Studies on Synthetic Inorganic Ion Exchangers and Detection and Spectrophotometric

Determination of Organic and Inorganic Compounds.

DISSERTATION SUBMITTED IN PARTIAL FULFILMENTS OF

THE REQUIREMENTS FOR AWARD OF

THE DEGREE OF

Master of Philosophy IN

Chemistry

BY

KHURSHEED ANWAR

DEPARTMENT OF CHEMISTRY ALIGARH MUSLIM UNIVERSITY

ALIGARH (INDIA) 1 9 8 4

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k» h ki k H T S

Z f«el 9r«8tiy pxlvileged to have Korktfd under the

ftipervision of Or* Seidu22«fer Uureshi, Header in Chemistry

Departoent. V̂ ozdis f a l i short of expressing my deep sense

of gratitude t o hia for the keen interes t , affectionate

guidance, constructive e r i t i c i s n , constant encouragenent and

advice throughout the tenure of th i s study.

I tm grateful to Profes&or M.S. Ahaad, CSiairoan,

Department of (^emistzy, Alig&zh Mjsiia Iftiiversity, Aiigarit,

for providing the necessary f a c i l i t i e s .

I aiB extremely briiolden to ay brother Er. Xdris Ahmad

Ansari for affectionate encourageoient and interest in my

academic pursuits.

I value and appreciate the cooperation of Dr. Aeeta

Bansal and wish to thank al l ay colleagues for providing ae

a congenial coapany and maintaining a cordi^tl ataosphere in

the laboratory.

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Th« detection and d«t«ialnatlon of muXal ions i s ono

of ths most fascinating chapters in the anaiytieai chemistxy.

Detection can be achieved by using foiiowin^l methods.

Instxumentdi methodsi or

Non-instrumental methods.

The non»instxumental methods of ansiysis g^ieraiiy include

the spot tests» which were generally used b̂ ^ Feigl (1) .

Rijimoto et al. (2) proposed the use of resin spot test

technique to make these tests more graceful!, which depend

on the intense colouration of the few grains of light

coloured ion exchange resin produced by the uptake from

the reaction medium of ions having characteristic colours.

The tes ts have t^e following advantages.

(1) They »n more sensitive because the coloured ionic

species i s concentrated on the resin surface.

(2) The colouration i s often more stable irii the resin

phase and some times becomes progressively more intense

on standing.

(3) These tests are more selective. Thus Ions having a

charge opposite to that of the ionic species adsorbed

by the resin, usually do not interfere.,

I

(4) Ih«8t tes t s need vezy l l t t i s •quipments dnd requires

very l i t t l e training on the part of the investigator.

Hesin spot technique has been widely used for the

detection of inorganic ions by using colour reactions

already lcfK>wn (3»4,5). Hov̂ ever resin beads can also be

used to develop new colour reaction as was described by

CMreshi for diphenylamine (6) , picric acid (7,b,9) and

for ethylenediaoainetetraacetic acid in humnn urine ( iO , i l } ,

Fujiffloto (12) described a very sensitive t

0

Another ioipoxtant ph«non«ion Is to conbine th«

hydroxy t i t and eataiiytle redctions of th« resin beads with

ths resin spot technique, A very interesting exampie of

this ai^roaeh i s the detection of ester (15). Ion exchanger

hydrolyxe esters more effectively than does an acid (16}

and no new ions are intzoduced into the solution.

^ 3 ^ ' ^ ^ 2 " 5 '*' "2^ ^ CH3CUJH I- C^H^UH

Another method in which the resin bt̂ ads have been

used for the catalytic hydrolysis and as the detection

media* i s the detection of aiaide, iiaide* anilides (17) and

nitz i les (IB). The hydrolysis of amides artd iaides is

brought about by H form cation exchange resin which

catalyses the acid hydrolysis to the corresponding acid

and aoMBonia or aniline. Aisatonia gas and aniline pick«up

one proton froiB resin in H foBB and they sre converted

to NĤ and Ĉ (%NK3. These ions easily replaced H'*' ions

fozffi froffl the resin and are detected on the besd surfcce

by neans of Nessler's reagent or pî K îmethyl-aminobenzal-

dehyde. In case of nit r i les two tests have been performed

because ni tr i les are not hydrolysed by ion axdiange resins.

They can be hydrolysed with d i l . H2S0̂ in presence of

resin beads (H^ f o n ) .

ISiL.zjL

XCN • HQH BĤ

•^ XCJQH • NH,

(X « aikyl or axyl groups)

XaX)H '*' NH3 -^ XCUOI*!^

Iti^ " il

m + XUXJNH, -^ «NH;J • XCQOH

posltiv* t e s t with N«8sler*s fifidgant.

XCN •• HOH nPIi ) Hydrolysis does not taks piaest negative t e s t with Nessler*s Reagent.

Qureshi et a l . (19) extended the use of the ion

exchange resins as a cata lysts aid as an ion exchanger

sinultaneously for the detemination of oaides and es ters .

The hydrolysis of aoides and esters i s done by using ion

exchange resin in the H fom. The ion exchange resin acts

both as a catalyst for hydrolysis and ion exchanger to

release an equivalent ataount of the acid. Therefore, the

ion exchanger i s easily removed fron the solution by f i l ter ing

through a glass wool plug.

Suerot« inv«rtlon {20), tster h/dsrolysis (21),

btnxoln cond«n8«tion (22) can also be cat«iy8«d by ion

«)«hang«rs in th* vazlout ionic fonat, Th« us« of ftolid

ion •xeh»)g«r« hat a nonber of advantagaa when compared

with disaolvedi eleetxolytet.

(X) The catalytt can be readily reiaoved frao reaction

products by filteration or by decantation.

(2) The (Hirity of product i t better since side reactions

are iBininised.

(3) The ion exchanger i t more selective, i . e . , i t dist in-

guishes more sharply between the various re act ant

molecules and i t oiay be considered to be half way

in the selectivity between dissolved electrolytes

and ensyaes*

(4) No new ions are introduced in the reaction oiedia

except the ions which aire produced as a result of

hydrolysis.

Spect ID photometric method has been applied for the

deteaaination of number of inorganic compounds. The forma-

tion of bluish violet osmium-diphenylcarbaside complex in

weakly acidic solution i s utilized for the detexmination

of osmium by s pact ro photometric ally (23). Oetermination

u

of molybdwium (24) and of sftleniuo with 4,5,6-trLamlno-

pyxiaidln* (25) havo also been detezmint spectxop^otomctri-

oalJLy, A highly scnsitivo and tttieetivo |prt>c«dur« for

spoetrof^otometxic d«t«ZBination of Ag hat b««n developed.

a» the red violet ecNiplex with 4*-(4-nitv>naphthyXtriaxeno)

asobenzene «^ich has an absorption isaximuiD at 565 nm (26).

Detezmination of arsenic, based on the foonation of an ion

association coapLex between arsenoantiinonoaolybdenuiii and

naLaehite green (27), aluminium with chlo:cophosphonaro I (26)

have been developed. Another sensitive m̂ ythod has also

been described for the spectsophotometrlc determination

of manganese (29) in foodstuffs by means of i t s complex

with i»(2-quinoiylazo)«2,4,5»trihydr9xybenzene, fozmed in

alkaline medium. Viebel has reviewed the detoction

char^terization and quantitative detezmination of thioles

and also of disul^^des, sulfides, thio acids, isothiocya-

nate and sulfones (30) spectrophotamtftricS*trla2ine i s a colorimetric reagent

for the spectzophotometric detezmination of tNh-oenzoyl^jlycine.

