三元配合物Tb(Et2dtc)3(phen)的热化学性质

以铜试剂(NaEt2dtc•3H2O)和邻菲咯啉(o-phen•H2O) 与水合氯化铽(TbCl3•3.75H2O)在无水乙醇中制得了三元固态配合物.化学分析和元素分析确定其组成为Tb(Et2dtc)3(phen).IR光谱研究表明配合物中Tb3＋与NaEt2dtc中的硫原子双齿配位,同时与phen的氮原子双齿配位.用Calvet微热量计测定了298.15 K下液相生成反应的焓变ΔrHmθ(l),为(－21.819±0.055) kJ•mol－1,通过热化学循环计算了固相生成反应焓变ΔrHmθ(s),为(128.476±0.675) kJ•mol－1.改变反应温度,研究了液相生成反应的热动力学.用精密转动弹热量计测得配合物的恒容燃烧能ΔcU为(－17646.95±8.64) kJ•mol－1,经计算其标准燃烧焓ΔcHHmθ和标准生成焓ΔfHmθ分别为(－17666.16±8.64) kJ•mol－1和(－1084.04±9.49) kJ•mol－1.

Thermochemistry of the Ternary Complex Tb ( Et2dtc )3 (phen)

The ternary solid complex, Tb(Et2dtc)3(phen),has been synthesized with sodium diethyldithiocarbamate(NaEt2dtc), 1,10-phenanthroline(o-phen•H2O) and low hydrated terbium chloride in absolute ethanol. IR spectrum of the complex showed that the Tb3＋ coordinated with six sulfur atoms of three NaEt2dtc and two nitrogen atoms of phen. The enthalpies change of liquid-phase reaction of formation,ΔrHmθ(l),was determined as(－21.819±0.055) kJ•mol－1 at 298.15 K by a microcalorimeter, the enthalpies change of the solid-phase reaction of formation,ΔrHmθ(s), was calculated as(128.476±0.675) kJ•mol－1 on the basis of a thermochemical cycle. The thermodynamic of reaction of formation was studied by changing the temperature of liquid-phase reaction. The constant-volume combustion energy of the complex,ΔcU, was determined as(－17646.95±8.64) kJ•mol－1 by a precise rotating-bomb calorimeter at 298.15 K. Its standard enthalpies of combustion,ΔcHmθ, and standard enthalpies of formation,ΔfHmθ, were calculated as(－17666.16±8.64) kJ•mol－1 and (－1084.04±9.49) kJ•mol－1, respectively.