Improvement of the Modeling of the Low-Temperature Oxidation ofn-Butane: Study of the Primary Reactions
- 18 January 2012
- journal article
- research article
- Published by American Chemical Society (ACS) in The Journal of Physical Chemistry A
- Vol. 116 (24), 6142-6158
- https://doi.org/10.1021/jp211434f
Abstract
This paper revisits the primary reactions involved in the oxidation of n-butane from low to intermediate temperatures (550–800 K) including the negative temperature coefficient (NTC) zone. A model that was automatically generated is used as a starting point and a large number of thermochemical and kinetic data are then re-estimated. The kinetic data of the isomerization of alkylperoxy radicals giving •QOOH radicals and the subsequent decomposition to give cyclic ethers has been calculated at the CBS-QB3 level of theory. The newly obtained model allows a satisfactory prediction of experimental data recently obtained in a jet-stirred reactor and in rapid compression machines. A considerable improvement of the prediction of the selectivity of cyclic ethers is especially obtained compared to previous models. Linear and global sensitivity analyses have been performed to better understand which reactions are of influence in the NTC zone.This publication has 61 references indexed in Scilit:
- High-Pressure Rate Rules for Alkyl + O2 Reactions. 1. The Dissociation, Concerted Elimination, and Isomerization Channels of the Alkyl Peroxy RadicalThe Journal of Physical Chemistry A, 2011
- Towards cleaner combustion engines through groundbreaking detailed chemical kinetic modelsChemical Society Reviews, 2011
- Uncertainty of Arrhenius parametersInternational Journal of Chemical Kinetics, 2011
- Detailed product analysis during the low temperature oxidation of n-butanePhysical Chemistry Chemical Physics, 2010
- Uncertainty driven theoretical kinetics studies for CH3OH ignition: HO2+CH3OH and O2+CH3OHProceedings of the Combustion Institute, 2010
- Theoretical Validation of Chemical Kinetic Mechanisms: Combustion of MethanolThe Journal of Physical Chemistry A, 2010
- A global sensitivity study of cyclohexane oxidation under low temperature fuel-rich conditions using HDMR methodsCombustion Theory and Modelling, 2009
- Primary Mechanism of the Thermal Decomposition of TricyclodecaneThe Journal of Physical Chemistry A, 2006
- Direct measurements of the neopentyl peroxy-hydroperoxy radical isomerisation over the temperature range 660–750 KSymposium (International) on Combustion, 1992
- The pyrolysis of organic hydroperoxides (ROOH)Symposium (International) on Combustion, 1992