pre-concentration and equilibrium isotherm studies of rhodium(iii) in environmental water samples

www.seipub.org/ijepr International Journal of Engineering Practical Research (IJEPR) Volume 2 Issue 4, November 2013

148

Pre‐concentration and Equilibrium Isotherm

Studies of Rhodium(III) in Environmental

Water Samples Sid Kalal Hossein1*, Mashhadizadeh Mohammad Hossein2, Almasian Mohammad Reza1, Hoveidi

Hassan3, Taghiof Mohammad1, Noroozi Maryam4

1NFCRS, Nuclear Science and Technology Research Institute, AEOI, P.O. Box 11365‐3486, Tehran, Iran 2Department of Chemistry, Tarbiat Moallem University of Tehran, Tehran, Iran 3Graduate Faculty of Environment, University of Tehran, Tehran, Iran 4Department of Chemistry, Faculty of Sciences, Payame Noor University (PNU), Ardakan, Iran

*[email protected]; [email protected]; [email protected]; [email protected];

[email protected]; [email protected]

Abstract

A new chelating resin was prepared by coupling Amberlite

XAD‐2 with 1,3‐Phenylene diamine through an azo spacer

and characterized by infra red(IR) spectroscopy. It was

examined for preconcentration of Rh(III) using Flame

Atomic Absorption Spectrometry(FAAS)for Rhodium

monitoring. The optimum pH value and the sorption

capacity have been found 8 and 6.9 mg/g, respectively.

Kinetic adsorption data were studied using four most

popular isotherm models, namely, Langmuir, Freundlich,

Temkin and Redlich‐peterson. The obtained results showed

that Langmuir type‐2 is the best fit in linear equations ( R2=

0.9907) and the Freundlich in the nonlinear equations (R2=

0.9978) . In addition, correlation co‐efficient was determined

for each isotherm analysis. Error functions used to determine

the alternative single component provide the best

parameters for the isotherm equation in this system. Also the

method was applied to Rhodium ions determination in

environmental samples with satisfactory results.

Keywords

Isotherm modelling; Error analysis; Rhodium; Amberlite XAD‐2;

1,3‐Phenylenediamine

Introduction

Rhodium is present at about 0.001 ppm in the earth’s

crust. Rhodium metal known for its stability in

corrosive environments, physical beauty and unique

chemical properties commands a premium price

because of its low abundance in nature. Rhodium, now

widely used in combination with platinum, is commonly

used for alloying platinum in thermocouples, crucibles,

evaporating dishes, weighing boats windings for high‐

temperature furnaces, and applications were found as

a coating material because of the hardness and luster

of its surface. Because of its commercial importance, a

wide variety of reagents have been proposed for

preconcentration of Rh before its spectrophotometric

determination.

The interest in ligand immobilized solid phase like

silica gel(Marshall &Mottola), organic polymer or

copolymers, cellulose(Gurnani etal.) and polyurethane

foam(Dmitrienko etal.) continues because of their several

application areas, such as solid phase extraction of

metal ions(Gal&Mshra) and heterogenization of

homogeneous catalysts(Price et al.). The solid phase

extraction of trace metal ions in a variety of samples

with complex matrices, like environmental and

biological samples, makes it possible to use analytical

techniques, such as flame atomic absorption

spectrometry (FAAS) and inductively coupled plasma

Atomic Emission Spectroscopy (ICP‐AES). Solid phase

extraction is preferable over ion exchange and solvent

extraction due to its several advantages like adjustable

selectivity by controlling of the pH, reusability, high

preconcentration factors, durability, versatility and

metal loading capacity(Camel). Adsorption of metal

ions is widely used in the removal of contaminants

from wastewaters. The design and efficient operation

of adsorption processes require equilibrium

adsorption data. The equilibrium isotherm plays an

important role in predictive modeling for analysis and

design of adsorption systems.

Amberlite XAD resins have been modified with

several chelating materials due to their good physical

and chemical properties, such as porosity, high surface

area, durability and purity. For instance, they were

covalently coupled with a polymer backbone through

International Journal of Engineering Practical Research (IJEPR) Volume 2 Issue 4, November 2013 www.seipub.org/ijepr

149

an azo (‐N=N‐) (Tewari&Singh). There are many

reports of functionalized Amberlite XAD 2, 4 and 7

resins in this respect (Saxena&Singh).

In this paper, Amberlite XAD‐2−1,3‐Phenylenediamine

(which will be referred to in this article simply as F‐

XAD‐2) was prepared by chemically bonding to be used

as an adsorbent for metal ions. 1,3‐Phenylenediamine is

able to form chelates with metallic ions on the surface

of the resin. Adsorption of Rh (III) from aqueous

solution and isotherm study using new synthesised

resin were investigated under optimum experimental

conditions and equilibrium adsorption data were

analysed by four isotherm models.

