References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-8-1087-2008

Effects of uncertainties in the thermodynamic properties of aerosol components in an air quality model – Part 2: Predictions of the vapour pressures of organic compounds

Clegg

S. L.

¹ Kleeman

M. J.

² Griffin

R. J.

³ Seinfeld

J. H.

⁴

School of Environmental Sciences, University of East Anglia, Norwich NR4 7TJ, UK

Department of Civil and Environmental Engineering, University of California, Davis CA 95616, USA

Institute for the Study of Earth, Oceans and Space, and Department of Earth Sciences, University of New Hampshire, Durham, NH 03824, USA

Department of Chemical Engineering, California Institute of Technology, Pasadena, CA 91125, USA

27 02 2008

8 4 1087 1103

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Air quality models that generate the concentrations of semi-volatile and other condensable organic compounds using an explicit reaction mechanism require estimates of the vapour pressures of the organic compounds that partition between the aerosol and gas phases. The model of Griffin, Kleeman and co-workers (e.g., Griffin et al., 2005) assumes that aerosol particles consist of an aqueous phase, containing inorganic electrolytes and soluble organic compounds, and a hydrophobic phase containing mainly primary hydrocarbon material. Thirty eight semi-volatile reaction products are grouped into ten surrogate species. In Part 1 of this work (Clegg et al., 2008) the thermodynamic elements of the gas/aerosol partitioning calculation are examined, and the effects of uncertainties and approximations assessed, using a simulation for the South Coast Air Basin around Los Angeles as an example. Here we compare several different methods of predicting vapour pressures of organic compounds, and use the results to determine the likely uncertainties in the vapour pressures of the semi-volatile surrogate species in the model. These are typically an order of magnitude or greater, and are further increased when the fact that each compound represents a range of reaction products (for which vapour pressures can be independently estimated) is taken into account. The effects of the vapour pressure uncertainties associated with the water-soluble semi-volatile species are determined over a wide range of atmospheric liquid water contents. The vapour pressures of the eight primary hydrocarbon surrogate species present in the model, which are normally assumed to be involatile, are also predicted. The results suggest that they have vapour pressures high enough to exist in both the aerosol and gas phases under typical atmospheric conditions.

References 1

Asher, W. E. and Pankow, J. F.: Vapour pressure prediction for alkenoic and aromatic organic compounds by a UNIFAC-based group contribution method, Atmos. Environ., 40, 3588–3600, 2006.

Asher, W. E., Pankow, J. F., Erdakos, G. B., and Seinfeld, J. H.: Estimating the vapour pressures of multi-functional oxygen-containing organic compounds using group contribution methods, Atmos. Environ., 36, 1483–1498, 2002.

Camredon, M. and Aumont, B.: Assessment of vapour pressure estimation methods for secondary organic aerosol modeling, Atmos. Environ., 40, 2105–2116, 2006.

Clegg, S. L., Brimblecombe, P., and Khan, I.: The Henry's law constant of oxalic acid and its partitioning into the atmospheric aerosol, Idojaras, 100, 51–68, 1996.

Clegg, S. L., Kleeman, M. J., Griffin, R. J., and Seinfeld, J. H.: Effects of uncertainties in the thermodynamic properties of aerosol components in an air quality model – Part 1: Treatment of inorganic electrolytes and organic compounds in the condensed phase, Atmos. Chem. Phys., 8, 1057–1085, 2008.

Clegg, S. L. and Seinfeld, J. H.: Thermodynamic models of aqueous solutions containing inorganic electrolytes and dicarboxylic acids at 298.15 K. II. Systems including dissociation equilibria, J. Phys. Chem. A, 110, 5718–5734, 2006.

Constantinou, L. and Gani, R.: New group contribution method for estimating properties of pure compounds, AIChE J., 40, 1697–1710, 1994.

Cordes, W. and Rarey, J.: A new method for the estimation of the normal boiling point of nonelectrolyte organic compounds, Fluid Phase Equilibria, 201, 409–433, 2002.

Devotta, S. and Rao, P. V.: Modified Joback group contribution method for normal boiling point of aliphatic halogenated compounds, Ind. Eng. Chem. Res., 31, 2042–2046, 1992.

Fraser, M. P., Cass, G. R., Simoneit, B. R. T., and Rasmussen, R. A.: Air quality model evaluation data for organics. 4. C<sub>2</sub> – C$_36$ non-aromatic hydrocarbons, Environ. Sci. Technol., 31, 2356–2367, 1997.

