Unraveling the low-temperature chemistry of ammonia is still an open challenge in combustion kinetics, yet of primary importance because of the novel combustion concepts operating in these conditions, as well as of the rising interest on ammonia as an energy carrier. In this work, a fundamental investigation of the H-abstraction reactions from H2NO by O2, NO2, NH2, and HO2 was performed. These reactions, which belong to the radical-radical abstraction class, associate a high sensitivity to the key low temperature ammonia combustion parameters, to a high uncertainty in rate constant values. Theoretically, the investigation of reactions belonging to this class is complicated by their intrinsic multireference nature. To address this issue, a structured theoretical methodology that relies heavily on the use of CASPT2 calculations was devised. The predicted rate constants highlighted significant deviations from the rates commonly adopted in the state-of-the-art mechanisms, most often based on analogies and estimations. In order to understand their impact on ammonia low-temperature kinetics, the obtained rates were integrated into a kinetic model, which was used to investigate ammonia oxidation and ignition at low-temperature and oxygen-rich conditions. It was found that O2 and NH2 play the major role, as abstractors, in regulating ammonia oxidation and ignition. In particular, ignition delay time predictions proved extremely sensitive to the adopted rates: modifying each of them within their theoretical uncertainty caused deviations by even an order of magnitude, and totally changed the predictive features of the mechanism. The kinetic analysis highlighted then the need of a targeted optimization of the critical rates, downstream of the present work and within their uncertainty boundaries, to further refine the mechanism capability over a wide range of operating conditions.
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