Measurements of Enthalpy Change of Reaction of Formation, Molar Heat Capacity and Constant-Volume Combustion Energy of Solid Complex Yb(Et_2dtc)_3(phen)  

作　　者：宋伟明 胡奇林 常旋 陈三平 谢钢 高胜利 

机构地区：[1]School of Chemical Science and Engineering, Key Laboratory of Energy Resources & Chemical Engineering, Ningxia University, Yinchuan 750021, China [2]Shaanxi Key Laboratory of Physico-Inorganic Chemistry, Department of Chemistry, Northwest University, Xi'an 710069, China [3]Shaanxi

出　　处：《Journal of Rare Earths》2006年第2期155-162,共8页稀土学报（英文版）

基　　金：ProjectsupportedbytheNationalNaturalScienceFoundationofChina(20171036;20471047);theNationalNaturalScienceFoundationofShaanxi(2003B19;FF05201andFF05203)Province;theEducationDepartmentFoundationofShaanxi(05JK291)andtheFoundationofNingxiaGasKeyLaboratory

摘　　要：A ternary solid complex Yb（Et2dtc）3（phen） was obtained from the reaction of hydrous ytterbium chloride with sodium diethyldithiocarbamate （NaEt2dtc）, and 1, 10-phenanthroline （o-phen·H2O） in absolute ethanol. The bonding characteristics of the complex were characterized by IR. The result shows Yb3^＋ bands with two sulfur atoms in the Na（Et2dtc）3 and two nitrogen atoms in the o-phen. The enthalpy change of liquid-phase reaction of formation of the complex △rHm^θ（Ⅰ）, was determined as being （-24.838±0.114） kJ·mol^-1 at 298.15 K, by an RD-496 Ⅲ type heat conduction microcalormeter. The enthalpy change of the solid-phase reaction of formation of the complex △rHm^θ（s）, was calculated as being （108.015±0.479） kJ·mol^-1 on the basis of an appropriate thermochemistry cycle. The thermodynamics of liquid-phase reaction of formation of the complex was investigated by changing the temperature during the liquid-phase reaction. 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 a combination of the reaction thermodynamic and kinetic equations with the data from the thermokinetic expenments. At the same time, the molar heat capacity of the complex cm. p, Was determined to be （86.34± 1.74） J·mol^-1·K^-1 by the same microcalormeter. The constant-volume combus- tion energy of the complex, △cU, was determined to be （ - 17954.08 ± 8.11） kJ·mol^-1 by an RBC-Ⅱ type rotating-bomb calo- rimeter at 298.15 K. Its standard enthalpy of combustion, △cHm^θ, and standard enthalpy of formation, △fHm^θ, were calculated to be （- 17973.29±8.11） kJ·mol^-1 and （-770.36±9.02） kJ·mol^-1, respectively.A ternary solid complex Yb（Et2dtc）3（phen） was obtained from the reaction of hydrous ytterbium chloride with sodium diethyldithiocarbamate （NaEt2dtc）, and 1, 10-phenanthroline （o-phen·H2O） in absolute ethanol. The bonding characteristics of the complex were characterized by IR. The result shows Yb3^＋ bands with two sulfur atoms in the Na（Et2dtc）3 and two nitrogen atoms in the o-phen. The enthalpy change of liquid-phase reaction of formation of the complex △rHm^θ（Ⅰ）, was determined as being （-24.838±0.114） kJ·mol^-1 at 298.15 K, by an RD-496 Ⅲ type heat conduction microcalormeter. The enthalpy change of the solid-phase reaction of formation of the complex △rHm^θ（s）, was calculated as being （108.015±0.479） kJ·mol^-1 on the basis of an appropriate thermochemistry cycle. The thermodynamics of liquid-phase reaction of formation of the complex was investigated by changing the temperature during the liquid-phase reaction. 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 a combination of the reaction thermodynamic and kinetic equations with the data from the thermokinetic expenments. At the same time, the molar heat capacity of the complex cm. p, Was determined to be （86.34± 1.74） J·mol^-1·K^-1 by the same microcalormeter. The constant-volume combus- tion energy of the complex, △cU, was determined to be （ - 17954.08 ± 8.11） kJ·mol^-1 by an RBC-Ⅱ type rotating-bomb calo- rimeter at 298.15 K. Its standard enthalpy of combustion, △cHm^θ, and standard enthalpy of formation, △fHm^θ, were calculated to be （- 17973.29±8.11） kJ·mol^-1 and （-770.36±9.02） kJ·mol^-1, respectively.

关 键 词：hydrous ytterbium chloride sodium dinedithiocarbamate （NaEt2dtc） 1  10-phenanthroline （o-phen·H2O） THERMOCHEMISTRY rare earths 

分 类 号：O621.25[理学—有机化学]