Theoretical predictions of hydrolysis and complex formation of group-4 elements Zr, Hf and Rf in HF and HCl solutions
Theoretical predictions of hydrolysis and complex formation of group-4 elements Zr, Hf and Rf in HF and HCl solutions
复制标题
第四族元素Zr、Hf和Rf在HF和HCl溶液中水解和形成络合物的理论预测
DOI：
10.1524/ract.2002.90.12_2002.869
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发表时间：
2002
影响因子：
1.8
通讯作者：
J. Kratz
中科院分区：
文献类型：
--
作者：
V. Pershina;D. Trubert;C. Le Naour;J. Kratz
总结完全相对论分子密度泛函计算的电子结构的水合，水解和氟/氯配合物已执行的第4族元素Zr，Hf，和元素104，Rf。使用的电子密度分布数据，水解和络合物形成反应的自由能变化的相对值被定义。结果表明，在第一步水解过程中，Zr > Hf > Rf，与实验结果一致。对于HF溶液中的络合物形成，从Zr到Hf的降低趋势随着Rf继续，只要不发生水解。当pH > 0时，在Rf ≥ Zr > Hf组中，水解物或氟配合物的进一步分解有相反的趋势，元素之间的差异很小。对于在HCl溶液中的络合物形成，继续与Rf的趋势，使Zr > Hf > Rf独立的pH值。水解或络合物形成过程中的一个决定性的能量因素被证明是一个主要的静电金属配体相互作用。第4族元素的Kd（分配系数）值的趋势预计将遵循那些复杂的形成。
Summary Fully relativistic molecular density–functional calculations of the electronic structures of hydrated, hydrolyzed and fluoride/chloride complexes have been performed for group–4 elements Zr, Hf, and element 104, Rf. Using the electronic density distribution data, relative values of the free energy change for hydrolysis and complex formation reactions were defined. The results show the following trend for the first hydrolysis step of the cationic species: Zr > Hf > Rf in agreement with experiments. For the complex formation in HF solutions, the trend to a decrease from Zr to Hf is continued with Rf, provided no hydrolysis takes place. At pH > 0, further fluorination of hydrolyzed species or fluoro–complexes has an inversed trend in the group Rf ≥ Zr > Hf, with the difference between the elements being very small. For the complex formation in HCl solutions, the trend is continued with Rf, so that Zr > Hf > Rf independently of pH. A decisive energetic factor in hydrolysis or complex formation processes proved to be a predominant electrostatic metal–ligand interaction. Trends in the Kd (distribution coefficient) values for the group–4 elements are expected to follow those of the complex formation.
DOI：
--
发表时间：
2003
期刊：
影响因子：
--
作者：
T.Nishigaki et al.;S.Itoh.et al.
通讯作者：
S.Itoh.et al.