Thermochemistry of Ternary Complex Dy(Et2dtc)3(phen)

来源 :Journal of Rare Earths | 被引量 : 0次 | 上传用户:ok2ejoo
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The ternary solid complex was synthesized with sodium diethyldithiocarbamate (NaEt_2dtc), 1,10-phenanthroline (phen) and low hydrated dysprosium chloride in absolute ethanol by improved method of reference. The title complex was identified as the general formula of Dy(Et_2dtc)_3(phen) by chemical and elemental analyses. IR spectrum of the complex shows that the Dy~(3+) coordinated with six sulfur atoms of three NaEt_2dtc and two nitrogen atoms of phen. It is assumed that the coordination number of Dy~(3+) is eight.The enthalpy change of liquid-phase reaction of formation, Δ_rH~θ_m(l), is determined as (-19.091±0.015) kJ·mol~(-1) at 298.15 K by a microcalorimeter, and the enthalpy change of the solid-phase reaction of formation, Δ_rH~θ_m(s), is calculated as (139.641±0.482) kJ·mol~(-1) on the basis of a thermochemical cycle. The thermodynamic of reaction of formation was studied by changing the temperature of liquid-phase reaction. The constant-volume combustion energy of the complex, Δ_cU, is determined as (-16730.21±9.25) kJ·mol~(-1) by a precise rotating-bomb calorimeter at 298.15 K. Its standard enthalpies of combustion, Δ_cH~θ_m, and standard enthalpies of formation, Δ_fH~θ_m, are calculated as (-16749.42±9.25) kJ·mol~(-1) and (-2019.68±10.19) kJ·mol~(-1), respectively. The ternary solid complex was synthesized with sodium diethyldithiocarbamate (NaEt_2dtc), 1,10-phenanthroline (phen) and low hydrated dysprosium chloride in absolute ethanol by improved method of reference. The title complex was identified as the general formula of Dy (Et_2dtc) _3 (phen) by chemical and elemental analyzes. IR spectrum of the complex shows that the Dy ~ (3 +) coordinated with six sulfur atoms of three NaEt_2dtc and two nitrogen atoms of phen. It is assumed that the coordination number of Dy ~ (3 +) is eight.The enthalpy change of liquid-phase reaction of formation, Δ_rH ~ θ_m (l), is determined as (-19.091 ± 0.015) kJ · mol -1 (298.15 K by a microcalorimeter, and the enthalpy The thermodynamic of reaction of formation was studied by ((c)) is calculated as (139.641 ± 0.482) kJ · mol -1 (-1) on the basis of a thermochemical cycle changing the temperature of liquid-phase reaction. The constant-volume combustion energy of the co mplex, Δ_cU, is determined as (-16730.21 ± 9.25) kJ · mol -1 by a precise rotating-bomb calorimeter at 298.15 K. Its standard enthalpies of combustion, Δ_cH ~ θ_m, and standard enthalpies of formation, Δ_fH ~ θ_m, were calculated as (-16749.42 ± 9.25) kJ · mol -1 (-2019.68 ± 10.19) kJ · mol -1, respectively.
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