KOMAR UNIVERSITY

OF SCIENCE AND TECHNOLOGY

Monica Diyya,
Department of Pharmacy,
College of Medicine.
Course Name: Physical Pharmacy-I

UNIT III: Dispersed systems-I

Lesson No: 03B-Emulsions

2
 UNIT III
Lesson 03B

Contents

➢Introduction to dispersed systems

➢Emulsions: Introduction and classification
➢Factors affecting type of emulsion
➢Stabilization of emulsion
➢Mechanism of action of emulsifying agent: Structure of
surfactant molecule
➢Theories of emulsification
➢Pharmaceutical applications of emulsion
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 Introduction to dispersed systems

Dispersed systems consist of particulate matter, known as

the dispersed phase, distributed throughout a continuous
or dispersion medium.

The dispersed material may range in size from particles of

atomic and molecular dimensions to particles whose size
is measured in millimeters.

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 Classification of dispersed systems on the basis of particle size
Class Range of Particle size* Characteristics of Examples
size
*1 nm (nanometer)=10-9;
1 µm (micrometer)=10-6

:÷¥É
Molecular Less than 1 nm Invisible in electron Oxygen molecules,
dispersion microscope. ordinary ions,
Undergo rapid glucose
diffusion
Colloidal < 1 µm Visible in electron Colloidal silver
dispersion microscope. Diffuse solutions, cheese,
very slowly butter, jelly, milk,
shaving cream etc.
Coarse dispersion > 1 µm Visible under Grains of sand, most
microscope. Do not pharmaceutical
diffuse emulsions and
suspensions, red
blood cells
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Emulsions
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.
unstable
Phase A
Emulsion
an
Agent
→ )
Phase B ☒ m

coat
-

A
B C w
D
A.Two immiscible liquids not emulsified
B. An emulsion of phase B dispersed in Phase A stabilize
C. Unstable emulsion slowly separates.
D. The emulsifying agent ( as a film) places it self on the interface between
phase A and phase B and stabilizes the emulsion.

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Types of emulsions
1. Simple emulsions (Macro emulsions)
• Oil-in-water (O/W)
• Water-in-oil (W/O)

2. Multiple emulsions
• Oil-in-water-in-oil (O/W/O)
• Water-in-oil-in-water (W/O/W)

3. Micro emulsions

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1. Simple Emulsions( Macro emulsions):

Parameter O/W Emulsion W/O Emulsion

Internal phase Oil Water
External phase (>45% Water Oil
by composition)
Emulsifying agent Hydrophilic emulsifier Lipophilic emulsifier
Application/Uses Oral administration, cosmetics, (treatment
cosmetics of dry skin, emollient
applications), oil
soluble vitamin
supplements)

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 2. Multiple emulsions :

•
➢They are developed with a view to delay the release of an active
ingredient.
➢They have three phases.
➢They may be oil-in-water-in-oil (o/w/o) or of water-in-oil-in-water
(w/o/w).
An emulsifier is present to stabilize the emulsions and various
ionic and nonionic surfactants are available for this purpose.

¥
:É⑤
Lipophilic (oil-soluble, low HLB) surfactants are used to stabilize
w/o emulsions, whereas hydrophilic (water-soluble, high HLB)
surfactants are used to stabilize o/w systems In these emulsions
within emulsions any drug present in innermost phase must now
cross two phase boundaries to reach the external continuous
phase.
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 Multiple emulsions

w/o/w o/w/o

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Multiple emulsions

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3. Micro emulsions:

They may be defined as dispersions of insoluble liquids in a second liquid

that appears clear and homogenous to the naked eye. They are frequently

•
called solubilised systems because on a macroscopic basis they seem to
behave as true solutions.
Microemulsions are thermodynamically stable optically transparent ,
mixtures of a biphasic oil –water system stabilized with surfactants.
Parameter Microemulsion Emulsion

Transparent Yes No
Size 10-120 nm 0.1 – 10 µ
Formation Spontaneous Require vigorous shaking

Type o/w, w/o o/w, w/o, w/o/w, o/w/o

Stability Thermodynamically stable Thermodynamically unstable

Viscosity Can accommodate 20 to 40% More viscous

without increase in viscosity 12
Micro emulsions

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 → simple
Factors affecting type of emulsion → micro Em .

→ multiple
1. Type of emulsifying agent used so / → EX Phase
2. Phase volume ratio
greater
amounts Ext
3. Viscosity of each phase
.

