Surface Chemistry

A branch of physical chemistry which deals with the study of physical

and chemical phenomenon that occur at the surface or interface of
two phases. For example corrosion, electrode processes,
heterogeneous catalysis, crystallation.

Due to complete miscibility, there is no interface between the gases.

Points to cover

1) Adsorption
2) Colloids
3) Catalysis
 PART # 1 Adorsoption
1.1 Introduction

The surface of a solid has the tendency to attract and retain the
molecules of gas and liquids. These molecules remain only at the
surface and do not go deeper into the bulk.

The accumulation of molecular species at the surface rather than in

the bulk of a solid or liquid is termed adsorption.

The substance, which adsorbed or accumulates at the surface is termed

adsorbate and the solid surface at the adsorption takes place is called
adsorbent.
 adsorbate

adsorbent

General adsorbents : charcoal,silica gel, alumina gel, clay, metals in finely

divided state, etc

The process of removing an adsorbed substance from a surface on

which it is adsorbed is called desorption.
1.2 Difference between Adsorption & Absorption

Adsorption Absorption
1. The substance is concentrated only 1. The substance is uniformly
at the surface and does not penetrate distributed throughout the bulk of the
through the surface to the bulk of the solid.
adsorbent

2.It is rapid in the beginning and 2.It occurs at a uniform rate.

slows down near the equilibrium.

3. It is a surface phenomenon. 3. It is a bulk phenomenon..

1.) Anhy. CaCl2  Absorption
H2O(g)
Silica gel  Adsorption

H2O() Absorption
2.) NH3(g)
Charcoal  Adsorption

Chalk  Absorption (water is absorbed)

3.) Ink
Chalk  Adsorption (ink is adsorbed)
When a substance is uniformly distributed throughout the body of a solid or liquid,
the phenomenon is called ABSORPTION.

The process in which both adsorption and absorption take place simultaneously
is known as SORPTION.

ABSORPTION
SORPTION
Adsorption of gases on metal surface voids is called OCCLUSION.
1.3 Mechanism of Adsorption
 Particles inside the adsorbent are completely
Air surrounded by other particles on all sides.
Hence the intermolecular forces are mutually
Surface balanced.
Layer
 Particles at the surface of adsorbent are not
surrounded by atoms or molecules on all
sides. Hence they possess unbalanced or
residual attractive forces.
Solid
 These forces of the adsorbent are responsible
for attracting the adsorbate particles on its
surface.
1.4 Thermodynamics of Adsorption
Adsorption involves attraction between molecules of adsorbate and surface
of the adsorbent. Due to this energy is released and thus heat of adsorption is
negative i.e. adsorption is always exothermic.

The molecules of adsorbate are held on surface of the solid adsorbent due
to this entropy decreases i.e. DS is negative.

DG = DH – TDS, Therefore adsorption will occur only when DG is

negative and this is possible only if |DH| > |TDS|

DG can be negative if DH has sufficiently high negative value as – TDS is

positive.
1.5 Types of Adsorption
There are mainly two types of adsorption of gases on solids.

(1) Physical adsorption (i.e. Physisorption) : If adsorption of gas on the surface

of a solid occurs due to weak vander Waals’ forces, the adsorption is termed
as physical adsorption or physisorption.

(2) Chemical adsorption (i.e. Chemisorption) : When the gas molecules or atoms
form chemical bond with solid surface, the adsorption is termed chemical
adsorption or chemisorption. The chemical bonds may be covalent or ionic in
nature. Chemisorption involves a high energy of activation and is, therefore,
also called activated adsorption.
S.No. PHYSICAL ADSORPTION CHEMICAL ADSORPTION

It is caused by intermolecular
1 It is caused by chemical bond formation
vander Walls’ forces.

2 It is not specific. It is highly specific.

3 Multi-layered. Single layered

4 It is reversible. It is irreversible.
S.No. PHYSICAL ADSORPTION CHEMICAL ADSORPTION
5 It depends on the nature of gas. It depends on the nature of gas.
More easilyliquefiable gases are adsorbed readily. Gases which form com- pounds with
the adsorbent exhibit chemisorption.

6 Enthalpy of adsorption is low (20-40 kJ mol–1) Enthalpy of adsorption is low

(80-240 kJ mol–1)
7 Low temperature is favourable. It decreases increase High temperature is favourable.
with increase of temperature. It increases in temperature upto
certain limit.
8 No appreciable activation energy is involved. High activation energy is involved.

9 High pressure is favourable. Decrease of pressure High pressure is favourable.

causes desorption. Decrease of pressure does not
cause desorption.
1.6 FACTORS AFFECTING EXTENT OF ADSORPTION

1. The nature of the gas (i.e. nature of the adsorbate) : The easily liquefiable gases
such as HCl, NH3, Cl2 etc. are adsorbed more than the permanent gases such as
H2, N2 and O2.
Extent of adsorption  critical temperature of gas  ease of liquification

2. Nature of adsorbent :
Extent of adsorption  surface area of solid.

3. Effect of temperature : Adsorption is exothermic and the reverse process i.e.

desorption is endothermic. With increase in temperature, the desorption will be
favoured i.e. extent of adsorption decreases.
Physisorption decreases continuously with increase in temperature
whereas chemisorption increases initially, shows a maximum in the curve and
then it decreases continuously.
The initial increase in chemisorption with increase in temperature is because
of activation energy required.
This is why the chemical adsorption is also known as “Activated adsorption”.
Graph at constant pressure
x x
m m

Temperature Temperature
Physical adsorption Chemical adsorption

A graph between degree of adsorption (x/m) and temperature ‘T’ at a constant

pressure of adsorbate gas is known as adsorption isobar.
4. Effect of Pressure :
On increasing pressure extent of adsorption increases.
Extent of adsorption of a gas = x/m
where : x – Mass of adsorbate,
m – Mass of adsorbent
i.e. x/m represents mass of adsorbed per unit mass of adsorbent.
A graph between the amount of adsorption and gas pressure keeping the
temperature constant is called an adsorption isotherm.
 x
m

