International Journal of Engineering and Technical Research (IJETR)

ISSN: 2321-0869, Volume-2, Issue-3, March 2014

SOLID PHASE EXTRACTION FOR THE

REMOVAL, PRECONCENTRATION VIA
RECOVERY AND SEPARATION OF Cu(II) AND
Ni(II) USING MODIFIED SILICA GEL
Mitali Sarkar, Mridula Das, Dhiman Santra, Rajib Joarder

Chemical precipitation, complexation, coagulation, and

Abstract Metal ion toxicity and pollution of water is a real flocculation [2] are although widely used techniques for
cause of concern to the environmentalist due to the non metal ion removal has limitation of secondary pollutant/
biodegradable character and long persistence of metals in the sludge generation. Liquid liquid extraction is a very popular
ecosystem. Metals in trace level are sometimes play crucial role
technique for trace level metal determination,
governing the enzymatic character of biomaterial and behavior
of complex matrix.
preconcentration and separation. However, use of large
Trace level determination and separation of copper and nickel volume of toxic organic solvents, large through output led the
from bisolute composition is studied in the present case using scientists in search of alternative techniques. Recently
salicylaldoxime immobilized silica gel. The process is optimized extraction of heavy metal ions by ionic liquid has reported [3]
for initial metal concentration, dose of adsorbent, pH, Solid phase extraction method using some solid extractants,
temperature, shaking time and speed. The pH dependent as have some advantages over liquid-liquid extraction, is
behavior of Cu(II) and Ni(II) can be utilized for mutual now gaining the popularity. The solid extractants range from
separation in batch mode. Column study reveals that retention the natural [4-6] to synthetic materials as well as the
of Cu(II) is independent of flow rate up to 10 ml/min while for biomaterials [7-9]. Ion exchange materials [10], activated
Ni(II) the tolerable flow rate is found to 6.5 ml/min. HNO 3 or
carbon [11] and activated slag [12] are used for the purpose
HClO4 is found to have excellent potential for elution of Cu(II)
and Ni(II). The distinct elution pattern of Cu(II) and Ni(II) can of metal ion separation and recovery. Chelate impregnated
be utilized for separation of Cu(II) and Ni(II) using gradient over solid substances like cellulose [13] and hybrid polymer
elution. A good preconcentration factor 66 and 50 respectively [14] show their marked potential. In our laboratory ligand
for Cu(II) and Ni(II) makes the operation a promising one for immobilized over silica gel was successfully used for the
removal and recovery of Cu(II) and Ni(II) from aqueous enrichment of metal ions from water [15, 16]. Silica gel, as a
solution. solid support for ligand immobilization, has some special
advantages like less swelling property, high resistance
Index TermsSalicylaldoxime, immobilized silica gel, towards heat and acid treatment. For the synthesis of solid
batch experiment, column experiment, preconcentration, solid phase extractant silica gel surface can be modified following
phase extraction
different routes [17-23]. The present communication deals
with solid phase extraction of Cu(II) and Ni(II) for the
I. INTRODUCTION
removal, recovery, preconcentration vis--vis separation
from bisolute composition following adsorption using
With the advent of material civilization the use of metals has salicylaldoxime immobilized silica gel (SISG) as the
been increased tremendously which adsorbent.
inevitably has resulted in an increased flux of metallic
pollutants in the aquatic environment. The toxicity generated II. II.EXPERIMENTAL
may disturb the ecological balance [1]. Again in trace level
some metals play important roles in enzymatic metabolism in A. Apparatus
biological system. The removal as well as trace level Batch experiment was performed in a glass container. A
determination of metals via preconcentration and separation glass column (160 x 6mm i.d) with a coarse sintered glass
from complex matrix becomes a challenging task from the disc and a tap at the bottom was used for the column study.
environmental, ecological and analytical chemistry view The absorbance spectra of the solution were recorded using a
point. UV-VIS Spectrophotometer (Shimadzu PC 1401). The IR
spectrum of the solid as thin film between KBr windows was
Manuscript received March 20, 2014 taken in an IR spectrophotometer (Perkin Elmer L
Mitali Sarkar, Department of Chemistry, University of Kalyani,Kalyani 120-000A). A systronics pH meter (Model 324) with glass
741 235, West Bengal
Mridula Das, Kalna College, Kalna, Burdwan, 713409, West Bengal
electrode was used for pH measurements. Atomic absorption
Dhiman Santra, Department of Chemistry, University of Kalyani, Kalyani measurement was recorded on an atomic absorption
741 235, West Bengal spectrophotometer (AAS; Perkin Elmer AA 1407) equipped
Rajib Joarder, Department of Chemistry, University of Kalyani,Kalyani with a standard burner with an air-acetylene flame. Standard
741 235, West Bengal, Jangipur Colege, Jangipur, Murshidabad, 742213,
West Bengal hollow cathode lamp was used as a line source. The operating

