Mechanism of the ozone-ethene reaction in dilute N2/O2 mixtures near 1-atm pressure

Kan, Charles S.; Su, Fu; Calvert, Jack G.; Shaw, John H.

doi:10.1021/j150616a013

Cited by 49 publications

(61 citation statements)

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“…The values obtained at room temperature and atmospheric pressure by Su et al (1980) Kan et al (1981) (37±2%), Niki et al (1981) (35±5%), ) (39.0±5.3%) and (39±11%) are in good agreement (with an average yield of 37%) and are preferred to the slightly higher value of 47% obtained by . The yield of stabilized Criegee intermediate appears to be pressure dependent although a significant fraction have been reported to be formed thermally "cold" at low pressures; by extrapolation of measurements over the range 13 mbar to 1.5 bar, found this fraction to be 20±3% at zero pressure.…”

Section: Comments On Preferred Valuesmentioning

confidence: 60%

“…These two studies result in rate coefficients (Bahta et al, 1984; which are somewhat lower than many of the previous determinations, including those of Su et al (1980) and Kan et al (1981) which are not used in this evaluation. Since did not tabulate the individual rate coefficients at the various temperatures studied, only their 298 K value can be used in the evaluation of the rate coefficient for this reaction.…”

Section: Comments On Preferred Valuesmentioning

confidence: 67%

“…Studies have been made of the reactions of RCHOO with aldehydes (Su et al, 1980;Fenske et al, 2000;Cox and Penkett, 1972;Hanst et al, 1958;Kan et al, 1981;Niki et al, 1975Niki et al, , 1981Neeb et al, 1995), SO 2 Su et al, 1980, Cox andPenkett, 1972;Kerr and Calvert, 1984;, H 2 O (Cox and Penkett, 1972;Akimoto et al, 1979;Kan et al, 1981), carboxylic acids (Neeb et al, 1995; and methanol , but detailed kinetic data are often lacking. Relative rate coefficients have been derived by , Su et al (1980) and Suto et al (1985) based on experimental measurements of the rates of consumption of molecular reactants relative to consumption of SO 2 in systems involving RCHOO Criegee intermediates.…”

Section: Comments On Preferred Valuesmentioning

confidence: 99%

Section: Comments On Preferred Valuesmentioning

confidence: 99%

“…However, the formation of ethene ozonide has not been observed in the reaction of CH 2 OO with HCHO or in the O 3 -ethene reaction (Su et al, 1980;Kan et al, 1981;Niki et al, 1981. The proposal that the reaction of the CH 2 OO Criegee intermediate with HCHO leads to HOCH 2 OCHO (Su et al, 1980;Kan et al, 1981;Niki et al, 1981 has now been shown to be incorrect. The spectrum observed in the CH 2 OO-HCHO reaction and assigned to HOCH 2 OCHO is now known to belong to HOOCH 2 OCHO (Neeb et al, 1995;Thamm et al, 1996), which is formed by the reaction of the CH 2 OO Criegee intermediate with HC(O)OH.…”

Section: Comments On Preferred Valuesmentioning

confidence: 99%

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Evaluated kinetic and photochemical data for atmospheric chemistry: Volume II – gas phase reactions of organic species

et al. 2006

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Abstract. This article, the second in the series, presents kinetic and photochemical data evaluated by the IUPAC Subcommittee on Gas Kinetic Data Evaluation for Atmospheric Chemistry. It covers the gas phase and photochemical reactions of Organic species, which were last published in 1999, and were updated on the IUPAC website in late 2002, and subsequently during the preparation of this article. The article consists of a summary table of the recommended rate coefficients, containing the recommended kinetic parameters for the evaluated reactions, and eight appendices containing the data sheets, which provide information upon which the recommendations are made.