N»6Ubstituted derivatives of sezine, threonine, tzyptophan

and glycine. Serine, threonine and tryptophan, however,

can be easily eliminated by oxidation without oxidizing

glycine. The method can be used for the spectzophotometric

detexxDination of glycine in the presence of other amino

acids (31). Phenols are detezmined spectzophotometric ally

with 4-aRinodntipyrin« In the presence of potassi^n f err i -

cyanide used ds an oxidizing agent (32,33,34) . A spectro-

photoaetric ciethod for the detezmination of i-r^apthoi in

the presence of 2«ndphthoi has been described (35) . The

method i s based on the faster rate of ciia:eotization of

i->na(^thoi than 2->naphthoi. Another spectrophotofaetric

detezmination of phenois with 3-rsethyi-2.benzothidZoiinone

hydrazone and cerium ammoniutn sui^^ate hai» been studied (36) .

The recognition of F^enomenon of ion exchange was

generally attributed v^ith base exch^ige in minerals present

in the soi l (37) . I t was found \Ahen soilii v êre treated

with aBtfflonium sa l t solutions, anmonia was taken up by the

soi l end an equivalent quantity of Ca was released, i t v\ds

also shown that a numbers of other sa l t s besides those of

t ^ . are capable of doing ion exchange pheriomenon.

d a y minerals comparises a coraplex series of

aluffiinosilicate structure. The simplest type clay mineral

i s Kaolinite having foxaiula ^^J^J^iQi'^a^' "^^ complex

type clay has formula i»i Al.02QiOH.)nH^O, The cation

exchange capc^city of these two types clay minerals greatly

exceeds the ir «iion exchange capacity. The capacity depends

upon partic le s ize as given below in tab le .

file:///Ahen

Typ# ^dnerai Capacity iseq/g

Kaollnite gzoup

l i i i t e 9ZOUP

Fibrous ciays

Mt>ntBK>riilonit« group

Micaceous derivativas

Kaoiinita

Muscovite

Attapuigita

^k>ntronit•

baponita

0,02 - O.iO

0,105

0.18 - 0.22

0.57 - 0.64

0.69 - 0.61

Montmorillonita 0.60 * 1.50

Biot i ta 0.03

Vermicuiita 1.00 - 1.50 (pure)

when the type of bentonites, roontmorlilonite cloys

are immersed in the aqueous solutions i t twel ls . i>wellin9

dtpttnds upon the s ize of cation entering the structure.

In the case of I l l i t e and lauscovita clays swelling i s

l e s s due to smaller cation entering the structure.

Exchange in clay minerals in non stoichioaatric , Cctpacity

may vary due to different degree of isomoxi^ious substitu-

t ions . The saturation capacity d«^pends upon the cheoical

cooposition of the clay and cation decreases in the order

SBontmozlllonite^ I l l i t e J> kaol inite . The clay minerals

lose VbStcr on heating. \/cr!Tiiculite clay i s very importent

s c i en t i f i ca l l y becasue i t represents the intezni&diate stage

between the mica and rr.ontmorillonite, i t also has an

agriculture and commercial iapoxtdnce» since i t i s coomon

sol i mineral and may be used for a variety of horticulture

purp08«i because of i t s high porosity to retain nutrient

media for plant growth, Because of i t s law density and

thezmal conductivity, i t i s also used as heat insulating

media* Vezroiculite i s derived from the mica b i o l i t e as

each may be converted into the other as follows.

MgiCX̂ solution Blot i t* • ^^, ^ • • • ^ Vermlculite

\ KCl solution

VexBiiculite may be used as an absorbent to renove

cat iom from radioactive waste, organic cation such as

alkyl substitutes aounoniusi ions may also exchange with clay

miner a l s .

The suggestions have bew) made that the clay minerals.

be used as ion exch^ge media in certain ce&es, particularly

«^ere spec i f i c i ty , cheapness or s t a o i l i t y towards radiation

or high t«&peratute water i s concerned,

Qans (38) who synthesixed inorganic mat)rrials of the

type ^'h^2^^:PlQ ^" which the Na*̂ was exchangeable. Gans

successfully applied his inorganic synthetic cation exchanger

to water sof t i l ing end Sij

I J

th« natuxAiiy oceur^ing exchangers or zeolites ds they ere

• U l l celled.

Ihe seolitee aay be regazxled as oelng derived from

the foimula (^Q,.).^ by replacing sil icon tif oluniniuD to

varying extents. The few selected zeolites with ^ e i r

conposition and exchange cspecity ere given below in Table.

Zeol i te

udingtonite Nat r o u t e

a i l b i t e Heulandite

Analcite Mozdenite Chabazite

Leucite sod e l i t e Ultramarine Cancrinite

Composition

(a) Fibrous zeo l i t e s Ba(Al2^30^o).^v> NtzCAl̂ SijOj^O .̂iH^O

(b) Lamellar z e o l i t e s

( c ) Three dimensional z e a l i t e s

M A I ^2.^6^*^^ (Qa^^Jia) ( /asl^O^).ai^O

(d) Felspathoids K ( A l ^ O ^ ) Na(Ali>iO^).2/3Nea Na(Ali.i0^.l/3Na^Sjj) (Na.Oa^^^HAl&iO^K^/a (Na2tCa)C03

cxch ange capacity meq/g

3.90 5.30

3.20 3.30

4.50 2.30 4.00

4.60 9.20 &.30

10.90

1 i.

Z.«oiit«8 which are crystailine aluoalnosilicates with

fibxoue, iaffl«Ilar or thr«« dimentionai stractaret ar« known

at EBoleeul ar si«v«s and hava the ability to sci activity

remova ion froa solution. This haa lad to their use as

watar softnen* Thara usa has bean extenjad to rentova metal

ions froe tha solution. Ona of the most notable applications

developed rec«itly i s their use as feed suppliments for

poultry, swine, cattle and fish. Beniflcial effects on crop

growth can also be achieved using zeolites in the soi l .

Another use of zeolite as water softners in detergents has

been known for sorae tiise, but this use i s likely to receive

a boost in coning years as sodivua t r polyphosphate i s phased

out, sodiuB trlpolyphosphate i s a detergent builder but

i t has the unfortunate ability to encourage the growth of

green algae in rivers ani ponds. The use of zeolites in

detergent has meant that coiBp«nies has be edged crystals.

A recent application of zeolite selectivity involves the

use of a synthetic ultramarine to separate) the franclum 223

isotopes Fr frcm i t s actinumi parents and other activi-t i e s (39). The highly charged cations ^^^Ac, ^^Th, "̂''̂ Po

O i l 5 O ^ >" '*VT '•* ^ ^

and ''̂ pb are strongly adsorbed while Fr, Tl and "^ Ha

a

past thxoagh th« colusn and may subaaqaently b« separated

fron eaeh other.

C.B. AaphXett (40 , 41) and Kraus (42,43) have done

much of the pioneering v̂ ork In th i s f ie ld who concentrated

the ir attention on zirconium oxide and zirconium phosphate.

The Mork upto 1963 has been summarized by C.B. Ami^lett in

h i s c las s i ca l book, "Inorganic ion exchangers'*. The l a t t e r

work upto 1970 has been condensed by Pekarek and Vesely (44)

under the following headings (45) .

