Yang Jie-Ning, Takahashi Kaito, Lin Jim Jr-Min
Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 10617, Taiwan.
Department of Chemistry, National Taiwan University, Taipei 10617, Taiwan.
J Phys Chem A. 2022 Sep 15;126(36):6160-6170. doi: 10.1021/acs.jpca.2c04596. Epub 2022 Aug 31.
This work investigated the reaction kinetics of HNO with four Criegee intermediates (CIs): CHOO, (CH)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, (3.54 ± 1.06) × 10, (3.93 ± 1.18) × 10, and (3.0 ± 1.0) × 10 cm s for reactions of HNO with CHOO, (CH)COO, -MVKO, and -MACRO, respectively. This is consistent with previous results for the reactions between CIs and carboxylic acids, but the rate coefficient of CHOO + HNO in the literature [Foreman 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 reactions with CHOO and (CH)COO under 100-400 Torr. Our results indicate that in a dry area with severe NO pollution, the reactions of CIs with HNO and their products may be worthy of attention, but these reactions may be insignificant under high-humidity conditions. However, CI reactions with HNO may not play an important role in the atmospheric removal processes of HNO because of the low concentrations of CIs.
本研究考察了HNO与四种Criegee中间体（CIs）：CHOO、(CH)COO、甲基乙烯基酮氧化物（MVKO）和甲基丙烯醛氧化物（MACRO）的反应动力学。我们的结果表明，这些反应极快，HNO与CHOO、(CH)COO、-MVKO和-MACRO反应的速率系数分别为(1.51 ± 0.45) × 10、(3.54 ± 1.06) × 10、(3.93 ± 1.18) × 10和(3.0 ± 1.0) × 10 cm³ s⁻¹。这与之前关于CIs与羧酸反应的结果一致，但发现文献[Foreman 2016, 128, 10575]中CHOO + HNO的速率系数被高估了3.6倍。此外，在100 - 400 Torr压力下，我们未观察到HNO与CHOO和(CH)COO反应有任何显著的压力依赖性。我们的结果表明，在NO污染严重的干燥地区，CIs与HNO及其产物的反应可能值得关注，但在高湿度条件下这些反应可能微不足道。然而，由于CIs浓度较低，CIs与HNO的反应在HNO的大气去除过程中可能不发挥重要作用。
