The reaction of CF(2)Cl(2) with gas-phase hydrated electrons(†)

The reaction of dichlorodifluoromethane (CF(2)Cl(2)) with hydrated electrons (H(2)O)(n) (−) (n = 30–86) in the gas phase was studied using Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. The hydrated electron reacts with CF(2)Cl(2), forming (H(2)O)(m)Cl(−) with a rate constant of (8.6 ± 2.2) × 10(−10) cm(3) s(−1), corresponding to an efficiency of 57 ± 15%. The reaction enthalpy was determined using nanocalorimetry, revealing a strongly exothermic reaction with ΔH(r)(CF(2)Cl(2), 298 K) = −208 ± 41 kJ mol(−1). The combination of the measured reaction enthalpy with thermochemical data from the condensed phase yields a C–Cl bond dissociation enthalpy (BDE) ΔH(C–Cl)(CF(2)Cl(2), 298 K) = 355 ± 41 kJ mol(−1) that agrees within error limits with the predicted values from quantum chemical calculations and published BDEs.