A combined photoionization time-of-flight mass spectrometry and laser absorption spectrometry flash photolysis apparatus for simultaneous determination of reaction rates and product branching

Abstract

In recent years, predictions of product branching for reactions of consequence to both combustion and atmospheric chemistry have outpaced validating experiments. An apparatus is described that aims to fill this void by combining several well-known experimental techniques into one: flash photolysis for radical generation, multiple-pass laser absorption spectrometry (LAS) for overall kinetics measurements, and time-resolved photoionization time-of-flight mass spectrometry (PI TOF-MS) for product branching quantification. The sensitivity of both the LAS and PI TOF-MS detection techniques is shown to be suitable for experiments with initial photolytically generated radical concentrations of ∼1 × 1012 molecules cm-3. As it is fast (μs time resolution) and non-intrusive, LAS is preferred for accurate kinetics (time-dependence) measurements. By contrast, PI TOF-MS is preferred for product quantification because it provides a near-complete picture of the reactor composition in a single mass spectrum. The value of simultaneous LAS and PI TOF-MS detection is demonstrated for the chemically interesting phenyl radical + propene system.