Post on 18-May-2020
CHAPTER 4
SOLID PHASE EXTRACTION: AZO-CALIX[4]PYRROLE AMBERLITE XAD-2 RESINS
FOR SEPARATION, PRECONCENTRATION AND TRACE DETERMINATION OF
Cu(II), Zn(II), Ni(II) and Cd(II)
Solid Phase Extraction of Transition Metals
Chapter 4 Page 143
RESUME
The immobilization of two new calix[4]pyrrole derivatives on the surface of
Amberlite XAD-2 polymer is described. Newly synthesized resins were characterised
by FT-IR and elemental analysis. The resins were efficiently employed for the
separation and preconcentration of metal ions such as Cu(II), Zn(II), Ni(II) and Cd(II)
in a column prior to their determination by Flame Atomic Absorption
spectrophotometer (FAAS) or UV/Vis spectrophotometer. Various physico-chemical
parameters like pH of maximum sorption, total sorption capacity, concentration of
eluting agents, flow rate, exchange kinetics, preconcentration factor, distribution
coefficient, breakthrough capacity, resin stability and reusability, effect of electrolyte
and associated metal ions were optimised for effective separation and
preconcentration. The present method was successfully applied to the analysis of
metal ions in synthetic, natural and ground water samples of Ahmedabad city.
Solid Phase Extraction of Transition Metals
Chapter 4 Page 144
TABLE OF CONTENTS
1. Introduction 145
2. Experimental Section 148
2.1. Instruments 148
2.2. Reagents 149
2.3. General column method for separation, preconcentration 151
and determination of metal ions
2.4. General batch method for preconcentration and determination 151
of metal ions
3. Results and Discussion 152
3.1. Optimization of the experimental conditions for separation and 152
preconcentration of Cu(II), Zn(II),Ni(II) and Cd(II)
3.1.1. Effect of pH on quantitative enrichment 152
3.1.2. Effect of flow rate on metal sorption 153
3.1.3. Effect of concentration of eluting agents 153
3.1.4. Sorption capacity and distribution coefficients 154
3.1.5. Exchange kinetics 155
3.1.6. Breakthrough studies 156
3.1.7. Stability and reusability of the resin 156
3.1.8. Preconcentration of Cu(II), Zn(II), Ni(II) and Cd(II) 157
3.1.9. Effect of electrolytes 158
3.2. Chromatographic separations 158
3.2.1. Separation of a binary mixture 159
3.2.2. Separation of a ternary mixture 159
3.3. Limit of quantification 159
3.4. Application 160
3.5. Comparison with other solid phase extraction methods 160
Conclusion 183
References 184
Solid Phase Extraction of Transition Metals
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1. INTRODUCTION
In general, heavy metal ions are toxic, non-biodegradable, and tend to be
accumulated in the human vital organs, where they can act progressively over a long
period through food chains. The determination of trace heavy metal ions in
environmental samples has received increasing attention [1–3]. The increasing levels
of heavy metals in the environment represent a serious threat to human health.
Environmental contamination with heavy metals gained lately more concern because
of their high persistence and the nervous system damage and even cancer, caused by
their accumulation at certain levels. Many metals listed as environmental hazards are
essential dietary trace elements required for normal growth and development of
animals and human beings. These metals are essential to the human life within
permissible limits. Those metals which have the adverse effect on human body are
known as toxic metals. Toxicity of metal ions such as copper, zinc, nickel and
cadmium in human beings are as follows:
(i) Copper: Copper is an economically important element which is found only in
trace quantity in earth's crust. For both plants and animals it is required as a
trace nutrient, but excessive amounts are toxic [4].
(ii) Zinc: Man and many animals exhibit considerable tolerance to high zinc
intakes. This tolerance is dependent on the nature of diet, and its Ca, Cu, Fe
and Cd contents with which zinc interacts in the process of adsorption and
utilization. Symptoms of zinc toxicity in humans include vomiting,
dehydration, electrolyte imbalance, abdominal pain, nausea, lethargy,
dizziness and lack of muscular disco-ordination [5].
Solid Phase Extraction of Transition Metals
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(iii) Nickel: Nickel plays important role in the biology of microorganisms and
plants [5]. Exposure to nickel metal and soluble compounds should not exceed
0.05 mg/cm³ in nickel equivalents per 40 hours work week. Nickel sulfide
fume and dust are believed to be carcinogenic, and various other nickel
compounds may be as well [5].
(iv) Cadmium: Cadmium is non-essential and toxic to human and animal systems
[6]. Small quantities of cadmium cause adverse changes in the arteries of
human kidneys and liver [7]. Teratogenic properties have been shown [8]
where as carcinogenic properties are suspected [9].
Wastewater discharged by enterprises processing ores and concentrates of
nonferrous metals are usually polluted with heavy metal ions, such as Cd(II), Cu(II),
Ni(II), and Zn(II). Environmental contamination by metals is mainly by the emission
of liquid effluents with relatively low, although harmful, metal concentrations (up to
some hundreds of mg/L) and therefore the removal of heavy metals from wastewaters
is required prior to discharge into receiving waters [10-13]. To cater to this need
either we should go for some sensitive instrumental technique or some separation or
enrichment technique for the determination of metal ions at trace level. Instrumental
technique usually suffers from matrix effects and need cumbersome sample
preparation, whereas separation/preconcentration of metal ions with some polymeric
chelating resins prior to their determination by FAAS/ICP-AES have been found to be
better alternative.
The most commonly employed techniques for the separation and
preconcentration of trace elements includes liquid–liquid extraction [14,15], flotation
[16, 17], coprecipitation [18], cloud point [19–22] and solid-phase extraction [23–25].
Solid Phase Extraction of Transition Metals
Chapter 4 Page 147
Solid-phase extraction (SPE) has become increasingly popular in trace elements
separation and preconcentration compared with the classical liquid–liquid extraction
method because of its advantages of high enrichment factor, high recovery, low cost,
rapid phase separation, low consumption of organic solvents and the ability to
combine with different detection techniques in on-line or off-line mode [26–28]. The
major requirements for substances used as solid-phase extractors are because of the
possibilities of extracting a large number of elements over a wide pH range, fast and
quantitative sorption and elution, high capacity, regenerability and accessibility.
