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A Simple Method for Spectrophotometric Determination

of Two-Components with Overlapped Spectra

M. Blanco, H. Runiaga, S. Maspoch, and P. Tarfn
Unlversitat Autonoma de Barcelona. 08193 Bellaterra, Spain

The spectrophotometric determination of mixtures of Apparatus

components with overlapped spectra has lately been the Spectra were recorded and absorbances measured on a Perkin-
subject matter of a number of chemometric studies (I, 2) Elmer model 554 spectrophotometer furnished with quartz cells of
dealing with various aspects of this major analytical prob- 10-mmlight path.
Quantitative instrumental analysis syllabuses usually in- Results and Dlscusslon
clude laboratory experiments involving the spectrophoto- The MLRA was applied to the determination of the com-
metric analysis of mixtures of two components with partly ponents of three binary mixtures in which the spectra of the
overlapped spectra. As a rule, the mixture components are absorbing species are overlapped to a greater or lesser ex-
quantized by solving a system of two linear equations ob- tent.
tained by applying Beer's law a t two different wavelengths. The mixtures resolved were
Further imorovements of this method involve the selection 1. Pemanganatedichromate. The spectra are only partly over-
of wavelengths providing optimum precision ( 3 . 4 ) or com- lapped, and it is possible to choose a wavelength at which only
oensatine for the matrix effect bv a simnlified version of the one of the components absorbs.
generalized standard-addition method (5). In order to intro- 2. Titanium(1V)-vanadium(V). H202was used as chromogenic re-
duce the chemistrv students to multicom~onentanalvsis. we agents. The spectra are quite overlapped and the reagent does
have developed a graphical/numerical mkthod for quantita- not absorb.
tive analvsis of mixtures of two comDonents with o v e r l a ~ ~ e d 3. Copper(I1)-zinc(I1). PAR was used as chromogenic reagent. The
spectra. he method (m~ltiwaveien~th linear regression spectra are very overlapped and the absorbance of the reagent is
analysis), allows easy handling of data obtained at several not negligible.
wavelengths, and the resultant accuracy and precision are
comparable to that of rather more complex mathematical Permanganate-Dichrornate Mixture
procedures (6,7). The permanganate-dichromate mixture is the commonest
subject of multicomponent mixture resolution cited in the
Multlwavelength Llnear Regression Analysls (MLRA) Standard solutions of 1.00 X M for each component
The absorbance of a mixture of two noninteracting species and a sample mixture, 1.77 X M dichromate and 0.8 X
absorbing UV-visible radiation in the same spectra zone, M permanganate, were prepared by appropriate dilu-
A,, is given by: tion of stocks. The spectra of standards and the sample are
shown in Figure 1.
The absorbance of each solution was measured at five
If c , ~and c.2 are the concentrations of standard solutions of wavelengths in the 250-400-nm range, where the spectra of
each component, then two species are widely overlapped.
A,, = qbe,~ A2
. =LZ~C,~

Substitution of the molar absorptivities into eq 1and rear-

rangement yields

By plotting A,/A,l as a function of AS2/A,1 a t various wave-

lengths one obtains a straight line, the slope and intercept of
which allow calculation c2 and cl, respectively.

10-2 M KMn04solution
10WM solution of K2Cr207in 0.1 M H2S04
CuSO, solution containing 1g n Cu
.ZnClzsolution containing 1g L Zn
10V M Ti(1V)solution obtained by dissolutionofTiOxinconcen-
trated H2SOnand subsequent dilution with Hz0 WAVELENGTH lml

2 x 10-2 M solution of V(V) in 0.1 M H2SOc obtained from

0.05% solution of 2-pyridyl-azo-resorcinol(PAR)ethanol
Figure 1. UV-visible spechum of 1.0 10-'MMn04i (-- -), 1.0 10-'MCr20,2-
(- -), and their mixture (---). :

178 Journal of Chemical Education

Table 1. Abwrbanws of Permanganate, Dlchromate, and meir
Mlxture Used In the Llnaar Regression for the Resolution of the

A Mn0,- standard Cr2072-standard Mixtvre

266 0.042 0.410 0.766

288 0.082 0.283 0.671
320 0.168 0.158 0.422
350 0.125 0.318 0.672
360 0.056 0.181 0.365

Table 2. Absorbances of the H20, Complexes 01 TI(IV) and V(V)

and Their Mlxture Used In the Linear Regression for the Resolution
at the Mlrture

Figure 2. Vlsible spechum of the H A complexes 01 83.1 ppm Ti (- -1. 96.4
A TI standard
V standard Mixture
ppm V(V) (- -I, and their mlxture (---I.

