Microemulsions

Microemulsions

Microemulsions are thermodynamically stable,

optically transparent, isotropic dispersions of aqueous
and hydrocarbon liquids stabilized by an interfacial
film of surfactant molecules

Microemulsions are monodispersed spherical droplets

(diameter < 100 nm) of water in oil or oil in water,
depending on the nature of the surfactant.
Microemulsions and (Macro) emulsions are Different

Microemulsion Macroemulsion

Thermodynamically Stable Kinetically Stable

Droplet size 10 - 100 nm (transparent) 1-10 m (opaque)

High surface area: 200 m2/g Low surface area: 15 m2/g

Ultra Low O/W IFT (10-2 – 10-3 mN/m) O/W IFT 1-10 mN/m

W/O , O/W and Bicontinuous types W/O or O/W types

Forms at CPP = 1 Forms at CPP > or < 1
 Formation of Microemulsions*
Gm  G1  G2  G3  T S

Oil
2

Gm = free energy change for microemulsion formation

G1 = free energy change due to increase in total surface area
G2 = free energy change due to interaction between droplets
G3 = free energy change due to adsorption of surfactant at the
oil/water interface from bulk oil or water
S = increase in entropy due to dispersion of oil as droplets
 Stability of Microemulsions
Why are microemulsions thermodynamically stable?*
ΔGm ΔGm > 0 for C & D  emulsion formation

+ve D
Unstable Δ Gm = Δ G1 + Δ G2 + Δ G3 - TΔS
C
R*
0 R
B
ΔGm*
A Stable
-ve ΔGm* < 0 for A & B in certain R range
↓
microemulsion formation in that R range

NOTE: Microemulsions form spontaneously only

when IFT is small. (order of 10-3 mN/m)
 Watch the apparent dichotomy !

 1 1 
ΔP  γ  
 R1 R 2 
The Young – Laplace Equation predicts an inverse relation of
pressure drop with droplet radius
 2 
G  V  
R
Further, free energy arguments should predict, a rapid
coalescence of droplets that are < 100 nm

Then why are microemulsions thermodynamically stable?

 Microemulsions are formed because ...

• The penalty for the apparent increase in free energy is

compensated by the lowering of IFT to ultra low
levels (10-2 – 10-3 mN/m)

• The work done in lowering IFT is achieved through a

gain in system entropy ΔS due to the creation of a
large number of sub-micron sized droplets

All this occurs when at molecular levels, surfactants form

the most condensed interfacial film between oil and water
 Microemulsions form when CPP = 1

The most condensed interfacial film between oil and water is

formed when maximum number of surfactants pack – Occurs
when surfactants orient vertically !
 Formulating Microemulsions – Bancroft’s rules
Surfactant Surfactant

Oil Water Oil Water

(CPP < 1) (CPP > 1)

O/W emulsion W/O emulsion

Change in variables (T, Salting out electrolyte etc.)

 Formulating Microemulsions – Bancroft’s rules

Surfactant 3 phase domain

1 phase (oil - E -water)
microemulsion (Bicontinuous E)

W/O or O/W Oil Water

microemulsion

CPP = 1
Sometimes, a co-surfactant such as a short chain alcohol is
used in conjunction with the surfactant to facilitate condensed
interfacial film formation