Decomposition of 4,4-Dimethylpent-1-ene in the Presence of Oxygen between 400 and 500 deg C: Oxidation Chemistry of Allyl Radicals

DOI: 10.1039/ft9918700681

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Journal of the Chemical Society - Faraday Transactions p. 681 - 689 (1991)

Update date:2022-08-17

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Authors:

Lodhi, Zulfiqar H.

Walker, Raymond W.

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Article abstract of DOI:10.1039/ft9918700681

The decomposition of 4,4-dimethylpent-1-ene (DMP) in the presence of O2 has been used as a source of allyl radicals over the temperature range 400-500 deg C.The reaction has been studied in both KCl-coated (peroxy species destroyed at the surface) and aged boric-acid-coated vessels (peroxy species preserved), and the basic mechanism shown to be: (1) (2).Previous studies have shown that 99percent of the t-butyl radicals undergo reaction (2), so that the system is an excellent source of allyl and HO2 radicals.A full product analysis has carried out over a wide range of mixture composition and associated mechanistic aspects discussed.It is shown that allyl radicals are unreactive towards both DMP and O2 and that they react mainly in radical-radical processes. (3) (8) (18).Values of k₈/k₁₈ = 0.37, 0.38 and 0.42 are obtained at 400, 440 and 480 deg C, respectively.From a reasonably reliable estimate of and , values of k₈ = (3.3 +/- 0.9) * 1E9 and k₁₈ = (7.4 +/- 2.4) * 1E9 dm³ mol^-1 s^-1 are obtained at 480 deg C.No previous estimates of these rate constants are available in the literature.Values of k₄ have been determined and when combined with independent data at higher temperatures give log(A₄/s^-1) = 14.19 +/- 0.25 and E₄ = 255.5 +/- 5.3 kJ mol^-1 over the range 400-1025 deg C.DMP -> (CH3)2C=CH2 + CH3CH=CH2 (4).A value of K₁₁ = (2.5 +/- 1) * 1E2 dm³ mol^-1 s^-1 has been obtained at 480 deg C and shown to be consistent with the reaction's high endothermicity. (11)

Full text of DOI:10.1039/ft9918700681

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