ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The rate of the reverse reaction of the system 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 \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k_{{\rm - 1}} (\sec ^{- 1}) = 14.67 - 39.4\,{\rm kcal}/{\rm mol}/(2.3{\rm RT}) $$\end{document} Combination with our published data for k1 permits the evaluation \documentclass{article}\pagestyle{empty}\begin{document}$$ \log K_1 ({\rm atm}^{ - 1}) = 7.94\,\,{\rm at}\,\,600{\rm K} $$\end{document}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 \documentclass{article}\pagestyle{empty}\begin{document}$$ \Delta H_ f^\circ(t - {\rm butyl},\,300\,{\rm K})({\rm kcal}/{\rm mol}) = 10.6 \pm 0.5 $$\end{document}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 \documentclass{article}\pagestyle{empty}\begin{document}$$ i - {\rm C}_{\rm 4} {\rm H}_{{\rm 10}} + {\rm I}\rightleftharpoons t{-} {\rm C}_4 {\rm H}_9 + {\rm HI} $$\end{document} which is significantly lower than the other values.We conclude that the value \documentclass{article}\pagestyle{empty}\begin{document}$$ \Delta H_ f^\circ(t - {\rm butyl},\,300\,{\rm K})({\rm kcal}/{\rm mol}) = 10.5 \pm 1.0 $$\end{document}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.
Additional Material:
9 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550130309
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