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首页 【放射化学系列】镤的放射化学.pdf

【放射化学系列】镤的放射化学.pdf

【放射化学系列】镤的放射化学.pdf

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】镤的放射化学pdf》,可适用于自然科学领域,主题内容包含INationalAcademy‘vofSciencesNationalResearchCouncilINUCLEARSCIENCESERIESTh符等。

INationalAcademy‘vofSciencesNationalResearchCouncilINUCLEARSCIENCESERIESTheRadiochemistryofProtactiniumCOMMITTEEONNUCLEARSCIENCELFCURTISS,ChairmanROBLEYDEVANS,ViceChairmanNationalBureauofStandardsMassachusettsInstituteofTechnologyJADeJUREN,SecretaryWestinghouseElectricCorporationCJBORKOWSKIJWIRVINE,JROakRidgeNationalLaboratoryMassachusettsInstituteofTechnologyROBERTGCOCHRANTexasAgriculturalandMechanicalCollegeSAMUELEPSTEINCaliforniaInstituteofTechnologyUFANONationalBureauofStandardsHERBERTGOLDSTEINNuclearDevelopmentCorporationofAmericaEDKLEMANorthwesternUniversityWWAYNEMEINKEUniversityofMichiganJJNICKSONMemorialHospital,NewYorkROBERTLPLATZMANLaboratoiredeChimiePhysiqueDMVANPATTERBartolResearchFoundationLIAISONMEMBERSPAULCAEBERSOLDCHARLESKREEDAtomicEnergyCommissionUSAirForceJHOWARDMcMILLENWILLIAMEWRIGHTNationalScienceFoundationOfficeofNavalResearchSUBCOMMITTEEONRADIOCHEMISTRYWWAYNEMEINKE,ChairmanHAROLDKIRBYUniversityofMichiganMoundLaboratoryGREGORYRCHOPPINGEORGELEDDICOTTEFloridaStateUniversityOakRidgeNationalLaboratoryGEORGEACOWANJULIANNIELSENLosAlsmosScientificLaboratoryHanfordLaboratoriesARTHURWFAIRHALLELLISPSTEINBERGUniversityofWashingtonArgonneNationalLaboratoryJEROMEHUDISPETERCSTEVENSONBrookhavenNationalLaboratoryUniversityofCslifornia(Livermore)EARLHYDELEOYAFFEUniversityofCalifornia(Berkeley)McGillUniversityCONSULTANTSNATHANBALLOUJAMESDeVOECentred’Etudedel’EnergieNucleaireUniversityofMichiganMolDonk,BelgiumWILLIAMMARLOWNationalBureauofStandardsCNEMTRYRADIATIONANDFUDDHWLSTRYTheRadiochemistryofProtactiniumByHWIURBYMoundLaboratoryOperatedbyMonsantoChemicalCompanyMiamisburg,OhioDeoemberSubcommitteeonRadiochemistryNationalAcademyofSciencesNationalResearchCouncilPrintedhIUSAPrice$AvaileblefromtOfficeofTeohnicdServices,DepartmentofCommerce,WasMngtonDCFOREWORDTheSubcoumttteeonRadiochemistryisonesubcommitteesworkingundertheCommitteewithintheNationalAcademyofSciencesofanumberOZonNuclearScienceNationalResearchCounciItsmembersrepresentgovernment,industrial,anduniversitylaboratoriesintheareasofnuclearchemistryandanalyticalchemistryTheSubcoumdtteehasconcerneditselfwiththoseareasofnuclearsciencewhichinvolvethechemist,suchasthecollectionanddistributionofradiochemicalprocedures,theestablishmentofspecificationsforradiochemicallypurereagents,theproblemsofstockpilinguncontaminatedmaterials,theavailabilityofcyclotrontimeforsenriceirradiations,theplaceofradiochemistryintheundergraduatecollegeprogram,etcThisseriesofmonographshasRrownoutoftheneedforuptodatecilationsofradiocemicalinformationandprocedureseSubcommitteehasendeavoredtopresentaserieswhichwillbeofmaximumusetotheworkingscientistsndwhichcontainsthelatestavailableinformationEachmonographcollectshonevolumethepertinentinformationrequiredforradiochemicalworkwithanindividualelementoragroupofcloselyrelatedelementsAnexpertintheradiochemistryoftheparticularelementhaswrittenthemonograph,followingastandardformatdevelopedbytheSubcommitteeTheAtomicEnergyCommissionhassponsoredtheprintingoftheseriesTheSubcommitteeisconfidentthesepublicationswillbeusefulnotonlytotheradiochemistbutalsototheresearchworkerlmotherfieldssuchasphysics,biochemistryormedicinewhowishestouseradiochemicaltechniquestosolveaspecificproblemWWayneMeinke,ChairmanSubconunitteeonRadiochemistryiiiINTRODUCTIONThisvolumewhichdealswiththeradiochernistryofrotEactiniumisoneofaseriesofmonographsonradiocemistryoftheelementsThereisincludedareviewofthenuclearandchemicalfeaturesofparticularinteresttotheradiochemist~adiscussionofproblemsofdissolutionofasampleandcountingtechniques~andfinally,acollectionofradiochemicalproceduresfortheelementasfoundintheliteratureTheseriesofmonographswillcoverallelementsforwhichradiochemicalproceduresarepertinentPlansincluderevisionofthemonographperiodicallyasnewtechniquesandprocedureswarrantThereaderisthereforeencouragedtocalltotheattentionoftheauthoranypublishedorunpublishedmaterialontheradiochemistryofprotactiniumwhichmightbeincludedinarevisedversionofthemonographAnynewreviewonprotactiniumatthistimehasbeenrenderedlargelysupe#luousbytherecent~ublicationofthecriticalarticlebyHaissinskyandBouissiereslThisexcellentcomprehensivemonographcoversthepublished(andmuchoftheunpublished)literaturethroughNovemberExceptfortranslationfromtheFrench,itcanhardlybeimproveduponSuchatranslationhasbeenmade,anditishopedthatpermissionforitsgeneraldistributionwillbegrantedbythepublisherinthenearfuture“ThepresentreorthasthelimitedobjectiveofacquaintingthereaderwitEthebroadoutlinesofprotactiniumchemistry,especiallyinrelationtomethodsofandanalysisTheliteraturesurveyEP:::ii::$a::ion’materialreortedsinceaboutEfortieolderliterature,theauthorasreliedheavilyontheHaissinsBouissieresreviewCriticalcomments,however,arethoseofthiswriterPatents,assuch,havebeenlargelyignored,asintheoptiionoftheauthor,theirsignificanceismorelegalthanscientificivCONTENTSIGENERALREVIEWSOFTHECHEMISTRYOFPROTACTINIUMlISOTOPESOFPROTACTINIUMCHEMISTRYOFPROTACTINIUMl*lllGeneralMetallicProtactiniumSolubleSaltsofProtactiniumInsolubleSaltsUsefulinSeparationandAnalysieCoprecipicationandCarryingofProtactiniumSolventExtractionofProtactiniumIonExchangeBehaviorofProtactiniumMiscellanyPaperChromatographyElectrochemistrySpectrophotometryDryChemistryIvDISSOLUTIONOFPROTACTINIUMSAMFLESlllvCOUNTIWGTECHNIQUESlProtactiniumProtactiniumvVIlDETAILEDRADKMXEMICALPROCEDURESPORPROTACTINIUM*ABcDEPreparationofCarrierFreeProtactinium(Procedurethrough)DeterminationofProtactinium(Proceduresthrough)SpecialPreparationsofProtactinium(Proceduresthrough)SeparationsofProtactinium(Proceduresthrough)UrinalysisofProtactinium(Proceduresthrough)VIIAPPENDIXllllSuumaryoftheProtactiniumProjectatMoundLaboratoryTheRadiochemistryofProtactinium*ByHKirbyMoundLaboratoryOperatedbyMonsantoChendcalCompanyMiaisburg,OhioDecemberIGENERALlia”~ssinsky,MREVIEWSOFTHECHEMISTRYOFPROTACTINIUMandBoulssl’eres,G,Protactinium,NouveauTraitdechideMin~rale,X,pp,edbyPPascMasaonetCie,Paris()(ThisshouldberequiredreadingforanyoneworkingwithprotactiniumThebibliography,containingreferences,iscompletetoNovember,)Salutsky,ML,Protactinium,ComprehensiveAnalyticalChemistry,Vol,ChapterIV,Section,pp,edbyCecilLWilsonElsevierPublishtigCo,Amsterdam(InPress)(PrimarilydevotedtoanalyticalaspectsReferences,)**vj~lscomma:PermissionfortheuseofcopyrightedmaterialhasbeenkindlygrantedbyPergamonPress,publishersoftheJournalofInorganicandNuclearChemistry,andbytheeditoroftheJournaloftheAmericanChemicalSocietyKatzin,L,editor,ProductionandSeparationofUCollectedPapers$USAtomicEnergyCoumTID,ppinVOLS()Availableat$fromOfficeofTechnicalServices,DeptofCommerce,Washington,DC(papersdevotedtothorium,protactinium,anduraniumchemistry,radiochemistry,separations,andnuclearcharacteristicsNotatruereview,butavaluablecollectionofresearchpapersanddata)GmelinsHandbuchdera~organischenChemle,ProtactiniumundIsotope,SystemNumber,pp,VerlagChemie,GmbH,Berlin()(Reviewstheliteratureto)Elson,RE,TheChemistryofProtactinium,TheActinideElements,Chapter,pp,NationalNuclearEnergySeries,DivisionIV,PlutoniumProjectRecord,VolA,edbyGTSeaborgandJJKatz,McGrw=HillBookCo,NewYork()(References,,thelatestoriginalreferencebeingdated)Hyde,EK,RadiochemicalSeparationsoftheActinideElements,Ibid,Chapter,ppLiteratureSurveyon:TheChemistryofActiniumandProtactiniumEspeciallyinAqueousSolutionsDete~inatioRofActiniumendProtactiniumTechnicalInformationonRadiumlndusEryResidueshon~AtomicEnergyCommission,TelAviv,Israel,LS,pp(Sept,)TABLEIISOTOPESOFPROTAC~INIUMassModeofDecayHalfLifeSource(Pa)m(UX)(UZ)aaaEC~EC~~adECXCYECBU,paPPBXITPPPsecminminhrsdaysdays,yrSdaysdaystin*SminminECelectroncaptureITisomerictransitionddeuteronThdThaThd,Uc,daughterNpThd,daughter~Thd,Pad,ThdT#n,mn,descen~q~uThdPan,ThaThd,ThnDescendantU(metastable)DaughterPmUp,Ud,daughterThUdPprotonnneutronCHEMISTRYOFPROTACTINIUMGeneralTheonlynaturallyoccurringprotactiniumisotopesareprotactiniumandprotactiniumBecauseoftheirshorthalfliVes,minuteprotactinium(UX)anditshouriso=r(UZ)areofrelativelylittleinteresttoradiochemistsThedayprotactiniumisreadilyproducedbyneutronirradiationofthoriumandisofconsiderablevaluebothasatracerandastheparentoffissileuraniumsignificantly,theypbranchingratioofUXwasdeterminedwiththeaidofprotactiniumasatracerAlthoughthenatualabundanceofprotactiniumisalmostasgreatasthatofradium,theknownworldsupplyoftheisolatedelenentanditscompoundsdidnotexceedoneortwogramsuntilthelate’sInterestinthorimnbreederreactorsgavenecessaryimpetustotherecoveryofgramquantitiesofprotactiniumforstudyofitsmacrochstryAbundantsourcematerialwasavailableasaresultoftheacceleratedproductionofuraniumfornuclearreactorsChemicaltechnology(solventex~action)andins~tation(scintillationspectr~ters)hadadvancedtoapointwhereseparationsandanalyseswhichwerepreviouslydifficultorimpossiblecouldbemadewithrelativeeaseandrapidityAlxmstgramsofprotactiniumwasrecentlyisolatedfromuraniumrefinerywastesInGreatBritain,andgroupsatCambridge,Harwell,andelsewhereareactivelyengagedinstudyingthechemistry(asdistinctfromtheradiochemistry)ofprotactiniumDrAGMaddockhaskindlysuppliedthisreviewerwithanunpublishedreportontheactivitiesoftheCambridgeprotactiniumgrouplO,inwhichhedescribesthepreparation,incentigramquantities,ofthepentaandtetrshalidesofprotactiniumandpolarographicstudiesofitsoxelate,chloride,fluoride,andsulfatesolutionsThesedatawillbepublishedshortlyItissafetopredictthatthe’swillseemuchofthemysteryandwitchcrafteliminatedfromprotactiniumchemietryNevertheless,thegreatestsmmuntofinformationpublishedtodatehascomefromwxkdonewithprotactiniumontracerlevelsThesedatahavenotbeenconsistentlyapplicabletothemicrochemistryofprotactiniumTosomeextent,thediscrepanciesareduetotheoriginsoftheisotopesProtactiniumislikelytobecontaminatedonlybythoriumProtactinium,ontheotherhand,maybecontaminatedwithanyoralloftheelementsingroupsIVaandVaofthePertodicTable,aswellaswithphosphateion,whichtendstomakeitschemistrysomewhaterraticFurthermore,radiochemicalanalyslaofprotactiniumiscomplicatedbythepresenceofitsowna,B,andyactivedescendants(TableII)andthoseofuraniumProtactiniumcanaLsobeproducedbytheneutronirradiationofthorium(ionlum),inwhichcaseitwillusuallyalsobecontaminatedbythorhunandprotactiniumToomuchhasbeenmadeoftheapparentlycapriciouschemicalbehaviorofprotactiniumInthepentavalentstate,itsTABLEIIURANIUMACTINIUMSERIES(n)IsotopeSynonymModeofDecayEnergies,MevHalfLife~I~IpaAcuUYlAcKAnAcAAcBAceAcc“AcC‘AcDaBaLPa)aBaaLa$B)aa(P)PaStable$”L$z$$$()r$:‘$:$$r$~$:$$$::()$“$o$()xYH“,YYDMDSSMsMMschemitryh“similartothatofitshomologiesingroupVaofthePeriodicTableLikeniobiumandtantalum,protactiniumiaalnmotcompletelyinsolubleinallthecommonaqueousmedialxceptsulfuricandhydrofluoricacMsIfisreadilyprecipitatedbyhydroxidesendphosphates,and,intracequantities,iscarriedmoreorlessquantitativelybyprecipitatesofawidevarietyofel~tsThewellpublicizedtendencyofprotactiniumtodepositonthewallsofglashveeselssprimarilyduetoits,insolubilitythiotendencyisnotapparentinappropriateconcentrationsofsulfuricendhydrofluoricacidaMetallicProtactiniumMetallicprotactiniumhasbeenpreparedbythermaldecompositionofitahalidesonatungstenfilamentandby,byreductionofthellectronbombardmentoftheoxidetetrafluoridewithbariumat,andbyelectrodepositioncmvariousmetalcathodesfromverydilute,sllghtlyacid,fluoridesolutionsmThemetalIsgrayinhardasuraniumOnskinofPaOcolor,malleable,and”a”pproximatelya’sexposuretoair,itacquiresathin*SolubleSaltsofProtactiniumNowhereitheliteratureofprotactiniummoreconfusedorambiguousthaninthereferencestomineralacidsTheonlysystematicitssolubilltyincommonstudyinthisareaisthepreliminaryworkofThompsonwithorderofml(Table)Thesolutionvolumeeoftheavailabilityofgramquantitiesofprotactiniummakesthisqpotentiallyfertilefieldforinvestigation“Tbest“solventforprotactiniumlahydrofluorlcacid,whichre”adilyditeolveutheignitedpentoxideandnearlyallprecipitates,formingthestablecomplexIonPaF”protactiniumpentoxidedlaaolveeslowlybhotconcentratedoulfuriclcid,butthe”OolubilltyislowProlongeddigestionconvartstheoxidetoasulfate,whichdieaolveaondilutionoftheacidAlolutloncontainingregmlofprotactinhminapproximet~ly~HShaabeen,stableforoverayearL,endonecontainingregmlinapproximately~DShenbeenstableforahmonthsIntheauthorlaexperience,onlyhydrofluoricendsulfuricacidaparmemantlydimolve”appreciablequantitiesofprotactiniumWithallothermineralacids,solutioneareunmtable,reeultinginprecipitatesorcolloidalsuepenoionaaftetperibdsrangingfromafewhourstoseveralweeksSolutionscontainiqto~rotactiniumh~~(ml)hydrolyzedslowly,but,atconcentqationebe~anend~protactinium,theoolutionnwereauff,icientlyotableforhouretoyieldreproducibleextractionendionexengedata“Althoughthelitera~reisprolificofreferenctiatothesolventextractionendionexchangeofprotactiniumfromTABLEIIIVOLUBILITYOFPaINCOMMMACIDS~Acid~NormalityVolubilityStarting(gliter)MaterialHCHydroxideDilutionHCHydroxideDilutionDilutionDilutionHNHydroxide::EvaporationQfHN*DilutionDilution:HydroxideHydroxideHSHF*EvaporationOfHSDilutionHydroxideDilution::DiLutionDilution*~HNReviewer’sNote:ThistablehincludedbecauseitistheonlyoneofItskindavailableInthelightofrecentexperience,however,thevalues,whichwerebasedonvolumesoftheorderofml,arehighlyquestionableHCsolutions,nodataotherthanThompson’saregiventoLndiaatethelimitsofsolubllityTheinsolubilityofprotactiniumin~HCisusefulasamethodofseparationfromdecayproducts:Whentheiodateprecipitateof!protactiniumisdigestedwithconcentratedHC,theprotactiniumdissolvestemporarily,thenreprecipitatesquantitativelyAfterdigestiononahotwaterbathandcentrifugation,thesup”ernatecontainsnodetectableprotactiniumWhereanorderofregardedtakentoion,theoccasionalreferenceoccurstoSOIUbilitieBoftheregmlofprotactiniuminHKC,itmustbeasquestionableWhenelaborateprecautionsareeliminateorganiccompletingagentsandfluoridesubsequentHCsolutionsareunstableAsolutioncontainingregmlofprotactinium,in~HCwaspreparedfromaperoxideprecipitate,but,overaperiodofthreeweeks,aboutpercentoftheprotactiniumprecipita”tedLInsolubleSaltsUsefulinSeparationendAnalysisThenormaloxidationstateofprotactiniumis,butprotactinium(V)probablydoesnotexistinsolutionasasimplecationOnreductiontoprotactinium(IV)eg,withzincamalgam~,thefluoridecsnbeprecipitatedandisinsolubleinwaterandmostacidsTetravalentprotactiniumisslowlyoxidizedInairtothepentavalentstate,andthefluorideredissolveszoProtactinium(V)canbeprecipitatedfromfluoridesolutionbytheadditionofastoichiometricamountofKF,whichformsanlnsolubl~doublefluoride,KPaPAdoublefluoridewithbariumhasalsobeenreportedAlkalihydroxidesandcarbonatesprecipitateprotactiniuminbothoxidationstates,andtheprecipitateisnotsolublehexcessofthereagentDependingontheconcentrations,~HHmavfailtoprecipitateprotactiniumquantitativelyfromfluoridesolutionThephosphate”andhypophosphateofcipitatedfromacidsolutionsItprotactiniumcmbeprehasbeenreportedthattheprecipitatewillnotredissolveeveninstrongmineralacidsHowever,theauthorhasregularlyredissolvedprotactiniumprecipitatedbyphosphate,whetherintraceamountscarriedbytitaniumorniobium,orincarrierfreemilligramquantitiesTheprecipitate,upondigestionwithasufficientquantityofwarm~HSeitherdissolvesorbecomessolubleondilutionwithHCtowhichsomeHhasbeenaddedThephosphatecanalsobeprecipitatedfromfluoridesolution,dependingupontherelativeconcentrationsoftheanionsIfex

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