Kinetics of CH2=CHCH2OCF2CF2H with atmospheric oxidants
- 1Universidad de Castilla-La Mancha, Facultad de Ciencias y Tecnologías Químicas, Departamento de Química Física, Avda, Camilo José Cela 1B, 13071, Ciudad Real, Spain
- 2Institut de Combustion Aérothermique, Réactivité et Environnement, Centre National de la Recherche Scientifique (ICARE-CNRS), Observatoire des Sciences de l'Univers en région Centre (OSUC), CS 50060, 45071, Orléans cedex02, France
- 3Le Studium Loire Valley Institute for Advanced Studies, Orléans 45071, France.
- 4Universidad de Castilla-La Mancha, Instituto de Investigación en Combustión y Contaminación Atmosférica, Camino de Moledores s/n, 13071 Ciudad Real, Spain.
As industries transition towards greener business models, many mass-produced chemicals are being replaced by low-global warming potential (GWP) alternatives. Allyl 1,1,2,2-tetrafluoroethyl ether (CH2=CHCH2OCF2CF2H) represents a potential replacement candidate. This molecule contains an olefinic bond, several abstractable hydrogen atoms, an ether linkage and a non-perfluorinated side-chain. As such it can react with various atmospheric oxidants in a variety of degradation mechanisms, each of which may serve to reduce its atmospheric lifetime and its impact upon the environment. Before widespread usage, it is crucial that these environmental sinks are quantified such that the risk that CH2=CHCH2OCF2CF2H poses to the environment can be thoroughly assessed. We present measurements of gas-phase relative rates with hydroxyl radicals (OH), atomic chlorine (Cl), ozone (O3) and nitrate radical (NO3) carried out in HELIOS simulation chamber at CNRS (Orléans, France) as described by Ren et al.1 and references within. Although previous measurements are available for OH2 and Cl,3 we find some discrepancies in comparison to our new determinations. In the case of O3 and NO3, these represent the first such measurements of which we are aware. Furthermore, we have determined the absolute rate coefficient of CH2=CHCH2OCF2CF2H + OH using a pulsed-laser photolysis–laser-induced fluorescence technique between 273 and 363 K performed at the Physical Chemistry department of UCLM (Ciudad Real, Spain) as described by Blázquez et al.4 and references within, representing the first temperature-dependent kinetic measurements for this molecule with OH radicals. In addition, the infrared absorption cross section is quantified between 400 and 4000 cm-1, in an extended range of wavenumbers with respect to the previously reported ones5. Combining each these observations, we are able to provide an improved estimate for the GWP of this molecule and its likely environmental fate.
References:
1. Ren, Y.; McGillen, M. R.; Daële, V.; Casas, J.; Mellouki, A. Science Total Environ. 2020, 749, 141406.
2. Heathfield, A. E.; Anastasi, C.; Pagsberg, P.; McCulloch, A. Atmos. Environ. 1998, 32, 711–717.
3. Papadimitriou, V. C.; Kambanis, K. G.; Lazarou, Y. G.; Papagiannakopoulos, P. J. Phys. Chem. A 2004, 108, 2666–2674.
4. Blázquez, S.; Antiñolo, M.; Nielsen, O. J.; Albaladejo, J.; Jiménez, E. Chem. Phys. Lett. 2017, 687, 297–302.
5. Heathfield, A. E.; Anastasi, C.; McCulloch, A.; Nicolaisen, F. M. Atmos. Environ. 1998, 32, 2825–2833.
How to cite: Blázquez, S., McGillen, M. R., Ren, Y., Albaladejo, J., Mellouki, A., and Jiménez, E.: Kinetics of CH2=CHCH2OCF2CF2H with atmospheric oxidants, EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-15483, https://doi.org/10.5194/egusphere-egu21-15483, 2021.
