International Journal of Chemistry; 2013[02]

ISSN 2306-6415

Spectrophotometric Studies and Application of a New Asymmetric Triazene Ligand for Solid Phase Extraction of Ultratrace Copper and Determination by Flame Atomic Absorption Spectrometry

Mahmood payehghadr1*, Ahmad Azizi1, Mohammad Kazem Rofouei2

1

Department of Chemistry, Payame Noor University, POBOX 19395-3697, Tehran, Iran

2

Faculty of Chemistry, Kharazmi University, Tehran, Iran

Abstract: A new triazene ligand, ([1-(ortoacyl benzene)3-(3,4-dichlorobenzene)triazene]) has been

synthesized and kf value of it is complexes with Hg2+ Ni2+ Cd2+ Pb2+Cu2+Ag+ has been determined spectrophometrically. Because this ligand have good selectivity to copper ion, a simple, reliable and rapid method for preconcentration and determination of the ultratrace amount of copper using octadecyl silica membrane disk modified by this ligand, and determination by flame atomic absorption has been presented. Various parameters including pH of aqueous solution (7-8), flow rates (10 ml. min-1), the amount of ligand (6.0 mg) and the type of stripping solvent (0.1M nitric acid) have been optimized. The breakthrough volume was greater than 500 ml with an enrichment factor of more than 220 and 50ng ml-1 detection limit. The capacity of the membrane disks modified by 6mg of the ligand was found to be 220g of copper. The effects of various cationic interferences on the percent recovery of copper ion were studied. The method was successfully applied to the determination of copper ion in different samples.

Keywords: Copper, SPE, Octadecyl, Triazene, FAAS, Spectrophotometry, Formation constant

1. Introduction
Aryl triazenes have been studied for their interesting structural, anticancer, and reactivity properties. They have been used in medicinal, combinatorial chemistry, in natural synthesis and as organometalic ligands [1]. Triazenes compounds characterized by having a diazoamino group (-N=N-N<), commonly adopt the Trans configuration in the ground state [2-3]. Recently, the structural and solution studies [4-8], application of these compounds as a selective modifier ligand for solid phase extraction and determination of toxic metal ions [9-12], potentiometric sensor [13-15], Hg (II) and Pt (II) ion selective electrodes [1617] have been reported. Copper is widespread anthropogenic pollutant of environment and the determination of this metal ion is an actual problem [18]. The determination of copper is usually carried out by flame [19-21] and graphite furnace [22-23] atomic absorption spectrometry, as well as spectrophotometry [24-25], chemiluminescence [26] and electrothermal methods [27-28]. However, due to presence of copper in low levels in environmental samples and the matrix effects, different separation and preconcentration

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techniques such as liquid-liquid extraction [29], precipitation [30], ion exchange [31], solid phase extraction [32-33] and membrane filtration [34] improve the analytical detection limit, increase the sensitivity by several orders of magnitude, enhance the accuracy of the results and facilitate the calibration. Among these techniques, solid phase extraction is preferred by many researchers and account of the fast, simple and higher preconcentration factor, rapid phase separation, time and cost saving [3536]. Liquidliquid extraction of copper with organic solutions containing different chelating agents such as dithiocabamates and macrocyclic ligands has attracted considerable attention. However, these classical extraction methods are usually time-consuming, labor-intensive and require large volumes of high purity organic solvents. In recent years, different trapped ligands on a variety of solid matrices have been successfully used for the preconcentration, separation and sensitive determination of trace metal ions [3738]. Solid phase extraction (SPE) is an attractive technique that reduces consumption of and exposure to solvent, disposal costs and extraction time. Solid-phase extraction has advantages over other preconcentration methods in terms of simplicity, economy, rapidity, reusability of the adsorbent; ease of automation, higher preconcentration factor, lower consumption of reagents, and more importantly its environmental friendliness (use of less organic solvents). The most extensively used SPE sorbents are modified C18 Silica [39], activated carbon [40], alumina [41] and Amberlite XAD resins [42-43]. For example silica and silica bonded adsorbents offer good advantages in terms of thermal, mechanical and chemical stability. In addition, they act selectively towards a particular metal ion. In fact, the modified silica gel surfaces are known to act as a weak cation exchanger via its weak silanol groups, through immobilization of organic complexing agents, either chemically or physically. These modified surfaces greatly enhance metal exchange capacity and improve selectivity of these phases to metal ion removal, separation or preconcentration prior to their determination by x-ray fluorescence or AAS analysis [44-48]. In this work, preconcentration of ultratrace copper (II) in aqueous media using octadecyl silica membrane disks modified by a recently synthesized triazene (Figure 1) and determination by FAAS have been reported. Different experimental conditions, e.g. the type and volume of eluting solvent, the effect of pH, the effect of sample and eluent flow rates and the amount of ligand, on the extraction efficiency and breakthrough volume, limit of detection and maximum capacity of the disks for Cu2+ ion recovery have been studied.

