Theory of Surface Forces in Multivalent Electrolytes
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, b...
| Main Authors: | , , , |
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| Format: | Article |
| Language: | English |
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American Chemical Society (ACS)
2019
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| Online Access: | https://hdl.handle.net/1721.1/122280 |
| _version_ | 1826202266744389632 |
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| author | Misra, Rahul Prasanna De Souza, John Blankschtein, Daniel Bazant, Martin Z |
| author2 | Massachusetts Institute of Technology. Department of Chemical Engineering |
| author_facet | Massachusetts Institute of Technology. Department of Chemical Engineering Misra, Rahul Prasanna De Souza, John Blankschtein, Daniel Bazant, Martin Z |
| author_sort | Misra, Rahul Prasanna |
| collection | MIT |
| description | 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. |
| first_indexed | 2024-09-23T12:04:49Z |
| format | Article |
| id | mit-1721.1/122280 |
| institution | Massachusetts Institute of Technology |
| language | English |
| last_indexed | 2024-09-23T12:04:49Z |
| publishDate | 2019 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/1222802022-10-01T08:03:02Z Theory of Surface Forces in Multivalent Electrolytes Misra, Rahul Prasanna De Souza, John Blankschtein, Daniel Bazant, Martin Z Massachusetts Institute of Technology. Department of Chemical Engineering Massachusetts Institute of Technology. Department 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. National Science Foundation (U.S.) (Award 1122374) 2019-09-23T18:57:45Z 2019-09-23T18:57:45Z 2019-07 2019-07 2019-09-20T13:39:20Z Article http://purl.org/eprint/type/JournalArticle 0743-7463 1520-5827 https://hdl.handle.net/1721.1/122280 Misra, Rahul Prasanna et al. "Theory of Surface Forces in Multivalent Electrolytes." Langmuir 35, 35 (July 2019): 11550-11565 © 2019 American Chemical Society en http://dx.doi.org/10.1021/acs.langmuir.9b01110 Langmuir Creative Commons Attribution-NonCommercial-NoDerivs License http://creativecommons.org/licenses/by-nc-nd/4.0/ application/pdf American Chemical Society (ACS) ACS |
| spellingShingle | Misra, Rahul Prasanna De Souza, John Blankschtein, Daniel Bazant, Martin Z Theory of Surface Forces in Multivalent Electrolytes |
| title | Theory of Surface Forces in Multivalent Electrolytes |
| title_full | Theory of Surface Forces in Multivalent Electrolytes |
| title_fullStr | Theory of Surface Forces in Multivalent Electrolytes |
| title_full_unstemmed | Theory of Surface Forces in Multivalent Electrolytes |
| title_short | Theory of Surface Forces in Multivalent Electrolytes |
| title_sort | theory of surface forces in multivalent electrolytes |
| url | https://hdl.handle.net/1721.1/122280 |
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