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首页 【放射化学系列】钒的放射化学

【放射化学系列】钒的放射化学.pdf

【放射化学系列】钒的放射化学

aidaoguangci 2010-08-07 评分 0 浏览量 0 0 0 0 暂无简介 简介 举报

简介:本文档为《【放射化学系列】钒的放射化学pdf》,可适用于自然科学领域,主题内容包含vISciencesNationalResearchCouncilNUCLEARSCIENCESERIESTheRadiochemistryofva符等。

vISciencesNationalResearchCouncilNUCLEARSCIENCESERIESTheRadiochemistryofvanadiumr=COMMITTEEONNUCLEARSCIENCELFCURTISS,ChairnaunROBLEYDEVANS,ViceCkuirmanNationalBureayofStandardsMaesaohusettsInstituteofTechnologyJADeJUREN,SecretaryWestinghouseElectricCorporationCJBORKOWSKIJWfRVINE,JROakRidgeNationalLaboratoryMassachusettsInstituteofTechnologyROBERTGCOCHM~~TexasAgriculturalandMechanicalCollegesAMUELEPSTEINCaliforniaInstituteofTechnologyUFANONationalBureauofStandardsHERBERTGOLDSTEINNuclearDevelopmentCorporationofAmericaEDKLEMANorthwesternUniversityWWAYNEMEINKEUniversityofMichiganJJNfCKSONMemorialHospital,NewYorkROBERTLPLATZMANLaboxiatoiredeCbimiePhysiqueDMVANPATTERBartolResesrohFoundationLIAISONMEMBERSPAULCAEBERSOLDCHARLESKREEDAtomicEnergyCommlsaionUSAirForceJHOWARDMcMILLENWILLIAMEWRIGHTNationalScienceFoundationOfficeofNavalResearchSUBCOMMITTEEONRADIOCHEMISTRYWWAYNEMEINKE,ChairmanHAROLDKIRBYUniversityofMichiganMoundLaboratoryGREGORYRCHOPPINGEORGELEDDICOTTEFloridaStateUniversityOakRidgeNationalLaboratoryGEORGEACOWANJULIANNIELSENLosAlamosScientificLaboratoryHanfordLaboratoriesARTHURWFALRHALLELLISPSTEINBERGlJntversiofWashingtonArgonneNationalLaboratoryJEROMEHUDISPETERCSTEVENSONBrookbavenNationalLaboratoryUniversityofCalifornia(Livermore)EARLHYDELEOYAFFEUniversityofCalifornia(Berkeley)McGUUniversityCONSULTANTSNATHANBALLOUJAMESDeVOECentred’Etudedel’EnergieNucleaireUniversityofMichiganMolDonk,BelgiumWILLIAMMARLOW,NationalBureauofStandardflCHEMISTRYc’TheRadiochemistryofvanadiumByJLBROWNLEE,JRDepartmentofChemistryUniversityofMichigunAnnArbor,MichiganDecembersubcommitteeonRadicichemistryNationalAcademyofSciencesNationalResearchCouncilPrintedinUSAPrice$AvailablefromtheOfficeofTechnicalServices,DepartmentofCommerce,Waddngtcm,DCFOREWORDTheSubcommitteeonRadlochemlstryoneofanumberofsubcommitteesworkingundertheCommitteeonNuclearSciencewithintheNationalAcademyofSciencesNationalResearchcouncilItsmembersrepresentgovernment,industrial,anduniversitylaboratoriesIntheareasofnuclearchemistryandanalyticalchemistryTheSubcommitteehasconcernedItselfwiththoseareasof“nuclearsciencewhichInvolvethechemist,suchasthecollectionanddistributionofradlochemlcalprocedures,theestablishmentofspecificationsforradiochemlcallypurereagents,availabilityofcyclotrontimeforserviceirradiations,theplaceofradlochemlstryIntheundergraduatecollegeprogram,etcThisseriesofmonographshasgrownoutoftheneedforuptodatecompilationsofradiochemlcalinformationandproceduresTheSubcommitteehasendeavoredtopresentaserieswhichwillbeofmaxtiumusetotheworkingscientistandwhichcontainsthelatestavailableinformationEachmonographcollectsInonevolumethepertinentinformationrequiredforradlochemicalworkwithanindividualelementoragroupofcloselyrelatedelementsAnexpertintheradiochemistryofthepartictiarelementhaswrittenthemonograph,followlngastandard~ormatdevelopedbytheSubcommitteeTheAtomicEnergyCommlsslonhassponsoredthe”printingoftheseriesTheSubcommitteeIsconfidentthesepublicationswIlbeusefulnotonlytotheradlochemlstbutalsototheresearchworkerhotherfieldssuchasphysics,biochemistryormedicinewhowishestouseradiochemlcaltechniquestosolveaspecificproblemWWayneMelnke,ChairmanSubcommitteeonRadlochemistryINTRODUCTIONThisvolumewhichdealswiththeradiochemlstryofvanadiumisoneofaseriesofmonographsonradiochemistryof’theelementsThereIsIncludedareviewofthenuclearandchemicalfeaturesofparticularInteresttotheradioc”hemist,adiscussionofproblemsofdissolutionofasampleandcountingtechniques,andfinally,acollectionofradiochemlcalproceduresfortheelementasfoundintheliteratureThseriesofmonographswillcoverallelementsforwhichradlochemlcalproceduresarepertinentPlansincluderevisionofthemonographperiodicallyasnewtechniquesandprocedureswarrantThereaderIsthereforeencouragedtocalltotheattentionoftheauthoranypublishedorunpublishedmaterialontheradlochetnistryofvanadiumwhichmightbeincludedinarevisedversionofthemonographivCONTENTSIGeneralReviewsoftheInorganicandAnalyticalChemistryofVanadiumIIGeneralRevlewEoftheRadlochemitryofVanadiumIIITableofIsotopesofVanadiumIvReviewofThoseFeaturesofVanadiumChemistryofChlefInteresttoRadiochemistsaMetallicVanadium,SolubleSaltsofVanadium,InsolubleSaltsofVanadiumPrecipitationandCoprecipitationCharacteristicsComplexIonsofVanadiumChelateComplexesofVanadium,ExtractionofThenoyltrifluoroacetoneComplexesofVanadiumintoOrganicSolvents,ExtractionofVanadiumintoOrganicSolventsIonExchangeBehaviorofVanadium,vProblemsAssociatedwithDissolvingVanadiumContainingSsmplesVICountingTechniquesforVanadiumIsotopesVIICollectedRadiochemicalProceduresforVanadiumuvTheRadiochemistryofVanadiumJLBROWNLEE,JRDepartmentofChemistryUniversityofMichigan,AnnArbor,MichiganIGENERALREVIEWSOFTHEINORGANICANDANALYTICALOFCHXMISTRYVANADIUMFriend,JN,“ATextbookofInorgsnlcChemistry,“VolVI,PtIII,CharlesGriffinandCo,Ltd,London,,PPgliEphralm,F,“DasVanadlnundSeineVerblndungen,“SanmilungChemlscheundChemlscheTechnlscheVortr~ge,Stuttgart,,ppFeEter,G,“DieChemlschetechnologiesdesVanadlns,”SsmmlungChemlscheundChemlscheTechnlscheVortre,Stuttgart,,ppFischer,S,“ContributionstotheKnowledgeoftheElectrolysisofAqueousSolutionsofVanadiumSalts,”PhDThesis,ColumbiaUniversity,NewYork,Hendel,JM~“ANewTypeofReductoranditsApplicationtotheDeterminationofIronandVanadium,”PhDThesis,ColumbiaUniversity,NewYork,Nlcolardot,P,“LeVanadium“EncyclopedleSclentlflquedesAideMemoire,Paris,Menancke~H,“DieQuantitativeUntersuchungsmethodendesMolybd!lns,Vanadium,undWolfrsms,”PrektlschesHandbuch,MKrayn,Berlin,Frank,AJ,“ChemistryofVanadiumASummaryofNonProjectLiteraturethroughNovember,,”TopicalReportACCO,AmericanCyanamidCompany,RawMaterialsDevelopmentLaboratory,Winchester,Massachusetts,Sldgwlck,NV,“TheChemicalElementsandtheirCompounds,”VolI,OxfordUnlversltyPress,Oxford,,ppEphralm,F,“InorganicChemistry,”GurneyandJackson,London,Hlllebrand,WF,Lundell,GEF,Bright,HA,Hoffman,JI,“AppliedInorganleAnalysis,”(ndEd),JohnWileyandSons,Inc,NewYork,,ppChariot,G,Bezler,‘QuantitativeInorganicAnalysis,”MethuenandCompany,Ltd,London,,PPMcAlplne,RKandSoule,BA,“QualltatlveChemicalAnalysls,”DvanNostrandCo,NewYork,,PPNoyes,AA,Bray,WC,“AS~stemofQualitativeAnalysisfortheRareElements,TheMacMillanCo,NewYork,Mellor,JW,“AComprehensiveTreatiseonInorganicandTheoreticalChemistry,”VolIX,Lon~an’s,Greenandco,London,,ppGmellnKraut,“HandbuchanorganischeChemle,”BandIII,Abtellung,CWinter,Heidelberg,,ppMoore,RB,Llnd,SC,Marden,JW,Bonardi,JP,Davis,CW,andConley,JE,“AnalyticalMethodsfor”CertainMetals,”DepartmentoftheInterior,Washington,DC,,ppoIIGENERALREVIEWSOFTHERADIOCHEMISTRYOFVANADIUMRamnussen,SW,andRodden,CJ,InRodden,CJ(Ed)“AnalyticalChemlstmoftheManhattanProect,”iMcGrawHillBookCo,Inc,NewYork,,PpStevenson,PCandHicks,HG,“Separation,TechniquesUsedInRadlochemlstry,”inBeckerley,JC,“AnnualReviewsofNuclearScience,”Vol,AnnualReviews,Inc,Stanford,California,,ppFlnston,HLandMlskel,“RadlochemlcalSeparationTechnlquea,”Ccit,Vol,,ppHome,R”A,Coryell,CD,sndGoldrlng,LS,“GeneralizedAcldltyInRadlochemlcalSeparations,”Ccit,VO,,ppKraus,KA,andNelson,F,“RadlochemlcalSeparationsbyIonExchange,”Ccit,Vol,,PPNote:Referencesthroughcontaingeneralradlochemlcalseparations,andarenotvanadiumseparationsourcesinformationonspecificallyTableofIsotopesofVanadlum*MethadofPreparation()T(p,n)VT(d,m)#RalfILfe($Kmrdance~fleaDecayScheme(~IeotopeV#,,’Tvqd)EC$o~ipMevcu(p,i)**()T(d,n)VTi(d,n)vminVdOYST(d,n)#()cu(p,E)**()!ogMew~,VadayaEGCU(P,E)**()~e(d,n)vm(PJY)vpVXyearn(,$)E,C,Naturallyoccurrins(*)Bj“V(n,i)V()V~Cr(n,p)V~(n,a)VVsl(d,p)voohV,minVVll*minqet~(P,B)**()p~E!ReferencesformuchofthedataoontainedhthistableerefoundInStrominger,D,,Hollander,JMSeaborg,GT,RevMadPhys,~,PtII,()ThetermgisusedheretoindicatespallationIvREVIEWOFTHOSEFEATURESOFVANADIUMCEEMISTRYOFCHIEFINTERESTTORADIOCHEMISTSMetallicVanadiumPuremetalllcvanadiumisextremelydifficulttoobtain,asitcombinesreadilywithcarbon,nitrogenandoxygen,formingsolidsolutionswithsomeoftheproductsSincevanadiumIsoftenproducedbyreductionofvanadiumhalideswithdryhydrogengasatelevatedtemperatures(),hydrogenisoftenpresentinthemetal,inadditiontotheaboveelementsTheamountsofthesecontaminantsmaycausesomeinterferenceordifficultywhentheirpresenceinanirradlabedvanadiumfoilIsnotlmownPurevanadiumIsfairlystableandisgenerallynotsubjecttooxidationbymoistairInpowdered~ormitburnsInairtoproducevanadiumpentoxidehowever,thereactiondoesnotgotocompletionandsomeloweroxidesarealsoformedVolatilevanadiumtetrachlorlde,vcl~,isformedwhenvanadiummetalisburnedinanatmosphereofformedonheatingvanadiumthionylchlorideorsulfurVanadiummetallanotchlorinegasThiscompoundisalsowithcarbonylchloride,flurfurylchloride,chlorideatCreadilyattackedbyaqueoussolutionsofalkalichlorides,brominewater,orcoldhydrochloricacid,whetherdiluteorconcentratedThemetalisattackedslowlybyhydrofluoricacidandbyhot,concentratedsulfurlcacidAtC,concentratedflulfurlcacidreactswithmetallicvanadiumtoproducevanadiumpentoxide,VJwithevolutionofSatlowertemperatures,vanadiumdioxideisformed,butIsconvertedtothepentoxideonrslsingthetemperatureMetal’llcvanadiunISconcentratednitricacidvanadicacidbeingformedreadilyattackedAquareglaalsoIneithercasebycolddiluteorattacksthemetal,Vanadicacidisalsoformedbytheactiononvanadiumofacid,perchlorlcacid,btiomlcacid,suchoxidizingagentsandpotassiumIodateaschloricSolublevanadatesofsodiumorpotassiumareproducedwhenpowderedvsnadlummetalisfusedwithsodiumcarbonate,potassiumhydroxideorpotastumnitrateSolubleSaltsofVanadiumVanadlcacidandvanadatesofammonium,lithiumsndthealkalimetalsaremoreorlesssolubleInaqueoussolutionThevsnadatesareslmilsrtothephosphatesInthatbothanionssrecapableofcondensingandforml~polycompoundsStartingwithahighlyalkalinesolutionofavanada’teandgraduallyreducingthePH,thefollowingchangesoccur:Inhighlyalkalinesolution,thestableformIsVbetweenPHand,pyrovanadate,‘~pred~lnatesAtaboutpH’,VIsOtableTheseformsareallcolorlessAtpHvaluesbelow,thesolutionsbecomehighlycolored,andvanadiumpentoxldemayprecipitateBelowPH,thevanadiumexistsaspervanadylion,V(OH),havingapaleyellowcolorThechlorides,oxychlorldes,fluorides,oxyfluorides,andbromidesofvanadiumareallfairlysolubleInaqueouasolutionsManyofthesedissociateInaqueoussolutiontoformcomplexIonsVanadium(IV)oxidecombineswithsulfuric,hydrochloricandhydrofluorlcacidstoformsalts,which,whendissolvedInwater,givebluesolutionsVanadium(III)ischemicallysimilartochromium(III)andIron(III),andformsaqueoussolublesaltswithmostofthecommonacidsSolublecomplexesareformedwithfluoride,cyanideandammoniaVandium(II)Issimilartothedlvalentstatesofchromiumandirm,andformasolublesaltswithmo~tacids,exceptthosecapableofundergoingreductionSolutionsofuncompletedvanadium(II)aregenerallyvioletandareeaOllyoxidizedSolublecomplexesareformedandammoniaOxldatlonReductionBehaviorPentavalentvanadiumiswithcyanide,fluoride,sulfatereducedInacidsolutionbysulfiteIon,orbybubbllngSgaathroughanacidsolutionvanadylIon,V,~formed,havingabluecolorOthermethodsforthereductionofvanadium(V)Include:ferrousIonInacidevaporationwithhydrochloricacid,preferablyInthepresenceofferricIronandsulfuricacid(),passagethroughaJonesreductor,inwhichvanadiumIsreducedtotheblvalentstate()reductiontothequadrlvalentstatebyhydrogenaulflde(),whichIsthenexpelledbybolllngwhlle,CIsblownthroughthesolutionshakingwithmercuryinadilutesolutionofhydrochloricorsulfurlcacid()containingsufficientsodiumchloridetoprecipitatetheresultingmercury(I)reductiontothequadrlvalentstatebyhydrogenperoxideInhotacid~olution()andreductiontovanadium(IV)inasilverreductorVanadiumcanbeoxidizedtothepentavalentstatebynitricacid,butthereactionhasbeenshown()tobeonlypercentcompleteBoilingperchloricacid,persulfateinthepresenceofsilverIons,andhotexcesspermanganateinacidsolutionalsooxidizesvanadiumtovanadium(V)Inneutralsolution,iodine,dlchromate,andpermanganateoxidizevanadium(II)tovanadium(III)IftheadditionIBterminatedatthephenosafranlnchangepointIodineinasaturatedsolutionofsodiumcarbonateoxidizesvanadium(IV)tovanadium(V)ThetextbyChariotandBezier()givesseveralotherproceduresfortheoxidationandreductionofvanadiumcompounds,aadomanyofthesourcesinsectionIInsolubleSaltsofVanadlwnPrecipitationandCoprecipitationCharacteristicsAInsolubleSaltsSomeofthereadilyobtainableInsolublecnmpoundsofvanadiumarelistedinTableIManyofthecompoundslistedofferpossiblemeansofseparatingradlovanadiumfromsolutionThereferenceslistedinPartsIandIIcontaininformationontheuaeofcertainofthecompoundsinseparationandanalyticalproceduresBCoprecipitationCharacteristicsAmmoniumPhosphomolybdateasaCarrierforVanadiumIthaslongbeenknownthatquinquevalentvanadiumcanbecarriedalongwithsmmoniumphosphomolybdateprecipitates,ImpartingtotheseprecipitatesanorangeorbrickredcolorThattheprecipitationcanbemadequantitativehasbeendemonstratedbyCainandHostetter(,),providedthattheamountofphosphorousisfivetotentimesthatofthevanadiumHowever,noneofthevanadiumiscarrieddownifitisinthequadrivalentstateandprecipitationismadeatroomtemperature()Coprecipitationofvanadiumwithphosphomolybdateaffordsagoodmeansofseparatingvanadiumfromsuchelementsascopper,chromium(VI),nickel,aluminum,iron,anduraniun~Inordertomsketheseparation,preparethesolutionasforanammoniumphosphomolybdateprecipitation,addtentimesasmuchphosphorousasthereisvanadiumpresent,andthenaslightlygreaterthanusualexcessofammoniumnitrateRendernearlyneutralbyaddingammoniumhydroxide,heattoboiling,addanexcessofsodiummolybdatesolution,andshakeforafewminutesTableIInsolubleCanpoundaofVenediumIiemerka(Ref)Reagent(a)**PrmclpltateSolubllltyInsolubleMditionofUtoneutralalkelivenadateoollodialwhiteprecipitate(J“JAluminummetavanadateAsA~VOhxHSilverorthovenadatosolubleinHNandNHum“‘reeh‘repWed‘vo*‘matedwithoerefullyneutalzedAENorangepowder(,)AdditionofneutralASeelttoVlY‘precipitateAgvWHSilverpyrovenadateIneolubleaaprecipitatedKqPxloAE’WSilvermetavanadateMditionofAsNtoneutralNHVgelatinousyellowprecipitate(,,)Ba(V~)”HBariummetavanadatePrecipitateatpHbyaddingSaCltoNWIVOsolutioninacidStabfeuptolhCLosesHctoformstableanhydroueqalt(,,)B~VBariumpyrovanadateInsolubleaeprecipitatedAdditionofBaCtosolutionof#lZei~~~~‘hi’e‘reBiVOBiemuthorthovanadateIneolubleasprecipitatedFormedbydoubledecompositionofalkelivermdateandBI(N)brightyellow()cavfiCaloiumpyrovenadateIneolubleccprecipitatedAdditionofCeCtoNCIVqolutionCaVHfmmedbydryingatoCwhiteprecipitate,()C(’H)cO(’ILJ(v)PreciDiateinaoeticaciddPHgelatinouOorenge,precipi:tateDryatCIgnitestoMoOVaboveX’()cd~#(voPrecipitateunderneutraloramnoniacalcondltionsDriedbetween~“endC,toCOF*between’c,Yelowpinkprecipitate()InsoIubleasprecipitatedPrecipitatebymixingCuqeltewithqolubleorthovanedatesGreenishyellowprecipitate(,)~uCU(V)CyprlcorthovanadateAdditionofCUStosolutionofNHVJgreeniehyellowprecipitate,)‘vxCupriopyrovanadateInsolubleaeprecipitatedmvo)OupricmetavanadateColloiddpreciitateformedbyadditionofCutoneutralclkelivenadateGreenprecipitate(),Insolubleaeprecipitated‘eUiFe(o”)Hg*Fe(V~)FerricnetavanadateImolubleinHandelcoholacidsolubleOlivereencolloidalprecipitate(,(vo)#(oN)VanadylferrocyanideHE(W)PrecipitationalmoetamupleteV(V)givesno~reoipitateYWeeniehyellow(AdditionofHg(N~)tovenadateunderneerlyneutralconditionloeesweightbetweencndcvfomedaboveCOrangeprecipitate(,B,)MercurOuaiuetavanadate’TableInsolubleCempoundaofVenadium(Cent)PreclpitateHE(V)VONHPVanadylammoniumphonphateVSVanadiumtrlsulfldeSolubilltyRemarka(Ref~lleaent(a)H~AdditlonHgCtoneutralvenadateqolutionwhiteprecipitate()HPoL=NHpI()HSNHCEIInsolubleHsolubleinelkaliqulfldeesliuhtlYsolubleThIocemplexeaprobablyformedinexoesaalkalisulfideV(III)sensitivetoairoxidation()In~lk~l,HN,HCandHS‘sVanadiumpentasulfideIn(V)HIridiummetavanedatellIiocanplexeEfennedinlxceeeofsulfidee()AdditionInCltoNaV~yellowpreci

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