Various SPE materials which have been used for the preconcentration of trace
metal ions as their chelates include, activated carbon [29], silica gel [30], polyurethane
foam [31], microcrystalline naphthalene [32], C18 cartridges [33], Chelex-100 [34],
Alumina [35] and Amberlite XAD resins [36]. Because of good physical and
chemical properties such as porosity, surface area, durability and purity [37]
Amberlite XAD-2 (styrene-divinyl benzene copolymer) is a support widely used to
develop several chelating resins for separation and preconcentration in last decade
[38]. Both the sorption capacity and sorption selectivity of chelating resins are
superior compared to ion-exchangers and adsorbents. That is why the reaction of
Amberlite XAD resin with suitable chelating agents was very popular in last decade.
In recent years many diazo-coupling techniques have been designed for the
synthesis of new azocalixarene dyes, which can also act as metal extractant [39]. A
few reports have been published in the field of polymer based calixpyrrole
macrocycles. Andrzej et al. [40] had demonstrated the synthesis of calixpyrrole
polymer matrix and their analytical performance towards anion as well as cation.
Sessler et al. [41] have developed the first bonafide polymeric systems containing a
calix[4]pyrrole anion receptor directly appended to a polymeric backbone which
Solid Phase Extraction of Transition Metals
Chapter 4 Page 148
could be readily optimized for use in a range of ion-binding and extraction
applications.
In earlier reports calix[4]pyrroles derivative having azo linkage [42], have
shown complexing ability with various metal ions. Further, these macrocylces were
loaded to Amberlite XAD-2 [43] through azo linkage to increase the complexing
properties and metal ions like Cu(II), Zn(II) and Cd(II) were studied for their solid
phase extraction, preconcentration and sequential separation.
Two new azo-calix[4]pyrrole Amberlite XAD-2 polymeric chelating resins
(I/II) were synthesised and used for solid phase extraction, preconcentration and
sequential separation of metal ions such as Cu(II), Zn(II), Ni(II) and Cd(II) in a
column prior to their determination by spectrophotometry/FAAS/ICP-AES. Various
factors influencing the separation and preconcentration of the trace metal ions, such as
pH, concentration of eluting agents, flow rate, total sorption capacity, exchange
kinetics, preconcentration factor, distribution coefficient, breakthrough capacity, resin
stability, effect of electrolytes and associated metal ions have been investigated. The
newly developed method has also been applied for the determination of Cu(II), Zn(II),
Ni(II) and Cd(II) in synthetic, natural and ground water samples of Ahmedabad city.
2. EXPERIMENTAL SECTION
2.1. Instruments
A flame atomic absorption spectrometer (FAAS) of Chemito equipped with
air–acetylene flame was used for metal ion determination. Chemito single-element
hollow cathode lamps were used in the AAS measurements. The operating conditions
adjusted in the atomic absorption spectrometer were carried out according to the
standard guidelines of the manufacturers. A 10 cm long slot-burner head, a lamp and
Solid Phase Extraction of Transition Metals
Chapter 4 Page 149
an air/acetylene flame were used. The analytical wavelength used for monitoring
Cu(II), Zn(II), Ni(II) and Cd(II) are 324.8, 213.9, 232.1 and 228.8 nm respectively.
Acetylene and air flow rates were 2 L min-1 for all elements. FT–IR spectra were
recorded on Bruker tensor 27 Infrared spectrophotometer as KBr pellets and
expressed in cm-1. A pH meter, Elico digital pH-meter, model L1 614 equipped with a
combined pH electrode was employed for measuring pH values in the aqueous phase.
The flow of the liquid through the column was controlled by Miclins Peristaltic pump
PP-10 EX.
2.2. Reagents
High purity reagents from Sigma-Aldrich and Merck were used for all
preparations of the standard and sample solution. All aqueous solutions were prepared
with quartz distilled deionized water, which was further purified by a Millipore Milli-
Q water purification system (Millipack 20, Pack name: Simpak 1, Synergy). All
glassware were washed with chromic acid and soaked in 5% HNO3 overnight and
cleaned with doubly distilled water before use.
The pH was adjusted with the following buffer solutions: PO4-3 /HPO4
-2 buffer for pH
2.0 and 3.0; CH3COO-1/ CH3COOH buffer for pH 4.0 and 6.0; HPO4-2/H2PO4
-1
buffers for pH 7.0 and 7.5; NH3/NH4+ buffers of pH 8 and 10. Standard stock
solutions (1000 μg mL-1) of Cu(II), Zn(II), Ni(II) and Cd(II) were prepared as given
below.
Cu(II): Dissolve 0.384 gm Cu(NO3)2.3H2O in water containing 1 mL
concentrated HNO3 and dilute upto 100 mL with water in volumetric flask.
Zn(II): Dissolve 0.4541 gm Zn(NO3)2.6H2O in water containing 1 mL
concentrated HNO3 and dilute upto 100 mL with water in volumetric flask.
Solid Phase Extraction of Transition Metals
Chapter 4 Page 150
NHNH N
HNH
CH3
CH3
CH3
CH3
OHHOHO
HO
OHHO
OH
HON
N
N
NN
N
N
NOH
OH OH
OH
CH CH2n
N
N
Ni(II): Dissolve 0.4045 gm NiCl2.6H2O in water containing 1 mL
concentrated HNO3 and dilute upto 100 mL with water in volumetric flask.
Cd(II): Dissolve 0.2744 gm Cd(NO3)2.4H2O in water containing 2 m
concentrated HNO3 and dilute upto 100 mL with water in volumetric flask.
Working solutions were subsequently prepared by appropriate dilution of the stock
solutions. The water samples from Sabarmati river were isokinetically collected in
clean polyethylene bottles from locations near a thermal power station, Ahmedabad.
The ground water samples were collected from the University area and Vatva
industrial zone of Ahmedabad city.
Figure 1.
Two novel azo-calix[4]pyrrole Amberlite XAD-2 polymeric chelating resins (resin I
and resin II) (Figure 1) were synthesized and characterized as described in chapter 2.
NHNH N
HNH
CH3
CH3
CH3
CH3
OHHOHO
HO
OHHO
OH
HO
CH CH2n
N
N
Resin I
Resin II
Solid Phase Extraction of Transition Metals
Chapter 4 Page 151
2.3. General column method for separation, preconcentration and determination
of metal ions
A glass column (10 cm long, 1 cm inner diameter) equipped with a stopcock
and a porous disk was used. 1 gm of the azo-calix[4]pyrrole Amberlite XAD-2
polymeric chelating resin (I/II) was mixed with CH3OH:H2O (1:1) to obtain a slurry
and then poured onto the column. The resin was washed with dilute acid, dilute base,
deionized water and finally, it was conditioned with 10-15 mL of a buffer solution of
desired pH prior for the passage of suitable aliquot of the sample solution containing
Cu(II) and/or Zn(II) and/or Ni(II) and/or Cd(II) at an optimum flow rate, controlled by
a peristaltic pump. The bound metal ions were stripped from the column with suitable
eluting agents such as HCl or HNO3. The eluants were collected and its volume was
made up to the mark with double distilled water in a 25 mL volumetric flask. Metal
content in the eluant was determined by spectrophotometry/FAAS/ICP-AES. After
each experiment, the column was regenerated by washing it with desired acid and
large amount of distilled water and stored for the next use.
