Addition of cyclopentane to slowly reacting mixtures of H2+ O2 between 673 and 783 K: reactions of H and OH with cyclopentane and of cyclopentyl radicals

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)× 1010 and k22=(1.84 ± 0.32)× 109 dm3 mol–1 s–1 at 753 K. Combination with independent data and critical analysis gives k21= 3.65 × 102T2.5 exp(519/T) dm3 mol–1 s–1, which is recommended between 250 and 1500 K, with error limits of 50 Torr, very little ring rupture has been observed in the initial products. The formation of C2H4 has been discussed in detail, and a value of k32= 1013.14 ± 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.

[1]  Michael J. Pilling,et al.  Evaluated Kinetic Data for Combustion Modelling , 1992 .

[2]  A. Wagner,et al.  Experimental and theoretical studies of the ethyl + oxygen reaction kinetics , 1990 .

[3]  J. Bott,et al.  A shock tube study of the reaction of the hydroxyl radical with H2, CH4, C-C5H10, and i-C4H10 , 1989 .

[4]  John T. Herron,et al.  Evaluated Chemical Kinetic Data for the Reactions of Atomic Oxygen O(3P) with Saturated Organic Compounds in the Gas Phase , 1988 .

[5]  F. P. Tully,et al.  Hydrogen-atom abstraction from alkanes by hydroxyl radical. 6. Cyclopentane and cyclohexane , 1987 .

[6]  R. Walker.  Temperature coefficients for reactions of OH radicals with alkanes between 300 and 1000 K , 1985 .

[7]  N. Cohen.  The use of transition-state theory to extrapolate rate coefficients for reactions of H atoms with alkanes , 1982 .

[8]  W. Carter,et al.  Ring opening of chemically activated cyclopentyl and methylcyclobutyl radicals , 1974 .

[9]  A. Gordon.  A STUDY OF SOME REACTIONS OF THE CYCLOPENTYL RADICAL , 1965 .

[10]  R. Holroyd,et al.  MERCURY-PHOTOSENSITIZED DECOMPOSITION OF ALIPHATIC HYDROCARBONS—RADICAL DETECTION WITH ETHYL-CARBON-14 RADICALS1 , 1963 .

[11]  A. Gordon,et al.  The Reaction of Methyl-d3Radicals with Cyclopropane and Cyclopentane , 1957 .

[12]  R. Walker,et al.  Oxidation of allyl radicals: kinetic parameters for the reactions of allyl radicals with HO2 and O2 between 400 and 480 °C , 1991 .

[13]  R. Walker,et al.  Addition of cyclohexane to slowly reacting H2–O2 mixtures at 480 °C , 1989 .

[14]  R. R. Baldwin,et al.  Studies of the decomposition of oxirane and of its addition to slowly reacting mixtures of hydrogen and oxygen at 480 °C , 1984 .

[15]  M. Hisham,et al.  Arrhenius parameters of elementary reactions involved in the oxidation of neopentane , 1982 .

[16]  R. R. Baldwin,et al.  Addition of n-pentane to slowly reacting mixtures of hydrogen + oxygen at 480 °C , 1980 .

[17]  R. R. Baldwin,et al.  Reactions of ethyl radicals with oxygen over the temperature range 400–540° C , 1980 .

[18]  R. R. Baldwin,et al.  Rate constants for hydrogen + oxygen system, and for H atoms and OH radicals + alkanes , 1979 .

[19]  R. R. Baldwin,et al.  Addition of n-C4H10 and C4H8 to slowly reacting mixtures of hydrogen and oxygen at 480°C. Part 1.—Formation of hydrocarbon products , 1975 .

[20]  R. R. Baldwin,et al.  Addition of ethane to slowly reacting mixtures of hydrogen and oxygen at 500°C , 1970 .

[21]  R. R. Baldwin,et al.  Addition of C3H8 to slowly reacting mixtures of hydrogen and oxygen at 480°C , 1970 .

[22]  R. R. Baldwin,et al.  Interpretation of induction periods in the hydrogen + oxygen reaction in aged boric-acid-coated vessels , 1967 .