4.7 Article

On the photolysis branching ratio of methyl ethyl ketone

期刊

ATMOSPHERIC ENVIRONMENT
卷 254, 期 -, 页码 -

出版社

PERGAMON-ELSEVIER SCIENCE LTD
DOI: 10.1016/j.atmosenv.2021.118383

关键词

Methyl ethyl ketone (MEK); Photolysis branching ratio; End product study; Master chemical mechanism (MCM)

资金

  1. Natural Sciences and Engineering Research Council of Canada (NSERC) [RGPIN/03849-2016]

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The methyl ethyl ketone photolysis branching ratio was re-evaluated through end product analysis and box model simulations. The experimental results indicated that the product distribution observed was consistent with current IUPAC recommendations under certain conditions.
The methyl ethyl ketone (MEK) photolysis branching ratio (alpha) was re-evaluated by an end product analysis and box model simulations with the Master Chemical Mechanism (MCM). Using light emitting diodes centered at 285 nm or 315 nm, MEK was irradiated in the presence of nitric oxide and oxygen to produce peroxyacetic and peroxypropanoic nitric anhydride, CH3C(O)O2NO2 (PAN) and C2H5C(O)O2NO2 (PPN), which were quantified by gas chromatography. Box model simulations indicated that PPN is partially produced as a secondary product from chemistry initiated by reaction of the hydroxyl radical (OH) with MEK. Under NOx-limited experimental conditions or in the presence of ethane as an OH quencher, the product distribution observed required alpha = (7 +/- 1)% + (1.1 +/- 0.7) x 10-4 x (T-298) for 250K < T 300K (2 sigma uncertainty), independent of pressure (at pressures 266 hPa) and consistent with current IUPAC recommendations.

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