Infrared frequency-modulation probing of product formation in alkyl plus O2 reactions:: I.: The reaction of C2H5 with O2 between 295 and 698 K

The production of HO2 in the reaction of ethyl radicals with molecular oxygen has been investigated using laser photolysis/cw infrared frequency modulation spectroscopy. The ethyl radicals are formed by reaction of photolytically produced Cl atoms with ethane, initiated via pulsed laser photolysis of Cl-2 and the progress of the reaction is monitored by frequency-modulation spectroscopy of the HO2 product. The yield of HO2 in the reaction is measured by comparison with the Cl-2/CH3OH/O-2 system, which quantitatively converts Cl atoms to HO2. At low temperatures stabilization to C2H5O2 dominates, but at elevated temperatures (> 575 K) dissociation of the ethylperoxy radical begins to contribute. Biexponential time behavior of the HO2 production allows separation of prompt, "direct" HO2 formation from HO2 produced after thermal redissociation of an Initial ethylperoxy adduct, The prompt HO2 yield exhibits a smooth increase with increasing temperature, but the total HO2 yield, which includes contributions from the redissociation of ethylperoxy radicals, rises sharply from similar to 10% to 100% between 575 and 675 K. Because of the separation of time scales in the HO2 production, this rapid rise can unambiguously be assigned to ethylperoxy dissociation. No OH was observed in the reaction, and an upper limit of 6% can be placed on direct OH formation from the C2H5 + O-2 reaction at 700 K. The time behavior of the HO2 production is at variance with the predictions of Wagner et al.'s RRKM-based parameterization of this reaction (J. Phys. Chem. 1990, 94, 1853). However, a simple ad hoc correction to that model, which takes into account a recent reinterpretation of the equilibrium constant for C2H5 + O-2 Ct C2H5O2, predicts yields and time constants consistent with the present measurements. The reaction mechanism is further discussed in terms of recent quantum chemical and master equation studies of this system, which show that the present results are well described by a coupled mechanism with HO2 + C2H4 formed by direct elimination from the C2H5O2 adduct.