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

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 + CHClCHOH) = (5.87 ± 0.96) × 10 and k(OH + CHClCHOH) = (5.54 ± 1.94) × 10 cm molecule s. Chlorine atom initiated oxidation of CHClCHOH in one atmosphere of air gives HCOCl, CHClCHO, and COCl in yields of (62 ± 5)%, (39 ± 10)%, and (8 ± 2)%, respectively. The rate constant k(Cl + CHClCHO) = (8.3 ± 16) × 10 cm molecule s was determined and the IR spectra of CHClCHO is reported for the first time. The atmospheric lifetime for CHClCHOH is estimated as 21 days. The experimental results are discussed in the context of the atmospheric chemistry of chlorinated alcohols.