INTERACTION OF HAFNIUM(IV) WITH 6,7-DIHYDROXY‑4-CARBOXYL‑2- PHENYLBENZOPYRYLLIUM SALTS IN BINARY SYSTEMS AND IN THE PRESENCE OF CATIONIC SURFACTANTS

Abstract

In the current study, the peculiarities of the complexation of Hafnium(IV) with 6,7-dihyroxy‑4-carboxyl‑2-phenylbenzopyrylium salts (CDC) in binary systems and in the presence of cationic surfactants (Surf) were studied. The CDC was synthesized by condensation of pyrogallol A with benzoylpyruvic acid in an acetic acid medium in the presence of perchloric acid. To obtain KDC bromide and chloride, the synthesis was carried out in the presence of bromide acid or by sparging of dry hydrogen chloride, respectively. Using classical spectrophotometric methods of molar ratios and Bent-French, it was found that at pH 2.5 in binary system one complex with stoichiometry Hf(IV): CDC1:2 was formed. Molar absorptivity coefficient was calculated for Hf(IV) complex with CDC and it was equal 3,9⸱104. It was shown that in the presence of cetylpyridinium chloride or cetyltrimetrylammonium bromide complexes with a molar ratio of Hf(IV): CDC: Surf = 1:2:2 were formed. It is noted that the complexes were formed within 10–15 minutes, and the absorbance of the solutions remains constant for at least 2 hours. It was established that the nature of the anion, which is part of the reagent, does not significantly affect the characteristics of the analytical form. It is shown that in the presence of cationic surfactants, the optimal pH of complex formation shifts to a more acidic region. In addition, the introduction of cationic surfactants leads to a batachromic shift of the absorption band by 10–15 nm and an increase in the molar absorptivity to 5.8⸱104 and 6.4⸱104 when cetylpyridinium chloride or cetyltrimetrylammonium bromide were used respectively. It is noted that the found analytical forms can be used as a basis for the development of combined spectroscopic methods for determining trace amounts of Hafnium(IV).