Detailed kinetic mechanism of CH3 + NP reaction on a theoretical study

Abstract

Bio-fuels (e.g., bio-ethanol, bio-diesel and bio-butanol) - the alternative to petroleumbased transportation fuels, have been received much attention as a renewable source of energy. The current discussion mainly focuses on solving their negative impact (e.g., polluted gases exhaustion) into the environment, which idealizes the bio-fuel usage. Herein, the understanding of CH3 + NO reaction, which plays an important role in reducing nitrogen emission during bio-fuel combustion, is of our interest. Accurate calculations at different levels of theory (e.g., W1U and CBS-QB3) have been performed to construct reliable reaction mechanism in which addition of CH3 to either N and O sites of NO can proceed through three accessible pathways, leading to multi and complicated reaction channels, then formed a variety of products. The HCN + H2O product was the most thermodynamically favorable channel while the NCOH + H2 is the least one. The calculated thermodynamic properties for species involved, with hindered rotation correction explicitly, are in good agreement with previous calculated and experimental data. In addition, the complete detailed kinetic analyses were carried out within the eigenpair master equation/Rice-Ramsperger-Kassel- Marcus (ME/RRKM) framework. The product branching ratios at different conditions were also examined. The detailed kinetic model of this title reaction is recommended to be used for detailed modeling of fuel combustion in an attempt to optimize the engine performance and reduce polluted emitted gases from alternate fuel combustion. Keywords: combustion, thermodynamics, kinetics, W1U, isomers, CBS – QB3.