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National
Academy v

of
Sciences

National Research Council
,
II
NUCLEAR SCIENCE SERIES

The Radiochemistry
of Fluorine, chlorine,
Bromine and Iodine

—————

COMMITTEE ON NUCLEAR SCIENCE

L. F. CIJRTIti&Ckrzfnnmt ROBLgY D. EVANS, Vice Chdmurn
NationalBureau ofStamlamls Maeeaohuae+rts
Inetltute
ofTeohnol~

J;&-~~ii;-S%&tq
_ “lW9etht@cg& EIFg@%c Cnrporatlon
-..-”
H. J.C~TIS ‘- G. (i MANov
BrockhavenNationalLaboratory T~6erlab, Iho.
SAMUEL EPSTHN W. WAYNE MEI.NKE
California
Inetitute
of Teohnolm UnlversltyofMichigan
HERBERT GCkDSTEIN A. H.SNELL
Corporationof
Nuolear3%weloprgent Oak RidgeNgtionalLaboratory
mrka
E. A. UEHZHG
H. J. GOMBERG UmlveieltyofWiehlngtOn
Universiw ofMichigan
D. M. VAN PATTER
“E.IL KLEMA BartolReseamih l%undatton
NorthwesternUnlverslty
ROBERT L. PLATZMAN
Argonne hIatbtalLaboratory

LIAISON *EMBERS”

PAUL C. AEBERSOLD w. D. ImRY
Atomic Energy Cotmglusion U. S. Air Foroe

J. HOWARD McMILLEN WILLIAM E. WRICiRT
Nattond Soknce Founthttlon O&ice of Naval Reaeamh

SUBCOMMITTEE ON RAD1OCHEMISTRY

W. WAYNE MEINKE ,Ckahwtan E~”L RYDE
Unkershy of Michig~ Unlverdw ofCalifornia
(Berkeley)
NATHAN @iLLOU HAROLD -Y
NWY Rdlologlcd D&mm Laboratory Mound Lahoiatory
GREGORY R. CHOPPLN GEORGE iEDDICOTTE
FlorCdaSf.m Uritvertgg Oak Ridge NationalLabormory
GEORGE A. COWAN ELLIS P. STEINBERG
Los ~6Jl10S fW2ieIltifiC
hhOWOry Argonue NationalLaboratory

ARTHUR W. FAIRHALL PETER C. STEVENSON
Universityof“Wad@ton Unlverfiity
d C alifomk [Livermore)
HARMON FINSTON LEO YAFFE
Brookhmen NatlomilLaboratory McGfll University

The Radiochemistry of Fluorine,
Chlorine, Bromine and lodine

By JACOB KLEINBERG and G. A. COWAN

University of California
Los Alamos Sm”entif?c Laboratory
Los Alamos, New Mexico

January1960

SEP 131960

PRWERTY

E Subcommittee on Radiochemietry
National Academy of Sciences—National Research Council

Printed
inUSA. Price$0.50.Aveifeble
fromtheOffice
ofTeclmlceLI
Services,
IWputmentofCommerce,WMMn@cm 25,D. C.

FOREWORD

The Subcommitteeon Radiochemistryis one of a numtir of
subcommitteesworking under the Committeeon Nuclear Science
within the National Acdeqy of Sciences - National Research
council. Its members represmt government,industrial,and
university klmratoties in the areaa of nuclear chemistry and
andyticd chemistry.

‘TheSubcommitteehas concerned itseM with those areas of
nucleex science which involve the chemist, such as the collec-
tion and distributionof radiochemicalprocedures,the estab-
Mshment of specificationsfor raikLochemlcalJ.y pure reagents,
the problems of stockpilinguncontaminatedmaterials, the
availabilityof cyclotrontime for service irradiations,the
plsce of radiochemistryh the undergraduatecollege program,
etc.

This series of monographshas gxown out of the need for
up-to-date compilationsof radlochemicalinfomnationaud pro-
cedures. The Subcommitteehas erdeavrmedto present a series
Which will be of maxhmm use to the work% scientistand
which contains the latest available IDformatlon. Each mono-
graph collects h one volume the perttient infors+tionrequired
for radlochemicalwork with an individualelment or a group of
closely related elements.

Au expert in the radiochemistryof the particular element
has written the mcno~aph, following a standard fomat developed
by the Subcommittee. The Atomic Energy Commissionhas .aponsored
the prtiting of the series.

The Subcommitteeis coflidentthese publicationswill be
useful not”only to the radiochemistbut alEo to the research
worker in other fields such as physics, biochemistryor”medictie
who wishes to use radiochemicaltechniquesto solve a specific
yroblem.

W. Wayne Meinke, Chairman
Subcommitteeon Radiochemistry

iii

Iv. 14 v’ . GeulefralReference6 ta m nlorgmlc End AnaLytlaid ClM51stry of 1 tbe I@logene.ecthm of Radiocbmlcal Rocedums for ntie. ~j Ercadne. CONTENTS 1. and Iodine. WJ.

bromine and iodine 18 one of a seriem of monographs on radiochemiatryof the elements. chlorine. bromine and iodine which might be included in a revised ~rsion of th rnnograph.and finally. Plans include revision of the monograph periodically as new technique and procedures warrsnt. a Collection of radiochemical procedures for the ele~nte as found in the literature. The series of mxmgrapti till cover all elemnts for which radiochemical procedures are pertinent.a discussionof problemB of dissolutionof a sample and counting techniques. There is included a review of the nuclear and chemical featurea of particularinterest to the radiochemist. vi . chlorine. INTRODUCTION This volume which deals with the radiochemistryof fluorine.. The reader is therefore encouraged to call to the at~ntion of the author eny published or onpubliehed material on the radiochemistry of fluorine.

Ch. 5 and 7.. G. Hildebmnd. *d Hditlon. 1953. A. mew Mexico J~ 1$%0 LGHWZML REFHRlmcHsTo TEE n’mRMNIc m AmUmmAL mRasl!RY m’ 5 HALwms W. Aualytlcal Chedalxy of the Manhattan Pro@2t. HaXL. MoeXLer. New York. ~C . Treatise on Inorganlc Chenllstxy(translatedby J. An Advanced Te@Aook. EIBtier Ptibllu CcmFSW. Bromine and Iodine JMMB HIEIIEtEHGAKD G.. Luudell. ti . Ch. M&raw HiJl Hook Co.The Chemical F3xamenteand !Iheti~ *. Aualytlcal Chedslry. 1952. COWM University of CalMbrnia Icm A1. UaMlo?l. M. 13. 17. Ch.mmq Mienti@3 I@oratory us AL5mos. H. Bright and J. John M1OY and Sone. HU. Inorganic 13M3mislzy. J&n ~by =d Scms. I. P. AlidtIWSOll) . New Yak. Cha.1959. hC. Hold Wversity Press. Iather and J. PP. T. 1 . F. V. W York. 2*323. Tcea&dl and W. 1S0. Hoffh5n. C. 1937. 47 and h8. Vol. S. E. Sidguick. New Yark. Chlorine. l?aferaum Bmk of ~~C chedstry.etid. J. W. pp. FyQpW3d ~c AnalySlEIJad Hdition.. 1. The Radiochemistry of Fluorine. A. gtb Wtiorl. lo$na%l.. Redden. x. 1951. H. H. Amaterdfnn. N. F. The MlJ-an Cmipany. Remy. F. hC . T. J& Wiley atldSons.1x6.

5$) NatuBKL *96 4.2n) Fm(7.n) ~=”(a.n) ma ti- Cl== .7) { EC(K) lofi Clge(d.n) a .n) Fm(n.2n) clss(P.n) 01e(P.7 sec r *(d. TABLEOF IwItm3*OF FImRllm.n) ~(p.3$ Cl=(n.cz) -0.24.*.n) c19*(7.3 eec P+ #2(p.IAble (dnmdence “ 75.10-~ -2. ~JUU2101UHE -70 Bec P+ r#(ap).4 nec B+ &( d. Om(d.P) ~=(n~y) NP(n.p) W C197(n.%) Heialrel ~3e 37 nlin Cls7(d.2U) -Uomin 13+9ti ole(a. II.7) end 0-s 2 .p) @17 stable (ebundence .pi) { Ec3$ O“(p.4 Xlflw B.a) end Otherm stab (Cb’lmdence 1*”) Eeidlrel 10.Pn) Mal@ltar cl=- #2(qn) ~(d.7) P3(7. C6mFmfE.

3n) { EC -1.n) 6.p) -40dn P+ mqc=.2n) L “57br = 9%.*) Netui-al B+@ -4. BRcMIXEMD I~IEE (Contld) Ieotope Half IAfa mofrlew Method of Prqurauml pJse -lhr P. A@(n.p ) 9em(p.n) m=(n.3 llr IT S&(d. Cu. - Bre1(n. A ‘( 7.n) S==( d. Co.p) Sem(d.p) Se=(p.%) *n(PA At375(a. Ae 1.n) -~(78n) Brw(n.XI. P+% *74( a. clmmmE.n) U.2n) #1 Staue (dnlndlwloe . P+ 11 9%.6 br B+ Cd=(c=.%) N@Ulw31 3 . II.49.P) ~ Fe.a) { EC se7q tl.4 min IT Ae=(a.4 Iuin B.ti) *n( a. TABIEm’ ~aFELummE.2n) <6min P+ Ikghtar Br7- ~7a stale (L&name .7) end o121ers #30 -181rdn p94 *m(p8n) { 13+-3$ -79(%7) (ye-z% *=( dsp) Rr%7.n) se74(P.7) “17br B+ A2=(u.

n) Y . 2$) EIP 15. S+%. -=2 +3 13.4 -321uin 6.tZ) SE@J.7) and Oti #9 -=( d.n) -.-flaaicmm. 2 Blssilm m.5 Bec P.a) W’y:im !% H6.n) -2.0 lldn P. Fassion u Ills -lgnlln P+ RP( ?#gill) or PdylT14.Imtope Half Life Type of Ikay Meaod of’- R’ep2uatiml ~82 ‘36hr P.7Q% P+ .2n) H%.3n) wm ~121 -2br P+ sb=(aJkrl) w- ~122 -hldn P+ ‘ Sb=1(a.4 hr P- IaP( 7. u. u-. u D3ugh* Se- 3. F#7( n.2n) mU@l* X&= &4 -4 day *U1(a. u Rklsiaa m.n) Se=(d.3n) Tel=(p. E%3sion u { fnl(.0 k’ m *u~(a.3Q’% m=S(a. m ---- #.n) and others 4 . Ilssiwl u #7 -Baec P. m.3n) TeE4(p.

3 b Spa31-flBeionu P- F’lsslonm. u. u mBSi~ Th.2n) Tel=(p. u Mssim u. Pu -.n) 11=(n. w-fission R).a) Teu4(tl. PU -.n) 0. ~=1 *132 -2. ~=s ps4 -52. u.n) pe 1. ~-fiBSiOn U FISsim m.2n) and O-B 1127 s-le (abmdame 10@) Ndillral 1128 -25* p-q I1=(n.7) Oe=g(n.n) a-fission m.2n) El!#”(p.44* Te=(d.7 x lo~ year P.n) IL-(n. Pu -* ~=4 5 . ~BSiOn U ~lso -12*5 hr P.n) ~-flBEiOn M DsU@ItelrXel= ~126 -13 day Ec 55$ Sb=(a.p5 -60&y EC m-(a. Te=O( d. ~.5 hr P. y) Te=qtL. u== D311@lter!rd= -p3 -Z?lbr P. u=.~) T+”(d.n) f& -~% Te12e(p. U.

