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Title: H-Abstraction reactions by OH, HO 2, O, O 2 and benzyl radical addition to O 2 and their implications for kinetic modelling of toluene oxidation

Abstract

Here, alkylated aromatics constitute a significant fraction of the components commonly found in commercial fuels. Toluene is typically considered as a reference fuel. Together with n-heptane and iso-octane, it allows for realistic emulations of the behavior of real fuels by the means of surrogate mixture formulations. Moreover, it is a key precursor for the formation of poly-aromatic hydrocarbons, which are of relevance to understanding soot growth and oxidation mechanisms. In this study the POLIMI kinetic model is first updated based on the literature and on recent kinetic modelling studies of toluene pyrolysis and oxidation. Then, important reaction pathways are investigated by means of high-level theoretical methods, thereby advancing the present knowledge on toluene oxidation. H-Abstraction reactions by OH, HO 2, O and O 2, and the reactivity on the multi well benzyl-oxygen (C 6H 5CH 2 + O 2) potential energy surface (PES) were investigated using electronic structure calculations, transition state theory in its conventional, variational, and variable reaction coordinate forms (VRC-TST), and master equation calculations. Exploration of the effect on POLIMI model performance of literature rate constants and of the present calculations provides valuable guidelines for implementation of the new rate parameters in existing toluene kinetic models.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]
  1. Materials and Chemical Engineering “G. Natta”, Milan (Italy)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1461435
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Name: Physical Chemistry Chemical Physics. PCCP (Print); Journal Volume: 20; Journal Issue: 16; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; PAH Oxidation; Theoretical Chemical Kinetics; Toluene Combustion

Citation Formats

Pelucchi, Matteo, Cavallotti, C., Faravelli, T., and Klippenstein, S. J. H-Abstraction reactions by OH, HO2, O, O2 and benzyl radical addition to O2 and their implications for kinetic modelling of toluene oxidation. United States: N. p., 2018. Web. doi:10.1039/c7cp07779c.
Pelucchi, Matteo, Cavallotti, C., Faravelli, T., & Klippenstein, S. J. H-Abstraction reactions by OH, HO2, O, O2 and benzyl radical addition to O2 and their implications for kinetic modelling of toluene oxidation. United States. doi:10.1039/c7cp07779c.
Pelucchi, Matteo, Cavallotti, C., Faravelli, T., and Klippenstein, S. J. Thu . "H-Abstraction reactions by OH, HO2, O, O2 and benzyl radical addition to O2 and their implications for kinetic modelling of toluene oxidation". United States. doi:10.1039/c7cp07779c. https://www.osti.gov/servlets/purl/1461435.
@article{osti_1461435,
title = {H-Abstraction reactions by OH, HO2, O, O2 and benzyl radical addition to O2 and their implications for kinetic modelling of toluene oxidation},
author = {Pelucchi, Matteo and Cavallotti, C. and Faravelli, T. and Klippenstein, S. J.},
abstractNote = {Here, alkylated aromatics constitute a significant fraction of the components commonly found in commercial fuels. Toluene is typically considered as a reference fuel. Together with n-heptane and iso-octane, it allows for realistic emulations of the behavior of real fuels by the means of surrogate mixture formulations. Moreover, it is a key precursor for the formation of poly-aromatic hydrocarbons, which are of relevance to understanding soot growth and oxidation mechanisms. In this study the POLIMI kinetic model is first updated based on the literature and on recent kinetic modelling studies of toluene pyrolysis and oxidation. Then, important reaction pathways are investigated by means of high-level theoretical methods, thereby advancing the present knowledge on toluene oxidation. H-Abstraction reactions by OH, HO2, O and O2, and the reactivity on the multi well benzyl-oxygen (C6H5CH2 + O2) potential energy surface (PES) were investigated using electronic structure calculations, transition state theory in its conventional, variational, and variable reaction coordinate forms (VRC-TST), and master equation calculations. Exploration of the effect on POLIMI model performance of literature rate constants and of the present calculations provides valuable guidelines for implementation of the new rate parameters in existing toluene kinetic models.},
doi = {10.1039/c7cp07779c},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = 16,
volume = 20,
place = {United States},
year = {2018},
month = {1}
}

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