Chapter 6 emulsification and

emulsification by surfactants
2006.4.19.

1. Introduction
1. Emulsion immiscible liquid phase, multiphase
dispersion, thermodynamics unstable system (from
a few minutes to a few years) e.g. milk , soybean
milk, bearnaise, finishing oil etc.
2. Formation
(1) Emulsification one fluid dispersed in a second
dispersephase , inner phase , discontinuous phase
dispersion medium outer phase continuous
phase
Three types: o/w, w/o, and w/o/w or o/w/o
two immiscible, pure liquids cannot form emulsion.

(2) Emulsifying agents the third component surfactants

3. Properties
(1) Size and aspect of particles
Macroemulsions: d>400nm, creamy white
Miniemulsions: 400nm>d>100nm, blue-white
Microemulsions: 100nm>d>50nm, translucence
Nanoemulsions: 50nm<d, transparence
(2) Viscosity Einsteins eq.
= 0 (1 + 2.5)
0 viscosity of outer phase
- volume fraction of inner phase

(3) Electric conductivity outer phase

o/w w/o ,
ionics nonioncs
4. Differentiation of emulsion types
(1) Dilution method
(2) Dyeing method
(3) Electric conductivity
(4) Filter paper method
(5) Light reflectance
(6) Fluorescence method

2. Theoretics and types of emulsions

Conversion in different types of emulsion
o/w w/o
1. Phase volume ratio
if particles(inner phase) are rigid ball with same
size, then volume fraction of inner phase
74.02%
water > 74%, then w/o o/w
water < 26%, then o/w w/o
monodisperse & rigid ball polydisperse & elastic
ball(w/o of oil=99%)

2. Wedge theory geometry theory Match model

3. Solubility rule hydrophilicity of surfactants

(1) Hydrophilic surfactants o/w
(2) Lyophilic surfactants w/o
4. Effects of wall
(1) Hydrophilic wall (high energy surface) o/w
(2) Lyophilic wall (low energy surface) w/o

5. Kinetic theory of emulsion type

Davies(1957)developed a quantitative theory of
emulsion type relating the type of emulsion formed to
kinetics of coalescence( ) of the two types of
droplets present: oil droplets & water droplets
Rate of coalescence of the particles:
dv/dt = Ae-E/kT
A collision factor; E energy barrier to coalescence
hydrophilic surfactants: Eoli, dv/dt of oil droplets,
dv/dt of water droplets, to form o/w emulsions
lyophilic surfactants: Ewater, dv/dt of water droplets,
dv/dt of oil droplets, to form w/o emulsions

6. Powder for emulsification

(1) Condition of emulsification
V/L Youngs eq. SV = SL + LV cos
Spreading S = SV - SL - LV = LV (cos-1) 0
O/w Youngs eq. SO = SW + OW cosW
or SW = SO + OW cosO
W+ O=180
SV

OW

vapor

oil
liquid

SV

SL

O
SO

water

SW

Spreading SW = SO - SW - OW = OW (cosW1) 0
or SO = SW - SO - OW = OW
(cosO-1) 0
If so ow + sw then W 0, the powder
is in water phase
If sw ow + so then o 0, the powder
is in oil phase
Else the powder is adsorbed at O/W
interface
0 < W < 180 or 0 < O < 180

(2) According O/w Youngs eq.

SO = SW + OW cosW or cosW = (SO - SW)/ OW
if SO > SW, W < 90, hydrophilic , mostly in water
phase o/w
if SO < SW, W > 90, lyophilic , mostly in oil
phase w/o
if SO = SW, W = 90, balance, o/w or w/o , but
unstable

3. Factors of effect on stability of emulsion

1.Reduces of interfacial tension between two liquids
e.g. 10ml n-octane( ) is dispersed in water to
0.1 m emulsion, then its surface area is 300m 2,
L/L= 50.8mJ/m2, then total surface energy=15.24J
if the surfactants are added into the disperse
system, then L/L 1 mJ/m2, then total surface
energy 0.3J.
Dynamic stability

2. Physical nature of the

interfacial film
(a) Mechanical stability
with strong lateral
intermolecular forces
and high film elasticity
(b) Liquidcrystal
formation with a
high-viscosity region
and a steric barrier to
stabilize of emulsion

3. Existence of an electrical or steric barrier to

coalescence on the dispersed droplets
(a) Electrical barrier -potential
of ionics:
-potential , stability
(b) Steric barrier

4. Viscosity of the outer phase - diffusion coefficient

of droplets:
D=kT/6a
- viscosity of the outer phase
a the radius of the droplets
, D, stability
5. Size distribution of droplets
larger particle have less interfacial surface per unit
volume than smaller droplets, so they are
thermodynamically more stable than smaller ones.
emulsion with uniform size distribution is more
stable.

