AbstractThe gas‐phase kinetics of thermal decomposition of ethyl difluoroacetate, pentafluoropropionate, and hepatfluorobutyrate have been studied. The normal ester decomposition route to ethylene plus carboxylic acid is taken in each case, but the fluorinated acids decompose rapidly at the temperatures used. The primary decompositions are homogeneous and unimolecular, and the three Arrhenius equations are\documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{l} \log k{\rm}({\rm CF}_2 {\rm HCO}_2 {\rm Et}){\rm}({\rm s}^{- 1}) = (12.81 \pm 0.39) - (46,740 \pm 1290){\rm cal/mol/2}{\rm .303}RT \\ \log k{\rm}({\rm C}_2 {\rm F}_5 {\rm CO}_{\rm 2} {\rm Et}){\rm}({\rm s}^{- 1}) = (12.16 \pm 0.32) - (43,760 \pm 970){\rm cal/mol/2}{\rm .303}RT \\ \log k{\rm}({\rm C}_3 {\rm F}_7 {\rm CO}_{\rm 2} {\rm Et}){\rm}({\rm s}^{- 1}) = (12.29 \pm 0.13) - (43,880 \pm 370){\rm cal/mol/2}{\rm .303}RT \\ \end{array} $$\end{document}The postulate of a slightly electron‐rich γ carbon in six‐center ester transition states is supported by the higher rates and lowered activation energies observed when increasingly electron‐withdrawing fluorinated groups are linked to this center. The stabilization is reflected in a ρ constant of +0.30. The results are compared with previous work on α substitution in fluorina