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Microchemical Journal 68 Ž2001

. 11 1

Simultaneous determination of cobalt and nickel.

Comparison of prediction ability of PCR and PLS using
original, first and second derivative spectra

J. Ghasemi, A. Niazi
Chemistry Department, Razi Uniersity, Kermanshah, Iran

Received June 17, 2000; received in revised form 18 August 2000; accepted August 21, 2000

Abstract

Two multivariate calibration methods, partial least squaresŽ.PLS and principal component regressionŽPCR., were
applied to the simultaneous determination of the divalent ions of nickel and cobalt based on the formation of their
complexes with 4-Ž 2-pyridylazo. resorcinol
Ž. PAR . The original, first and second derivative absorption spectra of the
binary mixtures were used to perform the optimization of the calibration matrices by the PLS and PCR methods. The
results obtained by the application of the different chemometric approaches are discussed and compared. The
SavitzkyGolay convolution method is used for calculating the first- and second-derivative absorption spectra of
binary mixtures. Calibration matrices were 15540 and 15560 ng ml1 for cobalt and nickel, respectively. 2001
Elsevier Science BV All rights reserved.

Keywords: Partial least-squares; Principal component regression; Cobalt; Nickel; Determination

1. Introduction 4 , atomic absorption spectrometry 5 , etc., have

Cobalt and nickel appear together in many realities
and synthetic samples. Several techniques such as
,
X-ray fluorescence 1 atomic fluorescence spec-
trometry 2 , polarography 3 , chromatography
Corresponding author.
E-mail address: ghasemi@razi.ac.irŽ J.
. Ghasemi .
been used for the immediate determination of
these ions in different samples. Among the most
widely used analytical methods are those based
on the ultraviolet UV Ž .visible spectrophotome-try
techniques, due to both the resulting experi-mental
rapidity and simplicity and the wide application.
However, the simultaneous determination
of these ions by the use of traditional spectropho-
tometry techniques is difficult because, generally,

