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Surfactants, Micelles, 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


Surface tension (mJ/m )
70 60 50 40 30 1 10 100 1000
SDS

Surface tension Solubilty Turbidity

-2

Concentration (mM)

What happen near cmc?

see Excel sheet

Micelles
Hydrocarbon chains inside,polar head groups outside Spherical object of typically 30100 surfactant molecules,oily phase inside (polydisperse) Typical diameters 36 nm. Interiors show liquid phase properties Micelles are dynamic structures. Exchange at s timescale.

Temperature Dependence
Ionic surfactants weak dependence at low T, precipitation as crystals Krafft temperature: solubility = CMC consequence: low efficiency below Krafft point

Temperature Dependence
Example: SDS

Temperature Dependence
Nonionic surfactants at high T, formation of separate phase cloud point

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 A0 NS = 0.33 NS = 0.5 LC A0 NS = 1 LC A0

Micelles

Cylinders

Bilayers

Structures of Surfactants
Micelle
Inverted Micelles

Cylinder or rod-like aggregate

Bilayer Vesicle or liposome

Calculation NS
VC (nC 0.027 + 0.029 )nm
3

LC (nC 0.127 + 0.15 )nm


0.215 0.21

AC
0.205

0.2 0 5 10 15 20

Example
SDS: A0 = 0.62 nm2

VC (11 0.027 + 0.056 )nm 3 = 0.37 = NS = 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
diss diss Eoil Ewater =

e2 8 0 water

e2 8 0 oil

= 33 kT

Receptor proteins may be triggered to open barrier

Bicontinuous structures

Emulsions

Emulsions
Dispersion of two immiscible liquid phases

Emulsions
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

(ln R ln R ) P= exp 2 R 2 2 R 1
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

Gem

3V = R

Energy required depends on surface tension between liquids -> surfactants In practice higher energies are necessary

R W

0.40.6

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 On stirring, W/O and O/W both are formed Criterion: which has lowest stability, disappears

Aging of emulsions
Flocculation Creaming Coalescence Phase separation

Stabilization of Emulsions
Emulsifiers usually surfactants Hydration force for oil-in-water Steric force for water-in-oil Electrostatic forces for charged surfactants Polymers steric force Powders hydrophobic force

Microemulsions
Thermodynamic equilibrium Spontaneous formation react on external changes droplet size 5-100 nm form for high surfactant concentrations (complete coverage of interphase) driving force is the spontaneous curvature of the surfactants

Estimation of drop size

4 3 V d = NR 3
V S = 4LS NR
R= 3LS d
2

Phase behavior of Microemulsions


Ionic surfactants: salt concentration (changes headgroup area) Nonionic surfactants: temperature (changes hydration and fluctuations) -> Phase Inversion Temperature

Phase diagram: Example


Water / octane microemulsion with alkylethyleneoxide more surfactant: easier to contain all oil in droplets (C12E5) PIT = 32C

curvature too large to contain all oil in droplets

Phase transition
When T , then
size of head group (less hydration) tail widens (thermal fluctuations)

Result: phase inversion through lamellar phase

Conclusion
No foams Surfactants form all kind of aggregates
controlled by relative size of components

Macro-emulsions very important for practice Micro-emulsions:


specialty modern research area