铁离子和亚硝酸对偏二甲基肼还原六价镎的影响

铁离子和亚硝酸对偏二甲基肼还原六价镎的影响

摘要

摘要: 用分光光度法研究了Ｆｅ３＋和ＨＮＯ２对硝酸体系中偏二甲基肼还原Ｎｐ（Ⅵ）的影响。结果表明，Ｆｅ３＋与偏二甲基肼反应生成Ｆｅ２＋；Ｆｅ３＋对偏二甲基肼还原Ｎｐ（Ⅵ）→Ｎｐ（Ⅴ）的反应有催化作用；在实验条件下，当ｃＦｅ３＋＝０．１ｍｍｏｌ／Ｌ时，反应２ｈ后，能检测到有Ｎｐ（Ⅳ）生成；ＨＮＯ２能与Ｎｐ（Ⅵ）及偏二甲基肼反应，当ＨＮＯ２存在于偏二甲基肼与Ｎｐ（Ⅵ）的反应体系中时，Ｎｐ（Ⅵ）→Ｎｐ（Ⅴ）的还原速率显著加快。

Abstract: EFFECTS OF Fe3＋ AND HNO2 ON THE REDUCTION OF Np(Ⅵ) WITH 1,1DIMETHYLHYDRAZINEYin Dongguang Zhang Xianye Hu Jingxin(China Institute of Atomic Energy,P.O.BOX 275(26),Beijing 102413)ABSTRACTThe effects of Fe3＋ and HNO2 on the reduction of Np(Ⅵ) with 1,1dimethylhydrazine are studied.The results show that Fe3＋ can be reduced by 1,1dimethylhydrazine and Fe3＋ can acts as a catalyst to the reaction of Np(Ⅵ) with 1,1dimethylhydrazine.Under the experimental conditon,Np(Ⅳ) can be produced when increasing the ferric ion concentration to 0.1 mmol/L.Nitrous acid can react with Np(Ⅵ).Its reaction rate equation can be expressed as follows:－dcNp(Ⅵ)dt=k″2cNp(Ⅵ)cHNO2where k″2=165 (L/mol)·min－1 at t=225 ℃.As nitrous acid and 1,1dimethylhydrazine are present in the system simultaneously,the reduction of Np(Ⅵ) to Np(Ⅴ) proceeds at a very high rate.The rate equation is as follows:－dcNp(Ⅵ)dt=k″3cNp(Ⅵ)cHNO2c05(CH3)2NNH2Where k″3=1.22×105(L/mol)1.5·min－1 at t=215 ℃,cHNO3=1.0 mol/L.Key words Ferric ion Nitrous acid 1,1Dimethylhydrazine Neptunium Reaction rate

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