Spectrophotometric and DFT study of Germanium(IV) interaction with 6,7-dihydroxy-2,4-diphenyl-1-benzopyran-1-ium bromide in solutions: Room-temperature cloud point extraction and its analytical application

In the current study, a novel and fast procedure for room-temperature cloud point extraction of Germanium (VI) followed by spectrophotometric detection is developed. A 6,7-dihydroxy-2,4-diphenyl-1-benzopyran-1-ium bromide (DPBP) reagent was proposed for binding Ge (IV) into the extractable colored complex. The interaction of Ge (IV) with the reagent DPBP was studied using spectrophotometry and density functional theory (DFT) calculations. It was established that the complex stoichiometry is 1:2. It was shown that with the increase of the charge of the resulting complex, the Gibbs free energy of the complex formation increases considerably. This means that the formation of neutral species with cis- location of the hydroxyl ligands is the most preferable process. The cloud point phenomenon at room temperature was immediately initiated via ammonium benzoate. The calibration plot for Ge (IV) was obtained in the concentration range of 4–490 μg L−1 under optimized conditions: pH = 1, concentration of DPBP 1.8–2∙10-5 mol/L, 0.12 mol/L aqueous ammonium benzoate and 1 % (v/v) Triton X-100). The limit of detection is 1.2 μg L−1. The method was successfully applied to the determination of Ge(IV) traces in vegetable and rock samples.