Journal of Saudi Chemical Society (2011) 15, 177–185

King Saud University

Journal of Saudi Chemical Society

www.ksu.edu.sa
www.sciencedirect.com

ORIGINAL ARTICLE

Sequential separation of selenium(IV) from tellurium(IV)

by solvent extraction with N-n-octylaniline: Analysis
of real samples
Balasaheb M. Sargar, Sandip V. Mahamuni, Mansing A. Anuse *

Analytical Chemistry Laboratory, Department of Chemistry, Shivaji University, Kolhapur, India

Received 12 May 2010; accepted 14 August 2010

Available online 19 August 2010

KEYWORDS Abstract A simple solvent extraction study of selenium(IV) was conducted. Selective and
Extraction; quantitative extraction of selenium(IV) by N-n-octylaniline in xylene occurred from 0.4 to 0.6 M
Selenium(IV); hydrochloric acid medium. Selenium(IV) was back extracted with 1:1 ammonia. The effect of
N-n-octylaniline; concentration of acid, N-n-octylaniline, the role of various diluents, stripping agents, loading
HCl medium; capacity of N-n-octylaniline, equilibrium time, aqueous to organic volume ratio on the extraction
Real sample analysis of selenium(IV) was studied. Selenium(IV) was extracted into the organic phase by ion-pair

formation complex as ½RR0 NHþ 2 HSeO3 ðorgÞ : The method is free from interferences due to
commonly associated elements and permits the separation of selenium(IV) from tellurium(IV) as
well as other metal ions. It was used for the determination of selenium(IV) in synthetic mixtures,
synthetic mixtures corresponding to alloys and pharmaceutical samples.
ª 2010 King Saud University. Production and hosting by Elsevier B.V.
Open access under CC BY-NC-ND license.

1. Introduction

The largest use of selenium worldwide is in glass and ceramic

manufacturing. The major consumer of selenium is the
* Corresponding author. Tel.: +91 231 2693487; fax: +91 231 electronic industry. It is well known that selenium is both an
2692333. essential and toxic trace element for man and animals with an
E-mail address: [email protected] (M.A. Anuse). upper intake limit of 400 lg/day of selenium (Fishbein, 1984).
Very few extraction methods of selenium(IV) are available in
1319-6103 ª 2010 King Saud University. Production and hosting by
the literature. The extraction of selenium(IV) with kerosene solu-
Elsevier B.V. Open access under CC BY-NC-ND license.
tion of N1923 from hydrochloric acid medium was studied by
Peer review under responsibility of King Saud University. Zhixian et al. (1998a,b), using n-octanol for the prevention of
doi:10.1016/j.jscs.2010.08.001 emulsification. The conditions of formation and extraction of
ion association in selenium(IV)-iodide/bromide-ions-N,N0 -dime-
thylinedodicarbocyanine organic solvent system were studied
Production and hosting by Elsevier
(Balog et al., 2000). Selenium species present in yeast samples
were extracted using pressurized liquid extraction (PLE). The
178 B.M. Sargar et al.

Table 1 Comparative study of proposed research work with other reported methods.
System Aqueous Organic phase Special features Author
phase
N-1923 (primary amine) Chloride Kerosene  Emulsion formation Zhixian et al.
 n-Octanol used to prevent emulsification
HCl –  98% efficiency Zhixian et al.
N,N0 -Dimethylinedodicarbocyanine pH, 4–9 Toluene  Analysis of semi-conductor film Balog et al.
Pressurized liquid extraction (PLE) PLE cell –  Selenium recovery influenced by time, Gómez-Ariza et al.
temperature and solvent
 Recovery of selenium from yeast samples
Toluene Sulphate- Toluene in the  Detection limit 0.005 g/L Torgov et al.
bromide presence of 1-hexene
2,3,5-Triphenyltetrazolium Thio-cyanate Cyclohexanol toluene  Stripping by sodium hypobromite Ramesh et al.
chloride  Analysis of copper concentrates,
incineration ash and In-Sb alloy samples
Tri-n-butyl phosphate (TBP) 3–5 M HCl Kerosene  Extraction endothermic in nature Chowdhury et al.
4.5 M HCl Polar and  Effect of dielectric constant Chowdhury et al.
non-polar diluents and polarity was studied
Di-ammonium calix [4] arene pH, 2.6 Chloroform  Increase in pH or addition of Aeungmaitr-epirom
decanol in chloroform decreases extraction et al.
 Interference of chromium
Polyether foam sorbents HCl, 4 M –  Separation from tellurium Stewart et al.
+ NaBr, 2 M  Two hours equilibration time
1-Hexene Perchlorate- Hexene  Determination of total selenium Torgov et al.
bromide in natural water, plant and soils