(1) Hydrous oxide.

(2) Acidic sa l t s of multivaliMrit methods.

(3 ) Sa l t s of heteropoly acids.

(4) Insoluble ferrocyanides.

(5) Synthetic aluminosilicates.

The most recent work on inorganic ion exchangers has

been sucamarixed by Clearfield, Noncollas and Blessing (46)

and Walton (47, 48, 49, 50 ) .

The role of heteropolyacids in the ion exchange

properties i s also a very important. The wide woric in th i s

f ie ld has been concentrated on airatonium molybdophosphate,

particulazly as regard the separation of ithe alkali metals.

A comparison of K, flb, and Cs molybdophos{>hate for the

10

rtmoval of traces of Cs» Sr, and yttxiun fzom neiitral

ftoivitiont ŝ K)w«d that nelth«r was &uperior to the amnioniua)

saltst v^ils the alkaXJLns anBoniuai moXybdophosphates wer«

distinctly inferior (91).

At present a large iMober of inorgimic ion exchangers

hav* been synthesized which are l isted in table I and IX

along with their choaical cOMpositions* ion exchange capacity

and soae inportant applications for the si^paration of metal

ions.

With ^ e develotsment of modern analytical instzuments,

i t becomes easy to understand the choBistiy of the material

prepared. Infra red spectzum predicts the presence of water

moleculest QH groups and metal oxygen bonds. X ray analysis

confiaas whether the material i s amorphous or crystalline.

The thexmogravlfliatry and differential thezroal analysis are

inportant techniques that record changes in the chemical

conposition of material at different t^Qperatures. These

techniques provide a great help in establishing the

structure and thermal stability of the ion exchanger.

The literature survey shows that most of the

synthetic inorganic ion exchangers prepareti t i l l now have

cation exchangers. ;>offie hydrous oxide gel including

FOjO ,̂ AI2O3, CtjOg, 81203, TiO ,̂ iiOjt Th(J2» î nô * ^̂ 0̂ 2

1J

s p sp e p 3 00 CM OQ GO 0 0 QO

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3 S 9 S P S R a J5

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CM CM

O CO • •

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5 3 a

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*̂ •»-< l2 Q*^ O V 4 ^ 0 • ' - 4 «*-4 M4') UC l i I s ?:l Sg 122 5Si .S.2

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are mphotezic and can act both cation as w«Xl as anion

exchanger. However, these oiaterials are of l i t t l e practical

importance because they are dissolved by acids and bases.

tv 'J

! • F. Felgl» "Spot Test in Inorganic Analysis", 5th edn.,

Elsevier, Aastezdam, p, 103-601, (195B).

2 . M. FujiiDOto, 6th Annual Meeting Cheai. boc. Japan Kejoto,

April 4 , (1953).

3 . M, Fuijiiiioto, Bull. Qiea, ^oc. Japan, 30, 93 (1957).

4 . M. Fujimoto, Ibid, 30, 283 (1957).

5 . H. Kakihana, Y. t^ri and M. Yaaasaki, Nippon Kagaku

^asthi , 75, 907 (1954).

6. M. Qureshi and S.Z. Qureshi, Anal. Cheat. 36, 13, 1956

(1966).

7. M. Qureshi and I.A. Khan, Anal. Chio. Acta, 86, 309

(1976).

8 . s.Z. Qureshi and izzatul lah. Anal. Ghim. Acta, 92, 201

(1977).

9 . S.^. Qureshi and izzatul lah, Talanta,, 24, 529 (1977).

10. b*Z, Qureshi, I z z a t u l l ^ and Reeta Bansal, Z, Anal.

Chem. 295, 415 (1979).

11. S.Z. Qureshi and R. Bansal, Talanta, 26, 661-682 (1979).

12. iA, Fujiaoto, H. Nakayama, M. I t o , H.Y^mai and T. Sagu,

MickroehiiB. Acta, 2 , 151 (1974).

13. L.H. Bolton, EdJC. Chm., 10(6), 231 (1973).

14. S.Z, Qureshl «nd M.^. Hathl, Anal. Chem., 47, 1124

(1973).

15. M. Qjrethl and S.Z. Qunshi, Anal. Chiis. Acta, 34,

IQB (1966).

16. C.v«. Davles and G. Thomas, J . Chmu, ^ o c , 78, 1607

(1955).

17. PJ(*, West, M, Qureshl and S.Z. uurcslil. Anal. Chlm.

/iCta, 36, 97 (1966).

18. M. Qursahl, S.Z. Qur«thi and N. Zahra, Anal. Chlm.

Acta, 47, 169 (1969).

19. M. Qunshl, S.Z. Oireshl and s.C. Slnghal, Anal.

Ch«B., 40(12), 1781 (1966).

20. W.A. Balmn, (American Cyananid Co.), U.S. patent, 2 ,

543, 694 (1950).

21 . C.v«. Oavies and G. Thocaas, J. Cham. Soc. (A) 1607

(1952).

22 . C.J. Schraldte and H.C. Mansfield, Ind. bng. Cheo].,

44, 1388 (1952).

23. S. Jaya and T.V. Hasakriahna, Talanta, 29(7) , 619-622

(1982).

24. asha Madan and L.H, Kakkar, Talanta, 29(7) , 623-625

(1982).

25. Mazio £• Bodini and Omar Alzoaora, £ . , Talanta, 30(6),

409-4X2 (1983).

26. Aei Fu«8h«ng and Yin Fang, Talanta, 30(3), 190-192,

(1983).

27. wu Qian»fang and Liu Pang-fai, Taiarrta, 30(4), 275-276

(1983).

28. Zhu Ying-quan, Zhang Lin and Li Jun-Yi, Talanta, 30(3),

291-293 (1983).

29. Ishwar Singh and Mrs. Poonum, Talanta, 31(2), 109-112

( i984) .

30. D.R. Grattatti (Arequipa Foundation) U.S., 3, 597, 160

(1961), appl. 02 Apzll, p. 4 (1969).

31. S. Shuichi, Yutaka Hachimozi and Jiehi Yaoada, Anal.

Chao., 42(1) , 101-3 (1970).

32. Svabodova, Drahoiaira, Oaspazic, J i r i , Acta Fac. Fhazm.

Univ. Comeniana, 22, 7-45 (1972).

33. M.S. Ettinger, C.C. iiuchhoft and H.J. Lishka, Anal.

Chan. 23 , 1783 (1951).

34. floza, Halasi, bagedinae and Mirjana, Mes. Ind., 32(2),

98-101 (1978).

35. J .S . Parson, ««. seaman and J.T. V^oods, Anal. Gham.,

27, 21 (1955).

36. Eijixo Kraato, Bull . Chcm. ^>oc. Japan, 3 7 ( U ) . 1674.7

(1964).

37. H.S. Thonpson, J. Hoy. Agr. boc. , Eiigl., 11 (1850).

68| J .F. Way, J . Boy. Agr. boc., I^gl . , 11 (1850) 313;

13 (1852) 123.

38. R. Ganst J ^ x b . prauts. gaol. Landasiinstalt (Berlin)

26, 179 (1905)} 27, 63 (1906); Cantr.. Minaral Gaol. 22,

728 (1913).

39. W. Haxx and H.J. Riadal, Radiochiia. Acta, 1 (1962)

32.

40. C.B. Amj^att, Proceedings of the sctcond International

Conferenca on peaceful uaat of Atomic Energy, Geneva,

1958, paper No. 15A*171 J.N. (1958).

