Colloidal dispersion

Md. Zahidul Islam Zahid

Lecturer
North South University
Dispersed System
• A dispersed system is defined as a system in which one phase, the dispersed phase, is distributed
uniformly as particles throughout another phase known as dispersion medium or continuous medium.
• Dispersed system can be classified on the basis of the physical state of two phase, i.e., the dispersed
phase and the dispersion medium

• Since states of matter exist as gas, solid and liquid, nine different types of dispersed phases are possible.
Dispersed System
Examples of dispersed system based on physical state:
Dispersion Dispersed Phase Colloidal Coarse
Medium
Gas Liquid Fog Spray

Gas Solid Smoke Dust

Liquid Gas Foam (aerosol) Foam

Liquid Liquid (immiscible) Oil globules Emulsion

Liquid Solid Colloidal gold in water Suspension of kaolin in

water
Solid Gas Solid foam (aerosol) Solid foam

Solid Liquid Mineral oil in wax Solid emulsion

Solid Solid Colloidal gold in glass Solid suspension

Dispersed System
• Dispersed systems can also be classified on the basis of the size of the dispersed
phase

Class Range of Characteristics of system examples

particle
size
1. Molecular Less than Particles invisible in electron Oxygen molecules,
dispersion 1.0nm microscope, pass through ultra filter & Ordinary ions,
semi permeable membrane, Glucose
particle diffuse rapidly
2. Colloidal 1.0 nm to Particles visible in electron microscope, Colloidal silver sols,
dispersion 1.0 µm pass through filter paper but do not pass
semi permeable membrane, natural & synthetic
particle diffuse very slow polymers
3. Coarse Greater than Particles visible under microscope, Grains of sand,
dispersion 1.0 µm do not pass through normal filter red blood cells,
paper or dialyze through semi pharmaceutical
permeable membrane, emulsions &
particle do not diffuse suspensions
Colloidal
Dispersion
• In colloidal dispersion, dispersed particles usually have a particle size ranging
from 1 nm to 1 µm.
• The dispersed particles in the colloidal system have an enormous surface area
which confers many unique properties to colloidal dispersions
• Colloidal dispersions can be broadly classified into the following types:

1. Lyophilic colloids

2. Lyphobic colloids

3. Amphiphilic colloids
Colloidal
Dispersion
 Lyophilic colloids: lyophilic colloids known as solvent loving colloids.

• The degree of interaction between dispersed phase and dispersion medium is very high

• When the dispersion medium is water they are known as hydrophilic colloids, e.g. acacia,
gelatin form colloidal dispersion in water
• When the dispersion medium is non aqueous then the colloidal dispersion is known as
lipophilic colloids, e.g. lipophilic dispersion of rubber in benzene
• Lyophilic colloids are thermodynamically stable,

• The dispersion is stable even in presence of electrolytes

• The viscosity of the dispersion medium will greatly increase on addition of dispersed phase
Colloidal
Dispersion
 Lyophobic colloids: lyophobic colloids are also known as solvent hating colloids

• Very little attraction exist between dispersion medium and dispersed phase

• In this type of colloids when water is used as dispersion medium, they are known
as hydrophobic colloids
• Lyophobic colloids are difficult to prepare and thermodynamically unstable

• The dispersed phase can be easily salted out even in presence of small
concentration of electrolyte
• The viscosity does not increase greatly upon addition of dispersed particles,
which tend to remain unsolvated
Colloidal
Dispersion
 Amphiphilic colloids: small molecules or ions having both polar and non-polar
groups exist separately in dilute solution but associate at critical micelle
concentration to form micelle of colloidal dimensions
• Amphiphilic colloids are also known as association colloids

• Amphiphilic colloids are thermodynamically stable

• Salting out may occur at higher salt concentration

• Viscosity of the dispersion medium increase gradually with increase in the

addition of amphiphiles
• They are easy to prepare
Colloidal
Dispersion

Shape of colloidal particles:

o The more extended the particle, the
greater its specific surface & the
greater the opportunity for attraction.
o Properties of colloids as Flow,
sedimentation rate & Osmotic pressure
are all affected by the shape of the
particles.
Colloidal
Dispersion
Sol: A sol is a dispersion of solid particles in a liquid medium. If the liquid is
water it is called hydrosol. If the liquid is alcohol it is called alcosol. If the
medium is air it is called aerosol. Thus the dispersion medium is shown as a
prefix to sol.
Emulsion: If one liquid is dispersed in another liquid the resultant system is
called an emulsion. Milk is an example.

