A.J. Bard, L.R. Faulkner - Electrochemical methods - Fundamentals and Applications (794273)
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SECOND EDITIONELECTROCHEMICALMETHODSFundamentals andApplicationsAllen J. BardLarry R. FaulknerDepartment of Chemistry and BiochemistryUniversity of Texas at AustinJOHN WILEY & SONS, INC.New Yorke Chichester • WeinheimBrisbane e Singapore e TorontoAcquisitions EditorDavid HarrisSenior Production EditorElizabeth SwainSenior Marketing ManagerCharity RobeyIllustration EditorEugene AielloThis book was set in 10/12 Times Roman by University Graphics and printed and bound byHamilton. The cover was printed by Phoenix.This book is printed on acid-free paper,ooCopyright 2001 © John Wiley & Sons, Inc.
All rights reserved.No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by anymeans, electronic, mechanical, photocopying, recording, scanning or otherwise, except as permitted underSections 107 or 108 of the 1976 United States Copyright Act, without either the prior written permission of thePublisher, or authorization through payment of the appropriate per-copy fee to the Copyright Clearance Center,222 Rosewood Drive, Danvers, MA 01923, (978) 750-8400, fax (978) 750-4470. Requests to the Publisher forpermission should be addressed to the Permissions Department, John Wiley & Sons, Inc., 605 Third Avenue,New York, NY 10158-0012, (212) 850-6011, fax (212) 850-6008, E-Mail: PERMREQ@WILEY.COM.To order books or for customer service, call 1 (800)-CALL-WILEY (225-5945).Library of Congress Cataloging in Publication Data:Bard, Allen J.Electrochemical methods : fundamentals and applications / Allen J.
Bard, Larry R.Faulkner.— 2nd ed.p. cm.Includes index.ISBN 0-471-04372-9 (cloth : alk. paper)1. Electrochemistry. I. Faulkner, Larry R., 1944- II. Title.QD553.B37 2000541.3'7_dc2100-038210Printed in the United States of America10 9 8 7 6 5 4 3 2 1PREFACEIn the twenty years since the appearance of our first edition, the fields of electrochemistryand electroanalytical chemistry have evolved substantially. An improved understandingof phenomena, the further development of experimental tools already known in 1980, andthe introduction of new methods have all been important to that evolution.
In the prefaceto the 1980 edition, we indicated that the focus of electrochemical research seemed likelyto shift from the development of methods toward their application in studies of chemicalbehavior. By and large, history has justified that view. There have also been importantchanges in practice, and our 1980 survey of methodology has become dated.
In this newedition, we have sought to update the book in a way that will extend its value as a generalintroduction to electrochemical methods.We have maintained the philosophy and approach of the original edition, which is toprovide comprehensive coverage of fundamentals for electrochemical methods now inwidespread use.
This volume is intended as a textbook and includes numerous problemsand chemical examples. Illustrations have been employed to clarify presentations, and thestyle is pedagogical throughout. The book can be used in formal courses at the senior undergraduate and beginning graduate levels, but we have also tried to write in a way thatenables self-study by interested individuals. A knowledge of basic physical chemistry isassumed, but the discussions generally begin at an elementary level and develop upward.We have sought to make the volume self-contained by developing almost all ideas of anyimportance to our subject from very basic principles of chemistry and physics.
Becausewe stress foundations and limits of application, the book continues to emphasize themathematical theory underlying methodology; however the key ideas are discussed consistently apart from the mathematical basis. Specialized mathematical background is covered as needed. The problems following each chapter have been devised as teaching tools.They often extend concepts introduced in the text or show how experimental data are reduced to fundamental results. The cited literature is extensive, but mainly includes onlyseminal papers and reviews.
