EMULSIONS

By: Mahpara Almas

Pharm-D, R.PH, M.Phil
(Pharmaceutics)
 Emulsions
1) DEFINITION.
2) TYPES OF EMULSIONS.
3) ADVANTAGES/ DISADVANTAGES.
4) TEST OF IDENTIFICATIONS.
5) EMULSIFYING AGENTS.
6) TYPES OF EMULSIFYING
AGENTS.
7) THEORIES OF EMULSIFICATION.
8) PREPARATION OF EMULSIONS.
9) STABILITY OF EMULSIONS.
 DEFINITION

 An Emulsion is a mixture of two or more

liquids that are normally Immiscible.

Oil
Oil Agitation Oil

Water Water
Water

Separate rapidly into two

clear defined layers

 Emulsion, is a thermodynamically unstable

system consisting of two immiscible liquids in
which one liquid is dispersed as fine globule
throughout the other with the help of
emulsifying agents.
INTERNAL PHASE OR EXTERNAL PHASE
IN EMULSIONS:

 The dispersed liquid is known as

the Internal or Discontinuous phase.

 whereas the dispersion medium is known as

the External or Continuous phase.
 TYPES 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
TYPES OF EMULSION
 Simple emulsions (Macro emulsions)
 Oil-in-water (O/W)
 Water-in-oil (W/O)
 Multiple emulsions
 Oil-in-water-in-oil (O/W/O)
 Water-in-oil-in-water (W/O/W)
 Micro emulsions
TYPES OF EMUSLION

Micro

emulsions
Multiple
Nano
Simple emulsions
emulsions -
emulsions
Oil-in-water-in- Thermodyna
(Macro emulsions)
oil (O/W/O) mically
Water-in-oil-in- stable
Oil-in-water water optically
(O/W) (W/O/W) transparent ,
Water-in-oil
-(W/O)
diameter
greater than
0.1 μm
 GENERAL TYPES OF PHARMACEUTICAL
EMULSIONS

Lotions Linime
-nts

Vitamin
drops Emulsions

Creams
Ointm-
ents
 ADVANTAGES OF EMULSIONS:
 Mask the unpleasant taste O/W is convenient means of
oral administration of water-insoluble liquids.

 Oil-soluble drugs can be given parentrally in form of oil-

in water emulsion. (e.g Taxol).

 Emulsion can be used for external application in

cosmetic and therapeutic Application because of Better
and faster absorption.

 Sustained release medication.

 Nutritional supplement.
 Inert and chemically non-reactive.
 Reasonably odorless and cost Effective.
 Radiopague agents for diagnostic purposes.

 Intravenous Nutrition (maintenance of

debilitated patients)- Intralipid, Nutralipid).
 DISADVANTAGES OF
EMULSIONS:

 Emulsions are thermodynamically unstable

and have short shelf-life.

 Improper formulation of emulsions leads to

creaming and cracking of emulsion.

 Improper selection of emulsifying agent leads

to phase inversion and some times it may
also lead to cracking.
IDENTIFICATION TEST FOR
EMULSIONS:
By using Naked eye, it is very difficult to
differentiate between o/w or w/o emulsions.
Thus, the following methods have been used
to identify the type of emulsions.

1) Dye Test
2) Dilution Test
3) Electrical conductivity Test
4) Fluorescence Test.
5) Cobalt Chloride Test.
1) DYE TEST:
 Water-soluble dye will dissolve in the
aqueous phase.
 Oil-soluble dye will dissolve in the oil phase.
Microscopic View

Oil-soluble dye (e.g. Scarlet) Water-soluble dye (e.g. Amaranth dye)

W/O O/W O/W W/O

Dye Solubility Test
In this test, when an emulsion is mixed with a water soluble dye
such as amaranth and observed under the microscope, if the
continuous phase appears red, then it means that the emulsion is
o/w type as water is the external phase and the dye will dissolve in it
to give color but if the scattered globules appear red and continuous
phase colorless, then it is w/o type. Similarly if an oil soluble dye
such as Scarlet red C or Sudan III is added to an emulsion and the
continuous phase appears red, then it w/o emulsion.
2) DILUTION TEST:
Based on the solubility of external phase of
emulsion.
 O/W emulsion can be diluted with water.

