ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-11-655-2011 Solid state and sub-cooled liquid vapour pressures of cyclic aliphatic dicarboxylic acids Booth A. M. 1 Montague W. J. 2 Barley M. H. 1 Topping D. O. 1 McFiggans G. 1 Garforth A. 3 Percival C. J. 1 School of Earth, Environmental and Atmospheric Science, University of Manchester, UK School of Chemistry, University of Manchester, UK School of Chemical Engineering and Analytical Science, University of Manchester, UK 21 01 2011 11 2 655 665 This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited. This article is available from http://www.atmos-chem-phys.net/11/655/2011/acp-11-655-2011.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/11/655/2011/acp-11-655-2011.pdf

Knudsen Effusion Mass Spectrometry (KEMS) has been used to measure for the first time the solid state vapour pressures of a series of aliphatic cyclic dicarboxylic acids with increasing ring size. Additionally the atmospherically important compounds; <i>cis</i>-pinonic acid and levoglucosan were also measured. Differential Scanning Calorimetry (DSC) was used to measure melting points, enthalpies and entropies of fusion, which were used to determine sub-cooled liquid vapour pressures for the compounds. The sub-cooled liquid vapour pressure of straight chain, branched and cyclic dicarboxylic acids was compared to a selection of estimation methods.

 References Barley, M. H. and McFiggans, G.: The critical assessment of vapour pressure estimation methods for use in modelling the formation of atmospheric organic aerosol, Atmos. Chem. Phys., 10, 749–767, doi:10.5194/acp-10-749-2010, 2010. Bilde, M. and Pandis, S. N.: Evaporation rates and vapor pressures of individual aerosol species formed in the atmospheric oxidation of $\alpha $- and $\beta $-pinene, Environ. Sci. Technol., 35, 3344–3349, 2001 2001. Bilde, M., Svenningsson, B., Monster, J. and Rosenorn, T.: Even – Odd Alternation of Evaporation Rates and Vapor Pressures of C3-C9 Dicarboxylic Acid Aerosols, Environ. Sci. Technol., 37, 1371–1378, 2003. Booth, A. M., Markus, T., McFiggans, G., Percival, C. J., Mcgillen, M. R., and Topping, D. O.: Design and construction of a simple Knudsen Effusion Mass Spectrometer (KEMS) system for vapour pressure measurements of low volatility organics, Atmos. Meas. Tech., 2, 355–361, doi:10.5194/amt-2-355-2009, 2009. Booth, A. M., Barley, M. H., Topping, D. O., McFiggans, G., Garforth, A., and Percival, C. J.: Solid state and sub-cooled liquid vapour pressures of substituted dicarboxylic acids using Knudsen Effusion Mass Spectrometry (KEMS) and Differential Scanning Calorimetry, Atmos. Chem. Phys., 10, 4879–4892, doi:10.5194/acp-10-4879-2010, 2010. Boy, M., Petäjä, T., Dal Maso, M., Rannik, Ü., Rinne, J., Aalto, P., Laaksonen, A., Vaattovaara, P., Joutsensaari, J., Hoffmann, T., Warnke, J., Apostolaki, M., Stephanou, E. G., Tsapakis, M., Kouvarakis, A., Pio, C., Carvalho, A., Römpp, A., Moortgat, G., Spirig, C., Guenther, A., Greenberg, J., Ciccioli, P., and Kulmala, M.: Overview of the field measurement campaign in Hyytiälä, August 2001 in the framework of the EU project OSOA, Atmos. Chem. Phys., 4, 657–678, doi:10.5194/acp-4-657-2004, 2004. Cappa, D. C., Lovejoy, E. R., and Ravishankara, A. R.: Determination of Evaporation Rates and Vapor Pressures of Very Low Volatility Compounds: A Study of the C<sub>4</sub>-C$_10$ and C$_12$ Dicarboxylic Acids, J. Phys. Chem., 111, 3099–3109, 2007. Chattopadhyay, S. and Zieman, P. J.: Vapor pressures of substituted and unsubstituted monocarboxylic and dicarboxylic acids measured using an improved thermal desorption particle beam mass spectrometry method, Aerosol Sci. Technol., 39, 1085–1100, 2005. Compernolle, S., Ceulemans, K., and Müller, J.