Gas- and liquid-phase oxidations of butane

Mill, Theodore; Mayo, Frank R.; Richardson, H. Wayne; Irwin, Katherine C.

doi:10.1021/ja00774a038

Cited by 46 publications

(52 citation statements)

References 3 publications

(5 reference statements)

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“…The ratio (k3/H)/(2k6)1/2 at 220°C is then calculated to be equal to 12 X 10-4M-1/2 sec-ll2. This value, together with those a t the lower temperatures, yields for (k3/H)/(2k6)ll2 an activation energy approximately equal to 13 kcal/mol, a value consistent with that observed in the autoxidation of n-butane at 100 and 125°C [21].…”

Section: Comparison Of P E T H and N-hexadecane Rate Parameterssupporting

confidence: 84%

Kinetics and mechanism of the autoxidation of pentaerythrityl tetraheptanoate at 180–220°C

Hamilton

Korček

Mahoney

et al. 1980

Int J of Chemical Kinetics

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A kinetic and mechanistic study of the autoxidation of liquid pentaerythrityl tetraheptanoate (PETH) a t 180-22OOC has been carried out utilizing a stirred-flow reactor. The results are consistent with the occurrence of a chain reaction scheme similar to that proposed for n -hexadecane autoxidation, namely, the formation of monohydroperoxides by the intermolecular abstraction reaction (3), the formation of a,?-and cu,d-dihydroperoxides and a,?-and a,b-hydroperoxyketones by intramolecular peroxy radical abstraction reactions (4) and (4*), the bimolecular termination of peroxy radicals, reaction (61, and the rapid conversion of a,?-hydroperoxyketones to the corresponding cleavage acids and methyl ketones, reaction (7). Comparisons ofvarious rate parameters for the n-hexadecane and PETH systems reveal that the values of k7 and (k&l atom)/(2 hfi)1/2 are within experimental uncertainties identical for the two systems a t 180°C. The proposed reaction scheme includes the concurrent formation of hydroxy radicals and hydroperoxyketone species. The results of kinetic analysis and the experimentally observed isomer distributions of primary and secondary monohydroperoxide products a t high and low oxygen pressures suggest that ~6 0 % of the hydrogen abstractions from PETH a t high oxygen pressures occur by hydroxy radicals.

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Section: Comparison Of P E T H and N-hexadecane Rate Parameterssupporting

confidence: 84%

Kinetics and mechanism of the autoxidation of pentaerythrityl tetraheptanoate at 180–220°C

Hamilton

Korček

Mahoney

et al. 1980

Int J of Chemical Kinetics

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“…A significant fraction of the overall reaction can apparently yield free alkoxy radicals. However, it is far from clear why, at similar temperatures, I-ethoxyethylperoxy pairs yield alkoxy radicals in (probably) 2 80% yield, while 1,2-diphenylethylperoxy pairs yield alkoxy radicals in -33% yield, and see-butylperoxy pairs yield sec-butoxy radicals in only -4% yield (4,6). Possibly dialkyl tetroxides that can yield alkoxy radicals, that are very subject to p-scission, decompose by multiple bond scission, i.e.…”

Section: Resultsmentioning

confidence: 99%

“…more slowly than low ~nolecular weight radicals experiments with initial hydroperoxide concentrations of 0. 18, 0.45, and 0.83 M were such that and so they will yield more peroxide if reaction 6 of Scheme 1 is the principal cage process. The cage lifetime may also be increased by hydrophobic bonding between the l-tert-butoxynonoxy radical pair.…”

Section: I-ethoxyethylperoxy Radicalsmentioning

confidence: 99%

“…concerted decomposition will be favored at The most frequently postulated alternative higher temperatures because it will have a higher mechanism involves decon~position of the activation energy than the concerted process. tetroxide to give two alkoxy radicals and oxygen For example, it has been estimated (6) that with (reaction 3). According to the Russell mechan-s-butylperoxy radicals k,/k, is -0.04 at 30" and ism the ketone, RR'CO, and the alcohol, -0.3 at 100".…”

mentioning

confidence: 99%

“…Numerous studies (1. 4,6,9,[13][14][15][16] attest to the fact that such products are the appropriate alcohol and Icetone and that these are formed in high yield and in approximately eyuiluolar amounts. Diaper's results prompted us, therefore, to investigate the products formed from an analogous perox] radical, I-ethoxyethylperoxy.…”

mentioning

confidence: 99%

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The Bimolecular Self-reactions of Secondary Peroxy Radicals. Product Studies

Lindsay¹,

Howard²,

Horswill³

et al. 1973

Can. J. Chem.

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The principal products formed from 1-ethoxyethyl hydroperoxide and 1,2-diphenylethyl hydroperoxide on oxidation with reagents that are presumed to generate the corresponding sec-alkylperoxy radicals (Ce(IV), tert-butoxy, and Ag2O) have been identified. The products formed when the corresponding alkoxy radicals are generated in pairs have also been identified. It is concluded that the Russell (1) concerted cyclic mechanism in which tetroxide decomposed to molecular products is not the exclusive route for the bimolecular self-reaction of sec-alkylperoxy radicals. It is suggested that there is also a second tetroxide decomposition process which yields radical products. The second process may yield "free" alkoxy radicals or it may, perhaps, yield the products of β-scission of the alkoxy radicals in a step concerted with O—O homolysis of the tetroxide. The relative importance of tetroxide decomposition to molecular and to radical products will depend on the structure of the alkyl groups, the temperature and, perhaps, the solvent.

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Photochemistry of the Troposphere

Levy¹

1974

Advances in Photochemistry

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Gas- and liquid-phase oxidations of butane

Cited by 46 publications

References 3 publications

Kinetics and mechanism of the autoxidation of pentaerythrityl tetraheptanoate at 180–220°C

Kinetics and mechanism of the autoxidation of pentaerythrityl tetraheptanoate at 180–220°C

The Bimolecular Self-reactions of Secondary Peroxy Radicals. Product Studies

Photochemistry of the Troposphere

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