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Issue 23, 2017
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Experimental and computational kinetic investigations for the reactions of Cl atoms with unsaturated ketones in the gas phase

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Abstract

Temperature dependent rate coefficients for the gas phase reactions of Cl atoms with 4-hexen-3-one and 5-hexen-2-one were measured as a function of temperature (298–363 K) and pressure (500–760 Torr; N2 and O2) relative to 1,3-butadiene, isoprene and 1-pentene. Gas Chromatography (GC) coupled with a Flame Ionization Detector (FID) was used to measure the concentrations of the organics. The derived temperature dependent Arrhenius expressions are k1 = (2.82 ± 1.76) × 10−12 exp [(1556 ± 438)/T] cm3 molecule−1 s−1 and k2 = (4.6 ± 2.4) × 10−11 exp [(646 ± 171)/T] cm3 molecule−1 s−1. The corresponding room temperature rate coefficients are (5.55 ± 1.31) × 10−10 cm3 molecule−1 s−1 and (4.14 ± 1.25) × 10−10 cm3 molecule−1 s−1 for the reactions of Cl atoms with 4-hexen-3-one and 5-hexen-2-one respectively. To complement our experimental results, computational calculations were performed for the reactions of Cl atoms with 4-hexen-3-one, 5-hexen-2-one and 3-penten-2-one over the temperature range of 275–400 K using Canonical Variational Transition state theory (CVT) with Small Curvature Tunneling (SCT) in combination with the CCSD(T)/6-31+G(d,p)//MP2/6-311++G(d,p) level of theory. Atmospheric implications, reaction mechanism and feasibility of the title reactions are discussed in this manuscript.

Graphical abstract: Experimental and computational kinetic investigations for the reactions of Cl atoms with unsaturated ketones in the gas phase

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Publication details

The article was received on 25 Aug 2017, accepted on 20 Oct 2017 and first published on 23 Oct 2017


Article type: Paper
DOI: 10.1039/C7NJ03209A
Citation: New J. Chem., 2017,41, 14299-14314
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    Experimental and computational kinetic investigations for the reactions of Cl atoms with unsaturated ketones in the gas phase

    S. Vijayakumar, A. Kumar and B. Rajakumar, New J. Chem., 2017, 41, 14299
    DOI: 10.1039/C7NJ03209A

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