the radio chemistry of trans curium elements.us aec

8/2/2019 The Radio Chemistry of Trans Curium Elements.us AEC

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Academyof

Sc iencesNat ional Researc hm

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NUCLEAR SCIENCE SERIES

The Radiochemistryof the Transcurium Elements


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COMM TTEE ON NUCLEAR SCIENCEL. F . CU RTI l%3, Cha i rma n R OBLE Y D. E VANS, ~iC~ Ch uin na iNa tion a l Bu r ea u of St an da rd s Ma a sa ch u ee t h In e t i t u t e o f Tech u o lo~

J . A. De J UREN, Secr e*yWe st ln gh ou ee E le ct r ic Cor p or a ti on

C. J . BOR KOWS KIOa k R id ge Na tion a l la bor a t or yR OBE RT G. COCE RANTexa s Agr icu lt ur al a nd Mechan i c a l

CollegeS AMUEL E P ST EL NCa lifor n ia I ne tlt u te o f Te ch n olo gyU. F ANONa tion a l Bu r ea u of St an da rd eH E RB ER T GOLDS TE INNw lea r Deve lop men t Cor por at ion ofAme r i c a

LIAISONP AUL C. AE BE RSO LDAtom t c En e~ Comm iss ionJ . H OWAR D MoMI LLE NN at io na l S cie noe F ou n da tio n

J . W. IRVINE , J R .Ma mmc hu ee tt e I nBt it u te of Te ch n olo gyE . D. KLEMAN or t h w es te r n U n iv er s it yW. WAYN E ME INI CEU niv er a i@ of Mich t ga oJ . J . NICKSONMem or ia l H oep it al, New Yor kR OBE RT L. P LATZMANLa bor at oir e d e Cb im ie P hys iq ueD. M. VAN P ATTERBh r ta l R ese ar ch F ou nd at ion

MEMBERSCH ARLES K. REEDU. S. Air F or ceWILLIAM E . WRIGH TOffice of Na va l R ese am h

SUBCOMMlllEE ON RADIOCHEMISTRYW. WAYNE MEINKE , Ch air ma nU nt ve r eit y of Mlch lg anGRE GOR Y R . CH OP P INF lor id a St at e U nive r sit yGE OR GE A. COWANLos Ala mos Sc ien tific La bor a tor yAR THUR W. F AI RHALLI@v ez 73 it y o f Wa s h in g t onJ E ROME H UDISBr ook h av en N at ion a l La bo ra t or yE AR L HYD EU ni ve r ai@ o f Ca lifo rn ia (Be rk ele y)

HAROLD K IR BYMo u nd L ab om t or yGEORGE LEDDICOTTEO ak R id ge N at io na l L alMm t or yJ UL IAN N IZL SENH a n fo nl L ab or a t or i esE LLIS P . STE IN BE RGAr gon n e N at io na l La bo ra to ryP ETE R C. STEVE NSONU niv er si ty o f Ca lifo rn ia (Liv er m or e )LE O YAF FEMcGU1 Un iv e r si t y

CONSULTANTSNATHAN H&LOU J AME S D eVO EN ava l R ad iolog ic al D efe ne e La bor a tor y U niv er si ty of Mic Mga n

WILLLAM MARLOWNa tion a l Bu r ea u of St an da rd s


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FOREWORD

Th e Subcom m it t e e on Rad loch em ls t ry Is on e of a n um be r ofsu bcom m it t e e s work in g u n de r t h e Com m it t ee on Nu c le a r Sc ie n c ewlt h ln t h e Na t ion a l Academ y of Sc ien ce s - Na t ion a l Re sea rc hcou n c il . It s m em ber s re p re sen t gove rnm en t , in du s t r ia l, an du n ive rs it y la bor a t o r ie s In t h e a re as of n u c lea r c h em is t ry en dan a ly t ica l ch em is t g

Th e Subcom m it t e e h a s con ce rn ed It s e lf wit h t h ose a re as ofn u c lea r sc ien c e wh ich In vo lve t h e ch em is t , su ch a s t h e colle c -t ion an d d is t r ibu t ion of r ad loch em lca l p roc edu r es , t h e es t ab-lishm en t of sp ec ific a t ion s fo r rad loch em lca l.ly pu r e re agen t s ,a va ila bilit y of cyc lot r on t im e for s e rvic e ir r ad la t lon s , t h ep lac e of r ad ioch em is t ry h t h e u n de rgr adu a t e co lle ge program ,e t c .

Th is s e r ie s o f m on ograph s h as grown ou t of t h e n e ed foru p -t o-d a t e com pila t ion s of rad loch em ica l In form a t ion an d p ro-c edu r e s . Th e Su bcom m it t e e h as en deavored t o p re sen t a se r ie swh ich will be of m axim um u se t o t h e work in g sc len t ls t a n dwh ich con t a in s t h e la t e s t a va ilable In fo rm a t ion . Ea ch m on o-gra ph co lle c t s In on e vo lum e t h e pe r t in en t in fo rm a t ion re qu ir edfor r ad loch em ic a l work wit h an in d ividu a l e lem en t or a grou p ofc lose ly r e la t e d e lem en t s .

An expe r t In t h e rad loch em ls t ry of t h e pa r t ic u la r e lem en th a s wr it t en t h e m on ograph , fo llowin g a s t a n da rd form a t deve lopedby t h e Su bcom m it te e . Th e At om ic En e rgy Com mls s lon h as spon soredt h e p r in t in g of t h e se r ie s .

Th e Su bcom m it t e e Is con fid en t t h ese pu blic a t ion s will beu s e fu l n o t on ly t o t h e rad loch em ls t bu t a lso t o t h e re se a rc hwork e r In ot h e r fie ld s su ch as ph ys ic s , bioch em is t ry or m ed lc t iewh o wish es t o u se rad loch em lc a l t ech n iqu es t o so lve a spe c lflcp rob lem .

l!. Wayn e Meln k e , c h a irm anSub c omm i t t e e on Radlochemls t ry

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INTRODUCTIONTh is vo lum e wh ich de a ls wit h t h e ra d ioch em is t ry of t h et r an scu r lum e lem en t s Is on e of a se r ie s o f m on ograph s on rad lo -ch em is t ry of t h e e lem en t s . Th e re is In c lu ded a r eview of t h en u c lea r an d ch em ica l fe ,a t u re s of pa r t ic u la r in t e r e s t t o t h er a d i o chem l s t , a d isc u ss ion of problem s of d isso lu t ion of asam p le an d cou n t in g t ech n iqu es , an d fin a lly , a collec t ion ofrad loch em lc a l p rocedu res fo r t h e e lem en t a s fou n d In t h e lit e r -a t u r e .Th e se r ie s o f m on ograph s will cove r a ll e lem en t s fo r wh ich

rad ioch em ica l p rocedu res a r e pe r t in en t . Pla n s In c lu de revls lonof t h e m on ograph pe r iod ica lly as .n ew t ech n iqu es an d p rocedu reswarran t . Th e reade r Is t h e re fo re en cou r aged t o ca ll t o t h ea t t en t ion of t h e au t h or an y pu blish ed or u n pu blish ed m at e r ia l ont h e rad ioch em is t ry of t h e t ran scu r lum e lem en t s wh ich m igh t be in -c lu ded in a r evis ed ve rs ion of t h e m on ograph .

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CONTENTSI. Gen e r a l Comm en t s . . . . .II. Gen e ra l Review s of t h e Ch em is t r y of

t h e Tr a n scu r iu m E lem en t s . . .I I I . Table of Iso t ope s of t h e

Tran s cu r ium Elem en t s , . . .IV. Review of Fea t u re s of Tran s cu r ium Elem en t

Ch em ist r y Most In t e r e s t in g t o Ra d ioch em is t sA.

B .

c .D.

Cop r ecip it .a t ion a n dP r ecip it a t ion Ch em ist r y , .Comp lex Ion s a n dCh e la t e F or m a t ion s . . .E xt r ac t ion Beh at iorIon Exch a n ge Ch em is t r y . .1. Sep a r a t ion s of t h e

a ct in id e e a n d la n t h a n id e a .2. Sep a r a t ion s of t h e t r a n a cu r iu m

e lem en t s fr om ea ch ot h e r .v. Disso lu t ion of Sam p le s a n d Sp ecia l

P r ob lem s Re la t ed t o Ha n d lin g t h eTr a n scu r iu m E lem en t s . . .

~. Cou n t in g P r oced u r e s a n dSou r ce P r ep a r a t ion s . . .

VII . Sp ecific Sep a r a t ion P r oced u r e s .

v

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1

2

3

5

5

668

8

14

18

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The Radioc hem ist ry of t he Transcur ium Element sG. EL HIGGINS

La wren ce Ra dia tion La bora toryUn ive rs it y o f Ca lifo rn iaLive rm o re , Ca liforn ia

I . GENERAL COMMENTSTh e t r a n scu r iu m e lem en t g r ou p is com posed of b e r k e lium (Bk ), a t om ic

n umb e r 9 7 ; ca liforn ium (Cf), n um be r 98 ; e in s t e in ium (EH ), n um be r 9 9 ;fe rm iu m (F r o), n um b er 100; m en d e levium (Md ), n u m be r 101; a n d n ob e liu m(No), n um be r 1 0 2 . :.

Th ese e lem en t s a re a ll syn t h e t ic ; t h a t is , t h ey are a ll u su a lly p roducedb y m ult ip le n eu t ron cap t u re or ch arged pa r t ic le r eac t ion s on isot opes o f e le -m en t s of lower a t om ic n um be r . Th e ir d iscovery an d produc t ion is d e sc r ibedb y Th omp son .,l With t h e in c lu s ion of t h e a s ye t u n d iscover ed e lem en t 103t h ey com pose t h e se con d h a lf o f t h e a c t in id e se r ie s in w h ich t h e 5f e le c t r onsh e ll i s b e in g com p le t ed . Th e ir ch em is t r y is ext r a o r d in a r ily s im i la r t o t h a tof t h e la n t h a n id e s or r a r e ea r t h s. Excep t in g Bk (a n d p oss ib ly No), t h eye t is t sole ly a s t r ip os it ive ion s in a qu eou s solu t ion s . Bk ca n b e oxid ized t ot h e +4 st a t e u n d e r con d it ion eq u iva len t t o t h ose r eq u i r ed fo r ot id a t ion ofCe+3 t o Ce w (=1 .6 v).

Th e ch em ica l p r op e r t ie s o f a n y on e of t h e se e lem en t s a r e q u i t e s im ila rt o t h ose of t h e r es t , s o it is a p p r op r ia t e t o sp e a k of m a n y of t h e ir ch em ica lp r op e r t ie s in collec t ive t e r m s. Th e r a d ioch em ica l p r oced u r e s ca n u su a llyb e d iv id ed in t o t h r ee p a r t s :

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1. Th e isola t ion of a t r ip os it ive la n t h a n id e -a ct in id e fr a c t ion .2. Sep a r a t ion of t h e t r ip os it ive a c t in id e s fr om t h e la n t h a n id e s .3, Sep a r a t ion of t h e a ct in id e s fr om ea ch o t h e r .

