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Title: Direct measurements of unimolecular and bimolecular reaction kinetics of the Criegee intermediate (CH3)2COO

Journal Article · · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
 [1];  [2];  [2];  [3];  [4];  [1];  [1];  [1];  [1];  [5];  [1];  [2];  [2];  [2];  [6];  [7];  [1];  [6];  [1];  [2]
  1. The Univ. of Bristol (United Kingdom)
  2. Sandia National Lab. (SNL-CA), Livermore, CA (United States)
  3. Sandia National Lab. (SNL-CA), Livermore, CA (United States); Univ. of Helsinki, Helsinki (Finland)
  4. Univ. of Southampton, Southampton (United Kingdom); The Hong Kong Polytechnic Univ., Hung Hom (Hong Kong)
  5. The Univ. of Bristol (United Kingdom); Univ. of Edinburgh (United Kingdom)
  6. The Univ. of Manchester, Manchester (United Kingdom)
  7. The Hong Kong Polytechnic Univ., Hung Hom (Hong Kong)
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Here, the Criegee intermediate acetone oxide, (CH3)2COO, is formed by laser photolysis of 2,2-diiodopropane in the presence of O2 and characterized by synchrotron photoionization mass spectrometry and by cavity ring-down ultraviolet absorption spectroscopy. The rate coefficient of the reaction of the Criegee intermediate with SO2 was measured using photoionization mass spectrometry and pseudo-first-order methods to be (7.3 ± 0.5) × 10–11 cm3 s–1 at 298 K and 4 Torr and (1.5 ± 0.5) × 10–10 cm3 s–1 at 298 K and 10 Torr (He buffer). These values are similar to directly measured rate coefficients of anti-CH3CHOO with SO2, and in good agreement with recent UV absorption measurements. The measurement of this reaction at 293 K and slightly higher pressures (between 10 and 100 Torr) in N2 from cavity ring-down decay of the ultraviolet absorption of (CH3)2COO yielded even larger rate coefficients, in the range (1.84 ± 0.12) × 10–10 to (2.29 ± 0.08) × 10–10 cm3 s–1. Photoionization mass spectrometry measurements with deuterated acetone oxide at 4 Torr show an inverse deuterium kinetic isotope effect, kH/kD = (0.53 ± 0.06), for reactions with SO2, which may be consistent with recent suggestions that the formation of an association complex affects the rate coefficient. The reaction of (CD3)2COO with NO2 has a rate coefficient at 298 K and 4 Torr of (2.1 ± 0.5) × 10–12 cm3 s–1 (measured with photoionization mass spectrometry), again similar to rate for the reaction of anti-CH3CHOO with NO2. Cavity ring-down measurements of the acetone oxide removal without added reagents display a combination of first- and second-order decay kinetics, which can be deconvolved to derive values for both the self-reaction of (CH3)2COO and its unimolecular thermal decay. The inferred unimolecular decay rate coefficient at 293 K, (305 ± 70) s–1, is similar to determinations from ozonolysis. The present measurements confirm the large rate coefficient for reaction of (CH3)2COO with SO2 and the small rate coefficient for its reaction with water. Product measurements of the reactions of (CH3)2COO with NO2 and with SO2 suggest that these reactions may facilitate isomerization to 2-hydroperoxypropene, possibly by subsequent reactions of association products.

Research Organization:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC04-94AL85000
OSTI ID:
1340693
Report Number(s):
SAND-2017-0648J; 650604
Journal Information:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Vol. 121, Issue 1; ISSN 1089-5639
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 74 works
Citation information provided by
Web of Science

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Cited By (22)

Theoretical Study of the Reaction of Carbonyl Oxide with Nitrogen Dioxide: CH 2 OO + NO 2 : THEORETICAL STUDY OF THE REACTION OF CARBONYL OXIDE WITH NITROGEN DIOXIDE journal August 2017
Catalysis and tunnelling in the unimolecular decay of Criegee intermediates journal January 2018
Experimental and computational studies of Criegee intermediate reactions with NH 3 and CH 3 NH 2 journal January 2019
Ozonolysis of 3-carene in the atmosphere. Formation mechanism of hydroxyl radical and secondary ozonides journal January 2019
Conformational preferences of Criegee intermediates: Isopropyl substituted carbonyl oxide journal August 2018
Products of Criegee intermediate reactions with NO 2 : experimental measurements and tropospheric implications journal January 2017
Tunneling effects in the unimolecular decay of (CH 3 ) 2 COO Criegee intermediates to OH radical products journal April 2017
The addition of methanol to Criegee intermediates journal January 2019
Unimolecular decay dynamics of Criegee intermediates: Energy-resolved rates, thermal rates, and their atmospheric impact journal December 2019
The atmospheric impacts of monoterpene ozonolysis on global stabilised Criegee intermediate budgets and SO 2 oxidation: experiment, theory and modelling journal January 2018
Unimolecular reaction of acetone oxide and its reaction with water in the atmosphere journal May 2018
Selective deuteration illuminates the importance of tunneling in the unimolecular decay of Criegee intermediates to hydroxyl radical products journal November 2017
Unimolecular decomposition kinetics of the stabilised Criegee intermediates CH 2 OO and CD 2 OO journal January 2018
Unimolecular decay strongly limits the atmospheric impact of Criegee intermediates journal January 2017
How does substitution affect the unimolecular reaction rates of Criegee intermediates? journal January 2017
Deep tunneling in the unimolecular decay of CH 3 CHOO Criegee intermediates to OH radical products journal December 2016
Structure-dependent reactivity of Criegee intermediates studied with spectroscopic methods journal January 2017
Kinetics of the reaction of the simplest Criegee intermediate with ammonia: a combination of experiment and theory journal January 2018
Calculation of the absolute photoionization cross-sections for C1–C4 Criegee intermediates and vinyl hydroperoxides journal April 2019
Measurements of a potential interference with laser-induced fluorescence measurements of ambient OH from the ozonolysis of biogenic alkenes journal January 2018
Criegee intermediates and their impacts on the troposphere journal January 2018
Evaluated kinetic and photochemical data for atmospheric chemistry: Volume VII – Criegee intermediates journal November 2020

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY