Infrared-matrix and microwave spectroscopy of the ethylene-ozone gas-phase reaction

Kühne, Heinz; Vaccani, S.; Ha, Tae–Kyu; Bauder, A.; Günthard, Hs. H.

doi:10.1016/0009-2614(76)80013-9

Cited by 38 publications

(17 citation statements)

References 10 publications

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“…Vereecken . Finally, CH 2 OO may react with CO to make formic anhydride (reaction E), as suggested by Kühne et al (48). As CO is a dissociation product of vibrationally excited formic acid, this reaction is certainly possible, and we see evidence of formic anhydride (13).…”

Section: Resultssupporting

confidence: 72%

Observation of the Simplest Criegee Intermediate Ch2oo in the Gas-Phase Ozonolysis of Ethylene

Womack¹,

Martin-Drumel²,

Brown³

et al. 2015

Proceedings of the 70th International Symposium on Molecular Spectroscopy

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Ozonolysis is one of the dominant oxidation pathways for tropospheric alkenes. Although numerous studies have confirmed a 1,3-cycloaddition mechanism that generates a Criegee intermediate (CI) with form R 1 R 2 COO, no small CIs have ever been directly observed in the ozonolysis of alkenes because of their high reactivity. We present the first experimental detection of CH 2 OO in the gas-phase ozonolysis of ethylene, using Fourier transform microwave spectroscopy and a modified pulsed nozzle, which combines high reactant concentrations with rapid sampling and sensitive detection. Nine other product species of the O 3 + C 2 H 4 reaction were also detected, including formaldehyde, formic acid, dioxirane, and ethylene ozonide. The presence of all these species can be attributed to the unimolecular and bimolecular reactions of CH 2 OO, and their abundances are in qualitative agreement with published mechanisms and rate constants.

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Section: Resultssupporting

confidence: 72%

Observation of the Simplest Criegee Intermediate Ch2oo in the Gas-Phase Ozonolysis of Ethylene

Womack¹,

Martin-Drumel²,

Brown³

et al. 2015

Proceedings of the 70th International Symposium on Molecular Spectroscopy

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“…There have been extensive studies of ozone reactions with ethylene [Herron and Huie, 1977;Kuhne et al, 1976]. The products are uncertain, but include mostly CO, H20, and CH20.…”

Section: Ch2oh + 02 --> Ch2ohoo Ch2ohoo + No --> Ch2oho + No2mentioning

confidence: 99%

“…The rate is only 1.6 x 10 -19 cm 3 s -1 so that the reaction of 03 with C2H4 is slow compared to that with OH. Kuhne et al [1976] has noted the possible formation of CH3CHO which can lead to the production of PAN in the presence of NO2. Most of the ethylene reaction paths lead to CH20 as the primary product.…”

Section: Ch2oh + 02 --> Ch2ohoo Ch2ohoo + No --> Ch2oho + No2mentioning

confidence: 99%

Atmospheric chemistry of ethane and ethylene

Aikin¹,

Herman²,

Maier³

et al. 1982

J. Geophys. Res.

117

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A detailed study of ethane and ethylene photochemistry is presented for the troposphere and stratosphere. It is demonstrated that the loss of ethane is controlled by OH in the troposphere and Cl in the stratosphere. Observations of ethane show a stratospheric behavior indicative of a free chlorine concentration below 30 km that is only 10% of the predicted value given by both our photochemical model calculations and those done by others. The inferred lower amount of chlorine cannot be explained by heterogeneous processes for concentrations of aerosols representing average background conditions, nor does current stratospheric photochemistry show agreement. Chemical destruction of ethane and ethylene within the atmosphere leads to the production of carbon monoxide, formaldehyde, and other products. Tropospheric concentrations of formaldehyde are enhanced by nearly a factor of 3 for an ethylene mixing ratio of 2 ppb. Simultaneous monitoring of formaldehyde and carbon monoxide, as well as other products, will greatly aid in determining the relative importance of different tropospheric CO sources. Peroxyacetyl nitrate (PAN) acts as a reservoir for odd‐nitrogen at the expense of HNO3, HO2NO2, NO, and NO2.

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“…Buras and co-workers ( 47 ) have measured this rate coefficient as k D = 6.0 × 10 −11 cm 3 molecule −1 s −1 . Finally, CH 2 OO may react with CO to make formic anhydride (reaction E), as suggested by Kühne et al ( 48 ). As CO is a dissociation product of vibrationally excited formic acid, this reaction is certainly possible, and we see evidence of formic anhydride ( 13 ).…”

Section: Resultsmentioning

confidence: 85%

Observation of the simplest Criegee intermediate CH ₂ OO in the gas-phase ozonolysis of ethylene

et al. 2015

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Infrared-matrix and microwave spectroscopy of the ethylene-ozone gas-phase reaction

Cited by 38 publications

References 10 publications

Observation of the Simplest Criegee Intermediate Ch2oo in the Gas-Phase Ozonolysis of Ethylene

Observation of the Simplest Criegee Intermediate Ch2oo in the Gas-Phase Ozonolysis of Ethylene

Atmospheric chemistry of ethane and ethylene

Observation of the simplest Criegee intermediate CH ₂ OO in the gas-phase ozonolysis of ethylene

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Infrared-matrix and microwave spectroscopy of the ethylene-ozone gas-phase reaction

Cited by 38 publications

References 10 publications

Observation of the Simplest Criegee Intermediate Ch2oo in the Gas-Phase Ozonolysis of Ethylene

Observation of the Simplest Criegee Intermediate Ch2oo in the Gas-Phase Ozonolysis of Ethylene

Atmospheric chemistry of ethane and ethylene

Observation of the simplest Criegee intermediate CH 2 OO in the gas-phase ozonolysis of ethylene

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Observation of the simplest Criegee intermediate CH ₂ OO in the gas-phase ozonolysis of ethylene