关闭

关闭

关闭

封号提示

内容

首页 【放射化学系列】钨的放射化学.pdf

【放射化学系列】钨的放射化学.pdf

【放射化学系列】钨的放射化学.pdf

上传者: aidaoguangci 2010-08-07 评分 0 0 0 0 0 0 暂无简介 简介 举报

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

!NationalAcademyofSciencesNationalResearchCouncilNUCLEARSCIENCESERIESTheRadiochemistryofTungstenLFCURTISS,ChairmanROBLEYDEVANS,ViceChairmanNationalBureauofStandardsMassachusettsInstituteofTechnologyJADeJUREN,SecretaryWestinghouseElectricCorporationCJBORKOWSKIJWIRVINE,JROakRidgeNationalLaboratoryMassachusettsItituteofTechnologyROBERTGCOCHRANTexasAgriculturalandMechanicalCollegeSAMUELEPSTEINCaliforniaInstituteofTechnologyUFANONationalBureauofStandardsHERBERTGOLDSTEINNuclearDevelopmentCorporationofAmericaEDKLEMANorthwesternUniversityWWAYNEMEINKEUniversityofMichiganJJNICKSONMemorialHospital,NewYorkROBERTLPLATZMANLaboratoiredeChimiePhysiqueDMVANPATTERBartolResearchFoundationLIAISONMEMBERSPAULCAEBERSOLDCHARLESKREEDAtomicEnergyCommissionUSAirForceJHOWARDMcMILLENWILLIAMEWRIGHTNationalScienceFoundationOfficeofNavalResearchSUBCOMMITTEEONRADIOCHEMISTRYWWAYNEMEINKE,Chai~manHAROLDKIRBYUniversityofMichiganMoundLaboratoryGREGORYRCHOPPINGEORGELEDDICOTTEFloridaStateUniversityOakRidgeNationalLaboratoryGEORGEACOWANJULIANNIELSENLosAlamosScientificLaboratoryHanfordLaboratoriesARTHURWFAIRHALLELLISPSTEINBERGUniversityofWashingtonArgonneNationalLaboratoryJEROMEHUDISPETERCSTEVENSONBrookhavenNationalLaboratoryUniversityofCalifornia(Livermore)EARLHYDELEOYAFFEUniversityofCslifornia(Berkeley)McGillUniversityCONSULTANTSNATHANBALLOUJAMESDeVOENavalRadiologicalDefenseLaboratoryUniversityofMichiganWILLIAMMARLOWNationalBureauofStandardsCHEMISTRYTheRadiochemistryofTungstenWTMULL(INSandGWLEDDICOTTEOakRidgeNationalLaboratoryOakRidge,Tennesseekuancehte:SeptembersSubcommitteeonRadiochemistryNatiomlAcademyofSciencesNationalResearchCouncilPrintedfnUSAPrice$AvallnblefromtheOfficeofTechnicalServicen,DepartmentofCommerce,Washington,DCFOREWORDTheSubcommitteeonRadlochemistryIsoneofanumberofSubcommitteesworkingunder”theCommitteeonNuclearSciencewithtitheNationalAcadetiofScienceBNationalResearchcouncilItsmembersrepresentgovernment,LnduBtrlal,aduniversitylaboratoriesIntheareasofnuclearchemistryandanalyticalchemistryTheSubcommitteehasconcernedltelfwiththoseareasofnuclearsciencewhichInvolvetheohemist,suchasthecollectionanddlstrlbutlonofradlochemlcalprocedures,theeatabllshmentofspeclflcatlon~forradlochemicallypurereagents,availabilityofcyclotrontimeforservicelrradlatlon,theplaceofradlocheml”stryintheundergraduatecollegeprogram,etcThisserleofmonographshasgrownoutoftheneedforuptodatecompilationsofradlochemlcalInformationandproceduresTheSubcommitteehasendeavoredtopresentaserle~whichwillbeofmaxlmmunuaetotheworkingscientistandwhichcontalnthelatestavailabletiformatlonEachmonographcollectInonevolumethepertinentinformationrequiredforradlochemlcalworkwithanIndividualelementoragroupofcloselyrelatedelementsAnexpertIntheradlochemlstryoftheparticularelementhaswrittenthemonograph,followlngastandardformatdevelopedbytheSubcommitteeTheAtomicKnergyCommissionhaesponsoredtheprlntlngoftheseriesTheSubcommitteeIsconfidenttheepubllcatlonewillbeusefulnotonlytotheradlochemlstbutalsototheresearchworkerInotherfieldssuchasphysics,biochemistryormedlctiewhowishestouseradiochemlcaltechniquestosolveaspecificproblemWWayneMelnke,ChairmanSubcommitteeonRadlochemlstryiiiINTRODUCTIONThisvolumewhichdealsw~ththeradiochemistrvoftungstenisoneofaseriesofmonographsonradiochemistryoftheelmentsThereisincludedareviewofthenuclearandchemicalfeaturesofparticularinteresttotheradiochemist,adiscussionofproblemsofdissolutionofasampleandcountingtechniques,smdfinally,a’collectionofradlochemicalproceduresfortheelementasfoundintheliteratureTheseriesofmonographswillcoverallelementsforwhichradlochemlcalproceduresarepertimentPlsmsincluderevisionofthemonographperiodically=newtechniquesandprocedureswsrrentThereaderIsthereforeencouredtocalltotheattentionoftheauthoranypublishedorunpublishedmaterialontheradiochemistryoftungstenwhichmightbeincludedinarevisedversionofthemonograph,ivCONTENTSIIIIIIIvvVIVIIGeneralReferencesonthehor~candAndyMcalChemistryofTungstenTheRadioactiveNuclldeaofTungstenmeClmmlatryofTunenandItsAppMcationTotheRadiochemlslmyoftheTmgstenRadlonuclideEATheB,lheGeneralChemistryofTungstenC!ompoundsofTungstenTheHexavalentTungstenzuntk:ThePentavalentTungtenCompoundsTheTetravalentTunstenCcmpounds::TheTrivalentTungstenCampundeTheDivalentTungstenCOmpmdeIulalyticalchemistryofTungstenseparationbyPrecipitation‘SewrationbyVolatilizationpartionbySolventExtractionaIonAssociationsystemsbChelateComplexSystems,SeparationbyC’hrcmatographyaByOrganicAbsorbents(otherthanIonexchangerestis)bByIonExchangeResinscByPaperChromatographyDecmupositionofMatefialsContningTungstenSafetyPracticesCourhlngTechniquesfortheRadioactivetenIsotopes‘llectionofDetailedRadiochemicalProceduresfortheTungstenReferencesRadionuclidesvTheRadiochemistryafTungstenWTMLJLLINSsndGWLEDDICOTTEOakRidgeNationalLaboratory*OakRidge,TennesseeIGENERALREFERENCESONTEEINORGANICANDANAIXTICALCBIMIS’RYOFHiUebmnd,WF,Lurtdell,GEF,Bright,HA,endHoffman,JI,Appliedkor~cAnalysis,p,JohuWileyandme,be,NewYork,Reed,EL,Tungsten,UnitedStatesAtomicEnergyReportAECD()Chariot,GendBezier,D,QuantitativeborganicAnalye,p,JohnWileySons,Inc,NewYork()~kK~~ndWW,CY,”Tungsten,p,Reinhold,NewSneed,MCendMFWUard,JL,GeneralInormcChemhtry,p,DVanNostrandCo,NewYork()ReIIV,H,!lreatlaeonfiorcchemistAmeterdml)W*PM,Elstier,Rodden,C,Ed,AnalyticalchemistryoftheManhattenProject,BookI,p,McGrawHinBcCo,Inc,NewYork,IITHERADtOACIVENUCLZDEOFTIJliGfI’ENThe~oactlvenuclidesoftungstenthatsreof’interestintheradiochemistryoftungstenaregiveninTableIThietablehasbeencompiledfromInformationappeerlngh“repxba”byStrominger,etal,‘)andbyHughesendHarvey()*operatedforUSAtcatlcEnCpmnlEsionbyUnionCarbideNuclearlco~‘Table:Halflifeaomm“dmmdamdhdTheRadioactive,hclidesofTungetenModeofDscayEC(~)B()~ECECECorITEC!ITITPP!