2.4. General batch method for preconcentration and determination of metal ions
After adjusting optimum pH, the sample solution (100 mL) containing Cu(II)
or Zn(II) or Ni(II) or Cd(II) was placed in a glass stopper bottle (250 mL). The
azocalix[4]pyrrole Amberlite XAD-2 polymeric chelating resin (I/II) (0.5 gm) was
added to the above solution. The bottle was tightly stoppered, shaken for 1 hour and
the chelated resin was filtered. Filtrate and resins were treated separately for metal
content determination. Metal content in chelated resin was determined by shaking it
again with suitable eluting agent (HCl/HNO3) for at least 10 minutes. The resin was
filtered, eluant was collected and its volume was made upto mark in a 25 mL
Solid Phase Extraction of Transition Metals
Chapter 4 Page 152
volumetric flask. Metal content in filtrate and eluant were determined by
spectrophotometry/FAAS/ICP-AES.
3. RESULTS AND DISCUSSION
3.1. Optimization of the experimental conditions for separation and
preconcentration of Cu(II), Zn(II), Ni(II) and Cd(II).
Separation and preconcentration procedures for quantitative solid phase
extraction of Cu(II), Zn(II), Ni(II) and Cd(II) on the calix[4]pyrrole loaded Amberlite
XAD-2 polymeric chelating resin (I/II), were optimized such as pH, flow rate,
concentration and volume of the eluting agents, total sorption capacity, distribution
coefficient (Kd), exchange kinetics, breakthrough studies, preconcentration factor,
reusability of the resin and effect of electrolytes.
3.1.1. Effect of pH on quantitative enrichment
As the pH of the aqueous medium is one of the important parameters for the
quantitative retention of analytes, calix[4]pyrroles in our case, in the solid phase
extraction studies, the influence of the pH of the aqueous solution containing 5 µg
mL-1: Cu(II), 4 µg mL-1 : Zn(II), 4 µg mL-1: Ni(II) and 7 µg mL-1 : Cd(II) on the
quantitative adsorption of analytes on Amberlite XAD-2 polymeric chelating resin
were investigated in the pH range of 3.0-9.0 using the batch method. 100 mL of metal
containing aqueous solutions were placed in glass stoppered bottles at different pH
and were stirred for 1 hour. Total metal sorption in percentage was estimated by
determining the metal content in raffinate by spectrophotometry/FAAS/ICP-AES.
The optimum pH for sorption for Cu(II), Zn(II), Ni(II) and Cd(II) was found to be
6.0, 5.0, 7.0 and 8.0 respectively for resin (I/II) both (Table 1, Figure 2). The pH
studies revealed selective sorption of metals ions which suggested the possibility of
separation of these metal ions in presence of each other in the column.
Solid Phase Extraction of Transition Metals
Chapter 4 Page 153
3.1.2. Effect of flow rate on metal sorption
In the column procedure, the degree of metal ion retention on the adsorbent
was studied at various flow rates of the solutions. Therefore, the effect of the flow rate
of the sample solution was studied by using peristaltic pump. The sorption of metal
ion on 1.0 gm resins (I/II) in a packed column was studied at various flow rates. Feed
solutions containing 5 μg mL-1 of Cu(II), Zn(II), Ni(II) or Cd(II) were passed
through the column at different flow rates (0.5, 1.0, 1.5, 2.0, 2.5 etc., mL min-1)
maintained by a peristaltic pump. Optimum flow rate may be defined as the rate of
flow of the effluent through the column at which more than 98% sorption takes place.
The optimum flow rates obtained for resins (I/II) were 2.0, 1.5, 2.5 and 1.0 mL min-1
for Cu(II), Zn(II), Ni(II) and Cd(II) in case of resin I and resin II respectively (Figure
3).
The studies showed that the flow rate had more influence on the sorption of
metal ions. It was observed that, as the flow rate increases the sorption decreases,
because the time required for the metal ion to come in contact with the chelating resin
is less, therefore the sorption of metal ion decreases (Table 1, Figure 3).
3.1.3. Effect of concentration of eluting agents
In this experiment, a series of experiments were designed and performed to
obtain a reasonable eluent to elute completely Cu(II) or Zn(II) or Ni(II) or Cd(II) ions
after their enrichment by chelation. The type and concentration of the eluant used for
stripping metal ions from the chelating resins (I/II) is one of the most important
factors that affects the separation procedure and reusability of resin. In order to obtain
maximum recovery of metal at the minimum concentration of the eluant, the effect of
eluting agents like HCl and HNO3 were studied at different concentrations. 1.0 gm
Solid Phase Extraction of Transition Metals
Chapter 4 Page 154
resins (I/II) in the column was conditioned at pH of maximum sorption and then fed
with 100 mL solutions containing 5 μg mL-1 Cu(II) , Zn(II), Ni(II) or Cd(II). The
metal ions were desorbed with different concentrations of acids and then determined
by spectrophotometry/ FAAS/ICP-AES (Table 1 and Table 2). It was observed that
quantitative elution was possible with 3.0 N HCl, 1.0 N HCl, 2.0 N HCl and 1.0 N
HNO3 for Cu(II), Zn(II), Ni(II) and Cd(II) on resin I; and with 3.0 N HCl, 1.0 N HCl,
2.0 N HCl and 1.0 N HNO3 for Cu(II), Zn(II), Ni(II) and Cd(II) on resin II,
respectively.
3.1.4. Sorption capacity and distribution coefficients
Sorption capacity determines the amount of the sorbent required for
quantitative determination of analytes in a given solution. Sorption capacity of the
modified resins was determined for each metal ion by using batch method. The
chelating resins (I/II) (1.0 gm) was equilibrated in the excess of metal ion solution
(100 mL, 800 μg mL-1) by shaking for 1 hour under optimum pH conditions. Then,
the solid resin was filtered and the filtrate was diluted. Concentration of metal ions in
the filtrate was determined by FAAS. The amount of metal ions sorbed on resins
(I/II) was calculated from the difference in the metal ion concentration before and
after sorption (Table 1). For resin I sorption capacity for Cu(II), Zn(II), Ni(II) and
Cd(II) was found to be 29000, 27300, 19486 and 46000 μg gm-1, respectively. For
resin II sorption capacity for Cu(II), Zn(II), Ni(II) and Cd(II) was found to be 33000,
29300, 23432 and 52500 μg gm-1, respectively. Sorption capacity for various metal
ions differed due to their size, degree of hydration and their binding constants with the
ligand immobilized onto the resins (I/II).
