物理化学学报 >> 1998, Vol. 14 >> Issue (01): 33-38.doi: 10.3866/PKU.WHXB19980107

研究论文 上一篇    下一篇

多元硝酸酯热解反应的理论研究

贡雪东, 肖鹤鸣   

  1. 南京理工大学化学系，南京 210094
  • 收稿日期:1997-04-28 修回日期:1997-06-16 发布日期:1998-01-15
  • 通讯作者: 肖鹤鸣

Theoreticl Studies on the Pyrolysis of Polynitric Esters

Gong Xue-Dong, Xiao He-Ming   

  1. Department of Chemistry,Nanjing University of Science and Technology,Nanjing 210094
  • Received:1997-04-28 Revised:1997-06-16 Published:1998-01-15
  • Contact: Xiao He-Ming

PDF

2700

赞

摘要：

运用SCF-MO－AM1方法，在RHF和UHF水平上，计算研究了四种多元硝酸酯在12种稳定构象下的热解反应．均裂氧硝基键（O-NO2）产生RCH2O•和•NO2的活化能较低，是硝酸酯热解的主要途径；通过α－H转移产生RCHO和HONO的环消除反应具有较高活化能. 均裂O NO2键的活化能与该键的Wiberg键级之间存在良好的线性关系

关键词: 硝酸酯, 构象, 热解反应, 活化能, AMl方法, RHF计算, UHF计算

Abstract:

The pyrolysis reactions of four polynitric esters at twelve conformations have been calculated using SCF-MO-AM1 method at RHF and UHF levels respectively. It has been found that homolysis of O-NO2 bond into two radicals RCH2O•and •NO2 has lower activation energy and is the main path way of pyrolysis. α-H transition elimination reaction of breaking O-NO2with the products RCHO and HONO has quite high activation energy. A good linear relationship exists between the activation energy of homolysis of O-NO2 and the Wiberg bond order of this bond.

Key words: Nitric esters, Conformation, Pyrolysis, Activation energy, AMlmethod, RHF calculation, UHF calculation