The Radio Chemistry of Platinum.us AEC

8/7/2019 The Radio Chemistry of Platinum.us AEC

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1at iona lAcademy vofSc iencesNat ional Researc h Counc i lI NUCLEAR SCIENCE SERIESThe Radiochemistryof Platinum


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COMMITTEE ON NUCLEA R SCIENCEL.F.CURTIM,Chai~ ROBLEY D.EVANS,V&e CkairmaaNdlnns.1ureaud Stadnrde Mass~ Indtute.fTeehmlQTY

J.A. rkJUHEN, tkwebyWeet@bOuw Hleotrloorporatlan .C.J.RORKOWBFJ ,. J.W.~VTNI$ JR.(MkRI* Nationalabontory Mnemchee.tksnOututeTOctmOIQyROBERT Q.COCHRANT- &rirdhudd hCbliOd

co l legeHAMIJELE~~CsllbrninetbtaofTenhno4DU.FANONatbndBureauofStndudaHEHBEHT 00LDSTEDJNulearI&velopmentorpmflonofmrioa

E,D.KLHUNortbwedmmUnlverel~W.WAYNE MEfNKEUniveWl@[email protected],ewYorkROBBRT L.PLAIZMANImbOratdre9Chide PhyefqwD.M. VAN PAITERBnrtolsaamh Fmrdatton

L IA ISON MEMBERSPAUL C.AEBEHSOLD CHAHLRSK RHEDAtomiaEnergyCnmmlmnlon U.S.AfrFormJ.HOWARD MnMLLHN . WfLLL4MB.WRI13RTNntlndalI[tUtW~dnd@inn, - ofNavdReseti. .

SU BCOMMl ll EE ON RADI OCHEMI ST RYW.WAYNE MEDU03,Cktirmow EARL -EUnlvwreityfMlnhfgm Univerai&fCal&xnia(Rerkeley)NATHAN BALLCW JUM NfEL8ENNavalHndiolcglnalMfeneedmratory Hartfordboralnrle~13REOORYR.CHOPPIN G.DAVIDOKELLEYFlnrid8tatenlvarel& OakRMge NaUnnellakmaimryGEORGE A C~AN ELLIBP.STEINBEHUIa9Alsmm SOfetioI.abOratory ArEonnedlonelI.dmr-abryA.RTEKIR. F~LL PETER C.~EVE~NUnfversi@fWaehingbm UntvwreityfCellforrdaLWermore)JEROME HUDIS DUANE N.SUNDKSMANBrooldmvenatfonelatoralmry RattdleenwielIUEtftute

CONSULTANTSEEmERT M.CLARK JOHNW. WDJCHESTER.R+lmllm Pnlytmlmianstitute MaemnhudtaIuatilutefTedwl~


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CFEWISTRY

The Radioc hem ist ry of Plat inum

G. W. LE DD ICOTT EOak R idge N at ionul Labov at ov yOak R id ge, Tenn essee

October 1961

S u bc omm it t ee o n R a di oc he m is tr yNa tion al Aca dem y of Scien ces Na tion a l R esea r ch Cou n cil

PrintednUSA. Price$0.S0.AvaUnblefromtheOfficefTeehnicdServlcee,efmrtrnentfCommerce.Waddngbn 25,D.C.


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FOREWORDThe Subcommitteesubcommittees working on Radiochemistry is one of a number ofunder the Committee on Nuclear Sciencewithin the National Academy of Sciences - National ResearchCouncil. Its members represent government, industrial, anduniversity laboratories in the areas of nuclear chemistry andanalytical chemist~y+

The Subcommittee has concerned itself with those areas ofnuclear science which involve the chemist, such as the collec-tion and distribution of radiochemical procedures, the estab-lishment of specifications for radiochemically pure reagents,availability of cyclotron time for service irradiations, theplace of radiochemistry in the undergraduate college program,etc .

This series of monographs has grown out of the need forup-to-date compilations of radiochemical information and pro-cedures. The Subcommittee has endeavored to present a serieswhich will be of maximum use to the working scientist andwhich contains the latest available information. Each mono-graph collects in one volume the pertinent information required?or radiochemical work with an individual element or aclosely related elements.

An expert in the radiochemistry of the particularhas written the monograph, following a standard formatby the Subcommittee. The Atomic Energy Commission hasthe printing of the series,

gro


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INTRODUCTIONThis volume which deals with the radlochemlstry of platinumIs one of a Beries of monographs on radlochemlatry of the elements.

There Is Included a review of the nuclear ad chemical featuresof partlculsx interest to tihe radiochemist, a dlacuBalon of prob-lems of dissolution of a sample and counting techniques, andfinally, a collection of radiochemical procedures for the elementas found in the literature.

The series of monographs will cover all elements for whichradiochemical procedures sre pertinent. Plans include revisionof the monograph periodically as new techniques and proceduresWsrrsnt . The reader is therefore encouraged to call to theattention of the author sny published or unpublished material onthe radlochemistryof platinum which tight be included in a revisedversion of the monograph.


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1.

II.III.

Iv.v.VI .

VII .

CONTENTSGeneral References on the horganic and AnalyticalChemistry of Platinum. . . . . . . . . . . . . . . . . . . .Radioactive Ruclides of Platinum . . . . . . . . . . . . . .The CheiIIs@y OY Platinum and Its Application to the-OCh8Ud8t~ of the Platinum %dlonuclidea . . . . . . . .A. The Geneti J3hemletryof Platinum. . . . . . . . . . . .

1. Metilic Platinum. . . . . . . . . . . .2. compmnde of Platinum. . . . . . . . . .a. The Oxide and Rydroxlde Ccnnp.nnda..b. The Halideb!npmde... . .. .c. TfieSul.fde, Selenide, and Tellurlde-~s . . . . . . . . . . . . . .d. The Cyano Com@mds .. . . . . . . .e. Camplex Plattium Compouuds . . . . .

f. The Al@l Compounds.. . . . . . ..

. . . . . .., ...,. . . . . .. . . . . .

. . . . . .. . . . . .. . . . . .. . . . . .B. The Analytical Chemistry of Platinum . . . . . . . . . .

1. Separation By Precipitation. . . . . . . . . . . . .2. separationsBy Volatility or Electrolysis. . . . . .3. SeparationBy Solven% Extraction . . . . . . . . . .a. Ion Association Systeme. . . . . . . . . . . . .b. Chelate cmnplex systems. . . . . . . . . . . . .

k. Chromatography Separations . . . . . . , . . . . . .a. By Organic and InorganicAdeorbents. . . , . . .b. WithkmE xchangeResha, . . . ... . . . . . .By Paper Clummatography, . . . . . . . . . . . .:: By Electro-ChromatograpbicMethcds . . . . . . .

mssolution of Sanples ContainingPlatinum . . . . . . . . .Sefety Practice6 . . . . . . . . . . . . . . . . . . . . . .Counting Techniques for the Radioactive Platinum Isotopes. .Radiochmical Procedure for the Platinum Radionuclldes. . .References . . . . . . . . . . . . . . . . . . . . . . . .

11

23

89910io101212121314141416i617ly181927


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The Radioc hem ist ry of Plat inumG . W. L EDDICOTTE*

Oak R idge N at ional Laborat oryOak R idge, T ennessee

I. GENERAL REFERENCES ON THE ~RGANIC AND ANALYTICAL CKEMIEZFRYOF PLATINUMSldgwlck, N. V., The Chemical Elements and Their Colqoinde,pp. 1454-1.628, Oxford University ~ss, London, 1950.Kleinberg, J., Argersinger,W. J., Jr., and Griswold, E,, InorganicChemistq , pp. 581-*, Heath, Burton (lg60).m , H., Treatise on Inorgamic chemistry,vOiu 1, pp. 342-351,Eli3evier, Ameterdam (1956).Beamiah, l?.E., A CriticalReview Qf Methods For Isolating and Separa-ting The Six PlatinumMetals, Talanta j, p. 1-35(1960).Scott, w. w., standard Methcae of chemical AnalyeiE, VO- i,PP. 712-728, Van No8tr=d, New York, 1939.Hillebrand, W. F., Lundell, G. E. F., Bfight, H. A., ead Hoffman, J. I.,Applied Mr&l c Analyeis, John Wiley, New York, 1953.Rcuiden,C. J., And@ Ical Chemdstryof the Manhattan Project, pp. 3-159,483 and 491-493,McGraw-Hill,New York (1950).

