Emulsion

Emulsions are biphasic systems consisting of two immiscible

liquids, one of which (the dispersed phase) is finely subdivided and
uniformly dispersed as droplets throughout the other phase (the
dispersion medium).
The dispersed phase is also called as the internal phase and the
dispersion medium as external phase.
These immiscible liquids are made miscible by adding a third
substance known as emulsifying agent.
They stabilize the system by forming a thin film around the globules
of the dispersed phase.
 Emulsion
o Dispersed phase
The phase in which oil or water exists in droplet form is known as the dispersed phase
or the internal phase or the discontinuous phase.
o Dispersion medium
The liquid in which droplets of either oil or water are dispersed is known as the
dispersion medium or the external phase or the continuous phase.
o Emulsifying agent
Emulsifying Agents are the substances added to an emulsion to prevent the
coalescence of the globules of the dispersed phase. They are also known as
emulgents or emulsifiers. They act by reducing the interfacial tension between
the two phases and forming a stable interfacial film.
All emulsifying agents concentrate at and are adsorbed onto the oil/water interface
to provide a protective barrier around the dispersed droplets.
 Advantages of Emulsion
a. Pharmaceutical emulsions may be used to deliver drugs that are poorly soluble in water but
readily soluble in oils. E.g., in oil-in-water emulsions the drug substance is dissolved in the
discontinuous or internal oil phase. Some drugs are more readily absorbed when administered
as an emulsion than as other oral comparator formulations.
b. They can mask the bitter taste and odor of drugs, thereby making them more palatable. e.g.
castor oil, cod-liver oil etc.
c. They can be used to prolong the release of the drug thereby providing sustained release action.
The oily phase can serve as a reservoir of the drug, which slowly partitions into the aqueous
phase for absorption.
d. Essential nutrients like carbohydrates, fats and vitamins can all be emulsified and can be
administered to bed ridden patients as sterile intravenous emulsions.
e. Emulsions provide protection to drugs which are susceptible to oxidation or hydrolysis.
f. Intravenous emulsions of contrast media have been developed to assist in diagnosis.
g. Emulsions are used widely to formulate externally used products like lotions, creams, liniments
etc.
 Properties of Emulsion
The basic properties which should be present in an emulsion include-
o appearance
o odor
o desirable viscosity
o consistency
o effectiveness and
o stability
These properties depends on the -
o ingredients,
o type of emulsion,
o ratio of the two phases,
o type and quantity of emulsifying agents and
o method of emulsification.
 Properties of Emulsion

O/W emulsions will generally have a sheen or matte surface as

compared to w/o emulsions which have a shiny or oily surface
due to the presence of oil as external phase.
W/O emulsions are oily and greasy in nature, not easily removable
from the surface of the skin whereas o/w emulsions are non
greasy and easily removable from the skin surface.
The viscosity of the emulsions depends generally on the viscosity
of the continuous phase. As the ratio of dispersed phase
increases, the viscosity also increases to a point where
emulsion starts loosing its fluidity.
 Criteria of Emulsifying Agents
An ideal emulsifying agent should posses the following characteristics:
 should be able to reduce the interfacial tension between the two immiscible
liquids.
 should be physically and chemically stable, inert and compatible with the
other ingredients of the formulation.
 should be completely non-irritant and non-toxic in the concentrations used.
 should be organoleptically inert i.e. should not impart any color, odor or taste
to the preparation.
 should be able to form a coherent film around the globules of the dispersed
phase and should prevent the coalescence of the droplets of the dispersed
phase.
 should be able to produce and maintain the required viscosity of the
preparation.
 How Emulsifying Agents Work?
All emulsifying agents concentrate at and are 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.
Some agents enhance stability by imparting a charge on the droplet
surface thus reducing the physical contact between the droplets and
decreasing the potential for coalescence. Thus these act in three ways:
o Formation of a protective barrier
o Reduction of interfacial tension
o Decreasing the potential for coalescence by forming an electrical
double layer
 Types of Emulsions

 Oil in water emulsions (o/w)

 Water in oil emulsions (w/o)
 Multiple emulsions
 Microemulsions
 Types of Emulsions

 Oil in water emulsion (o/w)

In this emulsion oil is the dispersed phase
and water is the dispersion medium.
These emulsions are used mainly for
internal/oral use as bitter or
disagreeable taste and odor of drugs
can be masked by emulsification.
Example: Castor oil emulsion, milk,
vanishing creams, foundation creams.
 Types of Emulsions

