EMULSIONS

UNIT 2
 An emulsion is liquid preparation containing two immiscible
liquids, one of which is dispersed as globules (dispersed phase) in
the other liquid (continuous phase).

Microemulsion : Droplets size range 0.01 to 0.1µm

Macroemulsion : Droplets size range approximately 5µm

Two Immiscible Liquids

dispersed phase Dispersed Phase

(Internal phase)
Continuous Phase
(External phase)

continuous phase

An emulsion is a thermodynamically unstable system consisting of

at least two immiscible liquid phases one of which is dispersed as
globules in the other liquid phase stabilized by a third substance
called emulsifying agent.
Emulsions are also called heterogeneous systems or biphasic systems
 Examples for emulsions:- milk, rubber latex, crude oil etc.

Phase A

Phase B
B C D
A

A.: Two immiscible liquids not emulsified

B. An emulsion of phase A dispersed in Phase B
C. Unstable emulsion slowly separates.
D. The emulsifying agent ( black film) places it self on the interface between phase A and phase
B and stabilizes the emulsion. 3
 Types of emulsions

Simple emulsions (Macro emulsions)

• Oil-in-water (O/W)
• Water-in-oil (W/O)

Oil is dispersed phase

water is dispersed phase
water is continuous phase
oil is continuous phase

O/W emulsion W/O emulsion

4
Multiple emulsions: the dispersed phase comprises smaller
droplets having same composition as external phase. It
occurs due to double emulsification & are also termed as
double emulsion.
Oil-in-water-in-oil (O/W/O) : Aqueous phase separates
internal and external oil phase. System in which water
droplets may be surrounded in oil phase which in true
encloses one or more oil droplets.
Water-in-oil-in-water (W/O/W): oily phase separates internal
and external aqqueous phase. System in which oil droplets
may be surrounded in aqueous phase which in true encloses
one or more water droplets.

Microemulsions: Thermodynamically stable optically

transparent , mixtures of a biphasic oil –water
system stabilized with surfactants with droplet size
of 5-140nm.
 using of naked eye, it is very difficult to differentiate between o/w or w/o
emulsions. Thus, the four following methods have been used to identify the type if
emulsions.
Dilution test:
In this test the emulsion is diluted either with oil or water. If the emulsion is
o/w type and it is diluted with water, it will remain stable as water is the
dispersion medium" but if it is diluted with oil, the emulsion will break as oil
and water are not miscible with each other.
o/w emulsion can be diluted with water.
w/o emulsion can be diluted with oil.

Add drops of water

Add drops of water

Water distribute
Uniformly

O/W Emulsion W/O Emulsion

Conductivity Test: water is good conductor of electricity whereas
oil is non-conductor. Therefore, continuous phase of water runs
electricity more than continuous phase of oil.

Emulsion Emulsion

Bulb glows with O/W Bulb doesn’t glow with W/O

 Water Soluble Dye Ex. Amaranth Dye
DYE TEST:

water is continuous phase

Oil is dispersed phase

O/W EMULSION

oil is continuous phase

water is dispersed phase

W/O EMULSION
Water-soluble dye will dissolve in the aqueous phase.
 Oil Soluble Dye Ex. scarlet

water is continuous phase

Oil is dispersed phase

O/W EMULSION

oil is continuous phase

water is dispersed phase

W/O EMULSION
Oil-soluble dye will dissolve in the oil phase.
 oils give fluorescence under UV
light, while water doesn’t. Therefore, O/W emulsion
shows spotty pattern while W/O emulsion fluoresces.

When a w/o emulsion is exposed to fluorescent light

under a microscope the entire field fluorescence. If the
fluorescence is spotty, then the emulsion is of o/w-type.
 However, all oils do not exhibit fluorescence under UV
light and thus the method does not have universal
application.
It is necessary that the results obtained by one method
should always be confirmed by means of other methods
5.Creaming test.

The direction of creaming identifies the emulsion type,

if the densities of aqueous and oil phases are known.

Water-in-oil emulsions normally cream downward as oil

is usually less dense than water.

Oil-in-water emulsions normally cream upwards.

(a) Flocculation and creaming
(b) Coalescence and breaking
(c) Miscellaneous physical and chemical changes
(d) Phase inversion.

