Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases p. 825 - 837 (1980)
Update date:2022-08-31
Topics:
Baldwin, Roy R.
Walker, Raymond W.
Walker, Robert W.
The decomposition of 2,2,3-trimethylbutane in the presence of O2 in KCl-cloated vessels has been studied at 480 deg C and 550 deg C over the pressure range 60-500 Torr.At low alkane pressures, where the chain contribution is small, the results are consistent with a simple mechanism comprising reactions (10), (11), (2) and (3). (CH3)3CCH(CH3)2 -> t-C4H9 + i-C3H7 (10), i-C3H7 + O2 -> C3H6 + HO2 (11), t-C4H9 + O2 -> i-C4H8 + HO2 (2), HO2 -> 1/2 H2O + 3/4 O2 (3).From measurements of the i-butene yields, accurate rate constants may be obtained for reaction (10) wich, when combined with Tsangs results, give log10(A10/s-1) = 16.46 +/- 0.12 and E10 = 305.0 +/- 1.5 kJmol-1 over the temperature range 480-925 deg C.Following a discussion of the thermochemistry of reaction (10) and the value of k-10, values of ΔfHo298(t-Bu) = 37.6 +/- 2.0 and ΔfHo298(i-Pr) = 80.8 +/- 4.0 kJmol-1 are recommended, wich correspond to Do298(t-Bu) = 390.2 +/- 2.0 and Do298(i=Pr) = 402.5 +/- 4.0 kJmol-1, respectively.Two of three species of radicals formed by radial attack on 2,2,3-trimethylbutane appear to react solely by C-C homolysis of the central C-C bond.The third radical, (CH3)3CC(CH3)2, reacts mainly by homolysis, but also forms the minor initial products 2,3,3-trimethylbut-1-ene, acetone and 2,3-dimethylbut-2-ene.A value of k17 = 1.4 * 103s-1 at 480 deg C has been obtained. (CH3)3CC(CH3)2 -> (CH3)2=C(CH3)2 + CH3 (17).
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