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 Mayonnaise: Oil in

continuous phase of Water emulsion
water/glycerol mixture.
 Outline

• Introduction
• Types of emulsions
• Emulsifying agents
• Tests for emulsion types
• Emulsion Stability
• Phase Inversion, Creaming
• Emulsion Breaking
 Introduction
Emulsion – Suspension 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

- Based on size of liquid droplets

0.2 – 50 m Macroemulsions (Kinetically Stable)
0.01 – 0.2 m 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
Stable suspensions of liquids constituting the dispersed
phase, in an immiscible liquid constituting the continuous
phase is brought about using emulsifying agents such as
surfactants

Surfactants must exhibit the following characteristics to be

effective as emulsifiers

- Good surface activity

- Should be able to form a condensed interfacial film
- Diffusion rates to interface comparable to emulsion forming
time
 Common Emulsifying Agents
Surfactants
Anionic – Sodium stearate, Potassium laurate
Sodium dodecyl sulfate, Sodium sulfosuccinate
Nonionic – Polyglycol, Fatty acid esters, Lecithin
Cationic – Quaternary ammonium salts,
Amine hydrochlorides

Solids
Finely divided solids with amphiphilic properties such as
soot, silica and clay, may also act as emulsifying agents
(Pickering Emulsions: Attribute of high stability)
 Surfactant Packing Parameter
• Conceptual framework that relates molecular parameters
(head group area, chain length and hydrophobic tail
volume) and intensive variables (temperature, ionic
strength etc.) to surfactant microstructures
• Critical Packing Parameter /
Packing Parameter
v
CPP or P 
l  a0
v: Volume of hydrocarbon core
l: hydrocarbon chain length
a0: Effective head group area
 Surfactant Packing Parameter
v
CPP or P 
l  a0
v: Volume of hydrocarbon chain= 0.027(n c + nMethyl)

 chain length= 0.15 + 0.127n c

l: hydrocarbon

Where nc = number of carbon atoms without the methyl group

nMethyl = number of methyl groups
ao: Effective head group area: difficult to calculate.
Surfactant Packing Parameter
Packing Parameter is inversely related to HLB
Mid Point of
Packing Parameter
P=1
analogous to
HLB 10

At P = 1/ HLB = 10,
surfactant has equal
affinity for oil and
water
 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).
 Bancroft’s Rule:
Relation to HLB & CPP of Surfactant
Surfactant
Surfactant

Oil Water
Oil Water

Surfactant more soluble in Surfactant more soluble in oil

water (CPP < 1, HLB > 10) (CPP > 1, HLB < 10)
O/W emulsion W/O emulsion
 Bancroft’s Rule:
Relation to HLB & CPP of Surfactant
Surfactant
Surfactant

Packing Parameter = 1

Oil Water
Oil Water

Microemulsion
Surfactant more soluble in Surfactant more soluble in
water (CPP < 1, HLB > 10) oil (CPP > 1, HLB < 10)
O/W emulsion W/O emulsion
 Tests for Emulsion Type
(W/O or O/W emulsions)

Based on the Bancroft’s rule, many emulsion properties are

governed by the properties of the continuous phase

1. Dye test
2. Dilution test
3. Electrical conductivity measurements
4. Refractive index measurement
5. Filter paper test
 Emulsions are Kinetically Stable!
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
(Analogous to stable foam bubbles)

Mixed surfactant system preferred over single surfactant.

(Lauryl alcohol + Sodium lauryl sulfate: hydrophobic interactions)
NaCl added to increase stability (electrostatic screening)
 Emulsions are Kinetically Stable!
(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 are Kinetically Stable!
(c) Viscosity of the continuous phase
Higher viscosity reduces the diffusion coefficient

Stoke-Einstein’s 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 are Kinetically Stable!
(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.
 Phase Inversion in 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.

Based on the Bancroft’s rule, it is possible to change an

emulsion from O/W type to W/O type by inducing changes
in surfactant HLB / CPP.

In other words...
Phase Inversion May be Induced.
Consider systems of 2 immiscible and 1 miscible pairs of liquids
Acetic Acid Surfactant

Tie line

Benzene Water Oil Water

Acetic acid & water are miscible in Surfactant and water are miscible
all proportions in all proportions
Benzene & water - partly miscible, Oil and water - partly miscible,
acetic acid & water - partly miscible surfactant and oil - partly miscible
Acetic acid added to a mixture of Surfactant added to a mixture of oil
benzene & water, preferentially & water, preferentially partitions
partitions into water (slope of tie line) into water (slope of tie line)
 Increase T: At a specific temperature, surfactant becomes Oil
Soluble across all proportions, Acetic Acid does not!
Acetic Acid Surfactant

Benzene Water Oil Water

Increase in Acetic Acid Surfactant Increase in T,
T, P Electrolyte

Benzene Water Oil Water

Why does Phase Inversion Take Place for system with Surfactants?
Surfactant Surfactant

Oil Water Oil Water

O/W emulsion W/O emulsion

Temperature for Non Ionics, Salting out electrolytes for ionics
Bancroft’s Rule: Manifested in Response of Surfactant Solubility

Temperature for Non Ionics, Salting out electrolytes for ionics

O/W emulsion W/O emulsion

Temperature and electrolytes disrupt the water molecules

around non-ionic and ionic surfactants respectively, altering
surfactant solubility in the process
– Also reflected by change in curvature of the interface
 Inversion of Emulsions (Phase inversion)
O/W W/O

1. The order of addition of the phases

W O + emulsifier  W/O
O W + emulsifier  O/W
2. Nature of emulsifier
Making the emulsifier more oil soluble tends to produce a W/O
emulsion and vice versa.
3. 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.
 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
4 3
a gH  kT
3
a - droplet radius, Δρ - density difference,
g - gravitational constant, H - height of the vessel,

Creaming can be prevented by homogenization. Also by reducing

Δρ, creaming may be prevented. This is achieved by producing
a polyphase emulsion
 Methods of Destabilizing Emulsions
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.
 Methods of Destabilizing 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.
 General Guidelines

1. HLB method – HLB indicative of emulsification behavior.

HLB 3-6 for W/O

8-18 for 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 HLB’s of oil and emulsifying agents;
also molecular volumes, shapes and chemical nature.

Limitation – necessary information is available only for

a limited no. of compounds.