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The product distribution and the mechanism of the reaction of Cl atoms with 2,2,2-trifluoroethyl 2,2,2-trifluoroacetate (CF3C(O)OCH2CF3) were investigated using a 1080 L environmental chamber with in situ FTIR spectroscopy detection. The experiments were performed at (296 ± 2) K and atmospheric pressure (760 ± 10) Torr of synthetic air free of NOx. A yield of (45 ± 3) % was obtained for the CF3C(O)OC(O)CF3 formation. CF2O and CO were found to be secondary products with estimated yields of 35 and 28 %, respectively. No trifluoroacetic acid (CF3C(O)OH) was observed. The measured yields determined are rationalized in terms of the competitive reaction channels for the fluoroalcoxy radicals formed in the H-abstraction process: a) reaction with O2, b) C-C, C-O, C-H decomposition and c) a possible á -ester rearrangement pathway. The negligible importance of the á-ester channel to produce trifluoroacetic acid was explained by the reduction of the stability of the five-membered transition state of the á-ester rearrangement. Atmospheric implications, especially with regard to the fluorocarboxylic acid formation, are discussed. 22-Apr-2010 22-Apr-2010 22-Apr-2010 22-Apr-2010 Dear Prof. Teruel, Dear Prof. Teruel, Dear Prof. Teruel, Dear Prof. Teruel, It is a pleasure to accept your manuscript entitled "Product distribution in the Cl-initiated photooxidation of CF3C(O)OCH2CF3" in its current form for publication in Journal of Physical Organic Chemistry. The comments of the referee(s) who reviewed your manuscript are included at the bottom of this letter. It is a pleasure to accept your manuscript entitled "Product distribution in the Cl-initiated photooxidation of CF3C(O)OCH2CF3" in its current form for publication in Journal of Physical Organic Chemistry. The comments of the referee(s) who reviewed your manuscript are included at the bottom of this letter. It is a pleasure to accept your manuscript entitled "Product distribution in the Cl-initiated photooxidation of CF3C(O)OCH2CF3" in its current form for publication in Journal of Physical Organic Chemistry. The comments of the referee(s) who reviewed your manuscript are included at the bottom of this letter. It is a pleasure to accept your manuscript entitled "Product distribution in the Cl-initiated photooxidation of CF3C(O)OCH2CF3" in its current form for publication in Journal of Physical Organic Chemistry. The comments of the referee(s) who reviewed your manuscript are included at the bottom of this letter. A signed copyright transfer agreement is needed for publication. If you have not already provided us with one you can access the copyright transfer agreement at: A signed copyright transfer agreement is needed for publication. 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Please note that this does not take away your rights to reuse your own article after publication, and that if the copyright belongs to your employing institution, they should sign the form instead of you. Please note that this does not take away your rights to reuse your own article after publication, and that if the copyright belongs to your employing institution, they should sign the form instead of you. Please note that this does not take away your rights to reuse your own article after publication, and that if the copyright belongs to your employing institution, they should sign the form instead of you. If you have already provided us with the signed form, you do not need to do anything at this stage. You will be contacted by our typesetters/copyeditors shortly. If you have already provided us with the signed form, you do not need to do anything at this stage. You will be contacted by our typesetters/copyeditors shortly. If you have already provided us with the signed form, you do not need to do anything at this stage. You will be contacted by our typesetters/copyeditors shortly. If you have already provided us with the signed form, you do not need to do anything at this stage. You will be contacted by our typesetters/copyeditors shortly. Thank you for your fine contribution. Thank you for your fine contribution. Thank you for your fine contribution. Thank you for your fine contribution. Sincerely, Sincerely, Sincerely, Sincerely, Faruk NomeEditor, Journal of Physical Organic Chemistryfaruk@qmc.ufsc.br Referee(s)´ Comments to Author: Reviewer: 3Comments to the AuthorThe revised version is now suitable for publication Reviewer: 1Comments to the AuthorIt is necessary to mention that the authors have made a great effort in order to improve the quality of the paper. Most of my recommendations have been followed and it has been suitably justified the realized changes. Title has been changed, errors have been corrected, some sentences and expressions have been rewritten as suggested and more references and explanations are now included in the paper. Experimental procedure and discussion are now much more comprehensible and the English also has been improved.Therefore, I havent new suggestions to do and I recommend the publication of this paper in the journal J. Phys. Org. Chem. Journal of Physical Organic Chemistry is participating in the PEER project, which aims to monitor the effects of systematic self-archiving (author deposit in repositories) over time. PEER is supported by the EC eContentplus programme (http://ec.europa.eu/information_society/activities/econtentplus/index_en.htm).As your manuscript has been accepted for publication you may be eligible to participate in the PEER project. If you are based in the European Union, your manuscript will be archived by Wiley-Blackwell on your behalf, as part of this project. 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