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Atmospheric Measurement Techniques An interactive open-access journal of the European Geosciences Union

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https://doi.org/10.5194/amt-2017-224
© Author(s) 2017. This work is distributed under
the Creative Commons Attribution 4.0 License.
Research article
06 Jul 2017
Review status
This discussion paper is under review for the journal Atmospheric Measurement Techniques (AMT).
A reference data set for validating vapor pressure measurement techniques: Homologous series of polyethylene glycols
Ulrich K. Krieger1, Franziska Siegrist1, Claudia Marcolli1, Eva U. Emanuelsson2, Freya M. Gøbel2, Merete Bilde2, Aleksandra Marsh3, Jonathan P. Reid3, Andrew J. Huisman4, Ilona Riipinen5, Noora Hyttinen6, Nanna Myllys7, Theo Kurtén6, Thomas Bannan8, and David Topping8 1Institute for Atmospheric and Climate Science, ETH Zürich, 8092 Zürich, Switzerland
2Department of Chemistry, Aarhus University, 8000 Aarhus, Denmark
3School of Chemistry, University of Bristol, BS8 1TS Bristol, UK
4Chemistry Department, Union College, Schenectady NY 12308, USA
5Department of Environmental Science and Analytical Chemistry, Stockholm University, 106 91 Stockholm, Sweden
6Department of Chemistry, University of Helsinki, FI-00014 Helsinki, Finland
7Department of Physics, University of Helsinki, FI-00014 Helsinki, Finland
8Centre for Atmospheric Sciences, School of Earth, Atmospheric and Environmental Sciences, University of Manchester, Manchester, M13 9PL, UK
Abstract. To predict atmospheric partitioning of organic compounds between gas and aerosol particle phase based on explicit models for gas phase chemistry, saturation vapor pressures of the compounds need to be estimated. Estimation methods based on functional group contributions require training sets of compounds with well established saturation vapor pressures. However, vapor pressures of semi- and low volatile organic molecules at atmospheric temperatures reported in the literature often differ by several orders of magnitude between measurement techniques. These discrepancies exceed the stated uncertainty of each technique which is generally reported to be smaller than a factor of two. At present, there is no general reference technique for measuring saturation vapor pressures of atmospherically relevant compounds with low vapor pressures at atmospheric temperatures. To address this problem we measured vapor pressures with different techniques over a wide temperature range for intercomparison and to establish a reliable training set. We determined saturation vapor pressures for the homologous series of polyethylene glycols (H–(O–CH2–CH2)n–OH) for n = 3 to n = 8 ranging in vapor pressure at 298 K from 10−7 Pa to 5 · 10−2 Pa and compare them with quantum chemistry calculations. Such a homologous series provides a reference set that covers several orders of magnitude in saturation vapor pressure, allowing a critical assessment of the lower limits of detection of vapor pressures for the different techniques as well as permitting the identification of potential sources of systematic error. Also, internal consistency within the series allows to reject outlying data more easily. Most of the measured vapor pressures agreed within the stated uncertainty range. Deviations mostly occurred for vapor pressures values approaching the lower detection limit of a technique. The good agreement between the measurement techniques (some of which are sensitive to the mass accommodation coefficient and some not) suggest that the mass accommodation coefficients of the studied compounds are close to unity. The quantum chemistry calculations were about one order of magnitude higher than the measurements. We find that extrapolation of vapor pressures from elevated to atmospheric temperatures is permissible over a range of about 100 K for these compounds, suggesting that measurements should be performed best at temperatures yielding the highest accuracy data allowing subsequent extrapolation to atmospheric temperatures.

Citation: Krieger, U. K., Siegrist, F., Marcolli, C., Emanuelsson, E. U., Gøbel, F. M., Bilde, M., Marsh, A., Reid, J. P., Huisman, A. J., Riipinen, I., Hyttinen, N., Myllys, N., Kurtén, T., Bannan, T., and Topping, D.: A reference data set for validating vapor pressure measurement techniques: Homologous series of polyethylene glycols, Atmos. Meas. Tech. Discuss., https://doi.org/10.5194/amt-2017-224, in review, 2017.
Ulrich K. Krieger et al.
Ulrich K. Krieger et al.

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A reference data set for validating vapor pressure measurement techniques: Homologous series of polyethylene glycols
U. Krieger
https://doi.org/10.3929/ethz-b-000168628
Ulrich K. Krieger et al.

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Short summary
Vapor pressures of low volatile organic molecules at atmospheric temperatures reported in the literature often differ by several orders of magnitude between measurement techniques. These discrepancies exceed the stated uncertainty of each technique which is generally reported to be smaller than a factor of two. We determined saturation vapor pressures for the homologous series of polyethylene glycols ranging in vapor pressure at 298 K from 1E−7 Pa to 5E−2 Pa as a reference set.
Vapor pressures of low volatile organic molecules at atmospheric temperatures reported in the...
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