Photochemistry of 2,2-dichloroethanol: kinetics and mechanism of the reaction with Cl atoms and OH radicals

• Published in: Environmental science--processes & impacts Vol. 22; no. 3; pp. 719 - 727
• Main Authors: Sulbaek Andersen, Mads. P, Hass, Sofie A, Lyster, Kjertan, Avetikyan, Mila, Wallington, Timothy J, Nielsen, Ole J
• Format: Journal Article
• Language: English
• Published: England Royal Society of Chemistry 01.03.2020
• Subjects: Alcohols; Atmospheric chemistry; Chlorine; Free radicals; Infrared spectroscopy; Kinetics; Measurement methods; Oxidation; Phosgene; Photochemistry; Reaction kinetics; Smog
• ISSN: 2050-7887; 2050-7895
• DOI: 10.1039/c9em00581a

Smog chamber/FTIR techniques were used to investigate the kinetics and mechanism of the Cl atom and OH radical initiated oxidation of 2,2-dichloroethanol at (296 ± 1) K. Relative rate methods were used to measure k (Cl + CHCl 2 CH 2 OH) = (5.87 ± 0.96) × 10 −12 and k (OH + CHCl 2 CH 2 OH) = (5.54 ± 1.94) × 10 −13 cm 3 molecule −1 s −1 . Chlorine atom initiated oxidation of CHCl 2 CH 2 OH in one atmosphere of air gives HCOCl, CHCl 2 CHO, and COCl 2 in yields of (62 ± 5)%, (39 ± 10)%, and (8 ± 2)%, respectively. The rate constant k (Cl + CHCl 2 CHO) = (8.3 ± 16) × 10 −12 cm 3 molecule −1 s −1 was determined and the IR spectra of CHCl 2 CHO is reported for the first time. The atmospheric lifetime for CHCl 2 CH 2 OH is estimated as 21 days. The experimental results are discussed in the context of the atmospheric chemistry of chlorinated alcohols. Smog chamber/FTIR study investigates the atmospheric chemistry and environmental impact of 2,2-dichloroethanol.