recovery of selenium was influenced by time, temperature and 2. Experimental

solvent (Gómez-Ariza et al., 2004). The solvent extraction of sele-
nium with toluene (or in the presence of 1-hexene) from sulphate 2.1. Apparatus
(perchlorate)-bromide (chloride) solutions was proposed (Tor-
gov et al., 1999). 2,3,5-Triphenyltetrazolium chloride was used A Model SL-171 digital spectrophotometer (Elico India Lim-
as an extractant for the quantitative extraction of selenium(IV) ited, Hyderabad) with 1 cm quartz cells was used for absor-
from thiocyanate medium using 1:1 cyclohexanol–toluene sol-
vent mixture. The method permits separation of selenium(IV)
from tellurium(IV) (Ramesh and Subramanian, 1998).
Organophosphorus compound tributyl phosphate (TBP) 1.2
was used as an extractant for selenium(IV). The separation
of selenium(IV) from tellurium(IV) using 1.1 M TBP in kero-
sene as an extractant was investigated, in which 10 M initial
acid concentration was required for the extraction of sele- 1
nium(IV) (Chowdhury and Sanyal, 1993, 1994).
The extraction of selenium(VI) using di-ammonium calix [4]
arene was investigated (Aeungmaitrepirom et al., 2001). It was
0.8
shown that selenium(VI) was extracted into chloroform as
   2
(LH2þ 2þ
2 , Cl , HSeO4 ) and [(LH2 Þ2 , 2Cl , SeO4 ] species at
Absorbance

pH 2.6. However the selenium(VI) extraction was drastically

decreased with increase in pH. The sorption of selenium(VI) 0.6
from 2.0 to 4.0 M hydrochloric acid solution was quantitative
by polyether foam but requires 2 h for complete extraction
(Stewart and Chow, 1993). Selenium(IV) was preconcentrated
from 2- to 40-fold using the selective extraction with 1-hexene 0.4
from a perchlorate-bromide medium as an organoselenium
compound (Torgov et al., 1998).
N-n-octylaniline was used for the extraction of tellu-
0.2
rium(IV) from hydrochloric acid media (Sargar and Anuse,
2001). In continuation of this work, N-n-octylaniline can be
used for the extraction of selenium(IV) from dilute hydrochlo-
ric acid media. The method is simple, selective, rapid and free 0
from the limitations described earlier (Table 1). It offers 0 10 20 30 40 50 60 70 80
sequential separation of selenium(IV) from tellurium(IV). Se(IV), μg/mL
The method is applied for the analysis of real samples such
as alloys and pharmaceutical samples. Figure 1 Calibration curve of Se(IV)-40 -bromo PTPT complex.
Sequential separation of selenium(IV) from tellurium(IV) by solvent extraction 179

bance measurements, pH measurements were carried out using 178 C at 25 mm pressure (found C, 82.1; H, 11.4; C14H23N re-
digital pH meter, model Li-120 (Elico India Limited, quires C, 81.9; H, 11.3%). The density of N-n-octylaniline was
Hyderabad). found to be 0.89 g/cm3. The p-toluensulphonyl derivative crys-
tallized from alcohol in fan-shaped clusters of needles, m.p.
2.2. Reagents 42–43 C (found: N, 4.1; C21H29O2NS requires N, 3.8%). Pro-
ton resonance assignment for the pure product was made using
A stock solution of 1 mg mL1 selenium(IV) was prepared by TMS as an internal standard and chemical shift was expressed
dissolving 1.404 g of selenium dioxide (Fluka) in concentrated in d values. PMR (CCl4, 90 MHz, Fig. 1): 0.9 (3H, t, CH3), 1.3
hydrochloric acid (11.1 M) and diluted to 1000 mL with water. (12H, br, s, –(CH2)6–), 3.0 (2H, t, –NH –CH2), 3.38 (3H, s, –
From this, a working solution of 400 lg mL1 selenium(IV) NH–), 6.5 (5H, m, Ar-H). The purity of the product was
was prepared by suitable dilution with water; and standardized checked by thin layer chromatographic technique.
with SO2 method (Vogel, 1961). 1-(40 -Bromophenyl)-4,4,6-trimethyl-1,4-dihydropyrimidine-
N-n-octylaniline was prepared by the method of Gardlund 2-thiol (40 -bromo PTPT) was prepared from 4-bromoaniline
et al. (1973) and its solution (0.15 M) was prepared in xylene. (Mathes, 1953). The purity of 40 -bromo PTPT has been
The N-n-octylaniline, after synthesis, was distilled and checked determined by non-aqueous titration of the thiol group using
for its purity on the basis of B.P., TLC and spectral analysis. Azo-violet (p-nitrophenyl-azoresorcinol) indicator, according
The yield and boiling range were as follows: 98.5%, 177– to the method of Verma (1975). A 10 mL of a 0.02 M solution

