Slides Self-assembly at interfaces

Micelles
Critical micelle concentration: critical surfactant concentration at which added surfactant no longer
dissolves molecularly, but forms micelles instead. CMC is determined by temperature, solubility of
the monomer (polarity of head group, length of alkyl chain)
Kraft point: temperature at which all the three phases – crystalline, micellar and monomeric – exist
in equilibrium.
Kraft temperature: temperature above which the solubility of a surfactant rises sharply. At this
temperature the solubility of the surfactant becomes equal to the critical micelle concentration.

CMC can be determined by measuring the fluorescence

spectrum of pyrene. This spectrum changes when the
environment changes from hydrophilic to hydrophobic, i.e.
when the molecules is starting to get dissolved in micelles.
The CMC can also be detected by examining various physical
parameters that change at the CMC:
 Solubility of apolar compounds
 Surface tension of the solution
 Electrical conductivity

Models for the structure of micelles

Hartley model

Menger’s Fjord model

Dill and Flory model

This model explains:

 The fact that different viscosities have been reported for the core of micelles using various
techniques and different probe molecules: each type of molecule will exist in a different
part of the core
 The fact that some techniques indicate the presence of water in the core, others not.
 Why some water insoluble molecules are at the surface-water interface: there are degrees
of order in the core, these molecules may dissolve better in the less ordered outer layer.

Driving force for micelle formation: the hydrophobic effect.

Formation of a micelle eliminates hydrocarbon-water interactions, yet increases hydrocarbon-
hydrocarbon interactions. Enthalpically, only the gain in hydrophobic interactions is favoured.
However the liberation of water from the aliphatic chains is entropically highly favoured, since they
were restricted in their motion by the chains. This drives the micelle formation.
Influence of changing various parameters on micelle formation:
Salt
For ionic surfactants: addition of salt decreases the CMC. This is because the added electrolyte
reduces the repulsion between charged head groups. The effect is larger for longer chain
surfactants, since the reduction in head group repulsion has a proportionally greater effect on
molecular packing than for amphiphiles containing short hydrophobic chains.
Surfactant type
Non-ionic surfactants generally have a lower CMC than ionic surfactants. This is due to the
electrostatic interactions that have to be overcome in the case of ionic surfactants. So the higher the
head group charge, the higher the CMC.
Hydrophobic chain length
Increasing chain length generally favours micellisation. So, increasing chain length lowers the CMC.

Micro emulsions
Micro emulsions are highly influenced by temperature, since it can drastically change the
stabilization characteristics of a surfactant. At higher temperatures:

 Hydrophobic tail will take more space

 Hydrophilic part will reduce its affinity for water (and become smaller)