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

Thermochemical Properties of Ternary Complex Yb [(C_5H_8NS_2)_3(C_(12)H_8N_2)]

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

出　　处：《中国稀土学报》2005年第6期645-649,共5页Journal of the Chinese Society of Rare Earths

基　　金：国家自然科学基金资助项目(20471047);陕西省自然科学基金资助项目(2003B19)

摘　　要：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YbCl3.3.84H2O作用,合成了三元固态配合物,确定它的组成为Yb[(C5H8NS2)3(C12H8N2)]。用RD496-Ⅲ微量热计测定了298.15 K下水合氯化镱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;推导了用该热量计测定固态物质比热容的计算式,并测定了该配合物298.15 K的比热容。A novel ternary solid complex, Yb（C5H8NS2）3（C12H8N2）, was obtained from treating hydrous ytterbium chloride, ammonium pyrrolidin edithiocarbamate （APDC） and 1, 10-phenanthroline （o-phen·H2O） in absolute ethanol, and characterized by elemental analysis. The enthalpies of solution of hydrous ytterbium 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 liquidphase reaction of formation for Yb（C5H8NS2）3（C12H8N2） at different temperatures were measured by using a RD496-Ⅲ microcalorimeter. Fundamental parameters, the activation enthalpy （△H≠^θ）, the activation entropy （△S≠^θ））, the activation free energy （△G≠^θ））, 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 complex formation from the reaction of the regents in solid phase, △rH≠^θ）（s）, was calculated on the basis of an appropriate thermochemical cycle and other auxiliary thermodynamic data. Based on a RD496-Ⅲ heat conduction microcalorimeter, a calculation model for determining the specific heat capacity of solid substance was developed, and the title complex, cm, were accordingly determined.

关 键 词：水合氯化镱 吡咯烷二硫代氨基甲酸铵 1 10-邻菲咯啉 热化学性质 稀土 

分 类 号：O614.33[理学—无机化学]