Page 3 of 145 Submitted to Chemical Reviews 1 2 3 Saturation vapor pressures and transition enthalpies of low- 4 5 volatility organic molecules of atmospheric relevance: from 6 7 8 dicarboxylic acids to complex mixtures 9 10 11 12 13 Merete Bilde,1* Kelley Barsanti,2 Murray Booth,3 Christopher D. Cappa,4 Neil M. Donahue,5 Eva 14 15 U. Emanuelsson, 1 Gordon McFiggans,3 Ulrich K. Krieger,6 Claudia Marcolli,6,7 David 16 17 3,8 9 3 10,11 12 18 Topping, Paul Ziemann, Mark Barley, Simon Clegg, Benjamin Dennis-Smither, Mattias 19 20 Hallquist,13 Åsa M. Hallquist,14 Andrey Khlystov,15 Markku Kulmala,16 Ditte Mogensen,16 Carl J. 21 22 3 17 12 18 19 23 Percival, Francis Pope, Jonathan P. Reid, M. A. V. Ribeiro da Silva, Thomas Rosenoern, 24 20 6,21 16,22 16 25 Kent Salo, Vacharaporn Pia Soonsin, Taina Yli-Juuti, Nønne L. Prisle, Joakim 26 23 24,25,26 27 28 27 Pagels, Juergen Rarey, Alessandro A. Zardini, Ilona Riipinen 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 ACS Paragon Plus Environment Submitted to Chemical Reviews Page 4 of 145 1 2 1 Department of Chemistry, Aarhus University, Aarhus, Denmark 3 4 5 2 Department of Civil and Environmental Engineering, Portland State University, Portland OR, 6 7 USA 8 9 10 3 Centre for Atmospheric Science, School of Earth, Atmospheric and Environmental Sciences, 11 12 13 University of Manchester, Manchester United Kingdom 14 15 4 Department of Civil and Environmental Engineering, University of California, Davis, USA, 16 17 18 5 Centre for Atmospheric Particle Studies, Carnegie Mellon University, Pittsburgh, USA 19 20 21 6 Institute for Atmospheric and Climate Science, ETH Zurich, Zurich, Switzerland 22 23 24 7 Marcolli Chemistry and Physics Consulting GmbH, Zurich, Switzerland 25 26 27 8 National Centre for Atmospheric Science (NCAS), University of Manchester, 28 29 30 Manchester, United Kingdom 31 32 33 9 Department of Chemistry and Biochemistry and Cooperative Institute for Research in 34 35 Environmental Sciences (CIRES), University of Colorado, Boulder, USA 36 37 38 10 School of Environmental Sciences, University of East Anglia, Norwich, United Kingdom 39 40 41 11 Air Quality Research Center, University of California, Davis, CA 95616, USA 42 43 44 12 School of Chemistry, University of Bristol, United Kingdom 45 46 47 13 Atmospheric Science, Department of Chemistry and Molecular Biology, University of 48 49 Gothenburg, Gothenburg, Sweden 50 51 52 14 IVL Swedish Environmental Research Institute, Gothenburg, Sweden 53 54 15 Division of Atmospheric Sciences, Desert Research Institute, Reno, USA 55 56 57 58 59 60 ACS Paragon Plus Environment Page 5 of 145 Submitted to Chemical Reviews 1 2 16 Department of Physics, University of Helsinki, Helsinki, Finland17 School of Geography, 3 4 Earth and Environmental Sciences, University of Birmingham, Birmingham, United Kingdom 5 6 7 18 Centro de Investigação em Química, Department of Chemistry and Biochemistry, Faculty of 8 9 10 Science, University of Porto, Porto, Portugal 11 12 13 19 Department of Chemistry, University of Copenhagen, Copenhagen, Denmark 14 15 20 Maritime Environment, Shipping and Marine Technology, Chalmers University of 16 17 Technology, Gothenburg, Sweden 18 19 20 21 Center of Excellence on Hazardous Substance Management, Chulalongkorn University, 21 22 23 Bangkok, Thailand 24 25 22 Department of Applied Physics, University of Eastern Finland, Kuopio, Finland 26 27 28 23 Ergonomics & Aerosol Technology, Lund University, Lund, Sweden 29 30 24 School of Chemical Engineering, University of KwaZulu-Natal, South Africa 31 32 33 25 DDBST GmbH, Oldenburg, Germany 34 35 36 26 Industrial Chemistry, Carl von Ossietzky University Oldenburg, Oldenburg, Germany 37 38 39 27 European Commission, Joint Research Centre (JRC), Institute for Energy and Transport, 40 41 Ispra, Italy 42 43 44 28 Department of Analytical Chemistry and Environmental Science (ACS), and Bolin Centre for 45 46 Climate research, Stockholm University, Stockholm, Sweden 47 48 49 50 51 52 * Author to whom correspondence should be addressed ( [email protected] ) 53 54 55 56 57 58 59 60 ACS Paragon Plus Environment Submitted to Chemical Reviews Page 6 of 145 1 2 Contents 3 4 5 1. Introduction .............................................................................................................................. 1 6 7 2. Theoretical background and framework for atmospheric aerosols .......................................... 4 8 9 10 2.1 Saturation vapor pressures ........................................................................................... 4 11 12 2.2 Vapor-liquid or vapor-solid equilibria over mixed solutions ...................................... 8 13 14 2.3 Equilibria over curved surfaces ................................................................................... 