Kinetics and nitro-products of the gas-phase OH and NO3 radical-initiated reactions of naphthalene-d8, Fluoranthene-d10, and pyrene

✍ Scribed by Roger Atkinson; Janet Arey; Barbara Zielinska; Sara M. Aschmann

• Publisher: John Wiley and Sons
• Year: 1990
• Tongue: English
• Weight: 957 KB
• Volume: 22
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.550220910

✦ Synopsis

The kinetics and nitroarene product yields of the gas-phase reactions of naphthalene-d8, fluoranthene-dl,,, and pyrene with OH radicals in the presence of NO, and in Nz05-NO3-NOz-air mixtures have been investigated at 296 2 2 K and atmospheric pressure of air.

Using a relative rate method, naphthalene-d8 was shown to react in Nz05-N03-N0,-air mixtures a factor of 1.22 ? 0.10 times faster than did naphthalene, with the 1-and 2nitronaphthalene-d, product yields being similar to those of 1-and 2-nitronaphthalene from naphthalene. From the measured PAH concentrations and the nitroarene product yields, formation yields of 2-, 7-, and 8-nitrofluoranthene-d, and 2-and 4-nitropyrene of 0.03, 0.01, 0.003, 0.005, and 0.0006, respectively, were determined from the OH radical-initiated reactions. Effective rate constants for the reactions of fluoranthene-d,, and pyrene with N205 in Nz0,-N03-NOz-air mixtures of ca. 1.8 X lo-', cm3 molecule-'^-^ and ca. 5.6 X 10-l7 cm3 molecule-' s-', respectively, were derived. Formation yields of 2-nitrofluoranthene-d9 and 4-nitropyrene of ca. 0.24 and ca. 0.0006, respectively, were estimated for these reaction systems. 2-Nitropyrene was also observed to be formed in these Nz05-N03-NOz reactions, but was found to be a function of the NOz concentration and, therefore, would be a negligible product under ambient NOz concentrations. These product and kinetic data are consistent with ambient air measurements of the nitroarene concentrations.