Preprints
https://doi.org/10.5194/acp-2021-775
https://doi.org/10.5194/acp-2021-775

  20 Sep 2021

20 Sep 2021

Review status: this preprint is currently under review for the journal ACP.

Comparison of computational and experimental saturation vapor pressures of α-pinene + O3 oxidation products

Noora Hyttinen1,a, Iida Pullinen1, Aki Nissinen1, Siegfried Schobesberger1, Annele Virtanen1, and Taina Yli-Juuti1 Noora Hyttinen et al.
  • 1Department of Applied Physics, University of Eastern Finland, P.O. Box 1627, FI-70211 Kuopio, Finland
  • aNow at: Department of Chemistry, Nanoscience Center, University of Jyväskylä, FI-40014 Jyväskylä, Finland

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 FIGAERO-CIMS experiments and COSMO-RS theory. 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 several orders of magnitude difference 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 measured and calculated 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.

Noora Hyttinen et al.

Status: open (until 01 Nov 2021)

Comment types: AC – author | RC – referee | CC – community | EC – editor | CEC – chief editor | : Report abuse
  • RC1: 'Comment on acp-2021-775', Anonymous Referee #1, 17 Oct 2021 reply

Noora Hyttinen et al.

Noora Hyttinen et al.

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Short summary
Accurate saturation vapor pressure estimates of atmospherically relevant organic compounds are critical for modeling secondary organic aerosol (SOA) formation. We investigated vapor pressures of highly oxygenated SOA constituents using state of the art computational and experimental methods. We found a good agreement between low and extremely low vapor pressures estimated using the two methods, while the smallest molecules detected in our experiment were likely products of thermal decomposition.
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