Atmospheric Chemistry of C8F17CH2CHO: Yield from C8F17CH2CH2OH Oxidation, Kinetics and Mechanisms of Reactions with Cl Atoms and OH Radicals.

MALISA S. CHIAPPERO, GUSTAVO A. ARGÜELLO, M. D. HURLEY, T. J. WALLINGTON.

Los Cocos, Argentina

Congreso; 9th Latin American Conference on Physical Organic Chemistry; 2007

Fluorinated alcohols are used in a variety of industrial applications (e.g. paints, coatings, polymers, adhesives, waxes, polishes, electronic materials, caulks).  The (8:2 FTOH) is the main material used in the manufacture of these fluorotelomer based-products. There is a concern, for example, that atmospheric oxidation processes convert fluorinated alcohols to perfluorinated carboxylic acids (PFCAs) of the form CnF2n+1C(O)OH, via fluorotelomer aldehyde.  PFCAs are persistent in the environment, resisting degradation via oxidation, hydrolysis, or reduction under biotic and abiotic conditions. [1, 2,3] Smog chamber/FTIR techniques were used to demonstrate the conversion of C8F17CH2CH2OH (8:2 FTOH) into C8F17CH2CHO under simulated atmospheric conditions. Relative rate technique were used to measure k(Cl+C8F17CH2CHO) = (1.9±0.4) x 10-11, k(OH+ C8F17CH2CHO) = (2.0±0.4) x 10-12 and k(Cl+C8F17CHO) =(1.8±0.9) x 10-12 cm3 molecule-1 s-1 in 700 Torr of N2 or air diluents at 296 ± 2K. The primary products of the oxidation of C8F17CH2CHO, in the presence of excess NO2, is C8F17CH2C(O)OONO2. The results are discussed with respect to the atmospheric chemistry of fluorinated alcohols.     [1] Martin, J. W.; Smithwick, M. M.; Braune, B. M.; Hekstra, P. F.; Muir, D. C. G.; Mabury, S. A. Environ. Sci. Technol. 2004, 38, 373.  [2] Sulbaek Andersen, M. P.; Nielsen; O. J.; Hurley, M. D.; Ball, J. C.; Wallington, T. J.; Ellis, D. A.; Martin, J. W.; Mabury, S. A. J. Phys. Chem. A 2004, 108, 5189. [3] Hurley, M. D.; Ball, J. C.; Wallington, T. J.; Sulbaek Andersen, M. P.; Nielsen; Ellis, D. A.; Martin, J. W.; Mabury, S. A. J. Phys. Chem. A 2006, 110, 12443.