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

Dodecane droplets in a
continuous phase of
water/glycerol mixture.

Sodas: Oil in Water emulsion

Mayonnaise: Oil in
Water emulsion

Milk: Oil in Water

emulsion

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
Nonionic
Cationic

Sodium stearate, Potassium laurate

Sodium dodecyl sulfate, Sodium sulfosuccinate
Polyglycol, Fatty acid esters, Lecithin
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
(unstable)
po

oil droplet in
water
(stabilized)

lym
er

solid
particles

oil droplet in
water
(stabilized)

G = H A >> 0
emulgeation requires large energy input

G = H A << 0
drop coalescence proceeds continuously

G = 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
W/O emulsions
water
oil

water

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)
Bancrofts 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

water
vz

oil

oil
water
water

HLB values for typical nonionic surfactants structures

tenzid

kereskedelmi nv

HLB

Bancrofts Rule: Relation to HLB & CPP of Surfactant

Surfactant

Surfactant

Water

Oil

Surfactant more soluble in

water (CPP < 1, HLB > 10)
O/W emulsion

Oil

Water

Surfactant more soluble in oil

(CPP > 1, HLB < 10)
W/O emulsion

Bancrofts Rule: Relation to HLB & CPP of Surfactant

Surfactant
Surfactant

Packing Parameter = 1
Water

Oil

Oil

Water

Microemulsion
Surfactant more soluble in
water (CPP < 1, HLB > 10)
O/W emulsion

Surfactant more soluble in

oil (CPP > 1, HLB < 10)
W/O emulsion

Tests for emulsion type

(W/O or O/W emulsions ?)
Based on the Bancrofts rule, many emulsion properties are
governed by the properties of the continuous phase
1.
2.
3.
4.
5.

dye test
dilution test
electrical conductivity measurements
refractive index measurement
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-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.)

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 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.

Phase inversion induced by the change in the HLB / CPP

Ba-soap

Na-soap

+ BaCl2

water
O/W

oil
W/O

O/W

W/O

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

Surfactant

Water

Oil
O/W emulsion

Water

Oil

W/O emulsion

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
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.

2.

3.

The order of addition of the phases

W O + emulsifier W/O
O W + emulsifier O/W
Nature of emulsifier
Making the emulsifier more oil soluble tends to produce a W/O
emulsion and vice versa.
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
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. 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
8-18

for
for

W/O
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 HLBs 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

stirring

aqueous phase

step 1
oil + lipophilic
surfactant

W / O emulsion

W / O emulsion

stirring

step 2
hidrophilic
surfactant

W/O/W
complex emulsion

primary emulsifier
oil phase
inner aqueous phase

Complex
(multiphase) emulsions

szekunderemulsifier
emulgelszer
secondary
outer aqueous phase
W / O / W emulsion

W/O/W

10 m
W/O/W

O/W/O

20 m
O/W/O

Hypothetic phase diagram

surfactant

water

oil

unstable
ma
c ro
em

uls
io

metastable

stable

ns

miniemu

lsions

microemulsions

stability

Micelles, solubilizates, emulsions

normal
micelle
thermodynamically
stable

microemulsion

solubilizate

O/W macroemulsion

thermodynamically
unstable

Emulsions microemulsions - internal structure

O/W
W/O
Bicontinuous structure (E)

- bicontinuous Es 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

100 % water

W/O

100 % oil

Appearance and properties

microemulsion

emulsion

Physico-chemical properties
property

microemulsions

emulsions

formation

spontaneous, no
energy input requied

energy input required

type

O/W; W/O;
bicontinuous structure

O/W; W/O; + complex:

O/W/O; W/O/W

stability

thermodynamically
stable

thermodynamically
unstable; kinetically
stable

optical properties

transparent;
translucent

turbid; milky

stabilizing agents

surfactants;
co-surfactants

surfactants; polymers;
solid particles (.90)

interfacial tension

(.0

($1 mJ/m2

size

20-400 nm

1-20 m

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

Winsor-I

Winsor-III

W/O
Winsor-II