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www.geosci-model-dev-discuss.net/4/1755/2011/
doi:10.5194/gmdd-4-1755-2011
© Author(s) 2011. This work is distributed
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Partial Derivative Fitted Taylor Expansion: an efficient method for calculating gas/liquid equilibria in atmospheric aerosol particles – Part 2: Organic compounds
1National Centre of Atmospheric Science, Univ. of Manchester, Manchester, M13 9PL, UK
2Centre for Atmospheric Sciences, School of Earth, Atmospheric and Environmental Sciences, Univ. of Manchester, Manchester, M13 9PL, UK
Abstract. A flexible mixing rule is presented which allows the calculation of activity coefficients of organic compounds in a multi-component aqueous solution. Based on the same fitting methodology as a previously published inorganic model (Partial Differential Fitted Taylor series Expansion; PD-FiTE), organic PD-FiTE treats interactions between binary pairs of solutes with polynomials of varying order. Using 13 example compounds extracted from a recent sensitivity study, the framework is benchmarked against the UNIFAC model. For 1000 randomly derived concentration ranges and 10 relative humidities between 10 and 99 %, the average deviation in predicted activity coefficients was calculated to be 3.8 %. Whilst compound specific deviations are present, the median and inter-quartile values across all relative humidity range always fell within ±20 % of the UNIFAC value. Comparisons were made with the UNIFAC model by assuming interactions between solutes can be set to zero within PD-FiTE. In this case, deviations in activity coefficients as low as −40 % and as high as +70 % were found. Both the fully coupled and uncoupled organic PD-FiTE are upto a factor of ≈12 and ≈66 times more efficient than calling the UNIFAC model using the same water content, and ≈310 and ≈1800 times more efficient than an iterative model using UNIFAC. The use of PD-FiTE within a dynamical framework is presented, demonstrating the potential inaccuracy of prescribing fixed negative or positive deviations from ideality when modelling the evolving chemical composition of aerosol particles.
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Notice on Discussion StatusCitation: Topping, D., Lowe, D., and McFiggans, G.: Partial Derivative Fitted Taylor Expansion: an efficient method for calculating gas/liquid equilibria in atmospheric aerosol particles – Part 2: Organic compounds, Geosci. Model Dev. Discuss., 4, 1755-1791, doi:10.5194/gmdd-4-1755-2011, 2011. Bibtex EndNote Reference Manager XML
