THE EXTRACTION OF ZINC IONS BY 1-ALKYL-4-AROYL-3-METHYL-2-PYRAZOLINE-5-ONES
Abstract
Using the example of zinc extraction from acetate buffer solutions, the effect of the structure of 1-alkyl-4-aroyl-3-methyl-2-pyrazolin-5-ones on their extraction properties in a chloroform solution have been discussed. Zn2+ ions are extracted by the cation exchange mechanism in the form of complexes with a Zn(II) : reagent ratio determined by the equilibrium shift method equals to 1 : 2. The dependence of the degree of extraction on pH has a standard S-shaped form. The interfacial distribution of 3-nitrobenzoylpyrazolones with alkyl radicals of various lengths in the first position of the pyrazoline ring between chloroform and acetate buffer solutions has been studied depending on the pH value. In alkaline media, the reagents completely pass into the aqueous phase. In acidic solutions, up to 1 mol/L in HCl, the compounds are almost completely in the organic phase. The maximum values of the distribution coefficient have been observed for reagents with the maximum length of the aliphatic substituent in the first position of the pyrazoline ring. The ionization constants of the reagents (Ka) in an aqueous-alcoholic medium have been determined. The values of the concentration constants of zinc extraction (Kex) have been calculated. A good correlation between the lgKex values of 4-aroyl-1-hexyl-3-methyl-2-pyrazolin-5-ones (AGMP) and the lgKa values of the reagents has been found. There is also a satisfactory correlation between the concentrations of the reagents providing 50% extraction of zinc ions and the values of the σ Hammett constants of the substituents in the aroyl fragment of the reagent has been existed. With quantum-chemical method AM1 the deprotonation energy (ΔНdepr.), as the difference between the heats of formation of the main and ionized forms of AGMP derivatives was calculated. And a satisfactory correlation has been established between ΔНdepr. and the values of lgKa, lgKex and pH50 of zinc extraction.
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