35 and 53. ~ 74. J. cqpksl m halogcma. 1. -a fi we ~ values for the elec+mm affinitiesof tie atma (F)& * 3. Ed bdine. ~ No. I?m I’hOrim. thi.ectawmgativity. en-tar C&= p8 2.4. CL 86. TNEiIEQFn3maf%wm~. ~.To Ekklmrg. small size. s 195$. Rsview of ~ Phyalce.cm). 17.c rnmbera 9.andaraud (3. kcal/ble: F=* * 3. clIzT57. 81.7 aec B.5. Half Life Typbof Ibcay WuMd of Preparation ps -6. W meat tendency for the hal. along with *-*. encehx Ba= ●(hly &ae Ieotopa m liatad which faU in categmiea A md B ti ale ~ Iaotqea”.9 Bec r Fission u. HolJ. GeQaral PmPartiea ofwmeEeloewe ~. BF. diatmic natureof tbs elemntary molecules. With w raepmtive atmi. ~salon U. Pu F { P-n(~ “*) pe 5. !Qmae el. Cmorine.7 hr Spall-fleeim U r FiEsicQ m. * ddffler- ence cbaerved are largely attributablem lb -y high el. Pu Daugb* m= ~197 -22aec FISslcm u.5.emeute poaaesa m :~s vakmca shell cmflgwaticm.5).a i6tlleolllycovalenceFerndtted+fm Uleu&alrhalcgem.2. n. branina. in the relatively Mimge amountsof -gy reqdmd to dissociate*se mleculna (heat of dissocia- tion. and Inebility to ~temare thlxleighteleclmme intllm valence shell.2 kceL/g at. 13F~45. M. G535. where mtioe 6 . D.ogeneto reach o*t cafigumtia la Feflectid intbeebundanceo fhdlde aaltaand intllalarge~of cm- pkfi-~~~ti ahwa Oovaleaoe of mm. Part n.~. u. 2. ~ differsm@mdly in its chemistry _ the oi2mr helngem. BRQ41HEAl!U)I_ [Cent’d) Isotope .

and mew are ~tly c~t in ~tar. iodine. brauln% end Iodine exblbit positive ofidatlon s-tes m It is ?mtewW that iodine.eclmcmegatlve dament known. canpsre FSCIS and F@c&).” ~s ~ -- stAble entity csa be considerablys-lized by co&dlnation with such m-c bases as PYI%UJN2. tbe ~~tlal relationebi~ wblch exist amcmg the mious oxidation states of tieee ed. which give rise to huge cations of W charge. m mti canpcamdswlth-tals the halogem areneceessmilylna negative me oxldatim stste. invariably may be qded es being In a negative oxidation state. As wuld be expectad. 130dllml. emong others. With actiws m. is ectually capable of f&uing tie cationtc spcicles1+.shared pedre. This *end is genemUy ao~ed by increasingvolatilityas well as increeelngmlubility in ncm-polax or~c solvents (e.g.g. emn active CUES eucb as barylMum and alumimm.ments are shown on page 8. the bands between halogen. have km ~qe~ nla21mlch2s Cbangee In cnlmatton sta* are frequmltlyof Bl&m?icmce In radlochmlcal procedures for the anelysis of chlorine. the covalent -acter mf my one hIsMde type Imresaes with imreaslng oSdatdon state of the Ineltal. fluorlqe. Ou the other hemd.brmdne and iodine. with a meW exhibitinga warlety of oxidation abates. !lheother hak@sus BR3Ybe C~idSr* ss tibiting eitk? ekXbO- negative m electropositive charactm depending upau ~ dectimegatlvlty ofti~ttowblcb they me Joined.* met el. Calcim. with metels. Thus Sudl cqguunds “ti“[1 Py21~ and [I PY21 ~04. particularlychlorim.. tie least ele~egative halogen. which are wtantlal sowrces of ions of relatively M@ charge dsnsity. braolne m lodMe. The most c~ Sixuone In wbicb -Ins. i. tbls oxldatlcm slate iElan ionic W. cen folm the greatest mnmer of mvlslsntbculds.. 7 . the lergest of t& halogem. D union with other non-me-.

0.49 8 .0. . Acidic Solutiana : Basic *lutims: I .09 .

8. ~-. Fm both elszmnts. bti bramine end iodine are fWrly strong oxhliz~ agents.3 x 10-=.. Ih solvents ex- blbiting no dcmor characteristics. cblmf m. pyridine]. but no sbsble solld salts of this anion have been isolated.. !lhe=flucmi* ion is unknown. far brmine 17.g. in wem concenixatedalka13ne solutions the hypobaliti icm dis~m- ates to halati (X%-) and halide ions. ~. and Q-. tie equKUhrium constant for this reaction ii35 x 10a.g. Br%mine 1s rathm mluble in water. properties of these sdbstanceeare desmibed. The trend in stabillty of the tl%baliae lone b ~ “Bolu- tion is shown by the values for &e equilibriumconstantifor &e reactian. the constant is 4 x 104. (For chlmfne.. carbon tetrachloride. There is little dmbt that in both the red end brown solutims solvaticm of tie Idine occurs. e. 9 .55 g dissolving h 100 g of water at 20°. is tie most stable. In Summtic solvents SUCh as benzene end tdllene the soluticmeare red. Cs+. b solvents which may be regsuded as typical Lewis bases (e.and for cbbrine . For brmdne. carbon ~d? . iodine Is most soluble and gives brown solutions. 10-=’ . soluti6n in water is accompaniedby the mdn re- action &+ H~=H++X-+HXO. 3. An ~t characteristicof elementaryicdine Is its abiJSty to cmitdne with iodide IOU to form FE31yiodide ticms. the mlu- bili~ of iodine is Dnlchsmaller (O. wblch vigmously liberates OXYWI =d OSae fim Uqtid water with the furmation of hydrofluorlc acid.g. I.. etier. for Icdd. maervatime m E@ecies of ~cance in the Analytical Qlemis* of mlogens ~ view of the fact that the f~tion d el~~y brmine end iodllleis of lmpmtame in a nmiber of mthode for the analytical *- terdnatim of these elements. other polyiodiae ions which have been identifiedare ~-.the solutions sre violet in C-. gpaternaryanmxmium Ions. &+ r. As is evident ~ the PtesJUal data citad a&ve.e. s. The re- action IS of no significance ftm fluorine. of which the tri- iodide ion. !lhemat s~le polyiodide salts are formed with large catbns. is ccqletdy miscible with ccmion organic solvents.% g per liter of solutim at 25°) . !lkibrauidee are known. w. Iodine Is genertiy appreciablysoluble in organic solvents.) In cold tits albllne solutionshypdmllte salts ae famed. 2.ne. ‘he existence of the tzichlorideim in solution has been definitelyeti-llshed.&- w Iodine the constit at 25° is 725. but they m much less s-le than triiodides.

Elution was performed at room temperature with ~ soditunnitrate at a PH of 10. low results ccmunonly being obtained. which converts iodide to free iodine and is without effect on the remaininghalides. 10 ’10 j @r filver fluoride exhibits a volubilityof 181.5 x lo-le.7 x 10-=. A simila separationhas been used for determining Cl and Br in mix- tures of the two by absorption on a strong base anion resin.4. Fluoride comes off firs”t.or iodide can be determinedby precipitationwith silver ion (Ksp 25°: *c1 1.6. Ion Exchmge Separations Ion exchange has been used infrequentlyfor separationof the halogens from each other. and 1. or the fluroine content can be determined indirectlyfrom titration of the chloride. Sep~ation of bromide from chloride can be accomplishedby oxidation of the fozmer to elementarybrcanineby potassium permanganatein acetic acid solution. A further applicationof this method has been lo . precipitationby means of -~um( II) chloride frcuua slightly acidic solution is a satisfactorymethodlfor the separationof iodide from chloride and bromide. Br-.56 x 7. Precipitationof lead chlorofluorideis usually carried out in the PH range 3.6 .) The analyticalprocedure maybe a gravimetricone m? a titra- tion. Peak to valley ratios of 100 to 600 between F-. MI ~.A ‘he mmnonium salts of fluoride. Most of the analytical determinationsfor the halogens involve pre- cipitationreactions of the halide ions.5g per 100 g of water at about 200. the pre- cipitate can be weighed as such. aud iodide were absorbed on Dowex-2 (100- 200 mesh) in the nitrate form.brcmide. XE 67 supplied by Rohm and k3S Company.whereas tie ‘chlorideis soluble. An ion exchange separationof the halide ions was demonstratedearly . A more cannon way of separating iodide from solution with the other halides is by the addition of nitrous acid. Chloride. 3.& NaNOS containinga nonionic wetting agent. chloride. Precipitationof the calcium salt is not entirely satisfact- ory even when the solution to be tested contains appreci&blesmounts of fluoride.4 x 10-1~) or as lead chloroflwride FbFa“PbC12).5.were obtained indicatinggood sepsxation. The eluting agent was O. AS a matter of fact. in the history of modern exchmge materials. Iodide may be precipitatedaud determhed as the ~di~( II) salt. silver bromide is essentiallyinsoluble in an aqueous solution of ammonium carbonate. Cl-. probably because the well known conversionto the free element followed by extraction into au organic solmt is so welL estab- lished.brcxuide. It can also be affected from the silver salts. Fluoriae may be precipitated as the calcium salt (Ksp 18°: 3.

very ccmmunlywad to ti- 12 creeee the speclflc activity of a halogen.udlng the h811deB have beau detemninedfor hydroue ZtiCODiUUl OXIde. ~uoride heE bm s-ted frcm dumlnum by el&g fra the alkB- llne form of a strong base red. ~. O. 4.7 F’horide hae been quantlktivd.ueed for the malytical egtia d ~. end cl In Orgmlc Ccqx!unde. solvent Wtcactllnl se~ticme Extraction of the free elmt form of * halogen into an Cmgmic solvant (C~. hcdllar heJl& mparatlon m a Blamllg haae reein used O. slz’cmgbaee resin waE cycled -e thee witi 3~ NaOH end ~ Ef21.n.m The affhlty s-es deixmdned with O. Br.4 A =thod for sg~ Cl-. and I a Ibwm l-~0 resin. A synthetic inorgmic la exchangerw ueed to remove tige quenti- tlea of unwanted F1e activity that fom@d ee a by-product in a c-m U kaalation . N& > Br-.3 the elu~ agent . Becauee many organic ca59unde d the halogms can be pewed. 1-.6 -w clmcm3tography =a activatluaanalyels have bean ccabm for tile aetemillationof s. Ratee of u@Qm end en affinity semiee for several mlcme Incl.makns wae of pmdpitatlm *cmaw*y . end m-. m: >> so.end M ta 15 ‘y ~m w. Sevwral detailed ~lee are @van in tie section on procedures..8 m 100-200 meh. Extraction of * orgenlc solution with water then yielde a high epciflc activity of the hallde. . re ex&action aye- SzllErd—chalme have b. aud more them ~ of IIM fluoride wae *sorbed.= NaOH. h halldee have baai squated m ~ ~ted witi AS@X34 . as much @m@mrue on a Dowex l-~0 colmnn in the hydroxide form.y sqaz?atedfmm 500 t.% NaNOS. elution W8e performed with O. Heution activationfolluwed by exb’acticm d Br and I aad & dis- IL .end 1-. Br. Br. end I. ‘lMeelumt cmcem&atlon w= then ticreaeed to 2g to accelez%atethe elutlan of Br. g !lheelmlnm ccmsm off the column flret. been a favorad separationmethod for Cl.lLJEolutlane is: Cl-. The aolutim In concentratedHCl wea Psed through an A12~ CO. !Jhe recoil energy of the Incident nuclear particle breake tie H between 12M3halogen end the carbcm alxm. me ut of i&ntificaticm is 8 7 for I. me Blx41re of lone is pawed ~~ Coluume and &ve@?3d lneunMghtfor5to 15minutiB.CE~ ) after uee of * proper oxldlzing agent w lcmg .% NaNDs to elute Cl-.5 ACOIUmU lmImde UfIlgt?OSOr4X)a endahmlnalna 1 to 9 ratio of mipltent to flllur. -left lnuhydroxldefonn. and 1.

