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首页 【放射化学系列】钍的放射化学.pdf

【放射化学系列】钍的放射化学.pdf

【放射化学系列】钍的放射化学.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】钍的放射化学pdf》,可适用于自然科学领域,主题内容包含INationcdAcademyofSciencesNationalResearchCouncilNUCLEARSCIENCESERIESTheRa符等。

INationcdAcademyofSciencesNationalResearchCouncilNUCLEARSCIENCESERIESTheRadiochemistryofThoriumCOMMITTEEONCHEMICALSCIENCESJamesL,Kinsey,Cochairrnan,MassachusettsInstituteofTechnologyAlanSchriesheim,Cochairman,ExxonResearchandEngineeringCompanyAndreasAcrivos,StanfordUniversityAllenJBard,UniversityofTexas,AustinFredBasolo,NorthwesternUniversityStevenJBenkovic,PennsylvaniaStateUniversityBruceJBerne,ColumbiaUniversityRStephenBerry,UniversityofChicagoAlfredEBrown,CelaneseCorporationErnestLEliel,UniversityofNorthCarolinaRoaldHoffmann,CornellUniversityRudolphPariser,EDuPentdeNemoursCo,IncNormanSutin,BrookhavenNationalLaboratoryBarryMTrost,University’ofWisconsinEdelWasserman,ElduPontdeNemoursCo,incSUBCOMMITTEEONNUCLEARANDRADIOCHEMISTRYGregoryRChoppin,Chairman,FloridaStateUniversityEugeneTChulick,BabcockWilcoxCoChristopherGatrousis,LawrenceLivermoreNationalLaboratoryPeterEHaustein,BrookhavenNationalLaboratoryDarleaneCHoffman,LosAlamosNationalLaboratoryPaulJKarol,CarnegieMellonUniversityMichaelJWelch,WashingtonUniversitySchoolofMedicineRaymondGWymer,OakRidgeNationalLaboratoryWilliamHZoner,UniversityofMarylandLIAISONMEMBERSFredBasolo,NorthwesternUniversityTheodoreLCairns,Greenville,DelawareGerhartFriedlander,BrookhavenNationalLaboratory(MembershipasofJanuary)TheRadiochemistryofThoriumByEKHYDELawrenceRadiationLaboratoryUm”versityofCaliforniaBerkeley,CaliforniaihnuaryReprintdbytheTechnicalInbrnationCemterU,SIhpwbmritofEnergySubcommitteeonRadiochemistryNatiomlAcademyofSciencesNationalResearchCouncilPrice$Availablefrom:NationalTachn”ulInformationServiceUSDepartmentofCommerceSpringfield,WginiaPrintedintieUnitedStatesofArnerlcaUDOETuchnkelInformationCenter,OakRkige,Tenn~Mastprind~JuneFOREWORDTheSubconnnitteesubcommitteesvorkimonRadiochemistryisoneofanumberofundertheCcdmuitteeonNuclearSciencewittitheNational~cademyofSciencesNationalResearchcouncilItsnumbersrepreseutgovernment,bluatrial,anduniversitylaboratoriesintheareasofnuclearchemistryandanalyticalchemistryTheSubcommitteehasconcerneditselfwiththoseareasofnuclearsciencewhichtivolvethechemist,suchasthecollectionanddistributionofradiochetnicalprocedures,theestabllsbmentofspeciflcationsformsdlochemicalJypurereagents,theproblemsofstockpilinguncontsminatedmaterlab,theamilabilltyofcyclotrontheforserviceirradiations,theplaceofmdiochemistryintheunderqduatecollegeprogmn,etcThisseriesofmnomaphshasgrownoutoftheneedforuptodatecmpilationaofradioclmnicalInfommtionandprocedureslheSubcommitteehasaudeavmedtopremmtaseriesvblchwiJbeofmadmunlusetotheworldngscientistsndwhichcontainsthelatestavailableinformationEachmonogWcomctainonevolumethepertinentinformationrequiredforradiochmicelworkwithanimlividualelementoragroupofcloselyrelatedelemmtsAnqrtintheradiochemistryofthe~icularelementhasvrittauthemnom,follmingastandardfomtvel~dbytheSubconunitteeTheAtmicEner~CamissionhassponsoredtheprintingoftheseriesTheSubcamitteeisconfidentthesepubllcationawlbeusefulnotonlytothemdiochemistbutalsototheresearchworkerhotherfleldasuchasphysics,biochemistryormedicinewhowishestouseradiochemicaltechniquestosolveaspecificproblemWWayneMeinke,ChairmanSubcommitteeonRadiochemistryiiiCONTENTSIGeneralRevieveoftheInorgmlcandAmlyticalChemist~ofThoriumIIGeneralRtievBoftheRadlochemistryofThoriumTableofIsotopesofThoriumIVReviewofthoseFeaturesofThoriumCheridstgofChiefInteresttoRsdiochmistaMetalllcthoriumSolublesaltsofthoriumInsolublesaltsofthoriumandcoprecipitstionofthoriumcoIexloneofthoriumChelatecomplexesofthoriumchancteristlcaMractionoftheTTAccqplexofthoriumIntoorgxLcsolventsHractionofthoriumIntaorganicsolventsIonExchangebehaviorofthoriumvCollectionofDetailedRadiochemicalF’rocdmesfor!lhcmiumvINTRODUCTIONThisvolumewhichdealswiththeradiochemistryofthoriumisoneofsseriesofmonographsonradiochemistryoftheelementsThereisincludedareviewofthenuclearandchemicalfeaturesofparticularinteresttotheradiochemiat,adiscussionofproblemsofdissolutionofasampleandcountingtechniques,andfinally,acollectionofradiochemicalproceduresfortheelementasfoundintheliteratureTheseriesofmonographswillcoverallelementsforwhichradiochemlcalproceduresarepertinentPlansincluderevisionofthemonographperiodicallyasnewtechniquesandprocedureswarrantThereaderisthereforeencouragedtocalltotheattentionoftheauthoranypublishedorunpublishednaterialontheradiochemistryofthoriumwhichmightbeincludedinarevisedversionofthemonographTheRadiochemistryofThoriumEKHYIE$IawrenceRadiationIdxxatorgUniversiofCaUfozmla,BerkeW,CtiorniaJanu~$)TableofIsotpesIGilRALREVWSOFTlElNIRGAICtCMDMiKLZTICALCHEMISTRYOFHCRIUMChapter,ppIn‘TheChatryoftheActimldeElements”,JJKatzandGTSlmrg,JohnWileyandSons,Inc,HewYork,chapter,pp,“TheChemLswofThorlwn”byLRlatzininthe“TheAbtbideElements”,HationalIhIclearEn==Serle,a,DivisionN,Plutonlumpro~ectRecordVolumeA,editedbyGTSeaborgandJJKatz,McGwMUBcmkCo,MewYork,klin’aHandhuchderAnornischenChemie,SyBtemlfr~,thEditIon(VerlagChemie,GmbHWeinhetiEergatrasse,)CJRodderIandJCWarf,pplIIn“analyticalChemLstryoftheManhattanProJectn,McGrawEllJBookCo,lVewYork,“Thorilml’pp,Volof“Scott‘sstandardMethoaeofChemicalAnalyis”,HH~,editor,DVanHostrandCo,Inc,NewYork,“TheAnalyticalAspectsofThoriumChemistry”,TMueller,GKSchveltzerandDD:Starr,ChmRevFebCollectedPapersonMethodsofAnalysisforUraniumandThoriumcoledbyFSGr~dl,IMay,MHFletcherandJTitcombGeologicalSurveyBuetinIo(I,,forWebySuperlntentofDocumentaUSGovermnentPrintgOfficeWahington,DcPrice#Chapter,“RadlochemicalSepmtioneoftheActlnideEtlemen,byE’KHydein“The~tinideEtknante”,editedbyGTSeaborgandJJKatz,McGrawHillBookCo,NewYork,perP,adiochemicalSepamtlonsMethodsfortheActinldeElements”byEKEfyde,pp,Vol,ProceedingsoftheInternationalConferenceinGeneva,AugustonthePeacefulUesofAtomicEnergy,HtedNations,NewYork,Singlecopiesofthispaperstore,HewmybeavaflableforcentsfunltedYorkGltyNitioneEookTABLEOFIEEYIO~OFTHRIUMIsotope=llfeTypeofMethdofPreparationDec~~~~~~(R~(R~wJ~(Ionium)~(msecSecndndll*yearyear,myelwrhhIXUaaa$ECaaaaaPmwxIOyearfaIdnIhmghterDaughterndnDt=minLDsughteraw#NaturalradioactivitydaughterACNaturalradioactivitydmiterAc(~)Dmghter*HatunslradioactivityWghter$NaturalradioactivitydaughterIVatumlthoriumis$ThTh*neutronsl’atwalradioactivityQter$FormreconeteinformationontheradisrtionsofthethoriumLsotapesforreferencestaoriginallitemture,see“TleofIsotupes”,DStmmIw,JMHn~=andNO,PartII,CLTBeabmg,ReviewsofModernPhysics,~MetalMcThorium!l!horlum=talshighlyelectropositiveanditspreparationisaztstterofnomeandifficulty“Methodswldchareusedforthispurposeincludereductionofthofiumoxidewithcalciqreductionofthoriumtetracblorideortetrafluorideortetrachloridebycalci~meeBiumorsodiumorelectrolysisoffusedsalts!Chotiummetalhasahigh=ltlngnt(C)andishighlyreactiveinthezmlten~tateThe~tentialofthethoriumthorium(IV)couplehasbeenestimatedeaXvoltsAfreshsurfaceofthoriumtsrnishesrapidlyinairandthefinelyditidedmetaliBpyrophoricThepresenceofoenadpssiblyofnitrogenandotherlightel~timpuritiesonthesurfaceofthoriumcsnbean!atterofsomei~rtanceinBorneqrimentsinnuclearchendstryorphysicswherethinfoilsoftkrlumeeoyedutmgetsThereactionofthorium=talwithaqueousmineralacitihassomefeaturesofgreatinteresttamdiochemistsDilute”hydrofluoricacid,fitricacid,sulfurlcacidandconcentmtedphosphoricacidorpercblorfcacidattackmassivethoriummetalslovlyConcentratedtitrlcacidrendersthoriumpassivebuttheaddltlonoffluorideioncausesthedissolutiontocontinueInthedissolutionofznWlthoriumtargets,itisfoundthatconcentratedEJcontainingnmlsr(NIIh)zSklF(orHF)tiesagoodsolventmixtureTheBolventshouldbeadddinbatcheswithheatingaudstirringInbetweenratherthanallatonceHYdxmcbloricacidattacksthoriumVigoroudybutamysteriousb=orblueblackresidueremxLmoncompletionofthereactionAamuchaspercentoftheoriginalnetal~bewnvertedbtheblacksolidbyeitherdiluteorconcentmtedhydrochloricacidtorallofthisresiduecanbedissolvedbyaddingfluorldeioninsnnUconcentrtiiontothemChlO’iCcidTheblackreaiduezraybeThOorit~beahydrlde~ForafurtherdiscussionofthismterialseeKatzinz,JmzesendStraumanlsj,andKatzandSe*rgThoriumoxidetargetscanbessolvedbyamixtureofhydmchloficCidPIUS()’iFOrOf~tficacidPhIS(~)#~Agood~SCUSS~OnOfthefluorideioncatalyzeddissolutionoftborlumretalorthmlwndioxideisgivenbySchuler,SteablyendtaughtonalubleSaltsofllmrimSincethoriumeriatsInsolutlonasaCompamtlvelysmallhighlyckgedcation,itUnqgesarkensiveinteractionwithwateraudwithmanymimeThereIsonegreatslmliictiionintheaqueouschemistryofthorlunlhthatithasonlyoneoxidationneedbbeconsideredThewatersolubleEtateBaltaandhenceoxidationreductionreactionsdonotofthoriumincludethetitrate,thesulphate,thechlorideamitheperchlorateInmlubleSaltsofThoriumPrecipitationandCoprecipitationCharacteriEticBofthoriumThecommninsolublecompoundsofthoriumarelistedinTableAninspectionofthetable~estsBnuniberofprecipitatewhichmaybesuitablefortheremovaloftracerawuntaofthoriumfromsolutionGooddescriptionsoftheinsolublecomp~ofthoriumadtheiruseinanalysisaregiveninthegeneralreferencesMatedinPeaIThoriumhydroxideisablghlyinsolublecompoundformingagelatinousprecipitatewhenelktioranmmiumhydroxideisaddedtaanaqudousolutionofThItismtamphotericThoriumhydxddedissolvesinaqueouasolutionscontainingionssuchsacitrate,carbonate,orsulfoseJicyldcacidwhichcomplexthoriumionTraceramountsofthoriumwillcoprecipi~tequantitativelywithawidevarietyofinsolublehydroxideslanthanum,ferricandzirconTABLEIISLUHIJiCOMPOLUJBOFTHOR~ResgentPrecipitateVolubilityinVolubilityinWaterotherReagentsOHFKFKFC=Th(OH)k‘”WK#hFT’h(Io)TMc)~veryinsolubleveryinsolubleveryinsoluble(eveninstrongHN)insolubleinwaterordiluteacidveryinsolublesolublehacids,ammoniumoxalate,alkalicarbonates,sodiumcitrate,etcsolublehacidaluminumnit~tesolutionsolublewithreasentswhichdestroy~BOlubleinexcessamoniumorpotassiumoxalatedissolveswithHcultyinconcentratedacidPZ{Tqpo)l’h(~)~oTMm)E#O~~#’~~~~‘Mo’tilemolesperMterONHcl~Th(w)smoveryinsolublesolublehstrongOIJH#okmineralacidTABLE(Cent’d)ReagentReuipltatasolubili*InsolublliinWaterothemRegallteso=Th(so)qoWUdlasolvedInexcesssulphltecr{m(c=)qinsolublein‘~soluble~(~)~”~~h=Th(Moo)qoinsolubleFe(Cl)AThFe(CN)”~veryinsolublesolublendneralinConeacidindiluteacidsIumhydroxidehavebeenusedSincehydroxidecarrierprecipitatesarenotoriouslynonspecific,theyshouldbecountedononlytiremovethoriumfromasinendxtureofcontaminanttsorasagroupsepamtiontobefollowedbynrmespecificchemicalpurificationsteps:Insomeoftheclassicalstudiesofthe~umseriesUXl(Th)wasseparatedfrom~umbyprecipitatingferrichydroxideandammoniumumnatetogetherandleachingtheuraniumfromtheprecipi~tewithammoniumcarbonateThoriumperoxideformawhenhydrogenperoxideisaddedtoadilutemcLneralacidcontainingthoriumItishighlyineolubleTheformulaSoftenvenas~butrecentinvestigationssuggestthatanionsmeIncorpomtedintothesolidastitegralconponentiThepreciseformulaoftheprecipitevariegwiththeconditionsofprecipltitionThephysicalfomIsalso~=tlydifferentdependhgontheacidltyz:vhenprecipitatedfromaneutralsolutionitisgelatinousandcon~namanycopreclpltstedanionswhenprecipitatedfromasLQhtlybasicsolution,itisnotsogelatinousandhaiialowerperoxidecontentwhenformedinanacidsolutlon,ItisopaqueandreadilyfilteredInsolubleperoxidecmpoundsaremreinthePeriodicSystemsotbstprecipitationofthoriumperoxidecanprovidecleanseparationofthoriumfrommostotherelementsPlutonium(N)foaperoxidestilartotofthorium(IV)Other(IV)stateelementssuchascerium(IV)andzirconium(IV)alsoformsuchinsolubleperoxideBUranim(IV)mdneptumlum(IV)alsoforminsolubleprecipitatesupontheadditionofperoxide,buttheBeseemtobeofascanewhattifferenttypethanthoseformedbythoriumandplutonlumTheseperoxidepreclpltesarereadilydissolvedbytheadditionbfreagentssuchasSn(II),,~~orCe(IV)whichcandestroyperoxideForamorec~letediscussionoftheperoxide=dforreferencestotheori~lite~ture,seeKatzandSeaborgbnthaumFluorideasCererforlbrlum!l’horlumtillcoprecipltatequantitativelywithlantkmmprecipitatedasthefluorideflmmstronglyacldlcsolutionsThlisaveryuseful~fortheseparationofamBUlmnuntslofthoriumfromuraniumsolutionsThefluoridemaybeconvertedtothehydrmddebydirectmetathesiswithalkalihydrofidepelletsorstrongalkalisolutions,oritmaybedissolvedinanaluminumnitratenitriccidaulution(whichthoroughlycomplexesthefluorideion)endthenbeprecipitatedasthehydroxldeThecoprecipitationofrareearthimpuritiesis,ofcourse,completeZirconiumandbariumintraceconcentrations~ecarriedbut,ifmilligramquantitiesoftheseelementsaxeaddedas“holdbackcarriers”,nocoprecipitationiBobservedHencecoprecipitationuithlmthanumfluoride“serveseaanexcellentmethodofflreeingthoriumfromthezirconiumcarrierusedinapreviousstepAualternatemethodwouldbetherenmvalofzirconiumonanauionexchangeresinfroman~nmlarsolutionofhydrochloricacidOtherin~olublefluoridesmWserveascarriersfortraceamountsofthoriumZirconiumIodateasOarrierZirconiuminaconcatrationoftomgml~beprecipitatedastheiodatefromastronglyacidicsolutiontocthorimne=lyquantitativelyTheiodateconcentrationisnotcriticalElementswhichforminsolubleiodatesareabocoprecipitated,butmany,suchasuraniqareseparatedThe~earthsandactiniumnedecontaminatediftheprecipitationisfmmastsmnglyacidicsolutionandtheprecipitateiswashedulthaniodatecontainingsolutionUnderconditionsoflowacidityandlowtotalionicstrength,thecarryingoftheseelementsmaybequitehigh,asshownforactiniumbyMcLaneandPetersonIfceriumispresentitisnecessarytoreduceCe(lf)toCe(III)withsoressuitablereducingagentsucheshydrogenperotide,beforeprecipitationThezirconiumiodatemaybedissolvedinnitricacidcontainingsulfurdiotideorsomeotherrducingagent,andthezirconiummaybereprecipitatedeathehydroxideafterthesolutionisboiledtorenuveiodineEagemannandhlscouorkemappliedthismethodtatheirstudyoftheisotopeThinthehnseriesTheirprocedureisreproducedinProcedureofSectionVbelowBallouguseditasameansofsubstitutingzirconiumcarrierforrareearthcarrieraftereninitiallanthanumfluorideprecipitationSeeRwcureinSectionVbelowPhosphatePrecipitatesTlmriumprecipitatesinavarietyofilldefinedformsinthepresenceofPhosphorouscontdningsniormThesecompundeareextremelyinsolubleinwateradinacidsolutionThehypophosphateiBparticularlyinsolubleEveniniiHclthevolubilityisODIYxnmlesperliterOtherinsolublephosphatessucheszirconiumphosphateserveasgoodcarriersforthermmwaloftraceamuntsofthoriumfrom”aqueoussolutionThoriumOxalateAuidelyusednethodofqmtitativeanalysisofthoriumistheprecipitationofthoriumoxalatefollowedbyigoitiontothoriumdioxideandweighingofthedioxideSomecompltingagentainterferewiththeprecipitationofthoriumoxalatebytheformationofsolublethoriumcomplexesGordonand~erreportamethodfortheseparationofrareearthionsftmnthoriumbyprecipitationofphosphatefreerareearthoxalatesinthepremnceofthestrongchelatingagent,ethylenedlaminetetraacetic”acld(~A)Organicacidswhichformwaterinsolublecompoundswiththoriumwhich=eofpossibleanalyticalormdiochemicalimportanceincludesebacic,entbranitic,phmylarsonic,gtiic,taunic,quiticdM~iCWidSComplexIonsofThoriumThehighlychargedpositiveIon,Th,haeastrongtendencytaformcoHLplexionswithanionswhi~maybepresentinsolutionSomefaudllaritywiththemreconuwnoftheBecomplexIonsierequireforapropertierstandlngofthebehaviorofthoriuminionexchangeseparations,intheextractionofthoriumintoorganicsolventsandsoonQuantitativeraeasurementswhichhavebeenmadeontheequilibriumcomtentsforcomplexionformationsaresununmxlzedinTbleTAEKXCPIEX~OFTHORIUM(ReprintedfromKatzandSeaborgp,reference)ConlplexhgReactionIonicKRefAgentStrengtherencesclNOClomlcl=ThclsTh*cl=ThcqTh*cl=TbcllThicl=ThcThmJo=Th(No)Th~No=Th(Ero)TloTTI(C),aaaaaaaaaaaaabc“cb!CABIE(Cent’d)Ccm!plexingRaactionIonicKRefAgentStrenherencesBroCIC~~HClzcmCCCOOH~mThBro=Th(Bro)•~Th~~=Th(Br)ThClCH#OOH=Th(CIC~COO)HTh*CCEX=Th(CCHCOO)HTh*CC~H=Th(C~CK’):HThCCCOOH=~(CCCOO)HTh$CCCOOH=Th(CCCOO)jH‘*~=‘(~~=~()ilTh=)ThABSO~=TW~Hmbmo~=m(so~)HTh*ESO~=Th(ES)HThAHP=Tb(~p)Tk#Hf=Th(H#)HTh~P=Th(H#~~)HThH<=Tb(H#)H~Am*H::~:H:Th*HAcAcTICAC)HTh*HACAC=Th(AcAc)HTh*EAcAc=!l!h(AcAc)HTh*#mAcAc=TM)hH

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  • 情人 2010-11-15 20:44:58

    钍是继铀之后最宝贵的能源原料。

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