COLLOIDS

Dispersed Systems:
 Dispersed systems consist of particulate matter (dispersed phase),
distributed throughout a continuous phase (dispersion medium).

 They are classified according to the particle diameter of the

dispersed material:

1- Molecular dispersions (less than 1 nm)

- Particles invisible in electron microscope
- Pass through semipermeable membranes and filter paper
- Particles do not settle down on standing
- Undergo rapid diffusion
- E.g. ordinary ions, glucose
 Dispersed Systems:
2- Colloidal dispersions (1 nm - o.5 um)
- Particles not resolved by ordinary microscope, can be detected by
electron microscope.
- Pass through filter paper but not pass through semipermeable
membrane.
- Particles made to settle by centrifugation
- Diffuse very slowly
- E.g. colloidal silver sols, naural and synthetic polymers

3- Coarse dispersions (> 0.5 um)

- Particles are visible under ordinary microscope
- Do not pass through filter paper or semipermeable membrane.
- Particles settle down under gravity
- Do not diffuse
- E.g. emulsions, suspensions, red blood cells
Dispersed Systems:
Types of colloids
COLLOIDAL DISPERSION ON THE BASIS OF STATE OF MATTER

A useful classification of colloidal dispersion is based on

the state of matter of the dispersed phase and dispersion
medium i.e. whether they are solid liquid or gaseous.
A sol is the colloidal dispersion of a solid in a liquid or
gaseous medium. Prefixes designate the dispersion
medium, such as hydrasol, alcosol, aerosol for water,
alcohol and air, respectively. Sols are fluid.
If the solid particles form bridged structures possessing
some mechanical strength, the system is called a gel
(hydrogel, alcogel, aerogel).
 COLLOIDAL DISPERSION ON THE BASIS OF STATE OF
Dispersed
MATTER Dispersion medium
phase
  Solid Liquid
Gas

Solid Zinc oxide, Sols: Bentonite Solid aerosols,

tooth paste magma NF smoke, dust
Liquid Absorption Emulsions mineral Liquid aerosols:
bases, emulsion oil, emulsion USP, mist, fog, nasal
bases milk, soybean oil in .relief sprays
water emulsion for
IV feeding
Gas Solid foams Foams, carbonated No colloidal
beverages, dispersions
effervescent salts in
water
 Types of colloids:

The nature of interaction between dispersed

phase and dispersion medium
A-Lyophilic colloids (solvent attracting) (solvent
loving) Lyo means solvent. Lyophilic colloids may be therefore
called as solvent loving colloids.
 Systems containing colloidal particles that interact to an
appreciable extent with the dispersion medium are referred to
as lyophilic (solvent-loving) colloids. Owing to their affinity for the
dispersion medium, such materials form colloidal dispersions, or
sols, with relative ease. Thus, lyophilic colloidal sols are usually
obtained simply by dissolving the material in the solvent being
used. For example, the dissolution of gelatin, acacia, and albumin
which form colloidal dispersions in water.
 Types of colloids:
The various properties of this class of colloids are due to
the attraction between the dispersed phase and the
dispersion medium, which leads to solvation, the
attachment of solvent molecules to the molecules of the
dispersed phase. In the case of hydrophilic colloids, in
which water is the dispersion medium, this is termed
hydration and if dispersed medium is water, the system is
said to be hydrophilic colloids.

Rubber and polystyrene form lyophilic colloids in non-

aqueous, organic solvents. These materials accordingly are
referred to as lipophilic colloids.
 Types of colloids:

Hydrophilic colloids dispersions are further divided into:

True dispersions
True solutions are formed by water soluble polymers (acacia and
povidone).
Gelled solutions
If the polymer is present in sufficiently high concentration and or at
temperature where their water solubility is low. Examples of such
hydrogels are relatively concentrated solution of gelatin and starch
which set to gels upon cooling or of methylcellulose
which gels upon heating.
Particulate dispersions
Particulate dispersions are those where the solids do not form
molecular solution but remain as discrete through minute particles.
Bentonite and microcrystalline cellulose form such hydrosols.
 Types of colloids:

Properties of lyophilic colloids

Because of high affinity or attraction between the dispersion medium

and the dispersed phase, lyophilic dispersions form spontaneously

when the liquid in contact is brought into contact with the solid
phase.
 Lyophilic colloids are thermodynamically stable.

They are stable even in the presence of electrolyte although the

dispersed phase can be salted out by high concentration of very

soluble electrolyte.
The viscosity of the dispersion medium generally increases on the

addition of dispersed phase at sufficiently high concentration.

 Types of colloids: charge

B-lyophobic (solvent repelling) (solvent hating)

The second class of colloids is composed of materials that
have little attraction, if any, for the dispersion medium.
These are the lyophobic (solvent-hating) colloids and
predictably, their properties differ from those of the
lyophilic colloids.
This is primarily due to the absence of a solvent sheath
around the particle.
Lyophobic colloids are generally composed of inorganic
particles dispersed in water. Examples of such materials
are gold, silver, sulfur, arsenous sulfide, and silver iodide.
When the dispersion medium in these types of colloid is
water, they are known as hydrophobic colloids.
 Types of colloids: charge