5.branlne.1pltatlaa. It is shakan uilh thee Successive5 nil~CQS Of Q end the -C layer LB evaporatedaud wei@d. Tracer qua brmllne exchanges rapidly Wltb freshly precipitated silver branide.19 XMQ h ~tic acid. m KH(I~)2 in dilute titiC acid. Three plausible mech- ~ aulms far excbmge have been postulated.125 millimole of tetrt@auyl BtibOUi~ sulfate la -d and t&e ~ brought to 19 ml. Jxstiuatlal aemtlcme Distillatitm of fluarine as hydrofluoellicicacid is ctxmol&yused for sepm3tlng fluoride frcm In-faring ions before a titration or pre- . 0. !IheeeInvolve the equlllbrla ehoun below: (1) & + X*. Br. TWm@auyl stlbmlum sulfate W been used to ertrect fluoride frm a aolutlcm in ~-~ @eId.tilJJ3tialofclhasbeenusedae smanalytical mlmlodtoae~ - eaxnlntsOfmimd u halldee. and Iodine csn be se~ted by Selectim odda- tion and dls~tion of the eleamt. I) Q . that is. K3=4X104 h Vleu of Vle M@ =Cbauge velocity It is extremly Mfficult b dis- tinguiti=betweenthese three mechenimne. CMorine can by addition be oxldl.A &w ~ of HzS04 me added to the solutlon cmtddng up to 5 mg ti F-.” h meUmd Is more useful fm concen- tratlcm purposes Ibn es a highly specific sepJu%stlcm. Iodine is axidizti by additla of HaN02 h dilute H2130~. ‘dmougb w- hallde ion fonnatlon.sed of ancen~ted EUOS. Obselrlmtiona on edlauge between various halngen entities b are ~ed aqueous Ilbedllml hlou . However. 6. lg-z (2) &+oE-=Hxo+r l&=4 xlolo (3) x2+Q=m+d+x. &change RWWticm A prime requisite in radlochemiualanalyticalprocedures Is the cm@ete exchsuwe betieen the radioactive species being determinedaud carrier.22 Exchangebetweeu elsmautery chlorine end chlorate ion in acidic J2 . there Is s- evidence that exchange occurs by meuhanlm (1). M Ermine cau be mddlzed ulth telluric acid.= & (X = cl. Exchange betweeu free halogen and haldde Im in solutla Is ccaqplete uithinm~ time of mhlng and se~tion.1-J7 Chlorine.

The =cbange in acldlc solution of elemm2taryIodine wltb iodate or ~odate (IO:) Icm.40 * 0.1.rapid exchauge can be ensured by the addition of b~ti csrrler 2% to the eaqple and its reduction b bradde Ion. Hxdmnge betseen chlorate Ion and pwrchlaraw Ion does not ocmr at r. and of Iodati witi perlodate inlacidlc or alkalbe Solution is s-.1 t 0. attdned wltbin a few seconds.* a. basic 25 or acidic soluticm.3 * 0.= .solution bow at roan tfmwralame and elevated ~lamee is exbmsly slow .7 * 0.may be PCblorate.= clo4.s”= mole-”= hr-l end kt Is appr~tely 0. The activationenergy Is about 20 kcal.15 1.25 l.2 & -1 for x.05.cal determinationof brcaulneactivitiesin fission products.7 t 1. m = 0.3.%amr cl-e chlorbe mm cblorlde ion exchange witA percbloric ion either In alkalhe a acidic solutian. At 250. or eveu at 9°.2”%r-z. It has bem rmdmthat .. n = 1. ad r is the appropriatefunction of tie activity coefficientsof tie reactate -d tiaueitlon Stites. (l-)(I&)( H+)s[ks(I&) + &x-)]r where at 25° ~ is (5. in neu-. The ~ti of exchengebetween freshly foti silver brmlde and qmoue brcsnideIan is very =pid. ‘$3 ~ q~~y obs.mols-~. mte law for the iodine-h-dateexchange reaction hea been de~d to be R = (~)0”6(H+)1”8(I& )0”8[k(IO:)+ k’(X-)]r in wbicb X.3) x loe 1. the rete law for the latter reaction at low iodide ion concen- tration is given by the ~eesion -d(I&)/dt . k has the value 7. nltrab!sor sulfate icm. T distributionOP activity be.5 ml-e= sec-L8 =d & for X.05. The exchange reaction has bm shown to occur by tie e mechenlem as the Iodide-lodatere- action. of chbrlne activitybetween ~chlorlte and cblorlte ions In besic eolu- * ticluis very slow.05. end p . It is Poposed tJmt the following set of reactkme is appll@le to the system: HBr+HBrOa”2Hmm HHrO+HBr =Hr2+H# In the nsdiochmd. _ature. mti of exchengebetween bhe end brcmate ion In aeidlc aqueous solutica is given by tie ~eesion R u k[I&2]m[~-]n[H+]p W* k = 0.2 ~~-9.023 mole-2”%.

Capl. !Qw precipi~teof PbU wee diesel. . we begun by Turkavich In 1!35. It w brcught Into a soluble fcma by fueicin in a I% cnacible with 22 sue ofanh@mua I@Qgti-ch5t iof cmmierhad beenadded(2. unpublishedLes Almoe wurk In 1955 ~. Ituaethen placed lnenovm at&30°C endthecarbcmateuea -1.s mole+ see-z. fo. then2ml of ~H~. 3. l!heva~ soluticm w neulxallzed in the pmmnce of brm@enol blue with ~ BHOS. t&emaee vae charred black. the mixhzre ~uaeetlrred auddlgeeted for one-halfhour to PrecipitatePbC1. !thegam- cedure vae not completelydevelopedbut ie m-eeen= here ae a starting ~tit for a modified procedure. end5 @@ s~= acetatein eolutim were added.g.A.llovedby ~ctlon to Iodib by 33 ~ of biaultlta in eCidiC sdutifXh Iv. ARD IODIHE ~1-FL~ Source .. s clo~ b tbut 1. ~s_vaecon-ed on2 gEtaoforganlc flberfilter~. =. by ~dlorits ion In b!MiC eoluticm. Tirkevloh. =diee of the iodine-lodati exchange mtitnl in mlutime of ametant hlic s~ allaiwiag U@ (@)/(l%-) =~OS @= * =.1 x MY l.RmE. -: R . After 30minat~°C. The covered I% cruciblevaa ~ ~- serted Inti a 500°C oven. BRumrB. m radio-cd aualyma for iodine. !Jheeolutim muet not be pemitted to becane acidic but ehmld remain sli@tly baeiC . coLucTIoH w RADI~cAL PRcmmms Fa FLm. 2. TIM@vea tJaemeQuetedvlth HwXItia fd. 14 .e~~ -* fa s~ tiutes.F.ved in 20 ml hot water ccm- ~afew~d-cHNO~ AgNOewae tbenaddedtiell@t excees. 5 ~Of _(~&)2 m SdUtiCm. k(f)(~-)(H+)g Ihls is entirely cmeistent witi 12M previous rate qpressicm noted Iamedlatew ab. l’hecooled melt wee diasolw3d In hot watar. nchibly brmdne aud iodine. vork on a radiochmicel procedure for fluorlw Which wuld ~vide a very high dBccmtadnation facti fra fiesion productE. 1. C%LORINE.ntbluelndlcator colcm.ete ~ of Iadlo- iodlne with carrier ~eunmbly can be db~ by the addition of the latter CM iodide la and eubaequentcdda~ to priodate. e.~gma KF”2Eb0 inloomlof H20).

. and ficient AgN% to precipitate the chlorine ee AgC1. (2) msw the al.3~eme copper fou) . lHneUy the flumine ehmld be T&Apitated ae lWIF. 2-3 dropsof conceu+mtidHHOS.u.n Cen—mles off. repcz% AECDJ2738.mane carrier (l-2 ml ccmcemlmatedHNQ9 for 0. AUE. h which fom It -d be wel.PP. PRoCEllURH2-CHUXUm 2ource . !IWS ehould then be followed by PbCIF end A@ scevmging stiFs end a seccmd distillationof HaSiFe.gbedand ccamted. ~ 1 (Cent’d) lhewec@itete ofAgClwmti. 1949 Elmmt sexratd Chlorhe . into a Cenlz?lfuge tube containing2 cc of water. ‘JheAgc!llwegd. The fm sap%: 30 uhutee Yield m Equigment require& s~ Procedure: (1) Dissolve tbe ~ m Concen+ratidma Conb?dning 5 mg of W. 30 m Of wa~r 1. of Purificatial:lF Wget mterial: Copper hCdlX@3 by: Batzel ~ Of bbdt: All . Kinke. . offandb the Sqpmeix?)a eMgbt excees of HCl wee added tO ~Wipit&MI exoees sfl. 22. WC8 collectidIn 45 mln in a flask ccmt4dniD& initi~. w. Itm_sted*t&f’iret step~fusiontidbe- distillaticmof -e.1-0.

