Citation: ZHANG Tian-Lei, WANG Wei-Na, LIU Chang, LU Na, CHEN Miao, GUO Sha, WANG Wen-Liang. Computational Study of the Reaction Mechanism and Kinetics of CH3CHC(CH3)COOCH3 Ozonolysis[J]. Acta Physico-Chimica Sinica, ;2013, 29(11): 2313-2320. doi: 10.3866/PKU.WHXB201310083 shu

Computational Study of the Reaction Mechanism and Kinetics of CH3CHC(CH3)COOCH3 Ozonolysis

  • Received Date: 9 July 2013
    Available Online: 8 October 2013

    Fund Project: 国家自然科学基金(21173139) (21173139)陕西师范大学国家级大学生创新性实验计划(1110718008)资助项目 (1110718008)

  • The reaction mechanism for the ozonolysis of trans-CH3CHC(CH3)COOCH3 as well as the isomerization reaction of CH3CHOO and CH3OC(O)C(CH3)OO) without and with a water molecule were investigated at the G3B3 level. The profile of the potential energy surface (PES) was constructed. Ozone adds to trans-CH3CHC(CH3)COOCH3 via a cyclic transition state to produce a highly unstable primary ozonide that can decompose readily to form P1(CH3CHOO + CH3OC(O)C(CH3)O) and P2(CH3CHO + CH3OC(O)C(CH3)OO) because the bond breaks in different positions. The total rate constants over the temperature range of 200-1200 K are obtained using the conventional transition state theory with Wigner tunneling correction. The calculated rate constant is 7.55×10-18 cm3·molecule-1·s-1 at 294 K, in od agreement with previous experimental data for similar reactions. The isomerization reaction of CH3CHOO and CH3OC (O)C(CH3)OO) with a water molecule can occur via α-addition process and β-hydrogen transfer mechanism. The former is more favorable than the latter. Compared with the naked isomerization reactions of CH3CHOO and CH3OC(O)C(CH3)OO), the presence of water molecules makes isomerization reactions much easier.

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