EMULSIONS
Comprehensive Study Notes with Explanations
Dr. Riffat | Pharmacy
1. Introduction to Emulsions
An emulsion is a coarse dispersion — a biphasic (two-phase) system in which oily substances and
aqueous (water-based) substances are mixed together and stabilized by a third component called an
emulsifier. The consistency of emulsions can range from a mobile liquid (like milk) to a semisolid (like a
cream).
💡 Teach Me: Imagine trying to mix oil and water in a bottle. They refuse to stay mixed! That
instability is the core problem emulsions solve. The emulsifier acts like a 'peacemaker' between the
oil and water phases.
1.1 Components of an Emulsion
• Dispersed (discontinuous) phase — the droplets scattered throughout, size: 0.1–100 µm
• Dispersion (continuous) phase — the surrounding medium (either oil or water)
• Emulsifying agent — stabilizes the system by sitting at the interface between the two phases
1.2 Thermodynamic Instability
Emulsions are thermodynamically unstable. This means that, left alone, they will always tend to
separate back into their two original phases. The emulsifier doesn't make the emulsion
thermodynamically stable — it provides kinetic stability by slowing down or preventing separation.
💡 Analogy: Think of it like a sand castle: it won't last forever, but good construction (emulsifier) can
keep it standing for a long time.
2. Types of Emulsions
2.1 Oil-in-Water (O/W) Emulsion
Oil droplets are dispersed within a continuous water phase. Water is the external phase.
• Examples: milk, oral emulsions, I/V injections of oily drugs
• Uses: internal use — oral and injectable routes
💡 Remember: O/W = Oil is Inside Water. The outer/continuous phase is WATER.
2.2 Water-in-Oil (W/O) Emulsion
Water droplets are dispersed within a continuous oil phase. Oil is the external phase.
• Examples: cold cream, butter, moisturizing creams
• Uses: external use — topical creams and lotions
💡 Remember: W/O = Water is Inside Oil. The outer/continuous phase is OIL. Because oil is on the
outside, W/O emulsions feel greasier on skin.
2.3 Multiple Emulsions (W/O/W or O/W/O)
These are complex systems where the dispersed droplets themselves contain even smaller droplets. For
example, W/O/W means water droplets inside oil, which is then dispersed in water.
• Novel (advanced) drug delivery systems
• Used for sustained/delayed release of drugs
• Increase stability of the Active Pharmaceutical Ingredient (API)
💡 Teach Me: Think of it like a Russian nesting doll: there's a doll inside a doll inside a doll. Multiple
emulsions give us greater control over when and where a drug is released in the body.
2.4 Microemulsions
Microemulsions are monophasic, optically isotropic, thermodynamically stable, and clear dispersions.
They are formulated from oil, water, surfactant, and a cosurfactant.
• Globule diameter is less than 0.1 µm (much smaller than regular emulsions)
• Cannot refract light — appear transparent/clear to the naked eye
• Thermodynamically STABLE (unlike regular emulsions — this is unique!)
💡 Key Difference: Regular emulsions are thermodynamically UNSTABLE; microemulsions are
thermodynamically STABLE. This is because of the extremely small droplet size and the high
concentration of surfactants used.
3. Significance and Advantages of Emulsions
3.1 Why Emulsions Matter in Cosmetics & Pharmacy
Emulsions are highly favored in the cosmetics industry because they can incorporate both hydrophilic
(water-loving) and lipophilic (fat-loving) substances. This dual nature allows formulators to create
products that deliver multiple benefits simultaneously.
• Hydrophilic phase provides an emollient action (softens and soothes the skin)
• Lipophilic phase provides a humectant action (locks in moisture)
• Suitable viscosity improves ease of application
3.2 Pharmaceutical Advantages
• Improved bioavailability — the oily phase enhances drug absorption
• Better spreadability of oily drugs
• Taste/odor masking for unpleasant drugs
• Improved absorption compared to other dosage forms
💡 Teach Me: Bioavailability means 'how much of the drug actually reaches the bloodstream and
works.' Some drugs absorb poorly on their own but much better when formulated as an emulsion
because the oily environment helps them cross the gut lining.
