The C2H2 + NO2 reaction: Implications for high pressure oxidation of C2H2/NOx mixtures

Paul Marshall*, Caroline Leung, Jorge Gimenez-Lopez, Christian T. Rasmussen, Hamid Hashemi, Peter Glarborg, Maria Abian, Maria U. Alzueta

*Corresponding author for this work

Research output: Contribution to journalJournal articleResearchpeer-review

Abstract

The reaction of C2H2 with NO2 has been studied theoretically. It is a complex overall reaction with multiple wells and multiple product channels. The calculated rate constant for the preferred channel, formation of a CHOCHON adduct, is compatible with the only experimental determination. The CHOCHON adduct is assumed to dissociate rapidly to form the triplet carbene CHCHO and NO. An experimental and kinetic modeling study of the interaction between C2H2, O2 and NOx was performed under flow reactor conditions in the intermediate temperature range (600–900 K), high pressure (50–60 bar), and for stoichiometries ranging from reducing to strongly oxidizing. The results show that presence of NOx serves both to sensitize and inhibit oxidation of C2H2. Calculations with a detailed chemical kinetic model, partly established in the present work, confirm that C2H2 + NO2 is the major initiation step, as well as the major sensitizing reaction. This reaction converts NO2 to NO, which is then partly converted to HCN by reaction with C2H3 and CHCHOH. The latter reactions are both chain terminating and serve as the major inhibiting steps.
Original languageEnglish
JournalProceedings of the Combustion Institute
Volume37
Issue number1
Pages (from-to)469-476
ISSN1540-7489
DOIs
Publication statusPublished - 2019

Keywords

  • C2H2 + NO2
  • Ab initio theory
  • High pressure flow reactor
  • Sensitization

Cite this

Marshall, Paul ; Leung, Caroline ; Gimenez-Lopez, Jorge ; Rasmussen, Christian T. ; Hashemi, Hamid ; Glarborg, Peter ; Abian, Maria ; Alzueta, Maria U. / The C2H2 + NO2 reaction: Implications for high pressure oxidation of C2H2/NOx mixtures. In: Proceedings of the Combustion Institute. 2019 ; Vol. 37, No. 1. pp. 469-476.
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title = "The C2H2 + NO2 reaction: Implications for high pressure oxidation of C2H2/NOx mixtures",
abstract = "The reaction of C2H2 with NO2 has been studied theoretically. It is a complex overall reaction with multiple wells and multiple product channels. The calculated rate constant for the preferred channel, formation of a CHOCHON adduct, is compatible with the only experimental determination. The CHOCHON adduct is assumed to dissociate rapidly to form the triplet carbene CHCHO and NO. An experimental and kinetic modeling study of the interaction between C2H2, O2 and NOx was performed under flow reactor conditions in the intermediate temperature range (600–900 K), high pressure (50–60 bar), and for stoichiometries ranging from reducing to strongly oxidizing. The results show that presence of NOx serves both to sensitize and inhibit oxidation of C2H2. Calculations with a detailed chemical kinetic model, partly established in the present work, confirm that C2H2 + NO2 is the major initiation step, as well as the major sensitizing reaction. This reaction converts NO2 to NO, which is then partly converted to HCN by reaction with C2H3 and CHCHOH. The latter reactions are both chain terminating and serve as the major inhibiting steps.",
keywords = "C2H2 + NO2 , Ab initio theory, High pressure flow reactor, Sensitization",
author = "Paul Marshall and Caroline Leung and Jorge Gimenez-Lopez and Rasmussen, {Christian T.} and Hamid Hashemi and Peter Glarborg and Maria Abian and Alzueta, {Maria U.}",
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The C2H2 + NO2 reaction: Implications for high pressure oxidation of C2H2/NOx mixtures. / Marshall, Paul; Leung, Caroline; Gimenez-Lopez, Jorge; Rasmussen, Christian T.; Hashemi, Hamid; Glarborg, Peter; Abian, Maria; Alzueta, Maria U.

In: Proceedings of the Combustion Institute, Vol. 37, No. 1, 2019, p. 469-476.

Research output: Contribution to journalJournal articleResearchpeer-review

TY - JOUR

T1 - The C2H2 + NO2 reaction: Implications for high pressure oxidation of C2H2/NOx mixtures

AU - Marshall, Paul

AU - Leung, Caroline

AU - Gimenez-Lopez, Jorge

AU - Rasmussen, Christian T.

AU - Hashemi, Hamid

AU - Glarborg, Peter

AU - Abian, Maria

AU - Alzueta, Maria U.

PY - 2019

Y1 - 2019

N2 - The reaction of C2H2 with NO2 has been studied theoretically. It is a complex overall reaction with multiple wells and multiple product channels. The calculated rate constant for the preferred channel, formation of a CHOCHON adduct, is compatible with the only experimental determination. The CHOCHON adduct is assumed to dissociate rapidly to form the triplet carbene CHCHO and NO. An experimental and kinetic modeling study of the interaction between C2H2, O2 and NOx was performed under flow reactor conditions in the intermediate temperature range (600–900 K), high pressure (50–60 bar), and for stoichiometries ranging from reducing to strongly oxidizing. The results show that presence of NOx serves both to sensitize and inhibit oxidation of C2H2. Calculations with a detailed chemical kinetic model, partly established in the present work, confirm that C2H2 + NO2 is the major initiation step, as well as the major sensitizing reaction. This reaction converts NO2 to NO, which is then partly converted to HCN by reaction with C2H3 and CHCHOH. The latter reactions are both chain terminating and serve as the major inhibiting steps.

AB - The reaction of C2H2 with NO2 has been studied theoretically. It is a complex overall reaction with multiple wells and multiple product channels. The calculated rate constant for the preferred channel, formation of a CHOCHON adduct, is compatible with the only experimental determination. The CHOCHON adduct is assumed to dissociate rapidly to form the triplet carbene CHCHO and NO. An experimental and kinetic modeling study of the interaction between C2H2, O2 and NOx was performed under flow reactor conditions in the intermediate temperature range (600–900 K), high pressure (50–60 bar), and for stoichiometries ranging from reducing to strongly oxidizing. The results show that presence of NOx serves both to sensitize and inhibit oxidation of C2H2. Calculations with a detailed chemical kinetic model, partly established in the present work, confirm that C2H2 + NO2 is the major initiation step, as well as the major sensitizing reaction. This reaction converts NO2 to NO, which is then partly converted to HCN by reaction with C2H3 and CHCHOH. The latter reactions are both chain terminating and serve as the major inhibiting steps.

KW - C2H2 + NO2

KW - Ab initio theory

KW - High pressure flow reactor

KW - Sensitization

U2 - 10.1016/j.proci.2018.06.202

DO - 10.1016/j.proci.2018.06.202

M3 - Journal article

VL - 37

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SN - 1540-7489

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