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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.


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


Chapter 4 Page 145

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].


Chapter 4 Page 146

(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].


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


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


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



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


Cd(II): Dissolve 0.2744 gm Cd(NO3)2.4H2O in water containing 2 m


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


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


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.


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


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).


Chapter 4 Page 155

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


Chapter 4 6

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


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).


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.


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.


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.


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).


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


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


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.


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.


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.


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


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)


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



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



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



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



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



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



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



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



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



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



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



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)


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


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.


Chapter 4 Page 184

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