additiaual aE- C~~ti~j silver ~mide iS fo~d aud the ~ rcamved se ● Versene (2erew0ti C3N?mdcalCo.5 ~ of ~carrlera8chlorlde tithe water intherecedver end after the C.5g m. (6) Oen&Muge and wash as before saving the ~te sad wash. prlmaEUy to remove chlorine fraa alkallne esa-thmetal ions. ti . to Br= end VOlatUlzX.W. and wash the precipitatetwice with 3 ml portions of 2 ~ ~. is to be diesolved the kt of reactifm may drive the chlorine mrrier into the receiving vessel be- fore the coppar Is ccqpletelydissolved. Burgue. considerabledecent.minaticmIs achievedby ferric hydroxide scavenging aud by precipitationof eilver iodide ficm ammoniacalmdb. 0.5 ~ WNOS). 1X 1. Hi. ZrI. cl-l. cau&lfuge the precipitateend wash with 3 cc of m_m. Azg.) is the dlsodium salt of etiyleua- ~etitmcetic acid. but elso to se~te thie ~t frcanmany o. far Cu. PRXEmRE3— CELOHmE Source . 2nd Ed. H. report l&1721. hhue odiizing the -. (7) Wke acid with HHOg to ~cipltati the A@. (4) DiBsolve *Agclin3ccof5 gMH&3and addadropofhola- back ~rs frcm stid!u% 10 m@l eolne.5 M ~ m% ~fOI’S PeciPi~~% q 5% of ~- ~er. activities. . Introduction Inthedeterdna tion of chlorlne In the ~sence of fission products.25 grams of smmnium pereulfate end beillng. The mcipltite CJ3nbe plated directly or dissolved h N&m allaan allquot taken.. IB b SO~ti~ W = ~tid 2. cen&ifuge. Add W wash to the supemate end add excees _ w precipitate W excess Iodh%s (5 drops of 0.m. ~ka : H = appreci~le amcunt of m. Pmclpita- tion of siJver chloride in tie presace of Versm* is fhn eu@oyed. ~ SOhltiOfl should then be reduced with h@raztie end the chlcdne peclpitated as A@@. In case brcmine is pres=t it may be r~ by _ we S~fiCQ o. (5) Cenb5fuge and wash the peclpi-ta wlti 2 cc of 5 g HE@. w(addas niizYAtAs Or SUEEAtAS) Isndthsn dd2dropsofo.5 W to tie ~ ScdU~_ aUd dietil as s~ted shove. ~ 2 (Contld) (3) Eeat allmst te bou. Co. If this OC_S add 2. V~sane forma ~ s~le soluble chelates with a large number of me=c iae.

fllx paw (9 an) No. m: 10hJ -: O. 60° funnels (two per ssmple) Ground-off~SCh funnels: Ccors 000A (one per mu@e ) F%lter ~ya (ane w ssmple) Filter fwks 125+ul 13epsmAoryfunnels (one per ample) 50-ml baakem (one per emqple) 40-ml conical centrifugetubes: ~ex 8130 (se.M= -tide with COnCen&ated Sulfurlc acid. P SSVIPM) No. HCHO: 3’7%w~ aolutian RE#H: Cone.lg solution h ailuta HNQs ● KN02: solid Versene : aisoaiuulSalt (Smalyticalreagent grade. Ca C2H@H: absolute Centrifuge wdJu - ~OCk for holdlng Cemlzafugelalbe8 Forceps hbun~ Plates PipetB : asBorted 8izea Wash bottle 2“. in which form it is cmlited. (added as I(Iin H@) Fe carrier: 10 mg Fe/ml. te cl. TM chedcal yield is about 7% and a single armlysis can be perfomed in two and one-halfhours. R. (added as Fe(NQ3)So6H@ ~ ~ ~1-ute ~) ENOS: cone. chlorine by --t IS finally ~ecipitited as the mm-Y (I) cmpound. Herswor’lil C31emical co. 42 Whahan filtercircles: 7/8” diameter-weighed stirring rods special still (~ ~ next page) 17 . h-oW&i. 2.ly H&@Q9)2: O.Ion c%rrler: 10 mg I-/ml.)+ aquecua solution. (Ivacl used * primary Stmlaara) 1.Ion carrier: 10 lug cl-/ml.

.

end discard the precipitate (Ho* 1). Add 4 drO’&e of ~ tier =d prSCipitfhS _(~)s Wi* -C. Heat to boildng to Coa8ulatitie metaUlc Ag precipitate.00 ml of s~d EaCi Carrie. Addk&q?aof O. transfer to a ~-ml cen~ tube. -far b a 125 ml eepsratm’yfunuel. e“ ~-~-ueoue W m 2-3 CC Of -C. add 15 ml of H@. &auBfer the supernate con12siniw cl. 2oiltoccms@ate *AgCl and vaehae in tbe pl!vloue step. and heat ta boiling ti ~ excess HO= icm. 60°fUnnel toeneure ccm@ete removal of AgI. HN09 ti preclpitdxsAgC1. men add 4-6 drops of Fe carrier aud Preciplate Fe(m)s by . Ikdmctb into *Qlayerti discard. hct 12. ~OH. ~ m. audheatlmboillng (Nota 2). cemtifbge. ~ter both @ ~CipititSS tOf@lar ~ No. However. Cool audaddhdropeof KI cexrier solution. Procedure g. and mpreclpi~ta @ll by illsaddition of ~C.~~and . I-9 . 10 drops of l% SCCH. NH@. add 50 ml of Q aud a feu qtab of KN02. ~fer the SU_tS ti a dean C=tiifU@ tube. tbie time filter the eupernatethrcmgh No. Acidify the RU-ta UiUl -C.@ containing 2 dro’peOf C~C. addition of a s-t excess of -C. ~. ~. and discard the pre- Cipikti . HE@. Discard tb supernateaud whin$e. -“ Dissolve tdleA@ in 40 drops of Cmc. m“ mtheeWernati add5mlofconc. &&l&” To the filtrate add 5 ml of ~ Versene solution and slowly acidify uitA cmc.. CentrifU@. ~ti tie pre~pi~te bY heating. add 1.and 10 &OpS Of 37$ H~. Hmg. To the Soluticsl Conixdning radioacum Cblmine end flssia products in a M)* conical ceutiifuge ~. lqH#alld4aropsof K( carrier solution. @o funnel. ~. Cenqe. Sw 3. To the euPernata a&sin add4 dropsof ~carrierand~ a AgI by-product precipitateas b tie previous step. 4. add 5 ml of en ~ Vereene soluticm.and discerd tie Q layer ~ each ~tdcm. collectingtie flltrata in a 125 ml Hlemsyer flask. HNDs. and wash the A@ viti 3040 ml of H. Add three separate additional lo+nl portions of Q. Boil to coagulata tie ~e- c@Itate. f’lle pa= h a 2’. Rwcipi-te ligI by * addition of a slight ~e of o-% -% solu~~. dilute to 30 ml. add an adaiumlal 2mlofthe acid. ~OS. ~ve a & precipitate. ion b a clm cautrifuge tube. Dissolve tie &Cl precipitatein 3 ml of cam. 40Uha~ filter ~pr (9 a) in a2-.

7/8” dimetir. tAan Cl.2S04~ecipi-tis A@l. H. w“ Predpitate H&C12 frm the solutla of HC1 dls~te (alter addins 1-2 ml of cone. Cautiouslyadd 6 ml of COllC . 4. The 123M volume in Step 1 should not =ceed 20 ml. PbC!12ie too soluble and therefore not suitable. Wash with absolute -OH and dry In an oven for 20 mimlte8 at UO’J . NH@I. . Agdnadd 4d1’0mof Fetiermd~m am(m)= scavenger peclpikte as in the pretioua step. cool.aw A@. ~ mast be taken to reduce it to one of these foma before be@nuing the procedure. H2S04 (~Oti 3) and heat until all the HClhaadlstilled overlnta a50mlb_ containlng20ml cKU. 20 . 2. and count (Nota 4).72 Mev 13-. E3LE” To the C1--ccatdnbg Supanate add O. 42 whatzmanfilter circle. mssdve the Agcl preclpi-te In 2 ml of Cone.% m32(m3)2 mlutlono Wash the preclpl~ti with H@ after filtering m a -d NO.lg AgNos to precl@- t. Otherwise the =diocblorlne may be lost as a result of Its fdlure to exchange with Cl. Bubble air tbrou@ the solution te ~ -t of the NH&I. If tie radiocblorineis orl&LneUy In a form o. and discard the ~cipltate. mount. weigh. can-e. Hoillmg is necee~ at Us a. Im3n2feirthe eupernata to a clean centrifuge tube. distwtlon continuebubbling * tAmugh the solution. using the stendard cblmney technique. mxxmm 3 (Cent’d) Nqcai. For counting 4 x l& y Clse. 3. Notee 1. Wash with seveml ml of H@ tit-oa epec~ dlh~ flask (see dlagmm of titiple still). Csdrlfuge end wash the precipitateas in Step 4. HN%) by the dropwise addition of O. H@12 ie used as tie cmpoun d nmunted in preference ta A@ because it does not form agglanerates as does AgC1. b remove most of tie voktile HCHO. step U.carrier. Atitiou of cone. a self’-absq- tian curve should be constructedand correctionsapplied for a 0.ion or C12. step9.

digest few EdXl. 1949 Elemsnt t3epmate& Madne Procadureby: Goe~ Tergetm~: -lg Bllwst21 Time fcm msp’n.22i as needed for ~ty. add.pp. 1-2 hrs. EtOH. Procedure: (1) Toallquot of~soln oft=@. Advan~s : Good yield of x Br. one might dIssc&ve the -get ti 6 ~ HMA wItb tie carrier ~. addafew&qsof o. 95. We@a es A#r (23. (3) Ccmblne c!cqhyerea ndwaehvith llJHK)g containiq FMu04. wamafewtitom@dlse & add fewdrqa O.th 5 ml IkO.l~EaHOa and extract 12 flwetlmeswlth 10ml -. To prevent mssibla 10SEKW of taace Br during dlssol~ of & bls?mxth. (6) F@eat 12 end Br2 ex&n C@. ad ether. and H@ In en ice bath. (7) Makelaet aq601nof Br31Jinm. (2) Addequalvol CC4to aquecnm @22eand addO. of ~flcatia: lhcontamlnatiou f. heat. Weah aq layer wI* CC~. (4) Mskelgin Hf@l. and er&act 12 into equal vol Q. Type of bbdt: ~t’ all paridcles Equimt I’eqlllrak cmlm- f’wm-.lg H~ &6pwise until both _scme colaless. add2mlo.w. pressmt in a glass still.5w ~ lomg m).lglw32. (5) Re~t KMn04 oxidation and Era * and reduction. addlOmg Br-end I-.10mg I-. dry 10 mln at llO°C.1~ frcm fiBBIOn end Spalbtion -Cta . WLu3h three -s W1. Make fivw _aoUm of Er2. Remarks: Tbe blmmti f%mion work tmly rquired -e 12-Rr2 erlam cycles. w. inter. report AECD-2738.ti~ Eleld: -w De. Meinke. .llJAgHOe 6*. m&e l~m HNOg. PmcEWHB4— BmmE SCnmce. A&ilOml&Oaud O. Aug.l~l$MnO* drop- wise until color persists. .

