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Surfactant micelles
surfactant = surface active agent
animal fat
The saponification of a triglyceride
Introduction to Surfactants
Presentation outline
Surfactant
Surfactants are compounds that stabilize mixtures of oil and water by reducing the surface tension at the interface between the oil and water molecules. Surfactants are amphiphilic in nature i.e.; they contain 2 distinct structural units:
Tail or hydrophobic group which has little affinity for water this group is usually hydrocarbon (alkyl) chain Head or hydrophilic group which has strong affinity for water & can be neutral or charged.
Surfactants - behavior
Surfactants reduce the surface tension of water by adsorbing at the liquid-gas interface. They also reduce the interfacial tension between oil and water by adsorbing at the liquid-liquid interface. At higher concentrations surfactants have the tendency to assemble into aggregates. Examples of such aggregates are vesicles and micelles. The concentration at which surfactants begin to form micelles is known as the critical micelle concentration or CMC.
Surfactant- micelle
In a micelle : The lipophilic tails of the surfactant molecules remain on the inside of the micelle The polar heads of the micelle form a hydrophilic outer layer that in effect protects the hydrophobic core of the micelle.
Classification of Surfactants
The most commonly used anionic surfactants are alkyl sulphates, alkyl ethoxylate sulphates and soaps.
Anionic Surfactant
Cationic surfactants
In solution, the head is positively charged. There are 3 different categories of cationic each with their specific application: In household and bathroom cleaners, cationic surfactants contribute to the disinfecting/saniti zing properties.
Non-ionic surfactants
These surfactants do not have an electrical charge, which makes them resistant to water hardness deactivation. They are excellent grease removers that are used in laundry products, household cleaners and hand dishwashing liquids. Most laundry detergents contain both non-ionic and anionic surfactants as they complement each other's cleaning action. Nonionic surfactants contribute to making the surfactant system less hardness sensitive. The most commonly used non-ionic surfactants are ethers of fatty alcohols
Amphoteric/zwitterionic surfactants
These surfactants are very mild, making them particularly suited for use in personal care and household cleaning products. They can be anionic (negatively charged), cationic (positively charged) or non-ionic (no charge) in solution, depending on the acidity or pH of the water.
How do surfactants work in detail?
Surfactants can work in three different ways: roll-up, emulsification, and solubilization.
Roll-up mechanism The surfactant lowers the oil/solution and fabric/solution interfacial tensions and in this way lifts the stain of the fabric. Emulsification The surfactant lowers the oil-solution interfacial tension and makes easy emulsification of the oily soils possible. Solubilization Through interaction with the micelles of a surfactant in a solvent (water), a substance spontaneously dissolves to form a stable and clear solution.
Such molecules display distinct behavior when interacting with water. The polar part of the molecule seeks to interact with water while the non-polar part shuns interaction with water. There are two ways in which such a molecule achieve both these states. An amphiphilic molecule can arrange itself at the surface of the water such that the polar part interacts with the water and the non-polar part is held above the surface (either in the air or in a non-polar liquid) as shown in Figure B above.
The presence of these molecules on the surface disrupts the cohesive energy at the surface and thus lowers the surface tension. Such molecules are called surface active molecules or surfactants.
Another arrangement of these molecules can allow each component to interact with its favored environment.
Molecules can form aggregates in which the hydrophobic portions are oriented within the cluster and the hydrophilic portions are exposed to the solvent. Such aggregates are called micelles.
An example of a spherical micelle is diagrammed above (illustration C).
The proportion of molecules present at the surface or as micelles in the bulk of the liquid depends on the concentration of the amphiphile. At low concentrations surfactants will favor arrangement on the surface. As the surface becomes crowded with surfactant more molecules will arrange into micelles. At some concentration the surface becomes completely loaded with surfactant and any further additions must arrange as micelles. This concentration is called the Critical Micelle Concentration (CMC).
It follows that measurement of surface tension may be used to find CMC. A graph of surface tension versus log of concentration of surfactant added will appear as follows:
In this graph you can see three phases: 1. At very low concentrations of surfactant only slight change in surface tension is detected. 2. Additional surfactant decreases surface tension 3. Surface becomes fully loaded, no further change in surface tension.
This is the same type of mechanism which causes detergents and soaps to remove oil and grease stains from your dishes or clothes.
CMC Explanation
Micelle Hydrophobic Dye
the length of hydrocarbon chain (minor interaction with water i.e facilitate the transfer from an aqueous phase to micelles) produces a decrease in the CMC B)increased polarity of the polar portion (greater interaction with water i.e retard the transfer from an aqueous phase to micelles) produces an increase in CMC
Additives
-With ionic micelles, electrolyte addition
reduces the repulsion between charged groups at the surface of the micelle CMC decreases as electrolyte increases.
Addition of electrolyte decreases the CMC &increases the micelles size. Following are the effect of NaCl addition on micelle size of Dodesyl trimethyl ammonium bromide.
Conc. Of NaCl mole/dm3 0 CMC in mole/dm3 Aggregaton number
0.146
61
0.1
0.00428
74
0.502
0.00171
90
-Addition of organic molecules affect CMC. Influence water structure. Sugars structure makers lower CMC; urea and formamide structure breakers increase CMC.
3-Nature of hydrocarbon chain The branched chain ring systems and double bonds tend to raise CMC. 4-Temperature the increased temperature increases CMC.
What is cloud point ? At temperature up to the cloud point an increase in micelle size &a corresponding decrease in CMC is noted for many non ionic surfactant.
THERMODYNAMICS OF MICELLIZATION
Phase Separation Model
Simplest approach treats micelles as a single phase.
Mass Action Model Association dissociation equilibrium between free surfactant & micelle phase.
G0M = 2.303 RT [log[CMC] - logW] where, G0M -: standard free energy change W -: mole/dm3 of water
1. 2.
- H0 = RT2 (dln [Xcmc]/dT) The entropy of micellization can be calculated from the relationship between G0M and H0 i.e., G0M = H0 TS0
Microemulsions
These are clear, thermodynamically stable, isotropic liquid mixtures of oil, water and surfactant, frequently in combination with a cosurfactant. The aqueous phase may contain salt(s) and/or other ingredients, and the "oil" may actually be a complex mixture of different hydrocarbons and olefins. In contrast to ordinary emulsions, microemulsions form upon simple mixing of the components and do not require the high shear conditions generally used in the formation of ordinary emulsions. The three basic types of microemulsions are direct (oil dispersed in water, o/w), reversed (water dispersed in oil, w/o) and bicontinuous.
The phenomenon of critical micelle concentration (or an analogous effect) is consequently not observed.
In an inverted micelle the polar groups of the surfactants are concentrated in the interior and the lipophilic groups extend towards and into the non-polar solvent.
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