Analytica Chimica Acta 442 (2001) 327–336

Simultaneous spectrophotometric determination of chromium(VI)

and iron(III) with chromogenic mixed reagents by H-point
standard addition method and partial least squares regression
H. Abdollahi∗
Department of Chemistry, Institute for Advanced Studies in Basic Science, Zanjan 45195-159, Iran
Received 12 March 2001; accepted 30 May 2001
Dedicated to my best teacher professor Afsaneh Safavi.

Abstract
Simultaneous determination of Cr(VI) and Fe(III) by partial least squares (PLS) calibration and H-point standard addition
method (HPSAM) is described. Mixed reagents of diphenylcarbazide and 1,10-phenanthroline in a non-ionic micellar solution
of Triton X-100 was used as a selective chromogenic system for determination of Cr(VI) and Fe(III). The presence of a micellar
system allows one to eliminate the previous solvent extraction step that is necessary for the determination of slightly soluble
metal complexes in the absence of micelles. This reduces the cost and toxicity of the method. The total relative standard
error for applying the PLS method to 15 synthetic samples in the ranges 0.20–6.00 ␮g ml−1 Cr(VI) and 0.20–8.00 ␮g ml−1
was 1.5%. The results of applying the H-point standard addition method showed that Cr(VI) and Fe(III) can be determined
simultaneously with weight concentration ratios of Cr(VI) to Fe(III) varying from 15:1 to 1:30 in the mixed sample. Both
proposed methods (PLS and HPSAM) were also successfully applied to the determination of Cr and Fe in several synthetic
alloy solutions. © 2001 Published by Elsevier Science B.V.
Keywords: Mixed chromogenic reagents; Partial least squares; H-point standard addition method

1. Introduction present in them. Although, the determination of

The need for chromium and iron analysis in envi-
ronmental and biomedical material has increased after
reports on the different biological roles of Cr(III),
Cr(VI), Fe(III) and Fe(II) species in plants, ani-
mals and humans. Several methods can be used for
chromium [1–8] and iron [9,10] determination. More-
over, chromium and iron are metals, which appear
together in very real samples, both natural and arti-
ficial. In most instances, the characterization of these
samples includes the determination of metal ions
∗ Tel.: +98-241-449-212; fax: +98-241-449-023.
E-mail address: abd@iasbs.ac.ir (H. Abdollahi).
chromium and iron has been studied in different sam-
ples and by using different techniques [11,12], some
of these methods require physical separation, pre-
liminary treatment or non-universal instrumentation.
Therefore, sensitive and selective methods for simul-
taneous determination of Cr(VI) and Fe(III) are very
desirable.
Mixed organic reagents have been proposed [13–16]
for spectrophotometric multicomponent analysis of
metal ions. The limitations on the use of such systems
usually arise from the necessity for finding a com-
promise condition with respect to the different metal
complexes. In spite of this, the use of mixed reagent
systems can be considered as an alternative means to

0003-2670/01/$ – see front matter © 2001 Published by Elsevier Science B.V.

