A theoretical kinetic study of the reactions of NH2 radicals with methanol and ethanol and their implications in kinetic modeling

Abstract

AbstractAmino (NH2) radicals play a central role in the pyrolysis and oxidation of ammonia. Several reports in the literature highlight the importance of the reactions of NH2 radicals with fuel in NH3‐dual‐fuel combustion. Therefore, we investigated the reactions of NH2 radicals with methanol (CH3OH) and ethanol (C2H5OH) theoretically. We explored the various reaction pathways by exploiting CCSD(T)/cc‐pV(T, Q)Z//M06‐2X/aug‐cc‐pVTZ level of theory. The reaction proceeds via complex formation at the entrance and exit channels in an overall exothermic process. We used canonical transition state theory to obtain the high‐pressure limiting rate coefficients for various channels over the temperature range of 300–2000 K. We discerned the role of various channels in the potential energy surface (PES) of NH2 + CH3OH/C2H5OH reactions. For both reactions, the hydrogen abstraction pathway at the OH‐site of alcohols plays a minor role in the entire T‐range investigated. By including the title reactions into an extensive kinetic model, we demonstrated that the reaction of NH2 radicals with alcohols plays a paramount role in accurately predicting the low‐temperature oxidation kinetics of NH3‐alcohols dual fuel systems (e.g., shortening the ignition delay time). On the contrary, these reactions have negligible importance for high‐temperature oxidation kinetics of NH3‐alcohol blends (e.g., not affecting the laminar flame speed). In addition, we calculated the rate coefficients for NH2 + CH4 = CH3 + NH3 reaction that are in excellent agreement with the experimental data.