MICELLE

0208-BH-E -CHEM-20

ZUNAIRA SHAHZAD 9/1/23 BIOCHEMISTRY 1

 TABLE OF CONTENT
1. Introduction: Micelle……………………………………………………………………………………………. 2
1.1 Micellization………………………………………………………………………………..3
2. Critical Micelle Concentration …………………………………………………………………………….4
2.1 Determination of CMC for a Surfactant…………………………………………………6
3. The Shape and Size of Micelle……………………………………………………………………………..7
4. Structure and Composition…………………………………………………………………………………8
4.1 Structure of micelle formed by ionic surfactants………………………………….8
4.2 Structure of micelle formed by nonionic surfactants……………………………..9
4.3 Structure of micelle in non aqueous solution…………………………………………10
5. Variation of micelle size and structure…………………………………………………………………10
6. Summary……………………………………………………………………………………………………………..11
7.Refrences………………………………………………………………………………………………………..11

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INTRODUCTION: MICELLE

A surface active agent (surfactant), when sent in less concentration in a system, assimilate at the
surfaces or interfaces extremely by varying the surface or interfacial free energy. When
molecules of surfactant are water soluble at the concentrations more than the critical micelle
concentration (CMC), they form aggregates termed as micelles, that are having importance in
science and pharmacy because they are having competency of increasing the dissolution of
mildly soluble substances in water. In a micelle, the hydrophobic tails attached to the inner core
to decrease their link with water, while hydrophilic heads remain at the outer surface to
maximize their interaction with water. They are movable structures and are repeatedly formed
and dissociated in solution (they must not be thought of as solid spheres). There exists a state of
equilibrium between micelle and free molecules of surfactant in solution.

Fig. 1 Representative model of the reversible monomer-micelle in thermodynamic equilibrium. The head
of surfactant is represented by dark circle (hydrophilic portion ) and the curved dark lines represent the
tail of surfactant (hydrophobic moieties).

A pile of molecules of surfactant called micelles is spread in a colloid of liquid . In liquefied

solution, an ideal micelle forms an aggregate with the hydrophilic "head" regions which
interacts with the surrounding solvent that is forming an outer shell, the sequestering the non-
polar or hydrophobic single-tail regions at center of micelle.
Hence, the micelle nucleus, which is consists of long non polar tails, resembles an oil or gasoline
drop that we see in the figure. The non -polar tail length , the nature and the size of the polar or
ionic head, the acidity of the solution, the temperature, and the presence of salts that are
added are the essential factors in determining the kind of the product obtained. If these
domains are changed, it is viable to change the shape and size of the micelles. A number of

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amphiphilic molecules form an aggregate gives aggregation number; it is the way to explain the
size of the micelle.

Fig. 2 Representation of a micelle in aqueous solution

The process of micellization in water execute mild balancing of intermolecular forces containing
hydrophobic, steric, electrostatic, hydrogen bonding and van der Waals interactions. The leading
force which results from the hydrophobic effect is formed with the non-polar surfactant tails,
and the leading adversing repulsive force which results from the interactions i.e steric and
electrostatic between the surfactant polar heads as represented in figure. Whether micellization
occurs and, if, at which flocking of monomeric surfactant, build upon the uniformity of the the
forces promoting micellization and some of those opposing it. We can mention l that it builds on
the balancing of two main effects i.e the readiness of the non polar tails to reject the contacts
with water and the repulsion between the polar or charged heads, an effect of destabilizing at
the aggregated process. Hydrocarbon tails reject the interactions with the solvent molecules
which is moving toward the aggregate/micelle interior, which have low water capacity. Inspite of
this , the repulsion between the charged heads on the micelle surface is governed by the
existence of oppositely charged ions (counter-ions). The suitable association of the non polar
tails in the micelle interior occur through the hydrophobic interaction, that is the prevailing
effect in the formation process of these aggregates.

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 Fig. 3

Amphiphilic molecules structure micelles in water, as well as in non-polar organic solvents. In

such cases, micelle aggregates are called inverse micelles because the situation is inverted as
respect to water .In this case, hydrocarbon tails are exposed to the solvent, whereas the polar
heads indicate towards the micelle interior so as to remove the contacts with the non-polar
solvent.

Fig. 4

Reverseible micelles are able to control huge amount of water in its interior. In this way, a
"pocket" is formed which is only suitable for the dissolution and transportation of polar solutes
through a non polar solvent.

