電極過程動力學陳勝利1課件

“電極過程動力學”授課教師：

Tel:68754693

Email:

Office:化學樓1－35授課教材查全性等著：《電極過程動力學導論》

（第三版，科學出版社，2002年）推薦參考書WrittenbyAllenJ.BardandLarryF.Faulkner,

《ElectrochemicalMethods:

FundamentalsandApplications》

（SecondEdition,Wiley,2001）

邵元華等譯,

《電化學方法：原理及應用》

（第二版，化學工業(yè)出版社,2005年）Electrochemistry?Thelaws(principles)andthetechnologiesconcerningtheconversionbetweenchemicalenergyandelectricalenergyInterrelationbetweenchemicalphenomena(chemicalreactions,chemicalchanges,etc.)andelectricphenomena(charge,current,potential,electricfield,etc.)Withahistoryofmorethan

twocenturies,electrochemistryhasbeenatypicalexampleofatrulyinterdisciplinary(各學科間的)areaofscienceandtechnology.Itsrootshavebeeninchemistry,physics,materialsandbiologicalscienceanditsapplicationsspreadingfromelectrochemicalanalysisandsynthesistoenvironmentalprotectionandenergyconversionandstorage.Everydaylifeitemssuchasbatteries,theglucose（葡萄糖）sensoranddomesticormedicalgassensorsarenowacommodity,whiletheprospectofmassproductionof"green"electricvehicles(Electricvehicles)isnomoreachallengebutaviableoption.Onanindustrialscale,apartfromthenowmaturechlor-alkaliandmetalfinishingandextractionindustries,thereissignificantactivityintheareasofenergyconversionandstoragebymeansoffuelcellsandsolarcellsaswellasintheuseofelectrochemicalmethodsforeffluenttreatment.“Electrochemistryprovidesmanyopportunitiesforsustainabledevelopment.”ElectrochemicalCellsandReactions

PtPtPtPtH2SO4SolutionH2O2H2O2H+H+H2OH+H2OH+e－e－e－e－Cathode:1/2O2+2H++2e-=H2OAnode:H2=2H++2e-Overallcellreaction:H2+1/2O2=H2OPositiveelectrode:H2O=1/2O2+2H++2e-Negativeelectrode:2H++2e-=H2Overallcellreaction:H2O

=H2+1/2O2

GalvanicCell（原電池）VoltaicCellH+H+Electrodereactionatelectrode/solutioninterfacesChargetransferplaneFeimilevelLUMOHOMOChargetransferplaneFeimilevelPotentialshiftsnegativelyeOz+eRz-1Fe3++e

Fe2+ForExample:PossibleprocessesinvolvedinanelectrodereactionO'adO'R'adR'O*R*neObRb

Masstransfer

MasstransferPrecedingChemicalreactionsFollowingChemicalreactions

ElectrodeChargetransferAdsorptionDesorptionWhatwillwedealwithinthiscourse?ThekineticsoftheelectrodereactionsofvarioustypeandthefactorsthataffectthesekineticsCurrent—PotentialdependenceStandardHydrogenElectrode(SHE)

Pt

CH+=1mol.l-1

H2H2Saturatedcalomelelectrode(SCE)

MetalwireKClsolutionHg2Cl2

HgPtwireStrategiestostudytheelectrodeprocessesPotential-controlledtechniquesCurrent-controlledtechniquesPotentiostatic（恒電勢）methodsPotentiodynamicmethodsThecapacitor（電容器）-likenatureoftheelectricdoublelayerRegardlessofthenatureofanelectrodeprocess,thedoublelayeritselfwouldresponsetotheelectrochemicalperturbationsasaseriesofcapacitorsThecapacitancevaluesofthedoublelayerarepotential-dependentMostoftheelectrochemicalmeasurementsaremoreorlessaffectedbythechargingprocessofthedoublelayerCcompactCdiffuseiRsolutionThedoublelayer