Acta Phys. -Chim. Sin. ›› 2013, Vol. 29 ›› Issue (11): 2313-2320.doi: 10.3866/PKU.WHXB201310083

• THEORETICAL AND COMPUTATIONAL CHEMISTRY • Previous Articles     Next Articles

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

ZHANG Tian-Lei1,2, WANG Wei-Na1, LIU Chang1, LU Na1, CHEN Miao1, GUO Sha1, WANG Wen-Liang1   

  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:2013-07-09 Revised:2013-10-07 Published:2013-10-30
  • Contact: WANG Wen-Liang E-mail:wlwang@snnu.edu.cn
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (21173139) and Student Innovation Foundation of Shaanxi Normal University, China (1110718008).

Abstract:

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 good 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.

Key words: CH3CHC(CH3)COOCH3, O3, Density functional theory, Reaction mechanism, Rate constant

MSC2000: 

  • O641