Flocculation
• Neighboring globules come closer to each other and form
colonies in the continuous phase. This aggregation of
globules is not clearly visible.
• This is the initial stage that leads to instability.
• Flocculation of the dispersed phase may take place before,
during or after creaming.
• The extent of flocculation of globules depends on
(a) globule size distribution.
(b) charge on the globule surface.
(c) viscosity of the external medium.

(a) Globule size distribution

• Uniform sized globules prevent flocculation.
• This can be achieved by proper size reduction process.

(b) Charge on the globule surface

• A charge on the globules exert repulsive forces with the
neighboring globules.
• This can be achieved by using ionic emulsifying agent,
electrolytes etc.
(c)Viscosity of the external medium.
• If the viscosity of the external medium is increased, the
globules become relatively immobile and flocculation can
be prevented.
• This can be obtained by adding viscosity improving agents
(bodying agents or thickening agents) such as
hydrocolloids or waxes.
• Flocs slowly move either upward or downward leading to
creaming.
Creaming
• Creaming is the concentration of globules at the top or
bottom of the emulsion.

• Droplets larger than 1 mm may settle preferentially to the

top or the bottom under gravitational forces.

• Creaming may also be observed on account of the difference

of individual globules (movement rather than flocs).

• It can be observed by a difference in color shade of the layers.

• It is a reversible process, i.e., cream can be redispersed easily
by agitation, this is possible because the oil globules are still
surrounded by the protective sheath of the emulsifier.
• Creaming results in a lack of uniformity of drug distribution.
This leads to variable dosage. Therefore, the emulsion should
be shaken thoroughly before use.
• Creaming is of two types, upward creaming and downward
creaming
• Upward creaming, is due to the dispersed phase is less dense than the
continuous phase.This is normally observed in o/w emulsions.

• Downward creaming occurs if the dispersed phase is heavier than the

continuous phase. Due to gravitational pull, the globules settle down. This
is normally observed in w/o emulsions.

• Since creaming involves the movement of globules in an emulsion, Stokes’

law can be applied.
ν = d2 (ρs – ρ0)g
18 η0
ν = terminal velocity in cm/sec,
d is the diameter of the particle in cm,
ρs and ρ0 are the densities of the dispersed phase and dispersion medium respectively,
g is the acceleration due to gravity and
η0 is the viscosity of the dispersion medium in poise.
• Creaming is influenced by,
– Globule size
– Viscosity of the dispersion medium
– Difference in the densities of dispersed phase and dispersion medium.

Creaming can be reduced or prevented by:

1. Reducing the particle size by homogenization. Doubling the diameter of

oil globules increases the creaming rate by a factor of four.

2. Increasing the viscosity of the external phase by adding the thickening

agents such as methyl cellulose tragacanth or sodium alginate.
3. Reducing the difference in the densities between the dispersed
phase and dispersion medium.

• Adjusting the continuous phase and dispersed phase densities

to the same value should eliminate the tendency to cream.
• To make densities equal, oil soluble substances such as
bromoform, β-bromonaphthalene are added to the oil phase
(rarely used technique).
Coalescence

• If the sizes of globules are not uniform, globules of smaller size

occupy the spaces between the larger globules. A few globules
tend to fuse with each other and form bigger globules.

• This type of closed packing induces greater cohesion which

leads to coalescence.

• In this process, the emulsifier film around the globules is

to a certain extent. This step can be recognized by
increased globule size and reduced number of globules.
Coalescence is observed due to:
 Insufficient amount of the emulsifying agent.
 Altered partitioning of the emulsifying agent.
 Incompatibilities between emulsifying agents.

• Phase volume ratio of an emulsion has a secondary

influence on the stability of the product and represents the
relative volume of water to oil in emulsion.

• As the concentration of dispersed phase increases in

comparison to continuous phase the stability decreases.
• At higher ratio (>74% of oil to water), globules are closely
packed, wherein small globules occupy the void spaces
between bigger globules.

• Thus globules get compressed and become irregular in shape,

which leads to fusion of adjacent globules.

• Ostwald and others have shown that if one attempts to

incorporate more than about 74% of oil in an o/w emulsion,
the oil globules often coalesce and the emulsion breaks.

• This value known as the critical point, is defined as the

concentration of the dispersed phase above which the
emulsifying agent cannot produce a stable emulsion of the
desired type.
Breaking

• Separation of the internal phase from the external phase is

called breaking of the emulsion.

