Emulsion

suitable for
intravenous
injection.

Balm: Water in oil emulsion

Emulsions

Sodas: Oil in Water emulsion

Milk: Oil in Water
emulsion

Dodecane droplets in a
continuous phase of
water/glycerol mixture.

Mayonnaise: Oil in
Water emulsion

Emulsion Dispersion of liquid droplets (dispersed phase) of

certain size within a second immiscible liquid (continuous
phase).
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
Water in Oil in water (W/O/W): Water in Oil emulsion
dispersed in water multiple emulsion

- Based on size of liquid droplets

0.2 50 mm Macroemulsions
0.01 0.2 mm Microemulsions

Advantages

Administration of Distasteful oil, mask the

unpleasant taste
Better and faster absorption
Less irritation to the skin
Sustained release medication
Nutritional supplement
Diagnostic purposes

Emulsions encountered in everyday life!

Pesticide

Asphalt

Skin cream

Ice cream
Metal cutting oils
Margarine
Stability of emulsions may be engineered to vary from
seconds to years depending on application

Emulsifying Agents
Stable dispersions of liquids constituting the dispersed phase,
in an immiscible liquid constituting the continuous phase is
brought about using emulsifying agents such as
Carbohydrates: acacia, tragacanth, agar, chondrus and pectin

Proteins: gelatin, egg yolk and casein

High mol wt alcohols: stearyl alcohol, cetyl alcohol,
glycery monostearate, cholesterol w/o stabilisers
Surfactants: SPAN, TWEEN, organic soaps
( triethanolamine oleate),
Non ionic- pH 3-10, cationic 3-7, anionic- greater than 8

Common Emulsifying Agents

Surfactants
Anionic Sodium stearate, Potassium laurate
Sodium dodecyl sulfate, Sodium sulfosuccinate
Nonionic Polyglycol, Fatty acid esters, Lecithin
Cationic Quaternary ammonium salts,
Finely divided Solids
Finely divided solids with amphiphilic properties such as
silica and clay, may also act as emulsifying agents
Others: bentonite, magnesium hydroxide, Al(OH)3

Tests for Emulsion Type

(W/O or O/W emulsions)
Based on the Bancrofts rule, many emulsion properties are
governed by the properties of the continuous phase
1.
2.
3.
4.

Dye test
Dilution test
Electrical conductivity measurements
Filter paper test

Thermodynamic instability
G=.A
Increase in the surface free energy =
interfacial tension X increased surface area

Mechanism of emulsification
Monomolecular theory
Surfactants
Reduce interfacial tension
Forms a protective film around globule
Ionic surfactant exert repulsion between
globules

Mechanism
Multimolecular theory
Hydrocolloids form multimolecular
physical barrier around globules there by
prevent coalescence of oil globules
Acacia, gelatin
Solid particle adsorption theory

Physical Instability
Creaming: Concentration of globules at the top or bottom of
emulsion.
Reversible process but leads to breaking
Influenced by: Stokes equation

V = h = d2st (so) g
t
18o
-globule size
-Viscosity of dispersion medium
-Difference in the densities of dispersed and dispersion
medium

Creaming of Emulsions
Droplets larger than 1 mm may settle preferentially to the top or the
bottom under gravitational forces.
Creaming is an instability but not as serious as coalescence or
breaking of emulsion
Probability of creaming can be reduced if

4 3
a gH kT
3
a - droplet radius, - density difference,
g - gravitational constant, H - height of the vessel,
Creaming can be prevented by homogenization. Also by reducing
, creaming may be prevented.

Creaming can be
reduced/prevented by
Reducing the globule size by
homogenization
Increasing the viscosity of dispersion
medium
Reducing the difference in densities

Coalescence
Separation of two phases due to fusion of globules.
Also called cracking of emulsion.
Irreversible process.
Sheath of EA around globules is lost.
Creaming leads to breaking- globules comes nearer
Breaking of emulsion is observed due to:
Insufficient amount of EA
Incompatibility between EA

Alteration in the properties of EA

Inversion of Emulsions (Phase inversion)

O/W W/O
1.

2.

3.