Th e t r a n scu r ium a c t in id es h a ve ch a r a c t e r is t ic a d e ca y en e r g ie s (n o t et h a t t h e ligh t P b -Bi iso t op e s m a y b e con fu sed w it h som e t r a n scu r iu m n u c lid es )a n d sh or t sp on t a n eou s fi s s ion h a lf-live s . Beca u se of t h e se p r op e r t ie s t h eyca n b e id en t ifie d a n d m ea su r ed w it h ou t b e in g en t ir e ly sep a r a t e d fr om fiss ionp r od u c t s , a n d h en ce som e of t h e p r oced u r e s d o n o t p r ovid e for com p le t ep u r ifica t ion s .

Th e ligh t e s t t r a n scu r ium e lem en t , Bk , i s five a t om ic n u m be r s b eyon dt h e la s t a b u n d a n t ly occu r r in g n a t u r a l e lem en t , u r a n ium . Th e lon ger -livediso t op es of Bk a r e seve r a l m a ss n u m b er s m or e t h a n 238, so even t h is m os te a s ily p r od u ced t r a n scu r ium elem en t is seve r a l t r a n sm u t a t ion gen e r a t ion sa w a y fr om n a t u r a l occu r r en ce . Th er e fo r e t h e se e lem en t s h a ve n ot ye t b e ena va ila b le for s t u d y in la r ge r t h a n m icr ogr am qu a n t i t ie s . C u n n in gh am 2 a n dTh om p son a n d Mu ga 3 h a ve r ep or t e d t h e m a gn e t ic su scep t ib il i t ie s of t h e t r i -p os it ive Bk a n d Cf ion s a s w ell a s t h e so lu t ion a b sor p t ion sp e c t r a in t h e r a n gefr om a b ou t 5300 t o 8700A. Ne it h e r ion is s t r on g ly color ed a lt h ou gh Cf +3

d isp la ys tw o w ea k a b sor p t ion p ea k s a t 7800 a n d 8300A. Th e se s t u d ie s a r er em a r k a b le in t h a t t h ey w er e p e r for m ed on su bm icr ogr am qu a n t it ie s o f Bka n d Cf. No su ch w or k . h a s b e en p oss ib le on E s , Fm , Md , or No, a n d in fa c t

a lm os t n o ch em ica l s t u d ies , e ven a t t r a ce r leve ls , h a ve b een p oss ib le on Mda n d No beca u se t h e h a lf-live s o f t h e ob se r ved iso t op e s a r e so sh or t . I t i scle a r t h a t t h e r e is ve r y lit t le in for m a t ion a b ou t t h e se e lem en t s excep t w h a ti s d e r ived fr om t r a ce r s t u d ie s a n d comp a r ison s w it h t h e ch em is t r y of t h ela n t h a n id e s .

11 . GENERAL REVIEWS OF THE CHEMISTRY OF THE TRANSCURHJ MELEMENTSGen e r a l r e view s of t h e ch em is t r y of

fou n d in t h e fo llow in g book s a n d a r t icles :t h e t r a n scu r ium e lem en t s ca n b e

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G. T. Seaborg , llTh e Tr an ~Ur an i Um Ele m en t s, II Ad &~On .We ~le YPublish in g Co. , In c . , Read in g, Mass . , 1 9 5 8 . [Re f. 4 . ]

J . K . Kat z an d G. T. Se aborg, I !ch em is t r y of t h e Act in id e E lem en t s , Met h u en a n d Co. , Lt d . , Lon d on , 1957. [R ef. 5. ]

S. G. Th om p son , B. G. Ha r vey , G. R . Ch op p in , a n d G. T. Sea b or g,J . Am . Ch em . Sot . 7 6 , 6 2 2 9 (1 9 5 4 ). [Re f.6 . ]

B. B. Cun n in gh am , J . Ch em . Edu c . 3 6 (J a n u a ry , 1 9 5 9 ). [Re f. 2 . ]S. G. Th om pson an d M. Lou is Mu ga , !lMet h od a of P r od u ct ion a n d

Re se a r ch on Tr a n scu r ium E lem en t s , P r oc . U. N. In t e r n . Con -f. P e a cefu lUses Atom ic En er gy, 2n d , Gen eva , ---- .-, ,----- .-.

III. TABLE OF ISOTOP ES OF THE

Nucl ide

97Bk 24 3Bk244Bk245

24 6BkBk247

Bk248Bk249Bk250

98CP4cf245cf246cf247cf248

9 8 c f 2 4 9cF50cf251cf252

1/2

4.5h4.4h4.98 d1.8d

4=10 y16 h314d3.13h

25 m44 m35.7 h2.5h350 d3 6 0 y10.9 y

CIS00 y2.2y

TRANSCURIUM ELEMENTS

Mod e of Deca y

EC, 99+ L70 ;, O. 15%EC, 99 +~a ; a , 6X 10-37,EC, 99 +~.; a, O. 11~ECa

$-, 70L7.; EC, 30~~-, 99+%; a 2 .2 x1 0-3 7 0; SF , 6 X1 0 -6 ~O.P-

aEC, 7 0 7 0 ; a, 307a ; SF , 2X 10-4%ECa ; SF>l .5X10 -270

a ; SF , 4X 10-4~0a ; SF -O . 1 5%a

a , 9 7 70 ; SF, 3 ~0

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111. TABLE OF ISOTOP ES OF THE TRANSCURIUM ELEMENTS

Nucl ide~f253

E~24699 ES247

E~248E~249~B250EB251E~252

~ooFm 24 8

Fm249Fr n20Fm25Fm252Frn23

,ooFm 25 4

Fm25F rn256

Md256

102N253

M_17 d

{ 56d/

7,3m

25 m2h8h1.5d

=140d20.03 d480 d37 h24 dE h o r t

0.6m150 B30 m7h

22.7h=3.0 d3.24h21.5h3-4h

=30 m

=10s

Mod e of Deca v

a, ECaEC, 9 9+~o; a , 0.3~oEC, 99 +~,; a , O. ls~oECEC, 99 +7,; a , 0.53~0aa ; SF , 8X10-670a ; n o ~-~-, 99+70; EC =0. 17,P -13 -

a

a

a, ECEC -9970; a =1 7 0a; SF < 4X10-2~0EC, 897.; a , 1 1 7 .a; SF, 5.50 X10-2~0a ; SF < 4. 5X 10-3~SF = 100~o

a+ ?

EC

a+ ?

(Co nt d. )

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HI. TABLE OF ISOTOP ES OF THE TRANSCURIUM ELEMENTS (Con t d , )

Nuc l ide k Mode of Deca y

N0254 38 1 a +?25 6~~3 (t en t a ti ve 0.25 s a +?iden t i f ica t ion )

Abb r ev ia t ion s in t h e t a b le a b ove a r e a s follow s:a = secon ds, m = m in u t e s, h = h ou r ~, d = d a ys, y = yea rm ,EC = ele ct r on ca p t u r e , a . a p a r t icle em iss ion , p - = n ega t r onem iss ion , SF = sp on t a n eou s fis s ion d eca y.

A mor e comp le t e d esc r ip t ion of m os t of t h e se n u c lid es ca n be fou n d int h e comp ila t ion by St r om in ger , Holla n d er , a n d Sea bor g in Rev iew s of Mod er nP h ys ics , Vol. 30, No. 2, P a r t II , p p . 585-904. Th e a p a r t icle en e r gie s ,d e ca y sch em es , a n d gen e t ic r e la t ion sh ip a r e t a bu la t ed .

IV. REVIEW OF FEATURES OF TRANSCURIUM ELEMENT CHEMISTRYMOST INTERESTING TO RADIOCHEMISTS

IV. A. Cop r ec ip it a t ion a n d P r ecip it a t ion Ch em is t r yTh e t r ip os it ive a c t in id es d isp la y su ch m a r k ed s im ila r it y t o t h e la n -

t h a n id e s t h a t on e of t h e la t t e r (u su a lly Ce or La ) is or d in a r ily u sed a s aca r r ie r d u r in g p r ec ip it a t ion st e p s. Th ey a ll for m in so lu b le flu or id es fr omst r on g ( ==3-5M ) a cid , oxa la t es fr om Less s t r on g a c id s (x 1-2M ), p h osp h a t es in s ligh t ly a cid ic so lu t ion s ( *O. lM ), a n d h yd r oxid e s or h yd r a t ed ofid es inb as ic so lu tion s. Th ese h yd r a t ed ox id e s a r e in so lu b le in d ilu t e ca r bon a t es ,b u t t h ey r ea d ily d iesolve in exce ss (40%) ca r bon a t e o r m a n y of t h e comp le t -in g a n ion s of o r ga n ic a cid s su ch a s cit r a t e ,

Wh iLe t h er e a r e seve r a l o th e r ion s wh ich cop r e cip it a t e a s in solu b leoxyflu or id es a t low er a cid con cen t r at ion s , t h e p r e cip it a t ion of flu or id es

+3 +3fr om =3M HC1 or HN03 u n iqu e Ly c a r r ies Sc , Y , t h e t r ip os it ive la n -th a n id e s a n d a ct in id es , t h or ium , a n d t h e a lk a lin e ea r t h s . Th e a lk a lin e ea r t h

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gr ou p is le ft in so lu t ion w h en t h e r em a in d e r of t h e se e lem en t s a r e p r ec ip i-t a t ed a s h yd r a t ed ox id e s fr om ca r bon a t e -fr e e solu t ion s . Hold ba ck Sr ++

en h a n ce s t h e sep a r a t ion a ch ieved w it h a n y s in gle p r ec ip it a t ion s t ep .Of cou r se , t h e t r a n scu r ium elem en t s d o n o t ca r r y a p p r e cia b ly on a cid

su lfid e s , lea d ch r om a t e , b a r ium su lfa t e , or s ilve r ch lor id e .Bk+4 cop r e cip it a t es w it h zir con ium ph osp h a t e , zir con ium iod a t e a n d

7ee r ie iod a t e , a n d in solu ble h yd r ox id e s.

IV. B. Comp lex Ion s a n d Ch e la t e F or m a t ion sTh e or d e r o f t h e comp le t in g p ow er of d iffe r en t a n ion s is flu or id e >

ch lo r id e > n it r a t e > p er ch lor a t e for m on on ega t ive a n ion s , a n d ca r bon a t e >oxa la t e > su lfa t e for d in ega t ive a n ion s . Th e comp lex/ch e la t e for m a t ion isof u tm os t im p or t a n ce in ion exch a n ge sep a r a t ion s s in ce t h e +3 ion s a r e sost r on gly a d sor b ed on ca t ion r es in t h a t sp e cia l, m ea su r e s a r e r equ ir ed fort h e ir r a p id e lu t ion . Comp lex ion s a r e for m ed w it h or ga n ic su b s t a n ces , a n dc i t r a t e , t a r t r a t e , la c t a t e , a -h yd r ox+s obu t y r a t e , EDTA, TTA, a ce t a t e , a n dt h iocya n a t e a r e k n ow n t o form m od er a t e ly s t r on g comp lexe s , F or in st a n ce ,t h e d issoc ia t ion con s t a n t o f t h e EDTA comp lex of Cf is lis t ed a s 10 - 19 .09+C.2

b y F u ger . 8

IV. C., Ext r ac t ion Beh av io rTh e on ly r a p id ext r a ct ion sep a r a t ion for t h e t r a n scu r iu m e lem en t s in -

-1-4volve s t h e ext r a ct ion of Bk awa y fr om Bk 3, Cm +3, a n d Cf+3 in t od i(2 -e t h y lh exyl) o r t h op h osp h or ic a cid -h ep t a n e fr om HN03 solu t ion s . Th er a t io o f ext r a c t ion coe fficie n t s fo r t h e +4 s t a t e is m or e t h a n 10 6 t im es t h a t

for t h e +3 st a t e . 9 P r oced u r e 6 (Sect ion VU of t h is r e p or t ) i s b a sed on t h isex t r a c t i o n .