Source . mmt Is impossibleand the method of distillationof t&e halogens is ~a. (7) -t (4) ~d [5) as -d (A toW of 3 times was used for Plmificatim above. ~ iS d(kd as required for solution of the foilk (see (a) un~ ~k.iS added. (3) ~ ~~t solutim iS boiled to remove &S.factor of “ 104 fYcsofission and 13palJ. tbe solution is mede 1 g h HNog 6 few drops of mmo~ is added and the iodine -acted inta 10 de of CC&.) the sq@rnatant *get Bolution Is r6wved.) (2) Aftzr target has dissolved tbs solution is aldawed h stand for 15 minutes. . In these cases glase equip.w-fora few minutes to~dize the&.1 M KMn04 solution is added until the brauine color persists. (See (b) under ~ke .l MNaN02and exbnactthe Ia5 WlleB Uiti Q. ) Wash aqueous layer vith CC!&.) 22 .ation poducts .addafew_of O. Aug. (exlzact a tatal of 5 thes). The -@ fOfi iS ~ illSOhltiOll and COIIC. . (4) 10rdsof Qisaddedto~ aqueous -e aud 0. (See (c) under r~ks. pp. repm’t AEC&q38. fulmel Yield: -w Degree of purification: excellent .1 ~ N. add 10 IUIEH@ and 0. 1949 EIEemaitaepsratad: Emcdne Procedure by: Unbar !J!agetmata%sl: Tantalulu Modified by: ~ Type of bbdt: m+3501&vwolzme Time for aep’n: 2 hours Equipment -eta: =. (6) Wel Nin HNOSaddlOmgSI. 10 w 1. 10 mls of water Is added end the slurry is saturatidwiti &@. Ex&act Bra 5 Wnles (tow). M?inlm. Procedure: (11 Freslmy precipiktea AgBr (well Vashed to ~ mes Ag+) C~~ 10 mgs of brauine as silver bmmuide Is added to 15 mls of ~ SF solution ccarbxbed in a lusteroid test Wbe. ~~ 1 y m cm~ -4. Advantages: Provides for the separationof Bra frau tergete reqa HF-HTXISmixhares for solutiou of the largst. dropwiseuntil both layers are colorless. w. (5) Ccaubinethe Br2-cc14 ~t.w. ths AgRr washed twice with 10 mls hot water. g6. then Centrifuged.

W. (e) Iz might elso be e~tedby thie procdme. E. moclmJm5 (Cent’d) (8) uhst aqulmue mlutialofw-llg inmoe. Melnke.10e excqpt fran 1. dnce the m is being aissolTmd it may be Ssmd re- &ctivec andiume@tandall the~ietiihefmof b~ or brtmdde. EKtract five *S Witi ccl+. Goe~ Cs Qrocedure for branine. g8.e 5 SUCCeSSiV13 ~tione with C~ . (2) Toaqueous add2ml~end10 mgI-. H20J5*W. -ks : (a) This reacticm pomade repidly -d at no tim shcmld t&sre be end.1-1 gpl) Tim fm 6ep%: “ 1 br. add2mle 0. (3) Add 104n04to oddize Br. (b) Procedure &ponds qpcm an equillbratim betmau A@r end tracer brasiik ion in the k~t SdUti~.exmss of m. PROCmmE6— HFmmE Somce .&c. repxt NW&&@. Wreetivith 5. add4drqpsof 0.5 --.lg mamsmlac~a C@hSS on sh&dn& Discard t& CQ.ngIs not requtred end lustxwoia lalbe mey be ice cooled if necessary. HCl+afewdrops. of Im?ifiaation: .SOH. RrY far 10 mine at U.(. . digest afewminubes. Add~I-and~t exhaction with foln-~~ofw. EMmact five tlame III* ccl+. (C) ~SEi the 13cihrtion is ks@ acid MnO~ ~ ~ci~tate.metal Hquqale?ltreq@re& ~ mu -X$ .2g sOhl~~ (~)~e to M ~ bti re8ih. ‘he HCl IS diluted to2g~d~~@ti. 9tim.. 23 . ‘lheMO= precipitation~ abo be avcdded if the solutlm is ~ be- fore ~ti -fl~= (d) fj@e (3) aud (9) are R. (1) Add Kl&@4 (0. Heald. pp.@ frm 1-) Roce&re: ‘lhs~-tal isdiemlvedinccac. If the tm3car brmine ~ In a hl@er Oxidatim state Ws eq@llbmtion would be ~ssible . AddlO~~-tiermdK)mg I-umriem.lH) dropwiseunti color ~iste (15 drops). heat. ~ of bbdt: 60. lb C@layer addloml uaterando. kfak. ~.llJA8EOS.114 Matioz. -_to~fil~ENOeti50 mlsepmatary funnel. hg. 1*9 Elment mepuated Bmmdne Procedure b~ Riwhn Target material: mm’ium lmtal (. Discard equemw . W.

by ~0 ~ Q -acti~ cycles. boil briefly ta _ the H2S. con~ NH@I. and trensfer the solu- few ~ of 1 M KMn04 (~Ote 3). and COUUti?l& !lhereductim of ~.ucticm to 13r-.= 23. Aaa Ag+tOppt A@r. m aqueous Sohltion is then =.Glendenln.and exhaction tito Q. The bradne is finally ~Cipitited 0s #@T fOr wei. Vol.products by tlw reduct- Ia of lir& umri= to m. using KMn04 for oxidation to I& and uaiq HaHt& for z+. foUowed by oaddatlon ta Brz vlth KMU04.HCl does not reduce 12 h 1-. N. lhe Br2is~vedltrmtbe C~ by ~ & -.ssicaactivities. discard the ~ -= lomlof H20cantdnlnglml of 10mlof&O contaidng afew .nceIt&OH. 1. and tbe tdne reqdred for a canplete analysis is abcut 1 br. inter.in the ftrst extrm2tlon cycle helps to decontm5nate the brmine frau iodine. Rev.451 . Is negligible.3 m ~ bm aB~ve~ of brcadne ematlon. !llhe chemical yield is 50 ~ cent or more. Rook 3. wash tlu’eetilmeB with5ml H# and.HCl. 1. add 20 M of braolne cm-i. 10 & end wei@.5 mg A@&. cool. with H* ensures the Interchange of msdlobrcmine with the ca-ricm.Edwards and Gest. ~ 17 (1s49)). PROCEWM7—~ -Ce E. as Br&analomgofioWle carrier -a-. sl. ~ke : !lhismethod hae been described ~lY (PhY’s. Intiodllctlm ~ 16 eepuated fhcm tie other fleei. Dry at 110°. h Pretiu ~ds !lheuse or I!TM31JKl to reduce Brz to Br.. Procedure SE!?lQ” To not more ~ 5 ml of a solution of neutrm-irradiated uranyl nlhte (Note 1) b a 50Z cen~ tube. witi II&. to ~.S.ticlndlng iodine. Failure to acbleYe a cqplete intar- 36. times wl-U15ml EtCH. 10 ng Br. Contaminationby otbr fi. ~6 (Cent’d) (4) El&act cc14viti NaHSOg. Rassin H2sforlta 2 mln (Note 2). 9.IV. pp. 2.

Filter With euctlon on a Weighed mter- paper disk(Nota 5)inasmiU~mh fuunel. endheat neemQtoboiMng (mt0e4). &fficlent XBh04ehculdbe added ta mainlaln e pnmenent .453 Swleuiun metal waefueedon acopperc~krgetendbdxmled inabeU@rwi tlldeuteroneat tJleBe&eleycyclu@& ‘me Selenilm is dissolved in cane.edfrcalthe SO1.lM~drc@ by drop wlthaUrring auddlgeet thepreci~- tate of A@r for a few aecande. Addlmlof 6MEN0. WdCh ia then weahed three -S Witi disti~ W&&r. 3. ue@ ee ~. endwaeh~timeswlth 5m. Vol. Ikryatll@Cfar10 ndn. !lhesolution is diluted b 4d.E. PP. Jacobson. HKOg. Add2mlof O. -= 4.. disk Ie weabed with ethenol end dried under the ccmditdoaeof the procedure before the wel@lng. end -t. is collected h ~. con~ m-=.tien excess ei~ Or &ma m’ of l?ea~o~ta @we a mlutlon of &ecer brcadne free of s~cant mounte OY braid. mocEDmE8— BRcMmB source . EEu” FlelnEat~ 5* *8. HWECURE i’ (Cent‘d) Sk!?I@”Rewet * ~. 1. ~ ~le solution 2hcald be neutral or slightly acldlc. 25 . Atthe endof tldBperlodtJle$c~~ if3~ted wi.R. -k 3. E. end the mixture isplaced indtcecteuwllght foratleeatlbr. me Wmkte.H. Notee. wldcb ndgbt Interfere in the #@r prwcipltauclh 5. edmetlle~ is lef% behind during the Q exixac~ cycles.aa2eetiefamehla of frew sulfur at this point. 2..utim.owcolar. end tie add le diatlxl.S. &ffiCieUt ClZ13a2iei added to We CQto produce atla-tiy idl. ~~semceof~in-ee@s wilJ. msdoeeno hawm. me solutlcm is aciddfied end heated to qpel ma. Owwakt and L. me fil--.lof H@endtbree tilmeewlth5 mlofethenol.ne CeJTler . 1. 9.

Reex&actlon tits a wa. Koltioff and O %ri-ihavw shuun that freshly Precipi-ted A@r ~ ra@- wlti Br.neat tracer concenta?atlons.source .alSO exchangesreadily at ccmcentitlcas below 10-%. Tracer bromine Stitim VerS pepsred by & neuticm ~adlatlon of dagamed ~ and . a reaction _clzsmLstlc of brauine at.and BrO-. Tlve studies of the reactivity of We tracer are presentid elsewhere.umsand not of Brz. Vol. 26 . Book 3. a emaXltiction ofiJwe activity is bound bythe Xed CC14..at mdnez’y ccmentitions.2s shown by the cauplete recovmy of 12m actlvlty with added ARET precipitate.E. About60~centofthe~h~2 iS found ln12ae Qx. Gest. *IS ~~t shows tht RrO.. glvea no precipitateor Cerltdfugab A kge tition (about 70 ~ cent) of tbe brcmlne activity can be ertracted frau the C% solutla by water.tX) * at rm taqperatureIn a neu= aol.R. N. 9.N. as f-d by DeVault and IAbby.lght witi etiylidenebraulde. these losses q be due to &radlatlon effects. Edwards and H. ~~2. although atanic bradne is not qected to ba present in appreciableamunta even in tlmae dilute solutionsunJAss it Is hl@lY s~~ by ccqplex f~tion wltb i2M solvent. ~ appre~le fmctIm (abat 16 per cent) is not ex- tracted by water but iS ~CtSd by NeHB&KRr SOhltiCM. PP ~~ In cmnectkn with studies on Uie -ad effects Msoclated with w formation of ~ ~ the decay of eelenlumSon tJiebtivlor e B of brad. since Ag+ le colloid.utlon. Brcmdne tiacer does not exchange a~eclsbly with O. R.40 lllxh-tIon -0 reacts In * absence of I. layer with N- glvee a solution of Rr. with the ~d of waw solutions of the tracer e~ frailme C% solution.Sevsmal Intereeidngreactionswere studied which are ~d brlafly here. It was * that 96 to 99 per mnt of UIS actlvlty is collectedby freshly prepared A@ in 10 ta 45 mdn of StdlZblg. !lhlsfmction Is provisianaUy designated8s %taulc” brauine. prhaFw to the wall.S. anda ~ _ ~ti~ ~S tist.concentrationof tie orrherof 10-%. h addition.1X ~ after 13tandlngfor 10 to I. in m presame of BIVOaend KMn04. pesumbly becmme of the hydrolysis of Brz ta Br. axbactlcu of the wa~ ~olutionby C.

