AMIT M.

GUPTA
LECTURER,
AGNIHOTRI COLLEGE OF PHARMACY, WARDHA
S U R F A C T A N T S

BASIC TERMINOLOGY
Hydrophilic: A liquid/surface that has a high affinity to water.
Hydrophobic: A liquid/surface that has very low affinity to water
Lipophilic: A liquid/surface that has a high affinity to oil.
Lipophobic: A liquid/surface that has a very low affinity to oil.
Hydro=Water
Lipo=Oil
Philic=Friendly
Phobic=Scared
Philic=Friendly
Phobic=Scared
+
+
Hydrophilic
Hydrophobic
Lipophilic
Lipophobic
Lyo=Dissolve
Philic=Friendly
Phobic=Scared
+
Lyophilic
Lyophobic
BASIC TERMINOLOGY
Hydrophobic Lipophilic
Lyophilic in oil
Lyophobic in water
Hydrophilic Lipophobic
Lyophobic in oil
Lyophilic in water
Surfactants
A molecule that contains a polar portion and a non polar portion.

A surfactant can interact with both polar and non polar molecules.

A surfactant increases the solubility of the otherwise insoluble
substances.

In water, surfactant molecules tend to cluster into a spherical geometry
non polar ends on the inside of the sphere
polar ends on the outside

These clusters are called micelles



Surfactants are molecules that preferentially adsorb at
an interface, i.e. solid/liquid (froth flotation),
liquid/gas (foams), liquid/liquid (emulsions).

Significantly alter interfacial free energy (work
needed to create or expand interface/unit area).

Surface free energy of interface minimized by
reducing interfacial area.
INTRODUCTION
Surfactants have amphipathic structure





Tail or hydrophobic group
Little affinity for bulk solvent. Usually hydrocarbon
(alkyl/aryl) chain in aqueous solvents. Can be linear or
branched.

Head or hydrophilic group
Strong affinity for bulk solvent. Can be neutral or
charged.
Tail
head
SURFACTANT STRUCTURE
SURFACTANT CLASSES
Anionic (~ 60% of industrial surfactants)
SURFACTANT CLASSES (contd.)
Cationic (~ 10% of industrial surfactants)
Non-ionic (~ 25% of industrial surfactants)
SURFACTANT CLASSES (contd.)
SURFACTANT CLASSES (contd.)
Amphoteric or zwitterionic (~ 10% of industrial surfactants).
Generally expensive specialty chemicals.
HYDROPHILIC-LIPOPHILIC BALANCE


Griffin (1949): the hydrophilic-lipophilic balance (HLB) of a
surfactant reflects its partitioning behavior between a polar
(water) and non-polar (oil) medium.

HLB number, ranging from 0-40, can be assigned to a
surfactant, based on emulsification data. Semi-empirical only.

Strongly hydrophilic surfactant, HLB 40
Strongly lipophilic surfactant, HLB 1

HLB dependent upon characteristics of polar and non-polar
groups, e.g. alkyl chain length, headgroup structure (charge,
polarity, pK
a
).
HYDROPHILIC-LIPOPHILIC BALANCE
-- Effect of Structure --
oil
water
C
oil

C
water

C
6
H
13
COO
-
C
8
H
17
COO
-
C
10
H
21
COO
-

HLB decreases

Surfactant


HLB

Sodium laury sulfate, C
12
H
25
SO
4
-
Na
+

Potassium oleate, C
17
H
35
COO
-
K
+

Sodium oleate, C
17
H
35
COO
-
Na
+

Oleic acid, C
17
H
35
COOH
n-butanol, C
4
H
9
OH
cetyl alcohol, C
16
H
33
OH

40
20
18
1
7
1

HYDROPHILIC-LIPOPHILIC BALANCE
A value of 10 represents a mid-point of HLB.


