UNIT I

COLLOID

Must know General characteristics, size & shapes of colloidal particles, classification of
colloids & comparative account of their general properties. Optical, kinetic &
electrical properties. Effect of electrolytes, coacervation, peptization &
protective action.
Desirable to Classification of dispersed systems
know
Nice to know Preparation and purification of colloids.

Molecular dispersions
Molecular dispersion is a true solution of a solute phase in a solvent. The dispersed phase (solute) is in
form of separate molecules homogeneously distributed throughout the dispersion medium (solvent). The
molecule size is less than 1 nm. The examples of molecular dispersions: air (a molecular mixture
of Oxygen, Nitrogen and some other gases), electrolytes (aqueous solutions of salts), metal alloys solid
solutions.

Coarse dispersions (suspensions)

Coarse dispersions are heterogeneous dispersed systems, size is greater than 0.5 μm. Coarse dispersions
are characterized by relatively fast sedimentation of the dispersed phase caused by gravity or other forces.
Dispersed phase of coarse dispersions may be easily separated from the continuous phase by filtration.

Colloids
Colloids are micro-heterogeneous dispersed systems, in which the size of the dispersed phase particles is
within the range 1nm – 0.5 μm . The colloids phases cannot be separated under gravity, centrifugal or
other forces. Dispersed phase of colloids may be separated from the dispersion medium by micro-
filtration. The examples of colloids: milk (emulsion of fat and some other substances in water), fog
(aerosol of water micro-droplets in air), opal (colloidal silica), Silica aerogel monolith, Alumina aerogel
monolith.

Definition of Colloids: A colloidal system is defined as a two phase heterogeneous system in which one
phase is dispersed in a fine state of sub-division into another phase called dispersion medium as such i.e.
dispersed phase +dispersion medium = Colloidal System. The size of the dispersed phase range from 1
nm to 0.5 μm
Characteristics of True Solutions, Colloidal Solutions and Coarse dispersions
Sl True Solutions Colloidal Solutions Coarse dispersions
No
1. The particle size are in the The particle sizes lie in the The particle sizes are
order of 1 m or 10Å range of 1 nm to 0.5 μm greater than 0.5 μm

2. Particles are invisible under Particles are invisible even Particles are visible to the
the electron microscope under the most powerful naked eye or at least
microscope but its scattering through
effect can be observed in a microscope
ultra microscope.
3. Particles diffuse readily Colloidal particles do not Particles do not diffuse
through parchment diffuse through parchment
membrane membrane
4. Particles readily pass through Particles pass through filter Particles do not diffuse
ordinary filter paper as well paper through filter paper or
as through parchment parchment membrane
membrane
5. No scattering occurs Particles scatter light. This They do not show Tyndall
scattering of light is called effect
Tyndall effect

Classification of colloids
Colloids are classified in following manner
a. Classification based on the dispersed phase and dispersion medium
b. Classification based on affinity of dispersed phase for dispersion medium (lyophilic and
lyophobic colloids)
c. Classification based upon molecular size:

a. Classification based on the dispersed phase and dispersion medium

Dispersion medium Dispersed phase Colloid type Examples

Solid Solid Solid sol Pearls, opals
Solid Liquid Solid emulsion Cheese, butter
Solid Gas Solid foam Pumice, marshmallow
Liquid Solid Sol, gels Jelly paint
Liquid Liquid Emulsion Milk, mayonnaise
Liquid Gas Foam Whipped cream, shaving
cream
Gas Solid Solid aerosols Smoke, dust
Gas Liquid Liquid aerosols Clouds, mist, fog
b. Classification based on affinity of dispersed phase for dispersion medium (lyophilic and
lyophobic colloids): Depending upon the nature of interactions between dispersed phase and dispersion
medium, colloidal solution can be classified as lyophilic (liquid-loving) and lyophobic (liquid-hating).

(a) Lyophilic colloids: These are the colloidal solutions in which the particles of the dispersed phase have
great affinity (love) for the dispersion medium. In case water acts as the dispersed phase, the lyophilic
colloid is called hydrophilic colloid. These are generally stable due to the strong attractive forces
operating between the two phases. These are reversible in nature. On evaporating the sol, the dispersed
phase obtained can be easily reconverted into the solution by simply agitating it with the dispersion
medium. Gums, gelatine and starch form lyophilic (hydrophilic) sols.

(b) Lyophobic sols: These are the colloidal solutions in which particles of the dispersed phase have no
affinity for the dispersion medium. Such solutions are relatively less stable and are not easily prepared.
These can be easily precipitated by heating the sol or on adding small amount of electrolyte to it. These
are irreversible. The solid obtained by precipitation cannot be reconverted into colloidal solution by
simply shaking it with the dispersion medium. Colloidal solutions of gold, silver, Fe(OH)3, As 2S3 etc. are
lyophobic. Lyophobic sols need stabling agents for their preservation.