It is impossible to cover the huge body of primary literaturein this field, so we have made no attempt in that direction.Our approach is first to give an overview of electrode processes (Chapter 1), showing the way in which the fundamental components of the subject come together in anelectrochemical experiment. Then there are individual discussions of thermodynamicsand potential, electron-transfer kinetics, and mass transfer (Chapters 2-4). Conceptsfrom these basic areas are integrated together in treatments of the various methods(Chapters 5-11). The effects of homogeneous kinetics are treated separately in a waythat provides a comparative view of the responses of different methods (Chapter 12).Next are discussions of interfacial structure, adsorption, and modified electrodes (Chapters 13 and 14); then there is a taste of electrochemical instrumentation (Chapter 15),which is followed by an extensive introduction to experiments in which electrochemistryis coupled with other tools (Chapters 16-18).
Appendix A teaches the mathematicalbackground; Appendix В provides an introduction to digital simulation; and Appendix Сcontains tables of useful data.vi • PrefaceThis structure is generally that of the 1980 edition, but important additions have beenmade to cover new topics or subjects that have evolved extensively. Among them are applications of ultramicroelectrodes, phenomena at well-defined surfaces, modified electrodes, modern electron-transfer theory, scanning probe methods, LCEC, impedancespectrometry, modern forms of pulse voltammetry, and various aspects of spectroelectrochemistry. Chapter 5 in the first edition ("Controlled Potential Microelectrode Techniques—Potential Step Methods") has been divided into the new Chapter 5 ("BasicPotential Step Methods") and the new Chapter 7 ("Polarography and Pulse Voltammetry").
Chapter 12 in the original edition ("Double Layer Structure and Adsorbed Intermediates in Electrode Processes") has become two chapters in the new edition: Chapter 12("Double-Layer Structure and Adsorption") and Chapter 13 ("Electroactive Layers andModified Electrodes"). Whereas the original edition covered in a single chapter experiments in which other characterization methods are coupled to electrochemical systems(Chapter 14, "Spectrometric and Photochemical Experiments"), this edition features awholly new chapter on "Scanning Probe Techniques" (Chapter 16), plus separate chapterson "Spectroelectrochemistry and Other Coupled Characterization Methods" (Chapter 17)and "Photoelectrochemistry and Electrogenerated Chemiluminescence" (Chapter 18).
Theremaining chapters and appendices of the new edition directly correspond with counterparts in the old, although in most there are quite significant revisions.The mathematical notation is uniform throughout the book and there is minimal duplication of symbols. The List of Major Symbols and the List of Abbreviations offer definitions, units, and section references. Usually we have adhered to the recommendations ofthe IUPAC Commission on Electrochemistry [R. Parsons et al., Pure Appl. С hem., 37,503 (1974)]. Exceptions have been made where customary usage or clarity of notationseemed compelling.Of necessity, compromises have been made between depth, breadth of coverage, andreasonable size. "Classical" topics in electrochemistry, including many aspects of thermodynamics of cells, conductance, and potentiometry are not covered here.
Similarly, wehave not been able to accommodate discussions of many techniques that are useful but notwidely practiced. The details of laboratory procedures, such as the design of cells, theconstruction of electrodes, and the purification of materials, are beyond our scope. In thisedition, we have deleted some topics and have shortened the treatment of others. Often,we have achieved these changes by making reference to the corresponding passages in thefirst edition, so that interested readers can still gain access to a deleted or attenuated topic.As with the first edition, we owe thanks to many others who have helped with thisproject. We are especially grateful to Rose McCord and Susan Faulkner for their conscientious assistance with myriad details of preparation and production.