The order of addition of the phases

W O + emulsifier W/O
O W + emulsifier O/W
Nature of emulsifier
Making the emulsifier more oil soluble tends to produce a W/O
emulsion and vice versa.
Phase volume ratio
Oil/Water ratio W/O emulsion and vice versa

Inversion of Emulsions (Phase inversion)

4. Temperature of the system
Temperature of O/W (polyoxyethylenated nonionic
surfactant) makes the emulsifier more hydrophobic and the
emulsion may invert to W/O.
5. Addition of electrolytes and other additives.
Strong electrolytes to O/W (stabilized by ionic surfactants)
may invert to W/O
Example. Inversion of O/W emulsion (stabilized by sodium
cetyl sulfate and cholesterol) to a W/O type upon addition
of polyvalent Ca.

W/O vs. O/W emulsions

Bancroft's rule
Emulsion type depends more on the nature of the emulsifying agent
than on the relative proportions of oil or water present or the
methodology of preparing emulsion.
The phase in which an emulsifier is more soluble constitutes the
continuous phase
In O/W emulsions emulsifying agents are more soluble in water
than in oil (High HLB surfactants).
In W/O emulsions emulsifying agents are more soluble in oil than
in water (Low HLB surfactants).

Emulsions
Rate of coalescence measure of emulsion stability.
It depends on:
(a) Physical nature of the interfacial surfactant film
For Mechanical stability, surfactant films are characterized
by strong lateral intermolecular forces and high elasticity
Mixed surfactant system preferred over single surfactant.
(Lauryl alcohol + Sodium lauryl sulfate: hydrophobic interactions)
combination of SPAN and TWEEN

Emulsions
(b) Electrical or steric barrier
Significant only in O/W emulsions.
In case of non-ionic emulsifying agents, charge may arise due to
(i) adsorption of ions from the aqueous phase or
(ii) contact charging (phase with higher dielectric constant is charged
positively)
No correlation between droplet charge and emulsion stability in W/O
emulsions
Steric barrier dehydration and change in hydrocarbon chain
conformation.

Emulsions
(c) Viscosity of the continuous phase
Higher viscosity reduces the diffusion coefficient
Stoke-Einsteins Equation
This results in reduced frequency of collision and therefore
lower coalescence. Viscosity may be increased by adding
natural or synthetic thickening agents.

Further, as the no. of droplets

(many emulsion are more stable in concentrated form than when
diluted.)

Emulsions
(d) Size distribution of droplets
Emulsion with a fairly uniform size distribution is more stable than
with the same average droplet size but having a wider size
distribution
(e) Phase volume ratio
As volume of dispersed phase stability of emulsion
(eventually phase inversion can occur)
(f) Temperature
Temperature , usually emulsion stability
Temp affects Interfacial tension, D, solubility of surfactant,
Brownian motion, viscosity of liquid, phases of interfacial film.

Preparation of emulsion
Dry gum method
Wet gum method
Bottle method

Selection of Emulsifiers
Correlation between chemical structure of surfactants and
their emulsifying power is complicated because
(i) Both phases oil and water are of variable compositions.
(ii) Surfactant conc. determines emulsifier power as well as the
type of emulsion.

Basic requirements:
1. Good surface activity
2. Ability to form a condensed interfacial film
3. Appropriate diffusion rate (to interface)

General Guidelines:
1.

Type of emulsion determined by the phase in which emulsifier

is placed.

2.

Emulsifying agents that are preferentially oil soluble form W/O

emulsions and vice versa.

3.

More polar the oil phase, the more hydrophilic the emulsifier
should be. More non-polar the oil phase more lipophilic the
emulsifier should be.

General Guidelines
1.

HLB method HLB indicative of emulsification behavior.

HLB

3-6
8-18

for
for

W/O
O/W

HLB no. of a surfactant depend on which phase of the final emulsion

it will become.

Limitation does not take into account the effect of temperature.

General Guidelines
2. PIT method At phase inversion temperature, the hydrophilic
and lipophilic tendencies are balanced.

Phase inversion temperature of an emulsion is determined

using equal amounts of oil and aqueous phase + 3-5%
surfactant.
For O/W emulsion, emulsifier should yield PIT of 20-600C
higher than the storage temperature.
For W/O emulsion, PIT of 10-400C lower than the storage
temperature is desired.

General Guidelines
3.

Cohesive energy ratio (CER) method

Involves matching HLBs of oil and emulsifying agents;
also molecular volumes, shapes and chemical nature.
Limitation necessary information is available only for
a limited no. of compounds.