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New and extended parameterization of the thermodynamic model AIOMFAC: calculation of activity coefficients for organic-inorganic mixtures containing carboxyl, hydroxyl, carbonyl, ether, ester, alkenyl, alkyl, and aromatic functional groups

Zuend, A. and Marcolli, C. and Booth, A. M. and Lienhard, D. M. and Soonsin, V. and Krieger, U. K. and Topping, D. O. and McFiggans, G. and Peter, T. and Seinfeld, J. H. (2011) New and extended parameterization of the thermodynamic model AIOMFAC: calculation of activity coefficients for organic-inorganic mixtures containing carboxyl, hydroxyl, carbonyl, ether, ester, alkenyl, alkyl, and aromatic functional groups. Atmospheric Chemistry and Physics, 11 (17). pp. 9155-9206. ISSN 1680-7316. http://resolver.caltech.edu/CaltechAUTHORS:20111010-152618974

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Abstract

We present a new and considerably extended parameterization of the thermodynamic activity coefficient model AIOMFAC (Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients) at room temperature. AIOMFAC combines a Pitzer-like electrolyte solution model with a UNIFAC-based group-contribution approach and explicitly accounts for interactions between organic functional groups and inorganic ions. Such interactions constitute the salt-effect, may cause liquid-liquid phase separation, and affect the gas-particle partitioning of aerosols. The previous AIOMFAC version was parameterized for alkyl and hydroxyl functional groups of alcohols and polyols. With the goal to describe a wide variety of organic compounds found in atmospheric aerosols, we extend here the parameterization of AIOMFAC to include the functional groups carboxyl, hydroxyl, ketone, aldehyde, ether, ester, alkenyl, alkyl, aromatic carbon-alcohol, and aromatic hydrocarbon. Thermodynamic equilibrium data of organic-inorganic systems from the literature are critically assessed and complemented with new measurements to establish a comprehensive database. The database is used to determine simultaneously the AIOMFAC parameters describing interactions of organic functional groups with the ions H^+, Li^+, Na^+, K^+, NH_(4)^+, Mg^(2+), Ca^(2+), Cl^−, Br^−, NO_(3)^−, HSO_(4)^−, and SO_(4)^(2−). Detailed descriptions of different types of thermodynamic data, such as vapor-liquid, solid-liquid, and liquid-liquid equilibria, and their use for the model parameterization are provided. Issues regarding deficiencies of the database, types and uncertainties of experimental data, and limitations of the model, are discussed. The challenging parameter optimization problem is solved with a novel combination of powerful global minimization algorithms. A number of exemplary calculations for systems containing atmospherically relevant aerosol components are shown. Amongst others, we discuss aqueous mixtures of ammonium sulfate with dicarboxylic acids and with levoglucosan. Overall, the new parameterization of AIOMFAC agrees well with a large number of experimental datasets. However, due to various reasons, for certain mixtures important deviations can occur. The new parameterization makes AIOMFAC a versatile thermodynamic tool. It enables the calculation of activity coefficients of thousands of different organic compounds in organic-inorganic mixtures of numerous components. Models based on AIOMFAC can be used to compute deliquescence relative humidities, liquid-liquid phase separations, and gas-particle partitioning of multicomponent mixtures of relevance for atmospheric chemistry or in other scientific fields.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.5194/acp-11-9155-2011DOIArticle
http://www.atmos-chem-phys.net/11/9155/2011/PublisherArticle
ORCID:
AuthorORCID
Zuend, A.0000-0003-3101-8521
Seinfeld, J. H.0000-0003-1344-4068
Additional Information:© 2011 Author(s) 2011. This work is distributed under the Creative Commons Attribution 3.0 License. Published by Copernicus Publications on behalf of the European Geosciences Union. Received: 26 April 2011; Published in Atmos. Chem. Phys. Discuss.: 20 May 2011; Revised: 25 August 2011; Accepted: 1 September 2011; Published: 7 September 2011. This work was supported by Swiss National Science Foundation (SNF) under project no. PA00P2 126227, by ETH Research Grant ETH-0210-1, and by the Competence Center Environment and Sustainability of the ETH Domain (CCES) project IMBALANCE. This work was also supported by US National Science Foundation grant AGS-1057183.
Funders:
Funding AgencyGrant Number
Swiss National Science Foundation (SNSF)PA00P2 126227
ETH ZurichETH-0210-1
Competence Center Environment and Sustainability of the ETH Domain (CCES) UNSPECIFIED
NSFAGS-1057183
Record Number:CaltechAUTHORS:20111010-152618974
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20111010-152618974
Official Citation:Zuend, A., Marcolli, C., Booth, A. M., Lienhard, D. M., Soonsin, V., Krieger, U. K., Topping, D. O., McFiggans, G., Peter, T., and Seinfeld, J. H.: New and extended parameterization of the thermodynamic model AIOMFAC: calculation of activity coefficients for organic-inorganic mixtures containing carboxyl, hydroxyl, carbonyl, ether, ester, alkenyl, alkyl, and aromatic functional groups, Atmos. Chem. Phys., 11, 9155-9206, doi:10.5194/acp-11-9155-2011, 2011.
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:27148
Collection:CaltechAUTHORS
Deposited By: Jason Perez
Deposited On:11 Oct 2011 14:12
Last Modified:06 Apr 2017 20:25

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