Distinction between Lyophilic and Lyophobic sols

SL Property Lyophilic Lyophobic sols

No
i. Preparation Can be easily prepared by direct Prepared only by special methods.
Mixing.

ii. Nature Reversible Irreversible

iii. Size of Comparable size as true Particles constitute aggregates of
particles molecules molecules.
iv. Stabilisation Self stabilised. Less stable and require traces of
stabilisers.
v. Visibility Particles are not visible even Particles are visible under
under ultra-microscope ultramicroscope.
vi. Viscosity Viscosity is much higher than Same viscosity as of dispersion
that of dispersion medium. medium
vii. Surface It is less than that of dispersion Same surface tension as of
tension medium. dispersion medium.
viii. Action of Particles may move towards Particles may move towards
electric anode or cathode or may not cathode or anode depending upon
field move at all. the charge.
ix. Action of For coagulation of sol, large For coagulation, small amounts of
electrolyte amounts of electrolytes are electrolytes are required
required
x. Tyndall effect It does not exhibit Tyndall Exhibits Tyndall effect
effect.
xi. Colligative Have high values of colligative These show high osmotic pressure,
properties properties, such as osmotic less elevation in b.pt and low
pressure, elevation in b.pt., depression in f.pt.
depression in f.pt. etc.
xii. Charge Little or no charge on particles Particles carry positive or negative
Charge
xiii. Solvation Particles generally solvated No solvation of particles.

c. Classification based upon molecular size: Depending upon the molecular size, colloids are
of three types:

(a) Multimolecular colloids: These are the sols in which the particles of dispersed phase consist of
aggregate of large number of atoms or small molecules having molecular size less than 1 nm and the
aggregate has dimensions of colloidal size. In these colloids, the particles are held together by van der
Waal’s forces. Some examples of such colloids are (i) Sols of gold atoms (ii) Platinum of (iii) Sulphur
sol. Sulphur sol consists of particles containing a thousand or more S8 molecules.

(b) Macromolecular colloids: In this type of colloids, individual molecules have very large size, which
is of colloidal dimensions. The macromolecules constituting the dispersed phase are generally polymers
having very high molecular weights. Naturally occurring macromolecules are proteins, enzymes, gelatin,
starch, cellulose, etc. Artificial macromolecules are polythene, polystyrene, nylon etc. Since the particle
size in case of macromolecules is comparable to those of colloids, solutions of macromolecular
substances are macromolecular colloidal solutions. Dispersions of macromolecules are quite stable and
resemble true solutions in many respects. Thus, common examples of macromolecular colloids are (i)
Proteins (ii) Starch (iii) Cellulose (iv) Plastics (v) Enzymes.

(c) Associated Colloids or Micelles:

Association 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 solution affinities within the same molecule or ion. When present in a liquid
medium at low concentrations, the amphiphiles exist separately and are subcolloidal in 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 50 A°, micelles lie within the size range we have designated as
colloidal. The concentration of monomer at which micelles form is termed the critical micelle
concentration (CMC). The number of monomers that aggregate to form a micelle is known as the
aggregation number of the micelle.
The phenomenon of micelle formation can be explained as follows. Below the CMC, the
concentration of amphiphile undergoing adsorption at the air–water interface increases as the
total concentration of amphiphile is raised. Eventually a point is reached at which both the
interface and the bulk phase become saturated with monomers. This is the CMC. Any further
amphiphile added in excess of this concentration aggregates to form micelles in the bulk phase,
and in this manner, the free energy of the system is reduced. Above the CMC, the surface tension
remains essentially constant, showing that the interface is saturated and micelle formation has
taken place in the bulk phase.

Comparison of some important characteristics of multimolecular, macromolecular and

associated colloids

Sl Multimolecular colloids Macromolecular colloids Associated colloids

No
They consist of aggregates of The particles of dispersed Behave as normal
 a large number of atoms or phase themselves are of electrolytes at low
molecules with diameter less large size e.g. polymers like concentrations and as
than 1 nm e.g. sols of gold, nylon, starch, protein, colloids at higher
sulphur etc. rubber etc concentrations due to the
aggregation of a large
number of ions in
concentrated solutions
Their molecular masses are They have high molecular Their molecular masses are
not very high. Masses. generally high

The atoms or molecules in The van der Waal’s forces The van der Waal’s forces
them are held by weak van holding the particles are depend upon the
der Waals’s forces. comparatively stronger due concentration.
to Higher the concentration,
the presence of long chain. greater are the van der
Waal’s forces
They are usually lyophilic in They are usually lyophobic Their molecules contain both
nature in lyophilic and lyophobic
nature. groups

Preparation of Colloidal Solutions

(a) Preparation of Lyophilic Sols: Hydrophilic colloids such as starch, gum, gelatin, etc. form colloidal
solution when warmed or left in contact with water for a long time. The particles are already of colloidal
size and they are readily dispersed in water forming colloidal solution. Sols of water insoluble high
molecular weight compounds may similarly be obtained by their dispersal in suitable liquids.