Cf, E s , Fm , a n d Cm ca n b e sep a r a t ed fr om ea ch ot h er a n d fr om th ela n t h a n id e s w it h a p p r op r ia t e ext r a c t ion s in t o d i(2 -e t h y lh exyl) p h osp h or ic a cid ,2 -e t h ylh exy l p h osp h or ic a cid jor d ip h en y l p h osp h or ic a cid fr om a q u eou s HC1

10so lu t ions . Th ese ext r a c t ion s a r e e ffec t ive w it h m a cr o con cen t r a t ion scf. 1

of

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p h a t ea g e n t

Th e ext r a c t ion s of t h e la n t h a n id e s a n d12a r e d iscu ssed b y Bes t e t a l. , a n d a

13is d esc r ib ed b y Hu le t .Ma gn u ssen e t a l. 14 h a ve r ep or t e d t h e

a c t in id e s in t o t r i-n -b u t yl p h os -p u r ifica t ion of Bk w it h t h is r e -

ex t r a c t ion coe ffic ie n t s of seve r a lof t h e t r a n scu r iu m e lem en t s fr om O. lM ammon ium ch lo r oa ce t a t e b u .t fe r in t oTTA-t o lu en e so lu tion s. Th e d a t a fit t h e eq u a t ion

K= E (H +)3 J(HT )3(fHT )3

w h e r e E is t h e ex t r a c t ion coe ffic ien t , HT is t h e TTA con cen t r a t ion in t h eor ga n ic la ye r , a n d f HT is t h e TTA a ct iv it y coe ffic ien t in t h e or ga n ic p h a se sg iven b y fHT = 1 0.24 (HT)0.48. Th e d a t a a r e lis t ed in Ta b le I , co r r ec t ed

t o b en zen e solven t b y P osk a n ze r a n d F or em a n 15 wh o su b t r a ct e d O. 2 pH u n itfr om t h e pH5 ~ va lu e ob t a in ed in t olu en e a n d r eca lcu la t e d K.

Ta b le I . Ext r a ct ion coeffic ien t s (K) of t h e t r a n scu r ium e lem en t s for ext r a c -t ion fr om O. lM amm on iu m ch lor oa ce t a t e in t o TTA-t o lu en e solu t ion s .

Ion K pH for 507. Ext r a ct ion (Ben zen e )Bk+3 -7==1.5X1O 3.0Cf 3 8X 10-8 3.1E +3 6X 10-8 3. 1Fm+3 8x1O -8 3. 1

Th e la n t h a n id e e ex t r a ct u n d e r n e a r ly t h e s am e con d it ion s , i . e . , PH50for La is =4. O a n d pH50 for Lu is -3.0, so la n t h a n id e -a c t in id e sep a r a t ion sa r e n ot r ea di ly fe a sib le . Gr ou p sep a r a t ion s fr om ion s of t h e a lk a lin e e a r t hgr ou p , t h e +4 Zr -H f fam ily, a n d t h e oxygen a t ed ion s ca n b e p e r fo r m ed byp r e -ex t r a c t in g Zr , Hf, P a , Np , P u , e t c . fr om a so lu t ion a d ju s t e d t o pH 2,d isca r d in g t h e or ga n ic p h a se , t h en a d ju s t in g t h e pH t o 4.5 a n d ex t r a c t in gt h e la n t h a n id e s a n d a c t in id e s . Th is s t ep h a s n ot b e en r ep or t ed in a n y of t h ecu r ren t ly u sed p r oced u r e.

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IV. D . on E xch a n ge Ch em is t r y-.[ Th e gr ea t s im i la r it y b e tw een t h e va r iou s t r a n scu r ium e lem en t s h a sin t e n s ifie d in t e r es t in a n d w or k on t h e i r ion exch a n ge b eh a v io r . Wit h t h e ex-cep t ion of No, t h e t r a n scu r ium elem en t s h a ve b een id en t ified b y t h e i r r e la t ive

e lu t ion p os i t ion s fr om ca t ion exch a n ge r es in . Wh ile sep a r at ion p r oced u r esh a ve b een d ev ised w h ich d o n ot m a k e u se of ion exch a n ge op er a t ion , t h eya r e n ot p r e sen t ly in gen e r a l u se .

In or d e r t o com p a r e d a t a fr om va r iou s sou r ce s , t h e ion -exch a n ge -co lum n e lu a t e vo lu m es h a ve b een r ed u ced t o u n it s o f I lfr e e colu m n volu m es .!!Th is vo lu m e , a b b r ev ia t e d F CV, is ch a r a c t e r is t ic o f a p a r t icu la r r e s in b edloa d in g a n d ca n b e d er ived fo r a n y colum n b y fin d in g th e e lu t ion p os it ion ofu n a b sor b ed m a t e r ia ls su ch a s or ga n ic d ye s , e t c . Th e F CV is a b ou t 55% oft h e volum e of t h e colu m n bor e .

IV. D. 1 Sep a r a t ion s of t h e a ct in id e s a n d la n t h a n id e s. Th e ch lor id e a n d t h io -cyan at e com plexe s o f t h e ac t in ide s a re s t ron ge r t h an t h e cor r e sp on d in g cOm -p lexe s of t h e la n t h a n id e s . Wh en m ix t u r e s o f La n t h a n id e s a n d a c t in id e s a r ee lu t e d fr om st r on g b a se ca t ion r e s in s su ch a s Dow ex-50 or Zeo-Ca r b 225w it h 12M HC1 or 2M NH4CNS, t h e a c t in id e s a r e e lu t ed b e fo r e t h e la n t h a n id e s an d gr ou p sep a r a t ion s a r e ob t a in ed . F igu r e 1 in d ica t e s t h e r e la t ive e lu t ionp os it ion s fr om Dow ex-50 AG w it h 2070 e t h yl a lcoh ol sa t u r a t e d w it h HC1 ga s

225 r es in . F igu r e 2 sh ow s t h e r e la t ive e lu t ion p os it ion s fr om17u s in g 1. 8M NH4CNS e lu a t e .

comp lexes of t h e a c t in id e s in ve r y s t r on g comp le t in g a gen t s su ch

6, 16a t 20C. Sim ila r sep a r a t ion s a r e ob t a in ed w it h t h e sam e e lu a n t fr omZeo-CarbDowex-50

Th ea s 13M H(ZL, IOM LiCl, a n d 2M NH4CNS a r e su ch t h a t a n ion ic sp ec ie s a r e fo rmed . Sim ila r a n ion ic sp e c ie s o f t h e la n t h a n id e s a r e n ot a s p r oba b le u n d e rt h e s am e con dit ion s, so gr ou p sep a r a t ion s a r e p oss ib le u s in g t h e se com p lex-

18in g a gen t s a n d a n ion exch a n ge r es in .F igu r e 3

Dow ex- 1 a n ionsh ow s t h e r e la t ive e lu t ion p os i t ion s of t h e a c t in id e s fr om

6..r e s in w i t h 13M HC1. Slm lla r or b e t t e r sep a r a t ion s h a ve

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1.0

0

Rh Fm Cf, Es Bk Am Cm Yb

o I 2 3 4 5 6FREE COLUMN VOLUMES

F ig . 1. Re la t ive e lu t ion p os it io n s of t r a n sp lu t on ium a ct in id e s , Y, Yb , a n d R h fr omDow ex-50 AC w it h 20% e t h yl a lcoh ol sa t u r a t ed (S= 12. 5~ ) w it h HC1. Th e t r a n sp lu t on ice lem en t s a p p e a r a s a gr ou p b e t w een O. 3 an d 3 fre e column vo l umee .


16/41

Lo

Es Cf Bk Cm Am

0.012 3 4 5 6 7 8 9

FREE COLUMN VOLUMESF ig. Z. Re la t ive e lu t ion p os it ion s of t h e t r a n sp lu t on iu r n a ct in id es fr om

Dow ex-50 w it h 1. 8~ amm on ium t h ioc~n a t e a t 87 C.

10


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0

I 1 I I I I I I I I I I

LANTHANIDES

mm

CfBk Es Fm

J 1 1 I2 4 6 0 10 12 14

FREE COLUMN VOLUMESFig . 3. Re la t ive e lu t ion p os it ion e of t h e la n t h a n id es a n d t r a n sp lu t on iu m

a c t in id es fr om Dow ex - 1 w it h 13~HCl a t r oom t em p e r a t u r e .

1 1


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o

I I I I I I I I I I I I I

Cm Am Es Bk Cf

2 4 6 8 10 12 14FREE COLUMN VOLUMES

F ig. 4. R e la t ive e lu t ion p os it ion s of t h e t r a n sp lu ton ium a c t in id e s fr omDow ex- 1 w it h 2. OM amm on ium t h iocya n a t e a t 87 C.

1 2


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b een r ep or t ed u s in g t h e sam e e lu a n t a n d Ambe r lit e IRA-400. 19 F igu r e 4sh ow s t h e r e la t ive e lu t ion p os it ion s fr om th e sam e r es in u s in g 2M NH4CNS.Lit h ium ch lor id e so lu t ion s of a bou t 10M give a d sor p t ion s a n d e lu t ion sequ iva len t t o 13M HC1.

Wh en t h e t r a n scu r ium a ct in id e s a r e e lu t ed fr om ca t ion r es in s lik eDowex-50 J %G(4~o cr oss -lin k ed ) w it h O. 1~ t o 6~ HC1, ver y lit t le sep a r a t ionbe tween t h e a ct in id e a a n d la n t h a n id e s is ob t a in ed , bu t sep a r a t ion s fr om mostot h e r ca t ion s ca n be effec t ed . P r oced u r e 7 (Sect ion VII of t h is r epor t ) byP h illip s a n d Ga t t i 20 u se s a I Ic lea n u p l! co lum n op er a t e d p r im a r ily t o r em oveim p u r it ie s of Ca , F e , a n d Al. Colum n s op er a t e d a t 87C a r e a ssem b leda s sh own in F ig. 5. Tr ich lor oe t h ylen e

A\ELUANT+

RESIN BED

TRICHLOROETHYLENE-F

is boile d a n d it s va p or is con d u c t ed

F ig. 5. Colu m n a p p a r a t u s for e lu -t ion s a t 87C. Tr ich lor oe t h ylen e isboiled in t h e fla sk , t h e va p or s con -du ct ed t h r ou gh th e colum n ja ck e ta r ou n d th e r e s in b ed , a n d th e con -1 d en sed va p or r e t u r n ed t o t h e fla sk .

a r ou n d t h e co lum n in t o a con d en ser a n d ba ck to t h e b oilin g fla sk , t h u s p r o-

vid in g h ea t exch a n ge a t 87 C. H igh er colum n t em p e r a t u r es a r e less p r a c-t ica l b e ca u se of t h e form a t ion of va p or bu b b le s in t h e solu t ion s a n d r es in b ed ;h ow ever , w it h a d eq u a t e ca r e , t em p er a t u r es t o 100C ca n be u sed .

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IV. D. 2. Sep a r a t ion s of t h e t r a n scu r ium elem en t s fr om ea ch o th e r . Wh ilesep a r a t ion s of t h e t r a n scu r ium e lem en t s fr om ea ch ot h er a r e ob t a in ed w it hr e la t ive ly con cen t r a t ed HC1 a n d NH4CNS, n o e lem en t is sep a r a t e d c lea n lyfr om it s n e igh b or .

Th e m os t con ven ien t a n d fr equ en t ly u sed m et h od for sep a r a t ion of t h esee lem en t s fr om ea ch ot h er h a s b e en to e lu t e t h em fr om ca t ion r e s in w it h ch e -La t in g or ga n ic a c id a n ion s . Sever a l a c id a n ion s in clu d in g t h ose of cit r ic ,glycolic , t a r t a r ic , la ct ic , a n d a -h yd r oxyis ob u t yr ic a cid h a ve b een u sed su c-

21cess fu lly a s e lu a n t s . Wh ile som e a d va n t a ge is ob t a in ed in sep a r a t ion fa c -t or s if a -~r oxyisobu t y r a t e is u sed , t h e gen er a l fea t u r e s of t h e e lu t ion a r et h e sam e w it h a n y of t h e e lu a n t s . F i g u r e 6 is a t yp ica l e lu t ion cu r ve of t h ea c t in id e s fr om Dow ex-50 ( 1270 cr oss -lin k ed ) w it h amm on iu m a -h yd r oxyiso -

b u t y r a t e . Sim ila r e lu t ion s a r e r ep or t ed a t r oom t em p er a t u r e fr om t h e sam e16r es in (4~0 cr oss -lin k ed ) 22a n d a t 77C fr om Zeo-Ca r b 225.Ta b le I I in d ica t es t h e e lu t ion p osi t ion s of t h e a c t in id e s a n d la n t h a n id es

fr om ca t ion r es in w it h a -h yd r oxyisobu t y r ic a cid , Th e d a t a a r e n orm a lizedto Cm = 1.00. Da t a h a ve been summa r ized fr om Ch op p in e t a l. , 21 Sm it h

16 22a n d H offm a n, a n d Milst ed a n d Bea d le .Sin ce t h e e lu t ion p os it ion of a p a r t icu la r e lem en t d ep en d s on t h e com -

p e t it ion be tween t h e r e s in a n d a so lu t ion p h a se ch e la t e ,, t h e p os it ion ca n be

va r ie d a t w ill b y a d ju s t in g t h e p a r am e t e r s t h a t d e t e r m in e t h e ch e la t e con cen -t r a tion . Th e se a r e t h e pH of th e solu t ion of w ea k a c id s wh ich fo rm ch e la t in ga n ion s , a n d th e t ot a l a cid con cen t r a t ion . F igu r e 7 sh ow s t h e e ffec t of va r y-in g t h e pH of solu t ion s of amm on ium a -h yd r oxy i sob u t yr ic a c id . Th e e ffec tof a ch a n ge of a -h yd r oxyis obu t y r ic a cid con cen t r a t ion ca n be ca lcu la t ed b ya ssum in g Kd w ill b e u n ch a n ged w h en t h e a n ion con cen t r a t ion is t h e s am e a n dt h e ion iza t ion con st a n t of t h e a cid is 1. 1 X 10-4.

Th e sp a cin g be tw een t h e h ea v ie r m em be r s of t h e se r ie s , Md a n d Fm ,

is m u ch le ss t h a n t h e sp a cin g b e tw een Cf a n d Bk for con s t a n t pH a n d con -cen t r a t ion of e lu a n t . Alt h ou gh n ea r ly equ a l sp a c in g h a s b een a t t a in ed forr a r e -ea r t h sep a r a t ion s in colum n s u t il izin g con t in u ou s ly va r ia b le e lu a n t s , 23

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I.0

>1-:;vau 0.1>LaJuc

0.01

F ig . 6.

I I I I 1 I I I I I I I I

o

Cm 1

~2 4 6 8 10

FREE COLUMN VOLUMES12 14

Rela t ive e lu t ion P O .s i t ion e of cu r ium a n d th e t r a n s cu r ium a c t in id esfr om Dow ex-50 1270 c r oss -lin k ed r es in w it h pH 4.2 a ~on ium a -h yd r oxyiso -b u t yr a t e a t 87 C.

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Ta b le I I . E lu t ion p os it ion s of a c t in id e s a n d la n t h a n id e s fr om ca t ion exch a n ger e s in w it h a -h yd r ox~Bob u t y r ic a c id .

E l emen t Dow ex-50 4L70a t Zeo-Ca r b 225 a t Dow ex-50 12~0 a t25C 77C 87 C

MdFmE sCfBkCmAmLuYbTmErHoYDyTbGdEuSmPmNdLaCe

----0.130.190.371.001.390.110.0160.22--0, 039

0.0690.0760.140.220.340.71.12.3--3.4

------

0.21--

1.001.38----------------------.------.

0.0500.0690.130,200.451.001.40.0150.0200.0260.0370.0550.060.0780.140.280.390.711.22.1r .3,5

t h e r e a r e n o r ep or t s t h a t t h is h a s b een a ccomp lish ed w it h t h e t r a n scu r iume lem en t s .

Th e flow r a t e a t w h ich a colum n is op er a t ed a ffec t s t h e a p p a r en t w id t hof t h e e lu t ion p ea k e . F igu r e 8 sh ow s t h e effect fo r Dow ex-50 127 r e s in ,gr a d ed to se t t le a t O. 5 t o O. 25 cm /m in in w a t e r , w h en t h e e lu a t e is O. 4~la ct ic a c id a n d t h e colum n is op e r a t e d a t 87*G. Th e cu r ve is d isp la cedtowa r d gr ea t e r h a lf-w id t h s a t t h e sam e flow r a t e w h en coa r se r r e s in is u sed .A lim it in g h a lf-w id t h of a b ou t 5 or 67 is fou n d w it h t h e fin e st r e s in a n d s low -e s t flow r a t e a .

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100

50

10

5

1.0

0.53.6 4.0 4.4 4.8

pHF ig . 7. Th e p ea k p osit ion of Cff a n d Cm a s a fu nct ion of .p Hfo r O.-4~ a mm on iu m

a -h yd roxyisobu ty r at e a n d Dowex-50, 12% cr oss -lin ked r es in . Th e p ea k p os it ion ofot h e r la n t h a n id es a n d a ct in id e s ca n be p r ed ic t ed fr om t h is cu r ve a n d th e t a b le in t h et ex t .

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I I I

I I I Io I 2 3 4FLOW RATE (ml/min/cm20F COLUMN AREA)

Fig . 8. Full w id t h a t h a lf m a xim um (h a lf-w id t h ) o f t h e e lu t ion p ea k ofcu r ium fr om Dow ex-50 12L70cr oss -lin k ed r es in w i th O. 4~ amm on ium la ct a t ea t 87 C on on e p a r t icu la r co lum n . Sim ila r cu r ve s wou ld b e ob t a in ed w it ho t h er e lu a n t s a n d ot h er co lum n s , b u t t h e r e s in p a r t ic le s ize , t em p e r a t u r e ofop e r a t ion , len g t h -t o -d iam e t e r r a t io of t h e r e s in b ed , t ech n iqu e , a n d th ep r e sen ce or a b sen ce of ca r r ie r s o r m a ss im p u r it ie s a ll a ffect t h e a b so lu t eva lu e of h a lf-w id t h a t a n y flow r a t e .

v . DISSOLUTION OF SAMP -LES AND SP ECIAL PROBLEMS RELATED TOUDLING TI-IX TRANSCURIUM ELEMENTS

Th e t r a n scu r ium e lem en t s a r e a ll u n s t a b le w it h r esp e ct t o a p a r t icleemi s s i on . Sp on t a n eou s fi s s ion is a lso a d isin t e gr a t ion m od e so t h a t con -s id e r a b le n um be r s of n eu t r on s m a y be em it t e d b y som e sam p le s a n d t a r ge t s .Th e se fa ct s m a k e t h e h a n d lin g of m icr ogr am or la r ge r q u a n t it ie s o f som et r a n scu r ium e lem en t s ve r y d ifficu lt a n d p o t en t ia lly h a za r d ou s . Mos t ch em -ica l op e r a t ion s m u st b e ca r r ied on in gloved b oxes , a n d in m a n y in s t a n ce s

18

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r em ot e -con t r ol h a n d lin g equ ipm en t is r e qu ir ed even a ft e r t h e sam p le s a refr ee of fi s s ion p r od u ct con t am in a t ion . F or in s t a n ce , 1 m icr ogr am of Cf 25 2

8em it s 42 X 10 n eu t r on s /m in a n d p r e sen t s a bou t a t o le r a n ce w or k in g d oseof n eu t r on s a t a d is t a n ce of 1 m et e r . La bor a t o r ie s eq ,u ip p ed t o h a n d le t h e

t r a n scu r ium elem en t s sh ou ld h a ve a -p a r t icle a n d n eu t r on su r vey m e t e r s a sw e ll a s t h e u su a l ~-y su r vey m et e r s .

Th e t r a n scu r ium e lem en t s a r e p r od u ced in a t lea s t t h r ee d iffe r en tk in d s of t a r ge t . Th e n eu t r on -d e fic ien t iso t op es a r e p r od u ced b y h ea vy-ionbomb a r dm en t s of u r a n iu m or p lu t on iu m by r e a c t ion s su ch a s

238 + ~12 >40n L + ~8Cf 24 692U 6

in w h ich t h e p r od u ct a t om s a r e colle ct e d on !I r e co il ca t ch e r si l se p a r a t e fr omt h e bomb a r d ed t a r ge t m a t e r ia l. Th e t e ch n iq u e s a n d d ifficu lt ie s a r e d iscu ssedb y Th om p son a n d Mu ga 3 24a n d Gh ior so a n d S ik k e la n d . Br ie fly , w h en t h ech em is t r y lS d on e , t h e t a r ge t or ca t ch er fo il is d is so lved in t h e a p p r op r ia t es t r on g a c id solu t ion a n d t h e a p p r op r ia t e Rep a r a t ion s a r e p e r fo rm ed . Wh ent h e t r a n a cu r ium e lem en t s a r e p r od u ced in t h is w a y n o sp ec ia l h a n d lin g equ ip -me n t , su ch a s g love b oxe s , m a y b e n eed ed a lt h ou gh it m a y b e n eed ed fo rt a r ge t p r ep a r a t ion if t r a n ep lu t on ium e lem en t s a r e b om ba r d ed . Th e t a r ge tit se lf i s se ld om d issolved or h a n d led w h en t h e r e co il t e ch n iqu e is u sed .Sin ce t h e r e co il a t om s r e t a in p os it ive ch a r ge s w h en st op p ed in h e lium ga s ,t h ey ca n b e e lec t r os t a t ica lly colle ct ed as t h in sam p les a n d som e t im e s t h e ird e ca y ch a r a c t e r is t ic s ca n be st u d ied w it h ou t ch em is t r y ; h ow eve r , som e ofth e P b a n d Bi isot op e s h a ve s im ila r a -d e ca y h a lf-l ive s a n d p a r t ic le en e r g ie sso t h a t id en t ifica t ion b y a p a r t ic le m ea su r em en t s a lon e m a y b e u n r e lia b le .Th e exp e r im en t s d on e b y Gh ior so, Sik k e la n d , Wa lt on , a n d Sea bor g lea d in gt o t h e d iscover y of e lem en t 102 (n obe liu m ) a r e c la ss ic in t h e sen se th a t eve r ya d va n t a ge h a s b e en t a k en of t h e se n on ch em ica l sep a r a t ion t e ch n iqu es . Lfch em ist r y is d on e on su ch e lec t r os t a t ica lly co llec t e d m a t e r ia l, t h e colle ct orp la t e s a r e s im p ly w a sh ed w it h con cen t r a t e d HC1 a n d t h e t r a n scu r ium ele -m en t s a r e r em oved w it h ou t d isso lu t ion of t h e p la t e .

