Electric surface potential of dodecane nano-drops in aqueous solutions of low ioinic strength

TL;DR

This study investigates how the surface potential of dodecane nanoemulsions in water varies with ionic strength, revealing a maximum potential at specific salt concentrations and identifying three destabilization regimes.

Contribution

It provides new insights into the relationship between ionic strength, surfactant adsorption, and surface potential in dodecane nanoemulsions, extending previous findings on hexadecane.

Findings

Surface potential peaks at specific NaCl concentrations.

Surface excess behavior differs from macroscopic predictions.

Three destabilization regimes identified based on ionic strength.

Abstract

While the surface charge of solid particles is a direct consequence of their synthesis, the one of suspended oil drops depends on the adsorption equilibrium of the surrounding molecules. The presence of salt raises the polarity of the water phase, favoring the salting out of the surfactant from the aqueous solution and increasing its surface excess. Yet, the electrolyte also screens the resulting surface charge of the drops [Debye-H\"uckel, 1923]. As a result, the electrostatic surface potential increases with the ionic strength until the saturation of the interface and then decreases. This behavior produces a maximum previously observed in hexadecane-in-water nanoemulsions [Urbina-Villalba, 2013; 2015]. Here, the variation of the surface potential of two dodecane-in-water (d/w) nanoemulsions is evaluated as a function of the sodium chloride concentration. As expected, maximum values are obtained for concentrations of 0.5 and 7.5 mM sodium dodecylsulfate (SDS). However, the surface excess of dodecane drops shows an intermediate behavior between the adsorption equilibrium predicted by macroscopic adsorption isotherms, and the one previously found on hexadecane drops. The stability of the prepared emulsions was followed monitoring the change in the average radius of the dispersions during five minutes, six times the lapse of time employed in a typical evaluation of the aggregation rate. In the case of 7.5 mM SDS, the smallest change in size coincides with the maximum surface potential found (40 mM NaCl). This is not observed for 0.5 mM SDS. Three regimes of destabilization are found to exist depending on the ionic strength of the aqueous phase. They correspond to the prevalence of: 1) solubilization/ripening, 2) aggregation, and 3) crystal precipitation.