xture. 27 . M3inke. repmt AECW2738. MeiDke.W. W.ution dmwly until a fdnt o&r of m r~ efter standing 10 mhutia . ~ *get mmariel: To (2 urn. m. (4) Astremof air~lnibbledthrou@ tbeeO1uti= fcm15minntee eadhtJle 601utionvae coolea euldlz’ealzldwithcmc. w. 21.km 13cd. pp. 1%1 memlnt aeparew Iodmle Proce&re by: H.w. AdmntageB : Faat. pp. ) ~ for m%: 3 we ha naturalredioectimTe (?) E@pmit reqdred: Smn&rd Yiel& 60$ Impw of ~cation: At leaet 10° frm Te Pmcedme: (1) Temeti= oxLdizedbycmic. 10-e bezm2 erOs6 Procedureby: Mxrquez secUon) Wget laaterlel: Su(-lgm) !lYmefor eep’n: 50 min. !J31emiXturewdi- geeted fm m -tee at 930C. m AECD-30&. EImgt43Te02 WCh WfUSe41 Ulth ITeOH. (5) AgIwaepp&d byadding A@Oa to the d.e. Mikee pesible sep’n of a q en@J emnmt of pure Ifmnkmge mmunte of otJleractivitle8. (3) ~ wae obtainedby centrifugingthe solution end theu &euting withlgal of&m* end15ml of H2ao~. me mea -a w diedolti b Water. -ke : PRccmmEK1-IoDmE scnuce . -oh. Agwoewedded slowly toexceesto ppt AgIti A@r. ~ 10 . Aug. am&ling palecipitatiml of A@. (2) 10~of I-and 20mg Br-vere added eecerriere totlMsolMtion.Io- mce . Yiel& 70+ =-t requ3xe& 100 CC diS~ti~ flack ‘1’yxEJ of bbdt: l&n ~~dp Sepamtory funneb Cenb-ifuge Iaibee Dsgree of XU3tion: Leas -1$ Impurity in final Iem@l. D. 1949 Ehlieut Elezam3tie& ~ (.

me ofbbdt: 60~aparticles Eqpipsent required: 100 distillationflasks sep funnels and centrifuge tubes Yield: 80$ or higher Degree of purification: At least a factor of 104 frcusother activities present.5-M_ NaOH solution. (3) Dissolve Sa and distill simultaneously. (2) Add ‘ 15 ml COnC. W. (Three cycles gave purity listed above. Remarks: Most of the loss in this procedure comes in the distillationprocess. report AECD-2’738. !lhe 12 washed out of the organic layer into S02 solution and the cycle repeated. The solution is then oxidizedwith HN02 and the 12 extracted went equal volume of CC14. (8) Heat in water bath and filter. S02 solutions can be used to collect the 12 from the distillation.(H2204 shotid be COld) to dissolve the W.into NaOH solution. (4) Acidify With H2S04 until iottineturns brown ~d oxidize with HNOa. (5) Wash 1. Meinke. pp. (NaN02 in acid solution). Advantages: Fast and good separation. PROCEDURE 12 . 1949 Element separated: Iodine procedure by: Msrquez Target material: Sb (-5oomg) Time for sepsn: *4O min. W. Add excess Ag+ and a few drops of cone.2S04. HN03. Extract with equal volume CC14.rce . 162. Ice cold H#50 used in (2) to allow assembly of distillationapparatus before solution of target starts.IODINE &m.carrier and *get foil to distillationflask. Aug. H. (6) Repeat NaOE-CC14 cycles as many times as wished. Blow air through solution to -l most of SOZ. 28 . !tbisS02 procedure is troublesomein the experi- ments above because the solution develops a gas pressure during the extractions. PROCEDURE 11 (Cent’d) Frocedure: (1) Add 10 mg 1.) (7) Acidify last NaOH solution with H2S04 and reduce with S02 gas. (9) Plate and count as AgI.collecting12 in 0.

lO~I-cm%er. hieinke. (!lhreecycles gave pu15ty llsted Shove. TYPS of bbdt: 184g ell ~cles w-t ~ “ msm- tion fZ&k.) (6) AcIdif’Ykt ~ soluti~ with HzS04 =d redUCS uIth ~ ~. unotlX21Xllbi@l asabuve.9watus before solution of -get Sterte ● solution of 2b h qm rc@a titeu’feree with 12 ~on. (2) ~S~ end C*Ct 12 h 0. Iw cold EINOgused in (1) h ellou 2SSS!llb~of diStitiCSl . (8) Plate end c-t es AgI. hg. ‘Em solution is then oxidisedwith 21!fOZ end tAe IS erlaacteduiti eqti ~ of-. ~Z solution cau be used b collect the 12 frun W@ distillaticm. 19+9 ~t seFu=te& Iodine ~dure by: mckemann Wgetnmteriel: -lgmmetal ‘mm? for Sep%: -2 he. > ld frm fiSSiWJ end -Mm products. Blowetr tllrougbaolutionta axplmostofm.tito N. HIW& (7) Heet in water bath and filw.W. PRmmlJm 12 (Cent‘d) mocedme: (1) Addtar@. (3) Acidify with H2&)4 untdl iodine turns brown end otidize vith HEOz. 4@ Dsgree d Purificatim: ~m~tioil f. Wnal?ke: Most M the loss in this procedural c-s in we distilhticm process. stitbn. hou- emr.5-1 N ~. Er&act utul equal VDlm c%. centrifuge. pp. !Qw12wcudmd outof Umorgmic ~tito~dhlthlsd the cycle repeatid. 163. tubes. ice. Ylel& Approx. W. (5) Repeat Mm-CC& cycles . ~ WQes M wished. 10-15 ml of Selan?alad ~c ecid aud 10-15 ml of Ice cold ~ to dietillatim ~tns . w oven. !lheradioactivemmity of the sqple. PmCEWRE13-IOMXE Smlrm . reportAECD-@. (NsN02 in acid soluticm). Advlmtsges: Fair yield of pzre I with llttle if eny mm-exchmge tile. 29 . An I-ssn@e could be bbtsdnedin 15-20 tibyppting the AgIdiz’ectly from tbe distillateof (2). (4) Weeh 1. AddelcceasAg+ and a few drOPS of -C.

PMCEWRElh . to 0. and e~ I= into an equal vohme of CC&. f-d se psc’iodate~ not exchange wttthUve her by this metimd.~ AgNCIS.1-1 ~) ~ far sep%. ~ ~~ cu. The HCl is diluted to 2 ~ end an aliquot -. Procedure by: 19ewtan mrget ma~: ‘mroIlnu. R61mrke: Active i. AHCD&?@. the 12 &uldafew nllHNOsillto H@ inen ice bath. fllk.50108 w 10mg I). Reducing ctmdltionpr=ly _ dufing dhsoluthm of the Q9rget. HCl + a few drops .digest. Welgb se A@ (J. pp. 131TOS.lg NaNCk. wash three thee ui~ H@.6. I. Heat.W. add 2 ml O. tluee *wit215ml eWllm. . (3) . ~ titi I-Oml H@. Mehke. Aug.% ~ ~s. 30 . &reetilaes wlti51ulc*CH. ~ 13 (Cent’d) %xeuure: {l) Place W@tln@aes sW.g~~ and afewdrqpeofl~~~2.distill O. add 3 ml 1 M l@#XLHCl(3) Exlract witi 10 ml C%. addlOmg I--dlOn&~Ht@& vexm to dissolve. Wti Q Vith dilute ENOS.. (2) Smlne wi~ 10 ml H@ ccmtdnlng a few drops NsHS3S until both @uw3e colorless. r. (2) RealcseIswitbandxdmum of N-S in the cold. (. el&au@ the I yields were not abnonnss low.: 1 br Type of bbdt: 60” a’s Ek@~t requlre& EHar&rd YLel* * Degree of purification: loe Proceti: !Chelh me= is dissolvedh cone. Acidify with 3 ml cone. add a few drops O.s~u~~ o.* NaOCl{z). IO= -Ce . When entirely dlseolved. adJust. (3) !Ibva&add lm16. Add 2 ml 2.2 y solution (l@@Fe b clear w black resi-. (5) ~ -t W. 164.5~ HI?&. Procedl?re: (1) Add sample to 10 ml 2 M Na2c09:! Add20mg I-ln6Qmlsep funnels. adding N-s unti both phases Colmless . (4) Repeat eucbaction cycle aevemJ tlnme. ~t to boi~. E&mct aqueous with eemnd -on C%. 1549 ~t s~ti~ I. W. Ektaact tits cm+. dl?y 10 * at llO°C.

(4) (5) -k9: (1) (2) (3) .

weaht&ee timsuith5mlof ~=dthree theswllh 5mlof~per cente12muol. #dd5nJ10f O. andheat nearly to bolMng (Now 2). Step2.tUld heat~lytabo~.including&canine. drop by drop with contlrawue6tlrrlngJ (Mgelatthe precl@- tate fa ebout 1 mln. and ulmlnt .HCl. a“ RePat step 2. 1. Addlmlof 6MRNOgend afeudropaof lMIWliOaJextxact tie IalntolQ mlof CC&.lM A@TOg drop by tiOp titi et-. 2. FHa3mmE15 (COnt’q me iodine ie fhally preclpi-ted ea A@ for weigblng md counting. and flltem quantitativelycm a wel@ed slntered- glass acible with SUCtiOJ1. Add 2 ml of O. and exlzact * 12 i. ins-d * aWOU8 e. waeh tbreetheB wlth5mlof&0 end three times with 5 ml of ethanol. rlneing dounthelneide of the crucibleviti each pmtton of Ihe waeh liquid.nti10 EL Of cu. Add 3 ml of Ill NH@H.lM . to heat). Umnyl nitita hexahydrati (el~ ae the solld a in 32 . Fnepscatimland Sb3?ldarwultlca of curia’ Mssolve 13gofreagemt -grade KI Inwater cmtdnlngafevti- _ of ~~J =d mute to 1 ~~= ~s ~olu~on con~ 10 U of lod5ne E Ilduluter.aud alla-d tie Q. or bet. add d?out 50 ml Of~EUldlldOf&~. Hmg. together with a dlecuesicmof lile&rve*t work. step3. wipe the outeide cd the Crucible dryand placein anovenat llO°Cftrr10 min. vei@ ee AgI. cca- ~tion by other fimston actititiee. Mpet5ml of the@u7rier Oolution introa beaker. Addlml of 6MHNOS. ~. Is glvm below. is negligible. and discard thequecue Qfer. Cool in a dealccator end wel@ u AgI. Mtie CQlayar withlOmlof H20 cmklmingafeu _ of ~ ~~~ UU~ bo~ ~ee ne colorless. aud acidify lb solutionby dowly adillng3 ml of Cone. with suction C&O a weighed filter-paPEudisk (Note k) lnaemeU Hlrschfunuel. and digest the ~cI- pitate of A@ for a few secondeby gautle boillng and brisk stlrrlng (Note 3). 3. The C-ti procedure. Ho&s . Add b * of flssitm 13aqple poducte ( contdmlng not more thau5gof urenylni&ate)lna 60+18~tmry funnel abmt10 ml of2MHa~(Notel)end2 mlof I-carrier. Addlmlof5 ~-t HaCIOJ mix wti (Nob: Itiadeelmble tig3vethe NaC10 tlmetitidtze radlolodlnespecies fully. Procedure ~. Fil. Dry at llO°C for 10 b.

