELECTROANALYSIS? Electroanalytical techniques are concerned with the interplay... at the electrode–solution interface. The distinction between various electroanalytical techniques reflects the type of electrical signal used for the quantitation. The two principal types ANALYTICAL ELECTROCHEMISTRY electrode (i.e., forced convection). Convection can also occur naturally as a result of density gradients. • Migration—movement of charged particles along an electrical field (i.e., where... (common OeRZ+→ − n ∫ kaD°π kaD°π kaD°π CYCLIC VOLTAMMETRY 35 1.3 ELECTRICAL DOUBLE LAYER The electrical double layer is the array of charged particles and/or oriented dipoles existing at every material interface. In electrochemistry, such a layer reflects the ionic zones formed in the solution, to compensate for the excess of charge on the electrode (q e ). A positively charged electrode thus attracts a layer of negative . ANALYTICAL ELECTROCHEMISTRY ANALYTICALELECTROCHEMISTRYThird EditionJoseph Wang Copyright © 2006 by John. www.wiley.com.Library of Congress Cataloging-in-Publication Data:Wang, Joseph, 1948–Analytical electrochemistry / Joseph Wang.—3rd ed.p. cm.ISBN-13 978-0-471-67879-3 (cloth)ISBN-10