NAME OF THE COURSE : B.

PHARM
COURSE CODE : BP407T
SEMESTER : FOURTH SEMESTER
YEAR : SECOND YEAR
NAME OF THE SUBJECT : PHYSICAL PHARMACEUTICS - II
STAFF INCHARGE : Mr.V. MANIKANDAN
UNIT NO :I
TOPIC : COLLIDAL DISPERSION

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 TABLE OF CONTENTS
Topic Page
Topic Name
No. No.
CHAPTER 1
COLLOIDAL DISPERSION

1.1 Introduction 1
1.2 Classification of dispersed systems 2
1.2.1 Molecular dispersions 2
1.2.2 Colloidal dispersions: 3
1.2.3 Coarse dispersions 3
1.3 Comparison of characteristics three dispersed systems 3
1.4 Shape of colloidal particles 4
1.5 Types of colloidal systems 5
1.5.1 Lyophilic colloids 6
1.5.2 Lyophobic colloids 6
1.5.3 Associations Colloids 7
1.5.4 7
Difference between Lyophilic colloids and lyophobic colloids

1.6 Preparation of colloids 8

1.6.1 Preparation of lyophilic colloids 8

1.6.2 Preparation of lyophobic colloids 8

1.7 Purification of colloids 9
1.8 Optical properties of colloids 12

1.8.1 Tyndall effect 12

Kinetic Properties of Colloids
1.9 13

1.10 Electrical properties of Colloids 18

1.11 Physical Stability of Colloidal Systems 21

1.12 Stability of lyophobic colloids 21

1.13 Stability of lyophilic Colloids 22

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 1.14 Coacervation 23
1.15 Protective Colloid Action 24
QUESTION BANK
Part – A (10 Marks)
Chapter 1 Part – B (5 Marks)
Part – C (2 Marks)

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 Chapter – I Colloidal Dispersion

CHAPTER 1

COLLOIDAL DISPERSION

• LEARNING OBJECTIVES •

After completing this chapter, students will be able to understand:

1. The concept of colloidal dispersions as a system where particles are dispersed in a

medium within the size range of 1 nm to 1000 nm.
2. The classification of dispersed systems into molecular, colloidal, and coarse dispersions
based on particle size.
3. The types of colloids (lyophilic, lyophobic, and association) and their preparation,
purification, and stabilization techniques.
4. The optical, kinetic, and electrical properties of colloids such as Tyndall effect,
Brownian motion, diffusion, and zeta potential.
5. The pharmaceutical importance of colloidal systems in enhancing drug delivery,
stability, bioavailability, and formulation performance.

1.1 INTRODUCTION
1. Colloid from the Greek word Kolla = glue
2. Introduced by Thomas Graham
3. A colloidal dispersion is a type of heterogeneous system in which one substance (called
the dispersed phase) is uniformly distributed in another substance (called the dispersion
medium), with particle sizes ranging from 1 nanometer to 1000 nanometers. These
particles are larger than molecules but too small to be seen with the naked eye, and they
do not settle under gravity.
4. Colloids occupy a unique position between true solutions (where solute is molecularly
dispersed) and suspensions (where particles are large and tend to settle). Due to their size

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 Chapter – I Colloidal Dispersion

and surface properties, colloidal particles exhibit unique behaviors such as light scattering
(Tyndall effect), Brownian motion, and electrical charge.
5. In pharmaceutical sciences, colloidal dispersions are important because of their role in
drug formulation, delivery systems (like emulsions, gels, liposomes), and stability
enhancement of formulations.

Figure 1 : Colloidal Dispersions

1.2. CLASSIFICATION OF DISPERSED SYSTEMS

1. By the nature of the dispersed phase and the dispersion medium IS three types of
dispersed systems are generally considered:
1. Molecular dispersions

2. Colloidal dispersions

3. Coarse dispersions

1.2.1 Molecular dispersions: Are the true solutions of a solute phase in a solvent. The solute
is in the form of separate molecules homogeneously distributed throughout the solvent.
Example: aqueous solution of salts, glucose.

