title: An instrument to measure fast gas phase radical kinetics at high temperatures and pressures.
abstract: Fast radical reactions are central to the chemistry of planetary atmospheres and combustion systems. Laser-induced fluorescence is a highly sensitive and selective technique that can be used to monitor a number of radical species in kinetics experiments, but is typically limited to low pressure systems owing to quenching of fluorescent states at higher pressures. The design and characterisation of an instrument are reported using laser-induced fluorescence detection to monitor fast radical kinetics (up to 25 000 s(-1)) at high temperatures and pressures by sampling from a high pressure reaction region to a low pressure detection region. Kinetics have been characterised at temperatures reaching 740 K and pressures up to 2 atm, with expected maximum operational conditions of up to ∼900 K and ∼5 atm. The distance between the point of sampling from the high pressure region and the point of probing within the low pressure region is critical to the measurement of fast kinetics. The instrumentation described in this work can be applied to the measurement of kinetics relevant to atmospheric and combustion chemistry.
authors.affiliation: School of Chemistry, University of Leeds, Leeds, United Kingdom.
authors.forename: Daniel
authors.initials: D
authors.lastname: Stone
authors.affiliation: School of Chemistry, University of Leeds, Leeds, United Kingdom.
authors.forename: Mark
authors.initials: M
authors.lastname: Blitz
authors.affiliation: School of Chemistry, University of Leeds, Leeds, United Kingdom.
authors.forename: Trevor
authors.initials: T
authors.lastname: Ingham
authors.affiliation: School of Chemistry, University of Leeds, Leeds, United Kingdom.
authors.forename: Lavinia
authors.initials: L
authors.lastname: Onel
authors.affiliation: School of Chemistry, University of Leeds, Leeds, United Kingdom.
authors.forename: Diogo J
authors.initials: DJ
authors.lastname: Medeiros
authors.affiliation: School of Chemistry, University of Leeds, Leeds, United Kingdom.
authors.forename: Paul W
authors.initials: PW
authors.lastname: Seakins