PII: S 0 0 0 3 - 2 6 7 0 ( 0 1 ) 0 1 1 7 4 - 6
328 H. Abdollahi / Analytica Chimica Acta 442 (2001) 327–336
extend the applicability of spectrophotometric multi-
component determination.
The organized molecular assemblies such as mi-
celles are used in spectroscopic measurements due to
their possible effects on the systems of interest. In the
field of metal ion complex, at a concentration above
the critical micelle concentration (cmc) micelles form
a ternary complex with advantageous properties, such
as hyperchromic and bathochromic displacements,
that can modify the sensitivity of the method by af-
fecting the interferences and matrix effects [17,18].
The ability of micellar systems to solublize slightly
soluble or even insoluble complexes and/or ligands
has been used to enhance the analytical merit of given
methods [19,20]. Most organic solvents that are used
as extraction solvents can be classified as toxic and
environmental pollutants [21], and some have been
listed as carcinogenic by the US Environmental Pro-
tection Agency (EPA) [22]. Application of micellar
systems avoids the previous step of solvent extraction
necessary following the formation of slightly soluble
complexes in the absence of the micelles.
Partial least squares (PLS) modeling is a powerful
multivariate statistical tool that has been successfully
applied to the quantitative analysis of spectroscopic
[23,24] and electrochemical [25] data. PLS is capable
of being a full-spectrum method and therefore enjoys
the signal averaging advantages of other full-spectrum
methods such as principal component regression
(PCR) and classical least squares (CLS). PLS also
has characteristics and advantages of the inverse least
squares (ILS) method, which is limited in the number
of spectral frequencies that can be included in the
analysis. [24]
The H-point standard addition method (HPSAM)
is a modification of the standard addition method that
transforms the incorrigible error resulting from the
presence of a direct interference in the determination
of an analyte into a constant systematic error. This er-
ror, can then be evaluated and eliminated. This method
also permits both proportional and constant errors
produced by the matrix of the sample to be corrected
directly. The basis of the method was established
previously [26,27]. This new technique was based on
the principle of dual wavelength spectrophotometry
and the standard addition method. The requirements
for the application of the method is that if necessary
to work only at two wavelengths where the analytical
signal due to the one of the species (X) is constant
and for another one (Y) to be as be different as possi-
ble. By plotting the analytical signal versus the added
Y concentration, two straight lines are obtained that
have a common point with coordinates H(–CH , AH ),
where –CH is the unknown Y concentration and AH
the analytical signal due to the X species. Absorbency
increments as analytical signals were used when only
the Y concentration was required [28]. The method
has been applied to eliminate the blank bias error due
to the use of absorbent blank [29,30], in liquid chro-
matography [31] and to the analysis of kinetic data
[32,33], with time as an additional variable.
This paper reports the simultaneous spectrophoto-
metric determination of chromium(VI) and iron(III)
with the use of mixed organic reagents in a Triton
X-100 micellar medium. Partial least squares regres-
sion and the H-point standard addition method were
employed for the resolution of binary mixtures of
Cr(VI) and Fe(III). The suggested methods were ap-
plied for the analysis of synthetic mixtures and artifi-
cial mixture solutions of several alloys.
2. Experimental
2.1. Reagents
A 100 ml stock solution of mixtures of 1,10-phena-
nthrolinium chloride and diphenylcarbazide was
prepared by dissolving 0.998 and 0.575 g of these
reagents, respectively, in 5.0 ml of acetonitrile, adding
4 g of Triton X-100 (Merck) and adjusting the volume
to 100 ml with triply distilled water. All standards
and prediction samples were 0.025 M with respect
to 1,10-phenanthrolinium chloride and diphenylcar-
bazide. An excess concentration of reagents has been
chosen to ensure quantitative oxidation and subse-
quent formation of the complexes in the whole the cal-
ibration region for Cr(VI) and Fe(III). A 500 ␮g ml−1
solution of chromium and iron ions was prepared from
their appropriate salts, K2 Cr2 O7 and Fe(NO3 )3 ·9H2 O
(Merck). All solutions were prepared fresh daily.
2.2. Apparatus
Digitized UV–VIS absorbency spectra were col-
lected using a CARY 5 spectrophotometer, with 1 cm
 H. Abdollahi / Analytica Chimica Acta 442 (2001) 327–336
quartz cells, a scan rate of 900 nm min−1 and a slit
width of 2 mm. All spectral measurements were per-
formed using the blank solution as a reference. The
recorded spectra were digitized with two data points
per nanometer. Measurements of pH were made with a
Metrohm 713 pH-meter using a combined glass elec-
trode. The computations were made with a Pentium II
computer. All the programs in the computing process
were written in MATLAB for Windows.
2.3. Procedures
2.3.1. Individual calibration
In two 25 ml volumetric flasks, a 150 ␮g ml−1 so-
lution each of chromium and iron was prepared from
their stock solutions. For preparation of each standard
sample solution, 5 ml of micellar mixed reagents, 1 ml
of 0.05 M HCl for adjusting the final pH to about
2.0 and appropriate amounts of considered metal ion
solution were added to a 10 ml volumetric flask and
made up to the mark with triply distilled water. The
final concentrations of chromium and iron must be be-
tween 0.20–6.00 and 0.2–8.00 ␮g ml−1 , respectively.
