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    Oxidation kinetics of n-pentanol: A theoretical study of the reactivity of the 1‑hydroxy‑1-peroxypentyl radical

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    Type
    Article
    Authors
    Duan, Yaozong
    Monge Palacios, Manuel
    Grajales Gonzalez, Edwing cc
    Han, Dong
    Møller, Kristian H. cc
    Kjaergaard, Henrik G.
    Sarathy, Mani cc
    KAUST Department
    Chemical Engineering Program
    Clean Combustion Research Center
    Combustion and Pyrolysis Chemistry (CPC) Group
    Physical Science and Engineering (PSE) Division
    KAUST Grant Number
    OSR-2016-CRG5-3022
    Date
    2020-06-04
    Online Publication Date
    2020-06-04
    Print Publication Date
    2020-09
    Submitted Date
    2019-12-01
    Permanent link to this record
    http://hdl.handle.net/10754/663461
    
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    Abstract
    n-Pentanol has been considered as a promising alternative fuel for compression-ignition engines due to its potential to reduce greenhouse gases and pollutant emissions. Engine performance is strongly dominated by fuel oxidation chemistry, and thus a more accurate determination of the coefficients of the reactions ruling its oxidation is essential for the utilization of n-pentanol in combustion engines. The reactions involving 1‑hydroxy‑1-pentyl and molecular oxygen were found to play an important role in controlling the low temperature oxidation chemistry, but have not been investigated experimentally or theoretically; this is also the case for the reactions of the 1‑hydroxy‑1-peroxypentyl radical, which is formed by the addition of oxygen to the radical center of 1‑hydroxy‑1-pentyl. This work presents a theoretical study with high level ab initio calculations at the CCSD(T)/aug-cc-pVTZ//M06-2X/cc-pVTZ level of theory to shed light on the fate of the 1‑hydroxy‑1-peroxypentyl radical. The rate coefficients of all the possible intra-molecular hydrogen shift reactions of that radical were computed using variational transition state theory with small curvature tunneling corrections. For certain reactions, tunneling and variational effects are very pronounced, proving the need for robust methodologies to account for these effects. The hydrogen shift reaction leading to a concerted HO2 elimination and formation of n-pentanal is the dominant pathway and governs the reactivity of 1‑hydroxy‑1-peroxypentyl radical at any temperature. The reverse of this reaction was thereby investigated as well. For this prominent pathway, the effects of multistructural (multiple conformers) torsional anharmonicity of the stationary points were taken into account in order to refine the forward and reverse rate coefficients. The rate coefficients calculated at room temperature are compared to those calculated using a previously developed cost-effective multi-conformer transition state theory approach. The system-specific quantum Rice-Ramsperger-Kassel (SS-QRRK) theory was used to compute the pressure-dependent rate coefficients, which indicate significant pressure dependence at intermediate and high temperatures. Implementation of the calculated reaction rate coefficients in chemical kinetics models of n-pentanol revealed that our computed rate coefficients enable better insights into the chemistry of n-pentanol, and help to understand how n-pentanal is formed.
    Citation
    Duan, Y., Monge-Palacios, M., Grajales-Gonzalez, E., Han, D., Møller, K. H., Kjaergaard, H. G., & Sarathy, S. M. (2020). Oxidation kinetics of n-pentanol: A theoretical study of the reactivity of the 1‑hydroxy‑1-peroxypentyl radical. Combustion and Flame, 219, 20–32. doi:10.1016/j.combustflame.2020.05.014
    Sponsors
    The research at Shanghai Jiao Tong University was supported by funding from the National Natural Science Foundation of China under Grant No. 51776124. The present work was also supported by funding from King Abdullah University of Science and Technology (KAUST) Office of Sponsored Research (OSR) under award No. OSR-2016-CRG5-3022. We would like to acknowledge resources of the Supercomputing Laboratory at KAUST. We are grateful for the funding from the Independent Research Fund Denmark, and the University of Copenhagen. The authors also would like to thank Prof. Heufer for providing us with the volume traces used in the RCM simulations.
    Publisher
    Elsevier BV
    Journal
    Combustion and Flame
    DOI
    10.1016/j.combustflame.2020.05.014
    Additional Links
    https://linkinghub.elsevier.com/retrieve/pii/S0010218020301954
    ae974a485f413a2113503eed53cd6c53
    10.1016/j.combustflame.2020.05.014
    Scopus Count
    Collections
    Articles; Physical Science and Engineering (PSE) Division; Chemical Engineering Program; Clean Combustion Research Center

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