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Section: Comments On Preferred Valuesmentioning

confidence: 60%

Section: Comments On Preferred Valuesmentioning

confidence: 67%

Section: Comments On Preferred Valuesmentioning

confidence: 99%

Section: Comments On Preferred Valuesmentioning

confidence: 99%

Section: Comments On Preferred Valuesmentioning

confidence: 99%

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Evaluated kinetic and photochemical data for atmospheric chemistry: Volume II – gas phase reactions of organic species

et al. 2006

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The reactions of the Criegee intermediate CH3 CHOO in the gas-phase ozonolysis of 2-butene isomers

Horie

Neeb

Moortgat

1997

Int. J. Chem. Kinet.

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The Ozonolysis of Ethylene: A Theoretical Study of the Gas-Phase Reaction Mechanism

1999

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The gas-phase reaction mechanism of ethylene ozonolysis has been investigated from a theoretical point of view. The formation of the ethylene primary ozonide (1,2,3-trioxolane, POZ) from the ozone ± ethylene reaction is calculated to be exothermic by 49.2 kcal mol À1 with an activation energy of 5.0 kcal mol À1 at 0 K, in agreement with experimental estimates. We have found two different paths for the cleavage of POZ, namely a concerted and a stepwise mechanism. The concerted path leads to the formation of Criegee intermediates (carbonyl oxide ± formaldehyde pairs), for which we have calculated an activation energy of 18.7 kcal mol À1 at 0 K. The non-concerted mechanism involves three different routes for the POZ decomposition, leading to the formation of Criegee intermediates with a computed activation energy of 21.6 kcal mol À1 at 0 K; to hydroperoxyacetaldehyde with a calculated activation energy of 22.8 kcal mol À1 at 0 K; and to oxirane excited molecular oxygen ( 1 D g ) with a higher activation energy. Moreover, hydroperoxyacetaldehyde is formed with an excess of energy, so that it can decompose yielding OH radicals. The reaction of carbonyl oxide and formaldehyde produces the ethylene secondary ozonide (1,2,4-trioxolane, SOZ) and involves the formation of a van der Waals complex on the reaction coordinate, prior to the transition state. The process is calculated to be exothermic by 46.0 kcal mol À1 and the energy of the transition state is computed to be lower than that of the reactants: this process can therefore be considered barrierless. SOZ cleaves by a stepwise mechanism and we have found two different fates for its decomposition: dioxymethane formaldehyde, and hydroxymethyl formate. The former is calculated to be endothermic by 33.3 kcal mol À1 with an energy barrier of 48.7 kcal mol À1, whereas the tautomerization of SOZ leading to hydroxymethyl formate is highly exothermic (72.2 kcal mol À1) and has an activation energy of 32.6 kcal mol À1 at 0 K. The unimolecular decomposition of dioxymethane, following three different paths, is also reported: dissociation into CO 2 H 2 , which is highly exothermic (111.6 kcal mol À1) and has a low energy barrier (3.0 kcal mol À1 ); isomerization to formic acid, also highly exothermic (101.9 kcal mol À1 ) with a low activation energy (2.2 kcal mol À1 at 0 K); and radical fragmentation into H HCOO, in a slightly endothermic process (4.9 kcal mol À1) with an activation energy of 18.4 kcal mol À1 at 0 K. The dissociation of formic acid into H 2 , CO 2 , CO and H 2 O and the decomposition of HCOO into H radicals CO 2 are also discussed.

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Mechanism of the ozone-ethene reaction in dilute N2/O2 mixtures near 1-atm pressure

Cited by 49 publications

References 1 publication

Evaluated kinetic and photochemical data for atmospheric chemistry: Volume II – gas phase reactions of organic species

Evaluated kinetic and photochemical data for atmospheric chemistry: Volume II – gas phase reactions of organic species

The reactions of the Criegee intermediate CH3 CHOO in the gas-phase ozonolysis of 2-butene isomers

The Ozonolysis of Ethylene: A Theoretical Study of the Gas-Phase Reaction Mechanism

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