Publication Date:
2013-04-13
Description:
Although carbonyl oxides, "Criegee intermediates," have long been implicated in tropospheric oxidation, there have been few direct measurements of their kinetics, and only for the simplest compound in the class, CH2OO. Here, we report production and reaction kinetics of the next larger Criegee intermediate, CH3CHOO. Moreover, we independently probed the two distinct CH3CHOO conformers, syn- and anti-, both of which react readily with SO2 and with NO2. We demonstrate that anti-CH3CHOO is substantially more reactive toward water and SO2 than is syn-CH3CHOO. Reaction with water may dominate tropospheric removal of Criegee intermediates and determine their atmospheric concentration. An upper limit is obtained for the reaction of syn-CH3CHOO with water, and the rate constant for reaction of anti-CH3CHOO with water is measured as 1.0 x 10(-14) +/- 0.4 x 10(-14) centimeter(3) second(-1).〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Taatjes, Craig A -- Welz, Oliver -- Eskola, Arkke J -- Savee, John D -- Scheer, Adam M -- Shallcross, Dudley E -- Rotavera, Brandon -- Lee, Edmond P F -- Dyke, John M -- Mok, Daniel K W -- Osborn, David L -- Percival, Carl J -- New York, N.Y. -- Science. 2013 Apr 12;340(6129):177-80. doi: 10.1126/science.1234689.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Combustion Research Facility, Sandia National Laboratories, Livermore, CA 94551-0969, USA. cataatj@sandia.gov〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/23580524" target="_blank"〉PubMed〈/a〉
Print ISSN:
0036-8075
Electronic ISSN:
1095-9203
Topics:
Biology
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Chemistry and Pharmacology
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Computer Science
,
Medicine
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Natural Sciences in General
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Physics
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