Reactions of fluoromethyl radicals

Abstract

1,3-difluoroacetone was photolysed by itself and in the presence of either diethylketone or di-isopropylketone and the rates of the following reactions of fluoromethyl radicals were measured: (i) CH₂F + CH₂FCOCH₂F, log₁₀(k/cm³ mol^–1 s^–1)= 11.10–40000//_2.303RT, (ii) CH₂F + C₂H₅COC₂H₅, log₁₀(k/cm³ mol^–1 s^–1)= 10.71–34050//_2.303RT, (iii) CH₂F + i-C₃H₇CO-i-C₃H₇, log₁₀(k/cm³ mol^–1 s^–1)= 11.18–31550//_2.303RT where R= 8.314 J mol^–1 K^–1.

The disproportionation–combination ratios (Δ) for the following pairs of radicals were found to be Δ(CH₂F, C₂H₅)= 0.047, Δ(CH₂F, i-C₃H₇)= 0.210, Δ(i-C₃H₇, i-C₃H₇)= 0.55, Δ(C₂H₅, C₂H₅)= 0.146.