P. Hanst
Nov 1, 1977
Citations
0
Influential Citations
40
Citations
Journal
Environmental Science & Technology
Abstract
Photochemical reactions among chlorine, nitrogen dioxide, and formaldehyde were studied, using parts-per-million concentrations in 1 atm of air. The reactant mixtures were irradiated by ultraviolet fluorescent lamps and simultaneously analyzed by the Fourier transform infrared technique by use of folded light paths up to 504 m. With an excess of NO/sub 2/ over Cl/sub 2/, the reaction products included O/sub 3/, CO, HNO/sub 3/,N/sub 2/O/sub 5/, HCl, and nitryl chloride (ClNO/sub 2/). When chlorine exceeded NO/sub 2/, the principal product was peroxy nitric acid (HOONO/sub 2/). Peroxy formyl nitrate, nitrous acid, and chlorine nitrate were not seen. The nitryl chloride was stable even with the ultraviolet lights on. The peroxy nitric acid disappeared from the cell with a half-life of about 10 min. Formyl radicals (HCO), unlike acetyl radicals, did not combine with O/sub 2/ and NO/sub 2/ by addition. HCO reacted with O/sub 2/ to yield CO and HO/sub 2/. The HO/sub 2/ will then add to NO/sub 2/ to yield HOONO/sub 2/. If NO is present, the HO/sub 2/ will prefer to react with it, oxidizing it to NO/sub 2/.