Gel: If the sol is concentrated and the discrete particles are present in a state of
bridged or cross-linked structure with some mechanical stability and elasticity the
system is called a gel. e.g. ordinary jam or jelly.
The main distinction between sol and gel lies in the pseudo-regular structure of
particles in a gel whereas in a sol the particles are wide apart in a completely
irregular fashion.
Colloidal
Dispersion
Moreover in a gel the liquid entrapped within the bridged or cross-linked
structure is immobilized i.e. this liquid is not available for free flow, but moves
along with the whole gel as if, it is an integral part of the whole structure.

Foam: If a gas is dispersed in a liquid, the resultant colloid is called foam. e.g.
ordinary soap solution. Thus sol, gel, emulsion and foam are the important
colloids which find use in our daily life.
Colloidal electrolyte: Small quantity of soap in solution behaves like a solution
of electrolyte since the soap is a salt. But in large concentration, undissociated
molecules and anions of soap form aggregates & assume colloidal dimension,
which behave both like a colloid and an electrolyte. They are therefore called
colloidal electrolytes.
Colloidal
Dispersion
 Preparation of colloids:

1. Lyophilic colloids:
• These colloids are relatively easy to form since lyophilic colloids have affinity for the
dispersion medium
• As there is considerable interaction between the disperse phase and dispersion medium,
they form spontaneously by placing the colloidal materials into a proper solvent
• For example acacia and gelatin disperse easily to form colloidal dispersions when kept
in contact with water
Colloidal
Dispersion
2. Lyophobic colloids:
• Since there is a lack of affinity between dispersed phase and dispersion medium lyophobic colloids are difficult to
prepare. Generally two methods are used:

A. Dispersion method:
• In this method the coarser particles are broken down into smaller particles of colloidal dimension through suitable
methods including –

1) Colloid mill:

Coarse materials are sheared between a static cone and a rapidly rotating cone

2) Electrical dispersion:

Certain metals may be dispersed by passage of an electric arc between electrode

3) Ultrasonic radiation:
• The passage of ultrasonic waves through the dispersion medium produces high frequency oscillations results in size
reduction of coarse particles to colloidal size
Colloidal
Dispersion
4) Peptization:
• This is a process of converting precipitates of large particle size to colloidal size by means of low
concentration of an electrolyte known as peptizing agent

B. Condensation method:
• Particle of colloidal dimension are prepared by aggregation of particles of molecular range.
• This is usually achieved by means of a chemical reaction
• Colloidal sulphur is obtained by passing hydrogen sulphide through an aqueous solution of sulphur
dioxide.

2H2S + SO2 3S + 2H2O

 Colloidal
Dispersion
Purification of colloids:
Many lyophobic sols contain more or less material in true solution which
may be undesirable for any number of reasons; e.g., electrolyte impurities :
cause the flocculation of the sol.
The purification process includes:
a) Dialysis.
b) Electro dialysis.
c) Ultra filtration.
Colloidal
Dispersion
A) Dialysis:
o Depend on difference in size between colloidal
particles & molecular particles (impurities).

