Abstract
The hydrophobic reagent 6-hexyl-4-(2-thiazolylazo)resorcinol (HTAR) was investigated as part of a cloud-point extraction (CPE) system for the spectrophotometric determination of Zn(II). In the system, complexes with different stoichiometries, including 1:1 and 2:2 (Zn:HTAR), are formed. Their ground-state equilibrium geometries were optimized at the B3LYP/6-31G level of theory. The obtained structures were then used to calculate vertical excitation energies in order to generate theoretical UV/Vis absorption spectra. The comparison between theoretical and experimental spectra demonstrated that, under optimal conditions, a binuclear complex containing oxygen-bridging atoms is the dominant species. The absorbance was found to be linearly dependent on the concentration of Zn(II) within the range of 15.7 to 209 ng mL-1 (R2 = 0.9996). The fraction extracted (%E), logarithm of the conditional extraction constant (log Kex), and molar absorption coefficient (ε) at λmax = 553 nm were calculated to be 98.3%, 15.9, and 4.47 × 105 L mol-1 cm-1, respectively. The method developed is characterized by simplicity, convenience, profitability, sensitivity, and ecological friendliness. It has been successfully applied to the analysis of pharmaceutical and industrial samples.
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