Solid Phase Extraction of Transition Metals
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Exchange equilibria are very often expressed in terms of the distribution
coefficient Kd. This quantity is given by the ratio of the equilibrium concentrations of
the same metal ion in the resin phase and in the solution.
The distribution coefficient Kd of the metal ions between resins (I/II) and aqueous
phase was determined by batch method.
0.5 gm resins (I/II) was equilibrated with 100 mL solution containing not
more than 145, 136.5, 97, 230 μg mL-1 and 165, 146.5, 117, 262.5 μg mL-1 of Cu(II),
Zn(II), Ni(II) and Cd(II) respectively for 1 hour at 30°C. The solution was filtered to
remove resins (I/II) and the filtrate was subjected to spectrophotometry/ FAAS/ICP-
AES for determination of the metal ion content (Table 1). Kd for Cu(II), Zn(II), Ni(II)
and Cd(II) were found to be 5800, 4520, 3233, 7666 and 6460, 4883, 3900, 8750 for
resin I and resin II respectively.
3.1.5. Exchange kinetics
Batch experiments were carried out to determine the rate of loading of Cu(II),
Zn(II), Ni(II) and Cd(II) on resin (I/II). 1 gm resin (I/II) was stirred with 100 mL of
solution containing 290, 273, 194, 460 and 330, 293, 234, 525 μg mL−1 of Cu(II),
Zn(II), Ni(II) and Cd(II), respectively, for resin I and resin II at room temperature.
Aliquots of 5 mL of solution was withdrawn at predetermined intervals and analysed.
The concentration of metal ions in the supernatant solution was determined by FAAS.
The sorption as a function of time for all the metal ions is shown in Figure 4. The
time taken for the sorption of 50 % of the metal ions (t1/2) for resin I was found to be
6.0, 8.5, 9.5 and 12.5 minutes and for resin II, it was found to be 5.0, 6.0, 8.0 and 10.5
takenreofAmountsolutiontheofVolume
solutiontheinremainingionmetaltheofAmountrethebyuptakenionmetaltheofAmountK d sin
sin
Solid Phase Extraction of Transition Metals
Chapter 4 Page 156
minutes for Cu(II), Zn(II), Ni(II) and Cd(II), respectively, which indicates very good
accessibility of these metal ions towards chelating sites. The faster uptake of these
metal ions on resin II probably reflects more accessibility to the chelating sites in
resin II in comparison to resin I.
3.1.6. Breakthrough studies
Actual working capacity of the resin in the column can be known through
breakthrough capacities. They are more significant and useful than total sorption
capacities in ion exchange chromatographic applications. Breakthrough capacity or
the effective capacity may be defined as the capacity at the moment when the analyte
starts appearing in the effluent. It is one of the most critical parameters when working
under dynamic condition. Breakthrough studies were carried out by taking 1.0 gm
resins (I/II) in the column and passing 10 µg mL-1 of metal ions [Cu(II) or Zn(II)or
Ni(II) or Cd(II)] at their optimum pH and flow rates. An aliquot of 1.0 mL eluant was
collected each time and analysed by ICP-AES for the determination of metal ion
content (Figure 5). Breakthrough capacities of resin I and resin II for Cu(II), Zn(II),
Ni(II), Cd(II) were found to be 7540, 7310, 5358, 9200 and 9249, 8350, 6326, 15450
µg gm-1, respectively, (Table 1).
3.1.7. Stability and reusability of the resin
Accuracy and reproducibility in analytical data is a challenging task when
reusing the same resin. The reusability of the present resin was examined after several
loading and elution cycles. The study was carried out on 0.5 gm of resins (I/II) beads
which were stirred with 100 mL, 300 µg mL-1 solution containing metal ions
[Cu(II)or Zn(II) or Ni(II) or Cd(II)] for 1 hour at room temperature. The elution
operations were carried out by shaking the resin with 50 mL of suitable eluant for 10
minutes to ensure complete desorption. The operating capacity was calculated from
Solid Phase Extraction of Transition Metals
Chapter 4 Page 157
the loading and elution tests. The results from both tests agreed within 3-4% error for
all the metal ions up to 10-14 cycles of sorption and desorption experiments (Figure
6). The resins (I/II) showed better reusability and stability towards these metal ions.
3.1.8. Preconcentration of Cu(II), Zn(II), Ni(II) and Cd(II)
The concentration of trace metal ions in water is too low for its direct
determination. Therefore, pre-concentration or enrichment step is necessary to bring
the sample to the detectable limit of existing detection method. Resins (I/II) was
studied for column concentration of Cu(II), Zn(II), Ni(II) and Cd(II) in terms of their
preconcentration factor (PF).
solutionfeedinmetalofionconcentratInitialsolutionstrippinginmetalofionConcentratPF
1000 mL solutions containing 6, 5, 5, 10 µg L-1 Cu(II), Zn(II) , Ni(II) and
Cd(II) at pH 6.0, 5.0, 7.0, 8.0 respectively, were passed through the column
containing 1.0 gm resins (I/II). Metal contents in the stripped solution were
determined by spectrophotometry and ICP-AES. The pre-concentrating ability of
resins (I/II) was assessed from the elution profile of metal ions by plotting the
concentration of effluents as a function of the volume of stripping solutions. For resin
I: 10.5 mL, 3.0 N HCl for Cu(II); 11.0 mL, 1.0 N HCl for Zn(II); 11.2 mL, 2.0 N HCl
for Ni(II); and 11.4 mL, 1.0 N HNO3 for Cd(II). For resin II: 11.0 mL, 3.0 N HCl for
Cu(II); 10.5 mL, 1.0 N HCl for Zn(II); 11.5 mL, 2.0 N HCl for Ni(II); and 11.5 mL,
1.0 N HNO3 for Cd(II). The pre-concentration factors for resin I were found to be
102, 111, 98, 120 and for resin II were found to be 107, 119, 101, 126 for Cu(II),
Zn(II), Ni(II) and Cd(II) with 95-97% recovery (Tables 1 and 3, Figure 7).
