SOLID PHASE EXTRACTION OF Cu(II) AND Fe(II) USING ...shodhganga.inflibnet.ac.in/bitstream/10603/3871/11/11_chapter 4.pdffor various metal cations and have been intensively studied

102 Ph.D. Thesis Dave Sudhir R.

CHAPTER-4 SOLID PHASE EXTRACTION OF Cu(II) AND Fe(II) USING

MERRIFIELD[MONO AZA DIBENZO 18-CROWN-6]


ABSTRACT

Solid phase sorbent, mono aza dibenzo 18-crown-6 ether immobilized on

an Merrifield resin has been prepared. Solid phase extraction of the trace metals, Cu(II)

and Fe(II) , using Merrifield functionalized with a mono aza dibenzo 18-crown-6 ether

has been developed. The optimum experimental conditions for the quantitative sorption

of two metals, sorption capacity, effect of flow rate, concentration of eluent, kinetics of

sorption and effect of matrix ions on the sorption of analytes have been investigated. At

pH 3.0 the quantitative sorption of Cu(II) and at pH 5.5 the quantitative sorption of Fe(II)

analytes was observed and complete elution of metals from resin has been achieved with

0.5 M nitric acid and 1 M hydrochloric acid respectively. The LOD was found to be 5.4

µg L-1 for Cu(II) and 4.9 µg L-1 for Fe(II). The analytes were determined by atomic

absorption spectrometry (GFAAS).


INTRODUCTION

Removal, separation and enrichment of trace metals in aqueous solutions play

important role for environmental remediation of municipal and industrial waste water. Among

many separation techniques, solid phase extraction is an efficient and widely applied separation

process that is comparable to other separation techniques in terms of technical and economical

feasibility. Many commercial separation problems are being solved by solid phase extraction,

which can be successfully used to treat industrial effluents. Liquid-liquid extraction, sorption,

precipitation, ion exchange and others are classic preconcentration and separation methods for

elements in geological, biological, environmental and industrial fluids.

Macrocyclic ionophores based on crown ethers are also the well known ligands

for various metal cations and have been intensively studied for applications in many areas due to

their selective affinity for cations1-3. Functionalized aza crown ethers are good candidates for

molecular receptors because crown ether moieties are well known for their ability to form strong

complexes with alkali metal, alkaline earth metal and organic cations. The derivatized crown

ethers and their analogue are also being studied for their applications in the analytical and

pharmaceutical fields4,5.

Functionalized, insoluble, cross-linked polymers are of considerable interest to

the synthetic chemist. Merrifield resin6 is crosslinked chloromethylated polystyrene. Merrifield

resin is used as solid supports for ion-exchange resins and solid support. Size exclusion and ion

chromatography packings, peptides in solid-phase synthesis, chlorometyl- substituted

polystyrenes are key intermediates in many of these resin preparations. This resin is synthesized

by copolymerization of a mixture m-/p-chloromethyl styrene, styrene, and divinyl benzene.

These type of polymers can be used as starting materials for the preparation of solid-supported


catalysts and ligand7 , as a support for solid-phase peptide synthesis or combinatorial chemistry8 ,

as a pharmaceutical agents9,10. Chloromethyl groups have been introduced most often by Feiedel-

crafts alkylation with chloromethyl methyl ether. Chlomethylation of alkylbenzenes gives

predominately the para isomer. The Friedel-crafts conditions also lead to cross-linking of

polystyrene by intrapolymer alkylation, first recognized by the formation of insoluble gels during

chloromethylation of soluble polystyrene and by decreased swelling of polystyrene resins after

chloromethylation. Chloromethylation of polystyrene beads often proceeds by a shell diffusive

mechanism in which functionalization starts on the bead surface and proceeds to the center as the

alkylating agent and Lewis acid diffuse into the bead.

