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Abstract  

A solid complex Eu(C5H8NS2)3(C12H8N2) has been obtained from reaction of hydrous europium chloride with ammonium pyrrolidinedithiocarbamate (APDC) and 1,10-phenanthroline (o-phen⋅H2O) in absolute ethanol. IR spectrum of the complex indicated that Eu3+ in the complex coordinated with sulfur atoms from the APDC and nitrogen atoms from the o-phen. TG-DTG investigation provided the evidence that the title complex was decomposed into EuS. The enthalpy change of the reaction of formation of the complex in ethanol, Δr H m θ(l), as –22.2140.081 kJ mol–1, and the molar heat capacity of the complex, c m, as 61.6760.651 J mol–1 K–1, at 298.15 K were determined by an RD-496 III type microcalorimeter. The enthalpy change of the reaction of formation of the complex in solid, Δr H m θ(s), was calculated as 54.5270.314 kJ mol–1 through a thermochemistry cycle. Based on the thermodynamics and kinetics on the reaction of formation of the complex in ethanol at different temperatures, fundamental parameters, including 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. The constant-volume combustion energy of the complex, Δc U, was determined as –16937.889.79 kJ mol–1 by an RBC-II type rotating-bomb calorimeter at 298.15 K. Its standard enthalpy of combustion, Δc H m θ, and standard enthalpy of formation, Δf H m θ, were calculated to be –16953.379.79 and –1708.2310.69 kJ mol–1, respectively.

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Abstract  

A novel solid complex, formulated as Ho(PDC)3 (o-phen), has been obtained from the reaction of hydrate holmium chloride, ammonium pyrrolidinedithiocarbamate (APDC) and 1,10-phenanthroline (o-phenH2O) in absolute ethanol, which was characterized by elemental analysis, TG-DTG and IR spectrum. The enthalpy change of the reaction of complex formation from a solution of the reagents, Δr H m θ (sol), and the molar heat capacity of the complex, c m, were determined as being –19.1610.051 kJ mol–1 and 79.2641.218 J mol–1 K–1 at 298.15 K by using an RD-496 III heat conduction microcalorimeter. The enthalpy change of complex formation from the reaction of the reagents in the solid phase, Δr H m θ(s), was calculated as being (23.9810.339) kJ mol–1 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 at the temperature range of 292.15–301.15 K. The constant-volume combustion energy of the complex, Δc U, was determined as being –16788.467.74 kJ mol–1 by an RBC-II type rotating-bomb calorimeter at 298.15 K. Its standard enthalpy of combustion, Δc H m θ, and standard enthalpy of formation, Δf H m θ, were calculated to be –16803.957.74 and –1115.428.94 kJ mol–1, respectively.

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