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Received 3 December 2002; received in revised form 17 April 2003; accepted 2 May 2003
Abstract
The partial least squares (PLS) applied to the simultaneous determination of the divalent ions of copper, nickel, cobalt and
zinc based on the formation of their complexes with 2-carboxy-2 -hydroxy-5 -sulfoformazyl benzene (zincon). The absorption
spectra were recorded from 515 through 750 nm. The effect of pH on sensitivity and the selectivity was studied in the range
3.010.0 and the pH 8.0 was choused according to net analyte signal (NAS) as a function of pH. The concentration range
for Cu2+ , Ni2+ , Co2+ and Zn2+ in solution calibration sets were 02.6, 04.6, 03.0 and 04.92 ppm, respectively. The root
mean squares differences (RMSD) for copper, nickel, cobalt and zinc were 0.0181, 0.0488, 0.0309 and 0.0463, respectively.
2003 Published by Elsevier Science B.V.
Keywords: Partial least squares; Copper; Nickel; Cobalt; Zinc; Spectrophotometric determination
1. Introduction
Copper, nickel, cobalt and zinc are metals that appear together in many real samples. Several techniques
such as X-ray fluorescence [1], atomic fluorescence
spectrometry [2], polarography [3], chromatography
[4], atomic absorption spectrometry [5,6], etc. have
been used for the simultaneous determination of these
ions in different samples. Among the most widely
used analytical methods are those based on the UV-Vis
spectrophotometry techniques [711], due to the resulting experimental rapidity, simplicity and the wide
application. However, the simultaneous determination
of these ions by the use of the traditional spectropho Corresponding author. Tel.: +98-8317233063;
fax: +98-8318231618.
E-mail address: jahan.ghasemi@tataa.com (J. Ghasemi).
182
(1)
(2)
NAS
b=
NAS2
(3)
1
= NAS2
b 2
(4)
SEL =
NAS2
1
=
b2 rn 2
rn 2
(5)
2. Experimental
3. Results and discussion
2.1. Reagent
All chemical were of analytical-reagent grade and
deionized water was used throughout. Stock solutions
of copper, nickel, cobalt and zinc were prepared from
183
Fig. 1. Absorption spectra of the zincon and copper, nickel, cobalt and zinc complexes in different pH-value. Concentration of zincon is
1.168 105 and each ion is 1 ppm, ( ) zincon, (---) Cu, () Ni, (+) Co, () Zn.
184
flask and diluted to the mark with distilled water. Different volumes of 100 ppm solution of copper were
added to 5.0 ml of zincon solution at pH = 8 in a
10.0 ml volumetric flask and diluted to the mark with
distilled water. After 30 min, the absorbance was read
at the 600 nm. The same procedure was followed for
nickel, cobalt, copper and zinc and the absorbance
of the solutions were read at 665, 656 and 630 nm,
respectively. Linear regression results, line equations
and R2 are shown on the Fig. 3.
3.2. Calibration and test mixtures
Fig. 3. Analytical curve for univariate determination of copper, nickel, cobalt and zinc complexes.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
Concentration (ppm)
Cu
Ni
Co
Zn
2.60
1.95
1.95
1.95
1.30
1.30
1.30
1.30
1.30
1.30
0.65
0.65
0.65
0.65
0.65
0.65
0.65
0.65
0.65
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
1.15
0.00
1.15
0.00
0.00
2.30
1.15
1.15
0.00
0.00
0.00
3.45
2.30
2.30
1.15
1.15
0.00
0.00
0.00
0.00
4.60
3.45
3.45
2.30
2.30
2.30
1.15
1.15
1.15
1.15
0.00
0.00
0.00
0.00
0.00
1.15
0.00
0.00
0.75
0.00
0.00
0.75
0.00
1.50
0.75
0.00
0.00
0.75
0.00
1.50
0.00
3.00
1.50
0.75
0.00
0.00
0.75
0.00
1.50
0.75
0.00
2.25
1.50
0.75
0.00
3.00
2.25
1.50
0.75
0.00
0.75
0.00
0.00
0.00
1.23
0.00
0.00
1.23
0.00
1.23
2.46
0.00
0.00
1.23
0.00
2.46
0.00
1.23
2.46
3.69
0.00
0.00
1.23
0.00
1.23
2.46
0.00
1.23
2.46
3.69
0.00
1.23
2.46
3.69
4.92
1.23
185
186
Fig. 4. Plot of PRESS vs. number of significant factors: () Ni, () Zn, () Co, () Cu.
