An FT-IR study of the isomerization of 1-butoxy radicals under atmospheric conditions |
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| Affiliation: | 1. Atmospheric Chemistry Division, National Center for Atmospheric Research, Boulder, Colorado 80303, USA;2. University Chemical Laboratory, Lensfield Road, Cambridge CB2 1EW, UK;1. CNRS-INSIS, 1C Avenue de la Recherche Scientifique, 45071 Orléans cedex 2, France;2. University of Orléans, PRISME, 8 Rue Léonard de Vinci, 45072 Orléans cedex 2, France;1. Dept. Macromolecular Chemistry, Institute of Science and Technology of Polymers, ICTP-CSIC, Juan de la Cierva 3, E-28006 Madrid, Spain;2. Institute of Biofunctional Studies (IEB), Tissue Engineering Group, (UCM), Associated Unit to the Institute of Polymer Science and Technology (CSIC), Paseo de Juan XXIII 1, E-28040 Madrid, Spain;3. Institute of Microbiology, Bulgarian Academy of Sciences, 1113 Sofia, Bulgaria;4. Sofia University “St. Kliment Ohridski”, Faculty of Medicine, 1407 Sofia, Bulgaria;1. Department of Pharmacognosy, School of Pharmacy, Second Military Medical University, Shanghai 200433, China;2. Key Laboratory of Standardization of Chinese Herbal Medicines of the Ministry of Education, College of Pharmacy, Chengdu University of Traditional Chinese Medicine, Chengdu 610000, China;1. Université Lille, CNRS, UMR 8522, PC2A – Physicochimie des Processus de Combustion et de l’Atmosphère, F-59000 Lille, France;2. Graduate School of Global Environmental Studies, Kyoto University, Yoshida-Nihonmatsu-cho, Sakyo-ku, Kyoto, Kyoto 606-8316, Japan |
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| Abstract: | Relative rate-studies of the reactions of 1-butoxy radicals have been carried out using a 47 L static reactor with detection of end products by FT-IR spectroscopy. Experiments were performed at 700 torr total pressure and over the temperature range 253–295 K. The chemistry of 1-butoxy is characterized by a competition between reaction with oxygen CH3CH2CH2CH2O + O2 → n-C3H7CHO + HO2 (R2), which yields butanal and isomerization CH3CH2CH2CH2O → CH2CH2CH2CH2OH (R3), to form a hydroxylated carbonyl-product. A reference spectrum attributed to the product of 1-butoxy isomerization was obtained and used to determine the competition between 1-butoxy isomerization versus reaction with oxygen. The results indicate that isomerization is the dominant fate of 1-butoxy radicals at ambient temperature and pressure and that its importance decreases with decreasing temperature. The rate-coefficient ratio k3/k2 (molecule cm−3) = 5.5 × 1023 exp[(−25.1 ± 0.9 kJmol−1)/RT] was obtained. This agrees with other estimates based on methods without monitoring of the isomerization product. |
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