II. TEE RADIOACTIVE NUCLDES OF PLATINUMThe tionuclidee of platinum that & of interest ii the radiochemlstry

of platinum are given.in.TableI. Thie table hae been completed fram informa-tion appem in reports by Strominger,et al(1) and by Hughes and Harveyj)

i. .

,..*Operat& for U. S. Atmic he.r~ Commi8Bionby U&on Caxblde Corpmation 4,,, .,

1.,


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Radlo-lTucldde+91

~19%

+m

#7

+%

Pt

Hal f -

Table ITEE RADIOACTIVE NUCIJDES OF PIAm

Mcde ofIire % Energy of Radiation3.0 d

4.3 d

3.8 d

Mm

18 h

31 m

82d

lx Y 0.083, o.0%, 0.173,0.6, 1.5

IT)Ec 7 0.1357 0.2, 1.5IT y O.0~, 0.097, 0 . L26,0.255IT 70.337

P- p - 0.677 0.077, 0.191B- p- 1.87 0.074, 0.197, othersP- p - 0.57 0.6

III. THE CHE!MISl!RYF PIA!KUWR4AND ITS APPLZCA!CIONOF TEE PM- RADIONOCLIDES

Produced ByIr-d+.%, Pt-n-2n

Ir-d-2n, Pbn-7,Pt-d-2n, P&d-p, Pt-y-nPt-n-y, Pt-d-p, Pt-y-n

Pt-d-p, Pt-n+.n, P&y-nHg-n-u, Au-n-pPt-n-y, Pt-d-p, Pt-7-nPt-n-2n, Hg-n-aPt-n-y, Pt-d-p, Hg-n-a

P&n-y

TO THE RADIOCHEMISIIRY

Radiochemletryip probably beat demcrlbed as being an anlyeie tecl?miqueusedp~ly either (1) IXJassist in obtaining a pure radionuclldeof some specificelement in a suitable form so that an abeolu%emeaaureqent of its radioactivity,raiclationenergies, and half-life canbe made, or (2) to determine the anmunt ofradioactivityof a particulm rsdloelementin a rsdlonuclddemixture, or (3) toCom let e a dmctivatkm amlysile being used to determine the stable elementconcentrationin a ~icular samplehaterial. In order b be an aid Inaccomplishing anyone of the above interests,radlocha!lstryusually consld&sthe isolation of the desired radlonuclideby either cmier or carrier-freeseparationmethmds.

Generally, carfiermethodb are used most frequently in radiochemistry.They Involve the addition of a stil amount of inactive stible element to asolution of the irradiatedmsterlal to seine as a carrier of the radlonuclideof that element through the se~tion method. Carrier-freese~tious

connote that no cmler is added. These radlochamical techniques are usedmcmtlyto obtain radlonuelldes for absolute radioactivitymeasurements, S@ It16 required that the desH mdloelement be isolated In 8 mqmner able to

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give either no amount or albinimalamount of etab~e element (either isotapic ornon-iBotoplcwith it) in tie final form to be ueed In the radioactivityueamre-mente.

In moat inatinces, radlocheg.latryis dependent upon more conventionalideasIn analytical chemistry Involving separationsby such metho& as precipitation,solvent extraction,chromatography,volatilization,and/or electrolysisand thesubsequentpreEentatlon of the isolatedradioelementin a form suitable for ameamrement of ite radioactivity. When carrier techniques are employed, onemajor d~ference exists between radlochemistxyand more conventionalanalysistechniques in that It is never alwaya neceBmry to recover completelythe addedmnount of carrier element. Each radioch&micalanaly8is ie designed to aeeurethat the atoms of a radioactive element achieve an Isotopic etate tith theatoms of the inactive elemmt and any low of the radlceetiveepecieeie propor-tional to the loge of carrier,,dm~ the separationproceee.

Colorlmetric, polarographic and volumetric analyais technlq~s areseldom ueed In radlochemlBtrybecause they do not separate the deelredradio-nuclide from cont9minante(either radioactiveor etable) inthe mlxbirebeinganalyzed. However, emne of the developmateueed in tbeee anal~is techniquemaY be useful for conalderation in radiocheucletry.

The following iuformatlon Ie intended to give come general Idea of thebehaviour of platinum and its compunde and their potential usefulness indeviBing radlochemicalanalysis metbode for the radionuclides of plattium.More detailed information can be obtained either from the reference given inthie eect.ionor from the general reference given in Section I of this monograph.

A. The General Chemietry of PlatinumPlatlnwn ie meet often found In alluvial depositeae native m?til and can.be found In these deposits in combinationwltb the other platinum group metile

and gold, eilver, copper, nickel, bon and lead. Platinum can aleo occur aeatineral In ultrabasicrocks, e.g. cooperlte, PtS, and s Pt.AB2. Thechief preeent-day,eourceOf platinwn Is the hudbury (Caneda) ore, a niakellferrous.pyrrhotite ore. Metallic ,platinmn(ss well asis recovered from tbe reeiduee obt ained I I I t heWds nickel-beari~ ore.

other r@als of tie platinum group)refinement processesusedto heat

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1. Metillic PlatinumPlatinum metal is obtained as a gray-white,lustroMS, metal. It fi a soft,,,, ,

ductile metal that has a density of 21.4p. It has a melting point of 1774.Metilllc platlnun can absorb botb oxygen and hydrogen. In a finely divided

state, it can absorb up ta lCO timsa lt~ own volume of each of these elements.Platinum can also abnorb anwll amounts of helimn.

Platlnum (lfie the other noble metals) will not be attacked by strongacids. Aqua regla must be used to diseolve It; hexachloroplatlnlcacid,H2(ptC16), is fonued by this reaction. Metallic platinum can tiact with,hot,. ,alkali peroxides to became brittle and to decompose. It will unite vithchlorine gas at ~mp-eraturesabove 250 C to form platlnum dichloride,PtC12;at a ddlred heat, it wI1l conibinewith fluorine to produce platlnum tetra-fluorlde~ PtF4, and platinum difluoride,PtF2. Sulfur, selenium, and tellurium

can readily attick platinum if proper condltioneexist. It will form fUBiblealloys with phosphoms and can be alloyed with -senic, antimony,bismuth, lead,silver, and tin. Cobalt, copper, gold, iron, and nickel all form mixed crystalswith phtinum. Although it Is at the end of the electrochemicalseries, platl-,.,num will also form ~ complex Ions.

2. The Compoundsof Platininn PlatfriumlIkepalladium] forms both dlvalent (+2) and tetriwalerit(~)

c~. The met c&n or e~le dipbeltlve compoundbexe the oxides, sulfides, and the halides. Telirapositivec&@ounds of platinum include blr&ycompmnds of ox$des, sulfides, eelenldes,and telhrldes. In addition,platinumfomns tetrahalidesand, unlike palladium, forms mny Other c6mplex cationic @n-pounds. Plattium lathe ody one of the platinummetals (ruthenium,osmium,rhodium, iridium,.plladlum, platinum) to form ~ compounds. Table II listssome of the platlnum compounds and gives information about their eoluillities.

a. The Oxldeand HydroXlde of Platinum. Although platinum can.ccablne directly with oxygen.at a m@emte tempera@re to fom an oxide, theseColrpunds are Umlally iqrpure.are formed by indirectmeans.num, doesnot exist in a pure

Moat frequentlypure o@des and their hydmtesPlatinummmoxide, PtO, the lowest oxideofplatl-state but in combtiationultimetallic platinum or

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platinum dlotide,Pt02. Ita COZTeBpOU&hg hydroxide, Pt(OH)2, a b- ~~r,is obtained by heating potae K#tC14, w i t h alkali hydro-xides. pt(OH)2 will oxidize readily and when stronglyheated it till decompoeeto give platlnwz=til and Pt02.

