A reference data set for validating vapor pressure measurement techniques : homologous series of polyethylene glycols

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dc.contributor.author Krieger, Ulrich K.
dc.contributor.author Siegrist, Franziska
dc.contributor.author Marcolli, Claudia
dc.contributor.author Emanuelsson, Eva U.
dc.contributor.author Gobel, Freya M.
dc.contributor.author Bilde, Merete
dc.contributor.author Marsh, Aleksandra
dc.contributor.author Reid, Jonathan P.
dc.contributor.author Huisman, Andrew J.
dc.contributor.author Riipinen, Ilona
dc.contributor.author Hyttinen, Noora
dc.contributor.author Myllys, Nanna
dc.contributor.author Kurten, Theo
dc.contributor.author Bannan, Thomas
dc.contributor.author Percival, Carl J.
dc.contributor.author Topping, David
dc.date.accessioned 2018-01-25T11:17:01Z
dc.date.available 2018-01-25T11:17:01Z
dc.date.issued 2018-01-08
dc.identifier.citation Krieger , U K , Siegrist , F , Marcolli , C , Emanuelsson , E U , Gobel , F M , Bilde , M , Marsh , A , Reid , J P , Huisman , A J , Riipinen , I , Hyttinen , N , Myllys , N , Kurten , T , Bannan , T , Percival , C J & Topping , D 2018 , ' A reference data set for validating vapor pressure measurement techniques : homologous series of polyethylene glycols ' , Atmospheric Measurement Techniques , vol. 11 , no. 1 , pp. 49-63 . https://doi.org/10.5194/amt-11-49-2018
dc.identifier.other PURE: 97584977
dc.identifier.other PURE UUID: 7a3fd08b-007f-4698-b4f5-07b64ab4e93d
dc.identifier.other WOS: 000419548000002
dc.identifier.other Scopus: 85040352378
dc.identifier.other ORCID: /0000-0003-0384-7277/work/41140319
dc.identifier.other ORCID: /0000-0002-6416-4931/work/41139716
dc.identifier.other ORCID: /0000-0002-6025-5959/work/41140337
dc.identifier.uri http://hdl.handle.net/10138/231563
dc.description.abstract To predict atmospheric partitioning of organic compounds between gas and aerosol particle phase based on explicit models for gas phase chemistry, saturation vapor pressures of the compounds need to be estimated. Estimation methods based on functional group contributions require training sets of compounds with well-established saturation vapor pressures. However, vapor pressures of semivolatile and low-volatility organic molecules at atmospheric temperatures reported in the literature often differ by several orders of magnitude between measurement techniques. These discrepancies exceed the stated uncertainty of each technique which is generally reported to be smaller than a factor of 2. At present, there is no general reference technique for measuring saturation vapor pressures of atmospherically relevant compounds with low vapor pressures at atmospheric temperatures. To address this problem, we measured vapor pressures with different techniques over a wide temperature range for intercomparison and to establish a reliable training set. We determined saturation vapor pressures for the homologous series of polyethylene glycols (H-(O-CH2-CH2)(n)-OH) for n = 3 to n = 8 ranging in vapor pressure at 298 K from 10(-7) to 5 x 10(-2) Pa and compare them with quantum chemistry calculations. Such a homologous series provides a reference set that covers several orders of magnitude in saturation vapor pressure, allowing a critical assessment of the lower limits of detection of vapor pressures for the different techniques as well as permitting the identification of potential sources of systematic error. Also, internal consistency within the series allows outlying data to be rejected more easily. Most of the measured vapor pressures agreed within the stated uncertainty range. Deviations mostly occurred for vapor pressure values approaching the lower detection limit of a technique. The good agreement between the measurement techniques (some of which are sensitive to the mass accommodation coefficient and some not) suggests that the mass accommodation coefficients of the studied compounds are close to unity. The quantum chemistry calculations were about 1 order of magnitude higher than the measurements. We find that extrapolation of vapor pressures from elevated to atmospheric temperatures is permissible over a range of about 100 K for these compounds, suggesting that measurements should be performed best at temperatures yielding the highest-accuracy data, allowing subsequent extrapolation to atmospheric temperatures. en
dc.format.extent 15
dc.language.iso eng
dc.relation.ispartof Atmospheric Measurement Techniques
dc.rights cc_by
dc.rights.uri info:eu-repo/semantics/openAccess
dc.subject THERMODYNAMIC PROPERTIES
dc.subject DICARBOXYLIC-ACIDS
dc.subject ORGANIC-MOLECULES
dc.subject AQUEOUS-SOLUTIONS
dc.subject ETHYLENE-GLYCOL
dc.subject SOLID-STATE
dc.subject AEROSOL
dc.subject EVAPORATION
dc.subject DROPLETS
dc.subject DENSITY
dc.subject 114 Physical sciences
dc.subject 116 Chemical sciences
dc.title A reference data set for validating vapor pressure measurement techniques : homologous series of polyethylene glycols en
dc.type Article
dc.contributor.organization Department of Chemistry
dc.contributor.organization Department of Physics
dc.description.reviewstatus Peer reviewed
dc.relation.doi https://doi.org/10.5194/amt-11-49-2018
dc.relation.issn 1867-1381
dc.rights.accesslevel openAccess
dc.type.version publishedVersion

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