 Water in oil emulsions (w/o)

In this emulsion oil is the dispersion
medium and water is the dispersed
phase. They are greasy and not water
washable. They are used externally to
prevent evaporation of moisture from
the surface of skin. Oil soluble drugs are
more quickly released from w/o
emulsions.
Example: Cold cream.
 Types of Emulsions
 Multiple Emulsions
In this emulsion, oil in water (o/w) or water
in oil emulsion (w/o) is dispersed in
another liquid medium. Thus, oil in water in
oil (o/w/o) emulsion consists of very small
droplets of oil dispersed in the water
globules of water in oil emulsion and water
in oil in water (w/o/w) emulsion consists of
droplets of water dispersed in the oily
phase of oil in water emulsion.
Multiple emulsions are primarily used for
formulating sustained release dosage
forms.
 Types of Emulsions
 Microemulsions
Microemulsions are thermodynamically stable clear isotropic
solution of oil, water and emulsifying agent.
The main difference between normal coarse emulsions and
microemulsions lies in the droplet size of the dispersed phase.
Microemulsions have droplets typically in the size range 10-100
nm and because of this small size range, they produce only a
weak scattering of visible light and hence, they appear transparent
and are more acceptable physically as compared to conventional
emulsions.
 Difference Between Microemulsions and Emulsions

Microemulsions Emulsions

Thermodynamically stable. Thermodynamically unstable.

Optically transparent. Cloudy colloidal systems.

May be single or multiple phase. Multiple phase only.

Require no energy in their

External energy required for formation.
formation.
Interfacial tension 10-2 - 10-4 mNm- Interfacial tension 20-50 m Nm-1
1
[milli newton per meter]
 Difference Between o/w and w/o Emulsions

Oil in water emulsion (o/w) Water in oil emulsion (w/o)

Water is the dispersion medium and oil is Oil is the dispersion medium and water is the
the dispersed phase. dispersed phase.
They are non greasy and easily removable
They are greasy and not water washable.
from the skin surface.
They are used externally to prevent evaporation
They are used externally to provide cooling
of moisture from the surface of skin e.g. Cold
effect e.g. vanishing cream.
cream.

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

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

The hydrophile-lipophile balance (HLB) method provides a

systematic method of selecting mixtures of emulsiying agents
to produce physically stable emulsions.
William C. Griffin developed the HLB method in 1949.
The system has an arbitrary scale of 1-18.
Although originally applied to non-ionic surfactants, its use has
now been extended to ionic surfactants.
 Application of HLB System

HLB Uses
Range
0-3 Antifoaming agents

4-6 W/O emulsifying agent

7-9 Wetting agents
8-18 O/W emulsifying agent
13-15 Detergents
10-18 Solubilizing agents

HLB Scale
 HLB Method
Significance of HLB Value
An emulsifier having a low HLB number indicates that the number of hydrophilic groups present in
the molecule is less and it has a lipophilic character.
For example, spans generally have low HLB number and they are also oil soluble. Because of
their oil soluble character, spans cause the oil phase to predominate and form a w/o emulsion.
A higher HLB number indicate that the emulsifier has a large number of hydrophilic groups on the
molecule and therefore is more hydrophilic in character.
Tweens have higher HLB numbers and they are also water soluble. Because of their water
soluble character, tweens will cause the water phase to predominate and form an o/w
emulsion.

Limitations of HLB Value

It does not take into account:
- the effect of temperature
- the presence of additives
- the concentration of emulsifier
 Calculation of HLB Value
Griffin's Method
Griffin's method for non-ionic surfactants as described in 1954 works
as follows:

HLB =

Where:
Mh = Molecular mass of the hydrophilic portion of the molecule, and
M = Molecular mass of the whole molecule, giving a result on a scale
of 0 to 20
 Calculation of HLB Value
Davies' Method
In 1957, Davies suggested a method based on calculating a value based on the chemical
groups of the molecule. The advantage of this method is that it takes into account the effect
of stronger and weaker hydrophilic groups. The method works as follows:
HLB = 7 + Σ(hydrophilic group numbers) - Σ(lipophilic group numbers)
or,
HLB = 7 + m×Hh - n×Hl
Where:
m = Number of hydrophilic groups in the molecule
Hh = Value of the hydrophilic groups
n = Number of lipophilic groups in the molecule
Hl = Value of the lipophilic groups
 Calculation of HLB Value
Davies' Method
The selected groups number/value used in the Davies method of estimating hydrophile-
lipophile balance (HLB) are:

Functional group Group Contribution

Number
Hydrophilic
–OH 1.9
–O– 1.3
–NH2; =NH 9.4
–COOH 2.1
Lipophilic (or hydrophobic)
–CH–; CH2–; –CH3–; =CH− 0.475
 Calculation of HLB Value

Davies' Method
An example calculation is given for Dipropylene Glycol
(H(OC3H6)2OH), where there are 2 OH groups, 1 O atom and 6
C atoms in the alkyl chain.

