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Analytica Chimica Acta, 212 (1988) 145-153

Elsevier Science Publishers B.V., Amsterdam -

145
Printed

in The Netherlands

CRITERIA
FOR SELECTING
ANALYTICAL
WAVELENGTHS
FOR MULTICOMPONENT
MIXTURES
BY THE CPA MATRIX
METHOD
AND SIMULTANEOUS
SPECTROPHOTOMETRIC
DETERMINATION
OF NIOBIUM
AND TANTALUM

ZHENQING

WANG, JIANJUN

LI and HANXI SHEN*

Department of Chemistry, Nankai University, Tianjcn (China)


(Received 4th May 1987)

SUMMARY
The reversed matrix representation
of the Lambert-Beer
law (CPA matrix method) is applied
in simultaneous spectrophotometric
determinations.
Restrictions
on the selection of analytical
wavelengths in applying the CPA matrix method are investigated experimentally
and theoretically. Four criteria for selecting suitable wavelengths are described. A spectrophotometric
procedure for niobium and tantalum with salicylfluorone and cetyltrimethylammonium
bromide in the
presence of tartaric acid was developed and used for the simultaneous determination
of niobium
and tantalum by the CPA matrix method. The absorption maxima were at 520 and 513 nm, respectively. Measurements
at six wavelengths in the range 500-530 nm provided data from which
niobium (0.04-0.4 B ml-) and tantalum (0.08-0.8 pg ml-) were evaluated, with relative standard deviations of < 2%.

Spectrophotometric
determinations
of metal ions which have very similar
chemical properties always require preliminary
separation procedures, which
are usually lengthy and inconvenient
for routine analysis. In recent years, several studies have been reported on rapid methods for the simultaneous analysis
of multicomponent
mixtures [l-7]. Brown et al. [ 31 proposed the CPA matrix
method and applied it to the infrared spectrometric
analysis of two-component
organic mixtures. Later, Wang and Yan [8] expanded part of the CPA matrix
method to give a procedure for the simultaneous determination
of niobium and
tantalum but numerous experiments
and calculations were needed to select
analytical wavelengths, and the relative errors were large (some > 10% ).
In order to broaden the range of applications of the CPA matrix method in
inorganic analysis, the key problem is the selection of suitable analytical wavelengths, which is discussed in some detail in this paper. Four criteria for selecting the analytical w,avelengths are proposed and the concepts of correlated
wavelengths
and correlated
components
are used. The analytical wavelengths could then be selected rapidly and precisely, and the error caused by
poor selection of analytical wavelengths could be minimized. The reaction behavior and spectrophotometric
properties of niobium and tantalum with sali-

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146

cylfluorone in the presence of the cationic surfactant cetyltrimethylammonium


bromide, and the optimum reaction conditions for the simultaneous
spectrophotometric
determination
of niobium and tantalum are also described. After
the absorbances of the mixed ternary complex solutions of niobium and tantalum had been input to a computer, the amounts of niobium and tantalum
were obtained rapidly by calculations based on the CPA matrix method.
THEORY

Spectrophotometric
determinations
are based on the Lambert-Beer
law A
= abc, where A is the absorbance, a the absorptivity,
b the pathlength, and c
the concentration.
For a multicomponent
system, if the absorption spectra of
the components overlap and the absorbances of each of the components at each
of the analytical wavelengths are additive, the Lambert-Beer
law can be expressed, assuming constant pathlength, as
A, = i

K,C,

(i=1,2,.

