The Radio Chemistry of Zinc.us AEC

8/3/2019 The Radio Chemistry of Zinc.us AEC

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Nat iona lAcademy

ofSciences

Na t io na l Resea rch CounciINUCLEAR SCIENCE SERIES

The- Radiochemistryof Zinc

_____ .- j.


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COMMITTEEL. F . CURTISS, Ch air ma nNa tion a l Bu r ea u of s t an d ar d s

ON NUCLEAR SCIENCER OBLE Y D. E VANS, Vice Ck u bn .u nMa a mch u a et t@ I ns ti tu t e o f T ec hn o lo gy

J . A. DeJ URE N, Secr et iyWe st t ng h ou a e E le ct r ic C or p r at lo n

C . J . B ORKOWSKI J . W. IRV~, J R .o ak R id ge Na tio na l b bo mt or y Ma ss ach u se tt s I ns t it u te of Teo hu cd ogyR OBE RT G. COCH RAN E . D. KLEMATe xa s Ag ricu lt ur a l a nd Me ch a nioa .1 N or t h we st er n U ni ve r si tyCollege W. WAYNE ME INKE

SAMUE L E P 8T ELN U ni ve r sit y o f Mlc hlg anC allfo rn t a I n st it u te o f T ed u olo gy J . J . NICKBONU . F ANO Mem or ia l H osp it al, New Yor kNa tion a l Bu r ea u o f St an d am la R OBE RT L. P LATZMANHERBERT GOLDSTELN Lsk tom toir e d a Ch id e P hysiq ueN uo le ar D ev elo pm en t Co r po fi ti on of D. M. VAN P ATTERAner tc a B a.r t ol R ea ea r oh F ou n d n tlo n

L IAISON MEMBERSP AU L C . AE BE RSOLD CH AR LE S K. R EE DAtom lo En e~ Com mia s lon U. S. Air F or ceJ . H OWARD McMI LL EN WI LL L4M E . WR IGH TN at io n al S ci en ce F ou n d at io n Office o f Na va l R ee ea r oh

SUBCOMMITTEE ON RADIOCHEMISTRYW. WAYNE ME INKE , Ch dn n on HAROLD kmBYU ni ve r si ty o f Mt oh ig an Mou n d L a h or s tc m yGREGORY R . CHOP P IN GEORGE LEDDICOTTEF lo rid a S ta t e Un iv er a l~ O ak R id g e N at io n al L ah o ra t cu yGE OR GE A. COWAN JULIAN N IE LSENL os Alsm os g clen tlflo La bor a to ry H a n fo r d L a lxm at o r ie sAR THUR W. F AI RHAL L E LLIS P . STE ~BE RGUn Iv er a i~ of Wa ah t ng bn Ar g on n e N at io n al L ab or a to ryJ E ROME H UDIS P E TI ?R C . S TE VENSONB ro ok h a ve n N at io n al L ab cm t or y U ni ve r sl@ o f C ali fo rn ia (L iv er m or e )E AR L H YDE L EO YAF F EU ni ve r sl@ o f C ali fo r ni a (B er k ele y) Mc@11 U r d v er a l t y

CONSULTANTSNATHAN BA L LOU JAMES D eVOECe nt r e d E tu d a d e lE ne rgle Nu ole sh e U ni ve r si ty o f Mio h ig anMol -D on k , B elg ium w I LL IAM MARLOW

Na tion a l Bu r ea u o f St ad ar d s


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The Radi ochem is t ryBy HARRY G. HICK 9

of Zinc

La w ren ce Rd ia t ion Laboratorylh iver8 it y of Ca li jbrn iaLiverm ore , Ca lif orn iaJ u ne 1960

Su bcom mit t e e on Ra d loch em ie t r yNa t iu n a l Aca d emy of Scien ce s Na t im a l Re8ea rch Cwnc f l

P r in t ed in USA. P r ~ 80.76. An lla b la fr om t h e -e of Tdmtcm.1~eom Dqmnmemt of Conmarca, WMhiB@OO25, D. C.


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Th e Su boomm lt t ee on

FOREWORDRa d io ch em is t r y I s on e of a n um ber o f

su b comm it t ee s w or k in g u n d e r t h e Comm it t ee on Nu c le a r Sc ien cew it h in t h e , Na t ion a l Aca d em y of Scie n ce s - Na t ion a l R es ea r chCounc i l . I t s m em be r s r ep r e se n t gove r n m en t , In d u s t r ia l, a n d ..u n lve r s lt y la b om t o r le a In t h e a r ea s of n u clea r ch em is t r y a n da n a lyt ica l ch em is t r y .

Th e Su b comm it t ee .h a s con ce r n ed I t se lf w it h t h ,o se a r e a s ofn u cle a r sc ie n ce w h ich In volve t h e ch em is t , su ch a s t h e d o llec -t lon a n d d is t r ib u t ion of ~d loch em lca l p r oced u r es , t h e es t a b -,llsh m en t o f e p ec lflca t lon s for r a d loch em lca lly p u r e r e a gen t s ,a va i la b i li t y of cyc lot r on t im e for se r vice i r r a d ia t ion s , t h ep la ce of r a d ioch em ls t r y in t h e u n d er g r a d u a t e co llege , p r ogr am ,etc . .

Th is s e r ie s ofm on ogr a p h s h a s gr ow n ou t of t h e , n e ed foru p -t o-d a t e comp ila t ion s o f r a d ioch em ica l In for m a t ion a n d p r o-ced u r e s .. Th e Su b c.omm lt t e e h a s en d e a vor e d h o p r ese n t a , s e r ie sw h ich w ill b e of m sxlm um u 6e t o t h e w or k ln g jsclen t ls t em dwh ich con t a in s t h e , la t ed a va ila b le In for m a t ion . E a ch m on o-g r a p h colle ct s In on e volu m e t h e p e r t in en t in for m a t ion r eq u ir edfo r r a d loch em ica I w or k w it h a n in d ivid u a l e lem en t o r a gr ou p of ~close ly r e la t ed e lem en t s .

An exp e r t In t h e m d loch em ls t r y of t h e p a r t icu la r e lem en t@a s w r i t t e n t h e m on ogr a p h , follow ln g a s t a n d a r d fo rm a t , d eve lop edby t ~ Su b c,om lt t e e . Th e .At om ic En er gy. Comm ie s lon h a s sp on so r edt h e p r ifi t in g of t h e se r ie s .

Th e Su b comm it t e e is con fid en t t h es e p u b lica t ion s w ill b e.u se fu l.n ot on ly t o t h e r a d loch em lst b u t a lso t o t h e r ese a r chw or k e r I n o t h e r fie ld s su ch a s p h ys ic s , b ioch em is t r y o r m ed ic in ew h o w ish e s t o u se r a d lo~h em lca l t e ch n iq u es .t o so lve a sp e ci ficp r o b l em .

. .,. W. Wayn e Me ln k e ; Ch a ir m a nSu bcom mit t ee on .Ra dloch em lst ry

.

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CONTENTS

I . Gen e r a l Re view s of t h e In oi ga n ic a n d AnalyticalCh em is t r y ,of Zin c . . . . . . .

n . Gen e r & Review of t h e R a d ioch em is t r y of Zin cI I I . Ta b le of Iso t op e s of Zin c . . . . .IV. R ev iew of t h ose F ea t u r e s of Zin c Ch em ist r y

of1.2.3.4.5.6.7.8.9.

10 .

Ch ie f In te r es t t o R a d ioch em ist sMe t a llic zin c . . . .So lu b le sa lt s of zin c . .In so lu b le sa lt s of zin c . .An a ly t ica l d e t e r m in a t ion of zin cCom p lex ion n of zin c . .Ch e la t e comp ou n d s of zin c .Solven t ex t r a c t ion of zin c .Ion exch a n ge b eh a t ior of z in c

. . .

. . .

. . .

. . ... . .. . .. . .. . .. . .

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.

.I zo t op ic exch a n ge of zin c . . . . .P a p e r ch r om a t ogr a p h y . . . . . .

v . D is so lu t ion of Samp le s Con t a in in g Com p ou n d s of Zin cVI . Cou n t in g Tech n iq u e s . . . . . . .VII. Colle c t ed R a d ioch em ica l Sep a r a t ion s P r oce d u r e s

for Zin c . . . . . . . . . .

. 1

. 2

. 2

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22337

131720283940

4143

. 43

v


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INTRODUCTION

This volume wh ich d ea ls w it h t h e r a d ioch em ls t r y of zin cis on e of a se r ie s of. m on ogr a p h s on r a d loch em is t r y of t h e e lem en t s .Th e r e i s In c lu d ed a r e v iew of t h e n u clea r a n d ch em ica l fe a t u r e sof p a r t icu la r In t e r e s t t o t h e r a d loch em lst , a d iscu s s ion of p r ob -lem s of d is so lu t ion of a ,sam p le a n d cou n t in g t e ch n iq u e s , a n dfin a lly , a co lle c t ion of r a d loch em ica l p r oced u r e s for t h e e lem en ta s fou n d In t h e li t e r a t u r e .

Th e se r ie s of m on ogr a p h s w ill cove r a ll e lem en t s for w h ichr a d loch em lca l p r oce d u r e s a r e p e r t in en t . F la n s In clu d e r ev is ionof. t h e m on ogr a p h p e r iod ica lly a t i n ew t ech n iq u e s a n d p r oced u r e sw a r r a n t . Th e r ea d e r ls t h e r e for e en cou r a ged t o ca ll t o t h ea t t en t ion of t h e a u t h or , a n y p u b lish ed or u n p u b lish ed m a t e r ia l ont h e r a d loch em is t r y of z in c w h ich m igh t b e In clu d ed .in a r ev ise dve r s ion of t h e m on ogr a p h .


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vol.

Ed . ,

The

..

Radioc hem ist ry of Zinc--G.H1- Ia vr en ce Ra dia tion La bor at o r y

Un ivp r si@ of Ca lifo r niaL ive zm m e, Ca Mfor DIa

J u n e 1s60

I . GENERAL REVIEWS OF THE INORGMWC ANDANUYTICU CHEMISTRY OF ZINC

M. C. Sn eed a n d . R . C . Br a ot ed , Cor n p r eh en a ive b cm ga n ic Ch em io t ry4IV (Va n Nost r a n d , ~in ce t on , 1%5), p p . 9-63.Scot tB o &a n d a r d Me t h od s of Ch em ica l ~yo ia , Vol. 1, N. H ., F u r r n en ,F ift h E d it ion (Va n Noei t r a n d , New Yor k , 1939), p p . 1054-1092.G. E . F . Lu n d@ a n d . J . I . Hoffm a n ; Ou t lin e o of Me t h od s of Ch em ic&

An a lys is (Wiley , New Yor k ,W. F . H iLleb r a n d , G-

Ap p lie d In or g-ic Am lya is ,A. E . Ma r t&ll &d M.

.- (P r en t ice -Ha ll, New

1951).E . F . Lu n d e ll, H . A. Br igh t , a n d J . L Hoffm a n ,Secon d Ed it ion (Wiley , New Yor k , 1953).Ca lvin , Ch em is t r y of t h e Me t a l Ch e la t e Com -Yor k , 1952).

E . B. Sa n d e ll, Ca lor im e t r ic De t e r m h a a t ion of Tr a ce e of Me t a le~ Th ir dE d it ion (In t e r scie n ce , New Yor k , 1959).

G. Ch a r lot a n d D. B&ie r , Qu a n t it a t ive In or ga n ic An a lys is (Wiley, N&wYor k, 1957). ..

E . Led e r e r =d ~. Led e r e r , Ch r om a it ogr a p h y (E loev ie r , New Yor k ,,1957).

J . A. Kit ch en e r , Ion -Exch a n ge R ea in a (Wiley , New Yor k , 1957).G. H . Mor k it ion @ EL F r e ioor , Solven t E t ir a c t ion b WWica l

Ch en xie t r y (Wiley, New Yo+k , .1957).C. Du va l, In or ga n ic Th e r m ogr a v im e6ic An a lyo io (E l~ev ie r , New Yor k ,

1953). ,,~.


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I I . GENER t i REVIEW OF THE R~IOCHEMISTRY OF ZINC

1% L. F in st on a n d J . Misk e I , Am . R ev . Nu clea r Sci. ~, 269 (1955)..,I I I . T~LE OF ISOTOP ES OF ZINC

I s o t ope T .l~z . - Typ e of d eca y Me th od of p rep ar at ion

Znbczn6zk62zn63%64

zn65%66

2k67~6 8

~691qz n69Zn ~7 lmzn71&z

2.1 m ip1.48min9.33 h r

38.3minStab le4s . 89%245 d a yS t a b l e27.817.S t a b l e4.11%

S t a b l e18, 56%13.8 lir57 m inS t a b l e0.62$

3 h r .2.2 m in49. oh r

B+, EC. Ni58 ( a# Zn )+p Ni5s (a , n )EC, ~: c u b (p , 2n ) or ?Ti60 (a , 2n )p+, 90%; EC, 10% CU63 (p , n )or Ni60 (a , n )

EC, 9974; ~+, 17. Zn 64 (n , y), Zn 66 (n , Zn )

1. T.P - zn68 b , y]

P- Zn b,.lf)P- Zn (n , y ) P- F id a ion

,.. . F or m or e comp le t e in for m a t ion on t h e r a d ia t ion of t h e a ik c im o top ea ,.a n d for r e fe r en ce s t o t ie or ig in a l li t e r a t u r e , n e e D. St r om in ge r , J . M.Holla n d@r , a n d G. T. Sea b or g , Ta b le of I so t op eo , Revn . Mod e r n P h ya . ~,585 (1958).

