EMULSION

EMULSION:

Emulsions are biphasic heterogeneous system consisting of two

immiscible phases ,one of which is (the dispersed phase) is finely
sub devided and uniformly distributed as droplets throughout the
other(the dispersion medium).

To prepare a stable emulsion a third ingredient ,emulsifying

agent ,is required.

Emulsion for external use are such as lotion if liquid,or creams if

semisolid in nature.

How ever they may also be administered intravenously ,rectally or

orally.
 TYPES OF EMULSION

1. Oil in water emulsion(O/W) Emulsion:

In this type of emulsion the oil is dispersed phase in the continuous
phase of water, the emulsion is termed oil-in-water (O/W).

Oil is the dispersed phase and water is the dispersion medium.

They are non greasy and are easily washed from the skin surface.

They are preferred for oral fomulations as the taste of oil can be masked.

O/W emulsions give a positive conductivity test since the external phase
is water, which is good conductor of electricity.
Preferred for internal use because the unpleasant and bitter
taste of oils can be masked.

Used externally to provide cooling effect e.g vanishing cream.

Water soluble drugs are more quickly released from O/W

emulsion.
Water in oil emulsion(w/o)
A system in which the water is dispersed as globules in the oil continuous
phase is termed water-in-oil emulsion (W/O).

Oil is the dispersed phase water is dispersion medium.

They are greasy and not easily washed by water.

Used externally to prevent evaporation of moisture from the surface of

skin e.g cold creams

Oil soluble drugs are more quickly released from w/o emulsion.
They are preferred for topical preparations such as creams.

W/O emulsion do not give a positive conductivity test since

the external phase is oil, which is a poor conductor of
electricity.
Complex Emulsion( Multiple Emulsion)
Multiple emulsion are the emulsion system in which the dispersed
phase contain smaller droplets that have the same composition as
the external phase.
Multiple emulsion are used in formulation of sunscreens,hand
creams ,makeup cleanser ,shaving creams and antiperspirants.

The multiple emulsions are also considered to be of two types:

Oil-in-Water-in-Oil (O/W/O) emulsion system:

In O/W/O systems an aqueous phase separates internal and
external oil phase. In other words, O/W/O is a 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) emulsion system:

In W/O/W systems, an organic phase separates internal and

external aqueous phases.

In other words, W/O/W is a system in which oil droplets may be

surrounded by an aqueous phase, which in turn encloses one or
several water droplets.

Thus, the multiple emulsions may be o/w/o, where the aqueous

phase is between two oil phase, or w/o/w, where the internal and
external aqueous phase are separated by an oil phase.
Advantages of Emulsion as Dosage form:

1. Unpalatable oils can be administered in a palatable form.

2. The aqueous phase is easily flavored.
3. The taste of oils can be masked.
4. Absorption is faster when compared to solid dosage forms.
5. Emulsions of the O/W type are administered orally for the
following purposes:
(a) Disguise the taste or oiliness of medicinal oils such as liquid
paraffin and cod liver oil.
The aqueous continuous phase, which will be pleasantly flavored,
isolates the unpleasant disperse phase from the tongue and, if the
patient wishes, allows the residue of the dose to be rinsed easily
from the mouth with water.
 b) To improve the absorption of oils.
c) Sometimes O/W emulsions of nutritive oils and fats are
administered intravenously to patients who are unable to ingest food
in the normal way.
6) Semisolid emulsions are O/W (vanishing creams) or W/O (cold
creams). O/W emulsions are preferred over W/O emulsions. They
can be easily rubbed into the skin and can be easily removed by
washing.
Disadvantages of Emulsions as Dosage form:

1. Calculation of primary emulsion formula and technical expertise

are needed for the manufacture of stable emulsions.
2. A measuring device is needed for administration.
3. Emulsions require shaking before use to ensure uniformity of
dose
4. If the preparation is not shaken well, the accuracy of dose is
likely to be less when compared to solutions.
5.Improper storage conditions can affect the disperse system.
6.Since emulsions are stored in glass or plastic containers, they are
bulky, difficult to transport and prone to container breakages.
7. Microbial contamination of emulsions can lead to cracking.
 Identification of emulsion types
There are range of tests available to identify emulsion type.

