−(530.7 ± 5.5) kJ·mol −1 , respectively. The enthalpies of sublimation: (136 ± 3), (128 ± 3), (179 ± 3), and (202 ± 3) kJ·mol −1 , were estimated. From the enthalpies of formation of the gaseous complexes, the homolytic and hemolytic and heterolytic mean standard molar element-sulphur bond enthalpies were calculated. These values are correlated with element-sulphur bond distances, and a larger phosphorus-sulphur
摘要 通过溶液反应量热法在 298.15 K 下测定的结晶三(二正
丁基二硫代氨基甲酸)e (III) (e = P、As、Sb 或 Bi) 的标准摩尔形成焓为 -(705.5 ± 7.3)、-(443.1±5.4)、-(526.2±2.5)和-(530.7±5.5)kJ·mol -1 分别。升华焓:(136±3)、(128±3)、(179±3)和(202±3)kJ·mol -1 被估计。从气体复合物的形成焓,计算均溶和溶血以及异溶平均标准摩尔元素-
硫键焓。这些值与元素-
硫键距离相关,较大的
磷-
硫键焓反映了键合形成中 d 轨道的更好重叠。