三元配合物Lu(C5H8NS2)3(C12H8N2)生成反应的热力学

摘要

A solid complex, Lu(C5H8NS2)3(C12H8N2),has been obtained from the reaction of hydrous lutetium chloride,ammonium pyrrolidinedithiocarbamate(APDC)and 1,10-phenanthroline(o-phen·H2O)in absolute ethanol.The enthalpy change of the reaction of complex formation from a solution of the reagents,ΔrHθm(sol),and the molar heat capacity of the complex,cm,were determined at 298.15 K by using a RD-496 Ш heat conduction microcalorimeter.The enthalpy change of complex formation from the reaction of the regents in solid phase,ΔrHθm(s),was calculated on the basis of an appropriate thermochemical cycle and other auxiliary thermodynamic data.The thermodynamics of reaction of formation of the complex was investigated by the reaction in solution.Fundamental parameters,the activation enthalpy,the activation entropy,the activation free energy,the apparent reaction rate constant,the apparent activation energy, the pre-exponential constant and the reaction order,were obtained by the combination of the thermochemical data of the reaction and kinetic equations with the data of thermokinetic experiments.%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LuCl3·3.63H2O反应制备了未见文献报道的三元固态配合物Lu[(C5H8NS2)3(C12H8N2)]. 用RD496-Ⅲ微量热计测定了298.15 K下水合氯化镥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;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)和动力学参数(速率常数、表观活化能、频率因子和反应级数);通过合理的热化学循环,求得了298.15 K时标题化合物的固相生成反应焓变.