FundamentalsofElectrochemistry2ndEd2006

FUNDAMENTALSOFELECTROCHEMISTRYSecondEditionV.S.BAGOTSKYA.N.FrumkinInstituteofPhysicalChemistryandElectrochemistryRussianAcademyofSciencesMoscow,RussiaAJOHNWILEY&SONS,INC.,PUBLICATIONTHEELECTROCHEMICALSOCIETY,INC.Pennington,NewJerseySponsoredbyffirs.qxd10/29/200511:56AMPageiiiCopyright©2006byJohnWiley&Sons,Inc.AllrightsreservedPublishedbyJohnWiley&Sons,Inc.,Hoboken,NewJerseyPublishedsimultaneouslyinCanadaNopartofthispublicationmaybereproduced,storedinaretrievalsystem,ortransmittedinanyformorbyanymeans,electronic,mechanical,photocopying,recording,scanning,orotherwise,exceptaspermittedunderSection107or108ofthe1976UnitedStatesCopyrightAct,withouteitherthepriorwrittenpermissionofthePublisher,orauthorizationthroughpaymentoftheappropriateper-copyfeetotheCopyrightClearanceCenter,Inc.,222RosewoodDrive,Danvers,MA01923,[phone],fax[phone],oronthewebat(201)748-6011,fax[phone],oronlineat:Whilethepublisherandauthorhaveusedtheirbesteffortsinpreparingthisbook,theymakenorepresentationsorwarrantieswithrespecttotheaccuracyorcompletenessofthecontentsofthisbookandspecificallydisclaimanyimpliedwarrantiesofmerchantabilityorfitnessforaparticularpurpose.Nowarrantymaybecreatedorextendedbysalesrepresentativesorwrittensalesmaterials.Theadviceandstrategiescontainedhereinmaynotbesuitableforyoursituation.Youshouldconsultwithaprofessionalwhereappropriate.Neitherthepublishernorauthorshallbeliableforanylossofprofitoranyothercommercialdamages,includingbutnotlimitedtospecial,incidental,consequential,orotherdamages.Forgeneralinformationonourotherproductsandservicesorfortechnicalsupport,pleasecontactourCustomerCareDepartmentwithintheUnitedStatesat(800)762-2974,outsidetheUnitedStatesat(317)572-3993orfax(317)572-4002.Wileyalsopublishesitsbooksinavarietyofelectronicformats.Somecontentthatappearsinprintmaynotbeavailableinelectronicformats.FormoreinformationaboutWileyproducts,visitourwebsiteat(VladimirSergeevich)Fundamentalsofelectrochemistry/V.S.Bagotsky—2nded.p.cm.Includesbibliographicalreferencesandindex.ISBN-13978-0-471-70058-6(cloth:alk.paper)ISBN-100-471-70058-4(cloth:alk.paper)1.ElectrochemistryI.Title.QD553.B232005541
.37—dc222005003083PrintedintheUnitedStatesofAmerica10987654321ffirs.qxd10/29/200511:56AMPageivCONTENTSContributorsxvPrefacetotheSecondEditionxviiPrefacetotheFirstEditionxixListofPhotographsxxiiAbbreviationsxxiiiSymbolsxxvPARTIBASICCONCEPTS11.ElectricCurrentsinIonicConductors31.1VariousTypesofConductors,31.2IonsinElectrolyteSolutions,41.3ConductivityofElectrolyteSolutions,51.4CircuitsInvolvingIonicConductors.Electrodes,91.5PassageofCurrentThroughElectrodes.ElectrodeReactions,101.6ClassificationofElectrodesandElectrodeReactions,121.7Faraday’sLaws,151.8EquationsforMassBalance,161.9SignConventionforCurrentsandFluxes,182.ElectrodePotentials192.1InterfacialPotentialDifferences(GalvaniPotentials),202.2ExchangeCurrents,232.3Open-CircuitVoltages,242.4ElectrodePotentials,262.5CellVoltageatNonzeroCurrent,293.ThermodynamicsofElectrochemicalSystems333.1ConventionalandUndefinedParameters,333.2ThermodynamicFunctionsinElectrochemistry,34vftoc.qxd10/29/200512:01PMPagev3.3ThermodynamicActivity,363.4EquationsfortheEMFofGalvanicCells,393.5ConcentrationDependenceofElectrodePotentials,413.6SpecialThermodynamicFeaturesofElectrodePotentials,464.MassTransferinElectrolytes514.1BasicLawsofIonicDiffusioninSolutions,514.2LimitingDiffusionCurrentsinElectrolytes,534.3IonicTransportbyMigrationandDiffusion,554.4ConvectiveTransport,605.PhaseBoundaries(Interfaces)BetweenMiscibleElectrolytes695.1TypesofInterfacesBetweenElectrolytes,695.2PotentialsBetweenSimilarElectrolytes(DiffusionPotentials),715.3DistributionoftheIonsBetweenDissimilarbutMiscibleElectrolytes,735.4DistributionofIonsinCellswithMembrane,755.5GalvanicCellswithTransference,766.PolarizationofElectrodes796.1BasicConcepts,796.2LawsofActivationPolarization,826.3DiffusionalConcentrationPolarization,896.4SuperpositionofConcentrationandActivationPolarization,937.AqueousElectrolyteSolutions997.1ElectrolyticDissociation,997.2IonicSolvation(Hydration)inSolutions,1067.3ActivityofRealElectrolyteSolutions,1127.4PhysicalTheoriesofIon–IonInteractions,1168.NonaqueousElectrolytes1278.1DifferentTypesofElectrolytesandTheirPracticalUtilization,1278.2NonaqueousElectrolyteSolutions,1288.3IonicallyConductingMelts,1318.4InorganicSolidElectrolytes,134viCONTENTSftoc.qxd10/29/200512:01PMPagevi9.ElectronWorkFunctionsandVoltaPotentials1399.1SurfacePotentialofaPhase,1399.2WorkFunctions,1409.3VoltaPotentials,1439.4TwoProblemsinElectrochemistry,14410.StructureandPropertiesofSurfaceLayers14710.1ElectricalStructureofInterphases,14810.2AdsorptionPhenomena,15610.3ThermodynamicsofSurfacePhenomena,16210.4MercuryElectrodeSurface,16910.5Platin