Properties of lyophobic colloids

Lyophobic colloids are thermodynamically unstable.
The dispersed phase can easily be salted out even in the
presence of very small concentration of electrolytes, by
heating or by shaking.
The viscosity of dispersion medium does not increase
greatly by the presence of lyophobic colloidal particles
which tends to remain unsolvated.
Once precipitated, it is not easy to reconstitute the sol by
simple mixing with the dispersion medium. Hence, these
sols are called irreversible sols.
 Types of colloids:
C- Association / amphiphilic colloids
Association colloids or amphiphilic colloids form the
third group in this classification. Certain molecules or
ions, termed amphiphiles or surface-active agents, are
characterized by having two distinct regions of opposing
solutions affinities within the same molecule or ion.
When present in liquid medium at low concentrations,
the amphiphiles exist separately and are of such a size
as to be subcolloidal. As the concentration is increased,
aggregation occur over a narrow concentration range.
These aggregates which may contain 50 or more
monomers, are called micelles.
Types of colloids:
The diameter of each micelle is of the order of 50Ǻ,
micelles lie within the size range we have designated
as colloidal. The concentration of monomer at which
micelle form is called as the critical micelle
concentration (CMC). The number of monomers that
aggregate to form micelle is known as aggregation
number of micelles.
 Types of colloids:
- At low concentration: amphiphiles exist separately
(subcolloidal size)
- At high concentration: form aggregates or micelles (50
or more monomers) (colloidal size)
Association colloids
 Types of colloids:
Critical micelle concentration (C.M.C) : the concentration
at which micelle form
- The phenomenon of micelle formation can be
explained:
1- below C.M.C: amphiphiles are adsorbed at the
air/water interface
2- As amphiphile concentration is raised: both the
interphase and bulk phase become saturated with
monomers (C.M.C)
3- any further amphiphile added in excess: amphiphiles
aggregate to form micelles
 Types of colloids:
- In water: the hydrocarbon chains face inwards into
the micelle forming hydrocarbon core and surrounded
by the polar portions of the amphiphile associated
with water molecules.
- In non-polar liquid: the polar heads facing inward and
the hydrocarbon chains are associated with non-polar
liquid.
- At concentrations close to C.M.C spherical
micelles
- At higher concentrations lamellar micelles
Association Colloids
 Types of colloids:
 The formation of association colloids is spontaneous,
provided the concentration of amphiphile in solution
exceed C.M.C.
 Association colloids are thermodynamically stable In
aqueous solutions, the CMC is reduced by the addition
of electrolytes. How ever salting out may occur at
higher salt concentrations. The viscosity of the
dispersion medium generally increases with increase in
concentration of amphiphiles.
 They are also easy to prepare and form spontaneously
once the CMC is exceeded.
Comparison of colloidal sols
Lyophilic Associated Lyophobic
Dispersed phase Dispersed phase Dispersed phase
(large organic mole. (micelles of organic (Inorganic particles as
With colloidal size) molec. Or ion –size gold)
below the colloidal
range)
Molec. of dispersed Hydrophilic and Not formed
phase are solvated lyophilic portion are spontaneously
Formed solvated ,
spontaneously Formed at conc. above
CMC
The viscosity ↑ with ↑ The viscosity ↑ with ↑ Not greatly increase
the dispersed phase the micelles conc.
conc.

Stable dispersion in CMC↓ with electrolytes Unstable dispersion in

presence of presence of
electrolytes electrolytes
 Preparation of Colloids
LYOPHILIC COLLOIDS
Because of the affinity of the lyophilic colloid for the
dispersion medium, these colloids are relatively easy to
form. As there is a considerable interaction between the
dispersed phase and the dispersion medium, they form
spontaneously by placing colloidal material in contact with
the proper solvent for e.g. acacia and gelatin dispersed
easily to form colloidal dispersion when kept in contact
with water.
 Preparation of Colloids
LYOPHOBIC COLLOIDS
Since there is a lack of affinity between the molecules of
the dispersed phase and the dispersion medium,
lyophobic colloids are more difficult to prepare. Generally,
two methods are used
Dispersion method
Condensation method
 Preparation of Colloids
MECHANICAL DISPERSION METHOD
In this method, the large particles of the material whose sol is
to be prepared are broken down in a machine called colloid
mill. Colloid mill consists of two heavy steel discs separated
by a little gap. They can be adjusted according to the particle
size desired. The two discs rotate at high speed (about 8000
revolutions per minute) in the opposite direction. A suspension
of the substance in water is added into the mill. The particles
present in the suspension are grinded to form the particles of
colloidal size and also get dispersed in water to form a sol.
Preparation of Colloids
 Preparation of Colloids
ELECTRICAL DISPERSION METHOD
This method is used for the preparation of sols metals such
as gold, silver, platinum etc.
In this method, two metal wires working as electrodes whose
sol is to be prepared are immersed into the dispersion
medium and an electric arc is produced by passing high
voltage current. The dispersion medium is cooled by
surrounding it with a freezing mixture. Due the heat produced
from electric arc, the metal starts vaporizing and the vapor
condense into the cold dispersion medium to form to the
particles of colloidal size on cooling.
Preparation of Colloids
 Preparation of Colloids
ULTRASONIC DISPERSION
The sound waves of high frequency are usually called
ultrasonic waves.
The passage of an ultrasonic waves through a dispersion
medium produces high frequency oscillation (20,000 –
200,000 cycles per second) resulting in size reduction of
coarse particles to colloidal size.
.
Preparation of Colloids
 Preparation of Colloids
  PEPTIZATION
The term, coined by graham, is defined as the
breaking up of aggregates or secondary
particles into smaller aggregates or into
primary particles in the colloidal size range.
Peptization is synonymous with deflocculation; it
can be brought about by the removal of
flocculating agents, usually electrolytes, or by the
addition of deflocculating or peptizing agents,
usually surfactants, water soluble polymers or ions
which are absorbed at the particle surface.  
 Preparation of Colloids
  When powdered activated charcoal is added
to the water with stirring, the aggregated
grains are broken up only incompletely and
the resultant suspension is gray and
translucent.The addition of 0.1% or less of
sodium lauryl sulfate disintegrates the grains
into finely dispersed particles forming a deep
black and opaque dispersion.
Preparation of Colloids
Ferric or aluminum hydroxide that has been
freshly precipitated with ammonia can be
peptized with small amounts of acids.
 Preparation of Colloids
CONDENSATION METHOD
In condensation methods, materials of subcolloidal
dimensions are caused to aggregate into particles
within the colloidal size range. This is usually
achieved by means of chemical reactions that result
in the formation of colloidal dispersion from true
solution. By carefully controlling the conditions the
solution is altered so that particles growth stop at
the colloidal state and larger size of particles
formation is avoided
 Preparation of Colloids
The required conditions for the formation of
lyophobic colloids by condensation or
aggregation involve a high degree of initial
supersaturation followed by the formation
and growth of nuclei. Supersaturation can be
brought about by change in solvent or
reduction in temperature. For example, if
sulfur is dissolved in alcohol and the
concentrated solution is then poured into an
Preparation of Colloids

