Kinetics and product studies of the BrO + ClO Reaction: Implications for Antarctic chemistry
The reaction of ClO with BrO has been investigated by two independent techniques, discharge flow‐mass spectrometry and flash photolysis‐UV spectrometry, over the temperature range 220‐400 K and the pressure range 1‐760 torr. Rate constants have been determined for three product channels; a) Br + ClO...
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American Geophysical Union
1988
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ftcaltechauth:oai:authors.library.caltech.edu:91343 2023-05-15T14:01:44+02:00 Kinetics and product studies of the BrO + ClO Reaction: Implications for Antarctic chemistry Sander, Stanley P. Friedl, Randall R. 1988-08 application/pdf https://authors.library.caltech.edu/91343/ https://authors.library.caltech.edu/91343/1/Sander_et_al-1988-Geophysical_Research_Letters.pdf https://resolver.caltech.edu/CaltechAUTHORS:20181129-163523694 en eng American Geophysical Union https://authors.library.caltech.edu/91343/1/Sander_et_al-1988-Geophysical_Research_Letters.pdf Sander, Stanley P. and Friedl, Randall R. (1988) Kinetics and product studies of the BrO + ClO Reaction: Implications for Antarctic chemistry. Geophysical Research Letters, 15 (8). pp. 887-890. ISSN 0094-8276. doi:10.1029/gl015i008p00887. https://resolver.caltech.edu/CaltechAUTHORS:20181129-163523694 <https://resolver.caltech.edu/CaltechAUTHORS:20181129-163523694> other Article PeerReviewed 1988 ftcaltechauth https://doi.org/10.1029/gl015i008p00887 2021-11-18T18:48:39Z The reaction of ClO with BrO has been investigated by two independent techniques, discharge flow‐mass spectrometry and flash photolysis‐UV spectrometry, over the temperature range 220‐400 K and the pressure range 1‐760 torr. Rate constants have been determined for three product channels; a) Br + ClOO, b) Br + OClO, and c) BrCl + O_2. The rate constants for the overall reaction and each reaction branch were found to be inversely dependent on temperature and independent of pressure. The results for the temperature dependence of the overall rate constant from the discharge flow and flash photolysis studies are in excellent agreement, and collectively disagree substantially with the only previous temperature dependence study. Also, in contrast to previous studies, the channel forming BrCl is found to be significant (≃ 8%). These kinetic measurements have an important impact on the modeling of Antarctic chemistry; for temperatures found in the Antarctic stratosphere the rate coefficients for the channels yielding ClOO and OClO are a factor of 2‐3 larger than previously estimated. In addition, the BrCl channel, which has an impact on the nighttime partitioning of BrO_X and the diurnal variability of OClO, has been omitted from previous atmospheric models. Article in Journal/Newspaper Antarc* Antarctic Caltech Authors (California Institute of Technology) Antarctic The Antarctic Geophysical Research Letters 15 8 887 890 |
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Caltech Authors (California Institute of Technology) |
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English |
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The reaction of ClO with BrO has been investigated by two independent techniques, discharge flow‐mass spectrometry and flash photolysis‐UV spectrometry, over the temperature range 220‐400 K and the pressure range 1‐760 torr. Rate constants have been determined for three product channels; a) Br + ClOO, b) Br + OClO, and c) BrCl + O_2. The rate constants for the overall reaction and each reaction branch were found to be inversely dependent on temperature and independent of pressure. The results for the temperature dependence of the overall rate constant from the discharge flow and flash photolysis studies are in excellent agreement, and collectively disagree substantially with the only previous temperature dependence study. Also, in contrast to previous studies, the channel forming BrCl is found to be significant (≃ 8%). These kinetic measurements have an important impact on the modeling of Antarctic chemistry; for temperatures found in the Antarctic stratosphere the rate coefficients for the channels yielding ClOO and OClO are a factor of 2‐3 larger than previously estimated. In addition, the BrCl channel, which has an impact on the nighttime partitioning of BrO_X and the diurnal variability of OClO, has been omitted from previous atmospheric models. |
format |
Article in Journal/Newspaper |
author |
Sander, Stanley P. Friedl, Randall R. |
spellingShingle |
Sander, Stanley P. Friedl, Randall R. Kinetics and product studies of the BrO + ClO Reaction: Implications for Antarctic chemistry |
author_facet |
Sander, Stanley P. Friedl, Randall R. |
author_sort |
Sander, Stanley P. |
title |
Kinetics and product studies of the BrO + ClO Reaction: Implications for Antarctic chemistry |
title_short |
Kinetics and product studies of the BrO + ClO Reaction: Implications for Antarctic chemistry |
title_full |
Kinetics and product studies of the BrO + ClO Reaction: Implications for Antarctic chemistry |
title_fullStr |
Kinetics and product studies of the BrO + ClO Reaction: Implications for Antarctic chemistry |
title_full_unstemmed |
Kinetics and product studies of the BrO + ClO Reaction: Implications for Antarctic chemistry |
title_sort |
kinetics and product studies of the bro + clo reaction: implications for antarctic chemistry |
publisher |
American Geophysical Union |
publishDate |
1988 |
url |
https://authors.library.caltech.edu/91343/ https://authors.library.caltech.edu/91343/1/Sander_et_al-1988-Geophysical_Research_Letters.pdf https://resolver.caltech.edu/CaltechAUTHORS:20181129-163523694 |
geographic |
Antarctic The Antarctic |
geographic_facet |
Antarctic The Antarctic |
genre |
Antarc* Antarctic |
genre_facet |
Antarc* Antarctic |
op_relation |
https://authors.library.caltech.edu/91343/1/Sander_et_al-1988-Geophysical_Research_Letters.pdf Sander, Stanley P. and Friedl, Randall R. (1988) Kinetics and product studies of the BrO + ClO Reaction: Implications for Antarctic chemistry. Geophysical Research Letters, 15 (8). pp. 887-890. ISSN 0094-8276. doi:10.1029/gl015i008p00887. https://resolver.caltech.edu/CaltechAUTHORS:20181129-163523694 <https://resolver.caltech.edu/CaltechAUTHORS:20181129-163523694> |
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other |
op_doi |
https://doi.org/10.1029/gl015i008p00887 |
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Geophysical Research Letters |
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15 |
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8 |
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887 |
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890 |
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1766271779098066944 |