Electron and proton magnetic resonance spectroscopic investigation of anthracene oxidation
The work reports a method for monitoring anthracene radical-mediated oxidation reactions using electron paramagnetic resonance (EPR) spectroscopy. The formation of anthracene dimer product was well-defined using 1H-NMR and 1H–1H correlation spectroscopy (COSY). Unrestricted 3-21G/B3LYP DFT was used...
| Main Authors: | , , , , , |
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| Format: | Article |
| Language: | English |
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Elsevier
2021-11-01
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| Series: | Heliyon |
| Subjects: | |
| Online Access: | http://www.sciencedirect.com/science/article/pii/S2405844021025779 |
| _version_ | 1819289710906834944 |
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| author | Mohamed A. Morsy Abdel-Nasser M. Kawde Muhammad Kamran Thomas F. Garrison Wissam Iali Salman S. Alharthi |
| author_facet | Mohamed A. Morsy Abdel-Nasser M. Kawde Muhammad Kamran Thomas F. Garrison Wissam Iali Salman S. Alharthi |
| author_sort | Mohamed A. Morsy |
| collection | DOAJ |
| description | The work reports a method for monitoring anthracene radical-mediated oxidation reactions using electron paramagnetic resonance (EPR) spectroscopy. The formation of anthracene dimer product was well-defined using 1H-NMR and 1H–1H correlation spectroscopy (COSY). Unrestricted 3-21G/B3LYP DFT was used to estimate radical hyperfine spacing (hfs), then to identify the characteristic EPR-spin transitions of anthracene radical intermediate. A detailed investigation of an anthracene oxidation reaction and its possible reaction mechanism in concentrated sulphuric acid is conducted as a model system for polyaromatic hydrocarbons. Peak-to-peak (p2p) intensities of selected EPR-spectral lines were used to evaluate anthracene's oxidation kinetic model. The findings showed that radical intermediate formation is a unimolecular autocatalytic process, dimerization is a pseudo-zero-order reaction, and the latter is the rate-determining step with a half-life of 48 ± 2 min at 25.0 °C. |
| first_indexed | 2024-12-24T03:11:11Z |
| format | Article |
| id | doaj.art-aaadf9612b4141c09a5804e9a259cac0 |
| institution | Directory Open Access Journal |
| issn | 2405-8440 |
| language | English |
| last_indexed | 2024-12-24T03:11:11Z |
| publishDate | 2021-11-01 |
| publisher | Elsevier |
| record_format | Article |
| series | Heliyon |
| spelling | doaj.art-aaadf9612b4141c09a5804e9a259cac02022-12-21T17:17:48ZengElsevierHeliyon2405-84402021-11-01711e08474Electron and proton magnetic resonance spectroscopic investigation of anthracene oxidationMohamed A. Morsy0Abdel-Nasser M. Kawde1Muhammad Kamran2Thomas F. Garrison3Wissam Iali4Salman S. Alharthi5Chemistry Department, College of Chemicals and Materials, King Fahd University of Petroleum & Minerals, P.O. Box 1624, Dhahran 31261, Saudi Arabia; Corresponding author.Department of Chemistry, College of Sciences, Research Institute of Sciences and Engineering, University of Sharjah, P.O. Box 27272, Sharjah, United Arab EmiratesChemistry Department, College of Chemicals and Materials, King Fahd University of Petroleum & Minerals, P.O. Box 1624, Dhahran 31261, Saudi ArabiaChemistry Department, College of Chemicals and Materials, King Fahd University of Petroleum & Minerals, P.O. Box 1624, Dhahran 31261, Saudi ArabiaChemistry Department, College of Chemicals and Materials, King Fahd University of Petroleum & Minerals, P.O. Box 1624, Dhahran 31261, Saudi ArabiaDepartment of Chemistry, College of Science, Taif University, P.O. Box 11099, Taif 21944, Saudi ArabiaThe work reports a method for monitoring anthracene radical-mediated oxidation reactions using electron paramagnetic resonance (EPR) spectroscopy. The formation of anthracene dimer product was well-defined using 1H-NMR and 1H–1H correlation spectroscopy (COSY). Unrestricted 3-21G/B3LYP DFT was used to estimate radical hyperfine spacing (hfs), then to identify the characteristic EPR-spin transitions of anthracene radical intermediate. A detailed investigation of an anthracene oxidation reaction and its possible reaction mechanism in concentrated sulphuric acid is conducted as a model system for polyaromatic hydrocarbons. Peak-to-peak (p2p) intensities of selected EPR-spectral lines were used to evaluate anthracene's oxidation kinetic model. The findings showed that radical intermediate formation is a unimolecular autocatalytic process, dimerization is a pseudo-zero-order reaction, and the latter is the rate-determining step with a half-life of 48 ± 2 min at 25.0 °C.http://www.sciencedirect.com/science/article/pii/S2405844021025779EPR SpectroscopyNMR SpectroscopyAnthracene cation radicalRadical kinetics |
| spellingShingle | Mohamed A. Morsy Abdel-Nasser M. Kawde Muhammad Kamran Thomas F. Garrison Wissam Iali Salman S. Alharthi Electron and proton magnetic resonance spectroscopic investigation of anthracene oxidation Heliyon EPR Spectroscopy NMR Spectroscopy Anthracene cation radical Radical kinetics |
| title | Electron and proton magnetic resonance spectroscopic investigation of anthracene oxidation |
| title_full | Electron and proton magnetic resonance spectroscopic investigation of anthracene oxidation |
| title_fullStr | Electron and proton magnetic resonance spectroscopic investigation of anthracene oxidation |
| title_full_unstemmed | Electron and proton magnetic resonance spectroscopic investigation of anthracene oxidation |
| title_short | Electron and proton magnetic resonance spectroscopic investigation of anthracene oxidation |
| title_sort | electron and proton magnetic resonance spectroscopic investigation of anthracene oxidation |
| topic | EPR Spectroscopy NMR Spectroscopy Anthracene cation radical Radical kinetics |
| url | http://www.sciencedirect.com/science/article/pii/S2405844021025779 |
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