Use of immobilized aza crown ether loaded organic and inorganic polymers for

preconcentration and separation of trace heavy metal ions are gaining a great interest. Heavy

metals are defined as metals of density higher than 5 g/cm3. They occur as pure elements, as ions

and complexes. Heavy metals were brought into the environment by human activities which has

influenced and modified natural cycles. Human activities started more than 4000 years ago with

metal mining. Unprecedented pollution came up with the industrialization and its consumption of

energy. The combustion of fossil fuels introduced a large amount of heavy metals in to the

atmosphere and the aquatic environment. Besides the fact that mercury, cadmium or arsenic are

highly toxic, some heavy metals such as iron, copper, zinc, manganese, cobalt, nickel, tin are

essential to many organisms. In these elements iron, copper, zinc, manganese, cobalt etc. are also

known as transition metals. These elements, along with amino and fatty acids and vitamins are

required for normal biochemical processes such as respiration, biosynthesis and metabolism.11

And under supply of these so called trace metals leads to deficiency, while oversupply results in


toxic effects12. Heavy metals show a large tendency to form complexes, especially with nitrogen,

sulphur and oxygen containing ligands of biological matter.

Copper is both vital and toxic for many biological systems13, 14. Copper is

essential for life but on the other hand, highly toxic to organism like certain algae, fungi and

many bacteria or viruses. In recent years copper is suspected to cause infant liver damages.

Drinking water can be a source for an intense copper exposition due to the common practice of

using copper pipes in domestic water distribution systems, especially in regions with soft water

at pH below 7.3. Copper is also widely used in electroplating and electronics industries, in

cooking utensils, in fertilizers, bactericides, fungicides, algaecides, anti-fouling paints,

production of wood preservatives and in manufacturing of azo-dyes.11 Thus the determination of

trace amounts of Cu is becoming increasingly important because of the increased interest in

environmental pollution. Pyrocatechol violet15, NaD-DTC16-18, 1-nitroso-2-naphthol-3, 6-

disulfonic acid19, 2-(2-quinolyazo)-5-diethylaminoaniline20, o,o-diethyldithiophosphate (DDTP)

21 have been tried for the preconcentration of metal ions. Shamspur et al22 studied the

determination of silver ion by FAAS after preconcentration on octadecyl silica membrane disk

modified with bis[5-((4-nitrophenyl)azosalicylaldehyde)] as a new Schiff-base ligand . Shamspur

et al23 have also studied the solid phase extraction of ultratrace copper (II) using octadecyl silica

membrane disks modified by a naphthol Schiff base.

Iron is one of the most important essential elements. Its deficiency or overload

may cause health problems. Iron occurs in two oxidation states (II, III) and equilibrium between

these forms is important for biological systems using iron for metabolic processes. Fe(II) is

favoured for absorption by cells. However, the toxic doses of iron and its compounds can lead to

serious problems, including depression, rapid and shallow respiration, coma, convulsions and


cardiac arrest.24-26 Iron and its compounds have widespread industrial applications such as

constructional material for drinking water pipes, food colors, coagulants in water treatment,

pigments in paints and plastics etc. Hence large quantities of iron are discharged in to the

environment. Thus, appropriate knowledge of the iron content of natural water is very desirable.

So, the toxicity of this element demands a fast and accurate method for its determination in

water.

Solid phase extraction has been developed to replace many traditional liquid-

liquid extraction methods for the determination of metal ion in aqueous samples.27 SPE is a

preconcentration technique of rapidly growing importance in trace metal determination which

can easily be adapted to flow separation and preconcetration system. SPE techniques allow us to

process samples quickly, eliminate some of the glassware necessary for liquid-liquid extraction

procedures, consume less solvent, isolate analytes from large volumes of water with minimal or

no evaporation losses, and reduce exposure of analysts to organic solvents relative to traditional

methods and can also provide more reproducible results. Different solid-phase extractants, such

as Amberlite XAD resins,28 activated cabon,29 polymeric fibers,30 Ambersorb,31 and silica gel,32

have been used to extract trace metal ions from various media.

The determination of trace amount of heavy metals is a challenging subject for

analytical chemists regarding concentration ranges set by standards and guidelines for reasons of

toxicity. In addition, similar chemistry of these metals is fastidious with respect to selectivity of

the determination method.

