Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases p. 3195 - 3207 (1984)
Update date:2022-08-16
Topics:
Baldwin, Robert R.
Drewery, George R.
Walker, Raymond W.
A detailed product analysis has been carried out over a wide range of mixture composition on the decomposition of 2,3-dimethylbutane (DMB) in the presence of O2 in KCl-coated vessels between 480 and 540 deg C.Propene, 2-methylbut-2-ene, CH4, HCHO and 2,3-dimethylbut-1-ene are the major initial products, with smaller amounts of 2,3-dimethylbut-2-ene, 3-methylbut-1-ene, but-2-ene and, at high O2 pressures, tetramethyloxirane.By extrapolation of product yields to zero O2 and DMB pressure to remove contributions from the chain processes, values of ko of 0.0211+/-0.0027 dm3mol-1s-1 at 500 deg C and 0.163+/-0.011 dm3mol-1s-1 at 540 deg C are obtained: (equation).No other values of ko available for DMB or any analogous reaction involving a hydrocarbon, despite the importance of this type of reaction in combustion.The recommended Arrhenius parameters are log10(Ao/dm3mol-1s-1) = 10.31+/-0.25 and Eo = 173+/-3.5 kJ mol-1.These parameters are consistent with a dissociation energy of 387 kJ mol-1 for the tertiary C-H bond in DMB, in excellent agreement with recent values for that in i-butane.Detailed studies of the relative yileds of the products have permitted rate constants to be obtained, and Arrhenius parameters to be recommended, for a number of the elementary steps in the DMB+O2 system.Patterns in the variation of rate constants for different alkyl radical homolyses and alkyl+O2 reactions are discussed.
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