Journal of Materials Science and Engineering B 1 (2011) 895-900 Formerly part of Journal of Materials Science and Engineering, ISSN

1934-8959

DA VID

PUBLISHING

Simultaneous Spectrophotometric Determination of Ag+ and Cu2+ by Partial Least Square Regression
Azimi Salameh1, Rofouei Mohammad Kazem2 and M. Sharifkhani Samira2
1. Department of Chemistry, Takestan Branch Islamic Azad University, Takestan, Iran 2. Faculty of Chemistry, Tarbiat Moallem University, Tehran, Iran Received: July 22, 2011 / Accepted: September 05, 2011 / Published: December 25, 2011. Abstract: Simultaneous determination of Cu (II) and Ag (I) was performed by spectrophotometric determination using chemometric techniques and new triazen ligand which was prepared by us. The calibration graphs of individual components were linear in the ranges of 1.1 103-3.5 103 gmL-1 and 1.4 103-8.2 103 gmL-1 for Ag+ and Cu2+, respectively. The root mean square errors of prediction (RMSEP) were 2.828 and 1.148 for Ag+ and Cu2+ respectively. The proposed method are simple, fast, inexpensive and do not need to any separation or preparation method. Key words: Cupper, silver, chemometric method, partial least squares regression, simultaneous determination, spectrophotometry.

1. Introduction
The Cu (II) complexes with high numbers of ligands have been used as the basis for the development of spectrophotometric methods. However, Ag is a metallic ion that has not been widely studied; the information on silver concentration in environmental samples is limited, primarily owing to the difficulties in measuring its levels [1]. A high concentration of copper and silver in waters has been identified as a potential health and environmental hazard [2], furthermore silver and copper are metals which appear together almost in all real samples. In most cases, the characterization of these samples includes the determination of their metal ion content. The need for silver and copper analysis in environmental and biochemical material has increased after reports on different roles of these metals in human health and diseases [3-5]. Several methods have been proposed for the individual or simultaneous determination of silver and
Corresponding author: Azimi Salameh, research field: simultaneous spectrophotometric determination of Ag+ and Cu2+ by partial least square regression. E-mail: Sally_azimi@yahoo.com.

copper using very different techniques. Silver and copper have very similar chemical behavior, and they have been simultaneously determined mainly electrochemically and chromatographically. Several techniques such as solid phase extraction coupled with chromatography [6], atomic absorption spectrophotometry [7, 8] and inductively coupled plasma mass spectrometry [9, 10], have been used for the simultaneous determination of these ions in different samples. UV-visible spectrophotometric techniques are among the most widely used analytical methods, due to both the simplicity and rapidness of the method [11-13]. However, the simultaneous determination of these ions by the use of the traditional spectrophotometric techniques is difficult. Interest in UV-VIS spectrophotometric methods has increased and been renewed through the use of signal processing and multivariate techniques [14] such as partial least squares (PLS) regression [15, 16] and artificial neural networks [17]. 1-(2-Ethoxyphenyl)-3-(4-nitrophenyl) triazene (ENTZ) reacts with several metal ions such as silver, copper to form colored metal complexes. This chelating agent has been used to determine several

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Simultaneous Spectrophotometric Determination of Ag+ and Cu2+ by Partial Least Square Regression

metal ions by ultraviolet-visible (UV-Vis) spectrophotometry. But these metal-1-(2-ethoxyphenyl)-3-(4-nitrophenyl) triazene (ENTZ) complexes do not dissolve in aqueous solution, so it is necessary to perform a solvent extraction. In this work PLS was employed for the resolution of binary mixtures of silver and copper. The suggested method was successfully applied to the determination of these ions simultaneously.

