RE(C5H8NS2)3(C12H8N2)的标准摩尔生成焓

在无水乙醇中, 使低水合氯化稀土 (RE = Ho, Er, Tm, Yb, Lu) 与吡咯烷二硫代氨基甲酸铵 (APDC)和1,10-菲咯啉 (o–phen•H₂O) 反应, 制得其三元固态配合物. 用化学分析和元素分析确定它的组成为RE(C₅H₈NS₂)₃(C₁₂H₈N₂) (RE = Ho, Er, Tm, Yb, Lu). IR光谱说明RE³⁺ 分别与3个PDC^–的6个硫原子双齿配位, 同时与o–phen的2个氮原子双齿配位, 配位数为8. 用精密转动弹热量计测定了它们的恒容燃烧热△_cU分别为(-16788.46 ± 7.74), (-15434.53 ± 8.28), (-15287.80 ± 7.31), (-15200.50 ± 7.22)和(-15254.34 ± 6.61) kJ•mol^-1; 并计算了它们的标准摩尔燃烧焓△_cH_m^θ和标准摩尔生成焓△_fH_m^θ分别为( -16803.95 ± 7.74), (-15450.02 ± 8.28), (-15303.29 ± 9.28), (-15215.99 ± 7.22), (-15269.83 ± 6.61) kJ • mol^-1和 (-1115.42 ± 8.94), (-2477.80 ± 9.15), (-2619.95 ± 10.44), (-2670.17 ± 8.22), (-2650.06 ± 8.49) kJ•mol^-1.

Standard Molar Enthalpy of Formation of RE(C5H8NS2)3(o‐phen)

Five solid ternary complexes of RE(C₅H₈NS₂)₃(o‐phen) (RE=Ho, Er, Tm, Yb, Lu) have been synthesized in absolute ethanol by rare earth chloride low hydrate reacting with the mixed ligands of ammonium pyrrolidinedithiocarbamate (APDC) and 1,10‐phenanthroline·H₂O (o‐phen·H₂O) in the ordinary laboratory atmosphere without any cautions against moisture or air. IR spectra of the complexes showed that the RE³⁺ coordinated with six sulfur atoms of three PDC^‐ and two nitrogen atoms of o‐phen·H₂O. It was assumed that the coordination number of RE³⁺ was eight. The constant‐volume combustion energies of the complexes, Δ_cU, were determined as (?16788.46±7.74), (?15434.53±8.28), (?15287.80±7.31), (?15200.50±7.22) and (?15254.34±6.61) kJ·mol^‐1, respectively, by a precise rotating‐bomb calorimeter at 298.15 K. Its standard molar enthalpies of combustion, Δ_c , and standard molar enthalpies of formation, Δ_f , were calculated as (?16803.95±7.74), (?15450.02±8.28), (?15303.29±9.28), (?15215.99±7.22), (?15269.83±6.61) kJ·mol^‐1 and (?1115.42±8.94), (?2477.80±9.15), (?2619.95±10.44), (?2670.17±8.22), (?2650.06±8.49) kJ·mol^‐1, respectively.