IV. REVIEW OF THOSE FEATURES OF ZINC CHEMISTRYOF C-F ~TEREST TO RADIOCHEMISTS

1. Me t a llic Zin cZin c m e t a l in ea oily ob t a in ed in ve r y p u r e for m ; u su +ly b y d is t i lla t ion

of t h e im p u r e m e t a l p r od u ced b y e le c t r o lye io . E is r n od e r a t e IY du ct fie a n dca n ea n ily b e for m ed in t o oh a p es Bu it a b le for t a r ge t s . Th e. m e lt in g p oin t,

. 2


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420C, is r a t h e r low a n d m a y p ose a p r ob lem in h igh -in t en s it y b om ba r d -me n t s .

a c i d sMe ta llic zin c is . a good r ed u c in g a gen t , d issolv in g r e a d i ly in m in er a la s we ll a s in s t r on g ba s e s , t h u s sh ow in g it s am p h ot e r ic ch a r a c t e r .Ox id a t ion p o t en t ia ls o f zin c a r e g iven be low :

Zn . zn +++ 2,- E = 0.762 VZn +20H - = Zn (OH)2 + 2 6- EO = -1.245 VZn +40H - = ZnO~+2H20+2C - E = 1.216 VZn +4NH3 = Zn (NH3)4 +++2c - E =1.03VZn +4CN- = Zn (CN)~ + 2 ~ - E = 1.26 VIn gen e r a l, n o d ifficu lt y ia en cou n t e r ed in t h e d issolu t ion of m e t a llic

zin c, a lt h ou gh ve r y p u r e zin c ia a t t a ck ed on ly e low ly by h yd r och lo r ic a c id .Ad d it ion of a uma ll am ou n t o f Ni t+ or Co+ c t iyze s t h e d isso lu t ion .Su r fa ce s of m e t a llic zin c w ill r em a in b r igh t fo r lon g p e r iod s of t im e in t h ea b sen ce of wa t e r va p or .

Zin c is e a s ily e le ct r op la t ed a n d ca n b e u sed for a fin a l cou n t in g sam p le .Tw o m e t h od s of e le ct r o lys is a r e d e sc r ib ed be low .

1. P u r ifie d zin c is ,p u t in t o 10 m l of a solu t ion th a t i s O. 2 0 t o O. 25M1 -.in NaOH, a n d 1 m l of 5 ~. KCN is a d d ed . Th e so lu t ion is t h en t r a n s fe r r e d

t o a g la ss ce ll fi t t ed w it h p la t in um a n od e a n d ca t h od e . E le c t r olys is ie ca r r ie dou t a t O. 1 t o O. 2 am p , o r m or e , for 1 t o 2 h ou r s .

2. So lu b le sa lt s of EDTA (e t h y len ed iam in e t e t r a a ce t ic a c id ), or p o ly -.m lfon ic a c id s of a n t h r a cen e or a n t h r oqu in on e , a r e a d d ed t o zin c cya n id e

2so lu t i o n s . With th e se so lu t ion s , t h e cu r r en t d en s it y ca n va r y fr om O. 5 t o15 amp /dm2 a n d t h e ca t h od e y ie ld is 95 t o 98%. Th e zt ic con t en t i s 20 t o70 g /1, a n d t h e t ot a l NaOH con cen t r a t ion is 15 t o 80 g /1. A t yp ica l b a t hcom pos it ion is : Zn , 25 g /l; t ot a I cya n id e , 46 g /l; NaOH, 46 g /l; sod iuma nt hr a ce ne t ri su lfon a t e, 15 t o 25 g /l; a n d so lu b ilized s t a r ch , 2 to 5 g /1.

Ot h er m et h od s of e le c t r o lysis a r e d esc r ib ed in t h e lit e r a t u r e . 3-9

2. Solu b le Sa lt s o f Zin cZin c ex is t s in solu t ion or d y w it h +2 ox id a t ion s t a t e , w h ich s i r n p lifie s

it s ch em is t r y in th a t ox id a t ion -r ed u ct ion r e a c t ion s n eed n o t b e con s id e r ed .Th e so lu b le sa lt s of zin c in c lu d e ch lor id e , b r om id e , iod id e , for m a t e ,

a c e t a t e , su lfa t e , t h ioc ya n a t e , p e r cb lor a t e , flu o s ilica t e , n it r a t e , cya n id e ,a lk a li m et a l zin ca t es , a n d zin c -ammon ia comp lex .

3. In so lu b le Sa lt e . of Zin cTh e comm on in so lu b le com pou n d s of zin c a r e li st e d b e low in Ta b Ie I.

F olIow in g Ta b le I i s a d iscu ss ion of t h e p r e c ip it a t ion a n d cop r ec ip it a t ionch a r a c t e r i st ics o f m a n y of t h e se comp ou n d s .

3


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Ta b le I . In so lu b le comp ou n d s of zin c.

C ompo u n d Volub i l i ty ,g/100 m l H20

znNH4P04znco3Zn 3~ [F e(cN)6]2-2Zn(OH)2a(m3)2zn(Io4)2ZnHg(SCN)4Zn (CZ04)* H 20Zn sZn - 1, 2- d i (a llylt hioca rb ar ny l )h yd ra %in eZn-- th rda teZn -5-b r om o-a n t h r a n ila t e -Zn-5- iodo-an th raa i la teZn - 5 -m et hy l- a nt hr an ila teZn -3, 5 -d i br om o -a n t h r a n i la t eZn-N-methy l -amthraAla teZn -O- (2-a mk o - l-n ap h t hyla ~o)b en zoa teZn-8-hydroxquko la teZn -8-h yd r n xyqu in oLin e -5-m l fon ic a c idZn -2-h yd roxy - 1 -n ap h t ha ld eh yd eZn -m er ca pt ob en ~ ot hia 801eZn -p yr id @e t iiocya na teZn -quka ld a t eZn -5, 6-b en =o qu in a ld a t e q H20Zn-aa l icy la ldox imeZn -t a r t r a t e , C4H 406 Zn - H20

(oo lu b le in excen o ~rtrate)Zn - t e t r ame thy l amt iod iph eny l an t i -

Py r i ny l c a rb ino l t h i o cy ana t e&-m e t h y l xtm th a t e 39&-e t h y l xa n t b a t e 39Zn -n -b u ty l xa n th at e 39Zu b or neo l glycu r on a t e

innol.O. 0206, a t 25-Cv . e l. so l.01. so l.O . 0000420.87, a t 25Cinoo l .0.24, a t 15-C0.000715, a t 26-CO. 0007, a t 18*Cqu an t. , pH 7.5-8.6in n ol. , p H >3.09inso l .inoo l .in so l .in so l .inoo l .qwm t . , pH 5.5-7qu an t. , pH 4.6-13.4qu a n t . , pH >3.6inso l .qwm t . , pH >7t io l .i n no l .qwit. , @ 2.85in a o l. , pH 8.50.036, a t 25C

inso l .

O. 360.150.12i r loo l .

4


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Zin c amm on ium ph osph a t e . Th e p r ecip it a t ion iq ca r r ied ou t a t t h e p h en o l-p h t h a le in en d p oin t a n d on e wou ld expect t h a t m a n y e lem en t s wou ld cop r ecip i-t a t e , Eu ch a s Cd , F e , r a r e ea r t h s, e t c .

Zin c ca rb on at e. AU e lem en tssh o~d cop recip it at e.

Zin c p ot ass iu m fer rocya nid e.

w it h in s o lu b l e ca r bon a t q s a n d h yd r oxid es

Zn 3KZ [F e(CN)6]2 p r ecip it a t ed a t pH 1 willca r r y d - Sb (I II ), Bi(I J .1), Cd (I I), Ce (II I ), Co(I I ), CU(H), Gd (?II ), Ga (II I), Ge (IV),In (II I ), Ir (I~), F e(II ), La (I II ), P b (I .1), Mn (ll), Hg(I I), Nd (II I), Ni(~), Sm (HI),SC(II I), Ag(I ), Th (IV), Ti{IV),. Y(II I), a n d Zr .(IV), wh ile F e(II I ), Mo(VI), P d (II),Ru (I I I), Te (IV), W (VI), .U(VI), en d V(V) d o n ot ca r r y. 10 In t h e p r e sen ce ofl% EDTA, on ly Fe (I I), lAn (H), Ag(I ), a n d Zr (IV) cop r ecip it a t e . In t h e p r esen ceof n it r iloa ce t ic a cid , F e (I I), Mn (I I), Ag(I ), a n d Zr (IV) ca r r y. Ag(I) d oe s n otcop r ec ip it a t e in t h e p r esen ce of t h iosu lfa t e a n d Zr (IV) d oe s n ot cop r ecip it a t efr om flu or id e evolu tion s. If t h e p r ecip it a t ion iB ca r r ie d ou t in lM HC1, Cd (I I)d oes n ot ca r r y, 1 1a n d t h e p r ec ip it a t ion is qu a n t it a t ive .

Zin c h yd r oxid e. Zb ic h yd r oxid e w ill p r ecip it a t e in t h e &I r a n ge 7 t o 13 inth e a b sen ce of ammon ium sa lt s . Th e solu b ili~ p r od u ct of Zn (OH)2 in wa t e ra t 20 C h a s b een r ep or t e d by Rich a r d e t a l. , 12 to b e 1.8 X 10-14. F e it k n ec ta n d H ab er li13 r ep or t t h e volu b ili t y p r odu ct of Zn (OH)2 w it h so lu t ion s of a

-17va r ie t y of ion ic s t r e n gt h s a n d a n ion s to r a n ge fr or p 5 x 10 -16to 6x10 .Th e r ea ct ion

Zn (H20)30H + H+= Zn (H2@~, PK = 9.36 ,14w a s s t u d ied by Ach en za .

In t h e pH r a n ge 6 t o 12, zt i .c d oe s n ot form r a d ioco llo id e a n d d oe s n otp la t e ou t on p la t in um excep t by p r ecip it a t ion of h yd r oxy for m s. 15 Kvamme , 16

on th e ot h er h a n d , st u d ied t h e a d sor p t ion of zin c on filt e r p a p er a t pH!s of3.5 t o 10.5. Mzim um ad sor p t ion of zin c in t r a ce con cen t r a t ion(2.7 x 10-6 ~) w a s90% a t pH 6.5.-4 Th e a d sor p t ion d ecr e a a es w it h in cr e a sh gzin c con cen t r a t ion t o 10~0 a t 3 X 10 M an d r em a k s con s t a n t t h e r ea ft e r .Th e zin c a lso a d sor b s we ll on gla ss a n d F e(OH)3, in t h is pH r a n ge .

Zt ic w ill a lBo cop r e cip it a t e F e(OH)3 a n d Cr (OH)3 to som e ext en t hn ea r ly n eu t r a l solu t ion even in th e p r esen ce of ammon ium ion s . 17

Kova len k o18 st u d ied t h e ca r r yin g of zin c on Al (OH) p r ec ip it a t ed fr om3NH cl

1 - 4QH O1u t iOn e 9Ad sor p t ion &cr ea sed w ith in cr e a s in g in it ia l

~+ + con cen t r a t ion , a n d d ecr e a sed w it h in c r e a s t ig NH4C1 a n d .NH40H con -c en t r a t i o n s . Ad sor pt ion in cr ea sed w it h in cr ea s t ig in it ia l Zn ++ con cen t r a t ion .Th er e w a s ver y lit t le a d sor p t ion a t pH 4; t h e m a xim um ad sor p t ion w a s a t

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pH 6. H igh con cen t r a t ion s of ~4Cl a n d low con e en t r a t ion s of NH40Hm in tiize cop rec ip it at ion .

Zt ic p er iod at e. Zin c w ill cop re cip it at e 19 w it h I?e (104)3 q 2~e203 - 7H20to t h e ext en t of O. 4% a t pH 3.5 a n d zin c con cen t r a t ion of. 7 X 10-3 M . Th eh igh e r t h e zk c con cen t r a t ion , t h e low er th e cop re cip it a t ion .

Zin c m er cu r it h iocya n a t e . Cu (Il), F e (m ) (in la r ge am ou n t s), Co(I I)r Ni(I I),W(3X, Bi(lIO, Cd (~),. Ag(I ), a n d Hg(D) a r e cop r e cip it a t ed w it h zin c , w h i leclo~, Cl-, NO;, SO:, K+, Na +, NH:, Mg++, Ca t +, Sr ++, Ba t +, l?e+~+(sm a ll ~~~t s ), P b (I I ), As (II I ), As (V), Sb (~), Sb (V), a n d Sr i(W) d o n oti n t e r f e r e . Accor d in g t o Ru lfs a n d I&by , 21 F e (II I ), Ni(I I ), CU(H ), a n dMn (lI) co lor t h e p r ec ip it a t e bu t a r e of n eg lig ib le we igh t .

Zinc oxzlate. Ca , Sr , Ba , F e(lI), Mn (lI ), Co , Ni, Cd , P b , a n d r a r e earthswill cop r ec ip it a t e w it h zin c oxa la t e fr om a ce t ic a cid so lu t ion s. 22

Zin c su lfid e. P r ec ip it a t ion of zin c su lfid e by amm on ium su lfid e ca n ca r r yh a lf t h e e lem en t s in t h e p e r iod ic t a b le (se e re f . 23, p . 6 1). Th e su lfid e ca nb e p r ecip it a t ed u n d er a w id e =r ie t y of con d it ion s (t h e fo llow in g e lem en t scop r e cip it a t ed im p ly t h a t t h e c la ss ica l sch em e of =a lys is h a s b e en u s cd ).Wit h pH 2 t o 3, a n d w it h for m a t e , c it r a t e , or cb lor oa ce t a t e b t ie r , T1 (I),Ga (H I), lh (DI), Cd (~), a n d Ni(I I ) ca r r y, bu t t h e r e is sep a r a t ion fr om Mn@),F e (lI ), a n d Al(IH ). 24 Wit h su lfa t e -b isu lfa t e bu ffe r , pH 2, a n d 20% NH4SCN,t h er e is sep a r a t ion fr om Co(,I I ). 25 Th er e is sep a r a t ion fr om n ick e l u n d er t h efollow in g con d it ion s: bu ffe r w it h NH40H NH4C1, p r ecip it a t e w it h t h ioa ce t -a r n id e , h ea t , cool qu ick ly a n d cen t r ifu ge a s soon a s p r ec ip it a t e s t a r t s t o t u r n

26gr ey @iS). Zin c su lfid e m a y a lso b e p r ec ip it a t e d fr om ba s ic cya n id e27 .s o lu t i on s.

Ca&n ium ca n b e sep a r a t e d fr om zin c b y p r e cip it a t ion of t h e ca dm ium28su lfid e fr om 3 ~, H2S04.

Zt ic su lfid e ca n be ca r r ie d ~ cop p er . su lfid e p r e cip it a t ed w it h t h io-a ce t am id e a t pHfs low er t h a n .0.5 a n d t em p er a t u r e les s t h a n 80C.

29..

Zin c d id ly ld it h ioca r bam id o h yd r azin e . Zin c is p r e c ip it a t b d qu an tit a t ive lyb e tw een pH 7.5 a n d 8.6 by a n a lcoh ol so lu t ion of t h e r e a gen t , w a sh ed w it ha ce t on e , d r ied a t .105-C , a n d w e igh ed a s Zn (C8H12N4S2). 30 Ni(I I) in t e r fe r e ,CU(I I) a n d P b (II ) m a y b e r em oved by fir s t p r e cip it a t b ig t h em a t low e r pH J s --2.5 t o 3.5 for Cu , a n d 5 t o 6 for P b .

Zin c a n th r a nila te .. Be low pH 3.09, a n t h r a n ilic a cid in exce ss w ill p r e cip it a t e31

zin c com p le t e ly in .on e-h s lf t o on e h ou r . Hg(I I ) a nd Cd (I I) cop rec ip it at e,31

CU(I I ) d oe s n o t ca r r y. 32

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Zi nc - 8-h yd r ox yq u in ola t e . Th is p r ec ip it a t e is fa r fr om sp ec ific , sin ce n ea r lya ll m e t a ls excep t a lk a li a n d a lk a lin e e a r t h s a r e cop r e cip it a t ed (se e r e f. 23,p . 115).

Zin c - 2-h yd roxy -1 -n ap ht ha ld eh yd e. Cu (ll), Mg(I I), Ca (I I), Sr (H ), Ba (J .1),Be(I I ), P d (I I), Mn (II ), Ni(ll), a n d Co(I I) cop r e cip it a t e . 40

Zi nc m e r ca p t ot h ia zo le . P r ec ip it a t e s zin c , a lu m in um , t h or ium , a n d b ism u t h33qu a n t it a t ive ly a t pH 8 or a bove .

zin c p yr id in e t hiocya na te . CU(LI), Cd (I I ),. a nd Ni(I I ) p yr id in e t h iocyem at esw ill ca r r y zin c ; t h e zin c -ca r r y in g is low er ed b y low er in g t h e zin c con cen t r a -t ion , lowe r in g t h e con cen t r a t ion of ot h e r m et a l, or in c r ea s in g t h e t em p er a -t u r e . 34 CU(I I), CO(D), Ni(ll), a n d F e(I I) w ill cop r ecip it a t e w it h zin c p yr id in eth io cy ana t e . 35

Zin c qu in a ld a t e . F e(I I I) a n d Ni(II ) cop r ec ip it a t e . 36

Zin c-5, 6 -b en zoq u in a ld a t e . Co (II ), Mn (II ), a n d Ni (I I )

Zin c m et h yl xa n th at e . Ni(I I), As(I I I), Cd (I I), CO(H ),

37cop r e c ip i t a t e o38a nd Cu (I l) cop re cip it at e.

Bor n eol glycu r on ic a cid . Zin c is p r e cip it a t e d fr om a n a cid or n eu t r a l solu t ion38aw it h b or n eol glycu r on ic a cid . Th e r ea gen t d oes n ot form in solu b le com -

p ou n d e w it h ot h e r common m et a ls excep t ca dm ium . Th e p r ec ip it a t e cor r e -sp on d e to Zn (C16H2507)2c 2H20.

4. An a lyt ica l De t e rm in a t ion s of Zin cA gen er a l r e v iew of gr a v im e t r ic a n d vo lum e t r ic a n a lyse s is p r e sen t ed

by Beam ish a n d Wed la n d . 41 Th e m or e common m et h od s a r e lis t ed b e low .

Gr av im et r ic Det er min at ion

z in c amm on ium ph osp h a t e . Accor d in g t o, H ille b r a n d e t a l. , 2 0 t h e p r ec ip it a ti onof zin c zm r n on ium ph osp h a t e follow ed by ign it ion t o t h e p yr op h osp h a t e is t h eb es t g r a v-im e t r ic m e th od for zin c . Th e con d i t ion s for p r e cip it a t ion a r epH 6.5, t em p er a t u r e 80-90C , a t e n fold exces s of p h o~p h a t e , 42 a n d a r a t ioof amm on ium ion t o zin c of a bou t 200 t o 143; t a r t r a t e b e low lN a n d c it r a t e

4-4 below O. 25N do n ot in t e r fe r e . Th e p r e cip it a t e is ZnNH4P 0 H O wh ich 4242.m a y b e d r ied a t 100-105 C (se e r e f. 20). Va n ce a n d Bor u p . r ecomm en dign it ion a t 500 C. ~va l 45 r e comm en d s ign it ion a t 6 IO C or a bove .

Zi nc m e r cu r it h io cy an a t e. Zin c m e r cu r it h iocya n a t e ca i b e p r ec ip it a t ed fr om5 ~0 H2S 04, 03 o r HC104 a t r oom t em p er a t u r e b y a so lu t ion of 31.5 g

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NH4S.CN a n d 27.1 g H gC12 in 1000 m l of w a t e r . Th e r ea gen t sh ou ld b efi lt e r ed a ft e r p r e p a r a t ion a n d sh ou ld b e r e n ew ed eve r y yea r o r SO. Th ep r ec ip i t a t e ca n b e d r ied fr om 710-2700C, 45 a n d h ae t h e com p osit ionZnHg(SCN)4. 21, 46

Zin c oxa la te . Th e p r oced u r e for p r ec ip i t a t in g zin c oxa la t e .is a s fo llow s :t o 10 t o 12 m l a q u eou s so lu t ion con t a in in g O. 5 t o 50 m g zin c , a d d 85 m lgla c ia l a ce t ic a c id con t a in in g 1 g -m on iu m oxa la t e . 47 Add 4 m l d ie t h y l-oxa l a t e , s t i r a n d h ea t q u ick ly t o a b ou t 100 C. Kee p a t t h is t em p e r a t u r e fora n h ou r a n d a h a lf; Mt e r w a sh in g , ign it e t o ZnO a t 900 C .

Zin c E ulfid e. Zin c su lfid e i s p r ec ip i t a t ed fr om H2S04 solu t ion s a t pH 2 t o 3a ft e r fu m in g off ch lor id e s a n d n it r a t e s . 20 Th e p r ec ip i t a t e is t h e n ign it ed t oZnO a t 1000C. 45

Zin c -1, 2 -d i (a lly lt h ioca r bam yl )h yd ra z in e. 30 Ad d amm on ia u n t il so lu t ion iab a s ic , a d d d ilu t e HZS04 u n t il som e p r e cip i t a t e r em a in s , c la r ify so lu t ionw it h c i t r ic a c id , a n d d ilu t e t o 200. m l. Add a s ligh t exce s s of r e a gen t , a n dh ea t in a w a t e r b a t h . Add sod iu m a ce t a t e a n d sod iu m h yd r o t id e , d ige s t , a n dffiter. Wa sh w ifi h o t w a t e r a n d a ce t on e , d r y a t 105 C, a n d w e igh a snc8Hl2N4s2-Zin c a n th r an ila te . P r e c ip it a t ion i s ca r r ied ou t in n e u t r a l so lu t ion (m e t h y lo r a n ge e r id p oin t ) a t a b ou t 100 C. Dige st 15 t o 20 m in u t e s , w a sh w it h d ilu t ed

t h en w it h a lcoh ol. 42, 48, 49r e a g e n t , Dr y a t 105 0-1 10C , w e igh a s Zn C7H602N.

Zin c-O- (2-am in o- 1 -n ap ht h yl- a zo)b en zoa t e . P rec ip i t a t ion is q u an ti t a tive 50in t h e pH r a n ge 5.5 t o 7. Th e con ve r s ion fa c t or t o zin c i s O. 1012. H ighr e su lt e a r e ob t a in ed in t h e p r e sen ce of la r ge am ou n t s of amm on iu m sa I t s .

Zin c -8 -h yd r ox yq ~fi le r a n d Hm t e r ,51u i no l a t e . g ive t h e foI Iow in g p r oced u refor t h e p r ec ip i t a t ion : Ad ju s t t o m e t h yl r ed en d p oin t a n d b u ffe r w it h amm on iu ma ce t a t e a ce t ic a c id . H ea t t o 60C, a d d . s low ly a 27. e xce s s of r e a ge n t inO. 8N a ce t ic a c id , h ea t t o n e a r ly b o~in g for 2 t o 3 m in u t e s , cool 30 m in u t e s ,wa sh w it h w a t e r , d r y a t 160 C, 4245 a n d w e igh a s Zn (C9H6NO)2. Th is com -

52p ou n d w ill su b lim e in va cu u m a t 275- 325C.

Zi n c -m e r c a p t o b e n z ot h i a z ol e. Zin c i s p r ec ip i t a t ed b y t h e r ea gen t a t pH 8,d r ied a t 105 - 120C, a n d w e igh ed a a Zn (C7H4NS2)2. 33

Zin c q u in a ld a te . Zin c is p r ec ip i t a t ed b y t h e r ea ge n t a t pH 7 a n d 100C ,36d r ied a t 105C, a n d w e igh ed a s Zn (C ,loH602N)2 H20.

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Zin c-5, 6, b en zo qu in a ld a te . Zin c is p r ecip it a t e d by t h e r e a gen t a t pH 2.85,a n d d r ie d a t 110 - 115 C; t h e p r e cip it a t e con t a in s on e mole cu le of wa t e r o f

37crys ta l l iza t ion .

Zi n c s a li cy la ld o xim e. P r e cip it a t ion is com p le t e a t pH 8.5, a n d is d iges t edfo r 10 m in u t es a t 90-100 C. 52a Th e con d it ion s m u s t b e con t r olled ca r e fu llyor on e ob t a im a m ixt u r e of m on o- a n d d i - t ia licy la ld oxim es. Th e m on o(ZnC7H502N) is t h e w eigh a b le form . Accor d in g to Du va l, 45 a n d Ryn a s iew icz53a nd F la gg , on e mu Et ign it e t o ZnO a t a bou t 950 C t o ob t a in a r ep r od u cib lewe igh t .

Zi n c t e t r am et h y ld i ar n i n od i ph e n yl an t i py r in yl ca r b in ol. P r ec ip it a t ion is com -p le t e in HC1 or H2S04 fr om O. 5 t o 1. 5N. Th e p r e cip it a t e is d r ied fr om105 -11oC; t h e con ve r s ion fa ct or t o zin c is O. 0 556.

F igu r es 1, 2, a n d 3 a n d Ta b le ~ a r e t a k en fr om Du va l. 45

Volu me tr ic De te rm in a t ion s

Zin c m er cu r it h ioc ya n a t e . Th e p r ec ip it a t e is d isso lved in 4M to 73 HC1an d is t i t r a t e d w it h s t a n d a r d iod a t e . Th e en d p o in t i s t h e d isa p p ea r a n ce of

t h e iod in e colo r in ch lor o form . 49, 55

Zin c oxa la t e . Th e p r ecip it a t e is d isso lved in d ilu t e su lfu r ic a cid a n d t h e47oxa la t e t it r a t ed w it h KMn 04.

Ver sen e . Zin c ca n be t it ia t e d a t pH 6.5 w it h d isod ium ve r sen a t e t o th eE r ioch r o r n e b la ck T en d p oin t . 56 P r ib i157 m a sk s Ag(I ), CU(II ), Mn (II ),Ni(~), Co ,(II ),, a n d Hg(II ) w it h CN-, t h e Zn (C,N)~ b e in g d es t r oyed by r e a c t ion

57 61w it h ch lor a l, o r for m ald eh yd e.

Co lor tie t r ic De t e r min at ion s

Di th izone . Zin c m a y be . d e t e r m in ed b a solu t ion of t h e zin c -d it h izon e com -p lex in ca r bon t e t r a ch lo r id e or , ch lor ofor m by t h e op t ica l d en s it y a t ~ 30 m ~. 49

Azo d ye s* Da s a n d Gu h a Sir ca r 58 u sed t h e r ed -b r own comp lex for m ed a tpH 3.4 t o 7 b y zin c 8-h yd r oxyqu t io la t e a n d m -~in o ben zoic a cid . No w a velen gt h w a s g iven .

Z incon . Ru sh a n d Yoe 59 d e t e r m t ied zin c color ir n e t r ica lly b e tw een pH 8.5a n d 9.5 w it h zin con (2-ca r b oxy-2 l-h yd r oxy-5 l-su lfofo r m a zylb en zen e) a t620 m ~.

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3 -- ____ ___ ___ ___ ___54 347 --- _10,~~

Ll

1100~

lm, .x? =.

W9q ,272 520

?

,811 f~ , mlgi 2s9 ,296 94s

F ig . 1. P yr o lys is cu r ve s of zin c d er iva t ive s .1. E lec t r olyt ic zin c. 2. Hyd r ox id e v ia a q u eou s amm on ia .. 3. Hy-d r ox id e v ia m e r cu r y (I I ) ox id e . 4. Hyd r oxid e v ia d i r n e t h ylam jn e .5. Hyd r oxid e v ia m or p h o lin e . 6. Hyd r ox id e v ia p ip e r id t ie . 7. M-ph id e . 8. Su lp h at e . 9. Zin c amm on ium ph o 6p h a t e .

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9132 ,Z& S& ma

I 590 946F ig. 2. P yr o lys is cu r ve s of zin c d er iva t ive .10. Ba s ic ca r bon a t e v ia a n .r n ot ium ca r bon a t e . 11. Zin c cya na mid e.12. Ba s ic ca r bon a t e via gu a n id in ium ca r bon a t e . 13. Ba s ic ca r b on a t evia t r im et h ylp h en ylammon im ca r bon a t e . 14. Dip yr id in ozin c (II )t h iocya n a t e . 15. Te t r a t h iocya n a t om er cu r a t e (II ). 16. Oxa la t e .

11


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42 127 284 9s5 f026B ma~ 2ss,47 so 1

,@ 20$ W2462 w

M

w

I

m100 q

972 ma407

f024

F ig . 3. P yr o lys is cu r ve s of zin c d e r iva t ive s .17 . b t h r a n it a t e . 18. 5- Br omo-a n t h r -i la t e . 19. Oxin e com ple x.20. 8-Hyd r oxyq u k a ld t ie comp lex- 21. Salcylaldcxdme complex.22. Dit h izon e com p lex. 23. 2. 7-- D ia mt io flu or en e com plex .24. Qu in a ld in e com p lex.