u?@ Work on tie develolmmt of a wocedure that would effect a fast and cqplete interchangeof radioiodlne with carrier iodine wee csrried out. the procedure Involvlng the addition of iodke carrlem ea IO: and reductiou to 1. k.4 h I dau@ter activity at equlli- briwm by COUll~ an aliquot of +Ju stock solution tJrra@ eufflcient ehnlnumtodmo rb~softer @radlatlon of the~h Te.~ fran 65 b 95 per cent. man these inter- change tests It was evident -t tie UJ3ualmetiods of Icdlne separation do not give a ccmpleti ramml of mdiolorkbe frmn fissicm material. The digestionprocedure aide b Coaglilatiug the euepemeionend also In breaklmg up tie Wge particles of Wecipltete. ~ ti~change tests on prevloue methods of Iodine separationConsls-d h pr~ing a stock Solutlon of n h !t’e. In these tests it was found tht tie wller methods dld not effect ei.. !EJSfilter-~per disk is washed with ethanol aud tiled under tie conditionsof the procedurebefore the welgbing.wI* NaHWS In dilute acid solution was found to give inccmplem eeparatiousof 2. For exmqple. If tiers iS much fhe acid in the uranyl nltiate. determlm@ the 2.and qploylng mddatlon-reduction reactions In acid solutla to obtalm 12 for se~atlon by extraction.involvl.fledend heated to aw@el ~z Which mi@t Interfere In the AgI precipltat. tie addition of more ~~ and gentle hea~ may be required b effect ccqplete solution. and ~ this actlvlty wIM the 2. 3. ~ 15 (Cent’d) solutlcm) Is readily soluble in Na2COS solutionby the formation of tie carbauate ccmPlax.4 h I frcan the stack solutlon. 4. ‘lhe130hltiOnis acidf. 2. S1l.4 h I tzacer tests mentioned dove and has been tico~ted h the ~ocedure describedIn tis paper.~S reaCtiC#lwas shown te @VS CU@Ste awl rapid Interchange”by the 2. rnscussim Previous methods of ~ fissicln-iodirle activities.ng ‘&e use of carriers2 In the form of 1. cmqplete or r~oduclble Inhsrchemgebetwea radio- active Iodine and tier iodine.have bean shown b give low and e-tic yieldsw evidently owing b inomqplete interchangebetween the radlolodineend tie tiers.ton. !he difficultyof Worldrlgm en alkak&e solution in the presence of U& has been Cticumvemtedby use of the cexbonate cacipk to prevent precipl- tatia of lmanllml ● .4 h I activity obtdned by vwrlous methods of iodine sepxratlon. idlti ** to f’orm both a roil@ suspenskm and large clumps of precipitate. aud a satisfactorymethod was found In tie &daticm of 1.to IO: by NcCIOtianaUaklne t301UtiOn.

md is re- 34 . is also added In etep 1 (see Sec. The iodine procedure can be adapted re@ly b a tidem method de- ~ Iodine md branine. pp 1635 1. Ikmk 3. ~ 16 . lhe sepera- tlau frcm iodine should be exceUent. aud tie other sepratlm is glvau by tie ex&actLon of 12 after ddatian witi HR02 (tlds does not @dlze W-). IQtcoff.to I& end thus prevents Iti extraction with Br2 end eince hydroxylamineEdUCeS I& to 12 and prevents its extractim With Br-. ofitied to F@ by the NaCIO. Two S%PXRZti~ ~ br~ = affaded in the procedure: me a~tlon is @ven by the redUCtiCm to Br. h tids case Br. !lhe1~ ie then redueed ti 12 with NH20H-HCl . N. 9. branine. illWhich W4 i6 used b dll. DnI=d. which should exdaangerapidly with 1. alrodllctlon me wocedure wesented h this pzper was developsdb separate iodine formed h the fIssion of uranium meti.U(IV) and 1.e. HN~ for the cddation of Br.N. !Lhe12 is . seihr and sugmuan.extract- ed.carrier &r@ solutim of the metal in U M HC1. lhwmver.Includhg the most ~cbehle con~ t.S. After the uranlwn metal is canpletelydissolved. with no evidence of con~tlon by other fission activities.ti. 3). ~ 15 (Cent’d) ~perate @acer taste with vericue fission activitieshave not been made. Caqplete exduange of tie radioiodinewith ~lar 1.ta Brz and hydr~lsnine IB used for the reduction of Rr2 ta Br-.. buttieprocedure has been usedina great dealofwmkon ehort- 47 livetlIodine actlvltles.Ion.E. end reduced to Br- by tie hydro~lamlne.ne activity Is not ~mnt In flsBlon-productsolutionsthat ere mae than a dlly@d. since KMM14 odties 1. as in the case of iodine (steps 2 and 4). corbactedwiti CC~. Hnston. hence brczui. mdd. The brcmdne is ~ipitated ae Ag13rfor Wew -a _u$8A9 as In tie case or Iodhe (s* 5). and tbe Br- in the aqueous layer is o~dlzed to Br2 with KMn04 aud la extracted inta Q.=e o~dlzed to ~~ and I& titi an excess of KMn04. by auo~er CC& ~tion Cy&Le.is expected. The brcauinecan then be purified. the longeet-llvedbranine tivlty in flsslon witi a sigdficaut yield is 2.IOD~ Suurce . since tie Iodine activity formed In umnium metal is In a highly reducing medium ad therefae 1s almost c~y Pres-t as 1. Vol.4 h &.with hydroxy~ ~ 12 is be.

me distillatiIs acl~ied. R’ocedure ~. Ihe exit tube of the distillingflask Is extended into 20 ml of 6N NaOH solutim. Add an excess of sat. Add60ml c%arrler ofconc. Refill the trap with 20 ml of fresh &l ~. 1. and stir the solutlcm. Addtke NaOHfrau tielm3p tot&solution inthedia~ flesk. andwash three tilmeswith~mlof &Oend12mee &snith5ml ofelhenol. 2. Filter wlti suctlcm on a walghed flltem- ~-kinasnwiLIHirwhfunwl. -+21elm layarwithloml of&0 drops of 1 M NeH~ unti both @aces are colcmlese. Heat the aquecue layer end add elowly 2 ml of Pd(Nos)a (lo 1+1) ta precipitate~. HCltodlesolve tilemetal. ‘he 12 Is removed frcm tie Q by ahaldng vlth quecn12 NaHms aud ie then ~ified by two more Q exbactims. end discard the qesaM layer. Addlmlof 6NHN%and afew dropsof the I= inti 10 ml of Q. Died the aqueous layer. wei@ = R&.e of irradiateduremim metal b a distllldngflask tit cca~s 2 ml of ~ (1. In which NaN02 is USA for the -W&m of 1. and IwuIlt. &%Qo ~~ the dls~te . DryatllO°C forlOmln. The iodine ie flnalJy Precipl-ted es PdQ for Wel@ng end Counldng. Under 12ieeecandltime tie NaN02 does not lAbemte &. NO*S. . and then add 20 ml more.ccmcentition of 10 m&l) .to L& and I&. and ~ is rmuved by extractionwiti CC4.% NHfi “HCl slowly until tie solutionbecamss Ilght yeUW. TO the emall residue of cerbide and ofide that remains. ~. and a S1OU sixeem of air is p3ssed ccmthuously mough the soluticm during this etep (Note 2). 35 . KMQ ta the eolution to oxftie U(IV) and 1. add 40 nil. sad extract tie I= with 10 ml of Ccq . ~. Heat the solution to distill tie 12 tito the MaOH solution. Q I#3yer. PH~ 16 (Cent’d) moved frm * other fission elementsby dlstlllattontito a NaOH solu- taon.to 12 and NsHWS ie used for the ~uction of 12 b l-. Add 1. 2. of IllIVaNOato caa- plete tie solution (Note 1).@X@” Repeat step ~. Tmsnsfer a Sulmle aa@. Anynpors of~or HItitqcune over Uecau@tint4m NaCH Solutlml. ~. w.

It cannot be used on o.N. SufficientClzgasls addedto the CC&ta X= adefinite yellow color.S. Nony. Ihe chemical yield for I& ~ocedure Is apprcdnmtely @ per cent..S. end tie ndxtwre is pkced h tUremt sudight fm at least 1 hr. N. =Xation fran brcmdne Is afforded In the procedureby re- ducticm with R&OHCHCl to Er.0 d 112e. 9. * A procedure developed (Glendentn. pp 1638 Telluriummetal is fused on a copper *get and ts banbarded with deuterons in a bell Ssr in tie cyclotmm.uding brmine. Vol. and 8. 9.● The poblem of mxqplete interchangeIs avoided In this case. me telJurlum is dissolved b 6N SNOS aud the solutionis dis~ed. Contaminationby tier flasion ativities. is mllected in @. Book 3.h~ . Di. 12.ccntdming the radioactive13.. Jacobson. Vol.Me-.carrier. VO1.N. which does not oxidize Br-.ion. Attheend oftbisperlodthe CQ mtxhu?e is ex&actid with en excess of either NazS3S or Na&OS +33give a solution of tracar iodine free of sig@Ekallt amounts of inactive Iodine cecrrieu’ .m~n !59 procedure describeddrove WS8 obmrved ta give a fast sad apparsm cqplete Interdmnge in the de~ tion of We flsslon mdd%on. !lhedlstlJlate. Hook 3. which exchengesrapidly with 1. and Coryell. PP 1625 by Glendenln and Metcalf (Procedure15). N. fiefion-woduct sources. Ovemtmet end L. 36 .R. since the active iodine Is in a re- dudng medium end is probably Pres-t u 1. evldentily bemuse of ticaqplete tiachange between the tracer Iodine and the carrier iodine.o d I“l. La ~b~ .while the 12 is being -acted. nammm 16 (Cent’d) 3. PP 16429)for use with Irradlabeduranyl nlla-ateIS pre- sauted In N.IOD~ source .scueslon PreviouE n&hods or detamrdrdng flssian-lodne activlHes have been abown to give low and erratic yields. The n&hod is dependent.ontie useof ~ted uranium metal.E. and by the exkaction of G ef%m cnd. PmcEmJm 17 .E. 9. Book 3.dissolved in HCl and NaNOZ to provide caqplete lnter&ange..N. 23 m 11=.7 h I.6 h 1=0.S. vhlch is then washed three thes with distilledwater.E.dation with NaN02. ticl.

