三元配合物La[(C_5H_8NS_2)_3(C_(12)H_8N_2)]生成反应的热动力学  

Thermodynamics of Formation Reaction of Ternary Complex La[(C_5H_8NS_2)_3(C_(12)H_8N_2)]

作　　者：焦宝娟[1] 孟祥鑫[1] 任宜霞[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：《中国稀土学报》2004年第2期183-188,共6页Journal of the Chinese Society of Rare Earths

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

摘　　要：在无水乙醇中,用吡咯烷二硫代氨基甲酸铵(APDTC)和1,10 邻二氮菲(phen)与LaCl3·3 94H2O作用,合成了未见文献报道的三元固态配合物,确定它的组成为La[(C5H8NS2)3(C12H8N2)]。X粉末衍射说明它为一新相化合物。IR光谱说明配合物中La3+分别与3个APDTC的6个硫原子双齿配位,同时与phen的两个氮原子双齿配位,配位数为8。TG DTG分析显示其热分解为一步生成1/2La2S3+3C。用微量热计测定了298 15K下水合氯化镧及两个配体在无水乙醇中的溶解焓,两个配体醇溶液的混合焓及不同温度下标题化合物液相生成反应的焓变。在实验和计算基础上,得到了液相生成反应的热力学参数(活化焓、活化熵和活化自由能)和动力学参数(速率常数、表观活化能、频率因子和反应级数),通过合理的热化学循环,求得了标题化合物的固相反应焓变。The title ternary complex of La[(C_5H_8NS_2)_3(C_(12)H_8N_2)] was synthesized in dehydrated ethanol by LaCl_3·3.94H_2O reacting with the mixed ligands of ammonium pyrolidinedithiocarbamate (APDTC) and 1,10-phenanthrolinephen (phen·H_2O) in the laboratory without any cautions against moisture or air sensitivity. The bonding characteristics of the complex were examined by IR, showing that La^(3+) banded with sulfur atom in the APDTC and coordinated with nitrogen atom in the phen. TG-DTG investigations indicate that the title complex is decomposed into La_2S_3 and deposited carbon in one step where La_2S_3 predominated in the final products. The enthalpy change of formation of the reaction of the title complex in liquid phase were determined by a microcalorimeter. Thermodynamic parameters(the activation enthalpy, the activation entropy and the activation free energy), kinetics parameters (rate constant and the apparent activation energy, the pre-exponential constant and the reaction order) of the title reaction were calculated. The enthalpy change at 298.15 K of the solid-phase reaction is obtained by a thermochemistry cycle.

关 键 词：无机化学 水合氯化镧 吡咯烷二硫代氨基甲酸铵 1 10-邻二氮菲 热化学 稀土 

分 类 号：O641.4[理学—物理化学] O614.33[理学—化学]