Kinetic Study of the Pyrolisis of Neopentane during Its Induction Period

Article abstract of DOI:10.1021/j100455a002

Induction periods have been observed for the formation of methane and 2-methyl-1-butene in the flow pyrolysis of neopentane at 823 deg K.The induction periods for methane were interpreted as evidence of the approach to the steady state.Independendent rate constants for the following reactions have been calculated from methane and ethane yields: (CH3)4C-->CH3 + (CH3)3C, k₁ = (1.7 +/- 0.1) x 1E-5 s_-1; CH3 + (CH3)4C --> CH4 + (CH3)3CCH2., k₅ = (1.6 +/- 0.1) x 1E6 L mol_-1 s_-1; and CH3 + (CH3)2CCH2 --> CH4 + CH3C(CH2)2., k₇ = 2.2 x 1E6 L mol_-1 s_-1.Values of the rate constant for the reaction 2CH3 --> C2H6 at 4-335 mmHg have been extrapolated to find the high-pressure limiting value, k_6,<*> = (2.2 +/- 0.5) x 1E10 L mol_-1 s_-1.The induction period found for 2-methyl-1-butene indicates that this is a secondary product; the vicinal methyl radical shift reaction, (CH3)3CCH2. --> (CH3)2C<*>C2H5, was not observed to contribute to formation of the product.