III Semester

Physical Chemistry –I
Paper-III
Course No. CHEM/3/CC/231

Unit 3 : Colloids and surface Chemistry

Classification of colloids, preparation of colloids, Bredig’s and condensation

methods, Peptization, Optical properties of colloids-Tyndall effect. Origin
of charge on colloidal particles, protective colloids, gold number

Physisorption & chemisorptions; molar enthalpy of adsorption,

Lanmgmuir, Freundlich & Gibbs adsorption isotherms.

True solution : An ordinary solution consisting of a solvent and a solutes. The particles of the
solutes are usually normal molecules or ions. For example, when a sugar is added to water a
true solution is formed.
Coarse Suspension solution : Solutions whose solutes are larger than the normal
molecules size. For example, when substances like a sand or powdered glass etc. are added to
water, they settle down easily on standing.
Between these two extremes of true solution and coarse suspension solution there
exists a solution/system having properties between them. This solution or system is called
colloids. Their difference lies only in their relative particle size of the solute.

Differences between the true solution, colloidal solution and suspension solutions

True solution Colloidal solution Suspension solution

Homogeneous solution Heterogeneous system Solution consisting of size
consisting of particles of consisting of particles of greater than 10-7 cm
molecular size (10Å ) size (10-4 to 10-7 cm)
dispersed in dispersion
medium

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 The particles don’t settle The particles settle down Particles settle down
down on standing very slowly on standing readily on standing
Not visible under the The particles are too small Visible even to naked eye.
ultra-microscope to be visible even under
the ultra-microscope
Readily pass through The particles diffuse very Do not diffuse through
parchment membrane slowly through parchment parchment membrane
membrane

Colloids
Colloids may be defined as “ particle of any substance dispersed in another medium in
the form of very small size having diameter between 10-4 to 10-7 cm (100 m to 1m)”. For
examples, starch, protein, gelatine, glues, etc
Colloidal Solution/System
A colloidal system may be considered as heterogeneous system consisting of two
phases : dispersed phase or continuous phase and dispersion medium in which particle is
present.
Dispersed phase + Dispersion medium Colloidal system/solution
The size of the dispersed phase lies between 10-4 to 10-7 cm and that of dispersion medium is
less than 10-7 cm in diameter. Each of the two phases of colloidal solution may be a gas,
liquid or a solid. Thus a several types of colloidal system are possible depending upon the
state of aggregation of the dispersed phase and the dispersion medium.

Classification of Colloidal system/colloids

Colloids can be classified on the following basis:
I. Depending upon the nature of the dispersion medium and disperse phase,
colloidal system are classified into eight categories as follow:

Categories Dispersion medium Disperse phase Examples

1. Gas Liquid Clouds, mists, fogs

2. Gas Solid Smoke, dust

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3. Liquid Gas Soap leather, foams
4. Liquid Solid Starch, proteins
5. Liquid Liquid Emulsions (Milk, Cream)
6. Solid gas Cake, bread
7. Solid Liquid Jellies, gels
8. Solid Solid Alloys, gems, coloured glass

Based on the state of the phase, colloidal solutions have given different names such as
liquid/solid aerosol when the dispersion medium is gas and disperse phase is liquid or solid.
A colloidal solution is termed as emulsions when both dispersion medium and
disperse phase are liquid
SOL : A colloidal solution whose the dispersion medium is either liquid or solid and gas: and
the dispersed phase is solid.
II. Depending upon the interaction of the two phases : colloids are classified as
(a) Lyophilic colloids and (b) Lyophobic colloids
(a) Lyophilic colloids : When the dispersed phase have a strong interaction with
dispersion medium, the colloids are termed as lyophilic colloids. E.g. Starch, proteins,
etc., as their molecules pass readily into colloidal state whenever they are brought into
contact with dispersion medium.
(b) Lyophobic colloids : When the dispersed phase has less affinity for the dispersion
medium, the colloid is termed as lyophobic colloid.

