Theory of Surface Forces in Multivalent Electrolytes

Misra, Rahul Prasanna; de Souza, J. Pedro; Blankschtein, Daniel; Bazant, Martin Z.

doi:10.1021/acs.langmuir.9b01110

Theory of Surface Forces in Multivalent Electrolytes

Journal Article · Tue Jul 16 00:00:00 EDT 2019 · Langmuir

DOI:https://doi.org/10.1021/acs.langmuir.9b01110· OSTI ID:1559966

^[1]; de Souza, J. Pedro ^[2]; ^[2]; ^[3]

Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Chemical Engineering; Massachusetts Institute of Technology
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Chemical Engineering
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Chemical Engineering and Dept. of Mathematics

Aqueous electrolyte solutions containing multivalent ions exhibit various intriguing properties, including attraction between like-charged colloidal particles, which results from strong ion–ion correlations. In contrast, the classical Derjaguin–Landau–Verwey–Overbeek theory of colloidal stability, based on the Poisson–Boltzmann mean-field theory, always predicts a repulsive electrostatic contribution to the disjoining pressure. Here, we formulate a general theory of surface forces, which predicts that the contribution to the disjoining pressure resulting from ion–ion correlations is always attractive and can readily dominate over entropic-induced repulsions for solutions containing multivalent ions, leading to the phenomenon of like-charge attraction. Ion-specific short-range hydration interactions, as well as surface charge regulation, are shown to play an important role at smaller separation distances but do not fundamentally change these trends. The theory is able to predict the experimentally observed strong cohesive forces reported in cement pastes, which result from strong ion–ion correlations involving the divalent calcium ion.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). The Center for Enhanced Nanofluidic Transport (CENT); Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0019112

OSTI ID:: 1559966

Journal Information:: Langmuir, Journal Name: Langmuir Journal Issue: 35 Vol. 35; ISSN 0743-7463

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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