excess of water, many small nuclei form in

the supersaturated solution. These grow
rapidly to form a colloidal sol.
Other condensation methods depend on
a chemical reaction, such as reduction,
oxidation, hydrolysis and double
decomposition
 Preparation of Colloids
OXIDATION
Sol sulphur is prepared by oxidizing an
aqueous solution of H2S with bromine water
or nitric acid or SO2 or any other suitable
oxidizing agent.

 
Preparation of Colloids
REDUCTION
Sols of gold, silver, platinum etc. are
obtained by the reduction of dilute
solutions of their salts with a suitable
reducing agent. For example, gold sol can
be obtained by reducing a dilute aqueous
solution of gold with stannous chloride. 
AuCl3+3SnCl2→3SnCl4+2AuGoldsol
 
 Preparation of Colloids
HYDROLYSIS
If a solution of ferric chloride is added to
a large volume of water, hydrolysis occurs
with the formation of a red sol of
hydrated ferric oxide. Chromium and
aluminum salts also hydrolyze in this
manner.
 
FeCI3    +  3H2O →       Fe(OH)3    +   3HCI
  
Preparation of Colloids
 DOUBLE DECOMPOSITION
Another reaction is the decomposition of
sodium thiosulfate by sulfuric acid, using
either very dilute or very concentrated
solutions to obtain colloidal dispersed
sulfur:
 Preparation of Colloids
 BY EXCHANGE OF SOLVENTS
If a solution of sulphur or phosphorus prepared
in alcohol is poured into water, a colloidal
solution of sulphur or phosphorus is obtained
due to low solubility of sulphur or phosphorus in
water. Thus, there are number of substances
whose colloidal solutions can be prepared by
taking a solution of the substance in one solvent
and pouring it into another solvent in which the
substance is relatively less soluble.
 Properties of Colloids
OPTICAL PROPERTIES
THE FARADAY–TYNDALL EFFECT
When a strong beam of light is passed
through a colloidal sol, a visible cone,
resulting from the scattering of light by the
colloidal particles, is formed. The
phenomenon of light scattering is called the
Faraday–Tyndall effect. This is due to the
fact that particles absorb light energy and
then emit it in all directions.
 Properties of Colloids
The optical properties of a medium are
determined by its refractive index. When the
refractive index is uniform throughout, light will
pass the medium undeflected. Whenever there
are discrete variations in the refractive index
caused by the presence of particles or by small
scale density fluctuations, part of light will be
scattered in all directions. An optical property
characteristic of colloidal systems, called the
Tyndall beam, is familiar to everyone.
 Properties of Colloids
When narrow beam of light is admitted through
a small hole into a darkened room, the
presence of minute dust particles suspended in
the air is revealed by bright flashing points. A
beam of light striking a particle polarizes the
atoms and molecules of those particles,
introducing dipoles which act as a secondary
source and reemit the weak light of same
wavelength as the incident light. This
phenomenon is called light scattering
 Properties of Colloids
The scattered radiation propagates in all
directions away from the particle. In a bright
room the light scattered by the dust particles is
too weak to be noticeable.
Colloidal particles suspended in a liquid
suspension also scatter light. When an intense,
narrowly defined beam of light is passed
through a suspension, its path become visible
due to the scattering of light by the particles in
the beam.
 Properties of Colloids
This Tyndall beam becomes most visible when
viewed against a dark background in a direction
perpendicular to the incident beam. When clear
mineral oil is dispersed in equal volume of a
clear aqueous surfactant solution, the resultant
emulsion is milky white and opaque due to light
scattering. Microemulsions where the emulsified
droplets are about 40nm (400A°) in diameter,
i.e. much smaller than the wavelength of visible
light, are transparent and clear to the naked eye
 