(b) Preparation of Lyophobic Sols: Lyophobic sols cannot be prepared by direct mixing of dispersed
phase and the dispersion medium. These are prepared by using special techniques. The methods
employed for the preparation of lyophobic colloids fall into two categories:
(i) Dispersion methods in which larger macro-sized particles are broken down to colloidal size.
(ii) Condensation methods in which particles of colloidal size are produced by aggregation of
single ions or molecules.

A. Dispersion Methods

1. Bredig’s Electric Arc Method: This method is employed to prepare sols of metals such as copper,
silver, gold or platinum. The two electrodes used in this method are made of the metal whose sol is to be
prepared. The electrodes are immersed in dispersion medium such as water. The dispersion medium is
cooled by immersing the container in an ice bath and a trace of alkali is added. An arc is struck between
the metal electrodes held close together. The tremendous heat generated by the spark across the electrodes
vapourises some of the metal and the vapour condenses immediately in the dispersion medium to give
colloidal solution. The trace of added alkali helps to stabilise the sol.
 Figure: Electrodispersion Process

2. Mechanical Dispersion(colloidal mill ): It is done with the help of a colloid mill. The mill consists of
two steel discs with a small gap between them. The discs rotate in opposite direction at high speed.The
substance whose sol is to be prepared is first ground as finely as possible and then shaken with the
dispersion medium to get a suspension. The suspension is now added to the colloid mill. The speed of the
rotating discs is adjusted so that the particles of the suspension are broken to produce the particles of
colloidal size

Figure: Colloid mill

Figure:Ultrasonic dispersion Process

3. Ultrasonic dispersion Process : The ultrasonic waves produced from a quartz generator
propagate through the oil andstrike the beaker containing mercury under water. The ultrasonic
waves transfer their energy to the atoms of mercury. Mercury gets vapourised and the vapours
disperse in water producing colloidal solution. This is the latest method for the preparation of
metal sols from their coarse suspension.
4. Peptization: The process, which involves the conversion of freshly prepared precipitate into colloidal
solution by the addition of a suitable electrolyte is called peptization. The electrolyte added is called
peptizing agent or dispersion agent. For example, if freshly prepared ferric hydroxide precipitate is treated
with a small quantity of FeCl3 (electrolyte) solution, a dark reddish brown colloidal solution of Fe(OH)3
is formed. Here FeCl3 is a peptizing agent. This process is reverse of coagulation. Similarly, a colloidal
solution of Al(OH)3 is obtained when freshly precipated Al(OH)3 is treated with a small quantity of
dilute HCl (acid added being insufficient to convert hydroxide completely into chloride)

Figure: Peptization

B. Condensation or Aggregation Methods

1. Lowering of solubility by exchange of solvent: In this method, a substance is dissolved in a solvent

and then the solution is added to another solvent in which it is less soluble. For example if an alcoholic
solution (true solution) of sulphur is added in excess of water, a colloidal solution of sulphur results.
Sulphur is insoluble in water.

2. Passing vapours of an element into a liquid: When the vapours of an element are passed through a
liquid, condensation takes place to give a colloidal solution. For example, colloidal solution of mercury
can be obtained by passing the vapours of mercury into cold water containing suitable stabilising agents
such as ammonium salts or citrates. Sulphur sol can also be prepared by using a similar procedure.

3. Excessive cooling: The method can be used to get colloidal solution of ice in an organic solvent like
chloroform or ether. A solution of water in the required solvent is frozen. The molecules of water, which
can no longer be held in the solution, get together to form particles of colloidal size.

4. Preparation of colloidal sol by chemical methods:

(1) Reduction Method: Gold or Silver sols are prepared by reduction of the corresponding salts. In this
method pure sols are prepared. The following reactions take place

Ag2O + H2 ⎯→ 2Ag + H2O

Silver sol.

(2) Oxidation Method: Sulphur sol is prepared by the oxidation of H2S by SO2.
2H2S + SO2 ⎯→ 3S + 2H2O

Sols of halides of silver, lead and mercury are obtained by oxidation of the corresponding metal
sols with chlorine, bromine or iodine until the characteristic colour of the metal sol is destroyed.
To stabilise the sol, some stabilising agent is to be added.

Purification of Colloidal Solutions

Colloidal solutions obtained by chemical methods contain appreciable amounts of electrolytes. To obtain
pure sol, it is necessary to remove those electrolytes which tend to coagulate the colloidal particles. The
methods employed for this purpose are:

1. Dialysis
2. Electro dialysis
3. Ultra filtration

1. Dialysis: We know that the particles of the colloidal solution cannot pass through the parchment paper,
cellophane or animal membrane while those of the true solution can easily pass through them. It is due
to the difference in their particle size. The process of separating a crystalloid from a colloid by diffusion
through a parchment paper or animal membrane is called dialysis. The apparatus which is employed to
effect such separation is called Dialyser.

2. Electrodialysis: Dialysis is a slow process. To hasten the process, dialysis is carried out under the
influence of an electric field. The cations and anions of the electrolyte will be attracted towards the
oppositely charged electrodes . Electrodialysis is not suitable for the removal of non-electrolyte impurities
such as sugar and urea.
3. Ultra filtration: The separation of crystalloids from colloidal system can also be carried out by ultra-
filtration. Ordinarily the filter papers have pores larger than one micron (10 −6 m). Thus, the colloidal
particles can pass through these filter papers along with ions or molecules. The pores of the filter paper
can be made smaller by soaking it in a solution of gelatin or a colloidal and then in turn hardening them
by soaking in formaldehyde. As a result the pores of the filter paper become smaller and the colloidal
particles cannot pass through them. Filter papers thus prepared are known as ultra-filters. The process of
separating colloids from crystalloids by using ultrafilters is called ultra-filtration.

Properties of Sols

1. Heterogeneity: A colloidal solution is heterogeneous in nature and consists of two phase i.e.the
colloidal particles (dispersed phase) and the dispersion medium. Since the colloidal particles are small in
size, a sol appears to be homogeneous to the naked eye. However, their heterogeneous nature can be
confirmed by seeing under electron microscope.
2. Filterability: Ordinary filter papers have large pore size. Therefore, colloidal particles can pass
through them. However, they cannot pass through animal and vegetable membranes and ultra filter
papers. This idea tells the basis of separation of colloidal particles from those of crystalloids.
3. Stable nature: Colloidal solutions are quite stable and the colloidal particles do not settle at the
bottom. This is because of the constant motion of colloidal particles.
4. Colligative properties: As the colloidal particles are the aggregates of simple molecules, the number
of particles per litre of the sol is relatively much smaller than in a true solution. Hence the values of the
colligative properties such as elevation in boiling point, depression in freezing point and lowering of
vapour pressure are much smaller as compared to true solutions. However, the osmotic pressure of
colloidal solutions, though smaller than true solutions is measurable and gives information regarding the
number of particles present in one kg of the dispersion medium. Osmotic pressure values thus can be used
for the calculation of molecular weights of polymers like proteins.

Important property of colloids

 Optical Properties of
 Kinetic property
 Electrical property
Optical Properties of Sols

1. Tyndall effect

When a strong beam of light is passed through a sol and viewed at right angles, the path of light shows up
as a hazy beam or cone. This is due to the fact that sol particles absorb light energy and then emit it in all
directions in space. This ‘scattering of light’, as it is called, illuminates the path of the beam in the
colloidal dispersion. The phenomenon of the scattering of light by the sol particles is called Tyndall
effect. The illuminated beam or cone formed by the scattering of light by the sol particles is often referred
as Tyndall beam or Tyndall cone. The hazy illumination of the light beam from the film projector in a
smoke-filled theatre or the light beams from the headlights of car on a dusty road, are familiar examples
of the Tyndall effect. If the sol particles are large enough, the sol may even appear turbid in ordinary light
as a result of Tyndall scattering. True solutions do not show Tyndall effect. Since ions or solute
molecules are too small to scatter light, the beam of light passing through a true solution is not visible
when viewed from the side. Thus Tyndall effect can be used to distinguish a colloidal solution from a true
solution.

2.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, τ , the fractional decrease in intensity due to
scattering as the incident light passes through 1 cm of solution. It can be expressed as the intensity of light scattered
in all directions, Is, divided by the intensity of the incident light, I.
At a given concentration of dispersed phase, the turbidity is proportional to the molecular weight of the lyophilic
colloid.
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:
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,
B is an interaction constant.
H is constant for a particular system

3. Ultramicroscope shows up the presence of individual particles

Sol particles cannot be seen with a microscope. Zsigmondy (1903) used the Tyndall phenomenon to set up an
apparatus named as the ultramicroscope. An intense beam of light is focussed on a sol contained in a glass vessel.
The focus of light is then observed with a microscope at right angles to the beam. Individual sol particles appear as
bright specks of light against a dark background (dispersion medium). It may be noted that under the
ultramicroscope, the actual particles are not visible. It is the larger halos of scattered light around the particles that
are visible. Thus an ultramicroscope does not give any information regarding the shape and size of the sol
particles.

4. Sol particles can be seen with an Electron microscope

The electron microscope, capable of yielding pictures of the actual particles, even those
approaching molecular dimensions, is now widely used to observe the size, shape, and structure
of colloidal particles.
The success of the electron microscope is due to its high resolving power, which can be defined
in terms of d, the smallest distance by which two objects are separated and yet remain
distinguishable. The smaller the wavelength of the radiation used, the smaller is d and the greater
is the resolving power. The optical microscope uses visible light as its radiation source and is
able to resolve only two particles separated by about 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° ). With current instrumentation, this results in d being approximately 0.5 nm (5
A° ), a much-increased power of resolution over the optical microscope.

