Mechanism for the reaction of peroxymethylene with sulfur dioxide

Hatakeyama, Shiro; Kobayashi, Hiroshi; Lin, Zi Yu; Takagi, Hiroo; Akimoto, Hajime

doi:10.1021/j100408a059

Cited by 72 publications

(82 citation statements)

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“…Hatakeyama and coworkers [64,65] proposed that the Criegee intermediate formed an adduct with SO 2 (suggested by Martinez and Herron [66] to have the structure of a secondary ozonide), and that reaction of this adduct with a second molecule of sulphur dioxide was necessary to release SO 3 . However, experiments seemed to indicate that the rate coefficient for reaction of Criegee intermediates with SO 2 was small enough that its importance would be limited to polluted urban atmospheres: measurements of the dependence of OH yields from 2-methylbut-2-ene ozonolysis on the addition of SO 2 led Johnson et al [67] to an upper limit of 4 × 10 −15 cm 3 molecule −1 s −1 for the reaction of Criegee intermediates with SO 2 .…”

Section: Reaction With Somentioning

confidence: 99%

The physical chemistry of Criegee intermediates in the gas phase

Osborn

Taatjes

2015

International Reviews in Physical Chemistry

244

207

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Carbonyl oxides, also known as Criegee intermediates, are key intermediates in both gas phase ozonolysis of unsaturated hydrocarbons in the troposphere and solution phase organic synthesis via ozonolysis. Although the study of Criegee intermediates in both arenas has a long history, direct studies in the gas phase have only recently become possible through new methods of generating stabilised Criegee intermediates in sufficient quantities. This advance has catalysed a large number of new experimental and theoretical investigations of Criegee intermediate chemistry. In this article we review the physical chemistry of Criegee intermediates, focusing on their molecular structure, spectroscopy, unimolecular and bimolecular reactions. These recent results have overturned conclusions from some previous studies, while confirming others, and have clarified areas of investigation that will be critical targets for future studies. In addition to expanding our fundamental understanding of Criegee intermediates, the rapidly expanding knowledge base will support increasingly predictive models of their impacts on society.

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Section: Reaction With Somentioning

confidence: 99%

The physical chemistry of Criegee intermediates in the gas phase

Osborn

Taatjes

2015

International Reviews in Physical Chemistry

244

207

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“…Direct measurements, indirect determinations via measurements and computational calculations of specific CIs reaction rate coefficients with these various compounds span over several orders of magnitudes and must be thought to be extremely uncertain (e.g. Welz et al, 2012;Mauldin III et al, 2012;Johnson and Marston, 2008;Hatakeyama and Akimoto, 1994;Hatakeyama et al, 1986;Kurtén et al, 2011). Measurements of the reaction rate coefficients are often done under low pressure due to practical issues.…”

Section: Uncertaintiesmentioning

confidence: 99%

Oxidation of SO<sub>2</sub> by stabilized Criegee intermediate (sCI) radicals as a crucial source for atmospheric sulfuric acid concentrations

et al. 2013

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Abstract. The effect of increased reaction rates of stabilized Criegee intermediates (sCIs) with SO2 to produce sulfuric acid is investigated using data from two different locations, SMEAR II, Hyytiälä, Finland, and Hohenpeissenberg, Germany. Results from MALTE, a zero-dimensional model, show that using previous values for the rate coefficients of sCI + SO2, the model underestimates gas phase H2SO4 by up to a factor of two when compared to measurements. Using the rate coefficients recently calculated by Mauldin et al. (2012) increases sulfuric acid by 30–40%. Increasing the rate coefficient for formaldehyde oxide (CH2OO) with SO2 according to the values recommended by Welz et al. (2012) increases the H2SO4 yield by 3–6%. Taken together, these increases lead to the conclusion that, depending on their concentrations, the reaction of stabilized Criegee intermediates with SO2 could contribute as much as 33–46% to atmospheric sulfuric acid gas phase concentrations at ground level. Using the SMEAR II data, results from SOSA, a one-dimensional model, show that the contribution from sCI reactions to sulfuric acid production is most important in the canopy, where the concentrations of organic compounds are the highest, but can have significant effects on sulfuric acid concentrations up to 100 m. The recent findings that the reaction of sCI + SO2 is much faster than previously thought together with these results show that the inclusion of this new oxidation mechanism could be crucial in regional as well as global models.

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“…activated CI can also dissipate their energy to the bath gas and become collisionally stabilized. [5][6][7] Alternatively, the CI can be formed with less nascent internal energy; their longer lifetime allows them to attain a thermal energy distribution prior to reaction. Such CI with a thermal energy content, i.e.…”

Section: Introductionmentioning

confidence: 99%