12


20/65

Ta b le II . Th e r m ogr a -e t r ic d a t a of zin c com pou n d s. 45

P rec ip it a t in g r ea gen t F or m w e igh ed Temp e r a t u r e lim it s

E lec t ro lys i sAqu eou s am mon iaMer cu r y (II) o t id eD ime t hy l am ineMorpho l i n eF i pe r i d i n e Hyd rogen Eu lp h id e

W%lph ur ic a c idSu lp h u r ic a c id

*~onim p h o s p h a t eAmmon iu m p h osp h a t eSod iu m p yr op hosp h at e#u n rn on iu r n ca rb on a t eAmmon ium ca r b on a t e

*Cyanam ideC y a n am i d eGwm Min iu m ca r bon at eT r i r n et h y lp h e n yl ammon i um

c a r b o n a t eTb iocya n at e + p yr id in eTh iocya n.a te + p yr id in e*Th .iocya n a t om er cu r at e (~)Th iocya n a t om er cu r a t e (I t )*oxa lic a c idOxa lic a c idA.n th r an .i lic a cid*5-Br om o-~t h r a n flic a c id5-Br om o-zn t h r a n ilic a c idOx ine*Ofine8 - hyd r oxyqu i nz l d i n eSa l i cy la ldoximeD i t h i z one2 . 7 -D ia r n i n o f lu o r e n e

*Qu in a ld ic d

ZnZn OZn OZn OZn OZn OZn Oznso4Zn OZnNH4P04Zn2P207Zn2P2075Zn O 2C02Zn OZnCN2Zn ONoneZn O[ Z4C5H5N2] (CW2:~Hg(CNS)4]Zn O~~~24 2H20Zn OZn (NH20 C6H3Br - C02)2Zn OZn (C9H60N)2 1-1/2 H20Zn(C9H60N)2Zn(C10H80N)2None;::13%ON4S~c10H602~2 H20

< 54>1010> 970>1000> 910> 920> 943

300-788> 950

Be tw e en 500a n d 167> 610> 610

370-879>looo~

105-152> 812DNone

> 247< 71> 78050-270> 820< 75> 590> 500< 123> 955< 65

127-284.100-220

None< 68.> 972< 126

Ta k en d ir t ly fr om t h e t a b le on p a ge 284 of Th e - o gr a v im e t n c Xum lys isb y C. Du vA.$g* Su it a b le for gr a v im e t r ic d e t e r m in a t ion of z in c .

4-ch lorore sorc ino l . St ew a r t a n d Ba r le t t 60 ext r a c t ed zin c in to ch lor ofor mfr om solu t ion s of d ie t h y l-d it h io- c=bm a t e a t pH 8.5. 4-ch lor or e sor c in o lw am u eed a s a ca lor im e t r ic r e a gen t a ft e r ex t r a c t ion .

5. Comp lex Ion s of Zin cZin c , w it h t h e 4s a n d 4p or b it a ls a va i la b le for b on d in g , for m s a la r ge

n um be r of comp lex ion e a n d ch e la t e comp ou n d s . Th e se a r e of gr ea t im por -

1~


21/65

t a n ce in t h e u n d e r st a n d in g of t h e ch em is t r y of zin c . Som e of t h e com p lexion s a r e li st e d b e low in Ta b le I ll. La g K is r ep or t e d a s t h e con s t a n t fo rfo r m a t ion of t h e g iven ion fr om &e ion w it h on e le ss liga n d . Th e liga n dis som e t im es r e fe r r e d t o in t h e t a b le a a A.

Ta b Ie HI . Comp lex ion s of zin c .

Comp le t in g a gen t Rea c t ion p r od u ct Log K Ref.

NH3

e t h ylen e d ia min e

c is - 1, 2-cyc lo -h exa n e d iam in et r am - ~, 2-cyc lo-h exa n e d ia r n in et r am -1, 2-c yc lo -h ep t a n e d iam in eTr ie t h y len e-t e t r am jn et e t r a e t hy l en e -p en t amin eca t e ch ol d isu lfon ic a cid (t ir on )

c it r ic a c id

CN -

glu t a r ic a cida ce t ic a c idS20;py r i d in eF -

ZnNH. ++> ++zn(NH3)2++zn(NH3)3++zn(NH3)4ove r a l lznA++znA2++znA3++z~t+znA++ZIA++znA++Zm%++ZIA=z+znA=(p= o)Znwi-{p= o)Zn Cit -Zn Ci t -Zn Ci t -Zn (Cit )~4Zn (OH) Cit ,pH 7 t o 12.5

Zn(CN)~Zn(CN)~Zti;zti~Zn(S203)jZnq+znF +zriF+

14

2.372.442.502.159.45.775.063.285.736.246.11

11.915.410.9217.811.684.584.714.253.551,919.4

19.017.02.3

-0.24.691,90.730.77

626262626263636363636380796464656566676967686270716269627273


22/65

Ta b le IL (Cen t d )

Com p le t in g a gen t Rea c t ion p r od u ct Log K Ref.

I

OH -SCN-

SCN-

b ioxa l a t e

oxa l a t e

cl - ZnCl+ZnC12ZnCl~ZnC1

Br - tZnBrZxiBr +ZnBr ~ZnB r2ZnB r~ZnBr -~ZnB r~ZnB r~Zn I+, Zn 12, Zn I~Zd :ZnO~Zn (SCN)+ se e r e f 77Zn(SCN)2Zn(SCN)~Zn(SCN)~Zn(SCN)=

+znHc204Zn(HC2Q4)2ove r a l lZn(C204)Zn(C204)=Zn(C204)2Zn(C204)~ove r a l lo v e r a l l

g lycolic a c id Z&t a r t a r ic a cid Z ruk ;su cc in ic a c id znA;m a lon ic a cid Znll=

$va l i n e 2AznA2

0.190.600.711.0

-0.600.0

>0.1-0.15>0.1-0.30-0.52-2.6>0.05-5.415.40.50.80.01.34.21.721.403.123.884.852.355.06.237.121.955.643.72,540678.97

747474 .62,7574767476747676627462627878787862666666667 06 6716669666971718181

15


23/65

No qu a n t it a t ive d a t e a r e a va i la b le on t h e zin c -t h ioa ce t am id e comp lex, 82Zn (SCNH2CH3)2++, or t h e p h osp h a t e com p lexe s . .83Sh in iga wa a nd Kob a ya eh lp os t u la t e t h a t t h e or t h o p h osp h a t e com p lexe s in volve fo rm a t ion of a ch e la t er in g . a n d s t r on g d issoc ia t ion of o r d in a r i ly -w ea k t e r m in a l h yd r ogen a t om s . Th er e la t ive s t r e n g t h s of t h e com p lexes a r e : F e >P b >Zn >Cu >Ni >Co, Cd >Mg >Ca >Sr >Ba . >K >Na .

A q u a lit a t ive d iscu s Bion of t h e h a lid e com p lexe s is of va lu e w h en con -s id e r in g sep a r a t ion u s in g a n a n ion r e s in co lum n . F or t h e h igh er com p lexe sMX~ an d MX~ wh e r e M is Zn ++, Cd++, or Hg++, a n d X is Cl-, B r -, o r1- th e eq u ilib r iu m is m or e in fa vor o f t h e com p lex ion , a ~ t h e a t om ic n u m be rof t h e ca t ion in cr ea Ben . Th e con c lu s ion s fr om va r iou s d a t a 85, 86,87 a r e fia tt h e r e la t ive s t r e n g t h s of zin c a n d ca dm ium comp lexe s a r e

Th e Zn Cl~ a n d CdCl~ com p lexe s a p p ea r t o b e of n e a r ly t h e s am e s t r en gt h , 88R ela t ive s t r e n g t h s of t h e b r om id e com p lexes a r e : 2n > Cu >Ga >Co >

Ni. 89F igu r e 4 sh ow s sp ec ies in h yd r och lo r ic a c id so lu t ion . 13 8

+2

~ +1aEa

-2

I 1 1 1 I 1 1 1 I 1 1 I 1 I 1 I Io

I l l I 1 ! I 1 1 I 1 I 1 1 10.05 0. I 0.5 I .0 5

MO LALITY OF HCI

F ig. 4. Ave r a ge ch a r ge of Zn (LI) in HC1 (a n ion exch a n ge E lop e m e t h od ).

16


24/65

6. Ch e la t e Com p ou n d s of Zin c ,Zin c for m s a b ew ild e r in g a r r a y of ch e la t e com p ou n d s , e v id en t fr om a

cu r so r y in sp ec t ion of Ta b le IV. (Com p ila t ion s of ch e la t e com p ou n d s of m a n yot h e r e lem en t s a r e fou n d in r e fe r en ce s 90 a n d 91. )

Ta b le IT. Ch e la t e com p ou n d s of zin c ,

L iga n d Log K Ref .

am in o a ce t ic a c ida -am in o p r op ion ic a c idp r o l i n eglu ta m ic a cida -N-p r op yla m in o a ce t ic a c ida -S-am in o va le r ic a c id2-a m in o h exa n oic a c id2, 6-d ia r n in o h exa n oic a c ida r g ti in e8 - hyd r oxyc i nno l i n e8 -h y d r o x y q u i n o li n e8-h y dr ox y - 4-m et h ylc in n olin e8-h y dr ox y - 2 -p h en ylq u in o lin e8-h yd roxyq u in olin e - 5- a u lfon ic

9.729.56

10.29.469.19,7.3010.47.67.8.12.7317.5613.6917.52

ac id 16.28-h yd r oxyq u in olin e - 2 -ca r b oxylic a c id8-h yd r ox y - 4-m et h ylq u in olin e8 -h yd r o xy - 2 -m et h ylq u in olin e8-h yd r oxy - 2, 4-m et hylq u in azo lin et y r o a i n e2- (o-h yd r oxyp h en yl )-b en zim id azolep t e r oylg lu t am ic a cida -isop r op yla m in oa c e t ic a c id2-a m in o- 4-m e t h ylp e n t a n oic a c id1, 2-d iam in o p r op a n ee t h ylen e d iam in edi f i e thy lg lyoxixned im et hylg lyo xim e -0-m on om et hyl etherG @-d iam in o p r op ion ic a c idt r opo l onek oj ic a c ida -b r om o t r op olon e

9.720.2418.7214.789.1

15.247.514.368.9310.8710.4313.914.3611.517.513.212.7

919191919191919191919191

10 1919191919191

1019191919191919191919191

17


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Ta b le IV. (Con t ld )

L ig and Log K Ref.

a -m eth yl t r op olon e~-methy l t ropo lonea- isopropy l t ropo lone~- isopropy l t ropo loneO, O-d im eth yl p ur pu roga llino xa lic a cidm a lon ic a cide th yl m a lon ic a cidd ie t h yl m a lon ic a ciddh n e t h yl .m a lon ic a c idd i-n -p r op yl m a lon ic a c idm et h yl m a lon ic a cidn -p r op yl m a lon ic a c id2 -me r c ap to e thy l amin ea -am in o- &mer ca p t op r op ion ic a cidqu in o lin e -8- ca r b oxylic a cida nt hr an ilic . a cid .5-b r om oa n t h r a n ilic a c idd ib en zoyl m eth an ed ib en zoyl m et ha nep -ch lor o d ib en zoy l m et h a n ep -m et h y l d ib en ~oy l m et h a n ep -m et h oxy d ib en zoy l m e t h a n em -m et h oxy d ib en zoyl m et h a n ea c e ty l a c e ton esa l icy la ldehydesa licyla ld eh yd e -5- m lfon ic a cidb enzoy l a c e ton e2-fu r o yl -b e n zo ylm et h a n e2-t hen oy l.-2-fu r oy lm et ha ne1, 3-d ia rn in op r op a n - 2-olh i e t am i n e1, 3-d ia min o-2, 2-d ir n et hylp rop an e2-o -hydro~heny lbenzo th iazo l~ir nid oa ce t ic a c idam in o eu ccin ic a cid

18

15.715.216.219.312.57.363.33.043.242.743.153.103.12

18.9018.29.0

20.935.6819.6515.0714.4215.2815.6415.078.818.105.410.39.569.289.02

10.5010.4113.667.035.84

91919191919190909090909090919i91929291999999999991919190909091 ,9191919191


26/65

Ta b le IV. (Cen t d )

L ig and Log K Ref .& ca r b oxym e t h y lam in op r op ion ic a cidm et h y l i r n in od ia ce t ic a c idcya n om e t h y lim in od ia ce t ic a c idN- (ca r b am oylm e t h y l )-ir n id od ia ce t ic a cidg lycy lg lyc ineglycylg lycy lgly c in eN- Z-h yd r oxye t h y lim in od ia c e t ic a c idd i- (2-h yd r oxye t h yl )am in o a ce t ic a c id3-h yd r oxy p r op y lir n in od ia c e t ic a c id2-m et h oxye t h ylir nin od ia ce t ic a c id2-m et h ylt h ioe t h ylim in od ia ce t ic a cid2- e t h oxyca r b am ylam in oe t h y lim in od ia ce t ic a c id2- (d ica rb oxy lm et hy l )-a min o e th ylt r t ie t hy la mm on iu m

ca t i o n3, 31 -d ir ne t h y lbu tylim in od ia c e t ic a c ide t h ylen ed iam in ed ia ce t ic a cid2-ca r boxye t h y lir n in od ia ce t ic a c idca r bo~e t h ylim in od ia c e t ic a cid2 -h yd r oxye t h y lim in od ip r op ion ic a cide t h y l en ed iam in e -N, N! -d ip r op ion ic a c idn it r ilop r op ion ic a cidp h en ylim in od ia ce t ic a cide t h y len e d iam in e -N, N, Nl, N1-t e t r a a ce t ic a cid (EDTA}N!- 2- (h yd r oxye t h y l)- e t h y len ed ia r nin e -N, N!,