2. Experiment
2.1 Reagents and Solutions All chemicals were of analytical-grade (Merck Co.). Double distilled water was used throughout. Standard Ag (I) and Cu (II) solution were made with 100 gmL stock solution prepared using their metal nitrate salts (Merck, Co.), 1-(2-ethoxyphenyl)-3-(4-nitrophenyl) triazene (ENTZ) was synthesized, purified and used as a ligand and absolute ethanol (99.98%) (Merck, Co) as a solvent of it. All of the solutions were prepared fresh daily. 2.2 Apparatus UV-vis absorption spectra were recorded using the double-beam in-time spectrophotometer (Perkin-Elmer model Lambda 25, USA) with a 1 cm quartz cell, a scan rate of 400 nm/min and slit width of 2 mm and the temperature of the cell holder was maintained at 25 C. Elemental analysis was performed by a CHNO Rapid Heraeus elemental analyzer (Hanau, Germany) IR spectra was found on a PerkinElmer model 843 (U.S.A). The 1H NMR spectrum was obtained using BRUKER AVANCE DPX 300 MHz apparatus (Germany). The computations were performed on a Pentium IV computer. All the programs in the computing process were written in MATLAB for Windows. 2.3 Synthesis and Characterization of ENTZ The 1-(2-ethoxyphenyl)-3-(4-nitrophenyl) triazene (ENTZ) is used as ligand and its structure is shown in

Fig. 1. It was synthesized as follows: A 100 mL flask was charged with 10 g of ice and 15 mL of water and then cooled to 0 C in an ice-bath. After that, 0.69 g (5 mmol) of paranitroaniline and 3.61 g (0.1 mol) of hydrochloric acid (d = 1.18 gmL-1) were added to the mixture, and then a solution of NaNO2 containing 0.35 g (5 mmol) in 10 mL of water was added during 15 min under stirring solution. Afterwards, 0.68 mL (5 mmol) of 2-ethoxyaniline (1.06 gmL-1) was added drop wise with vigorous stirring for a period of 30 min to this mixture. Finally, a solution containing 14.76 g (0.18 mol) of sodium acetate in 45 mL of water was added and stirred for 45 min. The orange-colored product was filtered and dissolved in diethyl ether. After the evaporation of diethyl ether, a purified sharp pale orange powder, which has a melting point of 101 C-102 C, was produced (yield, 72%) [18]. Infrared and 1H NMR spectra and CHN analysis, were confirmed the ENTZ structure. IR (KBr): 3,389 cm-1, 3,325 cm-1, 2,984 cm-1, 1,600 cm-1, 1,519 cm-1, 1,468 cm-1, 1,343 cm-1, 1,253 cm-1, 1,209 cm-1, 1,113 cm-1, 1,045 cm-1, 894 cm-1, 739 cm-1, 1H NMR (DMSO): 1.37 (CH3, 3), 4.13 (CH2, 2), 6.94-8.06 (phenyl protons, 8), 12.89 (NH, 1), CHN: (C14H14N4O3) C: 58.66%, H: 4.82%, N: 19.52%. 2.4 Spectrophotometric Study The stoichiometry and stability of the complexes between the ligand and various metal ions, in acetonitrile solution was investigated. A constant concentration of ligand (5.0 10-5 M) was titrated by (5.0 10-3 M) metal ions. It was observed that Cu (II) and Ag (I) complexes have a LogKf = 5.56 and 4.21, respectively.

Fig. 1 (ENTZ).

1-(2-ethoxyphenyl)-3-(4-nitrophenyl)

triazene

Simultaneous Spectrophotometric Determination of Ag+ and Cu2+ by Partial Least Square Regression

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The electronic absorption spectra of the titration of ENTZ with Cu (II) and Ag (I) are shown in Figs. 2 and 3, respectively. In Fig. 2, the absorbance band of ENTZ at wavelength 270 nm increases and at 400 nm decreases by increasing in metal ion concentration. Fig. 3 shows that the absorbance band of ENTZ at wavelength 284 nm increases and at 373 nm decreases

by increasing in metal ion concentration. The electronic absorption spectra of ENTZ with Cu (II), Ag (I) separately and with each other are shown in Fig. 4. The formation constants of different complexes were determined by non-linear least-squares curve-fitting program KINFIT [19]. The formation-constant values (Kf) of the different complexes are reported in Table 1.

Fig. 2 (a) Electronic absorption spectra of ligand [ENTZ] in acetonitril (5.0 10-5 M) in the presence of increasing concentration of Cu (II) nitrate at room temperature. (b) Corresponding mole ratio plot at 400 nm.

