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Prediction of Vapor Pressures and Enthalpies of Vaporization Using a COSMO Solvation Model

Lin, Shiang-Tai and Chang, Jaeeon and Wang, Shu and Goddard, William A., III and Sandler, Stanley I. (2004) Prediction of Vapor Pressures and Enthalpies of Vaporization Using a COSMO Solvation Model. Journal of Physical Chemistry A, 108 (36). pp. 7429-7439. ISSN 1089-5639. doi:10.1021/jp048813n. https://resolver.caltech.edu/CaltechAUTHORS:20170408-141842180

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Abstract

We have developed a general predictive method for vapor pressures and enthalpies of vaporization based on the calculation of the solvation free energy that consists of three components; the electrostatic, dispersion, and cavity formation contributions. The electrostatic contribution is determined using the quantum mechanical COSMO solvation model. Thermodynamic perturbation theory for hard-core molecules is used for the cavity term, and the dispersion term is modeled using a mean field term proportional to the density and molecular surface area. The proposed model uses one set of van der Waals atomic radii to describe molecular shape, two universal interaction parameters for the electrostatic interaction, one set of atom-specific dispersion coefficients, one universal parameter to scale the atomic exposed surface area, and a single universal parameter for the ratio of the hard-core to atomic radii. The model parameters have been determined using 371 pure substances of varying molecular structure, functionality, and size. The average accuracy of the model for vapor pressures and enthalpies of vaporization at the normal boiling temperature is found to be 76% and 4.81 kJ/mol, respectively, with temperature-independent parameters. The average error in the normal boiling temperature is found to be 16 K for species whose boiling points range from 191 to 610 K.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/jp048813nDOIArticle
http://pubs.acs.org/doi/suppl/10.1021/jp048813nPublisherSupporting Information
ORCID:
AuthorORCID
Lin, Shiang-Tai0000-0001-8513-8196
Goddard, William A., III0000-0003-0097-5716
Additional Information:© 2004 American Chemical Society. Received: March 17, 2004; In Final Form: June 24, 2004. Financial support of this research was provided from contract DE-FG02-85ER13436 from the division of Basic Energy Sciences of the U.S. Department of Energy and Grant CTS-0083709 from the U.S. National Science Foundation.
Funders:
Funding AgencyGrant Number
Department of Energy (DOE)DE-FG02-85ER13436
NSFCTS-0083709
Issue or Number:36
DOI:10.1021/jp048813n
Record Number:CaltechAUTHORS:20170408-141842180
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170408-141842180
Official Citation:Prediction of Vapor Pressures and Enthalpies of Vaporization Using a COSMO Solvation Model Shiang-Tai Lin, Jaeeon Chang, Shu Wang, William A. Goddard III, and Stanley I. Sandler The Journal of Physical Chemistry A 2004 108 (36), 7429-7439 DOI: 10.1021/jp048813n
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:75921
Collection:CaltechAUTHORS
Deposited By: 1Science Import
Deposited On:19 Apr 2017 22:49
Last Modified:15 Nov 2021 16:56

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