Page 87 - Introduction to Colloid and Surface Chemistry

Liquid-gas and liquid-liquid interfaces 77

The strong adsorption of such materials at surfaces or interfaces in
the form of an orientated monomolecular layer (or monolayer) is
termed surface activity. Surface-active materials (or surfactants)
consist of molecules containing both polar and non-polar parts
(amphiphilic). Surface activity is a dynamic phenomenon, since the
final state of a surface or interface represents a balance between this
tendency towards adsorption and the tendency towards complete
mixing due to the thermal motion of the molecules.
The tendency for surface-active molecules to pack into an interface
favours an expansion of the interface; this must, therefore, be
balanced against the tendency for the interface to contract under
normal surface tension forces. If TT is the expanding pressure (or
surface pressure) of an adsorbed layer of surfacant, then the surface
(or interfacial) tension will be lowered to a value

T = To - TT (4.14)

Figure 4.10 shows the effect of lower members of the homologous
series of normal fatty alcohols on the surface tension of water. The
longer the hydrocarbon chain, the greater is the tendency for the
alcohol molecules to adsorb at the air-water surface and, hence,
lower the surface tension. A rough generalisation, known as Traube's
rule, is that for a particular homologous series of surfactants the
concentration required for an equal lowering of surface tension in
dilute solution decreases by a factor of about 3 for each additional
group.
CH 2
If the interfacial tension between two liquids is reduced to a
sufficiently low value on addition of a surfactant, emulsification will
readily take place, because only a relatively small increase in the
surface free energy of the system is involved. If TT ** y 0> a
microemulsion may form (see page 269).
In certain cases - solutions of electrolytes, sugars, etc. - small
increases in surface tension due to negative adsorption are noted.
Here, because the solute-solvent attractive forces are greater than
the solvent-solvent attractive forces, the solute molecules tend to
migrate away from the surface into the bulk of the liquid.