400 μg Se(IV)
Adjust the acidity to 0.5 M HCl in a total volume of 25 mL and extract with
10 mL 0.15 M N-n-octylaniline in xylene for 3 min.

Aqueous phase Organic phase

Reject Se(IV)

Strip with 1:1 ammonia

(2 × 10 mL) for 5 min

Evaporate the aqueous phase to

moist dryness and leach with dilute
hydrochloric acid

Adjust the acidity to 5.5 M HCl in a total volume of 25 mL and shake with
10 mL 0.02 M 4’-bromo PTPT in chloroform for 4 min.

Aqueous phase Organic phase

Reject Se(IV)
Collect in a 10 mL standard
flsk, made upto the mark with
chloroform, if necessary.
Measure the absorbance of
the extracted complex at 350
nm against reagent blank The
amount of selenium(IV) was
computed from the
calibration curve

Flow chart diagram 1

180 B.M. Sargar et al.

of 40 -bromo PTPT in chloroform was used for the determina- hydrochloric acid and diluted to 25 mL with water. The solu-
tion of selenium(IV) (Kolekar and Anuse, 1998a,b). All chem- tion was transferred into 125 mL separatory funnel. The aque-
icals (s.d. fine, India) used were of A.R. grade. Double distilled ous phase was shaken with 10 mL of 0.15 M N-n-octylaniline
water was used throughout. solution in xylene for 3 min. The phases were allowed to sepa-
rate and the metal from the organic phase containing the ex-
2.3. General procedure for the extraction and determination of tracted ion-pair complex of selenium(IV) was equilibrated
selenium(IV) with two 10 mL portions of 1:1 ammonia, in order to back
strip. The back stripped solution was evaporated on hot plate
An aliquot containing 400 lg of selenium(IV) in a 25 mL vol- to moist dryness to remove excess of ammonia and leached
umetric flask was made to 0.5 M by adding 1.1 mL conc. with dilute hydrochloric acid; and selenium(IV) was estimated

Table 2 Extraction, separation and determination of selenium(IV) and added metal ions from binary mixtures.
Metal ion Amount taken (lg) Average recovery* (%) R.S.D. (%) Method of estimation of added metal ion
Se(IV) 400 99.6 0.4
Te(IV) 100 99.7 0.3 40 -Bromo PTPT
Se(IV) 400 99.5 0.5
Sb(III)a 300 99.7 0.3 Iodide
Se(IV) 400 99.7 0.3
Pb(II) 35 100.0 0.0 PAR
Se(IV) 400 99.7 0.3
Ge(IV)b 400 100.0 0.0 Phenyl fluorone
Se(IV) 400 99.7 0.3
Sn(IV) 400 99.6 0.4 Pyrocatechol violet
Se(IV) 400 99.7 0.3
Bi(III) 300 99.5 0.5 40 -Bromo PTPT
Se(IV) 400 99.7 0.3
Cu(II) 400 99.6 0.4 40 -Chloro PTPT
Se(IV) 400 99.7 0.3
Mo(VI) 30 100.0 0.0 Thiocyanate
*Average of six determinations.
a
Prior extraction of Sb(III) from 3 M HCl in the presence of 400 mg fluoride.
b
Masked with 400 mg fluoride.

400 μg Se(IV) + 100 μg Te(IV)

Adjust the acidity to 0.5 M HCl in a total volume of 25 mL and extract with
10 mL 0.15 M N-n-octylaniline in xylene for 3 min.

Aqueous phase Organic phase

Te(IV) Se(IV)
Reduce the volume of aqueous phase
adjust the HCl concentration to 7.5 M and Strip with 1:1 ammonia
extract with 2 × 10 mL of 0.15 M N-n-octylaniline (2 × 10 mL) for 5 min

Aqueous phase Organic phase Te(IV) Evaporate to the aqueous phase

Reject moist dryness, determine with
Strip with 1:1 ammonia 4′-bromo PTPT method at
λ max 350 nm
Evaporate to moist dryness and
determine with 4′-bromo PTPT
method at λ max 400 nm

Flow chart diagram 2 Separation scheme.

