目的合成、表征4种稀土与二乙氨基荒酸二乙铵(D-DDC)配合物并计算其标准摩尔生成焓。方法精密转动弹量热法。结果标题化合物的恒容燃烧热△cU分别为(-19490.07±8.23),(-19391.14±10.72).(-19208.32±8,99)和(-18439.79±7,77)kJ/nol;计算了它们的标准摩尔燃烧焓△cHm^θ,砩和标准摩尔生成焓△fHm^θ;分别为(-19517.96±8.23),(-19419.03±10.72),(-19236.21±8.99).(-18467.68±7.77)kJ/mol和(-628.91±8.88),(-742.97±11.71),(-918.15±9.59),(-1690.32±8.50)kJ/mol;估算出未研究的同类配合物Et2NH2[Ce(S2CNEt2)4]和Et2NH2[RE(S2CNEt2)4]的△cHm^θ和△fHm^θ分别为-19495,-18930kJ/mol和-673,-1262kJ/mol。结论以配合物的△cHm^θ和△fHm^θ对轻稀土原子序数作图,得到一条曲线而非单向变化的直线,说明配合物中RE^3+配体间的化学键有一定程度的共价性。
Ahn To synthesize and, characterize four complexes of RE ( RE = La, Pr, Nd, Sm) coordinated with diethylammonium diethyldinedithiocarbamate (D-DDC) and calculate their standard molar enthalpies of formation. Methods Using precise rotating-bomb calorimeter. Results The constant-volume combustion energies of title complexes, AcU, were determined as ( - 19 490.07 ± 8.23), ( - 19 391.14 ±10.72), ( - 19 208.32 ± 8.99) and ( - 18 439.79 ±7.77) kJ/mol, by a precise rotating -bomb calorimeter at 298.15 K. Their standard molar enthalpies of combustion, △cHm^θ, and standard molar enthalpies of formation, △fHm^θ, were calculated as ( - 19 517.96 ±8.23), ( - 19 419.03 ± 10.72), ( - 19 236.21 ±8.99), ( - 18 467.68 ±7.77) kJ/mol and (-628.91±8.88), ( -742.97 ±11.71), ( -918.15 ±9.59) , ( -1 690.32 ±8.50) kJ/mol. Furthermore, corresponding △cHm^θ and △fHm^θ of Et2NH2 [ Ce ( S2CNEt2 )4 ] and Et2NH2 [ Pm ( S2CNEt2 )4 ] were estimated as - 19 495, - 18 930 kJ/mol and -673, - 1 262 kJ/mol, respectively. Conclusion With increasing atomic number, △cHm^θ, and △fHm^θ of the complexes present non-linear change, showing that certain covalence exists in the coordination between RE^3+ and ligands.