 W/O emulsion can be diluted with oil.

Few drops
of water Water distribute
uniformly O/W emulsion

Few drops Water separate

of emulsion out as layer W/O emulsion
3) ELECTRICAL CONDUCTIVITY TEST:
 As we know water is good conductor of
electricity whereas oil is non-conductor.
Therefore, continuous phase of water runs
electricity more than continuous phase of oil.

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

Electrode
Emulsion
Conductivity Test
This test is based on the basic principle that water is a good conductor of
electricity. Therefore in case of o/w emulsion , this test will be positive as
water is the external phase. In this test. An assembly consisting of a pair
of electrodes connected to a lamp is dipped into an emulsion. If the emulsion
is o/w type, the lamp glows.

01/22/2025 PHT 312 19

3) FLUORESCENCE TEST:
 Oils give fluorescence under UV light, while
water doesn’t.

 Therefore, O/W emulsion shows spotty

pattern when observed under UV.

 while W/O emulsion fluoresces.

4) COBALT CHLORIDE TEST:
 Principle:
 Cobalt Chloride solution is used for

identification of Emulsion. It is water soluble

so it changes colour when encountered by
O/W emulsion.
Procedure:
Filter paper is Dipped in Emulsion.
Filter paper changes its color from blue to Pink

Result:
Emulsion is O/W otherwise not.
DIFFERENCE BETWEEN O/W AND W/O EMULSIONS
Water in oil emulsion (w/o) Oil in water emulsion (o/w)

Oil is the dispersion medium and water Water is the dispersion medium and oil
is the dispersed phase is the dispersed phase

They are greasy and not water washable They are non greasy and easily
removable from the skin surface

They are used externally to prevent They are used externally to provide
evaporation of moisture from the cooling effect e.g. vanishing cream
surface of skin e.g. Cold cream

Oil soluble drugs are more quickly Water soluble drugs are more quickly
released from w/o emulsions released from o/w emulsions

They are preferred for formulations They are preferred for formulations
.meant for external use like creams meant for internal use as bitter taste
.of oils can be masked

W/O emulsions go not give a positive O/W emulsions give a positive

conductivity test as oil is the external conductivity test as water is the
phase which is a poor conductor of external phase which is a good
.electricity .conductor of electricity
01/22/2025 PHT 312 22
 EMULSIFYING AGENT:
 Definition:
 Emulsions are stabilized by adding an
emulsifying agent. These agents have both a
hydrophilic and a Lipophilic part in their
chemical structure.
 All emulsifying agents get adsorbed onto the
Oil : water interface to provide a protective
barrier around the dispersed droplets.
 In addition to this protective barrier,
emulsifiers stabilize the emulsion by
reducing the interfacial tension of the
system.
CLASSIFICATION OF EMULSIFYING
AGENTS:
 Emulsifying agents can be classified
according to: 1) chemical structure:
 Synthetic Emulsifying Agents
 Natural Emulsifying Agents
 Finely Dispersed Solids
 Auxilary Agents

2) Mechanism of action:
 Monomolecular

 Multi-molecular

 Solid particle films.

SYNTHETIC EMULSIFYING AGENTS

1) Anionic: (pH > 8)

 Sodium stearate

 Potassium laurate

 Sodium dodecyl sulfate

 Sodium sulfosuccinate.

 Sodium or potassium oleate

 Triethanolamine stearate

 sodium lauryl sulfate.

2) Cationic: (pH 3-7)

 Benzalkonium chloride,

 Benzethonium chloride

 Quaternary ammonium salts.

 3) NON IONIC (PH 3-10)

 Polyglycol,
 Fatty acid esters,
 Lecithin.
 Sorbitan esters (Spans).
 Polyoxyethylene derivatives of sorbitan
esters (Tweens),
 Glyceryl esters.