4. Pharmaceutical Applications of Emulsions
4.1 Based on Route of Administration
• Oral route: for water-insoluble or unpleasant-tasting drugs (O/W preferred)
• Intravenous (I/V): O/W emulsions used to deliver oily APIs directly into blood
• Intramuscular (I/M): injectable emulsions
• Topical: W/O creams and lotions for skin applications
4.2 Based on Emulsion Type
• W/O emulsions: external use — creams, lotions, ointments
• O/W emulsions: internal use — oral, injectable (I/M, I/V)
• Multiple emulsions: sustained release dosage forms
• Microemulsions: internal and external use
4.3 Industrial & Other Applications
• Tanning and dyeing industries
• Manufacturing of plastics and synthetic rubber
• Delivering vaccines (microemulsions can kill various microbes)
• Nanoemulsions (e.g., soybean oil) used as antimicrobials
• Food industry: Mayonnaise is an O/W emulsion (egg yolk as emulsifier)
💡 Fun Fact: Mayonnaise is a classic O/W emulsion. The lecithin in egg yolk acts as the emulsifier,
allowing oil and vinegar/lemon juice to form a stable, creamy mixture.
5. Emulsifying Agents (Emulsifiers / Emulgents)
5.1 Function of Emulsifying Agents
The primary function of an emulsifying agent is to maintain the dispersed state of the emulsion for an
extended period after agitation stops — i.e., to impart kinetic stability to the emulsion.
Emulsifiers work by adsorbing at the oil-water interface and forming either a mechanical or electrostatic
barrier (interfacial film) around droplets. This inhibits or delays the processes of coalescence (droplets
merging together).
💡 Teach Me: An emulsifier is like a security guard at a droplet's surface. It forms a protective coat
around each oil droplet, preventing them from bumping into each other and merging back into a big
pool of oil.
5.2 Classification of Emulsifying Agents
A. Natural Surfactant Agents
• Vegetable sources: tragacanth, agar, pectin, acacia (gum arabic), lecithin
• Animal sources: egg yolk, gelatin, casein, cholesterol, wool fat
B. Synthetic Agents (Surfactants)
• Anionic: sodium dodecyl sulfate (negatively charged head group)
• Cationic: benzalkonium chloride (positively charged head group)
• Non-ionic: PEG 400 monostearate (no charge — most widely used in pharmacy)
• Ampholytic: long-chain amino acid derivatives (can be + or - depending on pH)
• Additional aids: viscosity builders like glycerine are also used
5.3 Characteristics of an Ideal Emulsifying Agent
• Stable — chemically and physically
• Tasteless and colorless — important for oral preparations
• Active at low concentration — economical and practical
• Non-toxic — safe for patients
• Compatible — with other formulation ingredients
💡 Memory Tip: Remember STANC: Stable, Tasteless, Active at low concentration, Non-toxic,
Compatible
6. Theories of Emulsion Stabilization
6.1 Theory 1: Interfacial Films Theory (Monomolecular Adsorption)
When two immiscible liquids (like oil and water) are shaken together, a temporary emulsion forms. The
subdivision of one phase into small droplets dramatically increases the surface area, which increases the
interfacial free energy (surface tension). This makes the system thermodynamically unstable.
The small droplets then coalesce (merge) to reduce surface area and return to the state of minimum
surface free energy — this is phase separation.
When a surfactant is added, it adsorbs at the globule interface, lowering the oil/water interfacial
tension, making emulsification easier and enhancing stability. Thickening agents like acacia form a
strong viscous interfacial film around globules — this mechanical barrier is more effective than reducing
surface tension alone.
💡 Teach Me: Imagine blowing soap bubbles. The soap (surfactant) coats each bubble's surface,
stabilizing it. Without soap, bubbles pop immediately. Similarly, surfactants 'coat' emulsion droplets
to keep them stable.
• Exhibited by: Surfactants (monomolecular adsorption)
6.2 Theory 2: Hydrophilic Colloids / Multimolecular Adsorption
Hydrophilic colloids such as proteins (gelatin, casein) and polysaccharides (acacia, cellulose derivatives,
alginates) adsorb at the oil-water interface and form multilayers (multiple molecular layers).
These multilayers have viscoelastic properties — they resist rupture — and form mechanical barriers to
coalescence. These agents exhibit little surface activity but are highly effective emulsifiers.
💡 Teach Me: Think of this like wrapping each droplet in multiple layers of plastic wrap. The layers
don't reduce surface tension much, but they create a strong physical barrier that's very hard to
break through.
• Exhibited by: Hydrophilic colloidal particles (acacia, gelatin, pectin)
• Generally used for EXTERNAL preparations
6.3 Theory 3: Solid Particle Adsorption (Colloidal Clays)
Finely divided solid particles can stabilize emulsions if they are preferentially wetted by one phase and
have sufficient adhesion to form a film around dispersed droplets. Particles must be small enough that
gravity does not disrupt the equilibrium.
• Aluminium and magnesium hydroxides, bentonite (clay) — preferentially wetted by water →
stabilize O/W emulsions
• Carbon black and talc — preferentially wetted by oil → stabilize W/O emulsions
• Other examples: Aluminium silicate (Bentonite), Magnesium aluminium silicate (Vegan/Veegum)
💡 Teach Me: Solid particles act like armor plating around droplets. If the particles like water more
than oil, they sit on the water side of the interface — and this arrangement favors O/W emulsions.
