Journal of Hazardous Materials 165 (2009) 886–892

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Journal of Hazardous Materials

journal homepage: www.elsevier.com/locate/jhazmat

Extractive separation and determination of chromium in tannery effluents

and electroplating waste water using tribenzylamine as the extractant
S. Kalidhasan, M. Ganesh, S. Sricharan, N. Rajesh ∗
Chemistry group, Birla Institute of Technology and Science, Pilani 333 031, India

a r t i c l e i n f o a b s t r a c t

Article history: A simple extractive separation method has been developed for the determination of chromium based
Received 26 May 2008 on the extraction of Cr (VI) as its ion-pair with tribenzylamine (TBA). The ion-pair is extracted at acidic
Received in revised form 20 October 2008 pH using toluene as the diluent. The concentration of chromium in the organic phase was measured
Accepted 20 October 2008
spectrophotometrically at 309 nm. The influence of experimental variables such as pH, sample volume,
Available online 7 November 2008
equilibration time, diverse ions etc. has been studied in detail. The extracted chromium (VI) could be
stripped to the aqueous phase using NaOH as the stripping agent. The extracts were characterized using
Keywords:
FT-IR spectroscopy. A detection limit of 0.08 ␮g mL−1 could be achieved and the validity of the method
Chromium (VI)
Tribenzylamine
was checked in real tannery effluent, electroplating waste water and spiked water samples.
Toluene © 2008 Elsevier B.V. All rights reserved.
Tannery effluent
Electroplating waste water

1. Introduction Organophosphorous extractants such as TBP and DEHPA have also

The growing concern for environmental pollution has necessi-
tated the study and determination of heavy metals in a variety of
matrices. Chromium is not an exception to this. The common oxi-
dation states of chromium are 0, +1 and +6 respectively. Chromium
(VI) is mainly used in electroplating and chromium (III) finds its util-
ity in leather tanning operations. Chromium (III) is required for the
maintenance of normal glucose metabolism, whereas chromium
(VI) is carcinogenic [1].
The widely used methods for the removal of chromium (VI) are
solid phase extraction (SPE) and liquid-liquid extraction (LLE). Solid
phase extraction has been explored with a variety of adsorbents for
the removal of chromium [2–10].
Even though, SPE offers high preconcentration factors, LLE is
still employed as a versatile technique in hydrometallurgy for the
recovery of industrially important metals such as cobalt and nickel
[11]. LLE is of great significance in the reprocessing of spent fuels
such as uranium and plutonium [12]. Long chain amines have
proven to be very good extractants for a number of metal ions [13].
The extraction of chromium with various long chain amines and
quaternary ammonium salts has been reviewed in detail [14,15].
Aliquat 336 is one such extractant which has been explored in detail
using membrane extraction, SPE and conventional LLE [16–19].
∗ Corresponding author. Fax: +91 1596 244183.
E-mail address: nrajesh05@gmail.com (N. Rajesh).
been studied for the extraction of chromium [20,21]. The extrac-
tion of chromium (VI) using tribenzylamine (TBA) in chloroform
has been reported for the analysis of chromium in steel alloys
[22].
A survey of the literature reveals that the utility of TBA as a
potential extractant for Cr (VI) in environmental samples is scarce.
Hence, it was decided to explore TBA as an extractant using rela-
tively less toxic diluents for the separation and determination of Cr
(VI) and Cr (III) and its application to real samples such as tannery
effluents, electroplating waste water, and water samples.
2. Experimental
2.1. Reagents
All reagents were of analytical grade. Triple distilled water
(TDW) was used in the preparation of the solutions. Potassium
dichromate was procured from S.d. Fine Chemicals (Mumbai, India).
2.826 g of potassium dichromate was diluted to 100 mL with TDW
to give 1000 ␮g mL−1 chromium (VI) solution. A working solution of
10 ␮g mL−1 was prepared by appropriate dilution. Sulfuric acid was
procured from Qualigens fine chemicals (Mumbai, India). A stock
solution of 1 mol L−1 sulfuric acid was prepared by appropriate dilu-
tion with triple distilled water. Sodium hydroxide of the required
concentrations was prepared by appropriate dilution with TDW.
Toluene and tribenzylamine were procured from Merck (Mumbai,
India). A 0.1 mol L−1 solution of tribenzylamine was prepared by

0304-3894/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jhazmat.2008.10.122
 S. Kalidhasan et al. / Journal of Hazardous Materials 165 (2009) 886–892 887

Table 1
Effect of diluents on extraction.

