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首页> 外文期刊>European journal of inorganic chemistry >The Np-V and Pu-V Carbonate Systems: Thermodynamics and Coordination Chemistry
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The Np-V and Pu-V Carbonate Systems: Thermodynamics and Coordination Chemistry

机译：NP-V和PU-V碳酸盐系统：热力学和协调化学

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摘要

New stability constants for Np-V and Pu-V carbonates have been established by coupling capillary electrophoresis (CE) and ICP-MS at the ionic strength of 0.202 mol/kg(water) in NaClO4 and at various temperatures. The thermodynamic data [variation of the molar enthalpy, Delta H-r(m)(T degrees) and entropy, Delta S-r(m)(T) of reaction] associated with the formation of the AnO(2)CO(3)(-) (An = Np, Pu), AnO(2)(CO3)(2)(3-), and AnO(2)(CO4)(3)(5-) complexes were determined. A drastic decrease in molar entropy was observed between the second and third complexes, suggesting important structural changes. Ab initio molecular dynamics showed that the 1:3 complex is formed with two carbonate ligands located at a shorter distance and one at a longer distance, suggesting that the closer ligands are coordinated in a bidentate fashion to the plutonyl(V) moiety whereas the third ligand is monodentate. The variation of the electrophoretic mobilities as function of charge/size ratio confirms unambiguously that the triscarbonate complex of pentavalent plutonium structurally differs from that of hexavalent plutonium where all carbonates anions are bidentate.
机译：通过在NaClO4和各种温度下在0.202mol / kg（水）的离子强度下，通过偶联毛细管电泳（Ce）和ICP-MS来建立NP-V和PU-V碳酸盐的新稳定性常数。热力学数据[摩尔焓的变化，ΔHr（m）和熵，反应的δsr（m）（t）与ano（2）co（3）（ - ）的形成相关（AN = NP，PU），ANO（2）（CO 3）（2）（3-）和ANO（2）（CO 4）（3）（5-）复合物。在第二和第三络合物之间观察到摩尔熵的激烈减少，表明重要的结构变化。 AB Initio分子动力学表明，1：3复合物形成有位于较短距离的碳酸盐配体，并且在较长距离处，表明较近的配体以双齿的方式与普卢托隆（V）部分相协调，而第三则配体是单一的。电泳迁移率的变化作为电荷/尺寸比的功能明确地证实，使得五价钚的小碳酸盐络合物结构与六价钚的结构不同，其中所有碳酸盐阴离子都是双齿的。

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