0026-265X01$ - see front matter 2001 Elsevier Science BV All rights reserved.
PII: S 0 0 2 6 - 2 6 5 X 0
Ž 0 0. 0 1 5 9 - 4
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2 ( 1 11
J. Ghasemi, A. Niazi Microchemical Journal 68 2001 )
the absorption spectra overlap in a bright region
and the superimposed curves are not suitable for
quantitative evaluation.
Under computer-controlled instrumentation,
derivative techniques and multivariate calibration
methods are playing a very important role in the
multicomponent analysis of mixtures by ultravio-let
UV Ž .visible molecular absorption spec-trophotometry
6 8 . The advantage of multicom-ponent analysis
using multivariate calibration is
the speed of the method of determination for
components of interest in a mixture, as a
separation step can be avoided.
The application of quantitative chemometrics,
particularly least classical squares CLS ŽŽ.. , inverse
least squares ILS , principal component regres- Ž . Ž.
sion PCR and , partial least squares PLS to ,
multivariate chemical data is becoming more
widely owing to the availability of digitized
spectroscopic data and commercial software for
laboratory computers.
The theory and application of PCR and PLS in
spectrometry has been discussed by several
workers 9 12 . Also several multicomponent de-
termination of inorganic substances based on the
application of these methods to spectrophotometer-
ric data have been reported 13,14 . Recently, the
combination of derivative techniques with multi-
variate calibration methods has been proposed,
and the convenience of such an approach has
evaluated by several workers with contradic-
tory results 15,16 .
In this work reports the simultaneous spec-
trophotometric determination of cobalt and nickel
with 4- Ž2-pyridylazo. resorcinol
Ž. PAR using PCR
and PLS algorithms is reported. The results ob-
tained by the two methods are compared and
discussed. discussed.
2. Experimental
2.1. Apparatus
Electronic absorption measurements were car-ried
out on a CECIL 9000 spectrophotometer slit Ž
width 0.2 nm and scan rate 500 nmmin using .
1.00 cm quartz cells. A Metrohm 692 pH-meter
furnished with a combined glass-saturated calomel
electrode was used for pH measurements. The
pH-meter was calibrated with at least two buffers
solutions at pH 3.00 and 9.00.
2.2. Computer hardware and software
All absorbance spectra were digitized and
stored at wavelengths from 380 to 620 nm in steps
of 1 nm and then transferred inŽ ASCII format .
to a Pentium 200 MHz computer for subsequent
manipulation by PCR and PLS programs.
The data treatment was performed with MATLAB
for windows math
Ž. works, version 4.2 . PCR and
PLS programs Žfor calibration-prediction and ex-
perimental design .were applied to a program
written in MATLAB according to the algorithm
described by Martens and Naes 9 .
2.3. Reagents
All the chemicals used were of analytical-
reagent grade, subboiling, distilled water were used
throughout.
Stock solutions of cobaltŽ.II and nickel Ž.
II were
prepared from their commercial salts nitrate
Ž or
sulfate. and standardized titrimetrically. Stan-
dards of working solution were made by appropri-
ate dilution daily as required. A stock PAR solu-
5
.
tion 4.010
Ž M was prepared by dissolving reagent.
. by sodium
A buffer solution pH 8.2 was Ž prepared
borate.
2.4. Procedure
Known amounts of the standard solutions were
placed in a 10-ml volumetric flask and completed
to the final volume with deionized water final pH Ž
8.2. . The final concentration of these solutions
varied between 15540 and 15560 ng ml1 for
cobalt and nickel, respectively.
3. Results and discussion
Fig. 1 shows the original, first and second
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J. Ghasemi, A. Niazi Microchemical Journal 68 2001 1 )(11
Fig. 1. I: Absorbance; II: first; and III: second derivative
Ž. Ž.
spectra of a cobalt a nickel , and binary mixture com- Ž .
b .
plexes c with PAR.
derivative absorption spectra in aqueous solution
of the individual metal complexes and a mixture
of them at pH 8.2. The SavitzkyGolay convolu-tion
method is used for calculating the first- and
second absorption derivative spectra 17 . With the
aim of investigating the possibility of de-
3
termining cobalt IIŽ. Ž.
and nickel II in mixtures, the
optimal working conditions were studied un-der
the conditions previously established for each
metal ion. A sodium borate buffer solution of pH
8.2 was selected. The effect of PAR concentration
was also investigated, a reagent concentration of
4.0105 M was chosen because it ensures a
sufficient reagent excess. In order to choose the
optimal pH value at which the minimum overlap
occurs, influence of the pH of the medium on the
absorption spectra of metal ions were studied
over the pH range 7.09.0.
The absorption depends critically on the order
of addition of reactants, the most suitable order
of addition was metal ion solutions, PAR and
buffer. buffer. Individual calibration curves were
con-structured with several points Ž Fig. 2, . as
absorbance vs. metal ion concentration in the range of
15540, 15560 ng ml1 for cobalt and nickel,
respectively. Linear regression results, line equa-
tions and R2 are also shown on the Fig. 2.
3.1. Calibration and prediction data sets
Multivariate calibration methods are suitable
for the analysis of large number of samples. How-
ever, they are not advised for the determination
of large numbers of analyzes because of the com-
plexity of the calibration matrix. Moreover, the
preparation and analysis of the standards belong
to the calibration set are the most expensive step
in the multivariate calibration procedure.
Multivariate calibration methods such as PLS
require a suitable experimental design of the
standards belonging to the calibration set in order
to provide good predictions. A synthetic set of 43
solutions of mixtures of Co2 and Ni2 were
prepared Tables
Ž 1 and 2 . From the series, 33
solutions were chosen for the calibration set and
the other 10 were used as prediction solutions.
This selection was performed on the basis of their
distributions on the first and second principal
components. Prediction solutions were chosen ac-
cording to their situation on the graph, inside the
range of calibration solutions ie liesŽ in the calibration
range ..
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4 J. Ghasemi, A. Niazi Microchemical Journal 68 2001( 1 ) 11

Fig. 2. Analytical curve for univariate determination of cobalt and nickel complexes.