Sequential separation of selenium(IV) from tellurium(IV) by solvent extraction 181

spectrophotometrically with 40 -bromo PTPT at 350 nm tory funnel and shaken for 4 min with 10 mL 0.02 M 40 -bromo
(Kolekar and Anuse, 1998a,b) (Flow chart diagram 1). PTPT in chloroform. After allowing the two phases to sepa-
rate, the organic phase was collected in a 10 mL standard flask
2.3.1. Determination procedure for selenium(IV) and made up to the mark with chloroform, if necessary. The
The back stripped solution after leaching was made to 5.5 M absorbance of the extracted complex was measured at
by adding 12.4 mL conc. hydrochloric acid in a total volume 350 nm against reagent blank prepared similarly. The amount
of 25 mL. The solution was transferred into a 125 mL separa- of selenium(IV) was computed from the calibration curve.

2.3.2. Calibration curve for selenium(IV)

Table 3 Determination of selenium(IV) in synthetic mixtures. The calibration curve was plotted under the optimum extrac-
tion conditions of selenium(IV). The graph obey the Beer’s
Composition of mixture (lg) Average recovery R.S.D. (%) law over the concentration range of 50–700 lg of selenium(IV)
of selenium(IV)*
per 10 mL of chloroform (Fig. 1).
Se(IV) 400; Te(IV) 400; aAu(III) 400 99.7 0.3
Se(IV) 400; aAu(III) 300; Pt(IV) 300 99.6 0.4 2.4. Separation of selenium(IV) in binary mixture
Se(IV) 400; bSb(III) 400; Bi(III) 400 99.7 0.3
Se (IV) 400; Pb(II) 500; Cu(II) 300 99.9 0.1
The difference in the extraction behavior of each of the metals
Se(IV) 400; cAg(I) 500; 99.5 0.5
Cu(II) 400; Au(III) 400
was fully exploited to provide complete separation of these
a
metals from selenium(IV) in various mixtures (Table 2).
Extraction of gold(III) and selenium(IV), stripping selenium(IV)
with 9 M hydrochloric acid.
b 2.5. Sequential separation scheme for selenium(IV) and
Prior extraction of antimony (III) from 3 M HCl in the presence
400 mg fluoride. tellurium(IV)
c
Prior separation of silver by treatment with 1 M HCl and filter.
*
Average of six determinations. The proposed extractive separation procedure was applied for
sequential separation of selenium(IV) and tellurium(IV). These

Table 4 Analysis of selenium(IV) in alloys.

Alloy sample Composition (%) Selenium(IV) taken (lg) Recovery* (%) R.S.D. (%)
BCS-387 nickel-base alloy nimonic-901 Cr, 12.46; Co, 0.21 400 99.9 0.1
Ti, 2.9; Al, 0.24
C, 0.030; Mn, 0.08
Si, 0.28; Fe, 36.0
Ni, 41.9; Cu, 0.032
S, 0.003; P, 0.007
Mo, 5.83; B, 0.016
BCS-320 carbon steel (mild steel) C, 0.22; Si, 0.02 400 99.6 0.4
S, 0.00 9; P, 0.019
Mn, 0.19; Ni, 0.022
Cr, 0.181; Mo, 0.22
V, 0.004; W, 0.17
Ti, 0.021; As, 0.031
Sn, 0.085; Al, 0.013
Sb, 0.003
434/1 tin-base white metal Sn, 82.2; Sb, 9.45 400 99.6 0.4
Cu, 4.58; Pb, 3.18
As, 1.15; Bi, 0.10
Cd, 0.14; Fe, 0.024
Ni, 0.17; Zn, 0.4
NBS-153a C, 0.90; Mo, 8.85 400 99.7 0.3
Mn, 0.192; W, 1.76
P, 0.023; S, 0.007
Si, 0.270; Cu, 0.094
Ni, 0.168; Cr, 0.372
V, 2.06; Co, 8.47
N, 0.024
NBS-50c C, 0.719; Mn, 0.342 400 99.7 0.3
P, 0.022; S, 0.01 Si, 0.31
Cu, 0.079; Ni, 0.069
Cr, 4.13; V, 1.16
M, 0.082; W, 18.44
Sn, 0.018; As, 0.022
N, 0.012
*
Average of six determinations.
182 B.M. Sargar et al.