Difference between lyophilic colloid and lyophobic colloid

Property Lyophilic colloid Lyophobic colloid
Affinity towards the Strong Less affinity
dispersion medium
Reversibility Reversible Irreversible
Surface tension Surface tension is generally lower Surface tension is usually
than that of the dispersion medium the same as that of the
dispersion medium
Viscosity Viscosity is much higher than that of Viscosity is about the same
the medium as that of the medium
Action of electrolyte Require large quantity to cause Small amount of

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 precipitation electrolyte can cause
precipitation
Visibility Particles can’t be detected readily Though invisible but can
even under ultra-microscope be readily detected under
ultra-microscope.

III. Depending upon the electrical charge on the disperse phase

Colloids

Positive colloids Negative colloids

When the dispersed phase When the dispersed phase carries –ve charge,
carries + ve charge, the colloids the colloids are known as –ve colloids
.are known as positive colloids E.g. the particles of As2S3 sol in H2O
E.g. Fe(OH)3 sol in H2O

IV. Depending upon the appearance of colloids

Colloids

Sol -When a colloidal solution appear Gel- When a colloidal solution has a
as fluids, sols are named after dispersion solid-like appearance
medium.

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 V. Depending upon the structure of colloid particle

Colloids

Micellar colloids Molecular colloids

Preparation of colloidal solutions

For the preparation of colloidal solution, the dispersed particle must be within the
1 m -200m in size.
Since the dispersde phase has strong affinity towards dispersion medium, the lyophilic sols
can be readily prepared. E.g. Starch, gelatine, protein, etc., when added to water, they swell
up and break down spontaneously into a particle of colloidal range.
However, for the preparation of lyophobic colloids, special methods should be
employed. The methods consists of either in
i. Breaking down the coarse/bigger particles into a particle of colloidal range and this
method is known as dispersion method and
ii. Starting with the particles of molecular size and then condensing into a particle of
colloidal size. This method is known as condensation method.

i. Dispersion methods: In this method, particles of larger size are broken down to the
particles of colloidal range in the dispersion medium. Starting with the particles in coarse
form, a colloidal solution is formed by using suitable devices and physical methods to
broken into particle of colloidal size as discussed below:
(a) Electrical dispersion :
Bredig’s Arc Method
This method is devised by G. Bredig and
hence the method is names as Bredig’s arc
method. In this method, the metal to be
dispersed is taken in the form of electrodes
and dipped in the vessel containing
dispersion medium with a trace of alkali.

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 The vessel is surrounded by an ice. The electrodes are connected to a high voltage
source. When this high voltage is applied an electric arc is struck between the tips of
two electrodes producing a large heat. Because of this heat metals melt, evaporate and
suddenly cooled due to the ice thereby condensing into particles of colloidal solution of
the metal. This method is usually used for the preparation of colloidal solution of Pb,
Ag or Cu or Au. Here alkali is used to stabilize the colloidal solution of the metals
Fig. : Bredig’s Arc Method
And this method is further modified by T. Svedberg by using organic solvents
instead of H2O. In Svedberg method, the electrodes are usually made of iron and
aluminium and alternating current is used. The material to be dispersed is taken in the
form of granules and pasted on the electrodes (immersed in organic solvents) through
which the electric arc is passed. This method is used for preparation of organosols of
several metals and non-metals.

(a) Peptization
The process of converting freshly prepared precipitates such as Fe(OH)3,
AgCl3 and Al(OH)3 into colloidal solution by the addition of a small amount of
electrolyte is called peptization. The peptization action is due to the preferential
adsorption of one of the ions of the electrolyte by the particles of the precipitates. That
is, the electrolyte having an ion in common with the material to be dispersed is
required for sol formation. As a result of preferential adsorption of the ion which is
more closely related chemically to the precipitate, the particles of precipitates acquire
a +ve or –ve charge depending upon the charge on the ion adsorbed.
Because of the presence of the same type charge, the particles of precipitate are
pushed apart causing the precipitate particles to disperse thereby resulting the
formation of stable sols. Thus, Fe(OH)3 sol is prepared by the addition of small
quantity of FeCl3 solution to freshly prepared precipitate of Fe(OH)3. The sol thus
obtained carry + ve charge due to the preferential adsorption of Fe3+ ions from FeCl3
on particles of Fe(OH)3 as {Fe(OH)3}Fe+++.
ii. Condensation methods
Colloidal systems can be obtained by varius chemical reactions such as double
decomposition, oxidation, reduction, hydrolysis, etc., under the controlled conditions
of temperature, concentration, agitation, etc.

