title: CH3CO + O2 + M (M = He, N2) Reaction Rate Coefficient Measurements and Implications for the OH Radical Product Yield.
abstract: The gas-phase CH3CO + O2 reaction is known to proceed via a chemical activation mechanism leading to the formation of OH and CH3C(O)OO radicals via bimolecular and termolecular reactive channels, respectively. In this work, rate coefficients, k, for the CH3CO + O2 reaction were measured over a range of temperature (241-373 K) and pressure (0.009-600 Torr) with He and N2 as the bath gas and used to characterize the bi- and ter-molecular reaction channels. Three independent experimental methods (pulsed laser photolysis-laser-induced fluorescence (PLP-LIF), pulsed laser photolysis-cavity ring-down spectroscopy (PLP-CRDS), and a very low-pressure reactor (VLPR)) were used to characterize k(T,M). PLP-LIF was the primary method used to measure k(T,M) in the high-pressure regime under pseudo-first-order conditions. CH3CO was produced by PLP, and LIF was used to monitor the OH radical bimolecular channel reaction product. CRDS, a complementary high-pressure method, measured k(295 K,M) over the pressure range 25-600 Torr (He) by monitoring the temporal CH3CO radical absorption following its production via PLP in the presence of excess O2. The VLPR technique was used in a relative rate mode to measure k(296 K,M) in the low-pressure regime (9-32 mTorr) with CH3CO + Cl2 used as the reference reaction. A kinetic mechanism analysis of the combined kinetic data set yielded a zero pressure limit rate coefficient, kint(T), of (6.4 ± 4) × 10(-14) exp((820 ± 150)/T) cm(3) molecule(-1) s(-1) (with kint(296 K) measured to be (9.94 ± 1.3) × 10(-13) cm(3) molecule(-1) s(-1)), k0(T) = (7.39 ± 0.3) × 10(-30) (T/300)(-2.2±0.3) cm(6) molecule(-2) s(-1), and k∞(T) = (4.88 ± 0.05) × 10(-12) (T/300)(-0.85±0.07) cm(3) molecule(-1) s(-1) with Fc = 0.8 and M = N2. A He/N2 collision efficiency ratio of 0.60 ± 0.05 was determined. The phenomenological kinetic results were used to define the pressure and temperature dependence of the OH radical yield in the CH3CO + O2 reaction. The present results are compared with results from previous studies and the discrepancies are discussed.
authors: †Earth System Research Laboratory, Chemical Sciences Division, National Oceanic and Atmospheric Administration, 325 Broadway, Boulder, Colorado 80305, United States.|‡Cooperative Institute for Research in Environmental Sciences, Colorado University, 216 UCB, Boulder, Colorado 80309, United States.|§Laboratory of Photochemistry and Chemical Kinetics, Department of Chemistry, University of Crete, Vassilika Vouton, 71003 Heraklion, Crete, Greece.
authors: Vassileios C
authors: VC
authors: Papadimitriou
authors: §Laboratory of Photochemistry and Chemical Kinetics, Department of Chemistry, University of Crete, Vassilika Vouton, 71003 Heraklion, Crete, Greece.
authors: Emmanuel S
authors: ES
authors: Karafas
authors: †Earth System Research Laboratory, Chemical Sciences Division, National Oceanic and Atmospheric Administration, 325 Broadway, Boulder, Colorado 80305, United States.|‡Cooperative Institute for Research in Environmental Sciences, Colorado University, 216 UCB, Boulder, Colorado 80309, United States.
authors: Tomasz
authors: T
authors: Gierczak
authors: †Earth System Research Laboratory, Chemical Sciences Division, National Oceanic and Atmospheric Administration, 325 Broadway, Boulder, Colorado 80305, United States.
authors: James B
authors: JB
authors: Burkholder