o Technique:
1) use semi permeable membrane (e.g. collodion
(nitrocellulose).
2) pore size of used semi permeable membrane prevent
passage of colloidal particles & permit passage of small
molecules & ions (impurities) such as urea, glucose, and
sodium chloride, to pass through.
o A type of dialysis equipment; “Needle dialyzer”
o At equilibrium, the colloidal material is retained in
compartment A, while the sub-colloidal material is
distributed equally on both sides of the membrane.
By continually removing the liquid in compartment B, it is
possible to obtain colloidal material in A that is free from
sub-colloidal contaminants
Colloidal
Dispersion
B. Electro dialysis:
Technique:
o An electric potential may be used to
increase the rate of movement of ionic
impurities through a dialyzing
membrane and so provide rapid
purification.
o Electro dialysis is carried out in a three
compartment vessel with electrodes in
the outer compartments containing
water and the sol in the centre
compartment.
O A typical apparatus is shown in the
figure. Application of electrical
potential causes cations to migrate to
the negative electrode compartment
and anions to move to the positive
Colloidal
Dispersion
c) Ultra filtration:
Technique:
Apply pressure (or suction) Solvent & small
particles forced across a membrane while colloidal
particles are retained.
• The membrane must be supported on a
sintered glass plate to prevent rupture
due to high pressure.
• Pore size of the membrane can be increased by
soaking in a solvent that cause swelling
• e.g. cellophane swell in zinc chloride
solution.
e.g. collodion (nitrocellulose) swell in
alcohol.
Colloidal
Dispersion
Properties of colloids:
A. Particle size D. Electrical properties
B. Optical properties 1. Electrical double layer
1. Tyndall effect 2. Electrophoresis
2. Ultra microscopy 3. Electro osmosis
3. Electron microscopy 4. Streaming potential
4. Light scattering 5. Sedimentation potential

C. Kinetic properties 6. Donnan membrane effect

1. Brownian motion
2. Diffusion
3. Osmotic pressure
4. Sedimentation
5. viscosity
Colloidal
Dispersion
Properties of colloids:
A.Particle size
B.Kinetic properties
C.Optical properties
D.Electrical properties

A. Particle size:
The particle size of colloids generally varies from 1 nm to 1 µm. The actual
particle size of colloidal dispersion can be determined by the use of ultra
microscope or by using graded filters during ultra filtration or by determining the
rate of sedimentation in a centrifuge
Properties of colloids
B) Kinetic properties:
Which relate to the motion of the particles within the dispersion
medium as following:
• Brownian motion
• Diffusion
• Sedimentation
• Osmotic pressure
• The Donnan membrane effect
• Viscosity
Kinetic properties
1) Brownian motion:
Definition: colloidal particles are subjected to
random collision with molecules of the
dispersion medium (solvent) so each particle
move in irregular and complicated zigzag
pathway.
o First observed by Robert Brown (1827) with
pollen grains suspended in water.
o The velocity of particles increases with
decreasing particle size and viscosity.
o Increasing the viscosity of dispersion medium
(by glycerin) decrease then stop
Brownian motion.
Kinetic properties
2) Diffusion:
Definition:
o As a result of Brownian motion particles pass
(diffuse) from a region of higher concentration to one
with lower conc.
o Rate of diffusion is expressed by; Fick’s first law:
dm/dt = -DA dc/dx
Where dm is the mass of substance diffusing in time
dt across an area A under the influence of a
concentration gradient dC/dx.
The minus sign denotes that diffusion takes place in
the direction of decreasing concentration.
D is the diffusion coefficient
Kinetic properties
3) Sedimentation:
• At small particle size (less than 0.5 um) Brownian motion is significant &
tend to prevent sedimentation due to gravity & promote mixing in stead.
• So, we use an ultracentrifuge which provide stronger force so promote
sedimentation in a measurable manner
Stoke’s law;
V = 2r2( p-po) g / 9 η
• v: velocity of sedimentation of spherical particles.
• p: density of the spherical particles.
•po: density of the medium.
•η: viscosity of the medium.
• g: acceleration due to gravity.
Kinetic properties
4) Osmotic pressure:

The method is based on Van Hoff's law;

P (osmotic pressure) = RTC / M
o From the equation;
a) The osmotic pressure (P) depends on molar concentration of the solute (C)
& on absolute temperature (T)
b) The osmotic pressure is inversely proportional to molecular weight (M)
R= molar gas constant
o The equation is valid for very dilute solutions in which the molecules do not
interact mutually
Kinetic properties
5) Viscosity
Definition:
The resistance to flow of a system under an applied pressure
o Viscosity of colloid allows - calculation of the molecular weight, Provide
useful information about the shape of the colloidal particles.
o Spherocolloidal dispersions are of relatively low viscosity.
o On the other hand linear colloidal dispersions are of high viscosity.
o If linear colloidal particles coil up into spheres The viscosity of the system
falls due to changing the shape.
Properties of colloids

