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: equation image Over the temperature range of 406–600 K the hexafluoro‐t‐butoxy radical decomposes exclusively by loss of a CF3 radical [reaction (‐2)] rather than by loss of a CH3 radical [reaction (‐1)]: equation image The limits of detectability of the product CF3COCF3, 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: equation image