Comparison of saturation vapor pressures of <i>α</i>-pinene + O<sub>3</sub> oxidation products derived from COSMO-RS computations and thermal desorption experiments
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Published:2022-01-24
Issue:2
Volume:22
Page:1195-1208
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ISSN:1680-7324
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Container-title:Atmospheric Chemistry and Physics
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language:en
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Short-container-title:Atmos. Chem. Phys.
Author:
Hyttinen NooraORCID, Pullinen IidaORCID, Nissinen Aki, Schobesberger SiegfriedORCID, Virtanen Annele, Yli-Juuti Taina
Abstract
Abstract. Accurate information on gas-to-particle partitioning is needed to model secondary organic aerosol formation. However, determining reliable
saturation vapor pressures of atmospherically relevant multifunctional organic compounds is extremely difficult. We estimated saturation vapor
pressures of α-pinene-ozonolysis-derived secondary organic aerosol constituents using Filter Inlet for Gases and AEROsols (FIGAERO)–chemical ionization mass spectrometer (CIMS) experiments and conductor-like screening model for real solvents (COSMO-RS). We found
a good agreement between experimental and computational saturation vapor pressures for molecules with molar masses around 190 g mol−1
and higher, most within a factor of 3 comparing the average of the experimental vapor pressures and the COSMO-RS estimate of the isomer closest to
the experiments. Smaller molecules likely have saturation vapor pressures that are too high to be measured using our experimental setup. The
molecules with molar masses below 190 g mol−1 that have differences of several orders of magnitude between the computational and
experimental saturation vapor pressures observed in our experiments are likely products of thermal decomposition occurring during thermal
desorption. For example, dehydration and decarboxylation reactions are able to explain some of the discrepancies between experimental and
computational saturation vapor pressures. Based on our estimates, FIGAERO–CIMS can best be used to determine saturation vapor pressures of compounds
with low and extremely low volatilities at least down to 10−10 Pa in saturation vapor pressure.
Funder
Horizon 2020 Academy of Finland
Publisher
Copernicus GmbH
Subject
Atmospheric Science
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