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Hydration Increases the Lifetime of Hso5 and Enhances Its Ability to Act as a Nucleation Precursor – a Computational Study : Volume 9, Issue 10 (25/05/2009)

By Kurtén, T.

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Book Id: WPLBN0003993361
Format Type: PDF Article :
File Size: Pages 13
Reproduction Date: 2015

Title: Hydration Increases the Lifetime of Hso5 and Enhances Its Ability to Act as a Nucleation Precursor – a Computational Study : Volume 9, Issue 10 (25/05/2009)  
Author: Kurtén, T.
Volume: Vol. 9, Issue 10
Language: English
Subject: Science, Atmospheric, Chemistry
Collections: Periodicals: Journal and Magazine Collection (Contemporary), Copernicus GmbH
Historic
Publication Date:
2009
Publisher: Copernicus Gmbh, Göttingen, Germany
Member Page: Copernicus Publications

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Stratmann, F., Berndt, T., & Kurtén, T. (2009). Hydration Increases the Lifetime of Hso5 and Enhances Its Ability to Act as a Nucleation Precursor – a Computational Study : Volume 9, Issue 10 (25/05/2009). Retrieved from http://www.ebooklibrary.org/


Description
Description: Department of Physics, P.O. Box 64, 00014 University of Helsinki, Helsinki, Finland. Recent experimental findings indicate that HSO5 radicals may play a key role in the nucleation of atmospheric SO2 oxidation products. HSO5 radicals are metastable intermediates formed in the SO2 oxidation process, and their stability and lifetime are, at present, highly uncertain. Previous high-level computational studies have predicted rather low stabilities for HSO5 with respect to dissociation into SO3+HO2, and have predicted the net reaction HSO3+OH→SO3+HO2 to be slightly exothermal. However, these studies have not accounted for hydration of HSO5 or its precursor HSO3. In this study, we have estimated the effect of hydration on the stability and lifetime of HSO5 using the advanced quantum chemical methods CCSD(T) and G3B3. We have computed formation energies and free energies for mono- and dihydrates of OH, HSO3, HSO5, SO3 and HO2, and also reanalyzed the individual steps of the HSO3+O2→HSO5→SO3+HO2 reaction at a higher level of theory than previously published. Our results indicate that hydration is likely to significantly prolong the lifetime of the HSO5 intermediate in atmospheric conditions, thus increasing the probability of reactions that form products with more than one sulfur atom. Kinetic modeling indicates that these results may help explain the experimental observations that a mixture of sulfur-containing products formed from SO2 oxidation by OH radicals nucleates much more effectively than sulfuric acid taken from a liquid reservoir.

Summary
Hydration increases the lifetime of HSO5 and enhances its ability to act as a nucleation precursor – a computational study

Excerpt
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