C) Optical properties

1. Tyndall effect
2. Ultramicroscope
3. Electronmicroscope
4. Light scattering
 Optical Properties
1) Tyndall effect
True solutions do not scatter light and appear clear but colloidal dispersions
contain opaque particles that do scatter light and thus appear turbid.
o Tyndall effect: when a beam of light pass through a colloidal sol, scattered
light cause the sol to appear turbid. This is known as Faraday-Tyndall effect

2) Light scattering
When a beam of light is passed through a colloidal dispersion, some of it is
absorbed, some is transmitted undisturbed through the sample and remainder is
scattered.
Importance of light scattering measurements:
1) Estimate particle size.
2) Estimate particle shape.
3) Estimate particles interactions.
4) Estimation of molecular weight
 Optical Properties
) Ultramicroscopy
The colloidal particles are too small to be seen with an optical microscope. When a
cell containing a colloidal dispersion is viewed through an ultramicroscope against a
dark background at right angles to an intense beam of incident light, the particles
appear as bright spots against the dark background. The ultramicroscopy is also used
in the technique of microelectrophoresis for measuring the particle charge.

) Electronmicroscopy
Ultramicroscopes are sometimes not able to resolve some lyophilic colloids and
hence electron microscopes are used for studying the colloidal dispersion.
Gives actual picture of the particles (up to 5A). Used to observe the size, shape
and structure of sols. High energy electron beams are used.
o One disadvantage is; only dried samples can be examined
Electrical Properties

1. Electrical double layer

2. Electrophoresis
3. Electro-osmosis
4. Streaming potential
5. Sedimentation potential
6. Donnan membrane effect
Electrical Properties
1. Electrical double layer
• The electrical double layer is a structure which
describes the variation of electric potential near a
surface and has a significant influence on the
behaviour of colloids and other surfaces in
contact with solution or solid state ion.
• Development of a net charge at the particle
surface affects the distribution of ions in the
surrounding interfacial region, as a result:
concentration of counter ions increase at the
surface, thus, an electrical double layer exists Negatively charged

around each particle.

Electrical double layer
 Electrical double layer
Consider the colloidal dispersion of silver iodide prepared by chemical reaction

AgNO3 + NaI AgI + NaNO3

If the reaction is conducted with an excess of sodium iodide, the surface layer of silver
iodide contains more I- ions than Ag+ ions while the aqueous solution contains relatively
high concentration of Na+ and NO3-. Since the silver iodide particles contain more of I - ions
on their surface, each of the silver iodide particles is negatively charged and it attracts
positive ions from the solution and repels negative ions. As a result, the aqueous solution
near the surface of the AgI particles contains much higher concentration of Na + ions (called
counter ions) and much lower concentration of NO3- ions than in the bulk of the solutions

The counter ions Na+ are pulled closer to the surface of

particles as closely as possible as the solvated layer on the
particle permit. The Na+ concentration is highest in the
immediate surface area of particles negative surface
forming a compact layer called stern layer and decreases
with distance from the surface throughout a diffuse layer
called Gouy-Chapman layer. The combination of the two
layers of charged ions constitutes an electric double layer
and thickness usually ranges from 10 to 100 Å
Electrical double layer
The first layer, the surface charge (either positive or negative), comprises ions
adsorbed onto the object due to chemical interactions. The second layer is
composed of ions attracted to the surface charge via the coulomb force. This
second layer is loosely associated with the object. It is made of free ions that
move in the fluid under the influence of electric attraction and thermal motion
rather than being firmly anchored. It is thus called the "diffuse layer.
Electrical double layer
There is a conventionally introduced slipping plane that separates mobile fluid that from
fluid that remains attached to the surface. Electric potential at this surface is known as zeta
potential, which is also denoted as ζ- potential. The electric potential at stern plane is
known as stern potential. Zeta potential is used for estimating the degree of double layer
charge. In other words, zeta potential is the potential difference between the
dispersion medium and the stationary layer of fluid attached to the dispersed particle.

