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Mikrochim.

Acta 122, 95-99 (1996)


Mikrochimica
Acta
9 Springer-Verlag 1996
Printed in Austria

Fast Spectrophotometric Determination of


Titanium in Rocks with 3,4-Dihydroxybenzoic Acid

S6rgio L. C. Ferreira*, Neyla M. L. de Araujo, Renato C. Matos, Andr6 L. C. Torres,


and A. C. Spinola Costa
Instituto de Quimica,UniversidadeFederal da Bahia,Campus Universitfirioda Federa9gto,40.170.290
Salvador, Bahia, Brazil

Abstract. A fast spectrophotometric method has been developed for titanium


determination in geological matrices, based on the mixture of the sample
solution with an exact volume of a single chromogenic solution containing
acetate buffer, ascorbic acid and 3,4-dihydroxybenzoic acid DHB, which forms
with titanium(IV) ions a yellow complex with absorption maximum at 380 nm.
The following parameters were studied: complex stability, pH effect, amount of
DHB, amount of acetate buffer, obedience to Beer's law, amount of ascorbic acid
and iron masking. The results demonstrated that titanium can be determined in
the pH range 4.0-5.0, with a molar absorptivity of 1.43 x 104 1 .mol- ~c m - 1 and
a limit of detection of 2.3 ng/ml. The methodology that allows analysis of 30
samples per hour. Common anions and cations do not interfere, even when
present in large amounts. Iron(III) interference can be easily eliminated by
reduction to iron(II) using ascorbic acid. Analytical characteristics of the pro-
posed procedure, such as calibration sensitivity, analytical sensitivity, limit of
detection and coefficient of variation:, were determined. The procedure was
applied for titanium determination in various standard geological matrices, with
results of satisfactory accuracy and precision (RSD < 1%).
Key words: titanium determination, 3,4-dihydroxybenzoic acid, spectro-
photometry, geological matrices.

The reaction of 3,4-dihydroxybenzoic acid DHB with titanium(IV) ions was studied
by Sommer [1] and Knyazeva and Klimenko [2]. Its potential as a spectro-
photometric reagent has been developed for the determination of iron and titanium
by flow injection analysis [3] and of titanium in geological matrices [4]. In the
present paper, we propose a fast methodology for spectrophotometric determina-
tion of titanium in geological matrices, based on a mixture of a known amount of
sample solution with an exact volume of the chromogenic solution, with DHB as the
reagent.

* To whom correspondenceshould be addressed


96 S.L.C. Ferreira et al.

Experimental

Reagents
All reagents were analytical reagent grade unless otherwise stated. Standard titanium(IV) solution
(1000 gg/ml) was prepared by dissolving titanium(IV) oxide (0.2000g) in concentrated sulfuric acid
(8 ml) and ammonium sulfate (3.2 g), with heating, and dilution to 11 with water DHB solution (0.75 %)
was prepared by dissolving 0.75 g (Aldrich) in 100 ml of water. Buffer solution (pH 4.75) was prepared by
mixing 68.0 g of sodium acetate trihydrate and 29.4 ml of glacial acetic acid in 11 of water. Chromogenic
solution was prepared by mixing 200ml of buffer solution, 25ml of DHB solution, and 10.0g of
ascorbic acid, and diluting to 250 ml with water. This solution should be prepared daily.

Apparatus
Absorption spectra and absorbances were recorded and measured with a Varian DMS-100 spec-
trophotometer using 1.0 cm cells.
Volumes of solutions were measured with a Radelkis automatic burette.

Procedure
Transfer a 10-ml aliquot of sample solution to a completely dry flask and add 10.0ml of the
chromogenic solution, mix thoroughly and measure the absorbance at 380 nm in a 1-cm cell, using an
appropriate blank.

