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Solutions of highly surface-active materials exhibit unusual physical properties. In
dilute solution the surfactant acts as a normal solute (and in the case of ionic
surfactants, normal electrolyte behaviour is observed). At fairly well defined
concentrations, however, abrupt changes in several physical properties, such as
osmotic pressure, turbidity, electrical conductance and surface tension. The rate
at which osmotic pressure increases with concentration becomes abnormally low
and the rate of increase of turbidity with concentration is much enhanced,
which suggests that considerable association is taking place. The conductance
of ionic surfactant solutions, however, remains relatively high, which shows that
ionic dissociation is still in force.

Critical micelle concentrations can be determined by measuring any micelle-influenced
physical property as a function of surfactant concentration. In practice, surface tension,
electrical conductivity and dye solubilisation measurements are the most popular. The choice
of physical property will slightly influence the measured c.m.c., as will the procedure adopted
to determine the point of discontinuity.
Information concerning the sizes and shapes of micelles can be obtained from dynamic light
scattering, ultracentrifugation, viscosity and low-angle X-ray scattering.
Factors affecting critical micelle concentrations
1. Increasing the hydrophobic part of the surfactant molecules favours micelle formation.
2. Micelle formation is opposed by thermal agitation and c.m.c.'s would thus be expected to
increase with increasing temperature.
3. With ionic micelles, the addition of simple electrolyte reduces the repulsion between the
charged groups at the surface of the micelle by the screening action of the added ions.
4. The addition of organic molecules can affect c.m.c.'s in a variety of ways.
Micellar theory has developed in a somewhat uncertain fashion and is still in many
respects open to discussion. Possible micelle structures include the spherical, laminar
and cylindrical arrangements illustrated schematically. Living cells can be considered
as micellar-type arrangements with a vesicular structure.
Typically, micelles tend to be approximately spherical over a fairly wide range of
concentration, but often there are marked transitions to larger, non-spherical liquid-
crystal structures at high concentrations. Systems containing spherical micelles tend to
have low viscosities, whereas liquid-crystal phases tend to have high viscosities. The free
energies of transition between micellar phases tend to be small and, consequently, the
phase diagrams for these systems tend to be quite complicated and sensitive to
Spherical (anionic) micelle.
This is the usual shape at surfactant
concentrations below about 40
per cent,
Spherical vesicle bilayer
structure, which is
representative of the living
(c) And (d) Hexagonal and lamellar phases
formed from cylindrical and laminar micelles,
respectively. These, and other structures, exist in
highly concentrated surfactant solutions
Solubilisation is of practical importance in the formulation of pharmaceutical
and other products containing water-insoluble ingredients, detergency, where
it plays a major role in the removal of oily soil, emulsion polymerisation and
micellar catalysis of organic reactions.
In micellar catalysis, reactant must be solubilised at a location near to the
micelle surface where it is accessible to reagent in the aqueous phase. The
strong electrostatic interactions which are likely at this location may influence
the nature of the transition state and/or reactant concentration; for example,
cationic micelles may catalyse reaction between a nucleophilic anion and a
neutral solubilized substrate.
Micelle-forming surfactants exhibit another unusual phenomenon in that their
solubilities show a rapid increase above a certain temperature, known as the
Krafft point. The explanation of this behaviour arises from the fact that
unassociated surfactant has a limited solubility, whereas the micelles are
highly soluble. Below the Krafft temperature the solubility of the surfactant is
insufficient for micellisation. As the temperature is raised, the solubility slowly
increases until, at the Krafft temperature, the c.m.c. is reached. A relatively
large amount of surfactant can now be dispersed in the form of micelles, so
that a large increase in solubility is observed.
The work of adhesion between two immiscible liquids is equal to the work
required to separate unit area of the liquid-liquid interface and form two
separate liquid-air interfaces (figure 4.15a), and is given by the Dupre

The work of cohesion for a single liquid corresponds to the work required to pull
apart a column of liquid of unit cross-sectional area (Figure 4.15b)

Spreading of one liquid on another

When a drop of an insoluble oil is placed on a clean water surface, it may
behave in one of three ways:
1. Remain as a lens, as in Figure 4.16 (non-spreading).
2. Spread as a thin film, which may show interference colours, until it is uniformly
distributed over the surface as a 'duplex' film. (A duplex film is a film which is
thick enough for the two interfaces - i.e. liquid-film and film-air - to be
independent and possess characteristic surface tensions.)
3. Spread as a monolayer, leaving excess oil as lenses in equilibrium,

The molecules in a monomolecular film, especially at high surface
concentrations, are often arranged in a simple manner, and much can be
learned about the size, shape and orientation of the individual molecules by
studying various properties of the monolayer. Monomolecular films can exist in
different, two-dimensional physical states, depending mainly on the
magnitude of the lateral adhesive forces between the film molecules, in much
the same way as threedimensional matter.
Surface pressure
The surface pressure of a monolayer is the lowering of surface tension due to
the monolayer - i.e. it is the expanding pressure exerted by the monolayer
which opposes the normal contracting tension of the clean interface, or

is the tension of clean interface
y is the tension of interface plus monolayer
The variation of surface pressure with the area available to the spread
material is represented by a -A (force-area) curve. With a little imagination,
-A curves can be regarded as the twodimensional equivalent of the p-V
curves for three dimensional matter. (N.B. For a 1 nm thick film, a surface
pressure of 1 mN m
is equivalent to a bulk pressure of 10
N m
, or ~ 10 atm.)
The Langmuir-Adam surface balance (or trough) uses a technique for containing
and manoeuvring insoluble monolayers between barriers for the direct
determination of ir-A curves. The film is contained between a movable barrier and
a float attached to a torsion-wire arrangement. The surface pressure of the film is
measured directly in terms of the horizontal force which it exerts on the float and
the area of the film is varied by means of the movable barrier.

The surface pressure of the film is determined by measuring
the force which must be applied via a torsion wire to
maintain the float at a fixed position on the surface (located
optically) and dividing by the length of the float. For precise
work, the surface balance is enclosed in an air thermostat
and operated by remote control. With a good modern
instrument, surface pressures can be measured with an
accuracy of 0.01 mN m