41. C.3. Aisphlatt and L.A. Mcdonald, Proc. (Cham, ^ o c . ) ,

276 (1962).

42. K.A. Krauftt and H.O. Ph i l l ips , J . Aiser. Chaffl. Soc., 78,

644 (1956).

43. K.A. Krauss, H.u. Ph i l l ip s , T.A. Carlson and J . s . Johnson,

Proceedings of the Second international Conference on

Peaceful uses of Atonic Energy, Geneva, 1958, paper No.

15/iP/l832, United Nations, Vol. 28, p. 3 (1958).

44. V. Vessely and V. Pekarek, Talanta, Beview, 19, 219

(1972).

i d ^

45. V. Pakartk and V. Vetsaly, TdXanta, 18, 1245 (1972).

46. A. Clearfield, Q.H. Nafwollas and K.H. Blessing, Ion

ex^ange and solvent extraction. Marcel Oekker, Inc . ,

New York, Vol. 5 (1973).

47. H.F, Vkalton, Anal. Chem., 42, 86K (1970).

48. H.F. Walton, Ibid, 44, 236A(1972).

49. H.F. Walton, Ibid, 46, 398R(1974).

30. H.F. Walton, Ibid, 48, 52H (1976).

51. A.vy.C. Broadbank, &. li^abananadana and R.D. Harding,

J . Inorg. Hucl. Chem., 23 (1961) 311.

52. I . ^ c . chujBDs, b, African Ind. Chemists, 19, 26, 46,

68, 87, 146 (1965).

53. J. Prospert Coma, anergic At. (France), Happt., GEAR

2835 (1966).

54. V.F. Tikavyl and L.I . Isukorava, I i v . Akad. Nauk.,

J.i>.S.R,, Neorgan Mater., 1, IQB, (1965).

55. V.I. Saveleva and V.A. Mlnaev, Tr. Mosk. Khira. Tekhnol.

I n s t . , 43, 82 (1963).

56. Q.H. Nancollas and V. Pekarek, J . Inorg. Nucl. Chem.,

27, 1409 (1965),

57. G. Qazbauskas and V.I. Shanaev, Zh. Neorgan. Khiia.,

15, 33 (1970).

98, J . Ullnieh, M, TyspXt V, p^karvk and V, V«&&el«y, J.

AAdioanal, Chen., 24 , 36l (1975).

59. ^. Ahrland and A, Otkarsson, J . Xnoiig. Nucl. (^•m.,

32, 2069 (1970).

60. G. AXbeztl, U. CofttanUno ^xi J.G. 3 U 1 , Ibid, 3B,

1733 (1976).

61. A. Clearfield, w.L. Diax, J.M. Garcesi and A.c>. Medina,

Ibid, 34, 329 (1972).

62. G. Albertl, B. Bertrami, M. Carebola, J. Costantino

and J.P. Guptal, I b i d . , 38, 843 (191'6).

63. G. Albert!, £. Torracca and A. Conte, J . Inorg. 4̂sJCl.

Ghem., 28, 607 (1966).

64. V.A. Parevozova and b.S. Biochinova, Zh, Prikl. Khlm.

(Leningrad), 40, 2679 (1967).

65. D. Cvjetleanin and N. N i l i e , Bull . Boris Kidrich Inst.

Nucl. S c l . , 15, 73 (1964).

66. N.H. Konlng and K. Oeoiel, J . Chrwnatogr., 39, 101

(1969).

67. N.H. Konlng and F. Hoyer, Atompramis, 11, 275 (1965).

68. K.H. Konlng and H. bchafer, HadlochlJB. Acta, l , 213

(1963).

69. i».N. Tandon and J. Mathew, Canad. J . Chem., 55, 3857

(1977).

Z>J

70« S. Ahriand, J , Albertson, B, Nlhlgard and L. Nilson,

Acta Ch«iB, Scand., l b , 707 (1964),

71. N.a. Oslpora and t-.b, Boiehinova, Zh, Pxlia, Khim.

(Leningrad), 41 , 2186 (1969),

72. K.A, Kraus, U.S, Patent, 3 , 382 (19(^8).

73. L»0, Madexios, J . Znorg. Nucl. Ch«m„, 28, 599 (1966).

74. M.J, Nunat, D,A, Costa and M,A.S, J«:coniiBO, Ib id . ,

3 , S46 (1961),

75. V,A, shlchko and b,S. Bolchlnova, Ih, Prikl . Khim.,

41 , 526, (1968).

76. G. Mberti and J, Constantino, J. Q^xomatogt,, 30,

482 (1970^,

77. A.K. De and K, Chowdhuay, Ibid, 101,, 63, 73, (1974).

78. M, Oixashi and W, Hussaln, J , Chain, Soc, (A), 1204

(1970).

79. A.K. Da and S.K, Das, Chxonatographia, 11, 350 (1978).

80. S.J, Naqvi, D, Kuys and L,H. Baestle , J, Inorg. Nucl.

Cham. 33, 4317 (1971).

81 . M. Qurashi and H.S, Rathoxa, J , ChaiD. soc. (A), 2515

(1969).

82. M. Qurashi, R. Kumar and H.S, Hathora, Anal. Cham.

44, 1061 (1972).

83. J . i , QUI and S.N, Tandon, TaXanta, i v , 1355 (1972),

84. J .S . a m and S.N. Tandon, Ib id . , 20, 285 (1973).

65. A.K. Ott and S.K. Oas, S«pt. Scl . Toch, 13, 465 (1978),

86. S.Vi. Husain and S.K. Kaxaa, Chzomatographia, 6, 277

(1976).

87. M. QuMshi and J.P. Hawat, J . Inorg, Nacl, Ch«s., 30»

305 (1968).

88. M. Qurashi and K.Q. Varshncy, Ib id , , 30, 3061 (1968),

89. M. Qur«shl, S.A. Nabi n̂d N. Zehra, Cand. J. Cham,,

54, (1976).

90. M. Qtirashit B. Kumar and H.S. Rathor£!» Talanta, 19,

1377 (1972).

91 . M. Quz«shi, J.P. Gupta and V. Shaxma, Anal. Chas,,

4S, 1901 (1973).

92. M. air«shl, J .P. Rawat and A.P. Gupta, J . Ghromatogr.

118, 167 (1976),

93. M. Qur«shl» A.P. Gupta and T. Khan, Ibid, 144, 231

(1977).

94. J .P. Gupta, O.V. Nowell, M. Qunshl 4ind A.p. Gupta,

J . Inorg. Nucl. Gham., 40, 545 (1978),

95. M. Qurtshl, K.G. Varahnay and N. Fatlma. J . Chromatogr.,

169, 365 (1979),

96. M. Qurttthi, K.a, Varshney and Fahmida Khan, J. Ch

togr . , 65, 547 (1972),

97. S. Kawanura, H. Kuraku and K.K. Kurotakl, Anal. Chlm.

Acta, 49, 317 (1970).

98. D. Naumann, Kaznenezgia, 6, 173 (1963).

99. K.U. Barsukova, Q.N. Radionova, Radio Klmiya, 14, 225

(1972).

100. H. Oons, P. Schonken, M, Doltlagan, L.H. Baetala and

M. O*hont, J . Inorg. Nucl* Chan., 36>, 665 (1974).

101. C.b. Ciibloly, L. ^xlrtas and L. Zslnka, Eadiochem.

Radloanai. Lat t . , 8, l l (1971).

