Gas-phase reaction of hydroxyl radicals with m-, o- and p-cresol

✍ Scribed by Cecile Coeur-Tourneur; Françoise Henry; Marie-Andrée Janquin; Laurent Brutier

• Publisher: John Wiley and Sons
• Year: 2006
• Tongue: English
• Weight: 351 KB
• Volume: 38
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.20186

✦ Synopsis

Abstract

The gas‐phase reaction of oxygenated aromatic compounds m‐cresol, o‐cresol, and p‐cresol with hydroxyl radicals has been studied by GC‐MS. Experiments have been performed in a large‐volume photoreactor (8000 L) at 294 ± 2 K and atmospheric pressure. The relative kinetic method was used to determine the rate constants for these reactions, with 1,3,5‐trimethylbenzene as a reference compound. The rate constants obtained are k~OH~(m‐cresol) = (5.88 ± 0.92) × 10^−11^ cm^3^ molecule^−1^ s^−1^, k~OH~(o‐cresol) = (4.32 ± 0.52) × 10^−11^ cm^3^ molecule^−1^ s^−1^, and k~OH~(p‐cresol) = (4.96 ± 0.75) × 10^−11^ cm^3^ molecule^−1^ s^−1^. The degradation products observed and their respective molar yields were methyl‐1,4‐benzoquinone 12.4 ± 1.2%, 5‐methyl‐2‐nitrophenol 1.5 ± 0.3%, and 3‐methyl‐2‐nitrophenol 1.4 ± 0.3% from m‐cresol, methyl‐1,4‐benzoquinone 5.6 ± 0.9%, and 6‐methyl‐2‐nitrophenol 4.7 ± 0.8% from o‐cresol, and 4‐methyl‐2‐nitrophenol 17.2 ± 2.5% from p‐cresol. This kinetic and product data are compared with the literature, and the reaction mechanisms are discussed. Our results are in accordance with the previous studies (Atkinson, J Phys Chem Ref Data 1989, Monograph (1), 1–246; Atkinson and Aschmann, Int J Chem Kinet 1990, 22, 59–67; Atkinson et al., Environ Sci Technol 1992, 26, 1397–1403; Atkinson et al., J Phys Chem 1978, 82, 2759–2805; Olariu et al., Atmos Environ 2002, 36, 3685–3697; Semadeni et al., Int J Chem Kinet 1995, 27, 287–304) and confirm the methyl‐1,4‐benzoquinone yields determined by a different experimental technique (long‐path Fourier transform infrared FT‐IR (Olariu et al., 2002)). © 2006 Wiley Periodicals, Inc. Int J Chem Kinet 38: 553–562, 2006