The kinetics of the gas phase decomposition reactions of the hexafluoro‐ t ‐butoxy radical

Hexafluoro‐ t ‐butoxy radicals have been generated by reacting fluorine with hexafluoro‐2‐methyl isopropanol:Over the temperature range of 406–600 K the hexafluoro‐ t ‐butoxy radical decomposes exclusively by loss of a CF 3 radical [reaction (‐2)] rather than by loss of a CH 3 radical [reaction (‐1)]:The limits of detectability of the product CF 3 COCF 3 , by gas‐chromatographic analysis, place a lower limit on the ratio k −2 / k ‐1 of ∼80. The implications of this finding in relation to the reverse radical addition reactions to the carbonyl group are briefly discussed. A thermochemical kinetic calculation reveals a discrepancy in the kinetics and thermodynamics of the decomposition and formation reactions of the related t ‐butoxy radical: