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The reaction of methoxy radicals with nitric oxide and nitrogen dioxide
Author(s) -
Batt L.,
Rattray G. N.
Publication year - 1979
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550111105
Subject(s) - chemistry , tetrafluoride , radical , torr , nitric acid , nitrogen , carbon dioxide , inorganic chemistry , analytical chemistry (journal) , medicinal chemistry , organic chemistry , physics , thermodynamics
By allowing dimethyl peroxide (10 −4 M ) to decompose in the presence of nitric oxide (4.5 × 10 −5 M ), nitrogen dioxide (6.5 × 10 −5 M ) and carbon tetrafluoride (500 Torr), it has been shown that the ratio k 2 / k 2′ = 2.03 ± 0.47: CH 3 O + NO → CH 3 ONO (reaction 2) and CH 3 O + NO 2 → CH 3 ONO 2 (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 k 2 / k 2′ is independent of temperature and from k 1 = 10 10.2±0.4 M −1 sec −1 we calculate that k 2′ = 10 9.9±0.4 M −1 sec −1 . Both k 2 and k 2′ are pressure dependent but have reached their limiting high‐pressure values in the presence of 500 Torr of carbon tetrafluoride. Preliminary results show that k 4 = 10. 9.0±0.6 10 −4.5±1.1 /Θ M −1 sec −1 (Θ = 2.303 RT kcal mole −1 ) and by k 4 = 10 8.6±0.6 10 −2.4±1.1 /Θ M −1 sec −1 : CH 3 O + O 2 → CH 2 O + HO 2 (reaction 4) and CH 3 O + t‐BuH → CH 3 OH + ( t ‐Bu) (reaction 4′).