Kinetic Properties
a. Brownian movement
When a sol is examined with an ultramicroscope, the suspended particles are seen as shining specks of
light. By following an individual particle it is observed that the particle is undergoing a constant rapid
motion. It moves in a series of short straight-line paths in the medium, changing directions abruptly.

The continuous rapid zig-zag movement executed by a colloidal particle in the dispersion medium is
called Brownian movement or motion.
The Brownian movement is not caused by external influences such as vibration, convection current or
effect of light nor does it originate from gravitational, magnetic, electrical or surface tension forces. This
rapid motion is caused by bombardment of colloidal particles suspended in the medium.
 Brownian movement

b. Diffusion

Diffusion is the tendency for molecules to migrate from a region of high concentration to a
region of lower concentration and is a direct result of Brownian motion. According to Fick’s first
law, the amount, dq, 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.

Fick’s law is written as

dc
dq=−DS dt -----------------------------------eq 1
dx

D is the diffusion coefficient, the amount of material diffusing per unit time across a unit time across a
unit area when dc/dx, called the concentration gradient is unity.

The diffusion coefficient of a suspended material is related to the frictional coefficient of the
particles by Einstein’s law of diffusion

Df = kT----------------------------------eq 2

K is Boltzmann constant and T is absolute temperature

The frictional coefficient is given by

F=6πηr ------------------------------------eq3

Where η is viscosity of dispersion medium and r is radius of particle

kT
D=
6 π ηr
Or
RT
D= −−−−−−−−−−−−−−eq 4
6 π η rN
N is Avogadro s number
The measured diffusion coefficient can be used for determining molecular weight of approximately
spherical molecules by using the below equation

where M is molecular weight and

¯ v is the partial specific volume (approximately equal to the volume in cm3 of 1 g of the solute, as obtained from
density measurements)

c. Osmotic pressure

Osmotic pressure of a colloidal solution is a colligative property useful in determination of molecular

weight of dispersed phase, which is given by Van’t Hoff equation for dilute colloidal solution
π=cRT ------------------eq 1
Where C is molar concentration of solute; replacing C with cg/M in the above equation in which cg is the
gram of solute per liter of solution and M is molecular weight

cg
π= RT -----------------eq2
M

π RT
= ------------------eq3
cg M

Equation 3 is applied for very dilute solution hence the above quation is modified as
π 1
=RT ( + B c g ) ------------------eq 4
cg M
Where B is a constant for any particular solvent/solute system and depends on the degree of interaction
between the solvent and the solute molecules. The term Bc g in equation4 is needed because equation 3
holds good for ideal solution .

π
A plot of against c g results in one of three lines as shown in figure, line I is for ideal solution line II
cg
RT
and III for real solution, the Y intercept is and slope gives B(interaction constant) and if the
M
temperature at which determination is carried out is known, molecular weight can be calculated. In line I
‘B’ is equal to 0 and is typical of a dilute spherocolloid.
 d. Sedimentation

The velocity v of sedimentation of spherical particles having a density ρ and

density of medium ρo and a viscosity η. Is given by stokes equation
2
2r ( ρ−ρ0 ) g
v=
9 η0

This law obeys only if the particles should be spherical and Stokes equation is for particle size larger than
0. 5μm. Because of Brownian movement sedimentation due to gravity is slow which promotes mixing. A
strong force must be applied to bring sedimentation, Ultracentruge can be used for the complete
sedimentation . 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.

e. Viscosity
The viscosity is an expression of the resistance to flow of a system under an applied stress. In this section
concerned with the flow properties of dilute colloidal systems.
1. We can determine the molecualr weight of the molecules in the dispersed system and shape of the
particles in solution

Einstein equation for dilute colloidal dispersions

η=η0(1+ 2.5 Ǿ) This is based on hydrodynamic theory

η0 = viscosity of the dispersion medium

η = viscosity of the dispersion when the volume fraction of colloidal particles present is Ǿ
Volume fraction: T he volume fraction is defined as the volume of the particles divided by the total
volume of dispersion

ELECTRICAL PROPERTIES OF COLLOIDS

The colloidal particle of a sol usually carry either positive or negative charge. Sols, which carry
positive charge are called positive sols. Examples of such types of sol are Fe(OH) 3,
Al(OH)3,Cr(OH)3, TiO2 and basic dye stuffs. Correspondingly sols, which carry negative charge,
are called negative sols. Examples of such types of sols are metal sols such as Ag, Cu, Au, Pt
etc., metal sulphides (As2S3, Sb2S3, CdS etc.), gums, starch soap solution and some acid
dyestuffs.

a. Electrophoresis: The migration of electrically charged colloidal particles under an applied

electric potential is called electrophoresis. When a sol is placed in an electric field, colloidal
particles move towards either cathode or anode depending upon the charge on them. This
migration of colloidal particles under the influence of an electric field towards an electrode is
called electrophoresis. If the movement of colloidal particles is towards the cathode, it is called
cataphoresis. By observing the direction of motion of sol particles under the influence of electric
field, we can determine whether they carry positive or negative charge
Applications: The process can be utilised in determining the charge on colloidal particles. It
finds application in removing carbon from smoke, dirt from sewage and in electro deposition of
rubber.

b. Electro-osmosis: Colloidal particles carry either positive or negative charge and the sol as a whole is
electrically neutral. Therefore, the dispersion medium carries an equal but opposite charge to that of the
colloidal particles. Thus the dispersion medium will move in opposite direction to the dispersed phase
under the influence of an electric field. When the dispersed phase is kept stationary, the dispersion
medium is actually found to move towards one or the other electrode. The movement of the dispersion
medium under the influence of an electric field is called electro-osmosis.

c.The Electric Double Layer

a-a’ : Solid- Liquid Interface with Potential-determining Ions

b-b’ : Shear Plane (Solvated Layer)

a-a’ to b-b’ : Tightly bound layer with counter ions (Stern Layer)

b-b’ to c-c’ : Gouy Layer (Diffuse Second Layer)

c-c’ : Electroneutral region

Consider the solid particles in a suspension prefer to adsorb Positive ions on Its surface in an
aqueous solution containing both positive and negative ions due to dissociation of salts. The ions
which adsorbed on the surface are called POTENTIAL DETERMINING IONS

These potential determining ions influence the distribution of the ions in the solution around the
suspended particle.
The positive potential determining ions will repel the other positive ions in the solution and
attract negative ions towards it. The negative ions will attracted and held close to the solid
surface
These negative ions are called COUNTER IONS or GEGENIONS. This layer is immediately
adjacent to the surface containing POTENTIAL DETERMINING IONS. Thermal motion also
will try for the equal distribution of the ions in the solution. When particles move relative to the
liquid, the tightly bound layer also moves along, Thus particle surface extend upto b-b’ rather
than a-a’ The boundary b-b’ is called shear plane. Concentration of anions will be more near to
b-b’ but will gradually decrease as moves to c-c’. The reagion b-b’ to c-c’ is known as Gouy
Layer or Diffuse Second Layer. Concentration of cations increases as we move to c-c’. The
number of cations and anions will be equal at c-c’ and this point is called ELECTRONEUTRAL
REGION.

Stern Layer (a-a’ to –b’) and Gouy layer (b-b’ to c-c’) together called ELECTRICAL DOUBLE
LAYER
NERNST POTENTIAL (E): potential of the solid surface due to the presence of potential
determining ions
Also called Electro-thermodynamic Potential.It is the potential difference between the surface
and electroneutral region.
ZETA POTENTIAL : potential observed at the shear plane (surface of the solvating layer)
Also called Electrokinetic Potential. It is the potential difference between the shear and
electroneutral point. Can be determined by using an electrophoretic cell or zeta meter. Based on
the movement of particles under the influence of electric field.

The potential energy will be highest at the surface and decrease sharply along the STERN LAYER and
gradually along GOUY LAYER and becomes zero at ELECTRONEUTRAL POINT

a. Donnan membrane equilibrium : (refer class notes )

Coagulation or Precipitation: Colloidal particles in a sol carry the same charge. Being similarly
charged, they repel each other. The repulsive forces between the similarly charged particles do not allow
them to come closer. Hence, they remain scattered or suspended throughout the dispersion medium.
However, if the charges are removed by some means, the colloidal particles come togethter to form
bigger aggregates and settle down under the influence of gravity.
This process by which the colloidal particles come closer and result in the precipitation of the colloidal
solution is called coagulation.
The coagulation or precipitation of a sol can be brought about in four different ways as follows:
(i) By addition of electolytes
(ii) By mixing two oppositely charged sols
(iii) By boiling
(iv) By electrophoresis
(v) By persistent dialysis
(i) By addition of electrolytes: When electrolyte is added to a sol, the charged colloidal particles adsorb
the oppositely charged ions produced by the dissociation of electrolyte. In this way, the charge on the
colloidal particles is neutralized and the resulting neutral particles come together to form bigger
aggregates and thus get precipitated. For example, when sodium chloride is added to the negatively
charged sol of As2S3, arsenous sulphide settles down in the form of yellow precipitate. On adding NaCl,
the Na+ ions neutralise the negative charge on the colloidal particles. After losing the charge, the particles
come together to form bigger aggregates which finally settle down as yellow precipitate.
Stability of Sols:
Hydrophobic sols are stabilized by the presence of like charges on colloidal. Due to the presence of
like charges, colloidal particles repel each other and move away from each other and thus do not
coalescence to form bigger aggregates. However, the coagulation begins immediately on the removal
of the charge. Stability of lyophilic colloids is for two reasons. Their particles possess a charge and in
addition they are heavily solvated and the solvent layer surrounding them prevents them to come into
intimate contact with each other. Hence their coagulation is prevented. For example, when sodium
chloride is added to a gold sol, it gets precipitated. However, when sodium chloride is added to a colloial
solution of gelatin, its particles are not precipitaed. This is because the water layer around gelatin particles
does not allow the Na+ ions to penetrate and destroy the charge on gelatine particles (Figure below).
Thus gelatin sol is not precipitated. This indicates that lyophilic sols are more stable than lyophobic sols.
To coagulate lyophilic sols, it is necessary to remove charge as well as the solvent layer. This is indicated
by the fact that after the addition of an electrolyte if we also add a dehydrating agent, the coagulation sets
in at once due to the removal of water layer. Thus the stability of the colloidal solutions is mainly due to
three reasons:
(i) Brownian motion
(ii) Presence of similar charge on colloidal particles.
(iii) Solvation of colloidal particles.

Protective action of sols

Lyophobic sols such as those of gold and silver, etc. are readily precipitated by the addition of small
amounts of electrolytes. However, their coagulation can be prevented by the previous addition of some
stable lyophilic colloid like gelatin, albumin, etc. For example, if a little gelatin (hydrophilic colloid) is
added to a gold sol (hydrophobic sol), the latter is not readily precipitated by the addition of sodium
chloride. The property of the lyophilic colloids to prevent the precipitation of lyophobic colloids by
electrolytes is called protection. The lyophilic sol used to prevent the precipitation of a lyophobic sol is
called protective colloid.
The protective action of lyophilic colloids is based on the fact that the particles of the hydrophobic sol
adsorb the particles of the lyophilic sol which form a protective coating around the lyophobic sol
particles. The hydrophobic sol, therefore, behaves as a hydrophilic colloid and is not readily precipitated
on the addition of an electrolyte.

Gold number: The protective power of different lyophilic sols is different. The protective action of
different colloids is expressed in terms of gold number introduced by Zsigmondy. It is defined as:

The number of milligrams of a hydrophilic colloid which just prevents the precipitation of 10 mL of
a gold sol on the addition of 1 mL of ten per cent sodium chloride solution.

The onset of precipitation of gold sol is indicated by change in colour from red to blue/violet. Thus gold
number is a measure of the quantity of protective colloid which just fails to prevent the coagulation of the
sol by the electrolyte. It is obvious, therefore, that smaller the gold number, greater is the protective
power of the given protective colloid.

Experimental Procedure to find Gold Number

The procedure is as follows
After determining the approximate concentration of protecting colloids required, 0.01, 0.1, 1.0 mL
proportion of sol are put into the beakers and 10 mL of gold sol is added to each. After shaking for three
minutes, 1 mL of 10% NaCl is added to each. If the colour changes in first beaker but not in others, then
gold number lies between 0.01 mL and 0.1 mL of protecting colloid. By repeating concentrations between
these limit more exact values are obtained. The gold number found in this way by Zsigmondy and
Gortner

The Schulze-Hardy Rule

This rule of coagulation states that (1) The effective ions in the preparation of sol by electrolytes is the ion
opposite in sign to the charge on the colloidal particles and (2) the precipitating powerof the effective ion
increases greatly with increasing valence of the ion. The effective ion is sometimes referred to as the
precipitating ion of an electrolyte, whereas the ion having the same sign of charge as the particle is called
stabilizing ion.

According to Schulze-Hardy Rule higher the valency of the flocculating ion added, the greater is its
power to cause coagulation. Thus, for precipitating an As2S3 sol (negative), the precipitating powerof
positively charged ions is in the order:

eg: Al3+ > Ba2+ Na+.

Coacervation is a phenomenon that produces coacervate colloidal droplets. When coacervation

happens, two liquid phase will co-exist: a dense polymer rich phase (coacervate phase or
coacervate droplets) and a very dilute polymer deficient phase (dilute phase). Coacervate
droplets can measure from 1 to 100 micrometres across, while their soluble precursors are
typically on the order of less than 200 nm. The name "coacervate" derives from
the Latin coacervare, meaning "to assemble together or cluster

Size and shape of colloids

Particles in the colloidal size range possess a surface area that is enormous compared with the
surface area of an equal volume of larger particles. To compare the surface areas of different
materials quantitatively, the term specific surface is used. This is defined as the surface area per
unit weight or volume of material.

The color of colloidal dispersions is related to the size of the particles present. Thus, as the
particles in a red gold sol increase in size, the dispersion takes on a blue color. Antimony and
arsenic trisulfides change from red to yellow as the particle size is reduced from that of a coarse
powder to that within the colloidal size range.

Because of their size, colloidal particles can be separated from molecular particles with relative
ease. The technique of separation, known as dialysis, uses a semipermeable membrane of
collodion or cellophane, the pore size of which will prevent the passage of colloidal particles, yet
permit small molecules and ions, such as urea, glucose, and sodium chloride, to pass through.