()EnergyofRadiations,MevB,:‘:L:(week)::::olo~o:p::NoneP::P::hdUCedbyWdpnWdpnWn,Wn,wnWn,Wnn,Vdt,WalphW*CQ,WppnPw(n,)##(n,)##(n,)PbaIfelementIsamorconBtituent”ofthesamplematrix,itcanundergoafeatneutronreactiontoproduceelementofInterestbAsecondomierneutronreactionIIITEESTRYOF~ANDITSAPPIZCATIONTQTEERADIOCKEMISI!RYOFTHETUNGSTEIiRADIONUCLZDESRadiochemitryisprobablybe~tdesribedasbeingp~lyauanalysistechniqueusedeither()toeaaisthobtainingapureradionuclldeinsomeformsothatemelaolutemeeauwnentofitsradioactivity,radiationenergiesandhalflifecanbemade,or()todetemnlnetheamountofradioactivityofapsrticulruradioelementinaredionuc~demixture,or()tocompletearadioactivationemaysisbeingusedtodeterndnethestableelemntconcntrationinaparticularsamplematerialInordertobeanaidinaccomplishinganyoneoftheaboveinterests,rediochemietryusuallyconsiderstheisolationofthedesirbdrdlonuclldebyeithercarrierorcarrierfreese~ationmethodsGenerally,the“umrler”separationsareusedmostfrequentlyinradlochemldryTheyinvolvetheadditionofaLmeUJemountofactivestableelementtoesolutionoftheirradiatedmaterialtoserveasacarrieroftheradionuclideofthatelementthroughthesgationmethodIn“ctierfree”separations,techniquesusedmostlyforabsoluteradioactivitymesauremarks,itisrelredthattheredioelementbeisolatedInamannerabletogiveeithernoamountoramhlmalamountofstableelementInthefinalfonatobewedintheradioactivityDbSS,B~tSInnmstinstances,radlochemistryisdependentuponmoreconventionalideasInanalyticalchemletryinvol~se~tionabysuchmethodsasprecipitation,solventextraction,chromatography,volatilization,andorelectrolysisandthemibsequentpresentationoftheIsolatedradioelementhaformmltableforameaaunmentoftbeIWLXlemntrstiioactltityGnemajordifferenceexistsbetweenradiochemistryandnmreconventionalsistec~qwsinthatitisnotswaysnecesearytarecovercom~letelytheaddedaumuntof“carrier”elemmt,sincearadiochemiceJanalysisIsdesignedtoassurethattheatqmeofaradioactiveelementachieveanIsotupicstatewiththeatomsoftheinactiveelement,andanylossoftheredhactlvespeciesisproprtlondtothelossof“cm’rier”duringtheseparationprocessColo*trlc,po~graphic,endsimilaranalysistechniquesareseldmusedInradiochemlstry,becausetheydonotseparatethedesired~ts(eitherradioactiveprstable)inthers,dionuclidesfrauconmixturesbehganalyzedHowever,sameofthedevelopmentsusedintheseanalysestecbnlquesmaybeusefulforconeidezationinradlochemlstryThefollowingMotionieintendedtagivesm!zegeneralideaofthebehatioroftungstenenditsc~untiandhowthisbehaviorcsnbeusedtidevlslng~ochemicalanalysisnsWmafortheredlonuclldeeoftungstenhkmedeiledInformationcanbereferencesgiveninthissectionorfromtheSectionIofthismono~phobtainedeitherfromthegerieralreferencesgiveninATheGeneralChstzyofTungstenTungstenisoneofthefourtransitionelemmts(Cr,thatconstitutesGroupKtBoftheperiodicsystemandiBbemainlysaacidformingelementTheelementsofGroupMCI,w,andu)consideredtoVIBhavetwoincompleteelectronheKiBtheoutermostandtheonenetitoIttherefore,irre~oxidationstiteBexistanddonotchangerapidlyinchemicalbehatiorTtmgatenexistsinthesamepositiveoxidationstatesasmolybdenumTunenformecompoundshavlngvalencestateBoffrumtoMeettungstencompoundscontaintuugatenintheoxidationstateofIttillformstablehexacuotides,hexefluoridesandunstablehexabromldeBThetungetateB,tungeticacid(frmnwhichthetungstatesmderived),andtheanhydrideoftungsticacid,tunetentrioxide,themostimportsntCompotisoftungstenTableIIliststhemore~rtantofthemecmnsandgivesinformationabouttheirsolubilitiescOmpOundaof!cUngistenaTheHexavalent!CuuenTungstentrloxide,W,occursinnat~andisformedbyheatingtheacidTheacidificationofacoldsolutionofatungatatewithhydrochloricacidbrlngeabouttheformationofCttungetlcacid,HWOhHahotsolutiontillformtungeticacid,~WOkE$WmHiSsolubletosomedegreeinwaterwhereas,HWObistisolubleInwaterandallacids,excepthydrOfluorlc!tbngsticacidformscomplextuntatecompmmdeComplexalkali,metalcorqmndsofthetype(N~O)m(WO)inwhichrn=~nv~ie~fromltoarelmownMsmymorecomplexesinwhich~or~isunityc=alsobefomned!’)Normalorsimpletungetatee,suchas~Wforms,canresultfromthefusingofWwithsodiumcarbonateorpotassiumcarbonateMetatungatates,whichcontdnWradicalsper~molecule,arelmownTheparatungstatesgenerallycontainWOradicalsforeveryhOmoleculesandcmbemadecommerciallyForexsmple,NaloW=OblHIsformedbyheatingwolframitewithsodaashandextractingthefusedMSwithwaterUponneutralizationwlthhydrochlorlcacid,thesotiumparatungstatesaltseparatesaslargetrlcliniccryataleTheadditionofstrongaciflstohotsolutionsofmmttungstatestillprecipitateyellowtungstlcacid,whichIBpracticallyipaolubleinwaterandinmostacidsMetatungstatesareusuallysolubleformsoftungetlcacidsaltsendwillgivenoprecipitatewithacidEThetreatmentoftungsticacid,tungetentrioxide,oralkaliarrlalkalineearthtuugs~testithreducingagentsathightemps=turescanusuallybringabouttheproductionofavexietyofcoloredcomrpoundaThemoBtfrequentcoloredproductproducedisusuallyanintenseblueincolorThesecampouudegenerallyhavecompositionswhichcorrespondtothepresenceoftungsteninameanoxidationstatelowerthan,buthigherthanExpamretosunlighttillcausetungstentrloxidetotakeonabluishtintwenwhenkeptunderwaterNascenthydrogen(ZnHC)tillprecipitatefromatungstatesolutionabluepreciplt’atethatiastableinair‘lTheblueprecipitatethatformswhenSnCandHCareusedtoreactwithatungstatesolutionwillgraduallydi~coloronstandinginairandwillbefinallytransformedintoyellowtungstic~id,HWOb()Whenhydrogenperoxidesolutionsatatemperatureofareusedtodissolveeithertungsticacidortungstentrloxide,apsroxyacid,HW,ortungstenoxidepemrate,WF$OPiSformedPeroxytungatatesresultwhentungetitesaretreatedwithhydrogenperoxideSilicotungetatecompundsareformedwhensi~cicacidistiesolubleinhotsolutionsofacidalkalitungatatesThesesaltscontainalargenuuberofWradicalsforeachSiJinadditiontoalkalioxideandwaterReqy(’)pointsoutthat,althoughthesesaltsgenerallycalledSilicotungstates,thenamepolytungetosilicatesismarecorrectsincetheyarederivedfromsillcicacidoritssaltsbytheadditionoftungaticecikradicals(tungetategroups)Thetuugstosilicatesareredllydecompxedwhent=atedwlthalkalisTungtlcaciddsoformscompoundsexactlyanalogoustothesiUcotungstateswhenboricacid(tungetoborates),phosphoricacid(tungetophosphates)andarsenicacid(tungstoenates)aretreatedwithhotsolutimofacidalkalitungstatesIneachinstance,thecompoundstilloontainalargenumberofWticalsmeupperIlmltisWradicalsforeachArsenideBorideBromidecarbideCarbnylChlorlaeFhumldeIodideFormulaWABW$“WO~‘WBrWBrWCWC‘(m)WCTableII:Solubili~ofTungetenCcmpudsWaterSolubilltyCQldHothsolubleInsolubleInublefieoltileDccmoaeeDeceOInsolubleInsolublehEblUbleDeccmposes~campoeesWCDecompaeWCDecmpeeBWC~DcompsesInsolubleWInsolubleInsol*