化学学报 ›› 2004, Vol. 62 ›› Issue (22): 2233-2238. 上一篇    下一篇

研究论文

RE(C5H8NS2)3(C12H8N2)(RE=La,Pr,Nd,Sm)的标准摩尔生成焓测定研究

孟祥鑫, 高胜利, 陈三平, 杨旭武, 谢钢, 史启祯   

  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
  • 收稿日期:2004-02-16 修回日期:2004-07-12 出版日期:2004-11-28 发布日期:2014-02-17
  • 通讯作者: 高胜利,E-mail:gaoshli@nwu.edu.cn E-mail:gaoshli@nwu.edu.cn
  • 基金资助:
    国家自然科学基金(No.20171036)和陕西省教育厅专项基金(No.01JK229)资助项目.

Determination of Standard Molar Enthalpy of Formation for RE(C5H8NS2)3(C12H8N2) (RE=La, Pr, Nd, Sm)

MENG Xiang-Xin, GAO Sheng-Li, CHEN San-Ping, YANG Xu-Wu, XIE Gang, SHI Qi-Zhen   

  1. Shaanxi Key Laboratory of Physico-inorganic Chemistry, Department of Chemistry, Northwest University, Xi'an 710069
  • Received:2004-02-16 Revised:2004-07-12 Online:2004-11-28 Published:2014-02-17

在无水乙醇中,使低水合氯化稀土(RE=La, Pr, Nd, Sm)与吡咯烷二硫代氨基甲酸铵(APDC)和1,10-邻二氮菲(σ-phen·H2O)反应,制得其三元固态配合物.用化学分析和元素分析确定它们的组成为RE (C5H8NS2)3(C12H8N2) (RE= La, Pr, Nd, Sm).IR光谱说明RE3+分别与3个PDC-的6个硫原子双齿配位,同时与σ-phen的2个氮原子双齿配位,配位数为8.用精密转动弹热量计测定了它们的恒容燃烧热ΔcU,分别为-17776.94±7.72, -17810.41±7.93, -17762.71±7.91和-17482.42±9.35 kJ·mol-1;并计算了它们的标准摩尔燃烧焓和标准摩尔生成焓,分别为-17792.43±7.72, -17825.90±7.93, -17778.20±7.91, -17497.91±9.35 kJ*mol-1和-83.05±8.60, -64.70±9.40, -104.77±8.78, -388.70±10.13 kJ·mol-1.估算出未研究的同类配合物Ce(C5H8NS2)3(C12H8N2)和Pm(C5H8NS2)3(C12H8N2)的分别为-17815, -17660 kJ·mol-1和-60, -217 kJ·mol-1.

关键词: 稀土氯化物, 吡咯烷二硫代氨基甲酸铵, 1,10-邻二氮菲, 固态配合物, 恒容燃烧热, 标准摩尔生成焓

Four solid ternary complexes of RE(C5H8NS2)3(C12H8N2) (RE=La, Pr, Nd, Sm) have been synthesized in absolute ethanol by rare earth chloride low hydrate with the mixed ligands of ammonium pyrrolidinedithiocarbamate (APDC) and 1,10-phenanthroline (σ-phen·H2O) without any cautions against moisture or air. IR spectra of the complexes showed that the RE3+ was coordinated with six sulfur atoms of three PDC- and two nitrogen atoms of σ-phen. It was assumed that the coordination number of RE3+ is eight. The constant-volume combustion energies of the complexes, ΔcU, were determined as -17776.94±7.72, -17810.41±7.93, -17762.71±7.91 and -17482.42±9.35 kJ·mol-1, by a precise rotating-bomb calorimeter at 298.15 K. Their standard enthalpies of combustion, , and standard enthalpies of formation, , were calculated as -17792.43±7.72, -17825.90±7.93, -17778.20±7.91, -17497.91±9.35 kJ·mol-1 and -83.05±8.60, -64.70±9.40, -104.77±8.78, -388.70±10.13 kJ·mol-1, respectively. Furthermore, corresponding and of Ce(C5H8NS2)3(C12H8N2) and Pm(C5H8NS2)3(C12H8N2) were estimated as -17815, -17660 kJ·mol-1 and -60, -217 kJ·mol-1.

Key words: rare earth chloride, ammonium pyrrolidinedithiocarbamate(APDC), 1,10-phenanthroline(σ-phen·H2O), solid complex, constant2volume combustion heat, standard molar enthalpy of formation