Direct evidence for enhanced inner-sphere chloro complexation of Eu(III) and Cm(III) in anion exchange resin phase studied by time-resolved laser-induced fluorescence spectroscopy
Direct evidence for enhanced inner-sphere chloro complexation of Eu(III) and Cm(III) in anion exchange resin phase studied by time-resolved laser-induced fluorescence spectroscopy
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DOI：
10.1524/ract.2002.90.4_2002.193
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发表时间：
2002-01-01
影响因子：
1.8
通讯作者：
Yoshida, Z
中科院分区：
文献类型：
--
作者：
Arisaka, M;Kimura, T;Yoshida, Z
在LiCl-水溶液和LiCl-（H_2O + CH_3OH）溶液的阴离子交换树脂体系中，M（III）（M=Eu，Cm）的氯络合程度由内球水合数（N-H_2 O）估算，从Eu（Ⅲ）发射光谱中D-5（0）→ F-7（2）跃迁（A（2））与D-5（0）→ F-7（1）跃迁（A（1））的峰面积比（A（2）/A（1）），可以反映出Eu（Ⅲ）内、外球内的配体环境。随着LiCl和CH_3OH浓度的增加，M（III）在溶液和树脂相中的N-H_2 O均减少，表明形成了内层M（III）-氯配合物。通过比较两相中的N-H_2 O，发现M（III）在树脂相中的内球氯络合程度高于在溶液相中的。两相中的A（2）/A（1）比值随Eu（III）与Cl-相互作用的增强而增大，这与N-H_2 O的结果有很好的相关性。通过比较氯络合程度和分配系数，讨论了M（III）的吸附平衡。
In anion exchange resin systems with LiCl-aqueous and LiCl-(H2O+CH3OH) solutions, the extent of chloro complexation of M(III) (M=Eu, Cm) was estimated from inner-sphere hydration number (N-H2O), i.e., the number of water molecules in the first coordination sphere of M(III) and from peak area ratio (A(2)/A(1)) of D-5(0) --> F-7(2) transition (A(2)) to D-5(0) --> F-7(1) transition (A(1)) in emission spectrum of Eu(III), which reflects the ligand environment both in the inner- and outer-spheres of Eu(III). The N-H2O of M(III) both in the solution and resin phases decreased with an increase of LiCl and CH3OH concentrations, indicating the formation of an inner-sphere M(III)-chloro complex. From the comparison of N-H2O between the both phases, it was found that the extent of the inner-sphere chloro complexation of M(III) in the resin phase is higher than that in the solution phase. The A(2)/A(1) ratio in the both phases increased with an increase of interaction of Eu(III) with Cl-, which are well correlate with the results of N-H2O. The sorption equilibrium of M(III) was discussed by comparing the extent of the chloro complexation with the distribution coefficient.