The early stages of pyrolysis and oxidation of methane

Tabayashi, Kiyohiko; Bauer, S. H.

doi:10.1016/0010-2180(79)90079-8

Cited by 96 publications

(43 citation statements)

References 30 publications

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“…Previous studies in this laboratory (3) established that the initial stages of the decomposition from 995 to 1103 K are well accounted for by reactions [4], [5], and [6], with reaction [4] exhibiting some unimolecular pressure dependence, and no evidence for the occurrence of reaction [2]. The present experiments have extended these measurements to 899 and 802 K at pressures of about 1000 Torr where k, should be close to its high-pressure limit.…”

Section: The Thermal Decomposition Of Methanesupporting

confidence: 68%

“…No ethylene was observed in any of these experiments, as would have been expected if secondary decomposition of ethane were occurring, and there is no reason to doubt that initial primary yields of ethane, and hence initial rates of reaction [4], were measured. It can be estimated that if reaction [2] had occurred to an extent 10% that of reaction [4] at our lowest temperature, we should have detected an enhanced rate of ethane formation.…”

Section: The Thermal Decomposition Of Methanementioning

confidence: 59%

“…Conversely, and its reverse, if E2 exceeded 54 kcal/mol the chain reaction could become important at high temperatures. It could also become important [3] H + CzH6 + CH3 + CH, at much higher temperatures when the dissociation of ethane Reaction [2] was suggested almost 50 years ago as a possible (the reverse of reaction [61) becomes fast, prechain propagation step in the thermal decomposition of rnethventing the L61 and ane (2), for reasons that are no longer valid, and recent studies their concentrations to UP high of this system (3) concluded that there was no evidence for its In fact, it has been suggested that this Occurs in the decomoccurrence at temperatures down to ,000 K , ~h~ initial stages position of methane in a shock tube at temperatures from 2000 of the methane decomposition appear to be accounted for by the to 2500 K (4). simple non-chain mechanism,…”

Section: Ch3mentioning

confidence: 99%

“…In the present study, the following systems were examined in an attempt to detect reaction [2] or to place upper limits on [4] CH,…”

Section: Ch3mentioning

confidence: 99%

“…its rate: ( I ) the thermal decomposition of methane; (2) the [5] H + CH, + Hz + CH3 mercury-photosensitized decomposition of methane; (3) the thermal decomposition of azomethane in the presence of methane; (4) three systems involve reaction [2] directly, the last two indirectly through reaction [3] to which it can be related thermochemically.…”

Section: Ch3mentioning

confidence: 99%

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A search for a gas-phase free-radical inversion displacement reaction at a saturated carbon atom

Back¹

1983

Can. J. Chem.

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Five thermal and photochemical reaction systems have been examined in an attempt to detect or to place upper limits on the rates of the simple inversion reaction, CH3 + CH4 → C2H6 + H, and its reverse. No positive evidence was obtained for the occurrence of these reactions. An upper limit for the rate constant for the forward reaction of 0.063 M−1s−1 at 802 K was obtained from the thermal decomposition of methane, and upper limits of 0.044 and 0.14 at 823 and 983 K respectively were estimated from the thermal decomposition of ethane. Other systems examined were the thermal decomposition of azomethane in the presence of methane, and the mercury-photosensitized decompositions of methane and ethane, which were complicated by unexpected side reactions.

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Section: The Thermal Decomposition Of Methanesupporting

confidence: 68%

Section: The Thermal Decomposition Of Methanementioning

confidence: 59%

Section: Ch3mentioning

confidence: 99%

“…In the present study, the following systems were examined in an attempt to detect reaction [2] or to place upper limits on [4] CH,…”

Section: Ch3mentioning

confidence: 99%

Section: Ch3mentioning

confidence: 99%

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A search for a gas-phase free-radical inversion displacement reaction at a saturated carbon atom

Back¹

1983

Can. J. Chem.

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Kinetic Modeling of CO Production from the Reaction of CH₃with O₂in Shock Waves

Hsu¹,

Shaub²,

Creamer³

et al. 1983

Ber Bunsenges Phys Chem

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CO concentration‐time profiles have been measured by using CO laser resonance absorption in shock tube experiments on the reaction of CH3 with O2 in the temperature range from 1150 to 1560 K. Computer kinetic modeling of our profile data yielded k2 = 1.0 x 1014 e−(15,500 ± 1,100)/T cm3mol sec for the CH3 + O2 → CH3O + O reaction. An RRKM calculation, which took into consideration branching of the CH3 + O2 reaction into different product channels, revealed that by assuming a loose transition state (allowing two free internal rotations) leading to the CH3O + O product channel, we could account very satisfactorily for our results as well as those reported previously for the reaction. A three‐parameter leastsquares fit of a smooth curve covering data from three independent studies gave rise to the expression: k2 = 2.20 x 1034 (T/K)−5.94 exp (–21,300 K/T) cm3mol sec for the temperature range 1150‐2300 K.

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