17 C. J. Jachimowski, Combust. Flame, 1984 , 55, 213.
values of K and k are probably known more accurately
than k , it is appropriate to use the present values of [buta-1,3-
15
13
18 D. Voisin, A. Marchal, M. Reuillon, J.-C. Boettner and M.
Cathonnet, Combust. Sci. T echnol., 1998, 138, 137.
19 D. L. Baulch, C. J. Cobos, R. A. Cox, C. Esser, P. Frank, Th. Just,
J. A. Kerr, M. J. Pilling, J. Troe, R. W. Walker and J. Warnatz, J.
Phys. Chem. Ref. Data, 1992, 21, 411.
b
diene]/[CXE] to calculate k reliably. From the values of
b
106K k /k \ 6.8, 3.3 and 0.43 mol dm~3, 104k \ 8.3, 5.3
15 b 13
b
and 1.5(2) s~1 at 773, 753, and 713 K, respectively; values at
673 K were not possible because the yields of buta-1,3-diene
were too low to measure accurately. As the analytical evidence
suggests that the butenyl radicals formed in (16) mostly react
with O , then k B k and, within the narrow temperature
20 S. W. Benson, T hermochemical Kinetics, Wiley, New York, 1976.
21 S. K. Gulati and R. W. Walker, J. Chem. Soc., Faraday T rans. 2,
1989, 85, 1799.
22 A. P. Zeelenberg and H. W. de Bruijn, Combust. Flame, 1965, 9,
281.
2
b
16
region used, Arrhenius parameters of E \ 130 ^ 8 kJ mol~1
23 B. H. Bonner and C. F. H. Tipper, Combust. Flame, 1965, 9, 317.
24 S. Zeppieri, K. Brezinsky and I. Glassman, Combust. Flame, 1997,
108, 266.
16
and log(A /s~1) \ 13.7 ^ 0.7 are recommended. The values
16
are similar to those given for use at 500 Torr by Handford-
25 R. R. Baldwin, I. A. Pickering and R. W. Walker, J. Chem. Soc.,
Faraday T rans. 1, 1980, 76, 2374.
Styring and Walker42 and imply that there is little fall-o† in
the rate constant at 15 Torr.
A similar analysis for the relative yields of propene and
CXE was not attempted because the data for propene were
more scattered, and secondary formation more important.
26 G. A. Evans and R. W. Walker, J. Chem. Soc., Faraday T rans. 1,
1979, 75, 1458.
27 G. Atri, R. R. Baldwin, G. A. Evans and R. W. Walker, J. Chem.
Soc., Faraday T rans. 1, 1978, 74, 366.
28 R. R. Baldwin, P. Doran and and L. Mayor, T rans. Faraday Soc.,
1960, 56, 93.
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8
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2052
Phys. Chem. Chem. Phys., 2001, 3, 2043È2052