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Titel |
Temperature dependent rate coefficients for the reactions of Criegee biradicals with selected alcohols and sulphides |
VerfasserIn |
Max McGillen, Laura McMahon, Basile Curchod, Dudley Shallcross, Andrew Orr-Ewing |
Konferenz |
EGU General Assembly 2017
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Medientyp |
Artikel
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Sprache |
en
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Digitales Dokument |
PDF |
Erschienen |
In: GRA - Volume 19 (2017) |
Datensatznummer |
250146115
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Publikation (Nr.) |
EGU/EGU2017-10117.pdf |
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Zusammenfassung |
The reactions of Criegee biradicals have received much attention in recent years, yet few
reactive systems have undergone direct experimental measurement, and fewer still have been
measured as a function of temperature.
In this study, absolute temperature-dependent rate coefficients for the gas-phase reactions of a
suite of alcohols and sulphides with both formaldehyde oxide (CH2OO) and acetone oxide
((CH3)2COO) are determined experimentally between 254 and 328 K using cavity ringdown
spectroscopy for detecting Criegee biradicals. Major differences in reactivity and
temperature dependence are observed both in terms of the functionality (between
alcohols and sulphides) and also the degree of alkyl substitution about the Criegee
biradical.
This diverse behaviour represents a uniquely challenging problem for atmospheric chemistry
since the atmosphere contains a large variety of both functionalized compounds and Criegee
biradicals, leading to a formidable parameter space which may be impossible to cover
experimentally. Notwithstanding, new experimental data such as these are vital
for understanding the general behaviour of Criegee biradicals in the atmosphere. |
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