102. H.Q. Saflna, N.£. Danlaova, E.S. Bolchlnova, Zh.

Pzikl . Khim. (Leningrad) 46, 2432 (1973).

103. M. Qurashl and R.C. Kauthlk, Anal. Chan., 49, 165

(1977).

104. P.S. Thind, s .S . Sandu and J.P. Rawat, Chlm. Anal.

(Viaraow), 24, 65 (1979).

105. M. Qurashl, R« Kumar and H.C. Kaushlk, £>«p. bcl . and

Tach., 13, 185 (1978).

106. M. Qurashl, R. Kumar, V. Shazna and T. Khan, J.

Chrooatogr., 118, 175 (1976).

')'

107. K«a* Varshn«y «nd A«A« Khan, J. Inor

'IJ

Colour reaction has b0«n studied for th« Identifica-

tion and th« 8p«ctioi:^otoD«trlc d«t«xffilnatlon of uranyl ion

with brichrooicyanine FU The detection limit was 7 f»q.

Beers la« Is obeyed in the concentration ran^e containing

13 M9 to 123 |J9/l

' ) -

Ftlgi (X) has describod « nufflb«r of t e s t s for th«

detection of uranium. Uranium produces a characterist ic red

coiour with anthraniiic acid and i t s oxidation product

(ft^odamins 6 G). I^e msthod i s sens i t ive aiid obeys Beers

Law in the concentration range 0.04 - 4.0G ppm of uranium ( 2 ) .

Another spectrof^tometric method of uraniutn deterciination

i s based on the foxmation of red v io l e t compiex between

2

'J .'v

«»ehan9« r«sin b«ads t«chnlqu« has played an important zx>l«

in d«tection and detazoination of a nvimbar of organic func-

tional gxoupa (8, 9* 10, 11).

A raview of literatura ravaalt that lixichrooicyanine R

i s on« of tha important dyas which fosss a water solubla

and stable violet red lake with aluninium at pH 5.4 to 6 with

a ^ naxi 330 nro requires about three days for eoaplete colour

developnent (12). »hen the pH i s lowered that i s 3.B i t

takes Ĵ bout four (4) hours at zoom temperature and one hour

at boiling temperature. It has been reported that the metal

ions Ni, Zn, Mn, Cr» Fe, Mg are also foxmedi coloured lakes.

The solution i s usually buffered to pH 4.6 -> 5.6 for aaximum

colour developnent. As far as our knowledge i s concerned

no colour reaction of uranyl ions with Erichnxncyanine R

has been reported. The present ccMBnunicatJlon describes the

detection and speetzophotametzie deteznination of uranyl

ion.

do

JXPiaRlMfeNTAL

/^Pgffrgltfi

A Bausch and Loob Sp6Ctzonic-20 (U.&.A.) wds us«d

f o r ai>ftozptioiB«trlc cl«texeBinatlon.

All c h i D i c a l s u»«d wttre of r«dg«nt grade.

Stock so lu t ion of O.i M uranlim was preparad by

d i s s o l v i n g uranyl n i t rata i n daatinaralizad water. Mora

dilute solution were prepared frooi the stock solution.

atMtn^ ffftf jOT f^ff^ffl

paper. Add a dzop of t«st solution followtiJ by a dzop of

roagent solution. Resin boads turn vioXat \K>hich indicates

a positive tes t .

Recomaended procedure for the detemination of uranvl ions

To an aiiquot volume of uranium solution containing

13 fiq to 125 fjq add 2.0 ml of Erichromcyanine H to a 10

mi l l i l i t re standard volisaetric flask. Make up the solution

upto the mark with dist i l led alcohol. Then measure the

absoxbance of the purple red colour solution at 570 ran

against a blank solution at roan temperature (25 Jt l^C).

J J

A nua^«r of mttal ion* were t«8t«d and found that only

uraniUB givts characterlstle puxplc red coiour» both tho

solution and in rosin phass. Tho limit of identification i s

givsn in table 3.

Tho ion exchange test was performed in the presence

of large amount of foreign substances (both organic and

inorganic) and found that no interfejronee was obtained.

Ihey are as followsi

Organic compounds were hydrocaxbons and their deriva-

tivest alcohols* ethers* csrboxylic acids* cazbohyd rates*

(^enols* heterocyclic bases* aldehydes* ketones* amides,

ni tr i les and amines.

Inorganic ions cobalt* manganese* zinc* co(^er*

platinum* indium, strontium* lead* calcium, cacfanium* gold,

antimony* arsenic, silver* mercuric* stannic* lithium, chloride,

phosphate* bromide, acetate, molybdate, ni tr i te , nitrate,

cazbonate, dichromate, iodate, iodide, van^^iatd.

The followii^ cations were found to interfere t^ith the

test in solution phase: Thronit^, aluminium, magnesium, nickel,

ixon, zirconiun), bismuth, cerium. However, these compounds

'la

did rK>t int«rf«r» «^«n th« tes t was performed in the presence

of ion exchange resin.

The abso^tion spectxuis of a solution containing 50 /jg

of uranyi ion was studied against blank retigent at room

temperature. The maxiaum absoXbance was obtained et 570 no.

As shown in figure I.

ttPUitfB gffliUiaD

The optimuro condition for the foxmation of purple*red

colour was studied and maintained throughout the studies.

There was no effect of time on the e t ^ i l i t y of

puzple»red colour for an hour. However* a slight decrease

in absozbanee was recorded after i t . Therefore, i t was

recomaended that the absorption should be measured within

this period.

The effect of reagent concentration was studied by

adding different volumes of Erichromeyanin«» H solution to a

constant amount (:K> ^g) of uranium. It was found that a

maximum absozbanee of the purple-red colour was with 2.0 ml of

reagentt beyond vdiich absorbanee was consto 2.0 ml of

Erichrorocyanine H was used throughout the experimental

observations as shown in Figure II .

t) i

The absorbanct measurements of uranium vtas made at

570 na. I t was found that Beer's law was obeyed for solutions

concentration with a range 13 jug to 125 jig/lO lal of uranium

Ions as shown In figure I I I .

To t e s t the reproducibility of the method ten repl i -

cate detezDlnatlons of 75.30 ;jg of uranium if»ere done. The

standard deviation was found 0.68 jug as shown In table 4.

The confidence Interval of 95>b from the mean value 75.96 /jg

l i e s In the range 75.47 • 76.50 fjg.

Study of charge on complex

The charge on the coaplex was detezmlned by adilng

two types of resini

(a) Anion exchange resin

(b) Cation exchange resin.

The anion exchange resin turned purple red, as they

are exchanged by negatively charged complex. Results are

given in table 5.

Effect of foreign substances i n uranvl ion deteia^ination:

In order to study the applicabil i ty of the method, the

3 6

A b s o r b a n c e

-n O

o> O 00 Sc/' -DO r- JO m 03 X H

tmmm

oo -n z C C/i 33 T3 > m z o î 2c

2 o "n H

m "D c 33 "D r-m 33 m C3

j ^ • » !

O

O

i n — o

W1

O

3

3

in

o

in VI

O

in o O

3y

Absorbance

o r\)

o o m

c5 o 3J m m 0;D -n

g z x

r -x j>

X - n O

m

o X ;D O I

o b

< o

= p 3 -̂ •o o

m o o

o 3 •< w

3

O

lU O

- o

3 «

i'\)

25.10 S0 .20 75.30 100.40 125.SO

Amount taken in ;ug /10 ml

FIG. 3 CALIBRATION CURVE OF URANIUM AT 570 nm

I

n 1 • •

3 o 3

1 1 1 1

1

K

5

M 3

I

3

C

o •rt

e «

•

4*

9

I

2. ti

i i

3 8 8 S $ S 8 3 8 S O I I I

• • • •

-i O O O

p 12 p js f: i e [2 le }S

f(f 12 J2 [2 J2 p 12 12 fCf 12

0* f*> "^ tn CD O

4cj

I

I s

5

s I 8 e o

5 I •

i s 9

i t 8 3

3

C

»

o

3 3

J I S

o 2J

1] •

I

z

I.

li'i

d«texmination of uranium was stuidied in the presenca of intexw

faranea inorganic metai ions. Tha aoKiunt at i^ich they ara

toiarabla ara givan in paranthatit*

Thosiua (57 mg)* aiuminium (36 mg), inagnaaiuin (26 mg),

nickal (29 mg), ixon (4i rag), airconium (34 mg), bismuth

(48 mg), cariun (44 mg).

Qthar inorganic compounds do not interfere with tha

datamination of uranium.

4 J

Pl^^is^

Erichrooeyanin* R one of the tzlphflnylffiathan* dy«t

haft b««n us«d for tha detection and datexmination of aluai-

niun at pH 5*4 to 6 or pH 3,d. Other metal ions v«hich also

f o n the water soluble coloured lakes are Ml̂ , Zx^ , m^^*

Cr ,Ft and Mg • The reaction mechaniw of aluminiua with

the dye has been proposed by replacesient of hydrogen atoa of

the cazt>oxylic gzoupt resulting the forastion of a chelate ring

structure (13) . The aietal ion mentioned al:>ove also react in

the saae fashion.

CQOH oc

y

/ = i a

oc

= 0 * Ĥ

JC H

/

• 1/3 Al

OC /•'x

\ Al/3

/ = 0 • H

Hotf̂ ever, in case of 002 ^^^ ^ * ^Y* ^^^cts in a differwit

fashion and therefore has a different reaction fsechanisffi.

'i U

liranyl ions foxm undissociated cootplex with carboxyiic

acid gxoupt (14) . Therefort the caxboxyiic group attached to

th« benz«n« ring in the dye resets with uxanyi ion and fosn

undissociated compiexes of uranyi carboxyiic acid. The

formation of colour i s obtained at a resuit of ( i ) UQ2

carboxyi eompiex (2) 1102̂ interaction with the dye i t s e l f ,

«^en JO2 reaction with dye was studied in the presence of a

buffer solution of fH range 3 .4 to 6.0 (as in the case of

aluminium) a different colour reaction was obtained and the

intensity of the colour diminishes with tiise.

The detection of uranyi ion on anion exchonc^e resin

in Cl" foxra i s se lect ive bt^cause the dye i s sorbed as nega-

t ive ly charged species, removing the HB* OX H* ions from the

pore liquid of the resin. The negatively charged c3rboxylic

group reacts with JO^ ion, however the metal ion, thorlusa,

aluminium, magnesiuni, nickel , iron, zirconium, bismuth, and

cerium gave no colour reaction on the resin f^ase due to lack

of pzot(m avai labi l i ty . The concentration of the residual Ĥ

ion due to partial dissociat ion of carboxyiic acid groups

remained low in the resin phase. Here 2 , 3 or 4 li*/m«ttal ions

are required. In solution they interfere to some extent,

because the carboxyiic acidic group can foxm the chelate bond-

ing with these metal ions. However, the colour intensity of

these complexes depends on sett ing of appropriate pH of the

buffer system.

a ;

Th« dy« solution was pr«par«d in diff«rent composition

of wates-aieohoi mixture. It was found that if the dye i s

prepared in pure alcohol or in pure tRrater the intensity of

the colour does not reach to the colour intensity obtained

by a recommended water alcoholic solution. The fact i s that

water faci l i tates the dissociation of the cazboxylic acid

9ZOUP or i t s salts . In view of the above facts a tentative

mechanism has been proposed.

CuuKa

m

"3= ^ ^ ^ ^ ^

r̂ *="-r

CoONs

COOH

H (0^)3^02

• JG^*

- - • :'Z'^'

C 7 /

' l o

1. F. Felgi • Spot Tests in Inorgdnlc Analysis, 5th bd.

p. 205, Elsevier Amsterddin (1958).

2 . T.V. Rooakri^na and H,&. i^reedhara /t^rthy, Taianta,

27(5) , 442 (1980).

3. Shu«Chi«h Huag, Chang-Lingqa and Shui-Siheng WU, Talanta,

29(7) . 629 (1982).

4 . T. Yaeiaiooto, Analytlea Chioica Acta, 65, 329 (1973).

5. B. Evtimova, Analytica Chimica Acta, 83, 397 (1976).

6 . &.C. Dubay aixl M.N. Nadkaxni, Talanta, 24(4) , 266 (1977).

7. F. Vaxnon, T.W. Kyffin and K.M. Nyo, Analytica Ghefsica

Acta, 87, 491 (1976).

8« S.21. Qurashi, Izatullah, a. Bansal, Z, /vnal. Oieca. 295,

415 (1979).

9. &* .̂ Qjrashi, Xzzatullah, R. Bansal, Biill. Soc. Chim.

France, 1-279-281 (1979).

10. S.^. Qmreshi, Xzzatullah, R. Bansal, iVU.cxochemical J . ,

26, 1981.

11. S.21. Qureshi and R. Bansal, Analysis, 1984.

12. Sptll and Snell , Colozimetzlc Methods of Analysis, 3zd

Ed. Vol. 2 , p. 250, (1959).

l y

13. F, Feigl , D. Goldstein, Anelytical Chemistxy, 29(3) ,

456 (1957).

14. F, F«igl | Spot t e s t s in organic analysis, 6th Bl»

p. 514, Elsevier Am St esd an (I960) .

^ttif^y I ft ft LLk

JU

The ion tf(chang« resins which had found appiicdtions

for soivin9 divers* pzobieas of industries* sijricjiture,

msdieine, hydrometaliurgy, separation science, inorganic and

biochemistxyt nuclear engineering, purific6tlon of radioactive

isotopes. Most of the c^a-ierclally present resins are stable

in all cooHson solvent but i t has some serious limitations as

follows.

( i ) There capacity, selectivity, and exchanje rate are changed

by the irradiation of the hig^ dose of ionized radistion.

(2) Decoiaposes at high tsmperature upto slightly more than

iOO C. Strong base anion exchanger resins begin to deter^

iorate above 60^C.

(3) and chemical distxuetion in strong oxidizing ag^ts or

reducing agents.

Due to all these above limitations the wosdc on the

synthetic inorganic ion exchanger has been started for the

last twimty years (1-8). The inorganic ion exchangers have

got the following distinct advantages over t̂he counter

pazts.

'J I

( i ) They can b« us«d conveniently even in the presence of

high ionizing radiation.

(2) They are more heat resistant and therefore can be used

at higher temperature.

(3) The selectivity i s usually higher due to their st i f f

structure.

Some of the more important uses of these inorg^iic

ion exchangers are.

(1) The separation of metal ions.

(2) The purification of water.

(3) The separation of orgwiie compounds.

(4) The preparation of ion selective membraine.