. . m)

(1)

J=l

where A, is the absorbance at the ith wavelength, K, is the absorptivity of the


jth component at the ith wavelength, and C, is the concentration
of the jth
component. This provides a matrix A = KC [31.
In spectrophotometry,
the absorption spectra of a chromogenic reagent and
its metal complex usually overlap. Because the chromogenic reagent is usually
present in large excess, the absorbance provided by the reagent at the relevant
ith wavelength can usually be regarded as a constant.
Brown et al. [ 31 considered the absorbance as the independent variable and
reversed the usual Lambert-Beer
equation to e = PA (in matrix notation);
here, C is the concentration
of a component, P is the proportionality
between
A and C and A is the absorbance, If there is a deviation from the LambertBeer law, the curved relationship
between absorbance and concentration
can
be approximated
to a straight line over a limited region of interest by adding a
non-zero intercept [ 31. The system c = Pii can be solved for P by the usual
least-squares procedure [ 31.
Criteria for selecting analytical wavelengths
The key problem in applying the CPA matrix method to the determination
of several components
is the selection of a set of suitable analytical wavelengths. According to the theoretical analysis and experimental
results, it was
concluded that four criteria can be used for this selection.
Criterion 1. In a region in which the spectra of the components overlap, the
selected wavelengths should be distributed over the spectral range of larger
absorptivities
for each of the components
such that higher sensitivities
are
obtained for each component at that wavelength. This will provide higher sensitivities for each of the components.

147

Criterion 2. The absorptivities for each component at all the selected wavelengths should be neither equal nor proportional to one another; similarly, the
total absorptivities of the components at each selected wavelength should not
be the same. Obviously, the larger the better with regard to the difference between the ratios of the absorptivities of each of the components at each selected
wavelength.
The matrix representation of Eqn. 1 is as follows:

A,

AL?
.
.
.
.A,

Ii
Cl

G?
.
.
.
.G .

(2)

To determine the concentrations of each of the components in a multicomponent system, it is necessary to solve for column C when column A and the
proportionality K matrix are known. If m = n, then C = K-A. If m > n, K is
not square, hence c = PA, where P = (RET) -lRT.
Obviously, only if Rank (K ) = n, and the K matrix and RTii are non-singular, can their inverse be obtained. If Rank(K) < n, Eqn. 2 becomes indeterminant and column C cannot be solved. If some of the analytical wavelengths
selected are inappropriate, the rank of the K matrix may be decreased. This
decrease will happen in two cases. If the absorptivities of any two components
of the system at all the selected wavelengths are equal, or proportional, to each
other, two columns of the K matrix will be linearly correlated, so that Rank(K)
will decrease by one. Conversely, if the absorptivities of all the components at
any two selected wavelengths are equal, or proportional, to each other, two
rows of the K matrix will be linearly correlated, and if m= n, Rank(K) will
again decrease by one. In the first case, the two components are defined as
correlated components, in the second case, the two wavelengths are called correlated wavelengths.
Not all the correlated wavelengths will cause failure of the determination,
but if there are two correlated wavelengths, one of these wavelengths is actually
useless, which will introduce an error in the absorbance, and this error will be
transferred to the final results by the matrix calculations. If more correlated
wavelengths are used for the determination, Rank(K) may be decreased so
much as to cause failure of the determination. Therefore, the absorbances
should not be measured at correlated wavelengths.
Criterion 3. At the selected wavelengths, the relationship between the absorbances A and the concentration of each of the components must be linear
and the absorbances for each of the components must be additive, if the absorbance data are to be processed accurately with the present method.

148

Criterion 4. The number of the selected wavelengths must be larger than the
number of components. This is necessary because selecting more analytical
wavelengths can decrease the errors resulting from any careless selection of
correlated wavelengths. Experiments have shown that more than five analytical wavelengths should be selected for the determination of a two- or threecomponent system.
For the simultaneous determination of niobium and tantalum by means of
the colored Nb (Ta) /salicylfluorone/cetyltrimethylammonium
bromide complex system and the CPA matrix method, six analytical wavelengths (505,510,
513,516,520,525 nm) were selected in the range 500-530 nm. Fifteen standard
mixtures of niobium and tantalum were used to solve for the P matrix, and
satisfactory results were obtained for synthetic solutions of niobium and
tantalum.

