Abstract
A homogeneous reaction of perfluoro methyl radicals with perfluoroacetone leading to the product perfluoro t‐butyl methyl ether is reported. The reaction to form the (CF3)2ĊOCF3 radical is proportional to the first power of both the perfluoro methyl concentration and the perfluoroacetone concentration, with an Eact=9.7±0.26 (std. deviation) kcal/mol. The reverse reaction of the (CF3)2ĊOCF3 radical decomposing to a perfluoro methyl radical and perfluoroacetone is 30.6±1.3 (std. deviation) kcal/mol, so that the heat of reaction to form the (CF3)2COCF3 radical is —20.9 kcal/mol.

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