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Th e secon d sou r ce of t r a n scu r iu m e lem en t s i s t h e d e b r is fr om t h e r m o -n u clea r exp lo sion s. E s a n d Fm wer e fir s t d iscove r ed in filt e r ed sa m p le sof t h e c lou d p r od u ced b y a mu lt i-m ega t on t h e r m on u c le a r e~los ion in w h icht h ey h a d b ee n p r od u ced b y m u lt ip le n e u t r on ca p t u r e in U 23 8 . Th e fi lt e r w a s

d is so lved b y r ep ea t ed ly d ige s t in g it in con cen t r a t ed HN03 a n d fin a lly d e s t r oy-in g t h e la s t t r a ce s of or ga n ic m a t e r ia l b y fu n in g t h e r e s id u e in con cen t r a t edHC104. Th e fum in g p e r ch lor ic a c id w a s t h en d ilu t ed w it h m or e t h a n 10 t im esi t s volu m e of 6N HC1, a n d a sep a r a t ion p r oced u r e s im ila r t o P r oced u r e 2(Sect ion VI I) w a s p er for m ed on a liq u ot s of t h is so lu t ion . Th e m a jor m a ss iv eim p u r i t ie s in su ch a so lu t ion a r e Ca , F e , Na , a n d Al. Th is k in d of sam p leu su a lly h a s so li t t le r a d ia t ion t h a t sp e cia l h a n d lin g eq u ipm en t is u n n ece ssa r y .

Th e la s t a n d mos t gen e r a lly en cou n t e r ed sou r ce of t h e t r a n scu r ium

e lem en t s is u r a n iu m , p lu t on ium , am e r ic iu m , or cu r iu m th a t h a s b ee n e x-p osed t o la r ge in t egr a t ed n eu t r on d ose s in a r ea c t or . Th e p r od u ct ion r a t e sa n d ch em ica l t e ch n iq u e s a r e d is cu s sed b y Th omp son a n d Mu ga . 3 Th e sam p leis u su a lly p r od u ced in a n a lu m in u m -c la d I ls lu g ll of a n ot id e or m e t a l a lloyof t a r ge t m a t e r ia l. Dis so lu t ion is a ccomp lish ed b y r em ovin g t h e a lu m in umin 6MNaO&M NaNO solu t ion , fi lt e r in g or cen t r ifu g in g t h e in so lu b le r e s i- 3d u e con t a in in g t h e t r a n scu r iu m . e lem en t s aw a y fr om t h e a lum in a t e so lu t ion ,a n d fin a lly d is so lv in g t h is r e s id u e w it h s t r on g m in e r a l a c id (u su a lly HC1, o r

occa s ion a lly HC1 w it h a t r a ce of HF a n d HN03). Th e se op e r a t ion s a r e p e r -for m ed b y r em ot e con t r o l in sh ie ld ed eq u ipm en t s in ce t h e t a r ge t m a t e r ia lsa n d in t e r m ed ia t e iso t op e s u n d e r go fis s ion w h ile t h e t r a n scu r iu m e lem en t sa r e b e in g for m ed . Th e com p le t e sep a r a t ion s , in c lu d in g t h e iso la t ion of ar a r e -e a r t h fr a c t ion a n d t h e sep a r a t ion of t h e Ia n t h a n id e a n d a c t in id e fr a c t ion s ,a r e u su a lly in c lu d ed in t h e !I ca ve !l op e r a t ion .typ ica l .

VI . COUNTING P RC)CEDURES AND SOURCEC Ou nt in g s a mp le s

I Im a a a -fr e e l! or llt h in ll

P r oced u r e 1 in Sec t ion VI I i s

PREPARATIONSof t h e t r a n scu r ium e lem en t s a r e u su a lly p r ep a r edb e ca u se t h e r e a r e n o s t a b le ca r r ie r s , o f cou r se , a n d

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vACUUM

F ig. 9. Sch em a t ic d ia g r am of va cu um vola t ilize r . Ca r r ie r -fr ee Bolu t ion aa r e eva p or a t ed on t h e t u n gs t en filam en t , t h e sys t em is eva cu a t ed , a n d t h et r a n scu r ium elem en t s a r e vola t i lized on t o t h e cou n t in g d ie t by p a ss in g a,sh or t -d u r a t ion h igh -cu r r en t p u lse t h r ou gh t h e tu n gst en fila men t .

b e ca u se som e of t h e m ost u se fu l m ea su r em en t s in volve th e a p a r t icles w h ichh a ve sh or t r a n ge s. Th e sam p le is u su a lly p r ep a r ed e it h e r by eva p or a t in g ad r op or seve r a l d r op s of colum n elu a t e on a p la t e of p la t in um or ot h er m et a la n d th en p e r for m in g t h e cou n t in g op er a t ion s, or b y eva p or a t in g t h e p u r eca r r ie r -fr e e solu t ion on t o a t a n t a lum or t u n gs t en filam en t a p p r oxim a t e ly5 mm w id e , 30 t o 50 mm lon g , a n d O. 1 mm th ick . Th is filam en t is p la cedb e tween e lec t r od es in a va cu um ja r a few m illim et e r s a w a y fr om a 7/8-in chp la t in um cou n t in g d isc, a s in d ica t ed in F ig. 9, a n d th e t r a n scu r ium elem en tsa lt s (u ~u a lly oxid e s ) a r e vola t i lized on t o th e cou n t in g d isc b y a llow in g mor eth a n 10 amp of cu r r en t t o flow t h r ou gh t h e filam en t for a few t en t h s of a sec -on d . Th is cu r r en t r a ises t h e filam en t t em p er a t u r e a bove 1400 C a n d effec -t ive ly va p or izes a ll t h e t r a n scu r ium ma t e r ia l. Ve r y th in u n iform cou n t in g

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p la t e s ca n b e p r ep a r ed in t h is w a y; h oweve r , t h e a ct ive m a t e r ia l w ill r ecoil,.off t h e p la t es a t a n a p p r ecia b le r a t e u n le ss t h ey a r e h ea t ed to a bou t 500 Cin a ir .

No sp ec ia l cou n t in g equ ipm en t is u sed for d e t ect ion of

ca p tu r e , o r a p a r t icles . Moa t t r a ce r w or k ie d on e w it h t h ee lem en t s b y u t i lizin g t h e fa ct t h a t isot op es of t h e se e lem en t s

~, e le ct r on -

t r a n s c u r i umh a ve u n iq u e a -

p a r t icle en e r gies . A p a r t icu la r p r oce se or bomb a r dm en t ca n be t r a ced b yin t r od u cin g k n own amou n t s, m ea su r ed in t e rm s of cou n t s p er u n it t im e , of

=f252a sp ec ific lon ger -lived iso t op e (e . g. , or Cf254 t o t r a ce a ll Cf iso -t op es ) an d su bm it tin g t h e re cove r ed sam ple s t o a p u lse -h e igh t a n a lysis . t od e t e rm in e th e r a t io of a cou n t s o f sever a l isot op es . An a pu lse -he igh ta n a lyzer is a va lu a b le a n d n ea r ly in d isp en sa b le p ie ce of cou n t in g equ ipm en t

for wor k w ith t h e t r a n scu r ium elem en t s ,Th e h igh sp on t a n eou s -fi s sion d eca y r a t e s a r e u t ilized in cou n t in g sam -

p les of t h e t r a n scu r ium e lem en t s. Sp on t a n eou s fis s ion cou n t e r s a r e e a s ilycon st r u ct ed by t a k in g a d va n ~a ge of t h e fa c t t h a t t h e sp ec ific ion iza t ion p r o-du ced b y fis s ion fr a gm en t s in a cou n t in g ga s is h igh e r t h a n th a t p r od u ced bya p a r t icles . La r ge e le ct r ica l p u lses a r e ob t a in ed fr om fiss ion fr a gm en t sb y mod ifyin g st a n d a r d a -p a r t ic le cou n t e r s t o op e r a t e w it h low er collec t orvo lt a ges . Sa t isfa c t or y op e r a t ion is u su a lly ob t a in ed w it h t h e collect or b e -

tw een 1/5 a n d 1/2 t h e volt a ge a t w h ich a n a p la t e au if fou n d . Th e gas flowp r op or t ion a l cou n t e r s u sed for bot h a - a n d ~ -p a r t icle cou n t in g a r e esp e cia llyu se fu l b eca u se th e ir collect or volt a ge s ca n u su a lly b e va r ie d w it h e a se . Sem i-con d u ct or d e t ect or s a n d ga s scin t illa t ion cou n t e r s ca n a lso b e u sed for d e -t ec t in g fie s im a fr agm e,n ta an d a pa r t ick s .

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VII . SP ECIF IC SEP ARATION P ROCEDURES

P r oced u r e 1

Th is p r oced u r e is for s ep a r a t ion of a n im p u r e t r a n scu r iu m e lem en tfr a c t ion fr om a p ile -ir r a d ia t ed p lu t on iu m or a m er ic iu m s lu g . 25 Th e p roce s sis d e s ign ed t o b e p e r for m ed on a 50-g a lu m in u m s lu g con t a in in g O. 1 t o 1.0 gof t a r ge t m a t e r ia l, Am a n d Cm a r e a lso p u r ified .

Th e slu g i s p la ced in a d is so lve r p ot su r r ou n d ed b y a n oil b a t h h ea t edt o 80C w it h a n e lec t r ic imm e r s ion h ea t e r . Th e n 800 m l of so lu t ion 6M inNaOH a n d 2M in NaN03 is added . Th e a lum in um vio len t ly reac t s an d goesin t o solu t ion (n o h ea t re qu ired a ft e r reac t ion s t a r t s ). Th e in so lu ble m at e r ia lis a llowed t o se t t le an d t h e su pe rn a t e is wit h dr awn t h rou gh a s in t e r ed s t a in -

le s s s t ee l filt e r s t ic k . Th e p re c ip it a t e is wash ed t wice wit h 5 0 -m l por t ion sof 2N NaOH sa t u r a t e d wit h NH3 gas , an d t h en wash ed wit h 1 0 0 m l of H20 .Th e -sh ed p rec ip it a t e is d is solved by add in g 5 0 m l of 1 2M HC1 O. lM ~03 and d iges t in g. Aft e r t h e re s idu e is d isso lved , 5 0 m l of llM LiCl ie . addedand t h e solu t ion is evapora t ed t o 5 0 m l,

Th e solu t ion is t r an s fe r red t o a 4 -cm -d iam X 20 -cm -lon g Dowex-1 1 0~0cross -lin ked res in colu m n w h ich i s h ea t ed t o 80 C w it h a w a t e r ja ck e t .(F r ee colu m n vo lu m e is -150 m l. ) Th e eva p or a t or con t a in e r a n d colum nw a lls a r e w a sh ed w it h tw o 50-m l p or t ion s of 10M LiCl w h ich a r e a llow ed t or u n t h r ou gh t h e colum n a t t h e r a t e of a b ou t 2 m l/m in . An a d d it ion a l 300 m lof 10M LiCl is p a s se d t h r ou gh t h e colu m n t o e lu t e t h e la n t h a n id e s , a lk a lin ee a r t h s , a n d a lk a li m e t a l ion s . Th e t r a n sp lu t on iu m a ct in id e s a r e n ext e lu t edw it h 200 m l of 6N HC1. P lu t on iu m r em a in s on t h e colu m n .