Pressure (P) Saturation

Pressure

It is clear from the graph that extent of adsorption (x/m) increases with
pressure and becomes maximum corresponding to pressure called
saturation pressure(Ps ).
Freundlich adsorption isotherm :
Freundlich gave a relationship between x/m and pressure at a particular
temperature. The relationship can be expressed by the following equation:
𝟏
𝒙
𝒏 ; Where n > 1
𝒎

k and n are constants which depend on the nature of the adsorbent

and the gas at a particular temperature.

x
m

Pressure (P) Saturation

Pressure
 𝒙
(i) At low pressure,
𝒎

𝒙
(ii) At high pressure, 𝟎
𝒎

𝟏
𝒙
(iii) At moderate pressure, 𝒏
𝒎
 𝟏
𝒙
𝒏
𝒎

In Logarithmic form

𝐱 𝟏
𝐦 𝐧

If a graph is plotted between log x/m on y-axis and log p on x-axis then
it comes to be a straight line.

In general is 0.1 to 0.5

The slope of the straight line gives the value of 1/n and the intercept
on the y-axis gives the value of log k.
 Slope=(1/n)
log(x/m)

intercept = log k
log p
Drawback of Freundlich adsorption Isotherm :
Explains Physical Adsorption upto moderate pressure but fails at high
pressure.
Adsorption from solution phase :
1. The extent of adsorption increases with increase in the surface area of
adsorbent.
2. The extent of adsorption decreases with increase in temp.
3. The extent of adsorption is related to concentration of solution through this
equation Freundlich isotherm :
(x/m) = k(C)1/n where c is the equilibrium concentration of the solute
in solution.
1.6 APPLICATIONS OF ADSORPTION :

(i) Production of high vacuum: The remaining traces of air can be adsorbed by
charcoal from a vessel evacuated by a vacuum pump to give a very high vacuum.

(ii) Gas masks: Gas mask is usually used for breathing in coal mines to adsorb
poisonous gases. Gas mask consists of activated charcoal or mixture of
adsorbents.
(iii) Control of humidity: Silica and aluminium gels are used as adsorbents for
removing moisture and controlling humidity.
(iv) Removal of colouring matter from solutions: Animal charcoal removes colours
of solutions by adsorbing coloured impurities. E.g. decolorisation of sugar
(vi) Separation of inert gases: Due to the difference in degree of adsorption of gases
by charcoal, a mixture of noble gases can be separated by adsorption on coconut
charcoal at different temperatures.
(v) Heterogeneous catalysis: Part #2

(vi) Adsorption indicators: Surfaces of certain precipitates such as silver halides have
the property of adsorbing some dyes like eosin, fluorescein, etc. and thereby
producing a characteristic colour at the end point.

(vii) Chromatographic analysis: Chromatographic analysis based on the phenomenon

of adsorption.
 𝐱
Q.1 The graph between log v/s log P is
𝐦
straight line inclined at an angle 45°
with intercept 0.60. What will be the
extent of adsorption at pressure of 0.3
atm. (Given: 100.08 = 1.2)

Sol.
Q. The given graph represents :

195K

x/m) 244K

273K

Pressure

Ans. Physisorption
PART # 2 CATALYSIS
1. Introduction :
Catalyst : Berzelius suggested the term catalyst for such substances. Substances,
which accelerate the rate of a chemical reaction and they remain chemically and
quantitatively unchanged after the reaction, are known as catalysts, and the
phenomenon is known as catalysis.

Promoters or Activators : Substances which increases the activity of a

catalyst. For example, in Haber’s process for manufacture of ammonia,
Molybdenum acts as a promoter for iron which is used as a catalyst.
Fe(catalyst)
N2  3H2  2NH3
Mo(promotor)
Poisons or Catalytic Poisions : Decrease the activity of a catalyst

Pd(catalyst)
RCOCl  H2  RCHO  HCI
BaSO4 ( poison)

Catalyst Inhibitor: The substance which decreases the rate of chemical

reaction is called inhibitor. It increases the activation energy for the reaction.
. For example, H3PO4 and glycerol decrease the
rate of decomposition of hydrogen peroxide.
Autocatalysts : When one of the product of the reaction begin to act as a
catalyst, it is called auto catalyst.

𝟒 𝟐 𝟐 𝟒 𝟐 𝟒 𝟒 𝟐 𝟒 𝟐 𝟐

𝟑 𝟐 𝟓 𝟐          𝟑      𝟐 𝟓
    

In the initial stage the reaction is slow but as soon as the product come into
existence the reaction rate increases.
2. Type of catalysis:
(A) Homogeneous catalysis
(i) Lead chamber process for formation of sulfuric acid :
Oxidation of sulphur dioxide into sulphur trioxide with dioxygen in the presence of
oxides of nitrogen as the catalyst.

(ii) Inversion of cane sugar : In aqueous solution, it is catalysed by dilute acid

(hydrogen ions)

(iii) Hydrolysis of methyl acetate is catalysed by H+ ion furnished by hydrochloric acid.

ℓ
(B) Surface Catalysis or Heterogeneous Catalysis :
(i) Contact process for formation of Sulfuric acid : Oxidation of sulphur dioxide into
sulphur trioxide in the presence of Platinised asbestos or V2O5.