N-t r ia ce t ic a cide t h ylen ed iam in e -N, N!-d ia ce t ic -N, Ni-d ip r op ion ic a c id2, 2 t -h is [d i(ca r bo~e t h y l )-am in o-] d ie t h yl su lfid ee t h y len ed iam in e -N, N, N!, N1-t e t r a p r op ion ic a cidN, N, Nr , Nl -t e t r a k is - (2-am in oe t h y l)- e t h y len e d ia r n in en it r flo a ce t ic a cid2 .2 -d i am i n o -d i e t h y la r n i n e2, 21 -d ia r nin od ie t hyl su lfid e2, 2 I , 2 I I -t r iam in ot r ie t h yla mt ieN, N - d i- (2 -am in o e t h yl )- e t h y len e d iam in e2-m e r ca p t oe t h ylir n in od ia ce t ic a c idd ie t hylen e t ria min et rie t hy len e t et ra rn in e

6.177.665.87.033.803.338.335.367.78.438.286.86

5.347.9211.939.87.94.67.65.33.22

16.26

14; 514.513.177.816.2410.458.95.3114.6512.115.9212.014.6

919191919191919191919191

91919191919191919191

91919191919191919191919090

19


27/65

Tab le IV. (Cen t id )

L ig and Log K Re f.

p rop ylen e d ia rn in e1, 2, 3-t r ia m h op r op a n eO-phenan th ro l t i ea l a n k ea a p a r a g i n ea sp a r t ic a cidh i s t i d i n el eu c in ep ro l i n et r y p t op h a nva l in eam in oba r b i t u r ic a c id -N, N-d ia ce t ic a c id

12.576.76.439.528.710.012.888.9310.29.38.103.2

909090909090909090909090

amm on ia t r ia ce t ic a c id 13.4 90g lyc in e -N-p r op ion ic a c id 10.1 90t i r o nN-h yd r oxye t h yl e t h y len ed iam in e t e t r a a ce t ic a c id 14.5 94N.h yd r oxye t h yli .m in o d ia ce t ic a c id 8.6 96N, N-d ih yd r oxye t h y lgly c in e 5.4 97p yr oca t e ch ol-3, 5 -d is od i&n su lfon a t e 11.07 931, 2-d iam in ocycloh exa n e t e t r a a ce t ic a c id 18.67 10 0p ico lin ic a c id 9.42 10 2

7. Solven t Ext r a c t ion of Zin cA good gen e r a l r e fe r en ce wor k on solven t ex t r a c t ion h a s b e en w r it t e n

by Mor r ie on a n d F r e ise r . 102a

Dit h izon e in Or mn ic Solven t sTh e ex t r a c t ion of zin c b y Holu t ion s of d i t h izon e in ch lo r o for m or ca r b on

t e t r a ch lo r id e h a s lon g b een u sed fo r a n a lya ie . F igu r e 5 sh ow s t h e pH d ep en d -10 3en ce of zin c ext r a ct ion in t h e p r e e en ce of t a r t r a t e .

I t i s a p p a r en t fr om F ig. 5 t h a t zin c ext r a c t s qu a n t i t a t ive ly fr om pH 8t o pH 10, w it h tw o m in u t e s m ixin g of t h e la ye r s . Wh en la r ge am ou n t s o f Cu ,Ag, a n d Hg a r e p r e sen t , t h ey m a y b e r em oved fir s t b y ex t r a c t ion a t pH 1. 10 4

Th e zin c m a y b e r ecove r ed b y ex t r a c t ion w i t h O. 1 t o O. OIN m in er a l a cid . k th is p r oced u r e , P b , Cd , a n d som e Bi a ccomp a n y t h e zin c .

20


28/65

Ida

, I I I I , I100 -

80 -

60 -

40 -,

20 02 4 6 8 10

pHF ig . 5. Ext r a c t ion of zin c b y d it h izon e .

Va r iou s comp lex t ig a gen t s m a y b e a d d ed t o t h e in it ia l a q u eou s p h a seto p r even t ex t r a ct ion of ot h e r m e t a ls . Cya n id e , for in n t a n ce , p r even t sext r a c t ion of Ni a n d Co. Ap p a r en t ly t h e b ee t p r oced u r e ia t h a t of Cr ow t h er ,Wa r bu r t on , a n d Br a cewe ll 10 5 w h o fir s t e xt r a ct Ni w it h a ch lo r ofo rm solu t ionof d ir n e t h y lg lyoxim e . Th en t h ey ext r a ct 10 p g of zin c fr om on e gr am ofu r a n ium in 5 m l of 40~0 amm on ium cit r a t e so lu t ion , pH 8.0 t o 9.0, a n d w a sht h e ch lo r o for m solu t ion of d i t h izon e w it h w a t e r . Th e d it h izon e la yer is t h enw a sh ed w it h .a O. 0 5 ~. solu t ion of Na 2S, a n d t h e zin c r em a in s in t h e or ga n icp h a se . Th is p r oced u r e sep a r a t e s fr om Tl, Hg , B i, Au , P t , P d , Cd , Ni,Co, P b , Cu , a n d Mn .

Schw eit ze r a n d Hon a k er 10 6 h a ve in ves t iga t e d a n ion s w h ich in t e r fe r ew it h t h e ex t r a ct ion . Th e i r d a t a a p p ea r in Ta b le V. Th e in it ia I zin c con cen -t r a t ion w a s 10 -5 ~ , t h e d it h izon e con cen t r a t ion in t h e or ga n ic solven t1.8x1O 3~, a n d th e ion ic s t r en g t h O. 10. Th ey d e fin e t h e ext r a ct ioncoe fficie n t a s follow s:

~ . ~ (HD)2(H+)2

Th e r a n ge of con d it ion s sh ow n in Ta b le VI m a k e s th e solven t ext r a c t ionof zin c w it h d it h izon e a n a t t r a c t ive p r oced u r e in d e ed . How ever , for n or r n ~r a d io ch em ica l p r oced u r e *L --- - - -- ---- --- - -*- - -- . ..volu bili t y of b ot h d it h izon eca r r ie r -fr ee a pp lica t ion s,

ULCL~ Lm a u er l uuu uravfDacK Decause 01 m ea n d zin c d it h izon a t e in t h e a bove solven t s . F orsu ch volu b ili t y con s id e r a t ion s va n ish .


29/65

Ta b le V. E ffe ct s o f va r iou a a n ion s u p on t h e ex t r a c t ion of, zin c10 6in to d it h izon e m olu tion g.

Or ga n ic An ion in Anion pH for 50~0so lven t a qu eou s p h a se mo la r i t y . e x t r a c t i o n K

ch lo ro fo rm p e r c h l o r a t eiod ideb r om i d et bioc ya n at ea c e t a t e

ch lo r i d ec i t r a t e

oxa l a t e

n it r i lo a ce t it e

EDTA

ph t h a l a t ec a r b o nt e t r a ch lo r id e p er ch lor a t e

b r om i d ec i t r a t e

EDTAb e n z e n e pe r ch . l o r a t e

c i t r a t ech lor o -b en zen e p er cb lor a t ed ich lo r o -m et h a n e p er ch lor at e

0.100.100.100.100.010.100.100.010.101.000.010.200.0010.010.0010.010.01

0.100.100.010.100.0010.100.010.100.10

3.5.-3.53.53.63.63.63.95.96.74.35.34.27.0

n o ex t n .n o ex t n .

2.7

1.91.92.02.0

n o ext n .2.32.42, 12.7

0.03--0.030.030.020.020.020.0055 x 10-71X1O -88 X 10-48 X 10-60.0013X1 O-9----1

50503030--8

5201

Met h y l- d ioc t yla r n in e in Or ga n ic Solven t sMa h Im a n , Led icot t e , a n d Moor e 10 7 sh ow ed t h a t in h yd r och lo r ic a c id

s olu t ion a , zin c ext r a ct s w e I l in t o so lu t ion s of m et h yl- d ioc t yla r n in e in o rg a n i cso lven t s . F igu r e 6 sh ow s t h e ext r a ct ion b eh a v io r of a n u mb e r of e Iem en t sin to d ich lo r oe t h ylen e so lu tion s. of m et h yl -d ioc t yla rn in e. Th e so lven t s e em s

22


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Tab le VI. Volu b ili t y of zin c d it h izon a t e a n d d it h izon e106in va r iou e or ga n ic solven t s .

So lven t KVolu b ili t y , g/1D it h i zo n e Zinc d l t h i z ona t e

CHC1 ~ 0.03 20.3 + 0.03 21.0 * 0.8CH2C12 1 12.6 +0.5 16.4 *0.3C6H6 8 3.6 +0.1 2.3 +0.3C6H5C1 20 2.5 +0.1 4.6 *0.3CC14 50 0.74 q 0.02 0.72 * 0.06

t o p la y a s ign ifica n t r ole h er e , in t h a t ex t r a ct ion of zin c in to d ich lo r oe t h ylen ea n d xylen e solu t ion s a b ove 2M HC1 is qu a n t it a t ive , wh ile on ly 75~0 is ex t r a ct e d

lo7in to ch lor ofor m so lu tion s. Moore108 sh owed th a t zin c .is ea s ily sep a r a t edfr om Hf, Zr , P a , a n d Th b y t h is ext r a ct ion . Scr ogg ie a n d Dea l 10 9 ex t r a c tcom p le t e ly 100 p g of zin c fr om 5 m l 2y HC1. in t o 10 m l 87. m et h yl-d ioct yl-am in e in m et h yl-is obu t yl k e t on e , w it h 3-m in u t e m ix in g t im e w it h a n on -equ ilib r a t ed or ga n ic p h a se .

Moore 10 8 po in t u ou t t h a t t h e ext r a c t ion con d it ion a r e ver y s ti i ia r t ocon d it ion s for a d sor p t ion on a n ion ,r e s in of. t h e qu a t e r n a r y ammon ium typ e .For in s t a n ce , u r a n ium ext r a ct a fr om d ilu t e su lfa t e solu t ion s a n d zin c d oe Hn ot 110.

Accor d in g t o Sc+ogg ie a n d Dea n , 109 zin c ex t r a ct e a s Zn Cl~ or.Zn C14, p r oceed ~g p r oba b ly t h r ou gh h yd r ogen bon d in g a n d ion a ssoc ia t ionw it h t h e am in e ion . Sch t idewolf 11 1 fou n d t h a t t h e loga r it hm of t h e ext r a ct ioncoefficien t w a a lin e a r w it h t h e loga r it hm of t h e am in e con cen t r a t ion w it h as lop e of +2. Th e ext r a c t ion of on e zin c a t om ta k es two am in e molecu les a n dp r ~ba b ly h a s th e form (RH)2 ZnC14. (RH+ st a n d s for t h e su b s t it u t ed ammon iumion . )

Th e zin c sp ec ie s is con s is t e n t w it h th a t fou n d by Kr a u s a n d Neleon , 13 8i. e . , ZnCl~ in 2~ HC1. Sch in d ew olf u sed HC1, LiCl, a n d Cs Cl so lu t ion sa n d sh owed th a t t h e ch a n ge in ex t r a ct ion coefficien t is in d ep en d en t of t h econ cen t r a t ion in t h e or ga n ic p h a se a n d mu st t h e r e for e h a ve it s ca u se b t h ea q u eou s p h aee . Th e r ea c t ion is t h en :

(1) 2RH+C1- + ZnCl~ = (RH)ZZnC14 + 2 Cl- .

23


31/65

Th e s lop e of +2 a t lowe r ch lo r id e con cen t r a t ion sext r a c t ion of zin c ca n b e d eecr ib ed by

(2) Zn ++ + 2 Cl- = ZnC12 ,(3) Zn C12 + 2RH+C1- = (RH)2ZnC14

su gge s t s t h a t t h e

Th e lowe r in g of t h e ext r a ct ion coe ffic ien t a t h igh ch lor id e con cen t r a t ion sca n be d e sc r ib ed b y t h e r eve r se of r e a c t ion (1). Th e r e fo r e t h e s Iop e of t h ecu r ve a t h igh ch lor id e con cen t r a t ion s sh ou ld a p p r oa ch -.L. Th is e ffect i s se enclea r ly w it h CsC1. Ma xim a occu r a t 2M HC1, 1~ CSC1, bu t n on e occu r s w it hLiC1.

Tr ibu t yl P hosp ha te

I r vin g a nd Ed gin gt on 11 2 ext r a ct ed zin c in t o k e r osen e , b en zen e , a n dca r b on t e t r a ch lor id e solu t ion s of t r ib u ty l p h osp h a t e fr om h yd r och lor ic a cidsolu t ion s . Maxim um ext r a c t ion (ex t r a c t ion coe fficien t . = 34) occu r r ed fr om2M to .3M HC1. Ni(I I), Mn (ll), Co(lI ), a n d CU(II) d id n ot ext r a c t , w h ile U{VI), In (II .I ), a n d F e(HI) d id . At h igh e r h yd r och lor ic a c id con cen t r a t ion s , t h eext r act ion coe ffic ien t d e cr ea sed . Th e ch lor o-com p lexe s a p p a r en t ly ext r a c tin r ou gh ly t h e sam e or d er a s t h e a d sor p t ion on a n ion r es in . If k e r osen e isu sed a s a d ilu en t , t h e r e a r e t h r e e p h a sek for m ed a b ove 5M h yd r och lor ic a cid :t h e u p p er is k er osen e ,, t h e m id d le is t r ib u t yl p h osp h a t e sa t u r a t e d w it h h yd r o-ch lor ic a cid , a n d t h e low er is a qu eou e . Ben zen e a n d ca r bon t e t r ach lor id ed id n ot exh ib it t h is r a t h e r in con ven ien t p h en om en on .

P ep p a r d , Gr a y, a n d Ma r cu s13 ex t r a ct ed zin c w ith u n d ilu t ed t r ib u t ylp h osp h a t e p u r ified fr Or n mon obu t yl a n d d ibu ty l p h osp h a t es . Th e ir d a t a a r ep r esen t ed in F ig. 7. Th ey con c lu d e th a t H2 Zn C14 is t h e ext r a ct in g sp e c ie sw h ich is sa lt ed ou t a t h igh e r ch lor id e con cen t r a t ion s .

