The Inhibition of Photochemical Smog

Abstract
Additional inhibitors for the conversion of NO to NO2 in C3H6—NO—02 irradiated mixtures have been tested at 25°C. These mixtures initially contained 16 mTorr C3H6, 8 mTorr NO, 0.012 mTorr NO2, additive, and enough O2 to bring the total pressure to 100 Torr. The NO2 pressure was monitored photometrically. In the absence of additive, the NO2 pressure first increases with irradiation time reaching a maximum conversion at about 15 minutes. As the irradiation time increases beyond 15 min, the NO2 pressure drops. Before adding the inhibitors, runs were done with 10 Torr of CO added, and in these runs the conversion was speeded so that the maximum in NO2 pressure occurred at 10 min. This enhancement in conversion rate is considered to be diagnostic for the presence of HO radicals. Next 10-min irradiations were done with various amounts of hexafluorobenzene (C6F6), nitrobenzene (C6H5NO2), or naphtha lene (C10H8) added. The NO2 pressure was reduced to one-half its value in the absence of inhibitor with 270 mTorr C6F6’, 220 mTorr C6H5N02, or 4 mTorr C10Hg. The C10H8 is a very efficient inhibitor, but additions of up to 1 8.5 mTorr C10H8 did not reduce the N02 pressure to zero. Studies of the percent conversion of NO to NO2 vs. irradiation time were done with either 4.2 mTorr C10H8 or 40 mTorr 2,6-di-ferf-butyl-4-methylphenol (Ph) added. In the former case the peak conversion was delayed from 15 to 22 min, while in the latter case no delay occurred. However, with the Ph added, there appeared to be some reduction in the maximum value of percent conversion.