Figure 1: The [1-(ortoacyl benzene) 3-(3,4-dichlorobenzene)triazene] ligand

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2. Experimental 2.1. Reagents

Extra pure methanol, acetonitrile, nitric acid, hydrochloric acid, acetic acid, sulfuric acid and perchloric acid (all from Merck) were used as received. The nitrate or chloride salts of the cations (all from Merck) were of the highest purity available and used without any further purification except for vacuum drying. Ligand synthesized, purified and dried as it has been described elsewhere [10]. Doubly distilled deionized water was used throughout. The standard stock solution of copper (II) (1000 ppm) was prepared by dissolving1.0000 g of copper wire (99.99%) in the least amount of HNO3 and dilution to 1000 ml in a calibrated volumetric flask with water. Working solutions were prepared by appropriate dilution of the stock solution with water. 0.1 M acetate and phosphate buffer solutions were used for the pH ranges 4.05.5 and 6.07.5, respectively.

2.2. Apparatus
All UV-Vis Spectra recorded on a computerized double-beam GBC Cintra20 spectrophotometer, using two matched 10 mm quartz cell. In a typical experiment, 2.0 ml of ligand solution (5.010-5 mol L-1) in acetonitrile was placed in the spectrophotometer cell and the absorbance of solution was measured. Then a known amount of the concentrated solution of metal ions in acetonitrile (1.310-3 mol L-1) was added in a stepwise manner using an l0l Hamilton syringe. The absorbance of the solution was measured after each addition. The metallic ions solution was continually added until the desired metal to ligand mole ratio was achieved. The determinations of copper were performed on a PG990 Atomic Absorption Spectrometer under the recommended conditions. A Metrohm E-603 digital pH meter equipped with a combined glass calomel electrode was used for the pH adjustments. All of spectrum was made on a UV-visible cintra20 spectrophotometer from GBC Company. The modified C18 extraction disks were used in conjunction with a standard 47 mm filtration apparatus (Schleicher and Schell, Dassel, Germany) connected to a vacuum.

2.3. Estimation of formation constants

The formation constant (kf) and the molar absorptivity () of the resulting 1:1 complexes between the triazene ligand and different metallic ions in acetonitrile at 25C were calculated by fitting the observed absorbance, Aobs , at various metallic ion / ligand mole ratios to the previously derived equations [49-50] (Equation 1), which express the Aobs as a function of the free and complexed metal ions and the formation constant evaluated from a non-linear least-squares program KINFIT [51].

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2.4. Sample extraction Extractions were performed with 47 mm diameter0.5mm thickness Empore membrane disks containing octadecyl-bonded silica (8 m particles, 60A pore size) from 3M Company. The typical composition of the disks was 90% w/w octadecyl bonded silica and 10% w/w PTFE fibers. The disks were used in conjunction with a standard Millipore 47 mm filtration apparatus connected to vacuum. In order to remove potential interferences and to ensure optimal extraction of the analyte of Interest, the disk cleaning and conditioning should be done before its use. Thus, after placing the membrane disk in the filtration apparatus, 10 ml methanol was poured onto the disk and immediately drowns through the disk by applying a slight vacuum. After all of the solvent has passed through the disk, it was dried by passing air through it for few minutes. The disk conditioning was then begun by pouring 10 ml methanol on to the disk. Immediately a low vacuum was applied and the solvent was drowning through the disk until solvent surface almost reaches the surface of the disk. The disk should not be allowed to soak without vacuum, and any air should not be allowed to contact with the surface of the disk. Then, a solution of 5 mg of ligand dissolved in 5 ml acetonitrile was introduced onto the disk and was drawn slowly through the disk by applying a slow vacuum. The passed solution was collected in a test tube. Then 2 ml water was added to the test tube and the resulting colloidal solution was again introduced to the passed through the disk slowly. The filtration step was repeated until the passed solution was completely clear. Finally, the disk was washed with 25ml water and dried by passing air through it. Thus, the membrane disk modified by the ligand is now ready for sample extraction. The general procedure for the extraction of Cu2+ ions on the membrane disk was as follows: The modified disk was first washed with 0.5 ml methanol followed by washing with 25 ml water. This step prewets the surface of the disk prior to the extraction of Cu2+ ions from water and ensures a good contact between the analyte and the ligand. It is important to note that the surface of the disk was not left to become dry from the time methanol was added until the extraction of Cu2+ ions from water was completed. The disk was then conditioned with 25 ml of a 0.1 M buffer solution with the same pH as the sample solution. Then 100 ml of sample solution containing 10 g Cu2+ at optimum pH was passed through the membrane (flow rate =10 ml min1). After the extraction, the disk was dried completely by passing air through it for a few min. The extracted copper was stripped from the membrane disk using 5ml of 0.1 M nitric acid by applying a slight vacuum. The eluted solution was collected in a test tube and then transferred into a 5 ml calibrated flask. The test tube was washed with another 1 ml portion of 0.1 M HNO3 and added to the flask. Finally, the flask was diluted to the mark with 0.1 M nitric acid. All working standard solutions of Cu2+ion were also prepared in 0.1 M nitric acid.

