Issue 2, 2018

Theoretical studies on the reaction kinetics of methyl crotonate with hydroxyl radical

Abstract

The potential energy surfaces (PES) for the reactions of methyl crotonate (MC) with hydroxyl radical, including H-abstraction and OH-addition, were explored by the QCISD(T)/CBS//M062x/6-311++G(d,p) and CBS-QB3 methods, respectively. The subsequent isomerization and β-scission reactions of the produced primary radicals were also investigated using these methods. The phenomenological rate coefficients of these reactions were predicted over 500 to 1800 K and 0.001 to 100 atm via solving the time-dependent master equations based on Rice–Ramsperger–Kassel–Marcus theory. The rate coefficients of the two dominant H-abstraction channels at 1 atm were expressed as the sum of two modified Arrhenius equations (units: cm3 per molecule per s and cal mol−1): k1 (MC + OH → PC1 + H2O) = 2.29 × 10−4T−2.02 exp(−10 204/RT) + 7.31 × 10−13T0.1 exp(−819/RT), k2 (MC + OH → PC2 + H2O) = 1.83 × 10−2T−2.39 exp(−10 360/RT) + 1.27 × 10−9T−0.57 exp(−2858/RT). The sub-mechanisms of MC + OH and its primary radicals were validated using a previously described combustion model; the updated model well reproduced the previous experimental results. The present rate coefficients provide valuable kinetic data to improve our understanding of the combustion mechanism of MC and can be used as a reliable reference for further investigation of practical fuels.

Graphical abstract: Theoretical studies on the reaction kinetics of methyl crotonate with hydroxyl radical

Supplementary files

Article information

Article type
Paper
Submitted
03 Sep 2017
Accepted
08 Nov 2017
First published
23 Nov 2017

Sustainable Energy Fuels, 2018,2, 392-402

Theoretical studies on the reaction kinetics of methyl crotonate with hydroxyl radical

X. Zhou, Y. Zhai, L. Ye and L. Zhang, Sustainable Energy Fuels, 2018, 2, 392 DOI: 10.1039/C7SE00426E

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements