Theoretical study of n-pentanol oxidation kinetics: Reactivity of the 1-hydroxy-pentylperoxy radical

Yaozong Duan, M. Monge-Palacios, E. Grajales-Gonzalez, Dong Han, S. Mani Sarathy

Research output: Contribution to conferencePaperpeer-review

Abstract

n-Pentanol, a promising oxygenated alternative to petroleum derived gasoline and diesel fuels, has attracted attention recently. Fundamental combustion characteristics, such as auto-ignition chemistry and emission formation are critically sensitive to fuel chemical structure. The presence of the hydroxyl group in n-pentanol affects the fuel combustion kinetics, especially at low temperatures. A more accurate determination of the rate constants for key reactions and a better understanding of the fuel oxidation chemistry is important for its practical utilization in combustors. In the present work, a theoretical kinetic study, based on high level ab initio calculations, has been carried out to investigate the fate of the 1-hydroxy-pentylperoxy radical. The reaction barrier heights and high pressure limit rate constants of all the possible intramolecular H-shift reactions were computed using the single structural variational transition state theory with small curvature tunneling corrections (SS-VTST-SCT) at the CCSD(T)/aug-cc-pVTZ//M06-2X/cc-pVTZ level of theory; the HO2 concerted elimination reaction was also investigated. All the studied reactions exhibit positive temperature dependence. The HO2 concerted elimination reaction forming n-pentanal is the most dominant reaction pathway in the oxidation of 1-hydroxy-pentylperoxy radical as it shows the lowest barrier height and therefore the largest rate coefficients. Its reverse reaction shows a non-Arrhenius behavior as a result of its submerged barrier. The calculated reaction rate constants are expected to benefit a more comprehensive understanding of the oxidation chemistry of n-pentanol.

Original languageEnglish (US)
StatePublished - 2019
Event12th Asia-Pacific Conference on Combustion, ASPACC 2019 - Fukuoka, Japan
Duration: Jul 1 2019Jul 5 2019

Conference

Conference12th Asia-Pacific Conference on Combustion, ASPACC 2019
Country/TerritoryJapan
CityFukuoka
Period07/1/1907/5/19

ASJC Scopus subject areas

  • Chemical Engineering(all)
  • Energy Engineering and Power Technology
  • Fuel Technology
  • Condensed Matter Physics

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