liquid ion exchangers and their uses in the separation of zirconium, niobium, molybdenum, hafnium,...

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LIQUID ION EXCHANGERS AND THEIR USES IN THESEPARATION OF ZIRCONIUM, NIOBIUM, MOLYBDENUM,HAFNIUM, TANTALUM AND TUNGSTENN.R. Das a & Sushanta Lahiri aa Nuclear Chemistry Division Saha Institute of Nuclear Physics, 1/AF, Bidhannagar, Calcutta,700064, IndiaVersion of record first published: 30 Mar 2007.

To cite this article: N.R. Das & Sushanta Lahiri (1991): LIQUID ION EXCHANGERS AND THEIR USES IN THE SEPARATION OFZIRCONIUM, NIOBIUM, MOLYBDENUM, HAFNIUM, TANTALUM AND TUNGSTEN, Solvent Extraction and Ion Exchange, 9:2, 337-381

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SOLVENT EXTRACTION AND ION EXCHANGE, 9(2), 337-381 (1991)

REVIEW

LIQUID ION EXCHANGERS AND THEIR USES IN THE SEPARATION OF

ZIRCONIUW, NIOBIUW, UOLYBDENIJH, HAFNIUM, TANTALUH AND TUNGSTEN

N.R.Das and Sushanta Lahiri Nuclear Chemistry Division

Saha Institute of Nuclear Physics 1IAF. Bidhannagar. Calcutta 700064.

India

ABSTRACT

Important liquid ion exchangers and the applications of their cationic and anionic forms in the studies of separation of zirconium, niobium, molybdenum, hafnium, tantalum and tungsten through solvent extraction and RPEC systems have been reviewed.

LIQUID ION EXCHANGERS

In recent years liquid ion exchangers, because of their

inherent ion exchange property, have drawn tremendous attention

to the analytical chemists. Liquid ion exchange primarily refers

to the liquid- liquid extraction systems that operate, at least

formally, by interchange of ions at the interface between an

aqueous solution and an immiscible organic solvent, with

negligible distribution of the extracting agent to the aqueous

phase. Actually, it has got the advantages of using both solvent

extraction and ion exchange techniques. Liquid ion exchangers or

extractants are frequently compared with solid resinous ion

Copyright O 1991 by Marcel Dekker. Inc.

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338 DAS AND LAHIRI

1 exchangers as they work in a more or less similar manner, and

sometimes these offer a' much more rapid method than resinous ion

exchange technique. H.~reen"~ and Coleman et a14 in their

reviews have elaborately discussed the properties and

applications of some of the liquid ion exchangers.

Depending on the nature of the extracted species and the

mechanism of their extraction behaviours, the liquid ion

exchangers can be broadly classified into three main categories :

(i) liquid anion exchanger, (ii) liquid cation exchanger and

(iii) neutral coreagents. The third category was introduced by 4 Coleman et al.

In liquid ion exchange systems, the extractable species are

primarily formed by the interaction between an ion in the aqueous

phase and an oppositely charged ion present in either the aqueous

or the organic phase. The mechanism involved in the extraction

processes with the liquid ion exchangers and the coreagents is

believed to take place generally by ion exchange equilibrium or

adduct formation which may be depicted as -

+ - (i) for a liquid anion exchanger, e.g. R3NH A , a quaternary

ammonium salt.

where MX"- is the metal anionic species in aqueous solution and

( R ~ N H + ) ~ M X ~ - is the resulting anionic salt responsible for the

extraction in the organic phase,

(ii) for a liquid cation exchanger, e.g. HB

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LIQUID ION EXCHANGERS 339

where Mnt is the metal cationic species in the aqueous solution

and MBn is the resulting species responsible for extraction and

(iii) for neutral coreagent. e.g. TBP

- > M:: + n ~ - + x TBP <-

aq MAn(TBP)x.org

where A- is the organic ligand present in the aqueous phase and

HAn(TBP)x is the extractable species formed by the coreagent,

TBP .

For general interest some of the liquid ion exchangers and

coreagents are cited in Tables I, I1 and I11

SOLVENT EXTRACTION SEPARATION OF ZIRCONIIRI, NIOBIUM,

MOLYBDENIRI, AAFNIIRI, TANTALUM AND TUNGSTEN VITA

LIQUID ANION AND CATION EXCHANGERS

In the present paper, attempts have been made to review

the potential use of liquid ion exchangers in the separation

studies of the elements, namely, zirconium, niobium, molybdenum.

hafnium, tantalum and tungsten, which are very much prone to form

complexes, both cationic and anionic, in aqueous medium and the

discussion will be concentrated mainly on the applications of

cationic and anionic liquid exchangers in which the ion exchange

or ion pair formation phenomenon are predominantly involved.

The elements mentioned above are significantly important

and are being used in various fields of industries and

technologies. Particularly, because of their favourable nuclear

properties. the elements have got special importance in nuclear

technology. For example. zirconium, due to its low absorption

cross section for neutron, is used for cladding of fuel elements

in nuclear energy. On the other hand, hafnium has good absorption

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DAS AND L A H I R I

Table I

SOUE IMPORTANT LIQUID ANION EXCHANGERS WITH THEIR

STRUCTURAL FORMULAE

Anion exchanger Structure formulae

Palmityl

Primene 81-R

Alkaylaniline C-12

Di-n-decyl amine

2,2-diethyldihexyl amine

Liquid Amberlite-1

(LA-1)

Liquid Amberlite-2

(LA-2)

N-Cyclohexyl-n-octyl amine

N-Cyclohexyl-n-dodecyl amine

t-C12-14H25-29NH2 (mol. wt. 185-213)

(mol. wt. 353-395)

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Anion exchanger Structure formulae

Cyclohexyl di-n-dodecyl amine

(CDDA)

N-Cyclohexyl-2-ethylhexyl amine

(CEHA)

Cyclohexyl di-2-ethylhexyl amine

(CDEHA)

Benzyl-2-etylhexyl amine (BEHA)

Benzyl-di-2-etylhexyl

amine (BDEHA)

Tris-2-ethylhexyl amine (TEHA)

~enzyl-di-n-dodecyl amine (BDDA)

N ,~~dimeth~loctadecyl amine

Dioctyl amine (DOA)

Tri-benzyl amine

Tri-n-hexyl amine

(continued)

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342

Table 1 c o n t i n u e d

Anion exchanger

DAS AND LAHIRI

Structure formulae

Amberlite XE-204

Tricaprylmethylamrnonium

Chloride (Aliquat 3 3 6 )

Tetrabutylammonium salt

Tetra-n-heptylammonium salt

N-[-CH CH CHCH CHCH3I3 2 1 2 1 CH3 CH3

cross section ( n = 105 barns) for thermal neutrons, so an

accurate removal of Hf is required if Zr is to be used in the

construction of thermal reactors. Similarly, niobium because of

its moderately low neutron capture cross section and its

resistance to liquid metals at high temperature is considered to

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LIQUID I O N EXCHANGERS 34 3

be an important constituent of nuclear technology and should be 5 essentially free from tantalum and other metals.

