摘要
利用文献结果，用统计热力学和过渡态理论计算了ＣＦ_３ＣＯ和ＣＦ_３Ｃ（Ｏ）Ｏ自由基分解反应的热力学和动力学数据；计算结果表明，计算值与最新实验数据甚相符合，并据此判断，ＣＦ_３ＣＯ和ＣＦ_３Ｃ（Ｏ）Ｏ均很不稳定，不可能参加Ｏ_３分解的循环催化反应。
Ozone in the stratosphere is important to the life of human being and the radicals CF_3CO and CF_3C(O)Omay play iniportant roles in the removal of ozone by participating in the circular catalytic reactions of the degradation of ozone. So it is essential to make clear the thermodynamic and kinetic properties of the decomposition reactions of the two radicals.Several experimental results had been reported on these reactions,but these results are quite different from each other.Theoretically,these reactions liad been studied by using ab initio method at 6-31G* level and the correlation energy was considered with PMP2.In this paper,the thermodynamic and kinetic data of the reactions had been calculated over the temperature interval from 100 K to 1500 K based on statistical thermodynamics and transition state theory by using the data obtained from ab initio calculation. The thermodynamic and kinetic data of these reactions such as K_p and k_r had been obtained.The result of calculation is well consistent with the latest experimental data and the conclusion was drawn that both CF_3CO and CF_3(O)O radicals are too unstable to participate in the catalytic cycles of the removal of ozone in the stratosphere.
出处
《高等学校化学学报》
SCIE
EI
CAS
CSCD
北大核心
1996年第5期777-780,共4页
Chemical Journal of Chinese Universities
基金
国家自然科学基金
