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<article xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink" article-type="research-article" dtd-version="3.0" xml:lang="en">
<front>
<journal-meta>
<journal-id journal-id-type="publisher">ACPD</journal-id>
<journal-title-group>
<journal-title>Atmospheric Chemistry and Physics Discussions</journal-title>
<abbrev-journal-title abbrev-type="publisher">ACPD</abbrev-journal-title>
</journal-title-group>
<issn pub-type="epub">1680-7375</issn>
<publisher><publisher-name>Copernicus GmbH</publisher-name>
<publisher-loc>Göttingen, Germany</publisher-loc>
</publisher>
</journal-meta>
<article-meta>
<article-id pub-id-type="doi">10.5194/acpd-1-77-2001</article-id>
<title-group>
<article-title>Oxidation of SO&lt;sub&gt;2&lt;/sub&gt; by H&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;2&lt;/sub&gt; on ice surfaces at 228 K: a sink for SO&lt;sub&gt;2&lt;/sub&gt; in ice clouds</article-title>
</title-group>
<contrib-group><contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Clegg</surname>
<given-names>S. M.</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
<xref ref-type="aff" rid="aff2">
<sup>2</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Abbatt</surname>
<given-names>J. P. D.</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
</contrib>
</contrib-group><aff id="aff1">
<label>1</label>
<addr-line>1Department of Chemistry, University of Toronto, 80 St. George St., Toronto, M5S 3H6 Ontario, Canada</addr-line>
</aff>
<aff id="aff2">
<label>2</label>
<addr-line>2now at: Combustion Research Facility, Sandia National Laboratory, P.O. Box 969, MS 9055, Livermore, CA 94551-0969, USA</addr-line>
</aff>
<pub-date pub-type="epub">
<day>03</day>
<month>09</month>
<year>2001</year>
</pub-date>
<volume>1</volume>
<issue>1</issue>
<fpage>77</fpage>
<lpage>92</lpage>
<permissions>
<license xlink:type="simple">
<license-p>This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.</license-p>
</license>
</permissions>
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<self-uri xlink:href="http://www.atmos-chem-phys-discuss.net/1/77/2001/acpd-1-77-2001.pdf">The full text article is available as a PDF file from http://www.atmos-chem-phys-discuss.net/1/77/2001/acpd-1-77-2001.pdf</self-uri>
<abstract>
<p>The heterogeneous reaction SO&lt;sub&gt;2&lt;/sub&gt; + H&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;2&lt;/sub&gt; to H&lt;sub&gt;2&lt;/sub&gt;SO&lt;sub&gt;4&lt;/sub&gt; on ice at 228 K has been studied
in a low temperature coated-wall flow tube. With H&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;2&lt;/sub&gt; in excess of SO&lt;sub&gt;2&lt;/sub&gt;, the loss of
SO&lt;sub&gt;2&lt;/sub&gt; on an ice surface is time dependent with the reaction most efficient on a freshly
exposed surface. The deactivation of the surface arises because the protons formed in 
the reaction inhibit the dissociation of adsorbed SO&lt;sub&gt;2&lt;/sub&gt;. This lowers the surface concentrations
of HSO&lt;sub&gt;3&lt;/sub&gt;&lt;sup&gt;-&lt;/sup&gt;, a participant in the rate-determining step of the oxidation mechanism.
For a fixed SO&lt;sub&gt;2&lt;/sub&gt; partial pressure of 1.4 &amp;times; 10&lt;sup&gt;-4&lt;/sup&gt; Pa, the reaction probabilities for SO&lt;sub&gt;2&lt;/sub&gt;
loss on a freshly exposed surface scale linearly with H&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;2&lt;/sub&gt; partial pressures between
2.7 &amp;times; 10&lt;sup&gt;-3&lt;/sup&gt; and 2.7 &amp;times; 10&lt;sup&gt;-2&lt;/sup&gt; Pa because the H&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;2&lt;/sub&gt; surface coverage is unsaturated in 
this regime. Conversely, the reaction probabilities decrease as the partial pressure of
SO&lt;sub&gt;2&lt;/sub&gt; is raised from 2.7 &amp;times; 10&lt;sup&gt;-5&lt;/sup&gt; to 1.3 &amp;times; 10&lt;sup&gt;-3&lt;/sup&gt; Pa, for a fixed H&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;2&lt;/sub&gt; partial pressure of 8.7
&amp;times; 10&lt;sup&gt;-3&lt;/sup&gt; Pa. This is expected if the rate determining step for the mechanism involves
HSO&lt;sub&gt;3&lt;/sub&gt;&lt;sup&gt;-&lt;/sup&gt; rather than SO&lt;sub&gt;2&lt;/sub&gt;. It may also arise to some degree if there is competition between
gas phase SO&lt;sub&gt;2&lt;/sub&gt; and H&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;2&lt;/sub&gt; for adsorption sites. The reaction is sufficiently fast 
that the lifetime of SO&lt;sub&gt;2&lt;/sub&gt; within ice clouds could be controlled by this heterogeneous
reaction and not by the gas-phase reaction with OH.</p>
</abstract>
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