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

ZHANG Tian-Lei ^1,2 ,
WANG Wei-Na ¹ ,
LIU Chang ¹ ,
LU Na ¹ ,
CHEN Miao ¹ ,
GUO Sha ¹ ,
WANG Wen-Liang ^1,

1.
1 Key Laboratory for Macromolecular Science of Shaanxi Province, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an 710062, P. R. China;
2 School of Chemical & Environment Science, Shaanxi University of Technology, Hanzhong 723001, Shaanxi Province, P. R. China

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.
- CH₃CHC(CH₃)COOCH₃,
- O₃,
- Density functional theory,
- Reaction mechanism,
- Rate constant
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Computational Study of the Reaction Mechanism and Kinetics of CH3CHC(CH3)COOCH3 Ozonolysis

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