Valuable commentshave been provided by S. Amemiya, F. C. Anson, D. A. Buttry, R. M. Crooks, P. He,W. R. Heineman, R. A. Marcus, A. C. Michael, R. W. Murray, A. J. Nozik, R. A. Osteryoung, J.-M. Saveant, W. Schmickler, M. P. Soriaga, M. J. Weaver, H. S. White, R. M.Wightman, and C. G. Zoski. We thank them and our many other colleagues throughoutthe electrochemical community, who have taught us patiently over the years. Yet again,we also thank our families for affording us the time and freedom required to undertakesuch a large project.Allen /. BardLarry R. FaulknerCONTENTSMAJOR SYMBOLS ixSTANDARD ABBREVIATIONSxix1INTRODUCTION AND OVERVIEW OF ELECTRODE PROCESSES2POTENTIALS AND THERMODYNAMICS OF CELLS3KINETICS OF ELECTRODE REACTIONS4MASS TRANSFER BY MIGRATION AND DIFFUSION144871375BASIC POTENTIAL STEP METHODS6POTENTIAL SWEEP METHODS7POLAROGRAPHY AND PULSE VOLTAMMETRY8CONTROLLED-CURRENT TECHNIQUES9METHODS INVOLVING FORCED CONVECTION—HYDRODYNAMICMETHODS 33110156226261305TECHNIQUES BASED ON CONCEPTS OF IMPEDANCE36811BULK ELECTROLYSIS METHODS12ELECTRODE REACTIONS WITH COUPLED HOMOGENEOUS CHEMICALREACTIONS 47141713DOUBLE-LAYER STRUCTURE AND ADSORPTION14ELECTROACTIVE LAYERS AND MODIFIED ELECTRODES15ELECTROCHEMICAL INSTRUMENTATION53458063216SCANNING PROBE TECHNIQUES17SPECTROELECTROCHEMISTRY AND OTHER COUPLED CHARACTERIZATIONMETHODS 68065918PHOTOELECTROCHEMISTRY AND ELECTROGENERATEDCHEMILUMINESCENCE 736APPENDICESAMATHEMATICAL METHODSВDIGITAL SIMULATIONS OF ELECTROCHEMICAL PROBLEMSСREFERENCE TABLESINDEX814808769785MAJOR SYMBOLSListed below are symbols used in several chapters or in large portions of a chapter.
Symbols similar to some of these may have different local meanings. In most cases, the usagefollows the recommendations of the IUPAC Commission on Electrochemistry [R. Parsons et al., Pure Appl. Chem., 37, 503 (1974).]; however there are exceptions.A bar over a concentration or a current [ej*., C o (x, s)] indicates the Laplace transform of the variable. The exception is when / indicates an average current in polarography.STANDARD SUBSCRIPTSaсDdanodic(a) cathodic(b) chargingdiskdiffusiondl double layereq equilibriumf(a) forward(b) faradaiclimiting/0PRrpertaining to species 0 in О + ne ±± Rpeak(a) pertaining to species R in О + ne ^ R(b) ringreverseROMAN SYMBOLSSymbolСCBcdc'tMeaningUsual UnitsSectionReferences(a) area(b) cross-sectional area of a porouselectrode(c) frequency factor in a rate expression(d) open-loop gain of an amplifierabsorbance(a) internal area of a porous electrode(b) tip radius in SECMactivity of substance j in a phase aaFv/RTcmcm 21.3.211.6.2depends on ordernonenonecm 23.1.215.1.117.1.111.6.216.4.12.1.56.3.113.5.31.2.2, 10.1.210.41.2.2, 13.2.2capacitanceseries equivalent capacitance of a celldifferential capacitance of the doublelayerintegral capacitance of the double layerconcentration of species;bulk concentration of species;concentration of species; at distance xnones" 1mol/cm2FFF, F/cm2F, F/cm2M, mol/cm3M, mol/cm3M, mol/cm313.2.21.4.2, 4.4.31.4Major SymbolsSymbolMeaningUsual UnitsSectionReferencesCjCx = 0)concentration of species j at theelectrode surfaceconcentration of species у at distance xat time tconcentration of species у at theelectrode surface at time tconcentration of species у at distance уaway from rotating electrodesurface concentration of species у at