A variety of analytical methods fulfilling these demands are available. Only some

of them have found application in routine analysis. Recommended procedures for the detection

of heavy metals in watery samples include photometric methods, graphite furnace atomic


absorption spectroscopy (GFAAS), inductively coupled plasma emission or mass spectrometry

(ICP-ES, ICP-MS), total reflection X-Ray flourimetry (TXRF) and anodic stripping voltammetry

(ASV).12, 33 While AAS and photometry are single element methods, ICP-ES, ICP-MS and

TXRF are used for multi-element analysis, and voltammetry is an oligo-element approach.

The Present investigation reports the mono aza dibenzo 18-crown-6

(MADB18C6) ether immobilized on to Merrifield resin. Merrifield resin was attached to

MADB18C6 through an aza group spacer. The application of the modified resin for solid phase

extraction of Cu(II) and Fe(II) from model solution for further determination by AAS have been

studied. Immobilized MMADB18C6 containing nitrogen and oxygen atom, which makes it a

good reagent for metal ion enrichment. Hence, MMADB18C6 is suitable for solid phase

extraction methods, where elution of metals is carried out with acids and analyzed by AAS. The

proposed method has been applied for determination of Cu(II) and Fe(II) in natural samples and

natural waters.


EXPERIMENTAL

Apparatus

The pH measurements were performed on a Systronics digital pH meter 335 using

a combined glass and calomel electrode. The Infrared (IR) spectra were recorded on a Bruker

Tensor 27 Fourier Transform Infrared (FTIR) spectrophotometer as KBr pellets. UV-Vis spectra

were recorded on Hitachi U-3210 double beam spectrophotometer using 10 mm matching quartz

cell. Atomic absorption measurements were performed on Perkin-Elmer model 420 atomic

absorption spectrophotometer (AAS) equipped with a HGA-76 graphite furnace. Pyrolytically

coated graphite tubes were used throughout the analysis. Copper and Iron hollow cathode lamps

used for determination of analytes and were operated at the 10, 10 mA currents. The most

sensitive analytical lines used were 324.8 Cu(II) and 248.3 Fe(II). The slit width was 0.7 nm for

these elements. The acetylene flow rate were 0.9 and 1.41/min for copper and iron, respectively.

Chemicals

All the chemicals used were of analytical grade and supplied from Aldrich unless

otherwise specified. Solvent were carefully purified and dried before use. Quartz distilled

deionized water, which was furher purified by Millipore milli-Q water purification system was

used. Merrifield resin (mesh size 100-200) was also procured from Aldrich.

Buffer solutions

Buffer solutions were prepared as described elsewhere.34


Sample preparation

Metal solutions

The stock solution 0.01M of Cu(II) and Fe(II) were prepared by dissolving 1.70 g

of copper sulphate dihydrate and 3.92 g ferrous ammonium nitrate hexahydrate in a litre of

double distilled water. These metal solutions were standardized spectrophotometrically (14, 15).

The solutions were diluted further as and when required.

Water sample

Natural water and waste water samples were collected from Sabarmati river,

Kankariya lake and three different stations in the industrial region of Vatva industrial region. The

water samples were filtered through a cellulose membrane filter (Millipore) of pore size 0.45 µg.

The filtered water samples were used to further determination of Cu(II), Fe(II).

Natural samples

A total of 100 g of weighed sample is ashed. 10 g of ash is transferred into

250 mL of Pyrex beaker and 100 ml of concentrated hydrochloric acid and 20 mL of

concentrated nitric acid is added to beaker. The sample solution is heated on plate for 30 min.

The hot solution is centrifuged and the supernatant liquid decanted from any siliceous matter.

The residue is boiled with 50 ml of 0.1 M hydrochloric acid and filtered. The filtrate is

evaporated to dryness and the solution is transferred to 100 mL volumetric flask and diluted upto

the mark with 0.1 M hydrochloric acid.


Synthesis and characterization of MMADB18C6 resin

MMADB18C6 resin was prepared by immobilization of mono aza dibenzo 18-

crown-6 ether on Merrifield (chlorometylated polystyrene) resin in presence of toluene and

diethanolamine. Synthesized MMADB18C6 sorbent was characterized by FT-IR spectrometer,

synthesis and characterization of MMADB18C6 is described in chapter 2.

Physico chemical properties

Physico chemical properties of synthesized sorbent such as void volume, density

etc., were investigated as described in chapter 3.

