Specific ion effects via ion hydration: II. Double layer interaction. 2003

Eli Ruckenstein, and Marian Manciu
Department of Chemical Engineering, State University of New York at Buffalo, Buffalo, NY 14260, USA. feaeliru@acsu.buffalo.edu

A simple modified Poisson-Boltzmann formalism, which accounts also for those interactions between electrolyte ions and colloidal particles not included in the mean potential, is used to calculate the force between two parallel plates. It is shown that the short-range interactions between ions and plates, such as those due to the change in the hydration free energy of a structure-making/breaking ion that approaches the interface, affect the double layer interaction at large separations through the modification of the surface potential and surface charge density. While at short separations (below the range of the short-range ion-hydration forces) the interaction can be attractive, at larger separations the interaction is always repulsive, as in the traditional theory. When the long-range van der Waals interactions between the ions and the system (ion-dispersion interactions) are accounted for in the modified Poisson-Boltzmann approach, an attractive force between plates can be generated. At sufficiently large separations, this attraction can become even stronger than the traditional van der Waals attraction between plates of finite thickness, thus generating a dominant long-range 'double layer attraction'. At small plate separations, the attraction generated by the ion-dispersion forces combined with the electrostatic repulsion due to the double layers overlap can lead to a variety of interactions, from a weak attraction (which is typically by at least one order of magnitude smaller than the traditional van der Waals attraction between plates) to a strong double layer repulsion (for sufficiently large surface charges). Both types of ion interactions (long-range van der Waals or short-range ionic hydration) strongly affect the magnitude of the double layer interaction, and can account for the specific ion effects observed experimentally. However, they do not affect qualitatively the traditional theory of the colloid stability, which predicts that the colloid is stable when there is a sufficiently large charge on the surface, and coagulates when the van der Waals interactions between two colloidal particles dominate. The only qualitative difference found when the ion-dispersion interactions were incorporated into the traditional double layer theory was the emergence of a 'double layer attraction' at very large separations, which, however, does not affect much the stability of colloids.

UI MeSH Term Description Entries
D007477 Ions An atom or group of atoms that have a positive or negative electric charge due to a gain (negative charge) or loss (positive charge) of one or more electrons. Atoms with a positive charge are known as CATIONS; those with a negative charge are ANIONS.
D003102 Colloids Two-phase systems in which one is uniformly dispersed in another as particles small enough so they cannot be filtered or will not settle out. The dispersing or continuous phase or medium envelops the particles of the discontinuous phase. All three states of matter can form colloids among each other. Hydrocolloids,Colloid,Hydrocolloid
D013816 Thermodynamics A rigorously mathematical analysis of energy relationships (heat, work, temperature, and equilibrium). It describes systems whose states are determined by thermal parameters, such as temperature, in addition to mechanical and electromagnetic parameters. (From Hawley's Condensed Chemical Dictionary, 12th ed) Thermodynamic
D014867 Water A clear, odorless, tasteless liquid that is essential for most animal and plant life and is an excellent solvent for many substances. The chemical formula is hydrogen oxide (H2O). (McGraw-Hill Dictionary of Scientific and Technical Terms, 4th ed) Hydrogen Oxide
D016012 Poisson Distribution A distribution function used to describe the occurrence of rare events or to describe the sampling distribution of isolated counts in a continuum of time or space. Distribution, Poisson

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