(ii) Haber process for NH3

( )
( )
(iii) Ostwald process for formation of nitric acid:

(iv) Hydrogenation of vegetable oils

Vegetable oil (l) + H2(g) Vegetable ghee (s)
3. Adsorption Theory of Heterogeneous Catalysis :
The old theory, known as adsorption theory of catalysis, was that the reactants are
adsorbed on the surface of the solid catalyst. The increase in concentration of the
reactants on the surface increases the rate of reaction. Adsorption is an exothermic
process, the released heat is used in increasing the rate of the reaction.
The modern adsorption theory is the combination of intermediate formation theory
(already studied in chemical kinetics) and the old adsorption theory.

Heterogeneous Catalysis is an example of chemisorption .

The mechanism involves five steps:
(i) Diffusion of reactants to the surface of the catalyst.
(ii)Adsorption of reactant molecules on the surface of the catalyst.
(iii)
Chemical reaction on the catalyst’s surface through formation of an intermediate.
(iv)Desorption of reaction products from the catalyst surface, and thereby, making the
surface available again for more reaction to occur.
(v) Diffusion of reaction products away from the catalyst’s surface.
 Adsorption of A
A+B reacting molecules
B
Reacting
molecules
Catalyst surface having
free valencies Adsorption of
reacting molecules

Desorption of A
A+B product molecules
Product B

Catalyst Intermediate

Fig. : Adsorption of reacting molecules, formation of

intermediate and desorption of products
Note :
This theory explains why the catalyst remains unchanged in mass and
chemical composition at the end of the reaction and is effective even in
small quantities.

This theory does not explain the action of catalytic promoters and
catalytic poisons.

Chemisorption occurs after physisorption i.e. at high temperature

physisorption can be converted into chemisorption.
4. General characteristics of catalysts :
(i) A catalyst remains unchanged in mass and chemical composition but can change their
physical state.
(ii) Only a very small amount of catalyst is sufficient to catalyse a reaction.
(iii) A catalyst does not initiate a reaction i.e. a catalyst can’t catalyse a non-spontaneous
reaction .
(iv) When a catalyst is a solid, it is usually more efficient when used in finely divided form.
(v) A catalyst does not change any thermodynamical parameter like enthalpy of reaction,
free energy, entropy and the equilibrium state of a reversible reaction.
(vi) Catalyst increases rate and rate constant of the reaction.
(vii) Catalysts are generally specific in nature.
(ix) Catalysts participate in mechanism of reaction.
(x) Catalysts changes the mechanism of reaction.
(xi) Heterogenous catalysis is an example of chemisorption.
(xii) They are highly active and selective.
5. Important features of Solid catalysis :
(i) Activity : The activity of a catalyst depends upon the strength of chemisorption to
large extent. The reactants must be adsorbed reasonably strongly on the catalyst.
They must not get adsorbed so strongly they are difficult to desorbed from the
surface and other reactants are left with no space on surface of catalyst for
adsorption.
It has been found that for hydrogenation the catalytic activity observed from group
5 to 11 and maximum activity is shown by group 7 to 9.
(ii) Selectivity : Selectivity of different catalysts for the same reactant is different for
example starting with CO and H2 and using different catalysts, we get different
products.
 Ni
CH4 + H2O

Cu/ ZnO-Cr2O3
CO + H2 CH3OH

Cu HCHO
5. Zeolites (Shape selective catalyst) :
(i) The catalytic reaction that depends upon the pore structure of the catalyst and the
size of the reactant and product molecules is called shape-selective catalysis. Zeolites
are good shape-selective catalysts because of their honeycomb-like structures.
Formula of Zeolite is Nax/n [(AlO2)x (SiO2)y] zH2O

(ii) They are microporous aluminosilicates with three dimensional network of silicates
in which some silicon atoms are replaced by aluminium atoms giving Al–O–Si
framework.

(iii) They are found in nature as well as synthesised for catalytic selectivity.
Application of Zeolite :

1. Normally used in petro chemical industries for cracking of hydrocarbon &

isomerisation.

𝒁𝑺𝑴 𝟓
R – OH asoline (Petrol)

2. Zeolite is also used as water softner & cationic exchanger (Exchange only cation
from hard water).
6. Enzyme Catalysis :

(i) Enzymes are complex nitrogenous organic compounds which are produced from
living plants and animals.
(ii) They are actually protein molecules of high molecular mass and form colloidal
solutions in water.
(iii) They catalyse biochemical reactions so also called biochemical catalyst.
Reactions Catalysed by Enzymes
S.No. Enzymes Source Reaction
(i) Invertase Yeast Sucrose  Glucose and Fructose
(ii) Zymase Yeast Glucose  Ethyl alcohol and carbon dioxide
(iii) Diastase Malt Starch  Maltose
(iv) Maltase Yeast Maltose  Glucose
(v) Urease Soyabean Urea  Ammonia and CO2
(vi) Pepsin Stomach Proteins  Amino acid
Characteristics of Enzyme Catalysis :

(i) Highly efficient : One molecule of an enzyme may transform one million molecules
of the reactant per minute.

(ii) Highly specific nature : One catalyst cannot catalyse more than one reaction. For
example, the enzyme urease catalyses the hydrolysis of urea only. It does not catalyse
hydrolysis of any other amide. Thus, the action of a catalyst is highly selective in nature.
A Substance which acts as a catalyst in one reaction may fail to catalyse another
reaction.

