(73c) A Computational Investigation into the Kinetics of NO + CH2CCH and Its Effect on NO Reduction
AIChE Annual Meeting
2018
2018 AIChE Annual Meeting
Catalysis and Reaction Engineering Division
Combustion Kinetics and Emissions
Monday, October 29, 2018 - 8:44am to 9:06am
A computational investigation into the kinetics of the NO + CH2CCH reaction is presented. The stationary points on the C3H3N1O1 potential energy surface are analyzed using the high-accuracy compound method ANL0, with key regions of the potential energy surface computed using multi-reference methods. The temperature- and pressure-dependent rate constants are computed using the RRKM/Master Equation. The results reveal multiple pathways that enable the reduction of NO (and oxidation of CH2CCH) with the dominant bimolecular products being CH2CO + HCN and CO + CH3CN. Additional calculations for the thermal decomposition of an unimolecular intermediate, isoxazole, are in good agreement with the available experimental data.
The new rate constants are implemented in a detailed chemical kinetic mechanism, taken from literature, for the oxidation of C2H4 by O2 + NO. Additional propargyl formation reactions were also included from a recently developed kinetic mechanism. Analysis of a constant temperature, constant pressure batch reaction suggests that NO + CH2CCH accounts for a significant portion of the total NO chemistry at lower temperatures under fuel-rich conditions. Accordingly, this reaction could be an important pathway for both NO reduction and CH2CCH oxidation in reburn chemistry.