Th en oy lt riflu or oa ce t on e

A good sep a r a t ion fr om ca dm iu m is e ffec t e d by ext r a c t ion of zin c in t od ibu ty l e t h e r solu t ion s of t h en oylt >t ilu or oa ce t on e (TTA). 114 F ir s t , 10 m gof zin c is ext r a c t ed in t o 40 m l O. 4M TTA fr om 20 n -d a q u eou s so lu t ion ofpH 4.5 (bu ffe r ed w it h O. 1~ for m ic a c id a n d 1~ sod ium form a t e ) w it h tw om in ut e s m ix in g. Th en t h e or ga n ic la yer is w a sh ed fou r t im e s w it h t h ebu ffe r ed solu t ion , a n d t h e zin c b a ck -ext r a ct e d w it h tw o p or t ion s of a pH 3.0bu ffe r ed solu t ion (O. 6~ ch lor oa ce t ic a cid a n d ,0. 4~ sod ium ch lor oa ce t a t e ).Zimc recovery is . 92% an d t h e sep a r a t ion fr om ca dm ium is 105.


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100

90

eo

7a

60nw~ 50au1-xE ~ 401-Zwv 3(ofwL

2C1(

,1

1 I 1 I 1 1~ nn

Te=

H Cl CONCENTRATION

F ig . 6. Ex t r a c t ion of zin c fr om HC1 so lu t ion s5% m et hyl d ioct yla min e in d ich lor om et ha ne .

i n t o

1 1 I [ I

.l__L0 1 0 12H Cl CONCENTRATIONF ig . 7. Ex t r act ion of zin c in t o p u r e t r ib u t ylp hosp ha t e fr om HC1 eolu tion s.


33/65

Meth yl -I sobu tyl Ke t on eZin c ext r a ct s in t o m e t h yl -isobu t yl k e t on e

11 4in h yd r o iod ic a cid a n d 6M in m -lfu r ic a c id .(h exon e) fr om a so lu t ion 1~Zin c r e t u r n O t o &e a q u eou s

p h a se w it h t h r e e eq u i lib r a t ion s w it h 6M h yd r och lor ic a cid . Cd (II ), Ag(I ),P d (lI ), CU(I I), a n d Hg(lI) s t a y in t h e h exon e bu t p b (~) is n o t sep a r a t e d fr omzinc .

Zin c Th iocya n at e Ext r ac t ionZin c ext r a ct s in t o d ie t h yl e t h e r fr om so lu t ion s 0. 5M in h yd r och lor ic

11 5 a cid con t a in in g amm on ium t h iocya n a t e . Va r yin g t h e p r op or t ion ofamm on ium t h iocya n a t e ch a n ge e t h e ext r a ct ion coeffic ien t , a s sh ow n inTa b le VII .

Ta b le VII . Ex t r a ct ion of zin c t h iocya n a t e in t o d ie t h yl e t h e r . 11 5

Zn con e . NH4SCN con e . HC1 con e . Ext n . coeff.

O. lM IM o. 5M 23.7O. lM 3M O. !5M 37.8 O. lM 5M 0.5M 18.3O. IM 7M 0. 5M 12.9

Cadm iu m d oes n o t ex t r a ct u n d e r t h e se con d i t ion s . 11 6Rosen he im a n d Hu ld sch in sk y 11 7 ext r a c t ed , zin c t h iocya n a t e in t o a r n y l

a lcoh ol -d ie t h y l e t h e r m ix t u r e s . Kin n u n en a n d Wen n e r st r a n d 11 8 inve s t i g a t e da n um b er of solven t s a n d h a ve ex t r a ct ed zin c t h iocya n a t e com p lex qu a n t it a t ive lyin t o h exon e , m et h y l i sop r op yl k e t on e , m e~yl n -p r op yl k e t on e , n .bu ty l p h os -p h a t e , a n d am yl a lcoh o l -d ie t h yl e t h e r so lu t ion s . Am yl a lcoh o l, e t h yl a ce t a t e ,d ie t h y l e t h e r , a n d d iisop r op y l k e t on e a r e p oor e r solven t s .

Th e be s t so lven t for t h e zin c t h iocya n a t e comp lex is h exon e . 11 8 Ex t r a c -t ion con d it ion s a r e a s follow s: Th e h yd r och lo r ic a c id con cen t r a t ion sh ou ld b ele ss t h a n O. 5~, a n d a n exce ss of amm on ium t h iocya n a t e cor r esp on d in g t o a tle a st a 47. so lu t ion is n e ce ssa r y fo r t h e comp le t e ext r a c t ion of 125 m g zin cfr om a n a q u eou s solu t ion volm e of 50 m l. In n eu t r a l o r a lk a lin e m ed ium ,ext r ac t ion is in com ple t e , a n d t h e zin c m a y b e b a ck -ex t r a ct e d q u a n t it a t ive lyw it h d ilu t e .am r non iu m h yd r ox id e . F e(I I I ), Ag(I ), a n d CU(II ) a lso ext r a ct ,a lt h ou gh F e (ILI) ca n be m a sk ed w it h flu or id e , a n d Ag(I ) a n d Cu (I I ) w i t ht h i o u r e a . H flu or id e is p r esen t , P b (lI ) a n d Ca (I I ) in t e r fe r e . k t h e p r e sen ceof Ca a n d P b , F e ca n b e m a sk ed w it h sod ium pyr op h osp h a t e or t a r t r a t e .b r ge sa lt con cen t r a t ion s a id ex t r a ct ion of zin c .

26


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Zin c P yr id in e Th iocya n a t e in t o Ch lor ofor m 119

Th e solu t ion is a d ju s t e d t o t h e m et h yl r ed en d p oin t . F or 80 m l ofsolu t ion , a d d 5 m l 2M NH4SCN an d 1 m l p yr id in e . Th en 10 m l of ch lor ofor mext r a ct s 95~o of t h e zin c . F e(lI), Mn (LI), a n d CU(II) a lso ext r a ct , bu tIn (II I), P b (I I), Ti(IV), Bi(IH ), Sb(HI), a n d U(VI) d o n ot

Cvc loh exanoneHa r t k am p a n d Sp eck er 12 0 ext r a c t ca dm ium w ith

extract.

c yc loh exanone

Ga(III) ,

s o lu t i o n sO. lM in KI or NH41 a n d O. 25M in NH40H. Zin c d oe8 n ot ext r a ct , w h ile99. 4% d t he ca dm ium ext r a c t s in on e equ ilib r a t ion .

Ox in e D er iva t iveA so lu tion of 7[ a (o -ca rbom et h oxya nilin o) b en zyl] -8 -h yd r oxyqu in olin e

in ch lor oform ext r a ct s CU(II ), Zn (I I), Cd (II ), a n d Hg(H) a t pH 6.121Na ph th yl Th ioc ar b azon e

Zin c (50 Kg) ex t r a ct ~ qu a n t it a t ive ly in t o 10 m l of a e olu t ion of n a p h t h ylt h ioca r b a zon e in ch lor oform fr om 30 m l of a solu t ion bu ffe r ed w it h cit r a t e

12 2of pH 8.25 t o 10.5.

Zi nc D it h io ca r b am a t eZin c a n d le a d d it b ioca r b am a t e s a r e ext r a ct ed fr om flu or id e so lu t ion s

by e t h yl a ce t a t e o r ch lor ofor m a t pH 3 for zin c a n d pH O. 3 for lea d . 123Zin c a n d lea d a r e b r ou gh t b a ck in t o t h e a qu eou s p h a se w it h 8M HN03.

Zi n c D ie t h yl di t h io ca r b am a t eZin c a n d ca dm ium a r e ex t r a ct ed in t o ch lor ofor m fr om d it h ioca r b am a t e

60so lu t ion s bu ffe r ed to pH 8.5 w it h a cit r a t e bu ffe r . TIM ch lor oform la yeris w a sh ed on ce w it h w a t e r a n d t h e zin c a n d ca dm ium r e tu r n ed t o t h e a q u eou sp h a se w it h O. 16 Mhyd r och lor ic a cid . Th is p r oced u r e sep a r a t e s fr om P b (lI),B i@U ), C o(I I),Ni(Il), CU(I I),

But-o]

T1(I .H ), Sb (ILI), Ag(I ), Cr ( II I ), F e (II I), Mg(II), Al(I II ), Ca (H),Na (I ), -d K(I).

Zin c p er ch lor a t e ext r a c t s in t o bu t a n ol fr om wa te r . 124 Th e e xt r act ioncoeffic ien t s for som e ot h er p er ch lor a t e s a r e lis t e d in Ta b Ie VII I .

27


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Ta b Ie VHI. Ext r a ct ion of m et a l p e r ch lo r a t es in t o bu t a n ol. 12 4

E lemen t Ext r a ct ion coeff. E lem en t Ext r act ion coe ff.

co 7.2 Mg 9.4Ni 7.7 Ca 9.5Mn 7.6 Sr 12.9Zn 8.3 Cu 6.9

8. Ion Exch a n ge Beh a vior of Zin cTh e in t en t of t h is se ct ion is t o p r e sen t t h e b eh a vior of zin c on va r iou s

ion exch a n ge r ee in s in a s m a n y d iffe r en t m ed ia a s p oss ib le . Cor ye ll a n dMarcus125 p r e sen t a comp r eh en s ive r ev iew of ion exch a n ge m ech a n ism s ,r e s i n s , a n d t ec hn iq u es .

Ca tion Exch an ge

Meye r , Ar ger s in ger , a n d Da vid son126

h ave st u died a c t ivit y coe fficie n tsin t h e ZnC12-HCl-Dow ex 50 x 8 sys t em . Th ey con sid e r t h e r ea c t ion

Zn+++2~=ZnR2+2 H+,w h e r e R - r ep r e sen t s t h e a ct ive r es in gr ou p . Th ey d efin e K a s

a ~+ 2a z nR 2 mH+ Y:cl ZnRZ fzfizK=~-= -2Zn ++ am Zn ++ ln C12 #m ~

w h e r e f = r e s in a ct ivit y coeffic ie n t on a mole fr a c t ion ba s is . F or con ven -ien ce , t h ey fu r t h e r d efin e

2mH+ NznR2Km=~ - Y:cl

N~,a n d Ka =K

Zn++ 3m ZnC12

fzfizso th a t K=K a~

F IR

Da t a fr om t h e ir s t u d y a p p ea r in Ta b le IX.

28


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Ta b le IX. Act iv it y coe ffic ien t s in t h e ZnCIZ-HCl-Dow ex 50 x 8 sys t em . 12 6

Mole p=o.5 K=lO. Zfrac t ionZnRZ fznRz f

p=l. o K=ll.7f Zn R Z f

o0.10.20.30.40.50.60.70.80.91.0

0.8180.8550.8910.9210.9470.9680.9891.0081.0131.0091.000

1.0000.9980.9910.9800.9650.9470.9240.8910.8810.901

0.8550.8970.9330.9620.9851.0031.0171.0251.0251.0151.000

1.0000.9980.9910.9810.9690.9540.9390.9240.9270.987

Sold a n o a n d Boyd 12 7 h a ve st u d ied t h e se lf -d iffu s ion of ca t ion s inh e t e r o ion ic ca t ion exch a n ge r s . Th ey r ep or t a se lf-d iffu s ion coeffic ien t fo rZn++ on Dow ex 50 X8 of 1.16 x 10-8 cm 2/~ec a t 25 C , t ie a c t iva t ion en e r gyb e in g 8520 ca l/r n o l. Sp iegle r a n d Cor ye ll 128 r ep or t a va lu e of 4.1 X 10 -7 cm2/secfo r t h e se lf-d iffu sion coe ffic ien t.

Bonm e r a n d Sm it h 12 9 p r esen t d a t a on t h e a d sor p t ion of a Ia r ge n u mb e r ofca t ion s on Dow ex 50 (Ta b le X).

Th e d a t a in Ta b le .x sh ow th a t t h e sep a r a t ion of Zn ++ fr om ot h e r ca t ion son Dow ex 50 is , a t b e E t , a g r ou p sep a r a t ion . Th e gr ou p con t a in in g zin c is n otva s t ly d iffe r en t fr om t h e cla ss ica l on e . How eve r , in t h e . p r e sen ce of com -p le t in g a gen t s , a ca t ion r e s in b e com es a mu ch mor e ve r sa t i le r ea gen t . Int h e se c t ion on com p lex ion s , i t is ev id en t t h a t t h e Cd I~ com p Iex is m u chs t r on ge r t h a n t h e Zn I~ com p lex . Th e a u t h or h a s sep a r a t ed ca dm ium an dzin c on Dow ex 50 X 8 u n d er t h e fo llow in g con d it ion s : su lfu r ic a c id con cen -t r a t i o n , 0. 05M; h yd r o iod ic a c id con cen tr a t ion , O. 0 0 lM; t ot a l vo lum e ., 10 m I .Th e ca dm ium doe s n ot a d sor b , w ~e t h e zin c r em a in s comp le t e ly on aco lum n 4 cm lon g a n d O. 6 cm in d iam e t e r . Zin c m a y be r e cove r ed , a ft e rw a sh in g w it h t h e iod id e so lu t ion b y e lu t ion w it h 20 m l of 3~ p e r ck d or ic a cidor 10 m l of 2M h yd r och lor ic a cid .

Br ow n a n d Ha ye s 13 0 sep a r a t e zin c a n d m a gn e s ium by comp le t in g zt icw it h cya n id e a t t h e b r om t h ymol b lu e en d p o in t . P a s s in g t h e solu t ion t h r ou gh

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Ta b le X. Re la t ive a d sor p t ion of m et a l ion s on Dow ex 50. 129

Meta l ion P er ce nt cr oe s-Ii nlca ge4$ 8 y . 12%

Li +H+.Na+

Rb+Cs +Ag+Tl +Uo++M$+Zn++co++cut+Cd++Ni++C.++~r++Pb++Ba++

1.001.321.581.902.272.462.674.736.712.362.953.133.233.293.373.454.154.706.567.47

1.001.271.982.552.903.163.258.1512.42.453.293.473.743.853.883.935.166.519.91

11.5

1.001.472.373.344.504.624.66

22.928.53.343.513.783.814.%4.954.067.2710.118.020.8

th e sod iu m form of am ber li t e IR - 120 r em oves t h e m a gn es ium fr om th esolu t ion w h ile t h e a n ion ic zin c cya n id e comp lex is n ot a d sor b ed .

