| 有机磷酸萃取剂的结构及其立体效应 |
| Structure of Organophosphorus Acid Extractants and their Steric Effect |
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| 摘要: 结构为R(R')P(O)OH的有机磷酸萃取剂的立体效应对其选择性有重要影响,但至今尚缺乏公认的表征有机磷酸立体效应的结构参数。本文以两个取代基与磷原子之间的夹角∠RPR'表征立体效应。在八面体构型中,配位于中心原子的两个有机磷酸的两对取代基大致在同一平面之中,夹角∠RPR'越大,相互作用越强,位阻越大。而在四面体构型中,两对取代基在互为正交的两个平面中,位阻小得多。实验表明,有机磷酸萃取钴时,八面体的钴萃合物转化为四面体的热力学参数与∠RPR'的变化趋势一致。 |
| 关键词: 有机磷酸萃取剂 立体效应 位阻 钴 镍 溶剂萃取 |
| 基金项目: 国家自然科学基金(No.29776045、29836130) |
| Abstract: Steric effect of organophosphorus acid extractants (OPA) with the structure of R(R')P(O)OHplays an important role in the selectivity for different metals. Until now,there is no widely accepted structure parameter for description of theeffect. It is suggested in the present paper to take the angle between the two substituting groups and the phosphorous atom, ∠RPR' as the steric parameter ofthe extactants. In an octahedral configuration of the extracts, the substituting groups from the two coor inated OPAare approximately in the same plane, larger the ∠RPR', larger the interaction between them, resulting in a higher steric effect. In a tetrahedral configuration, the substituted groups sre locatedin two perpendicular planes, the streric effect is much weaker. As Co2+ is extracted by OPA, the change of the thermodynamic parameters of conversion of octahedral to tetrahedral configuration of the cobalt extracts is in accordance withthe ∠RPR' of the extractants. |
| Keywords: organophosphorus acid extractants steric effect cobalt nickelsolvent extraction |
| 投稿时间：1999-09-27 |
| 摘要点击次数: 988 |
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| 朱屯.有机磷酸萃取剂的结构及其立体效应[J].无机化学学报,2000,16(2):305-309. |
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