Atmospheric Chemistry and Physics Discussions www.atmos-chem-phys-discuss.net 1680-7367 1680-7375 7 4 2007 10.5194/acpd-7-11839-2007 http://www.atmos-chem-phys-discuss.net/7/11839/2007/ http://www.atmos-chem-phys-discuss.net/7/11839/2007/acpd-7-11839-2007.html http://www.atmos-chem-phys-discuss.net/7/11839/2007/acpd-7-11839-2007.pdf 11839 11894 2007-08-13 SIMPOL.1: A simple group contribution method for predicting vapor pressures and enthalpies of vaporization of multifunctional organic compounds J. F. Pankow pankow@ebs.ogi.edu W. E. Asher Department of Environmental and Biomolecular Systems, OGI School of Science & Engineering, Oregon Health & Science University, Beaverton, Oregon 97006-8921, USA Air-Sea Interaction and Remote Sensing Department, Applied Physics Laboratory, University of Washington, Seattle, Washington 98105, USA The SIMPOL.1 group contribution method is developed for predicting the liquid vapor pressure pLo (atm) and enthalpy of vaporization ΔHvap (kJ mol-1) of organic compounds as functions of temperature (T). For each compound i, the method assumes log10pL,io(T)=Σkνk,ibk(T) where νk,i is the number of groups of type k, and bk(T) is the contribution to log10 pL,io(T) by each group of type k. A zeroeth group is included that uses b0(T) with ν0,i=1 for all i. A total of 30 structural groups are considered: molecular carbon, alkyl hydroxyl, aromatic hydroxyl, alkyl ether, alkyl ring ether, aromatic ether, aldehyde, ketone, carboxylic acid, ester, nitrate, nitro, alkyl amine (primary, secondary, and tertiary), aromatic amine, amide (primary, secondary, and tertiary), peroxide, hydroperoxide, peroxy acid, C=C, carbonylperoxynitrate, nitro-phenol, nitro-ester, aromatic rings, non-aromatic rings, C=C–C=O in a non-aromatic ring, and carbon on the acid-side of an amide. The T dependence in each of the bk(T) is assumed to follow b(T)=B1/T+B2+B3T+B4lnT. Values of the B coefficients are fit using an initial basis set of 272 compounds for which experimentally based functions pL,io=fi(T) are available. The range of vapor pressure considered spans fourteen orders of magnitude. The ability of the initially fitted B coefficients to predict pLo values is examined using a test set of 161 compounds and a T range that is as wide as 273.15 to 393.15 K for some compounds. σFIT is defined as the average over all points of the absolute value of the difference between experimental and predicted values of log10pL,io(T). After consideration of σFIT for the test set, the initial basis set and test set compounds are combined, and the B coefficients re-optimized. For all compounds and temperatures, σFIT=0.34: on average, pL,io(T) values are predicted to within a factor of 2. Because d(log10pL,io(T))/d(1/T) is related to the enthalpy of vaporization ΔHvap,i, the fitted B provide predictions of ΔHvap,i based on structure. Asher, W. E., Pankow, J. F., Erdakos, G. B., and Seinfeld, J. H.: Estimating the vapor pressures of multi-functional oxygen-containing organic compounds using group contribution methods, Atmos. Environ., 36, 1483–1498, 2002. Asher, W. E. and Pankow, J. F.: Vapor pressure prediction for alkenoic and aromatic organic compounds by a UNIFAC-based group contribution method, Atmos. Environ., 40, 3588–3600, 2006. Banerjee, T., Singh, M. K., and Khanna, A.: Prediction of binary VLE for imidazolium based ionic liquid systems using COSMO-RS, Ind. Eng. Chem. Res., 45, 3207–3219, 2006. Barsanti, K. C. and Pankow, J. F.: Thermodynamics of the formation of atmospheric organic particulate matter by accretion reactions. 2. Dialdehydes, methylglyoxal, and diketones, Atmos. Environ., 39, 6597–6607, 2005. Barsanti, K. C. and Pankow, J. F.: Thermodynamics of the formation of atmospheric organic particulate matter by accretion reactions. 1. Aldehydes and ketones, Atmos. Environ., 38, 4371–4382, 2004. Barsanti, K. C. and Pankow, J. F.: Thermodynamics of the formation of atmospheric organic particulate matter by accretion reactions. 3. Carboxylic and dicarboxylic acids, Atmos. Environ., 40, 6676–6686, 2006. Capouet, M. and Müller, J.-F.: A group contribution method for estimating the vapour pressures of $\alpha $-pinene oxidation products, Atmos. Chem. Phys., 6, 1455–1467, 2006. Haagen-Smit, A. J.: Chemistry and physiology of Los Angeles smog, Ind. Eng. Chem., 44, 1342–1346, 1952. Hansen, H. K., Rasmussen, P., Fredenslund, A., Schiller, M., and Gmehling, J.: Vapor-liquid-equilibria by UNIFAC group contribution. 