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
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-
0003-2670/88/$03.50
B.V.
146
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
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
149
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
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
as printed
by the PC-
REFERENCES
1
2
3
4
5
6
7
8
9
10