Ph
↑ viscosity → EX

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1. Type of emulsifying agent :
• Type of emulsion is a function of relative solubility of emulsifying
agent . The phase in which it is soluble becomes the continuous phase.
2. The phase volume ratio: (the relative amount of oil and water)
• This determines the relative number of droplets formed and hence
the probability of number of collision. The greater the number of
droplets, greater is the chance for collision. Thus, the phase present in
greater amount becomes the external phase.
• The polar portions of the emulsifying agents are better barriers to
coalescence than hydrocarbon counterparts. So o/w emulsions can be
formed with relatively high internal phase volume. In w/o emulsion (
in which the barrier is of hydrocarbon nature) if the amount of internal
phase is increased more than 40 % , it inverts to o/w emulsion
because hydrocarbon part of surfactant can not form a strong barrier.
3. Viscosity of each phase :
• An increase in viscosity of a phase helps in making that phase the
external phase.
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 Stabilization of Emulsion
Globules (dispersed phase) can be stabilized by
the following methods:

1. By reducing interfacial tension

2. By formation of rigid interfacial film
3. By forming electrical double layer

↓ Interfacial
Rigid ← ⑧ tension
layer charge
*
¥1m
↳
£
-

in
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 Stabilization of emulsion:

1. Reduction of interfacial tension

Change from A to B
A increases surface area of
Phase A
phase A, hence the due to
Phase B increased surface energy, the
system is thermodynamically
B unstable.

• Emulsifying agents are needed to decrease the interfacial

tension and to stabilize the emulsion.
• To make a stable emulsion droplets have to be stabilized so
that they do not coalesce.
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 Mechanism of action of emulsifying agents

• Droplets can be stabilized by making use of emulsifying

agents .
➢Emulsifying agents assist in the formation of emulsion by
lowering the interfacial tension.
• Lowering of interfacial tension results in thermodynamic
stabilization.
• Interfacial tension can be reduced by using surfactants.

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 Surfactant molecule
Emulsification

Interfacial encapsulation

Lipophilic Tail Hydrophilic

which prefers oil Head which
prefers water

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2. By formation of rigid interfacial film
Formation of rigid film around the droplets prevents coalescence
of droplets of dispersed phase.

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3. By forming Electrical Double Layer

• Presence of a well developed charge on the droplet surface

increases stability by causing repulsion between
approaching drops.
• This charge is likely to be greater if ionized emulsifying
agent is employed. i/v fat emulsions are stabilized with
lecithin due to the electrical repulsion.

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 Formation of electrical double layer
-
+
- -

+
-
+ + Emulsion made with
-
sodium soap.
- + -
OIL -
-
WATER+
+
+
- -
+
-
-

Electrical double layer at oil-water

interface KUST/Pharmacy/Monica Diyya 22
• In an o/w emulsion stabilized by sodium soap, the
hydrocarbon tail is dissolved in the oily phase and ionic heads
are facing the continuous aqueous phase.

• As a result the surface of the droplet is studded with –vely

charged carboxylic group. This produces a surface charge on
the droplet. The cations of opposite charge are oriented near
the surface , producing a double layer of charge. The potential
produced by double layer creates a repulsive effect between
the oil droplets and thus hinder coalescence.

‫ ينتج عن هذا شحنة‬.‫ فإن سطح القطرة مرصع بمجموعة كربوكسيلية مشحونة بالكامل‬، ‫ونتيجة لذلك‬
‫ مما ينتج عنه طبقة‬، ‫ يتم توجيه الكاتيونات ذات الشحنة املعاكسة بالقرب من السطح‬.‫سطحية على القطرة‬
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‫ تخلق اإلمكانية الناتجة عن الطبقة املزدوجة تأثيًرا مثيًرا لالشمئزاز بني قطرات الزيت‬.‫مزدوجة من الشحنة‬
 THEORIES OF EMULSIFICATION

• When a liquid is broken into smaller particles, the interfacial

area of globules/droplets constitutes a surface that is enormous
compared with the surface area of the original liquid.

https://www.youtube.com/watch?v=Rhqam9U4Dz4

• There is an enormous increase in free energy associated with

the large increase in surface area of the oil and hence system
becomes thermodynamically unstable and separates into two
phases. Due to coalescence of oil droplets.
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• In order to stabilize the emulsion, emulsifying agents are added.
These act by reducing the interfacial tension between the two
phases and by forming a stable interfacial film between the two
phases.

• The stability of a prepared emulsion is determined by the

strength and nature of the interfacial film formed.

An ideal Emulsifying agent for pharmaceutical use should be:

1. Stable, inert and free from toxic and irritant properties.
2. Preferably be odourless, tasteless, colourless and should
produce stable emulsions even at low concentrations.