4. Emulsifying agent and HLB value

HLB method which was advanced by Griffin in
1949, is the most frequently used method in
the selection of emulsifying agents.
1.HLB value Hydrophilic-Lipophilic Balance
HLB = Hydrophilic portion/Lipophilic portion
= 0 ~ 40
Paraffin ~ 0, sodium dodecyl sulfate ~ 40
HLB value < 10 lipophilic
HLB value >10 hydrophilic

HLB value for typical nonionic surfactants structures

2. HLB value
1~3
3~6
7~9
8 ~ 18
13 ~15
15 ~18

&

application
anti-foaming agent
w/o emulsifying agents
wetting agents
o/w emulsifying agents
detergents
solubilizing agents

3. Estimate of HLB value

(1)Nonionics:
HLB = mass fraction of hydrophilic group20
(a) Fatty acid of many polyhydric alcohols( )
HLB = 20(1-S/A)
S saponification number( ) of the ester;
A acid number( ) of the fatty acid in the ester.

e.g. C17H35COOCH2CH(OH)CH2OH
S=161, A=198, then HLB = 3.7
(b) Nonionics of POE & polyol
HLB = (E + P)/5
E the weight percentage of oxyethylene content
P the weight percentage of polyol content
e.g. C16H33(OC2H4)10OH
E = (44 10+17)/(44 10+17+225) = 67.0%;P = 0
HLB = (E+P)/5 = 67.0/5 = 0.67 20 = 13.4
(c) Logarithm: HLB=7+11.7ln(MW/MO)
MW or MO- molecular weight of hydro- or lipo-philic
group: MW=441, MO=225, then HLB=14.9

(2) Ionic surfactants

group numbers could
be calculated based
upon group
contribution accord-ing
to the formula:
HLB = 7 + (group
numbers)
e.g.C12H25SO4Na
HLB=7+38.70.47512=40
e.g. C16H33(OC2H4)10OH
HLB=7+0.33 10+0.50.475 16=3.20

(3) Mensuration
(a) behavior in water
no dispersibility
poor dispersion
milky dispersion after
vigorous agitation
stable milky dispersion
(upper end almost translucent)
from translucent to clear
clear solution

HLB Range
14
36
68
8 10
10 13
13 +

(b) Cloud point POE nonionics 1% aq.

TP , HLB, TP>100C, HLB>15,
TP HLB

(4) HLB of a mixyure

HLBmix= fiHLBi =fAHLBA+(1-fA)HLBB
fi the weight fraction of surfactant i in mixture
4. Emulsifying agents
(1) Synthetical surfactants
(a) Anionics HLB > 8 , o/w type
(b) Nonionics HLB < 18, o/w or w/o type
(c) Cationics - a few
(2) Natural surfactants lecithin( ),
cholesterin( ) etc
(3) Polymeric emulsifying agents
(4) Powder emulsifying agents

5. Application - selection of surfactants using HLB

value as emulsifying agents
(1) Optimal HLB value for emulsification
(A)Using the data handbook
(a) HLB value for emulsification of some oils

(b) Mixture of oils

HLBmix= Fj HLBj= FAHLBA+(1-FA)HLBB
Fj ,HLBj weight fraction and HLB of j oil.

