三元配合物Tb(Et_2dtc)_3(phen)的热化学性质  

Thermochemistry of the Ternary Complex Tb(Et_2dtc)_3(phen)

作　　者：焦宝娟[1] 朱丽[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,西安710069

出　　处：《物理化学学报》2004年第7期767-771,共5页Acta Physico-Chimica Sinica

基　　金：国家自然科学基金(20171036);陕西省教育厅专项基金(01JK229)资助项目

摘　　要：以铜试剂(NaEt2dtc·3H2O)和邻菲咯啉(o-phen·H2O)与水合氯化铽(TbCl3·3.75H2O)在无水乙醇中制得了三元固态配合物.化学分析和元素分析确定其组成为Tb(Et2dtc)3(phen).IR光谱研究表明配合物中Tb3+与NaEt2dtc中的硫原子双齿配位,同时与phen的氮原子双齿配位.用Calvet微热量计测定了298.15 K下液相生成反应的焓变△rHm (1),为(-21.819±0.055)kJ·mol-1,通过热化学循环计算了固相生成反应焓变△rHm (S),为(128.476±0.675)kJ·mol-1改变反应温度,研究了液相生成反应的热动力学.用精密转动弹热量计测得配合物的恒容燃烧能△cU为(-17646.95±8.64)kJ·mol-1,经计算其标准燃烧焓△cHm 和标准生成焓△fHm 分别为(-17666.16±8.64)kJ·mol-1和(-1084.04±9.49)kJ·mol-1.The ternary solid complex, Tb(Et(2)dtc)(3)(phen), has been synthesized with sodium diethyldithiocarbamate (NaEt(2)dtc), 1,10-phenanthroline (o-phen . H2O) and low hydrated terbium chloride in absolute ethanol. IR spectrum of the complex showed that the Tb3+ coordinated with six sulfur atoms of three NaEt(2)dtc and two nitrogen atoms of phen. The enthalpies change of liquid-phase reaction of formation, Delta(r) H-m(circle minus) (1), was determined as (-21.819 +/- 0.055) kJ (.) mol(-1) at 298.15 K by a microcalorimeter, the enthalpies change of the solid-phase reaction of formation, Delta(r) H-m(circle minus) (s), was calculated as (128.476 +/- 0.675) kJ (.) mol(-1) on the basis of a thermochemical cycle. The thermodynamic of reaction of formation was studied by changing the temperature of liquid-phase reaction. The constant-volume combustion energy of the complex, Delta(c) U, was determined as (-17646.95 +/- 8.64) kJ (.) mol(-1) by a precise rotating-bomb calorimeter at 298.15 K. Its standard enthalpies of combustion, Delta(c) H-m(circle minus), and standard enthalpies of formation, Delta(f) H-m(circle minus), were calculated as (-17666.16 +/- 8.64) kJ (.) mol(-1) and (-1084.04 +/- 9.49) kJ (.) mol(-1), respectively.

关 键 词：Tb(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：O642.3[理学—物理化学]