Mechanistic Insights into Chloric Acid Production by Hydrolysis of Chlorine Trioxide at an Air-Water Interface.
Chlorine oxides play crucial roles in ozone depletion, and the final oxidation steps of chlorine oxide potentially result in the formation of chloric acid (HClO3) or perchloric acid (HClO4). Herein, the solvation and reactive uptake of three stable isomers of chlorine trioxide (Cl2O3), namely, ClOCl...
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Online Access: | https://doi.org/10.1021/jacs.4c06269 https://pubmed.ncbi.nlm.nih.gov/39013148 |
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ftpubmed:39013148 2024-09-09T19:26:02+00:00 Mechanistic Insights into Chloric Acid Production by Hydrolysis of Chlorine Trioxide at an Air-Water Interface. Fang, Ye-Guang Wei, Laiyang Francisco, Joseph S Zhu, Chongqin Fang, Wei-Hai 2024 Jul 31 https://doi.org/10.1021/jacs.4c06269 https://pubmed.ncbi.nlm.nih.gov/39013148 eng eng American Chemical Society https://doi.org/10.1021/jacs.4c06269 https://pubmed.ncbi.nlm.nih.gov/39013148 J Am Chem Soc ISSN:1520-5126 Volume:146 Issue:30 Journal Article 2024 ftpubmed https://doi.org/10.1021/jacs.4c06269 2024-07-31T16:03:00Z Chlorine oxides play crucial roles in ozone depletion, and the final oxidation steps of chlorine oxide potentially result in the formation of chloric acid (HClO3) or perchloric acid (HClO4). Herein, the solvation and reactive uptake of three stable isomers of chlorine trioxide (Cl2O3), namely, ClOCl(O)O, ClClO3, and ClOOOCl, at the air-water interface were investigated using classical and hybrid quantum mechanics/molecular mechanics (QM/MM) molecular dynamics (MD) coupled with advanced free energy methods. Two distinct mechanisms were revealed for the hydrolysis of ClOCl(O)O and ClClO3: molecular and ionic mechanisms. A comparison of the computed free-energy profiles for the gaseous and air-water interfacial systems indicated that the air-water interface could markedly lower the free-energy barrier for ClO3- or HClO3 formation while stabilizing the product state. In particular, the hydrolysis of ClClO3 at the air-water interface was barrierless. In contrast, our calculations showed that the hydrolysis of ClOOOCl was very slow, indicating that ClOOOCl was inert to water at the air-water interface. This study provides theoretical evidence for the hypothesis that HClO3 is a sink for chlorine oxides and for the widespread distributions of HClO3 recently observed in the Arctic region. Article in Journal/Newspaper Arctic PubMed Central (PMC) Arctic Journal of the American Chemical Society 146 30 21052 21060 |
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English |
description |
Chlorine oxides play crucial roles in ozone depletion, and the final oxidation steps of chlorine oxide potentially result in the formation of chloric acid (HClO3) or perchloric acid (HClO4). Herein, the solvation and reactive uptake of three stable isomers of chlorine trioxide (Cl2O3), namely, ClOCl(O)O, ClClO3, and ClOOOCl, at the air-water interface were investigated using classical and hybrid quantum mechanics/molecular mechanics (QM/MM) molecular dynamics (MD) coupled with advanced free energy methods. Two distinct mechanisms were revealed for the hydrolysis of ClOCl(O)O and ClClO3: molecular and ionic mechanisms. A comparison of the computed free-energy profiles for the gaseous and air-water interfacial systems indicated that the air-water interface could markedly lower the free-energy barrier for ClO3- or HClO3 formation while stabilizing the product state. In particular, the hydrolysis of ClClO3 at the air-water interface was barrierless. In contrast, our calculations showed that the hydrolysis of ClOOOCl was very slow, indicating that ClOOOCl was inert to water at the air-water interface. This study provides theoretical evidence for the hypothesis that HClO3 is a sink for chlorine oxides and for the widespread distributions of HClO3 recently observed in the Arctic region. |
format |
Article in Journal/Newspaper |
author |
Fang, Ye-Guang Wei, Laiyang Francisco, Joseph S Zhu, Chongqin Fang, Wei-Hai |
spellingShingle |
Fang, Ye-Guang Wei, Laiyang Francisco, Joseph S Zhu, Chongqin Fang, Wei-Hai Mechanistic Insights into Chloric Acid Production by Hydrolysis of Chlorine Trioxide at an Air-Water Interface. |
author_facet |
Fang, Ye-Guang Wei, Laiyang Francisco, Joseph S Zhu, Chongqin Fang, Wei-Hai |
author_sort |
Fang, Ye-Guang |
title |
Mechanistic Insights into Chloric Acid Production by Hydrolysis of Chlorine Trioxide at an Air-Water Interface. |
title_short |
Mechanistic Insights into Chloric Acid Production by Hydrolysis of Chlorine Trioxide at an Air-Water Interface. |
title_full |
Mechanistic Insights into Chloric Acid Production by Hydrolysis of Chlorine Trioxide at an Air-Water Interface. |
title_fullStr |
Mechanistic Insights into Chloric Acid Production by Hydrolysis of Chlorine Trioxide at an Air-Water Interface. |
title_full_unstemmed |
Mechanistic Insights into Chloric Acid Production by Hydrolysis of Chlorine Trioxide at an Air-Water Interface. |
title_sort |
mechanistic insights into chloric acid production by hydrolysis of chlorine trioxide at an air-water interface. |
publisher |
American Chemical Society |
publishDate |
2024 |
url |
https://doi.org/10.1021/jacs.4c06269 https://pubmed.ncbi.nlm.nih.gov/39013148 |
geographic |
Arctic |
geographic_facet |
Arctic |
genre |
Arctic |
genre_facet |
Arctic |
op_source |
J Am Chem Soc ISSN:1520-5126 Volume:146 Issue:30 |
op_relation |
https://doi.org/10.1021/jacs.4c06269 https://pubmed.ncbi.nlm.nih.gov/39013148 |
op_doi |
https://doi.org/10.1021/jacs.4c06269 |
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Journal of the American Chemical Society |
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146 |
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30 |
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21052 |
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21060 |
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1809895741442752512 |