Electrokinetic Properties of Electrolyte Mixtures

Abstract

This thesis aims to find out whether electrokinetic transport of a calcium chloride solution can be controlled by adding sodium ions by performing molecular dynamics simulations. The idea that electrokinetic transport control is a possibility originates from research that found that charge inversion is reduced when monovalent ions are added to a multivalent solution. Consequently, flow reversal suppression is expected. Many mechanisms are known to contribute to charge inversion and ion competition, but it is unclear how they exactly relate to charge inversion reduction and flow reversal suppression. This work aims to replicate charge inversion reduction and flow reversal suppression in a system with an amorphous silica interface for mixed electrolytes with calcium, sodium and chloride. To allow insight into the structural behaviour of the electrical double layer and the electrokinetic properties for varying concentrations, molecular dynamics simula- tions are used. No variation in charge inversion and flow reversal reduction was found for the simulated concentrations. However, the adsorption behaviour of ions in the electrical double layer changed due to ion competition between sodium and calcium, where sodium outcompetes calcium for inner sphere surface complex adsorption. This work also shows that the electroosmotic flow behaviour for mixtures is sensitive to the dynamic adsorption behaviour of ions, emphasizing the importance of correctly tuned force field parameters between surface and ions.