EXPERIMENTAL

Apparatus and reagents


A Model UV-240 recording spectrophotometer (Shimadzu, Japan) and a
Model PC-1500 pocket computer (accessory CE-161, 16K RAM; Sharp, Japan) were used.
Standard solutions of niobium and tantalum (A). Transfer an accurately
weighed portion of Specpure Nb,O, (0.1430 g) or TazO, (0.1221 g) to a porcelain crucible. Add 5 g of potassium pyrosulfate, heat gently to evaporate any
water and then heat more strongly for about 30 min, until the melt is clear.
After cooling, leach the solid cake with 1 M tartaric acid. Transfer the solution
to a l-l volumetric flask and dilute to the mark with 1 M tartaric acid. A standard solution with 0.100 mg ml- Nb (Ta) is obtained. Dilute suitable aliquots
of the Nb (Ta) solution with 0.5 M tartaric acid to give working solutions (2.0
pg ml- Nb or 4.0 pg ml- Ta).
Standard solutions of niobium and tantalum (B). Transfer accurately weighed
Specpure Nbz05 (0.1430 g) or Ta205 (0.1221 g) to a porcelain crucible containing sodium carbonate (4.0 g) and heat at 950 C for 30 min. After cooling,
leach the solid cake with 0.5 M potassium hydroxide. Transfer to a l-l volumetric flask and dilute to 1 1 with the same solution. The solution contains
0.100 mg ml-l Nb (Ta). Dilute suitable aliquots with 0.5 M potassium hydroxide to give working solutions (2.0 hg ml-l Nb or 4.0 ,ug ml- Ta).
Prepare an ethanolic 1 x 10B3 M salicylfluorone (SaF) solution [9,10] from
the pure reagent in ethanol containing 0.1 M hydrochloric acid. Cetyltrimethylammonium bromide (CTMAB) was dissolved in water. All other reagents
were prepared from analytical-grade reagents dissolved in distilled water.

149

Recommended procedure for the simultaneous determination of niobium and


tantalum
To a 25ml volumetric flask, transfer an aliquot of sample solution mixed by
standard solutions (A) containing niobium (O-10 pug) and tantalum
(O-20
pg). Add 2 ml of 2 M hydrochloric acid, 2.5 ml of 1.0~ 10m3 M salicylfluorone
and 3.0 ml of 1.0 x lo- M CTMAB. Dilute to the mark with distilled water
and mix well. After about 30 min, measure the absorbances in a l-cm glass cell
against the reagent blank at the selected wavelengths of 505,510,513,516,520
and 525 nm. Input the absorbance data to the PC-1500; then the concentrations of niobium and tantalum are calculated.
RESULTS AND DISCUSSION

Effects of auxiliary complexing agents and of mineral acid


In order to investigate the effect of auxiliary complexing agents on the
Nb (Ta) /SaF/CTMAB
system, tartaric acid, citric acid, oxalic acid or sodium
fluoride was added to the standard KNb03 (KTa03) solution, and then the
recommended procedure was applied. The absorbance of the complex was measured at its absorption maximum (520 nm for Nb and 513 nm for Ta). The
results are shown in Fig. 1. As can be seen, in the absence of the auxiliary
complexing agent, the sensitivity for niobium or tantalum complex was low,
but changed significantly when the auxiliary complexing agent was added. Of
the four ligands tested, citric acid, oxalic acid and sodium fluoride had different
effects on the absorbances of the niobium and tantalum complexes, and so
could not be used as the auxiliary complexing agent for the simultaneous determination.
In contrast, tartaric acid provided similar moderate increases in
sensitivity for both the niobium and tantalum complexes, and could be used
over a wide range of concentration
in which the absorbances remained constant. Therefore, 0.08 M tartaric acid was chosen as the reaction medium for
further studies.

06-

1
Volume

added

(ml 1

12

14

(bl

10

Volume

added

(ml)

12

14

Fig. 1. Effect of auxiliary complexing agents on the absorbances of the niobium and tantalum
complexes: (a) niobium complex; (b ) tantalum complex. Auxiliary complexing agent: ( 1) 0.1 M
oxalic acid, (2) 0.1 M sodium fluoride; (3) 0.1 M citric acid, (4) 0.1 M tartaric acid.

