546 Jl /((54~

C*4

I
II

National Academy of v

Sciences Research Council ,

National

NUCLEAR SCIENCE SERIES

The

Radiochemistry chlorine, Iodine

of Fluorine, Bromine and

COMMITTEE
L. F. CIJRTIti&Ckrzfnnmt National Bureau ofStamlamls

ON

NUCLEAR

SCIENCE

ROBLgY D. EVANS, Vice Chdmurn Maeeaohuae+rts Inetltute ofTeohnol~

J;&-~~ii;-S%&tq _ lW9etht@cg& EIFg@%c Cnrporatlon -..- H. J.C~TIS BrockhavenNational Laboratory SAMUEL EPSTHN Californianetitute Teohnolm I of HERBERT GCkDSTEIN Nuolear3%weloprgentorporation C of mrka H. J. GOMBERG Universiw ofMichigan E. KLEMA IL NorthwesternUnlverslty ROBERT L. PLATZMAN Argonne hIatbtal Laboratory G. (i MANov T~6erlab, Iho. W. WAYNE MEI.NKE Unlverslty ofMichigan A. H.SNELL Oak RidgeNgtional Laboratory E. A. UEHZHG Umlveielty ofWiehlngtOn D. M. VAN PATTER BartolReseamih l%undatton

LIAISON
PAUL C. AEBERSOLD Atomic Energy Cotmglusion J. HOWARD McMILLEN Nattond Soknce Founthttlon

*EMBERS
w. D. ImRY U. S. Air Foroe

WILLIAM E. WRICiRT O&ice of Naval Reaeamh

SUBCOMMITTEE
W. WAYNE MEINKE ,Ckahwtan Unkershy of Michig~ NATHAN @iLLOU NWY Rdlologlcd D&mm GREGORY R. CHOPPLN FlorCdaSf.m Uritvertgg GEORGE A. COWAN Los ~6Jl10S fW2ieIltifiC hhOWOry ARTHUR W. FAIRHALL University ofWad@ton HARMON FINSTON Brookhmen Natlomil Laboratory

ON RAD1OCHEMISTRY
E~L RYDE Unlverdw ofCalifornia Berkeley) ( HAROLD -Y Mound Lahoiatory GEORGE iEDDICOTTE Oak Ridge National Labormory ELLIS P. STEINBERG Argonue National Laboratory PETER C. STEVENSON Unlverfiity C alifomk [Livermore) d LEO YAFFE McGfll University

Laboratory

The Radiochemistry Chlorine, Bromine

of Fluorine, and lodine

By JACOB KLEINBERG

and G. A. COWAN

University of California Los Alamos Smentif?c Laboratory Los Alamos, New Mexico January1960

SEP 131960
PRWERTY

Subcommittee on Radiochemietry National Academy of SciencesNational Research Council

Printed inUSA. Price $0.50. Aveifeble fromthe Office ofTeclmlceLI Services, IWputment ofCommerce, WMMn@cm 25, C. D.

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 collection and distributionof radiochemicalprocedures,the estabMshment of specificationsfor raikLochemlcalJ.y reagents, pure 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 procedures. The Subcommitteehas erdeavrmedto present a series Which will be of maxhmm use to the work% scientistand which contains the latest available IDformatlon. Each monograph 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 notonly to the radiochemistbut alEo to the research worker in other fields such as physics, biochemistryormedictie who wishes to use radiochemicaltechniquesto solve a specific yroblem. W. Wayne Meinke, Chairman Subcommitteeon Radiochemistry

iii

CONTENTS
1. GeulefralReference6 tbe I@logene.

ta m nlorgmlc

End AnaLytlaid ClM51stry

of

Iv.

WJ.ecthm of Radiocbmlcal Rocedums Ercadne, and Iodine.

for ntie,

~j

14

INTRODUCTION
This volume which deals with the radiochemistryof fluorine, chlorine,bromine and iodine 18 one of a seriem of monographs on radiochemiatryof the elements. There is included a review of the nuclear and chemical featurea of particularinterest to the radiochemist,a discussionof problemB of dissolutionof a sample and counting techniques,.and finally, a Collection of
radiochemical procedures for the ele~nte literature. as found in the

The series of mxmgrapti till cover all elemnts for which radiochemical procedures are pertinent. Plans include revision of the monograph periodically as new technique and procedures warrsnt. The reader is therefore encouraged to call to the at~ntion of the author eny published or onpubliehed material on the radiochemistry of fluorine, chlorine, bromine and iodine which might be included in a revised ~rsion of th rnnograph.

vi

The Radiochemistry of Fluorine, Chlorine, Bromine and Iodine

JMMB HIEIIEtEHG AKD G. A. COWM University of CalMbrnia Icm A1.mmq Mienti@3 I@oratory us AL5mos, mew Mexico J~ 1$%0 LGHWZML REFHRlmcHsTo TEE nmRMNIc m
mRasl!RY m 5 HALwms AmUmmAL

W. F. HU.etid,
FyQpW3d ~c

G. E. F. Luudell, H. A. Bright and J. 1. Hoffh5n,

AnalySlEIJad Hdition, John M1OY

and Sone, hC .,

New Yark, 1953, Ch. 47 and h8.

W. M. Iather and J. H. Hildebmnd, l?aferaum Bmk of ~~C

chedstry, *d Hditlon, The MlJ-an Cmipany, 1951, Ch. x. J& Wiley

T. MoeXLer, Inorgani 13M3mislzy,n Advanced Te@Aook, c A

atldSons, hC., New Yak, 1952, Ch. 13.

c (translatedby J. S. H. Remy, Treatise on Inorganl Chenllstxy

AlidtIWSOll) , EIBtier Ptibllu CcmFSW, Amaterdfnn,1x6,

ti . 17. *, Hold

N. V. Sidguick,The Chemical F3xamente and !Iheti ~ Wversity Press, UaMlo?l, 1959, pp. lo$na%l.

F. P. Tcea&dl
Vol. I, J&n

and W. T. HaXL, Aualytlcal Chedslry, gtb Wtiorl, =d Scms, ~C ., New York, 1937, PP. 2*323.

~by

C. J. Redden, Aualytlcal Chedalxy of the Manhattan Pro@2t, Cha. 5 and 7, M&raw

HiJl Hook Co., W

York, 1S0.

II. TABLEOF

IwItm3* F FImRllm, C6mFmfE, O

~JUU2101UHE

-70

Bec

P+

r#(ap). Om(d,n) 01e(P,7) P3(7,2U)

-Uomin

13+9ti { Ec3$

ole(a,pi)
O(p,n) Fm(n,2n) Fm(7,n)
~=(a,a) end Otherm

stab 10.7 sec

(Cblmdence 1*) r

Eeidlrel *(d,P) ~=(n~y) NP(n,cz)

-0.3 eec

P+

#2(p,n)

a - 10-~ -2.4 nec

B+ &( d,n)

~(p,n) c19*(7,2n) clss(P,Pn)

Mal@ltar cl=#2(qn) ~(d,n) ma Cl==

*96 ,IAble

ti-

(dnmdence 75.5$) B- *.3$ { EC(K) lofi

NatuBKL Cl=(n,7) Clge(d,p) Heialrel Cls7(d,p) C197(n,7) end 0-s

4.4 Xlflw

@17 ~3e

stable (ebundence - 24.%) 37 nlin W

II.

TABIEm ~aFELummE,
BRcMIXEMD I~IEE (Contld)

clmmmE,

Ieotope
pJse

Half IAfa
-lhr

mofrlew

Method of Prqurauml

P~

A ( 7,P) Fe, Co, Cu, Ae A@(n,p)

1.4 Iuin

B-

-40dn

P+
{ EC
br

mqc=,3n)

-1.6

B+
{ EC

Cd=(c=,a)

se7q tl,n)
se74(P,7)

17br

B+

A2=(u,%) *n(PA

57br

L
=

9%; 9%;

P+ 11 P+%

At375(a,2n) *74( a,p)

Sem(d,n) 6.4 min IT Ae=(a,n) S==( d,p ) 9em(p,n) -~(78n) Brw(n,2n)

<6min
~7a stale

P+ (L&name - XI.*) IT

Ikghtar Br7Netui-al S&(d,ti) *n( a,p) Se=(p,n) m=(n,7) end o121ers

B+@

-4.3

llr

#30

-181rdn

p94
{ 13+-3$

*m(p8n) -79(%7) *=( dsp)

(ye-z%
U-

Rr%7,n) Bre1(n,2n) N@Ulw31

#1

Staue

(dnlndlwloe - 49.%)

Imtope

Half Life

Type of Ikay

Meaod of- ep2uatiml R

~82

36hr

P-

S+%,n) Se=(d,2n) H%,7)

and Oti

#9

-2.4 hr

P-

-=(

d,n)

IaP( 7,a) Wy:im 2 !% H6, m, u, m

Blssilm m, u-,
---#.4 -321uin

6-

F#7( n,tZ)

SE@J.-flaaicmm, Rklsiaa m, D3ugh* u Se-

3.0 lldn #7 -Baec

PP{ fnl(P-

Ilssiwl u E%3sion u 2$) Fassion u

RP( ?#gill) or PdylT14,3n) wm

EIP
Ills

15.5 Bec
-lgnlln

P+

~121

-2br

P+
P+
--

sb=(aJkrl) w-

~122

-hldn

Sb=1(a,3n) Tel=(p,n) -=2

*u~(a,2n) mU@l* X&=

+3

13.0 k

&4

-4

day

Y
4

- 7Q%

*U1(a,n)

P+ - 3Q%

m=S(a,3n)
TeE4(p,n) and others

p5

-60&y

EC

m-(a,a)
Teu4(tl,n)
~-flBEiOn DsU@ItelrXel= M

~126

-13

day

Ec 55$ 0- 44* f& -~%

Sb=(a,n) Te=(d,n) Te12e(p,n) IL-(n,2n)

and O-B
1127 1128 s-le (abmdame 10@)

Ndillral I1=(n, y) Te=qtL,2n) Tel=(p,n)

-25*

p-q

pe
~lso

1.7 x lo~ year -12*5 hr

PP-

~BSiOn

Te=O( d,2n)
El!#(p,n)

11=(n,7) Oe=g(n,~) T+(d,n) a-fission

mBSi~

m,

Th, U, ~,

PU

-*132

~=1

-2.3 b

P-

Spa31-flBeionu
Flsslonm, u, u==

D311@lter!rd= -p3 -Z?lbr

P-

w-fission Mssim -u, Pu ~=s

R), u

ps4

-52.5

hr

P-

~-fiBSiOn FISsim -* m,

U u, u=, Pu

~=4

n.

TNEiIEQFn3maf%wm~,~, BRQ41HEAl!U)I_ [Centd)

Isotope ps

Half Life

Typbof Ibcay

WuMd

of Preparation

-6.7

hr

Spall-fleeim U FiEsicQ m, Daugb* m= u, Pu

~197

-22aec

F { P-n(~ *)

FISslcm u, Pu

pe p8

5.9 Bec
2.7 aec

r Bliatad which faU

Fission

u, en-tar

C&= Ba=

~salon U, encehx
in categmiea A md B ti

q &ae (hly
ale ~

Ieotopa

Iaotqea, D. ~, Phyalce, ~

J. M. HolJ.andar aud (3.To Ekklmrg, No. 2, Part n, s 195$.

Rsview of ~

1. GeQaral PmPartiea ~, Cmorine, branina, Ed

ofwme Eeloewe
bdine, With w cqpksl

raepmtive atmi.c
m halogcma. ~ * ddffler-

rnmbera 9, 17, 35 and 53, along with *-*, !Qmae el.emeute oaaesa m p differsm@mdly in its chemistry _

:~s vakmca shell cmflgwaticm. the oi2mr helngem. lb -y

ence cbaerved are largely attributablem small size, and Inebility to ~temare valence shell.

high el.ectawmgativity,

thlxleighteleclmme intllm

diatmic natureof tbs elemntary molecules, in the relatively amountsof -gy

tion, kcal/ble:

Mimge fi we ~

reqdmd F=*

to dissociate*se

mleculna

(heat of dissocia-

* 3; clIzT57.2; 13F~45.4; G535.5), (F) &

-a

values for the elec+mm affinitiesof tie atma 81.5; ~ 74.2 kceL/g at.cm). W

* 3; CL 86.5; BF, cafigumtia la cm-

meat tendency for the hal.ogene reach o*t to Oovaleaoe of mm. Uleu&alrhalcgem,

Feflectid intbeebundanceo fhdlde pkfi-~~~ti ahwa

aaltaand intllalarge~of where mtioe

I?m IhOrim, thi.a

i6tlleolllycovalenceFerndtted+fm

shared pedre. As wuld be expectad, iodine, the lergest of t& halogem, cen folm the greatest mnmer of mvlslsntbculds. m mti canpcamdswlth-tals the halogem areneceessmilylna which give rise to huge negative me cations of W ionic W. oxldatim stste. With actiws m-

charge, i.g., 130dllml, Calcim, tbls oxldatlcm slate iElan

Ou the other hemd, with metels, emn active CUES eucb as

barylMum and alumimm, which are wtantlal sowrces of ions of relatively

M@

charge dsnsity, the bands between halogen, particularlychlorim, lodMe, and mew are ~tly c~t in ~tar. with

braolne m a meW mf my
Ineltal.

exhibitinga warlety of oxidation abates, the covalent -acter one hIsMde type Imresaes with imreaslng oSdatdon state of the This *end is genemUy ao~ed by increasingvolatilityas solvents (e.g., canpsre

well as increeelngmlubility in ncm-polax or~c FSCIS and F@c&). D union with other non-me-, fluorlqe, *

met

el.eclmcmegatlve eitk? ekXbOdectimegatlvlty

dament known, invariably ay be qded m

es being In a negative oxidation

ss tibiting

state. !lheother hak@sus BR3Ybe C~idSr*

negative m electropositive charactm

depending upau ~

ofti~ttowblcb wbicb -Ins,

they me

Joined. The most c~

Sixuone

In

brauln% end Iodine exblbit positive ofidatlon s-tes m

It is ?mtewW

that iodine, tie least ele~egative

halogen, is

ectually capable of f&uing tie cationtc spcicles 1+. ~s ~ -stAble entity csa be considerablys-lized by co&dlnation with such m-c bases as PYI%UJN2. Thus Sudl cqguunds ti[1 Py21~ ~qe~
and [I PY21

~04, emong others, have km

nla21mlch Cbangee In cnlmatton sta* are frequmltlyof Bl&m?icmce 2s In radlochmlcal procedures for the anelysis of chlorine,brmdne and iodine, tbe ~~tlal relationebi~ wblch exist amcmg the mious oxidation

states of tieee ed.ments are shown on page 8.

Acidic Solutiana :

Basic *lutims:

- 0.09 ,

- 0.49

2.

maervatime

m E@ecies of ~cance

in the

Analytical Qlemis* ~
view of

of mlogens
d el~~y

the fact that the f~tion

brmine end

iodllle of lmpmtame is terdnatim desmibed.

in a nmiber of mthode for the analytical *properties of these sdbstanceeare

of these elements, sAs is evident ~

the PtesJUal data citad a&ve, bti agents. Br%mine 1s rathm 100 g of water at 20; the mlu-

bramine end iodine are fWrly strong oxhliz~ mluble in water, 3.55 g dissolving h bili~

of iodine is Dnlchsmaller (O.% g per liter of solutim at 25) . re-

Fm both elszmnts, soluti6n in water is accompaniedby the mdn action &+ For brmdne, tie H~=H++X-+HXO.

equKUhrium constant

for this reaction ii35 x 10a; The re-

for

Icdd.ne, x 10-=. 3

(For chlmfne, the constant is 4 x 104.

ftm

action IS of no significance OXYWI =d in wem OSae fim acid.) In cold tits

fluorine, wblch vigmously liberates famed;

Uqtid water with the furmation of hydrofluorlc albllne solutionshypdmllte salts ae

concenixatedalka13ne solutions the hypobaliti icm dis~m. miscible with ccmion organic solvents Iodine , cblmf m, In Summtic solvents

ates to halati (X%-) and halide ions. wis ccqletdy Is genertiy appreciablysoluble in organic solvents. Ih solvents exblbiting no dcmor characteristics, e.g., carbon ~d? carbon tetrachloride,the solutions sre violet in C-.
solvents SUCh as

benzene end tdllene the soluticmeare red. b

as

which may be regsuded

typical Lewis bases (e.g., etier, pyridine],

iodine Is most soluble and gives brown solutions. There is little dmbt that in both the red end brown solutims solvaticm of tie Idine occurs. An ~t characteristicof elementaryicdine Is its abiJSty to of which the tricmitdne with iodide IOU to form FE31yiodide icms, ~, t

iodide ion, ~-, is tie most stable. other polyiodiae ions which have been identifiedare ~-, I; and Q-. !lhe mat are known, but they m the tzichlorideim much less s-le s~le polyiodide salts are

formed with large catbns, e.g., Cs+, gpaternaryanmxmium Ions. !lkibrauidee than triiodides. he existence of

in solution has been definitelyeti-llshed, but no ion

sbsble solld salts of this anion have been isolated. !lhe=flucmi* is unknown. The trend in stabillty of the tl%baliae lone b tion is shown by the values for &e &+ w r.&~ equilibriumconstantifor &e

Bolureactian,

Iodine the constit at 25 is 725; far brmine 17.8;and for cbbrine

.,

10-= .
9

Most of the analytical determinationsfor the halogens involve precipitationreactions of the halide ions. Fluoriae may be precipitated as the calcium salt (Ksp 18: 3.4 x 10-1~) or as lead chloroflwride

FbFaPbC12 ). Precipitationof the calcium salt is not entirely satisfactory even when the solution to be tested contains appreci&blesmounts of fluoride, low results ccmunonly eing obtained. Precipitationof lead b chlorofluorideis usually carried out in the PH range 3.6 - 5.6; indirectlyfrom titration of the chloride. Chloride,brcxuide, iodide can be determinedby precipitationwith or silver ion (Ksp 25: *c1 filver
j @r 7.7 x 10-=; MI ~.5 x lo-le. fluoride exhibits a volubilityof 181.5g per 100 g of water at 10 10

the pre-

cipitate can be weighed as such, or the fluroine content can be determined

1.56 x

about 200.) The analyticalprocedure maybe a gravimetricone m? a titration. Iodide may be precipitatedaud determhed as the ~di~( salt. AS a matter of fact, precipitationby means of -~um( II) II)

chloride frcuu slightly acidic solution is a satisfactorymethodl a for the separationof iodide separating iodide
from

chloride and bromide. A more cannon way of

with the other halides

from

solution

is by the addition

of nitrous acid, which converts iodide to free iodine and is without effect on the remaininghalides. Sep~ation of bromide from chloride can

be accomplishedby oxidation of the fozmer to elementarybrcanine by potassium permanganatein acetic acid solution. It can also be affected from the silver salts; silver bromide is essentiallyinsoluble in an aqueous solution of ammonium carbonate,whereas tie chloride soluble. is 3. Ion Exchmge Separations

Ion exchange has been used infrequentlyfor separationof the halogens from each other, probably because the well known conversionto the free element followed by extraction into au organic solmt lished. An ion exchange separationof the halide ions was demonstratedearly . in the history of modern exchmge materials.A he mmnonium salts of fluoride, chloride,brcmide, aud iodide were absorbed on Dowex-2 (100200 mesh) in the nitrate form. Elution was performed at room temperature with ~ soditun nitrate at a PH of 10.4. Fluoride comes off first. Peak is so welL estab-

to valley ratios of 100 to 600 between F-, Cl-, Br-, and 1- were obtained indicatinggood sepsxation. A simila separationhas been used for determining Cl and Br in mixtures of the two by absorption on a strong base anion resin, XE 67 supplied by Rohm and k3S
nonionic Company. The

eluting agent was O.& NaNOS containinga

wetting agent. A further applicationof this method has been

lo

ueed for the malytical egtia

~, Br, and I a

3 Ibwm l-~0 resin,

a Blamllg w=

the elu~

agent -

O.% NaNOS. hcdllar heJl& mparatlon m

haae reein used O.% NaNDs to elute Cl-. lMeelumt cmcem&atlon then ticreaeed to 2g to accelez%ate the elutlan of Br- end 1-.4 A =thod for sg~ *cmaw*y 1 to 9 ratio ~~ ut Cl-, ~-

and 1- makns wae of pmdpitatlm endahmlnalna 15minutiB. end m-. me

Blx41re of lone is pawed

.5 ACOIUmU lmImde UfIlgt?OSOr4X)a

of mipltent

to flllur.

me

Coluume and &ve@?3d h halldee have

lneunMghtfor5to

of i&ntificaticm is 8 7 for I- end M

baai squated m ~

ta 15 y ~m w~ted

witi AS@X34 .6 for tile as much 100-200 Ef21,

-w

clmcm3tography =a

activatluaanalyels have bean ccabm

aetemillationof s, Br, end cl In Orgmlc Ccqx!unde .7

Fhoride hae

been quantlktivd.y sqaz?atedfmm

500 t-

@m@mrue meh, -left NaOH.

on a Dowex l-~0 colmnn in the hydroxide form.8 m lnuhydroxldefonn.

slzcmg baee resin waE cycled -e -

thee witi 3~ NaOH end ~

elution W8e performed with O.= fra the alkB-

~uoride heE bm

s-ted

frcm dumlnum by el&g !lheelmlnm

llne form of a strong base red.n. g flret. Ratee of u@Qm

ccmsm off the column

end en affinity semiee for several mlcme Incl.udlng

ZtiCODiUUl OXIde.m The

the h811deB have beau detemninedfor hydroue

affhlty s-es deixmdned with

O.lLJ Eolutlane is: Cl-, N& > Br-, 1-, exchangerw ueed to remove tige quenti-

m:

>> so;. A synthetic inorgmic la

tlea of unwanted F1e activity that fom@d ee a by-product in a c-m U kaalation . The aolutim In concentratedHCl wea Psed through an A12~ COaud more them ~ 4.
Extraction

of IIM fluoride wae *sorbed. se~ticme halogen into an Cmgmic

solvent Wtcactllnl

of the free elmt

form of *

solvant (C~,CE~ ) after uee of * proper oxldlzing agent w lcmg , been a favorad separationmethod for Cl, Br, end I. Sevwral detailed ~lee are @van in tie section on procedures.
Becauee many

organic ca59unde d

the halogms can be pewed, very ccmmunlywad

!Jhe

re SzllErdchalme ex&action ayecreeee the speclflc activity of

a

halogen.

have b12

to ti-

recoil energy of the

Incident nuclear particle breake tie H carbcm alxm. Extraction of *

between 12M3halogen end the

orgenlc solution with water then yielde Br and I aad & dis-

a high epciflc activity of the hallde. Heution activationfolluwed by exbacticm d

IL

tilJJ3tial ofclhasbeenusedae eaxnlnts Ofmimd TWm@auyl

frm

smanalytical mlmlodtoae~

u halldee.
stlbmlum sulfate W been used to ertrect fluoride meUmd Is more useful fm ~ 0.125 brought end concenof

a aolutlcm in ~-~

@eId. h

tratlcm purposes Ibn es a highly specific sepJu%stlcm.A &w HzS04 me added to the solutlon cmtddng up to 5 mg ti F-. and t&e ~

millimole of tetrt@auyl BtibOUi~ sulfate la -d to 19 ml. the -C

It is shakan uilh thee Successive5 nil~CQS layer LB evaporatedaud wei@d. 5. Jxstiuatlal aemtlcme

Of Q

Distillatitm .1pltatlaa.1-J7

of fluarine as hydrofluoellicicacid is ctxmol&yused ions before a titration or pre-

for sepm3tlng fluoride frcm In-faring

Chlorine,branlne, and Iodine csn be se~ted

tion

by Selectim odda-

and dls~tion

of the eleamt.