 Properties of Colloids
 
Properties of Colloids
WHY SKY IS BLUE
When a beam of light passes through a
colloid, colloidal particles scatter the light.
The intensity of scattered, Is, light is
inversely proportional to the fourth power
of the wavelength, λ (Rayleigh law):
 Properties of Colloids
Thus, shorter-wavelength light (blue) is
scattered more intensely than longer-
wavelength light (yellow and red), and so the
scattered light is mostly blue, whereas
transmitted light has a yellow or reddish
color. Because of the constant motion of
molecules, the atmosphere is inhomogeneous
and constantly forms clusters with higher
density of air.
 Properties of Colloids
These inhomogeneities may be considered as
colloidal particles. The scattering of short-
wavelength light gives the sky its blue color. In
contrast, transmitted light has a yellow color. At
sunrise and sunset, sunlight has to travel a longer
distance through the atmosphere than at noon. This
is especially important in the lower atmosphere
because it has a higher density (i.e., more gas
molecules).
 Properties of Colloids

Because of this longer distance, the

yellow light also scatters. Sunsets can be more
spectacular than sunrises because of an
increase in the number of particles in the
atmosphere due to pollution or natural causes
(wind, dust), throughout the day.
Properties of Colloids
 Properties of Colloids
LIGHT BEAMS FROM HEAD LIGHTS OF
CAR
When a beam of light is emitted from the
headlights of the car, it is refracted due to the
dust particles in the air. Due to this refraction
the light is scattered and dust particles become
visible.
 Properties of Colloids
LIGHT BEAM FROM A PROJECTOR
When a beam of light is flashed on a screen
from the projector the particles. The particles
become visible due to refraction
LIGHT BEAM IN THE FOG
If we see a beam of light in a fog the water
droplets in air refract the light and become
visible.
 Properties of Colloids
ELECTRON MICROSCOPY
The electron microscope has high resolving
power and is used in getting the picture of
colloidal particles. Hence, size, shape and
structure of the colloidal particles can be
studied. The radiation source of electron
microscope is a beam of high energy electrons.
The resolving power, of electron microscope
can be defined in terms of d.
 Properties of Colloids
The smaller is d and the greater is the resolving
power. The optical microscope uses visible light as its
radiation source and d is approximately
20 nm (200 A° ).
The radiation source of the electron microscope is a
beam of high-energy electrons having wavelengths in
the region of 0.01 nm (0.1 A°). This results in d being
approximately 0.5 nm (5 A°), a much-increased power
of resolution over the optical microscope.
 Properties of Colloids

ULTRA MICROSCOPY
The colloidal particles are too small to be seen with an
optical microscope. The ultramicroscope permits
observation of particles much smaller than wavelength
of light and used to detect submicroscopic particles
before the advent of electron microscopy. A colloidal
dispersion viewed through an ultra-microscope against
a dark background at right angles to an intense beam
of incident light, the particles appear as bright spots.
Properties of Colloids
 Properties of Colloids
LIGHT SCATTERING
This property depends on the Faraday–Tyndall effect and is widely used
for determining the molecular weight of colloids. It can also be
used to obtain information on the shape and size of these particles.
Scattering can be described in terms of the turbidity. At a given
concentration of dispersed phase, the turbidity is proportional to
the molecular weight of the lyophilic colloid. Because of the low
turbidities of most lyophilic colloids, it is more convenient to measure
the scattered light (at a particular angle relative to the incident beam)
rather than the transmitted light.
 Properties of Colloids
The turbidity can then be calculated from the intensity
of the scattered light, provided that the dimensions of
the particle are small compared with the wavelength
of the light used. The molecular weight of the colloid
can be obtained from the following equation:
 
 Properties of Colloids
 

Where, τ is the turbidity in cm−1, c is the concentration

of solute in g/cm3 of solution, M is the weight-average
molecular weight in g/mole or daltons, and B is an
interaction constant, H is constant for a particular
system.
 Properties of Colloids
 
 Properties of Colloids
 
 Properties of Colloids
 
KINETIC PROPERTIES
BROWNIAN MOTION
The colloidal particles in the dispersion are always in a
state of continuous and random motion with in the
medium due to bombardment by the molecules of the
dispersion medium. The continuous zigzag motion
executed by a colloidal particle in the dispersion
medium is called Brownian motion.
 Properties of Colloids

 Suspension and true solutions do not exhibit

Brownian motion. The explanation of Brownian
motion was given by Albert Einstein by
mathematical considerations based on kinetic
molecular theory. According to him, at any
instant, a colloidal particle is under continuous
bombardment by the molecules of the
dispersion medium. This causes the particle to
move.
 Properties of Colloids

This movement of particles is caused by

unequal number of molecules of the medium
striking the colloidal particle, which causes the
particle to change the direction of movement.
 Properties of Colloids
Brownian motion is an excellent
proof that molecules are in
ceaseless motion in liquids. It
also explains how action of
gravity is counter acted which
ordinarily causes the settling of
the particles. The constant
pushing of the colloidal
particles has a stearic effect
which does not allow the
particle to settle down.
 Properties of Colloids
DIFFUSION
It is a spontaneous process where solute particles
move from the region of higher concentration to the
region of lower concentration until the concentration
gradient become uniform throughout. Colloidal
particles also exhibit diffusion which in their case is
direct result of Brownian motion. The rate of
diffusion is expressed by ficks law which is written
as
 Properties of Colloids
Where dq is the amount of material diffusing in time
dt across an area S under the influence of a
concentration gradient dc/dx. D is the diffusion
coefficient and has dimensions of area per unit time.
It is possible to determine the molecular weight of
approximately spherical particles from the diffusion
coefficient
 Properties of Colloids
Where,
M= Molecular weight
V= Partial specific volume
R= Molar gas constant
T= Absolute temperature
R= Radius of the sphere
N= Avogadro’s number
η = Viscosity of the solvent
 Properties of Colloids
OSMOTIC PRESSURE
Osmotic pressure is colligative property which
depends on number of particles in dispersion. The
osmotic pressure, π, of a dilute colloidal solution is
described by the van’t Hoff equation:
 Properties of Colloids
Where c is molar concentration of solute. This
equation can be used to calculate the molecular
weight of a colloid in a dilute solution. Replacing c
with cg/M in above equation in which cg is the
grams of solute per liter of solution and M is the
molecular weight, we obtain
 Properties of Colloids