150

In the tartaric acid medium, Nb (Ta) /SaF/CTMAB systems provided higher


sensitivity in hydrochloric acid solution than in other acid solutions. The optimum acidities for the niobium and tantalum complexes were found to be
0.08-0.2 M and 0.08-0.5 M hydrochloric acid, respectively. For the simultaneous determivrition of niobium and tantalum, the acidity chosen was 0.16 M
hydrochloric acid.
Absorption spectra of the reagent and complexes
The absorption spectra of the reagents and complexes of niobium and tantalum in the absence and in the presence of CTMAB are shown in Fig. 2. Niobium and tantalum did not react with SaF in the absence of CTMAB (curves 1
and 2 coincided), but when CTMAB was added to the systems, niobium and

08-

0.6 -

I-
a
04-

0.2 -

420

460

500

540

580

A (rim)

Fig 2. Absorption spectra: (1) 2.0 x 10e5 M SaF, (2) 2.0~ 10m5 M SaF with 4.0x 10e5 M Nb or
Ta; (3) 2.0x lOA M &F/1.2x
low3 M CTMAB; (4) 1.0x 10m4 M &F/1.2x
lop3 M CTMAB
with5.0x10-6MNb;
(5) 1.Ox10-4MSaF/1.2x10-3MCTMABwith5.Ox10~sMTa.Spectra
l-3 measured vs. water blank; spectra 4 and 5 measured vs. reagent blank.
Fig. 3. Absorption spectra of different concentrations of the niobium and tantalum complexes:
(l-10) 1,2 ,... 9,lO pgNb/25 ml); l-10) 2,4 ,... l&20 ,ugTa/25ml.

151

tantalum reacted to form orange complexes. The maximum absorption wavelengths for Nb/SaF/CTMAB
and Ta/SaF/CTMAB
are at 520 and 513 nm,
respectively
(curves 4 and 5). In the presence of CTMAB, the maximum absorption wavelengths of the reagent lies at 465 nm, so that ;1maxfor the niobium
and tantalum complexes are separated by 55 and 48 nm, respectively.
As calculated from the absorption spectra, the molar absorptivities
for the
niobium and tantalum complexes were 2.0 x lo5 (513 nm) and 2.1 x lo5 1 mol-
cm- (520 nm) respectively, and therefore provide very sensitive methods for
determining niobium and tantalum. From curves 4 and 5 (Fig. 2), it is evident
that the absorption spectra of the two complexes overlap, so that the mutual
interference
will be severe. In order to determine the concentrations
of niobium and tantalum simultaneously
in a solution by the CPA matrix method, it
is necessary to prove the linearity between the concentrations
and the absorbances of the components and to select the proper analytical wavelengths. The
absorption spectra of different concentrations
of Nb (Ta) complex are shown
in Fig. 3. From these spectra, it is clear that good sensitivity was provided over
the wavelength range 500-530 nm. Moreover, the relations between the absorbances and concentrations
showed good linearity for the ranges 0.04-0.4 ,ug
ml- niobium and 0.08-0.8 lug ml- tantalum and the absorbance were strictly
additive. Therefore, the analytical wavelengths were selected over the range
500-530 nm.
Effects of reagent concentrations, temperature and time
The absorbances of the niobium and tantalum complexes were found to reach
constant values when 1.5-3.0 ml of 1.0~ 10m3 M SaF was used, 2.5 ml was
chosen for the determination.
With more than 1.0 and 2.0 ml of 1.0 x 10e2 M
CTMAB, respectively, the niobium and tantalum complexes reached constant
absorbance values, therefore, 3.0 ml of 1.0 x 10V2 M CTMAB was chosen for
the simultaneous
determination
of the two elements.
At room temperature, the Nb/SaF/CTMAB
ternary complex formed slowly;
about 2 h was required to give a stable absorbance. In contrast, the Ta/SaF/
CTMAB complex developed very quickly, requiring only a few minutes. It was
found that when niobium and tantalum were present together, the color development was fast; only 30 min was needed for the niobium and tantalum
complexes to exhibit their highest absorbances,
i.e., the tantalum
system
speeded up the formation of the niobium complex. The absorbances of both
complexes were stable for at least 4 h.
Calibration of the P matrix
Fifteen standard mixtures containing various proportions
of niobium and
tantalum were used to calibrate the P matrix. The absorbances of the complexes were measured by the recommended procedure and these data were used

