Mechanistic insight into the competition between interfacial and bulk reactions in microdroplets through N2O5 ammonolysis and hydrolysis
Abstract Reactive uptake of dinitrogen pentaoxide (N2O5) into aqueous aerosols is a major loss channel for NOx in the troposphere; however, a quantitative understanding of the uptake mechanism is lacking. Herein, a computational chemistry strategy is developed employing high-level quantum chemical m...
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2024-03-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-024-46674-1 |
| _version_ | 1827315938342469632 |
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| author | Ye-Guang Fang Bo Tang Chang Yuan Zhengyi Wan Lei Zhao Shuang Zhu Joseph S. Francisco Chongqin Zhu Wei-Hai Fang |
| author_facet | Ye-Guang Fang Bo Tang Chang Yuan Zhengyi Wan Lei Zhao Shuang Zhu Joseph S. Francisco Chongqin Zhu Wei-Hai Fang |
| author_sort | Ye-Guang Fang |
| collection | DOAJ |
| description | Abstract Reactive uptake of dinitrogen pentaoxide (N2O5) into aqueous aerosols is a major loss channel for NOx in the troposphere; however, a quantitative understanding of the uptake mechanism is lacking. Herein, a computational chemistry strategy is developed employing high-level quantum chemical methods; the method offers detailed molecular insight into the hydrolysis and ammonolysis mechanisms of N2O5 in microdroplets. Specifically, our calculations estimate the bulk and interfacial hydrolysis rates to be (2.3 ± 1.6) × 10−3 and (6.3 ± 4.2) × 10−7 ns−1, respectively, and ammonolysis competes with hydrolysis at NH3 concentrations above 1.9 × 10−4 mol L−1. The slow interfacial hydrolysis rate suggests that interfacial processes have negligible effect on the hydrolysis of N2O5 in liquid water. In contrast, N2O5 ammonolysis in liquid water is dominated by interfacial processes due to the high interfacial ammonolysis rate. Our findings and strategy are applicable to high-chemical complexity microdroplets. |
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| format | Article |
| id | doaj.art-d0abab93e2b94f5681aa82f27baa842e |
| institution | Directory Open Access Journal |
| issn | 2041-1723 |
| language | English |
| last_indexed | 2024-04-24T23:05:22Z |
| publishDate | 2024-03-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj.art-d0abab93e2b94f5681aa82f27baa842e2024-03-17T12:30:44ZengNature PortfolioNature Communications2041-17232024-03-0115111110.1038/s41467-024-46674-1Mechanistic insight into the competition between interfacial and bulk reactions in microdroplets through N2O5 ammonolysis and hydrolysisYe-Guang Fang0Bo Tang1Chang Yuan2Zhengyi Wan3Lei Zhao4Shuang Zhu5Joseph S. Francisco6Chongqin Zhu7Wei-Hai Fang8Key Laboratory of Theoretical and Computational Photochemistry, Ministry of Education, College of Chemistry, Beijing Normal UniversityKey Laboratory of Theoretical and Computational Photochemistry, Ministry of Education, College of Chemistry, Beijing Normal UniversityKey Laboratory of Theoretical and Computational Photochemistry, Ministry of Education, College of Chemistry, Beijing Normal UniversityDepartment of Chemistry, University of PennsylvaniaKey Laboratory of Theoretical and Computational Photochemistry, Ministry of Education, College of Chemistry, Beijing Normal UniversityKey Laboratory of Theoretical and Computational Photochemistry, Ministry of Education, College of Chemistry, Beijing Normal UniversityDepartment of Chemistry, University of PennsylvaniaKey Laboratory of Theoretical and Computational Photochemistry, Ministry of Education, College of Chemistry, Beijing Normal UniversityKey Laboratory of Theoretical and Computational Photochemistry, Ministry of Education, College of Chemistry, Beijing Normal UniversityAbstract Reactive uptake of dinitrogen pentaoxide (N2O5) into aqueous aerosols is a major loss channel for NOx in the troposphere; however, a quantitative understanding of the uptake mechanism is lacking. Herein, a computational chemistry strategy is developed employing high-level quantum chemical methods; the method offers detailed molecular insight into the hydrolysis and ammonolysis mechanisms of N2O5 in microdroplets. Specifically, our calculations estimate the bulk and interfacial hydrolysis rates to be (2.3 ± 1.6) × 10−3 and (6.3 ± 4.2) × 10−7 ns−1, respectively, and ammonolysis competes with hydrolysis at NH3 concentrations above 1.9 × 10−4 mol L−1. The slow interfacial hydrolysis rate suggests that interfacial processes have negligible effect on the hydrolysis of N2O5 in liquid water. In contrast, N2O5 ammonolysis in liquid water is dominated by interfacial processes due to the high interfacial ammonolysis rate. Our findings and strategy are applicable to high-chemical complexity microdroplets.https://doi.org/10.1038/s41467-024-46674-1 |
| spellingShingle | Ye-Guang Fang Bo Tang Chang Yuan Zhengyi Wan Lei Zhao Shuang Zhu Joseph S. Francisco Chongqin Zhu Wei-Hai Fang Mechanistic insight into the competition between interfacial and bulk reactions in microdroplets through N2O5 ammonolysis and hydrolysis Nature Communications |
| title | Mechanistic insight into the competition between interfacial and bulk reactions in microdroplets through N2O5 ammonolysis and hydrolysis |
| title_full | Mechanistic insight into the competition between interfacial and bulk reactions in microdroplets through N2O5 ammonolysis and hydrolysis |
| title_fullStr | Mechanistic insight into the competition between interfacial and bulk reactions in microdroplets through N2O5 ammonolysis and hydrolysis |
| title_full_unstemmed | Mechanistic insight into the competition between interfacial and bulk reactions in microdroplets through N2O5 ammonolysis and hydrolysis |
| title_short | Mechanistic insight into the competition between interfacial and bulk reactions in microdroplets through N2O5 ammonolysis and hydrolysis |
| title_sort | mechanistic insight into the competition between interfacial and bulk reactions in microdroplets through n2o5 ammonolysis and hydrolysis |
| url | https://doi.org/10.1038/s41467-024-46674-1 |
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