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Kinetic study of 2-furanaldehyde, 3-furanaldehyde, and 5-methyl-2-furanaldehyde reactions initiated by Cl atoms

✍ Scribed by B. Cabañas; A. Tapia; F. Villanueva; S. Salgado; E. Monedero; P. Martín


Publisher
John Wiley and Sons
Year
2008
Tongue
English
Weight
168 KB
Volume
40
Category
Article
ISSN
0538-8066

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✦ Synopsis


Abstract

Rate coefficients for the gas‐phase reactions of chlorine atoms with a series of furanaldehydes have been determined at 298 ± 2 K and atmospheric pressure (708.5 ± 0.1). The experiments were performed using the relative technique combined with solid‐phase microextraction (SPME) sampling and gas chromatography with flame ionization detection (GC‐FID). Rate constants were determined relative to the reaction of Cl with n‐nonane and 2‐ethylfuran. The absolute rate coefficients k (in units of 10^−10^ cm^3^ molecule^−1^ s^−1^) obtained were 2.61 ± 0.27 for 2‐furaldehyde, 3.15 ± 0.27 for 3‐furaldehyde, and 4 ± 0.5 for 5‐methyl‐2‐furaldehyde. This study shows that the reactions of furanaldehydes and Cl are very fast with little influence of the position of the aldehyde group or the presence of other substituent on the reactivity. The results seem to indicate a mechanism involving two main reaction channels, addition of chlorine atom to the double bond of the aromatic ring, and the abstraction of the aldehydic hydrogen. Further product studies are necessary to determine the mechanism of these reactions in more detail. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 670–678, 2008


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## Abstract The mechanisms of the reactions: CH~3~CFCl~2~ + Cl (R1) and CH~3~CF~2~Cl + Cl (R2) are studied over a wide temperature range (200–3000 K) using the dual‐level direct dynamics method. The minimum energy path calculation is carried out at the MP2/6‐311G(d,p) and B3LYP/6‐311G(d,p) levels,