Atmospheric Oxidation Mechanism of Methyl Propionate
J. Phys. Chem. A, Vol. 104, No. 48, 2000 11317
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For conditions prevailing in polluted urban air masses the
dominant fate of the peroxy radicals will be reaction with NO
leading to alkoxy radicals as the major products with small
amounts of organic nitrates (7%). From the results presented
in sections 3.4-3.6 we recommend that for the purposes of
modeling oxidant formation in urban air masses, the atmospheric
chemistry of methyl propionate be represented as
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OH + CH3CH2C(O)OCH3 + 1.32 NO f 0.07 RONO2 +
0.32 HCHO + 0.23 HC(O)C(O)OCH3 + 0.93 HO2‚ +
0.32 CH3C(O)C(O)OCH3 + 0.09 CH3CHO +
0.09 CO2 + 0.17 CH3CH2C(O)OH + 0.17 CO +
0.12 CH3CH2C(O)OC(O)H + 1.25 NO2
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In the derivation of the above equation we assume that the 7%
organic nitrate yield is composed of 3% CH3CH2C(O)OCH2-
ONO2, 2% CH3CH(ONO2)C(O)OCH3, and 2% O2NOCH2-
CH2C(O)OCH3 and that the fate of ‚C(O)OCH3 radicals is
addition of O2, reaction with NO, and decomposition to give
CO2 and CH3O radicals. The overall reactivity of methyl
propionate toward OH radicals is low compared to conventional
solvents such as chlorocarbon aromatic and unsubstituted
hydrocarbon based solvents and the bulk of the oxidation of
methyl propionate produces multifunctional oxygenated com-
pounds such as HC(O)C(O)OCH3, CH3C(O)C(O)OCH3, and
CH3CH2C(O)OH which have a lower reactivity toward OH
radicals than the parent compound. Methyl propionate has a
low atmospheric reactivity with respect to oxidant formation.
Acknowledgment. F. Cavalli gratefully acknowledges the
European Commission for funding her research at the Bergische
Universita¨t Wuppertal within the framework of the Environ-
mental and Climate Research and the Specific RTD Programme.
Financial support within the fourth Framework Programme,
project EUROSOLV, is also gratefully achnowledged. T.J.W.
thanks the Alexander von Humboldt Foundation for an AvH
fellowship.
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