Abstract To investigate the extraction of uranium(VI) in HCl media by Aliquat® 336 in 1:99 (v:v) 1-decanol:n-dodecane mixture, our objective is to identify the complexe(s) in the organic phase by time-resolved laser-induced luminescence spectroscopy (TRLS). The extraction mechanism is supposed to involve the formation of [ U O 2 C l 4 2 − ⋅ ( R 4 N + ) 2 ] $[U{O_2}Cl_4^{2 - } \cdot {({R_4}{N^ + })_2}]$ in the organic phase. The occurrence of such a species leads to the presence of the UO 2 Cl 4 2 − ${\rm{U}}{{\rm{O}}_2}{\rm{Cl}}_4^{2 - }$ species in the organic solution, which luminescence shows particular features. The luminescence spectra and decay time evolutions are obtained in the organic phase as a function of HCl concentration in the aqueous phase (0.5–6 M). The extraction of UO 2 Cl 4 2 − ${\rm{U}}{{\rm{O}}_2}{\rm{Cl}}_4^{2 - }$ is confirmed by the particular spectrum of uranium(VI) in the organic phase, and the typical splitting of the luminescence bands, due to the crystal field effect, is clearly evidenced. The stoichiometry is verified using luminescence intensity variation as a function of the activity of Cl−, and extraction constants are calculated both using the specific interaction theory and Pitzer model. A decomposition of the spectrum of the extracted complex in the organic phase is also proposed. The decay time variation as a function of temperature allows estimating the activation energy of the luminescence process of the extracted complex.

中文翻译：

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用 Aliquat® 336 在正十二烷:1-癸醇中从 HCl 液-液萃取铀 (VI) 后的发光时间分辨激光诱导发光光谱

摘要 为了研究 Aliquat® 336 在 1:99 (v:v) 1-癸醇:正十二烷混合物中萃取 HCl 介质中的铀 (VI)，我们的目标是通过时间分辨激光诱导发光光谱 (TRLS)。提取机制应该涉及 [ UO 2 C l 4 2 − ⋅ ( R 4 N + ) 2 ] $[U{O_2}Cl_4^{2 - } \cdot {({R_4}{N^ + })_2}]$ 在有机相中。这种物种的出现导致了 UO 2 Cl 4 2 − ${\rm{U}}{{\rm{O}}_2}{\rm{Cl}}_4^{2 - }$有机溶液中的物种，其发光显示出特殊的特征。发光光谱和衰减时间演变是在有机相中作为水相中 HCl 浓度 (0.5-6 M) 的函数获得的。UO 2 Cl 4 2 − ${\rm{U}}{{\rm{O}}_2}{\rm{Cl}}}_4^{2 - }$的提取由铀的特定光谱证实( VI) 在有机相中，由于晶体场效应，发光带的典型分裂得到了明显的证明。使用作为 Cl− 活性函数的发光强度变化来验证化学计量，并且使用特定相互作用理论和 Pitzer 模型计算提取常数。还建议对有机相中提取的复合物的光谱进行分解。作为温度函数的衰减时间变化允许估计提取的复合物的发光过程的活化能。由于晶体场效应，清楚地证明了这一点。使用作为 Cl− 活性函数的发光强度变化来验证化学计量，并且使用特定相互作用理论和 Pitzer 模型计算提取常数。还建议对有机相中提取的复合物的光谱进行分解。作为温度函数的衰减时间变化允许估计提取的复合物的发光过程的活化能。由于晶体场效应，清楚地证明了这一点。使用作为 Cl− 活性函数的发光强度变化来验证化学计量，并且使用特定相互作用理论和 Pitzer 模型计算提取常数。还建议对有机相中提取的复合物的光谱进行分解。作为温度函数的衰减时间变化允许估计提取的复合物的发光过程的活化能。