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 (a) Double decomposition: Usual ways of forming sols of insoluble salts. Eg. A sol of
arsenious sulphide is prepared by passing H2S gas through a dilute solution of
As2O3 and removing the excess H2S by boiling.
As2O3 + 3 H2S As2S3 + 3H2O
(b) Oxidation : Sols os some non-metals are obtained by oxidation. Eg. Sulphur sol is
obtained by the oxidation of an aqueous solution of h2S with air or SO2
2H2S + O2 2S + 2H2O
2H2O + SO2 3S + 2H2O
During the oxidation of H2S to S, a complex reaction occurs simultaneously resulting in
the formation of polythionic acids. These acids readily get associated with colloidal particles
of sulphur to form bigger colloidal particles called micelles.
Similarly, iodine sol is obtained by oxidising hydriodic acid with HI.
HIO3 + 5HI 3H2O + 3I2
(c) Reduction : Used for the preparation of metal sols,. Eg. Sols of metals such as Ag,
Cu, Au and Pt are obtained by reducing the aqueous solutions of their salts by non-
electrolytes such as HCHO, phenyl hydrazine, CO and phosphorous.
Zsigmondy prepared the gold hydrosol by reducing potassium aurate with
HCHO. Potassium aurate is formed by reacting chloroauric acid H[AuCl4] with
potassium carbonate in aqueous solution.
2 [AuCl4] + 5 K2CO3 2 KAuO2 + 5 CO2 + 8KCl + H2O
And the resulting solution of potassium aurate is heated and a dilute solution of
HCHO is added dropwise when the reduction occurs as
2 KAuO2 + 2HCHO + K2CO3  2 Au(Sol) + 3 HCOOK + KHCO3 + H2O

(d) Hydrolysis : Colloidal sols of heavy metals are obtained by the hydrolysis of their
salt solutions. Eg. When a small amount of FeCl3 is added to boiling H2O, a red-
brown sol of Fe(OH)3 is obtained.


FeCl3 + 3H2O Fe(OH)3 + 3HCl
The HCl so formed is removed by boiling.
Properties of colloids
i. Heterogeneous phase/system
ii. Diffusibility : They do not diffuse readilty through parchment membrane.

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iii. Optical properties : Lyophobic colloids exhibit well defined optical properties called
Tyndall effect while lyophilic colloids do not show well defined optical properties.
When a beam of light is passed through a colloidal solution, it becomes visible
as a bright streak in the path of the beam. This is observed by Tyndall and the
phenomenon is commonly known as Tyndall effect, and the illuminated path
(streak of light) is known as Tyndall Cone.

Fig. The Tyndall effect

Tyndall effect is due to the scattering of light by the colloidal particles. The colloidal
particles first absorb light and then a part of the absorbed light is scattered from the surface of
the colloidal particles. The intensity of the scattered light depends on the difference between
the refractive indices of the disperse phase and dispersion medium. Greater the difference, the
Tyndall effect is well-observed. So, in lyophobic colloids, the difference is appreciable and
hence show well defined Tyndall effect. However, in lyophilic colloids, the Tyndall effect is
not well defined due to the small difference in the refractive indices of two phases. And this
effect has been used by Zsigmondy and Siedentopt in devising the ultra-microscope.

Specific properties of lyophobic colloids (Electrical property)

All the particles in a given lyophobic colloidal solution dispersed phase carry the
same charge and dispersion medium has an opposite and equal charge and hence whole
system is electrically neutral. So, the presence of similar charges on colloidal particles is
essential to prevent them from coalescing and aggregating because of mutual forces of
repulsion between the similar charges and hence giving the stability to colloidal system.
The origin of charge on colloidal particles:
Since the colloids are invariably associated with traces of electrolytes to make them
stable, the charge on the colloidal particles is due to the preferential adsorption of either +ve
or -ve ion from the electrolyte on their surface. If the particles have a preference to adsorb
+ve ions, the particles acquire +ve charge and if they prefer -ve ions, the particles acquire -