But due to lanthanide contraction, the elements, in general.

have strong affinities of forming the pairs, like Zr-Hf, Nb-Ta

and Mo-W, and the pair forming elements have very similar values

in their atomic radii, oxidation states, magnetic properties,

metal-metal bonding, etc: and hence their separation always

constituates an interesting study; especialy where the purity is

an essential factor. Thus, the mutual separation of the elements

forming the critical pairs or separation of the individual

elements from the mixture with other elements in pure form is

always a facinating p ~ o b l e m . ~

SEPARATION WITH LIQUID ANION EXCHANGERS

Generaly the high molecular weight amines (primary,

secondary, tertiary ) and the quaternary ammonium compounds are a

used as liquid anion exchangers . The term 'liquid anion

exchanger', some of which are presented in Table I. was derived

from its analogy with anion exchange resins. These compounds

fulfil a number of basic requirements for liquid - liquid

extraction such as good extraction power, low solubility in

aqueous solutions but highly soluble in many aliphatic and

aromatic hydrocarbons, high molecular weight alcohols, etc, and

have sufficient chemical stability. Metals forming anionic

complexes in mineral acid solutions become extracted by these

anion exchangers in different degrees depending on the

experimental conditions.

Primene JMT, a long chain primary amine, was used by

El-Yamani et a19 in the separation of Zr and Uf from H SO 2 4

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Table I1

DAS AND LAHIRI

SOME IHPORTANT LIQUID CATION EXCHANGERS WITH THEIR

STRUCTURAL FORMULAE

Cation exchanger Structural formulae

mono-2-ethylhexylphosphonic CH2CH3 0

acid (H2EHPA . I

(OH) 2-P-O-CH2CA- (CH2) 3CH

monododecylphosphonic acid iH3

monoheptadecylphosphoric acid

di-(2-ethylhexy1)phosphoric acid

(HDEHP)

di-n-butylphosphoric acid

(HDBP I 2-ethylhexylphenylphosphonic acid

- , (OH) 2-P-O-CH

I (CH2) 2CH(CH2CH3)

HO-P- [-0-CH,CH- (CH,) 3CH3] , 0

HO-P- [-0- (Ct12) 3CH31

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Cation exchanger Structural formulae

dinonylnaphthalene sulphonic acid HO-SO2-C10H6-CgHl9

salicylic acid HOOC-C6H9-OH

trans cinamic acid HOOC-CH:CH-C6H5

perfluorobutyric acid HOOC- (CF2) 2CF3

perfluorooctanoic acid HOOC- (CF2) 6-CF3

naphthenic acid

versatic 911

medium. Primary amines are poor extractants in ~ 1 - and NO- media, 3 but their extractant capacity is considerably enhanced in SO-

4 medium. ~himizu'"found suitable conditions for the extraction of

Sc, Th, Zr and U from 0.1M H2S04-0.001M ammonium sulphate medium

with a 10% solution of the secondary amine. Amberlite LA-2, in

xylene. The tertiary amines, in general, are better extractant 2 , 1 1 than primary or secondary amines. The extraction efficiency of

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DAS AND L A H I R I

Table I11

SOME IMPORTANT LIQUID NEUTRAL COREAGENTS WITH THEIR

STRUCTURAL FORMULAE

Name Structural formulae

tri-n-butyl phosphate OP-[4-mi2) 3CH31

(TBP)

di-n-butylphosphonate

(DBBP)

tri-n-butylphosphine oxide OP-[-(CH2)3CH313

(Bu3PO)

tri-n-octylphosphine oxide OP-[-(CH 1 CH ] 2 7 3 3 (TOPOI

these amines increases with chain length of alkyl group and

decreases if the chain is branched. The reagents become more

effective when benzene or chloroform is used as solvent.

Detailed studies on the extraction of Zr(IV) in HC1

mediumwith different high molecular weight amines were conducted 11.12

by Sato and his groups. The extent of extraction is very much

dependent on the acidity of the aqueous phase and increase of

temperature has a retarding effect on its extraction. They also

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LIQUID ION EXCHANGERS 34 7

observed that tertiary amines are more effective in its

extraction than secondary amines and the efficiency of these

reagents were found to increase with increasing chain length but

unlike re en', it is enhanced further when the chain is branched. 12 . Another interesting feature is that the presence of a benzyl

group has a positive effect on the extraction of Zr(1V).

Extraction of Zr(IV) from H2S04 medium with various long chain

secondary and tertiary amines like DOA, TOA, TDA and TEHA were

also investigated in detail. In sulphuric acid medium, secondary

amines were found to be dore efficient as extractant for Zr(IV)

than tertiary one and their extraction behaviour towards Zr(1V)

which is extracted as (R3NH)4Zr(S0 ) from H2SOq varies as DOA > 4 4 TDA ) TOA ) TEHA. Effect of diluent in the extraction systems was

also considered.

The quaternary ammonium salt,in general, is very efficient

as anion exchanger for the anionic species, especially for metal

anionic complexes. Mishra et all3 extracted Zr(IV) from HC1

solution by a mixture of Aliquat 3361 Alamine 336 with a neutral

donor like TBP. At lower acidity, the extraction efficiency of

Zr(IV) is enhanced with a reagent mixtures than that with the

individual extractant. The extractable species formed was

tentatively assigned to be of the type Q2ZrC16.TBP, where Q =

R3Ef(~H3) for Aliquat 336 and R 3 h for Alamine 336. It was also

indicated that under identical conditions, extraction of Zr(IV)

by Aliquat 336 alone or with its mixture with TBP was better than

that by Alamine 336 alone or by its mixture. Similarly, studies1'

on the phenomenon of synergism in the extraction of Zr(1V) with

the mixtures of Aliquat 3361Alamine 336 (10% vlv) and a neutral

donor. dioctyl sulfoxide (DOSO) from HC1 solution indicated the

formation of the extracted species like Q~z~c~~.Doso'~. Sato et / alls also extracted Zr (IV) as (R3R N)n-4ZrCln by Aliquat 336 in

benzene from HC1 where extraction follows an increasing trend

with increasing acidity but it diminishes in presence of LiC1.

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348 DAS AND LAHIRI

Extraction of Zr (IV) using 0.1-0.2M Aliquat 336 in kerosene 16

at different acidities of H2S04 were reported. Higher D Values

were obtained at acidities arround 0.02M H2SOq and further

increase in acid concentration resulted in decrease of D values.

They also observed sharp decrease in values of D with rise of Zr

concentration. Studies on the effect of diluents showed that the

extractibility follows more or less the sequence of aromatic )

cyclic paraffin ) straight chain hydrocarbons. Increase of

temperature upto 50'~ has a positive effect on the extraction

behaviour but with further rise of temperature extraction

gradually decreases.

Sawant et al17extracted Zr from malonic acid media by

various long chain amines like Primene JMT LA-1, LA-2, Aliquat

3369, TIOA, etc., in different diluents. The effects of pH,

diluents, interfering metal ions, etc., were also studied and the

optimum pHs for quantitative extraction of Zr were found to be

2.25 - 5.55 with primene JMT, 2.0-5.0 with LA-1 or LA-2, 2.5- 5.5

with Aliquat 336 S. and the nature of the species formed was

thought to be an ion assosiation complex of the type

[ R ~ N H ~ ] [Zr~(malonate) i] . Distribution of Zr (IV) between ACl and

Hyamine 1622 was studied and a method was proposed'7A for

separation of Zr from Hf.

Niobium and Tantalum are very much prone to form negatively

charged halide complexes5 which can undergo ion exchange process

with the salt of high molecular weight amine. Djordjevic kt a1 18

studied the extraction of oxalato complexes of Nb and Ta by TOA,

TDA and TDDA in carbon tetrachloride. Quantitative extraction of

the elements was possible with a 3% exchanger solution from an

aqueous phase containing 0.2M oxalate solution and less than 0.5M

sulphuric acid. KO" seperated Pu from traces of Ta by TOA from

nitric acid solution in which the concentration of Ta was as low

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LIQUID ION EXCHANGERS 34 9

20 as 20 ppm in 100 mg of Pu. The author also investigated the

separation of Pu, Ta, Ti, W and Zr by 20% TOA in xylene from

HN03. Effects on the presence of F- ion in the extraction of Ta,

Ti, W, Zr and Pu were also studied in detail.