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 Chapter – I Colloidal Dispersion

1.2.2 Colloidal dispersions: are micro-heterogeneous dispersed systems. The dispersed

phases cannot be separated under gravity or centrifugal or other forces. The particles do
not mix or settle down.

Example : aqueous dispersion of natural polymer, colloidal silver sols jelly.

1.2.3 Coarse dispersions: are heterogeneous dispersed systems in which the dispersed phase
particles are larger than 0.5µm. The concentration of dispersed phase may exceed 20%.
Example: pharmaceutical emulsions and suspensions.

Figure 2 : Dispersed Systems

2. By the nature of the dispersed phase and the dispersion medium:

1) Solid in liquid (suspensions): These are mixtures of solid particles suspended in a liquid.
The solid particles are large enough to settle out of the mixture if left undisturbed. Examples
include sand in water, mud, and paint.

2) Liquid in liquid (emulsions): These are mixtures of two immiscible liquids where one
liquid is dispersed in droplets throughout the other liquid. Examples include mayonnaise,
salad dressing, and homogenized milk.

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 Chapter – I Colloidal Dispersion

3) Gas in liquid (foams): These are mixtures of gas bubbles dispersed in a liquid. Examples
include shaving cream, whipped cream, and beer. 4) Solid in gas (aerosols): These are
mixtures of solid particles or liquid droplets dispersed in a gas. Examples include fog, smoke,
and hairspray. 5) Gas in solid (solid foams): These are mixtures where a gas is trapped within
a solid matrix. Examples include pumice and styrofoam. 6) Liquid in solid (gels): These are
dispersions where a liquid is dispersed in a solid matrix. Examples include jelly and some
contact lenses.

1.3. COMPARISON OF CHARACTERISTICS THREE DISPERSED SYSTEMS

Molecular dispersions Colloidal dispersions Coarse dispersions

Particle size <1nm 1nm to0.5µm >0.5µm
Appearance Clear, transparent Opalescent Frequently opaque
Invisible in electron Visible in electron Visible under optical Microscope or
Visibility
microscope microscope naked eye

Pass through semi - Pas through filter paper Do not pass through normal filter
Separation permeable membrane, filter but do not pass through paper and semipermeable
paper semipermeable membrane membrane
Diffusion Undergo rapiddiffusion Diffuse veryslowly Do not diff use
Fast sedimentation of
Sedimentation No question of setling Do not settle down Dispersed phase by gravity or other
forces

Table 1 : Comparison of Characteristics Three Dispersed Systems

1.4. SHAPE OF COLLOIDAL PARTICLES

The shape adopted by colloidal particles in dispersion is important because the more extended
the particle, the greater is its specific surface and the greater is the opportunity for attractive
forces to develop between the particles of the dispersed phase and the dispersion medium. In
a friendly environment, a colloidal particle unrolls and exposes maximum surface area.
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 Chapter – I Colloidal Dispersion

Under adverse conditions, it rolls up and reduces its exposed area.

The shapes that can be assumed by colloidal particles are: (a) spheres and globules, (b) short
rods and prolate ellipsoids (rugby ball-shaped/elongated), (c) oblate ellipsoids (discus-
shaped/flattened) and flakes, (d) long rods and threads, (e) loosely coiled threads, and (f)
branched threads
The following properties are affected by changes in the shape of colloidal particles:
a) Flowability
b) Sedimentation
c) Osmotic pressure
d) Pharmacological action.

Figure 3 : Shapes of Colloidal Particles

1.5. TYPES OF COLLOIDAL SYSTEMS

Based on the interaction between dispersed phase and dispersion medium, colloidal
systems are classified as
1.5.1. Lyophilic colloids (solvent-loving) Particles have greater affinity to dispersion medium
(solvent).

