Time-resolved measurements of HO2 radical in a heated plasma flow reactor

Abstract

Time-resolved, absolute HO2 number density in diluted H2O2-Ar, CH4O2-Ar, and C2H4O2-Ar mixtures excited by a repetitive ns pulse discharge in a heated plasma flow reactor is measured by Cavity Ringdown Spectroscopy (CRDS). The experimental results are obtained at T = 300–600 K and P = 130 Torr, both during the discharge pulse burst and in the afterglow. The HO2 number density is inferred from the CRDS data using a spectral model exhibiting good agreement with previous measurements of absolute HO2 absorption cross sections. In the room-temperature H2O2 mixture, as well as in CH4O2 and C2H4O2 mixtures over the entire temperature range studied, HO2 is generated only during the discharge burst and decays in the afterglow. However, in the H2O2 mixture at elevated temperatures, T = 400–600 K, HO2 persists in the afterglow up to 10 ms after the discharge burst, comparable with the flow residence time in the reactor. Comparison with kinetic modeling shows that the sustained reactivity after the source of radicals is turned off is due to a chain propagation/ hydrogen oxidation process, which dominates the radical recombination reactions. The kinetic modeling predictions are in good agreement with the relative HO2 number density measured in all three mixtures, although the model underpredicts the absolute number densities in H2O2 at T = 400–600 K by up to a factor of two. Detection of the sustained low-temperature reactivity in H2O2, initiated by the radical generation in the plasma, suggests that the plasma excitation may also affect kinetics of oxidation and reforming of fuels exhibiting low-temperature chemistry below hot ignition point.