Where,    
π = Osmotic pressure
C= Grams of solute per liter solvent
M= Molecular weight
R= Gas constant
T= Temperature in Kelvin
 Properties of Colloids
SEDIMENTATION
In normal dispersion, the dispersed particles tend to
settle down under the influence of gravity and the
phenomena is called sedimentation. The velocity, v,
of sedimentation of spherical particles having a
density ρ in a medium of density ρ0 and a viscosity
η0 is given by Stokes’s law
Properties of Colloids

Where g is the acceleration due to gravity.

However, colloidal particles do not undergo
sedimentation as brownian movement
promotes mixing and tends to offset
sedimentation.
 Properties of Colloids

Therefore, stronger force must be applied to

bring about sedimentation of colloidal particle.
Ultracentrifuge is generally used to bring about
sedimentation. In an ultracentrifuge, particle
tends to settle down according to their
molecular weight hence it is also helpful in
determining the molecular weight.
 Properties of Colloids
Ultracentrifuge can produce a force one million
times that of gravity. In a centrifuge, the
acceleration of gravity is replaced by ω2x, where ω
is the angular velocity and x is the distance of the
particle from the center of rotation.
 Properties of Colloids
It is possible to determine the molecular weight
of a polymer, such as a protein, by use of the
below expression which is derived from

Where, where R is the molar gas constant, T is

the absolute temperature, v is the partial specific
volume of the protein, and ρ0 is the density of
the solvent.
 Properties of Colloids
VISCOSITY
Viscosity is an expression of the resistance to
flow of a system under an applied stress. The
more viscous liquid is, the greater is the applied
force required to make it flow at a particular
rate. Viscosity data can be used to obtain the
molecular weight of material comprising the
disperse phase.
 Properties of Colloids
Viscosity studies also provide information
regarding the shape of particle in a
solution. The viscosity of colloidal dispersion is
affected by the shapes of particles of the
disperse phase. Spherocolloids form dispersions
of relatively low viscosity, whereas system
containing linear particles is more viscous.
 Properties of Colloids
The relationship of shape and viscosity reflects the
degree of solvation of the particles. If a linear
colloid is placed in a solvent for which it has a low
affinity, it tends to ball up that is, to assume a
spherical shape, and the viscosity falls. This
provides a mean of detecting changes in the shape
of flexible colloidal particles and macro molecules.

.
 Properties of Colloids
ELECTRICAL PROPERTIES
Colloidal particles carry electrical charge of either
positive or negative type. Negatively charge
colloidal particles include that of kaolin, sulphur
and arsenious sulphide while positively charged
ones include ferric oxide and other metal hydroxide
colloidal dispersions.
 Properties of Colloids

In certain colloidal dispersions such as that of

proteins, the charge on the particle may be positive,
negative or neutral depending upon the pH of
medium. The particles in a colloidal dispersion
acquire charges from several sources mainly by
ionization or by adsorption. Some electrical properties
of colloidal dispersions are discussed below:
 Properties of Colloids
ELECTRIC DOUBLE LAYER
Consider the colloidal dispersion of silver iodide
prepared by the following reaction.
AgNO3 + NaI → AgI (s) + NaNO3
In the bulk of silver iodide particles there is a 1:1
stoichiometric ratio of Ag+ to I− ions. If the reaction is
carried out with an excess of silver nitrate, there will
be more Ag+ than I− ions in the surface of particles.
 Properties of Colloids
The particles will thus be positively charged and the
counterions surrounding them will be NO3−. If the
reaction is carried out using an exact stoichiometric 1:1
ratio of silver nitrate to sodium iodide or with an excess
sodium iodide, the surface of particles will contain an
excess I− over Ag+ ions. The particles will be negatively
charged, and Na+ will be the counterions surrounding
the particles and neutralizing their charges.
 Properties of Colloids
The surface layer of silver iodide particles
prepared with an excess of sodium iodide contain
more I− than Ag+ ions, whereas its bulk contains
the two ions in exactly equimolar proportion. The
aqueous solution in which this particle is
suspended contains relatively high concentrations
of Na+ and NO3−, a lower concentration of I− and
traces of H+, OH− and Ag+.
 Properties of Colloids
The negatively charged particle surface attracts
positive ions from the solution and replaces negative
ions. The solution in the vicinity of the surface
contains a much higher concentration of Na+, which
are counterions, and a much lower concentration of
NO3− ions in the bulk of solution. A number of Na+
ions equal to the number of excess I− ions in the
surface and equivalent to the net negative surface
charge of particles are pulled towards its surface.
 Properties of Colloids
These counterions tend to stick to the
surface, approaching it as closely as their
hydration spheres permit (Helmholtz double
layer), but the thermal agitation of the water
molecules tends to disperse them throughout
the solution. As a result, the layer of
counterions surrounding the particles is
spread out.
 Properties of Colloids
The Na+ concentration is highest in the
immediate vicinity of the negative surface, where
the form a compact layer called as stern layer,
and decreases with distance from surface,
throughout a diffuse layer called the Gouy-
Chapman layer. The sharply defined negatively
charged surface is surrounded by a cloud of Na+
counterions required for electroneutrality.
 Properties of Colloids
The combination of two layers of oppositely
charged ions constitutes an electric double
layer. The presence of electric double layer
around each particle in a colloidal dispersion
gives rise to electro-kinetic effects. They are
electrophoresis, electro osmosis, sedimentation
potential and streaming potential.
 