two metals are present in the same group, having similar 400 mg fluoride as masking agent for selenium(IV). Here
physical and chemical properties and hence it is difficult to antimony(III) gets quantitatively extracted in the organic
separate. However, we have developed the separation proce- phase while selenium(IV) remained in the aqueous phase.
dure based on the difference in acidity (HCl) (Flow chart Antimony(III) from the organic phase was stripped with two
diagram 2). 10 mL portions of 0.5 M ammonia and was determined by
To an aliquot solution containing 400 lg of selenium(IV) iodide method (Marczenko, 1976). Selenium(IV) in the aqueous
and 100 lg of tellurium(IV) in a 25 mL volumetric flask, the phase was demasked with 2 mL of conc. hydrochloric acid and
solution was made to 0.5 M by adding 1.1 mL conc. hydro- solution was evaporated to moist dryness, and selenium(IV) was
chloric acid and diluted to 25 mL with water. The aqueous determined as per the recommended procedure (Table 2).
solution was transferred to a 125 mL separatory funnel. It
was then shaken with 10 mL of 0.15 M N-n-octylaniline. Un- 2.8. Analysis of synthetic mixtures
der this condition selenium(IV) was extracted into the organic
phase as an ion-pair complex, leaving behind tellurium(IV) in Analyzing synthetic mixtures containing varying amounts of
the aqueous layer quantitatively. The organic layer was sepa- several ions assessed the validity of the developed procedure
rated from the aqueous layer. After reduction the volume of for the separation of selenium(IV) and these elements after
the aqueous layer, it was made 7.5 M with hydrochloric acid applying a sequential procedure, as described earlier. The
by adding 15.1 mL conc. hydrochloric acid and diluting to results are furnished in Table 3, from which it is evident that
water in a total volume of 25 mL. It was then equilibrated with developed separation procedure works satisfactorily for the
0.15 M N-n-octylaniline in xylene for 5 min. various mixtures.
Selenium(IV) and tellurium(IV) from the respective organic
extracts were quantitatively stripped using 1:1 ammonia. 2.9. Analysis of alloys
Selenium(IV) was estimated by recommended procedure while
tellurium(IV) was estimated spectrophotometrically with 40 - Since standard alloy samples containing selenium(IV) were not
bromo PTPT (Kolekar and Anuse, 1998a,b) (Table 3). available at this working place, we analyzed BCS-387, BCS-
320, NBS-153 a, NBS-50c and tin-base white metal 434/1
2.6. Separation of selenium(IV) from lead(II), (The Bureau of Analyzed Samples Ltd., UK) to which a
germanium(IV), tin(IV), bismuth(III), copper(II) and known amount of selenium(IV) had been added. Selenium(IV)
molybdenum(VI) was recovered from hydrochloric acid media by the proposed
method (Table 4). The procedure is given below.
Selenium(IV) was separated from lead(II), germanium(IV), A known weight (1 g) of alloy was dissolved in a mixture of
tin(IV), bismuth(III), copper(II) and molybdenum(VI) by its 9 mL concentrated sulphuric acid and 50 mL of water. After
extraction with 10 mL of 0.15 M N-n-octylaniline in xylene the initial reaction was over, the solution was heated with
from 0.5 M HCl. Germanium(IV) was masked with 400 mg 5 mL portion of nitric acid until white fumes were observed,
fluoride. Under this condition lead(II), germanium(IV), boiled to dissolve the soluble matter, filtered to remove silica
tin(IV), bismuth(III), copper(II) and molybdenum(VI) re- or metastannic acid and to the filtrate solution, 10 mL of
mained quantitatively in the aqueous phase, where they were 1 mg mL1 of selenium(IV) solution was added and the solu-
determined spectrophotometrically with PAR, phenyl fluo- tion was diluted to 100 mL with water. An aliquot of 4 mL fil-
rone, pyrocatechol violet (Marczenko, 1976), 40 -bromo PTPT trate containing approximately 400 lg of selenium(IV) was
(Kolekar et al., 1998), 40 -chloro PTPT (Kuchekar et al., taken for extraction and determination by the proposed
1986) and thiocyanate (Marczenko, 1976) methods, method.
respectively.
2.10. Procedure for determination of selenium in pharmaceutical
2.7. Separation of selenium(IV) from antimony(III) samples

Selenium(IV) was separated from antimony(III) by extraction The proposed method was used for the determination of sele-
with 10 mL of 0.25 M N-n-octylaniline in xylene at 3 M nium(IV) in pharmaceutical samples such as Antoxide, I-VIT,
hydrochloric acid (Sargar et al., 2004) in the presence of Glace, Oxigard and Revup.

Table 5 Determination of selenium(IV) in pharmaceutical samples.

Sample Certified Selenium* Recovery* (%) R.S.D. (%)
value found
Antoxide (Soft caps Pvt. Ltd., Keelakattalai, Madras, India) 49.80 lg 49.62 lg 99.63 0.37
I-VIT (Semit Pharmaceutical and Chemicals Pvt. Ltd., Pavane, Mumbai, India) 16.71 lg 16.67 lg 99.76 0.24
Glace (Banner pharma-caps Pvt. Ltd., 811,GIDC, 45.90 lg 45.70 lg 99.56 0.44
Sarigam, Dist-Valsad, Gujarat, India)
Oxigard (Glenmark pharmaceuticals Ltd., Somnath Road, Dabhel Daman-India) 75.00 lg 74.97 lg 99.96 0.04
Revup (Universal Medicare Limited GIDC, Sarigam, Dist-Valsad, Gujarat, India) 106.74 mg 106.71 mg 99.97 0.03
SELSUN (Vival Laboratories, S. V. Road, Mumbai, India) 138.00 mg 137.45 mg 99.6 0.40
*
Average of six determinations.
Sequential separation of selenium(IV) from tellurium(IV) by solvent extraction 183

The samples (3–4 tablets) were heated with the minimum to be incomplete in sulphuric acid (81.3% at 4 M), perchloric
amount of conc. hydrochloric acid followed by the addition acid (31.3% at 6 M) and in hydrobromic acid (36.6% at
of 2–3 drops of concentrated nitric acid. The organic matter 8 M). There was no extraction from nitric acid medium
was destroyed by treatment with 5 mL conc. perchloric acid. (Fig. 2).
The solution was slowly evaporated to moist dryness. The res-
idue was dissolved in hot dilute hydrochloric acid and made up 3.2. Extraction as a function of N-n-octylaniline concentration
to required volume with water. Selenium(IV) was determined
by the recommended procedure (Table 5). In order to optimize the conditions for extraction of sele-
nium(IV), the solutions of N-n-octylaniline in xylene with
2.11. Procedure for determination of selenium(IV) in medicated varying concentration (0.005–1.0 M) were employed. It was
shampoo found that 10 mL of 0.1 M N-n-octylaniline was sufficient
for the quantitative extraction of 400 lg selenium(IV) from
The procedure for determination of selenium(IV) is also appli- 0.5 M hydrochloric acid. However, in a recommended proce-
cable for its determination in medicated shampoo such as Sel- dure 0.15 M N-n-octylaniline in xylene was used to ensure
sun. Shampoo (10 mL) was taken in 100 mL beaker. To this, a the complete extraction of metal ion. There was no adverse
mixture of 1:1 perchloric acid and nitric acid was added and effect, if one uses excess of N-n-octylaniline concentration.
evaporated to moist dryness. The residue was extracted in di-
lute hydrochloric acid and finally in water. A 100 mL stock 3.3. Effect of equilibration time
solution was prepared and definite aliquot of this solution
was subjected to the recommended procedure (Table 5). The two phases were shaken for a period ranging from 5 s to
20 min. It was found that minimum of 2 min equilibration time
3. Results and discussion was adequate for the quantitative extraction of selenium(IV)
from 0.5 M hydrochloric acid media. In general procedure,
3.1. Effect of acid concentration 3 min equilibration time was recommended in order to ensure
complete extraction of metal ion. However, prolonged shaking
Extraction of selenium(IV) with 0.15 M N-n-octylaniline in up to 20 min had no adverse effect on the extraction.
xylene was carried out from a solution of 0.1–10 M hydrochloric
acid and was found to be quantitative from 0.4 to 0.6 M 3.4. Effect of stripping agent
hydrochloric acid and again there is a decrease of extraction.
This may be due to the formation of stable hydrochloride of A variety of stripping agents such as mineral acids, alkali, and
the N-n-octylaniline. The extraction of selenium(IV) was found buffer solutions were employed. It was found that the stripping
of selenium(IV) was quantitative with >5.0 M ammonia and
>2.0 M hydrochloric acid. Stripping was incomplete with
100 the acids such as nitric acid and acetic acid, and bases such
as sodium hydroxide and potassium hydroxide, and buffer like
A acetate buffer (pH 4.5) and also with water (Table 6). Hence a
90 B
C 1:1 ammonia solution is a suitable strippant for selenium(IV)
D than hydrochloric acid because removal of ammonia by evap-
80
oration is easier process.

