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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
-2
Concentration (mM)
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
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
Calculation NS
VC (nC 0.027 + 0.029 )nm
3
AC
0.205
0.2 0 5 10 15 20
Example
SDS: A0 = 0.62 nm2
Biological Membranes
e2 8 0 water
e2 8 0 oil
= 33 kT
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
4 3 V d = NR 3
V S = 4LS NR
R= 3LS d
2
Phase transition
When T , then
size of head group (less hydration) tail widens (thermal fluctuations)
Conclusion
No foams Surfactants form all kind of aggregates
controlled by relative size of components