A value of 25 mV (positive or negative) can be

taken as the arbitrary value that separates low-
charged surfaces from highly-charged surfaces.
The presence of electrical double layer around each
particles of a colloidal dispersion gives rise to
electrokinetic effects. They are electrophoresis,
electro-osmosis, streaming potential and
sedimentation potential.
Electrical Properties

2) Electrophoresis
When an electric field is applied to a colloidal dispersion, the negatively
charged particles (e.g. kaolin) move towards anode while positively charged
particles (e.g. ferric hydroxide) move towards cathode. When the particles
move, the counter ions within the solvation layer are dragged along with the
surface of the hydration layer and the counter ions in the free or mobile solvent
moves towards the other electrode. This phenomenon is termed as
electrophoresis.
Electrical Properties
3) 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.
Hence, as the particles move towards one pole,, the liquid tend to move towards
the opposite pole. This flow of liquid medium under the influence of electric
field is known as electro-osmosis and the pressure produced by the process is
known as electro-osmosis pressure.
Electrical Properties
4) Streaming potential
This is converse of electro-osmosis, where electrodes 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. This streaming
potential is due to the displacement of the charges equilibrated in the double layer around
the solid. This technique is used to measure the zeta potential.

5) Sedimentation potential

This is the potential difference set up between top and bottom of a suspension of solid
particles in a liquid when the particles settle under the influence of gravity.
Electrical Properties
6) The Donnan membrane effect
Definition:
The presence of charged macromolecules (colloids) on one side of a semipermeable
membrane affects the diffusion of small ions such as drug ions through the semipermeable
membrane. This effect is due to the electrical gradient across the membrane and as a
consequence , the charged drug ions of the same charge as the macromolecules are driven
to opposite side of the membrane altering the concentration of the drug ions. This is termed
as Donnan membrane equilibrium or simply Donnan efffect.
Application:
• Facilitating the absorption of ionizable drugs from GIT by co-administration of
macromolecules of same charge so mutual ionic repulsion occurs.
Interaction of colloids
The following effects are observed during mixing different colloids:

1.Mutual precipitation – when two oppositely charged hydrophobic colloids are mixed
precipitation occur
2.Coacervate formation- when oppositely charged hydrophilic colloids are mixed, a colloid
rich layer separates which is called as coacervate. This phenomenon in which
macromolecular dispersions on mixing separate into two liquid layers is called coacervation.
•For an example, gelatin at a pH below 4.7 (iso-electric point) is positively charged while
acacia is negatively charged. When the two are mixed together two separate layers are
formed. The upper one is low viscous colloidal dispersion and the lower high viscous
colloidal dispersion. Coacervation can also be brought about by the addition of alcohol,
sodium sulphate or macromolecular substance like starch.
Interaction of colloids

3. Sensitisation – in the presence of very small amounts of hydrophilic colloids, the

hydrophobic colloids may become even more susceptible to precipitation by
electrolyte. Sensitization is attributed to a reduction in zeta potential below the
critical value (the value at which coagulation occurs). It may be also due to the
reduction in the thickness of the ionic layer surrounding the colloidal particles.
4. Protection - larger concentration of hydrophilic colloids increase the stability of
hydrophobic colloids towards precipitation by electrolytes. The hydrophilic colloids
adsorb on the surface of hydrophobic colloids and form a protective layer thus
preventing them from precipitation on addition of electrolytes. This phenomenon is
called protection.
Stability of colloids
The stability of colloidal dispersion depends on two factors –
1.The presence of charge on the dispersed colloidal particles and
2.The presence of solvent sheath surrounding each dispersed particles

When the colloidal particles collide as a result of Brownian movement, the above two
factors will prevent mutual adherence. The stability of lyophobic colloid is largely due
to the electric charges on the surface of the dispersed particles and for lyophilic colloids
it is the solvent sheath that is significant in stabilizing the system.

