Multi-Phase Flow, Dept. of Chemical Engg.

EMULSION

- Onkar Kotpalliwar (16JE002326)

Ayush Parasar (16JE002170)
Shivam Shakya (16JE002115)
What is an emulsion?
• A dispersion of one or more immiscible liquid phases in
another, the distribution being in the form of tiny
droplets
• Emulsions are metastable –from a thermodynamic
standpoint they can exist in a form that is not the state
of lowest energy
• Examples of emulsions include vinaigrettes, milk,
mayonnaise, and some cutting fluids for metal
working. The photo-sensitive side of photographic film
is an example of a colloid.
 Theories of Emulsification
• Surface tension theory – emulsification takes place by the
reduction of interfacial tension between two phases
• Repulsion theory – the emulsifying agent creates a film over
one phase that forms globules, which repel each other. This
repulsive force causes them to remain suspended in the
dispersion medium
• Viscosity modification – Certain emulgents such as
carboxymethylcellulose, polyethylene glycol, etc. increase
the viscosity of the medium, which helps create and
maintain the suspension of globules of the dispersed phase
 Simple emulsion types
Oil-in-water Water-in-
oil

Water
Oil
(continuous phase)
(continuous phase) Water droplet
Oil droplet
(dispersed (dispersed phase)
phase)
Multiple Emulsion Types
Detection Tests:
DILUTION TEST:
• based on the solubility of external phase of emulsion.
- o/w emulsion can be diluted with water.
- w/o emulsion can be diluted with oil.
Detection Tests:
CONDUCTIVITY TEST:
• water is good conductor of electricity whereas oil is
non- conductor. Therefore, continuous phase of water
runs electricity more than continuous phase of oil.
Detection Tests:
DYE-SOLUBILITY 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
• if the scattered globules appear red and continuous
phase colorless, then it is w/o type.
Detection Tests:

FLUORESCENCE TEST:
• Oils give fluorescence.
• Under UV light, while water doesn’t. Therefore,
O/W emulsion shows spotty pattern while W/O
emulsion fluoresces.
What is an emulsifier?

Water loving Oil loving

head tail

'Hydrophilic 'Lipophilic'
' 'Hydrophobic
'Lipophobic' '
 What is an emulsifier?
•
An emulsifier is a surface active agent with an affinity
for both the oil and the water phases on the same
molecule

•
An emulsifier reduces the surface tension at the oil /
water interface and protects the newly formed droplet
interfaces from immediate coalescence
 Mechanism Of Action
When two immiscible liquids are agitated together so that one
of the liquids is dispersed as small droplets in the other. To
prevent coalescence between globules, it is necessary to use
emulsifying agent.

Emulsifying agent may be classified in accordance with the

type of film they form at the interface between the two
phases.

There are three types of films:

Monomolecular Films.
Multimolecular Films.
Solid Particle Films.
 Mechanism Of Action
1. Monomolecular Film:

Coherent monomolecular film.

Flexible film formed by SAA.
Can prepare O/W or W/O emulsion.
Lower surface tension and increase stability of emulsions.

Examples:
Potassium Laurate
Polyoxyethylene sorbitan monooleate
 Mechanism Of Action
2. Multi-molecular Film:

o Strong rigid film formed. mostly by the hydrocolloid.

o Produce o/w emulsion.
o Have low effect on surface tension.

Examples:
o Acacia
o Gelatin
 Mechanism Of Action
3. Solid Particle Film:
o Film formed by solid particles that are small in size compared
to the droplet of the dispersed phase.
o Can form o/w and w/o emulsions.
o Particles must be wetted by both phases in order to remain
at the interface and form stable film.

Examples:
o Bentonite
o Graphite
o Magnesium Hydroxide
Types of emulsifiers - Anionics
The emulsifier carries a negative charge e.g. Sodium Stearate
soap
C H C -
17 35 OO Na +
Pros and Cons
•
Were very common
•
Old fashioned
•
Not as versatile
•
Cheap
•
Limitations for actives due to high pH
•
Give negative charge to the oil droplet
Types of emulsifiers -
Cationics
The emulsifier carries a positive charge
e.g. Palmitamidopropyl Trimonium Chloride

O CH3
_
CH3(CH2)14C NH(CH2)3 + Cl
N CH 3
CH3
Types of emulsifiers – Non-ionics
Emulsifier carries no overall charge and can be
made to form both Water-in-oil or Oil-in-
water emulsifiers e.g. Steareth-2

CH3(CH2 )16CH2 (OCH2 CH2)2OH

Improving emulsion stability
• Charge stabilisation
• Interfacial film strengthening
• with powders
• with polymers
• with non-ionic emulsifiers
• Steric stabilisation
• Continuous phase viscosity
• Droplet size
• Co-emulsifiers / polar waxes
• Liquid crystals
 Improving emulsion stability
Charge stabilisation

+ + + + +
+
+
+ -- - -- + + - - -- +
+ -- - -- - - --
- - + +- -
+ - + + - +
- -- + +
- - -
+
- -- +
- + + - --
+ +
+ -- +
- +
+ -+ - +- + - -
+ + - - - -+ -- - --
- - -
+ + - + + - -
+
+ ---
Negatively charged oil droplets repel each other

Stability affected by quantity of electrolyte and whether M+ or M++

Improving emulsion stability
• In this system
• The negatively charged Stearate groups migrate to
the interface
• The positively charged ions in solution (counter
ions) are attracted to these now charged droplets
• A layer is formed where the impact of the charge
is
reduced
• This layer, called the Helmholtz double layer, can
reduce the repulsive effect and so stability
 Improving Emulsion Stability
Helmholtz double layer effect
+
+
- +
-
-
- + + -
- + -
- +
- + - -
+
- + -
- + - + - Water phase
Oil droplet
- + - +
-
- + - +
- +
- + -
-
- -
+
- +
+ -
+ - +

Electrical double layer

Improving emulsion stability
• The double layer is likely to be more diffuse the further
away from the droplet you go (Gouy and Chapman
and Stern)
• the same can happen for cationic and non-ionic
emulsifiers
• The effect is impacted by the presence of electrolytes
• Adding electrolyte increases instability by reducing the
shielding effect
• The extent of this depends on the amount of
electrolyte added and the valency of the electrolyte
Improving emulsion stability
• Interfacial film strengthening
• Reduces the probability of coalescence when
droplets collide
Improving emulsion stability
Interfacial film strengthening
• with powders

Powder particle size must be

very small

Powder must have an affinity

for
both the oil and water phase
Improving emulsion stability
Interfacial film strengthening
• with polymers

Polymer sits at emulsion interface

Polar groups orient into the water phase

e.g. Cetyl PEG/PPG-10/1 Dimethicone

Acrylates/vinyl isodecanoate
crosspolymer
Steric stabilisation
• Polymer molecules adsorb on
the surface of oil droplets,
leaving tails and loops
extending into the water phase
• Polymer molecules must be
strongly adsorbed at interface
• There must be high coverage of
droplet surface with polymer
• The 'tails and loops' must be
soluble in the water phase
• e.g. Cetyl PEG/PPG-
10/1 Dimethicone