leInsolubleheolubleholubleDecmpseeIhccwpaeeDeccmpoBeeDec~sesLbcumposesOtherSolventsDeccuqposesinhotBNendhotHSOhSohibleaquareaHelliblealkaM,absolutealcohol,Chlorofom,etherSolubleNHhOHHolubleHNBF,aquaregjatilubleHNHCDec~sesifumingHNVerysllghtlysolubleinCVeqvsolubleInCSJsolubleinalcohol,etherbenaeneHolublealkaldHcdubleinKOHalkaliinnolubleinSandalcoholSolubleinabsolutealcoholinsolubleInether,chloroformturpentineoxidePhoaphidesulfide‘UW~rbWOwocWC$WOFbWgWP‘WSIhaolublelneohibleIheolubleInsolubleDecOluposesDccnnposesIkcompsesWconqmsesHolublelcompsesDecmposesInsolubleInsolubleInsolubleInsolubleslightlySolublesolubleSoltibleInacidandKOHSolubleinhotalkellaidotheracids‘l*lehCS’bmzSolubleindkdi,n~SFinsolubleinhaol*leinalcoholSlightlysolubleinCSinsolubleinCCSolubleinfusedNaCHeNInsolubleInacldOaquareaSolubleinEU=HFInsolublehalltaldandHCSolubleinHNO~HF,slcohol,etheSolubleinHRHF,alcoholSolubleinkaaquaregiainsolubleinfusedalkaliInsolubleInmoleculeoftheotheracidthislimitisneverexceededThecharacteriatlcpropertyofthesecompounds,ie,thehetero~lyacIda,isthattheycontainatleasttwodifferentacidradlcsls,oneofwhichIsusuallyinImgenumbereR=W(’)noteethattheIntroductionofoneormoreWrmiScaleintoHWOkcanproduceaseriesofisopolyacidcompoundscapableofreactingtiformJXXmgetatesaltsHowever,ithasnotbeenpasibletodistinguishthesereactionsbyanalyticaldataTungstentrloxide,WO’resultsfromtheoxidationoftungstenor~tsc~undsbyheatinginair,Thedioxide,W,iSformedfrrnnthisbytreatingItwithreducingagenteWasoftlemonyellowpciderthatwillturnorangewhenheatedWhenitedathightempe=turea,oriffusedwithborax,itbecomescrystallineWmeltsatandwillvolatilizeabovenohowever,Itcanbecompletelyvolatilizedasanvo~de~~“Ift~votitilizatlonoccursILastreemofhydrogencblofidegasTungstentrioxideisinsolubleInwaterCausticalkallswilldiaaolveIttoformtungetates,thesaltsoftungsticacidAlthouWcanbeformedbyignitingtuugmticacid,itcannotbereconvertedtotheacidformbysddlngwatertotheignitedBaitTungstentrioxldedoesnotappeartoyieldatruesaltinvhlchthemetalisapartofthec,ationIntermediateoxides,suchasWandW>exeformedinthereductionoftungetentrioxldetothemetalHexahalidesarefomnedbythereductionoftungeteninahydrogenatmosph~Inccmblnatlonwithchlorineandbyheating,thesereactionscanproducetungsten‘hextilQride,WCThehexachlorideisinsolubleincoldwaterIttilldecomposeinwamnwaterItissolublehalcohol,etherandotherorganicaolventa~halides,suchseWOCandCareknownTheWCisvolat~lewhenheatedThehexabromide,WBr,issfilartoWCIQbutItismorere~lydecompmedAcomplexgaeeoushexafluoride,WF=,canresultfromtheactionofhydrofluorlcacidontungstateccsn~deThehexahalidesandtheoxyhalideaarequicklyh’ozedbywatertotungsticacidandthecorrespondinghydrogenhalideThetreatmentofatungetatesolutionwithhydrogensulfidebrlngaboutatfirstapartialreplacementoftheoxygagofthetungatlcacldwithsulfurtoformanoxothlotungstateUltimately,theoxygediscompletelyreplacedbytheeulfurtoformatbiotungstate,~(WSh)Theadditionofacidetoaeolutionofathiotungetwbawillproducetungstentri~W,achocolatib~preclpititeHexavalenttungstencan

用户评论(0)

0/200

精彩专题

上传我的资料

每篇奖励 +2积分

资料评价:

/46
0下载券 下载 加入VIP, 送下载券

意见
反馈

立即扫码关注

爱问共享资料微信公众号

返回
顶部