The rate constant for t‐C4H9 → H + i‐C4H8 and the thermodynamic parameters of t‐C4H9

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Abstract
The rate of the reverse reaction of the system equation image has been measured in the range of 584–604 K from a study of the azomethane sensitized pyrolysis of isobutane. Assuming the published value for the rate constant of recombination of t‐butyl we obtain Combination with our published data for k1 permits the evaluation We have modified a previously published structural model of t‐butyl by the inclusion of a barrier to free rotation of the methyl groups in order to calculate values of the entropy and enthalpy of t‐butyl as a function of temperature. Using standard data for H and for i‐C4H8 we obtain We have obtained other, independent values of this quantity by a reworking of published data using our new calculations of the entropy and enthalpy of t‐butyl. There is substantial agreement between the different values with one exception, namely, that derived from published data on the equilibrium which is significantly lower than the other values.We conclude that the value obtained from the present work and a reworking of published data which involves the use of experimental data on t‐butyl recombination is incompatible with the result based on iodination data.

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