EMULSIONS

EMULSIONS

 An emulsion is a dispersion in which the dispersed

phase is composed of small globules of a liquid
distributed throughout a vehicle in which it is
immiscible.
 Disperse system consisting of two immiscible
liquids one of which is distributed in small
globules throughout the other, the system being
stabilized by the presence of third substance
called the emulsifying agent.
 Classification of emulsions :

 Based on dispersed phase

• Oil in Water (O/W): Oil droplets dispersed in water
• Water in Oil (W/O): Water droplets dispersed in oil
• Multiple Emulsions
• O/W/O
• W/O/W
Based on size of liquid droplets
0.2 – 50 mm Macroemulsions
(Kinetically Stable)
0.01 – 0.2 mm Microemulsions
(Thermodynamically Stable)
 Emulsions encountered in everyday life!

Pesticide Asphalt Skin cream

Metal cutting oils Margarine Ice cream

Stability of emulsions may be engineered to vary from
seconds to years depending on application
Emulsifying Agents:
It is a substance which stabilizes an emulsion .

Pharmaceutically acceptable emulsifiers must also :

 be stable.
 be compatible with other ingredients .
 be non – toxic .
 possess little odor , taste , or color .
 not interfere with the stability or efficacy of the
active agent .
Emulsion Type and Means of Detection:
Tests for Emulsion Type (W/O or O/W emulsions)
1) Dilution Test:
- o/w emulsion can be diluted with water.
-w/o emulsion can be diluted with oil.

2) Conductivity Test:
Continuous phase water > Continuous phase oil.
3) Dye-Solubility Test:
- water soluble dye will dissolve in the aqueous
phase.
- oil soluble dye will dissolve in the oil phase.

4) Filter paper test

 Theories of emulsification
1 The viscosity theory
More viscous the emulsion, the less readily will the
dispersed globules move and coalesce.
2. Fischer’s theory of hydrates
Fisher believed that emulsion was a dispersion of an oil in
a colloidal hydrate and not simply a dispersion of oil in
water.
3. Interfacial tension theory
It was shown by Donnan, Hillyer and others that
When high interfacial tension existed between two liquids
emulsification was difficult and that if tension could be
reduced emulsification was facilitated.
4. The Adsorption theory
Bancroft suggestion
Emulsification depended upon the concentration of
emulsifier particles with the formation of film.
Adsorbed particles form a film between the phases and
was wetted by each
Surface tension of different values exist at the two sides
of interfacial film
The side possessing the higher tension would tend to
make the film become concave towards that side.
5. Oriented Adsorption theory
Langmuir and Harkins in 1916 and 1917
The molecules constituting the film are arranged or oriented
in a particular way, depending upon the forces acting upon
them.
A theory of emulsion type
Emulsifier are partly polar and partly non polar
If the molecule is more polar than non polar, tendency to
form bulky hydrates at the polar end.
Oil globules will be formed and oil in water emulsion results.
6. Harkin’s Oriented wedge theory
Experience of soap emulsifiers
Alkali soaps are oil/water emulsifiers and soaps of di and
trivalent elements are water/oil emulsifiers.
Harkins explanation
Diameter of emulsifier molecule differed at each end.
Sodium oleate (C18H33NaO2)has greater diameter at sodium
end wedge shaped
By close packing of such molecules at oil/water interface
curvature of interface towards oil
 Emulsifying agents
These are classified as
Non ionizing substances
Ionizing substances
• Cationic emulsifiers
• Anionic emulsifiers
Natural colloids
Non ionizing substances
Generally they are esters derived from fatty acids
and alcohol.
General formula RCOOR’
Both water in oil and oil in water emulsifiers are
possible.
Glycol monostearate or distearate w/o emulsifiers.
Sorbitan monooleate w/o emulsion
Anionic emulsifying agents
soaps
Alkali soaps and other soaps of inorganic elements
RCOONa and (RCOO)2Ca
Alkali soaps form oil/water emulsions
Soaps of di and trivalent elements form water/oil emulsions
Organic sulphates and sulphonates
In sulphates the sulphur is linked to carbon through an atom
of oxygen
In sulphonates direct linkage of sulphur to carbon
Sodium lauryl sulphate
Lanette wax mixture of cetyl and stearyl alcohols
Sodium cetyl sulphonate
Cationic emulsifying agents
Quaternary ammonium compounds
Cetyl trimethyl ammonium bromide
 Natural colloids
• Phospholipids
Lecithin
• Carbohydrates
Dextrin
Starch
• Cellulose derivatives
• Sterols
cholesterol from wool wax
• Proteins
Gelatin and casein
 Stability of emulsions
An emulsion is considered to be physically unstable if
• Disperse phase upon standing forms aggregates of
globules
• These aggregates rise to the top or fall to the bottom of
the emulsion
The instability of pharmaceutical emulsions may be
classified as
• Creaming
• Coalescence and Breaking
• Phase inversion
 Creaming
Reversible process
Upward creaming o/w emulsions
Downward creaming w/o emulsions
Described by stoke’s law
v r2(d-d1)
18n
Coalescence and Breaking (cracking)
Destruction of the emulsion system
coalescence of dispersed globules and seperation of two
phases
It may be caused by
Presence of substances incompatible with emulsifying
agent
Change in pH
High or low temperature
Bacterial action
Phase inversion
Change in emulsion from oil in water to w/o
type and vice versa
Example
An o/w emulsion stabilized with sodium
stearate can be inverted to w/o type by adding
calcium chloride to form calcium stearate