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.
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.
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.
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
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]
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.