Results and Discussion

Complex Formation
The titanium(IV) cation forms a yellow complex with DHB with absorption
maximum at 380 nm. The complex is instantaneously formed and stable for at least
8 h. DHB has an absorption maximum at 280 nm (at pH 4.75).
The influence of pH on the titanium determination using DHB by the fast
procedure was studied and the results demonstrated that the absorbance signal for
was maximal and constant in the pH range 4.0-6.0. However, iron masking with
ascorbic acid was effective only up to pH 5.0. pH control was made by use of an
acetate buffer. Therefore, the procedure proposes the use of an acetate buffer at pH
4.75, because at this pH the buffer index of the acetate buffer is maximal. The effect of
the buffer concentration on the titanium(IV)-DHB complex was studied and the
results demonstrated that it did not affect the absorbance signal of the system in the
concentration range 0.2-0.8 M acetate.

Effect of Interfering Ions


Solutions containing 25.00 ~tg of titanium(IV) and various proportions of several
cations and anions were analysed. The interference limit of an ion (Table 1) was
taken as the concentration at which a change of _+ 2% in absorbance was observed.
There was no difference between the conventional [4] and fast procedures in terms of
selectivity. The effect of ionic strength on the system was negligible for 0.1 M
concentrations of sodium chloride and potassium nitrate.
Fast Spectrophotometric Determination of Titanium 97

Table 1. Effect of foreign ions on determination


of 25.0 gg of titanium (IV)

Interference
Ions limit ~(gg/ml)

Vanadium(V) 20
Manganese(II) 20
Cobalt 40
Aluminium(III) 50
Nickel(III) 60
Calcium(II) 75
Magnesium(II) 75
Lead(II) 40
Bismuth(III) 40
Strontium(II) 40
Sulfate 200
Chloride 200
Nitrate 200

a Less than 2% error.

Iron(III) cation is the principal interference, as it forms a D H B complex with


absorption maxima at 380 and 570nm. l[n the conventional procedure [4], this
interference can eliminated by reduction of the iron(III) to iron(II) using hydro-
xylamine hydrochloride or ascorbic acid. However, in the fast procedure hy-
droxylamine hydrochloride was not efficient. The addition of 400 mg of ascorbic acid
was enough to mask at least 500 gg of iron during the determination of 25 gg of
titanium by the fast procedure.

Application
A comparison of the analytical characteristics of the procedures is summarized in
Table 2. The calibration sensitivity is lower in the fast procedure, but, the calibration
curves are linear. The procedures were applied for titanium determination in
andesite, bauxite, basalt, bentonite and clays. Samples of geological matrices [4]

Table 2. Analytical characteristics of the procedures

Parameters Conventional [4] Fast

Calibration sensitivity (ml/gg) 0.303 0.250


Analytical sensitivity 145.26 152.16
Limit of detection, 3o (ng/ml) 1.9 2.3
Limit of quantitation, 10~ (ng/ml) 6.4 7.7
Linear dynamic range (gg/ml) 0.01 3.00 0.01-3.00
Coetficient of variation (%) 0.31 0.36
98 S . L . C . Ferreira et al.

Table 3. Titanium determination in standards (as T i O j

Conventional Fast Value


method" method a certified
Standards (%) (%) (%)

Clay 1 (IPT) 0.28 + 0.01 (3) 0.27_+ 0.01 (3) 0.26


Andesite (GSJ) 0.85 _+0.02 (3) 0.84 _+0.01 (7) 0.87
Clay 2 (IPT) 1.01 _+0.04 (4) 1.02 + 0.02 (4) 1.04
Bentonite (CEPED) 1.33 _+ 0.02 (4) 1.26 ___0.01 (4) 1.28
Basalt (GSJm_lJ 1.33 _+0.04 (3) 1.33 _+ 0.02 (4) 1.30
Clay 3 (IPT) 1.41 _+ 0.02 (4) 1.40 + 0.02 (4) 1.40
Bauxite (NIST) 2.81 _+0.01 (7) 2.77 _+0.03 (7) 2.78

a With 95% confidence limits, (N) = number of determinations.

