A study of the IR and UV-Vis absorption cross-sections, photolysis and OH-initiated oxidation of CF3CHO and CF3CH2CHO

Stig R. Sellevåg; Tanya Kelly; Howard Sidebottom; Claus J. Nielsen

doi:10.1039/B315941H

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A study of the IR and UV-Vis absorption cross-sections, photolysis and OH-initiated oxidation of CF₃CHO and CF₃CH₂CHO†

Stig R. Sellevåg,^a Tanya Kelly,^b Howard Sidebottom^b and Claus J. Nielsen*^a

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* Corresponding authors

^a Department of Chemistry, University of Oslo, P.O. Box 1033, Blindern, Norway
E-mail: claus.nielsen@kjemi.uio.no
Fax: +47 22 85 54 41
Tel: +47 22 85 56 80

^b Department of Chemistry, University College Dublin, Belfield, Ireland

Abstract

Infrared and ultraviolet-visible absorption cross-sections, effective quantum yields of photolysis and OH reaction rate coefficients for CF₃CHO and CF₃CH₂CHO are reported. Relative rate measurements at 298(2) K and 1013(10) hPa, give k(OH + CF₃CHO)/k(OH + CH₃CH₃) = 2.00(13), k(OH + CF₃CH₂CHO)/k(OH + CH₃CH₂OH) = 1.21(5) and k(OH + CF₃CH₂CHO)/k(OH + HC(O)OC₂H₅) = 3.51(9) (2σ). The effective quantum yield of photolysis was measured under pseudo-natural conditions in the European simulation chamber, Valencia, Spain (EUPHORE). Over the wavelength range 290–400 nm, the effective quantum yields of photolysis for CF₃CHO and CF₃CH₂CHO are less than 2 × 10⁻² and 4 × 10⁻², respectively. The tropospheric lifetimes are estimated to be: τ_OH(CF₃CHO) ∼ 26 days; τ_photol(CF₃CHO) > 27 days; τ_OH(CF₃CH₂CHO) ∼ 4 days; τ_photol(CF₃CH₂CHO) > 15 days.

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Supplementary files

Absorption cross-sections of CF ₃CHO (Table S1), CF ₃CH ₂CHO (Table S2), and FACSIMILE kinetic model of the CF ₃CHO/CH ₃CH ₃/O ₃/H ₂ reaction system (Table S3) TXT (17K)

Article information

DOI: https://doi.org/10.1039/B315941H
Article type: Paper
Submitted: 09 Dec 2003
Accepted: 27 Jan 2004
First published: 23 Feb 2004

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Phys. Chem. Chem. Phys., 2004,6, 1243-1252

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A study of the IR and UV-Vis absorption cross-sections, photolysis and OH-initiated oxidation of CF₃CHO and CF₃CH₂CHO

S. R. Sellevåg, T. Kelly, H. Sidebottom and C. J. Nielsen, Phys. Chem. Chem. Phys., 2004, 6, 1243 DOI: 10.1039/B315941H

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