Thermochemistry of Ternary Complex Dy(Et2dtc)3(phen)
来源期刊：JOURNAL OF RARE EARTHS2004年第4期
论文作者：高胜利 朱丽 杨旭武 史启祯 帅琪 焦宝娟
Key words：Dy(Et2dtc)3(phen); microcalorimeter; thermodynamic; constant-volume combustion energy; standard mole enthalpy of formation; rare earths;
Abstract: The ternary solid complex was synthesized with sodium diethyldithiocarbamate (NaEt2dtc), 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(Et2dtc)3(phen) by chemical and elemental analyses. IR spectrum of the complex shows that the Dy3+ coordinated with six sulfur atoms of three NaEt2dtc and two nitrogen atoms of phen. It is assumed that the coordination number of Dy3+ is eight.The enthalpy change of liquid-phase reaction of formation, ΔrHθm(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, ΔrHθm(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, ΔcU, 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, ΔcHθm, and standard enthalpies of formation, ΔfHθm, are calculated as (-16749.42±9.25) kJ·mol-1 and (-2019.68±10.19) kJ·mol-1, respectively.
高胜利1，朱丽1，杨旭武1，史启祯1，帅琪1，焦宝娟1
(1.Shaanxi key Laboratory of Physico-Inorganic Chemistry,Department of Chemistry,Northwest University,Xi′an 710069,China)
Abstract:The ternary solid complex was synthesized with sodium diethyldithiocarbamate (NaEt2dtc), 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(Et2dtc)3(phen) by chemical and elemental analyses. IR spectrum of the complex shows that the Dy3+ coordinated with six sulfur atoms of three NaEt2dtc and two nitrogen atoms of phen. It is assumed that the coordination number of Dy3+ is eight.The enthalpy change of liquid-phase reaction of formation, ΔrHθm(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, ΔrHθm(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, ΔcU, 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, ΔcHθm, and standard enthalpies of formation, ΔfHθm, are calculated as (-16749.42±9.25) kJ·mol-1 and (-2019.68±10.19) kJ·mol-1, respectively.
Key words:Dy(Et2dtc)3(phen); microcalorimeter; thermodynamic; constant-volume combustion energy; standard mole enthalpy of formation; rare earths;
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