The absorbencies were measured at 538 and 510 nm,
against a reagent blank, for chromium and iron ions,
respectively.
2.3.2. PLS calibration
Each standard, prediction and synthetic mixture was
prepared as follows: 5 ml of micellar mixed reagents
solution, 1 ml of 0.05 M HCl to adjust the pH to about
2.0 and appropriate amounts of each metal (from the
150 ␮g ml−1 solution of metal ion) were added to
a 10 ml volumetric flask and made up to the mark
with triply distilled water. The concentration range
in these mixtures was 0.20–6.00 ␮g ml−1 for Cr(VI)
and 0.20–8.00 ␮g ml−1 for Fe(III). The concentration
ranges were chosen so that the absorbencies obtained
for all standard samples were > / 1.5. The composi-
tions of the samples were randomly designed in order
to obtain maximum information on each ion from the
calibration procedure. The artificial sample solutions
were prepared according to the reported composition
of some alloys.
2.3.3. H-point standard addition analysis
For preparation of each standard sample solution,
5 ml of micellar mixed reagents, 1 ml of 0.05 M HCl
329
for adjusting the final pH to about 2.0 and appropriate
amounts of desired metal ion solution were added to
10 ml volumetric flask and made up to the mark with
triply distilled water. For each measurement, about
2 ml of the above solution was transferred to a spec-
trophotometer cell and absorbencies were measured at
appropriate wavelengths. Synthetic samples contain-
ing different concentration ratios of Cr(VI) and Fe(III)
were prepared, and standard additions of Cr(VI) (up
to 6.00 ␮g ml−1 ) were made. Simultaneous determina-
tion of Cr(VI) and Fe(III) with HPSAM was performed
by measuring the absorbencies at 490 and 510 nm
for each sample solution. The concentration ranges of
Cr(VI) and Fe(III) for construction of the HPSA cali-
bration graph were 0.20–6.00 and 0.20–8.00 ␮g ml−1 ,
respectively.
3. Results and discussion
Diphenylcarbazide and 1,10-phenanthroline are
commonly used for spectrophotometric determina-
tion of Cr(VI) and Fe(II), respectively. In a solu-
tion containing a mixture of these two reagents, the
Cr(VI) and Fe(III) reactions occurring seems to be
the simultaneous oxidation of diphenylcarbazide to
diphenylcarbazone, reduction of Cr(VI) and Fe(III) to
Cr(III) and Fe(II) and chelate formation of diphenyl-
carbazone with Cr(III) and 1,10-phenanthroline with
Fe(II) [34]. Therefore, the system seems to be appro-
priate for simultaneous indirect spectrophotometric
determination of Cr(VI) and Fe(III).
The influence of pH values on the spectrum of each
complex at a constant concentration was investigated
separately. Although, no significant changes were ob-
served in the spectrum of the Fe–1,10-phenanthroline
complex in the pH range 2–6, the spectrum of the
chromium complex shows a decrease in maximum
absorbencies at pH > 3, so, for achieving higher
sensitivity and stability, pH 2 was selected as op-
timum for simultaneous determination of Cr(VI)
and Fe(III).
3.1. Individual calibrations
To verify the governing Beer’s law, four calibra-
tion graphs were constructed over the whole range of
wavelengths (in 10 nm increments). These calibration
330 H. Abdollahi / Analytica Chimica Acta 442 (2001) 327–336
Fig. 1. Individual calibration graphs for Fe at 510 nm (r = 0.9989) and Cr at 538 nm (r = 0.9996).
graphs were prepared for Cr(VI) and Fe(II), separately
and in the presence of a fixed amount of each other.
The appropriate correlation coefficients obtained (in
the range 0.9988–0.9999) indicate that the interaction
between the two complexing systems either does not
exist or at least does not affect the linear correlation
prevailing between absorbancy and concentration of
each ion. Thus, chemometric methods based on factor
analysis such as PLS seem to be suitable for use in
this system.
Individual calibration graphs were constructed with
several points (Fig. 1), as absorbancy versus metal ion
concentration in the range 0.20–6.00 for Cr(VI) and
0.20–8.00 ␮g ml−1 for Fe(III) and evaluated by linear
regression. The intercepts on the ordinates were negli-
gible in the two graphs. Limits of detection, calculated
as 3s0 per slope where s0 is the standard deviation of
the intercept on the ordinate were Cr (0.08 ␮g ml−1 )
and Fe (0.05 ␮g ml−1 ).
3.2. H-point standard addition method (HPSAM)
Fig. 2 shows the absorption spectra for the indi-
vidual metal complexes and a mixture of them. For
selection of appropriate wavelengths for applying
HPSAM, the following principles were followed. At
the two selected wavelengths, the signal of X species
must remain equal, even if the concentrations of Y
species are changed, and the analytical signals of the
mixture composed from the X and the Y should be
equal to the sum of the individual signals of the two
species. In addition, the slope difference of the two
straight lines obtained at ␭1 and ␭2 must be as large
as possible in order to get good accuracy.
When Cr(VI) is selected as the analyte (Y species),
it is possible to select several pairs of wavelengths
where they present the same absorbancy for the Fe
complex. After this, the selected wavelength pairs
were sorted following the criteria to give high values
for the difference of the calibration slopes. The equa-
tion that is used for calculation of CH can be seen as
a ratio between an absorbancy increment (A) and a
slope increment (M). M depends on the analyte
absorption characteristics, and also A depends on
the sample analyte concentration. As shown previ-
ously by Compins-Falco et al. [35], the higher the
value for the slope increment the smaller the error
for the analyte concentration. So, the wavelength
 H. Abdollahi / Analytica Chimica Acta 442 (2001) 327–336 331