 Properties of Colloids
 
 Properties of Colloids
 
 Properties of Colloids
  ELECTROPHORESIS
When the electrical field is applied to the
colloidal dispersion, the particles carrying
charge either negative or positive move
towards the electrode of opposite charge.
Negatively charged particles move towards
anode while positively charged particles move
towards cathode. The movement of the sol
particles under an applied electrical potential is
called electrophoresis or cataphoresis.
 Properties of Colloids
An electrophoresis cell fitted with two
 
electrodes contains the dispersion. When a
potential is applied across the electrodes, the
particles migrate to the oppositely charged
electrode. The rate of particle migration is
observed by means of an ultramicroscope and
is a function of the charge on the particle.
From knowledge of the direction and rate of
migration, the sign and magnitude of the zeta
potential in a colloidal system can be
determined.
 Properties of Colloids
 
 Properties of Colloids
 
 Properties of Colloids
  ELECTRO OSMOSIS
The atmosphere of counter ions around the
particles confers a charge on the dispersion
medium. The sign of this charge is opposite to
that of the particles. Electroosmosis is
essentially opposite in principle to
electrophoresis. In electrophoresis, the
application of a potential causes a charged
particle to move relative to the liquid, which is
stationary.
 Properties of Colloids
If  the solid is rendered immobile (e.g., by
forming a capillary or making the particles into a
porous plug), however, the liquid now moves
relative to the charged surface. This is
electroosmosis, so called because liquid moves
through a plug or a membrane across which a
potential is applied. Electroosmosis provides
another method for obtaining the zeta potential
by determining the rate of flow of liquid through
the plug under standard conditions.
 Properties of Colloids
The
  pressure produced by the process of electro-
osmosis is known as the electro-osmotic pressure.
The phenomena of electro osmosis can be
demonstrated by using a tube in which a plug of
wet clay (a negative colloid) is fixed as shown in
the figure below. The two limbs of the tube are
filled with water the same level. The platinum
electrodes are immersed in water and potential is
applied across them.
 Properties of Colloids
 
Water level will rise on the cathode side and falls
on anode side. The movement of the medium
towards the negative electrode shows that the
charge on the medium is positive. Similarly, for a
positive charge on the medium, electro osmosis
takes place in the reverse direction. Technically this
phenomenon has been applied for the removal of
water from moist clay and in drying dye.
 Properties of Colloids
 
 Properties of Colloids
 SEDIMENTATION POTENTIAL
Sedimentation potential, the reverse of
electrophoresis, is the creation of a potential
when particles undergo sedimentation under
the influence of gravity.
 Properties of Colloids
STREAMING POTENTIAL
This is opposite of electro osmosis. If the
electrodes in the electro osmosis apparatus
are replaced by a galvanometer in the circuit,
no current will be detected when the liquid is
stationary. However, if the liquid is forced
through the tube, the galvanometer will
indicate a current.
 Properties of Colloids

This streaming potential is due to the

displacement of the charges equilibrated in
the double layer around the solid. This
technique can be used to measure the zeta
potential of relatively coarse solids which
would sediment rapidly in the electrophoresis
cell.
 Purification of Colloids
PURIFICATION OF COLLOIDS
Many hydrosols contain low molecular weight,
water soluble impurities. Inorganic dispersions
often contain salts formed by the reactions
producing the dispersion phase. Salts are
especially objectionable in case of hydrophobic
dispersion because they tend to coagulate such
dispersions. Protein solution often contains salts
added as part of separation procedure.
 Purification of Colloids
The dissolved impurities of small molecular size are
removed from the colloidal dispersions by means of
membrane with pore size smaller than the colloidal
particles. Conventional filter papers are permeable to
colloidal particles as well as to small molecules. Most
membrane in current use consist of cellulose,
cellulose nitrate prepared from collodion, cellulose
acetate or synthetic polymers and are available in
variety of shapes, gauges and pore sizes.
 Purification of Colloids
DIALYSIS
The colloidal dispersion is placed inside a cellophane
sac, dipping in water. The small solute molecules
diffuse out into water while the colloidal material
remains trapped inside because of its size. The rate of
dialysis is increased by increasing the area of
membrane, by stirring and by maintaining a high
concentration gradient across the membrane. The
water is replenished continuously or at least frequently.
 Purification of Colloids
The membrane configuration which provides a
particularly exclusive surface area for a given volume
of dispersion is the hollow fiber. The dispersion to be
dialyzed is circulated inside a bundle of parallel fibers
while water is circulated outside the fibers throughout
the bundle. Dialysis of diffusing species takes place
across a thin fiber wall. Dialysis is used in laboratory
to purify sols and to study binding of drugs by
proteins, as well as some manufacturing processes. 
 Purification of Colloids
ELECTRODIALYSIS
If low molecular weight impurities to be removed are
electrolytes, the dialysis can be speeded up by applying
an electric potential to the sol which produces
electrolysis.An electrodialyzer (Fig below) is divided into
three compartments by two dialysis membrane supported
by screens. The two outer compartments in which the two
electrodes are placed are filled with water while the sol is
placed into the central compartment.
 Purification of Colloids
Under the influence of the applied potential, the
anions migrate from the sol into the anode
compartment, while the cations migrate into the
cathode compartment. Lower molecular weight non-
electrolyte solutes diffuse into the either
compartment. Colloidal particles usually are charged
and therefore tend to migrate towards the
membrane, sealing off the compartment with the
electrode of opposite charge.
 Purification of Colloids