HLBDipropylene Glycol = 7+(2×1.9)+(1×1.3) - (6 × 0.475)

= 9.25
 Preparation of Emulsions

1. Trituration Method
a. Dry Gum Method
b. Wet Gum Method
2. Bottle Method
 Dry Gum Method
In this method the oil is first triturated with gum with a little amount of
water to form the primary emulsion. The trituration is continued till a
characteristic ‘clicking’ sound is heard and a thick white cream is
formed. Once the primary emulsion is formed, the remaining quantity
of water is slowly added to form the final emulsion.

Wet Gum Method

As the name implies, in this method first gum and water are triturated
together to form a mucilage. The required quantity of oil is then added
gradually in small proportions with thorough trituration to form the
primary emulsion. Once the primary emulsion has been formed
remaining quantity of water is added to make the final emulsion.
 Bottle Method
This method is employed for preparing emulsions containing volatile and
other non-viscous oils. Both dry gum and wet gum methods can be
employed for the preparation. As volatile oils have a low viscosity as
compared to fixed oils, they require comparatively large quantity of
gum for emulsification. In this method, oil or water is first shaken
thoroughly and vigorously with the calculated amount of gum.
Once this has emulsified completely, the second liquid (either oil or water)
is then added all at once and the bottle is again shaken vigorously to
form the primary emulsion. More of water is added in small portions
with constant agitation after each addition to produce the final volume.
 Bottle Method
Proportions of Oil, Water and Gum required for formation of
primary emulsion.

Type of Oil Oil Water Gum

Fixed Oil 4 2 1

Mineral Oil 3 2 1

Volatile Oil 2 2 1
 Points to be considered during formulations
of emulsions

• Stability of the active ingredient  Concentration of emulsifier

• Stability of the excipients  Order of addition of ingredients

• Visual appearance  Particle size distribution of

dispersed phases
• Color
 pH
• Odor (development of pungent
odor/loss of fragrance)  Temperature of emulsification

• Viscosity, extrudability  Type of equipment

 Method and rate of cooling
 Points to be considered during formulations
of emulsions
• Loss of water and other volatile vehicle components
• Texture, feel upon application (stiffness, grittiness, greasiness,
tackiness, spreadibility)
• Microbial contamination/sterility (in the unopened container and
under conditions of use)
• Release/bioavailability (percutaneous absorption)
• Phase distribution, phase Inversion (homogeneity/ phase
separation, bleeding)
 Identification of Emulsion Type
 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.
Oil in water emulsion can easily be diluted with an aqueous
solvent whereas water in oil emulsion can be diluted with a oily
liquid.
 Dilution test

Fig: Dilution Test for o/w emulsion

 Dilution test

Fig: Dilution Test for w/o emulsion

 Identification of Emulsion Type
 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.
 Conductivity Test

Fig: Conductivity test for o/w emulsion Fig: Conductivity test for w/o emulsion
 Identification of Emulsion Type
 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.
 Identification of Emulsion Type

 Cobalt Chloride Test

When a filter paper soaked in cobalt chloride solution is added to
an emulsion and dried, it turns from blue to pink, indicating that
the emulsion is o/w type.
Instabilities in Emulsions
 Instabilities in Emulsions
 Creaming
An emulsion is said to cream when the oil or
fat rises to the surface, but remains in the
form of globules, which may be redistributed
throughout the dispersion medium by
shaking.
An oil of low viscosity tends to cream more
readily than one of high viscosity. Increasing
the viscosity of the medium decreases the
tendency to cream. Creaming is a reversible
phenomenon which can be corrected by
mild shaking.
 Instabilities in Emulsions
 Creaming
The factors affecting creaming are best described by Stoke's law-
V= 2r2 (d1-d2) g/9η
Where,
V= rate of creaming
r =radius of globules
d1 = density of dispersed phase
d2 = density of dispersion medium
g = gravitational constant
η = viscosity of the dispersion medium
 Creaming
The following approaches can be used for decreasing creaming-
a. Reduction of globule size: According to Stroke’s law, rate of creaming
is directly proportional to the size of globules. Bigger is the size of the
globules, more will be the creaming. Therefore in order to minimize
creaming, globule size should be reduced by homogenization.
b. Increasing the viscosity of the continuous phase: Rate of creaming
is inversely proportional to the viscosity of the continuous phase i.e.
more the viscosity of the continuous phase, less will the problem of
creaming. Therefore to avoid creaming in emulsions, the viscosity of
the continuous phase should be increased by adding suitable viscosity
enhancers like gum acacia, tragacanth etc.
 Instabilities in Emulsions