Effluent history studies

The column was preconditioned by deionsed double distilled water, methanol, and

appropriate buffer solution. The metal ion solution and buffer solution were mixed and passed

through the column at the desired flow rate and the concentration of the metal ion in effluent was

determined by spectrophotometry and GFAAS.

Batch experiment

A 1 g of the MMABD18C6 resin was shaken with (50 ml of 0.01M) aqueous

synthetic solution of metal ions using 100 ml of stoppered glass bottles for 24 h at pH 2-7 at 30

°C temperature. After 24 h the resin was filtered off and the filtrate was analyzed for

determination of the metal concentration in solution by AAS and spectrophotometry. Maximum

metal uptake capacity was calculated as mg g-1 of resin. Figure 1 shown sorption capacity of of

Cu (II) and Fe(II) at various pH.


Column packing

MMADB18C6 resin was suspended into a beaker containing water and allowed

to stand for 5 min. The unsettled particles of the resin were discarded. A glass column

(5 × 200 mm) with a plastic stopcock was used for separation of the metals. MMADB18C6 resin

bead was washed with ethanol, double distilled water, 1 M nitric acid, finally with double

distilled water. Before placing 1 g of merrifield[mono aza dibenzo 18-crown-6] sorbent into the

column, a small amount of glass wool was placed in the lower part of the column to prevent loss

of the MMADB18C6 resin. The sorbent was washed with ethanol and 1 M nitric acid. The resin

was thoroughly washed with water until effluents were neutral. After each use, the resin in the

column was washed thoroughly with water, and appropriate buffer solution, and then stored in

water for further applications. The column must be preconditioned by passing appropriate buffer

solution before the sample is loaded.

Preconcentration procedure

Present method was tested with standard solutions. A glass column was packed

with 1 g of MMADB18C6. The packed glass column was washed sequentially with 1M HNO3,

water and acetone and finally with suitable buffer solution to establish the desired pH. A 50 mL

solution containing 15 µg and 20 µg of Cu (II) and Fe (II) was permitted to flow through the

column under gravity. The column was then washed with the same buffer solution as that used

for preconditioning. The retained metal Cu (II) on MMADB18C6 was eluted by 1 M HNO3 and

Fe (II) was eluted by HCl. The metal concentration in solution was quantified by

spectrophotometry and GFAAS. The preconcentration is expressed by the following equation.

Concentration of metal in stripping solutionPF = Initial concentration of metal in feed solution


Distribution coefficient (Kd)

The distribution coefficient Kd of metal ions was determined by using batch

equilibrium technique. The amount of metal adsorbed was determined from the difference

between initial and final concentration in clear supernatant solution using standard

spectrophotometry methods. The distribution coefficient is expressed as following

Amount of metal sorbed by 1 g of resind = Amount of metal ions in 1 ml of solution

K

Kinetic of metal sorption

To determine the rate of loading of Cu(II) and Fe(II) metals on the resin, batch

experiments were carried out. The MMADB18C6 beads, 1 g, were stirred with a 50 ml of

solution containing 0.01 M Cu(II) and Fe(II) at 30 °C temperature for 1, 5, 10, 20, 30, 40, 60,

80, 100, 120 min. The concentration of metal loaded onto the resin as well as present in the

supernatant liquid was determined by the recommended procedure.

Separation of Cu(II) and Fe(II)

A metal ion synthetic mixture (50 mL of 0.01M) was shaken with 1 g of resin.

The metal ions retained on sorbent were eluted by suitable eluting agent and determined by

general procedure. The results shows that sorption pH of Cu(II) is 3.0 and Fe(II) is 5.5. Due to

the difference in the sorption pH of metal ions on the sorbent quantitative separation of their

binary mixture was achieved by selective sorption.


