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The kinetics of the gas phase decomposition reactions of the hexafluoro‐ t ‐butoxy radical
Author(s) -
Drew Roger M.,
Kerr J. Alistair
Publication year - 1983
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550150308
Subject(s) - chemistry , radical , kinetics , decomposition , gas phase , free radical reaction , methyl radical , thermodynamics , organic chemistry , physics , quantum mechanics
Abstract 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: