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.
基金
ProjectsupportedbytheNationalNaturalScienceFoundationofChina(20171036
20471047)
theNationalNaturalScienceFoundationofShaanxi(2003B19
FF05201andFF05203)Province
theEducationDepartmentFoundationofShaanxi(05JK291)andtheFoundationofNingxiaGasKeyLaboratory