1-Miscibility test/ Dilution test:

An emulsion will only mix with a liquid that is miscible with
continuous phase,
therefore an o/w emulsion is miscible with water
a w/o emulsion miscible with oil.

2-Cobalt Chloride Test:

Anhydrous cobalt is blue and hydrated cobalt is red.
Treat filter paper with cobalt chloride solution and dry it.
Dip the dry treated paper in the emulsion.
The change in color from blue to pink red indicates an O/W emulsion
if there is no change in color, it indicates W/O emulsion.
3- Conductivity test:
Immerse the pair of electrodes in the emulsion and connect them to
a bulb.
When current is applied, if the bulb glows it indicates the O/W
emulsion this is because water is continuous phase and it is good
conductor of electricity.
If bulb does not glow it indicates W/O Emulsion this is because oil
is the continuous phase and it is the bad conductor of electricity.

4-Dye Solubility test or Staining test

If an oil soluble dye (scarlet red) is used and examined
microscopically,an o/w emulsion will appear as colored globules on
a colorless background.
w/o emulsion will appear a colorless globules against a colored
background.
If an water soluble dye(amaranth) dye is used and examined
microscopically an o/w emulsion will appear as colorless globules
on colored background.
w/o emulsion will appear as colored globules on colorless
background.

5-Fluorescence Test:
Many oils shows fluorescence when exposed to UV light.
The emulsion is observed against UV light under microscope.
When an emulsion shows continuous fluorescence after exposure to
ultraviolet radiation, it is an w/o type emulsion.
When an emulsion shows only spotty fluorescence it is o/w type.
 FORMULATION OF EMULSION
The formulation of emulsion involves the following:

1.Emulsifying agent(emulgent):
An emulsifying agent enhances the stability of an emulsion
i.e, Prevention of coalescence of globules and reducing
interfacial tension by forming the barrier at the interface).

The ideal emulsifying agent is colorless , odorless, tasteless,

non-toxic, non irritant, and able to produce stable emulsion
at low concentration.
2.Oil phase: The oil (medicament or vehicle) used for the
preparation of emulsion may be of fixed oil(olive oil, soybean oil,
sunflower oil ,flax seed oil etc). mineral oil( Liquid parafin,parafin
oil,petrolatum oil). volatile oil (Lavender oil,peppermint oil,lemon
oil). Depending upon the origin, suitable ratio of oil, water and
emulgent must be used for the preparation of primary emulsion.

3. Aqueous phase: Freshly boiled and cooled purified water is

normally used because of the increased risk of microbial
contamination.

4.Preservative: The desirable features of a preservative suitable for

use in an emulsion include the following:

(a)Wide spectrum of activity against all bacteria, yeast and molds

(b) Bactericidal rather than bacteriostatic activity
(c) Freedom from toxic, irritant and sensitizing activity
(d) Compatibility with the other ingredients in the preparation and
with the container.

(e) Stability and effectiveness over a wide range of pH and

temperature

(f) Freedom from color and odor.

Examples: benzoic acid (0.1%-0.2%), methyl and propyl paraben

(0.1%-0.2%), chloroform (0.25%), and phenyl mercuric nitrate
(0.004%-0.01%)
5. Antioxidant: This is used to increase the stability of the oil
phase in the emulsion by preventing the oxidation of the oil
during its shelf life.
Examples: butylated hydroxy anisole (BHA), butylated hydroxy
toluene (BHT) and tocopherol.

6. Flavoring agent: This is used to increase the palatability of the

final preparation.
Examples: pineapple, orange, chocolate and mint flavors.

