The reaction of CF₂Cl₂ with gas-phase hydrated electrons

Abstract

The reaction of dichlorodifluoromethane (CF2Cl2) with hydrated electrons (H2O)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 CF2Cl2, forming (H2O)mCl(-) 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 ΔHr(CF2Cl2, 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) ΔHC-Cl(CF2Cl2, 298 K) = 355 ± 41 kJ mol(-1) that agrees within error limits with the predicted values from quantum chemical calculations and published BDEs.

Communication: Charge transfer dominates over proton transfer in the reaction of nitric acid with gas-phase hydrated electrons

“…8 A nanocalorimetric fit reveals a result of 5.7 ± 1.6 and 2.3 ± 0.2 evaporated water molecules for reactions (1) and (2), respectively. With the energy required to evaporate a single water molecule from the cluster, ∆E vap = 43.3 ± 3.1 kJ mol 1 , 31,32 and thermal corrections as detailed in the supplementary material, 8,33,34 this translates to ∆ r H exp (298 K) = 241 ± 69 kJ mol 1 for reaction (1) and 94 ± 11 kJ mol 1 for reaction (2). Table I summarizes the measured reaction enthalpy in comparison with ab initio calculation and literature thermochemical data from bulk aqueous solution.…”

Mass spectrometry of aerosol particle analogues in molecular beam experiments

“…In contrast to the surface enhancement, cluster beam experiments did not found any significant increase in the low‐energy electron attachment to mixed CF 2 Cl 2 /NH 3 clusters . Recently, we have observed an efficient exothermic reaction of the solvated electron with CF 2 Cl 2 by −208 ± 41 kJ mol −1 (−2.16 eV) . The reaction of with CF 2 Cl 2 resulted in the (H 2 O) n Cl − ions which suggested the CF 2 Cl 2 orientation with the Cl atoms toward the cluster.…”

Carbon-carbon bond formation in the reaction of hydrated carbon dioxide radical anions with 3-butyn-1-ol

“…Previous comparisons to literature thermochemistry illustrate that the method works well, provided a sufficient number of data sets is analyzed so that some averaging is possible [49,65,73,94,95].…”