Tetravalentphtinm oxide, Pto2, IS the mst Stible ofidJ=cmpound ofplatinum. It is usually obtained as a reddish-brownhydrate precipitate byboili~PtCl~ with alkalis. Pt02 is soluble in acids; however, wkn heatedfor .8long time at a tkperature of 203 C, it becometiinsoluble. Continuedheating abo,ve200 C transforms It either ta platinum uonoxide or to mel@llcplatinm and oxygen. Pt02, when freshly precipitated, Is alao Bolubleincon-centrated elkali solutions.

~ Pt$3, can be obtiined only in We ~ Et=te W3dis produced by the action of NaOHon dlsulfatoplatinum(III) acid, Hfi(S04)~ .(3)Pt203 is oxidized by warming with o~gen and will give up water in this procem.

A hexavelent oxiygen compound of platinum, I.e., ple t inun (VI) ox ide, p to3JaPPe=Btohave beeu characterized.(31 ob~inedbythe anodlc oxidatiOUOfPt02 in pota8h at temperature below 0 C, i,tis a very u~cable compound. It willElowly decompoeeat ordinary temperatureaandwill lose oxygen,when suependedin water. If it la gently heated, it will lose o~gen rapidly. Dilute hydro-chloric acid treatment of Ptl)3will produce free chlorine.

b. The Halide CmnpoundE of Platinum. Platinum dichloride,P11212Jaudplatlmnn dib=de, P_W2,* uost frequently obt=iwd by tie tie-l dec~Wsi-tion of the tetrahalide compounds. PtC12 can also be obtained from the ~ermald~compoeitionof cbloroplatinicacid> H2@l~. The ~de compountime OUIYSK=iWW soluble in ~ter. PtCl~, a greenish-greyor brownish powder, will dia-eolve in wtrong HC1 to form the cmnplex acid, tet~chlo roput~ (II) Mid,H2@lJ . This acid forms tetrachloroplatinitesalts, e.g. K2[FWl~ , whentreated with reagents containingthe corr~spondingalkali.

Of the tetrapositivehali& compounds, only platinum tetrafluorida,~k,ayellowlEh-redsolid, iE made by a tiect cmzbinationOf the elem&ta. Extreme(red) heat muetbe ueedto effect this combination. Platlnum tetracbloride,PtJ214,a reddish-brown,hydroscopicmass, is producedby thermally tiCOIUPOEiW(at 3000C) chloropiatinicacid ina chlorine a+mmsphere. Platinum tetrabromide,

)5


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Table IISOLUB~ITY OF PLATINUMCOMRXNDS

Water Solubili.tycold Hot . Other Solvent8

Insoluble

Formula

ptAe2 :PtBr2

CompoundArsenideBromides

InsolubleVery slightly Iusolublesoluble

Soluble in H& snd KM

Very soluble in alcohol, ether,andHHr.

Bligntly slightlysoluble soluble

Chlorides P-W12 Very slightly Iheolublesoluble

SolublelnHCl and~OH. Slightlysoluble:lnNH3. Insoluble in alcoholand ether. :Very slightlysolublein cone. HC1.Soluble in hot HC1.slightly Solubleeoluble

P-w13Very soluble Very soluble Soluble in acetone. Slightlysolublein alcohol andNH3. Insoluble in ether.Very soluble Very soluble 6oluble In alcohol a nd ether.

acids,moluble Insoluble

Insoluble Insoluble

Cyanide

Fluorides

Pt(cN)2 SQluble in KCN. Insoluble inalkalls, S.ndalcohol.

Soluble; Very soluble&composes

Soluble in acids and alJssJ3s.

Soluble inHCl, ESr, alkdd&inH#304 and diluteHN03.Pt(OH)2ydroxides Insoluble Insoluble Insoluble

Pt(OH)2,2H@ Insoluble Insoluble Soluble in COUC, a cid s

Iodidee Insoluble Insoluble Soluble in HI. Slightlyaolublein N@03. Insolublein acids.Ft12


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Soluble in alcohol,alkal~ acetone,HI, IU, and NH3.Soluble in HC1. HcSO.. Insoluble

Pt14 Soluble;&composesIneolubleoxides PM Ineoluble in ac ids ma iqu-l+a.

Soluble in COUC. HCl, ~04HN03.Ineoluble in acide and aqpa

Ineolubleto.2H.20 Ineoluble and

r em .u801uble InsolubleIneoltile

*94Pt205.Xq3 Soluble in COUC. H#04 and cauaticaMia .

Ineoluble in =Ide and aqua ragia.

Insoluble

IneolubleInsoluble

InsolubleIusoluble Slightly soluble inNaOE. Ineol-uble in acetic acid, aqua regla,and EC1.

Soluble inHCl, aqua regia, andKOH.Insoluble in HCl and aqua regia.

~2=2?PU12.~oPm2 .4H#l

InsolubleInsolubleIneoluble

InsolubleInBolubleInsoluble

-J

Soluble Inalkalia.Soluble insoluble in

acida and dilute caudic

Ineolt ib leneolm.e HCl andHfl . SlightlyHN03 and d4.

Phosphid.a M207 Very slightlysolubleSolubleIneoluble

acid, alcohol,and ether.su l fa tesulfides

pt(so4)2-4H@Pta

Soluble ineccnnpOBeEIneoluble Soluble in (NHL),-$3.IneolubleinaCideand ~~s.

Slowly soluble in aqua regla.Iwoluble in acids.Soluble inHCl and HN03.IqeolubleIn (NH4)#.

Pt,-#3 InsolublenBohble

Pts2 Ineuluble InBoluble


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PtBr4, is formed by dlasolvingplatlnwn metil in a hydrobromic acid-brominemix.ture, then reIiiOViUg the .901VWIt .SUd dK@US the reBidUe. The d31tiOU Of a hotaqueous Bolution of KI to a concentrated~~~16] acid Bolutionwill producephtinun iodide, Pt14.

Platinum tetrafluoride,PtT4, decomposes very vigorously in water; platinum...tetrachloride,PtC1-6,is very soluble in water and depending upon the temperature

can be recovered from the resulting solution in hydrate fOrIUB~tb varied ~nt~of -t-er of crystallization. It 1s present in the aqueouB solutionas the complexacid, dihydr-tetrachloroplatinum (IV) acid, ~[P~14(0H2] , which can be isolatedby heating the hydrated compounds to 10QO C. PbBr4 and Pt14 are not very soluble.in water. PtC14, PtBr4, and Pt14 will decomp&e when heated ta form the freehalogen and the corresponding-lide.

A hexavalent@_atinum fluoride, p~6, haE been isolatedby reacting aplatinum filament wltb fluorine at 300 mm preBsure.(4) .mi~cwmdiBfomdas a red-black msterial and appeare to be the mostof the known hexafluoridea.

