Overcharging in Colloids: Beyond the Poisson–Boltzmann Approach
10.1002/cphc.200390040
Crossref journal-article
Wiley
ChemPhysChem (311)
Abstract

AbstractA broad range of manufactured products and biological fluids are colloids. The ability to understand and control the processes (of scientific, technological and industrial interest) in which such colloids are involved relies upon a precise knowledge of the electrical double layer. The traditional approach to describing this ion cloud around colloidal particles has been the Gouy–Chapman model, developed on the basis of the Poisson–Boltzmann equation. Since the early 1980s, however, more sophisticated theoretical treatments have revealed both quantitative and qualitative deficiencies in the Poisson–Boltzmann theory, particularly at high ionic strengths and/or high surface charge densities. This review deals with these novel approaches, which are mostly computer simulations and approximate integral equation theories based on the so‐called primitive model. Special attention is paid to phenomena that cannot be accounted for by the classic theory as a result of neglecting ion size correlations, such as overcharging, namely, the counterion concentration in the immediate neighborhood of the surface is so large that the particle surface is overcompensated. Other illustrative examples are the nonmonotonic behavior of the electrostatic potential and attractive interactions between equally charged surfaces. These predictions are certainly remarkable and, on paper, they can have an effect on experimentally measurable quantities (for instance, electrophoretic mobility). Even so, these new approaches have scarcely been applied in practice. Thus a critical survey on the relevance of ion size correlation in real systems is also included. Overcharging of macroions can also be brought about by adsorption of oppositely charged polyelectrolytes. Noteworthy examples and theoretical approaches for them are also briefly reviewed.

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Quesada‐Pérez, M., González‐Tovar, E., Martín‐Molina, A., Lozada‐Cassou, M., & Hidalgo‐Álvarez, R. (2003). Overcharging in Colloids: Beyond the Poisson–Boltzmann Approach. ChemPhysChem, 4(3), 234–248. Portico.

Authors 5
  1. Manuel Quesada‐Pérez (first)
  2. Enrique González‐Tovar (additional)
  3. Alberto Martín‐Molina (additional)
  4. Marcelo Lozada‐Cassou (additional)
  5. Roque Hidalgo‐Álvarez (additional)
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Dates
Type When
Created 22 years, 5 months ago (March 14, 2003, 12:05 p.m.)
Deposited 1 year, 10 months ago (Oct. 10, 2023, 7:44 p.m.)
Indexed 3 months, 1 week ago (May 13, 2025, 4:05 a.m.)
Issued 22 years, 5 months ago (March 11, 2003)
Published 22 years, 5 months ago (March 11, 2003)
Published Online 22 years, 5 months ago (March 11, 2003)
Published Print 22 years, 5 months ago (March 17, 2003)
Funders 0

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@article{Quesada_P_rez_2003, title={Overcharging in Colloids: Beyond the Poisson–Boltzmann Approach}, volume={4}, ISSN={1439-7641}, url={http://dx.doi.org/10.1002/cphc.200390040}, DOI={10.1002/cphc.200390040}, number={3}, journal={ChemPhysChem}, publisher={Wiley}, author={Quesada‐Pérez, Manuel and González‐Tovar, Enrique and Martín‐Molina, Alberto and Lozada‐Cassou, Marcelo and Hidalgo‐Álvarez, Roque}, year={2003}, month=mar, pages={234–248} }