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Addition of Pentenes to Slowly Reacting Mixtures of Hydrogen and Oxygen at 480 deg C

DOI: 10.1039/f19807602396

Source and publish data:

Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases p. 2396 - 2412 (1980)

Update date:2022-08-04

Topics:

Authors:

Baldwin, Roy R.Baldwin, Roy R.

Bennett, Joan P.Bennett, Joan P.

Walker, Raymond W.Walker, Raymond W.

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Article abstract of DOI:10.1039/f19807602396

A detailed analysis has been made of the products formed when 1percent of pent-1-ene and of cis-pent-2-ene are added to slowly reacting mixtures of H2 + O2 in aged boric-acid-coated vessels at 480 deg C.The primary products are formed through four different types of attack on the pentenes of almost equal importance, radical addition of H, OH, and HO2, and H atom abstraction from the pentenes by all three radicals.Penta-1,3-diene is the only C5 diene observed, in marked contrast to an earlier study of pentene oxidation.From measurements of the initial relative yields of penta-1,3-diene and buta-1,3-diene, a value of k2 = 2.1 x 1E6 dm3 mol-1 s-1 at 480 deg C is obtained. This is the first value determined for a reaction of this type and is at least ten times lower than rate constants for the formation of an alkene from an alkyl radical.This decrease is consistent with the considerably lower enthalpy change in reaction (2).Product analysis suggests that H atoms add almost equally at the two positions in pent-2-ene, and in the ratio of 0.65 +/-0.2 for non-terminal/terminal addition in pent-1-ene.In contrast to the behaviour of vibrationally-excited propyl and butyl radicals formed by H atom addition to alkenes, there is no evidence for an enhanced rate of decomposition of the pentyl radicals formed from the pentenes.Conjugate oxirans are formed mainly by HO2 addition to the pentenes, and lower aldehydes mainly by OH addition.

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