Reaction Kinetics of Criegee Intermediates with Nitric Acid

This work investigated the reaction kinetics of HNO₃ with four Criegee intermediates (CIs): CH₂OO, (CH₃)₂COO, methyl vinyl ketone oxide (MVKO), and methacrolein oxide (MACRO). Our results show that these reactions are extremely fast with rate coefficients of (1.51 ± 0.45) × 10^-10, (3.54 ± 1.06) × 10^-10, (3.93 ± 1.18) × 10^-10, and (3.0 ± 1.0) × 10^-10 cm³ s^-1 for reactions of HNO₃ with CH₂OO, (CH₃)₂COO, syn-MVKO, and anti-MACRO, respectively. This is consistent with previous results for the reactions between CIs and carboxylic acids, but the rate coefficient of CH₂OO + HNO₃ in the literature [Foreman Angew. Chem. 2016, 128, 10575] was found to be overestimated by a factor of 3.6. In addition, we did not observe any significant pressure dependence in the HNO₃ reactions with CH₂OO and (CH₃)₂COO under 100-400 Torr. Our results indicate that in a dry area with severe NO_x pollution, the reactions of CIs with HNO₃ and their products may be worthy of attention, but these reactions may be insignificant under high-humidity conditions. However, CI reactions with HNO₃ may not play an important role in the atmospheric removal processes of HNO₃ because of the low concentrations of CIs.