Iodine is axidizti by additla of

HaN02 h XMQ h

dilute H2130~. Ermine cau be mddlzed ulth telluric acid,19 M ~tic acid, m KH(I~)2 in dilute titiC acid. CMorine can
of ancen~ted

be oxldl.sed y addition b

EUOS.

6.

&change RWWticm

A prime requisite in radlochemiualanalyticalprocedures Is the cm@ete

exchsuwe betieen the radioactive species being determinedaud carrier. Obselrlmtionan edlauge between various halngen entities b o

aqueous Ilbedllml ~ed are

hlou . in solutla Is ccaqplete Three plausible mech-

Exchange betweeu free halogen and haldde Im uithinm~ time of mhlng and se~tion.

~ aulms far excbmge have been postulated. ehoun below: (1) &
(2)

!Iheee Involve the equlllbrla

+ X*- = &

(X = cl, Br, I)

. lg-z xlolo

&+oE-=Hxo+r

l&=4

(3) x2+Q=m+d+xh Vleu of Vle M@

K3=4X104 dis-

=Cbauge velocity It is extremly Mfficult b

tinguiti=between these three mechenimne. However, there Is sevidence that exchange occurs by meuhanlm (1), that is, dmougb whallde ion fonnatlon. Tracer qua 22 silver branide. brmllne exchanges rapidly Wltb freshly precipitated

Exchangebetweeu elsmautery chlorine end chlorate ion in acidic

J2

solution slow

.%amr cl-e

bow at roan tfmwralame and elevated ~lamee chlorbe

is exbmsly of

mm
a

cblorlde

ion exchange witA

percbloric

ion either In alkalhe

acidic solutian.* a-

chbrlne activitybetween ~chlorlte and cblorlte ions In besic eolu* Hxdmnge betseen chlorate Ion and pwrchlaraw Ion ticluis very slow. does not ocmr at ror acidic soluticm. The ~ti qmoue be_ature, or eveu at 9, in neu-, basic

25
silver brmlde and distributionOP activity It has bem rmdmthat mti

of exchengebetween freshly foti

brcsnide Ian is very =pid, T attdned wltbin a few seconds.

of exchengebetween bhe
given by tie ~eesion

end brcmate ion In aeidlc aqueous solutica is

R u k[I&2]m[~-]n[H+]p W* k = 0.023 mole-2%.2%r-z, m = 0.3 * 0.05, n = 1.7 * 0.05, end to the system:

p - 1.1 t 0.05. It is Poposed tJmt the following set of reactkme is appll@le

HBr+HBrOa2Hmm

HHrO+HBr

=Hr2+H#

In the nsdiochmd.cal determinationof brcaulne activitiesin fission

products,rapid exchauge can be ensured by the addition of b~ti 2% to the eaqple and its reduction b bradde Ion. ~odate

csrrler

The =cbange in acldlc solution of elemm2taryIodine wltb iodate or (IO:) Icm, and of Iodati witi perlodate inlacidlc or alkalbe ~ q~~y obsmte law for the Solution is s-. $3 to be

iodine-h-dateexchange reaction hea been de~d

R = (~)06(H+)18(I& )08[k(IO:)+ k(X-)]r in wbicb X- may be PCblorate, tiaueitlon Stites. At 250, k

hr-l

nltrab!s sulfate icm, ad or

r is the

appropriatefunction of tie activity coefficientsof tie reactate -d has the value 7.40 * 0.25 l.s= mole-=
~~-9.2 & -1

end kt Is appr~tely

0.15 1.3.2

for x- =

clo4.

The activationenergy Is about 20 kcal.. mols-~. The exchange reaction has bm shown to occur by tie e mechenlem as the Iodide-lodatereaction; the rete law for the latter reaction at low iodide ion concentration is given by the ~eesion -d(I&)/dt . (l-)( I&)( H+)s[ks(I&) + &x-)]r where at 25 ~ is (5.7 t 1.3) x loe 1.5 ml-e= sec-L8 =d & for X- =

clo~

tbut 1.1 x MY l.s mole+ in mlutime =~OS @=

see-z. =diee

of the iodine-lodati alla iwiag

exchange mtitnl U@ (@)/(l%-)

of ametant hlic s~ * ==-:

R . k(f)(~-)(H+)g Ihls is entirely cmeistent witi 12M previous rate qpressicm noted Iamedlatew abm radio-cd . aualyma for iodine, Capl.ete ~ can be db~ of Iadlo-

iodlne with carrier ~eunmbly ~dlorits ~ ion In b!MiC

by the addition of the to priodate, e.g., by to Iodib by

latter CM iodide la and eubaequentcdda~

33

eoluticm, fo.lloved ~ctlon by

sdutifXh

of biaultlta in eCidiC

Iv.

coLucTIoH

RADI~cAL

PRcmmms

Fa

FLm.RmE,

C%LORINE, BRumrB,

ARD IODIHE

~1-FL~ Source - A. Tirkevloh, ~wuld ~vide unpublishedLes Almoe wurk In 1955

vork on a radiochmicel procedure for fluorlw Which a very high dBccmtadnation facti fra fiesion productE,

nchibly brmdne aud iodine, we begun by Turkavich In 1!35. !the gamcedure vae not completelydevelopedbut ie m-eeen= ~tit for a modified procedure. 1. It w ~s_vaecon-ed on2 gEtaoforganlc flberfilter~. here ae a starting

brcught Into a soluble fcma by fueicin in a I% cnacible with 22 sue I@Qgti-ch5t

H20).

ofanh@mua

iof

cmmierhad

beenadded(2.~gma ~t&emaee vae charred

KF2Eb0 inloomlof

The covered I% cruciblevaa ~

serted Inti a 500C oven. After 30minat~C, black. Ituaethen -1.e~~ -* hot watar. 2. l!he va~ fa placed lnenovm s~ tiutes.

at&30C endthecarbcmateuea lhecooled melt wee diasolw3d In

in the pmmnce of brm@enol

soluticm w

neulxallzed

blue with ~

BHOS. !Jheeolutim muet not be pemitted to becane acidic

but ehmld remain sli@tly baeiC . TIM@vea tJaemeQuetedvlth HwXItia fd.ntbluelndlcator colcm, then2ml of ~H~, 5 ~Of _(~&)2 m SdUtiCm, end5 @@ s~= auddlgeeted acetatein eolutim were added; the mixhzre ~uaeetlrred for one-halfhour to PrecipitatePbC1.F. 3. !Qw precipi~teof PbU

wee diesel.ved in 20 ml hot water ccmAgNOewae tbenaddedtiell@t excees.

~afew~d-cHNO~

14

1 (Centd)

lhewec@itete ofAgClwmtiexcees of HCl wee added tO ~Wipit&MI

Cenmles off.

offandb
exoees sfl-

the Sqpmeix?)a eMgbt . JheAgc!llwegd.n

WC8 collectidIn 45 mln in a flask ccmt4dniD& initi~,

30 m Of wa~r

1.

Itm_sted*t&firet

step~fusiontidbeend A@

distillaticmof -e.
scevmging stiFs end a

!IWS ehould then be followed by PbCIF seccmd distillationof HaSiFe. lHneUy ae lWIF, h which fom It -d

the be

flumine ehmld be T&Apitated wel.gbed and ccamted.

PRoCEllURH2-CHUXUm 2ource - u. w. Kinke, repcz% AECDJ2738,PP. 22. AUE. 1949 Elmmt

Wget

sexratd
mterial:

Chlorhe
Copper

hCdlX@3

of Purificatial:lF by: Batzel sap%: 30 uhutee s~

Of

bbdt: All m

The

fm

Yield

Equigment require&

Procedure:

(1) Dissolve tbe ~ m Concen+ratidma Conb?dning 5 mg of W.mane carrier (l-2 ml ccmcemlmatedHNQ9 for 0.1-0.3~eme
copper fou) . (2) msw
water, the alinto a Cenlz?lfuge tube containing2 cc of

2-3 dropsof conceu+mtidHHOS, and ficient

AgN% to

precipitate the chlorine ee AgC1.

~ (3) (4) Eeat allmst te bou, with 3 cc of m_m. DiBsolve *Agclin3ccof5

back

2 (Contld) cau&lfuge the precipitateend wash gMH&3and addadropofholam. Add

~rs

frcm stid!u% 10 m@l

niizYAtAs Or SUEEAtAS)

eolne, far Cu, Hi, Co, ZrI, wlti 2 cc of 5 g HE@. w

w(addas

Isndthsn dd2dropsofo.5g precipitate sad wash. cen&ifuge, and

(5)

Cenb5fuge and wash the peclpi-ta W W

wash to the supemate end add excees _

(6) (7)

excess Iodh%s (5 drops of 0.5 ~ WNOS). Oen&Muge and wash as before saving the ~te acid with HHOg to ~cipltati the A@,

Wke

wash the precipitatetwice with 3 ml portions of 2 ~ ~. mcipltite CJ3n plated directly or dissolved h be N&m

The allaan

allquot taken. ~ka

of

= may

appreci~le amcunt of mdrive the chlorine

is to be diesolved the kt
into

reactifm

mrrier

the receiving

vessel

beof

fore the coppar Is ccqpletelydissolved. If this OC_S ~carrlera8chlorlde CIB b SO~ti~ W = tithe water intherecedver ~tid 2.5 W to tie ~

add 2.5 ~

end after the ScdU~_ aUd by of ~-

dietil as s~ted shove. In case brcmine _ ~er, -we S~fiCQ o.5 M ~

is pres=t it may be r~ q

m% ~fOIS PeciPi~~% ~

5%

0.25 grams of smmnium pereulfate end beillng, hhue odiizing the

SOhltiOfl should then be reduced with

to Br= end VOlatUlzX.

h@raztie end the chlcdne peclpitated as A@@. PRXEmRE3 CELOHmE

Source - W. H. Burgue, report l&1721, 2nd Ed., cl-l, Azg. 1X 1.