Abdel Gawad et.a12' extracted " ~ b from citric, oxalic and

acetic acid solutions by a number of structurally related

tertiary amines and quaternary ammonium salts, namely, TPA, TOA,

Alamine 336, TDDA, Adogen, Aliquat 336, etc. In all cases,

increase in pH resulted in a decrease of Nb extraction. 22 .

Extraction of Nb from HC1 solution by amines Indicated that in

>7H HC1 solution, the extractable species is N ~ o c ~ ~ T Quantitative

separation of Nb from Ta was achievedz3 by TBA from oxalate and

sulphate media by adjusting the organic to aqueous volume ratio

at 15 to 1. Further, in HC1 medium, niobium is thought to be

extracted into the solvent phase by the formation of oxychloride

complexes of the type H(NbOClq) or A2(NbOCl5), whereas, the lack

of extraction of Ta by the reagent is perhaps due to its

non-existence as chloro- or oxychloride complex in aqueous

solution. Leddicote et alZ4 also extracted niobium from 9.6 M HC1

solution by methyldioctylamine in its separation from Ta.

Extraction of tungsten by TOA in the form of peroxy compounds

from HC1, H SO and HNO solution was achieved. A schemezs for 2 4 3

isolation of radiotracer, lS3ue, from tungsten was also proposed. 26

Aliquat 336 has been employed as an efficient anionic

extractant for the radiochemical separation of 9 5 ~ b and 9 5 ~ a from

HF medium.

Trialkyl methyl ammonium nitrate in toluene was used26A as

an effective reagent for extraction of molybdenum from nitrate

and peroxide solutions at the pA range of 2-6. At low molybdenum

concentration ( - 5 x H 1 , the extraction involves simple

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DAS AND LAHIRI

Table IV

EXTRACTIONS WITH LIOUID ANION EXCHANGERS

Element Aqueous Extractantl

seperated phase diluent

References

H2S04, NaF,

HzOz

Aliquat 336, (5% v1v)lbenzene 13

Alamine 336, (5% v1v)lbenzene

TBPlbenzene

DOA, TDA, TOA, TEHA /benzene/ 12

chloroform

Aliquat 336 SI chloroform 27

Aliquat 336 S 27

TOAI cyclohexane 28

Various aminesl diluents 29

LA-1 (4%) 1 chloroform 3 0

Aliquat 3361 benzene 15

DOA, BEHA, TOA, TDA, CEHA, 11

TEHA, BDDA, BDEHA, CDDA,

CDEHAfbenzene

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Element Aqueous Extractant1


References

Zr

Zr- Nb

12 N HC1 Methyl di-n-octyl aminel 31

xylene

9-12N HC1 TOA

8-91 HC1 Aliquat 336 (10% vlv), 14

Alamine 3361 benzene + DOSO

Zr-Nb Diff. ~1-conc. Alamine 336, Aliquat 336 3 4

Zr-Nb,Tc ('411) (NH4) 2C03, Trioctylmethyl ammonium 3 5

I(1) (NR4) 2S04 chloride

Zr-Nb-Ru-Th, HC1

alkali-alkal-

ine earths-

rare earths,U

Zr- Hf H SO (0.81) Aliquat 336lkerosenel 16 o4

(10 C) octanol, (3% vlv) (modifier)

Zr-Hf H2S04 Primene JMTI kerosene 9

Zr-Hf H2S04 TOA 3 7

Zr-Hf HC1 Hyamine 1622 53

Zr-Ta-Ti-W-Pu 6M HN03 TOA (20%) I xylene 20,

38 (continued)

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352 DAS AND LAHIRI

Table IV continued

Element Aqueous Extractant/ References


Zr,U,Th,Pa,Ru H2S04 Primene JMT, LA-2, TOA 3 9

Zr-Al-Fe(I1)- Complexon I11 O.lM TOAl carbon tetra- 40

V-Ti-Mn(I1)- 0.02% Arsenazo chloride1 benzene

Cr (111) -Cu-U

HC1 ( H 11) TOA/ toluene P

Alizarin Red S

Zr-Cd 2M H2S04

Nb Acetic acid

(0.01N-5.ON)

Oxalic acid

citric acid

so;

TOAI cyclohexane 42

TPA, TOAIchloroform 2 1

Alamine 336/benzene,

Aliquatlxylene

TPA, TOA/ chloroform,

Alamine-336/benzene ,TDA/

benzenelchloroform.

Adogen-363 ( 9 5 % ) , Aliquat 336/

xylene

TOA 4 3

TOA 44

MDOA/ trichloroethylene 4 5

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Element Aqueous Extractant1


References

Nb-Ta, Acidic LA-1, Primene JUT. 46,

fission solution Alamine-336/ 47.

products carbon tetrachloride 4 8

Nb-Ta <0.5M H2S04 TOA, TDA, TDDA/ 18

carbon tetrachloride

Nb-Ta

Nb-Ta

Nb-Ta

Nb- Ta

Nb- Ta

Nb- Ta

Nb-Pa

Tribenzylamine/

methylene chloride

DOA, Triisoamylamine/hexanol 49,

2 2

9.6 U HCl Uethyl dioctyl amine/xylene 24,

49

HF- HNO, TIOA (3%)/carbon tetrachloride 50

Tartaric acid TOA

HF- H2S04 DO A 5 1

Oxalic acid, TOA/chloroform

pyrocatechinate

Nb(V)-Ti(IV) 8.5MHC1 0.2M TOA/ carbon tetrachloride 55

Nb. Ta HF (0.05U Aliquat 336/ octanol(32) v / v 26

(modifier) (cont inued)

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Table IV continued

Element Aqueous Extractantl References


Nb, Ta

Nb, Ta

Nb-Ta

Nb-Ta

MO

Mo

Oxaliic acid

HC1, HF

Tartaric acid

9.6M HC1

Acidic medium

Acetic acid,

thioglycollic

acid

~ 1 - , SO; NO^-

NO;, peroxide

solution

1M H3P04

<lM HN03

H2S04+H202

- so;, CH~COO-

Oxalic acid

TOA

N,N-dioctyl aniline

Tetraoctyl ammonium bromide

MDOAI xylene

Aliquat 336

TOA (5%) I chloroform

TO A

Trialkylmethylammonium-

nitrate

Aliquat 336 fcyclohexane

Various amineldiluent

Aliquat 336ltolune

TO A

TOAI xylene

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Element Aqueous Extractantl


References

Hf -Th SO;, NO; TO A 6 5

Hf (IV) ,Ta(V), HCI

no (VI)

0.1M Hyamine 1622/

1.2 dichloroethane

Ta, Pu 4M HN03 TOAlxylene 19

W-Re HC1,H2SOq, TOA/ carbon tetrachloride 2 5

HN03, H202

W-Au- 0 s 1M HF, TOA

In HCl + thiourea

anion exchange mechanism to give the compound, NR4HHo06, but at

higher concentration, the compound extracted is predicted to be

(NR4HUo0 H Moo6. Quantitative separation of tungsten6' from 6 2 2 molybdenum in their tracer scale concentrations was possible with

Aliquat 336 in cyclohexane from an aqueous solution of H3P04. The

efficiency of separation of the elements which form varieties of

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356 DAS AND LAHIRI

poly- and heteropoly anionic species in aqueous medium is very

much dependent on the types of the acids as well as the reagent

concentrations.

