三元配合物La(Et_2dtc)_3(phen)的热化学性质  

Thermochemistry of the ternary complex La(Et_2dtc)_3(phen)

作　　者：朱丽[1] 焦宝娟[1] 杨旭武[1] 陈三平[1] 高胜利[1] 史启祯[1] 

机构地区：[1]西北大学化学系/陕西省物理无机化学重点实验室,陕西西安710069

出　　处：《西北大学学报（自然科学版）》2005年第3期303-308,共6页Journal of Northwest University（Natural Science Edition）

基　　金：国家自然科学基金资助项目(20471047);陕西省自然科学基金资助项目(2003B19)

摘　　要：目的研究三元配合物La(Et2dtc)3(phen)的热化学性质。方法采用了微量热法和燃烧法。结果铜试剂(NaEt2dtc·3H2O)和邻菲咯啉(phen·H2O)与水合氯化镧(LaCl3·3.94H2O)在无水乙醇中反应,制得三元固态配合物La(Et2dtc)3(phen)。在298.15K下测得了该配合物的液相生成反应的焓变△rHmθ(l),为(-8.801±0.043)kJ/mol,计算了固相生成反应的焓变△rHmθ(s),为(70.428±0.293)kJ/mol;配合物的恒容燃烧能△cU为(-17455.98±7.98)kJ/mol,其标准燃烧焓△cHmθ和标准生成焓△fHmθ经计算分别为(-17475.19±7.98)kJ/mol,(-1257.78±8.84)kJ/mol。结论IR光谱表明该配合物中La3+与3个NaEt2dtc中的6个硫原子双齿配位,同时与邻菲咯啉中的2个氮原子双齿配位,配位数为8。Aim To study thermochemistry of the ternary complex La(Et_2dtc)_3(phen).Methods Microcalorimetry and combustry.Results The ternary solid complex La(Et_2dtc)_3(phen) has been synthesized with sodium diethyldithiocarbamate (NaEt_2dtc), 1,10-phenanthroline (phen) and hydrated lanthanide chloride in absolute enthanol.Conclusion IR spectrum of the complex showed that the La^(3+) is coordintaed six sulfur atoms of three NaEt_2dtc and two nitrogen atoms of phen, It was assumed that the coordination number of La^(3+) is eight.The enthalpy change of liquid-phase reaction of formation,△_rH~θ_m (l) was determined as (-8.801 ± 0.043) kJ /mol at 298.15 K, the enthalpy change of the solid-phase reaction of formation, △_rH~θ_m (s) was calculated as ((70.428) (0.293)) kJ / mol. The constant-volume combustion energy of the complex, △_cU was determined as (-17 455.98 ± 7.98) kJ / mol at 298.15 K. Its standard enthalpy of combustion, △_cH~θ_m and standard enthalpy of formation, △_fH~θ_m were calculated as (-17 475.19 ± 7.98) kJ / mol and (-1 257.78 ± 8.84) kJ / mol, respectively.

关 键 词：La(Et2dtc)3(phen) 微量热法 热动力学 恒容燃烧能 标准摩尔生成焓 

分 类 号：O6423[理学—物理化学]