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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">ACP</journal-id>
<journal-title-group>
<journal-title>Atmospheric Chemistry and Physics</journal-title>
<abbrev-journal-title abbrev-type="publisher">ACP</abbrev-journal-title>
</journal-title-group>
<issn pub-type="epub">1680-7324</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/acp-5-1577-2005</article-id>
<title-group>
<article-title>Uptake of hypobromous acid (HOBr) by aqueous sulfuric acid solutions: low-temperature solubility and reaction</article-title>
</title-group>
<contrib-group><contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Iraci</surname>
<given-names>L. T.</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Michelsen</surname>
<given-names>R. R.</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>Ashbourn</surname>
<given-names>S. F. M.</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
<xref ref-type="aff" rid="aff3">
<sup>3</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Rammer</surname>
<given-names>T. A.</given-names>
</name>
<xref ref-type="aff" rid="aff4">
<sup>4</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Golden</surname>
<given-names>D. M.</given-names>
</name>
<xref ref-type="aff" rid="aff5">
<sup>5</sup>
</xref>
</contrib>
</contrib-group><aff id="aff1">
<label>1</label>
<addr-line>Atmospheric Chemistry &amp; Dynamics Branch, NASA Ames Res. Center, Mail Stop 245-5, Moffett Field, CA 94035, USA</addr-line>
</aff>
<aff id="aff2">
<label>2</label>
<addr-line>National Research Council Associate, USA</addr-line>
</aff>
<aff id="aff3">
<label>3</label>
<addr-line>now at: Earth Tech, Ltd., 91 Brick Lane, London EI 6QL, UK</addr-line>
</aff>
<aff id="aff4">
<label>4</label>
<addr-line>SRI International NSF Research Experiences for Undergraduates Program, Menlo Park, CA 94025, USA</addr-line>
</aff>
<aff id="aff5">
<label>5</label>
<addr-line>Department of Mechanical Engineering, Stanford University, Stanford, CA 94305, USA</addr-line>
</aff>
<pub-date pub-type="epub">
<day>21</day>
<month>06</month>
<year>2005</year>
</pub-date>
<volume>5</volume>
<issue>6</issue>
<fpage>1577</fpage>
<lpage>1587</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>
<self-uri xlink:href="http://www.atmos-chem-phys.net/5/1577/2005/acp-5-1577-2005.html">This article is available from http://www.atmos-chem-phys.net/5/1577/2005/acp-5-1577-2005.html</self-uri>
<self-uri xlink:href="http://www.atmos-chem-phys.net/5/1577/2005/acp-5-1577-2005.pdf">The full text article is available as a PDF file from http://www.atmos-chem-phys.net/5/1577/2005/acp-5-1577-2005.pdf</self-uri>
<abstract>
<p>Hypobromous acid (HOBr) is a key species linking inorganic bromine to the
chlorine and odd hydrogen chemical families. We have measured the solubility
of HOBr in 45-70wt% sulfuric acid solutions representative of upper
tropospheric and lower stratospheric aerosol composition. Over the
temperature range 201-252 K, HOBr is quite soluble in sulfuric acid, with an
effective Henry&apos;s law coefficient, &lt;i&gt;H&lt;sup&gt;*&lt;/sup&gt;&lt;/i&gt;=10&lt;sup&gt;4&lt;/sup&gt;-10&lt;sup&gt;7&lt;/sup&gt;mol L&lt;sup&gt;-1&lt;/sup&gt;atm&lt;sup&gt;-1&lt;/sup&gt;.
&lt;i&gt;H&lt;sup&gt;*&lt;/sup&gt;&lt;/i&gt; is inversely dependent on temperature, with &amp;Delta;&lt;i&gt;H&lt;/i&gt;=-45.0&amp;plusmn;5.4 kJ mol&lt;sup&gt;-1&lt;/sup&gt;
and &amp;Delta;&lt;i&gt;S&lt;/i&gt;=-101&amp;plusmn;24 J mol&lt;sup&gt;-1&lt;/sup&gt;K&lt;sup&gt;-1&lt;/sup&gt; for 55-70wt% H&lt;sub&gt;2&lt;/sub&gt;SO&lt;sub&gt;4&lt;/sub&gt; solutions. Our study includes
temperatures which overlap both previous measurements of HOBr solubility.
For uptake into 55-70wt% H&lt;sub&gt;2&lt;/sub&gt;SO&lt;sub&gt;4&lt;/sub&gt;, the solubility is described by
log &lt;i&gt;H&lt;sup&gt;*&lt;/sup&gt;&lt;/i&gt;=(2349&amp;plusmn;280)/T-(5.27&amp;plusmn;1.24). At temperatures colder than
~213K, the solubility of HOBr in 45wt% H&lt;sub&gt;2&lt;/sub&gt;SO&lt;sub&gt;4&lt;/sub&gt; is at
least a factor of five larger than in 70wt% H&lt;sub&gt;2&lt;/sub&gt;SO&lt;sub&gt;4&lt;/sub&gt;, with log
&lt;i&gt;H&lt;sup&gt;*&lt;/sup&gt;&lt;/i&gt;=(3665&amp;plusmn;270)/T-(10.63&amp;plusmn;1.23). The solubility of HOBr is
comparable to that of HBr, indicating that upper tropospheric and lower
stratospheric aerosols should contain equilibrium concentrations of HOBr
which equal or exceed those of HBr. Upon uptake of HOBr into aqueous
sulfuric acid in the presence of other brominated gases, particularly for 70wt%
H&lt;sub&gt;2&lt;/sub&gt;SO&lt;sub&gt;4&lt;/sub&gt; solution, our measurements demonstrate chemical
reaction of HOBr followed by evolution of gaseous products including
Br&lt;sub&gt;2&lt;/sub&gt;O and Br&lt;sub&gt;2&lt;/sub&gt;.</p>
</abstract>
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