Some of the important uses of the liquid anionic extractants

in the solvent extraction studies of the elements are presented

in table IV.

SEPARATION WITH LIQUID CATION EXCHANGER

Most of the liquid cation exchangers are organophosphorus

acids. Other cation exchange systems include carboxylic acids,

fluorocarboxylic acids and sulphonic acids.

Scadden et a16" found that mixed butyl phosphoric acid

extractants in di-n-butyl ether are very effective in isolating

Zr and Nb from various fission products. Extraction of Zr (99%)

and Nb (98%) in carrier free states was possible by 0.06M

di-n-butyl phosphoric acid from 1M aqueous solution of HN03. HC1,

HZS04 or HC104 and also from 0.004M oxalic acid. However,

addition of H202 or presence of monobutyl phosphoric acid reduces

the extraction of Nb. Extraction of Zr from nitrate solution with

HDBP was studied69A as a function of nitric acid, nitrate ion,

and hydrogen ion concentration. The distribution coefficient for

zirconium is found to be proportional to the second power of the

final [HDBP] over the range I O - ~ - I O - ~ M HDBP, and to the first

power of [NO3] but independent of hydrogen ion concentration.

Sato7' extracted Zr(IV) from HC1 solution by HDEHP in kerosene at

20% in which the partition coefficient for Zr follows a

decreasing trend upto 2M acid concentration and then increases

steeply. It was assumed that the initial decrease in partition

coefficient was governed by the reaction,.

m zrc12+ + ( m + ~ ) (HX) H + 2m A+ 2 aq ' ( Z r C 1 ~ ' m X ~ ( m + ~ ~ 2 org . aq

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and the increase in partition coefficient at higher acidity was

due to the reaction,

However, the extraction of the elements is very much dependent on

the temperature and the nature of the diluent.

7 1 - 7 3 . Das et a1 investigated the use of HDEHP in different

diluents as an extractant for mutual separation of the elements

in the pairs, Zr-Hf, Nb-Ta, and No-U, in tracer concentrations

from diferent aqueous media like HCl, HNOJ, H2SOq and H3P04.

Extractibility of the elements is very much dependent on the

nature of the acids and their acidities as well as the

concentration of the metals. The diluents such as cyclohexane,

n-heptane, benzene, carbon tetrachloride, etc. have no

significant effect on the extraction behaviour of the elements,

but, in general, lowering of extraction take place in presence of

chloroform. In the sequential seperation of Hf, Zr and Nb using

HDEHP as an extractant, Nb and Zr become totally nonextractable

with the reagent upto 0.01M concentration from 0.08N H2S04

solution, whereas Hf is preferentially extracted by the reagent

in this region. Addition of small amount of tartaric acid in the

system helps further in the enhancement of separation of Hf as it

hinders the extraction of Zr and Nb. The effects of ~ 1 - ions,

oxalic acid as well as HDEHP concentration on the extraction of 71

niobium and tantalum in macroscales were also studied. It was

proposed that the interaction of hydrated tantalum with HDEHP is

either of dipole-dipole type or of hydrophillic nature instead of

strong cation exchange type as indicated

6 - . . . . . . .Ta 0 .x H20 2 5

where R = 2-ethylhexylgroup

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358 DAS AND LAHIRI

The reagent, di-octyl-methylene-bis-phosphonic acid.

(DOMPA), was used as an extractant in Nb-Ta-H2S04, Nb-Ta-HC1. 7 5 Nb-Ta-HF, systems in presence of oxalic acid. Best extraction

for both the elements occurs in H2S04 medium over a narrow

normality range and the extraction mechanisms proposed are -

[Nb(OH)4(C204)];q + 2 DOMPA + [N~O(DOMPA)~]- + H2C204 + 3 H20

[ T ~ ( O H ) ~ ( C ~ O ~ ) ] ; ~ + DOMPA + [T~O~(DOMPA)]- + H2CZ04 + 2 H20

A detailed study on the extraction of Hf(1V) by dibutyl,

diamyl, diethylhexyl and dioctylphosphoric acid in different

diluents, namely, benzene, chloroform, carbontetrachloride,

cyclohexane and n-octane from perchloric acid medium were made by

~ a v r a t i l ~ ~ . In strong acid medium ( above 4N HC104 1 , the primary

ion exchange mechanism was replaced by an addition type of

reaction which results in the formation of highly extractable

species, Hf(C104) (HA)4. (where HA = dialkylphosphoric acid).

Concentration of Hf played a prominent role in all the systems

and D decreases with increasing C and after certain critical Hf

concentration, formation of polymeric Hf(IV) complexes with HA in 7 7

aqueous phase starts. It was also revealed that in moderately

acid solutions of HBr or HI, Hf is extracted as HfXA3(HA)3 and in

strong acid medium, ion exchange mechanism is replaced by an

addition type of reaction where the original ion exchange

mechanism changes to a solvation type of mechanism.

78 Similar type of solvation mechanism was also proposed for the

extraction Hf by dialkylphosphoric acid from HC1 and HN03 media.

72,79-90 Different groups of workers in various laboratories

have utilised HDEHP in their studies on the extraction separation

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of Mo from W and other elements in various aqueous media. Das et

a17' quantitatively extracted Mo with HDEHP from H3P04 leaving W

completly in the aqueous phase. IR studies reveals that the

Mo-HDEHP complex has a closed ring structure of the type -

, where R = 2-ethylhexylgroup

The method is applicable to both tracer and macro-scale

concentrations of Mo and the extent of extraction is dependent

primarily on the type of the acid and the acidity of the aqueous

solution. At the optimal experimental condition, Mo which is +

mainly present as MOO species exchanges with HDEHP, 2

t Moo2 + 2 HDEHP = Mo02(DEHP12 + 2 H+

~tudies" on the extraction of molybdenum and tungsten from

HC1, HN03 and H2S04, with HDEHP further indicated that almost

quantitative extraction of molybdenum could be achieved from HC1

and for tungsten a linear course of the dependence, log Dw =

f (CHC1) in certain acid region was followed. The extraction of

both Mo and W in sulphuric acid medium is nearly constant.

However, HDEHP was shown to be a good extractant for Mo from HNO

medium, in which with increasing C higher DMo were obtained. HN03 3

Long chain fatty acids in suitable organic diluents have

also been found t o be quite useful as liquid cation exchangers

for the separation of the elements 92-113 . With In solution of

naphthenic acid in kerosene, extractions of the isotopes. 134~s,

9 5 ~ r and 9 5 ~ b , in nitrate forms were investigated 110 in which

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360 DAS AND LAHIRI

the ratio of the aqueous to organic phase was adjusted to 5:l.

With the same reagent extractions of 45 elements including Zr(1V)

and Nb(V) were studied1". The separation of Zr and Nb has been

achieved with lM C7-Cg fatty acid fraction solution in benzene at

pH 6 in presence of H 0 94. The distribution ratios of micro 2 2 quantities of Zr, Nb Cs, Sr, Y, Cu and Ce in presence of uranyl

nitrate were studied with palmitic (hexadecoic) acid in paraffin 96 as a function of the degree of alkalinity of the aqueous phase .

The extraction of Zr at low concentration with fatty acids in

benzene was found to be dependent on the organic acid

concentrations, their chain lengths, pHs and type of solvents

used." Quantitative extraction of zirconium took place at pH

2.4 with SRS-100 ""

Some of the important applications of the liquid cationic

extractants in the separation studies of the elements are

presented in table V.

USE OF LIQUID ION EXCHANGER IN REVERSED PHASE EXTRACTION

CHRONATOGRAPHIC SEPARATION OF THE ELEMENTS

Another unique use of liquid exchangers is its application

in reversed phase extraction chromatography (RPEC). Since the

techniques of RPEC and solvent extraction are almost

complementary to each other, similar types of extraction

mechanisms involving the liquid ion exchangers are followed in

both the procedures.

~ a a e n " ~ described reversed phase thin layer chromatographic

(RPTLC) studies of 31 metal ions including Zr, Nb and Hf on the

layers of polytetrafluoroethylene with HDEHP. Similarly the

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Table V

EXTRACTION WITH LIQUID CATION EXCHANGERS



H2S04 (90%) ,1M

NaF (10%)

so;

Zr,Ti,Sn,Sc Muriatic acid

HDEHPI kerosene 114

HDBP + TBP 115

HDEHP

HDEHPf cyclohexane 121

Di-n-hexylphosphoric acid, 122

Di-n-heptylphosphoric acid,

Dioctyl phosphoric acid

HDEHPI kerosene 70

HDEHPIcarbon tetrachloride 73

HDEHP 124

( c o n t i n u e d )

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Table V continued



Zr,Nb HN03 Dibutylthiophosphonic acid 125

Zr.Nb H202 (pH 6) C7-Cg fatty acidlbenzene 94

Zr.Nb,U,Fe HN03 C -C fatty acid solution 95, 7 9 106

Zr. Nb,Cs, Uranyl nitrate Palmitic acid1 paraffin 96

Sr,Y,Cu,Ce

Zr,Nb,Cs,Ru HN03 Napthenic acid 110.

111

Zr ,Hf ,Ti Acidic medium n,brornobutyric acid 9 9

Zr,Nb,Am,Eu c~o;, citrate HDEHP 127

Zr (IV) ,Nb(IV) ~10;. Citrate, ADEHP t TBPIn-hexane 128

Eu(II),

Am(1II)

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Element Aqueous Extractant1 References


Zr-Nb,

fission

products

Hf (IV)

Hf

Hf (IV)

Nb (V) , Th.

REE

HN03, HC1,

H2S04, HC104,

oxalic acid

Acidic medium

HN03, HC1

HBr, HI,

H2S04

so;, c10;,

c1-

- so,, ,lo;,

HDBP, mono-n-butyl- 6 9

phosphoric acid

HDBP, HDAP,HDEHP, HDOPI

benzeneloctanelcyclohexane

Di-p-cresyl phosphoric acid 130

HDBPIchloroforrnlbenzene; 7 8

HDAPltoluene, HDOPIn-octane

HDEHPIn-octane,

Di(n-butoxyethy1)phosphoric 131

acid

HDBPI chloroform1 carbon- 77

tetrachloride1 benzene

HDAPI toluene

HDEHPI C6H6/n-octane

HDOPI benzene

HDEHP + TOPO; HDEHP + TOA 132

HDBP 133

HDBP

(continued)

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Table V continued

Element Aqueous

seperated phase

Extractant/ References

diluent

Nb

Nb,Sb,I,

fission

products

Nb, Ta

Nb, REE

Nb, Ta

Nb,Ta

Nb-Ta

Mo, W

Mo (VI)

no

Mo(V1)

NO; Napthenic acidlkerosene 110

111

9N HC1 - NaC10, HDEHP

(50%)

1.6 N HC1, 0.1M HDEHPI n-heptane 71,74

oxalic acid

(30'~)

CIO;, HDEHP/hexane

citric acid

Oxalic, H2S04, di-octyl-methylene-bis- 7 5

HC1, HF phosphonic acid

Dil. acid, Caproic acidlbenzene 107

KC1, CaCIZ 108

H2S04+ DOMPA

oxalic acid, HF

HC1. H2SOq HDEHP 9 1

NO;, CI-, SO; HDEHP/ cyclohexane 121

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no-v H C ~ , H N O ~ , H ~ S O ~ ,

H3P04

Ho-W 0.lM HN03

Mo-Tc HC1

HDEHPIkerosene + 2-ethyl hexanol

HDEHPI benzene/ 72

n-heptane/cyclohexane/

carbon tetrachloride

HDEHPIkerosene 80

HDEHP 142

technique of reversed phase circular paper chromatography has

been appliedy4' to the systems of u6+-zr-Th, Zr-Hi, U-Zr-Ti 4+

zr-Ti4+-Th, etc.. in their separation, where paper was

impregnated with TOA, and 4N HC1 was used as an eluating agent

and the RF value for each of the elements has been compared with

the published data. In the RPEC separation150 of Zr(IV), Th(IV),

U(VI), the column was packed with LA- SO;) impregnated silica

gel. From the column, Th(1V) was removed easily by elution with

0.1M H2S04, and Zr(IV), U(V1) were separated by successive

elution with 4M HC1 and 1M HC104 respectively. A column of TIOA

impregnated R 51/83 corvic material has been ernpl~yed''~ for RPEC

separation of several metals including Zr, Hi, Nb, Ta, Mo and V

under different experimental condition.

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DAS AND LAHIRI

Table VI

REVERSED PHASE EXTRACTION CHROMATOGRAPHIC SEPARATION

WITH LIQUID ION EXCHANGERS

Elements Inert Stationary Mobile References

separated support Phase phase

31 elements

including

Zr-Nb-Hf-W

Chromosorb

HC1 and HC1

+ 1-

Plaskon polymer

Polytetra-

fluoroethylene

Silica gel

Kel F

Cellulose

Silica gel

Corvic

R 51/83

HDEHP HN03,

HC1 + I-

TEHP- 5% HDEHP 8N HN03

HDEHP in MIBK HN03

HDEHP HC104

Aliquat 336 0.25M HC1

TO A HC1, HN03

LA-2 H2S04, HC1,

HC104

TIOA HC1

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Elements Inert Stationary Mobile References

separated support phase phase

Nb-Ta Kieselguhr

Kel-F

Chromosorb

Hostaflex

Kieselguhr

XAD-2

Aliquat 336 0.1M HF,

ION HN03

Ta(V)-Re(V1II

Zr-Th

Aliquat 336

HDEHP HN03-HC1 i

I-+ DTPA

Mo-Tc HDEHP

Aliquat 336

Aliquat 3361

toluene

Aliquat 3361

toluene (5%) Cr (VI)

Nb-Ti PTFE

Nb-Ti-Mo Ftoroplat-4 TOAI

benzene

Zr-Nb-Hf Kieselguhr HDEHP

HDEHP

H2SO4+oxalic

acid t H 0 2 2 H2S04+oxalic

acid + H202 Zr-Nb-Hf Vhatman No.1

paper

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368 DAS AND LAHIRI

~tronski'~' described a reversed phase method for seperation

of mixtures of small quantities of Mo(V1)-W(V1)-Cr(V1) and

Ta(V)-Re(VI1) in which polytrifluoromonochloro ethylene (Kel-E)

impregnated with aliquat 336 was used as a column material.