Fig. 2. Absorption spectra of: (a) 1.00 ␮g ml−1 Cr(VI); (b) 2.00 ␮g ml−1 Fe(III); and (c) 1.00 ␮g ml−1 Cr(VI) + 2.00 ␮g ml−1 Fe(III) with
the mixed reagents at pH 2.

pair value that gives the greatest slope increment
was selected, for this reason the wavelength pair
490–520 nm were employed for obtaining the best
accuracy. Also, according to the characteristics of
HPSAM at the H-point, CH (concentration of Cr(IV))
is independent of the concentration of another consid-
ered species (Fe(III)) and so AH (absorbance corre-
sponding to Fe(III) concentration) also is independent
of the Cr(VI) concentration. Figs. 3 and 4 clearly
show the effect of change in concentration of Cr(VI)
and Fe(III) on the position of the H-point.
Several synthetic mixed samples with different
concentration ratios of Cr(VI) and Fe(III) were ana-
lyzed by the suggested method. The concentration of
Fe(III) was calculated in each test solution by employ-
ing the calibration line obtained from ordinate values
of H-point for standard binary solutions. As can be
seen from Table 1, the accuracy of each result is

Table 1
Results of several experiments for the analysis of Cr(VI)–Fe(III) mixtures in different concentration ratios
A–C equation r Sample (␮g ml−1 ) Found (␮g ml−1 )
Cr(VI) Fe(III) Cr(VI) Fe(III)

