稀土(Ⅲ)-冠醚配位反应的热力学性质 Ⅱ. 镧系(Ⅲ)高氯酸盐与二苯并18-冠-6在无水乙腈中配位反应的量热滴定研究

Thermodynamic Properties of Rare Earth (III) -Crownether Coordination Reactions Ⅱ. Calorimetric Tit-ration Studies on Coordination Reactions of Lanthanide Perchlorates with Dibenzo-18-Crown-6 in Anhydrous Acetonitrile

用滴定量热计于298.15 K测定了除钷、镥以外的全部十三种镧系(Ⅲ)高氯酸盐与二苯并-18-冠-6在无水乙腈中的配位作用.借助计算机用自编程序算出了配位反应的生成常数和焓变,进而算出了配位反应的自由能变化和熵变化.探讨了镧系(Ⅲ)阳离子对配位反应的影响.此外,还比较了几种不同冠醚与高氯酸镧在无水乙腈中配位反应的热力学性质.

The coordination reactions of dibenzo-18-crown-6 with lanthanide perchlorates except Pm, Lu in anhydrous acetonitrile were investigated at 298.15 Kby titration calorimeter. The formation constants and enthalpies of coordination reactions were calculated uaing computer program made by ourselves. The changes of free energy and entropy of every coordination reaction were obtained. The influences of lanthanide cations (Ⅲ) on the coordination reactions were discussed. Comparisons were also made on the thermodynamic properties for coordination reaction of lanthanum perchlorate with dibenzo-18-crown-6 and with other crowns in anhydrous acetonitrile, respectively.