* * * Cationic and Anionic surfactants are

generally limited to use in topical, o/w
emulsions * * *
 NATURAL EMULSIFYING AGENTS
Derived from Plants and Animals:
Vegetable derivatives:
 Acacia

 Tragacanth

 Agar

 Pectin

 Carrageenan

 Lecithin

Animal derivatives:
 Gelatin

 Lanolin

 Cholesterol
 FINELY DIVIDED OR FINELY
DISPERSED SOLID PARTICLE EMULSIFIERS
 These agents form a particulate layer around
dispersed particles. Most will swell in the
dispersion medium to increase viscosity. Most
commonly they support the formation of o/w
emulsions, but some may support w/o
emulsions. For Instance,,
 Bentonite
 Veegum,
 Hectorite,
 Magnesium Hydroxide,
 Aluminum Hydroxide
 Magnesium Tri silicate.
 AUXILIARY EMULSIFYING AGENTS

 A variety of fatty acids (e.g., stearic acid),

fatty alcohols (e.g., stearyl or cetyl alcohol),
and fatty esters (e.g., glyceryl monostearate)
serve to stabilize emulsions through their
ability to thicken the emulsion..
 A system was developed to assist in making

systemic decisions about the amounts and

types of surfactants needed in stable
products. The system is called the HLB
(hydrophile-lipophile balance) system and
has an arbitrary scale of 1 - 18. HLB numbers
are experimentally determined for the
different emulsifiers. .
 Low HLB Indicates ?
 Low number of hydrophilic groups on the
Molecule thus imparting Lipophilic character:

 Spans have low HLB numbers, Because of their

oil soluble character, Spans will cause the oil
phase to predominate and form an w/o emulsion.
 High HLB indicates ?

 Emulsifier has a large number of hydrophilic

groups on the molecule thus imparting

hydrophilic Character.
 Tweens have higher HLB numbers, Because of

their water soluble character, Tweens will cause

the water phase to predominate and form an o/w
emulsion.
 HLB VALUE & APPLICATION

 1~3 Anti-foaming
agent.
 3~6 W/o emulsifying
agents.
 7~9 Wetting agents.
 8 ~ 18 O/w emulsifying
agents.
 13 ~15 Detergents.
 15 ~18 Solubilizing
Agents.
HOW TO CALCULATE HLB ????
 Combinations of emulsifiers can produce
more stable emulsions than using a single
emulsifier with the same HLB number. The
HLB value of a combination of emulsifiers can
be calculated as follows:
NUMERICAL 1:
 What is the HLB value of a surfactant system
composed of 20 g Span 20 (HLB = 8.6) and 5
g Tween 21 (HLB = 13.3)?
METHODS OF PREPARATION OF
EMULSIONS:
 Commercially, emulsions are prepared in
large volume mixing tanks and refined and
stabilized by passage through a colloid mill
or homogenizer. Extemporaneous production
is more concerned with small scale methods.

 1) Dry Gum Methods

 2) Wet Gum Methods
 3) Bottle Method
 4) Beaker Method
DRY GUM METHOD FOR PREPARATION
OF EMULSIONS:
 Dry gum method is used to prepare the initial
or primary emulsion from oil, water, and a
hydrocolloid or "gum" type emulsifier.

Dry Gum Methodology

(4 parts oil, 2 parts water, and 1 part

Emulsifier).
 Procedure: Take mortar, 1 part gum is levigated
with the 4 parts oil until the powder is
thoroughly wetted; then the 2 parts water are
added all at once, and the mixture is vigorously
triturated until the primary emulsion formed is
creamy white and produces a "crackling" sound
as it is triturated.

 Active ingredients, preservatives, color, flavors

are added as a solution to the primary emulsion.

