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Improved AIOMFAC model parameterisation of the temperature dependence of activity coefficients for aqueous organic mixtures

Ganbavale, G. and Zuend, A. and Marcolli, C. and Peter, T. (2015) Improved AIOMFAC model parameterisation of the temperature dependence of activity coefficients for aqueous organic mixtures. Atmospheric Chemistry and Physics, 15 (1). pp. 447-493. ISSN 1680-7316. http://resolver.caltech.edu/CaltechAUTHORS:20150219-132622070

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Abstract

This study presents a new, improved parameterisation of the temperature dependence of activity coefficients in the AIOMFAC (Aerosol Inorganic–Organic Mixtures Functional groups Activity Coefficients) model applicable for aqueous as well as water-free organic solutions. For electrolyte-free organic and organic–water mixtures the AIOMFAC model uses a group-contribution approach based on UNIFAC (UNIversal quasi-chemical Functional-group Activity Coefficients). This group-contribution approach explicitly accounts for interactions among organic functional groups and between organic functional groups and water. The previous AIOMFAC version uses a simple parameterisation of the temperature dependence of activity coefficients, aimed to be applicable in the temperature range from ~ 275 to ~ 400 K. With the goal to improve the description of a wide variety of organic compounds found in atmospheric aerosols, we extend the AIOMFAC parameterisation for the functional groups carboxyl, hydroxyl, ketone, aldehyde, ether, ester, alkyl, aromatic carbon-alcohol, and aromatic hydrocarbon to atmospherically relevant low temperatures. To this end we introduce a new parameterisation for the temperature dependence. The improved temperature dependence parameterisation is derived from classical thermodynamic theory by describing effects from changes in molar enthalpy and heat capacity of a multi-component system. Thermodynamic equilibrium data of aqueous organic and water-free organic mixtures from the literature are carefully assessed and complemented with new measurements to establish a comprehensive database, covering a wide temperature range (~ 190 to ~ 440 K) for many of the functional group combinations considered. Different experimental data types and their processing for the estimation of AIOMFAC model parameters are discussed. The new AIOMFAC parameterisation for the temperature dependence of activity coefficients from low to high temperatures shows an overall improvement of 28% in comparison to the previous model version, when both versions are compared to our database of experimentally determined activity coefficients and related thermodynamic data. When comparing the previous and new AIOMFAC model parameterisations to the subsets of experimental data with all temperatures below 274 K or all temperatures above 322 K (i.e. outside a 25 K margin of the reference temperature of 298 K), applying the new parameterisation leads to 37% improvement in each of the two temperature ranges considered. The new parameterisation of AIOMFAC agrees well with a large number of experimental data sets. Larger model–measurement discrepancies were found particularly for some of the systems containing multi-functional organic compounds. The affected systems were typically also poorly represented at room temperature and further improvements will be necessary to achieve better performance of AIOMFAC in these cases (assuming the experimental data are reliable). The performance of the AIOMFAC parameterisation is typically better for systems containing relatively small organic compounds and larger deviations may occur in mixtures where molecules of high structural complexity such as highly oxygenated compounds or molecules of high molecular mass (e.g. oligomers) prevail. Nevertheless, the new parameterisation enables the calculation of activity coefficients for a wide variety of different aqueous/water-free organic solutions down to the low temperatures present in the upper troposphere.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.5194/acp-15-447-2015 DOIArticle
http://www.atmos-chem-phys.net/15/447/2015/acp-15-447-2015.htmlPublisherArticle
ORCID:
AuthorORCID
Zuend, A.0000-0003-3101-8521
Additional Information:© 2015 Author(s). This work is distributed under the Creative Commons Attribution 3.0 License. Published by Copernicus Publications on behalf of the European Geosciences Union. Received: 2 June 2014 – Published in Atmos. Chem. Phys. Discuss.: 26 June 2014; Revised: 13 October 2014 – Accepted: 17 October 2014 – Published: 14 January 2015. This work was supported by the Swiss National Foundation, project 200020-125151 and by the CCES projects IMBALANCE and OPTIWARES funded by the ETH Domain.
Funders:
Funding AgencyGrant Number
Swiss National Foundation (SNF)200020-125151
ETH Domain CCES project IMBALANCEUNSPECIFIED
ETH Domain CCES project OPTIWARESUNSPECIFIED
Record Number:CaltechAUTHORS:20150219-132622070
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20150219-132622070
Official Citation:Ganbavale, G., Zuend, A., Marcolli, C., and Peter, T.: Improved AIOMFAC model parameterisation of the temperature dependence of activity coefficients for aqueous organic mixtures, Atmos. Chem. Phys., 15, 447-493, doi:10.5194/acp-15-447-2015, 2015
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:55019
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:20 Feb 2015 04:14
Last Modified:06 Apr 2017 20:11

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