E.atitm of the Ioune La be6un. L. Vol.etia~ of18NH2so* md~percemt CrOglna2til ~on.but soon -re Is fimtlling. BalLmtlne.D. ~koff.y) reactia. antire- movIns W mmg by diatluticm. !llue Iml activity. h a mLX- Zeof18NH&04endm per cent~in a2tol~porkLon.S.t2Sble detw period the radlactlms io. me general featuree of this mlbd ~ sugseetedby I. The iodine is s~t. After a eul. afta & reducUon of I& b & by the addltidl of malic acid. ‘Ihe 1~- Ie then reducad to 12 with tic acid aud is ~d frm the flsstcm ~te by distillation. tAle_ Ie placed in a distillationflask equipped with a reflux ccrdeneer. The reduction of We Iodine in tlieHNOS soluthm is not practical because the IVOevelved ties wlti it nm~ of tie io-. The a~atue ccmsiete of the original flack used in 37 . In whl~ state it is not volatile. is oxidized to I& _ * eoluticm Of . An alternatingsmrce of I‘1 is tie HNOS mndaneate . * di8- 1301utia of neutrcm-activatedummlum metal. Ilie malctlon is WzI@ete. S.8-IODIIilI SnnCe . pp1639’ stale tdJJ?JduDlis irradLa*aulti pile neutromtoproduce2@ ‘IeE1 end30 h Te‘m by lhe (n. N.ad frm EIRI=by oxLdlzlng alJ.. Book>. ~1.eizm. mm oxalic acid Should be adaed. ‘me oddauon is parf. end a SUit2bb d9ky (b allow the 30 h T4~n to deq b 1=1). If We Solution is not aeflnitelygreen. tb n3dloaoUve talluri~ *deqt08d IU1.)In this step the tellurlm is Mesolved and tie radioactivei.the active iodine to I&. Iae actual M.N. To this-eadded18NH@04and50 percent ~tia2tolproporMon. end the reaction beonmea vigorom fcm a mlnuta cm nmre. n Eufflcient OXdiC acid has been added. is B~td frcuntie ~m by distlllaticQ into a &ap con~ dll. Mter the solutionhae been allowed to cool ta rca ~Xe. A reaction starts slowly. izradia~ ~- mea@. Is oxi- -ed to IOg-. NaOH. end the mixlmre Is digested on a steam bafh for 1 hr. (A 15-g m req@?es about 100 ml.aout50to@t30ftic acidand Xto75mlof W HsS04 me added.of &f134 and ehout 50 ml of ~ BtiUtiCC1. 9. the SdlltiOn ti Ialrnfrcm a clerk-brown color ti a dark~ color ae the chraaate Is reduced to chrrmdc ion.

W -~ Hiti HZSXJ4SZldtiO -d and redisUJ31ng. end a trap con- tfdningdLIVaQE. dxmt 10N h HNOS is found to cm.lliin H#Oq but iB Shiler to the first aistilhte illthat it is dmut 0. and leBs than O. as measured by titition vitb stendartied NaOH. This distillateis ebout o. by maldng the dl. as determinedby titrationwith standardizedl~. ~ 18 (Cent’d) the dieBolm step. en appreciablefraction of * fission-iodineactlvlty tO- gether with tmces of iron end &rcsuium frcm the stdnless-steel equip- mt . 38 . The progress of dietiJlationcan be observedby placing a direct- reading radlOtd~ =ter under the receiving vessel and obsez%dng the in- creaee in radiation Intensim as tie iodine is distiJled. at-time thetellurlun was ~d frcanthe pile. To date.00IN In reducing agents emd con. Further distillationwilJ-yteld 25 to 30 per cent more of the titsl Iodine. W. lbls firdi distillateIs apprmdmately 0. end the radiochemicalpurity exceeds 99 per cent. About&p cent of the tatal activity can be obQained in tie first 15 a 20 ml of the distillate. 3. fl~ded 75 ~-es h m first Msmte and *out 30 U- curies in Iim second distilhte.followed by 2 days of _. Reccmtry of 1=1 fran lINOS~UtiOll ‘whenneu--actimted Urenlum metal is dissolved k aud the fumes are ccmdms~ tie solution. tie totel * iodine Woduced amounted to ebout 125 miJMcuries.001 N in reducing agentB. however. a receiving weed.- nate solution.buttbis is obtained eloulyand inavolumeof 100 ti200 ml. !Eieyield a tbls second distillationrune dmut 90 percent tiavolmmofebout 20 ml. By correctingfor decay it was frond that.01 M in H@04. T. a condemear.05m b O. Anyvapor that fdlstocondaneein *condenser is bubbled through the EacH -p so that none of tie iodine can escape. the lsrgeet amount of tellurium -t has been used 16 a 50-8 -b= !Ibis50-g Bample at saturation. mly a few railllm of solld ma&lxkl .stiJlati basic with ~ ad kthg to -SS. _ and W. Heduction of the iodbe to tie elemrla Bt2ti and ~CtiOll with ● EU* ‘ m-k: m~t SW* of the ported h aeteu by A. The Soldd materials ueueUy tdal &out 2 * 3 *. l%ie cm be cmcerdrated.

!lJie ~ condensateis placed In a dlsti13ingflask eqyipped wlti a condenserend a receivingvessel. liieHl#& h dia~ed off while lhe hdlne b mdn~ed In ths iodate s-te. T%ismixtuxe ls distilled tithe ~ &scrlbe& drove. and it @mltzxinsonly a feu ~ of Solla mterial . About 80 pea cent of the M activity is thus obtained in a volum of 25 ml. l%e radiochemia91purity is more -99 ~ cent. ~ 18 (Cent’d) CQ Is not Pactlcal.lngSgemts. !Che ml.Illin &@4 and less Iiuano.utlon is . one-to-one E2s04 and 50 ~ cent Ccog sreaddadb2tol proporWon until tie -acerl. ‘he dxture is Man dlstiJledti remove all tJM ~ Unw Wbiti fulms of EM04 qpaar .@N to O. 39 . cooled.oo111 h reduc. ~s dis-ti is shout o. and sbout10 gofoxalic acidsndabcut 2Smlof18N &S04areaddedti re8u- allmm. For easy tidllng.stlc &k dmcamte cola Is obtdned.

J. ~.. Wm. W. Z& llgg (1952).. 4R. L. 5 (1949: mm. Anal.and H. 466. C. @’P~ed ‘or@ c Analysls. ~ ~ (1~). John Wiley end Son6. C!bem.&C.. P. et d. AnS1. Am. Uahl and N. J. J. Gooch and F. S~er. R. D. ~ 31O (U57). l?rog. Rsdloa. Bonner. J. E. SdUUSISeraud D. 8ZIPk@ I. M=. 7K. A. [31 ~.. and Boyd. 13J. Amstiong.. S02. Potratz. l&O (1%4). Cos~ove. 17’D.~ @ (1-). Ch-staj ~ 3~ (1936).. p. W. Moffett. Kunin. REFERENCES lAttebemry. C. New York (1%1). 741 (1953). W. letties et scin. w.ctivity Applied to Chanis~. =1S0. Chem. Si!mQler.. !md G. u A. 2 Bleman. Teige. Assoc. Jerchel. J. A. F. Abs. Sci. No. ‘F. 6 C. ~~ebrmd. Rleanan.~ end S. D. Idmlenbuu. roy. 40 . C&m. Chem. Wickmann. Ewmtlan. ~ 297 (1937). E. ~so?l.26. Office Agr. 4EJ 5a22 (1554). John Wiley and Sons. Nle 8A. 3R. A. Chenn. Anal. =. m~ (X@). p. R. end h~. ~ 1356 (1956). ~. Chem. G. record @em. so. _. Chem.R. Ckbese SC1. ~ 366 (15!33). u K. 293 (l@). me ~d H. Anal. W.

-.. Mmetics. ‘M. tiC. HdssinaQ and D. F. wards and T. Halfmd. m.S. [41fi 257 (1*). A. & 1503 (1*) ‘{R. 1629. N. J. & @7 (1950). Book 3. Gsst. N. Isotapic Exdlange =Cticae and -. ~sm.. 2.. W. IV. 1449 35R.S. Am. p. John ~y and Sons. ~w. =.Glen~. pp~ 237 36L. Chem. 541. Vol.. RadiaAemicd Stidiee: ‘Them6Bia --. 25D. C!hem. 43G. Prestiood.. &c. W. Cottin. xds. p. Kol=. pesti~. N. Dod&n. m. S. a 3.S. 237. n 40 D. E.Mmrds. n mtice-~j ~c.N. ibid. fi. @43. J New York. Brady. J. & 3330 (199) ● ~~m A. R. 9. & 25W (U%)= s 3409. p. 28Q9. R. R. MacKenzie. 3*R. ~ 3233 (1~0). Jr. E.E.. a Med b GhemietrYt O. r&’. 9. No. Ct@l. Gest. 1?. VO1. 9.4(1939). mltndf ma A. *C. ~ ~ (19X). ibid. Ikvles. heel J.. Bmk 1. ~. H. Ikvies. J. Edwards and H. Taube end H. GOOchand H.. Sot. langsdorf and E.SOc. end T. D. New York. Rev. ~taf. ~ 655 (1951). ~ -d A. Burw ead T. ~ 2214 (1936).in tiO&OtfVi_ ~ A. Nuclear wrgy =ea. ~. Cl=h Sot. Z2. R. 15. 3. Phya. Vol. ~ 3216 (1%1) %. K?nnedy. 39 255. Am. An. R. Wabl end N. SOC. pp 237. N. J.N. A.E. Sook 3J pp 1623. rnvies. Cod?. B. Am. E. 164 (VW).J. H. m. _iS. M. M. Sd.s ~ 3@3z ~~ (>939) ● 42Em E. 13KL-C~. 1454 (1951). W. ref.. ‘R. Brookhaw=n =. H. 57: 105 (1940) *R. Hat’l. Chem. 33LG & Gl~-. SePt. Cole. H. Wvault and W. E. Coryell.Sot. ~. and T. Can.N.. L. &em. I&zLes. 2aR. R. C. pp. Conuick and Z. T. Homer. Brady and G. 1%1. Ekmk 1. Chanl. Ohm. H. J. p. Z. 310.H. A. Report CC-%0. ~. & I. Gest and T. Am. Editors.‘A ~~ Of M. et al. J. ~. Gest. ref. M. -U and E. J. L.‘9F. J. E. F@@. 1939. IiLbby. ~. 2@. ‘A.E. Myers end R. u . R. C. Div. 3. J. Am. ~tts and A. CaqpbeU. H. ~S and J. J. Edwaxds. 0’=%=) J= lm. S%lift. H. IMvles. ‘R. N-y and C..

. CcryeU. A.. 9. F“hMle. ibid. D. B. Gest. Glendenln end R.E. Book 2. E.N. -d H. 52lcatcoff. pp lW. pp 1629. Metcelf. Mstcelf’. P.u L. E. C. P. Book 2.E. Feb. Vol. Ed-de.nend R.S. ‘T. Flnkle.N. Glendenin. D. and Susmmen. P.S. HO’Vey. 49 L. FIP~. H.N. E. IHUard. Sefler.N.S. L@tcoff.S. ~. L. AK Tdmkal lnfammlan Scrvtcc Exmmlm OakMd~ T—e 42 . ~. 9. 9. and N. FP =. PP 1449. wiwate ccmmlllc8tion. Coryell. PP 1~. ‘S. E. R. wk 2.. PP lh51. N.R. W&men. GleudenS. @ E. ibid. Brady and G. 1X. Vol.N. R. %. Repat CC-1331. FYnsti. Flnkle.E.1*. and N. Katcoff. W. VO1. J. ~tcm. ‘S. 9.aud C..E. ibid. Book 3. B. B. Mew. Gleudenin. 50T. N. Cempbell. Book 2. N. Dlllard. 47 L.R. B. Vol. NoveY end C. 7.