A520 = 0.240 Ci + 0.110 0.9997 0.25 0.50 0.22 0.48

A490 = 0.111 Ci + 0.082 0.9998
A520 = 0.230 Ci + 0.537 0.9996 1.45 1.00 1.47 1.00
A490 = 0.113 Ci + 0.365 0.9982
A520 = 0.231 Ci + 1.029 0.9995 0.24 4.88 0.21 4.85
A540 = 0.111 Ci + 1.003 0.9993
A520 = 0.235 Ci + 1.320 0.9996 0.72 5.83 0.68 5.86
A490 = 0.111 Ci + 1.236 0.9995
A520 = 0.236 Ci + 0.758 0.9997 3.00 0.20 3.05 0.18
A490 = 0.114 Ci + 0.386 0.9997
A520 = 0.232 Ci + 0.429 0.9996 1.00 1.00 0.99 1.00
A490 = 0.109 Ci + 0.307 0.9995
332 H. Abdollahi / Analytica Chimica Acta 442 (2001) 327–336
satisfactory when the concentration ratio of Cr(VI) and
Fe(III) varies from 15:1 to 1:30.
3.3. Partial least squares (PLS) method
The first step in the simultaneous determination of
different metal ions by PLS methodology involves
constructing the calibration matrix for the binary
mixture Cr–Fe. A number of 20 binary mixtures were
selected as the calibration set. Their composition was
randomly designed for obtaining more information
from the calibration procedure. Under these con-
ditions, the calibration models were obtained. The
obtained model was validated with a 15 synthetic
mixture set containing the considered metal ions in
different proportions that were randomly selected. To
select the number of factors in the PLS algorithm, a
cross-validation method, leaving out one sample at a
time, was employed [24]. The prediction error was
calculated for each metal ion for the prediction set,
Fig. 3. Plots of H-point standard addition method for fixed Fe(III) concentration (5.83 ␮g ml−1 ) and different concentrations of Cr(VI).
which are the samples not participating in the con-
struction of the model. This error was expressed as
the prediction residual error sum of squares (PRESS).
PRESS was calculated for the first variable, which
built the PLS modeling in the calibration step. After
that, another latent variable was added for the model
building and the PRESS was calculated again. These
calculations were repeated for one to 15 latent vari-
ables, which were used in the PLS modeling. This
procedure was repeated for each element. Fig. 5 shows
a plot of the PRESS against the number of factors for
each individual component. For finding the smallest
model (fewest number of factors), the F-statistic was
used to carry out the significance determination [24].
The PLS modeling for each element had a different
number of factors. The optimal number of factors for
Cr and Fe was obtained as three and four, respec-
tively. The results obtained are given in Table 2. The
prediction error of a single component in the mixture
was calculated as the relative standard error (R.S.E.)
 H. Abdollahi / Analytica Chimica Acta 442 (2001) 327–336 333

Fig. 4. Plots of H-point standard addition method for fixed Cr(VI) concentration (0.24 ␮g ml−1 ) and different concentrations of Fe(III).

of the prediction concentration [36,37]: 3.4. Interference analysis

N 2
1/2
j =1 (Ĉj − Cj ) For analyzing interference, the influence of several
R.S.E. (%) = N × 100 (1) ions was tested, including those that most frequently
2
j =1 (Cj )
accompany Cr(VI) and Fe(III) in real samples. The
where N is the number of samples, Cj the concentra- effect of interfering ions at different concentrations
tion of the component in the jth mixture and Ĉj the on the absorbancy of a solution containing 1 ␮g ml−1
estimated concentration. The total prediction error of of each analyte was studied. An ion was considered
N samples is calculated as follows: to interfere when its presence produced a variation in
the absorbency of the sample >5%. This increment of

M N 2
1/2 absorbency was evaluated at two wavelengths, corre-
i=1 j =1 (Ĉij − Cij )
R.S.E.t (%) = M N sponding to the maximum absorption of Cr and Fe
2
i= j =1 (Cij ) complexes, to establish the different effects of the in-
×100 (2) terfering ions on each analyte. Among the interfer-
ing ion tested CO3 2− , CN− , F− , I− , Br− , CH3 COO− ,
where Cij is the concentration of the ith component NO3 − , Ba2+ , Mg2+ , Ca2+ , Li+ , Na+ , Zn2+ , Bi3+ ,
in the jth sample and Ĉij its estimation. Table 2 also Hg2+ , In3+ , Ni2+ , Co2+ , Cu2+ , Cd2+ , Cr3+ , Se(IV),
shows reasonable single and total relative errors for Sn(II) and Al3+ did not interfere of concentrations
such a system. Fig. 6 shows the recovery results ob- 1000 times higher than those of the analytes. However,
tained by the application of the PLS model on the V(IV) and Mo(VI) showed interferences at nearly 30
spectral data of the prediction set. times concentration level.
334 H. Abdollahi / Analytica Chimica Acta 442 (2001) 327–336

Fig. 5. Plot of PRESS against the number of factors for Cr(VI) and Fe(III).

