J.RADIOANAL.NUCL.CHEM.

,LETTERS 96 /5/ 471-480 /1985/

A STUDY ON THE SOLVENT EXTRACTION OF Se/IV/ WITH

2 - M E R C A P T O B E N Z O T H I A Z O L E INTO CHLOROFORM

R.K. Itawi, Z.R. Turel

Nuclear Chemistry Division,

The Institute of Science,
Bombay - 400 032, India

Received 17 July 1985

Accepted 23 July 1985

The e x t r a c t i o n of Se/IV/ from h y d r o c h l o r i c

acid m e d i u m w i t h 2 - m e r c a p t o b e n z o t h i a z o l e / 2 - H M B T
into chloroform has been studied. The effect
of various parameters on the e x t r a c t i o n coef-
ficient value such as molarity of hydrochloric
acid, time of equilibration, effect of cations
and anions etc., has been evaluated. The
s t o i c h i o m e t r y of the extracted species was
determined by the method of substoichiometric
extraction and slope ratio m e t h o d and was
found to be 1:4. D e c o n t a m i n a t i o n factors for
many elements in the s u b s t o i c h i o m e t r i c ex-
traction of Se/IV/ was also obtained.

INTRODUCTION

2-HMBT has b e e n used for the extraction and spectro-

photometric d e t e r m i n a t i o n of Se/IV/ from an acid m e d i u m
1-3
into c h l o r o f o r m The aim of the present work is to
develop a rapid and selective method for the extraction
of m i l l i g r a m amounts of Se/IV/ with 2-HMBT with a view
to use it for radiochemical separation of 75Se from neutron

1 ~1 E~evier Sequo~ ~ A., Lausan~

Akaddm~ Kiad6, Budap~t
ITAWI, TUREL: EXTRACTION OF Se]IV/

irradiated samples. 75Se was used as a tracer for develop-

ing the method. Ideal conditions'for the extraction have
been established.

EXPERIMENTAL

Chemicals and rea@ents

75Se and the isotopes used for studying the inter-

ference of the other elements were supplied by the Iso-
tope Group of The Bhabha Atomic Research Centre, Trombay.
Stock solution of selenium/IV/ was prepared by dissolving
selenium dioxide in IM HCI solution. Solution of cations
and anions were prepared by dissolving the appropriate
salts in distilled water. The strength of these solutions
were determined by the standard methods given by Vogel 4.
2-HMBT of BDH made was used without further purification.
All the chemicals and reagents used were of A.R. Grade.

Instrumentation

B-Emitters were counted on a y-ray spectrometer in

conjunction with 3.5x3.5 cm NaI/TI/, well-type detector.
8-Emitters were counted on a thin end-window G.M. counter
in conjunction with a decade scaler, high voltage unit
and timer. 75Se was counted on a y-ray spectrometer at
the channel corresponding to the 0.268 MeV peak of 75Se.
Peak-area method was employed.

Extraction procedure

15 ml of aqueous solution containing 1.O2 mg of Se/IV/

labelled with 75Se/IV/ was taken in a separatory funnel.
The acid concentration was adjusted with HCI and the
mixture was equilibrated for 1.0 min w i t h 15 ml of 1%
2-HMBT in chloroform. A 2-ml aliquot of the organic and

472
 ITAWI, TUREL: EXTRACTION OF Se/IV/

the aqueous phase was taken for counting on a y-ray spectro-

meter. The extraction coefficient value was calculated
with the help of the equation given below:

E = A c t i v i t y of 2-ml aliquo t of the organic phase

A c t i v i t y of 2-ml aliquot of the aqueous phase

The stoichiometry of the extracted species was determined

by the method of the substoich~ometric extraction which
was carried out as given below: Increasing amounts of
Se/IV/ labelled with 75Se in 15 ml of 5.7M HCI solution
were taken in a series of separatory funnels, and equi-
librated with 15 ml of c h l o r o f o r m c o n t a i n i n g 18 m g of
2-HMBT for 3.0 min. A 2-ml aliquot of the organic phase
was taken for counting. The slope ratio method involved
the extraction of m i c r o g r a m amount of 75Se/IV/ from 5.7M
HCI with d i f f e r e n t amounts of 2-HMBT in c h l o r o f o r m and
nitrobenzene.