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ve charge. So, the +ve charge on Fe(OH)3 sol prepared by hydrolysis of FeCl3 is due to the
preferential adsorption of Fe3+ ions on the surfaces of particles of ferric hydroxide Fe(OH)3 .
The ferric ions, Fe3+ come from the ionisation of FeCl3 present in traces in the sol.
FeCl3 Fe3+ + 3Cl-
Similarly, the -ve charge on As2S3 (arsenic sulphide) is due to the preferential adsorption of
S2- ions on the surface of arsenic sulphide particles. The S2- ions are due to the ionisation of
H2S present is traces in As2S3 sol.
However, some sols carry +ve charge as well as -ve charge. E.g. Sols of AgI.
But if a dilute solution of NaI is added to a slight excess of dilute solution of AgNO 3, a
positively charged sol of AgI is formed due to the adsorption of Ag+ ions (figure 1).

If a dilute solution of AgNO3 is added to a slight excess

of dilute solution of NaI, a negatively charged sol of AgI is
formed due to the adsorption of I- ions as shown in figure 2.
The reactions involved are
AgNO3 (aq) + Na I (aq) → Ag I (S) + NaNO3 (Aq)

(excess) -ve charge

Due to the presence of excess electrolyte, NaI,

particles of AgI adsorb preferentially the I – ions on their
surface and hence acquire -ve charge. Therefore, a
electrical double layer exist on the surface of AgI
particles (Fig. 3 ) which can be represented in the form
of the diagram as given below :

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 The layer of I- ion adsorbed peferentially on Ag I particles
constitute fixed part of the double layer and the counter ions, Na+ ions as well as No3 _ ion
are present in the layer called diffuse or mobile part. The existence of charges of opposite
signs on the fixed and the mobile part of the double layer leads to the appearence of a
potential difference between the layers, called zeta potential, . The value of 
decreases on adsorption of ion of opposite charge on colloidal particles. This reduces the
mutual repulsion between the similar charged particles and hence the particles come closer
to one another to aggregate to form bigger aggregates. This phenomenon is known as
coagulation, flocculation or precipitation of colloidal solution leading to decrease in the
stability of the colloids.
Protected colloids
In order to prevent the precipitation of lyophobic colloids or hydrophobic colloids by
electrolytes, the lyophilic colloids is added and hence the stability of lyophobic colloids are
increased.
The stability of the hydrophobic colloids are found to be increased on addtion of certain
hydrophilic colloids. The hydrophilic colloids prevent the precipitation of the hydrophobic
colloids on the addition of a small amount of electrolyte. This action of the hydrophilic
colloids to prevent the precipitation of the hydrophobic colloids by the electrolyte is called
protection and the hydrophilic colloids is called protected colloids.
The increase in the stability of the hydrophobic colloids is due to the mutual
adsorption of the hydrophilic and hydrophobic colloids. So, the particles of the protected
colloids get adsorbed on the particles of hydrophobic colloids, thereby forming a protective
layer around it. This potective layer prevents the precipitating ions from coming in contact
with the colloidal particles.

It is further observed that the

protective colloids not only increase
the stability of the hydrophobic
colloids but the latter can be
evaporated to dryness and the dry mass

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peptised by simply shaking with H2O. Thus, the protective colloids converts an irreversible
(hydrophobic) colloids into a reversible colloid (Lyophilic colloids).

Gold Number :
The power of the hydrophilic colloid to prevent the precipitation of a hydrophobic colloid
by addition of an electrolyte depends upon the nature of the substance.
The protected character of various hydrophilic substances can be expressed
quantitatively by gold number. According to Zsigmondy, Gold number may be defined as
“The number of milligrams of the protective colloids which must be added to 10 c.c.
of a given gold sol so as to just prevent its precipitation by addition of 1 c. c of 10% NaCl
solution.”
Smaller the gold number, the higher is the protective power of a colloid. Gold number of
some protective colloids are given below :

Protective colloids Gold number

haemoglobin 0.03 to 0.07
Starch 15 to 25
Gelatin 0.005 to 0.01

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