Properties of the diffuse double layer at high electrolyte concentrations.

The equations necessary to calculate the potential drop across the diffuse layer and its differential capacity are derived for 1:1 electrolytes on the basis of the Eigen and Wicke theory for concentrated electrolyte solutions. The results of this model are then compared with Monte Carlo data for more concentrated solutions and solutions with ions of large diameters. It is shown that the Eigen-Wicke model is inadequate because it fails to consider the change in potential at a given ion due to its surrounding atmosphere.

Restricted primitive model for electrolyte solutions in contact with solid surface modified by grafted chains: a density functional approach.

We have studied the microscopic structure and the thermodynamic and electric properties of the restricted primitive model for electrolyte solutions in contact with a chemically modified uncharged and charged solid surface. The modification of the surface is performed by the tethering of chain particles via a specific single segment at the stage preceeding the adsorption of the restricted primitive model. Some fraction of segments belonging to a chain particle can be charged such that the system models adsorption on an electrode covered by an electrolyte brush.

Series approach to modeling ion size effects for asymmetric electrolytes in the diffuse double layer.

The theory of the diffuse layer for asymmetric electrolytes is reconsidered with emphasis on the effects of ion size on the diffuse layer potential drop and differential capacity. For asymmetric 2:1 and 1:2 electrolytes, this potential drop is expressed in terms of a polynomial with a linear, quadratic, and cubic term in the corresponding estimate in the Gouy-Chapman theory. Optimal polynomial coefficients and model validation for 2:1 electrolytes are provided by least-squares regression of Monte Carlo data obtained for a restricted electrolyte in a primitive solvent.

An experimental Raman and theoretical DFT study on the self-association of acrylonitrile.

The liquid structure of acrylonitrile (propenenitrile) has been investigated using Raman spectroscopy and density functional theory (DFT) ab initio calculations with the 6-311++G** basis set. Two different and complementary experimental approaches were undertaken: FT-Raman spectra of 13 acrylonitrile solutions in carbon tetrachloride (concentration range=0.25-12.

Series approach to modeling ion size effects for symmetric electrolytes in the diffuse double layer.

An analytical model is developed for the potential drop and differential capacity across the diffuse layer which considers the effects of ion size on these properties. For symmetric electrolytes, this potential drop is expressed in terms of a cubic polynomial in the corresponding estimate in the Gouy-Chapman theory. Optimal polynomial coefficients and model validation for 1:1 and 2:2 electrolytes are provided by fits of Monte Carlo data obtained for a restricted electrolyte in a primitive solvent.