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Reactions of Cl Atoms with Selected VOCs: Kinetics, Products and Mechanisms
Authors:Gaia Fantechi  Niels R Jensen  Ole Saastad  Jens Hjorth  Jozef Peeters
Institution:(1) The European Commission, Joint Research Centre, Environment Institute, TP 272, I-21020 Ispra (VA), Italy;(2) Katholieke Universiteit Leuven, Department of Chemistry, Celestijnenlaan 200F, B-3001 Heverlee, Belgium
Abstract:The reactions of isoprene, MBO (2-methyl-3-buten-2-ol) and toluene with chlorine atoms have been studied at 298 ± 5 K and 740 ± 5 Torr with the use of FTIR spectroscopy. Major products of the isoprene-Cl reaction and of the MBO-Cl reaction have been identified and quantified, and reaction mechanisms have been tentatively proposed in order to explain the products formed. The reaction between isoprene and Cl atoms yields mainly HCl, formyl chloride, formic acid, methylglyoxal (pyruvic aldehyde), CO and CO2, while the MBO-Cl reaction forms acetone, HCl, formyl chloride, formic acid, CO, CO2. As products from the reaction between toluene and Cl we identified and quantified HCl and benzaldehyde. The rate constants for the reactions of isoprene and toluene with Cl atoms have also been determined using a relative rate method. The measured values are: kisoprene = (5.5 ± 1.0) × 10–10 cm3 molecule–1 s–1 and ktoluene = (5.6 ± 1.3) × 10–11 cm3 molecule–1 s–1. Atmospheric lifetimes have been estimated from these values.
Keywords:isoprene  methacrolein  methyl vinyl ketone  methyl butenol  toluene  chlorine atoms  gas-phase
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