One of the mdst Importint platinum compounds,

unBtible and rcmt reactive

chloroplatinicacid,H2~16], is formed by treatingplatinum Bponge with hydrochloricacid containingchlorine. It can be cryB~liZed from It# solutions as brownish-reddelequia-cent prime. It is soluble in water, alcohol, and ether. It forms hexacliloro-platinate salts,~[~lg], when alkalisaltsare added to its BOlutiOne.&mmnium chloroplatinate,(liH4)2[PtC16]is the best known of these. It la notvery soluble in water or alcohol, and it will decompose completelywhen heatedand leave a residue of platinum sponge. The potassium salt, K2[PtC16] is alsoinsolublein water and alcohol; however, Bodium Chloroplatinateis very solubleIn both water and alcohol. Insoluble silver chloroplatlnate,Ag2@~] can beprecipltited If silver nitiate Bolutlon la added to a solution of a chloro-platinate.

c. Sulfide, Selenide, and !l?ellurideompounds of Platinum. Platinummonoatiidej PtS, can be formed either by heating a mixture of finelydlvidedplatinum and powdered sulfur or by saturatinga chloroplatinate(II) salt ortetiaChbrOplatin~ (II) acid with hydrOgeIIsulfide. The grayish-blackneeue-like precipitate produced will not react with either ac ids or alkalis and is

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inBoluble iU aqua regi~. Platinum dlsulfide,Pt92, is produced by 8aturatlngboiling solution of a cbloroplatlnate(IV) ualt or hexachloroplatinicacid,H2&l~, with hydrogen sulfide. The black precip~t.ateIB very in801uble Inaclde amOhhg s low ly in concentratednitiic acid and in aqua regia. It 18alBo insoluble in a lk a l i solutions and can ohly be put into solution & it ismlxedwlth other soluble sulfides. It wI1l dlesolve in polyeulflde solutionz

a

and can be much more rapidly Bolublltied if amenic, tin, antimony, or gold sul-fideO me preoent.

Double comFounde, or thiosalta, of the platinum suJfides have been obtiinedbyheatlng finely divided platinum metal vitb alkali cabonate and ulfur. (5 )The general compositionsof this thioaalts are M4Pt$6 and M1Pt4S6, and they canform dlplatinum triaulfide,Pt.#5, when oxldlzed in air.

Selenium and tellurium form binary compminds with platinwn. The compounds,platinum selenide,PtSe2, and platimnn tellurid.e,Pbl?e2,are very resiBtant toacids.

d.. Cyano Compounds of Ptitinum. Tetracyanoplatinum(II) acid, H2~(CE)~,can be formed by eaturatlng ita silver or copper salts with hydrogen Bulfide.It is a strong, dlbasic acid, and Its aMali and alk a l ine e=t h sa l t s are verysoluble in water. The beat known of these compounds are ptasallml tetmcyanO~latlnate, ~~t(CIT)~ ~@ and barimn tetracyanoplatinate(II), Ba[Pt(CN)4]-hH#3,

e. Cam@ex Platinum Compounds. Many coordinationcompounds of platinumare knovn. It can form acido canpoundE in both the +2 cmd ~ utatea and tillunite with a?mrmnlaand nltTOgSnb.SQeBto form platimnn anmlnee. The hexachl.oro-platlnate~ (IV), ~~Cl~ are the beat Imownof the= cmrpcmnds. Whenthese salts exe heated with alkali solutions,hexahydroxoplatinates (IV),~ ~(OH)~ , are fornsd. If acid IE added to aolutiona of these salts; a wblteprecipitate of hexahydroxoplatinicacid, ~ ~(OH)~ , wllJ_be prduced.

The tetrachlomplatinates,(II) are the cblef .%cidocompounds of divalentplatinum and they have ae their antecedentthe correspondingacid, ~ PtC14 .Tetracbloroplattium(II) acid, ~~Cl~ cannotbe isolated, but exists ofiyasa dark red solution and as its salte. The cyanopl.atinatesentioned earlier arealso acldo compounds of dlvaleritplatinum.-

The pldlhun .amulnesexi81iIn very large nunibers. No atteqpt will be tie

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t% characterizewhere(778). In

these compounds,since more specific infomatlon is given else-ad~tion to the -neaj many C-I= plat~nmn ccmwundacontaining

organic sulfldea, R2S, tertiary phofipkdnea,R P and tertiaxy arsines,R Aa etc.3 3are tiown.(8) Each of the~e compoundsclosely reseniblethe am@nes.

f. The AlIcy Comp unds of Platinum. Platinum ie the only one of theplatinum mtal group that uI1l form alkyl compounds.(9) The triaklyl plati-num halide, trimethylplatlnumicdide, (CS ) PtI, Is characteristicof this33~up of Cozqmnds. It can be produced by the action of @ignard reagenton PtClh. Its crystals are ormge in color;they till not dissolve in waterbut can be put inta solutionwith organic solvents. Tetremethyl platinum,(CH3)4Pt, 18 formed by the action of sodium methyl on (CH3)3PbI. It i.etable In air and is soluble only in organic solvents.

B. The Analytical ChemiOtry of PlatinumPlatinum, after its Isolation and separationfrom other elements, is

usually determined gravimetricallyas the metal.(10,11) Reducing agents suchas fonnlc acid or sodium formate, or its dleplacementwith powdered zinc,aluminum, or mgneeium metal, are most frequentlyu~ed to precipitate platinumas the metal.

The reviews by Gilchrist(u) and Beards remrt on many of the methodsused to ieolate and eeparateplatinum and the other platinum group metals fromother elemente and from each other. Some of these methods have been or can beconelderedby radioch~ete in their work with the platinum rsdionuclidesandthe informationpreeentedbelow is intended to provide ideas for poseible ;ein other radlochemicalreparationmethods for the platinum radloleotopes.

1. S&paretion By PrecipitationThe platinum metals can be se-ted from rest of the other chemical

elementsby a precipititlonwith hydrogen sulfide In an acid solution.(14,15)Silver, copper, cadmium, mercury, indlum, germanium, tin, lead, arsenic, anti-mony, bismuth, molybdenum, selenium, tellurium,and rhenium can titerfe= inthis separation. All of the platinum metal stiidee are readily solublein aqua regia and the compmnde that result can contain cloeely bound sulfategroups which may affect any subsequent reactionsoftheee compcwm.dewith

10


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other reagents. l!ahlni and Salerla(16) have u.md the aolubllltyof the metalsulfides in alkaline solutions to Eeparateplatinum,aswell u the otherplatifuunmetals,from many of the other chemicalelements. Richmond, et al(17)Ixwe.aleoused hydrogen EuUide ee~tiona in their work on binsxy alloys of

platinum and uranium.As early a+ lgOO, Leldie(18) showed that a digestion of the chloro com-

pounds of the platinummetala tith sodium nitrite would convert these compoundsinto soluble s~ble nitrite complexes so that base mstals couldbe readily.eeparatedfrom the platlnum metal by precipitatingthem from the solution asoxides or aa hydrated oxideg. Such a method haa been used to sepaxate goldand ba~e metals from rhodium, iridium, ruthenium,platinum, aud palladlum. Forexample, after a conversionof the nitfite solutions,platinum (and iridium)were isolated with emczordumchlorlde.(19) Gilchrietand Wlchers(20) have alsouwsd thi8 approach ta isolate the phtlnum metals. In each of these applica-tions, It was shown that it w- necessary to reconvert the nitritecomcpoundato the chloro compaundebefore they could be further processed.(18)

Blackmore, et al(21) and GiMrrlst@) have preciyi.tatedplatinum 8ssmmonium chloroplatinate. 0,+4This separates it from inanyother elements. ,~+4 +4,andIr also precipitate. The amnonium chloroplatinatecan be calcinedto produce platinum mtal. Sodium fomnate(1023)3) and zinc metal(01121)have also been used to preclpltite platinum metal. Hagen(24) has shown thatsmall amounts of platinum metal could be reduced and collectedby coprecipitationu- ~cro =Unts of te~uri~ metal from a hot acid solution reduced with a20$ stdnous chloridesolution. Westland and Beemiah(25).tive~~ a stiwmethcd to Isolate platinum and palladium.