(9) Preparation of artif icial kidney machines.

Analytical application depervis to a large extent on

the understmding of the physical characteristics of these

materials. The more important aspects vi^ich have been

studied are.

(1) The cxystallixation and characterization of ion exchange

materials.

(2) The mechanism of ion exchange.

(3) Ion exchange between solids.

(4) The surface pxoperties of gels.

The counter Ion matrix interactions art more inportant

in inorganic ion exchar^ers than in oxganic res ins . They

soiaetitne iead to irreversibie adsorption (which an ion i s

incorporated in the matrix) and often iead to sei^ct ive or

specif ic separation*

Qureshi (9) has recentiy reviewed the application of

these ion exchangers and showed very high se l ec t iv i ty towazds

cesivxa ions (iO}« The se l ec t iv i ty of other ion exchangers

towazds certain metal ions has been reported in the l i terature

( i i * 1 3 ) . The synthesis of crystal l ine compounds of the poly-

basic acids of known composition and well defined structure

has pxoflaoted ansany invest igations and advances in recent years,

which have been reviewed by Clearfield et a l . (14) , Klberti

and Constantino (15) .

Another very ioportant use of ion exchanger i s the use

of i t s cata lyt ic act iv i ty . Heactions of liquid and solutes

are catalysed by counter ions in the pores and at the surface

of the ion exchanger part ic les and shows higher se l ec t iv i ty

than dissolved e lectro lytes .

The various naturally occurring z e o l i t e s are effect ive

as catalyst for certain oxidation reactions. To a large

extend these inorg^ic z e o l i t e s served mearXy as carriers

for certain metall ic catalyst and the ir chief attributes were

J J

high porosity and thexniai stabiXity, Jaeger (X6) prepared a

s e o l i t e cdtelyst containing vanadium v^ich was effect ive for

the oxidation of ^0^ to SO • Various other catalyst vcere

developed fzcMn aluminium s i l i c a t e ^els to Mhlch were added

alkali metals and nixaerous other heavy metals (17) . Jaegers

l e o l i t e catalyst containing non exchangeable Ni, Cu, or Mn,

were ef fect ive for several reductions including aaniTKtnia

synthesis (18) , reduction of nitzobenzene to ani l ine, and

piridine to piperidine (16) and the hydrsgenation of naphtha->

lene, acetylene, and linseed o i l (19) .

Probably the largest consumer of ion exchange material

for use as for catalyst in the petrolium refining industzy

in the ir cracking and refining process* Thomas (20) studied

the structure relationships of alumino-silica z e o l i t e and

suggested that the active s i t e i s located in the acidic

hydzogen of the gel (H^ SiO.). Maximum acidity and {naximuai

catalyt ic act ivi ty i s correlated with aluraiinium to s i l i con

ratio of unity*

Ion exchanger i s also used to separate the rare eazth

metals that i s best application of the ion exchanger.

Ketelle and Boyd (21) separated the rare earth metals frgni

one another by using 5% c i t ra te buffer ipri 3.28)• The very

similar ionic radii (exchange a f f i n i t i e s ) of these metals

preclude a separation by ion exchange of the simple ions

'J 4

«lon«» I t i s Accessdzy that coisplexinvj agent sjch ds c i t r i c

acid, be U6«d to enhdnce the differences ^nong the ions .

If a separation i s to be achieved. The recCtion which are

postulated are as foXio««x

M^ • 3NĤ R ; ^ m^ •• 3NHJ

tliH^Oit)^ ^ M^ • SHgCit"

The separation of a pair of raxe eaxth i s independant

of the NH/i and c i t ra te ion cone, in solutions and of p>H es

long as the conposition of the complex does not vary. The

role of the c i t ra te then i s to enhance the difference in the

adsoibabil i t ies of the tvto toetals by controll ing the degree

of complexation in the aquous phase.

Taken al l together, the re lat ive adsorbability of the

rare earths i s as follows:

La>Ce>Pr>^kl>PlB>an)Eu>CJd > Tb > Oy > Y ) Ho > Er>

Tte > Yb > Lu.

The progression i s in the saine order as that of

crystal ionic radii and bas ic i ty .

Another ai,plication of ion exchanger i s the separation

of amino acids the method was given by btein and Moore (22) .

They did the separation of the cDost coonnon amino acids by

.J J

meant of a 6t«|wls« • iutlon fxom a 9 by iOQO am column of

Oovtex 50 in tho Ha torn, Elutlon was achieved with sodium

c i trate buffers of progressively increasing pH.

Since the amino acids iire amphoteric and exhibit

i soe lec tr ic points v.hich vary over a considerable pH range

i t i s possible urider certain conditions to obtain separations

into groups corresponding to the basic* neutral and dicazbo-

xylic amino groups (23) .

Synthetic redox ion exchangers* electron ion exchanger

are special ly mentioned. These are solid o;itiddtion ani reduc-

t ion agents. They are insoluble but able to si^ell to a

limited extent. They are reversible agents,, i . e . , after

having oxidized (or reduced) a substrate, '[he electron

exchanger can be regenerated by a suitable oxidation (or

reduction) agent. The reactivity of the el

O'J

reduction couples such as Cu /Cu» F« /Fe » methylen« b lue /

LeukocBethylene blue e t c , have been introduced.

Ouolite S»10 i s d redox ion exchantjcr* This resin

i s an snion exchanger containing complexed cupric ions .

I t has been developed for removal of dissolved oxygen from

water.

Synthetic redox ion exchangers deserves special

mention. These are cross linked polymers of chlorophyll or

haendn de r iva t ives containing metal ion redox couples such

99 Fe /iFe m the fozm of very strong coiaplexes.

The aos t important adv^itage of e lec t ion exchangers

over dissolved oxidat ion o r reduction agents in t h e i r

i n s o l u b i l i t y . After oxidat ion or reduction of a subs t r a t e ,

the res in i s readi ly removed froia the so lu t ion . No contaoii-

nat ion of t he solut ion by redox agents o r t h e i r products

occurs. Another advantage i s t h a t they are r e a i i l y regenera-

ted a f te r use.

As fa r as our knowledge i s concerned a very few anion

exchangers have been prepared. Therefore wo dec I ad t o

prepare anion exchangers in order to balance to some extent

the ex is t ing gap with t h e i r counter pa r t s c

bV

An amorphous matezlat Zxi-.-Uiiour«a->PQ^ showing ths

anion exehango pxopeztiest has basn prepared by us. Physical

and chemical studies of this material are under investigation.

.J 0

EXPfcKlMfiWTAL

A B«itch and Lotab Sp«ctxonic«20 •p«ctzophot(»i«t«r

was usad for spactxophotoottrle dataxiaination. An « i « c t r i c

tanparatura contzoXlad shakar (i>ICU) was usad f o r shaking.

pH was maasurad with an b l i c o L, .^ pK matar.

( O . i M) Zirconitm oxycblorida ( 3 . D . R . ) , ( 0 , i M)

(^oaphoric acid and thiouraa (O.OQi M) wara usad. All

other chaaica le wara of M)«lyticai 9 red a.

