Atmospheric chemistry of n-C6F13CH2CHO: formation from n-C6F13CH2CH2OH, kinetics, and mechanisms of reactions with chlorine atoms and OH radicals.

Smog chamber FTIR techniques were used to measure k(Cl + n-C(6)F(13)CH(2)CHO) = (1.84 +/- 0.22) x 10(-11), k(Cl + n-C(6)F(13)CHO) = (1.75 +/- 0.70) x 10(-12), and k(OH + n-C(6)F(13)CH(2)CHO) = (2.15 +/- 0.26) x 10(-12) cm(3) molecule(-1) s(-1) in 700 Torr of N(2) or air diluent at 296 +/- 2K. The chlorine-atom-initiated oxidation of n-C(6)F(13)CH(2)CH(2)OH in air gives n-C(6)F(13)CH(2)CHO in a molar yield of 99 +/- 8%. The atmospheric fate of n-C(6)F(13)CH(2)C(O) radicals is reaction with O(2), while the fate of n-C(6)F(13)C(O) radicals is decomposition to give n-C(6)F(13) radicals and CO. The results are discussed with respect to the atmospheric chemistry of fluorinated alcohols and the formation of perfluorocarboxylic acids.