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Reactions of Ethyl Radicals with Oxygen over the Temperature Range 400-540 deg C

DOI: 10.1039/f19807602374

Source and publish data:

Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases p. 2374 - 2382 (1980)

Update date:2022-08-17

Topics:

Authors:

Baldwin, Roy R.Baldwin, Roy R.

Pickering, Ian A.Pickering, Ian A.

Walker, Raymond W.Walker, Raymond W.

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Article abstract of DOI:10.1039/f19807602374

The reactions of C2H5 radicals with O2 have been studied by adding ethene to mixtures of 2,2,3,3-tetramethylbutane + O2 and of H2 + O2.The only initial products from C2H5 radicals are ethylene and ethylene oxide in relative yields of ca. 100:1.For all mixtures studied, the ratio / is constant at low extents of reaction but then decreases due to formation of ethylene oxide by reaction (14).The initial value of the product ratio is independent of variations in mixture composition, total pressure and vessel surface.Over the temperature range 400-540 deg C, values of A1/A2 = 13.6 +/-2.1 and E2 - E1 = 12.5 +/-1.0 kJ mol-1 are obtained, where reaction (2) is the overall reaction for the formation of ethylene oxide..By the use of the trace amounts of butane formed at 540 deg C to calculate the concentration of C2H5 radicals, k1 = 7.7*1E7 dm3 mol-1 s-1 is obtained: combination of this with independent results at 440 deg C gives E1 = 16.2 kJ mol-1 and A1 = 1E8.93 dm3 mol-1 s-1, which are considered the most reliable parameters available for this reaction.Based on the formation of ethylene oxide in a peroxy radical isomerisation and decomposition sequence, values of log10(A16/s-1) = 13.29 +/-0.50 and E16 = 143.7 +/-10 kJ mol-1 are calculated for the transfer of a primary H atom (1.4p) in reaction (16).This A factor is higher, by a factor of about ten, than the figure suggested by Benson for a (1.5)H atom transfer. .

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