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采用骤冷法对反应REBr3(s)+(3/2)Al2Br6(g)=REAl3Br12(g)进行研究,实验温度和压力范围分别是600~850 K和0.0077~0.22 MPa,反应平衡时间为6 h。测定它们在不同温度下的稳定常数。结果显示,中稀土的气态配合物稳定常数最大。以气态配合物REAl3Br12的lgKp与Z+/r作图,可将镧系稀土元素分为La-Eu,Eu-Er和Er-Lu三组,在每一组内,REAl3Br12的稳定常数均呈线性关系。在稀土气态配合物RE-Al3Br12稳定常数与原子序数及离子势(Z+/r)的变化关系中都存在着钆断现象。REAl3Br12稳定常数的对数值对RE(Ⅲ)的基态角量子数作图,得到四条直线,类似斜W效应。
The temperature and pressure range of REBr3 (s) + (3/2) Al2Br6 (g) = REAl3Br12 (g) were studied by using the quenching method. The reaction temperatures ranged from 600 to 850 K and from 0.0077 to 0.22 MPa, respectively. h Determine their stability constants at different temperatures. The results show that the stability constant of the rare earth complex is the largest. The lanthanide REE can be divided into three groups of La-Eu, Eu-Er and Er-Lu by plotting lgKp and Z + / r of the gaseous complex REAl3Br12. Within each group, the stability constants of REAl3Br12 show a linear relationship . The phenomenon of gadolinium decay exists in the relationship between the stability constants of RE-Al3Br12 and atomic number and ion potential (Z + / r). The logarithm of the stability constant of REAl3Br12 is plotted against the ground state quantum numbers of RE (III), resulting in four straight lines, similar to the oblique W effect.