The spectral region between 380 and 580 nm, eral methods to obtain the number of significant
which implies working with 201 experimental factors. factors. At first according to Malinowski
points Ž. Ž per
thespectrum
spectra are
as digi-. algo-rithm ,18 a significant factor analysis applied
tized every 1-nm interval was selected for using the Malinowski indicator function INDŽ . ,
analysis. In this spectral region, the maximum spectrum
REV, Eigenvalue and Real Error Indicator. The
information is shown. The obtained spectra were obtained results are shown in Fig. 3. As can be
just mean centered. seen from Fig. 3 at least a significant factor of 3 is
needed to reconstruct the absorbance data
3.2. Number of significant factors matrix. Another function to confirm the number of
significant factors latent
Ž variables in. the PCR
In order to model the system without and PLS algorithm, is a cross-validation method,
overfitting the data concentration, we employ the sev-leaving out one sample at a time 19 . Given the
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J. Ghasemi, A. Niazi Microchemical Journal 68 2001 1 ) 11 ( 5

Table 1
Concentration data for the different mixtures used in the calibration set for the determination of cobalt and nickel

Mixture Cobalt Nickel Mixture Cobalt Nickel

first first first first

ng ml ng ml ng ml ng ml

m1 550 538 m18 25 175

m2 536 538 m19 390 452
m3 17 75 m20 263 402
m4 320 410 m21 240 250
m5 481 510 m22 115 132
m6 217 104 m23 456 502
m7 246 285 m24 257 357
m8 450 487 m25 65 40
m9 230 210 m26 498 532
m10 362 426 m27 435 462
m11 506 537 m28 250 325
m12 115 165 m29 25 175
m13 221 130 m30 285 402
m14 355 417 m31 225 160
m15 171 103 m32 374 435
m16 516 537 m33 106 74
m17 490 518

set of 33 calibration spectra, the PCR and PLS PLS models are as follows:
calibration on 32 calibration spectra were per- No. PRESS
Calibration Metal Type of spectra method
formed, and using this calibration, the concentra- ion factor 10000
2
tions of the compounds, in each sample were PLS Co Original 12 0.0206 First derivative 12 0.0464
2
PLS Co Second derivative 13 0.0701 Original 11
compared with the known concentrations of the 2
PLS Co 3.2329 First derivative 13 0.0640 Second
compounds in this reference sample and the pre-. 2
PCR Co derivative 11 0.7644 Original 11 0.0144 First
diction error sum of squares PRESSŽ was calculated. PCR Co
2
derivative 12 0.0047 Second derivative 13
The PRESS was calculated in the same PCR Co
2
0.0701 Original 13 0.1736 First derivative 12
2
manner each time a new factor was added to the PLS Ni 0.0236 Second derivative 13 0.3202
2
PLS or PCR models. PLS Ni
2
PLS Ni
One reasonable choice for the optimal number of 2
PCR Ni
factors would be that number which yield PCR Ni
2
2
the minimum PRESS. However, using the number PCR Ni
of factors h . that
Ž yields a minimum PRESS

usually leads to some overfitting. A better crite-rion
for selecting the optimal number of factors
involves the comparison of PRESS from models
with fewer than h factors. The F-statistics was
used to make the significance determination. Hol-
land and Thomas 20 empirically determined that an
F-ratio probability of 0.75 is a good choice.
We selected as the optimum the number of factor-
Print Fig. 4, the cumulative PRESS obtained by
optimizing the calibration matrix of the original,
first- and second derivative of absorption spectra
with these methods, are shown. By inspection of
PRESS plots of different cases, using the PLS on
original spectra gives fewer significant factors than
PLS on derivative and PCR on all types of spectral
data. data.

