物理化学学报 >> 2009, Vol. 25 >> Issue (10): 1945-1950.doi: 10.3866/PKU.WHXB20091001

研究论文 上一篇    下一篇

新型镧三元配合物La(Glu)(Im)6(ClO4)3·4HClO4·4H2O的合成和热化学性质

吕雪川, 谭志诚, 高肖汉   

  1. 辽宁石油化工大学化学与材料科学学院, 辽宁 抚顺 113001|中国科学院大连化学物理研究所, 热化学实验室, 辽宁 大连 116023|中国科学院大连化学物理研究所, 中国离子液体实验室, 辽宁 大连 116023
  • 收稿日期:2009-05-13 修回日期:2009-06-23 发布日期:2009-09-29
  • 通讯作者: 谭志诚 E-mail:tzc@dicp.ac.cn

Synthesis and Thermochemical Properties of New Ternary Lanthanum Complex La(Glu)(Im)6(ClO4)3·4HClO4·4H2O

LV Xue-Chuan, TAN Zhi-Cheng, GAO Xiao-Han   

  1. School of Chemistry and Material Science, Liaoning Shihua University, Fushun 113001, Liaoning Province, P. R. China|Thermochemistry Laboratory, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning Province, P. R. China|China Ionic Liquid Laboratory, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning Province, P. R. China
  • Received:2009-05-13 Revised:2009-06-23 Published:2009-09-29
  • Contact: TAN Zhi-Cheng E-mail:tzc@dicp.ac.cn

摘要:

合成了新型镧三元配合物La(Glu)(Im)6(ClO4)3·4HClO4·4H2O(Glu, 谷氨酸; Im, 咪唑). 用高精度全自动绝热量热仪测定了该配合物晶体80-390 K温区的热容, 利用实验热容数据, 建立了热容随温度变化的多项式方程; 根据焓、熵与热容的关系, 求出了配合物在80-390 K温区内相对于298.15 K的标准热力学函数(HT-H298.15)和(ST-S298.15). 绝热量热和差示扫描量热(DSC)分析均发现配合物在216和246 K附近存在玻璃态和晶型转变, 其机理可能是配合物中高氯酸根离子重取向运动. 用热重法(TG)检测了配合物的高温热稳定性并提出了可能的热分解机理.

关键词: 热容, La(Glu)(Im)6(ClO4)3·4HClO4·4H2O, 绝热量热法, 热力学函数, 相转变, 热稳定性

Abstract:

A new ternary lanthanum complex, La (Glu) (Im)6 (ClO4)3·4HClO4·4H2O (Glu: glutamic acid, Im: imidazole), was synthesized and its thermodynamic properties were studied. Heat capacities of the complex were measured with a high-precision automatic adiabatic calorimeter over a temperature range from 80 to 390 K and the thermodynamic functions (HT-H298.15) and (ST-S298.15) were derived from the heat capacity data with a temperature interval of 5 K. Glass and phase transitions of the new complex at around 216 and 246 K were observed both by adiabatic calorimetry and differential scanning calorimetry (DSC) analyses. Thermodynamic data of the phase transitions were calculated and the transition mechanism was determined to be a re-orientational process of the perchlorate ions in the complex. The thermal stability of the complex was tested by the thermogravimetric (TG) technique and a possible mechanism for its decomposition was proposed.

Key words: Heat capacity, La(Glu)(Im)6(ClO4)3·4HClO4·4H2O, Adiabatic calorimetry, Thermodynamic function, Phase transition, Thermal stability

MSC2000: 

  • O642.3