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 Chapter – I Colloidal Dispersion

 Solvent forms a sheath on particle- thermodynamically stable

dispersion.
 Lyophilic colloid preparation and purification is easy.
 Lyophilic colloid prepared with/without charge.
Acacia colloid (+) Iso-electric point Neutral charge

Dispersed particles

a)Hydrophilic- acacia, gelatin (water)

b)Lipophilic- rubber, polystyrene (organic solvents)

Dispersion medium

a)Hydrophilic – water

b)Lyophilic- organic solvents (benzene, ethyl methyl ketone)

1.5.2. Lyophobic colloids (solvent-hating) (If the dispersion medium is an organic solvent,
it is called hydrophobic colloids) Particles have less affinity to dispersion medium
(solvent). Solvent do not form a sheath on particle- thermodynamically unstable
dispersion. Dispersed particles-same charges- repulsions- uniform distribution.

1.5.3. Associations Colloids:

 Certain molecules termed Amphiphilic or surface active agents characterized by two
regions of opposing solution affinities within the same molecule.

 These substances act as a strong electrolyte when they are in low concentrations, but
they react as colloidal sols when they are in high concentration.

 In higher concentration, particles aggregate showing colloidal behaviour.

 These aggregated particles are known as the micelles. They are also known as the
associated colloids.


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 Chapter – I Colloidal Dispersion

1.5.4. Difference between Lyophilic colloids and lyophobic colloids

Lyophilic colloids Lyophobic colloids

Colloidal particles have greater affinity for the Colloidal particles have little affinity
dispersion medium for the dispersion medium
Owing to their affinity for the dispersion medium, Material does not disperse spontaneously,
the molecules disperse spontaneously to form and hence lyophobic sols are prepared
colloidal solution by dispersion or condensation methods
These colloids form ―reversible sols These colloids form ―irreversible sols
Viscosity of the dispersion medium is increased Viscosity of the dispersion medium is
greatly by the presence of the lyophobic colloidal not greatly increased by the presence of
particles lyophilic colloidal particles
Dispersions are stable generally in the presence of Lyophobic dispersions are unstable in the
electrolytes; they may be salted out by high presence of even small concentrations of
concentrations of very soluble electrolytes electrolytes
Dispersed phase consists generally of large Dispersed phase ordinarily consists of
organic molecules such as gelatin, acacia lying inorganic particles, such as gold or
within colloidal size range silver
Table 2 : Lyophilic colloids and lyophobic colloids

1.6. PREPARATION OF COLLOIDS

1.6.1. PREPARATION OF LYOPHILIC COLLOIDS

This Simple dispersion of lyophilic material in a solvent leads to the formation of

lyophilic colloids.
1.6.2 PREPARATION OF LYOPHOBIC COLLOIDS

The lyophobic colloids may prepared by

a) Dispersion method

b) Condensation method

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 Chapter – I Colloidal Dispersion

a. Dispersion methods: This method involves the breakdown of larger particles into
particles of colloidal dimensions. The breakdown of coarse material may be effected
by the use of the Colloid mills, Ultrasonic treatment in presence of stabilizing agent
such as a surface active agent.
b. Condensation method: In this method, the colloidal particles are formed by the
aggregation of smaller particles such as molecules. These involve a high degree of
initial super saturation followed by the formation and growth of nuclei.
c. Change in solvent: For example, if sulfur is dissolved in alcohol and the concentrated
solution is then poured into an excess of water, many small nuclei form in the
supersaturated solution. These grow rapidly to form a colloidal sol. If a saturated
solution of sulphur in acetone is poured slowly into hot water the acetone vaporizes,
leaving a colloidal dispersion of sulphur.
d. Chemical reaction: For example, colloidal silver iodide may be obtained by reacting
together dilute solutions of silver nitrate and potassium iodide. If a solution of ferric
chloride is boiled with an excess of water produces red sol of hydrated ferric oxide by
hydrolysis.

1.7. PURIFICATION OF COLLOIDS

When a colloidal solution is prepared, it often contains certain electrolytes which tend
to destabilize it. The following methods are used for purification of colloids:
a) Dialysis:
At equilibrium, the colloidal material is retained in compartment A, whereas 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 compartment-A which is free from sub-colloidal contaminants. The
process of dialysis may be hastened by stirring, so as to maintain a high
concentration gradient of diffusible molecules across the membrane and by renewing
the outer liquid from time to time.

