Kinetics of the reactions of OH radicals with selected acetates and other esters under simulated atmospheric conditions

Abstract

AbstractThe relative hydroxyl radical reaction rate constants from the simulated atmospheric oxidation of selected acetates and other esters have been measured. Reactions were carried out at 297 ± 2 K in 100‐liter FEP Teflon®‐film bags. The OH radicals were generated from the photolysis of methyl nitrite in pure air. Using a rate constant of 2.63 × 10−11 cm3 molecule−1 s−1 for the reaction of OH radicals with propene, the principal reference organic compound, the rate constants (×1012 cm3 molecule−1 s−1) obtained for the acetates and esters used in this study are: n–propyl acetate 3.42 ± 0.87 n–butyl acetate 5.71 ± 0.94 n–pentyl acetate 7.53 ± 0.48 2–ethoxyethyl acetate 10.56 ± 1.31 2–ethoxyethyl isobutyrate 13.56 ± 2.32 2–ethoxyethyl methacrylate 27.22 ± 2.06 4–pentene‐1‐yl acetate 43.40 ± 3.85 3–Ethoxyacrylic acid ethyl ester 33.30 ± 1.22 Error limits represent 2σ from linear least‐squares analysis of data.A linear correlation was observed for a plot of the measured relative rate constants vs. the number of CH2 groups per molecule of the following acetates: methyl acetate, ethyl acetate, n‐propyl acetate, butyl acetate, and pentyl acetate. © 1993 John Wiley & Sons, Inc.