Four ternary solid complexes were synthesized with sodium diethyldithiocarbamate (NaEt2dtc) (b), 1,10-phenanthroline (o-phen) (c) and hydrated lanthanide chlorides in absolute ethanol by an improved reported method. T...Four ternary solid complexes were synthesized with sodium diethyldithiocarbamate (NaEt2dtc) (b), 1,10-phenanthroline (o-phen) (c) and hydrated lanthanide chlorides in absolute ethanol by an improved reported method. The complexes were identified as the general formula of RE(Et2dtc)3(phen) (RE=La, Pr, Nd, Sm) by chemical and elemental analyses. IR spectra of the complexes showed that the RE3+ was coordinated with sulfur atoms of NaEt2dtc and nitrogen atoms of o-phen. The constant-volume combustion energies of complexes, ?cU, were determined by a precise rotating-bomb calorimeter at 298.15 K. The standard enthalpies of combustion, , and standard enthalpies of formation, , were calculated for these complexes, respectively.展开更多
A ternary solid complex Lu(Et2dtc)3(phen) has been obtained from the reaction of hydrated lutetium chloride with sodium diethyldithiocarbamate (NaEt2dtc), and 1,10-phenanthroline (o-phen·H2O) in absolute ethanol....A ternary solid complex Lu(Et2dtc)3(phen) has been obtained from the reaction of hydrated lutetium chloride with sodium diethyldithiocarbamate (NaEt2dtc), and 1,10-phenanthroline (o-phen·H2O) in absolute ethanol. IR spectrum of the complex indicates that Lu3+ binds with sulfur atom in the Na(Et2dtc)3 and nitrogen atom in the o-phen. The enthalpy change of liquid-phase reaction of formation of the complex, △CHM- (l), was determined to be (-32.821 ± 0.147 ) 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, △CHM- (s), was calculated to be (104.160 ± 0.168) 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 of liquid-phase reaction. Fundamental parameters, such as the activation enthalpy (△HM-), the activation entropy (?驻SM-), the activation free energy (△GM-), the apparent reaction rate constant (k), the apparent activation energy (E), the pre-exponential constant (A) and the reaction order (n), were obtained by combination the reaction thermodynamic and kinetic equations with the data of thermokinetic experiments. The molar heat capacity of the complex, cm, was determined to be (82.23 ± 1.47) J·mol-1·K-1 by the same microcalormeter. The constant-volume combustion energy of the complex, ΔcU, was determined as (-17 898.228 ± 8.59) kJ·mol-1 by an RBC-Ⅱtype rotating-bomb calorimeter at 298.15 K. Its standard enthalpy of combustion, △CHM-, and standard enthalpy of formation, △CHM-, were calculated to be (-17 917.43 ± 8.11) kJ·mol-1 and (-859.95 ±10.12) kJ·mol-1, respectively.展开更多
The treatment of RECl3.xH2O （RE = Ho, Er, Tm, Yb, Lu; x = 3-4） with sodium diethyldithiocarbamate （NaEtEdtc-3H2O） and 1,10-phenanthroline hydrate （o-phen.H2O） in absolute ethanol yielded five ternary solid compl...The treatment of RECl3.xH2O （RE = Ho, Er, Tm, Yb, Lu; x = 3-4） with sodium diethyldithiocarbamate （NaEtEdtc-3H2O） and 1,10-phenanthroline hydrate （o-phen.H2O） in absolute ethanol yielded five ternary solid complexes RE（EtEdtC）a（phen）. IR spectra of the complexes showed that RE^3＋ coordinated to two sulfur atoms in NaEt2dtc and two nitrogen atoms in o-phen. The constant-volume energies of combustion of the complexes have been determined by a precise rotating-bomb calorimeter at 298.15 K. The standard enthalpies of combustion and standard enthalpies of formation were calculated.展开更多
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 ...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.展开更多