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 Chapter – I Colloidal Dispersion

Figure 4 : Start And Equilibrium in Dialysis

[Open circles: colloidal particles, solid dots: electrolyte particles]

b. Ultrafiltration
Colloidal dispersion can pass through an ordinary filter, because the pore size of the
filter is large. If this filter paper is impregnated with collodion (syrupy solution of
nitrocellulose), the pore size reduces. Such modified filter papers are called
ultrafilters. By applying pressure (or suction) the solvent and small particles may be
forced across a membrane but the larger colloidal particles are retained. This process is
referred to as ultrafiltration.

Figure 5 : Ultrafiltration
c. Electro dialysis
In the dialysis unit, the movement of ions across the membrane can be speeded up by
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 Chapter – I Colloidal Dispersion

applying an electric current through electrodes induced in solution. The electric

potential increases the rate of movement of ionic impurities through a dialysing
membrane and so provide a more rapid means of purification. The dialysis
membrane allows small particles (ions) to pass through but the colloidal size particles
(hemoglobin) do not pass through the membrane.

Figure 6 : Electro dialysis

d. Amphiphilic Colloids

Surface active agents have two distinct regions of opposing solution affinities
within the same molecule or ion and are known as amphiphiles. When present in a
liquid medium at low con centrations, the amphiphiles exist separately and are of
subcolloidal size. As the concentration is increased, aggregation occurs over a narrow
concentration range. These aggregates, which may contain 50 or more monomers, are
called micelles. Because the diameter of each micelle is of the order of 50Å, micelles
lie within the colloidal size range. The concentration of monomer at which micelles are
formed is termed as critical micelle concentration (CMC). The number of monomers
that aggregate to form a micelle is known as the aggregation number of the micelle.
In water, the hydrocarbon chains of amphiphiles face inward into the micelle to
formtheir own hydrocarbon environment. Surrounding this hydrocarbon core are the
polar portions of the amphiphiles associated with the water molecules of the continuous
phase.
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 Chapter – I Colloidal Dispersion

The association colloid can be classified as anionic, cationic, nonionic, or

ampholytic (zwitterionic) depending upon the charges on the amphiphiles. The
opposite ions bound to the surface of charged micelles are termed counter ions or
gegenions, which reduces the overall charge on the micelles.
The viscosity of the system increases as the concentration of the aniphiphile
increases because micelles increase in number and become asymmetric. In aqueous
solutions, the CMC is reduced by the addition of electrolytes, salting out may occur at
higher salt concentrations.

Figure 7 : Spherical micelle of an anionic association colloid in aqueous media

1.8. OPTICAL PROPERTIES OF COLLOIDS

1.8.1. Tyndall effect

When a strong beam of light is passed perpendicularly through two solutions

(1) True solution and

(2) Colloidal solution place against a dark background:

 The path of light beam is not visible in case of true solution.

 The path of light beam is visible (scattered) in case of colloidal

solution and further it is forming a shadow (beam or cone) at the
dark background.

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 Chapter – I Colloidal Dispersion

Figure 8 : Tyndal Efffect

This phenomenon of scattering of light by the colloidal particles is called Tyndall

effect. The illuminated beam or cone formed by the sol particles is called Tyndall beam or
Tyndall cone. The Tyndall effect is due to the fact that colloidal particles scatter light in all
directions in space. The scattering of light illuminates the path of beam in the colloidal
dispersion.

1.9. Kinetic Properties of Colloids

Kinetic properties of colloidal systems relate to the motion of particles with respect to
the dispersion medium. The kinetic properties are:
1. Brownian motion
2. Diffusion
3. Osmotic pressure
4. Sedimentation
5. Viscosity

The motion may be thermally induced (Brownian movement. diffusion. osmosis).

Gravitational force induced (sedimentation), or applied externally (viscosity).