-F.: Technical Note: Vapor pressure estimation methods applied to secondary organic aerosol constituents from a-pinene oxidation: an intercomparison study, Atmos. Chem. Phys., 10, 6271–6282, doi:10.5194/acp-10-6271-2010, 2010. Epshtein, Ya. V., Durynina, L. I., and Pashinkin, A. S.: Vapor Pressure of Levoglucosan, Zh. Prikl. Khim. (Leningrad), 37 2543, 1964. Fowler, D., Pilegaard, K., Sutton, M. A., Ambus, P., Raivonen, M., Duyzer, J., Simpson, D., Fagerli, H., Schjoerring, J. K., Neftel, A., Burkhardt, J., Daemmgen, U., Neirynck, J., Personne, E., Wichink-Kruit, R., Butterbach-Bahl, K., Flechard, C., Tuovinen, J. P., Coyle, M., Fuzzi, S., Gerosa, G., Granier, C., Loubet, B., Altimir, N., Gruenhage, L., Ammann, C., Cieslik, S., Paoletti, E., Mikkelsen, T. N., Ro-Poulsen, H., Cellier, P., Cape, J. N., Isaksen, I. S. A., Horva' th, L., Loreto, F., Niinemets,Ü., Palmer, P. I., Rinne, J., Laj, P., Maione, M., Misztal, P., Monks, P., Nemitz, E., Nilsson, D., Pryor, S., Gallagher, M. W., Vesala, T., Skiba, U., Brüeggemann, N., Zechmeister-Boltenstern, S., Williams, J., O'Dowd, C., Facchini, M. C., de Leeuw, G., Flossman, A., Chaumerliac, N., and Erisman, J. W.: Atmospheric composition change: Ecosystems-Atmosphere interactions, Atmos. Environ., 43, 5193–5267, 2009. Frosch, M., Zardini, A. A., Platt, S. M., Müller, L., Reinnig, M.-C., Hoffmann, T., and Bilde, M.: Thermodynamic properties and cloud droplet activation of a series of oxo-acids, Atmos. Chem. Phys., 10, 5873–5890, doi:10.5194/acp-10-5873-2010, 2010. Fu, P., Kawamura, K., Chen, J., and Barrie, L. A.: Isoprene, Monoterpene and Sesquiterpene Oxidation Products in the High Artic Aerosols during Lawte Winrer to Early Summer, Environ. Sci. Technol., 43, 4022–4028, 2009. Gao, S., Keywood, M., Ng, N. L., Surratt, J., Varutbangkul, V., Bahreini, R., Flagan, R. C., and Seinfeld, J. H.: Low-Molecular Weight and Oligomeric Components in Secondary Organic Aerosol from the Ozonolysis of Cycloalkenes and $\alpha $-Pinene, J. Phys. Chem. A., 108, 10147–10164, 2004. Goldstein, A. H. and Galbally, I. E.: Known and Unexplored Organic Constituents in the Earth's Atmosphere, Environ. Sci. Tech., 41, 1514–1521, 2007. Grant, D. J. W., Mendizadeh, M., Chow, A. H.-L., and Fairbrother, J. E.: Non-linear van Hoff Solubility Temperature Plots and their Pharmaceutical Interpretation, Int. J. Pharm., 18, 25–38, 1984. Guenther, A., Karl, T., Harley, P., Wiedinmyer, C., Palmer, P. I., and Geron, C.: Estimates of global terrestrial isoprene emissions using MEGAN (Model of Emissions of Gases and Aerosols from Nature), Atmos. Chem. Phys., 6, 3181–3210, doi:10.5194/acp-6-3181-2006, 2006. Ge, X., Wexler, A. S., and Clegg, S. L.: Atmospheric Amines – Part II. Thermodynamic properties and gas/particle partitioning, Atmos. Environ., doi:10.1016/j.atmosenv.2010.10.013Ge, Atmos. Chem. Phys. Discuss., 10, C10429–C10429, 2010. Hallquist, M., Wenger, J. C., Baltensperger, U., Rudich, Y., Simpson, D., Claeys, M., Dommen, J., Donahue, N. M., George, C., Goldstein, A. H., Hamilton, J. F., Herrmann, H., Hoffmann, T., Iinuma, Y., Jang, M., Jenkin, M. E., Jimenez, J. L., Kiendler-Scharr, A., Maenhaut, W., McFiggans, G., Mentel, Th. F., Monod, A., Prévôt, A. S. H., Seinfeld, J. H., Surratt, J. D., Szmigielski, R., and