【放射化学系列】磷的放射化学

“5+6.a . .._ H75%4’ C.5 ! National Academy ““”v of Sciences National Research Council NUCLEAR SCIENCE SERIES The Radiochemistry of Phosphorus . . I COMMlllEE ON NUCLEAR SCIENCE L.F.CUHTIM,Chd- HOBLliWD.EVANS,ViC#Ckal- N6ibndBureanofSbudar& MMU~ttn InatUubofTechdcsY J.A. DeJOHHN, .SwmItmy WeOUnglmussHleotrbCorpxntbn C.J.MMtK~ J.w.mvmx,JR. OakRidgeNatid I.mbOmtorg Mastiudts hBtiblb d TeohmlosY ROBERTG.COCWEAN TaX8#AgriOultaualandMechaldd collage SAMUELEP61’KIN Cdlfomln hmtihrteofTeahmlc# u.FANO NatlandBureauofShndar& EHBBERTGO~ IUndearmvelopmemtcorponnon0! Amarl13a E.D.KLEMA NorthwesternIJnlveralty W.WAYNBMSINKE Untvern[&ofMtuhlgna J.J.NIC-N MemorialHoaPlt4NewYork HOBBETI.PLATZMAN IahOlatdredeChimlePhyOiqw D.M. VAN PATTER BmtolEaseorahF~on LIAISONMEMBERS PAULC,.AEB~LD ~S K. REED Atomfo EnmsY Cammlmdon U.E.Ah Force J.HOWABDMo~ WILLIAME.WRIGHT NatlondSdem?aFoundation Ofbsd NavalRmenrah SUBCOMMlllEEON RADIOCHEMISTRY W,WAYNEMEINKS,Chairman EARLHYDE Unlv8r0i~ofMicblgnn Unlvmsi~.ofCdfomda(Berkeley) NATNANBALI.OU JUIJANNIEIAEN Nwd HxIIologlcalDefense Iabmalory HanfordIatarntc.fien GREQORYFLCHOPPIN G.DAVIDO’IOZLLEY PloritiStatsUntveraItg OakHidseNntlonalIahorntnry GEORGEA CCfWAN ELIJSP.STEINBERG I.DOAlamoaS4ientfficIabxatory ArEonneNation.dI.mlwrbry ARTHUHW,FAIRHALL PETERC.STEVENSON Ur&ersiWofWn9htrgbm Untveral&ofCdlfOrnln(Ltvermore) JEROMEHuDIS DUANEN,SUNDEHMAN BnmkhavmNauonnlLaboratory BaUd10MeumrldInstitita CONSULTANTS HERBERTM.CI.AHK JOHNW.WINCHESTER R&mluerPolytedmlcInstitute MamwtwettaJnsuhJwofTectmdc@y $wd. pq94r%p C*5 CHEMISTRY ..h The Radiochemistry of Phosphorus W. T. MULLINS and G. W. LEDDICOTTE Oak Ridge National Laboratory Oak Ridge, Tennessee IssuanceDate:?vlarch1962 LQs AIAMos scmNTIFxc LABORATORY MAY4-1962 ImmARIEs PROPERTY Subcommittee on Radiochemistry NationalAcademy ofSciences—National Research Council PrintedInUSA.Price$0.50.AvatlablefromtheOfficeofTed.mical Services,DeparbnentofCommerce,Washington25,D.C. FOREWORD The Subcommittee on Radlochem36try Is one of a number of subcommittees working under the Committee on Nuclear science within the National Academy of Sclencee - National Research council . Its members represent government, industrial, and university laboratories @ the areas of nuclear chemlBtry and analytical chemistry. The Subcommittee has concerned Itself with thoee areas of nuclear science which involve the chemist, such as the collec- tion and dlstrlbutlon of radlochemlcal procedures, the estab- lishment of speclf~catlons for radlochemically pure reagents, avallablllty of cyclotron tti for service irradiations, the place of radlochemlstry In the undergraduate college program, etc. This series of monographs has grown out of the need for up-to-date compilations of radlochemical tiformatlon and pro- cedures. The Subcommittee has endeavored to present a series which will be of maximum use to the workin&Bclentlst and which contains the latest available information. Each mono- graph collects in one volume the pertinent information required for radlochemlcal wark with en individual element or a group of closely related elements. An e~ert In the radlochemistry of the particular element haB written the monograph, following a