• Exhibited by: Colloidal clays
6.4 Summary Table: Theories vs. Emulgents
Theory Mechanism Emulgent Examples
Interfacial Film (Monomolecular) Reduces surface tension at Surfactants: SDS, Tween, Span
interface
Hydrophilic Colloids Forms viscoelastic multilayer Acacia, Gelatin, Casein, Alginates
(Multimolecular) around droplets
Solid Particles Physical armor around droplets Bentonite, Mg(OH)2, Carbon
black, Talc
7. Stability of Emulsions
7.1 Characteristics of a Stable Emulsion
• Absence of coalescence (droplets not merging)
• Absence of creaming (phases not separating)
• Elegant appearance — consistent color, odor, and texture
7.2 Causes of Destabilization (Breakdown)
A. Flocculation
Loosely aggregated droplets cluster together due to attractive and repulsive forces between globules.
The droplets are still separate but grouped. This can be reversible.
💡 Analogy: Like grapes in a bunch — they're close together but each grape is still distinct.
B. Creaming
Phase separation due to the density difference between the two phases. The lighter phase (usually oil)
rises to the top — just like cream rising in non-homogenized milk. Creaming is usually reversible with
shaking.
💡 Everyday Example: Unshaken natural peanut butter — the oil rises to the top. That's creaming in
action!
C. Coalescence (Breaking / Cracking)
Droplets merge together and the emulsion permanently separates into its two constituent phases. This
is irreversible. Any agent that destroys the interfacial film will crack the emulsion.
Factors that cause cracking:
• Addition of chemicals incompatible with the emulsifying agent
• Bacterial growth (degrades the emulsifier)
• Temperature: heating above 70°C destroys most emulsions
• Freezing also cracks emulsions
💡 Teach Me: Cracking is the ultimate failure of an emulsion. Once the protective film breaks and
droplets merge, you can't easily reverse it — like trying to un-scramble eggs.
D. Phase Inversion
An O/W emulsion converts to W/O, or vice versa. This happens when the dispersed phase exceeds a
critical volume.
• Ideal emulsion: 50/50 ratio
• Dispersed phase should be less than 74% for stability
• Pharmaceutical emulsions typically contain 10–30% dispersed phase
💡 Teach Me: If you pour too much oil into an O/W emulsion, eventually there's more oil than water.
The system 'flips' to make water the dispersed phase instead — this is phase inversion.
E. Physical and Chemical Changes
Changes in temperature, pH, electrolyte concentration, or chemical degradation of the emulsifier can all
destabilize the system.
8. Method of Emulsion Preparation
In practice, oil-soluble components are dissolved in the oil phase and water-soluble components are
dissolved in the aqueous phase. The two phases are then mixed together, and the emulsifier migrates to
the interface and forms a complex.
Alternatively, an emulsifying wax (a blend of a fatty alcohol and a vicosylising/cetostearyl agent) may be
used. The wax is dispersed in the oil phase and the aqueous phase is added at the same temperature.
This principle also applies with non-ionic emulsifying systems because they have good emulsifying
properties.
💡 Teach Me: The key principle in preparation is that the emulsifier needs to be where the action is
— at the interface. Heating both phases to the same temperature ensures the emulsifier can spread
evenly.
9. Quick Review: Key Concepts at a Glance
What is an emulsion?
A two-phase (biphasic) system of oil + water, stabilized by an emulsifier. Thermodynamically
unstable but kinetically stabilized.
O/W vs W/O
O/W = oil droplets IN water (used internally). W/O = water droplets IN oil (used externally/topically).
Microemulsion vs Regular Emulsion
Microemulsions are thermodynamically STABLE (regular ones are not), transparent (globule < 0.1
µm), and require surfactant + cosurfactant.
How does an emulsifier work?
It forms an interfacial film (mechanical and/or electrostatic) around dispersed droplets, preventing
coalescence.
Why do emulsions fail?
Flocculation, creaming, coalescence (cracking), phase inversion, or chemical/physical changes
degrade the interfacial film.
Ideal emulsifying agent
Stable, tasteless, colorless, active at low concentration, non-toxic, compatible (STANC).
References
Physical Pharmacy by S.P. Agarwal, pp. 131–140
Pharmaceutical Practice by A.J. Winfield, pp. 198–205
Remington: The Science and Practice of Pharmacy
The Design and Manufacturing of Medicines, 5th Edition — Part 1: Dispersed Systems; Part 5: Emulsions and
Creams