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Mechanism and kinetics of low-temperature oxidation of a biodiesel surrogate−methyl acetate radicals with molecular oxygen

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Abstract

Accurate description of reactions between methyl acetate (MA) radicals and molecular oxygen is an essential prerequisite for understanding as well as modeling low-temperature oxidation and/or ignition of MA, a small biodiesel surrogate, because their multiple reaction pathways either accelerate the oxidation process via chain branching or inhibit it by forming relatively stable products. The accurate composite CBS-QB3 level of theory was used to explore potential energy surfaces for MA radicals + O2 system. Using the electronic structure calculation results under the framework of canonical statistical mechanics and transition state theory, thermodynamic properties of all species as well as high-pressure rate constants of all reaction channels were derived with explicit corrections for tunneling and hindered internal rotations. Our calculated results are in good agreement with a limited number of scattered data in the literature. Furthermore, pressure- and temperature-dependent rate constants were then computed using the Quantum Rice–Ramsperger–Kassel and the modified strong collision theories. This procedure resulted in a thermodynamically consistent detailed kinetic mechanism for low-temperature oxidation of the title fuel. We also demonstrated that even the detailed mechanism consists of several reactions of different reaction types, only the addition of the reactants and the re-dissociation of the initially formed adducts are important for low-temperature combustion at engine-liked conditions.

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Acknowledgments

We thank Dr. Carstensen (Ghent University) for helpful discussion and Dr. Villano (Colorado School of Mines) for providing calculation information on alkyl+O2 systems. This research is funded by Vietnam National Foundation for Science and Technology Development (NAFOSTED) under grant number 104.03-2012.75. Computing resources and financial support were provided by the Institute for Computational Science and Technology—Ho Chi Minh City is gratefully acknowledged.

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Authors and Affiliations

  1. Institute for Computational Science and Technology at Ho Chi Minh City, Ho Chi Minh City, Vietnam

    Tam V.-T. Mai, Xuan T. Le & Lam K. Huynh

  2. International University, Vietnam National University-HCMC, Ho Chi Minh City, Vietnam

    Lam K. Huynh

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  1. Tam V.-T. Mai
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  2. Xuan T. Le
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  3. Lam K. Huynh
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Correspondence to Lam K. Huynh.

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Mai, T.VT., Le, X.T. & Huynh, L.K. Mechanism and kinetics of low-temperature oxidation of a biodiesel surrogate−methyl acetate radicals with molecular oxygen. Struct Chem 26, 431–444 (2015). https://doi.org/10.1007/s11224-014-0495-2

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