(iii) Highly active under optimum temperature (298 K to 310 K)

(iv) Highly active under optimum pH (5 to 7)

(v) Increasing activity in presence of activators and co-enzymes: The enzymatic
activity is increased in the presence of certain substances, known as co-
enzymes.
Vitamins are co-enzymes. It has been observed that when a vitamin is present
along with an enzyme, the catalytic activity will be greater.
Activators are generally metal ions such as Na+, Mn2+, Co2+, Cu2+.
E.g. Amylase in presence of sodium chloride i.e., Na+ ions are catalytically
very active.
 Mechanism of enzyme catalysis (key lock theory) :
 There are number of active centres of definite shape
present on the surface of colloidal particles of enzymes.
 The molecules of the Substrate, which have complementary
shape fit into these cavities just like a key fits into a lock.
 In the presence of active groups an activated complex is
formed which then decomposes to yield the product.
Enzyme Substrate Activated complex Enzyme Product
E + S [E – S]  E + P
Active site
P

E + S E S E
+
P

Enzyme Substrate Enzyme substrate Enzyme Product

(catalyst) (reactants) complex

Fig : Mechanism of enzyme catalysed reaction

 Part # 3 : Colloids
True solutions are homogeneous systems. Sand in water when stirred gives
a suspension, which slowly settles down with time. Between the two
extremes of suspensions and solutions there are third types of systems
called colloidal dispersions or colloids.

Colloidal solution is a heterogeneous system consisting of 2 phases :

(1) Dispersed /Disperse Phase (D.P) : The phase which is dispersed
through the medium is called dispersed phase i.e. just like solute.
(2) Dispersion Medium (D.M) : A medium in which colloidal
particles are dispersed is called dispersion medium. i.e. just like
solvent.
Colloidal solution = D.P. + D.M.
For example, In colloidal solution of gold : Gold is D.P and water is D.M.
The essential difference between a solution and a colloid is that of particle
size. In a solution, the solute particles are very small. DP particles of
colloids are larger than simple molecules (solute) but smaller than
suspensions.

> 1000 nm 1 – 1000 nm < 1 nm

suspension colloidal solution True solution
1. Classification of colloids
Colloids are classified on the basis of the following criteria:
(i) Physical state of dispersed phase and dispersion medium
(ii) Nature of interaction between dispersed phase and dispersion medium
(iii) On the basis of chemical composition:
(iv) Type of particles of the dispersed phase.
1.1 Classification Based on Physical State of D. P. and D. M.:
Depending upon whether the dispersed phase and the dispersion medium are solids,
liquids or gases, eight types of colloidal systems are possible
Dispersed phase Dispersion medium Type of olloid Example
Solid Solid Solid sol Coloured glasses and
gem stones

Solid Liquid Sol Paints, cell fluids

Solid Gas Aerosol Smoke, dust
Liquid Solid Gel Cheese, jellies
Liquid Liquid Emulsion Milk, hair cream
Liquid Gas Aerosol Fog, mist, cloud,

Gas Solid Solid sol Pumice stone, foam

rubber.

Gas Liquid Foam Froth, whipped

cream, soap lather
1.2 Classification Based on Nature of interaction between dispersed phase and
dispersion medium :

Colloidal sols are divided into two categories, namely, lyophilic (solvent attracting) and
lyophobic (solvent repelling). If water is the dispersion medium, the terms used are
hydrophilic and hydrophobic.

(i) Lyophilic colloids: The word ‘lyophilic’ means liquid-loving. The colloidal
solution in which the particles of the dispersed phase have a great affinity (or love) for
the dispersion medium (heavily hydrated), are called lyophilic colloids. They are
directly formed by mixing substances like gum, gelatine, starch, etc., with a suitable
liquid (the dispersion medium) and reversible in nature.
(ii) Lyophobic colloids:
The word ‘lyophobic’ means liquid-hating. The colloidal solutions in which there is no
affinity between particles of DP and the DM are called lyophobic colloids.

Substances like metals, their sulphides, etc. , when simply mixed with the DM do not
form the colloidal sol. Their colloidal sols can be prepared only by special methods.
They are not stable so need stabilizing agents for their preservation.

To get stability colloidal particles acquire charge on their surface.

These sols are precipitated (or coagulated) upon addition of small amounts of
electrolytes. Further, once precipitated, they do not give back the colloidal sol by simple
addition of the dispersion medium. Hence these sols are also called irreversible sols.
S.No. Property Lyophilic colloids Lyophobic colloids
There are easily formed by direct These are formed only by special
1 Preparation
mixing. methods

2 Reversibility These are reversible in nature These are irreversible in nature.

These are less stable and require

3 Stability These are very stable
stabilizers
The particles move in a specific
The particles have very small direction either towards anode or
4 Charge on particles amount of charge or do not carry cathode depending upon their charge
any charge. in an electric field

The addition of small amount of

Action of No effect electrolytes causes precipitation
5
electrolytes (called coagulation).

The particles of colloids are heavily

The particles of colloids are not
6 Hydration hydrated due to the attraction for
appreciably hydrated.
the solvent.
S.No. Property Lyophilic colloids Lyophobic colloids

It is higher than that of dispersion It is nearly same as that of dispersion

7 Viscosity
medium medium
They show less Tyndall effect or
8 Tyndall effect They show Tyndall effect.
do not show Tyndall effect.
It is nearly same as that of dispersion
9 Surface tension Lower than dispersion medium
medium

Migration in May or may not migrate as they Migrate toward anode or cathode as
11
electric field may not carry charge these particles carry charge
Inorganic nature; Transition metal
Mostly organic nature; Starch and
12 Example salt in water, gold etc., Metal
Gelatin
solution
1.3 On the basis of chemical composition :
On the basis of chemical composition of DM:
(i) Metal sols : Cu, Ag, Au, Pt Sols.

(ii) Non Metal sols : S, I2, Graphite

(iii) Sol of oxide and hydroxide : SnO2, TiO2, Fe2O3, Fe(OH)3, AI(OH)3,

(iv) Salt Sol - AgBr, AgI, As2S3, etc.

On the basis of D.M. : Colloidal solution are classified as

D.M. Name of colloidal system

Water Hydro sol or aqua sol
Alcohol Alco sols
Benzene Benzo sols
Air Aero sols
1.4 Classification Based on Type of Particles of the Dispersed Phase

1. Multimolecular colloids : The colloidal particles are formed by aggregation of atoms

or small molecules size less than 1 nm. For example, sols of gold atoms and sulphur
(S8) molecules.

2. Macromolecular colloids: Particles of the DP are sufficiently big in size (macro) to be

of colloidal dimensions. These macromolecules forming the DP are generally
polymers or macromolecules like starch, cellulose, proteins, enzymes, gelatin, etc.

3. Associated colloids (Micelles): These are the substances which behave as normal
strong electrolytes at low concentration but behave as colloidal particles at higher
concentration. These associated particles are also called micelles
 MICELLES (Associated colloids)
There are some substances which at low concentrations behave as normal strong
electrolytes, but at higher concentrations show colloidal behavior due to the
formation of aggregates. The aggregated particles thus formed are called micelles.
Or associated colloids.

The formation of micelles takes place only above a particular concentration called
critical micelle concentration (CMC).

The formation of micelles takes place only above a particular temperature called
Kraft temperature (Tk)
On dilution, these colloids revert back to ions.
Surface active agents such as soaps and synthetic detergents belong to this class.
Micelles may contain as many as 100 molecules or more.
 O
CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 C

ONa
CH3 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2

Sodium stearate (C17H35COO)

O
CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 C
O
CH3 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2

Hydrophobic tail stearate ion Hydrophobic

head

Hydrophilic head

Hydrophobic tail

Hydrophobic and hydrophilic parts of stearate ion

2. Preparation of Colloids
(1) Preparation of lyophilic sols : The colloidal solutions of lyophilic colloids like
starch, gum, glue, gelatin etc., can be prepared by dissolving these substances in
water either by cooling or warming.
(2) Preparation of lyophobic sols : There are two concepts to lyophobic sol.
(i) Dispersion methods : Broken of bigger particles into into fine particles of
colloidal dimension (1Å to 103 Å )

(ii) Condensation methods : By aggregating very small particles (atoms, ions or

molecules) into colloidal size.
3.1 Dispersion Methods
(i) Mechanical dispersion : Solid material is finely ground in a colloidal mill with
dispersion medium which gives a colloidal solution. The suspension is now
introduced into the colloid mill. The particles are ground down to colloidal size and are
then dispersed in the liquid . A stabilizer is often added to stabilize the colloidal
solution. Colloidal graphite (a lubricant or Indian ink) and printing ink

Suspension

Tannin and gum arabic is used as a Driving belt

stabilizer in the preparation of colloidal

graphite (Indian ink).
Discharge Discharge
Discs Metal disc
(ii) Electro-dispersion (Bredig's arc method) : This method is suitable for the
preparation of colloidal solutions of metals like gold, silver, platinum, etc. A very
voltage is used between the metal electrodes container in an ice bath. The intense heat
produced due high voltage vaporises some of the metal which condenses under cold
water.
In this method charge at the surface sol particles is acquired by electron capture.
(iii) Ultrasonic dispersion : The sound waves of high frequency are usually called ultrasonic
waves. These waves used to prepare to prepare colloid solutions of oils, mercury, sulphur,
sulphides and oxides of metals

(iv) Peptization : Peptization is the process of converting a freshly prepared precipitate into
colloidal sol by addition of a small amount of electrolyte. The electrolyte used for this
process is called peptizing agent. During peptization, the precipitate adsorbs one of the ions
of the electrolyte on its surface. This causes the development of positive or negative charge
on precipitates, which break up into smaller particles of the size of a colloid.
The ion adsorbed on the surface of ppt is always a common ion of the electrolyte.

A few examples of sols obtained by peptization are :

(a) Ferric chloride (acts as a peptizing agent) is added to freshly prepared ferric
hydroxide reddish brown colloidal solution is obtained. Freshly precipitated Fe(OH)3
adsorbs Fe3+ ions (common ions) and breaks up into small-sized particles.
 +3 +3
+3
+3 +3 +3 +3
+3 +3
+3 +3 +3
+3
+ Fe
3+
+3 +3
+3 +3 +3
Peptizing agent +3
+3 +3 +3 +3 +3 +3
ppt of Fe (OH)3 +3
+3 +3
+3 +3
+3 +3 +3 +3
+3 +3

Charge Colloidal particals of Fe (OH)3

(b) Freshly precipitated silver chloride can be converted into a colloidal solution
by a small amount of hydrochloric acid.
Q. Which of the following will form negatively charged colloidal solution ?

a.) 100ml 0.1M AgNO3 + 100ml 0.1M KI

b.) 100ml 0.2M AgNO3 + 100ml 0.1M KI
c.) 100ml 0.1M AgNO3 + 100ml 0.2M KI
d.) 100ml 0.2M AgNO3 + 200ml 0.1M KI
3.2 Condensation Methods :
(i) By exchange of solvents : Sulphur or phosphorus are highly soluble in alcohol but
very less soluble in water so, if a solution of sulphur or phosphorus prepared in alcohol is
added into water, a colloidal solution of sulphur or phosphorus is obtained.

(ii) By change of physical state : Colloidal solutions of certain elements such as

mercury and sulphur are obtained by passing their vapour through cold water containing a
stabilizer (an ammonium salt or a citrate)

(iii) Chemical methods : Colloidal solutions can be prepared by chemical reactions

leading to formation of molecules by double decomposition, oxidation, reduction or
hydrolysis.
As2O3 + 3H2S 
Double decomposition
 As2S3(sol) + 3H2O

SO2 + 2H2S 

Oxidation
 3S(sol) + 2H2O

2AuCl3 + 3HCHO + 3H2O 

Reduction
 2Au(sol) + 3HCOOH + 6HCl
PURIFICATION OF COLLOIDAL SOLUTION :
(a) Dialysis :
 The process of separating crystalloid (small particles and
ions) from colloid colloids by diffusion through a suitable
membrane is called dialysis.
 Its principle is based upon the fact that colloidal Water
+
particles can not pass through a parchment or Crystalloid
cellophane membrane while the ions of the
electrolyte can pass through it. Water
Sol particle

 The impurities slowly diffuse out of the bag

leaving behind pure colloidal solution.
 The distilled water is changed frequently to avoid Crystalloid

accumulation of the crystalloids otherwise they may start

diffusing back into the bag.

