A Theoretical Study of NH2 Radical Reactions with Propane and Its Kinetic Implications in NH3-Propane Blends’ Oxidation

Abstract

The reaction of NH2 radicals with C3H8 is crucial for understanding the combustion behavior of NH3/C3H8 blends. In this study, we investigated the temperature dependence of the rate coefficients for the hydrogen abstraction reactions of C3H8 by NH2 radicals using high-level theoretical approaches. The potential energy surface was constructed at the CCSD(T)/cc-pV(T, Q)//M06-2X/aug-cc-pVTZ level of theory, and the rate coefficients were computed using conventional transition state theory, incorporating the corrections for quantum tunneling and hindered internal rotors (HIR). The computed rate coefficients showed a strong curvature in the Arrhenius behavior, capturing the experimental literature data well at low temperatures. However, at T > 1500 K, the theory severely overpredicted the experimental data. The available theoretical studies did not align with the experiment at high temperatures, and the possible reasons for this discrepancy are discussed. At 300 K, the reaction of NH2 with C3H8 predominantly occurs at the secondary C-H site, which accounts for approximately 95% of the total reaction flux. However, the hydrogen abstraction reaction at the primary C-H site becomes the dominant reaction above 1700 K. A composite kinetic model was built, which incorporated the computed rate coefficients for NH2 + C3H8 reactions. The importance of NH2 + C3H8 reactions in predicting the combustion behavior of NH3/C3H8 blends was demonstrated by kinetic modeling.