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Theoretical study of the ozonolysis of allyl acetate: mechanism and kinetics

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Abstract

The potential energy surface (PES) and mechanism of the reaction of allyl acetate (AAC) with O3 are investigated by using density functional theory (DFT) and ab initio (MP2 and CCSD(T)) methods. The kinetics and main product branching ratios over the temperature range of (200–2,000 K) and at various pressures are obtained by employing multichannel Rice–Ramsperger–Kassel–Marcus (RRKM) theory. The results show that the main products are 2-oxoethyl acetate and formaldehyde. Two channels are found for the decomposition of primary ozonides: one path is corresponding to the 2-oxoethyl acetate + CH2OO formation (R1); the other channel products formaldehyde + CH3C(O)OCH2CHOO (R2). In the whole temperature range, R1 is calculated to be preferable and its product yield accounts for 60–77% of the total while R2 is found to contribute 20–40% to the total product yield. The overall rate constants show pressure independence and strong positive temperature dependence.

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Acknowledgments

This work was supported financially by the National Nature Science Foundation of China (NSFC Nos. 21077067, 20877049, 20737001). Independent Innovation Foundation of Shandong University (IIFSDU, project No. 2009JC016).

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Authors and Affiliations

  1. Environment Research Institute, Shandong University, Jinan, 250100, People’s Republic of China

    Maoxia He, Yanhui Sun, Haijie Cao, Dandan Han & Jingtian Hu

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  1. Maoxia He
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  2. Yanhui Sun
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  3. Haijie Cao
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  5. Jingtian Hu
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Correspondence to Jingtian Hu.

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He, M., Sun, Y., Cao, H. et al. Theoretical study of the ozonolysis of allyl acetate: mechanism and kinetics. Struct Chem 23, 201–208 (2012). https://doi.org/10.1007/s11224-011-9866-0

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