Elucidation of the structures of tributyl phosphate/Li complexes in the presence of FeCl₃ via UV-visible, Raman and IR spectroscopy and the method of continuous variation

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• 作者：Zhiyong Zhou ; Wei Qin ; Yifeng Chu ; Weiyang Fei
• 关键词：Chemical analysis ; Extraction ; Mathematical modeling ; Separations ; Association reaction ; Structural characterization
• 刊名：Chemical Engineering Science
• 出版年：2013
• 出版时间：20 September, 2013
• 年：2013
• 卷：101
• 期：Complete
• 页码：577-585
• 全文大小：845 K

文摘

The method of continuous variation, in conjunction with UV-visible, Raman and infrared spectroscopy, has been applied to the structural characterization of complexes resulting from tributyl phosphate (TBP), Li⁺ and FeCl₃ in an organic extraction solvent. Data derived from various spectroscopic analyses confirmed the presence of FeCl₄^? in the solvent, and also demonstrated that the combination of Li⁺ and FeCl₃ produces LiFeCl₄. From the method of continuous variation, it was determined that more than one complex results during the extraction of Li⁺ from aqueous solution, and that these complexes have the general structural formula LiFeCl₄¡¤nTBP, where n is greater than or equal to 1. The coordination mode of the complex was investigated by applying a curve-fitting algorithm to the IR spectra of the organic solvent following the extraction of various cations. The results showed that high molecular weight organic cations are produced by the coordination of the TBP extractant and the cation, and that the selective recovery of Li⁺ occurs via an ion association reaction involving the organic cation and the FeCl₄^? anion. Finally, the structural formulae of the complexes formed during the extraction were confirmed to be [Li(TBP)(H₂O)₃]⁺¡¤FeCl₄^- and [Li(TBP)₂(H₂O)₂]⁺¡¤FeCl₄^-, and the planar and stereo structures of both are given.