tors for the PRESS value the F-ratio probability

of which drops below 0.75. The maximum number 3.3. Statistical parameters
of factors used to calculate the optimum PRESS
was selected as 15 and the optimal number of The root mean squares difference RMSD Ž is an .
factors obtained by the application of PCR and indication of the average error in the analysis
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6
Table 2

Mixture Co

P1
P2
P3
J.
Added and found results of the synthetic mixtures of cobalt and nickel by PLS and PCR methods using original, first and second derivative spectral data

Added

440.5
250.0
430.0
Ni

410.5
75.0
395.0
2
Found

Original data
PCR

Co

434.1
211.7
459.5
2
Ni

432.1
101.1
331.6
2
PLS

Co

438.8
242.9
435.5
2
Ni

411.7
79.7
394.1
2
First derivative data

PCR

Co

435.7
222.2
446.9
2
Ni

387.2
2

83.8
387.3
PLS

Co

436.6
223.6
439.1
2
Ni

409.3
97.8
391.2
2
Second derivative data

PCR

Co

436.9
220.3
454.5
2
Ni

396.6
99.4
349.7
2
PLS

Co

426.2
240.1
437.4
2
Ni

406.8
77.3
369.4
2

P4 305.0 380.0 335.9 340.0 304.0 380.8 356.4 344.2 331.9 371.4 342.6 351.3 312.4 390.8
P5
P6
P7
P8
P9
P10
Ghas
462.5
450.0
537.5
125.0
210.0
375.0
307.5
207.5
312.5
175.0
275.0
200.0
483.8
424.5
541.9
158.9
209.6
359.0
328.4
226.7
317.7
116.8
284.0
206.3
459.0
448.1
539.0
129.1
212.5
379.0
304.9
204.7
315.6
170.5
273.1
199.5
455.9
439.7
548.0
127.0
244.3
351.1
330.0
216.6
306.2
157.9
251.8
223.5
462.0
442.4
538.9
140.4
226.3
376.2
299.1
216.8
311.2
150.9
242.2
202.4
479.0
435.1
497.5
162.4
174.4
342.6
314.5
226.4
328.9
135.9
318.5
225.4
478.2
440.0
539.2
135.8
211.1
366.4
305.5
216.0
325.4
162.5
278.5
200.8

1
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J. Ghasemi, A. Niazi Microchemical Journal 68 2001 7

Fig. 3. Significant factor analysis results of calibration matrix of cobalt and nickel mixtures.

for each component, is PCR and PLS, are summarized in Table 3. Ac-
cording to PRESS and statistical values, PLS on

(
n
original spectral data has given the best results
RMSD 1n x Italy Ž ˆi xi .2
with respect to the other mentioned data manipu-
i1 lation methods.
2
and the square of the correlation coefficient R .,Ž
which is an indication of the quality of fit of all 3.4. Application to alloy matrix and synthetic
the data to a line, is mixtures

n n
2
R 2Italy Italy iŽ. Ž. ˆx x xx i
2 Four synthetic mixtures of the two components
i1 i1 that their compositions have been prepared ac-
cording to some known alloys 21 . The proposed
where x isi the true concentration of the analyte in PLS and PCR methods were applied to the origi-
the sample i, ˆx represents
i the estimated con- nal, first and second derivative spectra, allowing the
centration of the analyte in the sample i, x is the resolution of their components. The composition
mean of the true concentration in the prediction of the binary mixtures assayed and PCR and PLS
set, and n is the total number of samples used in predictions are shown in Table 4.
the prediction sets, that were calculated. Print Fig. 5a,b show the recovery results obtained
The statistical parameters found for the original, by the application of the PLS and PCR methods
first and second derivative spectral data using on the three types of spectral data are repre-
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J. Ghasemi, A. Niazi Microchemical Journal 68 2001 1 ) 11

sent. Satisfactory recovery values are obtained

in most of the binary samples analyzed. Recovery
values for Co2 and Ni2 by using PLS and PCR
and three types of spectral data are as follows:
Calibra- Type of spectral llltion Range of recovery %Ž .
data method
Co 2 Ni 2

