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 abso...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 liquid- phase reaction of formation for Yb （ C5H8NS2 ）3 （ C12H8N2） at different temperatures were measured by using a RD496-Ⅲ microcalorimeter. Fundamental paconduction microcalorimeter, determining the specific heat a calculation model for capacity of solid subrameters, the activation enthalpy （ΔH≠^θ）, the activation entropy （ΔS≠^θ）, the activation free energy （ΔG≠^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, ΔrH≠^θ（s）, was calculated on the basis of an appropriate thermochemical cycle and other auxiliary thermodynamic data. Based on a RD496-Ⅲ heat stance was developed, and the title complex, c m, were accordingly determined.展开更多
A new method is described to synthesize phendione derivatives from 1,10-phenanthrolines using potassium bromate and 60% sulfuric acid as oxidant,which was easily applicable to scale-up.The reaction conditions are mild...A new method is described to synthesize phendione derivatives from 1,10-phenanthrolines using potassium bromate and 60% sulfuric acid as oxidant,which was easily applicable to scale-up.The reaction conditions are mild and the yields are excellent.The target compounds have been characterized by 1H NMR,and IR.展开更多
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 etha...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.展开更多
文摘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 liquid- phase reaction of formation for Yb （ C5H8NS2 ）3 （ C12H8N2） at different temperatures were measured by using a RD496-Ⅲ microcalorimeter. Fundamental paconduction microcalorimeter, determining the specific heat a calculation model for capacity of solid subrameters, the activation enthalpy （ΔH≠^θ）, the activation entropy （ΔS≠^θ）, the activation free energy （ΔG≠^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, ΔrH≠^θ（s）, was calculated on the basis of an appropriate thermochemical cycle and other auxiliary thermodynamic data. Based on a RD496-Ⅲ heat stance was developed, and the title complex, c m, were accordingly determined.
基金financial support from National Natural Science Foundation(No.20674071)Provincial Natural Science Foundation of Zhejiang(No.Y4090281)
文摘A new method is described to synthesize phendione derivatives from 1,10-phenanthrolines using potassium bromate and 60% sulfuric acid as oxidant,which was easily applicable to scale-up.The reaction conditions are mild and the yields are excellent.The target compounds have been characterized by 1H NMR,and IR.
文摘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.
