Identification, monitoring, and reaction kinetics of reactive trace species using time-resolved mid-infrared quantum cascade laser absorption spectroscopy: development, characterisation, and initial results for the CH<sub>2</sub>OO Criegee intermediate

Abstract

Abstract. The chemistry and reaction kinetics of reactive species dominate changes to the composition of complex chemical systems, including Earth's atmosphere. Laboratory experiments to identify reactive species and their reaction products, and to monitor their reaction kinetics and product yields, are key to our understanding of complex systems. In this work we describe the development and characterisation of an experiment using laser flash photolysis coupled with time-resolved mid-infrared (mid-IR) quantum cascade laser (QCL) absorption spectroscopy, with initial results reported for measurements of the infrared spectrum, kinetics, and product yields for the reaction of the CH2OO Criegee intermediate with SO2. The instrument presented has high spectral (< 0.004 cm−1) and temporal (< 5 µs) resolution and is able to monitor kinetics with a dynamic range to at least 20 000 s−1. Results obtained at 298 K and pressures between 20 and 100 Torr gave a rate coefficient for the reaction of CH2OO with SO2 of (3.83 ± 0.63) × 10−11 cm3 s−1, which compares well to the current IUPAC recommendation of 3.70-0.40+0.45 × 10−11 cm3 s−1. A limit of detection of 4.0 × 10−5, in absorbance terms, can be achieved, which equates to a limit of detection of ∼ 2 × 1011 cm−3 for CH2OO, monitored at 1285.7 cm−1, based on the detection path length of (218 ± 20) cm. Initial results, directly monitoring SO3 at 1388.7 cm−1, demonstrate that SO3 is the reaction product for CH2OO + SO2. The use of mid-IR QCL absorption spectroscopy offers significant advantages over alternative techniques commonly used to determine reaction kinetics, such as laser-induced fluorescence (LIF) or ultraviolet absorption spectroscopy, owing to the greater number of species to which IR measurements can be applied. There are also significant advantages over alternative IR techniques, such as step-scan FT-IR, owing to the coherence and increased intensity and spectral resolution of the QCL source and in terms of cost. The instrument described in this work has potential applications in atmospheric chemistry, astrochemistry, combustion chemistry, and in the monitoring of trace species in industrial processes and medical diagnostics.