Estimating the saturation vapor pressures of isoprene oxidation products C5H12O6 and C5H10O6 using COSMO-RS

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Kurten , T , Hyttinen , N , D'Ambro , E L , Thornton , J & Prisle , N L 2018 , ' Estimating the saturation vapor pressures of isoprene oxidation products C5H12O6 and C5H10O6 using COSMO-RS ' , Atmospheric Chemistry and Physics , vol. 18 , no. 23 , pp. 17589-17600 .

Title: Estimating the saturation vapor pressures of isoprene oxidation products C5H12O6 and C5H10O6 using COSMO-RS
Author: Kurten, Theo; Hyttinen, Noora; D'Ambro, Emma Louise; Thornton, Joel; Prisle, Nonne Lyng
Contributor organization: Department of Chemistry
Institute for Atmospheric and Earth System Research (INAR)
Date: 2018-12-12
Language: eng
Number of pages: 12
Belongs to series: Atmospheric Chemistry and Physics
ISSN: 1680-7316
Abstract: We have used COSMO-RS (the conductor-like screening model for real solvents), as implemented in the COSMOtherm program, to compute the saturation vapor pressures at 298 K of two photo-oxidation products of isoprene: the dihydroxy dihydroperoxide C5H12O6, and the dihydroperoxy hydroxy aldehyde, C5H10O6. The predicted saturation vapor pressures were significantly higher (by up to a factor of 1000) than recent experimental results, very likely due to the overestimation of the effects of intramolecular hydrogen bonds, which tend to increase saturation vapor pressures by stabilizing molecules in the gas phase relative to the liquid. Modifying the hydrogen bond enthalpy parameter used by COSMOtherm can improve the agreement with experimental results - however the optimal parameter value is likely to be system-specific. Alternatively, vapor pressure predictions can be substantially improved (to within a factor of 5 of the experimental values for the two systems studied here) by selecting only conformers with a minimum number of intramolecular hydrogen bonds. The computed saturation vapor pressures were very sensitive to the details of the conformational sampling approach, with the default scheme implemented in the COSMOconf program proving insufficient for the task, for example by predicting significant differences between enantiomers, which should have identical physical properties. Even after exhaustive conformational sampling, COSMOtherm predicts significant differences in saturation vapor pressures between both structural isomers and diastereomers. For C5H12O6, predicted differences in p(sat) between structural isomers are up to 2 orders of magnitude, and differences between stereoisomers are up to a factor of 20 - though these differences are very likely exaggerated by the overestimation of the effect of intramolecular H-bonds. For C5H10O6, the maximum predicted differences between the three studied structural isomers and their diastereomer pairs are around a factor of 8 and a factor of 2, respectively, when only conformers lacking intramolecular hydrogen bonds are included in the calculations. In future studies of saturation vapor pressures of polyfunctional atmospheric oxidation products using COSMOtherm, we recommend first performing thorough conformational sampling and subsequently selecting conformers with a minimal number of intramolecular H-bonds.
116 Chemical sciences
1172 Environmental sciences
114 Physical sciences
Peer reviewed: Yes
Rights: cc_by
Usage restriction: openAccess
Self-archived version: publishedVersion

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