Th e 6~ HC1 is d ilu t ed t o 600 m l a n d p a ssed t h r ou gh a Dow ex-50 12~0r e s in b ed 4 cm in d iam a n d 20 cm lon g. Th e colu m n is t h en w a sh e d w it h 300m l of 2M NH4C1 wh ich r em oves Cr , Ni, a n d se ve r a l o t h e r im p u r it ie s a n dcon ve r t s t h e r e s in t o t h e NH4 + for m. Th e a c t in id e s a r e t h en e lu t ed w it hO. 4M a -h yd r oxyis ob u t y r ic a c id a d ju s t ed t o a su it a b le P H . Th e d es ir ed e le -m en t s a r e colle c t ed in fou r or fiv e I lcu t s t l s e le c t ed on t h e b a s is of t h e e le -


30/41

P roced u re 1 (Con t in ued )

m en t s d e s ir ed for fu r t h e r w or k a n d t h e n u m be r of F CVie p r ed ic t ed fr omF ig . 7 a n d t h e pH . Th e F (ZV is = 150 m l. Th e t r a n scu r iu m e lem en t fr a c -t ion t h u s ob t a in ed m a y b e p u r e en ou gh t o b e p r oce s sed w it h ou t r em ot e -con t r ole q u ipm en t a n d is u su a lly fu r t h e r p u r ified b y a p r oced u r e s im ila r t o P r o-ced u r e s 2 a n d 3 fo llow in g .

f rom

P r oced u r e 2Th is p r oced u r e w a s d e vis ed t o se p a r a t e t h e t r a n sp lu t on iu m e lem en t sd a y-o ld fis a ion p r od u ct s am p le s con t a in in g 10 15 t o 1016 f i s s ions . 26

Th e se e lem en t s a r e ca r r ied w it h yt t r iu m or la n t h a n um flu or id e a n d h yd r oxid ep r ec ip i t a t e s , w h ich a r e su b seq u en t ly d is so lved in HC1; t h e r e su lt a n t so lu t ioni s p a s sed t h r ou gh seve r a l a n ion r e s in colu r r m s t o r em ove U, No, P u , a n dm os t of t h e r em a in in g fiss ion p r od u ct s (in p a r t icu la r , Zr a n d Te ). Ane t h a n ol -HCl e lu t ion fr om a ca t ion r e s in colu m n is u sed t o r em ove t h e la n -t h a n i d e s .

To p r ep a r e t h e ion e xch a n ge colu m n s, t h e colu m n t ip s a r e p lu gged w it hg la s s w ool o r sa n d . A s lu r r y of r eE in is in t r od u ced a n d a llow ed t o se t t le ,a n d t h e s u p e m a t e d is ca r d ed . Th e r e s in i s w a sh ed b y p a s s in g seve r a l m l ofe lu a n t t h r ou gh t h e colu m n . A u n ifor m ly d ep osi t ed b ed of r e s in ,a ir b u b b le s or ch a n n e ls , is e s sen t ia l t o a su cce ss fu l e lu t ion .

1. To a n a liqu ot of t h e sam p le in a 40-m l cen t r ifu ge t u b e ,

fr e e fr om

a d d 2 d r op se a ch of 10 m g/m l Zr , Te , a n d Sr ca r r ie r s a n d 1 d r op of 10 m g/m l Y ca r r ie r .Usin g p h en olp h t h a le in in d ica t or , a d d NH40H to p r ec ip it a t e t h e Y(OH)3. Cen -t r i fu ge , d isca r d t h e su p e r n a t e , a n d w a sh t h e p r ec ip i t a t e tw ice w it h O. 5- 1.0m l H20.

2. Disso lve t h e p r ec ip i t a t e in a m in im um am ou n t of 3M HC1 a n d t r a n s -fe r t o a p olye t h ylen e t e s t t u b e . Ad d 2 d r op s con e HF p e r m l of so lu t ion ,(I f t h e so lu t ion con t a in s a la r ge a m ou n t of F e o r U, a d d en ou gh HF t o d e -

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P roced u r e 2 (Con tin ued )

co lor ize t h e so lu t ion , t h en 2 d r op s p e r m l in a d d it ion . ) Le t t h e so lu t ion s t a n dfor 5 m in u t e s , cen t r ifu ge , d isca r d t h e su p e r n a t e , a n d w a sh t h e p r ec ip it a t ew it h O. 5 m l of 2M HF 2M HN03 solu t ion .

3, Dis so lve t h e flu or id e p r ec ip i t a t e b y a d d in g 1 d r op sa t u r a t ed H 3B03,s t i r r in g , a n d t h e n a d d in g 2 m l con e HC1, Tr a n sfe r t h e so lu t ion t o a 40-m lgla ss cen t r ifu ge t u b e . Add 2 d r op s of 10 mg/m l Sr ca r r ie r a n d t h en b oilt h e so lu t ion b r ie fly . P r ec ip it a t e t h e Y(OH)3 w it h NH40H , cen t r ifu ge , d is -ca r d t h e su p e r n a t e , a n d w a sh t h e p r ec ip i t a t e tw ice w it h O. 5 - 1.0 m l H20.

4. D isso lve t h e p r ec ip i t a t e in 3 m l 1 0M HC1 . Add 1 d rop con e HN03 .Tran sfe r t h e solu t ion t o a 5-cm X 2-cm Dowex - 1 AG a n ion r e s in colum nwh ich h a s b e en w a sh ed w it h se ve r a l co lum n volu m es of 10M HC1 solu t ioncon ta in in g O. lM HN03, P u sh t h r ou gh w it h p r e s su r e . Aft e r a d d in g 1 d r opea ch of 10 .m g/m l Zr a n d Te ca r r ie r s , p a ss t h e so lu t ion t h r ou gh tw o a d d i-t ion a l 10-cm X 8-cm a n ion colu m n s w h ich h a ve a lso b een t r e a t ed w it h 10MHC1 con t a in in g O. lM I+UJ 03 (t h e sm a ll co lum n con t a in s P u if p r e se n t in t h ein it ia l s olu t io n).

5. Ad d NH40H t o t h e com b in e d 10M HC1 solu t ion t o p r ec ip it a t eY(OH)3 . Cen t r ifu ge , d isca r d t h e su p e r n a t e , a n d w a sh t h e p r ec ip it a t e tw icew it h 0.,5 m l H20.

6. Disso lve t h e p r ec ip it a t e in a m in im um am ou n t of O. 1~ HC1 a n dp a s s t h e so lu t ion t h r ou gh a l-cm X 2-cm Dow ex -50 AG ca t ion r e s in colu m nwh ich h a s b e en p r eviou s ly w a sh ed w it h seve r a l co lu m n volum e s of O. 1~ HC1.Wa sh t h e colu m n w it h 1 m l of O. lM HC1, t h en 2 m l of t h e O. 006M HF 0, lM HC1 solu t ion , a n d fin a lly 1 m l O. 5M HC1.

7. Us in g a t r a n sfe r p ip e t a n d a m in im um of H20, t r a n s fe r t h e ca t ionr e s in fr om th e l-cm colu m n t o t h e t op of a 12-cm X 2-cm Dow ex-50 r e s incolum n wh ich h a s b ee n p r e viou sly w a sh e d w it h seve r a l co lu m n volu m es oft h e e t h a n ol -HCl e lu t r ia n t . Aft e r t h e r e s in h a s se t t led , w it h d r aw th e exce ssH20 a n d . w a sh ou t t h e colum n a b ove t h e r e s in w it h a sm a ll p or t ion of e t h a n ol-

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HC1 . E lu t ep r e seu r e t o

P roced u re 2 (Con t in ued )

t h e a ct iv it y w it h t h e 2070 e t h a n ol -HCl so lu t ion , u Bin g su ffic ien tg ive a p p r oxim a t e ly 1 d r op eve r y 45 secon d s . Colle c t t h e d e -

s ir ed fr a c t ion (u su a lly d r op s 6-25) in a 40-m l cen t r ifu ge t u b e . (See F ig . 1for t yp ica l e lu t ion p osi t ion s . )

Th is so lu t ion w ill b e fr e e of m ost con t am in a n t s ; h ow eve r , t h e colu m nsep a r a t ion ca n b e r ep ea t e t for co r n@e t e se p a r a t ion of t h e la n t h a n id e a ct iv i t ie s .Th e p u r e a ct iv i t ie s ca n b e sep a r a t ed fr om ea ch ot h e r w it h P r oced u r e 3.

Not e : Seve r a l va r ia t ion s of s t ep s 6 a n d 7 a r e r ep or t ed b y d iffe r en t w or k e r s .Som e p r e fe r loa d in g t h e r e s in s lu r r y on t o t h e r e s in b ed of t h e colu m n in s t ep7. Ot h e r s p r e fe r t o r u n t h e so lu t ion fr om st ep 6 d ir e c t ly in t o t h e lon g colu m na n d t o follow it w it h 10 t o 20 colu m n volu m es of 2M HC1, t h e n t h e a lcoh olicHC1. Th e 2M wa sh m ove s t h e t r a n scu r ium e lem en t s d ow n th e colu m n a bou t10~e of t h es t ir r in g of

Th i s

len gt h a n d t h ey a r e le s s p e r t u r b ed b y t h e sh r in k a ge a n d a ccid en t a lt h e r e s in t h a n ot h e r w ise .

P r oced u r e 3p r oced u r e ia for se p a r a t in g t h e a c t in id e s fr om ea c li o t h e r in so lu -

t ion s fr e e of la n t h a n id e s , o t h e r m a ss im pu r i t ie s , a n d r a d ioa ct iv i t ie s . I t i s6 .s im ila r t o t h e p r oced u r e of Th om p son e t a l. excep t t h a t i t u se s a h yd r oxy -

isob u t yr ic a c id in s t e a d of la c t ic a c id , a n d con seq u en t ly g ive s b e t t e r s ep a r a -t ion s . 27

1, P r ep a r a t ion of r e s in e lu a n t a n d , eq u ipm en t .A. Dow ex-50 12~0 cr oss-lin k ed r e s in , 200-400 m e sh sp h e r e s

(ob t a in ed fr om Bio-Ra d La b s . , 32n d a n d Gr iffin Ave . , R ichm on d , Ca lif. ),is fu r t h e r gr a d ed for s ize b y se le c t in g t h e fr a c t ion t h a t se t t le s b e tw een O. 5a n d O. 25 cm /m in fr om wa t e r .

B . Th e gr a d ed r e s in is w a sh ed a lt e r n a t e ly w it h 12M HC1 an dNH40H a n d fin a lly s t or ed in t h e amm on iu m for m .

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\P roced u re 3 (Con t in ued )c . Th e e lu a n t i s p r ep a r ed fr om comm er c ia l a -h yd r oxy isobu t y r ic

a c id d ilu t e d t o O. 4M w it h t h e pH a d ju st e d be tw een 3.8 a n d 4.4 t o g ive t h eden ir ed e lu t ion t im e -p ea k sep a r a t ion . (See F ig. 7. ) P h en o l m a y b e a d d edu n t il t h e so lu t ion is O. O IM to p r even t t h e gr ow t h of m old .

D. App a r a t u s is se t u p a s in F ig . 5. Th e co lum n b or e is 2 mmin d iam a n d a bou t 10 cm lon g ove r t h e ca p illa r y r egion . Th e t ip is p lu ggedw it h g la s s w ool. . Th e co lum n is h e a t ed to t h e bo ilin g p o in t o f t r ich lo r oe t h yl -e n e a n d t h e b or e is filled w it h d ist i lle d w a t e r ; t h en sm a ll am ou n t s of r es ins lu r r y a r e a d d ed t o t h e colu m n a n d a llowed t o se t t le in t o t h e bor e u n t il ase t t led b ed 5 cm in h e igh t i s ob t a in ed . Th e e xce ss d is t i lle d w a t e r is r em oveda n d s eve r a l m l of e lu a n t i s a d d ed t o fu r t h e r r em ove t r a ce im p u r it ie s . J u s tp r io r t o u s in g t h e co lum n , t h e e lu a n t r e se r vo ir is low er ed , t h e top of t h eco lum n is w a sh ed w it h d is t i lle d w a t e r , a n d a d r op or two of d is t i lled w a t e ri s a llow ed t o r u n in t o t h e colu m n .

2. An HC1 or HN03 so lu t ion con t a in in g t h e a c t in id e e lem en t m ix t u r eis eva p or a t ed t o n ea r d r yn e ss in a 5-m l cen t r ifu ge con e , a n d d ilu t ed w it h=s0. 1 m l of h o t 0.05 MHC1. Th is so lu t ion is t r a n s fe r r e d t o t h e r e s in b ed a n da llow ed t o r u n t h r ou gh , Th e con e a n d s id e s of t h e co lum n a b ove t h e r e s in

b ed a r e w a sh ed w it h 50 p l of O. 05M HC1 solu t ion w h ich is a llow ed t o r u nin t o t h e r e s in . Th e w a sh in g p r oced u r e is r ep e a t ed .

3. Th e cen t r ifu ge con e is w a sh ed w it h 50 p l of e lu a n t w h ich is t h ent r a n s fe r r e d t o t h e co lum n a n d a llow ed t o r u n in t o t h e colu m n . Th e fir s t d r opto fa ll fr om t h e co lum n a ft e r t h is i s d r op 1 1 ! of t h e e lu t ion .

4. Th e bor e of t h e co lum n a b ove t h e r e s in is filled w i t h h ot e lu a n tca r e fu lly so a s t o a vo id s t ir r in g t h e r e s in b ed , a n d t h e e lu a n t r e se r vo ir i slift ed t o p r ov id e t h e d es ir e d flow r a t e (se e F ig . 8). Sa t is fa c t or y sep a r a t ion s

a r e ob t a in ed w it h flow r a t e s o f 1/2 t o 1 d r op p e r m in u t e .5. E a ch d r op is co llec t e d on a p la t in u m p la t e w h ich is d r ie d u n d er a

h e a t lam p a n d h ea t ed t o r ed h ea t in a n in d u c t ion h ea t e r t o r em ove t h e la s t


34/41

Procedure9 (Comt inu@t ia cem of orga n ic m a t er ia l . Ph t on a re rea d y t o co~t n .,

Th e q p r o k t e e lu t ion pom it ion p can b. predic t ed from the cu rve in. .Fig. 7 an d from Ta b le ~, a ssu m in g a 3-&op free c olu m n vo lu m e; however ,

. .qight m riat im in a lu en t an d r ada m ak e it d e s ir able t o Ilca libr t it e fi eechco lum n wit h a t rece r of qom a t r en sp lu t am ium ac t id e bdor e qp ara t ion f i a rea t t em p t ed . If c i rr t e rm m e in clu d6 d In t he qolu t ion t ie sarne p roced u re cep ib e fo llowe d , bu t t ie . col~ s is e h ou ld b e ~u e t ed t o p r ovid e 0.4 Cm z ofcol~ q ea for ee ch m ilh qu in len t of ca rr ier , eqd t ie len g t h o f t h e co l umnshou ld b e a t lea n t 10 t im eh t h e d i am e t e r .

Roced u re 4 .,6This p r o c e d u r e e~ra t em t h e a ct in idm f rom t h e la a~de s . Dowex- 1

r e~in is u eed wit h en HC1 fiolu t ioa conMa in g t he acdn id e e lem en t -, lan tlm -dde ic t lv i tiem , en d qbout 1 m g lan -um car r ie r .

A . Dowex-1 8 % c ro mm -l in k e d r em i n , 2 0 0 -4 0 0 me-h ~phe r em , im dne -graded by q le c t k g - fr ac t ion t it s e t t le s from O. 1 5 t o 0 .2 5 cm @n iawa t e r . Th e g r aded r em in is wm h ed d t e rn a t bly wit h 1 2 # HCl -d NH40Han d i- s t or ed k t h e ch lor id e fo rm m ft e r c ft il HCL -ah.

B. Elu 8 n t is prepred by a tk ua ~ comme r c i a l 8 n 8 1 y t k l gra d e HClw i t h HCl IB8 8 . Im m erm ia g t h e bot t le - in roo=t em perm tu re t Ap w et er he lpsd is a ipk t e t h e h ea t . Th e fin d c aac en t rm tion of a c id -t 2 0 -2 2 C will be abou t1 3 g .

C. Th e cohm m is p r epa r e d by q t a c h i ng q qec t iom of 3 -m m -d iem cap -illa ry t u bin g t o q 1 5 -m l t e a t .Afage con e , p8 cMn g * t i p w it h g lm m wool,. .8 n d f i l l in g t h e bck e t o m h e igh t o f 5 cm wit h t h e r e dn . Th e co lum a -bou ld. .be a l t e r xm t e l y washed w ith e lum it a n d wa t e r be for e u ee . Th e fin a l w? -h i-m 8de wit h e lu an t.

1 . Th e so lu t ion t o be p u r ifie d i - eva p ora t ed t o -3 0 p l w i t h a nqir je t in q 5 -m l c ea t ~u ge con e . Th e con e is plac ed in an ic e -&a t e r ba t h

aa


35/41

P roced u r e 4 (Con t in u ed )

a n d t h e solu t ion sa t u r a t ed w it h HC1 fr om a ga s cylin d er .2. Th e solu t ion is t r a n sfe r r e d t o t h e top of t h e

fir s t d r op to fa ll a ft e r t h is is ca lled d r op 1. Th e con e iso f e lu a n t w h ich ia t r a n sfe r r ed to th e colum n . Th is wa sh is

co lumn . Th er in sed w it h 30t hen r ep ea te d.

p l

On e m illilit e r o f e lu an t is c a r e fu lly p la ced on t op of t h e co lum n an d d rop sa r e collect ed t h r ou gh d r op 12. Th e flow r a t e ca n b e m a in t a in ed a t a bou t 3m in u t e s p e r d r op w it h a h yp od e rm ic syr in ge a n d r u bbe r st op p er .

3. Aft e r d r op 12 h a s fa llen , t h e e lu a n t is r em oved a b ove th er e s in , a 15-m l cen t r ifu ge con e is p la ced u n d er t h e colum n , a n d 1 m l of 10MHCL is p la ced on t op of t h e r e s in . Th is is p a ssed t h r ou gh t h e r es in a n de lu t es t h e t r a n scu r ium elem en t s. Am , Cm , a n d t h e la n t h a n id e s a r e fou n din d r op s 1- 12.. Ur e s in a n d m ay b e

a n d P u (in th e IV or VI oxid a t ion st a t e ) r em a in on th esu bsequ en tly r em oved .

P r oced u r e 5Th is p roced ur e 27 .I s for p u r ifica t ion of

25 3p a r t icle bomba r dm en t of E s . It i s t yp ica lMd r ecoils p r odu ced by aof t h e ca t ch e ,r foil ch em ica l

t ech n iqu e s . Ot h er a c t in id e t a r ge t s a n d p r od u c t s a r e sim ila r ly h a n d led . ,Th e t a r ge t con sis t ed of = 109 25 3a t om s of E s e lect r op la t ed on a l/32-in .

X l /4-i n . a r e a of la r ge r O. 002-in , -t h ick go ld foil. A 48-Mev a b eam wa sa llow ed t o p a ss t h r ou gh t h e gold t a r ge t foil a n d Ilk n ock offll t h e Md a t om son t o a O. 0001 -in . -t h ick go ld Ilca t ch e r r i foil.

1. Th e ca t ch er foil w a s d issolved in a qu a r eg i?, a n d t h e gold ext r a ct edw it h a n eq u a l liq u id volum e of e th yl a ce t a t e for =S1 m in .

2. Th e a qu eou s p h a se w a s p a ssed t h r ou gh a 2-mm -d iam X l-cm -lon g

bed of Dow ex - 1 a n ion r e s in h ea t ed to 87 C (se e F ig. 9A a t a r a t e of a bou tfive 30-p l d r op s p er m in u t e . Th e or igin a l volum e p lu s 5 d r op s con t a in in gt h e a c t in id e e lem en t s w a s collect ed a n d eva p or a t ed w it h a . je t of h ot a ir .


36/41

P r oced u r e 5 (Con t in u ed )

3. Tr a ce r E s 25 3 w a s a d ded a n d t h e solu t ion w a s p a ssed t h r ou gh a2-mm -d iam by 5-cm -lon g bed of Dow ex-50 X 12 ammon ia -for m ca t ion r e sinh ea t ed to 87 C. Th e a d sor b ed a ct in id es we r e se lec t ive ly e lu t ed w it h a 0.4Msolu t ion of a -h yd r oxyisobu t y r ic a cid w h ich h a d been a d ju st ed to pH s=4. Ow it h ammon ium h yd r oxid e . Th e e lu a n t w a s p a ssed t h r ou gh t h e colu r r&- a t aflow r at e of a p p r oxim at e ly fou r 20-pl d r op s p er m in u t e . Th e Md fr a ct ion ewe r e collect ed in d r op s 8-13, Fm in d r op s 15-19, E s in d r op s 27-31, a n dCf in d r op s 39-47.

P r oced u r e 6Th is p r oced u r e is for oxid a t ion a n d ex t r a ct ion of Bk fr om a solu t ion

9con t a in in g la n t h a n id e s a h d a c t in id e s. No ca r r ie r s a r e u sed .1. Th e so lu t ion is eva p or a t e d to n ea r d r yn ea a tw o or t h r ee t im es w ith

16M HN03 . Aft e r t h e la st eva p or a t ion , t h e Bamp le is d ilu t ed a n d KBr 03 isad d ed t o m a k e th e Eolu t ion 10M in HN03 a n d 1~ in KBr 03 (Not e 1). Th evolum e of th e solu t ion is m ea su r ed in m illi li t e r ~ (ca lled V in t h e follow in g).