RESULTS AND DISCUSSION

The effect of the molarity of HCI and pH on the ex-

traction coefficient value of Se/IV/ was studied and it
was found that the %E was better than 99% over a HCI
molarity range of 5.6-5.9. A m a x i m u m E value of 238 was
obtained at an acidity of 5.7M HCI /Table i/.
The effect of time of equilibration on the E value of
Se/IV/ was studied. An E value of 311 was obtained with
an e q u i l i b r a t i o n time of 3.0 min. The %E was found to be
better than 99% over an equilibration time of 1.0-7.O
min /Fig. i./.
The extraction coefficient value of Se/IV/ w i t h 1%
solution of 2-HMBT in different solvents showed that

l* 473
ITAWI, TUREL: EXTRACTION OF Se/IV/

TABLE 1

Effect Of molarity of HCI and pH on the extraction co-

efficient of Se/IV/ w i t h 2-HMBT into chloroform.
Aqueous phase = 15 ml of XM HCl containing 1.02 mg of
Se/IV/ labelled with 75Se. Organic phase = 15 ml of 1%
2-HMBT in chloroform. Temperature = 28+2 ~ Time of
equilibration: 1.0 min

Molarity of HCI E %E

1.0 2.3 70.50

2.0 7.8 88.66
3.0 9 .O 90.O1
4.0 i0 91.23
5.0 12 92.64
5.3 20 95.25
5.6 131 99.24
5.7 230 99.56
5.7 256 99.62
5.7 227 99.56
5.9 129 99.23
6.0 96 98.96
7.0 5.0 83.60
8.0 3.5 77.87
9.0 0.95 48.71
i0.0 0.93 48.18

2.0 0.12 10.95

5.0 0.21 17.62
7.0 0.68 40.54
8.0 0.89 47.14

chloroform, pentane-l-ol and nitrobenzene can be used for

the quantitative extraction of Se/IV/. E value was found
to decrease in the order given below:

474
 ITAWI, TUREL: EXTRACTION OF Se/IV/

o~ 100
,%

uJ
80

60

40

0 1 2 3 4 5 6
Equitibration time ~min

Fig. i. Effect of time of e q u i l i b r a t i o n on the % ex-

traction of Se/IV/ w i t h 2-HMBT into chloroform.
Aqueous phase = 15.O ml of 5.7M HCI c o n t a i n i n g
1.02 mg Se/IV/ labelled with 75Se. Organic phase =
15.O ml of 1% 2-HMBT in chloroform. Temperature =
28+2 ~

Chloroform >> pentane-l-ol > nitrobenzene > 1,2-di-

E = 311 126 102 83
chlorobenzene > benzene > heptane-l-ol > methyl iso-
E = 76 48 29
butyl ketone > amyl acetate > ethyl acetate > diethyl
E = 15 14 3.4
ether.

No phase separation was obtained w i t h iso-propyl alcohol,

butane-l-ol and nitromethane. The reagent was found to
be insoluble in carbon tetrachloride, ethyl methyl ketone,
diethyl glycole, xylene, cyclohexane and octanol.
The effect of sodium, p o t a s s i u m or a m m o n i u m salts on
the % extraction of Se/IV/ was determined and it was
found that i00 mg each of borate, chloride, fluoride,
bromide, cyanide, sulphate, phosphate, hypophosphite,
nitrate, carbonate, acetate, tartrate, citrate and oxalate,
50 mg of EDTA, 25 mg each of bromate, periodate and sul-

475
ITAWI, TUREL: EXTRACTION OF Se]IV/

phite, iO mg of chromate and chlorate does not lower the

%E of Se/IV/. The interference of sulphide, thiosulphate,
iodide, nitrite, thiocyanate and thiourea were remoyed
by expelling them with nitric acid prior to the ex-
traction of Se/IV/.
Of the ions studied Cr/VI/, CI/I/, Cs/I/, Mn/II/, Co/II/
Ce/IV/, Sb/V/, In/III/, S/VI/, Ru/III/, Sb/III/, and
Ca/II/ were extracted to less than O.1%. Eu/III/, Zn/II/,
Ba/II/, TI/I/, Ce/III/, Sn/II/, P/V/, Sn/IV/, Ir/IV/,
Rb/I/, Na/I/ and Cr/III/ were extracted to less than 1%.
Ni/II/, Cd/II/, W/VI/ and Sc/III/ were extracted to
less than 4%. Ag/I/, Pd/II/, Hg/II/ and Au/III/ were
extracted between 50 and 99%. Ag/I/ was removed as AgCI,
Pd/II/ and Hg/II/ were removed by precipitation of metal-
lic Se with SO 2 water from acidic solution, Au/III/ was
removed by precipitation as metallic Au by oxalic acid
from a cold neutral solution.
The stoichiometry of the extracted species was deter-
mined by the method of substoichiometric extraction and
it was found that the ratio of Se/IV/: 2-HMBT was 1:4
/Fig. 2./. This stoichiometry was further supported by
the slope ratio method. The plot of ig /HR/ vs. ig /E/
gave a straight line with a slope of 4.0. Chloroform
and nitrobenzene were the extracting solvents /Fig. 3./.
Decontamination factors for many elements were de-
termined by substoichiometric extraction of Se/IV/ and
found to be better than 105 for most of the elements
/Table 2/.
1.O2 mg of Se/IV/ can be back-extracted into 5 ml
concentrated nitric acid. The recovery of Se/IV/ was
found to be better than 97%. The reproducibility of
the method was 3.5%.

