高氯酸锂与4-叔丁基苯并-15-冠-5配合物的远红外位移

冠醚化合物对金属离子具有特定的络合作用 [1,2 ] .在冠醚萃取分离锂同位素过程中 ,4-叔丁基苯并 -1 5 -冠 -5 (4 -t-BB1 5 C5 )是锂同位素效应较大且最接近实用的多醚之一 .它容易合成[3] ,而且已有若干萃取研究[4～ 6 ] .本文合成了高氯酸锂与 4-叔丁基苯并 -1 5 -冠 -5配合物 ,测定了若干表征值和远红外位移 ,并根据已有的理论框架[7] 算得配合物的相对约化配分函数比 [(s/s′) f ]org和碘苯 -水溶液两相平衡过程中锂同位素分离系数 α.为在冠醚体系的锂同位素分离研究中应用红外光谱取代质谱 ,直接测定和计算(1 +εp)值提供了可能性 .…

Far Infrared Shift of Lithium Perchlorate Complex with 4- tert -Butylbenzo-15-crown-5

The solid complex of lithium perchlorate with4-tert butylbenzo-15-crown-5(4-t-BB15C5) has been prepared in iodobenzene.The composition of the solid was determined as Li(4-t-BB15C5)ClO₄and its melting point was119_121 ℃. The far IRshift of the complex is obvious.The far IRabsorption band of the complex containing100% ⁶Li can be found by extrapolation, resolving the difficulty in obtaining a sample of100% ⁶Li up to now.Arelative reduced partition function ratio, [( s/s′)f ] _org, being1.045 is calculated.Since the [ (s/s′)f ] _aqof lithium perchlorate in solid state had been obtained as_1.025and may act as that in aqueous phase, the phase equilibrium separation factor α may be obtained as 1.019 by the quotient of 1.045/1.025 for the extractive system of (4-t-BB15C5) C₆H₅I/LiClO₄H₂oThe value of α is just equal to the value of intrinsic separation factor (¹⁺ε_p) described previously