Saturation vapor pressures and transition enthalpies of low-volatility organic molecules of atmospheric relevance: From dicarboxylic acids to complex mixtures

Merete Bilde, Kelley Barsanti, Murray Booth, Christopher D. Cappa, Neil M. Donahue, Eva U. Emanuelsson, Gordon McFiggans, Ulrich K. Krieger, Claudia Marcolli, David Topping, Paul Ziemann, Mark Barley, Simon Clegg, Benjamin Dennis-Smither, Mattias Hallquist, Åsa M. Hallquist, Andrey Khlystov, Markku Kulmala, Ditte Mogensen, Carl J. PercivalFrancis Pope, Jonathan P. Reid, M. A V Ribeiro Da Silva, Thomas Rosenoern, Kent Salo, Vacharaporn Pia Soonsin, Taina Yli-Juuti, Nonne L. Prisle, Joakim Pagels, Juergen Rarey, Alessandro A. Zardini, Ilona Riipinen

Research output: Contribution to journalReview article

117 Citations (Scopus)

Abstract

There are a number of techniques that can be used that differ in terms of whether they fundamentally probe the equilibrium and the temperature range over which they can be applied. The series of homologous, straight-chain dicarboxylic acids have received much attention over the past decade given their atmospheric relevance, commercial availability, and low saturation vapor pressures, thus making them ideal test compounds. Uncertainties in the solid-state saturation vapor pressures obtained from individual methodologies are typically on the order of 50-100%, but the differences between saturation vapor pressures obtained with different methods are approximately 1-4 orders of magnitude, with the spread tending to increase as the saturation vapor pressure decreases. Some of the dicarboxylic acids can exist with multiple solid-state structures that have distinct saturation vapor pressures. Furthermore, the samples on which measurements are performed may actually exist as amorphous subcooled liquids rather than solid crystalline compounds, again with consequences for the measured saturation vapor pressures, since the subcooled liquid phase will have a higher saturation vapor pressure than the crystalline solid phase. Compounds with equilibrium vapor pressures in this range will exhibit the greatest sensitivities in terms of their gas to particle partitioning to uncertainties in their saturation vapor pressures, with consequent impacts on the ability of explicit and semiexplicit chemical models to simulate secondary organic aerosol formation.

Original languageEnglish
Pages (from-to)4115-4156
Number of pages42
JournalChemical Reviews
Volume115
Issue number10
Early online date1 May 2015
DOIs
Publication statusPublished - 27 May 2015

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