Atmospheric photooxidation and ozonolysis of sabinene: reaction rate coefficients, product yields, and chemical budget of radicals
<p>The oxidation of sabinene by the hydroxyl radical (OH) and ozone (O<span class="inline-formula"><sub>3</sub>)</span> was investigated under atmospherically relevant conditions in the atmospheric simulation chamber SAPHIR (Simulation of Atmospheric Photochem...
| Main Authors: | , , , , , , , , , , , |
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| Format: | Article |
| Language: | English |
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Copernicus Publications
2023-10-01
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| Series: | Atmospheric Chemistry and Physics |
| Online Access: | https://acp.copernicus.org/articles/23/12631/2023/acp-23-12631-2023.pdf |
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| author | J. Y. S. Pang F. Berg A. Novelli B. Bohn M. Färber P. T. M. Carlsson R. Dubus G. I. Gkatzelis F. Rohrer S. Wedel A. Wahner H. Fuchs H. Fuchs |
| author_facet | J. Y. S. Pang F. Berg A. Novelli B. Bohn M. Färber P. T. M. Carlsson R. Dubus G. I. Gkatzelis F. Rohrer S. Wedel A. Wahner H. Fuchs H. Fuchs |
| author_sort | J. Y. S. Pang |
| collection | DOAJ |
| description | <p>The oxidation of sabinene by the hydroxyl radical (OH)
and ozone (O<span class="inline-formula"><sub>3</sub>)</span> was investigated under atmospherically relevant
conditions in the atmospheric simulation chamber SAPHIR (Simulation of
Atmospheric Photochemistry In a Large Reaction Chamber) at Forschungszentrum
Jülich, Germany. The rate coefficients of the reactions of sabinene with
OH and with O<span class="inline-formula"><sub>3</sub></span> were determined. The temperature dependence between 284 to 340 K of the rate coefficient of the reaction of sabinene with OH,
<span class="inline-formula"><i>k</i><sub>SAB+OH</sub></span>, was measured for the first time using an OH reactivity
instrument, resulting in an Arrhenius expression of (1.67 <span class="inline-formula">±</span> 0.16) <span class="inline-formula">×</span> 10<span class="inline-formula"><sup>−11</sup></span> <span class="inline-formula">×</span> exp((575 <span class="inline-formula">±</span> 30)/<span class="inline-formula"><i>T</i>)</span> cm<span class="inline-formula"><sup>3</sup></span> s<span class="inline-formula"><sup>−1</sup></span>. The values agree with those determined in chamber experiments in
this work and reported in the literature for <span class="inline-formula">∼</span> 298 K within
the uncertainties of measurements. The ozonolysis reaction rate coefficient
of sabinene (<span class="inline-formula"><i>k</i><sub>SAB+O3</sub>)</span> determined in chamber experiments at a temperature
of (278 <span class="inline-formula">±</span> 2) K is (3.4 <span class="inline-formula">±</span> 0.8) <span class="inline-formula">×</span> 10<span class="inline-formula"><sup>−17</sup></span> cm<span class="inline-formula"><sup>3</sup></span> s<span class="inline-formula"><sup>−1</sup></span>, which is 58 % lower than the value reported in the literature
for room temperature. The measurement of products from the oxidation of
sabinene by OH resulted in an acetone yield of (21 <span class="inline-formula">±</span> 15) %, a
formaldehyde yield of (46 <span class="inline-formula">±</span> 25) %, and a sabinaketone yield of
(18 <span class="inline-formula">±</span> 16) %. All yields determined in the chamber experiments agree
well with values from previous laboratory studies within their
uncertainties. In addition, the formaldehyde yield determined in this study
is consistent with that predicted by the sabinene OH-oxidation mechanism
which was devised from quantum chemical calculations by Wang and Wang (2018), whereas the acetone yield is about 15 % higher than that
predicted by the mechanism. In the ozonolysis experiments, the analysis of
product measurements results in an acetone yield of (5 <span class="inline-formula">±</span> 2) %, a
