Lanthanide tetrad effects : Extension of Jorgensen's theory and its new developments

作为一个案例研究的热力学数据为水溶液的Ln（III）-螯合物的形成，这些数据为Ln（III）-DTPA和Ln-EDTA络合物的形成已被检查的Jorgensen-Kawabe（JK）方程的镧系元素四分体效应。Ln-螯合物的形成是指Ln（III）水溶液中的H-2 O配体被（DTPA+H-2 O）或（EDTA+H-2 O）取代的反应。H和。S表现出类似的四分体效应，但在中四分体效应几乎完全被抵消。G通过。G=. H-T。S.作为实验研究，在10~ 200 ℃温度范围内测定了稀土元素在BaSO_4/水溶液体系中的分配系数。C.稀土配分反应中△H和△S的四元效应。利用Gibbs-Helmholtz方程和JK方程分析了四分体效应，稀土矿物（木村石和镧石）球粒陨石标准化的REE丰度模式反映了四分体效应。我们证实JK方程能很好地再现四分体效应。这是稀土元素地球化学中首次用简单的理论方程拟合稀土元素矿物的稀土元素组成，为了帮助研究生和青年研究人员理解Jorgensen-Kawabe方程的理论基础，编写了统计力学、电磁物理学和量子力学三本教材，并在国立大学图书馆资源库注册，供开放使用。Jorgensen-Kawabe方程本身和本研究的结果在另一本正在编写的教科书《REE化学与地球化学》中进行了讨论和引用。

As a case study of thermodynamic data for aqueous Ln(III)-chelate complex formations, those data for Ln(III)-DTPA and Ln-EDTA complex formations have been examined in view of the Jorgensen-Kawabe(JK) equation for the lanthanide tetrad effect. Ln-chelate formations represent such reactions that ligands of H-2O of aqua Ln(III) ions are replaced by(DTPA+H-2O) or(EDTA+H-2O), where. H and. S show similar tetrad effects, but the tetrad effects are cancelled almost totally in. G through. G=. H-T. S. Previous studies overlooked this mechanism, and led to misunderstanding.As an experimental study, REE(Ln+Y) partition coefficients for the pair of BaSO4/aqueous solution have been determined in the temperature range of 10~ 200. C. The tetrad effects of△H and△S for REE partitioning reaction have been shown. Using the Gibbs-Helmholtz equation and JK equation, the tetrad effects have been analyzed.REE abundance patterns of rare-earth minerals(kimuraite and lanthanite) normalized by chondrite, indicate the tetrad effects. We confirmed that the tetrad effects can be well reproduced by JK equation. This is the first demonstration in REE geochemistry that REE compositions of REE minerals can be fitted to the simple theoretical equation.In order help graduate students and young researchers understand the theoretical base of Jorgensen-Kawabe equation, the three textbooks on Statistical Mechanics, Physics on Electricity and Magnetism, Quantum Mechanics have been prepared and registered them in Repository of NU Library for their open uses. Jorgensen-Kawabe equation itself and the results of the present study are discussed and cited in another textbook"REE Chemistry and Geochemistry", which is now in preparation.