Atmospheric Chemistry of C6F13CH2CHO: Yield from C6F13CH2CH2OH Oxidation, Kinetics and Mechanisms of Reactions with Cl Atoms and OH Radicals.

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

Mar del Plata

Congreso; V Congreso Iberoamericano de Física y química ambiental. SiFYQA; 2008

Socidad Iberoamericana de Física y Química ambiental

Perfluorocarboxylic acids (PFCAs, CxF2x+1C(O)OH) have been detected in Arctic fauna, water, and ice.  PFCAs are bioaccumulative, resist degradation via oxidation, hydrolysis, or reduction under biotic and abiotic conditions, and appear to be persistent in the environment.  There is a significant research effort to identify the sources, fate, and transport of PFCAs.  Fluorotelomer alcohols (FTOHs, CxF2x+1CH2CH2OH) are used in a variety of industrial applications (e.g., paints, coatings, polymers, adhesives, waxes, polishes, electronic materials, caulks). It has been suggested that the atmospheric oxidation of FTOHs is a significant source of PFCAs in remote locations [1, 2, 3, 4].  The atmospheric oxidation of FTOHs is believed to give fluorotelomer aldehydes, CxF2x+1CH2CHO, as primary products.    Smog chamber/FTIR techniques were used to demonstrate the conversion of C6F13CH2CH2OH (6:2 FTOH) into C6F13CH2CHO under simulated atmospheric conditions. Relative rate techniques were used to measure k(Cl+C6F13CH2CHO) = (1.8±0.4) x 10-11 and k(OH+ C6F13CH2CHO) = (2.2±0.4)) x 10-12 cm3 molecule-1 s-1 in 700 Torr of N2, or air, diluents at 295 K. C6F13CH2CHO is oxidized further to give C6F13CH2C(O)OH and C6F13CHO. 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., 38, 373, 2004. [2] Stock, N. L., Furdui, V.I., Muir, D. C. G., and Mabury, S. A. Environ. Sci. Technol., 41, 3529, 2007. [3] 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, 108, 5189, 2004. [4] 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, 110, 12443, 2006. Acknowledgements: MSC and GAA thank the financial support for this research by CONICET, SECyT-UNC, ANPCyT. The authors thank to DuPont de Nemour for providing the C6F13CH2CHO sample for this work.