Gold can be separated from the platinum metals by precipitationmethodsusing such reagentsM ferrous sulfate(25), sulfur dioxide(lo), oxalic acid(lO),hydroc@none(26) 27); and sodium nitrite.(23) Thetetraethylammoniumchloridechoice of reagent depends upon the aeparatlonprocedure to be followed In

(lo)analyzing the flolutionfor platinum.Be@sh(13) reports that In practically all of the acceptableanalytical

schemefifor separatingthe platinum Mti16, osmium Is removed first by a dis-tillation as OsOk froma nitric acid solution. Ruthenium is then removed 8s

11


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RuOh from a dilute H2SOh solution containingbromate. PaM_a&~, rhcdium, andiridium axe separated,either singly or collectively,from phtlnumby controlledhydrolysis,oftheir chloro complexes In the presence of bromate. The precipi-tate(s) are readily filterableand contain ve~ little platinum.

Sometimes platinum and palladlum are isolated together. A number of pre-cipitationmethods exist.to.se~rate them. Besides the hydrolysis of the cblonoconvex,latti~. can be separated from palladium by a precipitation8s

(21>=) the hmachlofide,ammontum chloroplatinate, (28) and a reduction withacetyleue~g) Hydrolytic separationsinvolving zlnc oxide,(w) Mme wat-er}y)W BOd.f~ hydrogen.carbonate32-34) have been used also to effect a separationof.platinum and palladlum. The .precipftation.f palledium quantltativel.yfroma chloride aolutlon by the addltlon of a soluble icdlde also has been used toseparate palladium and platinum.(35) Mercuric cyanide solutions(36) and ethy-lene an alao be used to precipitate palladium salts and separatethemfrom platinum.

,,2. Separation By volat.ili~ or ElectrolySis

Although platinum is consideredto be one of the nonvolatile me@oereof the platinum group (the others sxe Pd, Ir, and Rh) volatile platinoue

..chloride, PtCIO, can be forme~ and lost if enmmnium chloroplatinateis.cigulted In a reduci~ atmosphere(lo);however, no separationalmethods forplatinumby such a volatilizationtechnique have been recorded. IJkewise,Beamlsh(13) eporte that there are no recorded electro~ic separationmethcda for platinum.

3. SeparationBy Alvent E2rtnctionMorrimn and Freiser(M) present Informationon the applicationsof

solvent extrqctlonIn the.analyticalchemistry of platinum. Some of thesemethods can be used b the radlochemistryof the plattium radfonuclides.

a. Ion Aeeociation Syeteme. (Meinke,39) repmt.ing on the preparationof radioactivetracer~desczlbes a radlochemicalprocedure in which greater

than 95~Pt@could be ext~cted frcsna 3 M HC1 - ll@ SUC12 solution intiethyl ether. Radioactive platinum haa also been isolated from a radloactim,

(b)osmiom target by extractinga 3 ~ HC1 solutionwith ethyl ether. An., .:

12


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(41)ethyl ether exti~ction frcm a 6.9 M HI solution has been ueed to qumlti-+2tatively extract AU+3, Sb+3, Hg@, Cd+2) and Sn frcm itide solutions con-

~~ (aewelle.e M,Ir, 0a, and Ru). The platknnn metals do not ex-tract umder theBe Conditions. Methyl Isopropyl.ketone till partially extractplatinum (and Ru

McBrytieand(Pal,Rh, Ir, andisoproI@ ether.

and Rh) from iodide - 5$ HC1 solutione.(42)~oe(43) +3 ~m~.have ,isolated.andcompletely separatedAuRu) by extracting the gold from a 2.5-3.0 ~ EBr solution into*1 acetatewillextractaii separate platinum from oBmlum

and ruthenium conktied in HC1-1?HkCl-SnC12olutione.(44) Rh,r, Au,.Te, and small amounts of Pd alao etiract in this system. ~e will Odypartially extract from a 1 ~ HCl solution intitri-n-octylphosphineoxide.(45)#6 +4+1, EAu +3 +6, Fe , Mo , 1%~, u+6&d Z# quantitativelyextiact inthis system. ,..

Cnelate Ccuuplexsystems. Q &, k,t (as well as Bi, Cd, Cu, Pd, Sn ,lh,C~~ ~, Feti, Hi, +, La, Ce+4, Inj Sc, and Eu) fo%a a water insoluble com-

(46) ,.Plex with 1-(2-~idylazti)-2-naphthol. These cou@~eH are soluble in an@Sandell(47) +2alcohol. repcn-b that Pt dithizon#ce forma a collodial solution

when a chloroformextraction of a weakly acid solution is made. The dlthizo-~tes of ~+4 a n d the other platinmmetals in the quadrivalentortrl-entstates do not reactugderthese condition.

+4Thiosemdcarbizideforma a colored compwnd with Pt in a weakly basic(48) tiesolutionthat c& be extracted into either ethyl or ZUW1 acetate.

+4phenyltblowrea complex of Pt is partially extracted (~~) from & dilute HC1solutionwith either ethyl or amyl acetate.(49) Under these condition, the+2Pd +2COU@eXextmctsquantitativelyand the Cu cmplex eirtractato about

16~. Less then l? of the Ir~, Rh+3, RU+3, 0s+4 +3 ~e+3, &+2, NI+2, and,Au,+6 ..Cr cmqplexestill extract in these 13yBteIU8.CoburnJetal.\X) followlng a cation ion exchange r&in method of separa-

ting platinum (and pall~um) from copper, iron and IIIckel,converted the Ptand Pd chlorides to diethyldithlocarb-tes and efirac~ them with chloroform.%lladiwm wae then extracted with p-nitroso-dimethyl=nine and determinedbydlmetl@glyoxime; platiniunwas determinedby thiophenol.

,., ,.

: 13


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21/36

the tetravalent state and after adsorption sepu-ated frm F% by elutionwith 1 ~ NaOH;PL remafiedon the columnandwas remved fromthe COIWJMwith a HNO elution.3

The anion-exchangeresin, Ibwex-2, b been used h edsorb and separatethe cbloro complexes or Pd, Pt, Rh, and Ir,(m) Elutlone with snmonlummide-~fiw chloridewere used to effect the separations. AmberliteIRA-w resin has been used in studies concernedwith the anion exchangese~mtims of Rfm~, Pd, tiIr. (6) ~stfi~~~~~*~eff~~~~tsfo~t&cblofides of these ratals were obtdmed; however, the recovery of platinumwas ticomplete since Pt+4 w reduced to Pt+2 during the reduction of Itidiumby hydroxylamine. @ part of this investigation,the authors(61) showed thatthe separation of Pt from Fb, I r , and Pd was best obtatied by a hydrolyticprecipitation of Hh, Ir, and Pd. Following this precipitation,these threemetals were seprated from each other by dissolvingthe oxides in HC1 andthen adsorbing the solution upon the Amberlite IRA-400 resin column and elutingtith HC1.

Stevenson, et al(e) have used the cation resti, Dewex-50, to se~te Ptfromm, Rh, ma Ir. Chloride solutions of the metals were convertedto theperchlorate form and passed through the Ibwex-~ column. Pallediwn, rhodium,and iridiumwereedsotied on the column, wblle platlnumpaesed through. Pd, Rh,and Ir were subsequentlysepmated,frcaneach other by elutione tith~ous

(60,63)~MacHevti and McKaYpolarities of HC1. MacIUevind Cmmmett (64)reporhon the use of the cation re~in, Amberlite IR-1OO, and elutionswithamncmlacal solutions to separatePt from Rh, Ir, and Pd.

Milligram amounts of Pt (and Pd, II?,andRh) se the chloride complexeshave been se-ted from copper, nickel, iron, and lesd by use of ths cation re-sin, Espatite-K-V-1,in either the H+ or # form.(65) The acid form of 8$cross-linkedWwex-50 resin has been used to separate iron, co~r, and nickelframplatinum and pall.dium.(50) HYdrOc~oric acid solutions (at pli1.5) ofthe metallic mixtures were passed through the column. Copper, iron, adnickel were retained on the column while Pt and Pd passed on through. Pt wasthen separated from Pd by convert@ the chloride solution to diethyl~tbio-carbanmtes end extracting with chloroform.