 Cracking/Breaking
Occasionally, it happens that an emulsion cracks during
preparation, i.e., the primary emulsion does not become white
but acquires an oily translucent appearance. In such a case, it is
impossible to dilute the emulsion nucleus with water and the oil
separates out.
Cracking of emulsion can be due to addition of an incompatible
emulsifying agent, chemical or microbial decomposition of
emulsifying agent, addition of electrolytes, exposure to increased
or reduced temperature or change in pH.
 Instabilities in Emulsions
 Phase Inversion
In phase inversion o/w type emulsion changes into w/o type
and vice versa. It is a physical instability. It may be brought
about by the addition of an electrolyte or by changing the
phase volume ratio or by temperature changes.
Phase inversion can be minimized by using the proper
emulsifying agent in adequate concentration, keeping the
concentration of dispersed phase between 30 to 40% and by
storing the emulsion in a cool place.
 Packaging, Labeling and Storage
o Packaging: Depending on the use, emulsions should be packed in
suitable containers. Emulsions meant for oral use are usually packed
in well filled bottles having an air tight closure. Light sensitive products
are packed in amber colored bottles. For viscous emulsions, wide
mouth bottles should be used.
o Labeling: The label on the emulsion should mention that these
products have to be shaken thoroughly before use. External use
products should clearly mention on their label that they are meant for
external use only.
o Storage: Emulsions should be stored in a cool place but refrigeration
should be avoided as this low temperature can adversely effect the
stability of preparation.
 Preservation of Emulsions
o 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.
 Preservation of Emulsions
o Preservation from microorganisms
Examples of antimicrobial preservatives used to preserve emulsified systems
include:
 parahydroxybenzoate esters such as methyl, propyl and butyl parabens;
 organic acids such as ascorbic acid and benzoic acid;
 organic mercurials such as phenylmercuric acetate and phenylmercuric
nitrate;
 quarternary ammonium compounds such as cetrimide, cresol derivatives
such as chlorocresol and
 miscellaneous agents such as sodium benzoate, chloroform and
phenoxyethanol.
 Preservation of Emulsions
o Preservation from oxidation
Oxidative changes such as rancidity [condition produced by aerial
oxidation of unsaturated fat present in foods and other products, marked by
unpleasant odour or flavour] 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.
Some of the commonly used antixidants for emulsified systems
include alkyl gallate such as ethyl, propyl or dodecyl gallate, butylated
sshydroxyanisole (BHT), butylated hydroxytoluene (BHT).
 Quality Control Tests for Emulsions
o Determination of particle size and particle count:
Determination of changes in the average particle size
or the size distribution of droplets is an important
parameter used for the evaluation of emulsions. It is
performed by optical microscopy, sedimentation by
using Andreasen apparatus and Coulter counter
apparatus.
 Quality Control Tests for Emulsions
o Determination of viscosity:
Determination of viscosity is done to assess the changes
that might take place during aging. Emulsions exhibit non-
newtonian type of flow characterstics. The viscometers
which should be used include cone and plate viscometers.
For viscous emulsions, the use of penetrometer is
recommended as it helps in the determination of viscosity
with age.
Viscometer Penetrometer
 Quality Control Tests for Emulsions
o Determination of phase separation: This is another parameter
used for assessing the stability of the formulation. Phase
separation may be observed visually or by measuring the volume
of the separated phases.
o Determination of electrophoretic properties: Determination of
electrophoretic properties like zeta potential is useful for assessing
flocculation since electrical charges on particles influence the rate
of flocculation. O/W emulsion having a fine particle size will exhibit
low resistance but if the particle size increase, then it indicates a
sign of oil droplet aggregation and instability.
Oral Emulsions Available in BD
Opthalmic Emulsions Available in BD