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. A
colloidal particle is something like a hedgehog—in a friendly environment, it unrolls and
exposes maximum surface area. Under adverse conditions, it rolls up and reduces its exposed
area. Some representative shapes of spherocolloids and fibrous colloids are shown in below
Figure. Particle shape may also influence pharmacological action helps careful consideration to
be given

DLVO Theory

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:
i. Providing the dispersed particles with an electric charge,
ii. 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. A lyophobic sol is
thermodynamically unstable. The particles in such sols are stabilized only by the presence of
electric charges on their surfaces.

Verwey and Overbeek and Derjaguin and Landau independently develop a theory that describes
the stability of lyophobic colloids ie DLVO theory .

The potential energy of two particles is plotted in Figure below as a function of the distance of
separation. Shown are the curves depicting the energy of attraction, the energy of repulsion, and
the net energy, which has a peak and two minima.
When the repulsion energy is high, the potential barrier is also high, and collision of the particles
is opposed. The system remains deflocculated, and, when sedimentation is complete, the
particles form a close-packed arrangement with the smaller particles filling the voids between the
larger ones. Those particles lowest in the sediment are gradually pressed together by the weight
of the ones above; the energy barrier is thus overcome, allowing the particles to come into close
contact with each other. To resuspend and redisperse these particles, it is again necessary to
overcome the high-energy barrier. Because this is not easily achieved by agitation, the particles
tend to remain strongly attracted to each other and form a hard cake.
When the particles are flocculated, the energy barrier is still too large to be surmounted, and so
the approaching particle resides in the second energy minimum, which is at a distance of
separation of perhaps 1000 to 2000 A° . This distance is sufficient to form the loosely structural
flocs. These concepts evolve from the Derjaguin and Landau, Verwey and Overbeek (DLVO)
theory for the stability of lyophobic sols.

A lyophobic sol is thermodynamically unstable. The particles in such sols are stabilized only by the
presence of electric charges on their surfaces. The like charges produce a repulsion that prevents
coagulation of the particles. If the last traces of ions are removed from the system by dialysis, the
particles can agglomerate and reduce the total surface area, and, owing to their increased size, they may
settle rapidly from suspension. Hence, addition of a small amount of electrolyte to a lyophobic sol tends
to stabilize the system by imparting a charge to the particles.
Addition of electrolyte beyond that necessary for maximum adsorption on the particles, however,
sometimes results in the accumulation of opposite ions and reduces the zeta potential below its critical
value.
The critical potential for finely dispersed oil droplets in water (oil hydrosol) is about 40 millivolts, this
high value signifying relatively great instability. The critical zeta potential of a gold sol, on the other
hand, is nearly zero, which suggests that the particles require only a minute charge for stabilization;
hence, they exhibit marked stability against added electrolytes. The valence of the ions having a charge
opposite to that of the particles appears to determine the effectiveness of the electrolyte in coagulating the
colloid. The precipitating power increases rapidly with the valence or charge of the ions, and a statement
of this fact is known as the Schulze–Hardy rule.

The Schulze-Hardy Rule

This rule of coagulation states that (1) The effective ions in the preparation of sol by electrolytes is the ion
opposite in sign to the charge on the colloidal particles and (2) the precipitating powerof the effective ion
increases greatly with increasing valence of the ion. The effective ion is sometimes referred to as the
precipitating ion of an electrolyte, whereas the ion having the same sign of charge as the particle is called
stabilizing ion.

According to Schulze-Hardy Rule higher the valency of the flocculating ion added, the greater is its
power to cause coagulation. Thus, for precipitating an As2S3 sol (negative), the precipitating powerof
positively charged ions is in the order:

eg: Al3+ > Ba2+ Na

Verwey and Overbeek and Derjaguin and Landau independently develop a theory that describes
the stability of lyophobic colloids ie DLVO theory .

The potential energy of two particles is plotted in Figure below as a function of the distance of
separation. Shown are the curves depicting the energy of attraction, the energy of repulsion, and
the net energy, which has a peak and two minima.
When the repulsion energy is high, the potential barrier is also high, and collision of the particles
is opposed. The system remains deflocculated, and, when sedimentation is complete, the
particles form a close-packed arrangement with the smaller particles filling the voids between the
larger ones. Those particles lowest in the sediment are gradually pressed together by the weight
of the ones above; the energy barrier is thus overcome, allowing the particles to come into close
contact with each other. To resuspend and redisperse these particles, it is again necessary to
overcome the high-energy barrier. Because this is not easily achieved by agitation, the particles
tend to remain strongly attracted to each other and form a hard cake.

When the particles are flocculated, the energy barrier is still too large to be surmounted, and so
the approaching particle resides in the second energy minimum, which is at a distance of
separation of perhaps 1000 to 2000 A° . This distance is sufficient to form the loosely structural
flocs. These concepts evolve from the Derjaguin and Landau, Verwey and Overbeek (DLVO)
theory for the stability of lyophobic sols.