Diluents Observation

Hexane Extract was highly turbid without clear separation

Heptane Extract was highly turbid without clear separation
Cyclohexane Negligible extraction
Xylene Extract cloudy with poor separation
Amylalcohol Negligible extraction
Toluene Clear phase separation with good extraction efficiency

dissolving the appropriate amount the reagent using toluene as

the diluent. Water samples were collected from our campus for
the analysis of total chromium.

2.2. Instrumentation

A JASCO V-576 model UV–visible spectrophotometer was used

to record the absorbance. 1 cm matched quartz cells were used for
absorbance measurements. An Elico LI-120 model pH meter was Fig. 1. Effect of pH.
used for pH measurements. The FT-IR studies were performed using
a Shimadzu FT-IR spectrometer.

2.3. General procedure for the extraction of chromium (VI)

xylene and isoamylalcohol. The effect of halogenated hydrocar-
bon diluents such as chloroform was not studied since it has been
The feed containing 1 mL volume of 10 ␮g mL−1
chromium (VI)
already reported in the literature [22]. The effect of the diluents
solution was mixed with 5 mL of 1 mol L −1 sulfuric acid in a
and the characteristic observations are summarized in Table 1.
60 mL separating funnel. The aqueous phase volume was main-
The studies indicated that chromium (VI) could be extracted
tained at 10 mL. The solution was extracted for 10 min with 10 mL
quantitatively with clear phase separation using toluene as the
of 0.1 mol L−1 TBA in toluene. The absorbance of the organic layer
diluent.
was measured at max 309 nm against a reagent blank. The con-
centration of chromium (VI) in the aqueous layer was analyzed
3.2. Effect of pH
using the standard diphenylcarbazide spectrophotmetric method
at 540 nm. The percentage of extraction (E) was calculated using the
The effect of pH was studied in the range 1.0–8.0. The percent-
relation
age extraction at various pH values are shown in Fig. 1. The results
D = (E/100 − E) × Vw /Vo indicate that the extraction is maximum in the pH range 1–3. Cr
(VI) exists as HCrO4 − , Cr2 O7 2− in acidic medium and as CrO4 2− in
where D is the distribution ratio, which is the [Cr]org /[Cr]aq ,
alkaline medium.
Vw , and Vo refer to the volume of aqueous and organic phases
respectively. H2 CrO4  H+ + HCrO−
4

3. Results and discussion HCrO− + 2−

4  H + CrO4

3.1. Selection of diluent The percentage extraction decreased at higher pH since the
species CrO4 2− does not form a stable ion-association complex with
The extraction of the Cr (VI) was studied using various diluents TBA in the organic phase. The ion-pair formation can be represented
for tribenzylamine such as toluene, hexane, cyclohexane, heptane, as follows:
888 S. Kalidhasan et al. / Journal of Hazardous Materials 165 (2009) 886–892

This fact is also further confirmed by FT-IR studies of the organic

extract. maintained at 10 mL and the absorbance of the extract measured
against a reagent blank. An optimum equilibration time of 8 min
3.3. FT-IR studies for the organic extract was sufficient for maximum extraction.

The FT-IR spectrum of organic phase for the sample extraction
is shown in Fig. 2. A new peak which appears at 897 cm−1 along
with other characteristic vibrational peaks such as C–N, N–H, C–H
(both aromatic and aliphatic), C C bond conjugation in aromatic
ring indicates the presence of HCrO4 − [23]. This shows that Cr (VI)
is extracted as an ion-pair of HCrO4 − with the protonated amine
in acidic medium. The peak intensity also highlights the fact that
HCrO4 − species to be the predominant species at low pH values.
3.5. Effect of tribenzylamine concentration
The concentration of tribenzylamine was varied from
0.02–0.2 mol L−1 and the extraction studies were carried out
as mentioned in the general procedure. The results are shown in
Fig. 3. The percentage extraction increases with increase in the
concentration of tribenzylamine and is maximum in the range
0.1–0.2 mol L−1 concentration.

