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

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 center dot+O-2 -> n-C3H7CHO+H2O (R2), which yields butanal and isomerization CH3CH2CH2CH2O center dot -> (CH2CH2CH2CH2OH)-C-center dot (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 isornerization 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 k(3)/k(2) (molecule cm(-3)) = 5.5 x 10(23) exp[(-25.1 +/- 0.9 kJmol(-1))/RT] was obtained. This agrees with other estimates based on methods without monitoring of the isomerization product. (c) 2005 Elsevier B.V. All rights reserved.