standard format developed by the Subcommittee. The Atomic ”Energy Commieslon has spon60red the printing of the series. The Subcommittee is confident these publications will be useful not only to the radiochemist but also ,tothe research worker in other fields such as physics, biochemistry or medictie who wlshee to use radlochemical techniques to solve a specific p~blem . W. Wayne Meinke, .Wizman Subcommittee on Radiochemistry 111 INTRODUCTION This volume which deals with the radlochemlatry of phosphorous is one of a series of monographs on radiochemlstry of the elements. There is Included a review of the nuclear and chemical features of particular interest to the radlochemlst , a discussion of prob- lems”of dissolution of a sample and counting techniques, and finally, a collection of radlochemlcal procedures for the element as found in the literature. The series of monographs will cover all elements for which radlochemlcal procedures are pertinent. Plans Include revision of the monograph periodically as new techniques and procedures warrant. The rehder is therefore encotiraged to call to the attention of the author any published cirunpublished materfal on the radlochemlstry of phosphorous which might be included In a re- vised version of the monograph. iv CONTENTS I. II. Iv. v. VI. VII. VIII. GeneralReferenceson the Inorganicand Analytical. Chemistryofphosphonla. . . . . . . . . . . . . . . . . . . . . The The A. B. The A. B. c. l.). E. RadioactiveNuclldesof l%osphoms . GeneralChemistryof phosphorus.. . ElementaryFnosphorue.. . . . . . . The chemical.Gm@uude of phosphorus 1. ReactiormwithHydrogen.. . . . 2. Reactionswith Oxygen.. . . . . 3. ReaCtiOIISwith ~ti. . . . . . k. Reaction5with the ~O@M . . . 5. Reactionswith Nitrogea.. . . . 6. Reactionswith Metal~. . . . . . AnalY-tid Chemistryof PhosphQrua. Separationby Precipitation.. . . . Separationby Electroly6ism. . . . . Separationby Volatility. . . . . . SolvsntExtractionSeptiona . . . ChrWL9to17raDhicSePamtions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1. With-In&nic-Adeofbent6. . . . . . . . . . . . . . . . 2. By Ion ExchangeRestis. . . . . . . . . . . . . . . . . 3. By PaperCbmm3togmphy. . . . . . . . . . . . . . . . . Dissolutionof SamplesContainingphosphorus. . . . . . . . . . &fe’qyRactices . . . . . . . . . . . . . . . . . . . . . . . . CountingTechniquesfor the RadioactivePhoephorueIsotopes.. . RadiochemlcalProceduresfor the phosphorusFdlonuclldes.. . . References. . . . . . . . . . . . . ...%. . . . . . . . . . 1 1 2 : 4 6 6 7 7 -I 8 9 9 10 10 10 I-1 I-1 12 12 13 13 29 v The Radioch6mistry of Phosphorus W. T. MULLINS and G. W. LkDDIC@TE Oak Ridge National Laboratory* Oak Ridge, Tennessee I. GENERALREFERENCESON THE INoRGAmc AND ANALYTICALCHmImRY OF PHOSPHORUS Renw,H., Treatim on Inorgsmlc Chelmtry, Volume1, Elsevier, Ametedsm (1956). Kleinberg,J., Argersinger,W. J., Jr., and Griswold,E., bor”@nlc Chemistry,Heath,Boston (1960). Hilleb&nd,”W. F., Luudell,G. E. F., Bright,H. A., and Hoffman, J. L., ApplledInorgmic Analysis,JohnWiley and Sons,New York, 1958. Wilson,C. L.,“andWilson,D. W., ComprehensiveAnalyticalchemistry, Elaevier,hetemhu, 1959. Slenko,M. J., and Plane,“R.A., Cheroistqy,McGraw-EHU,New