Molecular‐modulation spectrometry: CH<sub>3</sub>ONO photolysis and detection of nitroxyl

McGraw, G. E.; Johnston, Herrick L.

doi:10.1002/kin.550010109

Cited by 20 publications

(7 citation statements)

References 34 publications

(16 reference statements)

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“…NO is observed but at concentrations which decrease with increasing 02 concentration. These observations are consistent with the additional reactions ch3o + o2 -ho2 + HCHO (9) HNO + 02 -H02 + NO (10) ho2 + NOoh + no2 (11) ch3o + no2 -CH30N02 (12) HNO formed in Reaction 3 is oxidized to N02 via Reaction 10 and CH30N02 forms via Reaction 12. Thus, the reaction which reforms CH3ONO, Reaction 4, is inhibited by reduction of the concentrations of both NO and CH30.…”

Section: Discussionsupporting

confidence: 86%

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Methoxyl radical reactions in atmospheric chemistry

Glasson¹

1975

Environ. Sci. Technol.

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Section: Discussionsupporting

confidence: 86%

“…B., Appleby, A., Lobban, L. A., Env. Lett., submitted August 1975. (10) Singh, . B., Lillian, D., Appleby, A., Anal.…”

mentioning

confidence: 99%

Methoxyl radical reactions in atmospheric chemistry

Glasson¹

1975

Environ. Sci. Technol.

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“…The presence of nitrogen oxides affects the oxidation of methanol through interaction with the radical pool as well as through direct reactions of NO and NO 2 with stable species. There are no direct studies of the reaction between CH 3 OH and NO, but low‐temperature data on the reverse reaction, HNO + CH 3 O → NO + CH 3 OH (R103), are in reasonable agreement 132,133. Measurements of the competing channel NO + CH 3 OH ⇌ HNO + CH 2 OH (R102b) are unavailable in either direction and an estimate is used 134.…”

Section: Chemical Kinetic Modelmentioning

confidence: 99%

Methanol oxidation in a flow reactor: Implications for the branching ratio of the CH₃OH+OH reaction

Rasmussen

Wassard

Dam‐Johansen

et al. 2008

Int J of Chemical Kinetics

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The oxidation of methanol in a flow reactor has been studied experimentally under diluted, fuel-lean conditions at 650-1350 K, over a wide range of O 2 concentrations (1%-16%), and with and without the presence of nitric oxide. The reaction is initiated above 900 K, with the oxidation rate decreasing slightly with the increasing O 2 concentration. Addition of NO results in a mutually promoted oxidation of CH 3 OH and NO in the 750-1100 K range. The experimental results are interpreted in terms of a revised chemical kinetic model. Owing to the high sensitivity of the mutual sensitization of CH 3 OH and NO oxidation to the partitioning of CH 3 O and CH 2 OH, the CH 3 OH + OH branching fraction could be estimated as α = 0.10 ± 0.05 at 990 K. Combined with low-temperature measurements, this value implies a branching fraction that is largely independent of temperature. It is in good agreement with recent theoretical estimates, but considerably lower than values employed in previous modeling studies. Modeling predictions with the present chemical kinetic model is in quantitative agreement with experimental results below 1100 K, but at higher temperatures and high O 2 concentration the model underpredicts the oxidation rate.

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“…The high-pressure limiting rate coefficient for reaction 14 is18 4 X 109 M"1 sec"1. Thus under all of our conditions, reaction 14 is negligible.…”

Section: Examination Of Tablementioning

confidence: 72%

Reactions of methylperoxy radicals with nitric oxide and nitrogen dioxide

Simonaitis¹,

Heicklen²

1974

J. Phys. Chem.

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The reactions of CH3O2 radicals with NO and NO2 were examined at 2 5 O . The CH3O2 radicals were produced from the photolysis of N20-CH4-02 mixtures at 2139 hi. With NO present NO2 and CH30NO were produced with no induction period and initial quantum yields of +i(NOzJ = 1.43 f 0.13 and Oi(CH30NOJ = 1.5. Therefore it is deduced that when NO reacts with CH302,80 f 15% of the reaction proceeds uia CH302 f NO -CH30 + NO2 (la). When both NO and NO2 are present, @(NO21 can either increase or decrease depending on the ratio [NO]/[NO2]. For a ratio of about 0.85, +(NO2] = 0, from which it could be concluded that h l a / k 3 = 2.2 where reaction 3 is the reaction between NO2 and CH302. The quantum yield of NO2 removal of 2.15 when NO was absent showed that NO3 could not be important in this system and that the two possible channels for reaction 3 are CH3O2 + NO2 -CH302N02 (3a) and CH302 c NO2 -CH2O + NON02(3b).

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Molecular‐modulation spectrometry: CH₃ONO photolysis and detection of nitroxyl

Cited by 20 publications

References 34 publications

Methoxyl radical reactions in atmospheric chemistry

Methoxyl radical reactions in atmospheric chemistry

Methanol oxidation in a flow reactor: Implications for the branching ratio of the CH₃OH+OH reaction

Reactions of methylperoxy radicals with nitric oxide and nitrogen dioxide

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Molecular‐modulation spectrometry: CH3ONO photolysis and detection of nitroxyl

Cited by 20 publications

References 34 publications

Methoxyl radical reactions in atmospheric chemistry

Methoxyl radical reactions in atmospheric chemistry

Methanol oxidation in a flow reactor: Implications for the branching ratio of the CH3OH+OH reaction

Reactions of methylperoxy radicals with nitric oxide and nitrogen dioxide

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Molecular‐modulation spectrometry: CH₃ONO photolysis and detection of nitroxyl

Methanol oxidation in a flow reactor: Implications for the branching ratio of the CH₃OH+OH reaction