of CF3CH2CHO compared with its removal by OH radicals.
In Fig. 6, a comparison of the first-order rate for the
homogeneous removal and the UV photolysis process of
CF3CH2CHO is shown together with the overall rate loss,
2 E. Jimenez, M. Antinolo, B. Ballesteros, E. Martınez and
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J. Albaladejo, ChemPhysChem, 2010, 11, 4079–4087.
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5 M. D. Hurley, T. J. Wallington, M. P. Sulbaek Andersen,
D. A. Ellis, J. W. Martin and S. A. Mabury, J. Phys. Chem. A,
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6 L. Chen, N. Takenaka, H. Bandow and Y. Maeda, Atmos.
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7 R. Atkinson, D. L. Baulch, R. A. Cox, J. N. Crowley,
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kloss (=
J + kOH[OH]avg). The overall lifetime of
CF3CH2CHO is estimated to be B2 days at the ground level
and 1 day at higher altitudes in the troposphere. The upper limit
for the contribution of the photolysis of CF3CH2CHO to kloss
could range from 50% at the ground level up to 80% at 10 km.
According to this study, in unpolluted atmospheres the
expected products of the photodegradation of CF3CH2CHO
can be CO, F2CO, HC(O)OH, CF3CHO, CF3CH2C(O)OH,
and CF3CH2OH. However, the volume mixing ratio of
CF3CH2CHO used in this work is several orders of magnitude
higher than that expected in the atmosphere and, therefore, at
the expected levels of CF3CH2CHO in the atmosphere, none of
photodegradation products pose any environmental threat.
8 M. Antinolo, E. Jimenez, A. Notario, E. Martınez and
´ ´
J. Albaladejo, Atmos. Chem. Phys., 2010, 10, 1911–1922.
9 S. R. Sellevag, T. Kelly, H. Sidebottom and C. J. Nielsen, Phys.
Chem. Chem. Phys., 2004, 6, 1243–1252.
10 M. S. Chiappero, F. E. Malanca, G. A. Arguello,
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S. T. Wooldridge, M. D. Hurley, J. C. Ball, T. J. Wallington,
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Conclusions
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´ ´
In this work, we report (i) the temperature dependence of
the UV absorption cross sections of CF3CH2CHO between
269 and 323 K; (ii) the first study on the pressure dependence
of Fl=308nm in CF3CH2CHO/air/cyclohexane mixtures,
(iii) the quantification of the final products (CO, HC(O)OH,
CF3CHO, F2CO, and CF3CH2OH) by FTIR spectroscopy,
and (iv) a proposed mechanism that justifies the observed final
products and their temporal evolution.
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Knowing the photolysis quantum yield at tropospheric
pressures is of great importance in order to better determine
the photolysis lifetime of this fluorinated aldehyde. On the
other hand, the wavelength dependence of Fl in the actinic
region (l Z 290 nm) is also needed to better quantify any
photolysis process in the troposphere. In this work, the
photolysis quantum yield of CF3CH2CHO at 308 nm has
been reported to decrease with total pressure. If a similar
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important than reported, since Fl and Fl increases with altitude.
Acknowledgements
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The authors would like to thank the Spanish Ministerio de
Ciencia e Innovacio
´
n (MICINN) (CGL2007-61835/CLI and
a de Educacion y Ciencia
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a, V. M. Ramı
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de la Junta de Comunidades de Castilla-La Mancha (PEII11-
0279-8538) for supporting this Project. M. Antinolo wishes to
thank MICINN for providing her a grant (AP2007-02706). We
would also like to thank Prof. Ian Barnes for providing a
reference spectrum of F2CO and Dr Christa Fittschen and
Dr Mary K. Gilles for helpful discussions.
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