Inthedeterdna

Introduction of fission products,

tion

of chlorlne In the ~sence

considerabledecent.minaticmIs achievedby ferric hydroxide scavenging aud by precipitationof eilver iodide ficm ammoniacalmdb.m. tion of siJver chloride in tie presace of Versm* Pmclpita-

is fhn eu@oyed,

prlmaEUy to remove chlorine fraa alkallne esa-th metal ions, but elso to se~te C~~ti~j thie ~t frcan many oactivities. aud the ~ additiaual aErcamved se silver ~mide iS fo~d

q Versene (2erew0ti
~etitmcetic

C3N?mdcal Co.) is the dlsodium salt of etiyleuas~le soluble chelates with iae.

acid. V~sane forma ~

a large number of me=c

ti

M=

with COnCen&ated Sulfurlc acid. chlorine IS finally ~ecipitited as the mm-Y (I) cmpound, in which form it is -tide by --t cmlited. TM chedcal yield is about 7% and a single armlysis can be

perfomed in two and one-halfhours.

2.

R-

te

cl- Ion

carrier:

10

lug

cl-/ml.

(Ivacl used * primary ~

Stmlaara)
~ ~1-ute ~)

1- Ion c%rrler: 10 mg I-/ml. (added as I(Iin H@) Fe carrier: 10 mg Fe/ml. (added as Fe(NQ3)So6H@ ENOS: cone. aolutian

HCHO: 37% w~ RE#H: m: -:

H&@Q9)2:

Cone. 10hJ
O.ly O.lg

solution h

ailuta HNQs

KN02: solid
Versene :

aisoaiuul Salt (Smalyticalreagent grade, Hersworlil C31emical co.)+ aquecua solution.

Ca

C2H@H:

absolute

Centrifuge

wdJu

~OCk for holdlng Cemlzafugelalbe8 Forceps hbun~

PipetB :

Plates
asBorted 8izea

Wash bottle

2, 60 funnels (two per ssmple) Ground-off~SCh F%lter ~ya Filter fwks 125+ul 13epsmAoryfunnels (one per ample) 50-ml baakem (one per emqple) 8130 (seP SSVIPM) 40-ml conical centrifugetubes: ~ex No. h-oW&ifunnels: Ccors 000A (one per mu@e (ane w ssmple) )

fllx paw (9 an) No. 42 Whahan filtercircles: 7/8 diameter-weighed

stirring rods special still (~ ~ next page) 17

4. Procedure g.
EaCi Carrie.

To the Soluticsl Conixdning radioacum

conical ceutiifuge ~, men add

Cblmine

end flssia

products in a M)*

add 1.00 ml of s~d

4-6 drops of Fe carrier aud Preciplate Fe(m)s

excess clion b of -C. a clm HE@. CentrifU@, tube, end &auBfer discard cautrifuge

by the

addition of a s-t
con12siniw (Ho*

supernate

the precipitate

1). add5mlofconc. ligI by * lqH#alld4aropsof addition of a slight ~e bY heating, Cenqe, and discard the preRwcipi-te

m K( carrier

mtheeWernati solution.

of o-% -% solu~~. ~ti ~fer the SU_tS ti a dean Cipikti . Sw 3.

tie pre~pi~te
C=tiifU@ tube,

To the euPernata a&sin add4 dropsof ~carrierand~ tie previous step. However, tbie time filter ~pr (9 a) in a2-,

a AgI by-product precipitateas b

filter the eupernatethrcmgh No. 40Uha~

60fUnnel toeneure ccm@ete removal of AgI. To the filtrate add 5 ml of ~ Versene solution and slowly &&l& acidify uitA cmc. HN09 ti preclpitdxsAgC1. Boil to coagulata tie ~ec@Itate, cemtifbge, and wash the A@ 2 drope C~C. HNDs. Discard tb Of ~. 5 ml of en ~ Dissolve tie &Cl
Vereene soluticm,
~OS.

viti 3040 ml of H.@ containing

supernateaud whin$e. add @ll

precipitatein 3 ml of cam. ~OH,

dilute to 30 ml, and mpreclpi~ta

by ills addition of ~C. in tbe pl!vloue step.

2oiltoccms@ate

*AgCl

and vaehae

Dissolve tdle A@ in 40 drops of Cmc. NH@, add 15 ml of - H@, 10 drops of l% SCCH, and 10 &OpS Of 37$ H~. Heat to boildng to Coa8ulatitie metaUlc Ag precipitate. Addk&q?aof ~ve a & precipitate. ~ter both @ O.~~and tOf@lar

~CipititSS

~ No. ~ mflle pa= h a 2; @o flltrata in a 125 ml Hlemsyer flask. ~. 2mlofthe Acidify the RU-ta b UiUl -C.

funnel, collectingtie

Hmg, add an adaiumlal Cool audaddhdropeof

acid, audheatlmboillng

(Nota 2).

KI cexrier solution. -far of Q aud a feu qtab

a 125 ml eepsratmyfunuel, add 50 ml into *Qlayerti hct

of KN02. Ikdmctb layer ~

discard. Add three separate additional lo+nl portions of Q, 12.,and discerd tie Q ~-~-ueoue e transfer to a ~-ml cen~ HO= icm. Add 4 drO&ef ~ o each ~tdcm. W m 2-3 CC Of -C.

~, excess
-C.

tube, and heat ta boiling ti ~

tier

=d

prSCipitfhS

_(~)s

Wi*

I-9

mxxmm
Nqcai. can-e, step9.

3 (Centd)
tube,

Im3n2feir the eupernata to a clean centrifuge

and discard the ~cipltate.

Agdnadd 4d10mof Fetiermd~m step.
to precl@-

am(m)=

scavenger peclpikte E3LE

t.aw A@.

as in the pretioua

To the C1--ccatdnbg

Supanate add O.lg AgNos

Csdrlfuge end wash the precipitateas in Step 4.

mssdve the Agcl preclpi-te tit-oa epec~ In 2 ml of Cone. NH@I. dlh~

step U.

Wash with seveml

ml of H@

flask (see dlagmm -t of

of titiple still). Bubble air tbrou@ the solution te ~ the NH&I.

Cautiouslyadd 6 ml of COllC H2S04 (~Oti 3) and heat until all . overlnta a50mlb_ containlng20ml cKU.

the HClhaadlstilled

Predpitate H&C12 frm the solutla of HC1 dls~te w (alter addins 1-2 ml of cone. HN%) by the dropwise addition of O.%
m32(m3)2 mlutlono

Wash the preclpl~ti with H@

after filtering m

a -d

NO. 42 whatzman filter circle, 7/8 dimetir, using the stendard and dry In an oven for weigh, mount, and count (Nota 4). Notee 1. If tie radiocblorineis orl&LneUy In a form otAan Cl- ion

cblmney technique. Wash with absolute -OH

20 mimlte8 at UOJ .
cool,

or C12, ~

mast be taken to reduce it to one of these foma before

be@nuing the procedure. Otherwise the =diocblorlne may be lost as a result of Its fdlure to exchange with Cl- carrier. The 123M volume in Step 1 should not =ceed 20 ml. 2. Hoillmg is necee~ voktile HCHO. 3. Atitiou of cone. H.2S04 ~ecipi-tis tAmugh the solution. A@l. distwtlon at Us ab remove most of tie

continuebubbling * 4. H@12

ie used as tie cmpoun d nmunted in preference ta A@

ie because it does not form agglanerates as does AgC1. PbC!12 too soluble and therefore not suitable. For counting 4 x l& y Clse, a self-absq-

tian curve should be constructedand correctionsapplied for a 0.72 Mev 13-.

20

PmcEWHB4 BmmE SCnmce- w. w. Meinke, report AECD-2738,pp. 95. Aug. 1949 Elemsnt t3epmate& Tergetm~: Type of bbdt: ~t Madne -lg Bllwst21 all paridcles Procadureby: Goe~

Time fcm mspn. 1-2 hrs. Equimt Ieqlllrak cmlmfwm-,ti~

Eleld: De-

-w of ~flcatia: Spalbtion -Cta lhcontamlnatiou f. Br. - 1~ frcm fiBBIOn end

Advan~s

: Good yield of x

Procedure: (1)
Toallquot of~soln oft=@,

addlOmg
o.lglw32,

Br-end I-, m&e

and er&act

l~m

HNOg, addafew&qsof

12

into equal vol Q. (2) Addequalvol CC4to aquecnm @22eand addO.l~l$MnO* drop-

wise until color persists. Make fivw _aoUm

of Er2.

llJHK)g containiq FMu04. (3) Ccmblne c!cqhyerea ndwaehvith A&ilOml&Oaud O.lg H~ &6pwise until both _scme colaless. (4) Mskelgin add fewdrqa Weah aq layer wI* CC~. & 10ml

Hf@l, add- 10mg I-, wamafewtitom@dlse O.l~EaHOa and extract 12 flwetlmeswlth

-. Re~t KMn04 oxidation and Era * and reduction. (5) (6) F@eat 12 end Br2 ex&n C@.22i as needed for ~ty. (7) Makelaet aq601nof
6*,

Br31Jinm,

heat, add2mlo.llJAgHOe W1.th 5

digest few EdXl, inter,

WLu3h three -s

ml IkO,

EtOH, ad ether, dry 10 mln at llOC. We@a es A#r ~ lomg m).

Remarks: Tbe blmmti f%mion work tmly rquired -e To prevent mssibla 10SEKW of taace Br during dlssol~ one might dIssc&ve the -get of &

(23.5w

12-Rr2 erlam cycles. bls?mxth, pressmt

ti 6 ~ HMA wItb tie carrier ~-

in a glass still, and

H@ In en ice bath.

Source - w. w. M?inlm, repmt AEC&q38, EIEemait aepsratad: Emcdne !J!aget mata%sl: Tantalulu Type of bbdt: m+3501&vwolzme

pp. g6. Aug. 1949 Procedure by: Modified by: Time for aepn: Equipment -eta: fulmel Unbar ~ 2 hours =.

Yield:

-w

Degree of purification: excellent - factor of 104 fYcso fission and 13palJ.ation poducts . Advantages: Provides for the separationof Bra frau tergete reqa HF-HTXIS mixhares for solutiou of the largst. In these cases glase equip. mmt Is impossibleand the method of distillationof t&e halogens is

~a. Procedure : (11 Freslmy precipiktea AgBr (well Vashed to ~

C~~

mes

Ag+)

10 mgs of brauine as silver bmmuide Is added to 15 SF solution ccarbxbed in a lusteroid test Wbe. fOfi iS ~ illSOhltiOll and COIIC. ~ (see (a) un~
iS d(kd

mls of ~ The -@
as

required for solution of the foilk

~k.) stand for

(2) Aftzr target has dissolved tbs solution is aldawed h 15 minutes, (See (b) under ~ke

.) the sq@rnatant *get

Bolution Is r6wved, ths AgRr washed twice with 10 mls hot water, 10 mls of water Is added end the slurry is saturatidwiti &@, then Centrifuged.