PLS Original 97.2103.2 97.4106.3

PLS First derivative 89.4112.3 86.2130.4
PLS Second derivative 96.0108.6 92.9104.1
PCR Original 84.7127.1 66.7134.8
PCR First derivative 88.9116.9 90.2111.8
PCR Second derivative 83.0129.9 77.7132.5

There is a good agreement between obtained

results using PLS on original spectral data, and
known values indicate the successful applicability
of proposed method for simultaneous determina-
tion of cobalt and nickel in complex real samples.

4. Conclusion

The cobalt and nickel mixture is a complex

Fig. 4. Cumulative PRESS as a function of number of factors.
I: original; II: first; and III: second derivative spectra.
system due to the high spectral overlap
observed between the absorption spectra for these
components. For overcoming the drawbacks of
spectral interferences, PLS and PCR multivariate
calibration approaches are applied and compared.
Analysis of the results for the two-component
system revealed difference in the accuracy of
prediction between the two procedures for origi-nal,
first- and second derivative data. The best
recovery values are obtained by the application of
PLS model for original absorbance data. The
good agreement clearly demonstrates the utility

Table 3
Statistical parameters of the PLS and PCR methods using of original, first and second derivative spectral prediction data sets at
optimal significant factors

Type of Component PLS PCR

spectral data RMSD R2 RMSD R2

Original Co 2 3.7293 0.9956 24.2107 0.9944

2
Ni 2.7074 0.9989 33.3348 0.9310
2
First derivative Co 14.4321 0.9522 23.9480 0.9773
2
Ni 15.5911 0.9316 19.9322 0.8526
2
Second derivative Co 9.7632 0.9833 29.5283 0.9514
2
Ni 10.9671 0.9762 31.4410 0.7673
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Table 4

Added

Udimet 700
J.
Actual composition and calculated concentration of cobalt and nickel in synthetic mixtures of some alloys

Co

37.2
2
Ni

106
2
Found

Original data
PCR

Co

22.2
2
Ni

81.6
2
PLS

Co

21.2
2
Ni

91.0
2
First derivative data

PCR

Co

34.4
2
Ni
2

24.5
PLS

Co

15.7
2
Ni

128.5
2
Second derivative data

PCR

Co

30.2
2
Ni

105.7
2
PLS

Co

50.9
2
Ni

112.4
2

Waspaloy
Niomonic 115
Rene 41

Ghas
aSnell and Ettre 21
27
26.4
22

.
115
120.1
110.1
20.7
71.9
23.2
124.3
111.1
120.4
22.7
22.7
28.0
113.8
120.7
111.9
37.2
27.8
27.5
75.4
100.6
121.9
30.8
18.0
23.1
136.5
146.8
103.5
49.3
63.7
30.6
101.9
123.6
124.5
13.3
24.6
25.9
108.4
116.1
116.1

1
9
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ten J. Ghasemi, A. Niazi Microchemical Journal 68 (20011 ) 11

Fig. 5. Diagrammatic representation of the percentage recovery found in the analysis of 10 mixtures of cobalt and nickel by PLS aŽ .
and PCR Ž
b .methods, using I: original; II: first; and III: second derivative spectral data.

of this procedure for the simultaneous determina- 4 N. Xic, C. Huang and HU Fu, 1990, sepu 8 2 , 114, Ž .
chem abstr. 113Ž1990 094170
tion of the cobalt and nickel in synthetic and alloy .

samples. 5 Z. Schen, F. Nie, Y. Chen, Fensi Huaxane November 19, 1991.

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