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 Emulsifying agents-classification
Emulsifying agents are broadly classified into three groups:
Emulsifying agent Adsorption site Mechanism of Action
Type
Surfactants Adsorbs at the Oil- Forms Monomolecular
(eg:tweens, spans) Water interface film around droplets
and thereby reducing
Interfacial tension.
Hydrophilic colloids Adsorbs at the Oil- Forms Multi-Molecular
(eg:carboxymethyl Water interface film around the
cellulose) droplets of oil in O/W
emulsion.
Finely divided solids Adsorbs at the Forms a film of
(eg:clays,bentonite,ino interface of two particles around the
rganic substances) immiscible liquid globules.
phases.
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 Surfactant molecule
The presence of charge on the surface of oil globules
create an electrical double layer around each globule.
Overlapping of these double layer gives rise to a repulsion
which opposes van der waals forces of attraction between
the globules.

Lipophilic Tail Hydrophilic

which prefers oil Head which
prefers water

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 Theories Of Emulsification

The theories of
emulsification include:
1. Monomolecular
Film/Adsorption
2. Multimolecular Film/
Adsorption
3. Solid Particles
Film/Adsorption

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 I Monomolecular Film Adsorption Theory
• Surfactants are
• This film acts as
substances containing
mechanical barrier to
both hydrophilic and
coalescence of the
lipophilic regions in their
globules of the
molecular structure.
dispersed phase.
• These act by getting Oil • Additional effect of
adsorbed at the oil-water
surfactant is promoting
interface in such a away
stability by the surface
that the lipophilic non-
charges which will
polar groups are oriented
cause repulsion
towards oil while the
between adjacent
hydrophilic polar groups
particles.
are oriented towards the
Eg: tweens, spans
water thus forming a
stable film.
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 Ii multimolecular film adsorption theory

• Hydrophilic colloids generally act by forming multimolecular

layers at the interface.
• The formed layers or films are strong and resist coalescence.
• They donot cause appreciable lowering of interfacial tension.
• An additional effect of these hydrocolloids is the significant
increase in the viscosity of the medium which in turn
decreases coalescence (eg: carboxy methyl cellulose).
• Since they are hydrophilic, they promote only O/W type
emulsions.

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 Iii Solid Particle Film Adsorption Theory

Certain finely divided solids having balanced hydrophilic and

lipophilic properties have a tendency to accumulate at the oil/water
interface to yield a coherent interfacial film that prevents
coalescence of the dispersed globules.
Note:
If the solid particle are wetted by the oil, a W/O emulsion is formed.
If the solid particle are wetted by the water, a O/W emulsion is
formed.

Eg: Colloidal clays, inorganic substances in finely divided state.

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Pharmaceutical applications

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 Pharmaceutical applications of emulsions
micelle-assisted solubility

1. Oral products
Emulsions are used for administering drugs orally due to
following reasons :
a. More palatable : Objectionable taste or texture of medicinal
agents gets masked.
b. Better absorption : Due to small globule size, the medicinal
agent gets absorbed faster.
Eg: oil-soluble vitamins, A,D and E and water-soluble vitamins
such as vitamins B and C can be formulated as palatable fine
emulsions.

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2. Topical products
• o/w emulsions are more acceptable as water washable drug
bases for cosmetic purposes.
• w/o emulsions are used for treatment of dry skin.
Emulsions have following advantages when used for topical
purpose:
a. Patient acceptance : Emulsions are accepted by patients due
to their elegance.
b. Easily washable
c. Acceptable viscosity
d. Less greasiness.
Eg: Creams, Lotions.
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3. Parenteral Emulsions :
a. i.v route :
• Lipid nutrients are emulsified and given to patients by i/v
rout. Such emulsions have particle size less than 100 nm.
b. Depot injections :
• W/o emulsions are used to disperse water soluble antigenic
materials in mineral oil for i/m depot injection.

4. Diagnostic purposes :
• Radio opaque emulsions have been used in X-ray
examination.

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5. Aerosol products
Emulsification has been used in aerosol products to prepare
foams.

6. Stability
Drugs that are susceptible to oxidation or hydrolysis can
sometimes be stabilized by formulating them in the form of
emulsion.

7. Bioavailability
Bioavailability of certain poorly soluble drugs can be
improved by dissolving them in oil and emulsifying.

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 Parenteral
Parenteral
(ophthalmic)
(I.M/S.C/I.V)

Oral

Topical Topical

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