Solid Phase Extraction of Transition Metals
Chapter 4 Page 158
3.1.9. Effect of electrolytes
Interference of electrolytes is one of the main problems in the spectrometric
determination of metal ions. To evaluate the selectivity of the synthesized resins,
several interfering electrolytes were tested. The limit of tolerance of anions on the
sorption of Cu(II), Zn(II), Ni(II) and Cd(II) is defined as that concentration which
causes an error of 2-3% in the recovery of these metal ions. The effect of anions and
their limit of tolerance on the sorption of Cu(II), Zn(II), Ni(II) and Cd(II) by resins
(I/II) was studied by taking different concentrations of electrolytes. The results are
presented in (Table 4). Except Na3PO4 and NaF, all others electrolytes did not
interfere between 1.5- 4.0M concentration ranges, which further augment the potential
application of resins (I/II) for the analysis of real samples.
3.2. Chromatographic separations
As observed from experimental practise synthesized resin II was found to be
better than resin I in terms of sorption capacity, distribution coefficient and exchange
kinetics, therefore resin II was used for the separation of Cu(II), Zn(II) and Cd(II)
from their binary and ternary mixtures by column method. The ternary mixtures of
Cu(II), Zn(II) and Cd(II) can be separated by selective adjustment of the pH and
eluting agents. Hence, the following mixtures (each 100 μg in 25 mL buffer solution)
were passed through the column at the pH of maximum sorption and optimum flow
rate. The column effluents were analyzed for the metal ions by spectrophotometry/
FAAS/ICP-AES.
Solid Phase Extraction of Transition Metals
Chapter 4 Page 159
3.2.1. Separation of a binary mixture
100 µg of both Zn(II) and Cd(II) in 25 mL of buffer solution of pH 5.0 were
passed through the column at a flow rate of 2.0 mL min1. At this pH, Cd(II) was not
sorbed on resin II and it came out with the effluent while Zn(II) was retained in the
column. Zn(II) was eluted with 23 mL, 1.0 N HCl. Quantitative separation was
achieved in binary mixture as shown in their separation pattern in Figure 8(a).
3.2.2. Separation of a ternary mixture
100 µg each of Cu(II), Zn(II) and Cd(II) in 25 mL of buffer solution of pH 5.0
were passed through the column at a flow rate of 2.0 mL min1. At this pH, Cd(II)
was not sorbed on resin II and it came out with the effluent, while Cu(II) and Zn(II)
were retained in the column. Cu(II) and Zn(II) were then separated on the basis of
selective eluting agents. Zn(II) was eluted first with 24 mL, 1.0 N HCl followed by
Cu(II) with 21 mL, 3.0 N HCl. Quantitative separation was achieved in the ternary
mixture as shown in their separation patterns in Figure 8(b).
3.3. Limit of quantification
Selectivity and sensitivity are two important factors in the extraction and the
separation process. To test the resin’s capability to detect trace amounts of metal ions,
studies were performed passing 1000 mL sample solutions containing metal ions in
the range of 4–10 μg through the optimized column. The quantification limit for
Cu(II), Zn(II), Ni(II) and Cd(II) for resins II were found to be 5.5, 4.5, 4.0 and 9.0 μg
L-1, respectively, indicating the resin’s capability to extract the trace metal ions of
interest from the real samples.
Solid Phase Extraction of Transition Metals
Chapter 4 Page 160
3.4. Application
To check the applicability of the present method for preconcentrating and
determining Cu(II), Zn(II), Ni(II) and Cd(II), the synthesized resin II was subjected to
various water samples analyses. For the determination of metal ions by the proposed
method, the results are compared by the standard addition technique. In this
experiment, 1000 mL of sample volume was spiked with known amount of metal ions
and then determined by spectrophotometry/ FAAS/ICP-AES. The data is given in
Table 5.
3.5. Comparison with other solid phase extraction methods
Comparison of sorption capacity and preconcentration factor of various
adsorbents (Table 6) showed that resins (I/II) have high sorption capacity and good
preconcentrating ability for Cu(II), Zn(II), Ni(II) and Cd(II) metal ions.
Solid Phase Extraction of Transition Metals
Chapter 4 Page 161
Table 1. Parameters optimized for sorption and desorption of Cu(II), Zn(II), Ni(II) and Cd(II) on resins (I/II).
No. Parameters Resin I Resin II
Cu(II) Zn(II) Ni(II) Cd(II) Cu(II) Zn(II) Ni(II) Cd(II)
1 pH range 5.5-6.0 4.5-5.0 6.5-7.0 7.5-8.0 5.5-6.0 4.5-5.0 6.5-7.0 7.5-8
2 Flow rate (mL min-1) 2 1.5 2.5 1 2 1.5 2.5 1
3 Concentration of acid for desorption
3.0 N HCl
1.0 N HCl
2.0N HCl
1.0 N HNO3
3.0 N HCl
1.0 N HCl
2.0N HCl
1.0 N HNO3
4 Total sorption capacity (μg gm-1 ) 29,000 27,300 19,486 46,000 33,000 29,300 23,432 52,500
5 Distribution coefficient (Kd) 5,800 4,520 3,233 7,666 6,460 4,883 3,900 8,750
6 Preconcentration factor (PF) 102 111 98 120 107 119 101 126
7 Breakthrough capacity (μg gm-1) 7,540 7,310 5,358 9,200 9,249 8,350 6,326 15,450
8 Average recovery (%) 97 97 97-98 96 96 95-96 97-98 97
9 t1/2 for exchange (minutes) 6 8.5 9.5 12.5 5 6 8 10.5
10 Relative standard deviation (%)* 2.2 2.3 2.4 2.7 2.8 2.7 2.9 2.8
*Average ten determination
Table 2(a). Effect of concentration of eluting agents for desorption of Cu(II), Zn(II),Ni(II) and Cd(II) from resins (I/II).
Solid Phase Extraction of Transition Metals
Chapter 4 Page 162
[Experimental conditions: Resins (I/II): 1.0 gm; Volume of solution passed: 100 mL; Metal ions: 5 µg mL-1 {Cu(II):pH 6.0; Zn(II): pH
5.0; Ni(II) : 7.0pH; Cd(II): pH 8.0}].