formaldehyde yield of (48 <span class="inline-formula">±</span> 15) %, a sabinaketone yield of
(31 <span class="inline-formula">±</span> 15) %, and an OH radical yield of (26 <span class="inline-formula">±</span> 29) %. The OH
radical yield is lower than expected from the theoretical mechanism in Wang
and Wang (2017), but the value still agrees within the uncertainty. An
analysis of the chemical budget of OH radicals was performed for the chamber
experiments. The analysis reveals that the destruction rate of the OH radical
matches the production rate of OH, suggesting that there is no significant
missing OH source for example from isomerization reactions of peroxy
radicals for the experimental conditions in this work.</p> |
| first_indexed | 2024-03-11T18:55:20Z |
| format | Article |
| id | doaj.art-2a5f08ac40bd40759d21a57c6cf83181 |
| institution | Directory Open Access Journal |
| issn | 1680-7316 1680-7324 |
| language | English |
| last_indexed | 2024-03-11T18:55:20Z |
| publishDate | 2023-10-01 |
| publisher | Copernicus Publications |
| record_format | Article |
| series | Atmospheric Chemistry and Physics |
| spelling | doaj.art-2a5f08ac40bd40759d21a57c6cf831812023-10-11T05:14:11ZengCopernicus PublicationsAtmospheric Chemistry and Physics1680-73161680-73242023-10-0123126311264910.5194/acp-23-12631-2023Atmospheric photooxidation and ozonolysis of sabinene: reaction rate coefficients, product yields, and chemical budget of radicalsJ. Y. S. Pang0F. Berg1A. Novelli2B. Bohn3M. Färber4P. T. M. Carlsson5R. Dubus6G. I. Gkatzelis7F. Rohrer8S. Wedel9A. Wahner10H. Fuchs11H. Fuchs12Institute of Energy and Climate Research, IEK-8: Troposphere, Forschungszentrum Jülich GmbH, Jülich, GermanyInstitute of Energy and Climate Research, IEK-8: Troposphere, Forschungszentrum Jülich GmbH, Jülich, GermanyInstitute of Energy and Climate Research, IEK-8: Troposphere, Forschungszentrum Jülich GmbH, Jülich, GermanyInstitute of Energy and Climate Research, IEK-8: Troposphere, Forschungszentrum Jülich GmbH, Jülich, GermanyInstitute of Energy and Climate Research, IEK-8: Troposphere, Forschungszentrum Jülich GmbH, Jülich, GermanyInstitute of Energy and Climate Research, IEK-8: Troposphere, Forschungszentrum Jülich GmbH, Jülich, GermanyInstitute of Energy and Climate Research, IEK-8: Troposphere, Forschungszentrum Jülich GmbH, Jülich, GermanyInstitute of Energy and Climate Research, IEK-8: Troposphere, Forschungszentrum Jülich GmbH, Jülich, GermanyInstitute of Energy and Climate Research, IEK-8: Troposphere, Forschungszentrum Jülich GmbH, Jülich, GermanyInstitute of Energy and Climate Research, IEK-8: Troposphere, Forschungszentrum Jülich GmbH, Jülich, GermanyInstitute of Energy and Climate Research, IEK-8: Troposphere, Forschungszentrum Jülich GmbH, Jülich, GermanyInstitute of Energy and Climate Research, IEK-8: Troposphere, Forschungszentrum Jülich GmbH, Jülich, GermanyDepartment of Physics, University of Cologne, Cologne, Germany<p>The oxidation of sabinene by the hydroxyl radical (OH) and ozone (O<span class="inline-formula"><sub>3</sub>)</span> was investigated under atmospherically relevant conditions in the atmospheric simulation chamber SAPHIR (Simulation of Atmospheric Photochemistry In a Large Reaction Chamber) at Forschungszentrum Jülich, Germany. The rate coefficients of the reactions of sabinene with OH and with O<span class="inline-formula"><sub>3</sub></span> were determined. The temperature dependence between 284 to 340 K of the rate coefficient of the reaction of sabinene with OH, <span class="inline-formula"><i>k</i><sub>SAB+OH</sub></span>, was measured for the first time using an OH reactivity instrument, resulting in an Arrhenius expression of (1.67 <span class="inline-formula">±</span> 0.16) <span class="inline-formula">×</span> 10<span class="inline-formula"><sup>−11</sup></span> <span class="inline-formula">×</span> exp((575 <span