COLLOID PROPERTIES: OPTICAL, KINETIC AND

ELECTRICAL

I. OPTICAL PROPERTIES OF COLLOIDS

1. Light scattering property:

❖ When a beam of light is allowed to fall on a
Colloidal dispersions, the colloidal particles
interact with the incident light and scatter the
incident light to produce a cone of light known as
the Tyndall cone. This property of light scattering
due to interaction of particles with light is known
as the Faraday-Tyndall effect
❖ The path of the beam of light becomes visible
because of the light scattered by the particles in
the beam
 ❖ Because of the scattered light the sol appears
turbid
❖ The magnitude of the turbidity or opalescence
depends upon the nature, size, and concentration
of the dispersed particles

❖ Light scattering measurements are of great value

for estimating particle size, shape and interactions,
particularly of colloids, as the turbidity depends on
the size (molecular weight) of the colloidal material
involved
❖ The light-scattering theory was modified by Debye
in 1947 for use in the determination of the molecular
weight of colloidal particles. He derived the
following relationship between turbidity τ and
molecular weight M:

Where C is the concentration of the solute and B an

interaction constant, H is an optical constant for a
particular system, depending on the refractive index
change
A plot of HC/τ against concentration results in a straight
line of slope 2B. The intercept on the HC/ τ axis is 1/M,
allowing the molecular weight to be calculated. The
molecular weight derived by the light-scattering
technique is a weight average value

❖ Ultra-microscopy and Electron microscopy :

o Colloidal particles are very small and hence are
not visible in an ordinary light microscope,
however, colloid particles are often visible in an
ultramicroscope and electron microscope
o In an ultramicroscope, a cell containing the
colloid is viewed against dark background at right
angles to the beam of incident light. The colloidal
particles which show irregular Brownian motion
appear as bright spots against the dark
background
o The electron microscope, capable of giving actual
pictures of the particles, is used to observe the
size, shape and structure of colloidal particles
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II. KINETIC PROPERTIES OF COLLOIDS

 Kinetic properties of colloidal systems relate to the
motion of particles with respect to the dispersion
medium

The motion may be thermally induced (Brownian

movement, diffusion, osmosis), gravitationally
induced (sedimentation), or applied externally
(viscosity).

Kinetic properties of colloidal dispersions are helpful

in predicting the stability of a system and determining
molecular weight of colloidal particles.

1. Brownian motion
Brownian motion describes the random
movement of colloidal particles.
Colloidal particles are subject to random collisions
with the molecules of the dispersion medium, so that
each particle pursues an irregular and complicated
zigzag path.
If the particles (up to about 2 μm diameter) are
observed under a microscope or the light scattered
by colloidal particles is viewed using an
ultramicroscope, an irregular motion is seen. This
movement is referred to as Brownian motion, after
Robert Brown who first reported his observation
The Brownian movement tendency4 of the particles
increases with decreasing particle size
Brownian motion may be seen in particles up to 5 μm
 Suspended colloidal particles and solute molecules
undergo both rotational and translational brownian
movements
Increasing the viscosity of the medium, by the
addition of glycerin or a similar agent,
decreases and finally stops the Brownian
movement.

2. Diffusion
As a result of Brownian motion, colloidal particles
spontaneously diffuse from a region of higher
concentration to the region of lower concentration
until the concentration of the system is uniform
throughout. Diffusion is a direct result of Brownian
movement.
The rate of diffusion is expressed by Fick's first law

Diffusion of colloids is a slow process

Smaller molecules diffuse faster
Einstein suggested the following equation for
spherical particles of radius r, under conditions
valid for Stokes’ law and Einstein’s law of viscosity,
(D is the diffusion coefficient)
 Passive diffusion (driven by a concentration
gradient and carried out through brownian motion)
is important in the release of drugs from topical
preparations and in the gastrointestinal absorption
of drugs
The diffusion coefficient can be used to obtain
the molecular weight of an approximately spherical
particle, such as egg albumin and haemoglobin, by
the following relationship:

Thus from the above equations,

3. Sedimentation:

The rate of sedimentation of uniform sized

spherical particles (velocity of sedimentation) is
expressed by Stokes' law. According to this
equation, the rate at which particles in dispersion
sediment is related to their size and density and the
viscosity of the suspension medium and also the
 gravitational force. (refer to the equation in coarse
disp pdf 2)

Brownian motion counteracts the effects of

sedimentation, maintains small colloidal particles in
suspension and prevents sedimentation

Hence, under normal conditions colloidal

particles undergo little or no sedimentation or
creaming.
Therefore, a stronger force than gravity is
therefore needed for colloidal particles to sediment;
hence a high-speed centrifuge called
ultracentrifuge is made use of to bring about
sedimentation of colloidal particles.
Also, as particle size increases, brownian
motion decreases and the gravitation force starts
influencing the motion.
Larger particles have a greater tendency to
settle to the bottom of the dispersion provided the
densities of the dispersed phase and the liquid
vehicle are sufficiently different
As brownian motion diminishes with increasing
particle size, the tendency of particles to sediment
or cream is increased
4. Viscosity
Viscosity of a polymer solution (which is a
colloidal dispersion) depends on a number of
parameters such as concentration, molecular
weight, shape and size of molecules, temperature,
and intermolecular attractions.
 Viscosity is an expression of the resistance to
flow of a system under an applied stress

η: viscosity of the polymer solution(poise) and η0 is the

viscosity of the pure solvent (poise)
ηsp the specific viscosity
c is the concentration of the polymer solution
expressed as g /dL (g/100ml)
ηred is the reduced viscosity (or viscosity number) =
ηsp/c
All polymers increase the viscosity of the solvent in
which they are dissolved. This allows for a convenient
method of determining the molecular weight of
polymers. By measuring the solution viscosity, we can
find the molecular weight
Extrapolation to zero polymer concentration is
intended to eliminate polymer intermolecular
interactions. When the polymer concentration is
expressed in g/dl, the units of [η] will be dl/g.
The molecular weight obtained by using the intrinsic
viscosity is called as viscosity average molecular
weight

√ Intrinsic viscosity gives the true viscosity-

enhancing properties of a polymer independent of
its concentration in solution. The intrinsic viscosity
is one of the most frequently determined
parameters used to characterize polymers.

5. Osmotic pressure:
Osmotic pressure, a colligative property of the colloidal
dispersion is made use of in the determination of
molecular weight of the dispersed phase.
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III. ELECTRICAL PROPERTIES OF COLLOIDS

The colloidal particle is either negatively charged

(kaolin, sulphur colloidal dispersion) or positively
charged (ferric hydroxide, metal hydroxide and other
metal hydroxide.)

i. Origin of Electric Charges

The particles acquire charge in a colloidal dispersion

mainly by adsorption and ionization

1. Selective adsorption of a particular ionic species

present in solution. This may be an ion added to the
solution or, in the case of pure water, it may be the
hydronium or hydroxyl ion. The majority of particles
 dispersed in water acquire a negative charge due to
preferential adsorption of the hydroxyl ion.
2. Charges on particles may arise from ionization of
surface groups (such as COOH) that may be situated
at the surface of the particle. In these cases, the
charge depends on pK and pH. Proteins, ionic
polymers, and polyelectrolytes, many of which are
widely utilized in pharmaceutical formulations. They
acquire their charge mainly through ionization and/or
dissociation
❖ Amino acids and proteins acquire their charge mainly
through the ionization of carboxyl and amino groups
to give –COO- and NH3+ ions.
❖ The ionization of these groups and hence the net
molecular charge depends on the pH of the system.

i. The electrical double layer and the zeta potential

and surface charge

Pls refer to the electrical double layer theory given in

coarse dispersion pdf 1, page 6-7

√ In addition to ions in the Stern layer a certain

amount of solvent will be bound to the ions and the
charged surface.
√ This solvating layer is held to the surface and the
edge of the layer, termed the surface or plane of
shear, represents the boundary of relative
movement between the solid (and attached material)
and the liquid.
√ The potential at the plane of shear is termed the
zeta, ζ, or electrokinetic, potential and its
magnitude may be measured using
microelectrophoresis or any other of the
electrokinetic phenomena

i i. Electrokinetic Phenomena

a. Electrophoresis:
This involves the movement of charged dispersed
particles through a liquid medium under the
influence of an electrical field.
 When an electric field is applied to dispersion, the
particles move toward the electrode having a
charge opposite to that on their surface.
b. Electroosmosis: the movement of liquid relative to
a stationary charged surface, by an applied
electric field.
c. Sedimentation potential, is the electric
field/potential created when particles sediment
d. Streaming potential, the electric field created
when liquid is made to flow along a stationary
charged surface
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