7. Coloring agent: This is used to identify the preparation and to

increase the aesthetic appeal of the preparation.
Examples: Food, Drug and Cosmetic Act-approved colors such as
erythrosine and tartrazine

8.Perfume: This is used only for external preparations such as

creams .
1,Naturally occurring emulsifying agents:

Polysaccharides:

(a)Acacia is the best emulsifying agents for extemporaneously prepared oral

emulsion as it forms thick film at the oil-water interface to act as a barrier to
coalescence.

Acacia emulsions are of low viscosity therefore thickening agents such as

tragacanth and sodium alginate are added, these emulsions are palatable and are
stable over a wide PH range(2-10).

(b) Tragacanth is rarely used alone because of its high viscosity. The emulsions are
coarse and are used as a stabilizer in acacia emulsions in the proportion 1:10
(acacia)

(c) Sodium alginate has high viscosity and is used as an emulsion stabilizer along
with acacia.
(d) Agar is the dried extract obtained from certain seaweeds. It is used as
an emulsion stabilizer in liquid paraffin emulsions prepared with acacia.
It is soluble in boiling water, producing solutions of high viscosity

(e) Starch is a poor emulsifying agent and is used for the preparation of
enemas containing oils.

(f) Pectin is obtained from the inner rind of citrus fruits or from the
apple pulp that remains after the making of cider. In acid media, it is a
good O/W emulgent but degrades in alkaline pH. It is employed in the
preparation or stabilizing of cosmetic creams and lotions.

(g) Chondrus is dried seaweed. It is not suitable for small-scale

emulsification because preparation of the mucilage is time consuming
and its emulsions must be homogenized.
It is used in the emulsification of cod liver oil emulsions to mask the
unpleasant odor and taste of the oil.
(h) Wool fat is a type of wax that consists of fatty acid esters of
cholesterol and other sterols together with normal fatty alcohols.
It can absorb 50% of water, but when mixed with other fatty
substances it can emulsify several times its own weight of aqueous
or hydroalcoholic liquids. The emulsions made are of W/O type.

(i) Gelatin is used for the emulsification of liquid paraffin emulsions

at a concentration of 1%.
Gelatin emulsions are prone to bacterial growth, and therefore, a
suitable preservative should be added.

(j) Egg yolk is an emulsifying agent because of the presence of

lecithin and cholesterol. It is rarely used in industrial preparations as
they are spoiled during transportation or if not preserved properly.
It is used for the emulsification of fish liver oils.
(2)Semisynthetic polysaccharides:
Following are the different semisynthetic polysachrides:
(a) Methylcellulose is of low viscosity and is suitable as emulgents
and emulsion stabilizer. It is suitable for emulsifying mineral and
vegetable oils and is used at a concentration of 2%

(b) Sodium Carboxy MethylCellulose (SCMC) is of medium

viscosity grade and is used at a concentration of 0.5% to 1% as
emulsion stabilizer.
3, Synthetic polysacchrides:
These agents are classified according to their ionic
characteristics.

(a)anionic surfactants:
These are organic salts have surface active anion.

They are incompatible with some organic and inorganic

cations,with large organic cation such as cetrimide.

They are widely used in external preparation as O/W

emulsifying agents.

Stable at more alkaline PH.

Examples:
Alkali metal and ammonium soaps such as sodium stearate(O/W).

Soaps of divalent and trivalent metals such as calcium

oleate(W/O).

Amine soaps such as triethanolamine oleate(O/W).

Alkyl sulphates such as sodium lauryl sulphate(O/W).

(b)Cationic surfactants:
They are usually quaternary ammonium compounds which
have surface active cation they bear a positive charge on them.

Used in preparation of o/w emulsion for external use.

Stable at acidic PH.

Also have antimicrobial activity.

E.g:Cetrimide( cetyl trimethyl ammonium bromide)

Benzalkonium chloride,Benzethonium chloride.
(c)Non-ionic surfactants:
They are used to produce either o/w or w/o emulsions for both
external and internal use.

These are compatible with both anionic and cationic substance.

Stable over wide range of PH and is not affected by the addition

of acids and electrolytes.

