三元配合物Pr[(C_5H_8NS_2)3_(C_(12)H_8N_2)]生成反应的热动力学  

Thermodynamics on Reaction of Formation of Ternary Complex Pr[(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：《稀有金属》2004年第2期391-396,共6页Chinese Journal of Rare Metals

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 邻菲咯啉 (o phen·H2 O)与PrCl3·3 .75H2 O作用 ,合成了三元固态配合物 ,确定它的组成为Pr[(C5H8NS2 ) 3(C1 2 H8N2 ) ]。X粉末衍射说明它为一新相化合物。IR光谱说明配合物中Pr3+ 分别与 3个APDTC的 6个硫原子双齿配位 ,同时与o phen的 2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Pr2 S3+ 2C。用微量热计测定了 2 98.15K下水合氯化镨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 ) ,速率常数和动力学参数 (表现活化能、频率因子和反应级数 ) ,通过合理的热化学循环 ,求得了 2 98 15K时标题化合物的固相反应焓变。The title ternary complex of Pr[(C 5H 8NS 2) 3(C 12H 8N 2)] was synthesized in absolute ethanol by PrCl 3·3.75H 2O reacting with the mixed ligands of ammonium pyrolidinedithiocarbamate (APDTC) and 1, 10-phenanthroline (o-phen·H 2O) in the ordinary laboratory atmosphere without any cautions against moisture or air sensitivity. The bonding characteristics of the complex were characterized by IR, showing that Pr 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 Pr 2S 3 and deposited carbon in one step where Pr 2S 3 predominated in the final products. The enthalpy change of formation of the reaction on the title complex in liquid-phase was determined by a microcalorimeter. Thermodynamic parameters(the activation enthalpy, the activation entropy and the activation free energy), rate constant and kinetics parameters(the apparent activation energy, the pre-exponential constant and the reaction order) of the title reaction were calculated. The enthalpy change of the solid-phase reaction at 298.15 K was obtained by a thermochemistry cycle.

关 键 词：水合氯化镨 吡咯烷二硫代氨基甲酸铵 l lo.邻菲咯啉 表征 热化学 

分 类 号：O641.4[理学—物理化学] O614.33[理学—化学]