HLB


USE

4-6
7-9
8-18
13-15
15-18

Water-in-oil emulsions
Wetting agents
Oil-in-water emulsion
Detergents
Solubilizing

0 2 6 8 10 12 14 16 18 4
No
dispersibility
in water
poor dispersibility
in water
Water in oil
emulsifier
Wetting agent
Milky
dispersion;
unstable
Translucent to
clear solution
Clear solution
Detergent Solubilizer
Oil-in-water
emulsifier
HYDROPHILIC-LIPOPHILIC BALANCE
triglycerol monooleate: Cream
and ointment stabilizers
Polysorbate 20
Insecticidal
sprays
HLB
MICELLES

If concentration is sufficiently high, surfactants can form
aggregates in aqueous solution micelles.

Typically spheroidal particles of 2.5-6 nm diameter.
(Klimpel, Intro to ChemicalsUsed in Particle Systems,p. 29, 1997, Fig 21)
McBain
Lamellar
Micelle
Hydrocarbon
Layer
Water
Layer
Water
Layer
Hartley
Spherical
Micelle
+
+
+
+
+
+
+
+
-
-
- -
-
-
-
-
-
-
-
-
-
-
-
-
Micelle Structure of a Surfactant



Hydrophilic head Hydrophobic tail
Amphiphiles
Coarse-grained
Model
beads connected by an anharmonic spring.
Interactions between every two beads are
governed by a Lennard-Jones (LJ) and
FENE potentials.
2 3
h t
MICELLES
--CMC--
Onset of micellization observed by sudden change in
measured properties of solution at characteristic surfactant
concentration
critical micelle concentration (CMC).
(Klimpel, Intro to ChemicalsUsed in Particle Systems,
p. 29, 1997, Fig 20)
MICELLES
--CMC Trends--

(1) For the same head group, CMC decreases with increasing
alkyl chain length.

(2) CMC of neutral surfactants lower than ionic

(2) CMC of ionic surfactants decreases with increasing salt
concentration.

(3) For the same head group and alkyl chain length, CMC
increases with increase in number of ethylene oxide groups.

(4) For mixed anionic-cationic surfactants, CMC much lower
compared to those of pure components.
MICELLES
--Example: Mayonnaise--
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
Water matrix containing fat
droplets. The surfactant
(emulsifier) is lecithin. It can
contain up to 12 g of fat in
15 ml
Water matrix
Oil
+
+
+

+

http://wilfred.berkeley.edu/~gordon/BLOG-images/mayo15.jpg
MICELLES
--Headgroup and Chain Length--
(Hunter, Foundations of Colloid Science, p. 569, 1993, Fig 10.2.1)


Surfactant


Temp (C)

b
0

b
1


Na carboxylates
K carboxylates
alkyl sulfonates
alkyl sulfates
alkylammonium chlorides

20
25
40
45
25

2.41
1.92
1.59
1.42
1.25

0.341
0.290
0.294
0.295
0.265

Branching or addition of double bonds or polar groups to alkyl chain
generally increases CMC.

Addition of benzene ring equivalent to addition of ~ 3.5 carbons
(methylene groups).

Replacement of hydrogens in alkyl chain with fluorine initially
increases CMC, followed by marked decrease as fluorine
substitution goes to saturation.
Cloud point versus Krafft point surfactants
The Krafft point is defined as the temperature at which
the solubility of the surfactant equals the critical
micellization concentration (cmc) = melting point of
hydrated surfactant
The Cloud Point is the LCST

MW PEO = 5 10
6
[C
m
H
2m+1
NHCO(CH
2
)
n
OSO
3
Me, abbreviated as
m-n-Me (Me=Na, 0.5 Ca)]

MICELLES
--Temperature and Pressure--
For ionic surfactants there exists a critical temperature above which
solubility rapidly increases (equals CMC) and micelles form
Kraft point or Kraft temperature (T
K
),

Below T
K
solubility is low and no micelles are present.
MICELLES
--Temperature and Pressure--
surfactant
crystals
T
K

Temperature

Surfactants much less effective below Kraft point, e.g. detergents.

For non-ionic surfactants, increase in temperature may result in
clear solution turning cloudy due to phase separation. This critical
temperature is the cloud point.

Cloud point transition is generally less sharp than that of Krafft
point.
MICELLES
--Electrolyte--
Addition of electrolyte significantly affects CMC, particularly
for ionic surfactants.

