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Gas-Phase Reaction between CF2O and CF3C(O)OH: Characterization of CF3C(O)OC(O)F
journal contribution
posted on 2019-05-03, 00:00 authored by Matias Berasategui, Gustavo A. Argüello, Maxi A. Burgos PaciThe
thermal decomposition of trifluoroacetic acid and carbonyl
fluoride (CF2O) has been extensively studied because of
their importance in the oxidation of hydrochlorofluorocarbons in the
atmosphere. We hitherto present the study of the thermal reaction
between these two molecules. The reaction mechanism was studied using
Fourier transform infrared spectroscopy in the temperature range of
513–573 K. The reaction proceeds homogeneously in the gas phase
through the formation of a reaction intermediate, here characterized
as CF3C(O)OC(O)F (detected for the first time in this work),
the major final products being CF3C(O)F, HF, and CO2. We demonstrate that the reaction is first-order with respect
to each reagent, second-order global and the mechanism consists of
two steps, the first being the rate-determining one. The Ea = 110.1 ± 6.1 kJ mol–1 and A = (1.2 ± 0.2) × 10–12 cm3 molec–1 s–1 values were
obtained from the experimental data. The low activation energy is
explained by the hydrogen-bond interactions between the −OH
group of the acid and the F atom of the CF2O. First-principles
calculations at the G4MP2 level of theory were carried out to understand
the dynamics of the decomposition. Thermodynamic activation values
found for this reaction are as follows: ΔH⧧ = 105.6 ± 6.4 kJ mol–1, ΔS⧧ = −88.6 ± 9.7 J mol–1 K–1, and ΔG⧧ = 153.7 ± 13.5 kJ mol–1. The comparison between theory and experimental results showed excellent
similarities, thus strengthening the proposed mechanism.