FREE RADICALS BY MASS SPECTROMETRY: XXXV. THE HEAT OF FORMATION OF ALLYL RADICAL FROM BIALLYL PYROLYSIS
- 15 September 1966
- journal article
- Published by Canadian Science Publishing in Canadian Journal of Chemistry
- Vol. 44 (18), 2211-2217
- https://doi.org/10.1139/v66-332
Abstract
The thermal decomposition of biallyl has been investigated from 977 – 1 070 °K at helium carrier gas pressures of 10–50 Torr. Under these conditions the rate of central C—C bond fission to give two allyl radicals can be measured without interference from secondary reactions. The reaction at the pressures employed is first order with respect to biallyl, but between first and second order in the total pressure. The temperature dependence of the rate constants, extrapolated to infinite pressure, and corrected to 298 °K, gives an activation energy of 45.7 kcal/mole for the reaction, corresponding to ΔHf(allyl) = 33.0 kcal/mole.Keywords
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