Four solid complexes of Ln(Me2dtc)3(phen) (Ln=Eu, Gd, Tb, Dy) were synthesized in anhydrous ethanol by the reaction of lanthanide chloride low hydrate with the mixed ligands of sodium dimethyldithiocarbamate and 1, 10...Four solid complexes of Ln(Me2dtc)3(phen) (Ln=Eu, Gd, Tb, Dy) were synthesized in anhydrous ethanol by the reaction of lanthanide chloride low hydrate with the mixed ligands of sodium dimethyldithiocarbamate and 1, 10-phenanthroline·H2O (abbreviated as phen·H2O), and characterized by elemental analysis, IR spectroscopy, TG-DTG and X-ray diffraction techniques. Combining with the crystal structures, the complexes are identified as the general formula of Ln(Me2dtc)3(phen). TG-DTG with X-ray powder diffraction showed that these compounds could decompose to lanthanide sulfides under relatively lower temperature, which indicated that the title complexes could be ideal precursors to prepare lanthanide sulfides.展开更多
Four solid complexes of Ln(Me2dtc)3(phen) (Ln=La, Pr, Nd, Sm) were synthesized in anhydrous ethanol by the reaction of lanthanide chloride low hydrate with the mixed ligand of sodium dimethyldithiocarbamate and 1, 10-...Four solid complexes of Ln(Me2dtc)3(phen) (Ln=La, Pr, Nd, Sm) were synthesized in anhydrous ethanol by the reaction of lanthanide chloride low hydrate with the mixed ligand of sodium dimethyldithiocarbamate and 1, 10-phenanthroline·H2O (phen·H2O), and characterized by elemental analysis, IR spectroscopy, TG-DTG, and X-ray diffraction analysis. TG-DTG with X-ray powder diffraction showed that these compounds could decompose to lanthanide sulfides at relatively lower temperature, which indicated that the title complexes could be favorable precursors to prepare lanthanide sulfides.展开更多
Solid complexes,RE(Et_(2)dtc)_(3)(phen)(RE=La,Pr,Nd,Sm-Lu),were synthesized with sodium diethyldithiocarbamate(NaEt_(2)dtc3H_(2)O),1,10-phenanthroline(o-phen·H_(2)O)and hydrated lanthanide chlorides in absolute e...Solid complexes,RE(Et_(2)dtc)_(3)(phen)(RE=La,Pr,Nd,Sm-Lu),were synthesized with sodium diethyldithiocarbamate(NaEt_(2)dtc3H_(2)O),1,10-phenanthroline(o-phen·H_(2)O)and hydrated lanthanide chlorides in absolute ethanol.The constant-volume combustion energies of complexes,Δ_(c)U,were determined by a precise rotating-bomb calorimeter at 298.15 K.The standard enthalpies of combustion,Δ_(c)H^(θ)_(m),and standard enthalpies of formation,Δ_(f)H^(θ)_(m),were calculated for these complexes,respectively.The experiment results showed the'tripartite effect'of rare earth.展开更多
The ternary solid complex has been synthesized with sodium diethyldithiocarbamate (NaEt2dtc?3H2O), 1,10-phenanthroline (o-phen?H2O) and hydrated neodymium chloride in absolute ethanol. The title complex was identifi...The ternary solid complex has been synthesized with sodium diethyldithiocarbamate (NaEt2dtc?3H2O), 1,10-phenanthroline (o-phen?H2O) and hydrated neodymium chloride in absolute ethanol. The title complex was identified as the general formula of Nd(Et2dtc)3(phen) by chemical and elemental analyses. IR spectrum of the complex showed that the Nd3+ coordinated with six sulfur atoms of three NaEt2dtc and two nitrogen atoms of o-phen. It was assumed that the coordination number of Nd3+ is eight.The enthalpy change of liquid-phase reaction of formation, ?rHm (l), was determined as (-12.274±0.050) kJ?mol-1 at 298.15 K by a microcalorimeter, the Θ enthalpy change of the solid-phase reaction of formation, ?rHm (s), was calculated as (149.069±0.314) kJ?mol-1 Θ on the basis of a thermochemical cycle. The thermodynamics of reaction of formation was studied by changing the temperature of liquid-phase reaction. The constant-volume combustion energy of the complex, ?cU , was deter- mined as (-18674.22±8.33) kJ?mol-1 by a precise rotating-bomb calorimeter at 298.15 K. Its standard enthalpy of combustion, ?cHm , and standard enthalpy of formation, ?fHm , were calculated as (-18693.43±8.33) kJ?mol-1 Θ Θ and (-47.03±9.17) kJ?mol-1, respectively.展开更多