9 15 16 2.4 Dynamic evaporation and condensation from and to an aerosol particle .................. 10 17 18 19 2.5 Ambient partitioning.................................................................................................. 14 20 21 3. Experimental methods ............................................................................................................ 17 22 23 3.1 Knudsen cell based methods...................................................................................... 19 24 25 26 3.1.1 Knudsen mass loss methods ..................................................................................... 19 27 28 3.1.2 Knudsen Effusion Mass Spectrometry (KEMS) ...................................................... 21 29 30 3.2 Single particle methods ............................................................................................. 22 31 32 3.2.1 Electrodynamic Balance (EDB) ............................................................................... 23 33 34 35 3.2.2 Optical tweezers ....................................................................................................... 26 36 37 3.3 Particle size distribution methods .............................................................................. 28 38 39 3.3.1 Flow-Tube Tandem Differential Mobility Analyzer (FT-TDMA) .......................... 30 40 41 42 3.3.2 Volatility Tandem Differential Mobility Analyzer (V-TDMA) .............................. 32 43 44 3.3.3 The Integrated Volume Method (IVM) .................................................................... 33 45 46 3.4 Thermal desorption methods ..................................................................................... 35 47 48 3.4.1 Thermal Desorption Particle Beam Mass Spectrometry (TDPB-MS) ..................... 35 49 50 51 3.4.2 Temperature Programmed Desorption Proton Transfer Chemical Ionization Mass 52 53 Spectrometry (TDP-PT-CIMS) .............................................................................................. 36 54 55 3.4.3 Atmospheric Solids Analysis Probe Mass Spectrometry (ASAP-MS) .................... 38 56 57 58 59 60 ACS Paragon Plus Environment Page 7 of 145 Submitted to Chemical Reviews 1 2 4. Experimentally determined saturation vapor pressures and transition enthalpies of 3 4 dicarboxylic acids ........................................................................................................................... 39 5 6 4.1 Straight chain dicarboxylic acids ............................................................................... 39 7 8 4.1.1 General fitting procedure ......................................................................................... 42 9 10 11 4.1.2 Oxalic acid (C2H2O4) ............................................................................................... 43 12 13 4.1.3 Malonic acid (C3H4O4) ............................................................................................. 45 14 15 4.1.4 Succinic acid (C4H6O4) ............................................................................................ 47 16 17 18 4.1.5 Glutaric acid (C5H8O4) ............................................................................................. 48 19 20 4.1.6 Adipic acid (C6H10 O4) .............................................................................................. 49 21 22 4.1.7 Pimelic acid (C7H12 O4) ............................................................................................. 50 23 24 4.1.8 C -C acids .............................................................................................................. 51 25 8 10 26 27 4.2 Conclusions on straight chain dicarboxylic acids...................................................... 52 28 29 4.3 Related dicarboxylic acids ......................................................................................... 55 30 31 4.3.1 Solid state saturation vapor pressures ...................................................................... 55 32 33 34 4.3.2 Subcooled liquid state saturation vapor pressures .................................................... 57 35 36 5. Saturation vapor pressure estimation methods ....................................................................... 59 37 38 5.1 Group Contribution Methods (GCMs) ...................................................................... 61 39 40 41 5.1.1 Temperature-dependent GCMs requiring boiling point ........................................... 62 42 43 5.1.2 Temperature-dependent GCMs not requiring boiling point ..................................... 63 44 45 5.1.3 Application and assessment of GCMs for dicarboxylic acids .................................