3.4. Effect of equilibration time 3.6. Effect of aqueous phase volume

The extraction studies were carried out for varying lengths The aqueous phase volume was varied from 10 to 60 mL and the
of time ranging from 1– 15 min. The aqueous phase volume was extraction studies were carried out as before. The results are shown

Fig. 2. FT-IR spectrum of Cr (VI) – TBA ion-pair in organic phase.

 S. Kalidhasan et al. / Journal of Hazardous Materials 165 (2009) 886–892
Fig. 3. Effect of concentration of TBA (mol/L).
Fig. 4. Effect of aqueous phase volume.
in Fig. 4. It was found that the system could tolerate an aqueous
phase volume of up to 60 mL. Beyond 60 mL aqueous phase volume,
there was a significant reduction in the percentage extraction.
3.7. Nature of extracted species
The nature of the extracted species was ascertained by equi-
librium shift method (A plot of log D vs. log C). The results are
presented in Fig. 5. From the best fit, the slope of the logarithmic
plot was found to be 1.35 indicating that the ion-pair between
889
Fig. 5. Plot of log D against log C.
Table 2
Effect of various stripping agents.
Stripping agent Volume (mL) % Stripped
Ascorbic acid (5%) 10 27.0
NaOH (0.5 mol/L) 10 99.0
Na2 SO3 (0.1 mol/L) 10 75.0
Cr (VI) and TBA to be associated as (HCrO4 − . . .+ HNR3 ). This fact was
also confirmed from the mole ratio method and Job’s continuous
variation method.
3.8. Stripping of chromium (VI) from the organic phase
The stripping of chromium (VI) from the organic phase was stud-
ied with NaOH and reducing agents such ascorbic acid and Na2 SO3
respectively. The objective of this study was to examine the re-
usability of the organic phase for further extraction. The extraction
studies were carried out with an aqueous phase volume of 10 mL.
The organic and the aqueous phases were separated and the organic
phase containing chromium (VI) was equilibrated with 10 mL of
the above mentioned reagents. The percentage of Cr (VI) stripped
with NaOH, ascorbic acid (5%) and Na2 SO3 (0.1 mol L−1 ) are shown
in Table 2. Cr (VI) could be quantitatively stripped using NaOH as
the stripping agent. However, with sodium sulfite the percentage
stripped increased to a maximum of 92% with 2 × 10 mL portions
of the reagent. In the case of ascorbic acid the percentage of Cr (VI)
stripped increased to a maximum of 67% with 2 × 10 mL portions of
5% ascorbic acid. This was confirmed by measuring the absorbance
of the organic layer and the concentration of Cr (VI) in the aque-
ous phase spectrophotometrically using diphenylcarbazide as the
complexing agent.
890 S. Kalidhasan et al. / Journal of Hazardous Materials 165 (2009) 886–892

Fig. 6. FT-IR spectrum of organic phase after stripping with NaOH.

The above fact was further confirmed from FT-IR studies of the
organic phase (Fig. 6). The spectrum clearly shows the absence of
the prominent peak obtained at 897 cm−1 for HCrO4 − in the extrac-
tion of the ion-pair. The organic phase could be re-used for at least
10 cycles with good precision and reproducibility.
sion studies were carried out at 0.5 ␮g mL −1 level of chromium
(VI) by carrying out 10 separate determinations. The relative stan-
dard deviation (r.s.d) was found to be 4.5%. A detection limit of
0.08 ␮g mL−1 (taken at 3 times the standard deviation of the blank)
could be attained by the proposed method.

3.9. Effect of concentration of NaOH used for stripping 3.11. Effect of diverse ions

The concentration of NaOH was varied in the range 0.05– The effect of various diverse ions on the extraction of the ion-pair
0.5 mol L−1 . The results are presented in Fig. 7. It was observed that was investigated at varying concentrations maintaining an aque-
quantitative stripping could be obtained with 0.5 mol L−1 NaOH ous phase volume of 10 mL. The results are presented in Table 3.
concentration. Anions such as chloride, sulfate, nitrate and cations such as iron (II),

3.10. Calibration, precision and detection limit Table 3

Effect of diverse ions [aq. volume 10 mL] on the extraction of Cr (VI).
The calibration graph was linear in the range 0–1 ␮g mL −1 of Ions Amount (␮g) % Extraction
chromium (VI), with a correlation coefficient of 0.998. The preci-
Cl− 1000 50.6
200 78.8
100 98.5

