دورية أكاديمية
The Homogeneous Gas-Phase Formation Mechanism of PCNs from Cross-Condensation of Phenoxy Radical with 2-CPR and 3-CPR: A Theoretical Mechanistic and Kinetic Study
| العنوان: | The Homogeneous Gas-Phase Formation Mechanism of PCNs from Cross-Condensation of Phenoxy Radical with 2-CPR and 3-CPR: A Theoretical Mechanistic and Kinetic Study |
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| المؤلفون: | Zhuochao Teng, Yanan Han, Shuming He, Mohammad Hassan Hadizadeh, Qi Zhang, Xurong Bai, Xiaotong Wang, Yanhui Sun, Fei Xu |
| المصدر: | International Journal of Molecular Sciences, Vol 23, Iss 11, p 5866 (2022) |
| بيانات النشر: | MDPI AG, 2022. |
| سنة النشر: | 2022 |
| المجموعة: | LCC:Biology (General) LCC:Chemistry |
| مصطلحات موضوعية: | polychlorinated naphthalenes, chlorophenols, formation mechanisms, rate constants, DFT calculations, Biology (General), QH301-705.5, Chemistry, QD1-999 |
| الوصف: | Chlorophenols (CPs) and phenol are abundant in thermal and combustion procedures, such as stack gas production, industrial incinerators, metal reclamation, etc., which are key precursors for the formation of polychlorinated naphthalenes (PCNs). CPs and phenol can react with H or OH radicals to form chlorophenoxy radicals (CPRs) and phenoxy radical (PhR). The self-condensation of CPRs or cross-condensation of PhR with CPRs is the initial and most important step for PCN formation. In this work, detailed thermodynamic and kinetic calculations were carried out to investigate the PCN formation mechanisms from PhR with 2-CPR/3-CPR. Several energetically advantageous formation pathways were obtained. The rate constants of key elementary steps were calculated over 600~1200 K using the canonical variational transition-state theory (CVT) with the small curvature tunneling (SCT) contribution method. The mechanisms were compared with the experimental observations and our previous works on the PCN formation from the self-condensation of 2-CPRs/3-CPRs. This study shows that naphthalene and 1-monochlorinated naphthalene (1-MCN) are the main PCN products from the cross-condensation of PhR with 2-CPR, and naphthalene and 2-monochlorinated naphthalene (2-MCN) are the main PCN products from the cross-condensation of PhR with 3-CPR. Pathways terminated with Cl elimination are preferred over those terminated with H elimination. PCN formation from the cross-condensation of PhR with 3-CPR can occur much easier than that from the cross-condensation of PhR with 2-CPR. This study, along with the study of PCN formation from the self-condensation 2-CPRs/3-CPRs, can provide reasonable explanations for the experimental observations that the formation potential of naphthalene is larger than that of 1-MCN using 2-CP as a precursor, and an almost equal yield of 1-MCN and 2-MCN can be produced with 3-CP as a precursor. |
| نوع الوثيقة: | article |
| وصف الملف: | electronic resource |
| اللغة: | English |
| تدمد: | 23115866 1422-0067 1661-6596 |
| العلاقة: | https://www.mdpi.com/1422-0067/23/11/5866Test; https://doaj.org/toc/1661-6596Test; https://doaj.org/toc/1422-0067Test |
| DOI: | 10.3390/ijms23115866 |
| الوصول الحر: | https://doaj.org/article/1a2c58e81580458998eda48c16f1d9b9Test |
| رقم الانضمام: | edsdoj.1a2c58e81580458998eda48c16f1d9b9 |
| قاعدة البيانات: | Directory of Open Access Journals |
Full Text Finder | تدمد: | 23115866 14220067 16616596 |
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| DOI: | 10.3390/ijms23115866 |