| Abstract
| - Smog chamber/FTIR techniques were used to study the Cl atom initiated oxidation of 4:2 fluorotelomeralcohol (C4F9CH2CH2OH, 4:2 FTOH) in the presence of NOx in 700 Torr of N2/O2 diluent at 296 K. Chemicalactivation effects play an important role in the atmospheric chemistry of the peroxy, and possibly the alkoxy,radicals derived from 4:2 FTOH. Cl atoms react with C4F9CH2CH2OH to give C4F9CH2C•HOH radicals whichadd O2 to give chemically activated α-hydroxyperoxy radicals, [C4F9CH2C(OO•)HOH]*. In 700 Torr of N2/O2 at 296 K, approximately 50% of the [C4F9CH2C(OO•)HOH]* radicals decompose “promptly” to give HO2radicals and C4F9CH2CHO, the remaining [C4F9CH2C(OO•)HOH]* radicals undergo collisional deactivationto give thermalized peroxy radicals, C4F9CH2C(OO•)HOH. Decomposition to HO2 and C4F9CH2CHO is thedominant atmospheric fate of the thermalized peroxy radicals. In the presence of excess NO, the thermalizedperoxy radicals react to give C4F9CH2C(O•)HOH radicals which then decompose at a rate >2.5 × 106 s-1 togive HC(O)OH and the alkyl radical C4F9CH2•. The primary products of 4:2 FTOH oxidation in the presenceof excess NOx are C4F9CH2CHO, C4F9CHO, and HCOOH. Secondary products include C4F9CH2C(O)O2NO2,C4F9C(O)O2NO2, and COF2. In contrast to experiments conducted in the absence of NOx, there was no evidence(<2% yield) for the formation of the perfluorinated acid C4F9C(O)OH. The results are discussed with regardto the atmospheric chemistry of fluorotelomer alcohols.
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