152
TABLE 1
The P matrix
-0.101
4.099

41.712
- 103.509

- 19.030
93.405

61.263
- 135.336

- 158.988
303.684

55.514
- 106.035

44.737
- 80.177

TABLE 2
Amounts of niobium and tantalum added in the synthetic sample mixtures (&25

ml)

Sample

10

Nb
Ta

9.0
1.0

8.5
2.0

7.0
6.0

6.0
8.0

5.5
9.0

4.5
11.0

3.0
14.0

2.0
16.0

2.5
18.0

0.5
19.0

TABLE 3
Amounts of niobium and tantalum found in the synthetic sample mixtures
Sample 1
Absorb. data

Sample 3
Absorb. data

Sample 5
Absorb. data

Sample 7
Absorb. data

Sample 9
Absorb. data

Al
A2
A3
A4
A5
A6

Al
A2
A3
A4
A5
A6

Al
A2
A3
A4
A5
A6

Al
A2
A3
A4
A5
A6

Al
A2
A3
A4
A5
A6

0.511
0.618
0.684
0.738
0.769
0.723

0.575
0.683
0.735
0.764
0.759
0.679

0.609
0.712
0.752
0.766
0.738
0.636

0.638
0.738
0.762
0.754
0.693
0.564

0.678
0.782
0.798
0.777
0.694
0.543

Calc. cont.
Cl
9.058
c2
0.970

Calc. cont.
Cl
6.958
c2
5.999

Calc. cont.
Cl
5.458
c2
9.169

Calc. cont.
Cl
2.974
c2
14.142

Calc. cont.
Cl
1.470
c2
17.802

Sample 2
Absorb. data

Sample 4
Absorb. data

Sample 6
Absorb. data

Sample 8
Absorb. data

Sample 10
Absorb. data

Al
A2
A3
A4
A5
A6

A 1
A2
A 3
A 4
A 5
A6

A
A
A
A
A
A

A 1
A 2
A 3
A4
A5
A 6

A
A
A
A
A
A

0.525
0.631
0.695
0.745
0.768
0.716

Calc. cont.
Cl
8.587
c2
2.040

0.587
0.691
0.736
0.756
0.737
0.645

Calc. cont.
C1
5.897
C2
7.998

1
2
3
4
5
6

0.610
0.712
0.745
0.751
0.711
0.601

Calc. cont.
Cl
4.391
C2
11.127

0.636
0.735
0.754
0.739
0.668
0.530

Calc. cont.
c 1
1.934
C2
15.974

1
2
3
4
5
6

0.675
0.781
0.796
0.770
0.679
0.520

Calc. cont.
Cl
0.493
c 2
19.599

*AI-& are the absorbances of the mixture solution measured at six analytical wavelengths; C, and
C, are the amounts of niobium and tantalum found in the synthetic sample mixture (pg/25 ml),
respectively.

153

for the calibration.


1500 computer.

Table 1 gives the solved P matrix

as printed

by the PC-

Determination of niobium and tantalum in synthetic sample mixtures


Ten sample mixtures containing arbitrary proportions of niobium and tantalum (see Table 2 ) were used to examine the proposed method. The amounts
of niobium and tantalum found are presented in Table 3 (as printed out). The
results are in good agreement with the added amounts. Statistical analysis
showed that the mean relative standard deviations were 1.78% for niobium
and 1.66% for tantalum.
The standard deviations show clearly that the CPA matrix method with the
Nb(Ta)/SaF/CTMAB
systems provides an effective method for the simultaneous determination
of niobium and tantalum which should find many applications. Moreover, the CPA matrix method should be applicable to the
simultaneous determination
of a larger number of components with very close
absorption maxima.

REFERENCES
1
2
3
4
5
6
7
8
9
10

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