文摘Four ternary solid complexes were synthesized with sodium diethyldithiocarbamate (NaEt2dtc) (b), 1,10-phenanthroline (o-phen) (c) and hydrated lanthanide chlorides in absolute ethanol by an improved reported method. The complexes were identified as the general formula of RE(Et2dtc)3(phen) (RE=La, Pr, Nd, Sm) by chemical and elemental analyses. IR spectra of the complexes showed that the RE3+ was coordinated with sulfur atoms of NaEt2dtc and nitrogen atoms of o-phen. The constant-volume combustion energies of complexes, ?cU, were determined by a precise rotating-bomb calorimeter at 298.15 K. The standard enthalpies of combustion, , and standard enthalpies of formation, , were calculated for these complexes, respectively.
文摘A ternary solid complex Lu(Et2dtc)3(phen) has been obtained from the reaction of hydrated lutetium chloride with sodium diethyldithiocarbamate (NaEt2dtc), and 1,10-phenanthroline (o-phen·H2O) in absolute ethanol. IR spectrum of the complex indicates that Lu3+ binds with sulfur atom in the Na(Et2dtc)3 and nitrogen atom in the o-phen. The enthalpy change of liquid-phase reaction of formation of the complex, △CHM- (l), was determined to be (-32.821 ± 0.147 ) 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, △CHM- (s), was calculated to be (104.160 ± 0.168) 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 of liquid-phase reaction. Fundamental parameters, such as the activation enthalpy (△HM-), the activation entropy (?驻SM-), the activation free energy (△GM-), the apparent reaction rate constant (k), the apparent activation energy (E), the pre-exponential constant (A) and the reaction order (n), were obtained by combination the reaction thermodynamic and kinetic equations with the data of thermokinetic experiments. The molar heat capacity of the complex, cm, was determined to be (82.23 ± 1.47) J·mol-1·K-1 by the same microcalormeter. The constant-volume combustion energy of the complex, ΔcU, was determined as (-17 898.228 ± 8.59) kJ·mol-1 by an RBC-Ⅱtype rotating-bomb calorimeter at 298.15 K. Its standard enthalpy of combustion, △CHM-, and standard enthalpy of formation, △CHM-, were calculated to be (-17 917.43 ± 8.11) kJ·mol-1 and (-859.95 ±10.12) kJ·mol-1, respectively.
基金[This work was financially supported by the Natural Science Foundation of China (No. 20171036), the Natural Science Foundation of Shaanxi Province (Nos. 01JK229, FF02328 and 05JK291) and Postgraduate Foundation of China.]
文摘The treatment of RECl3.xH2O （RE = Ho, Er, Tm, Yb, Lu; x = 3-4） with sodium diethyldithiocarbamate （NaEtEdtc-3H2O） and 1,10-phenanthroline hydrate （o-phen.H2O） in absolute ethanol yielded five ternary solid complexes RE（EtEdtC）a（phen）. IR spectra of the complexes showed that RE^3＋ coordinated to two sulfur atoms in NaEt2dtc and two nitrogen atoms in o-phen. The constant-volume energies of combustion of the complexes have been determined by a precise rotating-bomb calorimeter at 298.15 K. The standard enthalpies of combustion and standard enthalpies of formation were calculated.
文摘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.
