RE(C_5H_8NS_2)_3(C_(12)H_8N_2)(RE=La,Pr,Nd,Sm)的标准摩尔生成焓测定研究  

Determination of Standard Molar Enthalpy of Formation for RE(C_5H_8NS_2)_3(C_(12)H_8N_2) (RE=La, Pr, Nd, Sm)

作　　者：孟祥鑫[1] 高胜利[1] 陈三平[1] 杨旭武[1] 谢钢[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,西安710069

出　　处：《化学学报》2004年第22期2233-2238,共6页Acta Chimica Sinica

基　　金：国家自然科学基金 (No .2 0 1 71 0 36);陕西省教育厅专项基金 (No.0 1JK2 2 9)资助项目

摘　　要：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 (o phen·H2 O)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 (C12 H8N2 ) (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o 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 3 5kJ·mol-1;并计算了它们的标准摩尔燃烧焓ΔcH m 和标准摩尔生成焓ΔfH m ,分别为 -17792 43± 7 72 ,-1782 5 90± 7 93 ,-17778 2 0± 7 91,-17497 91± 9 3 5kJ·mol-1和 -83 0 5± 8 60 ,-64 70± 9 40 ,-10 4 77± 8 78,-3 88 70± 10 13kJ·mol-1.估算出未研究的同类配合物Ce(C5H8NS2 ) 3 (C12 H8N2 )和Pm(C5H8NS2 ) 3 (C12 H8N2 )的ΔcH m 和ΔfH m分别为 -17815 ,-17660kJ·mol-1和 -60 ,-2 17kJ·mol-1.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 (o-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 o-phen. It was assumed that the coordination number of RE3+ is eight. The constant-volume combustion energies of the complexes, Delta(c)U, 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, Delta(c)H(m)(circle minus), and standard enthalpies of formation, Delta(f)H(m)(circle minus), were calculated as m M - 17792.43 +/- 7.72, - 17825.90 +/- 7.93, 17778.20 +/- 7.91, - 17497.91 +/- 9.35 U - mol and - 83.05 +/- 8.60, - 64.70 +/- 9.40, - 104.77 +/- 8.78, 388.70 +/- 10.13 kJ.mol(-1), respectively. Furthermore, corresponding Delta(c)H(m)(circle minus) Delta(f)H(m)(circle minus) of Ce(C5H8NS2)(3)(C12H8N2) and Pm(C5H8NS2)3 (C12H8N2) were estimated as - 17815, - 17660 kJ.mol(-1) and - 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 标准摩尔燃烧焓 标准摩尔生成焓 固态配合物 恒容燃烧热 

分 类 号：O621[理学—有机化学]