arotating electrodespace charge capacitancepseudocapacityspeed of light in vacuodiffusion coefficient for electrons withinthe film at a modified electrodediffusion coefficient of species уconcentration density of states for species уmodel diffusion coefficient in simulationdiffusion coefficient for the primaryreactant within the film at a modifiedelectrodedistance of the tip from the substrate inSECMdensity of phase у(a) potential of an electrode versus areference(b) emf of a reaction(c) amplitude of an ac voltage(a) pulse height in DPV(b) step height in tast or staircasevoltammetry(c) amplitude (1/2 p-p) of ac excitationin ac voltammetryelectron energyelectric field strength vectorelectric field strengthvoltage or potential phasor(a) standard potential of an electrode ora couple(b) standard emf of a half-reactiondifference in standard potentials fortwo coupleselectron energy corresponding to thestandard potential of a coupleformal potential of an electrodeactivation energy of a reactionac component of potentialbase potential in NPV and RPVdc component of potentialM, mol/cm31.4.2M, mol/cm34.4M, mol/cm34.4.3M, mol/cm39.3.3M, mol/cm39.3.4F/cmFcm/scm /s18.2.210.1.317.1.214.4.2cm2/scm 3 eV~ !nonecm2/s1.4.1,4.43.6.3B.1.3.B.1.814.4.2/xm, nm16.4.1g/cm3V1.1,2.1VVmVmV2.110.1.27.3.47.3.1mV10.5.1eVV/cmV/cmVV2.2.5, 3.6.32.2.12.2.110.1.22.1.4VV2.1.46.6eV3.6.3VkJ/molmVVV2.1.63.1.210.1.17.3.2, 7.3.310.1.1Cj(x, t)Cj(O, f)Cj(y = 0)CscСDj(A, E)DM£sd*\EAEE%%E£°AE°E°E0'EAEacEbEdcMajor SymbolsSymbolMeaningUsual UnitsSectionReferencesЕщEFequilibrium potential of an electrodeFermi levelflat-band potentialbandgap of a semiconductorinitial potentialjunction potentialmembrane potentialpeak potential(a)|£pa-£pc|inCV(b) pulse height in SWVpotential where / = /p/2 in LSVanodic peak potentialcathodic peak potentialstaircase step height in SWVpotential of zero chargeswitching potential for cyclic voltammetryquarter-wave potential inchronopotentiometry(a) measured or expected half-wavepotential in voltammetry(b) in derivations, the "reversible"half-wave potential,Eo> + (RT/nF)\n(DR/D0)l/2potential where i/i^ = 1 / 4potential where ///d = 3/4(a) electronic charge(b) voltage in an electric circuitinput voltageoutput voltagevoltage across the input terminals of anamplifiererror function of xerror function complement of xthe Faraday constant; charge on onemole of electrons(a) F/RT(b) frequency of rotation(c) frequency of a sinusoidal oscillation(d) SWV frequency(e) fraction titratedFermi functionfractional concentration of species / inboxy after iteration к in a simulationGibbs free energyGibbs free energy change in a chemicalprocesselectrochemical free energystandard Gibbs free energyVeVVeVVmVmVVVmVVVVmVVVV1.3.2,3.4.12.2.5, 3.6.318.2.218.2.26.2.12.3.42.46.2.26.57.3.56.2.26.56.57.3.513.2.26.58.3.1V1.4.2,5.4,5.5V5.4VV5.4.15.4.1EmEgE;ЩEmEPA£PEp/2£pa£pc£Z*лЕфE\I2ЕщЕЪ1Аee\e0ег%)erfc(x)Ff/(E)fUk)GAGGG°сVVV/xV10.1.1,15.115.215.1.115.1.1nonenoneСA.3A.3V" 1r/ss- 1s- 1nonenonenone9.310.1.27.3.511.5.23.6.3B.1.3kJ, kJ/molkJ, kJ/mol2.2.42.1.2,2.1.3kJ, kJ/molkJ, kJ/mol2.2.43.1.2xixiiMajor SymbolsSymbolMeaningUsual UnitsSectionReferencesAG°standard Gibbs free energy change in achemical processstandard Gibbs free energy of activationstandard free energy of transfer forspecies j from phase a into phase /3(a) gravitational acceleration(b) interaction