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Physical Chemistry (CHM3101)

Colloids
(Macromolecules and Self Assembly)

Reference: Atkins, 10th Edition, Chapter 17

Colloids

v Colloids
v Classification and Preparation
v Structure and Stability
v The Electrical Double layer
v Micelles
v Micelle Formation
v Determination of Size and Shape
v Mean Molar Mass
v The Techniques
v Sedimentation
v Viscosity

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Introduction

Ø Self-assembly is the spontaneous formation of complex

structures of molecules or macromolecules held together by
molecular interactions.

Ø These interactions involve Coulombic, dispersion, hydrogen

bonding, or hydrophobic interactions.

Ø liquid crystal is an example of self-assembly system.

Ø Here, we will concentrate on small aggregate of self-assembled

system which are mostly related to detergents.

Ø A colloid is a dispersion of small particles of one material in

another that does not settle out under gravity.

Ø Small means that one dimension at least is smaller than 500 nm in

diameter.

Ø Many colloids are suspensions of nanoparticles (particles of

diameter up to about 100 nm)

Ø Colloids are aggregates of numerous atoms or molecules which are

too small to be seen with an ordinary optical microscope.

Ø They can be detected by light-scattering techniques or through

sedimentation.

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Classification
Ø Colloids are classified based on the two phases involved:

– A sol is a dispersion of a solid in a liquid (clusters of gold atoms in

water) or of a solid in a solid (ruby glass)
– An aerosol is a dispersion of a liquid in a gas (fog and many sprays)
or a solid in a gas (smoke)
– An emulsion is a dispersion of a liquid in a liquid (milk)
– A foam is a dispersion of a gas in a liquid

Ø Colloids can be:

– Lyophilic or solvent attracting (if solvent is water, hydrophilic). They

include metal sols.
– Lyophobic or solvent repelling (if solvent is water, hydrophobic)
– A gel is a semi-rigid mass of a lyophilic sol.

Preparation of colloids
• For example, an emulsion is a mixture of two or more
immiscible liquids. It can be prepared by shaking the two
components together vigorously.
• It consists of droplets of a dispersed phase in an continuous
phase.
• However, for stabilization of the product, emulsifier will be
needed. An emulsifier can be a salt or a surfactant or even a
lyophilic sol.
• Emulsion can be formed as:

-Water in oil (W/O) -Oil in water (O/W)

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Cont’…
Ø Emulsion can be formed as: water in oil (W/O) or oil in water (O/W)

An oil-in water (a) and water-in-oil

(b) emulsion. (Taken from NSBHS
Notes and HSC Resources Wiki).

Ø Nano-emulsions are emulsions with droplet size in the range of 50-200 nm

(Solans et al., 2005).

Surfactants
Ø Surfactants can lower the surface tension of a liquid, the interfacial
tension between two liquids (emulsion), or that between a liquid and a
solid. Surfactants may act as detergents, wetting agents, emulsifiers,
foaming agents, and dispersants.

Surfactant molecules arranged on an air–water Surfactant classification according to the

interface. (Taken from WikiPedia). composition of their head: nonionic, anionic,
cationic, amphoteric. (Taken from WikiPedia).
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Pharmaceutical
Personal Care

APPLICATIONS OF
NANO-EMULSION

Food technology
Cosmetics

Structure and Stability

Ø Colloids are thermodynamically unstable but kinetically stable.

Ø The change in the Helmholtz energy; dA = γ dσ

– γ is the interfacial surface tension.

– dσ is the change of surface area of the sample at constant temperature
and pressure.

Ø Therefore, if dσ < 0, then dA < 0.

Ø By this, the stability of colloids is a consequence of the kinetics of

collapse.

Ø But how?

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Ø Colloidal particles attract each other over large distances. The energy of
attraction between two particles i and j separated by a distance Rij varies as
1/R6ij .

