Kinetics of free radicals produced by infrared multiphoton-induced decompositions. 1. Reactions of allyl radicals with nitrogen dioxide and bromine

Article abstract of DOI:10.1021/ja00391a027

A new versatile technique to study quantitatively the gaseous reactions of polyatomic free radicals is described in detail. Free radicals are generated homogeneously in a tubular reactor by the infrared multiphoton-induced decomposition (MPD) of suitable radical precursors. The concentrations of reactants and products (both stable and labile) are monitored by using photoionization mass spectrometry. Reactions of the allyl radical, generated by the MPD of allyl bromide, with nitrogen dioxide and bromine have been studied at 300 K. The measured rate constants are 3.9(±0.8) × 10^-11 cm³ s^-1 for the C₃H₅ + NO₂ reaction and 9.0(±1.8) × 10^-12 cm³ s^-1 for the C₃H₅ + Br₂ reaction. The potential of the experimental facility for other kinds of studies is discussed.