Wildt, J.: The formation, properties and impact of secondary organic aerosol: current and emerging issues, Atmos. Chem. Phys., 9, 5155–5236, doi:10.5194/acp-9-5155-2009, 2009. Henze, D. K. and Seinfeld, J. H.: Global secondary organic aerosol from isoprene oxidation, Geophys. Res. Lett., 33, L09812, doi:10.1029/2006GL025976, 2006 Hilpert, K.: Potential of mass spectrometry for the analysis of inorganic high temperature vapors, Fresen. J. Anal. Chem., 370, 471–478, 2001. Joback, K. G. and Reid, R. C.: Estimation of pure-component properties from group contributions, Chem. Eng. Commun., 57, 233–243, 1987. Kawamura, K., Kasukabe, H., and Barrie, L. A.: Source and reaction pathways of dicarboxylic acids, ketoacids and dicarbonyls in arctic aerosols: One year of observations, Atmos. Environ. 30, 1709–1722, 1996. Kawamura, K., Imai,Y., and Barrie, L. A.: Photochemical Production and Loss of Organic Acids in High Arctic Aerosols During Long-Range Transport and Polar Sunrise Ozone Depletion Events, Atmos. Environ., 39, 599–614, 2005. Koponen, I., Riipinen, I., Hienola, A., Kulmala, M., and Bilde, M.: Thermodynamic properties of Malonic, Succinic and Glutaric acids: Evaporation rates and saturation vapor pressures Nucleation and Atmospheric Aerosols, Environ. Sci. Technol., 8, 920–923, 2007. Mauger, J. W., Paruta, A. N., and Gerraughty, R. J.: Solubilities of Sulfadiazine, Sulfomidine, and Sulfadimethoxine in Several Normal Alcohols, J. Pharm. Sci., 61, 94–97, 1972. Mønster, J., Rosenørn, T., Svenningsson, B., and Bilde, M.: Evaporation of methyl- and dimethyl-substituted malonic, succinic, glutaric and adipic acid particles at ambient temperatures, J. Aerosol. Sci., 35, 1453–1465, 2004. Moller, B., Rarey, J., and Ramjugernath, D.: Estimation of the vapour pressure of non-electrolyte organic compounds via group contributions and group interactions, J. Mol. Liq., 143, 52–63, 2008. Myrdal, P. B. and Yalkowsky, S. H.: Estimating pure component vapour pressures of complex organic molecules, Ind. Eng. Chem. Res., 36, 2494–2499, 1997. Oja, V. and Suuberg, E. M.: Vapor Pressures and Enthalpies of Sublimation of D-Glucose, D-Xylose, Cellobiose, and Levoglucosan, J. Chem. Eng. Dat., 44, 26–29, 1999. Nannoolal, Y., Rarey, J., Ramjugernath, D., and Cordes, W.: Estimation of pure component properties Part 1. Estimation of the normal boiling point of non-electrolyte organic compounds via group contributions and group interactions, Fluid Phase Equilibr., 226, 45–63, 2004. Nannoolal, Y., Rarey, J., and Ramjugernath, D.: Part 3. Estimation of the vapor pressure of non-electrolyte organic compounds via group contributions and group interactions, Fluid Phase Equilibr., 269, 117–133, 2008. Pankow, J. F.: An absorption-model of gas-particle partitioning of organic-compounds in the atmosphere, Atmos. Environ., 28, 185–188, 1994. Pope, F.D., Tong H., Dennis-Smither, B. J., Griffiths, P. T., Clegg, S. L., Reid, J. P., and Cox, R. A.: Studies of Single Aerosol Particles Containing Malonic Acid, Glutaric Acid, and Their Mixtures with Sodium Chloride. II. Liquid-State Vapor Pressures of the Acids, J. Phys. Chem. A., 37, 10156–10165, 2010. Prausnitz, J. M., Lichtenhaler, R. N., and de Azevedo, E. G.: Molecular Thermodynamics of Fluid-phase Equilibria, Prentice-Hall