Tantalum which forms a highly stable complex with aliquat 336 was

eluted out first by a mixture of acetone with the extractant

unlike W and Mo which were separated out later from the column

with 2N HC1. For seperation of Mo(V1)- W(V1)- V(V) with Aliquat

336 on a coiumn of inert macroreticular resin XAD-2, Fritz et

alsz used mixture solutions of H2S04 + H202 various

concentrations. Partition chromatographic separation of Zr in

Pu-U-Zr alloys was possible with 0.5N HN03- 3N HE solution by using 95% tris(2-ethylhexyl) phosphate (TEHP) - 5% HDEHP mixture as extractant on .Flaskon polymer column. Das et a126:60"57 made

detailed studies on the RPEC separation of the elements forming

the systems, Nb-Ta, Zr-Nb-Hf and also Mo-W, on kieselguhr column

imprignated with liquid cation and anion exchanger like HDEHP and

Aliquat 336. The elements were separated using different acids as

eluants depending on the complexing properties of the elements

concerned. In case of separation of Mo and W, presence of small

amount of tartaric acid in alkaline medium enhances the

separation.

Recently a reversed phase paper chromatographic procedure'5R

for radiochemical separation of 9 5 ~ r , 9 5 ~ b , '*'~f in a mixture

has been reported in which sheets of Whatman No. 1 paper

impregnated with HDEHP was employed as the stationary phase and

mixtures of oxalic acid + H2S04 + H 0 were used as mobile phase 2 2 in which a clean separation of the elements concerned was

achieved.

Some of the important applications of the liquid exchangers

in the RPEC separation of the elements are cited in table VI.

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CONCLUSION

The article comprising the citation of some important liquid

ion exchangers along with their respective structural formulae

and a review on the potential uses of the liquid anion and cation

exchangers in the separation studies of some rare elements,

namely, zirconium, niobium, molybdenum, hafnium, tantalum and

tungsten, may be helpful to the analytical chemists dealing with

such separation problems. The review is confined mainly to the

solvent extraction and RPEC separation of the elements with

liquid anion and cation exchangers, although the uses of liquid

ion exchangers since the introduction of the technique of 'liquid

ion exchange' by Smith et all" in 1940, in general, has got wide

applications in the analytical separation of several elements by

means of various chemical procedures. The efficiency of the

applied procedures primarily lies in the inherent ion exchange

property of the liquid ion exchangers to form suitable

extractable complex species with the metal ionic complexes in

aqueous medium under different experimental conditions. In both

the procedures, similar types of extraction mechanisms are

involved and the methods are complementary to each other as the

experimental results derived from one of the procedures can be

supplementary to each other.

REFERENCE

1. A.M.Yilson, L-Churchill, K.Kiluk and P.Hovsepian, Anal.

Chem, 340, (1962). 203

2. H.Green, Talanta, 20, (1973), 139

3. H.Green, Talanta, 11, (19641, 1561

Dow

nloa

ded

by [

Uni

vers

ity o

f E

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r] a

t 08:

39 1

7 A

pril

2013

370 DAS AND LAHIRI

4. C.F.Coleman, C.A. Blake,Jr. and K.B.Brown, Talanta, ~,

(1962), 297

5. S. N. Bhat t acharyya and B. (Nandi) Ganguly; Solv. & Extr. Ion

Exch., 2(4_~~, (1984), 699

6. J. D. Lee, A New conc i se Inorganic ChemistrJ~~, Van Nostrand

Reinhold Company Ltd., London, (1979), p 295

h P. Chat topadhyay, RadiochemicaJl Separation ~:~ Some Critical

Pairs of Elements Through Solvent Extracti(~ and Reversed

Phase Extraction Chromatograpll~, Ph. D thes:i.es, Submitted

to University of Calcutta, India

~ T.Barun and G.Ghersini (ed.), Extraction ~::hromatography,

Vol-2, Elsevier Scientific publishing Company, Amsterdam,

London, New-York, (1975)

9. I.S.El-Yamani, M.Y.Farah and F.A.Abd EI-Aleim, Talanta,

25, (1978) 523

10. T.Shimizu, Bunseki Kaqaku , 17,. (1968),1187

11. T.Sato and H.Watanabe, Anal. Chim. Acta, ~:~, (1971), 439

12. T.Sato and H.Watanabe, J.lnoqJ.Nucl.Chem, ::!i, (1974),2585

13. P.K.Mishra, V.Chakravortty, K.C.Dash, N.R.Das, and S. N.

Bhattacharyya; J. Radioanal. Nucl. Chem, Articles,

134 (2), (1989), 259

14. P.K.Mishra~ V.Chakravortty, K.C.Dash, N.R.Das, and S.N.

Bhattacharyya; J. Radioanal. Nucl. Chem., Articles,

131(2), (1989), 281

15. T.Sato and H.Watanabe, Anal~ Chim. Acta, (~, (1970), 463

Dow

nloa

ded

by [

Uni

vers

ity o

f E

xete

r] a

t 08:

39 1

7 A

pril

2013


16. I.S.El-Yarnani, M.Y.Farah, and F.A.Abd El-Aleirn, J.

Radioanal. Chern, 45, (1978), 125

17. M.A.Sawant and S.M.Khopkar, Talanta, 27, (1980),209

371

18. C.Djordjevic, H.Gorican and S.L.Tan; J.Less-Cornrnon metals,

11, 1966,342

19. R.Ko, Anal. Chern., 36 (7), 1964, 1290

20. R.Ko, Anal. Chern., 360.1.1., 1964, 2513

21. A.S.Abdel-Gawad, A.A.Abdel-Rassoul, H.B.Maghrawl and She A.

Sherif, Ind. J. Chern., 8, (1970),293

22. N.A.Ivanov, LP.Alirnarin, LI'LGibald and G.F.Bebikh; Izv,

Akd: Nauk, SSSR, ser Khirn, 12, (1970), 2664

23. J.Y.Ellenburg, G.W.Leddicote and r.L.Moore; Anal.

Chern., 26 (6), (1954), 1045

24. G.W.Leddicotte and F.L.Moore, J. Am. Chern. Soc., 74, 1952,

1618

25. G.A.Brodskaya, E.S.Gureev and O.U.Gapurova, Zhur. Struct.

Khim., 30(6), (1988), 769

26. N.R.Das and P.Chattopadhyay, J. Radioanal. I~ucl. Chem,

Articles, 109 (1), (1987), 45

27. R. Pribil and V. Vesely, Talanta, 17, (1970), 801

28. E.Cerrai and C.Testa, Energia Nucleare, ~, (1959), 707

29. C.F.Coleman, K.B.Brown, J.G.Moore and D.J.Crouse, Ind.

Eng.Chem., 50, 1958, 1756

30. H.Green, Brit. Cast. Iron Res. Assoc. J., !J~, (1962), 586

Dow

nloa

ded

by [

Uni

vers

ity o

f E

xete

r] a

t 08:

39 1

7 A

pril

2013

DAS AND LAHIRI

31 F.L. Noore, Anal.Chem., 29, (1957), 1660

E.Cerrai and C. Testa, Anal. Chim. Acta. 23, (1962), 204

B.Floh. A. Abrad and L.Federgruen, 1.E.A- 427, (1976). 10

D.S.Flett and D.W.West. Proc. Int. Solv. Ext. Conf, Moscow,

(1988). Preprint 4., 240

K.Ueno and A.Saito, Anal. Chim. Acta, 56, (1971),427

Z.Malek, D.S.Herova, V-Jedinakova, M.Mrnka and J.Celeda,

Proc. Int. Solv. Ext. Conf. Lyon, France, (19741, 477

R.KO. U. S. At. Energy Comm. Rept, HW-83072. (1964)

J.Shankar, K.S.Venkateswarlu, J.M.La1 and R.Shankar:

Proc. Nucl. Radiation. Chem. Symp.; Bombay, (1964). 11

I.A.Tserkovnitskaya, and T.T.Bykhovtseva, Metody Kolichestv.

