Relative rate constants for the reactions of hydroxyl radicals and chlorine atoms with a series of aliphatic alcohols

Abstract

Abstract Rate constants for the gas‐phase reactions of hydroxyl radicals and chlorine atoms with a series of alcohols have been determined by using the relative method. The experiments were performed at 295 ± 2 K and at 1 atmospheric pressure. The obtained values of the rate constants in units of 10 −12 cm 3 molecule −1 s −1 are as follows: Alcohol Rate Constants for OH with Rate Constants for Cl with Propane Cyclohexane Propane Cyclohexane Ethyl alcohol 3.40 ± 0.25 – 103 ± 4 96 ± 7 n ‐Propyl alcohol 5.47 ± 0.44 – 153 ± 13 147 ± 11 Isopropyl alcohol 5.31 ± 0.39 – 73.5 ± 3.7 82.7 ± 7.4 n ‐Butyl alcohol 8.66 ± 0.66 – 211 ± 11 223 ± 10 Isobutyl alcohol 9.08 ± 0.35 9.59 ± 0.45 182 ± 4 196 ± 11 tert ‐Butyl alcohol 1.11 ± 0.07 – 31.5 ± 2.4 34.1 ± 2.5 n ‐Pentyl alcohol 12.2 ± 1.0 12.4 ± 0.5 257 ± 25 258 ± 12 Isopentyl alcohol 13.8 ± 0.5 13.2 ± 1.1 237 ± 7 235 ± 9 The above relative rate constants are based on the values (in units of 10 −12 cm 3 molecule −1 s −1 ) of k (OH + propane) = 1.08, k (OH + cyclohexane) = 7.22, k (Cl + propane) = 131 and k (Cl + cyclohexane) = 307. The results are compared with previous determinations. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 35: 81–87, 2003