Direct Observation of the Gas-Phase Criegee Intermediate (CH2OO)

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• 作者：Craig A. Taatjes ; Giovanni Meloni ; Talitha M. Selby ; Adam J. Trevitt ; David L. Osborn ; Carl J. Percival ; Dudley E. Shallcross
• 刊名：Journal of the American Chemical Society
• 出版年：2008
• 出版时间：September 10, 2008
• 年：2008
• 卷：130
• 期：36
• 页码：11883-11885
• 全文大小：148K
• 年卷期：v.130,no.36(September 10, 2008)
• ISSN：1520-5126

文摘

Carbonyl oxide species play a key role in tropospheric oxidation of organic molecules and in low-temperature combustion processes. In the late 1940s, Criegee first postulated the participation of carbonyl oxides, now often called “Criegee intermediates,” in ozonolysis of alkenes. However, despite decades of effort, no gas phase Criegee intermediate has before been observed. As a result, knowledge of gas phase carbonyl oxide reactions has heretofore been inferred by indirect means, with derived rate coefficients spanning orders of magnitude. We have directly detected the primary Criegee intermediate, formaldehyde oxide (CH₂OO), in the chlorine-initiated gas-phase oxidation of dimethyl sulfoxide (DMSO). This work not only establishes that the Criegee intermediate is formed in DMSO oxidation also but opens the possibility for explicit kinetics studies on this critical atmospheric species.