F r it z a n d Umbr e it 13 1 u se EDTA in a s im ila r m a n n er . Th eir colu mnis 4 cm lon g con t a in in g 5 g Dow ex 50 X 4. Th ey p a ss 55 m l of soI t i t iont h r ou gh t h e r e sin , a n d 30 m l of wa sh w it h th e b~fe r ed EDTA solu t ion . Th eyu se a gly.c t ie bu ffe r a cid ifie d w i@ h yd r oclilor ic a c id . Ad sor p t ion of t h e zin ca t pH 1.,2, w a sh , e lu t ion w it h PH 2. 1 a n d wa sh , sh ou ld sep a r a t e ZfiC fr omF e(lJ l), Bi(ILI ), CU(H), Zr (IY), SC(I II ), Y(m ), Sm (I II ), ~(~) -d u (~); bu tn ot Th (IV), Yb (II I ), or Hg(I I).

Olive r a n d F r it z 132 h a ve wor k ed in a m u n be r of sys t em s emp loyin g tw ocomp le t in g a gen t s. Th ey a d d h vo r e a gen t s t o a b in a r y sys t em , on e to form . ap osit ive comp lex w it h on e compon en t , a n ot h er t o form a n ega t ive comp lex w itht h e ot h er . Th e solu t ion is t h en p a ssed th r ou gh a n ion exch a n ge r es in column

3 0


38/65

Tab le XI. Ad sor p t ion of zin c on Dow ex 50 X 4 fr om O. 0 2~ EDTA solu t ion s . 13 1

pH s Zin c a d eor b ed

10 2 10 01.5 83.51.8 39.42.1 0.0

w h e r e on e com pon en t a d sor b s w h ile t h e o th er e lu t e s. Th ey r ep or t a sep a r a t ionof zin c a n d u r a n ium a t pH 9 by for m in g a n ega t ive ly ch a r ged com p lex of u r a n iumw it h su lfosa licy lic a c id , a n d a p os it ive ly ch a r ged com p lex of zin c w it h e t h ylen ed i am i n e . Th e r esu lt in g so lu t ion is p a ssed t h r ou gh a colu m n of Dow ex 1 X 8a n ion exch a n ge r es in ; t h e u r a n ium a d sor b s a n d t h e zin c e lu t e s . Sep a r a t ion ofzin c a n d ir on m ay b e effect e d in t h e sam e sys t em a t pH 10. E lem en t s fo rm in gn ega t ive com p lexe s w it h su lfosa licylic a cid a r e F e , U, Al, Th , Zr , a n d Y;t h ose for m in g p os i t ive comp lexe s w i t h e t h y len e d iam in e u n d e r t h e sam e con d i-t ion s a r e Cu , Ni, Zn , a n d Cd . Qu a n t i~t ive sep a r a t ion of b in a r y m ix t u r e scon t a in in g on e e lem en t of ea ch gr ou p w a s p e r fo rm ed a t pH1s 8, 9, a n d 10u s in g Dow ex 50 X 12 a n d Am ber li t e IRA-401.

Kr a u s , Mich e lson , a n d Ne lson 13 3 r ep or t a s t r on g a d sor p t ion of som ea n ion ic sp e cie s b y ca t ion exch a n ge r e s in s . Th is s t r a n ge b eh a v io r a p p ea r s t ob e con fin ed t o t h ose com p lexes w h ich a r e ve r y s t r on g ly a d sor b ed by a n ionexch a n ge r e s in s fr om con cen t r a t e d ch lor id e so lu t ion s. In a so lu t ion 10M inLiC l a n d O. lM in HC1, AuCl~, F eCl~, a n d GaCl~ h a ve KD!s of g r e a t e r t h a n105. In 12~ h yd r och lo r ic a cid , Au Cl~, F eCl~, a n d GaCl~ h a ve KDs of t h eor d er o f 100. In e it h e r ca se , Zn (LI), Mn (H), Co(n ), Bi(I I I ), a n d Sn (IV) sh own o t en d en cy t o a d sor b , w h ile Sb (V) a n d T1 (~) a d sor b on ly s ligh t ly . Th isp h en om en on cou ld p r ove t o b e a r a t h e r u se fu l on e .

Da v ie s a n d Th om a s 13 4 p o in t ed ou t t h a t t h e con cen t r a t ion of w a t e r int h e r es in p h a se is h igh e r t h a n in t ie liq u id p h a se . Th is su gge s t s t h a t a d d it ionof m isc ib le o r ga n ic solven t s sh ou ld h a ve a la r ge e ffe ct u p on r e s in b eh a v io r .Kem be r , McDon a ld , a n d We lls , 13 5 e lu t in g m et a l ion s fr om ca t ion r e s in s w i thm ix t u r e s of m e t h yl e t h yl k e t on e , w a t e r , a n d h yd r och lor ic a c id , fou n d t h a t t h issys t em d id im p r ove r ep a r a t ion s . E t h ey u sed a n h yd r ou s k e t on e a n d HC1 ga s ,e ve r yt h t ig e lu t e d qu ick ly . Th ey con clu d ed t h a t t h e r e a in p h a se a n d t h e liq u idp h a se m u st b e in w a t e r equ i lib r ium bu t n e ed n ot b e in a cid equ ilib r ium .

Ca r l e son 13 6 in ve s t iga t e d t h e m e t h yl n -p r op yl k e t on e -h yd r och lo r ic a c idsys t em . He sep a r a t ed Zn (H ), Cd (II ), CU(I I), CO(H ), Mn (lI ), Ba (I I ), Bi(UI),a n d Ni(II ) a s follow s: t h e m e t a l ion s w e r e a d sor b ed on Dow ex 50; w it h k e t on e

31


39/65

p lu s 2~0 10M HC1, t h e or d e r of e lu t ion a n d sep a r a t ion w a s , Bi(I .11), Zn (II), a n dCd (I I) t oge t h e r , CU(I I), a n d Co(II ); w it h k e t on e p lu s 15% 8M HC1, Mn (II) e lu t ed ;w it h k e t on e p lu s 30~0 8~ HC1, Ni(H ) e Iu t ed ; w it h 8M HC1, Ba (I I ) e Iu t ed .

Ion e scu , Con st a n t in e scu , a n d Top or 137 e lu t ed zin c fr om ca t ion r e s in sKU-2 o r R -21 w it h 79. 5~o a ce t on e , O. 5 ~0 con e . HC1, 20~0 w a t e r , o r 597.a c e t one , l% con e . HC1, 40~. w a t e r (volu m e p e r cen t a ge s ) a n d ob t a in e d a goodsep a r a t ion fr om cop p e r .

~ion Exch a n geKr a u s a n d Ne lson 13 8 h a ve st u d ie d t h e b eh a v ior of z in c on Dow ex .1 X 8

in h yd r och lor ic a c id so lu t ion s . Th e d is t r ib u t ion coe ffic ien t is sh ow n in F ig . 813 8a s a fu n ct ion of h yd r och lor ic a c id con cen t r a t ion .

Beh a v ior of o t h e r e lem en t s is sh ow n in F ig . 9, t a k en fr om e a r lie r w or kb y Kr a u s a n d Ne lson . 88

Home , 13 9 14 0a n d P ie r son a n d Sch in d ew olf h a ve sh ow n th a t t h e sp e cie sa d so r b in g on Dow ex 1 is Zn Cl~ w h ich a gr ee s ve r y w e ll w it h t h e sp ec ie sp r e se n t in so lu t ion a s d e t e r m in ed b y Kr a u s a n d Ne lson 13 8 a n d sh own in F ig . 4.

Th e t em p e r a t u r e coe ffic ien t of t h e a d sor p t ion p r oce ss is sm a ll. 14 6As t h e cr os s-lin k in g of t h e r e s in in c r ea se s , t h e KD for zin c in c r ea se s

14 1in ch lor id e so lu tion s.Kr au s, Ne lson , Clou gh , zn d Ca r ls t on 14 2 r ep or t ed KDIs of m a n y m e t a l

ion s in Dow ex 1 t o b e in cr ea sed m or e t h a n a h u n d r ed fo ld b 12M LiCl ove rt h ose in 12~ HC1. Som e of t h e m e t a ls t h e y m en t ion a r e Sc(llI )~ Mn (II ), Co(II ),Zn (II ), Au (II I), F e (m ), a n d Gz(~~). Th e d iffe r en ce is p r ob a b ly d u e t o la r ged ~e r en ce s in a ct iv i t y coe ffic ien t s in t h e r e s in p h a se w h en t h e r e s in i s imm er sedin t h e s .e tw o m ed ia . Ho r n e 139 n ot ed t h a t a t t h e ch lor id e con cen t r a t ion of tw om ola r , t h e KD of zin c w a s h igh e s t for L i+ >H+ >Na+ >NH~ >K+ >Ca . +Kr a u s a n d Ne lson 14 3 sh ow t h e e ffe c t of t h e ca t ion of t h e su p p or t in g e lec t r o ly t eb F ig . 10.

Th e h a lf-t im e of e it h e r a d sor p t ion or r e sor p t ion of Zn Cl~ on 50-10014 4m e sh Dow ex 1 a t 25 C is 5 m in u t e s . Th e h a lf-t im e for e xch a n ge of zin c in

14 5solu t ion w it h z in c on t h e r e s in is 13 * 2 m in u t e s .Yosh in o a n d Ku r im u r a 14 6 st u d ied t h e e ffe c t of or g-ic so lven t s on t h e

KD of zin c on Dow ex 1 X 8 in HC1 so lu t ion s . Th e ir d a t i a r e p r e sen t ed in F igs .11 a n d 12. Th e y sh ow ed t h a t t h e a d d it ion of som e or g -ic so lve n t s m a r k ed lyin c r ea se s t h e a d sor p t ion of zin c in low h yd r och lor ic a c id con cen t r a t ion s . The ysu gges t t h a t t h e se so lven t e ffe c t s m a y b e exp la in ed b y t h e in cr ea se in t h e for -m a t ion of n ega t ive ly ch a r ged ch lor id e com p lexe s of z in c a s a con seq u e n ce oft h e d ee r e a se in t h e t en d e n cy for h yd r a t ion of t h e zin c ion s in m ixed solven t s .

89Hu b e r a n d I r t ie a d sor b ed CU(I I), Co(I I), Zn (II ), a n d Ga (I II ) on

Dow ex 1 in st r on g h yd r ob r om ic a cid so lu t ion s . Ni(I I) d id n ot a d sor b , CO(H ) -

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Q

./

1 I 111111 1 1 11[1.1110.OO1

I I 1 111111 I 1 I 1111110.01 0.1 1.0 10Molality of HCI

F ig . 8. Ad sor p t ion fu n ct ion s of Cd (II ) a n d Zn (I I) in HC1.

e lu t ed w it h 5~ HBr , CZ(II I ), w it h 3~HBr , CU(II ) w it h 1~ HBr , a n d Zn (II )w it h w at e r .

Far is147 st u d ied t h e a d sor p t ion of m a n y e lem en t s fr om h yd r oflu or ica cid on Dowex 1 X 10, 200 m esh , in t h e con cen t r a t ion r a n ge fr om lM to2% (F ig. 13).

Zin c d oe s n ot a d sor b a t a n y con cen t r a t ion , a n d m a y b e s ep .

a r a t e d e a s i ly fr om Mo(VI), Te(IV), Sb (V), Sn (IV), Zr (IV), Nb (V), P d (II ), a n dAs (V) w it h 5M HF .

Hom e, Helm , a n d Meyer s 14 8 s t u d ied th e a d sor p t ion of zin c on Dow ex1 X 8 in a va r ie t y of m ed ia . Th ey fou n d n o a d sor p t ion in con cen t r a t ion u pt o 8M in a ce t ic a cid , 2. 5M in su lfu r ic a cid , 5M in h yd r oflu or ic a cid or p e r - ah lor ic a cid , a n d 13M in HN03. Ad sor p t ion coeffic ien t s for o t h e r m ed ia a r ea s follow s: p h o sp h e r ic a cid , in c r e a se s r a p id ly in t h e lM t o 3M r eg ion t o 18a n d r em a in s con s t a n t a t h igh e r con cen t r a t ion ~; cy-id e , ~=~.8x105 a tO. 5~ NaCN, d r op s t o 4000 a t 2~ NaCN an d r em a in s con st a n t a t h igh e r con .cen t r a t ion s ; oxa lic a c id , KD . 1000 a t O. O1y H2C204, d r op s to 10 a t O, 2~,a n d s t a ye con s t a n t a t h igh er con cen t r a t ion s; ZnO~ d oe s n ot a dmor b wel l .Meye r B a n d Hom e 14 0 r ep or t good a d sor p t ion of zin c fr om h yd r oxylam in eh yd r och lo r ic so lu t ion s of zin c fr om lM t o 7M.

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w4=

EHHEEIMMIMF ig. 9. Ad sor p t ion of t h e e lem en t s fr om h yd r och lor ic a cid .


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I I I I 1 1 [

10 I 1 I I I I I Io 2 4 6 e 10 12 14Molor it y o f Chlor ido

F ig. 10. Ad so r p t ion o f zin c (II ) fr om ch lor id e so lu t ion s(-10 p e r cen t loa d in g of r es in ).

f Molarity of HC1

F ig. 11. An ion exch a n ge a d s or p t ion of Zn (lI).1. in HC1 solu t ion2. in HCl - 30 ~ . (v/v ) m et h an ol m ixu tr e3. in HC1 - 60% (v/v ) m e t h a n o l m ixt u r e


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{

7 0

Or ga n ic solven t a d d ed , w t ~~

F ig . 12. E ffec t s o f va r iou s or ga n ic so lven t s on t h ea n ion exch a n ge a d sor p t ion of Zn (lI ) in O. 1 M HC1.1.2.3.4.::7.

AcetoneE*o1Me th ano ln - P r op an olMet h a n o l (Dow ex 1-X4)RN03 +Cr , ~ .0. 003, (NaCl) Met h a n o lRN03 +Cr , p = O. 1, (KN03) Me t h a o l

L t id en b a u m , Boyd , a n d Mye r s 14 9 h a ve s t u d ied a n ew t yp e of r e s in ,St a r n ex S-44, a su lfon it u n a n ion exch a n ge r . 15 0 Th ey r ep or t t h a t zin c h a sh igh er KD!s on St a r n ex S -44 t h a n on Dow ex 1 for b ot h h yd r och lor ic a c id a n dli t h ium ch lo r id e solu t i~n s.

