Vapor Pressure of Nine Perfluoroalkyl Substances (PFASs) Determined Using the Knudsen Effusion Method
Open accessAbstract
Sublimation vapor pressures of nine pure perfluoroalkyl substances, including ammonium perfluoro(2-methyl-3-oxahexanoate) (GenX), 1 H,1 H,2 H,2 H -perfluoro-1-decanol (8:2 FTOH), 1 H,1 H,2 H,2 H -perfluoro-1-dodecanol (10:2 FTOH), and C6 to C11 perfluorocarboxylic acids (PFCAs), were measured using the Knudsen technique at near-ambient temperatures. Melting temperatures and fusion enthalpies of these compounds were also measured by differential scanning calorimetry. The vapor pressure of GenX ammonium salt is comparable to that of the much higher molecular weight perfluoroundecanoic acid. GenX ammonium salt also did not show actual melting behavior but instead decomposed at around 470 K. The measured near-ambient temperature sublimation vapor pressures of the PFCAs and FTOHs were compared with some earlier reported liquid phase vapor pressures obtained at higher temperatures, and reasonable agreement exists between the data obtained in the different studies. The sublimation enthalpies of the PFCAs indicate that the contribution to the sublimation enthalpy of the CF 2 group in the alkyl chain is comparable to that of the CH 2 group in the corresponding nonfluorinated analogues, even though the PFCAs show consistently higher vapor pressures than do the corresponding carbon number alkanoic acids.
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Available data suggest that both the melting temperature and melting enthalpy of PFAS increase with the length of the fluorinated carbon chain.
“Available data suggest that both the melting temperature and melting enthalpy of PFAS increase with the length of the fluorinated carbon chain [20,21].”
From The EU’s Per- and Polyfluoroalkyl Substances (PFAS) Ban: A Case of Policy over Science (2023) · cites this paper as [21]
In Results and Discussion, “Melting temperature and enthalpy of fusion” (page unavailable), the paper reports a higher melting temperature for PFDA than PFOA and says PFDA has much higher fusion enthalpy than other PFCAs. These comparisons are consistent with the suggested trend, but the copy does not establish that both properties generally increase with fluorinated-chain length across PFAS. The explicit chain-length trend in “Vapor Pressures” concerns sublimation enthalpy, not melting enthalpy. (LLM, conf=0.82)
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- Authors
- Zhang, M., Yamada, K., Bourguet, S., Guelfo, J., & Suuberg, E. M.
- Affiliations
- Brown University (US)
- Corresponding author
- Suuberg, Eric M.
- Venue
- Journal of Chemical & Engineering Data
- Publisher
- American Chemical Society (ACS)
- Published
- 2020-04-21
- Volume
- 65
- Issue
- 5
- Pages
- 2332-2342
- ISSN
- 0021-9568 (ISSN-L)
- 1520-5134
- PMC
- PMC7505237
- OpenAlex
- W3019957006
- Cited by
- 42
- References
- 61
- Citations by year
- 2026: 7 · 2025: 8 · 2024: 9 · 2023: 10 · 2022: 7 · 2020: 1
- FWCI
- 1.67
- Type
- journal article
- Language
- en
- Open access
- green
- www.ncbi.nlm.nih.gov
- Licence
- Locations
- Journal of Chemical & Engineering Data (publishedVersion)
- PubMed (publishedVersion)
- PubMed Central (acceptedVersion)
- Funders
- National Institute of Environmental Health Sciences (2P42 ES013660)
- Topics
- Physical Sciences › Environmental Science › Environmental Chemistry › Per- and polyfluoroalkyl substances research
- Physical Sciences › Chemistry › Organic Chemistry › Chemical Thermodynamics and Molecular Structure
- Physical Sciences › Engineering › Biomedical Engineering › Phase Equilibria and Thermodynamics
- Keywords
- perfluorinated compounds, vapor pressure, GenX, perfluorocarboxylic acids, enthalpy of sublimation, melting point, heat of fusion, Knudsen effusion
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