For non-ionic and zwitterionic surfactants;

log
10
CMC = b
2
+ b
3
C
s


where C
s
is salt concentration (M)
b
2
and b
3
are constants for specific surfactant, salt and
temperature.

Change in CMC attributed to salting in or salting out
effects. Energy required to create volume to accommodate
hydrophobic solute is changed in electrolyte solution due to
water-ion interactions
change in activity coefficient.
MICELLES
--Electrolyte--

If energy required is increased by electrolyte, activity
coefficient of solute is increased and salting out occurs
micellization is favored and CMC decreases.

Conversely, for salting in, CMC increases.

Effects of electrolyte depend on radii of hydrated anions and
cations and is greater for smaller hydrated ions, i.e. follow
lyotropic series.
CMC depression follows order:
F
-

> BrO
3
-
> Cl
-
> Br
-
> NO
3
-
> I
-
> CNS
-

and
NH
4
+
> K
+
> Na
+
> Li
+

In a typical surfactant system, bulk concentration, surface
concentration -- until cmc is reached.

cmc (critical micelle concentration) surfactant conc. where
micellization occurs.
A. Review: Micelles
log C
B
S
u
r
f
a
c
e

t
e
n
s
i
o
n
,

CMC
T
C d
d
|
.
|

\
|
ln

Surface excess

Forces driving micelle formation:
a) hydrophobic force
b) entropy


Forces opposing micelle formation:
a) concentration gradient
b) thermal (Brownian) motion
c) charge repulsion between ionic polar heads

Note: cmcs of nonionic surfactants are much lower than those of
ionic surfactants. Why?



B. Micellar Kinetics
Micelles are NOT static structures.

Micelles are unstable structures with two characteristic relaxation
times fast relaxation time (
1
) and slow relaxation time (
2
)
+ +
Fast relaxation time, microseconds
Slow relaxation time, milliseconds to minutes
+
t
1
t
2
C. Techniques Used to Measure Micellar Kinetics
Pressure-Jump (conductivity or optical detection)

Temperature-Jump (optical detection)

Stopped-Flow (conductivity, optical detection and
fluorescence)
Ultrasonic Absorption

Fluorescence

Shock-Tube
D. Effect of Surfactant Conc. on Micelle Lifetime
It has been shown that
micelle slow relaxation
time,
2
, is a function of
surfactant concentration
For all surfactants that
form micelles,
2

increases to a certain
maximum value
For ionic surfactants,
2

begins to decrease from
the maximum value
0.001
0.01
0.1
1
10
0 100 200 300 400 500 600 700
SDS Concentration (mM)
CMC
S
l
o
w

R
e
l
a
x
a
t
i
o
n
T
i
m
e
,

2
(
s
e
c
)
0.001
0.01
0.1
1
10
0 100 200 300 400 500 600 700
SDS Concentration (mM)
CMC
S
l
o
w

R
e
l
a
x
a
t
i
o
n
T
i
m
e
,

2
(
s
e
c
)
For nonionic surfactants,
2
remains constant at a maximum
value.


Remember: nonionic surfactants have much longer micellar
relaxation times (
2
) than ionic surfactants on the order of
seconds to minutes!
E. Technological Processes
Foaming (foamability & foam stability)

Fabric Wetting

Solubilization

Emulsification
Importance of Micellar Kinetics in
Technological Processes
The Importance of Micelle Break-up
in Foaming
Thin Liquid Film
Air
Air
Air
Surfactant
solution
More stable micelles Less monomer flux
Lower foamability
The Importance of Micelle Break-up
in Emulsification
Oil
Droplet
Water
More stable micelles Less monomer flux
Higher interfacial tension Larger droplet size
Geometrical Effects in
aggregation
Packing Parameter
V
al
=
J. N. Israelachvili, Intermolecular and surface forces, Academic, New York (1985).
Critical Micelle Concentration
(CMC)
Definition of the
CMC
Brownian Dynamics Results for amphiphiles
with different sizes of the hydrophilic group
Effect of the large head on micelle
size distribution
The geometry of amphiphile
effects the Cluster Distribution

Bigger head group molecules
form smaller clusters with
narrower distribution