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1、247J.Electroanal.Chem.,347(1993)241-255ElsevierSequoiaS.A.,LausanneJEC02457Micro-rheologychangesofNafion@filmswithelectrochemicalmass-transportinhydroquinonesolutionsandinsitumeasurementusingaquartzcrystalanalyzerHiroshiMuramatsul,XuanjingYel*andTatsuakiAtakaResearchLaboratoryforAdvancedT
2、echnology.SeikoInstrumentsInc.,Takatsuka-shinden,Mat&o-shi,Chiba271(Japan)(Received30June1992;inrevisedform1September1992)AbstractThispapershowsthattheelectrochemicalmasstransportinfilm-coatedelectrodesinvolvestherheologychangeofthefilmsandthatthesechangescanbedetectedbymeasuringtheresona
3、ntfrequencyandresonantresistanceofacoatedquartzcrystal.WeusedaNafione-coatedquartzcrystalandmeasuredthecyclicvoltammogramsinhydroquinonesolution.ThechangesoftheresonantfrequencyandresonantresistanceshowedthatmasstransportandviscoelasticchangeshadoccurredintheNafionfilms.Thediagrammedreson
4、antfrequencyandresonantresistancechangessuggestedthattheNaionde-dopingfromthefilmsdecreasedthefilmmassandincreasedthefilmrigidityinthefirstoxidationprocess,thebenzoquinoneaccumulationandaniondopingincreasedthefilmmassinthefollowingoxidationprocess,whiletheNaionre-dopedinthefirstreductionp
5、rocess,andbenzoquinonewasreducedfromthefilmsinthefinalreductionprocess.Studyofthechargeexpendedfromthereactionsuggestedtheparticipationofanionorwatertransport.INTRODUCTIONTheprincipleoftheuseofthequartzcrystalisbasedontherelationbetweenthemasschangeofsurfaceelasticfilmsandtheresonantfrequ
6、encychangesofthequartzcrystal[ll.In1980,itwasreportedthatthequartzcrystalcanbeusedincontactwithaqueoussolution[2],andthiswidenedtheapplicationofthequartz*Towhomcorrespondenceshouldbeaddressed.l*Presentaddress:TheInstituteofPhysicalandChemicalResearch,2-1,Hirosawa,Wako-shi,Saitama351-01,Ja
7、pan.0022-0728/93/$06.0001993-ElsevierSequoiaS.A.Allrightsreserved248crystalinthefieldofchemicalanalyses.Inparticular,thequartzcrystalhasbeenusedasaneffectiveanalyticaltoolinelectrochemistry[3-51.Furthermore,theviscosityeffectofliquidsincontactwiththequartzcrystalhas