Micelle formation

When the concentration of surfactant reaches a

critical concentration, the hydrophobe of the
surfactant will organize to form micelle. In the
micelle, the lipophilic hydrocarbon chains are
orientated towards the interior of the micelle,
leaving the hydrophilic groups on contact with the
aqueous medium.
The concentration above which micelle formation
becomes appreciable is termed the critical micelle
concentration (CMC).

Properties of micelle
Several physical properties of surfactant solution abruptly
change at CMC.

Osmotic pressure
Turbidity
Surface tension

Molar conductivity
CMC

Concentration

Measurement of CMC
Surface tension method
Measure the surface tension of the solution with
different concentrations; Plot the -lnc curve. Extend the
two line at the turning point. The concentration at the
cross point is CMC.

CMC

Characteristic
1.
2.
3.

Simple, convenient
Valid for all of the surfactants
Sensitivity is independent of surfacetants, activities
and temperature etc..

 Electrical conductivity
In this method, the variation of electrical conductivity with
surfactant concentration is determined.

1. Only available for ionic

surfactant solution
2. The accuracy is related to the
CMC
3. The sensitivity affects by
inorganic electrolyte

 Dye solubilization
Adding dye into water and then dropping the surfactant
solution to color change,
Or adding dye into the solution which concentration is
larger than CMC and then diluting the solution to the
color change.
CMC is the concentration when the color changes.

Simple, convenient
The accuracy is affected by the amount of dye

 Turbidity method
Probe compound is added into the surfactant solution.
When the concentration is below CMC, it is cloudy. When
the concentration is above CMC, the solution is clear.
CMC is the concentration when the abrupt change occures.

Simple, convenient
The accuracy is affected by the amount of
compound

 Light scattering
CMC is determined through measurement the variation of
intensity of light scattering with the concentration.
Valid for all of the surfactant solutions.

Factors affecting critical micelle concentrations

Structure of the surfactant
When the hydrophobe is same, the CMC of ionic
surfactant is larger than non-ionic.
Increasing the hydrophobic part of the surfactant favours
micelle formation. The CMC of ionic surfactants is
approximately halved by the addition of each CH2 group.
For non-ionic surfactants, The CMC is approximately
decreased to 1/10 by the addition of two CH2 groups.
This law is valid for the C8~C16 members. Above the C18
member the CMC tends to be approximately constant.
log[cmc] = A - Bm
where m is the number of carbon atoms in the chain and
A and B are constants for a homologous series

When the length of the carbon chain is same, the CMC

depends on the component. For example, the CMC of
Fluorocarbons is greatly lower than that of hydrocarbons.
When the length of the carbon chain is same, the CMC
is also depends on the structure. The CMC of the
surfactant of which the hydrophobe has branches or
polar groups is high. The CMC of the surfactant whose
hydrophile locates the middle of hydrophobic chain is
also high.

 Electrolyte
The counter-ions decrease the CMC of ionic surfactants,
for a particular cationic surfactant, as the counter-ion is
changed according to the series F-, Cl-, Br-, and for a
particular anionic surfactant, as the counter-ion is
changed according to the series Li+, Na+, K+, Cs+.
Addition of high concentrations of salt to ionic surfactants
decreases the CMC. This effect is simply explained in
terms of the screening action of the counter-ions, i.e. the
associated counter-ions reduces the magnitude of the
forces of repulsion between the charged head groups in
the micelle and consequently decrease the electrical
work of micellization.
Electrolyte has small effect on the CMC of non-ionic
surfactants.

Effect of electrolyte concentration on the micellar properties

of dodecyltrimethylammonium bromide

 Organic molecules
The addition of organic molecule affect CMC in a variety
of ways.
Polar organic molecules with medium chain-length and
strong polar organic molecules can decrease the CMC;
Polar organic molecules with low molecular weight can
increase the CMC;

 Temperature
An increase in temperature can have varying effect on
the CMC of different surfactants.
In the case of ionic surfactants, the CMC is influenced
little by temperature. However, the CMC of non-ionic
surfactants decrease with increase in temperature.

Variation of CMC with

temperature for
1, CH3(CH2)N(CH3)3Br;
2, CH3(CH2)11SO4Na;
3,CH3(CH2)11(OCH2CH2)7OH.

solubilisation
Surfactant solutions above the CMC can
solubilise otherwise insoluble organic
material by incorporating it into the interior
of the micelles. This is known as micellar
solubilisation, the solubilised substance
being termed the solubilisate.