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 SOLID PHASE EXTRACTION FOR THE REMOVAL, PRECONCENTRATION VIA RECOVERY AND
SEPARATION OF Cu(II) AND Ni(II) USING MODIFIED SILICA GEL

characteristics of the instrument for the metal ion estimation uniformly packed with SISG was used. Respective metal ion
are as follows: solution at a definite pH was percolated at a definite flow rate
of 5.0 ml/min. After washing the column with about 20 ml of
Metal Lamp Wavelength Slit width deionsed water, an eluting solution of definite composition
ion current (mA) (nm) (mm) (HNO3 or HClO4) was passed through at a flow rate of 3.0
Cu(II) 4.0 324.8 0.5 ml/min. The metal ion concentration in the eluate, after
Ni(II) 4.0 232.0 0.2 diluting to the desired volume, was determined by atomic
absorption spectrophotometer (AAS).

B. Materials III. RESULTS AND DISCUSSION

A. Characterization of SISG
All chemicals were of analytical reagent grade. Silica gel H
4267 of particle size 60m, specific surface area 420 m2/g The IR spectrum (Fig.1) of SISG show characteristic peaks of
and pore size 1200A was obtained from Sigma. Stock SALD [24] suggesting that the ligand was immobilized as
solutions of copper and nickel (200 mg/l) were prepared by such without any structural change on the silica gel. In
dissolving respective metal chloride in doubly distilled water. another experiment ethanol was passed through the column
pH of the experimental solution in the range 3.5-6.0 was packed with a weighed quantity of SISG to remove all the
maintained by acetate buffer by mixing the required volumes SALD immobilized with silica gel. The eluate gave identical
of 0.2 mol/l acetic acid and sodium acetate. pH below 3.5 was absorption band of SALD (Fig.2). Quantitative
maintained by HCl while pH above 6.0 was maintained by determination showed that the amount of SALD in SISG was
NaOH solution. Salicylaldoxime (GR) was obtained from 272 mg/g of silica gel.
Merck, India.

C. Synthesis of salicylaldoxime loaded silica gel (SISG)

The present adsorbent salicylaldoxime loaded silica gel

(SISG) was synthesized by first refluxing the silica gel with
6.0 mol/l HCl for about 3 hours to free any contaminating
metal such as iron. It was then washed with deionised water
and dried under reduced pressure at 1500C. The dried silica
gel was refluxed with salicylaldoxime (SALD) in ethanol
(10% w/w) at 70-800C for 4 hours. The solid thus obtained
was filtered and dried under vacuum.

D. Retention procedure

a) Batch Experiment:
Batch experiments were performed to obtain optimum
adsorption condition and equilibrium data. The flask
containing 20 ml of metal solution (20-200 mg/l) maintained
at definite pH was shaken with 1.0 g of SISG in a mechanical
shaker for the attainment of the equilibrium. The remaining
metal ion in the solution was determined by atomic
absorption spectroscopy. The amount of metal ion retained
by SISG was determined by the equation,
Mf = (X-Y)/W
where, X is the initial amount of metal ion added (g), Y the
equilibrium amount of metal ion remained in solution (g),
W the mass of SISG (g) and Mf the equilibrium amount of
metal ion (g) retained per gram of SISG.