• This is indicated by complete separation of oil and aqueous

phases, is an irreversible process, i.e., simple mixing fails. It is
to resuspend the globules into an uniform emulsion.

• In breaking, the protective sheath around the globules is

completely destroyed and oil tends to coalesce.
THEORIES OF EMULSIFICATION/ MOA OF EMULSIFYING AGENTS

1. Monomolecular Adsorption and Film Formation Theory

Surfactants adsorb at the oil water interface and form a monomolecular film
which rapidly envelopes the droplets as soon as they are formed.
Monomolecular film should be compact and strong enough so that it cannot be
easily distributed or broken. Even if it breaks it should be elastic and flexible
enough so that it can be reformed rapidly on moderate agitation.

Usually inspite of a single surfactant a combination of surfactant is used to

impart these characteristics to the interface. Surfactant blend consist of blend
of oil and water soluble surfactants.

Hydrophilic surfactant approaches interface from aqueous phase side while oil
soluble surfactant approaches from oil phase side. At interface two surfactants
interact to form a complex and condense as a monomolecular film.
Surfactants are capable of reducing the interfacial tension which facilitates the immediate
formation of small droplets which can be understood by considering surface free energy
changes during emulsification.

∆G= γo/w x ΔA
γo/w= interfacial tension of oil-water interface
∆A = increase in surface area of the interface due to droplet formation
In equation (1), the interfacial tension, γo/w may be reduced, so that the system can
be stable.

Hence the term ∆G cannot be made zero. However surface active agents are added
to reduce γo/w value to a minimum.

Thus, the system can be stabilized to a certain extent.

Certain emulsifying agents can reduce the surface tension thereby prevent
coalescence.
Multimolecular Layer Adsorption Theory

• The emulsifying agents such as acacia and gelatin, tend to form

a

• Their action as emulsifying agents is mainly due to the

formation of multimolecular film at the interface and because
the films thus formed are strong and resist coalescence.

• They do not cause appreciable lowering of interfacial tension.

• An additional effect of these hydrocolloids is significant

increase in viscosity of medium which in turn decreases
coalescence

• Since the emulsifying agents that form multilayer films around

the droplets are , they tend to
promote the formation of
 SOLID PARTICULATE ADSORPTION THEORY

• Finely divided solid particles that are wetted by both oil and water
i.e. having suitably balanced hydrophilic and lipophilic properties
.

• They
, where they produce a
around dispersed droplets.

• This film acts as a mechanical barrier and prevents the coalescence

and tend to produce coarse emulsions.

• Depending on the affinity of the emulsifier to a particular phase one

can prepare both types of emulsions

• Powders preferentially wetted by water results in o/w emulsions eg.,

bentonite.
• Powders easily wetted by oil results in w/o emulsions eg., veegum
 Preservation of Emulsion
• Preservation from microorganisms:
• It is necessary to preserve the emulsions from microorganisms as these can
proliferate easily in emulsified systems with high water content,
particularly if carbohydrates, proteins or steroidal materials are also
present.
• Contamination due to microorganisms can result in problems such as color
and odor change, gas production, hydrolysis, pH change and eventually
breaking of emulsion.
• Therefore is necessary that emulsified systems be adequately preserved.

An ideal preservative should be nonirritant, nonsensitizing and nontoxic in

the concentration used.
• It should be physically as well as chemically compatible with other
ingredients of the emulsions and with the proposed container of the
product.
• It should not impart any taste, color or odor to the product.
Preservation from oxidation:

• Oxidative changes such as rancidity and spoilage due to atmospheric oxygen

and effects of enzymes produced by micro-organisms is seen in many
emulsions containing vegetables and mineral oils and animal fats.
• Antioxidants can be used to prevent the changes occurring due to
atmospheric oxygen.
• Antioxidants are agents having a high affinity for oxygen and complete for it
with labile substances in the formulation.

The ideal antioxidant should be:

• nontoxic, nonirritant,
• effective at low concentration under the expected conditions of storage and
use,
• soluble in the medium and stable.
• Antioxidants for use in oral preparation should also be odorless and
tasteless.
• Some of the commonly used antixidants for emulsified systems include alkyl
gallate such as ethyl, propyl or dodecyl gallate, butylated hydroxyanisole
(BHT), butylated hydroxytoluene (BHT)
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