class="inline-formula">±</span> 30)/<span class="inline-formula"><i>T</i>)</span> cm<span class="inline-formula"><sup>3</sup></span> s<span class="inline-formula"><sup>−1</sup></span>. The values agree with those determined in chamber experiments in this work and reported in the literature for <span class="inline-formula">∼</span> 298 K within the uncertainties of measurements. The ozonolysis reaction rate coefficient of sabinene (<span class="inline-formula"><i>k</i><sub>SAB+O3</sub>)</span> determined in chamber experiments at a temperature of (278 <span class="inline-formula">±</span> 2) K is (3.4 <span class="inline-formula">±</span> 0.8) <span class="inline-formula">×</span> 10<span class="inline-formula"><sup>−17</sup></span> cm<span class="inline-formula"><sup>3</sup></span> s<span class="inline-formula"><sup>−1</sup></span>, which is 58 % lower than the value reported in the literature for room temperature. The measurement of products from the oxidation of sabinene by OH resulted in an acetone yield of (21 <span class="inline-formula">±</span> 15) %, a formaldehyde yield of (46 <span class="inline-formula">±</span> 25) %, and a sabinaketone yield of (18 <span class="inline-formula">±</span> 16) %. All yields determined in the chamber experiments agree well with values from previous laboratory studies within their uncertainties. In addition, the formaldehyde yield determined in this study is consistent with that predicted by the sabinene OH-oxidation mechanism which was devised from quantum chemical calculations by Wang and Wang (2018), whereas the acetone yield is about 15 % higher than that predicted by the mechanism. In the ozonolysis experiments, the analysis of product measurements results in an acetone yield of (5 <span class="inline-formula">±</span> 2) %, a formaldehyde yield of (48 <span class="inline-formula">±</span> 15) %, a sabinaketone yield of (31 <span class="inline-formula">±</span> 15) %, and an OH radical yield of (26 <span class="inline-formula">±</span> 29) %. The OH radical yield is lower than expected from the theoretical mechanism in Wang and Wang (2017), but the value still agrees within the uncertainty. An analysis of the chemical budget of OH radicals was performed for the chamber experiments. The analysis reveals that the destruction rate of the OH radical matches the production rate of OH, suggesting that there is no significant missing OH source for example from isomerization reactions of peroxy radicals for the experimental conditions in this work.</p>https://acp.copernicus.org/articles/23/12631/2023/acp-23-12631-2023.pdf |
| spellingShingle | J. Y. S. Pang F. Berg A. Novelli B. Bohn M. Färber P. T. M. Carlsson R. Dubus G. I. Gkatzelis F. Rohrer S. Wedel A. Wahner H. Fuchs H. Fuchs Atmospheric photooxidation and ozonolysis of sabinene: reaction rate coefficients, product yields, and chemical budget of radicals Atmospheric Chemistry and Physics |
| title | Atmospheric photooxidation and ozonolysis of sabinene: reaction rate coefficients, product yields, and chemical budget of radicals |
| title_full | Atmospheric photooxidation and ozonolysis of sabinene: reaction rate coefficients, product yields, and chemical budget of radicals |
| title_fullStr | Atmospheric photooxidation and ozonolysis of sabinene: reaction rate coefficients, product yields, and chemical budget of radicals |
| title_full_unstemmed | Atmospheric photooxidation and ozonolysis of sabinene: reaction rate coefficients, product yields, and chemical budget of radicals |
| title_short | Atmospheric photooxidation and ozonolysis of sabinene: reaction rate coefficients, product yields, and chemical budget of radicals |
| title_sort | atmospheric photooxidation and ozonolysis of sabinene reaction rate coefficients product yields and chemical budget of radicals |
| url | https://acp.copernicus.org/articles/23/12631/2023/acp-23-12631-2023.pdf |
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