b) Column Experiment:
Column experiment was performed for retention as well as
elution of respective metal ion. A funnel type glass
chromatographic column, plugged with cotton at the end and

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 International Journal of Engineering and Technical Research (IJETR)
ISSN: 2321-0869, Volume-2, Issue-3, March 2014
B. Retention behavior of metal ions on SISG

1) Batch experiment:

a) Effect of initial metal ion concentration and

shaking time:
The adsorption of each metal ion on SISG is found to depend
on both initial metal concentration and the shaking period.
The time at which equilibrium is attained is considered as the
equilibrium time and the corresponding concentration in the
solution is the equilibrium concentration.
It is found that the uptake of metal increases with lapse of
time and reaches a maximum in 30 minutes for Cu(II) and in
85 minutes for Ni(II). The maximum retention of 98% for
Cu(II) and 93% for Ni(II) was observed corresponding to an
initial concentration of 20 mg/l.With increase of metal ion to
200 mg/l, the percent adsorption was found to be 46.7 and
53.6% for Cu(II) and Ni(II) ion respectively. It may be
thought that with increase in metal ion concentration, the
ratio of the initial number of moles of metal ions to the
available retention sites becomes fewer. A comparison of
adsorption behavior indicates that both the equilibrium time
and the extent of metal retention follow the order Cu(II)
Ni(II).

b) Effect of agitation speed:

The agitation speed was varied from 100 to 400 rpm keeping
each initial metal concentration at 20 mg/l. It is found that
adsorption increases from 61 to 98% for Cu(II) and from 53.6
to 93.0%. for Ni(II). It may be thought that the resistance to
mass transfer in the bulk solution decreases resulting in the
increased driving force and hence the increased adsorption
on SISG.

c) Effect of the dose of SISG.

It is found that as the dose of SLSG increases the adsorption

increases both for Cu(II) and NI(II). The optimum dose for
Cu(II) and Ni(II) was found to be 0.65 and 0.80 g for Cu(II) e) Effect of temperature:
and Ni(II) respectively corresponding to even the highest The temperature has an influence on the metal adsorption. It
concentration studied of 200 mg/l. However, all subsequent is found that for both Cu(II) and Ni(II) the adsorption
experiments were performed using 1.0g of SISG. increases with increase of temperature. This is probably
because the equilibrium constant of the process that is
expected to increase with increased temperature. The
d) Effect of pH:
adsorption is found to increase from 46.7 to 56.1% for Cu(II)
and 53.6 to 67.0% for Ni(II) for an increase of temperature
The metal ion adsorption is found to be pH dependent where from 298 to 318K corresponding to each metal concentration
both the pattern and extent of adsorption vary with change of of 200 mg/l.
pH for each metal ion. A maximum adsorption of 98%
occurred at pH 2.2 for Cu(II) while for Ni(II) a maximum f) Tolerance level of electrolytes, foreign ions:
adsorption of 93% occurred at pH 3.5. The pH dependent Different electrolytes such as sodium chloride, potassium
adsorption behavior as illustrated in Fig.3 can be utilized for nitrate and potassium chloride possess higher tolerance
separation of Cu(II) and Ni(II) from their mixture in batch during metal adsorption. Other ions and salts show different
mode. However, the extent of adsorption corresponding to level of tolerance (Table 1).
each pH for Cu(II) and Ni(II) is presented in Fig.4.

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 SOLID PHASE EXTRACTION FOR THE REMOVAL, PRECONCENTRATION VIA RECOVERY AND
SEPARATION OF Cu(II) AND Ni(II) USING MODIFIED SILICA GEL

volume unit while band width is found to be < 6.0 volume

unit. Similarly separation of Cu(II) and Ni(II) can be made by
Table.1. Tolerance level of added salts on metal adsorption gradient elution with HClO4. The retention and elution
Salt added Tolerance level Effect on parameters for Cu(II) and Ni(II) in the column mode is
adsorption described in Table 2.
Cu(II) Ni(II)
KCl, KNO3, NaCl, 1g 1g unchanged
NaNO3,
CH3COONa, NH4Cl 1g 1g unchanged
KH2PO4, NaClO4 500 mg 500 mg unchanged
NH4F 100 g 150 g decrease
KI 100 g 200 g decrease
KCNS 100 g 200 g decrease
NaCN 5 g 10 g decrease
EDTA 5 g 5 g decrease
CaCl2, MgCl2, 1g 1g unchanged
AlCl3, MnCl2
Metal ion: 20 cm3 (20 mg/l) at the optimum condition

