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

✍ Scribed by Roger M. Drew; J. Alistair Kerr

Publisher: John Wiley and Sons
Year: 1983
Tongue: English
Weight: 392 KB
Volume: 15
Category: Article
ISSN: 0538-8066
DOI: 10.1002/kin.550150308

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✦ Synopsis

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 CF3 radical [reaction (-2)] rather than by loss of a CH3 radical [reaction (-111:

The limits of detectability of the product CF3COCF3, by gas-chromatographic analysis, place a lower limit on the ratio k-Zlk-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:

( 5 ) (-5) (CH3)aCO + (CH3)zCO + C H 3

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