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 Chapter – I Colloidal Dispersion

1. Brownian motion
Colloidal particles undergo random collisions with the molecules of the dispersion
medium and follow an irregular and complicated zigzag path. If the particles up to about
0.5 µm diameter are observed under a microscope or the light scattered by colloidal
particles is viewed using an ultra- microscope, an erratic motion is seen. This movement is
referred to as Brownian motion.
2. Diffusion
As a result of Brownian motion colloidal particles spontaneously diffuse from a region
of higher concentration to one of lower concentration. The rate of diffusion is expressed
by Fick's first law:
𝒅𝑴/dt = -DS dc/dx

According to the law, the amount, dM of substance diffusing in time, dt across a

plane of area (S) is directly proportional to the change of concentration, dc, with distance
traveled, dx.

D is diffusion coefficient and has dimension of area per unit time, dc/dx is concentration
gradient. Theminus sign denotes that the diffusion takes place in the direction of decreasing
concentration. The diffusion coefficient of a dispersed material is given by Stokes-
Einstein equation.

D = RT/6𝜋𝜂𝑟𝑁

Where N=Avogadro’s number (6.023×1023 molecules per mole), R=molar gas constant
and r is the radius of spherical particle.

The analysis of above equations allows us to formulate three main rules of diffusion:

 The velocity of molecules increase with reduction of particle size

 The velocity of molecules increase with increasing temperature
 The velocity of molecules decrease with increasing viscosity of the medium.
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 Chapter – I Colloidal Dispersion

3. Osmotic Pressure
Osmosis is the spontaneous net movement of solvent molecules through
semipermeable membrane into a region of higher solute concentration in the direction that
tends to equalize the solute concentration on the two sides. The external pressure required
to be applied so that there is no net movement of solvent across the membrane is called
osmotic pressure.

The osmotic pressure, 𝜋of a dilute colloidal solution is described by the van't Hoff equation:

𝜋 = 𝑐𝑅𝑇

Where c =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.

𝜋 = C/g. RT

𝜋/Cg=RT/M

The above equation is true when the concentration of colloids is low (ideal system).

For linear lyophilic molecules or high molecular weight polymers (real system), the following
equation is valid.

𝜋/Cg=RT(1/M+BCg)

Where B is an interaction constant for any particular solvent/solute system. A plot of 𝜋/Cg
Vs Cg is liner.

The extrapolation of line to the vertical axis where Cg=0 gives RT/M and if the
temperature at which the determination was carried out is known, the molecular
weight of solute can be determined. From the slope of the line the value of interaction
constant (B) can be determined.
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 Chapter – I Colloidal Dispersion

Line II is typical of a linear colloid in a solvent having a high affinity for the
dispersed particles. Type I line is observed for the same collid if it is present in a
relatively poor solvent having areduced affinity for the dispersed material. However, the
extraplotaed intercept on y-axis is identical for lines I and II. This indicatethat the
calculate molecular weight is independent of the solvent used.

Figure 9 : Osmotic Pressure

4. 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 Stoke's law:
2𝑟2 (𝜌 − 𝜌 0)
𝑣𝑔=9η0

where g is the acceleration due to gravity. If the particles are subjected only to the force of
gravity, then the lower size limit of particles obeying Stokes's equation is about 0.5 µm.
This is because Brownian movement becomes significant and tends to offset
sedimentation due to gravity and promotes mixing instead. Consequently, a stronger
force must be applied to bring about the sedimentation of colloidal particles. A high

speed centrifuge (ultracentrifuge), can produce a force of about 106g. In a centrifuge, g is

replaced by ω2x, ω=angular velocity or angular acceleration=2π times the speed of rotor in
revolution per second, x= the distance of particle from the centre of rotation.

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 Chapter – I Colloidal Dispersion

5.Viscosity

Einstein equation of flow for the colloidal dispersions of spherical particles is given by:

η = η0(1 + 2.5ϕ)

η0 is the viscosity of dispersion medium, η is the viscosity of dispersion when

volume fraction of colloid particles is ϕ. The volume fraction is defined as the volume of
the panicles divided by the total volume of the dispersion.

Relative viscosity (ηrel) = η/η0 = (1 + 2.5ϕ)

Specific viscosity (ηsp ) = η/η0 = (1 - 2.5ϕ)

or ηspϕ = 2.5

By determining η at various concentration and knowing η0 the specific viscosity can be

calculated. Because the volume fraction is directly related to concentration, we can write,
ηsp/C =K, Where C=gm of colloid particles per 100ml.

Figure 10 : Viscosity

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 Chapter – I Colloidal Dispersion

For highly polymeric materials, Huggin’s equation is used. Specific viscosity expresses
incremental viscosity due to presence of polymer in solution. Intrinsic viscosity is a
measure of solute’s contribution to the viscosity of a solution or limiting value of specific
viscosity/concentration ratio at zero concentration.

ηsp /C = 𝜂i + k 𝜂i 2 C

If ηsp/C is plotted against C and the line extrapolated to infinite dilution, the intercept is
intrinsic viscosity (𝜂i).

This constant, commonly known as the intrinsic viscosity 𝜂i and is used to calculate
the approximate molecular weights of polymers. According to the so-called Mark–
Houwink equation

𝜂 i = 𝑘𝑀 a

Where k and a are constants, characteristics of a particular polymer-solvent system and

are virtually independent of molecular weight.

log 𝜂i = log 𝑘 + 𝑎 𝑙𝑜𝑔 𝑀

These constants are obtained initially by determining 𝜂i experimentally for polymer

fractions whose molecular weights have been determined by other methods such as
light scattering, osmotic pressure, or sedimentation.

Then the specific viscosity for each fraction is determined and then intrinsic viscosity can
be obtained.

'
If we plot log 𝜂i 𝑣𝑠. log M 𝑡ℎ𝑒𝑛 𝑡ℎ𝑒 𝑠𝑙𝑜𝑝𝑒 𝑤𝑖𝑙𝑙 𝑔𝑖𝑣𝑒 ′𝑎 𝑣𝑎𝑙𝑢𝑒 𝑎𝑛𝑑 𝑡ℎ𝑒 𝑖𝑛𝑡𝑒𝑟𝑐𝑒𝑝𝑡 𝑤𝑖𝑙𝑙
𝑔𝑖𝑣𝑒 ′𝑘′ 𝑣𝑎𝑙𝑢𝑒. Then, the molecular weight (M) of unknown fraction of the polymer can
be obtained from Mark– Houwink equation.

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 Chapter – I Colloidal Dispersion

1.10. Electrical properties of Colloids

The colloidal particles acquire a surface electric charge when brought into contact with
an aqueous medium. The principal charging mechanisms are discussed below.
1. Surface Ionization

Here the charge is controlled by the ionization of surface groupings. For example,
carboxymethyl cellulose frequently has carboxylic acid groupings at the surface which
ionize to give negatively charged particles. 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. At a pH below the pKa of the COO-
group the protein will be positively charged because of the protonation of this group,

-COO- —> COOH, and the ionization of the amino group -NH2 —> - NH3+, which
has a much higher pKa; whereas at higher pH, where the amino group is no longer
ionized, the net charge on the molecule is now negative because of the ionization of
the carboxyl group. At a certain definite pH, specific for each individual protein,
the total number of positive charges will equal the total number of negative charges
and the net charge will be zero. This pHis termed the isoelectric point of the protein
and the protein exists as its zwitterion. This may be represented as follows:

2. Ion Adsorption

Surfaces in water are more often negatively charged than positively charged, because
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 Chapter – I Colloidal Dispersion

cations are generally more hydrated than anions. Consequently, the former have the
greater tendency to reside in the bulk aqueous medium, whereas the smaller, less
hydrated and more polarizing anions have a greater tendency to reside at the
particle surface; Surface-active agents are strongly. Adsorbed and have a
pronounced influence on the surface charge, imparting either a positive or negative
charge depending on their ionic character.

3. Electrical double layer

The theory of the electric double layer deals with this distribution of ions and hence
with the magnitude of the electric potentials that occur in the locality of the charged
surface. Consider a solid charged surface in contact with an aq ueous solution of
electrolyte.

Figure 11 : Electrical Double Layer

Suppose that some of the cations are adsorbed onto the solid surface (aa’) giving it a
positive charge and these are called potential determining ions. Then the counter
anions are attracted tothe positively charged surface by electric forces and forms a
region called tightly bound layer. In this layer there are fewer anions than cations
adsorbed onto the solid surface and hence the potential at bb’ is still positive.
In addition to these electrical forces, the thermal motion tends to produce an equal
distribution of all the ions in solution. As a result, some of the excess anions approach the
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 Chapter – I Colloidal Dispersion

surface, whereas the remainders are distributed in decreasing amounts as one proceeds
from the charged surface. At a particular distance from the surface, the concentration
of anions and cations are equal and forman electrically neutral region. The system as a
whole is electrically neutral even though there are regions of unequal distributions of
anions and cations.

The region bounded by bb’ and cc’ is called diffuse second layer where an excess anions
are present. Beyond cc’, the distribution of ions is uniform and an electrically
neutral region exists.
The potential at the solid surface is called Nernst potential and is defined as the
difference in potential between actual solid surface and the electrically neutral region of
the solution. The potential at plane bb’ is called zeta potential and is defined as the
difference in potential between surface of tightly bound layer and the electrically neutral
region of the solution.
If zeta potential falls below a particular value (+30mV or -30mV), the attractive force
exceed the repulsive force and results in aggregation of colloidal particles. The stability
of colloidal particles is evaluated based on zeta potential value. Zeta potential
decreases more rapidly when the concentration of electrolytes is increased or the valency
of counter ions is higher.

1.11. Physical Stability of Colloidal Systems

The presence and magnitude, or absence, of a charge on a colloidal particle is an
important factor in the stability of colloidal systems. Stabilization is accomplished
essentially by two means: providing the dispersed particles with an electric charge, and
surrounding each particle with a protective solvent sheath that prevents mutual adherence
when the particles collide as a result of Brownian movement. This second effect is
significant only in the case of lyophilic sols.

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 Chapter – I Colloidal Dispersion

1.12. Stability of lyophobic colloids

A lyophobic sol is thermodynamically unstable. The particles in such cols are stabilized
only by the presence of electric charges on their surfaces. The like charges produce a
repulsion that prevents coagulation of the particles. Hence, addition of a small amount
of electrolyte to a lyophobic sol tends to stabilize the system by imparting a charge to
the particles.In colloidal dispersions frequent encounters between the particles occur as
a result of Brownian movement. Such interactions are mainly responsible for the
stability of colloids. There are two types of interactions- van der Waals attraction
and electrostatic repulsions. When attractions predominate, the particles adhere after
collisions and aggregate is formed. When repulsions predominate, the particles
rebound after collisions and remain individually dispersed. At low electrolyte
concentration, repulsive forces predominate so that the particles experience only
repulsive forces upon approach. The particles remain independent and the system is
considered dispersed or peptized. At high electrolyte concentration, the double layer
repulsive forces are greatly reduced, so that van de Waals attractive forces
predominate. These net attractive forces between particles causethe formation of
aggregate of particles, a process known as coagulation.The concentration of electrolyte
necessary, to collapse the repulsive force and permit coagulation depends on the
valence of ions of opposite charge. Schulze-hardy rule states that the precipitation
power of an ion on dispersed phase of opposite charge increases with increase in
valence or charge of the ion.

The higher the valency of ion, the greater is the precipitation power.

Cations: Al+3> Ba+2>Na+ Anions: SO42- > Cl-

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 Chapter – I Colloidal Dispersion

1.13. Stability of lyophilic Colloids

The addition of an electrolyte to a lyophilic colloid in moderate amounts does not

result in coagulation, as was evident with lyophobic colloids. . If sufficient salt is
added, however, agglomeration and sedimentation of the particles may result. This
phenomenon, referred to as "salting out‖. In general lyophilic colloids are stable
because of the solvent sheath around the particles.

