Colloid Chemistry

COLLOID CHEMISTRY
Dr. Ngo Thanh An

Email: ngothanhan@gmail.com
1
1. Introduction
Emulsion Suspension of liquid droplets (dispersed

phase) of certain size within a second immiscible liquid
(continuous phase).
1. Introduction
Classification of emulsions
- Based on dispersed phase
Oil in Water (O/W): Oil droplets dispersed in water
Water in Oil (W/O): Water droplets dispersed in oil
Beside these two mayor groups of emulsions also
more complex emulsion systems are possible
(W/O/W and O/W/O).
- Based on size of liquid droplets
0.2 50 mm Macroemulsions (Kinetically Stable)
0.01 0.2 mm Microemulsions (Thermodynamically
Stable)
1. Introduction
1. Introduction
1. Introduction
Pesticide Asphalt Skin cream
Metal cutting oils Margarine Ice cream

Stability of emulsions may be engineered to vary from
seconds to years depending on application
2. Emulsion agent
Reduction of the surface tension is the key to avoid the

coagulation of the emulsion.
Substances which reduce the surface tension are called
surfactants.
In O/W and W/O, surfactants play a role of emulsifying
agent.
Surfactants must exhibit the following characteristics to be
effective as emulsifiers
- Good surface activity
- Should be able to form a condensed interfacial film
- Diffusion rates to interface comparable to emulsion
forming time
2. Emulsion agent
2. Emulsion agent
2. Emulsion agent
Surfactants
Anionic Sodium stearate, Potassium laurate, Sodium
dodecyl sulfate, Sodium sulfosuccinate
Nonionic Polyglycol, Fatty acid esters, Lecithin
Cationic Quaternary ammonium salts, Amine
hydrochlorides
Solids
Finely divided solids with amphiphilic properties such as
soot, silica and clay, may also act as emulsifying agents
(Pickering Emulsions: Attribute of high stability)
2. Emulsion agent
2. Emulsion agent
2. Emulsion agent
2. Emulsion agent
Hydrophil area Lipophil area Reduction of the surface

(= lipophob) (= hydrophob) energy
Generation of steric and
Emulsifier is solved in the outer phase electrostatic inhibitions
(inhibition of coalescence of the
drops)
2. Emulsion agent
water
water
oil
oil
W/O O/W
Hydrophil head
Lipophil chain
2. Emulsion agent
2. Emulsion agent
Conceptual framework that relates molecular parameters

(head group area, chain length and hydrophobic tail
volume) and intensive variables (temperature, ionic
strength etc.) to surfactant microstructures
Critical Packing Parameter / Packing Parameter

v
CPP or P
l a0
v: Volume of hydrocarbon core
l: hydrocarbon chain length
a0: effective head group area
2. Emulsion agent
v
CPP or P
l a0
v: Volume of hydrocarbon chain= 0.027(nc + nMethyl)

l: hydrocarbon chain length= 0.15 + 0.127nc

Where nc = number of carbon atoms without the methyl
group
nMethyl = number of methyl groups
ao: Effective head group area: difficult to calculate.
2. Emulsion agent
2. Emulsion agent
Bancroft's rule
Emulsion type depends more on the nature of the
emulsifying agent than on the relative proportions of oil or
water present or the methodology of preparing emulsion.
The phase in which an emulsifier is more soluble constitutes
the continuous phase
In O/W emulsions emulsifying agents are more soluble in

water than in oil (High HLB surfactants).
In W/O emulsions emulsifying agents are more soluble in
oil than in water (Low HLB surfactants).
2. Emulsion agent
Surfactant
Surfactant
Oil Water
Oil Water
Surfactant more soluble in Surfactant more soluble in oil

water (CPP < 1, HLB > 10) (CPP > 1, HLB < 10)
O/W emulsion W/O emulsion
2. Emulsion agent
Surfactant
Surfactant
Packing Parameter = 1
Oil Wate
r Oil Water
Microemulsion
Surfactant more soluble in Surfactant more soluble
water (CPP < 1, HLB > 10) in oil (CPP > 1, HLB < 10)
2. Emulsion agent
2. Emulsion agent
2. Emulsion agent
2. Emulsion agent
2. Emulsion agent
Mid Point of
Packing
Parameter
P=1
analogous to
HLB 10
At P = 1/ HLB =
10, surfactant has
equal affinity for
oil and water
2. Emulsion agent
2. Emulsion agent
3. STABILITY OF EMULSION
Rate of coalescence measure of emulsion stability.

