Reaction Kinetics of Criegee Intermediates with Nitric Acid.

This work investigated the reaction kinetics of HNO 3 with four Criegee intermediates (CIs): CH 2 OO, (CH 3 ) 2 COO, 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 cm 3 s -1 for reactions of HNO 3 with CH 2 OO, (CH 3 ) 2 COO, 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 CH 2 OO + HNO 3 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 HNO 3 reactions with CH 2 OO and (CH 3 ) 2 COO under 100-400 Torr. Our results indicate that in a dry area with severe NO x pollution, the reactions of CIs with HNO 3 and their products may be worthy of attention, but these reactions may be insignificant under high-humidity conditions. However, CI reactions with HNO 3 may not play an important role in the atmospheric removal processes of HNO 3 because of the low concentrations of CIs.