Chemistry of Simple Organic Peroxy Radicals under Atmospheric through Combustion Conditions: Role of Temperature, Pressure, and NO x Level
Organic peroxy radicals (RO2) are key intermediates in the oxidation of organic compounds in both combustion systems and the atmosphere. While many studies have focused on reactions of RO2 in specific applications, spanning a relatively limited range of reaction conditions, the generalized behavior...
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| Format: | Article |
| Language: | English |
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American Chemical Society (ACS)
2023
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| Online Access: | https://hdl.handle.net/1721.1/148588 |
| _version_ | 1811071344830316544 |
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| author | Goldman, Mark Jacob Green, William H Kroll, Jesse H |
| author2 | Massachusetts Institute of Technology. Department of Chemical Engineering |
| author_facet | Massachusetts Institute of Technology. Department of Chemical Engineering Goldman, Mark Jacob Green, William H Kroll, Jesse H |
| author_sort | Goldman, Mark Jacob |
| collection | MIT |
| description | Organic peroxy radicals (RO2) are key intermediates in the oxidation of organic compounds in both combustion systems and the atmosphere. While many studies have focused on reactions of RO2 in specific applications, spanning a relatively limited range of reaction conditions, the generalized behavior of RO2 radicals across the full range of reaction conditions (temperatures, pressures, and NO levels) has, to our knowledge, never been explored. In this work, two simple model systems, n-propyl peroxy radical and γ-isobutanol peroxy radical, are used to evaluate RO2 fate using pressure-dependent kinetics. The fate of these radicals was modeled based on literature data over 250-1250 K, 0.01-100 bar, and 1 ppt to 100 ppm of NO, which spans the typical range of atmospheric and combustion conditions. Covering this entire range provides a broad overview of the reactivity of these species under both atmospheric and combustion conditions, as well as under conditions intermediate to the two. A particular focus is on the importance of reactions that were traditionally considered to occur in only one of the two sets of conditions: RO2 unimolecular isomerization reactions (long known to occur in combustion systems but only recently appreciated in atmospheric systems) and RO2 bimolecular reactions of RO2 with NO (thought to occur mainly in atmospheric systems and rarely considered in combustion chemistry). |
| first_indexed | 2024-09-23T08:49:42Z |
| format | Article |
| id | mit-1721.1/148588 |
| institution | Massachusetts Institute of Technology |
| language | English |
| last_indexed | 2024-09-23T08:49:42Z |
| publishDate | 2023 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/1485882023-03-17T03:47:30Z Chemistry of Simple Organic Peroxy Radicals under Atmospheric through Combustion Conditions: Role of Temperature, Pressure, and NO x Level Goldman, Mark Jacob Green, William H Kroll, Jesse H Massachusetts Institute of Technology. Department of Chemical Engineering Massachusetts Institute of Technology. Department of Civil and Environmental Engineering Organic peroxy radicals (RO2) are key intermediates in the oxidation of organic compounds in both combustion systems and the atmosphere. While many studies have focused on reactions of RO2 in specific applications, spanning a relatively limited range of reaction conditions, the generalized behavior of RO2 radicals across the full range of reaction conditions (temperatures, pressures, and NO levels) has, to our knowledge, never been explored. In this work, two simple model systems, n-propyl peroxy radical and γ-isobutanol peroxy radical, are used to evaluate RO2 fate using pressure-dependent kinetics. The fate of these radicals was modeled based on literature data over 250-1250 K, 0.01-100 bar, and 1 ppt to 100 ppm of NO, which spans the typical range of atmospheric and combustion conditions. Covering this entire range provides a broad overview of the reactivity of these species under both atmospheric and combustion conditions, as well as under conditions intermediate to the two. A particular focus is on the importance of reactions that were traditionally considered to occur in only one of the two sets of conditions: RO2 unimolecular isomerization reactions (long known to occur in combustion systems but only recently appreciated in atmospheric systems) and RO2 bimolecular reactions of RO2 with NO (thought to occur mainly in atmospheric systems and rarely considered in combustion chemistry). 2023-03-16T18:56:01Z 2023-03-16T18:56:01Z 2021 2023-03-16T18:51:11Z Article http://purl.org/eprint/type/JournalArticle https://hdl.handle.net/1721.1/148588 Goldman, Mark Jacob, Green, William H and Kroll, Jesse H. 2021. "Chemistry of Simple Organic Peroxy Radicals under Atmospheric through Combustion Conditions: Role of Temperature, Pressure, and NO x Level." Journal of Physical Chemistry A, 125 (48). en 10.1021/ACS.JPCA.1C07203 Journal of Physical Chemistry A Creative Commons Attribution-NonCommercial-NoDerivs License http://creativecommons.org/licenses/by-nc-nd/4.0/ application/pdf American Chemical Society (ACS) ACS |
| spellingShingle | Goldman, Mark Jacob Green, William H Kroll, Jesse H Chemistry of Simple Organic Peroxy Radicals under Atmospheric through Combustion Conditions: Role of Temperature, Pressure, and NO x Level |
| title | Chemistry of Simple Organic Peroxy Radicals under Atmospheric through Combustion Conditions: Role of Temperature, Pressure, and NO x Level |
| title_full | Chemistry of Simple Organic Peroxy Radicals under Atmospheric through Combustion Conditions: Role of Temperature, Pressure, and NO x Level |
| title_fullStr | Chemistry of Simple Organic Peroxy Radicals under Atmospheric through Combustion Conditions: Role of Temperature, Pressure, and NO x Level |
| title_full_unstemmed | Chemistry of Simple Organic Peroxy Radicals under Atmospheric through Combustion Conditions: Role of Temperature, Pressure, and NO x Level |
| title_short | Chemistry of Simple Organic Peroxy Radicals under Atmospheric through Combustion Conditions: Role of Temperature, Pressure, and NO x Level |
| title_sort | chemistry of simple organic peroxy radicals under atmospheric through combustion conditions role of temperature pressure and no x level |
| url | https://hdl.handle.net/1721.1/148588 |
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