Theoretical Studies on Thermal Decomposition of Benzoyl Peroxide in Ground State

作     者：SUNCheng-ke YANGSi-ya LINXue-fei MASi-yu LIZong-he 

作者机构：DepartmentofChemistryBeijingNormalUniversityBeijing100875P.R.China；DepartmentofChemistryQujingNormalCollegeQujing655000P.R.China DepartmentofChemistryQujingNormalCollegeQujing655000P.R.China DepartmentofChemistryBeijingNormalUniversityBeijing100875P.R.China 

出 版 物：《Chemical Research in Chinese Universities》 (高等学校化学研究（英文版）)

年 卷 期：2003年第19卷第3期

页      面：355-361页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 08[工学] 0817[工学-化学工程与技术] 070303[理学-有机化学] 0703[理学-化学] 

基　　金：Supported by National NaturalScienceFoundation of China( No.2 97730 0 7) and the NaturalScienceFoundation of Qu-jing Normal College( No.2 0 0 0 0 9) 

主　　题：Benzoyl peroxide Thermal decomposition Radical UAM1 

摘      要：Systematic studies of the thermal decomposition mechanism of benzoyl peroxide(BPO) in ground state, leading to various intermediates, products and the potential energy surface(PES) of possible dissociation reactions were made computationally. The structures of the transition states and the activation energies for all the paths causing the formation of the reaction products mentioned above were calculated by the AM1 semi-empirical method. This method is shown to to be one predict correctly the preferred pathway for the title reaction. It has been found that in ground state, the thermal decomposition of benzoyl peroxide has two kinds of paths. The first pathway PhC(O)O-OC(O)Ph→PhC(O)O · →Ph · +CO 2 produces finally phenyl radicals and carbon dioxide. And the second pathway PhC(O)OO-C(O)Ph→PhC(O)OO · +PhC(O) · → PhC(O) · +O 2 →Ph · +CO+O 2, via which the reaction takes place only in two steps, produces oxygen and PhC(O) · radicals, and the further thermal dissociation of PhC(O) · is quite difficult because of the high activation energy in ground state. The calculated activation energies and reaction enthalpies are in good agreement with the experimental values. The research results also show that also the thermal dissociation process of the two bonds or the three bonds for the benzoyl peroxide doesn′t take place in ground state.