高等学校化学学报

高等学校化学学报 ›› 1991, Vol. 12 ›› Issue (12): 1669.

• 研究论文 • 上一篇    下一篇

H2NNO2裂解与重排反应的理论热力学、动力学研究

居冠之, 居泉   

  1. 山东大学理论化学研究室, 济南, 250100
  • 收稿日期:1990-09-08 出版日期:1991-12-24 发布日期:1991-12-24
  • 通讯作者: 居冠之
  • 基金资助:

    国家自然科学基金

The Theoretically Thermodynamic and Kinetic Studies on the Scission and Rearrangement of NH2NO2

Ju Guan-zhi, Ju Quan   

  1. Institute of Theoretical Chemistry, Shandong University, Jinan, 250100
  • Received:1990-09-08 Online:1991-12-24 Published:1991-12-24

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摘要： 硝胺化合物的N-N键断裂和硝基-亚硝基重排(>N-NO2→>N-ONO)是一类重要的化学反应。最近Golden等重新测定了DMNA[(CH3)2NNO22]消失的速度常数,认为其分解应包括N-N键断裂和硝基-亚硝基重排后的再分解等过程,并得到分子束实验的确认,但理论研究尚不多见。Melius和McKee等都曾对该类体系进行过量化计算,但结果并不令人满意。

关键词: H2NNO2裂解与重排, 热力学和动力学计算, A因子

Abstract: Using the computational results of quantum chemistry at CI4d level, this paper has finished the thermodynamic and kinetic calculations theoretically for the reactions NH2+NO2←NH2NO2←NHONO←NH2O+NO The results show, the rate of NH2O-NO scission is much larger than that of the rearrangement of NH2NO2for the direction of nitro-nitrite rearrangement, while the N-NO2bond scission and the rearrangement should be competed quite evenly. It is expected that factor A of them is larger The above results are all in agreement with Golden' s experiment on DMNA[(CH3)2NNO2] basically, showing the thermodynamic and kinetic calculations on the system are successful. In addition, a set of thermodynamic functions of the reactions is given. All the results have never been found in literatures.

Key words: Scission and rearrangement of NH2NO2, Thermodynamic and kinetic calculations, Factor A

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