锂盐-冠醚络合物化学交换体系中的同位素效应
ISOTOPIC EFFECT OF A CHEMICAL EXCHANGE SYSTEM FEATURING Li-CROWN ETHER COMPLEX
-
摘要: 对8种锂盐-冠醚络合物的两相体系进行化学交换并确定了平衡单级分离系数。证实了同位素效应与两相化合物种的键强差有很大关系,揭示了影响分离系数的因素。找到了一种迄今尚未公开发表的4甲基-苯并-15-冠-5体系,其萃取分离锂同位素的单级分离系数达到了1.035—1.047。环己基-15-冠-5体系单级分离系数为1.035。 在没有价态变化的条件下进行~6Li的浓集。所有情况,~6Li均浓集在有机相中。采用一种新的大有机阴离子——三氯乙酸根作为对离子进行萃取,代替Jepson使用过的三氟乙酸(HTFA)。 研究了溶剂对分离系数的影响,采用介电常数稍高的1.2-二氯乙烷为溶剂,物化性能好、两相比重适宜,有利于同位素分离。 在实验的基础上,探讨了结构与性能之间的内在联系。表明,大环效应是显著的。展示了锂盐-冠醚络合物化学交换体系萃取分离锂同位素的前景是乐观的。进一步为发现新的体系,探讨工艺应用可能性,提供依据。Abstract: Single stage separation factors are determined for 8 different chemicalexchange systems consisting of aqueous and organic phases containing complexesof Li salt with crown ethers. The isotopic effect is found to be dependentstrongly on the bond strength of the chemical species in the two phases, and asystem containing 4 methyl--benzo 15--crown--5 is found to yield a single stageseparation factor of 1.035--1.042, very high for a system involving no valencechange of Li. With cyclohexyl 15--crown--5 as the complexing agent, a separationfactor of 1.035 is found. ~6Li is concentrated in the organic phase for all the systems studiedTrichloroacetate is used as the counter anion instead of the more expensivetrifluoroacetate. Based on the study of the effect of solvent properties on isotopiceffect, 1, 2 dichloro--ethane is recommended as the solvent to be used for theseparation of Li isotopes with crown ether as the complexing agent.