Conc. (N)
Resin I HCl HNO3
Cu(II) Zn(II) Ni(II) Cd(II) Cu(II) Zn(II) Ni(II) Cd(II) (%) (%) (%) (%) (%) (%) (%) (%)
0.01 0.5 4.8 5.7 2.1 2.7 2.9 7.9 19.2 0.1 10 21.8 19.8 8.2 20 18.3 38.9 45.2 0.5 19 45.2 41.9 31.9 45.7 48.8 67.4 78.5 1 25 98.3 68.3 55.5 98.3 81.9 97.5 98.6
1.5 49 98.4 81.7 60.8 98.4 97.4 97.7 98.7 2 70.7 98.5 98.1 74.7 98.5 97.6 97.8 98.7
2.5 85.1 98.5 98.5 97.2 98.5 97.8 98.1 98.8 3 98.4 98.6 98.7 97.6 98.6 97.9 98.2 98.9
Solid Phase Extraction of Transition Metals
Chapter 4 Page 163
Table 2(b) Effect of concentration of eluting agents for desorption of Cu(II), Zn(II), Ni(II) and Cd(II) from resins (I/II).
[Experimental conditions: Resins (I/II): 1.0 gm; Volume of solution passed: 100 mL; Metal ions: 5 µg mL-1 {Cu(II):pH 6.0; Zn(II): pH
5.0; Ni(II) : 7.0pH; Cd(II): pH 8.0}].
Conc. (N)
Resin II HCl HNO3
Cu(II) Zn(II) Ni(II) Cd(II) Cu(II) Zn(II) Ni(II) Cd(II) (%) (%) (%) (%) (%) (%) (%) (%)
0.01 1.5 8.8 8.2 1.2 2.1 11.1 9.9 10.2 0.1 3.5 23.4 32 3.5 8.8 22.9 34.2 47.8 0.5 11.9 63.5 54.6 7.8 39.4 39.1 67.3 75.1 1 22.3 98.3 71.5 13.8 98.9 61.2 98.1 97.7
1.5 60.4 98.4 85 24.6 99.1 98.8 98.2 97.9 2 98.1 98.5 98.6 35.7 99.2 98.8 98.3 98.0
2.5 98.5 98.7 98.7 77.6 99.3 98.9 98.4 98.0 3 98.6 98.8 98.9 98.7 99.3 99.0 98.4 98.1
Solid Phase Extraction of Transition Metals
Chapter 4 Page 164
Table 3 Preconcentration factors for the sorption of Cu(II), Zn(II), Ni(II) and Cd(II) on resins (I/II). [Experimental conditions: For resin
I: 1 gm; Cu(II): pH 6.0; Elution by 3.0 N HCl; Zn(II): pH 5.0; Elution by 1.0 N HCl; Ni(II): pH 7.0; Elution by 2.0 N HCl; Cd(II): pH 8;
Elution by 1.0 N HNO3. For resin II: 1 gm; Cu(II): pH 6.0; Elution by 3.0 N HCl; Zn(II): pH 5.0; Elution by 1.0 N HCl; Ni(II): pH 7.0;
Elution by 2.0 N HCl; Cd(II): pH 8.0; Elution by 1.0 N HNO3]
Metal ions
Volume of Solution Passed
(mL)
Concentration of Feed Solution
(µg L-1)
Volume of eluted
Solution(mL) Recovery (%)
Preconcentration Factor (PF)
Resin I Cu(II) 1000 6 10.5 97 102 Zn(II) 1000 5 11 97 111 Ni(II) 1000 5 11.2 97-98 98 Cd(II) 1000 10 11.4 98 120
Resin II Cu(II) 1000 6 11 96 107 Zn(II) 1000 5 10.5 95-96 119 Ni(II) 1000 5 11.5 97-98 101 Cd(II) 1000 10 11.5 97 126
Values given are an average of ten determinations.
Solid Phase Extraction of Transition Metals
Chapter 4 Page 165
Table 4 Tolerance limits of electrolytes on the sorption of Cu(II), Zn(II), Ni(II) and Cd(II) on resins (I/II). [Experimental Conditions:
Resin: 1 gm; Volume of solution passed: 100 mL; Cu(II): pH 6.0; Zn(II): pH 5.0; Ni(II): pH 7.0; Cd(II): pH 8.0].
Metal ions Concentration of Electrolytes (mol L-1)
(2.5 (µg mL-1) NaF NaCl NaBr NaNO2 CH3COONa Na2SO4 Na3PO4 Resin I Cu(II) 0.6 2.6 1.8 3.1 2.3 1.5 0 Zn(II) 0.7 3.7 2.1 3.5 2.8 1.3 0.1 Ni(II) 0.4 3.2 1.9 3.2 2.5 1.2 0.1 Cd(II) 0.8 2.0 2.9 2.9 2.8 1.2 0.2
Resin II Cu(II) 0.5 2.3 2.8 2.9 2.4 1.4 0.15 Zn(II) 0.4 2.0 2.9 3.2 2.5 1.6 0.25 Ni(II) 0.1 2.8 2.1 3.3 2.3 1.3 0.13 Cd(II) 0.8 2.5 1.9 2.6 1.9 1.5 0.21
Values given are average of ten determinations.
Solid Phase Extraction of Transition Metals
Chapter 4 Page 166
Table 5 Determination of Cu(II), Zn(II),Ni(II) and Cd(II) in natural water samples on resin II. [Experimental conditions: Resin II: 1 gm;
Sample volume: 1000 mL].
Sample
Method
Cu(II) Zn(II) Ni(II) Cd(II)
Amount
(µg L-1)
R.S.D.*
(%)
Amount
(µg L-1)
R.S.D.*
(%)
Amount
(µg L-1)
R.S.D.*
(%)
Amount
(µg L-1)
R.S.D.*
(%)
Sabarmati river, near
thermal power station,
Ahmedabad
Present Method 42.5±0.5 1.2 15±0.5 1.1 11±0.5 1.2 12.5±0.5 1.1
Standard Addition
45 1.15 20 1.2 12 1.15 14 1.3
Ground water, university area,
Ahmedabad
Present Method 10.5±0.5 1.3 14.5±0.5 1.15 10.5±0.5 1.6 13±0.5 1.3
Standard Addition 15 1.4 15 1.25 12 1.23 14.5 1.1
Ground water, Vatva Industrial
Zone, Ahmedabad
Present Method 58±0.5 1.25 29±0.5 1.3 25±0.5 1.63 40±0.5 1
Standard Addition 60 1.35 30 1.15 27 1.1 42 1.1
*Average of ten determinations.
Solid Phase Extraction of Transition Metals
Chapter 4 Page 167
Table 6. Comparable methods for preconcentration and determination of Cu(II), Zn(II), Ni(II) and Cd(II).