Opred. Elementov, Leningr. Gos-Univ, (19641, 101

N.Ishibasi, H. Kohera and K. Fakamachi, Bunseki Kagaku, u. (l968), 1524

G.Ghersini and S.Mariottini, Talanta, 18, (19711, 442

L.V.Zverev, N.V.Petrova and G.N.Mura1, Myneral'n Syr'e,

Vses. Nauchn. Issled. Inst., (1963). 25

N.A. Mymrik and I.M. Gibalo, Vestn. Mosk. ~ n i v . , Khim., 12, (1971). 738

F.L.Moore, Liquid liquid extraction with high molecular

weight amines, National Academy of Science, Nuclear

Science Series, NAS-NS-3101, (1960)

Dow

nloa

ded

by [

Uni

vers

ity o

f E

xete

r] a

t 08:

39 1

7 A

pril

2013


A.N.Nevzorov and L.A.Bychkov. Zhur. Anal. Khim., 19, (1964),

1336

H.Green, Metallurgia, 63. (1963). 143

C Carl Merrill and D.E.Conch. Bureau of mines, Bolder city,

New Boulder city, Metallurggy Research Lab. (19721, 10

I.P.Alimarrin, 1.M.Gibalo and N.A. Mymrik, Vestn. Mosk.

Univ, Ser. Khim, 12, (19711, 457

H. Marchart and F. Hecht, Mikrochim. Acta. (1962)' 1152

C.Djordjevic and D.Sevdic, Croat. Chem. Acta, 39_, (19671,

115

M.A.Hobkin. A.S.De Sousa and E.J.Bielecki, TMS paper No A

71-56, New York, American Institute of Mining,

Metallurgical and Petroleum Engineers (1971)

1.S.El-Yamani, M.Y.Farah and F.A.Abd El-Aleim, Talanta, 23,

(1978). 714

I.P. Alimarin, N.A. Ivanov and I.M.Gibalo, Zh. Anal. Khim,

24, (19691, 1521

I.P. Rube1 and V.A. Nazarenko. Zh. Neorg. Khim, 22, (1976),

2187

V.A.Pronin and V.A. Tayurskii, Zh. Neorg. Khim, 21, (1976),

1288

R. Pribil and J. Adam, Talanta, l8, (1971), 349

59. M.Golinski and W.Korpak, Przemysl Chem. 44, (19651, 312

Dow

nloa

ded

by [

Uni

vers

ity o

f E

xete

r] a

t 08:

39 1

7 A

pril

2013

374 DAS AND LAHIRI

N.R.Das and P.Chattopadhyay, Bull.Chem.Soc.Jpn., 62,

(1989). 3278

V.C.A. Vaughen and E.A.Mason, Equilibrium Extraction 1

Characteristics of Alkyl Amines and Nuclear Fuel

Metals in Nitrate Systems. ORNL sub-contract No 1327.

Massachusetts Inst. of Technology, Summary report 1958 to

1960, AEC report TID-12665, (1960)

J.S Fritz and J.J.Topping, Talanta, 13, (1971). 865

R.K.Biswas, M.Wakihara and Taniguchi , Bangladesh J.Sc.,

23(14), (1988), 86

K.Yakate and S.Minami, J.Inorg.Nucl.Chem., 31, (1975). 1973

D.Richter and H.Grosse-Ruyken, Theory Struct. Complex

Compounds, papers, sym, Poland, (1964). 457

J. Mikulski, Nukleonika, 11, (1966). 57

G.M.Vol'dman, O.A.Sotnikova, E.A.Mironova and N.I.Gavrilov,

Russ. J.Inorg.Chem.,29(8), (19841, 1175

G.S. Katykhin, 15th Conf. Nucl. Spectroscopy, Moskow-

Leningrad, (1963), 28

E.M.Scadden and N.E.Ballou, Anal. Chem., 2 5 0 . (1953).

1602

C.J.Hardy and D.Scragil1, J. Inorg. Nucl. Chem., 4., (1957),

334

T.Sato, Anal. Chim. Acta, 52, (1970), 183

N.R.Das. B.Nandi and S.N.Bhattacharyya, J. Radioanal.

Chem., 62(1-2). (1981), 53

Dow

nloa

ded

by [

Uni

vers

ity o

f E

xete

r] a

t 08:

39 1

7 A

pril

2013

LIQUID I O N EXCHANGERS 375

N.R.Das, B.Nandi and S.N.Bhattacharyya, Anal. Chim. Acta.

159, (1984). 256

N.R.Das, B.Nandi, S.N.Bhattacharyya, Int. J. Appl. Radiat.

Isot., 32, (1981). 205

S.N.Bhattacharyya and B.(Nandi) Ganguly. J. Radioanal.

Nucl. Chem., Articles, , 9 8 0 , (1986), 247

C.Djordjevic and X.Gorican, J.Inorg.Nucl.Chem, 28, (1966),

1451

O.Navrati1, J. Inorg. Nucl. Chem., 29. (1967), 2007

Y.B.Kletenik, I.A. Bykhovskaya and L.V.Sekretova, Zh. Anal.

Khim. 24, (l969), 707

B.N.Laskorin. V.S.Ul'yanova and R.A.Sviridova. Zh.Prik1.

Khim (Leningrad), 35, (19621, 2409

T.S.Urban'ski, M.Chojecki and R.Kaczynlska, J.Radioana1

Chem., 30, (1976), 369

83. A.A.Palant and V.A.Rejnickenko, J.Appl.Chem, USSR, 45,

(1973). 1124

84. A.N.Zelikman and V.M.Nerezov, Zh.Neorg.Khim, 14, (1969). 1307

85. T.D.Titkova and V.I.Levin, Radiokhimiya, 12, (1969), 1307

86. V.L.Bychovtsov, Radiokhimiya, 12, (19711, 657

Dow

nloa

ded

by [

Uni

vers

ity o

f E

xete

r] a

t 08:

39 1

7 A

pril

2013

DAS AND L A H I R I

F.Cerrai and G.Ghersini, J.Chromatogr., 24, (1966). 383

A.N.Zelikman. Molybdenum (in Russian), Atomizdat, tfoscow,

1972

1.L.Jenkines and A.G.Wain, J.Appl.Chem, l4, (1964), 449

S.M.Karpacheva, V.S.Smelov, Y.I.Vershehagin, 1.V.Davydov.

V.T.Moskaleva, M.N.Ryzhov and A.V.Strakhova, Zh. Neorg.

Khim, (1967). 1925

R.Caletka and V.Krivan, Fresenius Z. Anal. Chem. 332, (1989). 866

M.Kyrs, V.Jedinakoval, and R.Caletka. Collect. Czech. Chem.

Commun., 30, (19651, 2179

93. N.P.Rudenko, 1.M.Kremenskaya and V.N.Aviline, Russ.

Inorg. Chem., ll, (1966). 511

94. M.Kyrs, Radiochim. Acta, 2, (1964), 202

95. M.Kyrs, P.Selucky and R.Pistek, Russ. J. Inorg. Chem.,

(l965), 1499

96. M.Novak and A.Have1, J. Inorg. Nucl. Chem., 29, (1967). 531

97. G.Kh.Efendiev and R.A.Alekperov, Agreb. Khim. Zh., 5 , (l962), 117

98. G.Kh.Efendiev and R.A.Alekperov, Radiokhimiya, l0, (1968).

241

99. 1.V.Pyatnitskij and V.I.Simonenko, Orqanicheskie,

Reagentrv, Analitiches KO] Khimii, Chast I, INIS-mf 4039,

Kiev, (19761, p 128

Dow

nloa

ded

by [

Uni

vers

ity o

f E

xete

r] a

t 08:

39 1

7 A

pril

2013


A.K.Dey and U.S.Ray. Sepr. Sci., 6, (1971). 25

F.K.Cole and L.H.Brown, Ind. Eng. Chem., 51, (1959). 38

J.C.White and R.F.Apple, U.S.A.E.C. Report, TID-7568.

