摘要
Four solid ternary complexes of RE (C_5H_8NS_2)_3(C_(12)H_8N_2) (RE=Eu, Gd, Tb, Dy) were synthesized in absolute ethanol by rare earth chloride low hydrate with the mixed ligands of ammonium pyrrolidinedi-thiocarbamate (APDC) and 1, 10-phenanthroline·H_2O (o-phen·H_2O) in the ordinary laboratory atmosphere without any cautions against moisture or air sensitivity. IR spectra of the complexes show that the RE^(3+) coordinated with six sulfur atoms of three PDC^- and two nitrogen atoms of o-phen·H_2O. It was assumed that the coordination number of RE^(3+) is eight. The constant-volume combustion energies of the complexes, Δ_cU, were determined as (-16937 88±9 79 ), (-17588 79±8 62 ), ((-17747 14±)8 25 ) and (-17840 37±8 87 ) kJ·mol^(-1), by a precise rotating-bomb calorimeter at 298.15 K. Its standard molar enthalpies of combustion, Δ_cH~θ_m, and standard molar enthalpies of formation, Δ_fH~θ_m, were calculated as (-16953 37±9 79), (-17604 28±8 62), (-17762 63±8 25), (-17855 86±8 87) kJ·mol^(-1) and (-857.04±10.52), (-282.43±9.58), (-130.08±9.13), (-55.75±9.83) kJ·mol^(-1).
Four solid ternary complexes of RE (C_5H_8NS_2)_3(C_(12)H_8N_2) (RE=Eu, Gd, Tb, Dy) were synthesized in absolute ethanol by rare earth chloride low hydrate with the mixed ligands of ammonium pyrrolidinedi-thiocarbamate (APDC) and 1, 10-phenanthroline·H_2O (o-phen·H_2O) in the ordinary laboratory atmosphere without any cautions against moisture or air sensitivity. IR spectra of the complexes show that the RE^(3+) coordinated with six sulfur atoms of three PDC^- and two nitrogen atoms of o-phen·H_2O. It was assumed that the coordination number of RE^(3+) is eight. The constant-volume combustion energies of the complexes, Δ_cU, were determined as (-16937 88±9 79 ), (-17588 79±8 62 ), ((-17747 14±)8 25 ) and (-17840 37±8 87 ) kJ·mol^(-1), by a precise rotating-bomb calorimeter at 298.15 K. Its standard molar enthalpies of combustion, Δ_cH~θ_m, and standard molar enthalpies of formation, Δ_fH~θ_m, were calculated as (-16953 37±9 79), (-17604 28±8 62), (-17762 63±8 25), (-17855 86±8 87) kJ·mol^(-1) and (-857.04±10.52), (-282.43±9.58), (-130.08±9.13), (-55.75±9.83) kJ·mol^(-1).
基金
Project supported by the Natural Science Foundation of China (2047104) and the Natural Science Foundation of Shaanxi Province (2003B19)