Results and discussion

Effect of Sample pH

The influence of sample pH on adsorption of Cu(II), Fe(II) metals on

MMADB18C6 resin was investigated by batch equilibrium technique using different pH values

of 2, 3, 4, 5, to 7. The pH values were adjusted by buffer solution. 1 g of MMADB18C6 resin

was shaken with 50 mL of 0.01 M metal ion solution using 100 ml stoppered glass bottle for

24 h. After 24 h the resin was washed and the retained anlyte was eluted using 1 M HNO3. Table

1 shows the influence of sample pH on recovery for Cu(II) and Fe(II). The sorption of metals on

resin was increasing with the increase of pH value after maximum sorption pH of metals on

resin, the sorption was decreasing with increase of pH values. Finally, the sorption pH 3 for

Cu(II) and pH 5.5 for Fe(II) was selected as optimum pH and used further experiments(Figure 1,

Table-1). pH 3.3 and 5 also indicate remarkable adsorption of Cu(II), Fe(II).

Effect of eluants type

Elution of retained Cu(II), Fe(II) metals on MMADB18C6 extractant was

investigated using various concentrations of HCl, H2SO4, HNO3, and Ammonium acetate. From

the study it can be seen that quantitative recovery of metal ions can be obtained using 20 mL of

0.5 M HNO3 and 1 M HCl. Therefore, 20 mL of 0.5M HNO3 for Cu(II) and 1M HCl for Fe(II)

was used as eluants in subsequent experiments. Table 2 shows the results obtained from this

study.


Effect of sample flow rate

Flow rate is a significant factor affecting to sorption of metals on resin because it

is directly affects the contact of resin and metal ion solution. The effect of sample flow rate on

metal ion adsorption on MMADB18C6 resin was studied at optimum pH in column operation

with different sample flow rate on 0.1 to 1.0 ml min-1. 50 ml sample solution of metal at

optimum pH was passed through column and eluted with suitable eluting agent. No significant

reduction in recovery was found for sample flow rate up to 0.2 mL. Flow rate of 0.2 mL min-1 as

an optimum value was then used for further experiments. Figure 2. shows the results obtained

from this experiment.

The effect of the volume of the eluant

The effects of eluants on desorption of Cu(II) and Fe(II) were investigated. The

optimum eluant volume was specified as 20-25 for the subsequent studies.

Effect of matrix ions

Various salts and metal ions were added individually to solution containing 10 µg

of Fe(II), Cu(II) and the general procedure was applied. The tolerance limit was set at the ion

concentration required to cause a 2.0 % error in the determination of Cu(II), Fe(II) (Table 3) .

Effect of electrolyte

The effect of various electrolytes like sodium chloride, sodium fluoride, sodium

bromide, sodium nitrate, ammonium nitrate, sodium acetate have been investigated on sorption

of Cu(II), Fe(II) on MMADB18C6 sorbent(Table 4).


Adsorption and batch capacity of the resin and loading half-time

The adsorption capacity of the sorbent was obtained between 17.8and 28.3 mg g-1

for the studied metals.

The sorption percentages of the tested metal (II) cations are shown as a function

of the time in Figure 3. Batch capacity of the sorbent obtained was 28.3 mg g-1 for Cu(II), 17.8

mg g-1 for Fe(II).The sorption was found to be complete within 8 min for Cu(II) and 11.5 for

Fe(II) metal ions.

The sorption half-time for Cu (II) and Fe(II) metal ions has been tabulated in

Table 2.The proposed method developed using MMDB18C6 has high sorption capacity and is

very fast, with a loading half time, t1/2 of less than 11.5 min(Figure 5).

Distribution co-efficient

Equilibrium distribution co-efficient (Kd) of the resin with metal ions Cu (II) and

Fe(II) were determined at maximum adsorption pH (Figure 4). The distribution co-efficient of

the resin with Cu(II) and Fe(II)was found to be 4101 and 2342.(Table 2, Figure 4)

Breakthrough capacity studies

Breakthrough capacity is a function of many parameters; it is a useful way to

demonstrate the effect achieved by changing one parameter while holding all others constant.

Breakthrough capacity is more significant parameter to find actual working condition of sorbent

during the column operation and actual sorption capacity of resin during column experiment.

Breakthrough capacity of metal ions were carried out with 1 g of resin in a column (5 × 200

mm), 10 µg of metal ion was passed through column at its optimum pH and flow rate(Figure 3).

The eluant was collected in 2.0 ml fractions and the metal ion concentration was determined by

spectrophotometry and GF


Reusability of the resin

The reusability of the MMADB18C6 resin was tested by loading Cu(II), Fe(II)

ion several times on a column at their optimum sorption pH and flow rate. It was found that the

sorption capacity after 17 cycle of sorption and desorption does not vary by more than 2 % for

sorbent. Therefore multiple use of the resin is feasible. Similar results are shown by batch

method also. The sorption capacity of MMADB18C6 resin does not change when it is treated

with 100 ml each of 6 M nitric acid for 2 h, 4 M of hydrochloric acid and 4M sulfuric acid. The

capacity of the MMADB18C6 resin stored for more than 6 months under ambient conditions has

been found practically unchanged. Therefore the resin is suitable for repeated use.

Precisions and Detection limits

The detection limits is evaluated as the concentration corresponding to three times

the standard deviation of 20 runs of the blank solution. A 50 ml blank solution was passed

through a column at optimum condition and retained metals were eluted by 20 mL of the eluting

agents. This solution was used to determine the LOD. The limit of quantification (LOQ) was

then set as ten times of the standard deviation of the blank signal (Table 2).

Separation of Cu(II) from binary mixtures Cu(II), Fe(II)

According to sorption and desorption studies of Cu(II), Fe(II) metal ions on

MMADB18C6 sorbent, the resin can used for separation of Cu(II), Fe(II) from their binary

mixtures. For separation of Cu(II) from Fe(II), 100 µg of each metal ions were loaded in column

at pH 3. Where Cu(II) was retained on the resin in column while Fe(II) does not show any

sorption on sorbent at pH 3 so Fe(II) was eluted out. The retained Cu(II) in column was desorbed

by 20 ml of 0.5 M HNO3 solution. The eluted analytes was determined further by

spectrophotometrically and GFAAS (Figure 6).


Separation of Fe(II) from binary mixtures Cu(II), Fe(II)

For separation of Fe(II) from mixture of Cu(II), Fe(II), 100 µg of each metal

performed in preconditioned column at pH 5.5. The Fe(II) was showed sorption at pH 5.5 on the

resin and Cu(II) ion does not absorb this pH so Cu(II) ion was eluted out from column. After

then the adsorbed Fe(II) metal ion was desorbed by 20 mL of 1M HCl solution. The metal was

analyzed by spectrophotometer and atomic absorption spectrophotometer (GFAAS) (Figure 7).

Sample analysis

The solid phase extraction methods developed were applied for the analysis of natural

samples like potato, apple and wheat flour and for the analysis of natural water from Kankaria

lake, Sabarmati river and Vatva industrial zone. The results are shown in Table 7 and 8.


Conclusion

The synthesized MMAD18C6 sorbent has been used for chromatographic

separation of Cu(II), Fe(II). The developed resin is highly selective towards Cu(II), Fe(II). The

resin showed excellent ability for separation of metal with good distribution coefficient and

preconcentration factor. The determination of metal was carried out successively with

spectrophotometry method. The metal ions were separated individually based on pH selectivity

and with different elutants from their binary mixture.


Table 1.

Parameters optimized for adsorption and desorption of Cu(II), Fe(II)

Parameters Cu(II) Fe(II)

pH 3 5.5

Flow rate (mL min-1) 0.3 0.2

Eluting agent 0.5M HNO3 1M HCl

Sorption capacity (mg g-1) 28.3 17.8

Distribution coefficient Kd 4101 2342

Breakthrough capacity (mg g-1) 3.2 4.0

Preconcentration factor PF 200 142

T1/2 for sorption (min) 8 11.5

R.S.D 1.0-1.8 1.0-1.7

LOD 5.4 4.9

LOQ 18 16


Table 2.

The effect of eluant solution type on the recovery of the Cu(II), Fe(II)

Type of eluant Concentration (M) Recovery (%)

Cu(II) Fe(II)

HCl 0.05 23.7 32.5

HCl 0.5 36.4 48.4

HCl 1 80.3 100

H2SO4 0.01 39.8 40.3

H2SO4 0.05 42.2 52.5

H2SO4 0.1 48.7 61.5

HNO3 0.5 20.2 *N.E.

HNO3 0.5 100 *N.E.

HNO3 1 54.6 *N.E.

