Journal
JOURNAL OF CHEMICAL PHYSICS
Volume 146, Issue 19, Pages -Publisher
AMER INST PHYSICS
DOI: 10.1063/1.4982885
Keywords
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Funding
- Israel Science Foundation (ISF) [438/12]
- U.S.-Israel Binational Science Foundation (BSF) [2012/060]
- ISF-NSFC [885/15]
- Alexander von Humboldt Foundation
- Blavatnik postdoctoral fellowship programme
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Ionic solutions are often regarded as fully dissociated ions dispersed in a polar solvent. While this picture holds for dilute solutions, at higher ionic concentrations, oppositely charged ions can associate into dimers, referred to as Bjerrum pairs. We consider the formation of such pairs within the nonlinear Poisson-Boltzmann framework and investigate their effects on bulk and interfacial properties of electrolytes. Our findings show that pairs can reduce the magnitude of the dielectric decrement of ionic solutions as the ionic concentration increases. We describe the effect of pairs on the Debye screening length and relate our results to recent surface-force experiments. Furthermore, we show that Bjerrum pairs reduce the ionic concentration in bulk electrolyte and at the proximity of charged surfaces, while they enhance the attraction between oppositely charged surfaces. Published by AIP Publishing.
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