Measured solid state and subcooled liquid vapour pressures of nitroaromatics using Knudsen effusion mass spectrometry


Knudsen effusion mass spectrometry (KEMS) was used to measure the solid state saturation vapour pressure (PsatS) of a range of atmospherically relevant nitroaromatic compounds over the temperature range from 298 to 328 K. The selection of species analysed contained a range of geometric isomers and differing functionalities, allowing for the impacts of these factors on saturation vapour pressure (Psat) to be probed. Three subsets of nitroaromatics were investigated: nitrophenols, nitrobenzaldehydes and nitrobenzoic acids. The PsatS values were converted to subcooled liquid saturation vapour pressure (PsatL) values using experimental enthalpy of fusion and melting point values measured using differential scanning calorimetry (DSC). The PsatL values were compared to those estimated by predictive techniques and, with a few exceptions, were found to be up to 7 orders of magnitude lower. The large differences between the estimated PsatL and the experimental values can be attributed to the predictive techniques not containing parameters to adequately account for functional group positioning around an aromatic ring, or the interactions between said groups. When comparing the experimental PsatS of the measured compounds, the ability to hydrogen bond (H bond) and the strength of the H bond formed appear to have the strongest influence on the magnitude of the Psat, with steric effects and molecular weight also being major factors. Comparisons were made between the KEMS system and data from diffusion-controlled evaporation rates of single particles in an electrodynamic balance (EDB). The KEMS and the EDB showed good agreement with each other for the compounds investigated.

Publication DOI:
Divisions: College of Engineering & Physical Sciences > School of Infrastructure and Sustainable Engineering > Chemical Engineering & Applied Chemistry
Additional Information: © Author(s) 2020. This work is distributed under the Creative Commons Attribution 4.0 License. Funding: This research has been supported by the Natural Environment Research Council (grant no. NE/L002469/1).
Uncontrolled Keywords: Atmospheric Science
Publication ISSN: 1680-7324
Last Modified: 08 Dec 2023 11:34
Date Deposited: 21 Jul 2020 07:07
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Related URLs: https://www.atm ... t/20/8293/2020/ (Publisher URL)
http://www.scop ... tnerID=8YFLogxK (Scopus URL)
PURE Output Type: Article
Published Date: 2020-07-17
Accepted Date: 2020-06-23
Authors: Shelley, Petroc
Bannan, Thomas J.
Worrall, Stephen David (ORCID Profile 0000-0003-1969-3671)
Alfarra, M. Rami
Krieger, Ulrich K.
Percival, Carl J.
Garforth, Arthur
Topping, David



Version: Published Version

License: Creative Commons Attribution

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