It depends on:
(a) Physical nature of the interfacial surfactant film
For Mechanical stability, surfactant films are characterized
by strong lateral intermolecular forces and high elasticity
(Analogous to stable foam bubbles)
Mixed surfactant system preferred over single surfactant.
(Lauryl alcohol + Sodium lauryl sulfate: hydrophobic
interactions)
NaCl added to increase stability (electrostatic screening)
(b) Electrical or steric barrier

Significant only in O/W emulsions.
In case of non-ionic emulsifying agents, charge may arise
due to
(i) adsorption of ions from the aqueous phase or
(ii) contact charging (phase with higher dielectric constant is
charged positively)
No correlation between droplet charge and emulsion stability
in W/O emulsions
Steric barrier dehydration and change in hydrocarbon
chain conformation.
(c) Viscosity of the continuous phase

Higher viscosity reduces the diffusion coefficient
Stoke-Einsteins Equation
This results in reduced frequency of collision and therefore

lower coalescence. Viscosity may be increased by adding
natural or synthetic thickening agents.
Further, as the no. of droplets
(many emulsion are more stable in concentrated form than
when diluted.)
(d) Size distribution of droplets

Emulsion with a fairly uniform size distribution is more
stable than with the same average droplet size but
having a wider size distribution
(e) Phase volume ratio
As volume of dispersed phase stability of emulsion
(eventually phase inversion can occur)
(f) Temperature
Temperature , usually emulsion stability
Temp affects Interfacial tension, D, solubility of
surfactant, Brownian motion, viscosity of liquid, phases
of interfacial film.
Types of Physical instability are:
Flocculation
Creaming or sedimentation
Aggregation or coalescence
Phase inversion
Creaming, in the laboratory sense, is the migration

of the dispersed phase of an emulsion, under the
influence of buoyancy.
The particles float upwards or sink, depending on
how large they are and how much less dense or
more dense they may be than the continuous
phase, and also how viscous or how thixotropic the
continuous phase might be.
For as long as the particles remain separated, the
process is called creaming
Creaming is usually seen as undesirable because it

causes difficulties in storage and handling, but it can be
useful in special cases, especially where it is desirable
to concentrate an emulsion.
A particular example is in the separation of dairy
cream, either to achieve a desired concentration of
butterfat, or to make butter.
Depending on whether the dispersed particles are less
dense or more dense than the continuous phase, they
may move either to the top of a sample, or to the
bottom.
the process of migration is called creaming while

the particles of the substance remain separated.
In this it differs ideally from flocculation (where
particles clump) or emulsion breaking (where
particles coalesce).
One important difference between creaming and
the other two processes; unlike flocculation and
breaking, creaming of an emulsion is largely a
simple process to reverse
Droplets larger than 1 mm may settle preferentially to the

top or the bottom under gravitational forces.
Creaming is an instability but not as serious as
coalescence or breaking of emulsion
Probability of creaming can be reduced if
4 3
a gH kT
3
a - droplet radius, - density difference,
g - gravitational constant, H - height of the vessel,
Creaming can be prevented by homogenization. Also by
reducing , creaming may be prevented.
Bancroft's rule
Emulsion type depends more on the nature of the emulsifying
agent than on the relative proportions of oil or water present
or the methodology of preparing emulsion.
Based on the Bancrofts rule, it is possible to change an

emulsion from O/W type to W/O type by inducing changes
in surfactant HLB / CPP.
In other words...
Phase Inversion May be Induced.
Acetic Acid Surfactant
Tie line
Benzene Water Oil Water

Acetic acid & water are miscible in Surfactant and water are miscible
all proportions in all proportions
Benzene & water - partly miscible, Oil and water - partly miscible,
acetic acid & water - partly miscible surfactant and oil - partly miscible
Acetic acid added to a mixture of Surfactant added to a mixture of oil
benzene & water, preferentially & water, preferentially partitions
partitions into water (slope of tie line) into water (slope of tie line)
Increase T: At a specific temperature, surfactant becomes Oil Soluble
across all proportions, Acetic Acid does not!
Acetic Acid Surfactant

Increase in Acetic Acid Surfactant Increase in T,
T, P Electrolyte

Why does Phase Inversion Take Place for system with Surfactants?
Surfactant Surfactant
il Water Oil Water

Temperature for Non Ionics, Salting out electrolytes for ionics
Bancrofts Rule: Manifested in Response of Surfactant Solubility
Temperature for Non Ionics, Salting out electrolytes for ionics
Temperature and electrolytes disrupt the water molecules

around non-ionic and ionic surfactants respectively, altering
surfactant solubility in the process
Also reflected by change in curvature of the interface
O/W W/O
1. The order of addition of the phases
W O + emulsifier W/O
O W + emulsifier O/W
2. Nature of emulsifier
Making the emulsifier more oil soluble tends to
produce a W/O emulsion and vice versa.
3. Phase volume ratio
Oil/Water ratio W/O emulsion and vice versa
4. Temperature of the system

Temperature of O/W (polyoxyethylenated nonionic
surfactant) makes the emulsifier more hydrophobic
and the emulsion may invert to W/O.
5. Addition of electrolytes and other additives.