(3) ~

~~t

added,

1- iS solutim iS boiled to remove &S, 10 w tbe solution is mede 1 g h HNog 6 few drops of mmo~ is inta 10 de of CC&. (exlzact a

added and the iodine -acted tatal of 5 thes).

(4) 10rdsof

Qisaddedto~

aqueous -e

aud 0.1 M KMn04

solution is added until the brauine color persists. Ex&act Bra 5 Wnles (tow). the Br2-cc14 ~t, (5) Ccaubine add 10 IUIEH@ and 0.1 ~ N~~ 1 y m cm~ -4, dropwiseuntil both layers are ) Wash aqueous layer vith CC!&. few minutes to~dize exbnactthe Ia5

colorless (See (c) under r~ks. .

(6) Wel

Nin HNOSaddlOmgSIO.l

,w-fora MNaN02and

the&.addafew_of WlleB Uiti Q.

(7) -t

(4) ~d

[5) as -d

(A toW

of 3 times was used for

Plmificatim above.)

22

moclmJm5 (8) uhst

(Centd) inmoe, heat, add2mle Wreetivith

aqulmue mlutialofw-llg 9tim, digest

0.llJA8EOS. 5-ks :
(a)
This reacticm

afewminubes, ---

H20J5*W.SOH,5

RrY far 10 mine at U.&c.

pomade

repidly

-d

at no tim

shcmld t&sre be

end.exmss of m.
(b)

Heald.ng not requtred end lustxwoia lalbe Is A@r end tracer

mey be ice cooled if necessary.

Procedure &ponds qpcm an equillbratim betmau

brasiik ion in the k~t

SdUti~.

If the tm3car

brmine ~
. re-

In a hl@er Oxidatim state Ws

~, dnce the m &ctivec andiume@tandall b~ (C) ~SEi or brtmdde. the 13cihrtion ks@ is

eq@llbmtion

would be ~ssible

is being aissolTmd it may be Ssmd the~ietiihefmof

acid MnO~ ~

~ci~tate.

lhe MO= be-

precipitation~ (d)

abo be avcdded if the solutlm is ~

fore ~ti -fl~= fj@e (3) aud (9) are R. E. Goe~

Cs Qrocedure for branine.

(e) Iz might elso be e~tedby

thie procdme.

PROCmmE6

HFmmE
pp. g8. hg. Procedure b~ Tim fm 1*9 Riwhn

Somce - W. W. Melnke, repxt NW&&@, Elment mepuated ~ mu Bmmdne

Target material: mmium lmtal (.1-1 gpl) of bbdt: 60- metal

6ep%: 1 br. ~

Hquqale?lt req@re&

-X$ of Im?ifiaation: - 10e excqpt fran 1- (- @ lhs~-tal

(~)~e

frm

1-)

Roce&re:
sOhl~~

isdiemlvedinccac.
to M ~ bti

HCl+afewdrops.2g
he

re8ih.

HCl IS diluted

to2g~d~~@ti. -_to~fil~ENOeti50 mlsepmatary funnel. AddlO~~-tiermdK)mg (1) Add Kl&@4 (0.lH) dropwiseunti
kfak.e 5

I-umriem. (15 drops).

color ~iste
C~ .

SUCCeSSiV13tione ~ addloml
on sh&dn&

with

Discard equemw . lb

C@layer
C@hSS

uaterando.lg Discard t&

mamsmlac~a CQ. 0.114

(2) Toaqueous add2ml~end10 Matioz. EMmact five tlame III*

exhaction with

mgI-, add4drqpsof
ccl+.

Add~I-and~t

foln~~ofw.
Witi ccl+.

to (3) Add 104n04 oddize Br- . EKtract five *S

23

~6

(Centd) A@r. inter, wash

(4) El&act cc14viti NaHSOg. Aaa Ag+tOppt tlueetilmeBith5ml w at 110, 10 & ~ke H# andend wei@.
described

times wl-U15ml EtCH. Dry

10 ng Br- = 23.5 mg A@&.

~lY (PhYs. Rev. ~

method hae been : !lhis (1s49)).

17

PROCEWM7~ -Ce - Glendenln,Edwards and Gest, N.IV..S., Vol. 9, Rook 3, pp. 1.451 E
1. ~ Intiodllctlm

16 eepuated fhcm tie other fleei- products by tlw reduct-

Ia

of lir& umri=

to mtito

witi II&, foUowed by oaddatlon ta Brz vlth

Q.

KMU04,and exhaction

lhe Br2is~vedltrmtbe NH@I.HCl. m

C~

by

~ =to I&

&

-by ~0 ~

con~ Q

aqueous Sohltion is then

and

uaiq

HaHt&

cycles, using KMn04 for oxidation for z+.ucticm to 13r-. The bradne is finally and COUUti?l&
with H*
Failure ensures to acbleYe the Interchange of

-acti~

~Cipitited

0s #@T

fOr weito ~-

!lhereductim
msdlobrcmine with

of ~the

ca-ricm.

a cqplete

of brcadne ematlon. !lhe use or I!TM31JKl to reduce Brz to Br- in the ftrst extrm2tlon cycle
m ~ bm aB~ve~ h Pretiu ~ds

intar36,3

helps to decontm5nate the brmine frau iodine, sl.nce It&OH.HCl

reduce

does not

12 h

1-. Contaminationby otbr fi.ssica activities,ticlndlng cent or more, and for a canplete analysis is abcut 1 br.
2. Procedure

iodine, Is negligible. !llhe chemical yield is 50 ~ tbe tdne reqdred

SE!?lQ

To not more ~

5 ml of a solution of neutrm-irradiated cen~ tube, add 20 M of braolne carrier -a-. Rassin H2sforlta
trensfer the solu-

uranyl nlhte cm-i2 mln

(Note 1) b

a 50Z

as Br&analomgofioWle
(Note 2),

boil briefly ta _

the H2S, cool, and few ~

of 1 M KMn04 (~Ote 3),

discard the ~ -= lomlof H20cantdnlnglml

of

10mlof&O

contaidng

afew

HWECURE

(Centd)

Sk!?I@Rewet
EEu *8. Add2mlof tate of A@r

~. 5* 6MEN0., endheat neemQtoboiMng by drop wlthaUrring (mt0e4).

FlelnEat~ Addlmlof O.lM~drc@

auddlgeet thepreci~-

for a few aecande. Filter With euctlon on a Weighed mterfuunel, endwaeh~timeswlth Ikryatll@Cfar10 tilmeewlth5 mlofethenol. end -t. solution 2hcald be neutral or slightly acldlc. wilJ.aa2eetiefamehla hawm, edmetlle~ is

paper disk(Nota 5)inasmiU~mh 5m.lof H@endtbree ndn, ue@ Notee. 1. 2. ee ~, ~ ~le

~~semceof~in-ee@s

of frew sulfur at this point. msdoeeno lef% behind during the Q 3. -= 4. 5. &fficlent exixac~

cycles.

XBh04ehculdbe added ta mainlaln e pnmenent

me

solutlcm is aciddfied end heated to qpel prwcipltauclh

ma,

wldcb

ndgbt Interfere in the #@r me fil---

disk Ie weabed with ethenol end dried under

the ccmditdoaeof the procedure before the wel@lng.

mocEDmE8 source - R. Owwakt

Swleuiun metal

BRcMmB

and L. Jacobson, E.H.E.S., Vol. 9, -k

3, PP. 1.453

waefueedon

acopper c~krgetendbdxmled
tJle Be&eleycyclu@& me Selenilm is 4d, end tie add
m-=,
W&&r.

inabeU@rwi

tlldeuteroneat

dissolved in cane. HKOg. !lhesolution is diluted b

diatlxl.edfrcalthe SO1.utim. h ~, WdCh me Wmkte,
Witi

le

con~
disti~

is collected
&ffiCieUt

ia then weahed three -S

to We CQto produce

ClZ13a2iei

added

atla-tiy

idl.owcolar,

end the

mixture isplaced indtcecteuwllght foratleeatlbr. tldBperlodtJle$c~~ if3~ted

Atthe endof
Or &ma

wi.tien excess ei~

m of l?ea~o~ta @we a mlutlon of &ecer brcadne free of s~cant

mounte OY braid.ne CeJTler .

25

source - R. R. Edwards and H. Gest, N.N.E.S., Vol. 9, Book 3.

In cmnectkn

PP ~~

with

studies

on

Uie

-ad

effects

Msoclated

with

formation of ~ ~ the decay of eelenlumSon tJie btivlor e B of brad..ne tracer concenta?atlons,Sevsmal Intereeidngreactionswere at studied which are ~d Tracer bromine Stitim of dagamed ~ m and brlafly here.
VerS pepsred

by &

neuticm ~adlatlon ~olutionby Cin

iS

axbactlcu of the wa~

presame of BIVOaend KMn04. About60~centofthe~h~2 Reex&actlon tits a walayer with N-

found ln12ae Qx.

glvee a solution of Rr- concentrationof tie orrher 10-%, of l glvea no precipitateor Cerltdfugab e colloid.
(about A kge tition

since Ag+

70 ~

cent) of tbe brcmlne activity can be ertracted frau the becmme of the hydrolysis of Brz ta (abat 16 per cent) is not exSOhltiCM, as

C%

solutla by water, pesumbly appre~le

Br- and BrO-. ~

fmctIm

tracted by water but iS ~CtSd 40 DeVault and IAbby. lllxh -tIon witi etiylidenebraulde, ~~2,

by NeHB&KRr -0

f-d

by

reacts In *

absence of I.lght of brauine

a reaction _clzsmLstlc

at.ums and not of Brz. !lhls fmction Is provisianaUy designated8s

%taulc

brauine, although atanic bradne is not qected

to ba present

in appreciableamunta even in tlmae dilute solutionsunJAss it Is hl@lY s~~ emaXltiction ~ _ by ccqplex f~tion wltb i2M solvent. h addition, a

ofiJwe activity is bound bythe Xed ~ti~

CC14, anda be

~S tist, prhaFw to the wall; these losses q

due to &radlatlon effects. Tlve tracer are presentid elsewhere. with the ~d C% of waw

studies of the reactivity of We

solutions of the tracer e~

frail me

solution, It was *

that 96 to 99 per mnt of UIS actlvlty is in 10 ta 45 mdn of StdlZblg. Koltioff *IS ~~t ~ ra@shows tht RrO- alSO

collectedby freshly prepared A@ and O %ri-ihavw

shuun that freshly Precipi-ted A@r

wlti Br- at mdnezy ccmentitions;

exchangesreadily at ccmcentitlcas below 10-%. Brcmdne tiacer does not exchange a~eclsbly 13tandlng for 10 to I.tX) * at rm with O.1X ~ after

taqperatureIn a neu=

aol.utlon, 2s

shown by the cauplete recovmy of 12m actlvlty with added ARET precipitate.