5. Revision and extension, Ind. Eng. Chem. Res., 30, 2352–2355, 1991. Hilal, S. H., Carreira, L. A., and Karickhoff, S. W.: Estimation of chemical reactivity parameters and physical properties of organic molecules using SPARC, in: Quantitative Treatments of Solute/Solvent Interactions, edited by: Politzer, P. and Murray, J. S., Elsevier, Amsterdam, 1994. Jensen, T., Fredenslund, A., and Rasmussen, P.: Pure component vapor pressures using UNIFAC group contribution, Ind. Eng. Chem. Fund., 20, 239–246, 1981. Khetarpal, S. C., Lal, K., and Bhatnagar, H. L.: Thermodynamic studies on melting of aliphatic dicarboxylic acids, Indian J. Chem., Section A, 19A, 516–519, 1980. Kolská, Z., R\`u\vzièka, V., and Gani, R.: Estimation of the enthalpy of vaporization and the entropy of vaporization for pure organic compounds at 298.15 K and at normal boiling temperature by a group contribution method, Ind. Eng. Chem. Res., 44, 8436–8454, 2005. Lasdon, L. S., Waren, A., Jain, A., and Ratner, M.: Design and testing of a generalized reduced gradient code for nonlinear programming, ACM Trans. Math. Software, 4, 34–50, 1978. Lee, S. C., Hung, H., Shiu, W.-Y., and Mackay, D.: Estimations of vapor pressure and activity coefficients in water and octanol for selected aromatic chemicals at 25°C, Environ. Toxicol. Chem., 19, 2623–2630, 2000. Lister, M. W.: Heats of organic reactions. X. Heats of bromination of cyclic olefins, J. Am. Chem. Soc., 63, 143–9, 1941. Makar, P.: The estimation of organic gas vapour pressure, Atmos. Environ., 35, 961–974, 2001. Meyer, E. F. and Hotz, R. D.: High-precision vapor-pressure data for eight organic compounds, J. Chem. Eng. Data, 18, 359–62, 1973. Pankow, J. F.: An absorption model of gas/particle partitioning of organic compounds in the atmosphere, Atmos. Environ., 28, 185–188, 1994a. Pankow, J. F.: An absorption model of the gas/particle partitioning involved in the formation of secondary organic aerosol, Atmos. Environ., 28, 189–193, 1994b. Pankow, J. F., Seinfeld, J. H., Asher, W. E., and Erdakos, G. B.: Modeling the formation of secondary organic aerosols. 1. Theory and measurements for the $\alpha $-pinene/, $\beta $-pinene/, sabinene/, $\Delta ^3$-carene/, and cyclohexene/ozone systems, Environ. Sci. Technol., 35, 1164–1172, 2001a. (See also: Errata, Environ. Sci. Technol., 35, 3272, 2001.) Pankow, J. F.: A consideration of the role of gas/particle partitioning in the deposition of nicotine and other tobacco smoke compounds in the respiratory tract, Chem. Res. Toxicol., 14, 1465–1481, 2001b. Pankow, J. F.: Gas/particle partitioning of neutral and ionizing compounds to single and multi-phase aerosol particles. 1. Unified modeling framework, Atmos. Environ., 37, 3323–3333, 2003a. Pankow, J. F., Tavakoli, A. D., Luo, W., and Isabelle, L. M.: Percent free-base nicotine in the tobacco smoke particulate matter of selected commercial and reference cigarettes, Chem. Res. Toxicol., 16, 1014–1018, 2003b. Pankow, J. F., Luo, W., Tavakoli, A. D., Chen, C., and Isabelle, L. M.: Delivery levels and behavior of 1,3-butadiene, acrylonitrile, benzene, and other toxic volatile organic compounds in mainstream tobacco smoke from two brands of commercial cigarettes, Chem. Res. Toxicol., 17, 805–813, 2004. Rathbun, R. E.: Vapor pressures and gas-film coefficients for ketones, Chemosphere, 16, 69–78, 1987. Reid, R. C., Prausnitz, J. M., and Poling, B. E.: The properties of gases and liquids, 4th Edition, McGraw-Hill, NY, NY, 741p, 1987. Steele, W. V., Chirico, R. D., Knipmeyer, S. E., Nguyen, A., Smith, N. K., and Tasker, I. R.: Thermodynamic properties and ideal-gas enthalpies of formation for cyclohexene, phthalan (2,5-dihydrobenzo-3,4-furan), isoxazole, octylamine, dioctylamine, trioctylamine, phenyl isocyanate, and 1,4,5,6-tetrahydropyrimidine, J. Chem. Eng. Data, 41, 1269–1284, 1996. Stull, D. R.: Vapor pressure of pure substances. Organic compounds, Ind. Eng. Chem., 39, 517–540, 1947. Tao, Y. and McMurray, P. H.: Vapor pressures and surface free energies of C14-C18 monocarboxylic acids and C5 and C6 dicarboxylic acids, Environ. Sci. Technol., 23, 1519–1523, 1989.