Figure 12 : Lyophilic Colloids

At high electrolyte concentration, ions get hydrated and water is no more available for
hydration of particles. This results in flocculation or salting out of colloidal particles.

The coagulating power of an ion is directly related to the ability of that ion to separate
water molecules from colloidal particles. Hofmeister or lyotropic series ranks cations and
anions in order of coagulation of hydrophilic sols.
Anions: citrate>tartrate>sulfate>acetate>chloride>nitrate> bromine>iodine
Cations: Mg+2>Ca+2>Ba+2>Na+>K+

Less polar solvents such as alcohol, acetone has greater affinity to water. When these are
added to hydrophilic colloids, dehydration of particles occurs. Now the stability of
particles depends on charge they carry. The addition of even small amount of
electrolytes leads to flocculation or salting out the colloid easily.

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 Chapter – I Colloidal Dispersion

1.14. Coacervation

When negatively and positively charged hydrophilic colloids are mixed, the
particles may separatefrom the dispersion to form a layer rich in the colloidal aggregates.
The colloid-rich layer is known as a coacervate, and the phenomenon in which
macromolecular solutions separate into two liquid layers is referred to as coacervation.
As an example, consider the mixing of gelatin and acacia. 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. The lower layer becomes rich in the coacervate.

1.15. Protective Colloid Action

When a large amount of hydrophilic colloid carrying opposite charge is added to

hydrophobic colloids, these gets adsorbed on the hydrophobic particles and form a
protective layer around it. This adsorbed layer prevents the precipitating ions reaching
the sol particles. Therefore, coagulation is prevented and the system becomes stabilized.
The entire colloid behaves like a hydrophilic colloid. The colloid that helps to stabilize
the other colloid is known as protective colloid. The protective property is expressed
most frequently in terms of the gold number. The gold number is the minimum weight
in milligrams of the protective colloid (dry weight of dispersed phase) required to
prevent a color change from red to violet in 10 mL of a cold sol on the addition of 1 mL of
a 10% solution of sodium chloride. The gold numbers for some common protective
colloids are: Gelatin (gold number 0.005-0.01), Albumin (gold number 0.1) Acacia
(gold number 0.1-0.2). Basically gold sol is a hydrophobic colloid and has red color.
When an electrolyte like NaCl is added coagulation of colloid is observed indicating
violet color. When protective colloids are added, these stabilize the gold sol and
prevent the change to violet color. Lower thegold number, greater the protective action.

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 Chapter – I Colloidal Dispersion

Figure 13 : .Protective Colloid Action

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 Chapter – I Colloidal Dispersion

QUESTIONS

Long Essays (10 Marks)

1. Discuss the electrical properties and kinetic properties of colloids

2. Discuss the optical and electrical properties of colloids.

3. Discuss the kinetic and optical properties of colloids.

4. What are colloids? Give example. Explain any four methods of preparation of

different types of colloids.

5. Explain different methods of preparation and purification of colloids.

6. Explain different purification methods and protection of colloids.

Short Essays (05 Marks)

1. What are colloids? Classify the colloids. Differentiate between different types of

colloids.

2. What are hydrophobic colloids? Describe any four preparation methods.

3. Discuss association colloids with example.

4. Explain protection of colloids.

5. With the help of a neat labeled diagram explain methods for purification of colloids.

6. Explain optical properties of colloids

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 Chapter – I Colloidal Dispersion

7. Explain kinetic properties of colloids

8. Explain electrical properties of colloids.

9. Explain DME and its applications.

10. Explain the concept DLVO theory with energy curves. How this theory is applied in

stabilizing the colloidal dispersion.

Short Answers (02 Marks)

1. State and explain Hardy schulze rule

2. What is craft point?

3. Define and classify colloids.

4. What are association colloids?

5. What is gold number?

6. What is Tyndall effect

7. What is zeta potential? Give example.

8. What is nernst potential? Give example.

9. What is electro osmosis and electrophoresis?

10. What is streaming potential?

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