Ammonium acetate

0.05 *N.E. 15.3

Ammonium acetate

0.5 *N.E. 25.7

Ammonium acetate

1 *N.E. 43.5

*N.E. = No elution


Table 3.

Tolerance limits of matrix ions on sorption of Cu(II), Fe(II)

Metal ion : 100 µg

Added

Cations

Added as Concentration

mg L-1

Metal ion

Cu(II), μg Fe(II), μg

Ag+1 AgNO3 5000 30 10

As+3 AsCl3 10000 10 25

Be+2 BeSO4 10000 10 35

Mg+2 MgSO4 12000 25 10

Ca+2 CaCl2 10000 30 20

Ba+2 Ba(NO3)2 15000 20 35

Sn+2 SnCl2 10000 10 10

Sn+2 PbCl2 10000 20 35

Cd+2 CdCl2 5000 35 25

Cr+3 CrCl2 5000 10 10

Al+3 AlCl3 10000 25 30

Hg+2 HgCl2 15000 15 10

Mn+2 MnSO4 10000 30 15

Zn+2 ZnCl2 10000 20 20

V+5 V2O5 5000 25 30

Nb+5 Nb2O5 12000 10 15

Ti+4 TiO2 5000 15 10

Ta+4 Ta2O5 10000 30 25


Table 4. Effect of electrolyte on sorption of Cu(II), Fe(II) on MMADB18C6

Metal ions

(100 µg)

Electrolyte (mol L-4)

NaF (100 mL)

NaCl (100 mL)

NaBr (100 mL)

NaNO3 (100 mL)

Na2SO4 (100 mL)

Na3PO4 (100 mL)

CH3COONa (100 mL)

Cu(II) 1.5 2 1 2.5 0.5 0.15 1

Fe(II) 1.5 1 1.5 2 1 0.25 0.5

Table 5. Separation of Cu(II) from binary mixture of Cu(II), Fe(II)

Amount loaded

(µg mL-1)

Element separated Eluants Amount recovered

(%)

Fe (II), 100

+

Cu (II), 100

Fe (II),

Cu (II)

3 pH buffer

0.5 M HNO3

99 ±1

99 ±1

Table 6. Separation of Fe(II) from binary mixtures Cu(II), Fe(II)

Amount loaded

(µg mL-1)

Element separated Eluants Amount recovered

(%)

Cu(II), 100

+

Fe(II), 100

Cu(II),

Fe(II)

5.5 pH buffer

1M HCl

99 ± 1

99 ± 1


Table 7. Determination of Cu(II), Fe(II) in natural sample. (n=5)

Sample Cu (II)

(µg g-1)

Fe (II)

(µg g-1)

Recovery (%)

potato 4.9 360.0 100

Apple 4.5 175.0 99 ±1

Wheat Flour 1.8 13.2 99 ± 1

Table 8. Determination of Cu (II) and Fe (II) in natural water.(n=3)

Sample Cu (II) µg L-1 Recovery (%) Fe (II) µg L-1 Recovery (%)

Kankaria lake 15.4 100 25.2 98±1

15.3 99±1 24.3 98±1

15.1 99±1 21.5 99±1

Sabarmati river 14.9 98±2 21.1 100

16.4 99±1 21.7 100

16.2 100 22.5 99±1

Vatva industrial zone 62.3 99±1 25.4 99±1

67.4 99±1 24.2 99±1

68.0 99±1 24.2 99±1


Figure 1. Sorption capacity of Cu(II), Fe(II) verses pH on extractant


Figure 2. Effect of flow rate on sorption of Cu(II), Fe(II)


Figure 3. Break through curve for sorption of metal ion on MMADB18C6


Figure 4. Log Kd vs. pH of Cu(II) and Fe(II)


Figure 5. Sorption kinetics of metal ion on sorbent MMADB18C6


Figure 6. Separation of Cu(II), Fe(II)

Figure 7. Separation of Cu(II), Fe(II)


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SOLID PHASE EXTRACTION OF Cu(II) AND Fe(II) USING ...shodhganga.inflibnet.ac.in/bitstream/10603/3871/11/11_chapter 4.pdffor various metal cations and have been intensively studied