 Prolonged dialysis can cause the colloid to coagulate.

(b) Electrodialysis :

 Process of dialysis can be made faster by applying an electric field if the dissolved
substances in the impure colloidal solution is only an electrolyte.

Dialysing
membrane

Water
+
Electrolyte
Anode + – + – Cathode

Water

Sol particle Crystalloid

(c) Ultrafiltration :

 Sol particles directly pass through ordinary filter paper because their pores are larger
than the size of sol particles.
 If the pores of the ordinary filter paper are made smaller by soaking the filter paper
in a solution of gelatin or collodion and subsequently hardened by soaking in
formaldehyde, the treated filter paper may retain colloidal particles and allow the
true solution particles to escape.
 Such filter paper is known as ultra filter and the process of separating colloids by
using ultra-filters is known as ultrafiltration.
 Collodion is a 4% solution of nitro cellulose in mixture of alcohol and ether.
4. Properties of Colloidal Solutions
Various properties exhibited by the colloidal solutions are described below:
(i) Heterogeneous character : Colloidal sols are heterogeneous in character as they
consist of two phases. (a) dispersed phase and (b) dispersion medium.
(ii) Visibility :
 Colloidal particles can not be seen with naked eyes.
 Colloidal particles, however scatter light and become visible as bright spots in a
dark background when seen through a ultra microscope.
 Solute particles of true solution are not visible through ultra microscope and
suspension particle are visible by naked eye.
(iii) Filterability : Colloidal particles pass through an ordinary filter paper. but the
particle do not pass through other fine membranes (parchment and SPM).
(iv) Colligative properties :

 Colligative properties depend on the relative number of

solute particles in solution.

 In case of colloidal solutions, colloidal particles are the aggregates of ions or

molecules and when compared to true solutions or normal solutions, the total no. of
particles of solute in solution are very less due to large size and hence these
solutions exhibit colligative properties of low order
(v) Optical properties (Sols exhibits Tyndall effect):

When light is focussed on a sol and observed perpendicular

to the beam of light rays, a cone is seen which is called
Tyndall cone. This was observed by Tyndall and is known as
Tyndall effect.

Tyndall effect can be observed only when following

two conditions can be satisfied:

1.) Diameter of dispersed particle is not much smaller

than wavelength of light used.
2.) The refractive indices of the dispersed phase and
dispersion medium differ greatly in magnitude.
Example of Tyndall Effect
 Blue colour of sky and sea water.
 Visibility of tail of comets.
 Light thrown from a projector in cinema hall.
 Appearance of dust particle in a semi darked room.
l Application of Tyndall Effect :
(i) In making ultramicroscopes.
(vi) Kinetic properties :
 When a sol is examined with an ultramicroscope, it is observed that the particle is in
a state of continuous motion in zigzag path.
 The continuous rapid zigzag motion of a colloidal particle in the dispersion medium is
called "Brownian movement or motion" (first observed by British
botanist Robert Brown).
 As per NCERT Brownian motions does not depend on nature of colloid solution.

Dependence :


1
Mobility Size of the particle

 1
Viscosity

 Temperature
(i) Charge on colloidal particles :
Colloidal particles always carry an electric charge. The mutual forces repulsion between
similarly charged particles prevent them from aggregation and settling under the
action of gravity. This gives stability to the solution.

Positively Charged Negatively charged

1. Metallic hydroxides Cr(OH)3, 1. Metallic sulphides like As2S3,
Al(OH)3, Fe(OH)3 & hydrated Sb2S3, CdS and Metal like: Au,
metallic oxides Al2O3.xH2O, Ag, Cu, Pt etc.
CrO3.xH2O
2. Basic dye in acidic medium stuff 2. Acid dye in basic medium
like:- Methylene blue sol stuff like:- Congo red sols
3. Haemoglobin (Hb) 4. Sols of starch, gum, gelatin,
clay & charcoal
NOTE:
Blood is a naturally occuring negatively charged colloid but Haemoglobin
(Hb) is a positively charged colloid.
 ELECTRICAL DOUBLE LAYER :
 The combination of the two layers of +ve and –ve charge
around the sol particle is called Helmholtz double layer.
The first layer of ions is firmly held and is termed as
Fixed layer or Compact layer. The second layer is mobile
which is termed as Diffused layer.
Mobile layer
 The diffused layer is only loosely attached to
Colloidal
Particles the particle surface and moves in the opposite
of Al(OH)3
Fixed layer direction under an applied electric field.

 The potential difference between the fixed layer and the

diffused layer of opposite charge is called Electrokinetic
Potential or Zeta Potential.
 High value of zeta potential represents high stability of
colloid solution.
 (j) Electrophoresis :
Reservoir
 If electric potential is applied across two
platinum electrodes dipped in a colloidal
solution, the colloidal particles move
Anode
Cathode Cathode
Anode towards one or the other electrode, due to
charge on them.

 The movement of sol particles under an

applied electric potential is called
Colloidal "Electrophoresis". Depending upon the
Water solution
(dispersion direction of movement of particles towards
medium) cathode or anode electrophoresis can be
called ‘Cataphoresis’ or ‘Anaphoresis’.
Stop cock
Electrophoresis provides an experimental proof to
show that the colloidal particles are charged
Fig. : Electrophoresis particles.
(k) Electro Osmosis :

 The medium will move in opposite direction to the

dispersed phase under the influence of applied electric
potential.
 The movement of dispersion medium under the influence of
applied potential is known as ‘Electro-osmosis’.(In presence
of plasma membrane)
(5) Coagulation or Flocullation :
The flocculation and settling down of the dispersed phase particles is called coagulation
or precipitation.

