三元配合物Tm[(C_5H_8NS_2)_3(C_(12)H_8N_2)]的热化学性质研究

Study on Thermochemical Properties of Ternary Complex Tm[(C_5H_8NS_2)_3(C_(12)H_8N_2)]

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·H2O)与TmCl3·3.65H2O作用,合成了未见文献报道的三元固态配合物,确定它的组成为Tm[(C5H8NS2)3(C12H8N2)]。用RD496-Ⅲ微量热计测定了298.15K下水合氯化铥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298.15K时标题化合物的固相生成反应焓变;推导了用该热量计测定固态物质比热容的计算式,并测定了题目配合物298.15K的比热容。用RBC-Ⅱ精密转动弹热量计测定了题目配合物的恒容燃烧热,计算了它们的标准摩尔燃烧焓和标准摩尔生成焓。

A novel ternary solid complex, Tm（C5H8NS2）3（C12H8N2）, has been obtained by treating hydrous thulium chloride, ammonium pyrrolidinedithiocarbamate（APDC） and 1, 10-phenanthroline （o-phen·H2O） in absolute ethanol, and characterized by elemental analysis. The enthalpies of solution of hydrous thulium chloride, APDC, o-phen·H2O, the mixture of APDC with o-phen·H2O in absolute ethanol at 298.15 K, and the enthalpy changes of liquid-phase reaction of formation for Tm（C5H8NS2）3（C12H8N2） at different temperatures were measured by using a RD496-Ⅲ microcalorimeter. Fundamental parameters, the activation enthalpy （ΔH≠^-）, the activation entropy （ΔS≠^-）, the activation free energy （ΔG≠^-）, the apparent reaction rate constant （k）, the apparent activation energy （E）, the pre-exponential constant （A） and the reaction order （n）, were obtained by the combination of the thermochemical data of the reaction and kinetic equations with the data of thermokinetic experiments. The enthalpy change of co- mplex formation from the reaction of reagents in solid phase, ΔrHm^-（s）, was calculated on the basis of an appropr- iate thermochemical cycle and other auxiliary thermodynamic data. The constant-volume combustion energy of the complex, ΔcU, was determined by a RBC-Ⅱ type rotating-bomb calorimeter at 298.15 K. Its standard enthalpy of combustion, ΔcHm^-, and standard enthalpy of formation, ΔfHm^-, were calculated, respectively. Based on a RD496-Ⅲ heat conduction microcalorimeter, a calculation model for determining the specific heat capacity of solid substances was developed, and the specific heat capacity of the title complex, cm, was accordingly determined.