 When all agents have been incorporated, the

emulsion should be transferred to a calibrated
vessel, brought to final volume with water.
 WET GUM METHOD
Methodology
(Oil 4 parts + Water 2 parts + Emulsifier 1 parts)
Procedure: In this method, the proportions of oil,
water, and emulsifier are the same (4:2:1), but
the order and techniques of mixing are
different. The 1 part gum is triturated with 2
parts water to form a mucilage; then the 4
parts oil is added slowly, in portions, while
triturating. After all the oil is added, the
mixture is triturated for several minutes to
form the primary emulsion. Then other
ingredients may be added as in the continental
method. Generally speaking, the English
method is more difficult to perform
successfully, especially with more viscous oils,
but may result in a more stable emulsion.
 BOTTLE METHOD
 This method may be used to prepare emulsions
of volatile oils, Oleaginous substances of very low
viscosities.

 This method is a variation of the dry gum

method.

 One part powdered acacia (or other gum) is

placed in a dry bottle and four parts oil are
added. The bottle is capped and thoroughly
shaken. To this, the required volume of water is
added all at once, and the mixture is shaken
thoroughly until the primary emulsion forms.
 Reference:
http://pharmlabs.unc.edu/labs/emulsions/beaker.h
tm
 BEAKER METHOD
 The most appropriate method.
 Dividing components into water soluble and
oil soluble components.
 All oil soluble components are dissolved in
the oily phase in one beaker and all water
soluble components are dissolved in the
water in a separate beaker.
 Oleaginous components are melted and both
phases are heated to approximately 70°C
over a water bath. The internal phase is then
added to the external phase with stirring
until the product reaches room temperature.
Water

Oil
CLASSIFICATION OF EMULSIONS
BASED ON MECHANISM OF ACTION:

1) Monomolecular film: To reduce the interfacial

tension Oil droplets are surrounded by a coherent
monolayer of the surfactant which prevents coalescence. If
the emulsifier is ionized, the presence of strong charge may
lead to repulsion in droplets and hence increasing stability.
Adsorbed at oil/water interface to form

2) Multimolecular film or Hydrophillic Colloids

3) Finely divided solid particles: They are adsorbed

at the interface between two immiscible liquid
phases to form Particulate film.
STABILITY OF EMULSION
 There are 2 intermolecular forces which affect the stability of
dispersed system.
 Van der Waals force is an attractive force, which tends to
destabilize the emulsion.
 Electrostatic force is a repulsive force, which gives stability to the
emulsion.
 When the total attractive forces > total repulsive forces, the
emulsion is unstable.
 When total repulsive forces > total attractive forces, the emulsion
is stable.
 Often, emulsions are inherently unstable.
 The small suspended droplets first coalesce into less stable, larger
droplets. This coalescence then continues until the emulsion breaks
into two layers.
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THEORIES OF EMULSIFICATION:
Many theories have been advanced to account
for the way or means by which the emulsion
is stabilized by the emulsifier. At the present
time no theory has been postulated that
seems to apply universally to all emulsions.

1) Electric Double Layer Theory.

2) Phase Volume Theory.
3) Hydration Theory of Emulsions
4) Oriented wedge theory.
5) Adsorbed Film and Interfacial tension
Theory
1) ELECTRIC DOUBLE LAYER THEORY:
A double layer (DL, also called an electrical
double layer, EDL) is a structure that appears
on the surface of an object when it is exposed
to a fluid. The object might be a solid particle,
a gas bubble, a liquid droplet, or a porous body
.
The DL refers to two parallel layers of charge
surrounding the object.
The first layer, the surface charge (either
positive or negative), comprises ions adsorbed
onto the object due to chemical interactions.
The second layer is composed of ions attracted
to the surface charge via the coulomb force,
electrically screening the first layer.
EDL
 This second layer is loosely associated with
the object. It is made of free ions that move
in the fluid under the influence of
electric attraction and thermal motion rather
than being firmly anchored. It is thus called
the "diffuse layer".
 The oil globules in a pure oil and pure water

emulsion carry a negative charge. The water

ionizes so that both hydrogen and hydroxyl
ions are present. The negative charge on the
oil may come from adsorption of the OH ions.
These adsorbed hydroxyl ions form a layer
around the oil globules.
 . A second layer of oppositely charged ions
forms a layer in the liquid outside the layer of
negative ions. These two layers of oppositely
charged ions are known as the Helmholtz
double layer. They are not confined to
emulsions but accompany all
boundary phenomena. The electric charge is
a factor in all emulsions, even those
stabilized with emulsifying agents.
 When a colloidal particle moves in the dispersion

medium, a layer of the surrounding liquid remains

attached to the particle.
 The boundary of this layer is called slipping plane

(shear plane).
ELECTRICAL DOUBLE LAYER.
 The Electric Double Layer is electrically neutral.
 It consists of three parts:

