Molecular insights of adsorption and structure of surfactants and inorganic ions at fluid – liquid interfaces

Abstract

Traditional approaches to studying fluid -liquid interfaces include the macroscopic measuring of interfacial properties such as surface tension and matching the collected data against adsorption models. This method is capable of producing valuable data about the thermodynamics of adsorption and has been widely used by the community to extract information about the adsorption of thousands of different surface-active molecules. Nonetheless, this methodology cannot produce any molecular-level information about the microscopic structure of adsorption layers and interfaces.As a result, the molecular origins of many interfacial phenomena remained unknown until the advent of surface-sensitive techniques such as computer simulation and non-linear spectroscopy.The new insights provided by these methods have challenged the traditional views about the origins of some interfacial phenomena and promise modification of classical theories which were developed to explain these phenomena.In general, this thesis aims to study the interfacial structure and adsorption of ionic surfactants, some surface-active alcohols as model nonionic surfactants including, n-pentanol, methyl isobutyl carbinol (MIBC) and n-hexanol and inorganic salts including LiCl, NaCl and CsCl at both microscopic and macroscopic levels. The employed methodology involves a combination of traditional adsorption modelling with some macroscopic measurements and sum frequency generation (SFG) spectroscopy, which is capable of distinguishing between bulk and interfacial molecules. Using SFG spectroscopy, the interfacial structure of adsorption layers and the composition of interfaces were investigated in detail and independently of the bulk solution.Specifically, the surface saturation of solutions of MIBC was identified directly using SFG spectroscopy and was then compared to equilibrium surface tension data to find that surface tension surprisingly continued to decrease even after full surface saturation. This is in contradiction to the traditional view that all surfactants adsorb at the outermost adsorption monolayer. Because of the limited surface area of the topmost adsorption monolayer, its full saturation is considered as the end of the adsorption process. This view is based on the notion of Gibbs dividing plane, which is usually taken as being equal to the physical adsorption monolayer in a surfactant solution. The postsaturation surface tension decrease, therefore, cannot be explained by the Gibbs convention. A different adsorption geometry, which considers the under-monolayer adsorption of alcohols, was proposed based on the Guggenheim extended interface model. In Chapter 5, a recent controversy about the applicability of the famous Gibbs adsorption isotherm to the analysis of surface tension data was addressed with regards to the new concept of under-monolayer adsorption. The results showed that the linearity of a surface tension plot is not necessarily indicative of a fully saturated ii surface. The same adsorption geometry was also proposed for t...