CRITICAL MICLLE CONCENTRATION

CMC i.e critical micelle concentration. The critical micelle concentration (CMC) is explained as
the concentration of surfactants above which micelles are formed and all additional surfactants
are added in the system so as to go to the micelles. The CMC is the accurate flocking of
surfactants at which aggregates become thermodynamically soluble in an liquid solution. There
is no high density of surfactant below the CMC which immediately precipitate into a separate t
phase. Above the CMC, the solubility of the surfactant in the aqueous solution go beyond.. The
energy which is required to keep the surfactant in the solution is no longer in the e lowest
energy state. To decrease the system free energy the surfactant is precipitated out .Now when

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we go from frame 1à4. with increase of surfactant concentration in water, slowly a layer is
formed at the surface and eventually micelles are formed at or above the CMC.

Fig. 5

You must be wondering how the CMC of surfactants is determined? It is done by establishing
inflection points for pre-determined surface tension of surfactants in solution. The design of
inflection point against the surfactant concentration will give picture of the critical micelle
concentration by representing the stabilization of phases.

Fig. 6

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In the setup as depicted in Fig. three phases ae shown which are
1. At very low concentrations of surfactant less changes in surface tension are detected.
2. Additional surfactants decreases the surface tension.
3. Surface become full weighted , no more change in the surface tension

DETERMINATION OF CMS OF SURFACTANTS

The CMC for a surfactant can be obtained by measuring physical properties, such as surface
tension (γ), conductivity (κ) ( ionic surfactants), osmotic pressure (π), detergency, etc. When
these properties are setup as a function of surfactant concentration (or its logarithm, in case of
surface tension), a sharp rupture is seen in the curves attain by signalling the formation of
micelles at this point (explain figure) Another important parameter that featured is the
aggregation number, Nagg, that correlates to the average number of monomers of surfactant in
each micelle.. Normally , in a micelle solution the aggregation number is relatively constant for a
broad range of total concentration (up to 100 times the CMC), with increasing number of
micelles. Infact, under undisturbed conditions micelles can grow with the aggregation number
which differs with the surfactant concentration.

Fig. 7: Change in the physical properties of detergency, conductivity (κ), osmotic pressure (π) and surface
tension (γ) of an aqueous solution of surfactant which is depicted as a function of surfactant
concentration. The break in the curve of each property indicates the Critical Micelle Concentration (CMC)

There are some other physical properties which can be used to induce the CMC value that
shows some change near CMC such as
❖ Electrical conductivity
❖ Molar (Equivalent) conductivity
❖ Light scattering

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 ❖ Refrective index

MICELLE SHAPE AND SIZE

Micelles are the labile entities which are outlined by the non-covalent combination of single
surfactant monomers. Therefore, they may be spherical, cylindrical, or planar (discs or bilayers)
as depicted in Figure the shape and size of micelle can be controlled by changing chemical
structure of the surfactant as well as by altering solution conditions such as temperature,
overall surfactant concentration, surfactant composition (in the case of mixed surfactant
systems), ionic strength and pH. Depending on the type of surfactant and the solution
conditions, the spherical micelles can grow one-dimensionally in cylindrical micelles or two-
dimensionally to bilayers or discoidal micelles. The growth of micelle is controlled generally by
the heads of surfactant , as the two i.e (one-dimensional and two-dimensional) growth requires
taking the surfactant heads closer to each other to reduce the available area per surfactant
molecule at the micelle surface, and also e the bend of the micelle surface Surfactant
aggregates.

Fig. 8

Surfactant self -assemblies

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Self-assembly of surfactant leads to a domain of different structures as we will discuss now:
➢ Spherical micelles with its interior is formed of the hydrocarbon chains and the polar
head group surface which is covering water . The radius of the hydrocarbon core is close
to alkyl chain length.
➢ Cylindrical micelles with its interior is formed of the hydrocarbon chains and polar head
groups surface water surface .The cross-section of hydrocarbon core is identical r to that
of spherical micelles. The micelle length is fluctuating so these micelles are polydisperse.
➢ Surfactants bilayers which is build up of lamellar liquids crystals have surfactantwater
system having a hydrocarbon core of thickness of 80% of the length of two extended
alkyl chains.
➢ Reversed or inverted micelle has core of water that is covered by the polar head groups
surfactants. The alkyl chains together with a non-polar solvent make up the continuous
medium. Like normal micelle they can reproduce into cylindrical form.
➢ A bicontinous structure having the surfactant molecules assembled into connected
films.
➢ Vesicles are built from bilayer like those of the lamellar phase and are featured by two
distinct water compartments, one producing the core and one the external medium.
Vesicles may have different shape and there are also reversed-type vesicles.
. In particular, depend on the type of surfactant and on the solution conditions, spherical
micelles which are one-dimensionally can grow to cylindrical micelles or two-dimensionally to
bilayers or discoidal micelles. The growth of micelle is controlled basically by the surfactant
heads, as both one-dimensional and two-dimensional growth require the surfactant heads
closer to each other to reduce the available area per surfactant molecule at the surface of the
micelle , and also the bend of the micelle surface. For all the micelle structures in aqueous
media, the surfactant molecules are turned with their polar heads in the water phase and their
tail away from it.

