EMULSIONS

Introduction (11.1-11.4)
Emulsifying agents
Types of emulsions
Tests for emulsion types
Emulsion Stability (11.5-11.6)
Phase Inversion, Creaming
Emulsion Breaking

Introduction
Emulsion Suspension of liquid droplets of certiain size
within a second immiscible liquid.
Stability of an emulsion may vary from a few seconds to
several years.
Classification of emulsions based on size of liquid droplets
0.2 50 m Macroemulsions
0.01 0.2 m Microemulsions

Applications
Agricultural emulsions pesticides
Bituminous emulsions surface coatings, roads, highways
Cosmetics lotions, foundation creams, cold creams,
shaving creams
Paints and Polishes
Metal cutting oils
Food margarine, ice cream.

Emulsifying Agents
Surfactants which exhibit following characteristics
Good surface activity
Should be able to form a condensed interfacial film
Diffusion rate to interface comparable to emulsion forming
time

Examples of Emulsifying Agents

Anionic

Sodium stearate
Potassium laurate
Sodium dodecyl sulfate
Sodium sulfosuccinate
Nonionic Polyglycol
Fatty acid esters
Lecithin
Cationic Quaternary ammo. Salts
Amine hydrochlorides
Finely divided solids may also act as emulsifying agents
e.g. soot and clay (continuous phase wets the powder)

Types of Emulsions
Based on the nature of the dispersed phase, emulsions
can be of two types
Oil in Water (O/W) or
Water in Oil (W/O)

O/W dispersion of a water immiscible liquid (always

called the oil) in an aqueous phase. Oil is the
discontinuous or inner phase and water is the continuous
or outer phase
W/O dispersion of water or an aqueous solution in a
water immiscible liquid

Bancroft's rule
Emulsion type depends more on the emulsifying
agent than on the relative proportions of oil or water
present or the methodology of preparing emulsion.
In general O/W emulsions emulsifying agents that
are more soluble in water than in oil.
W/O emulsifying agents that are more soluble in oil
than in water phase.

Tests for Emulsion Type (W/O or O/W)

Based on the fact many emulsion properties are similar
to continuous phase properties
1.
2.
3.
4.
5.

Dye test
Dilution test
Electrical conductivity measurements
Refractive index measurement
Filter paper test

Emulsion Stability
Rate of coalescence measure of emulsion stability. It
depends on:
(a) Physical nature of the interfacial film for
mechanical stability, surfactant film with strong
lateral intermolecular forces and high film elasticity
is desired.
(consider similarity between emulsion droplets and
bubbles in a foam).
Mixture of two or more surfactants preferred over a
simple surfactant.
Lauryl alcohol + Sodium lauryl sulfate.
NaCl added to increase stability.

(b) Electrical or steric barrier

Significant only in O/W emulsions. In case of nonionic 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.

(c) Viscosity of the continuous phase

Higher viscosity reduces the diffusion coefficient

Which results in reduced frequency of collision and

therefore lesser coalescence.
Viscosity can be increased by adding natural or synthetic
thickening agents.
Also as the no. of droplets
(many emulsion are more stable in concentrated form than
when diluted.)

(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, solubility of surfactant,
thermal agitation, viscosity of liquid, phases of interfacial
film.

Inversion of Emulsions (Phase inversion)

1.

2.

3.
4.

O/W W/O
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
Phase in which the emulsifying agent is dissolved
Dissolving hydrophilic surfactants in the aqueous phase
appears to favor O/W emulsion formation.

5. Temperature of the system

Temperature of O/W (polyoxyethylenated
nonionic surfactant) makes the emulsifier more
hydrophobic and the emulsion may invert to W/O.
6. 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.

Creaming of Emulsions
Droplets larger than 1 m 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
a - droplet radius
WP density difference
H height of the vessel in cm
Creaming can be prevented by homogenization. Also by
reducing WP, creaming may be prevented. This is
achieved by producing a polyphase emulsion
Add water to a W/O emulsion inverts to a O/W

Methods of Emulsion Breaking

1.

Physical methods
(i) Centrifuging
(ii) Filtration media pores preferentially wetted by the
continuous phase
(iii) Gently shaking or stirring
(iv) Low intensity ultrasonic vibrations

2.

Heating
Heating to ~ 700C will rapidly break most emulsions.

3. Electrical methods

Most widely used on large scale

20 kV results in coalescence of entrained water

droplets (W/O) e.g. in oil field emulsions and jet
fuels. (mechanism deformation of water drops into
long streamers)

For O/W, electrophoretic migration of charged

groups to one of the electrodes. Ex. Removing traces
of lubricating oil emulsified in condensed water.

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.

Selection methods (11.8-11.9)

1. HLB method HLB indicative of emulsification
behavior.
HLB

3-6 for
8-18 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.

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 20600C higher than the storage temperature.
For W/O emulsion, PIT of 10-400C lower than the
storage temperature is desired.

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.