parameter in adsorptionisotherms(a) enthalpykJ, kJ/mol2.1.2,2.1.3kJ/molkJ/mol3.1.22.3.6дс!transfer, jjH2cm/s22J-cm /molkJ, kJ/mol-l/2sMiA#°//(0/7А/8i/(0)*АOd)maxenthalpy change in a chemical processstandard enthalpy change in a chemicalprocessstandard enthalpy of activationPlanck constantcorrected mercury column height at a DMEamplitude of an ac currentconvolutive transform of current;semi-integral of currentcurrent phasordiffusion current constant for averagecurrentdiffusion current constant for maximumcurrentpeak value of ac current amplitudecurrentdifference current in SWV = if — irdifference current in DPV = /(r) - Z(r')initial current in bulk electrolysischaracteristic current describing flux of theprimary reactant to a modified RDEanodic component current(a) charging current(b) cathodic component current(a) current due to diffusive flux(b) diffusion-limited currentaverage diffusion-limited current flowover a drop lifetime at a DMEdiffusion-limited current at tm.dX at aDME (maximum current)characteristic current describing diffusionof electrons within the film at amodified electrode(a) faradaic current(b) forward currentkinetically limited currentcharacteristic current describingcross-reaction within the film at amodified electrodekJ, kJ/molkJ, kJ/mol13.5.22.1.25.5.12.1.22.1.23.1.2kJ/molJ-scmAC/s1/27.1.410.1.26.7.1A^A-s1/2/(mg2/3-mM)10.1.27.1.3M-s 1/2 /(mg 2/3 -mM)7.1.3AAAAAA10.5.11.3.27.3.57.3.411.3.114.4.2AAAAAA3.26.2.43.24.15.2.1AAAAAA7.1.27.1.214.4.25.79.3.414.4.2Major SymbolsSymbolMeaningUsual UnitsSectionReferencesЧlimiting currentlimiting anodic currentlimiting cathodic currentmigration currentcharacteristic current describingpermeation of the primary reactantinto the film at a modified electrodepeak currentanodic peak currentcathodic peak currentcurrent during reversal step(a) characteristic current describingdiffusion of the primary reactantthrough the film at a modified electrode(b) substrate current in SECMsteady-state currenttip current in SECMtip current in SECM far from thesubstrateexchange currenttrue exchange currentimaginary part of complex function wflux of species j at location x at time t(a) current density(b) box index in a simulationAAAAA1.4.21.4.21.4.24.114.4.2AAAAA6.2.26.5.16.5.15.714.4.2AAAA16.4.45.316.4.216.4.1k&kch>P'pa*pc'r'S4sh*T,ooh*0,tIm(w)/jfe t)j(c)V^IhКкk°Кkf*??k°exchange current densityequilibrium constantprecursor equilibrium constant forreactant j(a) rate constant for a homogeneousreaction(b) iteration number in a simulation(c) extinction coefficientBoltzmann constantstandard heterogeneous rate constant(a) heterogeneous rate constant foroxidation(b) homogeneous rate constant for"backward" reaction(a) heterogeneous rate constant forreduction(b) homogeneous rate constant for"forward" reactionpotentiometric selectivity coefficient ofinterferenty toward a measurementof species /true standard heterogeneous rateconstant•AAmol c m " 2 s" 1A/cm2nonenoneA/cmnonedepends on case3.4.1,3.5.413.7.1A.51.4.1,4.11.3.2B.1.2A.53.4.1,3.5.43.6.1depends on ordernonenoneJ/Kcm/scm/sB.I17.1.2depends on order3.1cm/s3.2depends on order3.1none2.4cm/s13.7.13.3, 3.43.2xuixivMajor SymbolsSymbolMeaningLL{f(t)}L~]{f(s)}I€length of a porous electrodeLaplace transform of/(0 = f(s)inverse Laplace transform of f(s)thickness of solution in a thin-layer cellnumber of