Abstract
Production of organic nitrates from OH reaction with cyclohexane, cyclohexene, n‐butane, 1‐bromopropane, and p‐xylene in the presence of NO was studied. The total organic nitrate yields for cyclohexane and n‐butane were determined to be 17 ± 4 and 7 ± 2% respectively, which is in good agreement with previous determinations. Total yields for cyclohexene, 1‐bromopropane, and p‐xylene were 2.5 ± 0.5, 1.2 ± 0.3, and 3.2 ± 0.7 respectively. The yield for cyclohexene was five times smaller than that for cyclohexane. The 1‐bromopropane yield is three times smaller that that for n‐propane, but similar to that for propene, indicating that the effect of Br substitution in the reactant may be similar to that for OH substitution. The only nitrooxy product detected for p‐xylene was 4‐methylbenzylnitrate, which was formed following H abstraction from either methyl group. No organic nitrate was detected for peroxy radicals produced from OH addition to the ring, which accounts for 90% of the OH oxidation of p‐xylene. The calculated k~3b~/k~3~ value for p‐methyl benzyl peroxy radicals (0.32) was slightly smaller than for n‐octyl peroxy radicals (0.39). These data imply that substituent inductive effects impact the k~3b~/k~3~ ratios. We found no significant difference in the k~3b~/k~3~ ratios for primary vs. secondary peroxy radicals of the same carbon chain. © 2005 Wiley Periodicals, Inc. Int J Chem Kinet 37: 675–685, 2005