Direct Coexistence Methods to Determine the Solubility of Salts in Water from Numerical Simulations. Test Case NaCl.

The solubility of NaCl, an equilibrium between a saturated solution of ions and a solid with a crystalline structure, was obtained from molecular dynamics simulations using the SPC/E and TIP4P-Ew water models. Four initial setups on supersaturated systems were tested on sodium chloride (NaCl) solutions to determine the equilibrium conditions and computational performance: (1) an ionic solution confined between two crystal plates of periodic NaCl, (2) a solution with all the ions initially distributed randomly, (3) a nanocrystal immersed in pure water, and (4) a nanocrystal immersed in an ionic solution. In some cases, the equilibration of the system can take several microseconds.

Modified colloidal primitive model as a homogeneous surface charge distribution: ζ-potential.

An integral equations theory is derived and applied to a modified colloidal primitive model (MCPM), for finite concentration colloidal dispersions. In MCPM, the charge on the colloidal particle is assumed to be smeared on its surface. We find important quantitative and qualitative differences of the ζ-potential, induced charge, and the colloid-colloid electric effective force, calculated in the MCPM, with those obtained from the colloidal primitive model (CPM), where the colloidal charge is assumed to be in the center of the particle, in spite of the fact that, due to Gauss's law, both models have the same particle distribution function.

Polarity inversion of ζ-potential in concentrated colloidal dispersions.

A concentrated colloidal dispersion is studied by applying an integral equations theory to the colloidal primitive model fluid. Important effects, attributed to large size and charge and to the finite concentration of colloidal particles, are found. We observe a polarity inversion of ζ-potential for concentrated colloidal dispersions, while it is not present for a single colloidal particle at infinite dilution.