4.6 Article

Experimental and computational studies of Criegee intermediate reactions with NH3 and CH3NH2 Electronic supplementary information (ESI) available. See DOI: 10.1039/c8cp06810k

Journal

PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Volume 21, Issue 26, Pages 14042-14052

Publisher

ROYAL SOC CHEMISTRY
DOI: 10.1039/c8cp06810k

Keywords

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Funding

  1. Natural Environment Research Council (NERC) [NE/K004905/1, NE/P013104/1]
  2. Marie Sklodowska-Curie Individual Fellowship HOMER [702794]
  3. US Air Force Office of Scientific Research (AFOSR) [FA9550-16-1-0051]
  4. National Aeronautics and Space Administration (NASA)
  5. Upper Atmosphere Research and Tropospheric Chemistry programs
  6. Office of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences, United States Department of Energy
  7. U.S. Department of Energy's National Nuclear Security Administration [DE-NA0003525]
  8. Office of Science, Office of Basic Energy Sciences, U.S. Department of Energy [DE-AC02-05CH11231]
  9. NERC [NE/P013104/1, NE/K004905/1, NE/J009008/1, NE/I014381/1] Funding Source: UKRI
  10. Marie Curie Actions (MSCA) [702794] Funding Source: Marie Curie Actions (MSCA)

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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)(2)COO) with NH3 and CH3NH2 were measured using cavity ring-down spectroscopy. Temperature-dependent rate coefficients, k(CH2OO + NH3) = (3.1 +/- 0.5) x 10(-20)T(2) exp(1011 +/- 48/T) cm(3) s(-1) and k(CH2OO + CH3NH2) = (5 +/- 2) x 10(-19)T(2) exp(1384 +/- 96/T) cm(3) 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 (N-2) range, and average rate coefficients k(CH2OO + NH3) = (8.4 +/- 1.2) x 10(-14) cm(3) s(-1) and k(CH2OO + CH3NH2) = (5.6 +/- 0.4) x 10(-12) cm(3) s(-1) were deduced at 293 K. An upper limit of <= 2.7 x 10(-15) cm(3) s(-1) was estimated for the rate coefficient of the (CH3)(2)COO + NH3 reaction. Complementary measurements were performed with mass spectrometry using synchrotron radiation photoionization giving k(CH2OO + CH3NH2) = (4.3 +/- 0.5) x 10(-12) cm(3) 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.

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