15


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c . ~ Paper Chromatopphy. Pt*hae been separated from other cations(66)by use of paper chromatography@ solvent ayatema such ae butanol-HCl ,

a.lcoh61-HCl(671), binary alcohol n&rkrea containingHC1(69), ketone-HCl(70),and butanol-FMr}71) Platinum (andPd@) have been separated completelyfrcsn

mdxburea containing copper and silver using paper chromatogmphy and HCl-aatu-rated butanol.(7273) If gold is present in thendxcure,It will ertractwiththe butanol phaae which travels ahead of the aqueous front. Keniberand Wells(74)deacrlbe ae~atione of plattium, rhodium, p.alledlum,and itidium In mlcro~amounta by use of paper-atrlp chromatographyand various aolventa. Ualng hexone-pentauol-HClrdxhrea, aepamtlona of rhoti,um,palladium, and platinum, and ofiridium, palladl~, and platinum, In that order} were achieved. When Ir-Pt-Pd-Fh were mixed and separated, the iridl~was reduced by the solvent mixture andit separated tith rhodium. Other teats In the same study showed that aeaociatedbase metals, copper, iron, nickel, etc., could be separated from the platlnummetals by use of n-butanol saturated tith 3 ~ HC1.

Burstall, et al(75) have ahcnm that methyl propyl ketone or methyl et~lketone-HCl mixtures will seprate gold, osmium, platinum, Pall~~, r~i~jirldlum, and ruthemlum in that order from a cNorlde system on a.cellulosecolumn. Stannoue chloridewas found to be a aultable reagent for separatingPt, Pd, Au, an&Hh. +4Acetone-HCl waa used to extract Ir . Lederer(73)haaalao noteda similar behavior tith gold, iridium, platinum, pallaiilum,rhodium,and ruthenium. Heea-liwina,et al(76) have used 15-30 cm cellulose columns pre-treated with such solvents as hexone-3~HCl to separatemilligram enmunta of Pt,Pd, Rh, ad Ir from each o~er and frcm iron, copper, zinc, nickel, aridmer~.Pt and Ir were separated together from the mixture and then from each other byuse of reducing conditionsIn order tb decrease the mobillty of the iridium onthe column.

d. llyElectro-C!bmmatograpC Methds. Platinum, palJadium, and gold havebeen separated from milligmm amounts of copperby aepamatiu the copper byappl@ng a current of 200 mllli~res acroaa a paper strip -raed in hydro-chloric acid and pctaaaIum cblorlde.(77) A potential of 12 Volta waa maintainedbetween the carbon electrc=fies.Ethyl ether-HCl rdxtwres were used as eolventa to

16


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further Beparatethe Pt, Pd, and Au; gold separated first with the ethyl etherfront.

Majum3ar and ChsJsrabartty(78)report on electro-chromatogr.aphyechniquesusing a ptential of 150 volts and different electrolytesto Oeparate theplatinum metals. MacNe\ti and Durrton(79)used det3cendingchromato~phy andhorizontal electm-chromtography to ~how that milligram smounta of ndxtures of2 or 3 of the platlnum metals (Pt, Pd, Ir, end Fib)could be separated. Lederer(O)showed that rhcdium could be separated chromatographicallyfrom Ptk ad Pd+2by paper electrophoresis. Cetini(81) used a similar tecbmique to separate~+2 +S,wo,ndco.Au +24Iv. DISSOIJICIOIiF SAMPLES CO=NG PLATCENUM

All of the platinum metals except palladium resist attack by singlemineral acidB.(13) SelectLve dissolutionmethods to Eeparatebase mtalsfrom matefialscontainingthe platinum metis have involved collectiveprec i -pitations by zinc or iron and subsequentattick with HIJO=and HC1,(82) concen-trated H2SOLandBdfur,(83) aqusregia}84>85) sulkl.e 13ions}86~87)leachingim) and malgsmakloll.(89)Manyprbcedm=s Involvingfire asa~methods of isolating the platinum metals from ores are.known.(13) &iCal ofnewer retbodB of fire aeBay is that propcmed by Phmmer, et al.(90,91) =general ., i t c oneistB of preparing abase meta l alloy buttonby reducttonwlthmechanicallymixed carbon, sodium carbonate,borax, and ore; base metal oxidesare added, if required. The reduction was carried out at a temperatureof1450 and, after its preparation, the button was dissolved in HC1 and HNC

3The platinummetalswere thenexhacted fromthe Bolutionby methodssimilarto thoEe described elee%here in tbls mmograph. .

Any one of these dissolutiontechniques canbe adapted for use In thertiochemlstry of the platinum radionuclidea. The addition of platinum carderto the ~ure before dissolutionbegins till assist in achlevlng an exchangeof the radioactive and inactive platinum atoms.

v. SAFETY PRM?TICESAdequate safety precautions shouldbe followedin dissolving anj eample

material whether It is radioactive or nonradimctive. The manual by Pieters and

17


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creyghtorws one of 6everal that report on the toxicolo~ of most Inactiveelemental coqpmnde. Such a manual =thls should be consultedbefore anymalyais Is undertaken.

Safe practices in handltig radi-ctive sample nderials are always importantin radiochemistry. The discharge of mdioactltity by explosion or wolutionInto a laboratoryarea can be hazardous and can result h tide-spread contamina-tion. Thus, some ~ource of Infonnatl.onon cafe-haudlingpractices for proce~slngradioactivematerials should be consultedbefore a radiochemicalanalysls isbeguu. Information on such practices appears in the Oak Ridge National kbora-

(93)tovfs Master AnalyticalManual. and in the Int.ernatlone.llxnnlcEuer~n(%)Agencyvs publication, entitled Safe-Handlhg of Re.dloisotapes. Many other

.dndlar sources of information exist and should be consulted.

VI. COUNTINOTE~QUES FOR THE RAIIICWCTIYEPLATINUMISOTOPESThe analysisof sample@cerlals containingplatinumradionuclldesaybe

completedeitherby a direct (nondestmctive) measurement of the radionuclide inthe irradiated smple or by obtai~ the radionuclideh some form by radio-chemlcallyProcessing the irradiated san@e. The use of either technique iadependent upon the spa?ific characteristicsof the platinum radioisotopebeingmeasured, I.e., its half-ltie, the type radiationsIt emits as it decays andthe enera of those radlatione. The ease with which a nondestmctlve analysismethod can be applied is nmst frequently influencedby the rndioactivltyof thee~le Mtrix containingthe platinum radionuclide. If this presents a consider-able interference,then the sample must be processed radiochemically.

Table I of this Monograph ahowe the nuclear characteristicsof each of theknown radioactive isotopes of platinum. The radioactivityof these csm bemeasured by either standmi Geiger-Mueller,ganuuasclntillationjorproPr-tional counting techniques.95-*) OrAof these, gamna scintillationspectro-~t#8) has been used by Miller(99) in determhing the stable platinum con-tent of platinum-rhodiumalloys. A nondestructiveanalysis of the irradiatedmaterials by using the 0.070-and 0.179-Mev @ma diatlon from the 31-udnutePtlW isotope was tie.

18


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26/36


27/36

PROCEOURE 2 (Continued)

3. Destroy all nitrates with k@roxylazClneor hy@razi,ne;.thenadd O.1:.w . snc12. Centrifuge out anyppt (~C~). we rti:,color18.PtC14 whichi s ext=cted In* ethyl acetate. , ...-

4. or ga n ic layer is washed twice with an equal vol~, of 6 ~ HC1, t=.evapomted to dryness. .. .

