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Atmospheric Chemistry of 4:2 Fluorotelomer Iodide (n-C4F9CH2CH2I): Kinetics and Products of Photolysis and Reaction with OH Radicals and Cl Atoms

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Department of Chemistry, University of Toronto, 80 St George Street, Toronto, Ontario, Canada M5S 3H6, Ford Motor Company, Mail Drop RIC-2122, Dearborn, Michigan 48121-2053
* To whom correspondence should be addressed. E-mails: [email protected]; [email protected]
†University of Toronto.
‡Ford Motor Company.
Cite this: J. Phys. Chem. A 2008, 112, 51, 13542–13548
Publication Date (Web):November 24, 2008
https://doi.org/10.1021/jp807322x
Copyright © 2008 American Chemical Society
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    Abstract

    Relative rate techniques were used to study the title reactions and determine rate constants of k(Cl + C4F9CH2CH2I) = (1.25 ± 0.15) × 10−12 and k(OH + C4F9CH2CH2I) = (1.2 ± 0.6) × 10−12 cm3 molecule−1 s−1 in 700 Torr total pressure at 295 K. The fluorotelomer aldehyde (C4F9CH2CHO), perfluorinated aldehyde (C4F9CHO), fluorotelomer acid (C4F9CH2C(O)OH), fluorotelomer peracid (C4F9CH2C(O)OOH), and several perfluorocarboxylic acids were detected by in situ FTIR spectroscopy and offline analysis as products of the chlorine atom initiated oxidation of C4F9CH2CH2I in air. The UV−visible spectra of C4F9CH2CH2I and C2H5Cl were recorded over the range of 200−400 nm. Photolysis of C4F9CH2CH2I gives C4F9CH2CHO as the major observed product. By assumption of a photolysis quantum yield of unity, it was calculated that the atmospheric lifetime of C4F9CH2CH2I is determined by photolysis and is a few days. A mechanism for the atmospheric oxidation of fluorotelomer iodides, (CxF2x+1CH2CH2I, where x = 2, 4, 6,...) is proposed. Atmospheric oxidation of fluorotelomer iodides is a potential source of perfluorocarboxylic acids.

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    Tabular UV cross-sections and photolysis rate constants by time of year and latitude. This information is available free of charge via the Internet at http://pubs.acs.org.

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