Direct detection of OH formation in the reactions of HO2 with CH3C(O)O2 and other substituted peroxy radicals T. J. Dillon and J. N. Crowley Max-Planck-Institut für Chemie (Otto-Hahn-Institut) Joh.-Joachim-Becher-Weg 27, 55128 Mainz, Germany
Abstract. This work details the first direct observation of OH as a product from (R1):
HO2+CH3C(O)O2→(products), which has generally been
considered an atmospheric radical termination process. The technique of
pulsed laser photolysis radical generation, coupled to calibrated laser
induced fluorescence detection was used to measure an OH product yield for
(R1) of α1(298 K)=(0.5±0.2). This study of (R1)
included the measurement of a rate coefficient k1(298 K)=(1.4±0.5)×10−11cm3 molecule−1 s−1, substantially
reducing the uncertainties in modelling this important atmospheric reaction.
OH was also detected as a product from the reactions of HO2 with three
other carbonyl-containing peroxy radicals, albeit at smaller yield, e.g. (R2):
HO2+CH3C(O)CH2O2→(products), α2≈0.15. By contrast, OH was not observed (α<0.06)
as a major product from reactions where carbonyl functionality was absent,
e.g. HO2+HOCH2CH2O2 (R8), and HO2+CH3CH(OH)CH2O2 (R9).
Citation: Dillon, T. J. and Crowley, J. N.: Direct detection of OH formation in the reactions of HO2 with CH3C(O)O2 and other substituted peroxy radicals, Atmos. Chem. Phys., 8, 4877-4889, doi:10.5194/acp-8-4877-2008, 2008.