NO3 − 1000 51.8

250 67.8
150 98.6

SO4 2− 1000 62.7

250 72.3
100 98.6

Fe(III) 1000 74.2

100 92.6

Cr(III) 1000 98.6

100 98.6

Hg(II) 1000 64.3

100 87.6
80 97.6

Ni(II) 1000 98.9

Mg(II) 1000 98.7
Ca(II) 1000 98.5

Cu(II) 1000 84.6

500 98.2

Pb(II) 1000 98.5

Fig. 7. Plot of % chromium (VI) stripped against the concentration of NaOH (mol/L).
 S. Kalidhasan et al. / Journal of Hazardous Materials 165 (2009) 886–892 891

Table 4
Percentage extraction of chromium (VI) in various synthetic waste water samples.

Sample code Composition of synthetic waste water (SW) % Extraction of Cr(VI)

− − −1
SW1 Cl (100 ␮g), NO3 (100 ␮g), Cu (500 ␮g), Cr (0.5 ␮g mL ), Cr (500 ␮g), SO4 (100 ␮g).
2+ 6+ 3+ 2−
98.5
SW2 Cu2+ (100 ␮g), Zn2+ (500 ␮g), Cr6+ (0.5 ␮g mL−1 ), Fe3+ (100 ␮g), SO4 2− (100 ␮g), Cl− (100 ␮g), NO3 − (100 ␮g). 96.1
SW3 Co2+ (200 ␮g), Mg2+ (1000 ␮g), Hg2+ (70 ␮g), Cr6+ (0.5 ␮g mL−1 ), Cr3+ (100 ␮g), Ca2+ (1000 ␮g), NO3 − (100 ␮g). 98.2
SW4 Fe3+ (100 ␮g), Ca2+ (1000 ␮g), Zn2+ (500 ␮g), Cr6+ (0.5 ␮g mL−1 ), Cr3+ (100 ␮g), Cl− (100 ␮g), NO3 − (100 ␮g), Pb2+ (500 ␮g). 96.5

Table 5 the above samples. Hence, it was decided to apply the proposed
Recovery studies for total chromium (aqueous volume 10 mL).
method to real samples.
Cr (III) added (␮g) Cr (VI) added (␮g) Total chromium Recovery (%)
found (␮g) 3.13. Analysis of Cr (III) and Cr (VI) in a mixture
3 5 7.9 98.7
4 3 6.9 98.6 Varying amounts of Cr (III) and Cr (VI) were taken an analyzed
2 6 7.8 97.5 using the proposed method. The total chromium concentration
was analyzed by oxidation with H2 O2 –NaOH mixture and the con-
mercury (II) interfered significantly at higher concentrations. The centration of Cr (III) was found by the difference. The results are
interfering effect of chloride, nitrate and sulfate could be ascribed presented in Table 5 which clearly shows satisfactory recovery in
to the fact that they might also form ion-pair with TBA and get the concentration range that was studied.
co-extracted with chromium.
3.14. Analysis of chromium in tannery effluent, electroplating
3.12. Recovery study in synthetic waste water wastewater and water samples

The proposed method was applied to study the recovery of
chromium (VI) in four synthetic waste water samples (SW1-SW4)
containing varying concentration of other ionic species. The results
are presented in Table 4. As can be seen from the table, it is evident
that the extraction of chromium (VI) is quantitative (>95%) with
The proposed method was applied to study the recovery of
chromium in tannery effluent, spiked water samples and elec-
troplating wastewater sample. The major constituent of tannery
effluent is Cr (III) in view of the organic matter and the reducing
agents used in the leather tanning process. The tannery effluent was

Table 6
Analysis of chromium in real samples.

Sample Chromium added (␮g mL−1 ) Chromium found (␮g mL−1 ) Total chromium (␮g mL−1 ) Recovery (%)

Cr(III) Cr(VI) Cr(III) Cr(VI)

– – 1392.7 29.85 1422.6 –

Tannery effluent 5 10 1375 38.6 1413.6 98.3

10 5 1382 34 1416 98.5
– – 26 143.7 169.7 –

Electro plating waste water 2 4 27.1 145.2 172.3 98.1

3 2 27.9 142.8 170.7 97.7

Tap water 2 1 1.9 0.96 2.86 95.3

Lake water 3 2 2.9 1.9 4.8 96

1 1 0.95 0.92 1.87 94

Table 7
Comparison of the proposed method with some of the reported solvent extraction methods in literature.