No. Adsorbent Sorption Capacity(μg/gm) Preconcentration factor Ref Cu(II) Zn(II) Ni(II) Cd(II) Cu(II) Zn(II) Ni(II) Cd(II)
1 1,6-bis(2-carboxy aldehyde phenoxy)butane -XAD-16 5,380 4,436 100 100 44
2 polyethyleneiminemethylene phosphonic acid 85,690 45
3
alumina-(N -{4-[4-{1-[4- (dimethylamino)phenyl]methylid
ene}-5-(4-H)oxazolone]phenyle}acetamide
8,000 14,000 400 160 46
4 [diamino-4-(4-nitro-phenylazo)- 1H-pyrazole (PDANP)]- XAD 7 7,200 58
5 MWCNTs -( D2EHPA-TOPO) 4,900 4789 47
7 gallic acid-modified silica gel 15,380 6,090 200 100 48
8 bis(2-hydroxy
acetophenone)ethylendiimine- activated carbon
2,100 2,100 49
9 Amberlite XAD-2-o-vanillinthiosemicarbazone 850 1,500 90 140 37(a)
10 Dowex Optipore SD-2 12,000 11,500 50 11 Azocalix[4]pyrrole Amberlite
XAD-2 27,250 14,400 19,636 87 91 96 43 I Resin I 29,000 27,300 19,456 46,000 102 111 98 120 II Resin II 33,000 29,300 23,432 52,500 107 119 101 126
Solid Phase Extraction of Transition Metals
Chapter 4 Page 169
Figure 2(a). Effect of pH on the sorption of Cu(II), Zn(II), Ni(II)
and Cd(II) by the resin I.
Experimental conditions: Amount of resin I in the column: 1.0 gm; Volume of metal
ion solution passed: 100 mL; Cu(II): 5 µg mL-1 Elution by: 3.0 N HCl; Zn(II): 4µg
mL-1, Elution by: 1.0 N HCl; Ni(II): 4 µg mL-1 Elution by: 2.0 N HCl; Cd(II): 7 µg
mL-1, Elution by: 1.0 N HNO3.
0
20
40
60
80
100
120
0 2 4 6 8 10
% S
orpt
ion
pH
Resin I
Cu(II)Zn(II)Ni(II)Cd(II)
Solid Phase Extraction of Transition Metals
Chapter 4 Page 170
Figure 2(b). Effect of pH on the sorption of Cu(II), Zn(II),Ni(II)
and Cd(II) by the resin II.
Experimental conditions: Amount of resin II in the column: 1.0 gm; Volume of
metal ion solution passed: 100 mL; Cu(II): 5 µg mL-1 Elution by: 3.0 N HCl; Zn(II):
4µg mL-1, Elution by: 1.0 N HCl; Ni(II): 4 µg mL-1 Elution by: 2.0 N HCl ; Cd(II): 7
µg mL-1, Elution by: 1.0 N HNO3.
0
20
40
60
80
100
120
0 2 4 6 8 10
% S
orpt
ion
pH
Resin II
Cu(II)Zn(II)Ni(II)Cd(II)
Solid Phase Extraction of Transition Metals
Chapter 4 Page 171
.
Figure 3(a) Effect of Flow rate on the sorption of Cu(II), Zn(II), Ni(II)
and Cd(II) on the resin I.
Experimental conditions: Amount of resin I in the column: 1.0 gm; Cu(II): 5 µg mL-
1, pH: 6.0; Zn(II): 5 µg mL-1, pH: 5.0; Ni(II): 5 µg mL-1, pH: 7.0; Cd(II): 5 µg mL-1,
pH: 8.0 .
0
20
40
60
80
100
120
0 1 2 3 4 5 6 7
% S
orpt
ion
Flow rate (mL/min)
Resin I
Cu(II)Zn(II)Ni(II)Cd(II)
Solid Phase Extraction of Transition Metals
Chapter 4 Page 172
Figure 3(b). Effect of Flow rate on the sorption of Cu(II), Zn(II), Ni(II)
and Cd(II) on the resin II.
Experimental conditions: Amount of resin (II) in the column: 1.0 gm; Cu(II): 5 µg
mL-1, pH: 6.0; Zn(II): 5 µg mL-1, pH: 5.0 ; Ni(II): 5 µg mL-1, pH: 7.0; Cd(II): 5 µg
mL-1, pH: 8.0)
0
20
40
60
80
100
120
0 1 2 3 4 5 6 7
% S
orpt
ion
Flow rate (mL/min)
Resin II
Cu(II)Zn(II)Ni(II)Cd(II)
Solid Phase Extraction of Transition Metals
Chapter 4 Page 173
Figure 4(a). Exchange kinetics of Cu(II), Zn(II), Ni(II)
and Cd(II) on the resin I
Experimental conditions: Amount of the resin I: 1.0 gm; Volume of the feed
solution: 100 mL; Cu(II): 290 µg mL-1; pH: 6.0; Zn(II): 273 µg mL-1; pH: 5.0; 100
mL; Ni(II): 194 µg mL-1; pH: 7.0; Cd(II): 460 µg mL-1; pH: 8.0 .
0
20
40
60
80
100
120
0 20 40 60 80
% S
orpt
ion
Time (Minutes)
Resin I
Cu(II)Zn(II)Ni(II)Cd(II)
Solid Phase Extraction of Transition Metals
Chapter 4 Page 174
Figure 4(b) Exchange kinetics of Cu(II), Zn(II)
and Cd(II) on the Resin II
Experimental conditions: Amount of the Resin II: 1.0 gm; Volume of the feed
solution: 100 mL; Cu(II): 330 µg mL-1; pH: 6.0; Zn(II): 293 µg mL-1; pH: 5.0; 100
mL; Ni(II): 234 µg mL-1; pH: 7.0; Cd(II): 525 µg mL-1; pH: 8.0 .
0
20
40
60
80
100
120
0 10 20 30 40 50 60 70 80
% S
orpt
ion
Time (Minutes)
Resin II
Cu(II)Zn(II)Ni(II)Cd(II)
Solid Phase Extraction of Transition Metals
Chapter 4 Page 175
Figure 5(a). Breakthrough curve for Cu(II), Zn(II), Ni(II)
and Cd(II) on the resin I.
Experimental conditions: Amount of the Resin (I) : 1.0 gm; Concentration of the
metal ion solution passed: 10 µg mL-1; Cu(II): 6.0 pH; Zn(II): 5.0 pH; Ni(II): 7.0 pH;
Cd(II): 8.0 pH
0123456789
0 200 400 600 800 1000 1200
Con
c of
effl
uent
(μg/
mL)
Effluent Volume (mL)
Resin I
Cu(II)Zn(II)Ni(II)Cd(II)
Solid Phase Extraction of Transition Metals
Chapter 4 Page 176
Figure 5(b). Breakthrough curve for Cu(II), Zn(II), Ni(II)
and Cd(II) on the Resin II.
