Measured solid state and sub-cooled liquid vapour pressures of nitroaromatics using Knudsen effusion mass spectrometry

Abstract

Abstract. Knudsen Effusion Mass Spectrometry (KEMS) was used to measure the solid state saturation vapour pressure (PSsat) 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 PSsat were converted to sub-cooled liquid saturation vapour pressures (PLsat) using experimental enthalpy of fusion and melting point values measured using differential scanning calorimetry (DSC). The PLsat 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 PLsat and the experimental 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 PSsat of the measured compounds the ability to hydrogen bond (H-Bond), and the strength of a 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.

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

“…Data availability. All data in this paper are available from https://doi.org/10.5281/zenodo.3613581 (Shelley et al, 2020b). Supplementary material is available from https://doi.org/10.5281/zenodo.3625641 (Shelley et al, 2020a).…”