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
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.
