A new instrument for time-resolved measurement of HO₂ radicals

Abstract

Abstract. OH and HO2 radicals are closely coupled in the atmospheric oxidation and combustion of volatile organic compounds (VOCs). Simultaneous measurement of HO2 yields and OH kinetics can provide the ability to assign site-specific rate coefficients that are important for understanding the oxidation mechanisms of VOCs. By coupling a fluorescence assay by gaseous expansion (FAGE) laser-induced fluorescence (LIF) detection system for OH and HO2 with a high-pressure laser flash photolysis system, it is possible to accurately measure OH pseudo-1st-order loss processes up to ∼100 000 s−1 and to determine HO2 yields via time-resolved measurements. This time resolution allows discrimination between primary HO2 from the target reaction and secondary production from side reactions. The apparatus was characterized by measuring yields from the reactions of OH with H2O2 (1:1 link between OH and HO2), with C2H4∕O2 (where secondary chemistry can generate HO2), with C2H6∕O2 (where there should be zero HO2 yield), and with CH3OH∕O2 (where there is a well-defined HO2 yield). As an application of the new instrument, the reaction of OH with n-butanol has been studied at 293 and 616 K. The bimolecular rate coefficient at 293 K, (9.24±0.21)×10-12 cm3 molec.−1 s−1, is in good agreement with recent literature, verifying that this instrument can measure accurate OH kinetics. At 616 K the regeneration of OH in the absence of O2, from the decomposition of the β-hydroxy radical, was observed, which allowed the determination of the fraction of OH reacting at the β site (0.23±0.04). Direct observation of the HO2 product in the presence of oxygen has allowed the assignment of the α-branching fractions (0.57±0.06) at 293 K and (0.54±0.04) at 616 K, again in good agreement with recent literature; branching ratios are key to modelling the ignition delay times of this potential “drop-in” biofuel.