1.) For Lyophobic Sol :

The stability of a lyophobic sol is due to the adsorption of positive or negative ions by
the dispersed particles.
If somehow, the charge is removed there is nothing to keep the particles apart from
each other. In such cases they aggregate or flocculate and settle down under the
action of gravity.
A lyophobic sol can be coagulated by following methods
(i) By electrophoresis: The colloidal particles move towards oppositely charged
electrodes, get discharged and precipitated.
(ii) By mixing two oppositely charged sols (mutual coagulation of colloids):
Oppositely charged sols when mixed in almost equal proportions, neutralise their
charges and get partially or completely precipitated. Mixing of hydrated ferric
oxide (+ve sol) and arsenious sulphide (–ve sol) bring them in the precipitated
forms. This type of coagulation is called mutual coagulation.
(iii) By boiling: When a sol is boiled, the adsorbed layer is disturbed due to increased
collisions with the molecules of dispersion medium. This reduces the charge on
the particles and ultimately leads to settling down in the form of a precipitate.
(iv) By cooling : Certain sol can also be coagulated by lowering temperature. For
example, accumulation of cream on the surface of milk on cooling. This is because
at lower temperature the Brownian motion becomes less effective.
(v) By persistent dialysis: On prolonged dialysis, traces of the electrolyte present in
the sol are removed almost completely and the colloids become unstable and
ultimately coagulate.
(vi) By addition of electrolytes: When excess of an electrolyte is added, the colloidal
particles are precipitated. The reason is that colloids interact with ions carrying
charge opposite to that present on themselves. This causes neutralisation leading to
their coagulation. The ion responsible for neutralisation of charge on the particles
is called the coagulating ion. A negative ion causes the precipitation of positively
charged sol and vice versa.
 Coagulation in value or flocculation value
The minimum concentration of an electrolyte in millimoles per litre required to
cause precipitation of one litre of a colloidal solution in two hours is called
(coagulation in value or flocculation value) of the electrolyte for the sol. The smaller
the quantity needed the higher will be the coagulating power of an ion.
Comparision of relative coagulating power of two electrolyte for the same colloidal
solution :
1
Coagulating power 
coagulation value

coagulating power of electrolyteA coagulation valueB


coagulating power of electrolyteB coagulation valueA
Factor-Affecting Coagulations :
(i) Nature of sols : The lyophobic colloid can easily coagulate because it is a less stable
colloid, but lyophilic colloids coagulate hardly.
(ii) Nature of electrolyte : In equimolar electrolyte, strong electrolyte have greater
coagulating power than weak electrolyte. Example : 0.1M NaCl > 0.1M
CH3COOH.
Hardy-Schulze Rule : It has been observed that, generally, the greater the valence of
the flocculating ion added, the greater is its power to cause precipitation. This is
known as Hardy-Schulze rule.
In case of positive charged sol, the coagulating power of anion is in the order of
[Fe(CN)6]4– > PO43– > SO42– > Cl–
In case of negative charged sol, the coagulating power of cation is in the order of
Al3+ > Ba2+ > Na+.
The coagulation value decrease with increase in charge of the coagulating ion.
Coagulation of lyophilic sols:
There are two factors which are responsible for the stability of lyophilic sols. These
factors are the charge and solvation of the colloidal particles.When these two factors
are removed, a lyophilic sol can be coagulated. This is done (i) by adding an
electrolyte and (ii) by adding a suitable solvent. When solvents such as alcohol and
acetone are added to hydrophilic sols, the dehydration of dispersed phase occurs.
Under this condition, a small quantity of electrolyte can bring about coagulation.
 PROTECTION OR PROTECTIVE ACTION :

 The property of lyophilic sols to prevent the

precipitation or coagulation of a lyophobic sol
is called Protection.
O
O O OOO  The lyophilic sol used for this purpose
O Lyophllic sol.
(Protective colloid) are called Protective Colloid.
OO
OO OOO

 lyophilic sols form a thin layer around

OO OOOO

lyophobic sol or around the ions furnished

by electrolyte and therefore the coagulation
O

Lyophobic sol.
O

can not take place (as the size does not

O

(Protected
OO
O O OO
colloid) increase much).
[Protection of lyphobic sol.]
 Gelatin, Albumin, Gum Arabia, Potato Starch are some
of the examples of Protective colloids.
 The lyophilic colloids differ in their protective power. The
protective power is measured in terms of Gold number.
 Gold number : (Zsigmondy)

 The number of milligrams of a hydrophilic colloid that will

just prevent the precipitation of 10 ml of standard gold sol
on addition of 1 ml of 10% NaCl solution is known as Gold
number of that protector (Lyophilic colloid).

