Rate constants for reactions of OH radicals with a series of asymmetrical ethers andtert-Butyl alcohol

Abstract

Absolute rate constants for the reactions of OH radicals with butyl ethyl ether (k1), methyl tert-butyl ether (k2), ethyl tert-butyl ether (k3) tert-amyl methyl ether (k4) and tert-butyl alcohol (k5) have been measured over the temperature range 230–372 K using a pulsed laser photolysis-laser induced fluorescence (PLP-LIF) technique. The temperature dependence of k1 − k5 when expressed in Arrhenius form gave: k1 = (6.59 ± 0.66) × 10 −12 exp|(362 ± 60)/T|, k2 = (5.03 ± 0.27) × 10−12 exp|&minus(133 ± 30)/T|, k3 = (4.40 ± 0.24) × 10−12 exp|(210 ± 37)/T|,k4 = (4.7 ± 0.7) × 10−12 exp|(82 ± 85)/T|, and k5 = (2.66 ± 0.48) × 10−12 exp| −(270 ± 130)/T|. However, the Arrhenius plots for k1–k5, were slightly curved and are best fitted by the three parameter fits which are given in the article. The room temperature values of k1, k2, k3, k4, and k5 are (2.08 ± 0.23) × 10−11, (3.13 ± 0.36) × 10−12, (8.80 ± 0.50) × 10−12, (6.28 ± 0.45) × 10−12, and (1.08 ± 0.10) × 10−12, respectively, in cm3 molecule−1 s−1. © 1996 John Wiley & Sons, Inc.