Strong electrolytes to O/W (stabilized by ionic
surfactants) may invert to W/O
Example. Inversion of O/W emulsion (stabilized by

sodium cetyl sulfate and cholesterol) to a W/O type
upon addition of polyvalent Ca.
4. METHODS OF DESTABILIZING EMULSIONS
1. Physical methods
(i) Centrifuging
(ii) Filtration media pores preferentially wetted by
the continuous phase
(iii) Gently shaking or stirring
(iv) Low intensity ultrasonic vibrations
2. Heating
Heating to ~ 700C will rapidly break most emulsions.
4. METHODS OF DESTABILIZING EMULSIONS
3. Electrical methods
Most widely used on large scale
20 kV results in coalescence of entrained water

droplets (W/O) e.g. in oil field emulsions and jet
fuels. (mechanism deformation of water drops
into long streamers)
For O/W, electrophoretic migration of charged

groups to one of the electrodes. Ex. Removing
traces of lubricating oil emulsified in condensed
water.
5. MANUFACTURING OF EMULSION
6. TEST OF EMULSION TYPE
Based on the Bancrofts rule, many emulsion properties are governed by the
properties of the continuous phase
Emulsion Type and Means of

Detection
Dilution
Refractive index
Conductivity Tests measurement
Dye-solubility Filter paper
Emulsion Type (W/O or O/W emulsions)

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.
The basic principle of this test is 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 is

used in which a pair of
electrodes connected to an
electric bulb is dipped into an
emulsion. If the emulsion is
o/w type, the electric bulb
glows.
In this test an emulsion is mixed with a water soluble dye (amaranth) and
observed under the microscope. If the continuous phase appears red, it
means that the emulsion is o/w type as water is in the external phase and the
dye will dissolve in it to give color. If the scattered globules appear red and
continuous phase colorless, then it is w/o type. Similarly if an oil soluble dye
(Scarlet red C or Sudan III) is added to an emulsion and the continuous phase
appears red, then it is w/o emulsion.
Fluorescence Test:
If an emulsion on exposure to ultra-

violet radiations shows continuous
fluorescence under microscope,
then it is w/o type and if it shows
only spotty fluorescence, then it is
o/w type.
Cobalt Chloride Test:
When a filter paper soaked in cobalt

chloride solution is dipped in to an
emulsion and dried, it turns from
blue to pink, indicating that the
emulsion is o/w type.

Colloid Chemistry - Chapter 10

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Colloid Chemistry - Chapter 10

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Dr. Ngo Thanh An

Emulsion Suspension of liquid droplets (dispersed

Pesticide Asphalt Skin cream

Metal cutting oils Margarine Ice cream

Reduction of the surface tension is the key to avoid the

Hydrophil area Lipophil area Reduction of the surface

Conceptual framework that relates molecular parameters

Critical Packing Parameter / Packing Parameter

v: Volume of hydrocarbon chain= 0.027(nc + nMethyl)

In O/W emulsions emulsifying agents are more soluble in

Surfactant more soluble in Surfactant more soluble in oil

Rate of coalescence measure of emulsion stability.

(b) Electrical or steric barrier

(c) Viscosity of the continuous phase

This results in reduced frequency of collision and therefore

(d) Size distribution of droplets

Creaming, in the laboratory sense, is the migration

Creaming is usually seen as undesirable because it

the process of migration is called creaming while

Droplets larger than 1 mm may settle preferentially to the

Based on the Bancrofts rule, it is possible to change an

Acetic Acid Surfactant

Benzene Water Oil Water

Benzene Water Oil Water

Benzene Water Oil Water

il Water Oil Water

O/W emulsion W/O emulsion

O/W emulsion W/O emulsion

Temperature and electrolytes disrupt the water molecules

4. Temperature of the system

5. Addition of electrolytes and other additives.

Example. Inversion of O/W emulsion (stabilized by

20 kV results in coalescence of entrained water

For O/W, electrophoretic migration of charged

Emulsion Type and Means of

Dye-solubility Filter paper

Emulsion Type (W/O or O/W emulsions)

The basic principle of this test is that

In this test, an assembly is

If an emulsion on exposure to ultra-

Cobalt Chloride Test:

When a filter paper soaked in cobalt

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