n
(xi x i )2
R2 = i=1
n
i )2
i=1 (xi x
0.5
n
100 1
2
REP(%) =
(xi xi )
x
n
the analyte in the sample i, x i the mean of true concentration in the prediction set and n is the total number
sample used in the prediction sets. The concentration
data, the predicted values and their relative errors of
the prediction set are shown in Table 2. The value of
RMSD, REP, R2 , number of factors and PRESS according the values listed in Table 2 are summarized in
Table 3.
3.5. Effect of foreign ions
i=1
The interference due to several cations and anions was studied in detail. For these studies different
amounts of the ionic species were added to a mixture of Cu, Ni, Co and Zn containing 0.9, 1.5, 0.58
Table 2
Prediction set composition, predicted values and relative errors
No.
1
2
3
4
5
6
7
Cu
Ni
Co
Zn
Cu
Ni
Co
Zn
Cu
Ni
Co
0.66
0.50
0.90
0.60
0.80
0.38
0.00
0.80
1.30
1.50
1.40
1.50
0.00
4.00
0.80
0.90
0.58
0.70
0.60
0.00
0.00
1.50
1.10
0.70
1.14
0.82
4.20
0.64
0.63
0.47
0.82
0.56
0.73
0.37
0.05
0.86
1.31
1.34
1.40
1.64
0.15
4.21
0.88
0.97
0.66
0.76
0.64
0.09
0.11
1.74
1.26
0.70
1.26
0.87
4.13
0.65
4.54
6.00
8.88
6.66
8.75
2.63
7.50
0.76
10.66
0.00
9.33
5.25
11.25
8.88
13.79
8.57
6.66
Zn
16.00
14.54
0.00
10.52
6.09
1.66
1.56
187
Fig. 5. Plots of predicted concentration vs. actual concentration for four cations in the prediction set.
Table 3
Statistical parameters of the test matrix using the PLS model
Cations
No. of
factors
RMSD
R2
REP (%)
Cu2+
Ni2+
Co2+
Zn2+
6
5
8
5
0.018
0.049
0.031
0.045
0.94
0.99
0.97
0.99
3.29
3.25
6.05
3.21
Table 4
Effect of various ions on the determination of four metals
Concentration
(ppm)
Foreign ions
>2000
1000
500
400
20
10
5
2
1
<1
188
Table 5
Some industrial alloys analysis
Sample
M1a
M2a
M3a
Cu2+
Ni2+
Co2+
(1.48),
(0.64),
(0.91)
Cu2+ (2.03), Ni2+ (0.30), Zn2+ (0.78)
Cu2+ (2.12), Zn2+ (0.94)
Recovery (%)
Cu
Ni
Co
Zn
Cu
Ni
Co
Zn
1.41
1.92
2.06
0.70
0.44
0.21
0.93
0.09
0.00
0.01
0.75
0.92
95.11
94.43
97.22
109.44
110
102.00
95.76
97.35
The number in parenthesis indicates the concentration of element taken for analysis in ppm.
a M1, M2 and M3 are permute, alloy sample and red brass, respectively.
4. Conclusions
The coppernickelcobaltzinc mixture is an extremely difficult complex system due to the high
spectral overlapping observed between the absorption
spectra for these components. PLS modeling was
established, with good prediction ability in the real
matrix samples. Results show that partial least square
is an excellent calibration method to determination of
these metals together without pretreatment in complex
samples.
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