Ø The sum of all these pairwise interactions decreases only as ≈ 1/R2. R is the
separation of the centers of the particles.

Ø It means that, the total interaction does not fall off as fast as the single
molecule-molecule interaction.

ØLook at the picture. Although the attraction

between individual molecules is proportional
to 1/R6, more molecules are within range at
large separations (pale region) than at small
separations (dark region).

ØSo, the total interaction energy declines

more slowly and is proportional to a lower
power of R.

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The electrical double layer

ü A major source of kinetic stability of

colloids is the existence of an electric
charge on the surfaces of the particles.

ü electrical double layer, the inner shell of

charge and the outer ionic atmosphere
around a colloidal particle.

ü zeta potential (electrokinetic potential),

ζ, the electric potential at the radius of
shear relative to its value in the distant,
bulk medium.
Michael Kaszuba et al. Phil. Trans. R. Soc. A 2010;368:4439-
4451

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Strength of interparticle forces

• Stability depends on the

balance of attractive and
repulsive interactions
• Attraction from van der Waals
forces between particles.
• Repulsion is a consequence of
interaction between similar
charged electric double layers
and/or particle -solvent affinity.
• Repulsion prevents particles to
get close enough and attach

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Micelle

Ø A surfactant molecule consists of two parts: Hydrophilic head (water

loving) & Hydrophobic tail (oil loving)

Ø Surfactants can be cationic, anionic, non-ionic, and amphoteric.

Ø Non-ionic surfactants may involve 1000 or more molecules in a

cluster.

Ø Ionic species (anionic, cationic, amphoteric) are limited to 100

molecules. The reason is that the electrostatic repulsions between
head groups depends more on the size of the head group.

Ø Surfactant molecules or ions can cluster together (spontaneous

aggregation) as micelles in aqueous solutions.

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Micelle
Ø Surfactant molecules can form micelles because of their hydrophobic
tails tend to congregate through hydrophobic interactions and their
hydrophilic head groups provide protection.

ØFor example, SDS (Sodium dodecyl sulfate) or CTAB

(hexadecyltrimethylammonium bromide) form rods at moderate
concentration but sugar surfactants form small spherical micelles.

Ø The shape of micelle varies with shape of the surfactant molecule,

surfactant concentration, temperature.

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Micelle Formation

Ø Micelle is formed above critical micelle

concentration (CMC) and above Kraftt
temperature (critical micelle
temperature).

Ø The CMC is detected by a noticeable

change in molar conductivity.

Ø There is no abrupt change in physical

properties at CMC.

Ø There is a transition region The typical variation of some

corresponding to a range of Physical properties of an aqueous
concentrations around CMC where the solution of SDS close to CMC.
properties vary smoothly but nonlinearly
with the concentration.
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Ø Enthalpies of micelle formation can be positive (endothermic) or

negative (exothermic).

Ø Non-ionic micelles form endothermically (10 kJ/mol) of surfactant

molecules.

Ø If micelles form above the CMC, the entropy change is positive as

well (+140 J/K mol) at room temperature.

Ø Therefore, hydrophobic interactions are very important in the

micelle formation.

Ø The micelle population is often polydisperse.

Ø A pure protein is nondisperse. It means that it has a single, definite

molar mass.

Ø A synthetic polymer is polydisperse. It is a mixture of molecules with

various chain length and molar masses.

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Ø We use the surfactant parameter, Ns, to predict the shape of a

micelle: Ns = V / A l

– V is the volume of surfactant hydrophobic tail. A is the area of the

hydrophilic head. l is the maximum length of surfactant tail.

Variation of micelle shape with the surfactant parameter

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Ø By increasing the ionic strength, the

repulsions between surface head groups
can be reduced. So, cylindrical micelles
can be formed.

Ø Lyotropic mesomorphs or liquid

crystalline phases are formed when
these cylinders stack together in
hexagonal arrays.

