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

镧系元素四分体效应：乔根森理论的延伸及其新发展

基本信息

批准号：
21654081
负责人：
KAWABE Iwao
金额：
$ 2.12万
依托单位：
Nagoya University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Challenging Exploratory Research
财政年份：
2009
资助国家：
日本
起止时间：
2009 至 2011
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-21654081/
关键词：
地殻・マントル物質地球化学希土類元素化学ランタニド化学四組効果希土類元素ヨルゲンセン-川邊式 REE分配係数希土類元素鉱物ランタニドランタニド四組効果ヨルゲンセン理論電子雲拡大効果ランタニド・キレート錯体ヨルゲンセン・川邊の式ランタニドの熱力学熱力学量

项目摘要

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.

作为LN（III） - 氯酸盐水溶液的热力学数据的案例研究，鉴于Jorgensen-Kawabe（JK）方程的灯笼中载体TetrAD效应，已检查了LN（III）-DTPA和LN-EDTA复合物的这些数据。 ln-氯酸盐的地层代表了这样的反应，即aqua ln（III）离子H-2O的配体被（DTPA+H-2O）或（EDTA+H-2O）代替。手。 S显示出类似的四局效应，但四局效应几乎完全取消。 g =。 H-T。 S.先前的研究忽略了这种机制，并导致了误解。作为一项实验研究，已经在10〜200的温度范围内确定了一对BASO4/水溶液的REE（LN+Y）分区系数。C。已显示了REE分配反应的△h和s s的Tetrad效应。使用Gibbs-Helmholtz方程和JK方程，已经分析了四型效应。通过软骨量标准化的稀土矿物（Kimuraite和Lanthanite）的稀土矿物的抽象模式，表明四局效应。我们证实，JK方程可以很好地再现二元效应。这是REE地球化学中的首次演示，即REE矿物质的组成可以安装到简单的理论等效性中。命令帮助研究生和年轻的研究人员了解Jorgensen-Kawabe方程的理论基础，这是三个关于电力和磁性机械学的统计学机制的教科书，已准备好了，他们已准备好了统计机制。 Jorgensen-Kawabe方程本身以及本研究的结果在另一本书正在准备的教科书“ REE化学和地球化学”中讨论并引用。