5. Residue ia taken up In 2 ~ HC1, Pt metal ia precipitatedwith magnesiummetal h formof powller.ordust. (Ibnlt use Zn since it fomne a slow dlsaolvlng

,.Sww -)

..I,, ,, .

P ROCE DUREProcedureusedb: Preparation of radioactiveplatinumtraEersMethcd: precipitationand solvent extractionsElement Separated: Radlcsactlveplattium tracer .,Type Material Analyzed: Ilml.wlTyp of NuclearBombardment:184 cyclotron (any ener~ protins)Procedure By: Thompson and Rasmuasen (Re@rtedby MeNe (39))Separation Time: 30 minutesChemicalYield of Ckrrier: .70$Decent.mmlnatlon:102 .Equlpzent$quired: standali Procedure: ,, ;,.,

1. Make a mel t of KOR and KN03 (.50-50, not c r i t i c a l ) ~ a smal lporcelain crucible, @atlng strongly oyer a Fisher bwr,.

2. To thiehot flux add the tar~t Zr mtal, continu@g to heat (andadding KOH If volume of flux gets too small) uuti,lthe metal,is completelydlseolved. (For a small strip of 1 mil foil this Ahould take no longer tm,5-M min.)

Au3. Allow flux to cool, then leach for .5

and Pt carriers in small emunts. (Ir @ves

>,.min. ulth cunc..HC1, _ ,,strong blue colored 601Jn.)

21


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4.5:

Extract tulce withAdd a little SnC~

PROCEOURE 3 (Coritinued)

eihyl acetate to n%we Aq.solutionIn HC1 tothe aqueoue phaee until a dark

red coloration (H#tC14) indicates the re~uction of Pt from +4 to +2state lamnplete (See remrli.a).

6. Extract the red coloration (W) into ethyl acetate. Wash org=iclayer %ce wiil,eq~l volinneof 31 HC1.

7. Pla%e organic layer and flame.Remark:

As most Ir foil contahe about --l%Pt Qurity, it Is well to provide astep for extractionof Au actititieB,whether or not the Au 1s desired for.later work, eve~ M it 16 simply a proton-bonibardedIr.

h SnC~ reduct$on the stro~,blue colorationof Ir(+6) disappear,permitting the red of reduced H2PtClk to .beseen..

By spe-nrme the leacmng the melt,.in(3) and,by using sevemlprtiona of leaching agent the chemicalyielde might be made alnmt quanti-tative. ,,,,

PROcmJm 4PTocedure Used b: Preparation of Radioactive Platinum Tracer;

from fisEion prcductsMethod: Distillation, ,901ventextraction and precipitationTypeMatetialAnal.jmed: UraniummeklType of NucleUBodardment: 184 cyclotron (@9-Mev alphaa)Procedure By: Wove (Rep6rtedbyMeinke (39))SeparationTim: Whours (when se~ated uith Trand Rh)Chemical Yield of Carrier:$Decontamination: 104Equi~nt Requl~:. StaudsniProcedure:

separation

22


29/36

PROCEOURE 4 (Continued)

1. Cut out the cenwal portion of the target and boil with concentratedHC1 to dlsaolve it and ta expel Ge.

2. Add5mg I-red Io3- and boil the solutlti again to expel iodine.3. Add 20 mg OB, Ir, Pt, and Au carriersplus 20 mg Ba, RUJ Rh, md

Pd carriers. Withdraw a 20$ aliquot for later determinationsof Ba, Ru and Hh.4. Place the re=inYng aolutfon In a s~cial all-glass diatillingflaak

having a thistle tube entry .md em air entry. Add concentratedHN03 throughtie thistle tube, and dlatlll OsOh Into 6 ~ NaOH in an ice bath. (Savefor0s dete~natlon.)

5. Place the residue from the 0s distillation in a beaker, add 10 mlT@HCIOk s.ndboil the solution to fumes of HCIOk to expel Hu.

6. Dilute the solution, sdd 5 mg more Ru carrier, and 5 mgma= 1- andIO~- kndrepeatthe fuming.

7. Add one ml dilute HC1, dilute the solution to \ ljand ex t rac t t w ic ewith an e qu al volu m of butyl acetate to decontaminatefrm Hg and fromAu.

8. Dilute the aolutionto -A).5~ inH+, add 5 ml dimethylg@xime .90hl-tlon (1% in alcohol) and filter off the palla@m ppt.

9. Ad d cone. HC1 to aupn. to tie -5!. Add SmC12 dropwise until thecheqry-red color of Pt+2 iB ap~rellt.

10. Ektract the Pt with three equal po~lons of butyl acetate.11. Waah the Flatlnum out of the organic layer with 6 ~ WOH, acidify

t o 5 N HC1 and reextract Into butyl acetate. Repeat cycle.12. Wash,Pt from organic layer into 6 ~ NaOE and ppt p-tSfrom this

alkaline solution gradually acidlfled to 6 ~.13 . Dissolve the sulfide ppt in aqua regla, make alkaline and scavenge

twlceuith 5mgpp t JM of ~(~)3.14. Buffer the supn. with acetate and scavenge three times with 1 mg

pptnsof Mo .& d Pd with 8-hydroxy qulnoline.15. Make eolution acid and ppt platinum metal with powdered magnesium.

Jelghthe metal to determine chemical yield and plate.

23


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PROCmmE 4 ( continued)

Remuka:Rh, Ir, and i% should ba aepamtui f- one b-~ leavdng O!a,Ru

and Pdforasacondbo - - . t unless Eeveml pl!oplem c~ting on the

The yield of ectltity of Oe, Ir, and ?t is -ry 10V in ~son uiti thatof the other platinm nnstis W may other fission producm fonmd in the bcaibti-nmzm. !Lbis fac t necessi t at es, fo r u and Pc , f igcmma - mpeek t ed decm t admation procedureE uhlch reeulz in low chemicalyleida.

PRocDmE>Procedm Ueed In: Rdimcrivation aaalyaifiMethod: Precipilaricul-~eme=LtSapamz-ed: PtiY (i8 h)rypa Hatefial IuEi@ed: ~ or@3niame(D2)Type Rucle= ~t : #6 (n,7)R1Y?roc*ara By: Fukai and lde~e(m)Seps+rationme : ( ~)Chem ic al Yield of Cam ier : ( -mkl luun)Decmulmhation : (-aukzlml)Eq@mmrt Reqylred: (-mhmm)Procedure:

_ W ad,hcr.(m)ot e : pdm mm That the 6pec* ware irradiatedfor a f ev h ou rs, th en p rocessed m .d loch em icd ly. = 1- radioactitimUaameaaurd by galmlapec t rmet ry .

.-

24


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PROCEIHIRE6Procedure U6ed In: RSdiOaCtiV8tiOn&L9~SiBType!Matel%al /Ulalyzed: (lb~)Refjned uilver and nickel cathodes,Type Nuc l ea r Bonibardment:Neutron%ocedure By: Zvyaghtmev, O. E., and Kulak, A. I.(~3)SeparationTime: (uulmovn)Decontamination: Radioactive gold also determined h this work. No.hformtion available on decontaarlna~on.EquipmentRequired: (unknown)Procedm: .,: .

Nt.te: Specific-imfornmtion on this proced~npt avai~ble. Publicationsh ou ld k con su l t ed . ,,,

,

PROCEDURE 7Procedure Used In: RadioactivationAnalysiBMethd : PrecipitationElement Seprated: Ptlm (18h)wMatetialJi?l@@ed , Metal.e(104) .. .Type Nuclear Bouibardment: Pt,196(n,)pt!nProcedure By: M%bban, H. A. (ReportedbySeparationTime: 3.0 hoursChemical Yield of Carriers: 65-7c@DecontaeMnation: >104??@@nent Required: StandardProcedure:

., . .

Leddic~,tte(104)

1. Dissolve the i r rad ia ted sample (Note 1) in HC1 pluE a few drope ofHN03 and add stv zed Ft,carrier. Add the follovlng holdback carriers:Cu, Fe, Co, Sr, Na, Au, Hg, and Ir. Evaporate to &y-neaa.