Ta b le XII s 15 1u r nm a r ize s t h e d a t a of J en t zck a n d F r o t sch er ob t a in edw it h Wolfa t i t L- 150 a n d h yd r och lor ic a c id so lu t ion s .

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ml-mm-n mt!ji!l:~--~-=-. FNO A05. - NO 40 SORPT ION FROM IM - 24 M HF,lR AO!%- STRC4AG AOSORPIION: IDG OIST. COEFF >2 Wii lJJ: , ROMAN NUMERALS REFER TO OXlOATION STATE 1uIN INITIAL SOLUTION. .1E!?!,W,i. ----I

F ig . 13. Rem ova l of e lem en t s fr om solu t iona c id w it h ZOO-m e sh a n ion ex ch an ge r eBfi .

h 1 M t o 2 4 M h y d r of lu o r ic


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Ta ble XII . E lu t ion of va r iou s m et a l ion s fr om Wolfa t i t L- 150w it h h yd r och lor ic a c id .

Hyd r och lor ic a cid con cen t r a t ion (r n o la r it y)E lem en t 12.5 11-10 7.5 6.5 5 4 1.5 1 0.5 0.05 0.005

Mh a gLiNaKAs (II I)CaNiFe(H)coMn(II)F e (I I I)Cusn( Iv )InZnCdP b

xxxxx

xxx

xxx

xx

xx

xx

x

Kr a u s a n d Moor e 152 sep a r a t e d zin c fr om Ni(ll), CO(I I ), CU(II ), a n dF e (lII ) b y p a ss in g a io lu t ion 12M in h yd r och lo r ic a cid t h r ou gh a Dow ex- 1co lum n p r eviou d y con d it ion ed w it h con cen t r a t ed h yd r och lor ic a c id . N i (I i)a p p ea r ed in t h e e lu a t e . E lu t in g w it h a u cce s s ive ly m or e d ilu t e a cid , Mn (H )e lu t ed w it h 6M HC1, Co(I t ) w it h 4M HC1, CU(I I) w it h 2. 5~ HC1, F e (II I ) w it h O. 5MHC1, a n d Zn (II ) w it h O. O05MHC1.

Mille r &d Hu n t e r 153 a d sor b ed zin c on IRA-400, ch lor id e for m in2M HC1, w a sh ed w ih 2M HC1, a n d e lu t ed w it h e it h e r w a t e r o r O. 25N HN03a s a sep a r a t ion fr om Al(UI), Mg(I I ), Ca (I I), CO(H ), Ni(H), Mn (J I), Cr (lI I),Th (IV), Zr (IV), Ti(IV), U(VI), Be (~), a n d CU(II). Zn (II ), Cd (I I ), a n d k (ILI)a r e e lu t ed t oge t h e r a lon g w it h 20% of t h e Sn (IV) a n d sm a II am ou n t s of Sb (I I I),Bi(IH ), a n d P b (H). Th e m a jo r it y ~f Sn (IV), Sb (I II ), Bi (I II ), a n d P b (I I ) r em a in sa d s o r b e d .

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F r e e g a r d e 15 4 sep a r a t ed zin c a n d cop p er a s fo llow s: zin c w a s a d sor b edon Dow ex 1 in O. 12~ HC1 w it h 100 g NaCl p er li t e r (t h e cop p er e lu t e d ), a n dw a s e lu t ed w it h e it h e r 2MNaOH w it h 20 g /1 NaCl or O. 0 05 NHC1, or 1NHN03.

Ka llm a n n , St ee le , a n d Ch u 15 5 a d sor b ed zt ic a n d ca dm ium on Dowex 1w it h O. 12NHC1 con t a in in g 10% NaC1. Zin c w a s e lu t ed w it h 2M NaOH, ca dm iumw it h IMH N03.

Be r g a n d .Tr uem p er 15 6 sep a r a t ed zin c , ca dm ium , a n d m e r cu r y on aDow ex 1, 60 t o 100 m esh co lum n 1.16 cm id . a n d 6 cm lon g in q u a n t it ie s u pt o 100 m g of e a ch . Th e flow r a t e w a s 1.5 t o 2 m l p er m in u t e . Th e m e t a lswe r e a d sor b ed fr om O. 5M HC1 a n d w a sh ed w ith 2M HC1. Zin c w a s e lu t ed w it h180 m l of a solu t ion 757.0. OINHC1 25~0 m e t h a n o l, ca dm ium e lu t ed in th efr a c t ion 200-500 m l; m er cu r y w a s t h en e lu t ed w ith O. OIMHC1 O. lMt h io-u re a so lu tion .

Ba ggot t a nd Willcock s 15 7 sep a r a t ed zin c a n d ca dm ium on Dow ex 1 bya d sor b in g ca dm ium fr om a d ilu t e solu t ion of IU, w h i le zin c p a ssed t h r ou ght he colu mn .

Hu n t e r a n d Mille r 15 8 a d sor b ed zin c a n d ca dm ium on lR&400 fr om2M HC1, a n d w a sh ed w it h 5M HI, t h en wa t e r . Th e zin c w a s e lu t ed w it h O. 25NHN03.

Ka llm a n n , Obe r t h in , a n d Liu 15 9 sep a r a t ed zin c a n d ca dm ium by a d sor b -in g t h e Cd I~ on Dow ex 1 fr om O. 7 5~ H2S04 w it h 5~0 KI so lu t ion s w h ile t h ezin c d id n ot a d sor b . Ca dm ium wa s r ecover ed by e lu t ion w it h 3~ HN03.

Th e u se of iod id e a s a p r e fe r en t ia l com p le t in g a gen t for ca dm ium is ,in t h e op in ion of t h e a u th or , t h e m ost con ven ien t , ea s ie s t , a n d most e ffec t ivem et h od of sep a r a t in g zin c a n d ca dm iu m .

9. Ieo t op ic Exch a n ge of Zin cIn gen e r a l, t h e r a t e s of zin c t r a ce r exch a n ge w it h zin c com pou n d s a r e

t oo r a p id t o m ea su r e ; even ch e la t e s sh ow t h is r a p id exch a n ge . Leven t h a l a n dGa rn e r160 fou n d com p le t e exch a n ge in le ss t h a n 30 secon d s (a t 25 C) of t r a cedd ip yr id in e zin c a ce t a t e a n d t h e follow t ig zin c comp lexes : a ce t y la ce t on e ,a c e t yla ce t on e e t hy l en ed ia min e, b en zoyla c e t on e ammon ia t e , ,n icot in yl, a c e t on e ,16 1a n d d ip yr id in e t h iocym at e . Atk in s a n d Oa r n e r fou n d t h a t Zn 65 t r a ce r d idn ot exck ge w it h zin c in t h e p h t h a locpm in e comp lex, bu t d id exch a n ge w it hzin c comp lexed w it h d ip h en ylt h ioca r b a zon e , 8-h yd r oxyq u in o lin e , a n t h r a n ilica cid , a nd sa licy la ld eh yd e.

I on e s cu e , Negoe s CU, a nd Ga in ar 162 s t u d ied t h e S1OW exch a n ge be tweenZn 65S04 solu t ion a n d ZnO a t 00, 15, 25, a n d 35*C bu t n o fu r t h e r d a t a w e r egiven . -

M iyagak i 16 3 h a s evid en ce th a t t h e zin c k sp h a le r it e w ill e xch a n ge w it hzin c in solu t ion in con t a ct w it h t h e or e .

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Barr ie ra 64 65r ep or t s t h a t Zn .t i su lfa te solu tion sw it h zin c m et a l sh e e t w it h a h a lf-t im e of t h e or d er of 10

exchange E . sIowlyd a ys. Ma tmm r a 165

s tu d ied t h is sys t em ca r e fu lly a n d fou n d th a t h e t e r ogen eou s exch sn ge occu r su n iform ly w it h in &e in t e r ior of zin c dum t t h a t h a s b e en le ft in con t a c t w it h~65S0 solu t ion

4 . He a lso fou n d th a t a few th ou sa n d la ye r .s a t t h e su r fa ce ofzin c foil a r e a va ila b le for exch a n ge . Ap pa r en t ly t h e d iffu e ion of zin c a t om st h r ou gh t h e solid , or r e cr yst a lliza t ion of t h e zin c m e t a l in t h e p r e sen ce ofsolu t ion , lim it ed th e r a t e o f exch a n ge . Th e r a t e -d e t e rm in in g st ep be low .10- 3~ in Zin C is t h e a d sor p t ion of Zn ++ on t h e su r fa ce . Th e fr a ct ion , F ;of exch a n ge is g iven a p p r oxim a t e ly by th e exp r e ss ion

-k r t -k s tF ~l Ar e + ABe ,

w h e r e k ~ = (0.20 q /v) (1 0.5p 1/2 ), in h r -l.

F or Zn -Zn ++ exch a n ge , q /v is t h e r a t io of su r fa ce a r e a to volum e ofso lu t ion , ~ i; t h e ion ic s t r en gt h , t i s t im e , Ar a n d As a r e con s t a n t s, a n d k ris a n ot h e r con st a n t s im ila r t o k ~.

10. P ap er Ch r om at ogr ap hyCh a p t e r 43 of Ch r om a t ogr a p h y by Led er e r a n d Led e r e r 16 6 is a n exce lle n t

r e view of th e fie ld of in or ga n ic p a p er ch r om a t ogr a p h y. Lit t le , if a n y , m or er ecen t d a t a on zin c b eh a v ior in p a p er ch r om a t ogr a p h y h a s b een fou n d . Sep a -r a t ion s of t h is t yp e a r e exce llen t for m icr ogr am qu t it i t ie s, b u t -b e ca u se of t h eca p a c it y of p a p efim illigr am or la r ger qu a n t it ie s of m e t a ls ca n n ot a s ye t b ea e pa ra te d con ve nien tly.

Ion s ca n b e m ad e t o m igr a t e t h r ou gh t h e liq u id en t r a in ed in th e p a p erby im p r ess in g a p ot en t ia l g r a d ien t p a r a lle l t o t h e d ir ect ion of m igr a t ion .Led er e r a n d Wa r d 16 8 h a ve sep a r a t ed . m et a I ion s in t o r a t h e r in t e r es t in ggr ou p s b y t h is m ea n s . Th e ir d a t a a r e sh own in Ta b le XII I ,

Ch a p t e r 18 of Led e r e r s book P a p er E lec t r op h or es is 167 give s a n u p -t o-d a t e r eview of th e fie ld w it h r esp ect t o in or ga n ic sep a r a t ion s, ea r lie r

Maki169ch a p t e r s r ev iew t h eor y a n d t ech n iqu es . sep a r a t ed Ni(II ), CO(H),a n d Zn (II) u s in g Na 4P 207 a t pH!s less t h a n 2, m e t a p h osp h a t e b e low pH 1.7,a n d t r ir n e t a p h osp h a t e b e low pH 5.6 u sin g p a p er e le ct r op h or esis . Ma k i170a lso sep a r a t ed Zn (I I) fr om Ni(I I), CO(I I ), a n d Mn (lI) w it h a m ix t u r e of a ce t on ea n d m et h a n ol a cid ifie d w it h h yd r och lor ic a cid .

S chnache r171 u sed a sim ila r t ech n iqu e ca lled focu s s in g ion exch a n ge .He a d d s a comp lext ig a gen t t o on e e lec t r od e of h is sys t em , im p r esses ap ot en t ia l gr a d ien t , a n d a llow s t h e ion s to m igr a t e . At t h e p oin t a lon g t h e

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Tab le XII I . Movem en t , o f m et a l ion s in O. 5~h yd r och lo r ic a c id in50 m in u t es u n d e r a p ot en t ia l g r a d ien t of 3.6 v/cm . 16 8

Anion ic Iso - Ca t i o n i c2. 5-1.5 cm 1. 5-0.5 cm e l e c t r i c 0. 5-1.5 cm 1. 5-2.5 cm

Hg(I I ), P d (I I) Au (I II ), I r (IV), Cd (II ) Mo(VI), Zr (IV), Cr (H I), U(VI),Bi(IH ), T1(II I ) Rh (lI I ; , As(m ), Ti(IV), Be (I I ),

S ri(n ), Sb (m ), F e(llI ), Co(II ),Pb( I I ) Ni(I I ); Al (I II ),

CU(H), Zn (H ),Sr (I I ), Ba (lI )

p a p er w h e r e t h e m e t a l com p lex is u n ch a r ged , t h e m igr a t ion ce a se s . Us in gt h is t ech n iq u e , h e a n d St r e iff 172 h a ve sep a r a t e d 10 p g ea ch of F e (II I ), Ni(I I),Zn (lI ), Al(H I), U(VI), Co(I I ), Cr(III), a n d Mn (II ) a d d ed a t t h e cen t e r of t h ep a p er in a so lu t ion of pH a bou t 5. Th e a n od e so lu t ion con t a in ed O. 5M h yd r o-ch lo r ic a c id , t h e ca t h od e so lu t ion O. 5M sod ium h yd r ox id e a n d O. 5M sod iumn it r iloa ce t a t e , t h e cu r r en t flow w a s 100 m a a t 500 v . Sep a r a t ion w a s com -p l e t e

v.

in five m in ut e s .

DISSOLUTION OF SAMPLES CONT~lNG COMPOUNDS OF ZINC

Accor d in g t o H illeb r a n d e t a l. , 20 t h e so lu t ion of zin c m in er a ls o ffe r sn o cliff i cu lt ie s a n d ca n u su a lly b e a ccom p lish ed b y a t t a ck w it h h yd r och lor ica c id , h yd r och lo r ic a c id followed b y n it r ic a c id , o r n it r ic a cid a lon e . Th ein so lu b le r e s id u e , w h ich or d in a r ily con t a in s n o zin c , ca n t h en be d ecom posedb y fu s ion w it h sod ium ca r bon a t e , fo llow ed b y solu t ion of t h e m e lt in a c id .

SoilsI n g en er a l, zin c a n a lys is of so ils d oe s n ot r eq u ir e com p le t e d isso lu t ion

of t h e so il . Ma r t in 173 -ige s t s t h e so i l w i t h a m t iu r e of h yd r och lor ic , n i t r ic ,a n d p e r ch lor ic a c id s

The Radio Chemistry of Zinc.us AEC

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