<正> 一、引言 本文研究HDBP(磷酸二丁酯)+TBPO(三丁基氧磷)体系协萃U(Ⅵ)的机理,实验中采用单浓度递变法及等摩尔系列法确定协萃物组成为UO_2A_2(HA)_2B,并测得协萃平衡常数lgβ_(12)=6.89.文中用锥角模型提出的“配位体立体角系数和”稳定规律解释了上述结果,并从温度对萃
To resolve the obvious discrepancy between the results of HDBP+TBP and HDEHP+ TBP systems, the extractive process U(VI) from aqueous sulphate media by HDBP+TBPO dissolved in benzene has been studied. The difference between two mechanisms lies in the fact that whether the constituent of the synergic extracted complex is UO_2A_2(HA)_2TBPO or UO_2A_2(HA)TBPO. The composition of the complex was found to be UO_2A_2(HA)_2TBPO by means of slope method and equimolar series method. This is considered reasonable by predicating with cone packing model. Thermodynamic parameters for the formation of UO_2A_2(HA)_2TBPO at 298K were evaluated. The entropy change associated with the synergistic reaction (3) is 20J/mol·K, contributed by releasing a water molecule in TBPO reaction, which is in harmony with the data of TOPO system. From this result, it is possible to conclude that the synergism process is associated with adduct formation but no replacement of HA molecules.
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