Fraser, M. P., Cass, G. R., Simoneit, B. R. T., and Rasmussen, R. A.: Air quality model evaluation data for organics. 5. C$_6$ – C$_22$ non-polar and semipolar aromatic compounds, Environ. Sci. Technol., 32, 1760–1770, 1998.

Griffin, R. J., Dabdub, D., and Seinfeld, J. H.: Secondary organic aerosol – 1. Atmospheric chemical mechanism for production of molecular constituents, J. Geophys. Res., 107(D17), 4332, doi:10.1029/2001JD000541, 2002.

Griffin, R. J., Dabdub, D., and Seinfeld, J. H.: Development and initial evaluation of a dynamic species-resolved model for gas phase chemistry and size-resolved gas/particle partitioning associated with secondary organic aerosol formation, J. Geophys. Res., 110(D5), 05304, doi:10.1029/2004JD005219, 2005.

Griffin, R. J., Nguyen, K., Dabdub, D., and Seinfeld, J. H.: A coupled hydrophobic-hydrophilic model for predicting secondary organic aerosol formation, J. Atmos. Chem., 44, 171–190, 2003.

Jaoui, M., Kleindienst, T. E., Lewandowski, M., Offenburg, J. H., and Edney, E. O.: Identification and quantification of aerosol polar oxygenated compounds bearing carboxylic or hydroxyl groups. 2. Organic tracer compounds from monoterpenes, Environ. Sci. Technol., 39, 5661–5673, 2005.

Joback, K. G. and Reid, R. C.: Estimation of pure component properties from group contributions, Chem. Eng. Commun., 57, 233–243, 1987.

Kleeman, M. J., Hughes, L. S., Allen, J. O., and Cass, G. R.: Source contributions to the size and composition distribution of atmospheric particles: Southern California in September, 1996, Environ. Sci. Technol., 33, 4331–4341, 1999.

Lei, Y. D., Chankalal, R., Cahn, A., and Wania, F.: Supercooled liquid vapour pressures of the polycyclic aromatic hydrocarbons, J. Chem. Eng. Data, 47, 801–806, 2002.

Marrero-Morejon, J. and Pardillo-Fontdevila, E.: Estimation of pure compound properties using group-interaction contributions, AIChE J., 45, 615–621, 1999.

Myrdal, P. B. and Yalkowsky, S. H.: Estimating pure component vapour pressures of complex organic molecules, Ind. Eng. Chem. Res., 36, 2494–2499, 1997.

Nannoolal, Y.: Development and critical evaluation of group contribution methods for the estimation of critical properties, liquid vapour pressure and liquid viscosity of organic compounds, Ph.D Thesis, University of Kwazulu-Natal, 2007.

Nannoolal, Y., Rarey, J., Cordes, W., and Ramjugernath, D.: 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 Equilibria, 226, 45–63, 2004.

Peng, C., Chan, M. N., and Chan, C. K.: The hydgroscopic properties of dicarboxylic and multifunctional acids: measurements and UNIFAC predictions, Environ. Sci. Technol., 35, 4495-4501, 2001.

Ribeiro da Silva, M. A. V., Monte, M. J. S., and Ribeiro, J. R.: Thermodynamic study on the sublimation of succinic acid and methyl- and dimethyl-substituted succinic and glutaric acids, J. Chem. Thermo., 33, 23–31, 2001.

Sanghvi, R. and Yalkowsky, S. H.: Estimation of heat capacity of boiling of organic compounds, Ind. Eng. Chem. Res., 45, 451–453, 2006a.

Sanghvi, R. and Yalkowsky, S. H.: Estimation of normal boiling point of organic compounds, Ind. Eng. Chem. Res., 45, 2856–2861, 2006b.

Stein, S. E. and Brown, R. L.: Estimation of normal boiling points from group contributions, J. Chem. Inf. Comput. Sci., 34, 581–587, 1994.

Wen, X. and Qiang, Y.: Group vector space (GVS) method for estimating boiling and melting points of hydrocarbons, J. Chem. Eng. Data, 47, 286–288, 2002a.

Wen, X. and Qiang, Y.: Group vector space method for estimating boiling and melting points of organic compounds, Ind. Eng. Chem. Res., 41, 5534–5537, 2002b.

Yu, J., Cocker III, D. R., Griffin, R. J., Flagan, R. C., and Seinfeld, J. H.: Gas-phase oxidation of monoterpenes: gaseous and particulate products, J. Atmos. Chem., 34, 207–258, 1999.

Zhao, L., Li, P., and Yalkowsky, S. H.: Predicting the entropy of boiling for organic compounds, J. Chem. Inf. Comput. Sci., 39, 1112–1116, 1999.