Reaction of phenylperoxy radicals with NO(2) at 298 K

In the present work, phenylperoxy radicals were generated by stationary 254 nm photolysis of iodobenzene and nitrosobenzene in the presence of O(2) and NO(2) at 298 K and a total pressure of 1 bar (M = N(2)). Experiments were performed on time scales of seconds or minutes in a temperature controlled photoreactor made of quartz (v = 209 L). Major gas phase products identified and quantified in situ by long-path IR absorption include N(2)O(5), NO, HONO, HNO(3), CO, and o-nitrophenol. In addition, evidence is presented for the formation of an aerosol consisting of p-nitrophenol. The occurrence of N(2)O(5) as a major product in both reaction systems, the strong loss of NO(2) in the iodobenzene system and the comparison of measured product distributions with the results of numerical model calculations suggest that the reaction C(6)H(5)O(2) + NO(2) --> C(6)H(5)O + NO(3), k(5)occurs in both photolysis systems, a major part of the NO(3) being scavenged as N(2)O(5). The results of ab initio calculations imply that proceeds via a short-lived peroxynitrate intermediate. In the photolysis of nitrosobenzene-NO(2)-O(2)-N(2) mixtures, NO and NO(2) compete for C(6)H(5)O(2) radicals. Comparison of measured and modelled product distributions allows to set a lower limit of k(5) > 1 x 10(-12) cm(3) molecule(-1) s(-1) at 298 K. This lower limit is consistent with the assumption that k(5) is equal to the high pressure recombination rate constant of RO(2) + NO(2) --> RO(2)NO(2) reactions, i.e. with k(5) approximately 7 x 10(-12) cm(3) molecule(-1) s(-1) at 298 K, 1bar.