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Issue 26, 2019
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Experimental and computational studies of Criegee intermediate reactions with NH3 and CH3NH2

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Ammonia and amines are emitted into the troposphere by various natural and anthropogenic sources, where they have a significant role in aerosol formation. Here, we explore the significance of their removal by reaction with Criegee intermediates, which are produced in the troposphere by ozonolysis of alkenes. Rate coefficients for the reactions of two representative Criegee intermediates, formaldehyde oxide (CH2OO) and acetone oxide ((CH3)2COO) with NH3 and CH3NH2 were measured using cavity ring-down spectroscopy. Temperature-dependent rate coefficients, k(CH2OO + NH3) = (3.1 ± 0.5) × 10−20T2 exp(1011 ± 48/T) cm3 s−1 and k(CH2OO + CH3NH2) = (5 ± 2) × 10−19T2 exp(1384 ± 96/T) cm3 s−1 were obtained in the 240 to 320 K range. Both the reactions of CH2OO were found to be independent of pressure in the 10 to 100 Torr (N2) range, and average rate coefficients k(CH2OO + NH3) = (8.4 ± 1.2) × 10−14 cm3 s−1 and k(CH2OO + CH3NH2) = (5.6 ± 0.4) × 10−12 cm3 s−1 were deduced at 293 K. An upper limit of ≤2.7 × 10−15 cm3 s−1 was estimated for the rate coefficient of the (CH3)2COO + NH3 reaction. Complementary measurements were performed with mass spectrometry using synchrotron radiation photoionization giving k(CH2OO + CH3NH2) = (4.3 ± 0.5) × 10−12 cm3 s−1 at 298 K and 4 Torr (He). Photoionization mass spectra indicated production of NH2CH2OOH and CH3N(H)CH2OOH functionalized organic hydroperoxide adducts from CH2OO + NH3 and CH2OO + CH3NH2 reactions, respectively. Ab initio calculations performed at the CCSD(T)(F12*)/cc-pVQZ-F12//CCSD(T)(F12*)/cc-pVDZ-F12 level of theory predicted pre-reactive complex formation, consistent with previous studies. Master equation simulations of the experimental data using the ab initio computed structures identified submerged barrier heights of −2.1 ± 0.1 kJ mol−1 and −22.4 ± 0.2 kJ mol−1 for the CH2OO + NH3 and CH2OO + CH3NH2 reactions, respectively. The reactions of NH3 and CH3NH2 with CH2OO are not expected to compete with its removal by reaction with (H2O)2 in the troposphere. Similarly, losses of NH3 and CH3NH2 by reaction with Criegee intermediates will be insignificant compared with reactions with OH radicals.

Graphical abstract: Experimental and computational studies of Criegee intermediate reactions with NH3 and CH3NH2

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Supplementary files

Article information

02 Nov 2018
08 Jan 2019
First published
08 Jan 2019

Phys. Chem. Chem. Phys., 2019,21, 14042-14052
Article type
Author version available

Experimental and computational studies of Criegee intermediate reactions with NH3 and CH3NH2

R. Chhantyal-Pun, R. J. Shannon, D. P. Tew, R. L. Caravan, M. Duchi, C. Wong, A. Ingham, C. Feldman, M. R. McGillen, M. A. H. Khan, I. O. Antonov, B. Rotavera, K. Ramasesha, D. L. Osborn, C. A. Taatjes, C. J. Percival, D. E. Shallcross and A. J. Orr-Ewing, Phys. Chem. Chem. Phys., 2019, 21, 14042
DOI: 10.1039/C8CP06810K

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