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 –22.214±0.081 kJ mol–1, and the molar heat capacity of the complex, c m, as 61.676±0.651 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 54.527±0.314 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 –16937.88±9.79 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 –16953.37±9.79 and –1708.23±10.69 kJ mol–1, respectively.
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Chen, S.P., Meng, X.X., Shuai, Q. et al. Thermochemistry of europium and dithiocarbamate complex Eu(C5H8NS2)3(C12H8N2). J Therm Anal Calorim 86, 767–774 (2006). https://doi.org/10.1007/s10973-005-6626-7
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DOI: https://doi.org/10.1007/s10973-005-6626-7