70
Percentage extraction, %E

Table 6 Extraction behaviour of selenium(IV) as a function of

stripping agents. Selenium(IV) = 400 lg, HCl = 0.5 M, N-n-
60
octylaniline = 10 mL of 0.15 M in xylene, equilibration time =
3 min, Aqueous: organic volume ratio = 2.5:1, volume of
50 stripping agent = 2 · 10 mL.
Molarity NH3 NaOH HCl HNO3
40 (M) recovery (%) recovery (%) recovery (%) recovery (%)
0.01 16.8 27.2 69.6 41.5
30 0.05 17.0 30.4 74.8 46.4
0.1 17.2 37.6 80.6 62.7
20
0.3 17.7 42.1 83.2 66.2
0.5 19.1 44.0 87.8 68.0
0.7 27.7 55.7 91.5 76.6
10 1.0 47.8 74.7 97.7 84.5
2.0 75.1 81.3 100.0 88.3
3.0 87.0 89.4 100.0 97.8
0
0 1 2 3 4 5 6 7 8 9 10 5.0 100.0 87.7 100.0 Decompose
Molarity of acid, [M] 7.0 100.0 63.0 100.0 Decompose
9.0 100.0 54.8 100.0 Decompose
Figure 2 Extraction of Se(IV) with 0.15 M N-n-octylaniline in
Other stippants (recovery %): water (74.3); acetate buffer of pH 4.5
xylene as a function of acid concentration, Se(IV) = 400 lg (71.5); CH3COOH of 1 M (68.5%), KOH of 0.5 M (47.8%).
[A = HCl, B = H2SO4 (in normal), C = HClO4, D = HBr].
184 B.M. Sargar et al.

3.5. Effect of various diluents diluents. With toluene (39.8%), chloroform (36.4%), carbon
tetrachloride (51.7%), methyl isobutyl ketone (53.6%), amyl
The extractions were performed from 0.5 M hydrochloric acid alcohol (33.6%), amyl acetate (34.9%), n-butane (34.3%)
medium using 0.15 M N-n-octylaniline in various solvents as and ethylene chloride (33.8%), the extraction was found to
be incomplete. It was observed that the extraction becomes
quantitative with amine solution in benzene and xylene. How-
0.6
ever, benzene is too toxic and is banned by the Government;
A hence xylene was preferred as a diluent for further study. No
B correlation between dielectric constant and percentage extrac-
0.4
tion was observed.

0.2 3.6. Effect of aqueous to organic volume ratio

Selenium(IV) was extracted from aqueous phase in the range

0 of 10–400 mL at 0.5 M hydrochloric acid with 10 mL of
0.15 M N-n-octylaniline in xylene. Selenium(IV) was stripped
Log D[se(IV)]

-2.5 -2 -1.5 -1 -0.5

Log C[N-n -octylaniline]
with a 1:1 ammonia solution and determined as described in
-0.2 the procedure. It was found that the extraction of selenium(IV)
was quantitative, when aqueous to organic phase volume ratio
was 1:1 to 4:1, while it decreases when the ratio was changed
-0.4 from 5:1 and 40:1. This may simply be due to the unavailability
of the reagent for metal extraction, so a crowding effect occurs
at low phase ratio. Hence, the aqueous to organic volume ratio
-0.6 recommended in the procedures is 2.5:1.

3.7. Loading capacity of N-n-octylaniline

-0.8

Varying concentrations of selenium(IV) (50 lg to 7 mg) was

extracted with 10 mL 0.15 M N-n-octylaniline in xylene from
-1
hydrochloric acid media. It was observed that extraction of
selenium(IV) was quantitative from 50 lg to 3 mg.
-1.2
3.8. Stoichiometry of the extracted species
Figure 3 Log–log plot of distribution ratio D[Se(IV)] as a function
of N-n-octylaniline concentration at 2 M (A, slope = 0.90) and Stoichiometry of the extracted species was investigated by ana-
3 M HCl (B, slope = 1.00). lyzing the experimental data with conventional slope analysis