2. Take up residue in 20 ml of 1 N HC1 and extract the solution twicewith equal volumes of ethyl acetate (Note 2). Discard organic layer~.

3. To the aqueous layer, dd hydroxylamlnebydxochloridedropwlse to

25


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PROCEDURE7 (continued)

deetroy ~ nitraten in the eolution. Adaomlmofqm caucrlfu@9enddiam #pt.

4. Ih e r ed color (?tClb) i s ex tm ctd f IWI t h e n u p ern a te b y 0~ WI*UI eq u al volme of ethyi awtuze (H0t4 3) . Wash the orgen ic I.qer tvice withequmlvolumo of6~HCle.nd thenevapxat i todrynem.

5. !13Mr es id ue 10 taken q in 2 ~ HC1 ead R mtd 10 ~cipitated ulth~1= ~ pouder. Centdfu@ end discard aupemte . Weah ppt wltb twolomlpamtione of21JEcl. Mlt7wh@ mnd dlE~ when.

6. ~t e r t h e P t t h r ou gh a t a r ed filter P8ar. Waah uith three lo-mlportlca d hot ~0 end two ml portione 0? alcohol. Dry for 15 minutes at11o c. Weigh 8s platinm nustal. Mount mnd count (Hot-e4).

ESS!!I1. qleE Irmdlated h the ORBL Gmpbim Reector at a f lux of dam

6.5 x IOU n/a2/eec. for i6 ham. -ts of -uremmt ImOut 1.0 dcro-

3. H e@eou o p hMe 10 still red h color repe8t Ux-tion with m%@ ~1~ of ethyl acetite. ~ Urtncte .

4. Msy be ca plet ed ei th er by Geiger -k h ael ler or gea m uscintilhtiauComting.

26


33/36


34/36

20.21.

22.23.24,25.26.

27 .28.

29 .30 .31 .32 .33 .34 .35 .36 .37 .3.

39 .

40 .

41 .42 ..43.44 .45 .

46.47.

Gl lch r l s t , R., ad Wlchers, E., J. Amer. ch~. SOC. ~, 2565 (1935 ).., M-ka, M. A., Barefoot, R. R., and Beamish,F. E.,=%e~.A&~ 1815 (1952 ).

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28


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48 .49.50.51 .

52 .53 .9.55 .%.57 .*.59 .60 .61 .62 :

63 .64 .65 .

64 .67 .68 .

69 .70 .71 .72 .73 .74 .75 .

76 .77 .

Arreguine, V., WV. fMEO. bioqti. krgentlna ~, 196 (1947).Ayr es, G. H., and Tuff~, B. L., Anal.Chem.~, 949 (1952).COburn, H. G., Be.muieh,F. E., and Lewis, C. L., Anal. Chem. 28, 1297 (1956).Thompson, S. O., Beamish, F. E., and Scott, M., Ind. Eng. Chem. Anal. Ed. ~,420 (1937).Beck, G., Mlkrochemiever. Mikrochim. Acta~, 188 (1947).Ihbrlsay, R., Compt. rend. 225, 300 (1947).Bauer, E., and Nagel, O., Chem. Abs. q, X9 (1915).SC-, G. M., and Ghosh, A. N., Z. Anorg. Chern.~, 323 (1949).VentureHo, G., and Sainl, G., b. Chem. APP1. ~, 375 (1949).tiaue, K. A., and Nelson, F., J. Am; chem.SOC. ~, 984 (1954).Kraue, K. A., Nelson, F., and Smith, G. W., J. P@. C&m. ~, 11 (1954).Blaeiue, E., and Wachtel, U., Z. fur. Anal. Chemie, ~~ 341 (1954).NacNwin, W. M., and Crunmett, W. B., hal. Chem.~, 1628 (1953).P en mn , s . S., and McBryde, W. A. E., Can.J. Chem.36, 835 (1958).::m;:b;i :i;5;~, A . A ., E!arg, R., and Nervik,W., J. Am. Chem.

MacNevln,W. M., end Crunme t t , W. B., Anal. Chim. ActalQ, 323 (1954 ).hc?kvin, w.M., and McKay, E. A., Anal.Chem.~, 1220 (1957).Pshenitsyn, N. K., Glady.9hevBkaya,K. A., and Ryakhova, L. M., Zhur. Neorg.Khlm. g,lo57 (1957).LedereGM., Anal. Chim. Acta~, 458 (1952).Lederer, M., Anal.DeCmwlho, R. G.,Lisbon, 1956.WaUer, W. R., and

~. Acta~, 185 (1951).Paper, Inter. ConP. of Analytical Chemistry,

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29


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78 .79 -80 .81 .82 .83 .

84 .85 .86 .87 .88 .

89 .w .91 .92 .

93 .gk .

95 .96 .97 .9.99 .100.101.102.103.104.

Majumdar, A.MacNevin, W.Lederer, M.,Cetini, G.,Wilm, T., J.Seliverstov,80 (1948).KarpQv, B. G.

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ITaturwlss . g 9 ( 19 57 ).Chem.~, 1806 (1957).

(1956-57 ) .

N. s., Inst.Olmhcheli Neorg.Khlm.Akad., and Fedorova,A. N., Ann.Inst.Plat.~,

Nauk ., SSSRg,106 (1932).

Zhemchuzhny, S. F., et al, ibid, ~, 339 (1*).Lovely , W. H. C., Chem.Eug.l.tLningev.fi, 19 (1941).Grlffth, L., !I&ans.Canad.Inst. Mining Met. ~, 153 (1*).Hoffman, I., Westland, A. D., Lewis, C. L., and Eeamish, F. E., Anal.Chem. ~, 1174 (1956).Plaksin,I..M.,and Schtamcva,S. M., Ann. Inst.Plat.,q 141 (1933).Plummer, M. E. C,, Lewis, C. L., and Beamlsh, F. E., ml. mem. ~,254 (1959). ,Plunwner,M. E. V., and Besmish, F. E., Anal. Chem. ~, ~kl (1959).Pieters,H. A. J., and Creyghton,J. W., Me ty in the chemicalLaboratory,Academicfiess,New York, 1957.Leddlcotte, G. W., Reynolds, S. A., Corbti, L. T., Safety, Method No.50150, ORNLMaster Analytical Msnusl, TCCD-7015,Section 5.InternationalAtomic Enerw Agency, Ekfety Series No. 1, Safe Handling ofRadioisotopes,Vie&sJ 195-9.Reynolds, S. A., Record of chamlcalpro~ess~, 99 (1955).Price, W. J., Nuclear Radiation Detection,McGIsw-RI1l,New York, 1958.Siegbahn, K., E.sta-and Gsmm-Ray SpeCtroscopy, hterficlence,New York, 1955.Crouthamel, C., Applied Gamma-Ray SpeCtrometry, Pergamon, lVewYork, 1*.Miller, C. E., T@utronActivatlonAnalysis Methods for the Group VIIIElements, USAEC Report, 0RNT=2715 (May, 1959).-, G. E., =. Ch~. ~, 335 (1949).Leddicotte, G. W., Pure and Applled chemistry~, 61-W (l@).mlrai, R., md Melnke, W. W., Umnology snd Oceaog. ~, 39I9 (1959).Zvyagintaw, O. E., and Kulak, A. I., Zhur. Neorg. Khlm. ~; l&97 (1957 ).Leddlcotte,G. W., TPlatinum,Neutron Ahtlvation Analysis (IeotopicCa?krler)Method, Methcd No. 5 1161o, to be issued in the Oak Ridge NationalIaboratoryMaster Analytical Manual.

USMCltidm of Tmlml.1 l~lm tim Gk Rl+, T

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The Radio Chemistry of Platinum.us AEC

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