This title appears in the Scientific Report :
2017
Please use the identifier:
http://dx.doi.org/10.1002/2017JD026950 in citations.
Please use the identifier: http://hdl.handle.net/2128/16025 in citations.
Temperature dependence of stable carbon kinetic isotope effect for the oxidation reaction of ethane by OH radicals: experimental and theoretical studies
Temperature dependence of stable carbon kinetic isotope effect for the oxidation reaction of ethane by OH radicals: experimental and theoretical studies
The stable carbon kinetic isotope effect (KIE) of ethane photooxidation by OH radicals was deduced by employing both laboratory measurements and theoretical calculations. The investigations were designed to elucidate the temperature dependence of KIE within atmospherically relevant temperature range...
Saved in:
Personal Name(s): | Piansawan, T. |
---|---|
Saccon, M. / Vereecken, L. (Corresponding author) / Gensch, I. (Corresponding author) / Kiendler-Scharr, A. | |
Contributing Institute: |
Troposphäre; IEK-8 |
Published in: | Journal of geophysical research / Atmospheres, 122 (2017) 15, S. 8310-8324 |
Imprint: |
Hoboken, NJ
Wiley
2017
|
DOI: |
10.1002/2017JD026950 |
Document Type: |
Journal Article |
Research Program: |
Tropospheric trace substances and their transformation processes |
Link: |
Published on 2017-08-05. Available in OpenAccess from 2018-02-05. Published on 2017-08-05. Available in OpenAccess from 2018-02-05. |
Publikationsportal JuSER |
Please use the identifier: http://hdl.handle.net/2128/16025 in citations.
The stable carbon kinetic isotope effect (KIE) of ethane photooxidation by OH radicals was deduced by employing both laboratory measurements and theoretical calculations. The investigations were designed to elucidate the temperature dependence of KIE within atmospherically relevant temperature range. The experimental KIE was derived from laboratory compound-specific isotope analyses of ethane with natural isotopic abundance exposed to OH at constant temperature, showing ε values of 7.16 ± 0.54‰ (303 K), 7.45 ± 0.48‰ (288 K), 7.36 ± 0.28‰ (273 K), 7.61 ± 0.28‰ (263 K), 8.89 ± 0.90‰ (253 K), and 9.42 ± 2.19‰ (243 K). Compared to previous studies, a significant improvement of the measurement precision was reached at the high end of the investigated temperature range. The KIE was theoretically determined as well, in the temperature range of 150 K to 400 K, by calculating the reaction rate coefficients of 12C and singly 13C substituted ethane isotopologues applying chemical quantum mechanics together with transition state theory. Tunneling effect and internal rotations were also considered. The agreement between experimental and theoretical results for rate coefficients and KIE in an atmospherically relevant temperature range is discussed. However, both laboratory observations and computational predictions show no significant temperature dependence of the KIE for the ethane oxidation by OH radicals. |