(B) Mensuration and check

e.g. using the Span-series (HLBSpen-60=4.3) and
Tween-series (HLBTween-80=15), the optimal HLB
value for emulsification
(2) Optimal emulsifying agents
two principles
(a) The structure of
hydrophobic groups
of emulsifying agents
is close to the oils
(b) The synergistic effect

6. Phase Inversion Temperature ( PIT)

(1) Disadvantage of HLB method
(a) Surfactants with same HLB value could possess
different emulsifying ability
(b) It makes no allowance for the change in HLB
value with change in the conditions for
emulsification (temperature, nature of oil & water
phase). E.g. POE T, HLB
(2) PIT the temperature when the POE is used to
emulsifying agents from o/w emulsion inversion to
w/o
(3) Mensuration of PIT emulsion : 3-5% emulsifying
agents and o:w volume ratio =1

(4) Emulsion stability

(a) o/w type : PIT TS =20-60C
TS storage temperature ( )of emulsion
(b) w/o type : TS PIT = 10-40C
(c) Preparing temperature of emulsificatopn by the PIT
Preparation at a temperature 2-4C below the PIT to
obtain a very fine average particles size
Cooled down to storage temperature( for o/w) to
increases it stability
(5) Factors affecting PIT
(a) PIT HLB selection of emulsion PIT according to

their HLB value

(b) Hydrophility of POE , PIT
(c) Distribution of POE , PIT, o/w stability

(d) Addition of electrolyte in water phase, PIT

(e) In oil phase

addition of nonpolar organics e.g. paraffin
PIT
addition of polar organics
e.g.
long chain, PIT
short chain, PIT
Mixture of oils
PITmix= i PITi = A PITA + (1- A) PITB
i volume fraction of i oil; PITi PIT of i oil in
this emulsifying system

7. Preparation method of emulsion

(1)
(a)
(b)
(c)
(d)

Addition of emulsifying agents

in water phase
in oil phase
nascent soap( )
mixed films (respectively addition of hydrophilic
surfactants in water and hydrophobic surfactants
in oil phase)
(e) alternately addition of oil and water
(2) Oil-Water mixing
(a) The addition of water to oil - to obtain a very fine
average particles size and stable o/w emulsion
(b) The addition of oil to water

(3) Methods of emulsification

(a) Direct emulsification 70 - 75C
(b) Phase inversion emulsification
(4) Equipment of emulsification
(a) Simple agitating - impulse type ( ), turbo
type( )
(b) Homogenizer high pressure 6.89-34.47 Mpa
(c) Colloid mill ( ) rotor( ) and
stator( ), rotate speed = 1000-20000
rpm high shearing force ( )

5. instability of emulsion and demulsification

1.
(1)
(2)
(3)
(4)

Inversion of emulsion o/w w/o

Phase volume ratio
Polyvalent ions
Temperature T>PIT
Addition of electrolytes
o/w w/o

e.g. Inversion of o/w to w/o

by an interface film of sodium
cetyl sulfate ( )
and cholesterol ( )upon
addition of polyvalent cations

2. The creaming( ),
flocculation( ),and
coalescence( ) the
reversible prelude of
emulsion breaking
(a) Creaming difference
in gravitational
(b) Flocculation - attractive
force between droplets
(c) Coalescence irreversible
- breaking, phase separation

3. Emulsion breaking( ) to break the

interface films
(1) Methods
(a) Physical method
Heating
Electrical precipitation
Ultrasonic
(b) Chemical method
De-emulsifying agent
Inorganic acid
Polyvalent ion to inversion

(2) Mechanism
(a) Displacing emulsifying agents are displaced
by de-emulsifying agent
(b) Wetting powder emulsifying agents
(c) Flocculating cross-linking agents
(d) Collision - deemulsification
(e) Make the interface film to distortion( ) and
tendering( )
(3) Factor affecting de-emulsification
(a) pH value e.g. carboxylate surfactant is
unstable at low pH.

(b) Electrolyte
Concentration I , , stability.
Valenta value polyvalent ion , stability
(c) Temperature - T, solubility of surfactants,
intensity of film
(d) Phase volume ratio volume fraction > 74.02%
(h) Stirring Reynolds number ( ) - 3500

6. Micro-emulsion
Generally : surfactants & cosurfactants and etc
In 1986,the cosurfactant-free microemulsion
have been prepared
The differentia with macro-emulsion

2. Mechanism of formation
(1) Negative interfacial tension theory Schulman
and co-workers: 0 spontaneous process
it may be a transient phenomenon( ), and at
equilibrium must be zero or slightly positive.
is macroscopy property and made no sense in
micro-emulsion
oil
(2 ) (duplex film?)

surfactants + co-surfactants
Mixed film

+ auxiliary agent( )
water
mo

mw

If mw mo, then the films is bended to water phase, w/o

If mw < mo, then the films is bended to oil phase, o/w

(3) Swollen micelles