Underscreening in concentrated electrolytes
Open accessAbstract
Screening of a surface charge by an electrolyte and the resulting interaction energy between charged objects is of fundamental importance in scenarios from bio-molecular interactions to energy storage. The conventional wisdom is that the interaction energy decays exponentially with object separation and the decay length is a decreasing function of ion concentration; the interaction is thus negligible in a concentrated electrolyte. Contrary to this conventional wisdom, we have shown by surface force measurements that the decay length is an increasing function of ion concentration and Bjerrum length for concentrated electrolytes. In this paper we report surface force measurements to test directly the scaling of the screening length with Bjerrum length. Furthermore, we identify a relationship between the concentration dependence of this screening length and empirical measurements of activity coefficient and differential capacitance. The dependence of the screening length on the ion concentration and the Bjerrum length can be explained by a simple scaling conjecture based on the physical intuition that solvent molecules, rather than ions, are charge carriers in a concentrated electrolyte.
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Earlier studies on highly concentrated solutions have reported an increase in decay length with concentration, contradicting the prediction of DH theory.
“Although this trend contradicts the prediction by DH theory, it has been reported by earlier studies on highly concentrated solutions [9,22,23].”
From Effect of Hofmeister Anions on Interfacial Properties of Mica Surface in Concentrated Aqueous Solution (2020) · cites this paper as [22]
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- Authors
- Lee, A. A., Perez-Martinez, C. S., Smith, A. M., & Perkin, S.
- Affiliations
- Harvard University (US)
- University of Oxford (GB)
- University of Geneva (CH)
- Corresponding author
- Lee, Alpha A.
- Perkin, Susan
- Venue
- Faraday Discussions
- Publisher
- Royal Society of Chemistry (RSC)
- Published
- 2017
- Volume
- 199
- Pages
- 239-259
- ISSN
- 1359-6640 (ISSN-L)
- 1364-5498
- OpenAlex
- W2580724977
- Cited by
- 175
- References
- 60
- Citations by year
- 2026: 11 · 2025: 18 · 2024: 23 · 2023: 19 · 2022: 23 · 2021: 16 · 2020: 19 · 2019: 19 · 2018: 21 · 2017: 6
- FWCI
- 13.08
- Type
- journal article
- Language
- en
- Open access
- green
- arxiv.org
- Locations
- Faraday Discussions (publishedVersion)
- PubMed (publishedVersion)
- arXiv (Cornell University) (submittedVersion)
- arXiv (Cornell University)
- Funders
- H2020 European Research Council (676861)
- Leverhulme Trust (RPG-2015-328)
- Topics
- Physical Sciences › Chemistry › Physical and Theoretical Chemistry › Electrostatics and Colloid Interactions
- Physical Sciences › Engineering › Biomedical Engineering › Membrane-based Ion Separation Techniques
- Life Sciences › Biochemistry, Genetics and Molecular Biology › Biophysics › Chemical and Physical Studies
- Keywords
- underscreening, concentrated electrolytes, Bjerrum length, screening length, surface charge, interaction energy, surface force measurement, activity coefficients, differential capacitance, ion concentration dependence
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