Ø Reverse spherical micelles form in

nonpolar solvents. At certain experimental
conditions, a liposome may
form. Liposomes may be
Ø Reverse spherical micelles involve a applied to carry nonpolar drug
small polar surfactant head groups in a molecules in blood.
micellar core and hydrophobic surfactant
tails extending into the organic bulk
phase.

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Determination of Size and Shape: Mean Molar Mass

Ø Osmometry is the measurement of the osmotic strength of a substance.

Ø This is often used by chemists for the determination of average molecular

weight.

Ø The mean obtained from molar mass determination is the number-

average molar mass;

– Ni is the number of molecules with molar mass Mi when there are N

molecules in total.

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Ø By this, the weight-average molar mass:

– mi is the total mass of molecules with molar mass Mi when m is the

total mass of sample.

Ø We know that; Ni = Mi/ NA . Thus:

Ø The ratio is called the heterogeneity (or

polydispersity) index which is equals to:

Ø The values of this index are different.

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Ø We can determine average molar mass by osmotic pressure of

polymer solution and reliability is ≈ 1000 kg per mole.

Ø For macromolecule like micelle which involve low molar mass, this is
a major problem.

Ø Micelles can percolate through membrane and show partial

permeability through the membrane. So, average molar mass will
be overestimated.

Ø Determination of molar mass and polydispersity can be done by

mass spectrometry, laser light scattering, ultracentrifugation,
electrophoresis, and viscosity measurement.

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Sedimentation
Ø Consider a column of suspension solution. Heavy particles tend to settle towards
the foot of the solution because of gravitational force. This process is called
sedimentation.

Sedimentation process. Source:

Casiday et al. (1999)

Ø The rate of sedimentation depends on the strength of gravitational force, masses

and shapes of particles.

Ø Sedimentation is usually slow and it is accelerated by ultracentrifugation. This

technique replaces gravitational force by a centrifugal force.

Ø There is a cylinder rotated at high speed about its axis with a sample in a cell near
its outer edge.
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Viscosity
Ø Flux (J) is the quantity of a property passing through a given area in
a given time interval divided by the area and the duration of
interval.

Ø Viscosity is the migration of linear momentum (P=mv) down a

velocity gradient and the flux of momentum is proportional to the
velocity gradient.
dv
J = -h x

dz

– η is the viscosity (kg m-1 s-1). It usually reported in poise (P).

– 1 P= 0.1 m-1 s-1 kg.

Ø We know that highly viscous liquids flow slowly and retard the
motion of objects through them.

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Ø The presence of a macromolecular solute increase the viscosity of

a solution.

Ø At low concentration:

h = h0 æç1 + [h ] c + [h ]¢ c 2 + ... ö÷
è ø

Ø The intrinsic viscosity, [η], will then be:

æh -1 ö
æ h - h0 ö ç h0 ÷
[h ] = lim ç ÷ = lim
c ®0 ç ÷
c ®0
è ch 0 ø ç c ÷
è ø

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Ø We can measure viscosity using different methods. For example,

Ostwald viscometer shown in picture.

Ø Here, the time taken for a solution to flow through the capillary is
noted, & compared with the standard sample.

Ø Therefore:
h t r
= ´
h 0 t0 r 0
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Ø There are viscometers (also called

rheometers) in the form of rotating
concentric cylinders.

Ø Here, the shear gradient between the

cylinders is simpler than the capillary.

Ø However, there are many

complications in interpretation of
viscosity measurements.

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Ø For example, some solutions obey Mark-Kuhn-Houwink-Sakurada

equation: h = KM a v

Ø K and a, are constants related to the solvent & the type of macromolecule. We can
see the viscosity-average molar mass as well.

Ø Sometimes, the flow is non-Newtonian. It means that the viscosity of the

solution changes as the rate of flow increase.

Ø A decrease in viscosity with

increasing rate of flow indicates
the presence of long rod-like molecules
that are oriented by the flow and thus
pass each other more freely.

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