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.
- C2H2 + NO2
- Ab initio theory
- High pressure flow reactor
Marshall, P., Leung, C., Gimenez-Lopez, J., Rasmussen, C. T., Hashemi, H., Glarborg, P., ... Alzueta, M. U. (2019). The C2H2 + NO2 reaction: Implications for high pressure oxidation of C2H2/NOx mixtures. Proceedings of the Combustion Institute, 37(1), 469-476. https://doi.org/10.1016/j.proci.2018.06.202