Free energy of electrical double layers: entropy of adsorbed ions and the binding polynomial

1989 ◽  
Vol 93 (18) ◽  
pp. 6737-6743 ◽  
Author(s):  
Dirk Stigter ◽  
Ken A. Dill
Keyword(s):  
Free Energy ◽  
Double Layers ◽  
Electrical Double Layers ◽  
Binding Polynomial

Theory of films. - I. Single dielectric films

1973 ◽  
Vol 334 (1596) ◽  
pp. 49-58 ◽  
Keyword(s):  
Free Energy ◽  
Charge Density ◽  
Surface Charge ◽  
Dielectric Layer ◽  
Surface Charge Density ◽  
Aqueous Electrolyte ◽  
Van Der Waals ◽  
Double Layers ◽  
Dielectric Films ◽  
Electrical Double Layers

The van der Waals free energy of a system of two half-spaces of aqueous electrolyte separated by a dielectric layer is studied. The coupling of the van der Waals free energy to the structure of the electrical double layers in the system is calculated in two cases: (i) fixed surface charge density; (ii) fluctuating surface charge density due to the ionization of long chain carboxylic acid groups adsorbed on to the surfaces of the dielectric layer.

Electrokinetics of polymeric fluids in narrow rectangular confinements

Soft Matter ◽  
2021 ◽  
Author(s):  
Aditya Natu ◽  
Uddipta Ghosh
Keyword(s):  
Cross Section ◽  
Rectangular Cross Section ◽  
Double Layers ◽  
Polymeric Fluids ◽  
Polymeric Liquids ◽  
Electrical Double Layers

Flow of polymeric liquids in narrow confinements of rectangular cross section, in the presence of electrical double layers is analyzed here. Our analysis is motivated by the fact that many...

Molecular solvent models of electrical double layers

1991 ◽  
Vol 36 (11-12) ◽  
pp. 1677-1684 ◽  
Author(s):  
G.M. Torrie ◽  
G.N. Patey
Keyword(s):  
Double Layers ◽  
Electrical Double Layers ◽  
Solvent Models

Phase equilibria in solutions of rod-like particles

1956 ◽  
Vol 234 (1196) ◽  
pp. 73-89 ◽  
Keyword(s):  
Free Energy ◽  
Phase Separation ◽  
Partition Function ◽  
Colloidal Particles ◽  
Double Layers ◽  
Positive Energy ◽  
Isotropic Phase ◽  
Electric Double Layers ◽  
Rigid Rod ◽  
Anisotropic Phase

A partition function for a system of rigid rod-like particles with partial orientation about an axis is derived through the use of a modified lattice model. In the limit of perfect orientation the partition function reduces to the ideal mixing law ; for complete disorientation it corresponds to the polymer mixing law for rigid chains. A general expression is given for the free energy of mixing as a function of the mole numbers, the axis ratio of the solute particles, and a disorientation parameter. This function passes through a minimum followed by a maximum with increase in the disorientation parameter, provided the latter exceeds a critical value which is 2e for the pure solute and which increases with dilution. Assigning this parameter the value which minimizes the free energy, the chemical potentials display discontinuities a t the concentration a t which the minimum first appears. Separation into an isotropic phase and a some what more concentrated anisotropic phase arises because of the discontinuity, in confirmation of the theories of Onsager and Isihara, which treat only the second virial coefficient. Phase separation thus arises as a consequence of particle asymmetry, unassisted by an energy term . Whereas for a large-particle asymmetry both phases in equilibrium are predicted to be fairly dilute when mixing is athermal, a comparatively small positive energy of interaction causes the concentration in the anisotropic phase to increase sharply, while the concentration in the isotropic phase becomes vanishingly small. The theory offers a statistical mechanical basis for interpreting precipitation of rod-like colloidal particles with the formation of fibrillar structures such as are prominent in the fibrous proteins. The asymmetry of tobacco mosaic virus particles (with or without inclusion of their electric double layers) is insufficient alone to explain the well-known phase separation which occurs from their dilute solutions at very low ionic strengths. Higher-order interaction between electric double layers appears to be a major factor in bringing about dilute phase separation for these and other asymmetric colloidal particles bearing large charges, as was pointed out previously by Oster.

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