The reaction of methoxy radicals with nitric oxide and nitrogen dioxide

✍ Scribed by L. Batt; G. N. Rattray

• Publisher: John Wiley and Sons
• Year: 1979
• Tongue: English
• Weight: 550 KB
• Volume: 11
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.550111105

✦ Synopsis

By allowing dimethyl peroxide ( 10-4M) to decompose in the presence of nitric oxide (4.5 X lOW5M), nitrogen dioxide (6.5 X 10-5M) and carbon tetrafluoride (500 Torr), it has been shown that the ratio kzlkz, = 2.03 f 0.47: CH30 + NO -CH30NO (reaction 2) and CH30 + NO2 -CH30N02 (reaction 2'). Deviations from this value in this and previous work is ascribed to the pressure dependence of both these reactions and heterogeneity in reaction (2). In contrast no heterogeneous effects were found for reaction (2') making it an ideal reference reaction for studying other reactions of the methoxy radical. We conclude that the ratio kz/k2, is independent of temperature and from kl = 10'0.2*0.4M-1 sec-' we calculate that kz, = 109.9i0.4M-1 sec-1. Both kz and kz. are pressure dependent but have reached their limiting high-pressure values in the presence of 500 Torr of carbon tetratluoride. Preliminary results show that k4 = 10.9.0i0.6 10-4.5*1.1/8M-' sec-' (8 = 2.303RT kcal mole-') and by kq, = 108.6i0.6 10-2.4i1.1/8M-1 sec-': CH30 + 0 2 -CHzO + HOz (reaction 4) and CH30 + t-BuH -CH30H + (t-Bu) (reaction 4').

Of particular interest to us were their decomposition [reaction (3)] [9] and the reaction with oxygen, especially the methoxy radical [reaction (4)]