Journal of the Chemical Society - Faraday Transactions p. 1431 - 1438 (1995)
Update date:2022-08-24
Topics:
Handford-Styring, Susan M.
Walker, Raymond W.
A number of elementary reactions involved in the oxidation of cyclopentane (CP) have been studied by adding CP to H2-O2 mixtures over the temperature range 673-783 K.Kinetic studies of the relative rates of consumption of CP and H2 have given values of k21 = (1.11 +/- 0.25)E10 and k22 = (1.84 +/- 0.32)E9 dm3 mol-1 s-1 at 753 K.Combination with independent data and critical analysis gives k21 = 3.65E2 T2.5 exp(519/T) dm3 mol-1 s-1, which is recommended between 250 and 1500 K, with error limits of < 20percent.Similarly, k22 = 2.4E6 T1.5 exp(-2440/T) dm3 mol-1 s-1 is recommended between 300 and 1250 K.OH + c-C5H10 --> c-C5H9 + H2O (21).H + c-C5H10 --> c-C5H9 + H2 (22).Analytical studies over a range of mixture compositions have shown that the major initial products are c-pentane, 1,2-epoxycyclopentane, acrolein and, at low a significant influence on parts of the mechanism.In particular, in the range 673-783 K and at a value of k32 = 1E(13.14 +/- 0.55) exp(-17260/T) s-1 has been obtained over the temperature range 580-783 K. c-C5H9 --> CH2=CHCH2CH2CH2 (32).The cyclisation of C3, C4, C5 and C6 alken-1-yl radicals has been discussed and it has been concluded that the predominant reaction of hex-5-en-1-yl radicals between 600 and 1300 K and at 1 atm O2 pressure is cyclisation giving c-hexyl radicals.As the latter rapidly undergo successive oxidation to cyclohexene, cyclohexadiene and then benzene, it has been further concluded that such C6 cyclisations could be major sources of benzene and substituted benzenes in the oxidation of conventional fuels.
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