Table 7 Effect of diverse ion on extraction of selenium(IV). Selenium(IV) = 400 lg, HCl = 0.5 M, N-n-octylaniline = 10 mL of
0.15 M in xylene, equilibration time = 3 min, aqueous: organic volume ratio = 2.5:1.
Ions Added as Tolerance limit (mg) Ions Added as Tolerance limit (mg)
Acetate Sodium acetate 500 W(VI) Na2WO4Æ2H2O 10
Tartrate Sodium tartrate 500 U(VI) UO2(NO3)2Æ6H2O 10
Fluoride NaF 400 Os(VIII) OsO4 10
Malonate Sodium malonate 200 Re(VII) KReO4 10
Oxalate (COOH)2Æ2H2O 200 Sn(II) SnCl2Æ2H2O 7
Thiosulphate Na2S2O3Æ5H2O 200 Te(IV) Tellurium metal 7
EDTA EDTA (disodium salt) 200 Cd(II) CdCl2Æ2½H2O 5
Nitrate KNO3 100 Be(II) BeSO4Æ4H2O 5
Iodide KI 100 Mn(II) MnCl2Æ6H2O 5
Thiourea SC(NH2)2 50 Mo(VI) (NH4)6Mo7O24Æ2H2O 5
Thiocyanate KSCN 50 Rh(III) RhCl3Æ3H2O 5
Co(II) CoCl2 15 Ru(III) RuCl3Æ6H2O 5
Sn(IV) Tin metal 15 Fe(III) FeCl3 5
Al(III) AlCl3 (anhydrous) 13 Ge(IV)a Germanium metal 5
Ni(II) NiCl2Æ6H2O 10 Ce(IV) Ce(SO4)2 5
Hg(II) HgCl2 10 Cu(II) CuSO4Æ5H2O 5
Mg(II) MgCl2Æ6H2O 10 Bi(III) Bi(NO3)3 3
Pb(II) Pb(NO3)2 10 Cr(III) CrCl3 2
Sr(II) Sr(NO3)2 10 Sb(III)a Sb2O3 2
Tl(I) TlNO3 10
a
Masked with 400 mg fluoride.
Sequential separation of selenium(IV) from tellurium(IV) by solvent extraction 185

method. The results show the expected increase in extraction associated metals such as tellurium(IV), antimony(III), bis-
with increase in reagent concentration. The nature of the ex- muth(III), lead(II), copper(II), germanium(IV), molybde-
tracted species was ascertained from the slope of the plots of num(VI) and tin(IV). A very low extractant concentration
log D vs. log[N-n-octylaniline] for different concentrations of (0.1 M) and less equilibrium time (2 min) are required for
hydrochloric acid (Fig. 3). The slopes at 2 M and 3 M hydro- quantitative extraction of selenium(IV). The method is suitable
chloric acid concentration are 0.90 and 1.00, respectively, indi- for the determination of selenium(IV) in synthetic mixtures, al-
cating that the metal to amine ratio in the extracted species is loys, pharmaceutical samples and medicated shampoo.

1:1. Hence probable extracted species is ½RR0 NHþ 2 HSeO3 ðorgÞ

containing HSeO3 anion (Cotton and Wilkinson, 1985).
Acknowledgements
The mechanism of extraction is as follows: N-n-octylaniline
reacts with hydrochloric acid in the acidity range 0.4–0.6 M to
 The authors thank Prof. M.B. Chavan for his help and inspi-
form ion-pair, RR0 NHþ 2 ClðorgÞ . This species acts as a liquid an-
ration in the research work. This work is supported by
ion exchanger. When this ion-pair is equilibrated with HSeO 3,
UGC-SAP and DST-FIST programmes.
under same optimum conditions, the Cl ions are replaced by
HSeO 3 easily. However, beyond this acidity range there is a
formation of stable hydrochloride of N-n-octylaniline, References

RR0 NHþ 2 Clð orgÞ . Hence there is a decrease in the extraction
with acidity. While stripping of selenium(IV) from organic Aeungmaitrepirom, W., Hegage, A., Asfari, Z., Vicens, J., Leroy, M.,
2001. J. Incl. Phen. Macro. Chem. 40 (3), 225.
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in the aqueous phase.
Khim. Zh. 66, 46.
½RR0 NHðorgÞ þ HClðaqÞ ½RR0 NH2 þ Cl ðorgÞ ðIÞ Chowdhury, M.R., Sanyal, S.K., 1993. Hydrometallurgy 32 (2), 189.
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½RR0 NHþ
2 Cl ðorgÞ þ HSeO3 ðaqÞ ½RR0 NHþ
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½RR0 NHþ
2 HSeO3 ðorgÞ þ 2NH4 OHðaqÞ ½RR0 NHðorgÞ 2, 541.
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