Examples:glycol and glycerol esters(glyceryl

monostreate) ,macrogol(polyethylene glycol) ,sorbitan
esters(spans) polysorbates(tweens) and polyvinyl alcohol.
4,Finely divided solids: (Inorganic agents)
Finely divided solids can be adsorbed at the oil and water
interface to form a film that prevents coalescence of the
dispersed globules.
If the solids particles are wetted by the oil, then W/O emulsion is
formed, whereas wetting by water results in O/W emulsion.

Examples:Milk of magnesia(10%-20%) ,magnesium oxide(5%-

10%) and magnesium aluminum silicate(1%)
5.Alcohols:
They are classified into following types:

(a)Carbowaxes are used in the preparation of ointments and creams.

The substances with molecular weight of 200-700 are viscous, light
colored, hygroscopic liquids,
whereas those with molecular weight above 1000 are wax like
solids.

(b)Cholesetrol is used only in combination with other emulsifying

agents to produce a stable emulsion.

(C)Lecithin is common natural emulsifier used in industries,

including food,pharmaceuticals,cosmetics in skin care products for
its emollient nd moisturzing properties.
It is extracted from sources like soyabeans,sunflowers or egg.
Preparation of emulsions:
Methods involved in the preparation of emulsions

The preparation of an emulsion involves two stages:

1. Preparation of the primary emulsion
2. Dilution of the primary emulsion

Calculation of Primary Emulsion Formula:

The amount of emulsifying agent used is dependent on the
amount and type of oil to be emulsified
Oils can be divided into three categories:
fixed oils, mineral oils and volatile oils.
 1. Fixed oils
Oil: 4 parts by volume
Aqueous phase: 2 parts by volume
Gum: 1 part by weight

2. Mineral oils
Oil: 3 parts by volume
Aqueous phase: 2 parts by volume
Gum: 1 part by weight

3. Volatile (aromatic) oils

Oil: 2 parts by volume
Aqueous phase: 2 parts by volume
Gum: 1 part by weight.
Primary Emulsion formulae
p of oil examples oil
Type water Gum(Emulg
ent)

Fixed oil Arachis 4 2 1

oil,cod liver
oil,castor oil
almond oil
Mineral oil Liquid 3 2 1
paraffin

Volatile(aro Cinnamon 2 2 1
matic) oil oil,
Terpentine
oil,peppermi
nt oil
Oleo resin Male fern 1 2 1
extract
There are two methods used in the preparation of emulsions:
1. Trituration method: This includes the dry gum and wet
gum methods.

(a) Dry gum or Continental method:

In this method the emulsifying agent (usually acacia) is
mixed with the oil before the addition of water. Acacia is
triturated with the oil in a perfectly dry porcelain mortar
until thoroughly mixed. After the oil and gum have been
mixed, the amount of water required for the primary
emulsion is added in small portions with continuous
trituration. Trituration is continued in one direction until
the primary emulsion is creamy white and a cracking sound
is produced by the movement of the pestle .
Cont:
Other soluble liquid ingredients are then mixed into the
primary emulsion. Solid substances such as preservatives,
stabilizers, colorants and any flavoring agents are usually
dissolved in a suitable volume of vehicle and added to the
primary emulsion. The emulsion is then made up to
volume with the remaining vehicle.
(b) Wet gum or English method:
In this method, the emulsifying agent is added to water to
form the mucilage and then the oil is slowly added to form
the emulsion.
In the wet gum method, the same proportions of oil, water
and gum as given in primary emulsion formulae table are
used, but the order of mixing is different. Mucilage of the
gum is prepared by triturating with water. The oil is then
added in small portions with trituration. After the addition of
the entire oil, the mixture is thoroughly triturated in one
direction to form the primary emulsion. Other soluble liquid
ingredients are then mixed into the primary emulsion. Solid
substances such as preservatives, stabilizers, colorants and
any flavoring agents are usually dissolved in a suitable
volume of vehicle and added to the primary emulsion. The
emulsion is then made up to volume with the remaining
vehicle.
2. Bottle or Forbes method: This method is employed for
preparing emulsions containing volatile and nonviscous oils.
Both dry gum and wet gum methods can be employed for the
preparation. Since volatile oils have a low viscosity as
compared to fixed oils, they require comparatively large
quantities of gum for emulsification. In this method, the oil
or water is first shaken vigorously with the calculated
amount of gum. Once this has emulsified completely, the
second liquid (water or oil) is then added all at once and the
corked bottle is again shaken vigorously to form the primary
emulsion. More water is added in small portions, with
constant shaking after each addition, to produce the final
volume. This method is not suitable for viscous oils as they
cannot be thoroughly agitated in the bottle when mixed with
the emulgent. When the intended dispersed phase is a
mixture of fixed oil and volatile oil, the dry gum method is
The HLB(Hydrophilic Lipophilic balance)
system
A surfactant contain two groups in the molecule, a hydrocarbon
group which is lipophilic and a polar group which is hydrophilic.

