Atmospheric chemistry of CF₃CH(OH)CH(OH)CF₃, CF₃C(O)CH(OH)CF₃, and CF₃C(O)C(O)CF₃: kinetics and mechanisms of reactions with Cl atoms and OH radicals, photolysis, and fate of the oxidation products.

Authors

Mads P Sulbaek Andersen, Morten Frausig, Thomas Rosenoern, Casper Vindahl Jensen, Timothy J Wallington, Ole John Nielsen

Published in

Physical chemistry chemical physics : PCCP. Aug 25, 2026. Epub Aug 25, 2026.

Abstract

Smog chamber experiments were conducted to investigate the Cl atom and OH radical reactions with CF₃CH(OH)CH(OH)CF₃ and the photolysis of CF₃C(O)C(O)CF₃. The initial reaction of CF₃CH(OH)CH(OH)CF₃ leads to formation of α-hydroxyalkyl radicals which, in the presence of O₂, are converted into CF₃C(O)CH(OH)CF₃, a suspected oxidation product of CF₃CHCHCF₃ (HFO-1336mzz). Rate constants of k(Cl + CF₃CH(OH)CH(OH)CF₃) = (5.2 ± 0.85) × 10^-14 and k(OH + CF₃CH(OH)CH(OH)CF₃) = (1.1 ± 0.3) × 10^-13 cm³ molecule^-1 s^-1 were measured using relative rate techniques in 700 Torr of air/N₂ diluents at 296 ± 2 K. The rate constant for reaction of Cl atoms with CF₃C(O)CH(OH)CF₃ was established as k(Cl + CF₃C(O)CH(OH)CF₃) = (3.0 ± 0.6) × 10^-14 cm³ molecule^-1 s^-1. Oxidation of CF₃C(O)CH(OH)CF₃ gives CF₃C(O)C(O)CF₃ in a yield of unity. IR spectra (cross sections) of CF₃CH(OH)CH(OH)CF₃, CF₃C(O)CH(OH)CF₃, and CF₃C(O)C(O)CF₃ are reported for the first time. The UV spectrum of CF₃C(O)C(O)CF₃ is reported and the photolysis rates were studied at 254 nm (UV-C) and 330 nm (broad band UV-B) radiation. Total quantum yields of (0.72 ± 0.10, 254 nm) and (0.010 ± 0.002, 330 nm) were established. Photolysis gives CF₃C(O) as a significant photofragment. The dominant atmospheric fate of CF₃C(O)C(O)CF₃ is expected to be photolysis. This study provides a comprehensive description of the atmospheric chemistry and fate of CF₃CH(OH)CH(OH)CF₃, CF₃C(O)CH(OH)CF₃, and CF₃C(O)C(O)CF₃. The products and the oxidation mechanism are discussed in the context of the atmospheric degradation of 3rd generation CFC-replacement compounds.

PMID:
42639909
Bibliographic data and abstract were imported from PubMed on 25 Aug 2026.

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