Direct Measurement of Radical-Catalyzed C₆H₆ Formation from Acetylene and Validation of Theoretical Rate Coefficients for C₂H₃+C₂H₂ and C₄H₅+C₂H₂ Reactions
The addition of vinylic radicals to acetylene is an important step contributing to the formation of polycyclic aromatic hydrocarbons in combustion. The overall reaction 3C2H2 → C6H6 could result in large benzene yields, but without accurate rate parameters validated by experiment, the extent of arom...
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| Language: | English |
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American Chemical Society (ACS)
2020
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| Online Access: | https://hdl.handle.net/1721.1/125689 |
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| author | Smith, Mica C. Liu, Guozhu Buras, Zachary Yang, Jeehyun Green Jr, William H Chu, Te-Chun, Ph. D. Massachusetts Institute of Technology. |
| author2 | Massachusetts Institute of Technology. Department of Chemical Engineering |
| author_facet | Massachusetts Institute of Technology. Department of Chemical Engineering Smith, Mica C. Liu, Guozhu Buras, Zachary Yang, Jeehyun Green Jr, William H Chu, Te-Chun, Ph. D. Massachusetts Institute of Technology. |
| author_sort | Smith, Mica C. |
| collection | MIT |
| description | The addition of vinylic radicals to acetylene is an important step contributing to the formation of polycyclic aromatic hydrocarbons in combustion. The overall reaction 3C2H2 → C6H6 could result in large benzene yields, but without accurate rate parameters validated by experiment, the extent of aromatic ring formation from this pathway is uncertain. The addition of vinyl radicals to acetylene was investigated using time-resolved photoionization time-of-flight mass spectrometry at 500 and 700 K and 5-50 Torr. The formation of C6H6 was observed at all conditions, attributed to sequential addition to acetylene followed by cyclization. Vinylacetylene (C4H4) was observed with increasing yield from 500 to 700 K, attributed to the β-scission of the thermalized 1,3-butadien-1-yl radical and the chemically activated reaction C2H3 + C2H2 → C4H4 + H. The measured kinetics and product distributions are consistent with a kinetic model constructed using pressure- A nd temperature-dependent reaction rate coefficients computed from previously reported ab initio calculations. The experiments provide direct measurements of the hypothesized C4H5 intermediates and validate predictions of pressure-dependent addition reactions of vinylic radicals to C2H2, which are thought to play a key role in soot formation. |
| first_indexed | 2024-09-23T09:26:58Z |
| format | Article |
| id | mit-1721.1/125689 |
| institution | Massachusetts Institute of Technology |
| language | English |
| last_indexed | 2024-09-23T09:26:58Z |
| publishDate | 2020 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/1256892024-05-15T09:27:59Z Direct Measurement of Radical-Catalyzed C₆H₆ Formation from Acetylene and Validation of Theoretical Rate Coefficients for C₂H₃+C₂H₂ and C₄H₅+C₂H₂ Reactions Smith, Mica C. Liu, Guozhu Buras, Zachary Yang, Jeehyun Green Jr, William H Chu, Te-Chun, Ph. D. Massachusetts Institute of Technology. Massachusetts Institute of Technology. Department of Chemical Engineering Massachusetts Institute of Technology. Department of Earth, Atmospheric, and Planetary Sciences The addition of vinylic radicals to acetylene is an important step contributing to the formation of polycyclic aromatic hydrocarbons in combustion. The overall reaction 3C2H2 → C6H6 could result in large benzene yields, but without accurate rate parameters validated by experiment, the extent of aromatic ring formation from this pathway is uncertain. The addition of vinyl radicals to acetylene was investigated using time-resolved photoionization time-of-flight mass spectrometry at 500 and 700 K and 5-50 Torr. The formation of C6H6 was observed at all conditions, attributed to sequential addition to acetylene followed by cyclization. Vinylacetylene (C4H4) was observed with increasing yield from 500 to 700 K, attributed to the β-scission of the thermalized 1,3-butadien-1-yl radical and the chemically activated reaction C2H3 + C2H2 → C4H4 + H. The measured kinetics and product distributions are consistent with a kinetic model constructed using pressure- A nd temperature-dependent reaction rate coefficients computed from previously reported ab initio calculations. The experiments provide direct measurements of the hypothesized C4H5 intermediates and validate predictions of pressure-dependent addition reactions of vinylic radicals to C2H2, which are thought to play a key role in soot formation. China Scholarship Council (Grant 201308120042) China. Ministry of Education. Program for New Century Excellent Talents (Grant NCET-13-0408) 2020-06-05T15:09:14Z 2020-06-05T15:09:14Z 2020-03 2020-05-18T15:50:29Z Article http://purl.org/eprint/type/JournalArticle 1089-5639 https://hdl.handle.net/1721.1/125689 Smith, Mica C. et al. “Direct Measurement of Radical-Catalyzed C₆H₆ Formation from Acetylene and Validation of Theoretical Rate Coefficients for C₂H₃+C₂H₂ and C₄H₅+C₂H₂ Reactions” Journal of Physical Chemistry. A, vol. 124, no. 14, 2020, pp. 2871-2884 © 2020 The Author(s) en https://dx.doi.org/10.1021/acs.jpca.0c00558 Journal of Physical Chemistry. A Creative Commons Attribution 4.0 International license https://creativecommons.org/licenses/by/4.0/ application/pdf American Chemical Society (ACS) ACS |
| spellingShingle | Smith, Mica C. Liu, Guozhu Buras, Zachary Yang, Jeehyun Green Jr, William H Chu, Te-Chun, Ph. D. Massachusetts Institute of Technology. Direct Measurement of Radical-Catalyzed C₆H₆ Formation from Acetylene and Validation of Theoretical Rate Coefficients for C₂H₃+C₂H₂ and C₄H₅+C₂H₂ Reactions |
| title | Direct Measurement of Radical-Catalyzed C₆H₆ Formation from Acetylene and Validation of Theoretical Rate Coefficients for C₂H₃+C₂H₂ and C₄H₅+C₂H₂ Reactions |
| title_full | Direct Measurement of Radical-Catalyzed C₆H₆ Formation from Acetylene and Validation of Theoretical Rate Coefficients for C₂H₃+C₂H₂ and C₄H₅+C₂H₂ Reactions |
| title_fullStr | Direct Measurement of Radical-Catalyzed C₆H₆ Formation from Acetylene and Validation of Theoretical Rate Coefficients for C₂H₃+C₂H₂ and C₄H₅+C₂H₂ Reactions |
| title_full_unstemmed | Direct Measurement of Radical-Catalyzed C₆H₆ Formation from Acetylene and Validation of Theoretical Rate Coefficients for C₂H₃+C₂H₂ and C₄H₅+C₂H₂ Reactions |
| title_short | Direct Measurement of Radical-Catalyzed C₆H₆ Formation from Acetylene and Validation of Theoretical Rate Coefficients for C₂H₃+C₂H₂ and C₄H₅+C₂H₂ Reactions |
| title_sort | direct measurement of radical catalyzed c₆h₆ formation from acetylene and validation of theoretical rate coefficients for c₂h₃ c₂h₂ and c₄h₅ c₂h₂ reactions |
| url | https://hdl.handle.net/1721.1/125689 |
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