The combination of electrophoresis and

gravitational sedimentation produces the
accumulation of negatively charged sol particles.
Hence the supernatant liquid can be changed by
decantation. This process which may be used to
speed up electrodialysis is called
electrodecantation.
 Purification of Colloids

.
 Purification of Colloids
ULTRAFILTERATION
When the sol is placed in a compartment closed by a
dialysis membrane and pressure is applied, the liquid
and the small molecules are forced through the
membrane while the colloidal particles are retained.
This process called ultra-filtration is based on a
sieving mechanism in which all components smaller
than the pore size of the filter membrane pass
through it.
 Purification of Colloids
The pressure difference required to push the
dispersion medium through the ultra-filter is
provided by the gas pressure applied on the sol side
or by suction on the filtrate side. The membrane is
usually supported on a fine wire screen. As
ultrafiltrate is being removed, the sol becomes more
concentrated because a constant amount of
dispersed particles is confined to a decreasing
volume of liquid.
 Purification of Colloids
Some dissolved small molecules or ions are left in the sol
together with the residual water. To avoid the increase
in concentration of the colloidal particles and to remove
the dissolved impurities completely, the ultra-filtrate
squeezed from the sol is replenished continuously or
intermittently with an equal volume of water. During
ultra-filtration, solids tend to accumulate on and near
the membrane. To prevent this buildup and maintain
uniform composition throughout the sol, it is stirred.
Purification of Colloids
 Purification of Colloids

HEAMODIALYSIS
The blood of uremic patients is dialyzed
periodically in artificial kidney “dialyzer” to
remove urea, uric acid, phosphate and
excess sodium and potassium chlorides.
 Purification of Colloids
The dialyzing fluid contains sodium,
potassium, calcium, chloride, dextrose,
acetate ions (the latter are converted into
the body to bicarbonate) and other
constituents in the same concentration as
normal plasma since it contains no urea,
creatinine, uric acid, phosphate nor any of
the other metabolites normally
eliminated by the kidney.
 Purification of Colloids
These compounds diffuse from the patient’s
blood into the dialyzing fluid until their
concentration is same in the blood and the
fluid. Sodium and potassium chloride diffuse
from the blood to fluid because of higher initial
concentration in the blood, and continue to
diffuse until the concentration is equalized.
 Purification of Colloids
The volume of the dialyzing fluid is much greater
than that of the blood. The greater difference in
volume and the replenishment of dialyzate with
fresh fluid is to ensure that the metabolite and
excess of electrolytes are removed almost
completely from the blood. Plasma proteins and
blood cells cannot pass through the dialysis
membrane because of their size.
 Purification of Colloids
Hemodialysis is also employed in acute
poisoning cases.
Edema resulting from water retention can be
relieved by ultrafiltration through the
application of a slight pressure on the blood
side or a partial vacuum on the fluid side.
Purification of Colloids
Stability of Colloids
PRECIPITATION OR COGULATION
When two uncharged hydrophobic particles are
in close proximity, they attract each other by
van der Waals secondary valences, mainly
London dispersion forces. For individual atoms
and molecules, these forces decrease with the
seventh power of the distance between them. In
the case of two particles, every atom of one
particle attracts every atom of the other particle.
 Stability of Colloids
Because the attractive forces are nearly additive,
they decay much less rapidly with interparticle
distance, approximately with the second or third
power of the distance between them. Therefore,
whenever two particles approach each other
closely, the attractive forces take over and cause
them to adhere. Coagulation occurs as the primary
particles aggregate into increasingly larger
secondary particles or floes.
 Stability of Colloids

When two oppositely charged hydrophobic

colloids are mixed, one having positive and the
other negative charges, the electrostatic
attraction between such oppositely charged
particles is superimposed on the attraction by
van der Waals forces and coagulation or
precipitation is accelerated.
 Stability of Colloids

If the dispersion contains only one kind of particle

with the same surface charge and charge density
(the most common case) then electrostatic
repulsion tends to prevent the particles from
approaching closely enough to come within the
effective range of each other's van der Waals
attractive forces. This stabilizes the dispersion
against interparticle attachments or coagulation
 Stability of Colloids
COACERVATION
When oppositely charged hydrophilic colloids are
mixed, a colloid rich layer separates which is
called as coacervate. This phenomenon in which
macromolecular dispersion on mixing separates
into two liquid layers is called coacervation.
Consider the mixing of gelatin and acacia.
 Stability of Colloids
Gelatin at a pH below 4.7 (its isoelectric point) is
positively charged; acacia carries a negative charge that
is relatively unaffected by pH in the acid range. When
solutions of these colloids are mixed in a certain
proportion, coacervation results. The viscosity of the
upper layer, now poor in colloid, is markedly decreased
below that of the coacervate, and in pharmacy this is
considered to represent a physical incompatibility.
Stability of Colloids

