Cited by 175Electrostatics and Colloid InteractionsMembrane-based Ion Separation TechniquesChemical and Physical Studies

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Underscreening in concentrated electrolytes

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Lee, Alpha A., Perez-Martinez, Carla S., Smith, Alexander M., Perkin, Susan·2017·Faraday Discussions

DOI 10.1039/c6fd00250a

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Abstract

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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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
ORCID: Lee, Alpha A.
Perez-Martinez, Carla S.
Smith, Alexander M.
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
DOI: 10.1039/c6fd00250a
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 › Chemical Engineering › Filtration and Separation › 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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Underscreening in concentrated electrolytes

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