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<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-5-11249-2005</article-id>
<title-group>
<article-title>A group contribution method for estimating the vapour pressures of &amp;alpha;-pinene oxidation products</article-title>
</title-group>
<contrib-group><contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Capouet</surname>
<given-names>M.</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>Müller</surname>
<given-names>J. F.</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
</contrib>
</contrib-group><aff id="aff1">
<label>1</label>
<addr-line>Belgian Institute for Space Aeronomy, 1180 Brussels, Belgium</addr-line>
</aff>
<pub-date pub-type="epub">
<day>03</day>
<month>11</month>
<year>2005</year>
</pub-date>
<volume>5</volume>
<issue>6</issue>
<fpage>11249</fpage>
<lpage>11276</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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<abstract>
<p>A prediction method based on group contribution principles is proposed for estimating the vapour
pressure of &amp;alpha;-pinene oxidation products.  Temperature dependent contributions are provided
for the following chemical groups: carbonyl, nitrate, hydroxy, hydroperoxide, acyl peroxy nitrate
and acid.  On the basis of observed vapour pressure differences between isomers of diols and
dinitrates, a simple refinement is introduced in the method, which allows to account for the
influence of the substitutions on the vapour pressure for the hydroxy and nitrate functionalities.
In general, the predicted vapour pressures of multifunctional compounds show a better agreement
with experimental data (within a factor 2&amp;ndash;3) than the UNIFAC method (Asher et al., 2002).  Among
the &amp;alpha;-pinene products identified to date, pinic acid and hydroxy pinonic acid are predicted
to be the least volatile compounds, with estimated vapour pressures of 3&amp;times;10&lt;sup&gt;&amp;minus;6&lt;/sup&gt; torr
and 6&amp;times;10&lt;sup&gt;&amp;minus;7&lt;/sup&gt; torr, respectively. The vapour pressure of the other
primary products range from 10&lt;sup&gt;&amp;minus;5&lt;/sup&gt; to 10&lt;sup&gt;&amp;minus;3&lt;/sup&gt; torr, with hydroxy hydroperoxides
presenting the lowest values. Noting that multifunctional carboxylic acids, in particular pinic
acid, are believed to be mostly present as dimers in laboratory conditions, we suggest that the
partial vapour pressure of the pinic acid dimer should be close to the experimental subcooled
vapour pressure for pinic acid (estimated at ~10&lt;sup&gt;&amp;minus;6&lt;/sup&gt; torr) due to its large
contribution to the total concentration (dimer+monomer) in experimental conditions.</p>
</abstract>
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