Bjerrum pairs in ionic solutions: A Poisson-Boltzmann approach

The Journal of Chemical Physics
Ram M AdarDavid Andelman

Abstract

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.

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Citations

Nov 28, 2019·Physical Review. E·Ram M AdarDavid Andelman
Aug 24, 2020·The Journal of Chemical Physics·Ryuichi OkamotoAkira Onuki
Aug 4, 2020·Physical Review Letters·Miha Ravnik, Jeffrey C Everts
Aug 10, 2018·The Journal of Chemical Physics·Ram M AdarDavid Andelman
Apr 13, 2019·Physical Review Letters·Douglas J GrzeticGlenn H Fredrickson
Feb 20, 2020·Physical Review. E·Yael AvniDavid Andelman
Mar 11, 2021·The Journal of Physical Chemistry. B·Michael McEldrewAlexei A Kornyshev
Jul 3, 2020·Journal of Colloid and Interface Science·Guangming LiuVincent Stuart James Craig
Apr 10, 2021·The Journal of Chemical Physics·Penelope JonesAlpha A Lee
Jul 17, 2019·Langmuir : the ACS Journal of Surfaces and Colloids·Rahul Prasanna MisraMartin Z Bazant
Jan 8, 2021·Langmuir : the ACS Journal of Surfaces and Colloids·Yufeng WangGary J Blanchard
Mar 10, 2020·Langmuir : the ACS Journal of Surfaces and Colloids·Yufeng WangGary J Blanchard
Dec 9, 2017·The Journal of Physical Chemistry Letters·Nir GavishArik Yochelis
Dec 21, 2021·Chemical Reviews·Stefan RingeKarsten Reuter

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