Table 4. Composition of standards analysed

TiOz Fe20 3 A120 3 SiO 2 CaO MgO Na20 K20


Standards (%) (%) (%) (%) (%) (%) (%) (%)

Clay 1 0.26 2.01 38.40 45.1 0.07 0.14 0.01 0.85


IPT
Andesite 0.87 6.95 14.98 64.0 5.68 1.61 3.86 0.82
GSJ
Clay 2 1.04 1.28 29.10 55.8 0.09 0.20 0.01 0.29
IPT
Bentonite 1.28 9.21 20.72 0.48 2.47 0.51 1.18
CEPED
Basalt 1.30 9.10 14.51 52.2 9.23 7.75 2.74 1.46
GSJ-JB-1A
Clay 2 1.40 1.56 45.0 30.7 0.07 0.13 0.06 1.26
IPT
Bauxite 2.78 5.82 55.0 6.01 0.29 0.02 0.01 0.01
NIST

IPT = Instituto de Pesquisas Tecnol6gicas do Estado de Sgo Paulo, Brazil. GSJ = Geological Survey
of Japan. CEPED = Centro de Pesquisa e Desenvolvimento da Bahia, Brazil. N1ST = National
Institute of Standards and Technology, U.S.A.

were prepared using hydrochloric acid, sulfuric acid and hydrofluoric acid. The
results are described in Table 3. The sample compositions are given in Table 4.
The F-test [7] revealed that there was no significant difference in the precision of
the two methods at the 95% confidence level. The paired t- test [7] showed that there
was no significant difference between the procedures at the 95% confidence level.
Least-squares analysis I-8, 9] was used for the comparison of the two procedures,
and it revealed that there was a good correlation (r = 0.9995) and that the calculated
slope and intercept did not differ significantly from the ideal values of 1 and 0,
respectively, and thus there was no evidence for systematic differences between the
conventional procedure 1-4] and this fast method.
Fast Spectrophotometric Determination of Titaniura 99

The analysis of variance [9] was applied to the results in Table 3, and showed
that there was no significant difference between the results obtained with DHB
procedures and certified values.

Conclusions
The proposed procedure has a more rapid methodology, diminishing the reagent
manipulation which consumes time in most spectrophotometric analyses. This
constitutes a big advantage, especially when the number of samples to be analysed is
large. The fast procedure has a calibration sensitivity lower than the conventional
method, but the calibration curves obtained are linear and have the same range.
Comparison with certified values for several matrices indicate that the fast pro-
cedure provides accurate and precise resutts. The proposed method is very useful for
routine analysis, due to its simplicity.

Acknowledgements. The authors acknowledge the financial support of the CNPg, FINEP and CAPES.

References
[1] L. Sommer, Coll. Czech. Chem. Commun. 1963, 28, 2102.
[2] E.N. Knyazeva, E. P. Klimenko, Vestn. Kiev Politekh. Inst. [Sec]: Khim. Mashinostr. Tekhnol.
1981, I8, 64; Chem Abstr. 1982, 96, 111114s.
[3] M. G. M. Andrade, S. L. C. Ferreira, B. F. Santos, A. C. Spinola Costa, Talanta 1992, 39, 1229.
[4] S.L.C. Ferreira, A. C. S. Costa, M. G. M. Andrade, N. O. Leite, Anal. Lett. 1993, 26, 1001.
[5] D.A. Skoog, J. J. Leary, Principles of Instrumental Analysis, Saunders, Florida, 1992.
[6] J. Medinilla, F. Ales, F. Garcia Sanchez, Talanta 1986, 33, 329.
[7] G. Christian, Analytical Chemistry, Wiley, New York, 1980.
[8] D. L. Massart, A. Dijkstra, L. Kaufman, Evaluation and Optimization of Laboratory Methods and
Analytical Procedures, Elsevier, New York, 1978.
[9] J.C. Miller, J. N. Miller, Statistics for Analytical Chemistry, Ellis Horwood, Chichester, 1984.

Received December 13, 1994. Revision April 22, 1995.