基金the National Natural Science Foundation of China (20471047 and 20771089)the National Natural Science Foundation of Shaanxi Province (2007B02)
文摘Four solid complexes of Ln(Me2dtc)3(phen) (Ln=Eu, Gd, Tb, Dy) were synthesized in anhydrous ethanol by the reaction of lanthanide chloride low hydrate with the mixed ligands of sodium dimethyldithiocarbamate and 1, 10-phenanthroline·H2O (abbreviated as phen·H2O), and characterized by elemental analysis, IR spectroscopy, TG-DTG and X-ray diffraction techniques. Combining with the crystal structures, the complexes are identified as the general formula of Ln(Me2dtc)3(phen). TG-DTG with X-ray powder diffraction showed that these compounds could decompose to lanthanide sulfides under relatively lower temperature, which indicated that the title complexes could be ideal precursors to prepare lanthanide sulfides.
基金Project supported by the National Natural Science Fundation of China (20471047 20771089)the National NaturalScience Fundation of Shaanxi Province (2007B02)
文摘Four solid complexes of Ln(Me2dtc)3(phen) (Ln=La, Pr, Nd, Sm) were synthesized in anhydrous ethanol by the reaction of lanthanide chloride low hydrate with the mixed ligand of sodium dimethyldithiocarbamate and 1, 10-phenanthroline·H2O (phen·H2O), and characterized by elemental analysis, IR spectroscopy, TG-DTG, and X-ray diffraction analysis. TG-DTG with X-ray powder diffraction showed that these compounds could decompose to lanthanide sulfides at relatively lower temperature, which indicated that the title complexes could be favorable precursors to prepare lanthanide sulfides.
基金supported by the National Natural Science Foundation of China(Grant No.20171036)Education Committee of Shaanxi Province(No.01JK229)Northwest University(02NW02)
文摘Solid complexes,RE(Et_(2)dtc)_(3)(phen)(RE=La,Pr,Nd,Sm-Lu),were synthesized with sodium diethyldithiocarbamate(NaEt_(2)dtc3H_(2)O),1,10-phenanthroline(o-phen·H_(2)O)and hydrated lanthanide chlorides in absolute ethanol.The constant-volume combustion energies of complexes,Δ_(c)U,were determined by a precise rotating-bomb calorimeter at 298.15 K.The standard enthalpies of combustion,Δ_(c)H^(θ)_(m),and standard enthalpies of formation,Δ_(f)H^(θ)_(m),were calculated for these complexes,respectively.The experiment results showed the'tripartite effect'of rare earth.
基金Project supported by the National Natural Science Foundation of China (No. 20171036) Education Committee of Shaanxi Province (No. 01JK229)the National Natural Science Foundation of Shaanxi Province (No. FF02328) and National State Post Doctoral Fou
文摘The ternary solid complex has been synthesized with sodium diethyldithiocarbamate (NaEt2dtc?3H2O), 1,10-phenanthroline (o-phen?H2O) and hydrated neodymium chloride in absolute ethanol. The title complex was identified as the general formula of Nd(Et2dtc)3(phen) by chemical and elemental analyses. IR spectrum of the complex showed that the Nd3+ coordinated with six sulfur atoms of three NaEt2dtc and two nitrogen atoms of o-phen. It was assumed that the coordination number of Nd3+ is eight.The enthalpy change of liquid-phase reaction of formation, ?rHm (l), was determined as (-12.274±0.050) kJ?mol-1 at 298.15 K by a microcalorimeter, the Θ enthalpy change of the solid-phase reaction of formation, ?rHm (s), was calculated as (149.069±0.314) kJ?mol-1 Θ on the basis of a thermochemical cycle. The thermodynamics of reaction of formation was studied by changing the temperature of liquid-phase reaction. The constant-volume combustion energy of the complex, ?cU , was deter- mined as (-18674.22±8.33) kJ?mol-1 by a precise rotating-bomb calorimeter at 298.15 K. Its standard enthalpy of combustion, ?cHm , and standard enthalpy of formation, ?fHm , were calculated as (-18693.43±8.33) kJ?mol-1 Θ Θ and (-47.03±9.17) kJ?mol-1, respectively.