Fig. 3 (a) Electronic absorption spectra of ligand [ENTZ] in acetonitril (5.0 10-5 M) in the presence of increasing concentration of Ag (I) nitrate at room temperature. (b) Corresponding mole ratio plot at 373 nm.

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Simultaneous Spectrophotometric Determination of Ag+ and Cu2+ by Partial Least Square Regression

Fig. 4 Absorption spectra of metal ions solution. Curve for 1.5 10-5 M Ag(I), 1.5 10-5 M Cu(II), 5 10-5 ML, the Ag & Cu spectras are consisted 5 10-3 M of Cu & Ag, 5 10-5ML. Table 1 Formation constants of different metal-ENTZ complexes in acetonitrile. Metal Ag+ Cu2+ U3+ Th3+ Hg2+ Cd2+ Zn2+ Pb Fe
2+ 2+

Logkf 4.21 4.56 4.83 4.28 4.93 4.01 1.98 3.45 2.47 3.28 2.46 2.12 2.23 3.08

Co2+ Mn2+ Ni2+ Cr3+ Al3+

3. Result and Discussion

The first step in the simultaneous determination of different metal ions by PLS methodology involved constructing the calibration matrix for the binary mixture Ag-Co. Fifteen binary mixtures were selected as the calibration set. Their composition was randomly designed for obtaining more information from calibration procedure. Under this condition, the calibration model was obtained. The calibration model
Table 2 Analyt Silver Copper

was validated with 3 synthetic mixtures containing the metal ions in different proportions that were randomly designed. The results obtained are given in Tables 2 and 3. Each solution was prepared to contain combinations of the concentration levels 0-5.1 gmL-1 of silver and 0.2416-7.25 gmL-1 of copper. Twelve of these solutions were used as a calibration set for PLS model development. Another 3 calibration mixtures, not included in the previous set were employed as an independent test set called the prediction set. To select the number of factors in the PLS algorithm, the leave one out cross-validation method, was used [20]. The prediction error was calculated for each component in the prediction set. The optimum number of factors (latent variables) was determined by computing the prediction error sum of squares (PRESS) for different numbers of latent variables (1-10 latent variables). Fig. 5 shows a plot of PRESS against the number of factors for each numbers of components. The 6 factors were selected as the optimum number of factors and the model with these numbers of factors was used for prediction of the test samples (Table 3), Table 4 shows the relative and absolute errors between the actual and prediction concentration by PLS model.

Characteristics of calibration graphs for the determination of silver and copper by the proposed method. slope 0.0553 0.034 Intercept 0.0278 0.0611 Correlation coefficient 0.9969 0.9958 Linear range (gmL 10-3) 1.1-3.5 1.4-7.82 Limit of detection (gmL) 0.01 0.04

Simultaneous Spectrophotometric Determination of Ag+ and Cu2+ by Partial Least Square Regression

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Fig. 5 Plot of PRESS against the number of factors for Ag and Cu. Table 3 Composition of prediction set, their predictions by PLS model and statistical parameters for the system. Ag (gmL-1) Sample 1 2 3 Actual concentration 1.7 2.37818 4.08 Prediction concentration 1.58 2.37087 4.07587 Cu (gmL-1) Actual concentration 4.832 3.8656 1.4496 Prediction concentration 5.0061 3.8759 1.451

Table 4 Absolute and relative errors by PLS model. Sample 1 2 3 Absolute error Ag(I) -7.2095e-007 -4.302e-008 -5.8698e-009 Cu(II) 7.2095e-007 4.302e-008 5.8698e-009 Relative errors Ag(I) -7.2095 -0.30729 -0.024458 Cu(II) 3.6048 0.26888 0.097831

4. Conclusions
The results showed that PLS model can be successfully applied for determination of binary mixture of silver and copper. The proposed methods show an improvement in simplicity and speed. This method has the advantage that does not need extraction steps and are more sensitive than ordinary spectrophotometric methods used for determination of silver and copper.
[7] [6] [5]

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