Table 2
Composition of synthetic samples, their predictions by PLS model and statistical parameters for the system
Synthetic (␮g ml−1 ) Prediction (␮g ml−1 ) Recovery (%)

Cr(VI) Fe(III) Cr(VI) Fe(III) Cr(VI) Fe(III)

4.80 0.90 4.85 0.98 101.0 108.9
2.06 3.54 2.05 3.45 99.5 97.5
5.91 4.69 5.95 4.78 100.7 101.9
2.95 5.14 2.98 5.27 101.0 102.5
2.42 5.34 2.42 5.25 100.0 98.3
5.48 0.31 5.41 0.39 98.7 125.8
5.61 4.82 5.55 4.73 98.9 98.1
3.70 2.77 3.75 2.70 101.4 97.5
2.47 9.78 2.55 9.86 103.2 100.8
4.70 1.01 4.66 0.96 99.1 95.0
0.26 5.75 0.23 5.68 88.5 98.8
1.61 5.38 1.63 5.30 101.2 98.5
4.42 1.77 4.44 1.71 100.5 96.6
4.97 7.88 5.05 7.93 101.6 100.6
0.72 4.32 0.77 4.26 106.9 98.6
Mean recovery 100.2 101.3
R.S.E. (%)a single 1.2 1.6
R.S.E. (%)b total 1.5 1.5
a Calculated by Eq. (1).
b Calculated by Eq. (2).
 H. Abdollahi / Analytica Chimica Acta 442 (2001) 327–336 335

Fig. 6. Diagrammatic representation of the percentage recovery found in the analysis of the 15 mixtures of Cr(VI) and Fe(III) by PLS model.

Table 3
Actual composition and calculated concentration of iron and chromium in synthetic mixtures of some alloys
Alloy Composition of synthetic mixture (␮g ml−1 ) Founda (␮g ml−1 )

PLS HPSAM
Fe Cr Fe Cr

Nichrome wire Fe (1.20), Cr (1.10), Ni (7.50), Mn (0.20) 1.24 ± 0.04 1.06 ± 0.04 1.18 ± 0.03 1.08 ± 0.05
Nichrome Fe (2.40), Cr (1.60), Ni (6.00) 2.31 ± 0.06 1.54 ± 0.04 2.45 ± 0.05 1.54 ± 0.04
Chromax castings Fe (5.00), Cr (1.50), Ni (3.50) 4.94 ± 0.03 1.52 ± 0.04 5.05 ± 0.06 1.52 ± 0.03
Cristite Fe (6.60), Cr (1.00), W (1.70), C (0.35), Mo (0.25) 6.68 ± 0.04 0.96 ± 0.05 6.54 ± 0.05 1.05 ± 0.04
a Mean ± S.D. (four replicates).

3.5. Analysis of synthetic mixtures
Both proposed methods (PLS and HPSAM) were
applied to the determination of Cr(VI) and Fe(III) in
several synthetic samples that had compositions pre-
pared according to some alloys [38,39]. The results are
shown in Table 3. The good agreement between these
results and known values indicates the successful ap-
plicability of the proposed methods for simultaneous
determination of Cr and Fe in complex samples. The
results, shown in Table 3 also indicate that there are
not significant difference between the outputs of the
PLS and H-point standard addition methods.
4. Conclusions
The most important characteristics of this work are:
(i) the possibility of simultaneous determination of
Cr(VI) and Fe(III) in an aqueous solution owing to
336 H. Abdollahi / Analytica Chimica Acta 442 (2001) 327–336
the presence of non-ionic micelles of Triton X-100;
(ii) NO extraction step is required and hence the use
of organic solvents is avoided; (iii) the proposed PLS
model and HPSAM are very suitable for simultane-
ous determination of chromium and iron and can be
employed to analyze complex synthetic samples; (iv)
determination of both Cr(VI) and Fe(III) are based
on indirect spectrophotometric responses; (v) selectiv-
ity is achieved mainly by choosing a suitable mixed
reagent system which leads to the selective determi-
nation of Cr(VI) and Fe(III) with sensitive spectral
characteristics; (vi) two powerful chemometric meth-
ods (PLS and HPSAM) are compared for analysis of
binary mixtures with strong signal overlapping.
Acknowledgements
The author wish to express their gratitude to the
Institute for Advanced Studies in Basic Science for
the support of this work.
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