Stability of colloids are best described by some general rules and theory including-
• Schulze-Hardy rule
• Gold number
• DLVO theory
• Lyotropic series
Stability of colloids
In certain circumstances, the particles in a colloidal dispersion may adhere to one another and
form aggregates of successively increasing size that may settle out under the influence of
gravity. An initially formed aggregate is called a floc and the process of its formation
flocculation. The floc may or may not separate out. If the aggregate changes to a much denser
form, it is said to undergo coalescence. An aggregate usually separates out either by
sedimentation (if it is more dense than the medium) or by creaming (if it less dense than the
medium). The term’s flocculation and coalescence have often been used interchangeably.
Usually coalescence is irreversible whereas flocculation can be reversed by the process of
deflocculating. The following figure schematically represents some of these processes.
Stability of colloids
Schulz-Hardy rules

 Coagulation of colloidal dispersions can be brought about by the addition of

electrolytes which reduce the zeta potential. The effectiveness of an electrolyte to
cause precipitation depends not only on the concentration but also on the valance of the
active ion (ion causing coagulation). The higher the valency of the ion, the greater is
the precipitation power. This is known as Schulz-Hardy rules. For an example Al +3 is
more effective than Mg+2 and Na+.

 Generally hydrophobic colloids need very small amount of electrolyte for

coagulation, whereas hydrophilic colloids need a large amount because the hydration
layer surrounding the dispersed particles has to be removed.
Stability of colloids
Gold number
 Gold number is a measure of the protective ability of hydrophilic colloid. It is defined
as the number of miligrams of hydrophilic colloids which when added to 10 ml of red
gold sol prevents the change of colour from red to violet on addition of 1 ml of 10%
solution of sodium chloride. The change in colour is due to the change in particle size.
 The lower the gold number, higher is the protective ability of the colloid. The gold
numbers of protective colloids gelatin, albumin, acacia and tragacanth are 0.01, 0.1, 0.2,
2.0 respectively. Thus gelatin is most effective protective colloid of the above four.

DLVO theory
The DLVO theory developed independently by Derijaguin and Landan; Verwey and
Overbeek describes the stability of lyophobic colloids. According to this theory two type of
forces act on the colloidal particles in a dispersion – the electrostatic repulsive forces due to
the electric double layer and the attractive London Van der Waals forces. These forces result
in potential energies of repulsion, VR and potential energies of attraction , VA between
particles and these parameters are additive.
Stability of colloids
Hence the total potential energy of interaction, VT is given by:

VT = VA + VR

At low electrolyte concentration the repulsive forces predominate so that the particles
experience only a repulsive forces upon approach. The particles remain individually and
the system is called dispersed or peptized. At a high concentration of electrolyte, the
electrical double layer forces are greatly diminished. As a result Van der Waals forces of
attraction predominate and the particle encounter net attractive forces ending in
coagulation.

Hofmeister or Lyotropic series (OMIT)

Lyophilic and amphiphilic colloids are thermodynamically stable and they exist in true
solution. Coagulation occur until sufficient amount of electrolyte is added which is
known as ‘salting out’ effect. The coagulation power in lyophilic colloids may be given
by Hofmeister or lyotropic series. Anions of Hofmeister series in decreasing order of
precipitating power are citrate, tartrate, sulphate, acetate, chloride, nitrate, bromide and
iodide. The precipitating power is due to their ability to dislodge solvent sheath from
the colloid particles.
Application of colloids
Colloids have found a number of pharmaceutical applications including:
1.Colloids have large surface area due to their small particle size therefore
provide greater efficiency for absorption or adsorption. e.g., colloidal
aluminium hydroxide shows better rate of neutralization of stomach acid.
2.Particle size reduction also alters some of the therapeutic properties of drug.
e.g., colloidal iodine is less toxic than their ionic salts and colloidal silver is a
more effective germicidal
3.Hydrophilic colloids are used as suspending agents and as protectives for
hydrophobic colloids
4.Dextran injection is a colloidal dispersion and is used as plasma substitute
5.Colloidal preparations have also been used as diagnostic agents.
Thank You 