气候变化领域集成服务门户(CCPortal): Technical note: Estimating aqueous solubilities and activity coefficients of mono- And α,ω-dicarboxylic acids using COSMOtherm

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DOI	10.5194/acp-20-13131-2020
	Technical note: Estimating aqueous solubilities and activity coefficients of mono- And α,ω-dicarboxylic acids using COSMOtherm
	Hyttinen N.; Heshmatnezhad R.; Elm J.; Kurtén T.; Prisle N.L.
发表日期	2020
ISSN	16807316
起始页码	13131
结束页码	13143
卷号	20 期号:21
英文摘要	We have used the COSMOtherm program to estimate activity coefficients and solubilities of mono- and -dicarboxylic acids and water in binary acid-water systems. The deviation from ideality was found to be larger in the systems containing larger acids than in the systems containing smaller acids. COnductor-like Screening MOdel for Real Solvents (COSMO-RS) underestimates experimental monocarboxylic acid activity coefficients by less than a factor of 2, but experimental water activity coefficients are underestimated more especially at high acid mole fractions. We found a better agreement between COSMOthermestimated and experimental activity coefficients of monocarboxylic acids when the water clustering with a carboxylic acid and itself was taken into account using the dimerization, aggregation, and reaction extension (COSMO-RS-DARE) of COSMOtherm. COSMO-RS-DARE is not fully predictive, but fit parameters found here for water-water and acid-water clustering interactions can be used to estimate thermodynamic properties of monocarboxylic acids in other aqueous solvents, such as salt solutions. For the dicarboxylic acids, COSMO-RS is sufficient for predicting aqueous solubility and activity coefficients, and no fitting to experimental values is needed. This is highly beneficial for applications to atmospheric systems, as these data are typically not available for a wide range of mixing states realized in the atmosphere, due to a lack of either feasibility of the experiments or sample availability. Based on effective equilibrium constants of different clustering reactions in the binary solutions, acid dimer formation is more dominant in systems containing larger dicarboxylic acids (C5-C8), while for monocarboxylic acids (C1-C6) and smaller dicarboxylic acids (C2-C4), hydrate formation is more favorable, especially in dilute solutions. © Author(s) 2020.
语种	英语
scopus关键词	atmospheric chemistry; carboxylic acid; mixing; solubility; solvent; thermodynamics
来源期刊	Atmospheric Chemistry and Physics
文献类型	期刊论文
条目标识符	http://gcip.llas.ac.cn/handle/2XKMVOVA/152838
作者单位	Nano and Molecular Systems Research Unit, University of Oulu, P.O. Box 3000, Oulu, 90014, Finland; Department of Chemistry and Institute for Atmospheric and Earth System Research (INAR), University of Helsinki, P.O. Box 55, Helsinki, 00014, Finland; Department of Chemistry and iClimate, Aarhus University, Langelandsgade 140, Aarhus C, 8000, Denmark
推荐引用方式 GB/T 7714	Hyttinen N.,Heshmatnezhad R.,Elm J.,et al. Technical note: Estimating aqueous solubilities and activity coefficients of mono- And α,ω-dicarboxylic acids using COSMOtherm[J],2020,20(21).
APA	Hyttinen N.,Heshmatnezhad R.,Elm J.,Kurtén T.,&Prisle N.L..(2020).Technical note: Estimating aqueous solubilities and activity coefficients of mono- And α,ω-dicarboxylic acids using COSMOtherm.Atmospheric Chemistry and Physics,20(21).
MLA	Hyttinen N.,et al."Technical note: Estimating aqueous solubilities and activity coefficients of mono- And α,ω-dicarboxylic acids using COSMOtherm".Atmospheric Chemistry and Physics 20.21(2020).