The proportion of these two groups in the molecule effects the

solubility in oil or in water.

The balance between the hydrophilic and lipophilic tendencies is

called the hydrophilic lipophilic balance (HLB).
It ensures that emulsifier has right balance of affinity for both
water and oil phase leading to stable emulsion.

This has been expressed empirically by Griffin in the terms of

numerical HLB scale.
Cont:

Surfactants with low HLB number is primarily lipophilic

and form W/O emulsion.

Surfactants with high HLB number is hydrophilic and

form O/W emulsion.

Emulsifying agents with high HLB value(8-18) indicate a

hydrophilic molecule which produce o/w emulsion.

Those with low HLB values (3-6) indicate the lipophilic

molecule which produces W/O emulsion.
 HLB values of emulsifying agents
S:no Name of HLB Applications Type of
emulsifying agent value emulsion

1 Acacia 8.0 Emulsifying agent O/W

2 Glyceryl 3.8 Emulsifying agent W/O
monostearate
3 Sorbitan monooleate 4.3 Emulsifying agent W/O

4 Sorbitan mono- 4.7 Emulsifying agent W/O

staerate
5 Polysorbate 20 16.7 Solubilising agent --
6 Polysorbate 60 14.9 Detergent --
7 Polysorbate 80 15.0 Solubilising agent --
8 Sodium lauryl 40.0 Emulsifying agent O/W
suphate
9 Sodium oleate 18.0 Solubilising agent --
10 Tragacanth 13.2 Emulsifying agent O/W
11 Triethanolamine 12.0 Emulsifying agent O/W
oleate
Choosing of emulsifying agents:
The emulsifying agent selected must have the following
qualities:

1.It should be capable of reducing the interfacial tension

between the two immiscible liquids.

2.It should be capable of keeping the globules of dispersed

phase distributed indefinitely throughout the dispersion
medium.

3. It should be non toxic.

4.The odor and taste should be compatible with the

preparation.
Cont:

5. It should be able to produce and maintain the required

consistency of the preparation.

6 .It should be chemically compatible with other ingredients

of the preparation.
ANTIOXIDANTS USED IN EMULSION:

Antioxidant is a molecule that inhibits the degradation by

oxidation, they can be used to prevent the changes occuring due to
atmospheric oxygen.
Therefore antioxidants may be added to the formulation.

They should be preferentially soluble in the oily

phase,nontoxic,nonirritant,ordorless,and tasteless.

Examples: ethyl gallate,propyl gallate, butylated

hydroxyanisole,butylated hydroxytoluene.
ANTlMICROBIAL PRESERVATIVES:

These substance are added to various pharmaceutical

products in order to prolong their shelf life.

Microbes produce unpleasant odors,color change and

gases and may affect the emulsifying agents, possibly
causing breakdown of emulsion.

Example: Benzoic acid, esters of

parahydroxybenzoicacid such as methylparaben.
ascorbic acid,benzoic acid,sodium benzoate etc
Stability of emulsion:
(i)Creaming:

Aggregation of globules of the disperse phase at the top of the

emulsion.

Creaming is temporary because it can be redistributed by mild

shaking or stirring to get a homogenous product.