Reagents and Materials

All chemicals were of analytical grade purchased from

Merck (Darmstadt, Germany). Amberlite XAD‐2 resin

(surface area 330 m2/g, pore diameter 9 nm and bead

size 20‐60 mesh) was obtained from Flucka (Germany).

All of the solutions were prepared in deionized water.

The stock solution (500 mg/L) of Rh (III) was prepared

by dissolving appropriate amounts of RhCl3.3H2O, in

deionized water. 0.1 mol/L acetate buffer (pH= 3 – 6.5)

and 0.01 mol/L phosphate buffer (pH= 6.5‐9) were

used to adjust the pH of the solutions, wherever

suitable.

Experimental

Apparatus and Instruments

Flame Atomic Absorption Spectrophotometer (FAAS)

Varian, model 20 (Salt lake city, Australia) was used to

measure the concentration of Rh (III) ions. The pH

measurements were made with a Metrohm model 744

pH meter (Zofingen, Switzerland). Infrared spectra

were recorded on a Jasco Fourier transform infrared

spectrometer (FT‐IR‐4100, Jasco Inc., Easton, Maryland)

by the potassium bromide pellet method. Elemental

analysis was carried out on a Thermo‐Finnigan (Milan,

Italy) model Flash EA elemental analyzer.

Synthesis Procedure of F‐XAD‐2

5 g Amberlite XAD‐2 beads acidified with 10 mL of

concentrated HNO3 and 25 mL of concentrated H2SO4

were stirred at 60ºC for 1 h on an oil bath. Then the

reaction mixture was poured into an ice water mixture.

The nitrated Amberlite resin was filtered, washed

repeatedly with distillated water until free from acid

and then treated with a reducing mixture of 40 g of

SnCl2, 45 mL of concentrated HCl and 50 mL of

ethanol. The mixture was refluxed for 12 h at 90ºC.

The solid precipitate was filtered and washed with

water and 2 mol/L NaOH which released amino resin

(R‐NH2) from (RNH3)2 SnCl6 (R= resin matrix). The

amino resin was first washed with 2 M HCl and finally

with distilled water to remove the excess of HCl. It

was suspended in an ice‐water mixture (350 mL) and

treated with 1 M HCl and 1 M NaNO2 (added in small

aliquots of 1 mL) until the reaction mixture showed a

permanent dark blue color with starch‐iodide paper.

The diazotized resin was filtered, washed with ice‐

cold water and reacted with 0.03 mol of 1,3‐

Phenylenediamine in 30 mL of 1 M HCl. The reaction

mixture stirred at ‐5ºC for 24 h. Then the resulting

colored beads were filtered, washed with water and

dried in air at room temperature.

Batch Adsorption Experiments

For the batch adsorption experiments, a sample

solution (50 mL) containing (0.3 μg/ml) of Rh (III) was

taken in a glass stoppered bottle, and the pH was

adjusted to optimum value. The 0.05 g of XAD2–1, 3‐

Phenylenediamine was weighed out and added to the

bottle. The mixture was facilitated by agitation on a

shaker for optimum time, the resin was filtered and

adsorbed metal ions were eluted with 1.5 M HCl (10

mL). The concentration of the metal ions in the eluant

was determined by FAAS.

Isotherm Studies

Adsorption Isotherm Experiments

Isotherm studies were carried out by adding a fixed

amount of adsorbent (0.05 g) to a series of beakers

filled with 50 ml solutions of Rh (III) (10‐100 μg/mL).

The beakers were sealed and placed in a water bath

shaker set at 200 rpm at 20°C and optimum pH (8).

After 5 hours, the beakers were removed from the

shaker, and the final concentrations of Rhodium ions

in the solutions were measured by FAAS. The amount

of Rh(III) at equilibrium qe (mg/g) on F‐XAD‐2 was

calculated from the following equation:

qe=v(C0‐Ce)/m (1)

Where C0 and Ce (mg/L) are initial and equilibrium

concentrations of Rh(III), respectively. V (L) is the

volume of the solution and m (g) is the mass of the

adsorbent used.