No. System Medium Method Recovery (%) Detection limit (␮g/mL) RSD (%) Reference

1 Cr (VI)-TPPB Chloroform Spectrophotometry 98.5–100 2.9 3.0 [15]

2 Cr (VI)-Aliquat Mixture of kerosene & xylene Spectrophotometry 97 – – [24]
336-SO4 2-
3 Cr (VI)-Aliquat Mixture of kerosene & xylene Spectrophotometry 55 – – [24]
336-NO3 −
4 Cr (VI)-Aliquat 336-Cl− Mixture of kerosene & xylene Spectrophotometry 95 – – [24]
5 Cr (VI)-TBAB CH2 Cl2 Spectrophotometry 95 – – [25]
6 Cr (VI)-capriquat CCl4 AAS 90 – – [26]
7 Cr (VI)-Zephiramine CHCl3 AAS 79 – – [26]
8 Cr (VI)-Aliquat 336 Xylene Spectrophotometry 100 – – [27]
9 Cr (VI)-Alamine 336 Xylene Spectrophotometry 100 – – [27]
10 Cr (VI)-TOA- Kerosene Spectrophotometry 55 – – [28]
ammonium carbonate
11 TBADBDTC Methanol ICP-AES 88 1.0 34 [29]
12 Cr (VI)-TBAB (NH4 )2 SO4 AAS 93–98 60 3.2 [30]
13 Cr (VI)-TBP Benzene Spectrophotometry – 2.6 – [14]
14 Cr (VI)-DPC Isoamylalcohol AAS 90–110 0.024 8–49 [31]
15 Cr (VI)-TBA Toluene Spectrophotometry 98.5 0.08 4.5 Present work

TPPB: tetraphenylphosphoniumbromide; TBAB: tetrabutylammoniumbromide; TBP: tributylphosphate; TBADBDTC: tetrabutylammoniumdibutyldiethyldithiocarbamate;

TOA: trioctylamine; DPC: diphenylcarbazide; TBA: tribenzylamine.
892 S. Kalidhasan et al. / Journal of Hazardous Materials 165 (2009) 886–892
highly concentrated and greenish blue in color. It was diluted to the
required concentration and the concentration of chromium (VI) was
analyzed by the proposed solvent extraction procedure. A known
volume of the effluent was oxidized with alkaline hydrogen perox-
ide and the total chromium concentration was analyzed. Cr (III) was
found from the difference. The electroplating wastewater sample
was diluted and the concentration of Cr (VI) was analyzed by the
proposed method. The concentration of chromium in tap water and
lake water samples (collected from our campus) were well below
the detection limit and hence the recovery of chromium was estab-
lished by spiking known concentration of chromium. The results
are presented in Table 6. The recovery of chromium was found to
be quantitative in the samples that were analyzed, which shows
the validity of the proposed method when applied to real samples.
3.15. Comparison of the proposed method with some of the
existing solvent extraction methods
The comparison of the present method with some of the exist-
ing solvent extraction procedures for Cr (VI) in the literature is
given in Table 7. Toxic chlorinated solvents were used in most of
the reported methods. The percentage of recovery is in the range of
79–95% and the reusability of the solvent (org. phase) is for about
5–6 cycles. Some of the methods also suffer from draw backs such
as third phase formation in the extraction. The detection limit,
percentage recovery and RSD values in the proposed method are
comparable to and also in some cases better than some of the
extraction procedures reported in literature. Moreover, the present
method is simple, facile and does not have the drawback of third
phase formation.
4. Conclusion
The proposed method for the determination of Cr (VI) is simple,
rapid and shows good sensitivity and selectivity. The calibration
graph was linear up to 1 ␮g mL−1 Cr (VI), with a detection limit of
0.08 ␮g mL−1 . The extracted chromium (VI) could be stripped using
0.5 mol L−1 NaOH and the organic phase could be re-used for
extraction with good precision and reproducibility for 10 cycles.
The proposed method was applied successfully to real samples such
as tannery effluent, electroplating waste water and spiked water
samples.
Acknowledgements
We thank University Grants Commission (UGC), New Delhi,
India (Project No: F-32-312/2006(SR)) for financial support.
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