The UV absorption spectra of CF(3)CHO, C(2)F(5)CHO, C(3)F(7)CHO, C(4)F(9)CHO, CF(3)CH(2)CHO, and C(6)F(13)CH(2)CHO were recorded over the range 225-400 nm at 249-297 K. C(x)F(2)(x)(+1)CHO and C(x)F(2)(x)(+1)CH(2)CHO have broad absorption features centered at 300-310 and 290-300 nm, respectively. The strength of the absorption increases with the size of the C(x)F(2)(x)(+1) group. There was no discernible (<5%) effect of temperature on the UV spectra. Quantum yields for photolysis at 254 and 308 nm were measured. Quantum yields at 254 nm were 0.79 +/- 0.09 (CF(3)CHO), 0.81 +/- 0.09 (C(2)F(5)CHO), 0.63 +/- 0.09 (C(3)F(7)CHO), 0.60 +/- 0.09 (C(4)F(9)CHO), 0.74 +/- 0.08 (CF(3)CH(2)CHO), and 0.55 +/- 0.09 (C(6)F(13)CH(2)CHO). Quantum yields at 308 nm were 0.17 +/- 0.03 (CF(3)CHO), 0.08 +/- 0.02 (C(4)F(9)CHO), and 0.04 +/- 0.01 (CF(3)CH(2)CHO). The quantum yields decrease with increasing size of the C(x)F(2)(x)(+1) group and with increasing wavelength of the photolysis light. The photolysis quantum yield at 308 nm for CF(3)CHO measured here is a factor of at least 8 greater than that reported previously. Photolysis is probably the dominant atmospheric fate of C(x)F(2)(x)(+1)CHO (x = 1-4) and is an important fate of C(x)F(2)(x)(+1)CH(2)CHO (x = 1 and 6). These results have important ramifications concerning the yield of perfluorocarboxylic acids in the atmospheric oxidation of fluorotelomer alcohols.

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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.

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Irradiation of the equilibrated gas mixture CF(3)O(2)NO(2)<==>CF(3)O(2) + NO(2) at room temperature using the output from UV fluorescent "blacklamps" provides a rapid and simple method for the production of pure samples of CF(3)ONO(2) in high yield (ca. 80%). This synthetic procedure is superior to that described in the literature in two aspects: (i) the yield of CF(3)ONO(2) is approximately a factor of 5 greater, and (ii) the present method avoids the need for a high pressure (70 bar) reactor.

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