三元配合物Er(Et_2dtc)_3(phen)的热化学性质  

Thermochemical Properties of Ternary Complex Er(Et_2dtc)_3(phen)

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

机构地区：[1]西北大学化学系

出　　处：《应用化学》2004年第12期1211-1216,共6页Chinese Journal of Applied Chemistry

基　　金：国家自然科学基金 ( 2 0 1710 3 6);陕西省教育厅专项基金 ( 0 1JK2 2 9)资助项目

摘　　要：在无水乙醇中 ,用铜试剂 (NaEt2 dtc·3H2 O)和邻菲咯啉 (o phen·H2 O)与水合氯化铒 (ErCl3 ·3 4 6H2 O)作用 ,制得三元固态配合物。化学分析和元素分析确定其组成为Er(Et2 dtc) 3 (phen)。IR光谱研究表明 ,配合物中Er3 + 与NaEt2 dtc中的硫原子双齿配位 ,同时与o phen中的氮原子双齿配位。用微热量计测定了标题配合物在2 98 15K下的液相生成反应焓变ΔrHθm(l)为 (- 13 85 7± 0 0 96 )kJ/mol,计算出它的固相生成反应焓变ΔrHθm(s)为 (119 6 6 2± 0 6 95 )kJ/mol ;得到了标题配合物液相生成反应的热动力学和动力学参数 ;测定了固态配合物的恒容燃烧能ΔcU为 (- 184 36 6 2± 9 11)kJ/mol,其标准摩尔燃烧焓ΔcHθm 和标准摩尔生成焓ΔfHθm 经计算分别为 (- 184 5 5 83± 9 11)kJ/mol和 (- 32 9 4 8± 9 91)kJ/mol。The ternary solid complex Er(Et 2dtc) 3(phen) was synthesized from sodium diethyldithiocarbamate (NaEt 2dtc), 1,10-phenanthroline(o-phen) and hydrated terbium chloride in absolute ethanol. The general formula of the complex was determined by chemical and elemental analyses. The IR spectrum of the complex shows that the Er 3+ is coordinated with the sulfur atoms of NaEt 2dtc and the nitrogen atoms of o-phen. The enthalpy change in the liquid-phase formation reaction of the complex, Δ rH θ m(l), was determined by means of a microcalorimeter to be (-13.857±0.096) kJ/mol at 298.15 K. The enthalpy change in the solid-phase formation reaction, Δ rH θ m(s), was calculated to be (119.662±0.695) kJ/ mol. The thermodynamic and kinetic parameters of the liquid-phase formation reaction of the complex were obtained. The constant- volumetric combustion energy of the complex Δ cU was determined to be (-18 436.62±9.11) kJ/mol at 298.15 K. Its standard enthalpy of combustion Δ cH θ m and standard enthalpy of formation Δ fH θ m were calculated to be (-18 455.83±9.11) kJ/mol and (-329.48±9.91) kJ/mol, respectively. [WT5HZ]

关 键 词：Er(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]