Colloid chemistry

Lecture 13: Emulsions

Emulsions

food

cosmetics

pharmaceutics

biological systems

bituminous carpet (asphalt)

etc.
 Emulsion
suitable for
intravenous
injection.

Emulsions
Balm: Water in oil emulsion Sodas: Oil in Water emulsion

Milk: Oil in Water

emulsion

Dodecane droplets in a Mayonnaise: Oil in

continuous phase of Water emulsion
water/glycerol mixture.
Emulsions encountered in everyday life!

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
 Introduction
Emulsion – Suspension of liquid droplets (dispersed phase) of
certain size within a second immiscible liquid
(continuous phase).
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
- Based on size of liquid droplets
0.2 – 50 mm Macroemulsions (Kinetically Stable)
0.01 – 0.2 mm Microemulsions (Thermodynamically Stable)
 Emulsifying agents

Stable suspensions of liquids constituting the dispersed phase, in an

immiscible liquid constituting the continuous phase is brought about
using emulsifying agents such as surfactants

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
 Common Emulsifying Agents
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)
 Making emulsions

surfactant

oil droplet in
water oil droplet in
(unstable) water
(stabilized)

po
lym
solid

er
particles

oil droplet in
water
(stabilized)
 ∆G = γ H ∆A >> 0
emulgeation requires large energy input

∆G = γ H ∆A << 0
drop coalescence proceeds continuously

∆G = γ H ∆A + desorption energy

high desorption energy

prevents/hinders coalescence
 Making emulsions

O/W W/O
 Surfactant Packing Parameter

• 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
 Surfactant Packing Parameter
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.
Surfactant Packing Parameter
Packing Parameter is inversely related to HLB

mid point of packing

parameter
P=1
analogous to
HLB 10

at P = 1/ HLB = 10,
surfactant has equal
affinity for oil and water
 W/O vs. O/W emulsions
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).
 optimum for
O/W emulsions

HLB

oil

optimum for water

W/O emulsions

water

oil
 The type of emulsion (O / W or W / O) is affected by:
• the ratio of the oil to water (non-polar to polar) phase;
• the chemical properties and the concentration of the emulsification agent;
• the temperature; the presence of additives;
• for solid particles as the stabilizing agents (Pickering emulsions)
the wetting conditions (contact angles of the oil and water phases on the solid)

Bancroft’s rule (1912): the dispersion medium of an O+W emulsion is the phase
in which the solubility of the emulsifying agent is higher.

HLB APPLICATIONS
1-3 antifoaming agents; inverse micelles
3-8 W/O emulsifiers
7-9 wetting agents
10-16 O/W emulsifiers
13-16 detergents
15-18 solubilizers
Application of surfactants on the basis of their HLB
 Pickering emulsions

oil

θ θ
víz
water
oil
oil

water
water
HLB values for typical nonionic surfactants structures

tenzid kereskedelmi név HLB

Bancroft’s Rule: Relation to HLB & CPP of Surfactant

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
 Bancroft’s Rule: Relation to HLB & CPP of Surfactant
Surfactant
Surfactant

Packing Parameter = 1

Oil Water
Oil Water

Microemulsion
Surfactant more soluble in Surfactant more soluble in
water (CPP < 1, HLB > 10) oil (CPP > 1, HLB < 10)
O/W emulsion W/O emulsion
 Tests for emulsion type
(W/O or O/W emulsions ?)

Based on the Bancroft’s rule, many emulsion properties are

governed by the properties of the continuous phase

1. dye test
2. dilution test
3. electrical conductivity measurements
4. refractive index measurement
5. filter paper test
Conductivity of emulsions

O/V

V/O
 Emulsions are kinetically stable!
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)
 Emulsions are kinetically stable!
(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.
 Emulsions are kinetically stable!
(c) Viscosity of the continuous phase
Higher viscosity reduces the diffusion coefficient

Stoke-Einstein’s Equation

This results in reduced frequency of collision and therefore

lower coalescence. Viscosity may be increased by adding
natural or synthetic thickening agents.

Further, η ↑ as the no. of droplets↑

(many emulsion are more stable in concentrated form than
when diluted.)
 Emulsions are kinetically stable!
(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.
 Phase inversion in emulsions
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 Bancroft’s 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.
Phase inversion induced by the change in the HLB / CPP

Na-soap Ba-soap

+ BaCl2
water oil
O/W W/O

O/W

W/O
 Why does phase inversion take place for system with surfactants?
Surfactant Surfactant

Oil Water Oil Water

O/W emulsion W/O emulsion

temperature for non ionics, salting out electrolytes for ionics
Bancroft’s rule: manifested in response of surfactant solubility

temperature for non ionics, salting out electrolytes for ionics

O/W emulsion W/O emulsion

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
 Inversion of emulsions (phase inversion)
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
 Inversion of emulsions (phase inversion)

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.
 Creaming of emulsions
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
πa ∆ρgH 〈〈 kT
3
a - droplet radius, ∆ρ - density difference,
g - gravitational constant, H - height of the vessel,

Creaming can be prevented by homogenization. Also by reducing

∆ρ, creaming may be prevented. This is achieved by producing
a polyphase emulsion
 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.
 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.
 Selection of emulsifiers

Correlation between chemical structure of surfactants and

their emulsifying power is complicated because
(i) Both phases oil and water are of variable compositions.
(ii) Surfactant conc. determines emulsifier power as well as the
type of emulsion.

Basic requirements:
1. Good surface activity
2. Ability to form a condensed interfacial film
3. Appropriate diffusion rate (to interface)
 General guidelines:

1. Type of emulsion determined by the phase in which emulsifier

is placed.

2. Emulsifying agents that are preferentially oil soluble form W/O

emulsions and vice versa.

3. More polar the oil phase, the more hydrophilic the emulsifier
should be. More non-polar the oil phase more lipophilic the
emulsifier should be.
 General guidelines

1. HLB method – HLB indicative of emulsification behavior.

HLB 3-6 for W/O

8-18 for O/W

HLB no. of a surfactant depend on which phase of the final emulsion

it will become.

Limitation – does not take into account the effect of temperature.

 General guidelines

2. PIT method – At phase inversion temperature, the hydrophilic

and lipophilic tendencies are balanced.

Phase inversion temperature of an emulsion is determined

using equal amounts of oil and aqueous phase + 3-5%
surfactant.

For O/W emulsion, emulsifier should yield PIT of 20-600C

higher than the storage temperature.
For W/O emulsion, PIT of 10-400C lower than the storage
temperature is desired.
 General guidelines

3. Cohesive energy ratio (CER) method

Involves matching HLB’s of oil and emulsifying agents;
also molecular volumes, shapes and chemical nature.

Limitation – necessary information is available only for

a limited no. of compounds.
Breaking emulsions

1 – phase separation
(creaming/sedimentation)

2 – Ostwald ripening

3 – aggregation processes
(flocculation;
coagulation;
coalescence)

4 – phase inversion
 Breaking emulsions
coalescence breaking

primary
emulsion

flocculation creaming
 Stabilization of emulsions
• emulsifiers: mostly surfactants
• hydration forces: O / W
• steric forces: W / O
• electrostratic forces: ionic surfactants
• polymers: steric forces (entropy stabilization)
• solid powders: hydrophobic forces (+ wetting)

Breaking emulsions
• sedimentation
• centrifugation
• filtration
• thermal coagulation
• electric treatment
• ultrasonication
• chemical additives (e.g. salting out)
Complex (multiphase) emulsions

aqueous phase stirring

step 1

oil + lipophilic W / O emulsion

surfactant

W / O emulsion stirring

step 2

hidrophilic W/O/W
surfactant complex emulsion
 Complex
primary emulsifier
oil phase (multiphase) emulsions
inner aqueous phase

szekunderemulsifier
secondary emulgeálószer

outer aqueous phase

W / O / W emulsion

W/O/W O/W/O

10 µm 20 µm

W/O/W O/W/O
 Hypothetic phase diagram
surfactant

water oil
 unstable metastable stable

ma
c ro
em
uls
io ns

miniemu
lsions

microemulsions

stability
 Micelles, solubilizates, emulsions

normal
micelle
solubilizate
thermodynamically thermodynamically
stable unstable

microemulsion O/W macroemulsion

Emulsions – microemulsions - internal structure

O/W W/O
Bicontinuous structure (µE)

- bicontinuous µEs do exist;

- bicontinuos emulsions do not exist!
 The interfacial tension (IFT) for microemulsions is ca.
1000-times less than the IFT of O/W or W/O emulsions !!!

IFT [mN/m]

O/W µE W/O

100 % water 100 % oil

Appearance and properties

microemulsion

emulsion
 Physico-chemical properties

property microemulsions emulsions

formation spontaneous, no energy input required
energy input requied
type O/W; W/O; O/W; W/O; + complex:
bicontinuous structure O/W/O; W/O/W
stability thermodynamically thermodynamically
stable unstable; kinetically
stable
optical properties transparent; turbid; milky
translucent
stabilizing agents surfactants; surfactants; polymers;
co-surfactants solid particles (Θ.90)
interfacial tension (.0 ($1 mJ/m2

size 20-400 nm 1-20 µm

 Winsor-microemulsions

phase inversion may be generated by the variations of temperature/salinity

nonionic surfactants: temperature increases

ionic surfactants: electrolyte (NaCl) concentration increases
 Winsor-microemulsions

pure oil pure water

O/W bicontinuous W/O

Winsor-I Winsor-III Winsor-II