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• W2045461190 abstract "Gas/solid and gas/liquid partition processes are pivotal for the transport and residence time of organic pollutants in the atmosphere. Commonly, experimentally determined partition constants (K) between air and condensed phases (i.e., aerosols, rain, fog, snow, soils, plants) of a series of compounds are evaluated as a function of their (subcooled) liquid saturation vapor pressure Frequently, a linear free energy relationship of the form ln K = m ln + constant has been found for groups of structurally related compounds. In many cases, in the literature, deviations of the slope m from −1 have been considered to be in contradiction to theory and have thus been taken as indicative of nonequilibrium conditions or experimental artifacts. In this paper, it is shown by theoretical considerations as well as by experimental data from the literature that m may deviate significantly from −1 for equilibrium adsorption and absorption and that such deviations do not necessarily indicate nonequilibrium effects. In fact, if true equilibrium partitioning data are available, the slope m is a characteristic parameter for the specific sorption process and can thus be helpful for obtaining information about unknown sorbents (e.g., from field data for gas/particle partitioning). Some examples demonstrate that earlier interpretations of experimental sorption constants may have to be revised. A review of slopes m for field data of gas/particle partitioning from the literature leads to the conclusion that aerosol particles sampled in different events at the same location may differ considerably in their chemical properties. Combining the information of the slopes m and the absolute sorption constants K, we further conclude that absorption rather than adsorption must have been the dominating sorption mechanism in many cases. Finally, it is shown that a linear free energy relationship directly relating the sorption coefficients for two sorbents (ln K1 vs ln K2) may provide more information with respect to the question of the chemical similarity of the investigated sorbents than a comparison of m values from plots of ln K1 and ln K2 vs ln" @default.
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• W2045461190 date "1998-06-02" @default.
• W2045461190 modified "2023-09-30" @default.
• W2045461190 title "Gas/Solid and Gas/Liquid Partitioning of Organic Compounds: Critical Evaluation of the Interpretation of Equilibrium Constants" @default.
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• W2045461190 doi "https://doi.org/10.1021/es9710518" @default.
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