Experimental conditions: Amount of the Resin (II) : 1.0 gm; Concentration of the
metal ion solution passed: 10 µg mL-1; Cu(II): 6.0 pH; Zn(II): 5.0 pH; Ni(II): 7.0 pH;
Cd(II): 8.0 pH
0123456789
0 500 1000 1500 2000
Con
c. o
f effl
uent
(μg/
mL)
Effluent Volume (mL)
Resin II
Cu(II)Zn(II)Ni(II)Cd(II)
Solid Phase Extraction of Transition Metals
Chapter 4 Page 177
Figure 6(a). Stability of the resin I for Cu(II), Zn(II), Ni(II)
and Cd(II) by Sorption and Elution
Experimental condition: Amount of the resin I in the column: 0.5 gm; Volume of
the feed solution: 100 mL; Concentration of feed solution: 300 µg mL-1; Cu(II): pH
6.0; elution by: 3.0 N HCl; Zn(II): pH 5.0; elution by: 1.0 N HCl; Ni(II): pH 7.0;
elution by: 2.0 N HCl; Cd(II) : pH 7.5; elution by: 1.0 N HNO3.
0
10
20
30
40
50
60
0 2 4 6 8 10 12 14 16
Sorp
tion
capa
city
(m
g/gm
)
Cycles
Resin I
Cu(II)Zn(II)Ni(II)Cd(II)
Solid Phase Extraction of Transition Metals
Chapter 4 Page 178
Figure 6(b). Stability of the resin II for Cu(II), Zn(II), Ni(II)
and Cd(II) by Sorption and Elution
Experimental conditions: Amount of the resin II in the column: 0.5 gm;
Concentration of feed solution: 300 µg mL-1 ; Cu(II): pH: 6.0 ; elution by: 3.0 N HCl;
Zn(II): pH : 5.0 ; elution by: 1.0 N HCl; Ni(II): pH: 7.0 ; elution by: 2.0 N HCl;
Cd(II): pH : 8.0 ; elution by: 1.0 N HNO3.
05
101520253035404550
0 2 4 6 8 10 12 14 16Sorp
tion
capa
city
(mg/
mL)
Cycles
Resin II
Cu(II)Zn(II)Ni(II)Cd(II)
Solid Phase Extraction of Transition Metals
Chapter 4 Page 179
Figure 7(a). Elution profile of Cu(II), Zn(II), Ni(II)
and Cd(II) on the resin I
Experimental conditions: Amount of the resin I: 1 gm; Concentration of the solution
passed: 1000 mL; Cu(II): 6 µg L-1; pH: 6.0; Elution by 3.0 N HCl; Zn(II): 5 µg L-1;
pH: 5.0 ; Elution by 0.5 N HCl; Cd(II): Ni(II): 5 µg L-1; pH: 7.0; Elution by 2.0 N
HCl : 10 µg L-1; pH:8.0 ; Elution by 1.0 N HNO3.
00.5
1
1.52
2.53
3.5
0 2 4 6 8 10 12
Met
al io
n in
effl
uent
(ug)
Volume of stripping soluiton (mL)
Resin I
Cu(II)Zn(II)Ni(II)Cd(II)
Solid Phase Extraction of Transition Metals
Chapter 4 Page 180
Figure 7 (b) The elution profile of Cu(II), Zn(II) , Ni(II)
and Cd(II) on the resin II
Experimental conditions: Amount of the resin II: 1 gm; Concentration of the
solution passed: 1000 mL; Cu(II): 6 µg L-1; pH: 6.0; Elution by 3.0 N HCl; Zn(II): 5
µg L-1; pH: 5.0; Elution by 1.0 N HCl; Ni(II): 5 µg L-1; pH: 7.0; Elution by 2.0 N
HCl : Cd(II): 10 µg L-1; pH:8.0; Elution by 1.0 N HNO3.
0
0.5
1
1.5
2
2.5
3
0 2 4 6 8 10 12
Met
al io
n in
effl
uent
(ug)
Volume of stripping solution (mL)
Resin II
Cu(II)Zn(II)Ni(II)Cd(II)
Solid Phase Extraction of Transition Metals
Chapter 4 Page 181
Figure 8(a). Separation of Zn(II) and Cd(II) on the resin II
Experimental conditions: Amount of resin II: 1 gm; Column maintained at pH 5.0;
Zn(II): 100 µg in 25 mL buffer; Cd(II): 100 µg in 25 mL buffer].
05
10152025303540
0 10 20 30 40 50 60 70
Elut
ion
%
Effluent volume (mL)
Resin II
Zn(II)
| 1.0 N HCl |
pH 5
Cd(II)
Solid Phase Extraction of Transition Metals
Chapter 4 Page 182
Figure 8(b). Separation of Cu(II), Zn(II) and Cd(II) on the resin II
Experimental conditions: Amount of resin: 1 gm; Column maintained at pH 5;
Cu(II): 100 µg in 25 mL buffer; Zn(II): 100 µg in 25 ml buffer; Cd(II): 100 µg in 25
mL buffer.
0
5
10
15
20
25
30
35
0 10 20 30 40 50 60 70 80
Elut
ion
%
Effluent volume (mL)
Resin II| 3 N HCl |
Cd(II) Zn(II) Cu(II)
| 1.0 N HCl
pH 5
Solid Phase Extraction of Transition Metals
Chapter 4 Page 183
CONCLUSION
The newly synthesized azo-calix[4]pyrrole Amberlite XAD-2 polymeric
chelating resins (I/II) were successfully applied for the separation, preconcentration
and determination of Cu(II), Zn(II), Ni(II) and Cd(II) metal ions from real samples.
The advantages found for the synthesized resin (I/II) are their faster exchange rates,
better sorption capacity and high preconcentration factors. The resins are highly
selective in extracting the analytes even in the presence of various electrolytes. The
reusability of resins was 10 to 14 cycles without any significant loss in its sorption
behaviour. Resin II showed greater affinity and sorption capacity for these metal ions
as compared to resin I, probably due to more azo groups present in it.
Separations of binary/ternary mixtures of metal ions are possible by control of
pH or gradient elution. Sorption capacity and preconcentration factor for Cu(II),
Zn(II), Ni(II) and Cd(II), attained by resin II, was found to be reasonably better than
some already reported solid phase extractants derived from Amberlite XAD-2.
Solid Phase Extraction of Transition Metals
Chapter 4 Page 184
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