Emulsion

PHRM 210
 Emulsion
• An emulsion is a thermodynamically unstable
system consisting of at least two immiscible
liquid phases, one of which is dispersed as
globules (dispersed phase) in the other liquid
phase (continuous phase), stabilized by the
presence of an emulsifying agent.
• Emulsified systems range from lotions of
relatively low viscosity, to ointments &
creams, which are semisolid in nature.
Fig: Good emulsion
 Types of Emulsion
• One liquid phase in an emulsion is essentially
polar (eg, aqueous), while the other is
relatively nonpolar (eg, an oil).

Oil-in-water (o/w) emulsion:

• When the oil phase is dispersed as globules
throughout an aqueous continuous phase, the
system is referred to as an oil-in- water (o/w)
emulsion.
 Types of Emulsion
Water-in-oil (w/o) emulsion:
• When the oil phase serves as the continuous
phase, the emulsion is termed an water-in-oil
(w/o) emulsion.

Multiple (w/o/w or o/w/o) emulsions:

• These are emulsions whose dispersed phase
contains droplets of another phase. Multiple
emulsions are of interest as delayed-action
drug delivery systems.
 Why emulsions? Or Advantages
• Permits administration of liquid drug in the
form of tiny globules rather than in bulk.
• o/w emulsion can be developed to mask the
offensive taste of oil.
• Irritating medicinal agents to be applied
externally onto the skin (i.e. lotion or cream)
 Why emulsions? or Advantages
o/w vs. w/o for topical preparations-
• w/o emulsions- spreads more evenly on
damaged skin to protect
• o/w emulsions- easily removed from skin
 Identification of emulsion
• Miscibility tests with oil or water- the
emulsion will only be miscible with liquids that
are miscible with its continuous phase.

• Conductivity measurements- systems with

aqueous continuous phases will readily
conduct electricity whilst systems with oily
continuous phases will not.
 Identification of emulsion
• Staining test- Water-soluble and oil soluble
dyes are used one of which will dissolve in and
color the continuous phase.
 Emulsifying agents
• To prevent coalescence (when small droplets
recombine to form bigger ones), it is
necessary to introduce an emulsifying agent
that forms a film around the dispersed
globules.
 Emulsifying agents: Properties
• Stable, nontoxic, nonirritating and inert
• Should be surface active
• Should prevent coalescence
• Should impart an adequate electrical
potential on the droplets of internal phase
• Should be effective in low concentration
• Should be odorless, tasteless and colorless
 Classification
Emulsifying agents may be divided into three
major groups:

• Surface active agents

• Hydrophilic colloids
• Finely divided solid particles
 Surface active agents
• The name surfactant is short for “surface
active agents”. Surfactants are adsorbed at oil-
water interfaces to form monomolecular films
and reduce interfacial tensions.
• Often a mixture of surfactants is used: one
with hydrophilic character and the other with
hydrophobic character. A hydrophilic
emulsifying agent is needed for the aqueous
phase, and a hydrophobic emulsifying agent is
needed for the oil phase.
 Surface active agents
• Nonionic surfactants are widely used in the
production of stable emulsions. They are less
toxic than ionic surfactants and are less
sensitive to electrolytes and pH variation.
• Examples include sorbitan esters,
polysorbates.
Fig: The action of surfactants creating the
oil/water interface
 Hydrophilic colloids
• A number of hydrophilic colloids are used as
emulsifying agents. These include gelatin,
casein, acacia, cellulose derivatives, and
alginates.
• These materials adsorb at the oil-water
interface and form multilayer films around the
dispersed droplets of oil in an o/w emulsion.
 Finely divided solid particles
• Finely divided solid particles are adsorbed at
the interface between two immiscible liquid
phases and form a film of particles around the
dispersed globules.
• Finely divided solid particles that are wetted
to some degree by both oil and water can act
as emulsifying agents.
 Finely divided solid particles
• For external use- bentonite and aluminum
magnesium silicate.
• For internal use- aluminum and magnesium
hydroxide.
 HLB (Hydrophile-Lipophile balance)
systems:
• Griffin’s method of selecting emulsifying
agents is based on the balance between the
hydrophilic and lipophilic portions of the
emulsifying agent; this is now widely known as
the hydrophile-lipophile balance (HLB) system.
 HLB System
• The higher the HLB value of an emulsifying
agent, the more hydrophilic it is. The
emulsifying agents with lower HLB values are
less polar and more lipophilic.
• The Spans, i.e., sorbitan esters, are lipophilic
and have low HLB values (1.8-8.6); the
Tweens, polyoxyethylene derivatives of the
Spans, are hydrophilic and have high HLB
values (9.6-16.7).
 HLB System
• The HLB of an emulsifier or a combination of
emulsifiers determines whether an o/w or
w/o emulsion results. In general, a value from-
- 3 to 6 indicates a w/o emulsifier
- 7 to 9 indicates a wetting agent
- 9 to 12 indicates an o/w emulsifier
- 12 to 15 indicates a detergents
- 15 to 20 indicates a solubilizer
 Emulsion stability
Stability of emulsion means it should retain its
original characters, it depends on-
» Size of particles
» Uniform distribution
Four major changes associated with physical
stability are:
- Flocculation - Creaming
- Coalescence & - Breaking
 Flocculation
• Particles within the emulsion form large
aggregates, which can be easily redispersed
upon shaking.
• It is a precursor of coalescence.

Fig: Flocculated emulsion

 Creaming
• It occurs when the disperse droplets or
floccules separate from the disperse medium.
• Generally a creamed emulsion can be restored
to its original state by gentle agitation.
• Reducing the droplet sizes and thickening the
continuous phase can minimize the creaming.
Fig: Creamed emulsion
 Coalescence
• It is a much more serious type of instability.
• It occurs when the mechanical or electrical
barrier is insufficient to prevent the formation
of progressively large droplets.

Fig: Coalescence
 Breaking
• Due to coalescence and creaming combined,
one phase separates completely from the
other phase so that it floats at the top in a
single, continuous layer.

Fig: Breaking
 w
o o

Flocculation

o o
w
Figure: Schematic
Coalescence presentation of
flocculation and
o coalescence of
emulsion droplet
 Preservation of emulsions
Growth of microorganisms in emulsion causes:
• Physical phase separation: Partitioning
• Discoloration: Turns white or brown
• Gas emission (possibly)
• Odor formation
• Changes in rheological properties
 Preservation of emulsions
• Microorganisms degrade the emulsifying
agent.
• Use of preservatives is essential, for example-
Methylparaben and Propylparaben may be
used.
 Phase inversion
• The relative volume of internal and external
phases of an emulsion is important.
• Increase internal phase concentration:
Increase viscosity up to a certain point.
 Phase inversion
• Viscosity will decrease after that point. At this
point the emulsion has undergone inversion
i.e. it has changed from an o/w to a w/o, or
vice versa.
• In practice, emulsions may be prepared
without inversion with as much as about 75%
of the volume of the product being internal
phase.