Surface charge - charged ions (commonly negative)

adsorbed on the particle surface.
 Stern layer – counter-ions (charged opposite to the surface

charge) attracted to the particle surface and closely attached

to it by the electrostatic force.
 Diffuse layer - a film of the dispersion medium (solvent)

adjacent to the particle. Diffuse layer contains free ions

with a higher concentration of the counter-ions. The ions of
the diffuse layer are affected by the electrostatic force of the
charged particle.
 It is sensitive to electrolytes and temperature.
2) PHASE VOLUME THEORY:
If spheres of the same diameter are packed as
closely as possible, one sphere will touch 12
others and the volume the spheres occupy is
about 74 per cent of the total volume. Thus if
the spheres or drops of the dispersed phase
remain rigid it is possible to disperse 74 parts of
the dispersed phase in the continuous phase;
but if the dispersed phase is increased to more
than 74 parts of the total volume, a reversal of
the emulsion will occur. However, the dispersed
phase does not remain rigid in shape but the
drops flatten out where they come in contact
with each other, nor are all the dispersed
particles the same, so that it is possible for the
dispersed phase to consist of from 1 to 99 per
cent of the emulsion.
3) HYDRATION THEORY OF
EMULSIONS:
 Fischer and Hooker state that hydrated
colloids make the best emulsifiers. Fischer
states the emulsifying agent, by which a
permanent emulsion is obtained, invariably
"proves to be a hydrophilic colloid when
water and oil emulsions are concerned.
 Fischer and Hooker have found albumin,

casein, and gelatin to be good emulsifying

agents.
4) ORIENTED WEDGE THEORY:
 This theory deals with formation of monomolecular layers
of emulsifying agent curved around a droplet of the internal
phase of the emulsion.
Example:
 In a system containing 2 immiscible liquids, emulsifying

agent would be preferentially soluble in one of the phases

and would be embedded in that phase.

 Hence an emulsifying agent having a greater hydrophilic

character will promote o/w emulsion and vice-versa.

 Sodium oleate is dispersed in water and not oil. It forms a

film which is wetted by water than by oil. This leads the film
to curve so that it encloses globules of oil in water.

 Sodium Oleate Zinc Oleate

ORIENTED WEDGE THEORY
5) ADSORBED FILM AND INTERFACIAL
TENSION THEORY:
 Lowering interfacial tension is one way to make
emulsion stable. Assuming the droplets are
spherical,

 ΔF= 6 γV
D
 V= volume of the dispersed phase in ml, d is the
mean diameter of the particles.
 γ = interfacial tension

 It is desirable that:
 The surface tension be reduced below
10dynes/cm by the emulsifier and Be absorbed
quickly.
SURFACE TENSION

 Surface tension is a phenomenon in which

the surface of a liquid, where the liquid is in
contact with gas, acts like a thin elastic
sheet.
 This term is typically used only when the

liquid surface is in contact with gas (such as

the air).
 If the surface is between two liquids (such as

water and oil), it is called "interface tension."

6) SURFACE TENSION THEORY
6) SURFACE TENSION THEORY:
 According to this theory, emulsification takes
place by reduction of interfacial tension
between two phases.
 when oil and water are mixed it becomes

immiscible due to the presence of surface

tension. The use of surfactants result in the
lowering of interfacial tension between two
immiscible liquids.
 Surface Tension- Force that has to be applied

parallel to the surface of liquid to

counterbalance exactly the internal inward
forces that tend to pull the molecule together.
 When there are two immiscible liquids-it is

called interfacial tension.

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