The pyrolysis of bromodifluoromethane has been examined over the temperature range 437–515 °C with initial pressures of reactant between 20 and 250 Torr. The predominant mode of decomposition involves an α-elimination of hydrogen bromide to give difluoromethylene as the initial step (i) but there is also a free-radical chain component CF2HBr = CF2+ HBr (i) to the decomposition which is reduced to negligible importance by the presence of propene. The α-elimination component of the reaction is homogeneous and of the first order in the initial stages, but inhibition by hydrogen bromide becomes important as the reaction proceeds. The first-order rate constant obtained from the initial rates is independent of pressure and is given by log k1/s–1= 14·33 ± 0·32 –(55,600 ± 1100)/4·576T. The rate constant (k2) for the reverse reaction has also been evaluated as log k2/l mol–1 s–1= 8·33 ± 0·37 –(9600 ± 1300)/4·576T and combination of these Arrhenius parametes with the relevant heats of formation and standard entropies give ΔH°f(CF2)=–42 kcal mol–1 and S°(CF2)= 66·2 cal mol–1 K–1 at 750 K, which are in good agreement with literature values.
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Journal of the Chemical Society B: Physical Organic
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