Theoretical Studies on Thermal Decomposition of Benzoyl Peroxide in Ground State

高等学校化学研究 ›› 2003, Vol. 19 ›› Issue (3): 355-361.

Theoretical Studies on Thermal Decomposition of Benzoyl Peroxide in Ground State

SUN Cheng-ke^1,2, YANG Si-ya², LIN Xue-fei², MA Si-yu¹, LI Zong-he¹

1. Department of Chemistry, Beijing Normal University, Beijing 100875, P. R. China;
2. Department of Chemistry, Qujing Normal College, Qujing 655000, P. R. China

收稿日期:2002-10-21 出版日期:2003-08-24 发布日期:2011-08-06
基金资助:
Supported by National Natural Science Foundation of China(No.29773007) and the Natural Science Foundation of Qujing Normal College(No.200009).

Theoretical Studies on Thermal Decomposition of Benzoyl Peroxide in Ground State

SUN Cheng-ke^1,2, YANG Si-ya², LIN Xue-fei², MA Si-yu¹, LI Zong-he¹

1. Department of Chemistry, Beijing Normal University, Beijing 100875, P. R. China;
2. Department of Chemistry, Qujing Normal College, Qujing 655000, P. R. China

Received:2002-10-21 Online:2003-08-24 Published:2011-08-06
Supported by:
Supported by National Natural Science Foundation of China(No.29773007) and the Natural Science Foundation of Qujing Normal College(No.200009).

摘要/Abstract

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^·+CO₂ produces finally phenyl radicals and carbon dioxide. And the second pathway PhC(O)OO-C(O)Ph→PhC(O)OO^·+PhC(O)^·→PhC(O)^·+O₂→Ph^·+CO+O₂, 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.

关键词: Benzoyl peroxide, Thermal decomposition, Radical, UAM1

Abstract: 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^·+CO₂ produces finally phenyl radicals and carbon dioxide. And the second pathway PhC(O)OO-C(O)Ph→PhC(O)OO^·+PhC(O)^·→PhC(O)^·+O₂→Ph^·+CO+O₂, 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.

Key words: Benzoyl peroxide, Thermal decomposition, Radical, UAM1

SUN Cheng-ke, YANG Si-ya, LIN Xue-fei, MA Si-yu, LI Zong-he. Theoretical Studies on Thermal Decomposition of Benzoyl Peroxide in Ground State[J]. 高等学校化学研究, 2003, 19(3): 355-361.

SUN Cheng-ke, YANG Si-ya, LIN Xue-fei, MA Si-yu, LI Zong-he. Theoretical Studies on Thermal Decomposition of Benzoyl Peroxide in Ground State[J]. Chemical Research in Chinese Universities, 2003, 19(3): 355-361.

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Theoretical Studies on Thermal Decomposition of Benzoyl Peroxide in Ground State

Theoretical Studies on Thermal Decomposition of Benzoyl Peroxide in Ground State

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