Exploring the reaction kinetics of methyl formate + NO2: implication for ignition behavior of methyl formate/NO2 mixtures

Abstract

The reaction pathways and potential energy profiles are theoretically explored for H-abstraction, addition and addition–dissociation reactions of methyl formate (MF, HC(O)OCH₃) + NO₂ using the high level quantum chemical compound method CCSD(T)/cc-pVxZ(x = T, Q)//M062X/6-311+G(2df,2p). Notably, three different HNO₂ isomers (cis-HONO, trans-HONO and HNO₂) are all considered in each reaction pathway. The corresponding temperature- and pressure-dependent rate constants are then computed by RRKM/ME simulations with one-dimensional hindered rotor approximation and asymmetric Eckart tunneling corrections. The calculations show that the rate constants are pressure independent. Although trans-HONO is the most stable HNO₂ isomer, the results reveal that the dominant channels are cis-HONO + HC(O)OCH₂/C(O)OCH₃ and cis-HC(O)(ONO)OCH₃ for the H-abstraction and addition, respectively. Moreover, the lowest energy barrier for the H-abstraction channel (cis-abs) is 11.2 kcal mol⁻¹ lower than the addition channel (cis-add), and thus the addition channel is less kinetically favored. The computed rate constants for the MF + NO₂ reaction are then incorporated into a kinetic model and the importance of the title reaction in predicting the ignition behavior of MF/NO₂ mixtures is demonstrated by kinetic modeling. The detailed reaction kinetics in this work will be helpful for kinetic model development of other ester-based fuels.