Inc, New Jersey, 419, 1986. Prausnitz, J. M., Lichtenhaler, R. N., and de Azevedo, E. G.: Molecular Thermodynamics of Fluid-phase Equilibria, Prentice-Hall Inc, New Jersey, 419, 1986. Riberio da Silva, M. A. V., Monte, M., and Ribeiro, J.: Vapour pressures and the enthalpies and entropies of sublimation of five dicarboxylic acids, J. Chem. Thermodynamics, 31, 1093–1107, 1999. Riberio da Silva, M. A. V., Monte, M., and Ribeiro, J.: Thermodynamic study on the sublimation of succinic acid and of methyl- and dimethyl-substituted succinic and glutaric acids, J. Chem. Thermodynamics, 33, 23–31, 2001. Riipinen, I., Koponen, I., Frank, G., Hyv'arinen, A.-P., Vanhanen, J., Lihavaninen, H., Lehtinen, K., Bilde, M., and Kulmala, M.: Adipic and Malonic Acid Aqueous Solutions: Surface Tensions and Saturation Vapor Pressures, J. Phys. Chem., 111, 12995–13002, 2007. Roux, M. V., Temprado, M., and Chickos, J. S.: Vaporization, fusion and sublimation enthalpies of the dicarboxylic acids from C<sub>4</sub> to C$_14$ and C$_16$, Journal of Chemical Thermodynamics, 37, 941–953, 2005. Salo, K., Jonsson, A. M., Andersson, P. U., and Hallquist, M.: Aerosol volatility and enthalpy of sublimation of Carboxylic acids, J. Phys. Chem. A, 114, 4586–4594, 2010. Sempere, R. and Kawamura, K.:. Comparative distributions of dicarboxylic-acids and related polar compounds in snow rain and aerosols from urban atmosphere, Atmos. Environ., 28, 449–459, 1994. Simoneit, B. R. T., Schauer, J. J., Nolte, C. G., Oros, D. R., Elias, V. O., Fraser, M. P., Rogge, W. F., and Cass G. R.: Levoglucosan, a tracer for cellulose in biomass burning and atmospheric particles, Atmos. Environ., 33, 173–182, 1999. Solomon, S., Qin, D., Manning, M., Chen, Z., Marquis, M., Averyt, K. B., Tignor, M. and Miller, H. L. (Eds.): Contribution of Working Group I to the Fourth Assessment Report of the Intergovernmental Panel on Climate Changes, Cambridge University Press, Cambridge, 2007. Stein, S. E. and Brown, R. L.: Estimation of normal boiling points from group contributions, J. Chem. Inf. Comp. Sci., 34, 581–587, 1994. Thalladi, V. R., Nüsse, M., and Boese, R.: The Melting Point Alternation in $\alpha $,$\omega $-Alkanedicarboxylic Acids, J. Am. Chem. Soc., 122, 9227–9236, 2000. Tsonopoulos, C.: Properties of Dilute Aqueous Solutions of Organic Solutes, Ph.D. Dissertation, University of California, CA, USA, 1970. Yalkowsky, S. H.: Solubility and Partitioning. 5. Dependence of Solubility on Melting-Point, J. Pharm. Sci., 70, 971–973, 1981. Zardini, A. A., Krieger, U. K., and Marcolli, C.: White light Mie resonance spectroscopy used to measure very low vapor pressures of substances in aqueous solution aerosol particles, Optics Express, 14, 2006. Zhang, Q., Jimenez, J. L., Canagaratna, M. R., Allan, J. D., Coe, H., Ulbrich, I., Alfarra, M. R., Takami, A., Middlebrook, A. M., Sun, Y. L., Dzepina, K., Dunlea, E., Docherty, K., DeCarlo, P. F., Salcedo, D., Onasch, T., Jayne, J. T., Miyoshi, T., Shimono, A., Hatakeyama, S., Takegawa, N., Kondo, Y., Schneider, J., Drewnick, F., Borrmann, S., Weimer, S., Demerjian, K., Williams, P., Bower, K., Bahreini, R., Cottrell, L., Griffin, R. J., Rautiainen, J., Sun, J. Y., Zhang, Y. M., and Worsnop, D. R.: Ubiquity and dominance of oxygenated species in organic aerosols in anthropogenically-influenced Northern Hemisphere midlatitudes, Geophys. Res. Lett., 34, L13801, doi:10.1029/2007GL029979, 2007.