TechniquesandMechanismsinElectrochemistryPA

TechniquesandMechanismsinElectrochemistryP.A.ChristensenandA.HamnettDepartmentofChemistryUniversityofNewcastleuponTyneKluwerAcademicPublishers1994PageivPublishedByBlackieAcademic&Professional,AnImprintOfChapman&Hall,WesterCleddensRoad,Bishopbriggs,GlasgowG642NZChapman&Hall,2-6BoundaryRow,LondonSE18HN,UKBlackieAcademic&Professional,WesterCleddensRoad,Bishopbriggs,GlasgowG642NZ,UKChapman&HallInc.,OnePennPlaza,41stFloor,NewYorkNY10119,USAChapman&HallJapan,ThomsonPublishingJapan,HirakawachoNemotoBuilding,6F,1-7-11Hirakawa-cho,Chiyoda-ku,Tokyo102,JapanDABook(Aust.)PtyLtd.,648WhitehorseRoad,Mitcham3132,Victoria,AustraliaChapman&HallIndia,R.Seshadri,32SecondMainRoad,CITEast,Madras600035,IndiaFirstedition1994©1994Chapman&HallTypesetin10/12ptTimesNewRomanbyThomsonPress(India)Ltd.,NewDelhiPrintedinGreatBritainattheAldenPress,OxfordISBN0751401293Apartfromanyfairdealingforthepurposesofresearchorprivatestudy,orcriticismorreview,aspermittedundertheUKCopyrightDesignsandPatentsAct,1988,thispublicationmaynotbereproduced,stored,ortransmitted,inanyformorbyanymeans,withoutthepriorpermissioninwritingofthepublishers,orinthecaseofreprographicreproductiononlyinaccordancewiththetermsofthelicencesissuedbytheCopyrightLicensingAgencyintheUK,orinaccordancewiththetermsoflicencesissuedbytheappropriateReproductionRightsOrganizationoutsidetheUK.EnquiriesconcerningreproductionoutsidethetermsstatedhereshouldbesenttothepublishersattheGlasgowaddressprintedonthispage.Thepublishermakesnorepresentation,expressorimplied,withregardtotheaccuracyoftheinformationcontainedinthisbookandcannotacceptanylegalresponsibilityorliabilityforanyerrorsoromissionsthatmaybemade.AcataloguerecordforthisbookisavailablefromtheBritishLibraryLibraryofCongressCataloging-in-PublicationdataChristensen,P.A.,1960–Techniquesandmechanismsinelectrochemistry/P.A.ChristensenandA.Hamnett.--1sted.p.cm.Includesbibliographicalreferencesandindex.ISBN0-7514-0129-3(PB:acid-free)1.Electrochemistry.2.Surfacechemistry.I.Hamnett,A.II.Title.QD553.C591993541.3'7--dc2093-11366TechniquesandMechanismsinElectrochemistrybyChristensen,P.A.;Hamnett,A.TableofContentsTechniquesandMechanismsinElectrochemistryPrefaceContentsListofSymbols1—IntroductiontoModernElectrochemistry1.1—StructureofSurfaces1.1.1—StructureoftheSolidElectrode1.1.2—TheStructureoftheElectrifiedInterface1.1.3—AdsorptionontheElectrodeSurface1.2—ElectronTransfer1.2.1—ThermodynamicConsiderations1.2.2—RateofElectronTransfer1.2.3—RateofTransportofSolutionSpecies1.3—ReactionMechanisms1.3.1—HomogeneousElectrochemicalMechanisms1.3.2—ElectrochemicalMechanismswithAdsorbedIntermediates1.3.3—TheDirectDetectionofIntermediatesFurtherReading2—TechniquesGivingMechanisticInformation2.1—SurfaceSpecificProcesses-InSituTechniques2.1.1—Electrocapillarity2.1.2—LinearSweepVoltammetryandCyclicVoltammetry2.1.3—ScanningTunnellingMicroscopy2.1.4—ScanningTunnellingSpectroscopy2.1.5—AtomicForceMicroscopy2.1.6—InfraredSpectroscopy2.1.6.1—Transmission2.1.6.2—InternalReflectance(AttenuatedTotalReflectanceATR)2.1.6.3—ExternalReflectance2.1.6.4—ElectricallyModulatedInfraredSpectroscopy,(EMIRS)2.1.6.5—PolarisationModulationInfraredReflection-AbsorptionSpectroscopy(PM-IRRASorIRRAS)2.1.6.6—In-SituFouriertransformUnfraredSpectroscopy2.1.7—TheRamanSpectroscopies2.1.8—Ellipsometry2.1.9—X-RaySpectroscopies2.1.9.1—X-RayDiffraction2.1.9.2—SurfaceExtendedX-RayAbsorptionFineStructure(SEXAFS)2.1.9.3—LongPeriodX-RayStandingWaves(XSW)2.1.9.4—SpecularX-RayReflection2.1.10—ACTechniques2.2—InSituProbesoftheNear-ElectrodeRegion2.2.1—Chronoamperometry,ChronocoulometryandtheButler–VolmerEquation2.2.2—Voltammetry2.2.3—TheControlled-ConvectionTechniques:TheRotatingDiscandRotatingRing-DiscElectrodes2.2.4—ElectronParamagneticResonance2.2.4.1—Theg-factor2.2.4.2—HyperfineSplitting2.2.5—UV-VisibleSpectroelectrochemistry2.2.6—TheElectrochemicalQuartzCrystalMicrobalance2.2.7—FTIRandRelatedTechniques2.2.7.1—Transmittance2.2.7.2—ExternalReflectance2.2.8—MassSpectrometryTechniques–DEMS2.3—ExSituEmersionTechniques2.3.1—StructuralandAnalyticalMethods2.3.2—MassSpectrometricTechniquesReferencesFurtherReading3—ExamplesoftheApplicationofElectrochemicalMethods3.1—TheCyclicVoltammogramofPlatinuminAcidSolution3.1.1—TheHydrideRegion3.1.2—TheOxideRegion3.1.3—TheVoltammetryofSingle-CrystalPlatinumElectrodes3.2—TheElectro-OxidationofMethanolatPlatinuminAcidSolution3.2.1—MethanolOxidationataSmoothPolishedPolycrystallinePlatinumElectrode3.3—TheElectrochemicalReductionofCO[sub(2)]3.3.1—TheDirectReductionofCO[sub(2)]inNon-AqueousSolvents3.3.2—TheCatalysedReductionofCO[sub(2)]3.4—ReactiveFilmFormationonElectrodes3.4.1—OxideFormationonMetals:TheNatureofthePassiveFilmonIron3.4.2—ConductingPolymers3.3.2.1—Structure3.3.2.2—StaticMeasurements3.3.2.3—DynamicProperties3.5—AdsorbedFilmsforthePromotionofEnzymeElectrochemistryReferencesFurtherReadingIndex