STRUCTURE AND COMPOSITION

a) The inner part of the micelle, i.e a hydrophobic core is formed of the hydrocarbon chain
of the surfactant molecule. It’s radius is approximately of the range of fully extended
hydrophobic chain.
b) (b) A Stern layer covering the core, is part of electrical double layer, which have
coordinated shell of hydrophilic head groups with (1 - α )N counter ions, where α is the
degree of ionization and N is the aggregation number (number of molecules in the
micelle). the degree of ionization for most of the ionic micelles is between 0.2 and 0.3;

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 c) that is, 70 - 80% of the counter ions may be treated as they are bound to the micelles.
d) The Gouy-Chapman portion of electrically two layer is diffused and surrounds the Stern
layer, it comprises of the N counter ions that are needed to neutralise the charge on the
micelle. The thickness of the double layer is the ionic strength function the solution and
can be higly reduced in the presence of electrolyte.

Fig. 9

Structure of micelle formed by non-ionic surfactants

(a) The structure is almost identical , except the counter ions which are not available t in the
outer region but rather are the loops of hydrated polyethylene oxide chain.
(b) They are bigger than than its ionic counterparts and occasionally be stretched into an
ellipsoid or rod-like structure.
(c) They contain a hydrophobic core which is formed of the hydrocarbon chains of the surfactant
molecules that is enclosed by a shell (the palisade layer) composed of the oxyethylene chains of
the surfactant which is heavily hydrated as depicted in the figure

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 Fig. 10

Another important features of micelles is the aqueous phase that diffuse into the micelle
besides the hydrophilic head groups, and the methylene groups that are adjoining to the head
are considered in the hydration sphere. Therefore, we can isolate micelle inner region into outer
core that is penetrated by water and the internal core is completely removed from water 5.3
Structure of micelle in non-aqueous solution
in non-aqueous solution the micelles are formed (reverse or inverted micelles) with their core
formed of the hydrophilic groups which is surrounded by a shell of the hydrocarbon chain
postioned on the geometry of the various micelle shapes and the space occupied by the
hydrophilic and hydrophobic groups of the surfactants, it is possible to conclude the structure of
a micelle.

Fig. 11

SUMMARY
Micelle is surfactant aggregate which is formed where surfactant concentration in solution is lie
above the critical micelle concentration (CMC). In aqueous solution, formation of micelle takes
place where polar or ionic head groups cast an outer shell and non-polar hydrophobic tails are
separated in the internal . In non polar solvents, hydrophobic tails are reveal to the solvent,
while polar head indicate to the inner of the aggregate, called inverse micelle. The process of
micelle formation lean on the balancing of intermolecular force i.e. hydrophobic, steric,
electrostatic, hydrogen bond and van der waals interactions. CMC is the accurate concentration
at which a aggregate become thermodynamically soluble in liquid solution and can be observed

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as inflection point when the physicochemical properties are outlined as function of
concentration. Structure of micelle formation by the ionic surfactants are composed of
(i) hydrophobic core formed by hydrocarbon chain,
(ii) (ii) An electrical twin layer divided into
(iii) (a) stern layer and
(iv) (b) Gouy-chapman layer.
(v) Stern layer is composed of the hydrophilic head group whereas gouy-chapman layer
contains the counter-ions that neutralize the charge on the micelle. Micelle formed
by the non ionic surfactant have hydrophobic core that is covered by the shell which
is composed of polyethylene oxide chain, no counter- ions are present in it. The
shape and structure of micelle can be estimated by the relationship of v/lmaxa.

REFRENCES
1. Hamley, IW (2007). Introduction to Soft Matter. John
Wiley. ISBN 9780470516102.
2. ^ McBain JW (1913). "Mobility of highly-charged micelles". Trans. Faraday
Soc. 9: 99–101.
3. ^ Hartley GS, Donnan FG (1936). Aqueous Solutions of Paraffin Chain Salts, A
Study in Micelle Formation. Paris: Hermann et Cie.
4. ^ "Micelle". Merriam-Webster Dictionary. Retrieved September 29, 2018.
5. ^ Turro NJ, Yekta A (1978). "Luminescent probes for detergent solutions. A
simple procedure for determination of the mean aggregation number of
micelles". Journal of the American Chemical Society. 100 (18): 5951–
5952. doi:10.1021/ja00486a062.

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