中华医学超声杂志

应用化学 ›› 2010, Vol. 27 ›› Issue (08): 916-923.DOI: 10.3724/SP.J.1095.2010.90543

• 研究论文 • 上一篇    下一篇

N,N-二甲基羟胺与HNO2的反应动力学

李高亮,何辉*   

  1. (中国原子能科学研究院 放射化学研究所 北京 102413)
  • 收稿日期:2009-08-20 修回日期:2010-01-12 出版日期:2010-08-10 发布日期:2010-08-10
  • 通讯作者: 何辉，男，博士，研究员; E-mail:hehui@ciae.ac.cn; 研究方向：核燃料循环与材料

Studies on the reaction kinetics between nitrous acidand N，N-Dimethylhydroxylamine

LI Gao-Liang, HE Hui*   

  1. (Radiochemistry Department of China Institute of Atomic Energy,Beijing 102413)
  • Received:2009-08-20 Revised:2010-01-12 Published:2010-08-10 Online:2010-08-10

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摘要：

分别在高氯酸和硝酸介质中研究了N,N-二甲基羟胺(DMHAN)与HNO2的反应动力学，通过考察溶液酸度、还原剂浓度、离子强度和温度等因素对反应过程的影响，获得高氯酸介质中反应动力学速率方程为-d[HNO2]/dt=k[DMHAN][HNO2]，在18.5 ℃，离子强度μ=0.73 mol/L时，反应速率常数k=(12.8±1.0) mol/(L·min)，反应活化能Ea=41.5 kJ/mol。 在硝酸介质中DMHAN与HNO2的反应比较复杂，硝酸浓度较高时，硝酸将参与反应重新生成HNO2，且硝酸浓度越大，HNO2的生成速度越快，HNO2与DMHAN的反应是自催化氧化的。 对DMHAN与HNO2的反应产物进行了分析，并推导了硝酸体系中DMHAN与HNO2的反应机理。

关键词: N,N-二甲基羟胺, 反应动力学, 反应机理, HNO2

Abstract:

The oxidation of N,N-dimethylhydroxylamine(DMHAN) by nitrous acid in a perchloric acid and nitric acid medium as well as the effects of c(H+), c(DMHAN), ion strength and temperature on the reaction were studied. The rate equation in perchloric acid was determined as follows:-d[HNO2]/dt=k[DMHAN][HNO2], where k=(12.8±1.0) mol/(L·min) when the temperature is 18.5 ℃ and the ion strength is 0.73 mol/L with an activation energy about of 41.5 kJ/mol. The reaction became complicated when it was performed in nitric acid medium. The reaction between nitric acid and DMHAN occurred and nitrous acid was produced when the concentration of nitric acid was higher than 1.0 mol/L. The reaction products were analyzed and the reaction mechanism was discussed.

Key words: N,N-dimethylhydroxylamine, reaction kinetics, reaction mechanism, nitrous acid

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