酰胺荚醚对Am(Ⅲ)和Eu(Ⅲ)的萃取行为研究Ⅱ.萃取热力学和萃合物光谱研究

    STUDY ON THE EXTRACTION OF Am(Ⅲ) AND Eu(Ⅲ) WITH AMIDO PODANDS Ⅱ.EXTRACTION THERMODYNAMICS AND ABSORPTION SPECTRA

    • 摘要: 以 40 %辛醇 /煤油为稀释剂 ,研究了 3种荚醚 :N ,N ,N’ ,N’ 四丁基 3 氧 戊二酰胺(TBOPDA)、N ,N ,N’ ,N’ 四异丁基 3 氧 戊二酰胺 (TiBOPDA)和N ,N ,N’ ,N’ 四丁基 3,6 二氧 辛二酰胺 (TBDOODA)在硝酸介质中对Am(Ⅲ )和Eu(Ⅲ )的萃取热力学。TBOPDA、TiBOPDA和TBDOODA萃取镅的反应焓变分别为 :- 80 5 4、- 81 99和 - 75 88kJ/mol;求出了萃取反应自由能和熵值的变化 ;观测了不同平衡酸度下萃入有机相中金属离子的可见吸收光谱。研究结果表明 ,水相酸度在一定范围内变化时 ,有机相中金属离子的吸收峰位置和形状没有改变 ,说明萃取机理在一定酸度内不变。萃合物红外光谱的测量结果表明 ,萃取金属离子后 ,3种荚醚的羰基吸收峰均发生了显著位移 ,TBOPDA和TBDOODA的醚氧键位移分别为 6cm- 1和 3cm- 1。

       

      Abstract: By using n octanol and kerosene as diluent, the extraction behavior of Am(Ⅲ) and Eu(Ⅲ) from nitric acid solution is studied with N,N,N’,N’ tetrabutyl 3 oxa pentanediamide(TBOPDA),N,N,N’,N’ tetraisobutyl 3 oxa pentanediamide(T i BOPDA) and N,N,N’,N’ tetrabutyl 3,6 dioxa octanediamide(TBDOODA). The extraction equilibrium is an exothermic reaction and the extraction enthapy of americium is -80.54、-81.99 and-75.88 kJ/mol for TBOPDA,T i BOPDA and TBDOODA,respectively.It is found that the remarkable variation of HNO 3 concentration in equilibrium only slightly changes the shape and position of the visible absorption peak of the loaded organic phase. It implies that the variation of HNO 3 concentration does not affect the extraction mechanism. In IR spectrum the carboyl absorption peaks of both TBDOPDA and TBDOODA shift strongly to long wavelength after extracting HNO 3 or Eu(Ⅲ), at the same time the peak of carbon-oxgy-carbon has 6 cm -1 and 3 cm -1 shift for TBOPDA and TBDOODA, respectively.

       

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