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Thermodynamics of Micellization

Micellization is the process by which surfactant molecules spontaneously aggregate to form colloidal particles called micelles in solution above a critical concentration. Thermodynamically, micellization is favorable as indicated by the negative Gibbs free energy, despite being endothermic with a positive enthalpy change, because the entropy change is positive due to the release of organized water molecules from the surfactant chains into solution. Micelles have many applications as emulsifiers in cleaning products and pharmaceutical formulations by enabling insoluble substances to be solubilized.

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2K views5 pages

Thermodynamics of Micellization

Micellization is the process by which surfactant molecules spontaneously aggregate to form colloidal particles called micelles in solution above a critical concentration. Thermodynamically, micellization is favorable as indicated by the negative Gibbs free energy, despite being endothermic with a positive enthalpy change, because the entropy change is positive due to the release of organized water molecules from the surfactant chains into solution. Micelles have many applications as emulsifiers in cleaning products and pharmaceutical formulations by enabling insoluble substances to be solubilized.

Uploaded by

bs19b006 Ansh Ruhela
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We take content rights seriously. If you suspect this is your content, claim it here.
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THERMODYNAMICS OF MICELLIZATION

ARYAN VERMA
BE19B015
INTRODUCTION:
The cycle of micellization is one of the most important characteristics of
surfactant solution and hence it is essential to understand its mechanism (the
main thrust for micelle formation). This requires examination of both the
kinetic and the equilibrium viewpoints of the cycles. Further, the laws of
thermodynamics are applied to get the free energy, enthalpy and entropy of
micellization.

Before we start let’s understand what is a micelle and terms related


to it.
When hundreds of surfactant molecule aggregate to form a colloid particle, the
particle formed is called micelle and the process of its formation is know as
micellization.
Micelle generally contains a hydrophobic tail of long hydrocarbon chains and a
hydrophilic head.
CMC- Critical micelle concentration (CMC) is the minimum concentration of
surfactant required for micelle formation. Above cmc micelle formation starts.
Kraft temperature – It is the minimum temperature required for micelle
formation. At this temperature solubility of surfactant is equal to the
surfactant’s critical micelle concentration.

Micelle formation
At lower concentration these surfactant ions stay as individual
species but at higher concentration, association of these ions take
place forming associative colloids.
At initial concentration when there is only water, surface is filled
with water molecules only. As we start adding surfactant, some of
the surface water molecules are replaced by surfactant molecules. As
we keep on adding solute, we reach a saturation point where no
more surface molecules can be replaced by surfactant. This is the
point or concentration when micelle formation starts. So, this is the
minimum concentration (CMC) required for micelle formation.
Looking into thermodynamics aspects of micellization:
Mass action model is the most accepted model for micellization.
The model assumes an equilibrium of association-dissociation
between surfactant monomer and micelle (in this case charge effect
is not their) as a whole.

nB ↔ B n
Generally, the cmc value ranges from 10^-2 to 10⁻⁴. So overall delta
G is negative, spontaneous process.
Case 2 - When we take charge into consideration. Micelle formed of
n ions, let dissociated counter ion be r. So, remaining associated
counter ions be (n-r).
Overall equation: nB⁻ + (n-r) Na⁺ ↔ Bn⁻ᴿ

If r=n that is complete dissociation of Na+ we get a result similar to


what we got above.
Max value for r/n will be 1 and so change in Gibbs free energy will be
negative proving it’s a thermodynamically favourable process.
Enthalpy and Entropy of micellization
By Gibbs-Helmholtz equation we know,

Putting value of delta G from above and on further solving we get,


𝑑 ln[𝑐. 𝑚. 𝑐]
−∆𝐻° = 𝑅𝑇 2
𝑑𝑡
Delta H can be calculated by plotting graph of ln [c.m.c] vs
temperatures for different values. Their slope will give the value of
d ln[cmc]/dt. We can also use a microcalorimetry to calculate the
value of delta H
After plotting and obtaining the values you will observe that delta H
value comes out to be positive i.e., it’s a endothermic process.
∆𝐺° = ∆𝐻° − 𝑇∆𝑆
So far we have calculated ∆Gᵒ and ∆Hᵒ.
∆Gᵒ = negative
∆Hᵒ = positive
Calculating entropy from above equation it comes out to be positive.
You might be thinking that in micelle formation free surfactant
molecule associates to form an aggregate colloid so its entropy
should be negative. But that’s just half story. Surfactant monomers
contain ''organized'' water around their hydrocarbon chain. On move
of such monomers to a micelle, these water atoms are released or
are freed and they contribute to positive entropy change. Entropy
change due to the release of water molecule is much higher than
association of surfactant monomers. So overall entropy change is
positive.
APPLICATIONS –
Micelles go about as emulsifiers when surfactants are over the basic
micelle fixation permitting a compound to break down which are
normally insoluble. For example, cleansers (soap and detergents),
which clean lipophilic materials that are less dissolvable which
cannot be eliminated with the assistance of water alone.
Micellization also have many applications in pharma industry.

CONCLUSION
We started with some definitions to get started with our topic.
Following we saw how micelle is formed and how it is supported
thermodynamically. Then we went through entropy and enthalpy
change during micelle formation and explained why its entropy is
positive. At last, we saw some application of micellization.
This should make us understand why the process of micellization is
one of the most important characteristics of surfactant solution.

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