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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-2-79-2002</article-id>
<title-group>
<article-title>Uptake and reaction of HOBr on frozen and dry NaCl/NaBr surfaces between 253 and 233 K</article-title>
</title-group>
<contrib-group><contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Adams</surname>
<given-names>J. W.</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>Holmes</surname>
<given-names>N. S.</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>Crowley</surname>
<given-names>J. N.</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
</contrib>
</contrib-group><aff id="aff1">
<label>1</label>
<addr-line>Max-Planck-Institut für Chemie, Division of Atmospheric Chemistry, Postfach 3060, 55020 Mainz, Germany</addr-line>
</aff>
<aff id="aff2">
<label>2</label>
<addr-line>Present address: Dept. of Chemistry, University of Cambridge, Lensfield Rd, Cambridge CB2 1EW, UK</addr-line>
</aff>
<pub-date pub-type="epub">
<day>19</day>
<month>04</month>
<year>2002</year>
</pub-date>
<volume>2</volume>
<issue>1</issue>
<fpage>79</fpage>
<lpage>91</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/2/79/2002/acp-2-79-2002.html">This article is available from http://www.atmos-chem-phys.net/2/79/2002/acp-2-79-2002.html</self-uri>
<self-uri xlink:href="http://www.atmos-chem-phys.net/2/79/2002/acp-2-79-2002.pdf">The full text article is available as a PDF file from http://www.atmos-chem-phys.net/2/79/2002/acp-2-79-2002.pdf</self-uri>
<abstract>
<p>The uptake and reaction of
      HOBr with frozen salt surfaces of variable NaCl / NaBr composition and temperature were investigated with a coated wall flow tube reactor coupled
      to a mass spectrometer for gas-phase analysis. 

       HOBr

      

       is efficiently taken up onto the frozen
      surfaces at temperatures between 253 and 233 K where it reacts to form the
      di-halogens BrCl and Br&lt;sub&gt;2&lt;/sub&gt;, which are subsequently released into the gas-phase. The uptake coefficient for
      

       HOBr

      

       reacting with a frozen, mixed salt surface of similar composition to sea-spray was
      &amp;lt;approx&amp;gt; 10&lt;sup&gt;-2&lt;/sup&gt;. The relative concentration of BrCl and Br&lt;sub&gt;2&lt;/sub&gt; released to the gas-phase was found to be strongly
      dependent on the ratio of Cl&lt;sup&gt;-&lt;/sup&gt; to Br &lt;sup&gt;-&lt;/sup&gt; in the solution prior to freezing / drying. For a mixed salt
      surface of similar composition to sea-spray the major product at low conversion of surface
      reactants (i.e. Br &lt;sup&gt;-&lt;/sup&gt; and Cl&lt;sup&gt;-&lt;/sup&gt;) was Br&lt;sub&gt;2&lt;/sub&gt;.&lt;br&gt;
      &lt;br&gt;
      Variation of the pH of the NaCl /
      NaBr solution used to prepare the frozen surfaces was found to have no significant influence on the results. The observations are explained in terms of
      initial formation of BrCl in a surface reaction of HOBr with Cl&lt;sup&gt;-&lt;/sup&gt;, and conversion of
      BrCl to Br&lt;sub&gt;2&lt;/sub&gt; via reaction of surface Br &lt;sup&gt;-&lt;/sup&gt;. Experiments on the uptake and reaction of
      BrCl with frozen NaCl /
      NaBr solutions served to confirm this hypothesis. The kinetics and products of the
      interactions of BrCl, Br&lt;sub&gt;2&lt;/sub&gt; and Cl&lt;sub&gt;2&lt;/sub&gt; with frozen salt surfaces were also investigated, and lower
      limits to the uptake coefficients of &amp;gt; 0.034, &amp;gt;0.025 and &amp;gt;0.028 respectively, were obtained.
      The uptake and reaction of 

       HOBr

      

       on dry salt surfaces was also investigated and the results
      closely resemble those obtained for frozen surfaces. During the course of this study the gas
      diffusion coefficients of 

       HOBr

      

       in He and H&lt;sub&gt;2&lt;/sub&gt;O were also measured as
      (273 ± 1) Torr cm&lt;sup&gt;2&lt;/sup&gt; s&lt;sup&gt;-1&lt;/sup&gt; and (51 ± 1) Torr cm&lt;sup&gt;2&lt;/sup&gt;
      s&lt;sup&gt;-1&lt;/sup&gt;, respectively, at 255 K. The implications of these results for
      modelling the chemistry of the Arctic boundary layer in springtime are discussed.</p>
</abstract>
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