^rconi«as«>thiouraa-phoftphata was praparad by mixing

aquoua so lut ion of Zirconium oxychiorida, ph.ios{^oric acid

and thiouraa in tha sama voluna r a t i o but d i f farent in

s trangth. F i r s t thiouraa s o l u t i o n , i s addad in aaetal ion

so lut ion than followad by phosphoric ac id . The pH was

•djustad by adding d i l u t a hydrochloric acid or sodium

hydZDRida s o l u t i o n . Tha prac ip i t e ta so foxnad was alXowad

t o s e t t l a fown for 24 hours, washed several t imes t o retnova

axcass reagents with deionixad water and than i s f i l tered

(mder mct ion. I t was then dried at 40^C in an oven. Then

\j:l

dzlad naterial i t ima»«rg«d in Oeionizod water resulting

cracking of substance into soai ier particles with s l ight

•volution of he«t. The material i s conveited in Cl'" form

by keeping i t in 2 M hydxochlorLc acid solution at 40^c.

for 24 hours. I t wii« then washed with deionized water,

dried, and converted into 30«50 aesh s i ze for detailed study

due to i t s higher ion exchange capacity and higher chemical

s tab i l i ty as conpared to other a a t e j i a l s .

y-j

^^^Mk

Ion •xchdng« capacity of the exchanger wss determined,

taken i.O gm of exchanger in a"" form into the coiuron. The

eluted Cl"* ions by passing 2M NaNQ̂ through the column were

collected in a beaker. The eluted Cl" ions in the effluent

were detezained volunatzically using ;̂ .ohr*s t i t ra t ion (24) .

Capacity was found 2 ,4 mEq/gm dry material.

To check the so lubi l i ty of the material, J .5 gta of the

material was equilibrated with 50 ml of solvent at room

temperature for 24 hours with shaking. Z.in:onium, phosphate

and thiourea were detexmined spectrophotometricaliy using

xylenol orange method (23) , moiybdovanedophosphoric acid (26)

and bismuth nitrate (27) respectively. The re&Jlts are

sumnarized in Table 6 .

Thermal s tab i l i t y , checoical composition, separations

are under invest igations.

•i

I a «n

o 2S •

•a i

1 M

« 9 O 1

o a.

s 8

'S 8 > a Oi

• 2 • •a

1

o» a

1 o •M

« 3

1

2̂

8

M

11 a > a H

• 1 • 1 s

9

^ i

s s s s • • • •

-* ^ p p U.v

8 8 8 8 • • • •

o « ? ?

8 •

o

(0

• -H

CM « O

8 •

o

s •

o

s •

«

8 • -<

R • O

« • ^

$ •

1

CD •

m to

s • -4

8 • *

2$ •

in 4

(0 •

o M

M » •

o

• • •

• • • •• • • •

•

1

•

8 •

8 o*

o CA

-f> s •

cr <

B

8 ^

«

s 4

o

H

O

9

(

-4

8 i "4

-4

o •4

ij »* H

8 o CO

81

O ci

z z

i)J

Olffex«fit §«Bpl«t of Z,jP-thiouMd*PO^ in the tase

voXuam ratios ( i l i t r e soiution of edch species) but in

different strength^ have been prepared.

( i ) Zr - thiourea • PÔ O.iM i Q.l i O.iM,

(2) Zx - thiourea - 90^ O.IM t O.OIM t O.iM.

(3) Zs^ thiourea « PÔ Q.iM i Q,CX3iM t O.lM,

The ssBpie thivi gave the nost stabi« exchanger »ftd

therefore ail the studies have been done on this exchanger.

Exchanger prepared at low pH (2 pH) was found more stable

thm at high pH.

The results of cheadcal stability Tal>le 6 shows

that the oaterlal i s faixiy stable in neutr^al and acidic

solutions, in highly basic solutions exchanger dissolves.

The naterial can be used again and again aft;er regeneration.

Howevert at a particular point, there has b4»en found a slight

decrease in i t s ion exchange capacity.

Apparent equilibriua capacity i s a n«asure of selec-

t iv i ty in point of theoretical intexpretetion which i s sane

t iaes Bore usefull thm the ion oMihange eapdcity. The

selectivity i s also neasured in tezas of Kd values which

U J

1. H,0« PhlUips and K.A. Kaxut, J . Am. Choa. Soe. , 84,

2267 ( i 962 ) .

a. Y. Inou«, Bull . SoG. Japan, 36, 1316 (1963).

3. Y. Inou«, Ibid . , 36, 1324 (1963); C.3. Aiapiaatt, p.

Eaton, L.A. McDonald and / ^ . j . iticl.

Chan., 26, 297 (1964).

4 . 0. Muys and L.H. Sa«tsle , Ib id . , 26, i:329 (1984).

5. a. Albertl, A. Conta and is. Torre^ca* Vaid,, 28, 225

(1966).

6. Q. Albexti, P.O. G a i n , U. Constantino 4ind î . Torraeca,

Ib id . , 29, 571 (1967).

7. £• Torraeca, U. Constantino «id M.A. Manetjcci, J .

Chzoaatogr., 30, 584 (1967),

8. Q. Albexti, and E. Torraeca, J. Xnorg. Nucl. Gham., 30,

317 (1968).

9 . M« Quroshi and J .P. Hawst, separation iscieneo 7, 615

(1972),

10, G.B. Aisphlatt, L.A. «4eOonald, J.;:>. aurgcss and J,i>,

Maynard, J. Inorg. Nucl. Chtm., l o , 69 (1959).

11, H.F, Mai ton. Anal. Chea. Hevie««8, 44, 256H (1972).

\)\}

12. H.F. i»«iton, An«l. Ch«&, Reviews, 46, 398 R ( i974) .

13, H.F. Walton, Anal. Cham. Ravlews, 46, ^ H (1976).

i 4 . A. Claarfiald, G.H. NanBolls and R.H. Slaa&ing, "Ion

•Jiehanga and aolvant axtraetion". Htm Yoifct Mazcal

Oakkar, \fol. 5 , (1973).

15. G. Albaxtl and U. Contantino, J . Chzooiat., 5 , 102,

(1974).

16. Jaagar, A.U. Britlah Patant 304, 640 (Januajcy 23, 192&).

17. i»o€. Chittlqua da La Qranda Paxoitta, Brit ish patant

343, 807 (Fab. 7, 1930).

18. Jaa9ar, A.Q., Bzit lsh Patant 307, 457 (Mazeh b, 192B).

19. Jaagar, A . j . , U.i». Patant 1931, 846 (Octobar 29, 1933).

20. Ihonaa, Q.a., Ind. tng, Cham. 41, 3964 (1949).

21 . Katalla, B.H., and G.E. Soyd, J. Am. Chan. Soc., 69,

2800 (1947); 73, 1862.

22. Moora, S. , and W.H. i»taln, J. B io l . Cham. 192, 663

(1951).

23 . Tlsal ius , A., B. Draka, and L. Hagdahl, Expariantia

3 , 21 , (1947).

24. H« Nauaa, 3 . Naiiaan, "Quantitativa Analyaia", 3xd adn.,

Mearaw^Hill, Naw York, p. 70 (1962).

y .

25. J«C« B«ll«r» H.J. EBi«l«us, H. Nyhola, A.F. Tzoman

Oiekenfton, "Cc»prih«nsiv« Inorganic ChenDistxy", 1st

Edn., Pcrjoaon PMM» Vol. 3, p. 423 (1973).

26. N.H. Fuman, "standsxd mothodt of ch«iaical an«lyti6*.

D. Van N«6tr«nd, Pzlneaton, Hm York, p. 619 (1962).

27. Sn«ll ani sn«ll«Colaxli&«txle Mothods of Analysis,

ard m,, Vbl. 3, p. 165 (19S9}.