26

~ mce - w. w. MeiDke, m Iodmle To (2 urn. )

10 - IoAECD-30&, pp. 21. -oh, Proce&re by:

~ for m%:

1%1

memlnt aeparew *get mmariel: 60$ of ~cation:

H. D. ~

3 we
Smn&rd

ha
Yiel& Impw

naturalredioectimTe (?)
At leaet 10 frm

E@pmit

reqdred:

Te

Pmcedme: (1) Temeti=

oxLdizedbycmic. -a w EImgt43Te02 WCh diedolti b Water. WfUSe41 Ulth ITeOH. me mea
(2)

10~of

I-and 20mg Br-vere added eecerriere totlMsolMtion. slowly toexceesto ppt AgIti A@r, am&ling

Agwoewedded

palecipitatimlf A@. o

(3) ~

wae obtainedby centrifugingthe solution end theu &euting end15ml at 930C. tbeeO1uti= fcm15minntee of H2ao~. !J31emiXturewdi-

withlgal of&m* geeted fm m -tee

(4) Astremof
eadhtJle

air~lnibbledthrou@

601utionvae coolea euldlzealzldwithcmc.km r~ efter standing

13cd.ution dmwly until a fdnt o&r of m 10 mhutia .

(5) AgIwaepp&d -ke :

byadding A@Oa to the d.xture.

PRccmmEK1-IoDmE scnuce - W. W. M3inke,

Ehlieut Elezam3tie& ~ (repmt AECW2738,

pp. m.

Aug. 1949 Mxrquez

10-e bezm2 erOs6 secUon)

Procedureby:

Wget Yiel&

laaterlel: Su(-lgm) 70+ ~~dp Leas -1$

!lYme for eepn: 50 min. =-t requ3xe& 100 CC diS~ti~

Sepamtory Cenb-ifuge funneb Iaibee flack

1yxEJf bbdt: l&n o Dsgree of XU3tion:

Impurity in final Iem@l.e. en@J emnmt of pure

AdmntageB : Faat. Mikee pesible sepn of a q Ifmnkmge mmunte of otJler activitle8.

27

PROCEDURE 11 (Centd) Frocedure: (1) Add 10 mg 1- carrier and *get

(2)

foil to distillationflask.

Add 15 ml COnC. H.2S04; (H2204 shotid be COld) to dissolve the W.

(3) Dissolve Sa and distill simultaneously,collecting12 in

0.5-M_ NaOH solution. (4) Acidify With H2S04 until iottine turns brown ~d oxidize with HNOa,

(NaN02 in acid solution). Extract with equal volume CC14.

(5) Wash 1- into NaOH solution. (6) Repeat NaOE-CC14 cycles as many times as wished. (Three cycles
gave purity listed above.) (7) Acidify last NaOH solution with H2S04 and reduce with S02 gas. Blow air through solution to -l and a few drops of cone. HN03. most of SOZ. Add excess Ag+

(8) Heat in water bath and filter. (9) Plate and count as AgI.
Remarks: Most of the loss in this procedure comes in the distillationprocess. Ice cold H#50 used in (2) to allow assembly of distillationapparatus before solution of target starts. S02 solutions can be used to collect the 12 from the distillation. The solution is then oxidizedwith HN02 and the 12 extracted went equal volume of CC14.
!lhe 12

washed out of the organic layer into S02 solution

and the cycle repeated. !tbisS02 procedure is troublesomein the experiments above because the solution develops a gas pressure during the extractions.

PROCEDURE 12 - IODINE
&m.rce -

W. W. Meinke, report AECD-2738, p. 162. Aug. 1949 p procedure by: Msrquez Time for sepsn: *4O min. Eqpipsent required: 100 distillationflasks sep funnels and centrifuge tubes

Element separated: Iodine Target material: Sb (-5oomg) me ofbbdt: 60~a particles

Yield: 80$ or higher other activities Degree of purification: At least a factor of 104 frcus present. Advantages: Fast and good separation.

28

PRmmlJm mocedme:

12

(Centd)

(1)
(2)

Addtar@,

lO~I-cm%er,

10-15 ml of Selan?alad c ~ to dietillatim ~tns .

ecid aud 10-15 ml of Ice cold ~

~S~ end C*Ct

12 h

0.5-1 N ~.

(3) Acidify with H2&)4 untdl iodine turns brown end otidize vith c%. HEOz, (NsN02 in acid soluticm). Er&act utul equal VDlm (4) Weeh 1- tito N(5) Repeat Mm-CC& kt (6) AcIdifY ~ stitbn. cycles ~ WQes M wished. (!lhree cycles redUCS uIth ~ ~.

gave pu15ty llsted Shove.) soluti~ with HzS04 =d Blowetr tllrougbaolutionta axplmostofm. and a few drOPS of -C. HIW& AddelcceasAg+

(7) Heet in water bath and filw. (8) Plate end c-t es AgI. Wnal?ke: Most M the
Iw loss

in this

procedural

c-s

in we distilhticm process.
.9watus

cold EINOgused in (1)

ellou 2SSS!llb~of diStitiCSl

before solution of -get

Sterte

solution of 2b h An I-ssn@e

qm

rc@a

titeufereeith 12 ~on. w the AgIdizectly

could be bbtsdnedin 15-20 tibyppting

from tbe distillateof (2). !lhe radioactivemmity of the sqple, houemr, unotlX21Xllbi@l asabuve. collect the 12 frun W@ distillaticm. Em

~Z solution cau be used b

solution is then oxidisedwith 21!fOZ tAe IS erlaacteduiti eqti ~ end of-.

the cycle

!Qw12wcudmd repeatid.

outof Umorgmic

~tito~dhlthlsd

PmCEWRE13-IOMXE
Smlrm

- W. W. hieinke, reportAECD-@,
Iodine -lgmmetal

pp. 163. hg. 19+9

by: mckemann

~t
TYPS of

seFu=te&

~dure

Wgetnmteriel:

mm? for Sep%:

-2

he.

bbdt: 184g ell ~cles

msmw-t ~ tion fZ&k, centrifuge, tubes, ice, w oven. f> ld frm fiSSiWJ end

Ylel&

Approx. 4@ Purificatim: ~m~tioil

Dsgree d -Mm

products . tile.

Advlmtsges: Fair yield of pzre I with llttle if eny mm-exchmge

29

~ %xeuure: {l) Place W@tln@aes

13 (Centd)

sW,

addlOmg

I--dlOn&~Ht@& the 12

vexm to dissolve. When entirely dlseolved,distill O&uldafew nllHNOsillto H@ (2) Realcse Iswitbandxdmum
HI?&., add a few drops

inen ice bath. in the cold, adJust, to 0.5~ and e~ I= into an equal C%.

of N-S
NaNCk,

O.lg

vohme of CC&. Wti (3) Q ~

E&mct

aqueous with eemnd -on

Vith dilute ENOS. titi I-O ml H@, adding N-s unti both phases

Colmless . ~ ~~ cu. (4) Repeat eucbaction cycle aevemJ tlnme. (5) ~ -t WI- s~u~~ o.% ~ ~s, ~t to boi~, eWllm, dl?y

add 2 ml O.~ AgNCIS, digest, fllk, &reetilaes wlti51ulc*CH, 10 * at llOC. Welgb se A@ f-d

wash three thee ui~ H@,

tluee *wit215ml (J.6.50108 w

10mg I).

R61mrke Active i: her

se psciodate ~

not exchange wttthUve

by this metimd, el&au@

the I yields were not abnonnss _ dufing dhsoluthm of the

low. Reducing ctmdltionpr=ly Q9rget.

PMCEWRElh

IO= pp. 164. Aug. 1549

-Ce ~t

- W. W. Mehke, r-

AHCD&?@,

s~ti~

ImroIlnu (.1-1 ~)

Procedure

by:

19ewtan

mrget ma~: YLel* *

far sep%.: 1 br requlre& EHar&rd

Type of bbdt: 60 as Degree of purification: loe Proceti: !Che me= lh is dissolvedh b clear w

Ek@~t

cone. HCl + a few drops .2 y The HCl is diluted

solution (l@@Fe

black resi-.

to 2 ~ end an aliquot -. Procedl?re:

(1) Add sample to Add

10 ml 2 M Na2c09:!
2 ml 2.* NaOCl{z). M

Add20mg
Heat.

I-ln6Qmlsep
with

funnels. cone. (2)

Acidify

3 ml
both

131TOS, add

3 ml 1

l@#XLHCl(3)

Exlract witi 10 ml C%.

NsHS3S until

Smlne wi~

10 ml H@

ccmtdnlng a few drops

@uw3e colorless.

(3) !Ibva&add

lm16,g~~

and afewdrqpeofl~~~2.

Ektaact tits cm+.

30

(4) (5)

-k9: (1) (2)

(3)

FHa3mmE15 me

(COntq for weigblng md counting. cca-

iodine ie fhally preclpi-ted ea A@

~tion The C-ti

by other fimston actititiee,including&canine, is negligible. procedure, together with a dlecuesicmof lile&rve*t

work, Is glvm below. 2.

Mssolve _
lod5ne

Fnepscatimland

Sb3?ldarwultlca

of curia

13gofreagemt
=d mute to

-grade
1 ~~=

KI Inwater
~s

cmtdnlngafevticon~ 10 U of

of ~~J
E Ilduluter.

~olu~on

Mpet5ml

of

the@u7rier

Oolution intro beaker, add d?out 50 ml a heat~lytabo~. #dd5nJ10f

Of~EUldlldOf&~,tUld O.lM tate fa

glass

drop by drop with contlrawue6tlrrlngJ (Mgelat the precl@ebout 1 mln, and flltem quantitativelycm a wel@ed slnteredwith SUCtiOJ1. weaht&ee timsuith5mlof ~=dthree of the

acible

theswllh

5mlof~per

cente12muol, rlneing dounthelneide

crucibleviti each pmtton of Ihe waeh liquid. wipe the outeide cd the Crucible dryand placein anovenat end wel@ u AgI. 3. ~. thau5gof Add b
*

llOCftrr10 min.

Cool in a dealccator

Procedure poducte ( contdmlng not more funnel abmt10 Addlmlof5 ~-t ml

13aqplef flssitm o
mlof

urenylni&ate)lna

60+18~tmry I-carrier.

of2MHa~(Notel)end2 HaCIOJ mix wti (Nob:

Itiadeelmble

tig3vethe

NaC10 tlmetitidtze solutionby

radlolodlnespecies fully, or betdowly adillng ml of Cone. Hmg. 3 * 12 i.nti EL Of cu. 10

Step2. Mtie

to heat), aud acidify lb * aWOU8 e.