In Table 1 are listed the ahsorhances nrovided hv the

mixture and the two standards at the waveiengths used.
The eauation of the straieht line obtained from the ab-
sorption coefficients was
y = 1.78~ + 0.81 (r2= 0.9999)
so that the concentration of the two components in the
mixture was 0.81 X 10-4 M (MnO;) and 1.78 X 10-4 M
(C&-). Similar results were ohtained a t several other
wavelengths in the same range.
The concentrations found by measuring the MnO, con-
centration a t 545 nm (where (2-0;- does not absorb a t all)
and that of CrzO;- by difference in the region where both . - ..
Flgure 3. Visible specbvm of PAR (- -1 the CU-PAR (- -) and Zn-PAR (- -)
species absorh-the difference is greatest a t 350 nm-were wmplexes formed by l-ppm Cu and Zn, and their mixture (---). PAR
concernration. 7.0 X M throughout.
0.84 X M (permanganate) and 1.77 X M (dichro-
mate), respectively, i.e., very similar to those ohtained with
the MLRA.
TI(1V)-V(V) Mixture Table 5. Abrorbances of the PAR Solutions, the CU-PAR and
Five milliliters of 10% Hz02 solution was added to 10 mL Zn-PAR Complexes, and Thelr Mlxture Used In the Linear
of stock solution and diluted to 100 mL. These solutions Regression for the Resolution of the Mlxture
containing 96.4 pprn V(V) and 63.1 pprn Ti(IV), respective-
ly, were used as standards and a mixture of 57.8 pprn V(V) Absorbance
and 31.5 pprn Ti(1V) as sample. The spectra of these solu- A PAR CU-PAR Zn-PAR Mixture
tions are shown in Figure 2.
480 0.211 0.698 0.971 0.556
The mixture was resolved hy using wavelengths in the 496 0.137 0.732 1.018 0.668
range 350-550 nm. The absorhances of the standards and 510 0.100 0.732 0.891 0.627
the mixture a t the wavelengths used are listed in Table 2. 526 0.072 0.602 0.672 0.498
The equation of the straight line ohtained. 540 0.056 0.387 0.306 0.290

yielded a concentration of 58.4 ppm for V and 31.5 pprn for

The wavelengths used in resolving the mixture were in the
Cu(I1)-Zn(l1) Mixture range of450-560 nm. In Table 3 are listed the ahsorhances of
The standard solutions were prepared by taking 1 mL of the Cu(I1) and Zn(I1) complexes, their mixture, and PAR a t
100 pprn Cu(I1) or Zn(I1) stock solutions, adding 3 mL PAR the wavelengths used. The absorbance of the standards and
stock solution and 10 mL of acetate buffer pH 7, and finally the mixture were corrected for the reagent absorbance. From
dilutingto 100 mL. The sample solution wasprepared by the the equation of the straight line ohtained,
same procedure and contained 0.25 pprn Zn and 0.50 pprn
Cu. The spectra of PAR, Cu-PAR, Zn-PAR and mixture are
shown in Figure 3. were calculated the concentrations of the components,

Volume 66 Number 2 February 1989 179

The MLRA is a straightforward procedure allowing the
accurate resolution of binary mixtures of compounds with
highly overlapped spectra.
The reliabilitv of the straight lines used and hence that of
the results increases with the number of wavelengths, yet
rather satisfactory results can be obtained with onlv four to
six wavelengths. The best wavelength region for application
of the method is that of maximal spectral overlap, i.e., that
where both components absorb significantly and where the
errors in the absorbance ratios are minimal.

The authors are grateful to the CAICyT (Project no. 8211
84) for financial support.

Figure 4.Plot of absorbance ratios for Cu(ll~Zn(l1)mixture resolution.

Llterature Clted
1. Howell, J. A,: Haqlo, L. G. A d . Chem. 1986,58,108R.
2. Ramos,L.S.:Beebe.K.R.;Carey.W.P.;Sbchez,E.M.;Wiison,B.E.M.;Wangen,L.
E.;Kouslski, B.R.Ano1. Chsm., 1986.58.294R
namely 0.26 PPm for Zn(II) and 0.51 PPm for Cu(II), consis- 3. P ~ I ~ ~ ~ ~ ~ ~ . A . T . : S ~ V ~ N~ ~. ~z~ ~~ ~. .~L . II . .; ~M ~~ ~ ~~ ~~ O .A .
tent with the concentrations added. , R.:schiit,~.
4. ~i ~ u s aM. A. J. them E ~ U CIS~P,~Z,GI.
5. Raymond M.: Jochum. C.; Kowakki. B.R.J. Chrm.Educ. 1983,60,1072.
~h~ plot of absorbance ratios defined in MLRA is shown 6. Blenco,M.;Gene, J.:ltwriaga,H.;Maamh,S.;Riba,J. Tolanfo,inp-
in Figure 4. 7. Blaneo, M.: Gene, J.; lturriaga. H.: Maspoeh, S. Anolysf 1987.112,619.

180 Journal of Chemical Education