Coacervation need not involve the

interaction of charged particles; the
coacervation of gelatin may also be brought
about by the addition of alcohol, sodium
sulfate, or a macromolecular substance such
as starch.
Stability of Colloids

SENSITIZATION
In the presence of very small amount
of hydrophilic colloids, the
hydrophobic colloids may become
even more susceptible to precipitation
from electrolytes.
Stability of Colloids

Sensitization is attributed to a reduction

in zeta potential below the critical value
(the value at which coagulation occur).
It is also reasoned that it is due to
reduction in the thickness of ionic layer
surrounding the colloidal particles and
decrease in coulombic repulsions
between the particles.
Stability of Colloids
PROTECTION
The addition of large amounts of hydrophilic
colloids increases the stability of hydrophobic
colloids towards the precipitation by the
electrolytes. The hydrophilic colloids adsorb on
the surface of hydrophobic colloidal particles
and form a protective layer thus preventing
them from precipitation on addition of an
electrolyte.
Stability of Colloids
This phenomenon is called protection.
The hydrophilic sol used for the
purpose of protecting the hydrophobic
colloids is known as protective
colloids. This protective ability is
indicated by gold number.
Stability of Colloids
GOLD NUMBER
Gold number is measure of protective
ability of hydrophilic colloid. It is defined
as “Minimum weight in milligrams of
hydrophilic colloids required to prevent a
color change from red to violet in 10mL
of gold sol on addition of 1mL of 10 %
solution of sodium chloride”.
Stability of Colloids

This change in color is due to change

in particle size. The lower the gold
number the higher is protective ability
of the colloid. The gold numbers of
some of protective colloids are given
below.
Stability of Colloids
Protective Colloid Gold Number

Gelatin 0.01

Albumin 0.1

Acacia 0.2

Tragacanth 2.0
Stability of Colloids

DETERMINATION OF GOLD NUMBER

For determination of gold number, a series of test
tubes containing 10mL of a gold sol are taken. To
each of test tubes is added a protective colloid in
increasing concentrations. To each of test tubes is
then added 1mL of 10% sodium chloride solution.
The test tubes are left undisturbed.
 Stability of Colloids

At higher concentration of protective colloid,

the gold sol does not change its color while at
lower concentration, the gold sol changes color
from red to violet. The test tube containing a
minimum quantity of colloids which prevent the
change in color of the gold sol is the gold
number of the protective colloid.
 APPLICATIONS

PHARMACEUTICAL APPLICATIONS OF
COLLOIDS
Because of large surface area, colloids show

greater efficiency for adsorption. Kaolin because

of its small particle size shows good adsorption
property for toxin. Colloidal aluminum hydroxide
shows better rate of neutralization of stomach
acid.
 Applications
 Certain medicinal have been found to possess unusual
or increased therapeutic properties when formulated
in the colloidal state. Colloidal silver chloride, silver
iodide, and silver protein are effective germicides and
do not cause the irritation that is characteristic of ionic
silver salts. Coarsely powdered sulfur is poorly
absorbed when administered orally, yet the same dose
of colloidal sulfur may be absorbed so completely as
to cause a toxic reaction and even death.
 Applications

 Colloidal copper has been used in the treatment

of cancer, colloidal gold as a diagnostic agent for
paresis, and colloidal mercury for syphilis.
 Dextran injection is a colloidal dispersion and is
used as plasma substitute
 Applications of Colloids

 Colloidal preparations have also been used as

diagnostic agents. For example, Lange’s gold sol
is used to detect syphilis in patients. Normal
spinal fluid protects the gold sol from the
precipitation effect of sodium chloride, where as
in syphilitic case, it fails to prevent.
 Applications of Colloids

 Many natural and synthetic polymers are colloids

and have very important role in modern
pharmaceutical drug delivery system. Polymers
are macromolecules formed by the
polymerization or condensation of smaller,
noncolloidal molecules
 Application of Colloids

 Proteins are important natural colloids and are

found in the body as components of muscle, bone,
and skin. The plasma proteins are responsible for
binding certain drug molecules to such an extent
that the pharmacologic activity of the drug is
affected. Naturally occurring plant macromolecules
such as starch and cellulose are used as
pharmaceutical adjuncts are capable of existing in
the colloidal state.
Application of Colloids

 Other synthetic polymers are applied

as coatings to solid dosage forms to
protect drugs that are susceptible to
atmospheric moisture or degradation
under the acid conditions of the
stomach.
Application of Colloids

 Colloidal electrolytes (surface-active

agents) are sometimes used to increase
the solubility, stability, and taste of
certain compounds in aqueous and oily
pharmaceutical preparations.
Application of Colloids

 In addition to pharmaceutical application,

colloids are used as delivery systems for
therapeutics. Seven main types of
colloidal drug delivery systems in use
are: Hydrogels, Microparticles,
Microemulsions, Liposomes, Micelles
and Nanoparticles.
Application of Colloids

 Colloidal dispersions containing

radioactive isotopes are diagnostic and
therapeutic agents’ nuclear medicines.
Technetium sulphur colloid is primarily
used in liver, spleen and bone scanning.
Application of Colloids

 Polycarbophil, a lightly cross-linked

polymer of acrylic acid, only ionizes and
swells in the merely neutral small
intestine, where it absorbs water and
reduces the fluidity of diarrheal stool.