H20

Add 3 ml of Ill NH@H.HCl, and exlzact

ins-d

CQlayar

withlOmlof

cmklmingafeu

of ~ step3.

~~~

UU~

bo~

~ee

ne

colorless,aud alla-d tie Q. lMIWliOaJextxact Qfer.

Addlmlof mlof

6MRNOgend

afeudropaof

tie IalntolQ a ~.

CC&, and discard thequecue

RePat step 2. Addlml of 6MHNOS, andheat nearly to bolMng

(Now 2).

Add 2 ml of O.lM A@TOg drop by tiOp titi et-, pitate of A@ lnaemeU ulmlnt . Ho&s . 1. Umnyl nitita hexahydrati (el~

and digest the ~cI-

for a few secondeby gautle boillng and brisk stlrrlng with suction C&O a weighed filter-paPEudisk (Note k) wlth5mlof&0 end three vei@ ee AgI, and

(Note 3). Fil-

Hlrschfunuel; waeh tbreetheB

times with 5 ml of ethanol. Dry at llOC for 10 b,

ae the solld a

in

32

15 (Centd)

solutlcm) Is readily soluble in Na2COS solutionby the formation of tie carbauate ccmPlax. If tiers iS much fhe tie addition of more ~~ ccqplete solution. 2.
Interfere

acid in the uranyl nltiate, may be required b effect

and gentle hea~

lhe130hltiOn acidf,fled is end heated to aw@el ~z

In the AgI precipltat.ton.

Which

mi@t

3.

S1l-

idlti

**

to form both a roil@

suspenskm and large Coaglilatiughe t

clumps of precipitate. The digestionprocedure aide b euepemeionend also In breaklmg up tie Wge k.

particles of Wecipltete.

!EJS filter-~per disk is washed with ethanol aud tiled under tie

conditionsof the procedurebefore the welgbing. 4. Previous methods of ~ rnscussim fissicln-iodirle activities,involvl.ng

&e use of carriers2 In the form of 1- and qploylng mddatlon-reduction reactions In acid solutla to obtalm 12 for se~atlon bean shown b give low and e-tic yieldsw by extraction,have inomqplete tests

evidently owing b ~

interchangebetween the radlolodineend tie tiers. on prevloue methods of Iodine separationConsls-d h Solutlon of n briwm by
COUll~

ti~change

pr~ing

a stock

h !te, determlm@
an

the 2.4 h I dau@ter activity at equlliTe, and ~

aliquot of +Ju stock solution tJrra@ eufflcient @radlatlon of the~h

ehnlnumtodmo rb~softer this actlvlty wIM

the 2.4 h I activity obtdned by vwrlous methods of methods

iodine sepxratlon. In these tests it was found tht tie wller

dld not effect ei.cmqplete or r~oduclble Inhsrchemgebetwea radioactive Iodine and tier iodine. For exmqple, the procedure Involvlng the addition of iodke carrlem ea IO: and reductiou to 1- wI* NaHWS In dilute acid solution was found to give inccmplem eeparatiousof 2.4 h I frcan the stack solutlon,~ change tests It was evident -t do not give a ccmpleti ramml fran 65 b 95 per cent. man these inter-

tie UJ3ual metiods of Icdlne separation u?@ of mdiolorkbe frmn fissicm material. with carrier iodine wee csrried out, CU@Ste

Work on tie develolmmt of a wocedure that would effect a fast and cqplete interchangeof radioiodlne NcCIOtianaUaklne t301UtiOn.~S aud a satisfactorymethod was found In tie &daticm of 1- to IO: by

reaCtiC#l was shown te @VS

awl rapid Interchangeby the 2.4 h I tzacer tests mentioned dove and has been tico~ted h the ~ocedure describedIn tis paper. !he en alkak&e solution in the presence of U& difficultyof Worldrlg m tatia of lmanllml
q

has been Cticumvemtedby use of the cexbonate cacipk to prevent precipl-

15 (Centd)

~perate @acer taste with vericue fission activitieshave not been made, buttieprocedure has been usedina great dealofwmkon ehort47 livetl Iodine actlvltles, with no evidence of con~tlon by other t, branine. Two

fission activities,Includhg the most ~cbehle con~

S%PXRZti~ ~ br~ = affaded in the procedure: me a~tlon is @ven by the redUCtiCm to Br- with hydroxy~ ~ 12 is beextracted, aud tie other sepratlm is glvau by tie ex&actLon of 12 after ddatian W-). lhwmver, the longeet-llvedbranine hence brczui.ne than a

witi HR02 (tlds does not @dlze tivlty

in flsslon witi a sigdficaut yield is 2.4 h &;

activity Is not ~mnt dlly @d.

In flsBlon-productsolutionsthat ere mae

The iodine procedure can be adapted re@ly ~ Iodine md branine. h

a tidem method deis also added In

tids case Br- ti-

etep 1 (see Sec. 3), ofitied to F@ by tie hydro~lamlne. Q. !Lhe12 is -

by the NaCIO, end reduced to Brcorbactedwiti CC~, and tbe Br-

in the aqueous layer is o~dlzed to Br2 with KMn04 aud la extracted inta The brcauine can then be purified, as in the case of iodine (steps Cy&Le, illWhich W4 i6 used b IB used for ae Ag13rfor 5). lhe sepera1- to I& end

2 and 4), by auo~er CC& ~tion dll. HN~

for the cddation of Br- ta Brz and hydr~lsnine

the reduction of Rr2 ta Br-. The brcmdne is ~ipitated Wew -a _u$8A9 as In tie case or Iodhe (s* tlau frcm iodine should be exceUent, since KMM14 odties
thus prevents
Iti extraction

with

Br2 end eince hydroxylamineEdUCeS

With Br-.

I&

to 12 and prevents its extractim

16 - IOD~
Hnston, mdd.e,

Suurce

IQtcoff, DnI=d,

seihr and sugmuan,

N.N.E.S.,

Vol. 9, Ikmk 3, pp 1635

1. me wocedure wesented h

alrodllctlon this pzper was developsdb separate

iodine formed h

the fIssion of uranium meti.

Caqplete exduange of tie

radioiodinewith ~lar

1- is expected, since tie Iodine activity formed therefae 1s almost

In umnium metal is In a highly reducing medium ad c~y &r@

Pres-t as 1- Ion, which should exdaangerapidly with 1- carrier solutim of the metal in U M HC1. After the uranlwn metal is o~dlzed to ~~ and I& titi an

canpletelydissolved,U(IV) and 1- =e excess of KMn04. !lhe1~

ie then redueed ti 12 with NH20H-HCl .md is re-

34

PH~ moved frm taon. CC4. *

16 (Centd)

other fission elementsby dlstlllattontito a NaOH soluand ~ is rmuved by extractionwiti In which NaN02 is USA
for the

me distillatiIs acl~ied,
he

12 Is removed frcm tie Q by two more Q

by ahaldng vlth quecn12 NaHms aud

for

ie then ~ified
the -W&m of

exbactims,

1- to 12 and NsHWS ie used

~uction

of 12 b
end Counldng.

l-. The iodine ie flnalJy Precipl-ted es PdQ 2. ~. Tmsnsfer a Sulmle cca~s Rocedure

for Wel@ng

aa@.e of irradiateduremim metal b 2 ml of ~ (1- ccmcentition of 10 m&l) tile metal. TO the emall

a distllldngflask tit c%arrler Add60ml .

ofconc. HCltodlesolve

residue of cerbide and ofide that remains, add 40 nil.f IllIVaNOa caao to plete tie solution (Note 1). Ihe exit tube of the distillingflask Is extended into 20 ml of 6N NaOH solutim, and a S1OU sixeem of air is p3ssed ccmthuously mough ~. the soluticm during this etep (Note 2). inthedia~

Addtke NaOHfrau tielm3p tot&solution

flesk, and stir the solutlcm. Refill the trap with 20 ml of fresh &l ~. Add an excess of sat. KMQ L& and I&. ta the eolution to oxftie U(IV) and 1- to

Add 1.% NHfi HCl slowly until tie solutionbecamss and then add 20 ml more. Heat the solution to distill tie

Ilght yeUW,

12 tito the MaOH solution. &%Qo Ccq . Died w. Q I#3yer. ~. Addlmlof 6NHN%and afew dropsof layer. ~~ the dls~te the aqueous layer. -+21elm , sad extract tie I= with 10 ml of

layarwithloml

of&0

drops of 1 M NeH~

unti both @aces are colcmlese,

the I= inti 10 ml of Q, .@X@ ~. (lo 1+1) &Oend12mee = R&,

end discard the qesaM

Repeat step ~. Heat the aquecue layer end ta precipitate~. &snith5ml

add

elowly

ml

of

Pd(Nos)a

Filter wlti suctlcm on a walghed flltemandwash three tilmeswith~mlof ofelhenol. DryatllOC forlOmln, wei@

~-kinasnwiLIHirwhfunwl, and IwuIlt. 1.

NO*S.

Under 12ieee candltime tie NaN02 does not lAbemte &. of~or HItitqcune over Uecau@tint4m NaCH

2. Anynpors Solutlml.

35

nammm 3.

16 (Centd)

Di.scueslon activlHes iodine.m~n have been !59 h

PreviouE n&hods or detamrdrdng flssian-lodne tiachange procedure cqplete I. between the tracer
in the de~

abown to give low and erratic yields, evldentilyemuse b Iodine and the carrier

of ticaqplete

describeddrove WS8 obmrved ta give a fast sad apparsm

Interdmnge

tion of We ,ontie

flsslon mdd%on.7 uranium

The n&hod is dependent,h~

useof ~ted

metal.dissolved in HCl and NaNOZ to provide caqplete lnter&ange; It

cannot

The poblem of mxqplete interchangeIs avoided In this case, since the active iodine Is in a redudng medium end is probably Pres-t u 1- ion, which exchengesrapidly

be used on o-

fiefion-woduct sources. q

with 1- carrier. Contamination by tier flasion ativities, ticl.udingrmine, La b ~b~ . =Xation fran brcmdne Is afforded In the procedureby reand by

ducticm with R&OHCHCl to Er- while the 12 is being -acted, the exkaction of G

ef%m cnd.dation ith NaN02, which does not oxidize w ~ocedure Is apprcdnmtely @ per cent.

Br-. Ihe chemical yield for I&

PmcEmJm 17 - IOD~ source - R. Ovemtmet end L. Jacobson, N.N.E.S., VO1. 9, Book 3, pp 1638

Telluriummetal is fused on a copper *get deuterons in a bell Ssr in tie cyclotmm. 6N SNOS aud the solutionis dis~ed. me

and ts banbarded with telJurlum is dissolved b

!lhedlstlJlate,ccntdming the

radioactive13.0 d 112e, 23 m 11=, 12.6 h 1=0, and 8.o d Il, is mllected in @, vhlch is then washed three thes with distilledwater. addedto the CC&ta X= adefinite yellow at least 1 hr.

SufficientClzgasls