iterations corresponding to t^in a simulationmercury flow rate at a DMEconvolutive transform of current;semi-integral of currentmass-transfer coefficient of species jcollection efficiency at an RRDE(a) acceptor density(b) Avogadro's numberdonor densitytotal number of moles of species j ina system(a) stoichiometric number of electronsinvolved in an electrode reaction(b) electron density in a semiconductor(c) refractive indexcomplex refractive indexnumber concentration of each ion in az: z electrolyteelectron density in an intrinsicsemiconductor(a) number of moles of species у in a phase(b) number concentration of ion у in anelectrolytenumber concentration of ion у in the bulkelectrolyteoxidized form of the standard systemО + ne ^ R; often used as a subscriptdenoting quantities pertaining tospecies Оpressure(a) hole density in a semiconductor(b) mjA/Vhole density in an intrinsic semiconductorcharge passed in electrolysischarge required for complete electrolysisof a component by Faraday's lawchronocoulometric charge from adiffusing componentcharge devoted to double-layercapacitanceexcess charge on phase уreduced form of the standard system,О + ne i=^ R; often used as a subscriptdenoting quantities pertaining tospecies Rmm(t)m-}NNANDiVjnnn°щщn®ОPpP\Q<2°gdQdicfRUsual UnitsSectionReferencescmnone11.6.2A.IA.I11.7.2B.1.4mg/s1/2C/s7.1.26.7.1cm/snone3cm"1тоГ3cm"mol1.4.29.4.218.2.2none1.3.2cm" 3nonenonecm" 318.2.217.1.217.1.213.3.2cm" 318.2.2molcm" 32.2.4, 13.1.113.3.2cm-318.2.211.3.113.3.2Pa, atmcm" 3s" 1cm" 3СС18.2.211.3.118.3.21.3.2,5.8.1, 11.3.111.3.4с5.8.1с5.8СдС1.2,2.2Major SymbolsSymbolMeaningUsual UnitsR(a) gas constant(b) resistance(c) fraction of substance electrolyzed ina porous electrode(d) reflectanceseries equivalent resistance of a cellcharge-transfer resistancefeedback resistancemass-transfer resistance(a) solution resistance(b) series resistance in an equivalentcircuituncompensated resistanceohmic solution resistanceradial distance from the center of anelectroderadius of a capillaryradius of an electroderadius of the disk in an RDE or RRDEinner radius of a ring electrodeouter radius of a ring electrodeReynolds numberreal part of complex function wentropy change in a chemical processstandard entropy change in a chemicalprocessstandard entropy of activationunit step function rising at t = т(a) Laplace plane variable, usuallycomplementary to t(b) specific area of a porous electrodeabsolute temperaturetimetransference number of species уknown characteristic time in a simulationdrop time at a DMEpulse width in SWVmobility of ion (or charge carrier) jvolume(a) linear potential scan rate(b) homogeneous reaction rate(c) heterogeneous reaction rate(d) linear velocity of solution flow, usuallya function of position(a) "backward" homogeneous reaction rate(b) anodic heterogeneous reaction rate(a) "forward" homogeneous reaction rate(b) cathodic heterogeneous reaction ratecomponent of velocity in the j directionJmol^K"RBRetR{RmtRsRuRarrcfor\Г2гъReRe(w)ASAS0AS*Sr(t)sTt4чтшх'pЩVVvhVfV\SectionReferences1ft10.1.211.6.2none17.1.210.41.3.3,3.4.315.21.4.2,3.4.61.3.41.2.4, 10.1.3noneftftaftftftftft1.3.4, 15.610.1.35.2.2,5.3,9.3.1cmcmcmcmcmcmnonekJ/K.kJmol^K"1kJ/K.kJmol^K"1kJmol^K"1none1cm"Кsnonesss7.1.35.2.2, 5.39.3.59.4.19.4.19.2.1A.52.1.22.1.23.1.2A.
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