Shimojo Kojiro, Aoyagi Noboru, Saito Takumi, Okamura Hiroyuki, Kubota Fukiko, Goto Masahiro, Naganawa Hirochika
Division of Chemistry for Nuclear Engineering, Nuclear Science and Engineering Directorate, Japan Atomic Energy Agency (JAEA).
Anal Sci. 2014;30(2):263-9. doi: 10.2116/analsci.30.263.
Liquid-liquid extraction of lanthanide ions (Ln(3+)) using N,N-dioctyldiglycolamic acid (DODGAA) was comprehensively investigated, together with fluorescence spectroscopic characterization of the resulting extracted complexes in the organic phase. DODGAA enables the quantitative partitioning of all Ln(3+) ions from moderately acidic solutions, while showing selectivity for heavier lanthanides, and provides remarkably high extraction separation performance for Ln(3+) compared with typical carboxylic acid extractants. Furthermore, the mutual separation abilities of DODGAA for light lanthanides are higher than those of organophosphorus extractants. Slope analysis, loading tests, and electrospray ionization mass spectrometry measurements demonstrated that the transfer of Ln(3+) with DODGAA proceeded through a proton-exchange reaction, forming a 1:3 complex, Ln(DODGAA)3. The stripping of Ln(3+) from the extracting phase was successfully achieved under acidic conditions. Time-resolved laser-induced fluorescence spectroscopy revealed that the extracted Eu(3+) ions were completely dehydrated by complexation with DODGAA.
使用N,N-二辛基二甘醇酰胺酸(DODGAA)对镧系离子(Ln(3+))进行液-液萃取,并对有机相中所得萃取配合物进行荧光光谱表征,对此进行了全面研究。DODGAA能使所有Ln(3+)离子从中性酸性溶液中进行定量分配,同时对重镧系元素具有选择性,并且与典型的羧酸萃取剂相比,它对Ln(3+)具有非常高的萃取分离性能。此外,DODGAA对轻镧系元素的相互分离能力高于有机磷萃取剂。斜率分析、负载试验和电喷雾电离质谱测量表明,Ln(3+)与DODGAA的转移通过质子交换反应进行,形成1:3配合物Ln(DODGAA)3。在酸性条件下成功实现了从萃取相中反萃Ln(3+)。时间分辨激光诱导荧光光谱表明,萃取的Eu(3+)离子通过与DODGAA络合而完全脱水。