2. V m l of O. 15~ HDEP mote 2.)-h ep t a n e solu t ion is w a sh ed t h r eet im es w ith V m l of fr eHh ly p r ep a r ed 10M HN03 lM KBr 03, for 3 m in u t ese a ch t im e . Th e a qu eou s p h a ses a r e d in ca r d ed ,

3. Th e solu t ion fr om st ep 1 is con t a ct e d w ith t h e or ga n ic p h a se fr omst ep ~ fou r 3 m in u t es a n d t h e p h a se s a r e Bep a r a t e d .

4. Th e or ga n ic p h a se fr om st ep 3 is w a sh ed tw ice for 3 m in u t es w it hV m l of fr esh ly p r ep a r ed 10M HN03 lM KBr 03. Th e w a sh solu t ion s a r ed i . q c a rd ed .

5. Th e wa sh ed or ga n ic p h a se fr om st ep 4 is b a ck -ext r a c t ed for 3 m in -u t es in t o V m l of fr esh ly p r ep a r ed 10M HN03 1. 5M H202 so lu t ion . Th eor ga n ic p h a a e ia d isca r d ed .

6 . Th e a qu eou s p h a ee fr om Step 5 is w a sh ed , fir st w it h V m l of O. 15M

9 0


37/41

P r oced u r e 6 (Con t in u ed )

HDEP h ep t a n e for 3 m in u t e s, a n d th en w it h V m l of h ep t a n e for 3 m in u t e B.Th e or ga n ic p h a EeB a r e d im ca r d ed ; t h e a q u eou B p h aEe con t a in B _97~0 of t h eBk , d econ t am in a t ed b y fa ct or s of * 104 fr om a ll ot h e r la n t h a n id es a n d a ct in -

6id e s excep t Ge , a n d b y fa c tor s of -10 fr om Cm an d Cf. (Not e 3.)

Not e B1. _. lM KBr 03 m a y be su b s t it u t ed a t a ll p oin t s ca llin g for 1~ KBr 03

w it h lit t le or n o d ecr ea se in yie ld .2. HDEP is d i(k t h ylh exyl) or t h op h oep h or ic a cid , [18H170 2

PH(OH), a n d iB a va ila b le in im p u r e form fr om t h e Vict or Ch em ica l Wor k s .It is p u r ified by t h e p r oced u r es r epor t e d by D. C. St ew a r t a n d H . W. Cr a n d a ll,J . Am . Ch em . Sot . 73, 13 77 (195 1).

3. Cu n n in gh am an d Wa llm a n n 11 h a ve u sed a p r oced u r e sim ila r t ot h is for ext r a ct in g su bm icr ogr am qu a n t it ie 8 of Bk fr om Cf a n d Cm . Solu t ionvo lum es we r e r ed u ced t o Bu bm icr olit e r qu a n t it ie s .

P r oced u r e 7Th is p r oced u r e is for r em ova l of m a cr o im p u r it ie s fr om t r a ce r t r a n s-

17cu riu m sam ples .1. A ja ck e t ed colum n for op er a t ion a t 87C is p r ep a r ed . Dow ex-50

AG 47O cr oss-lin k ed r es in (se t t lin g r a t e O. 5 t o O. 25 cm /m in ) is u sed in t h eH+ for m (HC1 w a sh la s t ), a n d p r ep a r ed ot h e r w ise a s in P r oced u r e 3, s t ep s1A a n d lB. Th e colum n b or e is 3 mm in d iam a n d t h e t ip con e iBt s of a p la t i-n um r od fu sed t o t h e g la ss ca p illa r y a n d bor ed ou t w it h a No. 6 4 dr i l l . Th iet ip d e live r s u n ifor m 13-I .U d r op e .

2. Th e solu t ion t o b e p u r ified is p r ep a r ed so a s t o b e O. lM in HC1a n d t h en a llow ed t o p a s B t h r ou gh th e colum n . Th e colum n wa llB a r e r in Bedw it h sever a l 1OO-P 1 p or t ion s of O. lM HC1.

3. Abou t 1 m l of 2M HC1 is ca r e fu lly in t r od u ced a bove t h e r es in b ed

3 1


38/41

P roced u r e 7 (Con t in u ed )

a n d for ced th r ou gh th e r e s in a t t h e r a t e of a b ou t 6 d r op s p er m in u t e u n t il50 d r op s h a ve b een collect ed .

4. Th e r em a in in g 2M HC1 is w it h d r awn a n d 1 m l of 6M HC1 is a d d eda n d for ced th r ou gh th e r es in a t t h e r a t e of 6 d r op s p er m in u t e u n t il 30 or 40d r op e a r e collect ed . Th e t r a n scu r ium e lem en t e e lu t e close t oge t h er a r n u n dd r op 80 (cou n t in g fr om t h e begin n in g, in c lu d in g t h e 50 d r op e fr om st ep 3).Oth er ca t ion s e lu t e a s in d ica t e d in Ta b le II I .

3 2


39/41

P roced u r e 7 (Con t ir iu ed )Table III. Orde r of e lu t ion of ca t ion s from res in colum n in P r oced u r e 7.

F r e e Colu m n Volu m esCa t i on s a Dr op No, (a ft e r fir st )AuP dP t 1BiCdP bLiMo 1CuF eNaBeMgRbNi 1CaAlSr 1BaAct in id ea a n dL a n t h a n i d e aZr

==7

131617

22

242 62 830

37

53

64

70

75-859 6

2.6 of 2MHC1

2.8

3 .64.0

4,4 -5 .1

5. 9

a Th e ox id a t ion r o t a t e of t h e se ion E w a n n ot sp e ci fied . Wh er e qu e a t ion aex is t , i t ca n b e a e su m ed t h a t t h e ox id a t ion s t a t e m os t e t a b le a n d solu b le in2N HC1 is t h e on e in d ica t ed . Th e co lu nm sp ecified w ill h a n d le 0.1 to0.2 m g of m a cr o im p u r it ie s , a n d p ea k h a lf-w id th (fu ll w id t h s a t h a lf m a x-im a ) gen er a lly r u n 6-8% u n d er t h e con d it ion s sp e ci fied . Th e se d a t a h a ven ot a ll b e en r ed u ced t o fr ee co lum n volum e u n it s b e ca u se sever a l o f t h e ion s(Au , P d , P t , Bi , Cd , a n d P b ) m ove a p p r e c ia b ly in O.1~ HC1 a n d t h e i re lu t ion p os i t ion w ill d ep en d on t h e vo lu m e of t h e so lu t ion fr om wh ich t h em a t e r ia l i s a d sor b ed . Th e p os it ion s of t h e a c t in id e e a n d la n t h a n id e s a r en o t s im i la r ly a ffect e d .

33


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REFERENCES1. S. G. Th omp son , llTh e Discove r y of t h e Tr a n su r a n iu m E lem en t s :

Th e ir H ist o r y a n d a P r e sen t a t ion of t h e Diffe r en t Met h od s Used inTh e i r Discove r y , f UC RL-86 15 (Ap r il, 1959).

2. B. B. Cu n n in gh am , J . Ch em . Ed u c. 36, (J a n u a r y, 1959).3. S. G. Th om p son a n d M, Lou is Mu ga , l Met h od n of P r od u ct ion a n d

Re sea r ch on Tr a n scu r ium E lem en t s . P r oc. U. N. Ln t e r n . Cod . P ea ce -fu l Use s At om ic En e r gy, 2n d , Gen eva , 1958, 15/P /825.

4. G. T. Sea bor g , I tTh e Tr a n su r a n ium E lem en t s , I I Ad d ison -Wes ley P u b -lish in g Co . , In c . , R ea d in g , Ma ss . , 1958.

5, J . K. Ka t z a n d G. T. Sea b or g , I Ich em is t r y of t h e Act in id e E lem en t s , Met h u en a n d Co. , Lt d . , Lon d on , 1957.

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7. S. G. .Th om p son , B. B. Gu n n &gh am , a n d G. T. Sea bor g , J . Am .Ch em . SOC. 72, 2 7 9 8 (1950).

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C h em .10. D. F .

I no rg .11. B. B.12. G. F .

C h em .

P ep p a r d , J . W. Molin e , a n d G. W. Ma son , J . In or g . & Nu clea r~, 344-8 (1957).P ep p a r d , G. W. Ma son , W. J . Dr iscoll, a n d S. McCa r ty , J .& Nu cle a r Ch em . 12, 141-8 (1959).Cu n n in gh am an d J . C. Wa llm a n n , u n p u b lish ed d a t a ( 1960).

Be s t , E . He sfo r d , a n d H . A. C, McKay , J . In or g, & Nu cle a r12 136-40 (1959).

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13 .14 .

15 .

16 ,

17 .

18 .

19 .

20 .

21 .

22 .23 .

24 .

25 .

26 .

27 .

E . K, Hu le t , U.S. P a t en t 2, 909,405 (1959).L. B, Magn u ssen a n d h f. L. An d e r ~on , J . Am . Gbem . SOC. 76, 6207(1954).A. M. P osk a n zer a n d B . M. F or em a n , J r . , p a p e r p r e sen t ed a t 136t hNa t ion a l Mee t in g of t h e Am e r ica n Ch em ica l Soc ie t y , New Yor k , Sep t , ,1 95 9, t o be p ublish ed .H. L. Sm it h a n d D. C. Hoffm a n , J . In or g . & Nu cle a r Ch em . ~, 243-7(1956).J . P . Su r ls a n d G. R . Ch op p in ,. J . In or g . & Nu clea r Ch em . ~, 62-73(1957),E. K. Hu le t , R . G. Gu tm a ch er , a n d H . S. Coop s , Gr ou p Sep a r a t ionof t h e Act in id e s fr om t h e La n t h a n id e s b y Ion Exch a n ge , 11UCRL-5639(1960).

J . Milst e d , At om ic En er gy E s t a b lish m en t , Ha r we ll, En gla n d } p r iva t ecomm u n ica t ion t o S. G, Th omp son r ep or t ed in r e fe r en ce . 5 a bove .L. P h illip s a n d R . Ga t t i , Un iv . Ca lif. , Be r k e ley , u n p u b lish ed(1960).G, R . Ch op p in , B. G. Ha r vey, a n d S. G. Th om p son , J . In or g .Nu cle a r Ch em . ~, 66 (1956).

dab.

J . Mila te d a n d A. B. Bea d le , J , In or g . & Nu cle a r Ch em , ~, 248 (1956).W. E , Ner v ik , J , P h ys . Ch em . 59, 690 (1955).A. Gh ior so a n d T. S ik k e la n d , I tH ea vy Ion Rea c t ion s w it h Hea vy E le -m en t a , + P r oc . U. N. Ln t e r n . Con -f, P e a ce fu l Use s At om ic En e r gy, 2n d ,Geneva , 1958, 15/P /2440.G. H . H igg in s a n d W, W. T. Cr a n e , P r oc . U.N. Con f. P e a ce fu l Use sAt om ic E n e r gy , 2n d , Gen eva , 1958, 17/P /1883.D. C. Hoffm a n , J . W. Ba r n e s , H . L . Sm it h , a n d W. R . Da n ie le ., u n -p u b lish ed p r oced u r e u sed a t Los Alam os Sc ien t ific La b or a t o r y (1958).A. Gh io r so, B . G. Ha r vey, G. R . Ch op p in , S. G. Th om p son , a n d

G. T. Sea b or g , P h ys . R ev . 98, 1518 (1955) .uSMC OHI- OFTuhnlcal lnfarwdlm Mmulm, W Rldw, T

?E

the radio chemistry of trans curium elements.us aec

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