3. Results and discussion 3.1. Spectrophotometric studies

Spectrophotometric studies of complexation reaction between the triazene ligand and metallic ions in acetonitrile solution revealed that ligand can form stable 1:1 (metallic ion to ligand) complexes with different metallic ions.

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The electronic absorption spectra of triazene ligand (5105 mol L-1) in the presence and increasing concentration of Cu2+ (1.310-3M) ions were recorded (Figure 2) in acetonitrile at 25C. The resulting complexe of Cu2+ with triazene ligand are distinguished by a little spectral shift toward longer wavelength. The stoichiometry of the metal complexes was examined by the mole ratio method. Sample of the resulting plots are shown in Figure 3, at 297 nm for Cu2+-L and 377 nm for Ag+-L complexes respectively, and it is evident that 1:1 (metallic ion to ligand) complexes are formed in solution. The formation constants of the resulting 1:1 metallic ions to the triazene complexes were obtained at 25C by absorbance measurements of solutions in which varying concentrations of metallic ions were added to fixed amounts (5.010-5 mol L-1) of ligand solution. All the resulting absorbance-mole ratio data were best fitted to Equation 1, which further supports the formation of ML in solution.

K f [ L]2 + (1 + K f C M K f C L )[ L] C L = 0

(1)

For evaluation of the formation constants and molar absorptivity coefficients from absorbance vs. [M]/[L] mole ratio data, a non-linear least squares curve fitting program KINFIT was used. The resulting kf of the ligand complexes at 25C are listed in Table 1. The data given in Table 1 revealed that, at 25C, the stabilities of the complexes varies in the order Hg2+> Cu2+> Ag+> Cd2+> Ni2+> Pb2+. Thus, considering the observed stability, we decided to use ligand as a suitable modifier for the selective concentration and extraction of Cu2+ ions on the octadecyl silica membrane disks. Some preliminary experiments were undertaken in order to investigate ligand retention of copper ions by the membrane disk in the presence of ligand, after the recommended washing, wetting and conditioning procedures were carried out. It was found that, the membrane disk modified by the triazene ligand is capable to retain Cu2+ ions in the sample solution quantitatively (the test solution used contained 10 g copper in100 ml water at pH 7.0).

Figure 2: The spectrum of ligand solution (5.0010-5M) in acetonitrile and increasing concentration of Cu2+ ion solution (1.3010-3M).

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Figure 3: Mole ratio plots of absorbance as [Cu2+]/[L] at 297 nm and [Ag+]/[L] at 377 nm.

Table1: Formation constants of different ligand-Mn+ complexes. Cation Hg2+ Cu2+ Ag+ Cd2+ Pb2+ Ni2+ Log kf 4.98 0.03 4.47 0.01 3.98 0.02 3.83 0.01 3.52 0.02 2.78 0.04

3.2. Solid phase extraction 3.2.1. Choice of effluent

In order to choose a proper effluent for the retained Cu2+ ions, after the extraction of 10 g copper from 100 ml water by the modified disks, the copper ions were stripped with different volumes of varying concentration of different acids and others solvent (Table 2). From the data given in Table2 it is immediately obvious that, while 5ml of the 0.1 M mineral acids can accomplish the quantitative elution of copper from the membrane disk, 5ml nitric acid can do the job better. As is also obvious, the lower the acid concentration used, are suitable for the quantitative elution of the retained copper ions. Thus, 5 ml of 0.1M HNO3 was used as effluent for further studies.

