New Instrument for Time-Resolved OH and HO2 Quantification in High-Pressure Laboratory Kinetics Studies.

Abstract

We have constructed a new time-resolved high-pressure fluorescence assay by gas expansion (HP-FAGE) apparatus, optimized for the detection of OH and HO2 radicals in complex gas-phase reactions. The new instrument fills a gap in the existing experimental toolkit for chemical kinetics by enabling the quantification of two key reactive species with microsecond time resolution from high-pressure sources, which was previously not attainable. The HP-FAGE is interfaced with a flow reactor, designed for pressures up to 100 bar and temperatures up to 1000 K, in which reactions are initiated by laser photolysis of radical precursors at repetition rates of 1-10 Hz. The HP-FAGE samples gas out of the reactor into a miniature FAGE chamber, where OH is detected by resonant laser-induced fluorescence using a time-delayed probe laser pulse. HO2 is converted to OH via reaction with NO and then detected by OH fluorescence. The novel FAGE design places the probe region very close to the gas expansion, minimizing the transport time of sampled molecules and resulting in time resolution better than 20 μs for both OH and HO2. We calibrate the sensitivity of HP-FAGE, validate its performance with measurements of well-known reaction kinetics (OH + CH4, OH + OH, OH + HO2, and HO2 + HO2), and discuss prospects for its future use.