476
 ITAWI, TUREL: EXTRACTION OF Se]IV/

O O

o 61 / 5e(IV): 2-HMBT
"~ 4 F /' 1:4

0 1 2 3 4 5 6
75Se(IV) ,, mg

Fig. 2. S u b s t o i c h i o m e t r i c e x t r a c t i o n of Se/IV/ w i t h
2-HMBT into c h l o r o f o r m .
A q u e o u s ~ h a s e = 15 ml of 5.7M HCI c o n t a i n i n g
x mg of 5Se/IV/. O r g a n i c p h a s e = 15 ml of chlo-
r o f o r m c o n t a i n i n g 18 mg of 2-HMBT. Eq. time =
3.0 min. T e m p e r a t u r e = 28~2 ~

- I o,~ i /~
,l--gJ

--2 --'
Lg [ HR]

Fig. 3. E x t r a c t i o n of Se/IV/ w i t h 2 - H M B T into c h l o r o f o r m .

A q u e o u s phase = 15 ml of 5.7M HCI c o n t a i n i n g
15.24 ug of 75Se/IV/. O r g a n i c phase = 15 ml chlo-
r o f o r m c o n t a i n i n g x mg 2-HMBT. Eq. time = 3.0
min. T e m p e r a t u r e = 28+2 ~

477
ITAWI, TUREL: EXTRACTION OF Se/IV/

TABLE 2

Decontamination factors for different elements in the

substoichiometric extraction of Se/IV/ with 2-HMBT
into chloroform.
Aqueous phase: 15 ml of 5.7M HCI solution containing
3 mg of Se/IV/ + isotope of the element concerned.
Organic phase: 15 ml of chloroform containing 18 mg
of 2-HMBT. Time of equilibration: 3.0 min. Temperature:
38+2 ~

D.F. > Elements

106 In/III/b.
105 Cd/II/a, Cs/I/a, Mn/II/a, Eu/III/b, Cs/I/b,
Mn/II/b, Zn/II/a, Sa/II/a, Co/II/a, Zn/II/b,
Ba/II/b, Co/II/b, Ce/III/a, Ce/IV/a,
Sn/II/a, Ce/III/b, Ce/IV/b, P/V/b, S/VI/a,
P/V/a, S/VI/b, Ru/III/a, Rb/I/a, Ru/III/b,
Rb/I/b, Ca/II/a, Na/I/a, Na/I/b, xPd/II/a,
Cl/I/a, Cr~III/a, Cr/III/b, Cr/IV/a,
Cr/VI/b, Sb/V/a, Sb/V/b, Tl/I/a, Tl/I/b,
XAu/III/a.
104 XHg/II/a, Sn/II/b.
103 W/VI/a, W/VI/b, Ir/IV/b, Ca/II/b, nAg/I/a,
Sb/III/a, Sb/III/b, Ir/IV/a, Sn/IV/a,
Sn/IV/b.
102 Sc/III/b, Pd/II/a, Pd/II/b.

Less Hg/II/a, Hg/II/b, Ag/I/a, Ag/I/b, Au/III/a,

than
Au/III/b.
10 2

a = with carrier.
b = without carrier.
XD.F. = after separation.

478
 ITAWI, TUREL: EXTRACTION OF Se/IV/

REFERENCES

1. R. Doicheva, V. Angelova, Cr. Acad. Bulg. Sci., 25

/1972/ 1359.

2. E. Ramanauskas, A. Suliuniene, Khim. Teknol., iO

/1969/ 25.

3. B.C. Bera, M.M. Chakraburtty, Analyst, London, 93

/1968/ 50.

4. A.I. Vogel, Textbook of Inorganic Quantitative

Analysis, Longmans, Green and Co. Ltd., London, 1975.

479