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Speciation of lanthanide ions in the organic phase after extraction from nitrate media by basic extractants

机译：碱性萃取剂从硝酸盐介质萃取后有机相中镧系元素离子的形态

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A speciation study was carried out for lanthanide complexes formed in the organic phase after solvent extraction with quaternary ammonium and phosphonium nitrate extractants. These extractants are liquid at room temperature and were applied in their undiluted form. A comparison was made between the quaternary compound trihexyl(tetradecyl)phosphonium nitrate, the nitrate form of the commercial extractant Cyphos IL 101, and Aliquat 336 nitrate, the nitrate form of the commercial trialkylmethylammonium chloride extractant Aliquat 336 (alkyl = mixture of C8 and C10 chains). The structures of the lanthanide complexes across the entire lanthanide series (with the exception of promethium) were determined by a combination of solvent extraction techniques, FTIR, NMR, high-resolution steady-state luminescence spectroscopy, luminescence life time measurements, elemental analysis and EXAFS spectroscopy. The results suggest that the lanthanide ions form an anionic nitrate complex in the organic phase by coordinating with five bidentate nitrate ligands. Charge neutralization is provided by two counter cations of the extractant present in the outer coordination sphere of the complex. Furthermore, it is suggested that the pentanitrato complex is the sole lanthanide species that is formed in significant concentrations in the organic phase.
机译：对用季铵和硝酸phospho萃取剂进行溶剂萃取后在有机相中形成的镧系元素络合物进行了形态研究。这些萃取剂在室温下为液体，并以未稀释的形式使用。比较了季铵化合物三己基（十四烷基）phosph（商业提取剂Cyphos IL 101的硝酸盐形式）和硝酸铵Aliquat 336（商业三烷基甲基氯化铵提取剂Aliquat 336的硝酸盐形式）（烷基= C8和C10的混合物）链）。通过溶剂萃取技术，FTIR，NMR，高分辨率稳态发光光谱，发光寿命测量，元素分析和EXAFS的组合来确定整个镧系元素（pro除外）中镧系元素络合物的结构光谱学。结果表明，镧系元素离子通过与五个二齿硝酸盐配体配合而在有机相中形成阴离子硝酸盐络合物。电荷的中和作用是由配合物的外部配位区内存在的萃取剂的两个抗衡阳离子提供的。此外，建议五苯二胺络合物是在有机相中以高浓度形成的唯一镧系物质。

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