Pt.-1, (1958), p 105

F.Miller, Talanta, 21(7), (1974), 685

W.Fisher and W.Chalybaens, Z. Anorg. U. Allgem. Chem., 2 5 4 .

(l974), 79

R.Bock and E.Bock, Z. Anorg. U. Allgem. Chem., 263, (19501,

146

N.M.Adamskii, S.M.Karpacheva and A.M.Rozen, Estraktsiya

Teoriya Primenenie Apparature Sb. Statei., 2, (19621, 80

N.I.Mikhajlichenko, L.D.Skrylov, Zh. V. Petrenko and

M.V.Mokbosoev, Izv. Vyssh. Uchebn. Zavod Khim.

Tekhnol., 22. (1974). 14

L.D.Skryley, Zh.V.Petrenko, N.I.Mikhajlichenko and

M.V.Mokbosoev, Izv. Vyssh. Uchebn. Zavod Khim. Tekhnol.,

17, (1974). 1338

V.B. Tikhomirov, Dolk. Akad. Nauk. SSR, 139, (1961). 1416

R.A.Alekperov, and N.N.Makov, Radiokhimiya, 13, (1968). 241

R.A.Alekperov. N.G.Efendieva and S.S.Geibatova, Azerb.

Khim. Zh., 5, (1968), 96

M. J.Heark, M. Jamko and K.Blazevic, Croat. Chem. Acta.. 41,

(1969). 85

A.K.Dey and U.S.Ray, Sepr. Sci., 1, (1972), 419

Dow

nloa

ded

by [

Uni

vers

ity o

f E

xete

r] a

t 08:

39 1

7 A

pril

2013

378 DAS AND LAHIRI

114. P.H. Tedesco, V.B.De Rumi and J.A.G.Quintana, J. Inorg.

Nucl.Chem., 29, (19671, 1307

115 C.J.Hardy and D.Scargil1, J. Inorg. Nucl. Chem., lJ, (1961),

337

116 G.A. Yagodin and V.V. Tarasov, Radiokhimiya, 120, (1970), 664

117 G.A. Yagodin and V.V. Tarasov, Radiokhimiya, 12(4), (19701,

666

118 T.V.Healy, Radiochim Acta, 2 , (1963), 52

119 J.W.Ardan, UKAEA, Report AERE-Am, (1963), 97

120 J.L.Carbonnier and K. Tiradar, Compt Rend. 281(22), (1975).

901

121 V.J.Ross and J.C.Vhite, ORNL, AEC Report. ORNL-CF-57-2-37,

(1957).

122. G.E.Kaplan, E.D.Noiseen, L.P.Dmitrieva and S.A.Kostotshkine

Ekstrahtshia, Part I, Atomizhdat, Moscow, (19621, 117

D.F.Peppard and J.R.Ferraro, J.Inorg.Nucl.Chem, 10, (19591, 275

G.I.Smirnov, G.G. Mineev and A.S.Chevnyak, Zh. Prikl. Khim,

SO(lO). (1977). 2179

P.I.Artyukhin, E.A.Startseva, I.L. Kotlyarevskii and Z.M.

Bobrova, Izv.Sib.Otd.Akad, Nauk, SSSR. No-9, Ser khim Nauk,

No-4, (19711, 131

126. I.H.Qureshi, L.I.Mc Cledon and P.D.La Fleur, Radiochim.

Acta. 12, (l969), 107

Dow

nloa

ded

by [

Uni

vers

ity o

f E

xete

r] a

t 08:

39 1

7 A

pril

2013


127 Z. Kolank. Proc. Int. Solv. Ext. Conf., Vol I and 11,

London, Chemical Society Industry, (19711,

129. F.Marsh, 155th ACS National Meeting, San Fransisco. 1968

130. V.V.Fomin and S.A.Popatova, Zh. Neorg. Khim, 12, (19671,

530

131. O.Navrati1, Collect. Czech. Chem. Commun. 42, (1977). 2140

132. D.H.Liem, Acta Chem. Scand.. 2 5 0 , (1971), 301

133. D.H.Liem, Acta Chem. Scand. 2 5 0 , (1971). 277

134. M.M.Privalova and V.F.Konovalova, Zh. Neorg. Khim, 10, (1965). 251

135. V.A.Sheka and E.I.Sinyavskaya, Zh.Neorg. Khim,?, (1964). 1974

136. R.Denig, N.Trautmann and G. Herrmann, J. Radioanal. Chem.,

6, (1970), 331

137. J.J.Mccown and L.P. Larsen, Anal.Chem., 26, (19601, 596

139. C.Djordjevic, H.Gorican and S.L.Tan, J.Inorg.Nucl.Chem,

29, (19671, 1505

140. K.Rimuria, Bull. Chem. Soc. Jpn., 3 3 0 . 1960. 1038

141. C.A.Blake, K.B.Brown and C.F.Coleman, ORNL, AEC Rept.,

ORML-1903. 1955

142. R.Denig, Inst. for Inorganic and Nuclear Chemistry, Univ,

Maniz, BRD (FRG), Thesis, (1967), 185

Dow

nloa

ded

by [

Uni

vers

ity o

f E

xete

r] a

t 08:

39 1

7 A

pril

2013

380 DAS AND LAHIRI

143. 1.Stronski. Radiochem. Radioanal. letters, 10, (1969). 191

144. E.A.Huff and S.A.Kulpa, Anal. Chem., 38(7), (1966), 939

147. Y.Cheng, Q.Huang, G.Quis. Fenxi Huaxue, ll(11). (1983), 813

148. M.N.Sastri, A.P.Rao and A.R.K. Sharma, Ind. J. Chem, 4.,

(1966). 287

149. T.Shimizu and K.Ikada, J.Chromatog.. 85, (1973), 123

150. E.Cerrai and C.Testa, J.Chromatog., 6, (1961), 443

151. 1.B.Pierce and V.M.Henry, J.Chromatog., 23, (19661,457

153. L.S.Bark, G.Duncan and R.J.T.Graham, Analyst, 92, (1967).

31

154. L.S.Bark, G.Duncan, and R.J.T.Graham, Analyst, 92, (1967),

347

155. 1.P.Alimarrin. I.M.Gibalo, and N.A. Mymrik. Vestn. Mosk.

Univ, Ser. Khim, 13, (1972). 435

156. R.Denig, N.Trautmann and G. Herrmann, J.Radioanal. Chem.,k,

(1970). 57

157. N.R.Das and Sushanta Lahiri, Communicated

Dow

nloa

ded

by [

Uni

vers

ity o

f E

xete

r] a

t 08:

39 1

7 A

pril

2013


158. N.R.Das and Sushanta Lahiri, Communicated

159. E.L.Smith and J.E.Page, J. Sac. Chem. Ind. 67, (1948), 48

Received by Editor

October 26, 1990

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liquid ion exchangers and their uses in the separation of zirconium, niobium, molybdenum, hafnium,...

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