The vapor pressures and activities of dicarboxylic acids reconsidered: the impact of the physical state of the aerosol
We present vapor pressure data of the C<sub>2</sub> to C<sub>5</sub> dicarboxylic acids deduced from measured evaporation rates of single levitated particles as both, aqueous droplets and solid crystals. The data of aqueous solution particles over a wide...
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doaj-1e2913fc23094a9cb25a9b208d853c122020-11-25T01:03:29ZengCopernicus PublicationsAtmospheric Chemistry and Physics1680-73161680-73242010-12-011023117531176710.5194/acp-10-11753-2010The vapor pressures and activities of dicarboxylic acids reconsidered: the impact of the physical state of the aerosolV. Soonsin0A. A. Zardini1C. Marcolli2A. Zuend3U. K. Krieger4Institute for Atmospheric and Climate Science, ETH Zurich, Zurich, SwitzerlandDepartment of Chemistry, University of Copenhagen, Copenhagen, DenmarkInstitute for Atmospheric and Climate Science, ETH Zurich, Zurich, SwitzerlandDepartment of Chemical Engineering, California Institute of Technology, Pasadena, California, USAInstitute for Atmospheric and Climate Science, ETH Zurich, Zurich, SwitzerlandWe present vapor pressure data of the C<sub>2</sub> to C<sub>5</sub> dicarboxylic acids deduced from measured evaporation rates of single levitated particles as both, aqueous droplets and solid crystals. The data of aqueous solution particles over a wide concentration range allow us to directly calculate activities of the dicarboxylic acids and comparison of these activities with parameterizations reported in the literature. The data of the pure liquid state acids, i.e. the dicarboxylic acids in their supercooled melt state, exhibit no even-odd alternation in vapor pressure, while the acids in the solid form do. This observation is consistent with the known solubilities of the acids and our measured vapor pressures of the supercooled melt. Thus, the gas/particle partitioning of the different dicarboxylic acids in the atmosphere depends strongly on the physical state of the aerosol phase, the difference being largest for the even acids. <br><br> Our results show also that, in general, measurements of vapor pressures of solid dicarboxylic acids may be compromised by the presence of polymorphic forms, crystalline structures with a high defect number, and/or solvent inclusions in the solid material, yielding a higher vapor pressure than the one of the thermodynamically stable crystalline form at the same temperature.http://www.atmos-chem-phys.net/10/11753/2010/acp-10-11753-2010.pdf |
collection |
DOAJ |
language |
English |
format |
Article |
sources |
DOAJ |
author |
V. Soonsin A. A. Zardini C. Marcolli A. Zuend U. K. Krieger |
spellingShingle |
V. Soonsin A. A. Zardini C. Marcolli A. Zuend U. K. Krieger The vapor pressures and activities of dicarboxylic acids reconsidered: the impact of the physical state of the aerosol Atmospheric Chemistry and Physics |
author_facet |
V. Soonsin A. A. Zardini C. Marcolli A. Zuend U. K. Krieger |
author_sort |
V. Soonsin |
title |
The vapor pressures and activities of dicarboxylic acids reconsidered: the impact of the physical state of the aerosol |
title_short |
The vapor pressures and activities of dicarboxylic acids reconsidered: the impact of the physical state of the aerosol |
title_full |
The vapor pressures and activities of dicarboxylic acids reconsidered: the impact of the physical state of the aerosol |
title_fullStr |
The vapor pressures and activities of dicarboxylic acids reconsidered: the impact of the physical state of the aerosol |
title_full_unstemmed |
The vapor pressures and activities of dicarboxylic acids reconsidered: the impact of the physical state of the aerosol |
title_sort |
vapor pressures and activities of dicarboxylic acids reconsidered: the impact of the physical state of the aerosol |
publisher |
Copernicus Publications |
series |
Atmospheric Chemistry and Physics |
issn |
1680-7316 1680-7324 |
publishDate |
2010-12-01 |
description |
We present vapor pressure data of the C<sub>2</sub> to C<sub>5</sub>
dicarboxylic acids deduced from measured evaporation rates of
single levitated particles as both, aqueous droplets and solid
crystals. The data of aqueous solution particles over a wide
concentration range allow us to directly calculate activities
of the dicarboxylic acids and comparison of these activities
with parameterizations reported in the literature. The data of
the pure liquid state acids, i.e. the dicarboxylic acids in
their supercooled melt state, exhibit no even-odd alternation
in vapor pressure, while the acids in the solid form do. This
observation is consistent with the known solubilities of the
acids and our measured vapor pressures of the supercooled
melt. Thus, the gas/particle partitioning of the different
dicarboxylic acids in the atmosphere depends strongly on the
physical state of the aerosol phase, the difference being
largest for the even acids.
<br><br>
Our results show also that, in general, measurements of vapor
pressures of solid dicarboxylic acids may be compromised by
the presence of polymorphic forms,
crystalline structures with a high defect number, and/or
solvent inclusions in the solid material, yielding a higher
vapor pressure than the one of the thermodynamically stable
crystalline form at the same temperature. |
url |
http://www.atmos-chem-phys.net/10/11753/2010/acp-10-11753-2010.pdf |
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