 The smaller the gold number of a protective

lyophilic colloid, greater is its protection power.
Gold Number of some hydrophilic colloids
𝟏
Lyophilic Colloid Gold Number Protection Capacity 
𝐆𝐨𝐥𝐝  𝒏𝒖𝒎𝒃𝒆𝒓
Gelatin 0.005 - 0.01
Egg albumen 0.08 - 0.1 𝐌𝐚𝐬𝐬  𝐨𝐟  𝐥𝐲𝐨𝐩𝐡𝐢𝐥𝐢𝐜  𝐬𝐨𝐥  (𝒎𝒈)
Gold number =
𝐕𝐨𝐥𝐮𝐦𝐞  𝐨𝐟  𝐥𝐲𝐨𝐩𝐡𝐨𝐛𝐢𝐜  𝐬𝐨𝐥  (𝒎𝑳)
Gum arabic 0.10 - 0.15
Potato - starch 25
 The precipitation of the gold sol is indicated by a colour change from Red to Blue
when the particle size just increases.
 Gelatin has the maximum protective power.
3.7 Emulsions
These are liquid-liquid colloidal systems, i.e., the dispersion of finely divided droplets in
another liquid. If a mixture of two immiscible or partially miscible liquids is shaken
emulsion is obtained. Generally, one of the two liquids is water. There are two types of
emulsions.
(i) Oil dispersed in water (O/W type) : In this emulsion, oil is the dispersed phase and
water is the dispersion medium. It is denoted by O/W or O in W. For example, milk
(liquid fat dispersed in water), vanishing cream.
(ii) Water dispersed in oil (W/O type) : : In this emulsion, water is the dispersed phase
and oil is the dispersion medium. It is denoted by W/O or W in O. For example, butter,
cream.
Preparation of emulsion (Emulsification) : Emulsification is the process of preparation of
emulsion. Generally, an emulsion is prepared by a mixture of the immiscible liquid. To
prevent the separation of layers and to get the stable emulsion, a small quantity of the third
substance is added. This substance which stabilizes the emulsion is called emulsifier or
emulsifying agent.
The commonly used emulsifying agents are soaps, detergents and lyophilic colloids.
Casein, a lyophilic colloid present in milk, acts as an emulsifier as it forms a protective
layer around fat molecules dispersed in water. Hence milk is a fairly stable emulsion.
Function of emulsifier : The main function of emulsifier or emulsifying agents is to lower
the interfacial tension (surface tension) between oil and water and thus helps the
intermixing of two liquids.
For example, a molecule of a soap or detergent (emulsifier) gets concentrated at the
interface between oil and water. The polar end of the emulsifier is in water and non-polar
end is in oil as shown in figure. In a soap, RCOONa, R is the non-polar end, whereas
COO– Na+ is the polar end.
Properties of emulsion :
(i) The size of particles of the dispersed phase of an emulsion is usually larger than in
sols.
(ii) Emulsions can be diluted with any amount of the dispersion medium.
(iii) The droplets in emulsions are often negatively charged and can be precipitated by
electrolytes.
(iv) Like colloidal particles, emulsions exhibit properties such as Tyndall effect, Brownian
movement (provided the particles are not too large), electrophoresis, coagulation, etc.
(v) Emulsions can be broken into constituent liquids (Coagulation) by heating, freezing,
centrifuging, chemical methods, etc.
 APPLICATIONS OF COLLOIDS :
Colloids are widely used in the industry.

High voltage (i) Electrical precipitation of smoke :

electrode
(30000 volts Gases free  Smoke is a colloidal solution of solid particles such
or more) from carbon as carbon, arsenic compounds, dust, etc. in air.
particles
 The smoke, before it comes out from the chimney,
is led through a chamber containing plates having
a charge opposite to that carried by smoke particles.
Smoke
 The particles on coming in contact with these plates
Precipitated ash lose their charge and get precipitated. The particles
thus settle down on the floor of the chamber. The
Fig : Cottrell smoke precipitator precipitator is called Cottrell precipitator.
(ii) Purification of drinking water:
The water obtained from natural sources often contains suspended impurities. Alum
is added to such water to coagulate the suspended impurities and make water fit for
drinking purposes.

(iii) Medicines :
Most of the medicines are colloidal in nature.
Colloidal medicines are more effective because they have large surface area and
are therefore easily assimilated.
(iv) Tanning :

 Animal hides are colloidal in nature. When a hide, which has positively charged particles, is
soaked in tannin, which contains negatively charged colloidal particles, mutual coagulation
takes place. This results in the hardening of leather. This process is termed as tanning.
 Chromium salts are also used in place of tannin.

(iv) Formation of delta: River water is a colloidal solution of clay. Sea water contains a
number of electrolytes. When river water meets the sea water, the electrolytes
present in sea water coagulate the colloidal solution of clay resulting in its
deposition with the formation of delta.
Q.1 On adding 1mL solution of 10% NaCl to Q.2 20 litres of a negative sol required
10 ml gold sol in presence of 0.025 g 0.104 g BaCl2 for its coagulation.
starch so that coagulation is just Determine the coagulation value of
prevented then what will be gold electrolyte ?
number of starch ?
(1) 0.25 (2) 2.5 Sol.1
(3) 25 (4) 0.025    ( )
Moles of BaCl2 =
  
Sol.1 1g = 1000 mg .
wt. of Starch = 25 mg Moles of BaCl2 = = 0.5 × 10–3 mol

𝐌𝐚𝐬𝐬  𝐨𝐟  𝐥𝐲𝐨𝐩𝐡𝐢𝐥𝐢𝐜  𝐬𝐨𝐥  (𝒎𝒈) m moles of BaCl2 = 0.5 m moles

Gold no. =
𝐕𝐨𝐥𝐮𝐦𝐞  𝐨𝐟  𝐥𝐲𝐨𝐩𝐡𝐨𝐛𝐢𝐜  𝐬𝐨𝐥  (𝒎𝑳)
20 L of Negative sol  0.5 m moles
×
Gold no. = = 25  1 L of Negative sol 
.
= 0.025
Q3. What is the correct sequence of the increasing
coagulation value of the following electrolyte for the
coagulation of ferric hydroxide solution :-
(I) Na3PO4 (II) KCI
(III) K2SO4 (IV) K4[Fe(CN)6]

(A) IV > I > III > II (B) II > III > I > IV
(C) I > II > III > IV (D) IV > III > II > I

Sol.
Ferric hydroxide solution have positive charge. So
order of coagulation value.

KCI > K2SO4 > Na3PO4 > K4[Fe(CN)6]

Charge coagulation value