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Emulsions
Surfactants
Surface active agents
Amphiphiles
Detergents
Tensides
In most cases, solvent is water
hydrophilic (polar) group (head group)
hydrophobic alkyl chains (tail group)
Surfactants
anionic
cationic
nonionic
amphoteric (zwitterionic)
Anionic Surfactants
head group negatively charged
e.g. carboxylate, sulfonate, sulfate
most commonly used surfactants
example SDS (C12H25OSO3Na)
Cationic Surfactants
Headgroup positively charged
not so common (low biodegradability)
example: DTAB C12H25N(CH3)3Br
Nonionic Surfactants
Uncharged, but polar headgroup
second most common used surfactants
example: Alkylethylene oxides as e.g.
C10H21(OCH2CH2)8OH, also writen as
C10E8
Amphoteric Surfactants
Headgroup contains both positive and
negative charge
seldom used (more expensive)
examples: mainly lipids
Surfactants
Surfactants
Micelles
Structure of Surfactants in Solution
Micelles
Cylinders
Bilayers
Critical Micellation Concentration
CMC
SDS
70
Surface tension
Surface tension (mJ/m )
-2
60 Solubilty
50
Turbidity
40
30
1 10 100 1000
Concentration (mM)
What happen near cmc?
Pluronic
Thermodynamics of Micelles
Entropy: bringing hydrocarbon tails out of
the water (hydrophobic effect) -> decrease
of CMC with increasing tail length
Lateral repulsion of headgroups: hydration
force, steric effects
Electrostatic repulsion for charged
surfactants -> influence of salt
concentration
Influence of chain length and salt
concentration on the CMC
Example:
alcylsulfate
in NaCl at
21C
Structure of Surfactants in Solution
Micelles
Cylinders
Bilayers
Determined by the
surfactant parameter
(packing ratio)
Surfactant Parameter
VC AC
NS =
LC A0 A0
VC = Volume of the hydrocarbon tail
LC = Length of hydrocarbon tail
A0 = Area per head group
Surfactant Parameter
VC AC
NS =
LC A0 A0
small values: high curvature
values ~ 1: small curvature
high values: inverse micelles
Surfactant Parameter
LC LC LC
A0 A0 A0
NS = 0.33 NS = 0.5 NS = 1
Cylinder
or rod-like
aggregate
Bilayer
Vesicle
or
liposome
Calculation NS
VC (nC 0.027 + 0.029 )nm 3
0.21
AC
0.205
0.2
0 5 10 15 20
n
Example
NS =
VC
=
(11 0.027 + 0.056 )nm 3
= 0.37
LC A0 (11 0.127 + 0.15)nm 0.62nm 2
Biological Membranes
Functions of biological membrane
Effective barrier for ionic transfer and charges
Eq. 12.8:
compare dissociation energy in both media
e2 e2
diss
Eoil Ewater
diss
= = 33 kT
8 0 water 8 0 oil
Oil-in-water
Water-in-oil
in this context, oil may denote any liquid not miscible with water!
Volume fraction d
Determines many properties, e.g.
Viscosity
Conductivity
Polydispersity
1 (ln R ln R ) 2
P= exp
R 2 2 R
2
Lognormal distribution
Types of emulsions
Macroemulsions
Only kinetically stable -> demulsification
0.5-10 m size of droplets
external driving force
Microemulsions
Thermodynamically stable
very small droplet size (nm)
equilibrium as driving force
Formation of Macroemulsions
3V
Gem =
R
Energy required depends on surface
tension between liquids -> surfactants
In practice higher energies are necessary
0.40.6
R W
oil-in-water or water-in-oil?
oil-in-water or water-in-oil?
Volume fraction has little influence!
Dependence mainly on NS
for NS < 1, mainly oil in water
for NS > 1, mainly water in oil
4
V d = NR 3
3
V S = 4LS NR 2
3LS d
R=
S
Phase behavior of Microemulsions
Water / octane
microemulsion
with alkylethyleneoxide
more surfactant: (C12E5)
easier to contain PIT = 32C
all oil in droplets
curvature too
large to contain all
oil in droplets
Phase transition
When T , then
size of head group (less hydration)
tail widens (thermal fluctuations)