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Published July 15, 2004 | public
Journal Article

Thermodynamic Properties of Multifunctional Oxygenates in Atmospheric Aerosols from Quantum Mechanics and Molecular Dynamics: Dicarboxylic Acids


Ambient particulate matter contains polar multifunctional oxygenates that partition between the vapor and aerosol phases. Vapor pressure predictions are required to determine the gas−particle partitioning of such organic compounds. We present here a method based on atomistic simulations combined with the Clausius−Clapeyron equation to predict the liquid vapor pressure, enthalpies of vaporization, and heats of sublimation of atmospheric organic compounds. The resulting temperature-dependent vapor pressure equation is a function of the heat of vaporization at the normal boiling point [ΔH_(vap)(T_b)], normal boiling point (T_b), and the change in heat capacity (liquid to gas) of the compound upon phase change [ΔC_p(T_b)]. We show that heats of vaporization can be estimated from calculated cohesive energy densities (CED) of the pure compound obtained from multiple sampling molecular dynamics. The simulation method (CED) uses a generic force field (Dreiding) and molecular models with atomic charges determined from quantum mechanics. The heats of vaporization of five dicarboxylic acids [malonic (C_3), succinic (C_4), glutaric (C_5), adipic (C_6), and pimelic (C_7)] are calculated at 500 K. Results are in agreement with experimental values with an averaged error of about 4%. The corresponding heats of sublimation at 298 K are also predicted using molecular simulations. Vapor pressures of the five dicarboxylic acids are also predicted using the derived Clausius−Clapeyron equation. Predicted liquid vapor pressures agree well with available literature data with an averaged error of 29%, while the predicted solid vapor pressures at ambient temperature differ considerably from a recent study by Bilde et al. (Environ. Sci. Technol. 2003, 37, 1371−1378) (an average of 70%). The difference is attributed to the linear dependence assumption that we used in the derived Clausius−Clapeyron equation.

Additional Information

© 2004 American Chemical Society. Received for review December 18, 2003. Revised manuscript received April 26, 2004. Accepted May 4, 2004. Publication Date (Web): June 11, 2004. This work was supported by National Science Foundation/Environmental Protection Agency Program TSE99-G No. 9985578 and the Electric Power Research Institute. We thank Dr. Shiang-Tai Lin and Rachel Niemer for their valuable discussions and suggestions. The facilities of the Materials and Process Simulation Center used in these calculations have been funded by DURIP-ONR, DURIP-ARO, NSF-MRI, and IBM (SUR Grant).

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