color, end tie ndxtwre is pkced h Attheend of either oftbisperlodthe NazS3S or Na&OS CQ

tUremt sudight fm

mtxhu?e is ex&actid with en excess of tracar iodine free of

+33give a solution

sig@Ekallt amounts of inactive Iodine cecrrieu .

A procedure developed (Glendentn,Me-,

Nony, and Coryell, N.N.E.S.,

Vol. 9, Book 3, PP 16429) for use with Irradlabeduranyl nlla-ate preIS sauted In N.N.E.S., Vol. 9, Hook 3, PP 1625 by Glendenln and Metcalf (Procedure15). 36

~1.8-IODIIilI SnnCe - D. S. BalLmtlne, N.N.E.S., Vol. 9, Book>, pp1639 stale *deqt08d iotdJJ?JduDlis irradLa*aulti IU1. pile neutromtoproduce2@ n3dloaoUve talluri~

IeE1 end30 h Tem

by lhe (n, reactia; tb y)

After a eul.t2Sble detw period the radlactlms _ * eoluticm Of md~percemt izradia~ ~-

is oxidized to I&

mea@.etia~ ~on.

of18NH2so*

CrOglna2til b & by the

!llue Iml activity, afta & dll. NaOH. me

reducUon of I&

addltidl of malic acid, is B~td into a &ap ~ con~

frcuntie ~m

by distlllaticQ

general featuree of this mlbd

sugseetedby I. L. ~koff. An alternatingsmrce of I1 is tie HNOS mndaneate * di8Iodine wlti

1301utia of neutrcm-activated ummlum metal. The reduction of We in tlie HNOS soluthm is not practical because the IVOevelved ties it nm~ of tie io-. The iodine is s~t.ad

frm EIRI= by oxLdlzlng

alJ.the active iodine to I&, In whl~ movIns W mmg by diatluticm. per

state it is not volatile, anti reis parfh a mLXIhe

me oddauon

Zeof18NH&04endm

cent~in

a2tol~porkLon. frm the

1~-

Ie then reducad to 12 with tic flsstcm ~te

acid aud is ~d

by distillation.

end

SUit2bb d9ky (b allow the 30 h T4~n Ie placed in a distillationflask this-eadded18NH@04and50

equipped

to deq
with

1=1), tAle_

a reflux ccrdeneer. To

percent ~tia2tolproporMon, (A 15-g m BtiUtiCC1.)In Is oxi-

end the mixlmre Is digested on a steam bafh for 1 hr. req@?es about 100 ml.of &f134 and ehout 50 ml of ~

this step the tellurlm is Mesolved and tie radioactivei-ed to IOg-. Mter the solutionhae
been

allowed to cool ta rca

~Xe,aout50to@t30ftic acidand Xto75mlof W HsS04 me added. A reaction starts slowly,but soon -re Is fimtlling, end the reaction beonmea vigorom fcm a mlnuta cm nmre. n OXdiC acid has been added, the SdlltiOn ti color ti a dark~ If We
adaed. Ilie Ioune La malctlon

Eufflcient

Ialrn frcm a clerk-brown

color ae the chraaate Is reduced to chrrmdc ion. oxalic acid Should be of the

Solution is not aeflnitelygreen, mm is

WzI@ete,

Iae

actual

M.eizm.atitm

be6un. The a~atue

ccmsiete of the original flack used in

37

~ the dieBolm
tfdningdLIVaQE. step, a condemear,

18 (Centd)
a receiving weed, end a trap con-

Anyvapor that fdlstocondaneein

*condenser

is bubbled through the EacH -p

so that none of tie iodine can escape.

The progress of dietiJlationcan be observedby placing a directreading radlOtd~ =ter under the receiving vessel and obsez%dng the increaee in radiation Intensim as tie iodine is distiJled. About&p cent of the tatal activity can be obQained in tie first 15 a the distillate lbls firdi distillateIs apprmdmately 0.01 . 20 ml of
M in

H@04,

as measured by titition vitb stendartied NaOH, and leBs than O.001 N in reducing agentB, as determinedby titrationwith standardizedl~.nate solution. The Soldd materials ueueUy tdal &out 2 * the radiochemicalpurity exceeds 99 per cent. Further distillationwilJ-yteld 25 to 30 per cent more of the titsl Iodine,buttbis is obtained eloulyand inavolumeof 100 ti200 ml. 3 *, end

l%ie cm be cmcerdrated, however, by maldng the dl.stiJlatiasic with b ~ ad kthg to -SS, W -~ Hiti HZSXJ4 SZldtiO -d and redisUJ31ng. !Eieyield a tbls second distillationrune dmut 90 This distillateis ebout o.05m b

percent tiavolmmofebout

20 ml.

O.lli H#Oq but iB Shiler to the first aistilhte illthat it is dmut in 0.00IN In reducing agents emd conma&lxkl . To date, the lsrgeet amount of tellurium -t 50-8 -b= _, has been used 16 a
2 days

mly a few railllm

of solld

!Ibis 50-g Bample at saturation,followed by h m first Msmte

of

fl~ded 75 ~-es

and *out 30 U-

curies in Iim second distilhte. that, at-time

By correctingfor decay it was frond

frcan the pile, tie totel * iodine Woduced amounted to ebout 125 miJMcuries. 3. Reccmtry of 1=1 fran lINOS~UtiOll Urenlum metal is dissolved k tie solution, dxmt 10N h HNOS is found

thetellurlun was ~d

whenneu--actimted aud the fumes are ccmdms~ to cm-

en appreciablefraction of *

fission-iodineactlvlty tO-

gether with tmces of iron end &rcsuium frcm the stdnless-steel equipmt . Heduction of
the

iodbe to tie elemrla

Bt2ti

and

~CtiOll

with

q EU*
ported h

m-k:

m~t aeteu by A. W. _

SW* of the and W. T.

38

~ CQ Is not Pactlcal.

18 (Centd) dia~ed off while

For easy tidllng, liie Hl#& h In ths iodate s-te.

lhe hdlne b mdn~ed !lJie ~

condensateis placed In a dlsti13ingflask eqyipped wlti a

one-to-one E2s04 and 50 ~

condenserend a receivingvessel.
sreaddadb2tol proporWon

cent Ccog dmcamte

until tie -acerl.stlc

&k

cola Is obtdned. Unw

he dxture is Man
EM04 qpaar . !Che

dlstiJledti remove all tJM ~ ml.utlon is cooled, and re8u-

Wbiti fulms of

sbout10 gofoxalic allmm.

acidsndabcut

2Smlof18N

&S04areaddedti

T%ismixtuxe ls distilled tithe ~

&scrlbe& drove.

About 80 pea cent of the M 25 ml. h ~s dis-ti

activity is thus obtained in a volum of and less Iiuan o.oo111 of Solla mterial .

is shout o.@N to O.Illin &@4

reduc.lng Sgemts, and it @mltzxins only a feu ~ ~ cent.

l%e radiochemia91purity is more -99

39

REFERENCES
lAttebemry,R. W., and Boyd, G. E., J. ~. 2 Bleman, w., end h~, 3R. C. =1S0, (1%4). W. Rleanan, ~ C!bem. &C. ~ ~ (1~).

so, Anal. C&m. Z&

llgg (1952).

end S. Idmlenbuu, Anal. Chenn. 26, l&O @ (1-).

4R. Kunin, record @em. l?rog. ~

6 C. Teige, Wm. S02. roy. letties mm. Abs. 4EJ 5a22 (1554). 7K. SdUUSISeraud D. Jerchel, _. 8ZIPk@

et

scin.

Ckbese

SC1.,

No.

5 (1949:

Chem. ~ L., =.

366 (15!33). Chem. ~ 31O (U57).

I., Amstiong, W. D., S~er,

u A. C. Uahl and N. A. Bonner, Rsdloa.ctivitypplied to Chanis~, A 8A, p. 466, John Wiley and Sons, New York (1%1). 13J. F. Cos~ove, R. P. Ewmtlan, !md G. E. ~so?l, (X@). u K. D. Moffett, J. R. Si!mQler, and H. A. Potratz, Anal. Chem. ~ (1956).

Nle

AnS1. Chem. ~,

m~

1356

~~ebrmd,

et

d,

@P~ed

or@

c Analysls, John Wiley end Son6,

p. 741 (1953).

17D. me
(1936); F.

~d

H.

J. Wickmann, J. Assoc. Office Agr. Ch-staj

3~

297 (1937). 293 (l@).

A. Gooch and F. W. M=, Am. J. Sci. [31 ~,

40

9F. A.
a
A. C.

GOOch and H. J. Cole, Am. J. Sd.

[41fi

257 (1*). ~ Med b GhemietrYt

O. E. Myers end R. J. Prestiood,in tiO&OtfVi_ Wabl end N. A. Homer, Editors, John ~y 3233 (1~0). York, 1%1, pp. 28Q9.

and Sons, tiC., New

R. R.

Halfmd, J. An. Chem. SOC. ~ Stidiee The : m6Bia

R. Edwards and H. Gest, Hatl. Nuclear wrgy --,

=ea,

Div. IV.,

RadiaAemicd

1454 (1951). 3330 (199)

q

a 3.
~~m

Taube

end

H. Dod&n, J. Am. C!hem. Sot. & A. R. Ohm, J. ~.

A. ~

-d

Chanl. SOc. ~

2214 (1936).

25D. A. heel J. Am. Chem. &c. & s I. M. Kol=, 1503 (1*)

25W (U%)= 3409, 541..4(1939); &

et al., J. Am. Cl=h Sot. &

{R. E. ~tts and A. N. MacKenzie, Can. J. ~sm. ~

655 (1951).

2aR. R. Edwaxds, H. Gest and T. E. Ikvles, ref. 3, p. 237. ~w. M. H. Burw Cottin,
~S

ead T. H. IMvles, r&. 3, p. 2@. M. HdssinaQ

and

and D. pesti~,

J. m.
&

~.

(19X).

310. E.

J. W. K?nnedy, J. Am. &em. *C., Jr., Brookhaw=n =. and -.

@7 (1950). F@@. 13KL-C~,

3*R. E. Conuick and Z. Z. -, Isotapic Exdlange =Cticae

Mmetics, Ct@l. Cod?. No. 2, 164

(VW),
33LG & Gl~-,
p.

R. p. ~taf,

T. B. N-y

and

C.

D.

Coryell,

ref.

Z2,

1629. L. Brady and G. W. CaqpbeU, N.N.E.S., VO1. 9, Book 3, m. 1449

~.

35R. R. xds, 36L. 1?.Glen~,

H. Gsst, end T.H. Ikvies, ibid, Ekmk 1, pp~ 237 Report CC-%0, SePt. 15, @43. Phya. Rev., 57: 105 (1940) 1, pp 237.

A. langsdorf and E. m, *R. 39 fi.Mmrds,

H. Gest, and T. H. I&zLes, N.N.E.S., Vol. 9, Bmk and T. H. rnvies, ibid, n ~. 255. Sot., ~ =.s ~ 3216 (1%1)

R. R. wards

40 D. C. Wvault and W. F. IiLbby, ~. J. %.

42Em M; E.

mltndf

ma A.

S.

0=%=)

J= lm. ~. _iS,

3@3z ~~

(>939)

S%lift, ~~ A

Of M-

n mtice-~j

~c. J New

York, 1939. 43G. W. -U and E. L. Brady, N.N.E.S., u

Vol.

9, Sook 3J pp 1623.

L. E. Glendenin,R. P. Mstcelf,T. B. HOVey, aud C. D. Coryell, ibid, pp 1629.

S. S.

L@tcoff, B. Flnkle, and N. ~, Katcoff, C. R. Dlllard, H. ~tcm, N.N.E.S., Vol. 9, Book

2,

Repat CC-1331, Feb. 7, 1X. B. FhMle, J. A. ~,

PP 1~.

and N.

W&men, 47

L. E. Glendenln end R. P. Metcelf, N. N.E.S., Vol. 9, Book 2, FIP~.

@ E. L. Brady and G. W. Cempbell,N.N.E.S., Vol. 9, Book 3, PP 1449.

49

L. E. Gleudenin,R. R. Ed-de,

-d

H. Gest, ibid, PP lh51.

50T. B. NoveY end C. D. CcryeU, wiwate ccmmlllc8tion,1*. %. E. GleudenS.n end R. P. Mew, N.N.E.S., VO1. 9, wk 2, FP =. 52lcatcoff, IHUard, FYnsti, Flnkle, Sefler, and Susmmen, ibid, Book 2, pp lW.

AK

Tdmkal

lnfammlan

Scrvtcc

Exmmlm
Te

Oak Md~ 42