The photolysis of C2F51 with CF3COOH in the temperature range 473-533 K was studied in the gas phase.Evidence is presented that supports a complex mechanism for the formation of CzFsH through the H-atom abstraction reaction from CFaCOOH by CzFs radicals as well as the participation of 1(2P*,2).
The reaction of CF3 radicals with Ha0 (D20) has been studied over the range of 533-723 K using the photolysis and the pyrolysis of CFJ as the free radical source. Arrhenius pa- where klkE/* is in ~r n~'~/ r n o l~'~-s~~~ and B = 2.303RT/cal/mol. The activation energy and the primary kinetic isotope effect have been compared with those derived from the BEBO method.
The reaction of CF3 radicals with HCN in the gas phase has been studied in the temperature range 573–673 K using CF3 radicals generated by thermal decomposition of CF3I. Arrhenius parameters for the reaction:
relative to CF3 recombination:
are given by:
Rate parameters are compared with those for other reactions of CF3 with polar and non‐polar substrates.
The reaction of CF3 radicals, generated by photolysis of CF3I or hexafluoroacetone with thiophene, was studied in the gas phase at 25 °C. At conversion of thiophene less than 20%, monosubstituted CF3-thiophenes were found as the main reaction products, in addition to CF3H, C2F6, and monosubstituted dihydro-CF3-thiophene, the latter in very low proportion. An isomeric mixture of 2- and 3-CF3-thiophene was obtained in a ratio of about 16, independent of the radical source used (CF3I or hexafluoroacetone) to produce the CF3 radicals. A plausible mechanism that accounts for the observed products is proposed, and the reactivity of thiophene toward the CF3 radical at 25 °C was determined as kadd/kc1/2 = 106 ± 4 cm3/2 mol–1/2 s–1/2.Key words: thiophene, trifluoromethyl radical, reaction mechanism, reactivity.
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