York, 1957. Ckrlot, G., and Bezier,D., @antltativeInorganicAndy ala,John Wileyand Sons,New York,.1957. Sidgwick,N. V., The Chemical.Elementsand TheirCompounde,university Press,oxford,1951. Vea Wazer,J. R., Phosphome and Its cow und.e: VolumeI: Chemistzy, Intersclence,New York,1958. Hutchh.eon,E., Chemistti- The Elementsand TheirReactions, Saunders,Pbiladelphla,1959. II. RADIOACTIVE~S OF PHOmORUS The radioactivenuclideaof phosphorusthat are of Interestin the rsdlo- chemistzyof phosphorusare .@venin TableI. Tbls tiblehas been coqlled *Operatedfor U. S. AtomicEnergyCommissionby UbionCarbideCorporation. ihum InformationappearingIn reportaby Strondnger,et al.,(1)and by I&he. ImdHarvey.(’) . THE Radio- Half- nucllde 13fe —— $9 4.6 s #o 2.55m Fe 14.3d. ~33 25.4 d p+ 1.2.4E TABLEI RADIOAGHVENUCLIDFSOF PHOSPHORUS Mode of Energyof = Radiation ProducedBy P+ Y 1.28,2.42 Si-p-n,Si-d-n,P-y-’n P+ p+ S.Labs Al-inn,Si-p-n,Si-He3-p, P-n-h, P-7-n,S-d-% C1-y-a,n P- @- 1.70 S5-d-y,Si-d-p,Si-He3-p P-d-p,P-n-7,S-n-p,S-d-a, Cl-n-a,C1-7-~n, Cl-d-pa B- P- 0.2$ abO S-n-p, S-7-p,Cl-y-a B- P- 5.1, 3.2 S-n-p,Cl-n-a III. THE GEKEHAL_STRY OFPHOSPHORUS Phosphorusis neverfoundin natureas the element. The Mef sources of phosphorusare phosphaterock,Ca (F04)2,and apatite,W2”3W3(F04)2.3 Itis usuallyobtainedfrom thesesourcesbyr&ing cokeand m.ndwith the crushedrock or ore and heatjngthe mixturein an electficfurnace. Since the temperatureof the reactionIs”quitehigh,the phosphorusdistillsaway frau the reactlm~ and is tn3~ed and condensedunderwateras yellow or whitephosphorus. A. Elemen@y Fhos@mle phosphorusexistsh at leastthreeallotropicforma. The whitephos- phorus(oryellowphosphorus,if it is hpure) obtitied of phcmphoruehas a nmltingpointof 4h°C.It dissolves crya~~zes h the cubicform,and burns spontaneously in the absenceof air to a tempe=+mxe of 250° C, it is by a titillation in organicliquids, in air. When heated convertedto red phosphorus.The colorand physicalpropertiesof red phosphorus depe&ieupen the temperatureand the lengthof the heatingpetibd.” It ui.12cryetdJlze in the rhoniboh~ fozm,and it is stablein air at roomtemperatllm.Red phoephozueIs insolublein organicIlquids. A b@ck allotropicform of phoephorueIs obtainedby heatingwhlte phoaphoms at 200° C and at Is rhombohedndin form and phosphoruscanbe converted above 500°. a FJ.=ssm of about13,000aizuospheres.It is a &ad ele’i+cricalconductor.Black to red phosphorusby heatingat &rperatures B. The ChemicalConP3undsOf Phcmphorue Tho~phorusexhibitsoxidationet%tesOf -3, -2, +1, +2, +3, +4, and +5. The principleoxidationstateof phosphorus1S +5; however,+3 cm- poundeare not uncommon. Phosphoruscan form compmnds ulth hydrogen,oxygen, m.dfur,the halogens,and nitrogen. It can reactwith certainmetalEto form phosphides.TableII liEtsmany of the phosphoruscompcmndeand givesinfor- mationon theirsolublli~ in waterand otheragents. Some geneml ll&onm- tion abouttheeeand otherphoephoruecompouudeis @ven below. More specific informationhae been givenin reviewsby Vsm Wazer‘3)and Hutcldneon.(4) mm. sOlubiutvOfPllamc~ Sol*lain(sls,m~maakwrln SOlllbl.einether, ham, cblOrO— *, a32mrldccl~ ~inaadmlmndadd Ir9dmlla 3 1. Reactionswith Hydrown The hydrogencompoundsof phosphome cannotbe preparedby a direct uuionof the elements. Phospbine,PH~, ~ ~P~EPMne, “p2H4,Sre USUdW fonnedby heatingvbitephosphorusin the presenceof aqueoussodiumhydrotide or by hydrolyzingaluminumphospbidewith m.dfuricacid. PH3 ip extremely volatileand is &l.aumble In air. Phosphinela a toxiccompoundand la conBide&blylese solublein water thau 16 smmmla. It is a muchweaksr b&.aethan auimonla,foming “onlya few phoaphofi~ PH4+,saltsilth the halides. These saltSati qti’onglyhydrolyzedin solutionand exhibitstr%ngacid charactefisticE. Diphosptie is not basic and formsno saltconpunib. 2. Reactionstith Oxygen Phoaphome formsthreeoxideccqoundS with cxggen: the trioxidej P203,the tetroxlde,P20h,and the pentoxide,P205. The trioiidead the pentoxideaI@ the mst importantof the oxygencOmpounds.JRrequentl.y, the formulasare writtenas Pk06 ~d P4010becauseof the densitiesof th@r vapors. ,~e trioxldeis producedby burningwbltephosphorusin a llmlted supplyof oxygen. P406 is a cclorlesssolidwhichmeltmat 24° aud bolls at 173°. PLOIO,a colorleesliquid,8ubljnEBat tMqeraimreBabove3643Q. . Phosphorustetroxide,P O~ ~, is’formedby heat&g P406 b lzemperature# o above200 . It Is 6 solid,havinga melting“pointhigherthan 160b. he ~entoxideis fonnedby burningphosphorusin oxygen. . .. : Pbo8 reactevigorouslywithwaterto form the oxyacld,phosphorous =’ ‘3m3 “ H3FQ3CL alEobe f,oxmedvery alow~ by reacti& P406with coldwater. In hot water,the H3P03that formsrapidlydeccmqmsesto pro- duce~hospQoric‘acidand ~hoaphlne. ~4%o also.reactmvlgorpuplywith water to ,flrst.pxuce uet.a-phospho~cacid,lIPO, and then~, a “further 3 hydrolysisreaction,orthophosphoricacid,H3m4. Phospho& acid,H FU 3 3’ cau alsobe fornmdby reactingphosphome halides,i.e.,““PC1 3’ ‘r3’ and P13 &th water. H3~.3is a ~olorlees crYstdJ_lneBolldwhichmeltsat 73°. When heatedabove~’”,’it d.eCOIIP .. poeeEto eve ~hospliiheand phosphoricacid. phosphon~ acid is an active reducingagentbecq~e it canbe readilyoxidizedto phosphoricacid. Its 4 alkallsalts(suchas NaH#03) wILL losewaterwhen heatedto 1.60°to give a w- spbdtisalt,e.g.,W2~p205. Hy@phoephoroueacid,H3P02,,isprcduced as tmspnt cv’etals W the reactionof bezlumsaltsof phosphoruswith H2SOh. The crystalsmelt at 26.5°. .+(), and ita adts,the hypophospmtes,m strongreducing agentt3(P.has an wdiatlon stateof P+l b theseccmpounde) and can be +3 used to reducesuch elementsas the halogensand Fe ions,e.g.,chlotie to cwotide and ferr5c”ionsta iron. Metsphosphorousacid,HF02,can be fomed by burdng phosphlnein a limitedsupplyof oxygen. *- acid’‘4p20Z’‘a a cOIOrless solidthat Is fo-d by heating.slkalInehypcphosphites,e.g.,NsH PO ,23 at 160°. H4P2 ~O meltsat ~“ and It tilldecompxe when it is heated abovel~”. ~2 ~ H4p205are mpld~ convetia b H3~3 in the presence of water. The @ QsphorousacidscontainphosphorusIn the +3 oxidation Etate. All of theseacidsand theirsalts=e ~ducing agenta. , at variousdegreesof _tion, react6to form the sefies ‘4°10 of oxyacidsof phosphorushewn as the phosphoricacids. Orthophosphorlc % H3~4, is fomed by reactingPkO1owith an adequat=supplyof water. H3~ is a colorlesssolidthatmeltsat l@°C. It is very 6olubleIn water. It ~ ~t tith ~t of the metalsto form oi%hophosphateS81tS, claaslfledeitheras @rary, Eecondary,or norml phosphates.The prim3ry, or dihydmgen, phosphates,e.g.,NaH2P04,are solublein waterand yield S~@~ acid solutions.The secondary,or monohydrcgen,phoaphtes, e.g., Na#04, althougho- slightlysolublein interyieldalkalinesolutions. The ~, or triphosphates,e.g.,NZ3P04,are more completelySQzed h aqueoussolutionto yieldalkalinesolutions.The pm and secondary @OSPhSteS deco-e =pldly when heatedinto“metaphosphatesand =hosphates. The triphosphatesare stablet.uwazdheat. H3R34loseswateru it Is he@4d to 250° C, sad it 10 gmdually convertedto pyrophosphoricacid,HbP207. Pyrophosphorlcacidwill tryst.slJlzefromthe melt as a colorlesssolld. The solidmeltsat 55°. 0 can alsobe prwiucedby stronglyheatingNa2~4. It ‘4P2 7 yieldstwu seriesof saltsh its reactionswith otherelements; ~~, nOrmSISdta, suchas NakP207or ~P2C17, and di_8en s~tB, fluch.ssNa2E2P207. The alkalimetalsaltsof both aetiesare soluble h most reagents;however,onlythe dihydrogensaltsof othermetal ionsare readilysoluble. ~P207, mgaesiumpyrophosphate,ia an acceptedgravimetficweighingform for the quantitativedeterrdnation -3of eitherphosphateiOnS,~k , or magnesi~in many differenttypes of samplematetials.(5) The insolublecompound,M@HkP04, is first precipitatedand then convertedbyheat intothe pyrophosphatecompound. 1~ H4P207is heatedto 200°,it will losewaterto formmetaphosphoric, or The acid is very eolublein waterand it will.chaugeslowlyin coldwaterintoorthophoaphoricacid,H3POb. In hot water (lOO°C)thischan&ais very rapid. The saltsof this acidare the metaphosphatea,e.g., (M~3)30r (H~3)6. Otherccmplexes,having the formula,(Ns.F03)X,are alsoknown. The hexa metaphosphatee,suchas (Na~3)G form solublecomplexeswith many ImiLti%aU!ntC8tiOn6,e.g.,Na2~2pb0i8* 3. Reactionstith Sulfur PhOSphONS and s-r can combinedirectlywith each otherto form sdfur compounds. If whitephosphorusis used,an explosivereactionoccurs. When red phosphorusand ,mdJ%rare mixed,chemicalcombinationoccureand proceed6qpiet~,an~according to the proportloneused for each element, will form eitherPLS3,PkS5,P4S7,or P4S10. Tetraphosphorustrisulfide, P4S3JIs the nmst inprtant of the @msPhoIm6 BU~ide compounds,beiw used chieflyin the manufactureof “sttike-anwhere”Mtches. Phosphorlae yentas~ide, PhSlo,u be hydro~ed to H3POk,and this reactionwith watermJses It possibleto uae p4S10to introducethe groupSH in the place of the hydroIwlgroupintoorganiccompoundE. 4. Reactionwwlththe Halogens Trivalentphosphoruscan combinedirectlywith all of the halogens to fomn the trihalides,PF3, PC13,PBr3,and P13. Pentavalentphospho= will only formpentahalldeswith fluorine,chlofine,and brcmdne. The pentatidideis not known;however,a tetraiodide,P214,cm be fo~d by dis661vinghydrogenand iodineh carbonMatiide, Severalmixedhalides .ofthe type PF2Brare als’oknown. 6 The ttihalidecompoundereactreadilywith waterto formhydrogen halidesand hypophosphorousacid,H FU 3 3“ Sincethe trlhal.ideecontain phosphorusin the +3 oxidationstate,they are easilyoxld3.zed.FOr example,PCl reactswith air to room tempsmtureto formthe oxyhalide 3 POC13or mixedoxyhalldesof the type,F0F2cl. PC13and PBr3 can react with chlotie and brcmdne,respectively,to form the pentamalenthalides, PC15 and PBr5. The pntaballde compoundeare all napidlyattackedby waterta form hydrogenhalidesand phosphoricacid,H3F134.PF5 18 stabletowardheat but PC15 and PBr5 can ea611ydissociateIntofreehalogenand the trivalent phosphorushalidewhen heated. The phosphoruspentahal.idecompoundscan undergohydrolysisto form oxyhalidesof the type,POF3,POC1 3’ and POBr . 3 5. Reactionswith NitroUen Phosphorusand nitrogendo not combinedirectly;however,a n.itx%ie, ‘3N5’ cm be fomed by heatingPhSIO In en ammla atmosphereat a temperatureof 230°. P3N5 is a colorlessaolddwhich canbe decomposed at 800° b givenitrogenand anothernlttide,PN. Hot inter”till hYdrOIYZeboth nitfidesto form amnonia -d oxyacldeof phosphorus.h reactionsof the phosphoruspen~dee with anmonlawill producephos- phorue-mltrogenhalidesof tha type,PNC~. All of thesecompoundewill -Qze ~ produceSmm3niaand oxyacidsof phoBpho?ms. 6. Reactionswith Metals Phoephome can alEo reactdirectlywith m?talsto form~hosphides, e.g.,Ha+. Seveti metalphosphldes,suchas CeP, canbe prepared32 by reducingthe correepmdlngphosphatewith carbon. The metalpliosphides are rapidlyhydrolyzedby wateror decoxqcmedby acideto formphoaphlne and metallicions. IV. TEE MAHIWAL CHMLSEW OF PHosFmRus Phosphorus,afterits separationfromotherchemicalelemente,Is mst frequerrtlyconvertedto orthophospborlcacid,and the orthophoephateIon determinedgravlmtz%cally. Suchprecipitating~ts ae megneeiandxture,(5) (6,7)~imowl chloride,ferriccblorldeand anmmniumacetate, (8)and mly- 7 btic acid,(5’9)bariumacetate, thalliumacetiteand silvernit=te,(11) and oxlne(w) havebeen used to precipitate!F04---- The precipitationof ‘he ‘hoBp&te ‘on’ ‘2°7‘---,tith zinc stiate has alsobeen used in the gzwlmetric detennl.nationof phosphozms.(13-15) ‘me Ccmpouuds resulting from tne reactions of theseagentsulth FOk-3 are 8s follows: aIm!lonlum magnesiumphosphate,NH@P04.6~O; ironPOSX te, Fernh;zirconylhydrwwn @lOS~bte, (ZIO)HP04; anmoniumphosphomlyb date, (NH4)3(MC03)~m~ barium ‘osp~te’ ‘k; ‘i~ver‘h-w ‘tispkte’ %TH4; *W 24-mubdo-2-phOs@ate’ 6C99 ON.P205.2h1003”llH20;ad zincphosphate, m4 . Any one of the abovegravlinetrlcformscanbe w“ed in a carrier radiocnemicalprocedurefor radioactivephosphorus.However,it is not alwzysnecessaryto obtainthe phosphoruscarrierand the radioactivity in a preclpitiblefomnbefon?the tioactlvlty measurements.One of the phasesobkined In .ssolventexhactlon uthod or an allquotof an eluate froman ion-exchangeseparationcolumncouldbe used. Thus,the informationthat followsgenemlly reportson current analysisideas used in Isolathg and determiningnonradicmctlvephosphoms. The same tecbnlquescanbe easilyappliedto analyticaldeterminationsof radi- oactivepho8phonm. A,. Separationby Precipitation A completeseparationof phosphorusfrommany otherelementscsm be obtainedby precipitatingphosphorusin nitficacid soltiionas azmmnium phosphonmlybdate.(5,9) Sodiumhydroxidewill precipitateand completely aep&ate iron,nickel,cobalt,trivalentchromium,titanium,and zirconium fromphospho?.ua.The acid-sulfideelementscanbe easilyeeperatedby saturatinga mineralacid solutionwith hydrogens~ide. The volatility of arsenicand gem.aniumchloridescanbe used to separatetheseelements from phosphorus. The amzonlmnphosphoudybdatepre