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An FT-IR study of the isomerization of 1-butoxy radicals under atmospheric conditions ☆

Paper ID Volume ID Publish Year Pages File Format Full-Text
28666 44085 2006 7 PDF Available
Title
An FT-IR study of the isomerization of 1-butoxy radicals under atmospheric conditions ☆
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.

Keywords
1-Butoxy; Isomerization; Tropospheric oxidation
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An FT-IR study of the isomerization of 1-butoxy radicals under atmospheric conditions ☆
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Publisher
Database: Elsevier - ScienceDirect
Journal: Journal of Photochemistry and Photobiology A: Chemistry - Volume 177, Issues 2–3, 25 January 2006, Pages 109–115
Authors
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Subjects
Physical Sciences and Engineering Chemical Engineering Bioengineering
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Price was $35.95
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