本文考察了 TBP 萃取 Pt(Ⅳ),Pd(Ⅳ),Ir(Ⅳ),Pt(Ⅱ),Pd(Ⅱ),Rh(Ⅲ),Ir(Ⅲ)等7种氯络酸时,HCl 浓度对分配系数的影响,进行了 TBP 与 TAPO 的对比实验;研究了萃取有机相的可见及红外光谱以及 H_2SO_4和 HClO_4对萃取的影响.认为萃取属于氢离子的水化溶剂化机理;推导了萃取能量变化公式;解释了实验获得的 MCl_6~(2-)>MCl_4~(2-)>MCl_6~(3-)规律及“最小电荷密度原理”,并根据从反应平衡式导出的分配系数近似式,解释了分配曲线中存在峰值的原因和 H_2SO_4助萃作用以及HClO_4抑萃作用的原因.
The influence of HCl concentration on the extraction distribution coefficients was examined when chloro-complex acids of Pt(Ⅳ),Pd(Ⅳ),Ir(Ⅳ),Pt(Ⅱ),Pd (Ⅱ),Rh(Ⅲ) and Ir(Ⅲ)extracted by TBP.The comparative tests between TBP and trialkyl phosphine oxide were also made.After the visible and ultrared spectra observations of the organic phases and the investigation of effect of H_2SO_4 and HClO_4 on extraction,it is reasonable to point out that the extraction is regarded as the mechanism of hydration and solvation of hydrogen ions.Thus, derivation of its energy change expression,explanation of the sequence of MCl_6~(2-)>MCl_4~(2-)>MCl_6~(3-) resulted experimentally and principle of the“least cherge density”are accomplished.According to the approximate formula of distribution coefficient derived from reaction equilibrium equation,the reasons of the peak occurred in the distribution curves and the auxiliary or inhibitory effect of H_2SO_4 or HClO_4 on extraction respectively were discussed.
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