Liquids and Solutions at Interfaces

Author:

Fawcett W. Ronald

Abstract

When the properties of liquids and solutions are considered, attention is normally focused on the bulk of the phase, and the properties of the system at its boundaries are ignored. Significant effects are associated with the region near the surface of a liquid phase and an understanding of these is an important part of solution chemistry. As a simple example, consider a beaker of pure water at room temperature in a closed inert environment. As has been seen in the consideration of liquid structure, the properties of water are strongly influenced by hydrogen bonding between neighboring molecules, and to a lesser extent by dipole–dipole interactions. As an observer at the molecular level, one would find that the molecules near the boundaries of the water phase have different properties. There are two boundaries in this system, the water | air interface and the water | glass interface. At the water | air interface, the important feature is the termination of intermolecular interactions, so that molecules must adjust to an environment where the number of nearest neighbors is reduced. At the water | glass interface, water molecules meet the components of glass, a supercooled liquid with silicon dioxide as the major component. Interaction between water and silicon dioxide is different from interaction among water molecules. It is clear that the molecular environment at these interfaces is very different than it is in the bulk. As a result, local properties are different. Now imagine that the water in the beaker is dispersed as a fog, that is to say, as many very small droplets for which the ratio of surface area to volume is much larger than for the water in the beaker. It is obvious that the thermodynamic properties of the fog, a colloidal system, are very different from those of the water as a macrosystem in a beaker. In order to create the fog considerable work must be done to form a system with a much larger surface area. This means that the Gibbs energy of a fog containing the same number of water molecules as the beaker of water is much higher.

Publisher

Oxford University Press

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