2) Column experiment:

a) Retention behavior Table 2: Column parameters for metal ions

Metal Maximum Eluent strength Elution Reco P. LOD
The effect of flow rate of the solution through the column on ion tolerable (mol/l) volume very F (g/l)
the retention behavior of each metal ion solution was studied flow rate (ml) (%)
over the range 1.0-10.0 ml/min. The extent of metal retention (ml/min )

was found to remain unchanged up to a flow rate of 10.0 HN HCl

O3 O4
ml/min for Cu(II) and 6.5 ml/min for Ni(II). In the present Cu(II) 10.0 1.4 0.4 15 98 66 1.0
study a flow rate for metal ion retention was maintained at
5.0 ml/min. Again when the volume of the sample solution Ni(II) 6.5 1.0 0.1 20 92 50 1.5
was varied no change in the extent of metal retention was
observed up to a volume of 1000 ml.
Influent sample volume: 1000ml; P.F: Preconcentration
factor; LOD: limit of detection
b) Elution behavior

In order to find the effectiveness of the process the recovery

In an aim to recover, preconcentrate or separate of Cu(II) and Ni(II) was determined from spiked samples.
metal ions from aqueous sample elution of the retained The results (Table 3) showing high recovery recommend
metals from SISG was studied. SISG after metal adsorption SISG as a promising adsorbent for Cu(II) and Ni(II).
was subjected to interaction with a varying concentration of
HNO3 or HClO4 for elution. The flow rate during elution was Table 3: Recovery of metal ions from synthetic and spiked
maintained at 3.0 ml/min. About 98.0% of retained Cu(II) samples
was recovered when treated with either 1.4 mol/l HNO3 or
0.4 mol/l HClO4 within a small volume of 15 ml. The elution Sl Metal added Cu(II) Ni(II)
was found effective with either HNO3 (0.4 mol/l) or HClO4 No. Mea Spik Found Reco Found Recovery
(0.01mol/l) and about 95.0% of the added Ni(II) was n ed (g/ml) very (g/ml) (%)
recovered within 25 ml of the eluent. The preconcentration (g/ml) (%)

factor for Cu(II) and Ni(II) were evaluated as 66 and 40 1 1.0 0.0 0.98 98.0 0.920.04 92.0
respectively. 0.04
2 1.0 0.5 1.47 98.0 1.380.04 92.0
In order to separate Cu(II) and Ni(II) from the bisolute
0.06
composition the difference in the elution character was 3 1.0 1.0 1.97 98.5 1.840.05 92.5
utilized and the gradient elution either with HNO3 or HClO4 0.05
was tested. Initially HNO3 at a concentration of 0.4 mol/l was 4 1.0 5.0 5.89 98.2 5.530.06 92.2
passed through the column and Ni(II) was recovered. Next a 0.04
5 1.0 10.0 10.82 98.4 10.160.05 92.4
higher concentration of HNO3 (1.4 mol/l) was passed and 0.04
Cu(II) is eluted. The recovery of Cu(II) and Ni(II) with HNO3 6 1.0 20.0 2.58 98.0 19.320.04 92.0
was shown in Fig.5. The resolution is found to be > 18.0 0.04

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 International Journal of Engineering and Technical Research (IJETR)
ISSN: 2321-0869, Volume-2, Issue-3, March 2014
(n = 5; Standard deviation < 0.06; 95% confidence level) [9] Cincotti A, Mameli A, Locci aM, Orru R, Cao G, Heavy metals uptake
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Functionalized Amberlite XAD-2 by Inductively Coupled
Plasma-Atomic Emission Spectrometry. Talanta, 62, 209-215
The present communication shows that (2004)
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