Larger the size of globules more will be creaming.

A good example of creaming is when milk is set aside for a

few hours, a thick layer of cream forms at the surface.
There are many factors which lead to creaming of emulsions but
the chief factor is the rising of dispersed globules to the surface of
emulsion.

The rate at which the globules will rise to the surface or the rate of
creaming is governed by Stoke’s Law.

V=2r2(d1-d2)g/9ŋ
where v=rate of creaming
r=radius of globules
d1=density of dispersed phase
d2=density of continuous phase
g=gravitational constant
ŋ=viscosity of the dispersion medium.
 Causes and prevention of creaming:
(a) Radius of globules:

As per stoke’s law the larger the size of globules the rate of creaming is
faster than that of small globules because small globules will rise less
quickly than larger globules.

Therefore creaming can be reduced by reducing the size of globules by

passing the emulsion through a homogeniser.

(b)Difference between densities of dispersed phase and continuous

phase:

Greater the difference between densities of dispersed phase and

continuous more will be creaming.
(c) Viscosity of the dispersion medium:

As per stoke’s law viscosity of medium is inversly

proportional to rate of creaming.

(d)Storage temperature:

The high temperature reduces viscosity of continuous

phase which incourage the creaming,therefore emulsion
should be stored in a cool place.

Freezing should be avoided which may lead to cracking.

(ii) Cracking:

In cracking the coalescence of the dispersed globules takes place and

separation of the disperse phase as a separate layer, redispersion cannot be
achieved by shaking.

Causes of cracking:

Cracking may take place due to following reasons:

(a)By addition of emulsifying agent of opposite type:

soaps of monovalent metals produce O/W type emulsions where soaps of

divalent metals produce W/O type emulsions.

But the addition of monovalent soap to an emulsion prepared with divalent

soap or vice versa will lead to instability and cracking of emulsion. Anionic
and cationic emulsifying agents are mutually incompatible.
(b)By addition of a common solvent:
Addition of liquid in which both disperse and continuous
phase are soluble forms a one phase system and destroy the
emulsion.

(c)By decomposition or precipitation of emulsifying

agents:

When an acid is added to an alkali soap emulsion,

(turpentine liniment) ,it causes the decomposition of the
emulsifying agent thus leads to cracking of emulsion.
(d)By high temperature:

when emulsions are stored for a long time in an increased

temperature may reduce viscosity of the emulsion and causes
creaming.

(e)By creaming:

A badly creamed emulsion is more liable to crack than a

homogeneous emulsion.
(f) By Microorganism:

If emulsion are not stored properly which leads to microbial

contamination on to the emulsion, hence the microbes get
deteriorate the emulsion and leads to cracking of emulsion.
So use preservatives to prevent the microbial growth on to
emulsion.
(iii)Phase inversion:

In phase inversion the oil in water type(o/w) emulsion changes into

water in oil type(w/o) and vice versa.

Occur by the addition of substances which alter the solubility of an

emulsifying agent, .

For stability of emulsion the optimum range of disperse phase

concentration is 30-60% if the concentration exceeds this
concentration, phase inversion occurs.
Shelf life and storage
Emulsion should be stored at room
temperature and will either be recently or
freshly prepared.
Some official preparations will have specific
expiry dated.They should not be frozen.

Containers
An ambered medicine bottle is used, plain
for internal use and ribbed for external use,
with a airtight child resistant closure.
Special Labeling and advice for
emulsions

Depending on the use, emulsions should be packed in suitable

containers. Emulsions meant for oral use are usually packed in
well-filled airtight bottles. Light-sensitive products are packed in
amber colored bottles. Viscous emulsions should be dispensed in
wide-mouthed bottles. The label on the emulsion should mention
that these products have to be shaken thoroughly before use.
Topical products should clearly mention on their label that they
are meant for external use only. Emulsions should be stored in a
cool place but refrigeration should be avoided to maintain the
stability of the preparation.

Labeling for Emulsions: SHAKE WELL BEFORE USE.