Chemistry of H2O+ with C2F4, C2F6, and CF3X (X = F, Cl, Br, I)

Article abstract of DOI:10.1021/j100186a050

The reactions of H2O⁺ with CF4, C2F6, C2F4, CF3Cl, CF3Br, and CF3I have been studied at 300 and 499 K.The measurements were conducted using a variable-temperature-selected ion flow tube apparatus.H2O⁺ reacts via charge transfer with C2F4 with rate constants equal to 1.4 x 10^-9 and 1.5 x 10^-9 cm³ s^-1 at 300 and 499 K, respectively.The reactions with CF3X (X = Cl, Br, I) all proceed at the collision rate at 300 and 499 K within experimental uncertainty.The rate constants are in the range 1.6 x 10^-9 - 2.1 x 10^-9 cm³ s^-1.The reactions of H2O⁺ with CF3X produce CF3⁺ and CF2X⁺ for X = Cl, Br, I, CF2OH⁺ for X = Cl, Br, and CF3X⁺ for X = Br, I.The reaction with CF3Cl also forms the ionic product CF3OH2⁺.No reaction was observed between H2O⁺ and the reactant neutrals CF4 and C2F6; the rate constants are less than 5 x 10^-12 cm³ s^-1 at 300 and 499 K.Upper limits to the heats of formation of CF2Cl⁺, CF2Br⁺, and CF2I⁺ have been derived from the data and are < 506, < 566, and < 624 kJ mol^-1, respectively.