Results and Discusion

Methodology and Characterization of Resin

The IR spectrum of F‐XAD‐2 is compared with that of

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0.9921

0.8843

0.9906

0.8181

0.8172

0.9978

0.9975

0.9430

0.9296

0.9972

0.9767

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0.9910

0.8819

0.9886

0.7919

0.8149

0.9974

0.9969

0.9336

0.9235

0.9974

0.9768

0.9358

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0.8821

0.9887

0.7919

0.8154

0.9974

0.9971

0.9339

0.9338

0.9974

0.9768

0.9369

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100

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0.9890

0.8718

0.9709

0.6012

0.7936

0.9971

0.9901

0.7914

0.7914

0.9971

0.9684

0.8875

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0.9890

0.8718

0.9826

0.6012

0.7936

0.9971

0.9966

0.9182

0.9182

0.9971

0.9684

0.9122

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0.9920

0.8843

0.9907

0.8180

0.8180

0.9978

0.9975

0.9430

0.9430

0.9977

0.9768

0.9417

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FIG. 5 LINEAR (

THE ADSOR

In this graph

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S PARAMETERS FR

sotherm model

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B / J mol‐1

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B /(dm3 mg‐1)g

g

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HODIUM(III) A

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m. According

0 and 1 indic

study, Tabl

the range of

the favora

R FUNCTION(ERR

Parameter

0.9908

11.4985

0.0833

0.7743

0.9978

1.2735

0.9080

0.9430

0.8129

2.7122

0.9977

27.9659

29.8034

0.2199

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www.seipub.org/ijepr International Journal of Engineering Practical Research (IJEPR) Volume 2 Issue 4, November 2013

154

indicates that the effects of other mentioned foreign

ions at given concentrations are negligible. The

adsorption of Rh ions on F‐XAD‐2 in presence of all

mentioned ions (with each ion having the

concentration of 20 mg/L) shows that the Rh ions can

be determined quantitatively in the environmental

samples.

TABLE.6 EFFECT OF OTHER IONS ON SORPTION

D E% L% A Interfering

0.72 59.7 0.0 11.94 ‐‐‐‐‐‐‐

0.67 55.5 7.0 11.1 Cu

0.73 60.5 ‐1.3 12.1 Zn

0.3 24.55 58.9 4.91 Fe

0.43 35.8 40.0 7.16 Ni

0.73 60.25 ‐0.9 12.05 Cd

0.12 9.6 83.9 1.92 Mixed above ion

A: Amount of adsorbed Rh(III) (mg/L), L: Loss adsorption (%), E:

extraction percentage (%) and D: distribution ratio

Application of Method

F‐XAD‐2 was used to preconcentrate and determine

Rh(III) ions in tap water (Tehran) and spring water

(BagheFaz, Tehran). The pH of water sample was

adjusted to the optimum pH 8. Solid phase extraction

with F‐XAD‐2 coupled with FAAS was applied to

determination of the Rh(III) in water sample. No Rh(III)

was detected in the water samples. The results are

shown in Table 7.

TABLE 7.RESULTS OBTAINED FOR RH(III) DETERMINATION IN TAP WATER

(I) AND SPRING WATER (II)

Found (without spiking of Rh(III)) I II

N.D. N.D.

Added Rh(III) (μg/mL) 0.4 0.8

Found Rh(III), after preconcentration (μg/mL) 3.2 6.6

Preconcentration factor 10 10

Recovery (%) 80.0 82.5

Standard deviation 0.01 0.01

Relative standard deviation (%) a 3.13 1.51

a: For three determinations

Conclusion

A new resin was synthesized by coupling of Amberlite

XAD‐2 with 1,3‐Phenylenediamine. The synthesis of

the resin is simple and economical. The resin has a

good potential for enrichment of trace amount of

Rh(III) from large sample volumes. The Rh(III)

adsorption was due to immobilized ligand‐metal ion

interactions. The resins also present the advantage of

high adsorption capacity, good reusability and high

chemical stability. The sorption/desorption of metal

ion takes place in moderate time, making the

analytical procedure reasonably fast. Finally, the

different isotherms were tested for their ability to

correlate with the experimental results by comparing

theoretical plots of each isotherm with the

experimental data for the adsorption of rhodium ions

on 1,3‐Phenylenediamine‐Amberlite XAD‐2 at 293 K in

Fig. 6.

In this graph, the amount of rhodium adsorbed per

unit mass of 1,3‐Phenylenediamine‐Amberlite XAD‐2,

qe, is plotted against the concentration of rhodium

remaining in solution. Ce. The good fit of the

Freundlich and Langmuir isotherms were not the

same even when the coefficient of determinations was

high for both isotherms.

Concerning application of this work in real sample

and environmental studies, these results have

demonstrated the applicability of the procedure for

Rhodium determination in samples with high

recovery (greater than 82%).

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pre-concentration and equilibrium isotherm studies of rhodium(iii) in environmental water samples

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