Example of solubilisation
Aqueous solution of:
sodium dodecyl sulphate (SDS, anionic surfactant) and
caproic acid (amphiphilic solubilisate)
At low concentrations of surfactant, the caproic acid and
SDS form mixed micelles

Increasing the concentration of surfactant results in the

formation of liquid crystals (LC phase)
Liquid crystals can also solubilise compounds but not as
efficiently as micelles
Further increases in surfactant concentration results in
inversion of the micelles, such that it is now the water
phase that is effectively solubilised
(L2 phase)

Inverted micelle

Nomenclature
L1 phase: clear (isotropic) solutions comprising micelles in
an aqueous continuous phase
L2 phase: clear (isotropic) solutions comprising inverted
micelles in a non-aqueous phase
LC phase: Clear (anisotropic) liquid crystaline phase
2L phase: Cloudy (isotropic) system comprising two
separate liquids
(the 2L phase may exist as a dispersion of one liquid within
another continous liquid phase, i.e. emulsion)
Heterogeneous (cloudy) systems may also be comprised of
a mixture of more than one single phases
eg. A birefringent solution of an L1 phase and LC phase
co-existing together

Nomenclature
In the general case for aqueous micellar solutions of ionic
or non-ionic surfactants:
a) Saturated solubilisates - dissolve in the interior non-polar
part of the micelle, eg. oils
b) Weakly polar or polarizable groups (such as double
bonds) on the solubilisate cause the molecule to locate
nearer the micelle surface
c) Amphiphillic solubilisates - these form mixed micelles
where the solubilisate molecules are orientated
alongside surfactant monomers
(In the case of non-ionic surfactants only)
d) Water soluble solubilisates are thought to complex with
the polyoxyethylene chains (i.e.the pallisade layer
surrounding the hydrocarbon core)

Determination of CMC by dye solubilisation

Effect of solubilisation on micelle size

Solubilisation in the micelle core results in an increase in
micellar size,
i) core is enlarged by the solubilisate
ii) aggregation number increases in an attempt to cover
the swollen core

Factors affecting solubilisation

Difficult to predict, only general rules may be applied
Depends on the nature of both the surfactant and solubilisate
Reference :
Physicochemical Principles of Pharmacy, 2nd edn., A.T.
Florence and D. Attwood
pp.221-224

Conductance
Factors affecting conductance of ionic surfactant solutions:
The total viscous drag on the surfactant molecules is
reduced on aggregation
Counter-ions become kinetically a part of the micelle,
owing to its high surface charge, thus reducing the
number of counter-ions available for carrying the current
and also lowering the net charge of the micelles.
Typically, 50 to 70% of the counter-ions are held in the
Stern layers; even so, the zeta potential of an ionic
micelle is usually high.
The retarding influence of the ionic atmospheres of the
unattached counter-ions on the migration of the
surfactant ions is greatly increased on aggregation.

Energetics of micellisation
mX=(X)m
c-x cx/m

cx / m
K
m
[c(1 x)]
Where c is the stoichiometric concentration of the
solution, x is the fraction of monomer units aggregated
and m is the number of monomer units per micelle.

 The standard free energy change

RT
G
ln K
m
RT cx

ln RT ln[ c(1 x)]

m m

At CMC, x=0, G=RTln(CMC)

d (G )
dT
d ln(CMC)
RT
R ln(CMC)
dT

Therefore, S

H G TS
2 d ln(CMC)
RT
dT

The Krafft phenomenon

Micelle-forming surfactants exhibit another
unusual phenomenon in that their solubilityes
show a rapid increase above a certain
temperature, known as the Krafft point.
When the temperature is raised to the krafft
temperature, a relatively large aount of
surfactant can be dispersed in the form of
micelles, so that a large increase in solubility if
observed.

Work of Cohesion and Adhesion

A
A

Work of cohesion: Wc=2A

Work of adhesion: Wa=A+ B -AB

Spreading of one liquid on another

Placing ways of one liquid on another :
Remain as lens (non-spreading).
Spread as a thin film until it is uniformly distributed over the
surface.
Spread as monolayer, leaving excess oil as lenses in
equilibrium.

Spreading coefficient:
S=Wa-Wc=B-A-AB
The condition for initial spreading is that S be positive or
zero.
Impurity affects the B,A and AB, then change the
spreading.
for example, see page 96.

Hydrophilic - Lipophilic Balance (HLB)

The HLB value for a given surfactant is the relative
degree to which the surfactant is water soluble or oil
soluble. The lower the HLB, value the more lipophilic.
The higher the HLB value, the more hydrophilic.

HLB Values and the use for those surfactants

HLB VALUE USE
EXAMPLE
1
Antifoaming Agent
Oleic Acid
2
Antifoaming Agent
Sorbitan Tristearate
3
Antifoaming Agent
Glyceryl Monostearate
4
Emulsifying Agent W/O Sorbitan mono-oleate (Span 80)
5
Emulsifying Agent W/O Glyceryl Monostearate
6
Emulsifying Agent W/O Diethylene glycol monolaurate
7
Emulsifying Agent W/O;
Wetting ans Spreading Agents {none}
8
Emulsifying Agent W/O;
Sorbitan monolaurate
Wetting and Spreading Agents
(Span 20)
9
Emulsifying Agent O/W;
Polyethylene lauryl
Wetting and Spreading Agents
ether(Brij 30)
10
Emulsifying Agents O/W Methyl Cellulose(Methocel15
cps)

11
12
13
14
15
16
17
18
19
20
40

Emulsifying Agents O/W Polyoxyethylene monostearate (Myrj 45)

Emulsifying Agents O/W Triethanolamine oleate
Emulsifying Agents O/W ;
Detergents
Polyethylene glycol 400 monolaurate
Emulsifying Agents O/W ;
Detergents
(none)
Emulsifying Agents O/W ; Polyoxyethylene sorbitan
Detergents
mono-oleate(Tween 80)
Emulsifying Agent O/W ; Polyoxyethylene sorbitan
Detergents: Solubilizing Agents monolaurate (Tween 20)
Solubilizing Agents
Polyoxylene lauryl ether(Brij 35)
Solubilizing Agents
Sodium oleate
Solubilizing Agents
None
Solubilizing Agents
Potassium oleate
Everything
Sodium Lauryl Sulfate (Tide)

The blending of Surfactants with HLB vaules to get a

desired HLB mixture is very easy.

For example if we want a surfactant mixture with an HLB

value of 9 we can blend surfactants with HLB values of 3
and 11. We use alligation and we now know that we
need 6 parts of the HLB 11 surfactant with 3 parts of the
HLB 3 surfactant to get our mixture with an HLB value of
9. We can use that mixture to make an oil in water
emulsion.

Monomolecular films
With the increasing of hydrophobic part of
surfactant, surfactant will tend to aggregate at
the surface and become insoluble in water. Thus,
the Insoluble substances can be spread on a
water surface to form a surface film. If space
permits, it will form a monomolecular films.
The molecules in a monomolecular film,
especially at high surface concentrations, are
often arranged in a simple manner, and much
can be learned about the size, shape and
orientation of the individual molecules.

Langmuir-Blodgett technology (LB)

LB technology is a technique to transfer a insoluble film
to a solid substrate. Based on LB technique, a molecular
assembly technology has been developed. The
molecular assembly technology is an important mean for
fabrication of advanced materials, .

(a)

x type

y type
(b)

z type

Experimental techniques for studying

insoluble monolayers
Surface pressure
The insoluble monolayer exerts pressure to the clean
interface due to the difference of surface tension.
Surface pressure is defined as =0-, where 0 is the
tension of clean interface and is the tension of interface
plus monolayer.

monolayer

Clean interface

Measurement of surface pressure

Surface balance (see page 98-99)
The trough walls, barrier and float must be hydrophobic
and the liquid level must be slightly above the brim of the
trough. Before spreading, the surface must be carefully
cleaned and freed from contamination. The surface
pressure is determined by measuring the force which is
applied via a torsion wire to maintain the float at a fixed
position on the surface.
Other methods
Wilhelmy plate method

-A curve
Where is the surface pressure (mN m-1) and A is the
average area occupied by each adsorbed molecule.

SM
A
WCN 0
Where S is the area of insoluble film, M is the molecular
weight, W is the weight of the spreading solution, C is the
concentration of the spreading solution, and N0 is the
Avogardro constant.

 Surface film potential

In heterogeneous systems, potential differences exist
across the various phase boundaries. The insoluble films
can be regarded as a capacitor, which will change the
potential.
The surface film potential is defined as the change in the
potential difference between the bulk substrate liquid and a
probe placed above the liquid which results from the
presence of the monolayer.
V=Vm-V0
The surface film potential can be measured by air-electrode
and vibrating-plate methods.

coulometer

Air-electrode
Ag/AgCl
electrode

potentiometer

Air-electrode method
Simple,
the distance between electrode and surface is large.
This method can be used to determine the
homogeneity of the film.

Vibrating-plate methods
Valid for liquid-gas and liquid-liquid interface

 The surface potential can be used to study the

orientation of film molecules.
To investigate the homogeneity
To investigate the structure of the film

Surface rheology
The monomolecular film influences the viscosity of the
surface layer.
Surface viscosity is defined as the change in the viscosity
of the surface layer hrought about by the monomolecular
film. It can be determined by a damped oscillation method.
(See page 101)
The study of surface rheology is useful in connection with
the stability of emulsions and foams and the effectiveness
of lubricants, adhesives, etc.

Electron micrographs of monolayers

See page 102
Used for studying the state of the surface.

The physical states of monomolecular films

Gaseous film

Expanded film

Condensed film

 Gaseous films, in which the molecules are

separate and move about the surface
independently, the surface pressure being
exerted on the barriers containing the film by a
series of collisions.
Obey an ideal two dimensional gas equation,
A=kT

 Condensed films, in which the molecules are

closely packed and steeply orientated towards
the surface.
Expanded films

Factors influencing the physical state of

monomolecular films

Structure
Temperature
pH of the substrate
Component of ions

Application of monomolecular films

Calculation of molar mass
at low compressions, films tend to be
gaseous: A=nRT=WRT/M, where W is weight
of the film, R is the gas constant, T is the
temperature, and M is the molar mass.
Thus, M=WRT/limA
0

Plot the -A curve and then calculate the limA (0)

 Determination of the structure of some

compounds
Preparation of cell membranes
Water conservation
.