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Table 2: Percent recovery of cu2+ from the modified membrane disk using different stripping solution Stripping solution HNO3 (0.1 M) HCl (0.1 M) H2SO4 (0.1 M) HNO3 (0.5 M) HCl (0.5 M) H2SO4 (0.5 M) EDTA (0.1 M) NH4SCN (0.1 M) % Recovery Cu2+ 100 64.8 100 100 65 100 71.1 2.2

3.2.2. Effect of pH The effect of pH on the extraction of copper ions was studied. In order to investigate the effect of pH on the SPE of copper (II) ion, the membrane disk was modified with 6mg of ligand and the pH of aqueous samples containing 10g Cu2+was varied from 4.0 to 8, using appropriate buffer solutions. The resulting percent recovery versus pH plot is show in Figure 4. As seen, the percent recovery of Cu2+ ion increases with increasing pH of solution until a pH of about 7 is reached. Quantitative extraction of copper ion occurs at a pH range 78. The pH values higher than 8 were not tested. Thus, a buffer solution of pH 7.0 was adopted for further studies.

Figure 4: The effect of pH of the sample on extraction recovery of Cu2+ ion.

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3.2.3. Effect of ligand amount

As the amount of loaded ligand on the membrane disk increases, the flow rate of solutions through the modified disk will decrease. Thus, the least amount of ligand necessary for the quantitative extraction of 10 g Cu2+ from a 100 ml aqueous sample at pH 7.0 was studied. The results are shown in Figure 5. As seen, the extraction of copper is quantitative using above 6 mg of ligand. Hence, subsequent extraction experiments were carried out with 6mg of the ligand. As seen, the extraction of copper decrease with 8mg ligand.

Figure 5: Effect of amount of the ligand on extraction recovery of Cu2+ ion.

3.2.4. Effect of flow rate

The effect of flow rates of the sample and stripping solutions from the modified membrane disk on the retention and recovery of copper (II) was investigated. It was found that, in the range of 5-30ml min1, the retention of copper by the membrane disk is affected the sample solution flow rate considerably (Figure 6). On the other hand, quantitative stripping of Cu2+ ions from the disk was achieved in a flow rate range of 10 ml min1, using 5 ml of 0.1 M nitric acid. At higher flow rates, quantitative stripping of copper decreased the recovery.

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Figure 6: Effect of flow rate on extraction recovery of Cu2+ ion.

3.2.5.

Analytical performance

The maximum capacity of the membrane disk modified by 6 mg ligand was determined by passing 500 ml portions of an aqueous solution containing 300g copper at pH 7.0, followed by the determination of retained metal ions using FAAS. The maximum capacity of the membrane disk was found to be 220g of Cu2+ion on the disk. The breakthrough volume of sample solution was tested by dissolving 10 g of copper in 100, 250, 500, and 1000 ml water and the recommended procedure was followed under optimal experimental conditions. In all cases, the extraction by the membrane disk was found to be quantitatively. Thus, the breakthrough volume for the method should be greater than 500 ml. Consequently, by considering the final elution volume of 5.0 ml and the breakthrough volume of 500ml, an enrichment factor of 100 was easily achievable. The limit of detection (LOD) of the proposed method for the determination of copper (II) was studied under the optimal experimental conditions. The LOD obtained from CLOD=KbSb/m for a numerical factor Kb=3 is 50 ng ml1. In order to investigate the selective separation and determination of Cu2+ion from its binary mixtures with diverse metal ions, an aliquot of aqueous solution (100 ml) containing 10 g Cu2+and different amounts (mg) of other cations was taken and the recommended procedure was followed and the results are summarized in Table 3. The results clearly indicate that 10 g of copper (II) ions in the binary mixtures are retained almost quantitatively by the modified membrane disk, even in the presence of up to about 19.66 mg of the diverse ions. In order to assess the applicability of the method to real samples, it was applied to the separation and recovery of copper (II) ions from100 ml of three different water and a synthetic sample, and the results are summarized in Figure 7. As is obvious, the copper (II) ions added can be quantitatively recovered from the water and synthetic matrices.

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Table 3: Separation of copper from binary mixtures. The initial solution contained 10 g copper and different amount of diverse ion in 100 mL. Diverse ion Zn2+ Ni2+ Pb2+ Ba2+ Ca2+ Mg2+ K+ Na+ Hg2+ Amount taken, mg 0.44 7.05 1.87 7.04 2.91 3.06 8.73 19.66 0.618 Recovery of Cu2+ 100 100 100 90.0 97.3 77.0 89.8 92.5 50.1

Figure 7: Recovery of 10 g Copper spied to 100 mL of the water sample.

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