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Soap Manufacturing |Micelle Formation |Factors Affecting CMC

Soap:
Soaps are metallic salts of fatty acids (saturated or unsaturated) containing from 8 to 22 carbon atoms.
Its a natural cleansing agent. There may be various kinds of metallic salt but sodium and potassium salts
are used as detergents. Commercially soap is produced by boiling natural fats/oils with aqueous solution
of sodium or potassium hydroxide. This reaction is called Saponification.
(The potassium soaps tend to be softer and more soluble in water than the corresponding sodium
soaps)

Chemistry of Soap Manufacturing:


1. Fat Saponification Process:

Fig: Fat Saponification Reaction

Sodium soaps are sparingly soluble in strong sodium chloride solution. The mixture of soap and glycerol
in aqueous solution obtained by saponification is saturated with common salt where the soap is
precipitated. As soap is lighter than glycerol itll rise to the surface. Then its skimmed off i.e. the best
parts from the surface is removed.
To remove excess alkali or salt solution its washed with cold water. Then its cast into cakes/bars and
dried.
The liquor is evaporated under reduced pressure and glycerol is recovered by distillation

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Soap Manufacturing |Micelle Formation |Factors Affecting CMC

2. Fatty Acid Neutralization Process:

(In this process alkalinity can be controlled as we add NaOH in known concentrations)

3. Fatty Methyl Ester Process:

(Glycerin found in this process are more pure than other processes)

Functional Properties of Soap:


1. Solubility:
An increase in the size of monovalent cation (base) increases solubility & an increase in
the size of di/tri valent cation decreases solubility
Carbon chain length of soap increases, solubility decreases but cleansing power
increases.
The presence of unsaturation results in an increase in solubility.
In general, with the increase of solubility the softness and mushiness property of soap also increases.

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Soap Manufacturing |Micelle Formation |Factors Affecting CMC


2. Lathering & Cleansing Attributes:
The use of fatty acids of 10 to 12 chain length is most preferred for lathering
attributes.
The use of fatty acid of 16 to 18 chain length is most preferred for cleansing attributes.

The most suitable soap is made from the combination of coconut ( to ) and
tallow ( to ) from the view point of lathering and cleansing attributes.

The effectiveness of a soap solution as a detergent will be influenced to a marked degree by


Nature of the fatty acid.
Conditions of temperature.
Concentration in which it is to be used.

Disadvantages:
Doesnt work on hard water.
Doesnt work on acidic solution.
Doesnt work in the presence of + as excess + precipitates soap.

Micelle:
As the concentration of surfactant in a solution is increased it becomes energetically favorable for the
individual molecules, or monomers, to combine together to form large aggregates, or micelles, which
shield the hydrophobic components from the solution.
Its a group of surfactant molecules associated in a cluster.
Here, a stearate ion is represented -

(The long alkaline chain is the hydrophobic and carboxylate ion is the hydrophilic part)

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Soap Manufacturing |Micelle Formation |Factors Affecting CMC

Fig: Schematic Illustration of the Reversible Monomer-Micelle

Fig: Micellar Reaction Kinetics

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Soap Manufacturing |Micelle Formation |Factors Affecting CMC

Structures of Micelle:

Spherical (Anionic) Micelle

Hexagonal Phase Formed From Cylindrical Micelle

Spherical Vesicle Bilayer Structure

Lamellar Phase Formed From Laminar Micelle


micelle

Fig: Micellar Structures


a) Spherical (anionic) Micelle: This is the usual shape at surfactant concentration below about
40%.
b) Spherical Vesicle Bilayer Structure: It is representative of the living cell.

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Soap Manufacturing |Micelle Formation |Factors Affecting CMC

CMC:
The concentration above which micelle formation becomes appreciable is termed as the Critical micelle
concentration (C.M.C.).
At low surfactant concentration the surfactant molecules arrange on the surface. When more surfactant
is added the surface tension of the solution starts to rapidly decrease since more and more surfactant
molecules will be on the surface. When the surface becomes saturated, the addition of the surfactant
molecules will lead to formation of micelles. This concentration point is called critical micelle
concentration.

Fig: Critical Micelle Concentration

1. At very low surfactant concentration only slight change in surface tension is detected.
2. Addition of surfactant decreases the surface tension drastically
3. At CMC point, surface becomes saturated and the addition of surfactant molecules do not effect
on the surface tension.

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Soap Manufacturing |Micelle Formation |Factors Affecting CMC

Fig: Changes in some physical properties for an aqueous solution of sodium dodecyl sulfate (SDS) in the
neighborhood of the CMC

Factors Affecting CMC:


1) No. of Carbon Atom:
Increasing hydrophobic part (no. of carbon atom) will result in a decrease of CMC. In aqueous medium,
the CMC of ionic surfactants is approximately halved by the addition of each 2 group .For non-ionic
surfactants this effect is usually even more pronounced. This trend usually continues up to about the
16member. Above the 18 member the CMC tends to be approximately constant. This is probably the
result of coiling of the long hydrocarbon chains in the water phase.

2) Thermal Agitation:
Micelle formation is opposed by thermal agitation and CMC's would thus be expected to increase with
increasing temperature but not always.

3) Addition of Electrolytes:
With ionic micelles, the addition of simple electrolyte reduces the repulsion between the charged
groups at the surface of the micelle. The CMC is, therefore, lowered.

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Soap Manufacturing |Micelle Formation |Factors Affecting CMC

4) Addition of Organic Molecules:


Organic molecules may influence CMC's at higher additive concentrations by virtue of their influence on
water structuring. Sugars are structure-makers and as such cause a lowering of CMC, whereas urea and
formamide are structure-breakers and their addition causes an increase in CMC.
Micelles containing more than one surfactant often form readily with a CMC lower than any of the
CMC's of the pure constituents.

References
[1] D. J. Shaw, Colloid & Surface Chemistry.
[2] E. R. Trotman, Dyeing and Chemical Technology of Textile Fibres, Charles Griffin & Company LTD,
2009.

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