SURFACE

CHEM STRY

JEETENDRA K ARYA
7077 6066 22

 SURFACE CHEMISTRY
!

1. Adsorption 2. Colloids 3. Catalysis

#1. Adsorption
INTRODUCTION
It has been known that the surface of a liquid is in a state of strain or unsatura-
tion due to the unbalanced or residual forces which act along the surface of a
liquid. Similar to it, the surface of a solid may also have residual forces or
valances. Thus, the surface of a solid has a tendency to attract and to retain
molecules of other species (gas or liquids) with which such surfaces come in
contact. This phenomenon of surfaces is termed as adsorption.

Adsorption : The accumulation of molecular species at the surface rather than in the bulk of a solid or
liquid is termed adsorption.

Absorption : The accumulation of molecular species in the bulk of a solid or liquid is termed absorption.
 !

The material on the surface of which adsorption takes place is called the adsorbent
and the substance adsorbed is called the adsorbate.

Adsorption stands for different concentrations of a substance at an interface.

If the concentration is more at an interface, the adsorption is said to be positive; if
the concentration is less at an interface, the adsorption is said to be negative. The
process of removal of an adsorbed substance from the surface of a solid is known as
desorption. "

CHARACTERISTICS OF ADSORPTION
The various characteristics of adsorption are as follows : -

(i)  Adsorption is a spontaneous process and takes place in no time.

(ii)  The phenomenon of adsorption can occur at all surfaces and five types of interfaces can exist: gas -solid,
liquid-solid, liquid-liquid, solid-solid and gas-gas. The gas-solid interface has probably received the most
attention in the literature and is the best understood. The liquid- solid interface is now receiving much atten-
tion because of its importance in many electrochemical and biological systems.

(iii)  It is accompanied by a decrease in the free energy of the system, i.e., ΔG. The adsorption will continue
to such an extent that ΔG continues to be negative.
Adsorption classified into 2 categories on the basis of bond formation :-

Table 1

PHYSISORPTION CHEMISORPTION

It arises because of van der Waals’ forces It is caused by chemical bond formation

Enthalpy of adsorption is low 20 - 40 kJ mol–1 Enthalpy of adsorption is high 80 - 240 kJ mol–1

It results into multimolecular layers on adsorbent surface It results into unimolecular layer.
under high pressure.

It is reversible in nature. It is irreversible.

It is not specific in nature. It is highly specific in nature.

It depends on the nature of gas. It also depends on the nature of gas.

More easily liquefiable gases are adsorbed readily. Gases which can react with the adsorbent show
chemisorption.

Low temperature is favourable for adsorption. High temperature is favourable for adsorption.
It decreases with increase of temperature. It increases with the increase of temperature then decrease.

No appreciable activation energy is needed. High activation energy is sometimes needed.

Examples of physisorption are as follows: Examples of chemisorption are as follows:

(i) Adsorption of various gases on charcoal (i) Adsorption of oxygen on tungsten."
(ii) Adsorption of nitrogen on mica (ii) Adsorption of hydrogen on nickel.
(iii) Ethyl alcohol vapours condensed on
. the divided nickel.
 Factor governing the extent of adsorbtion :-
1. Nature of adsorbent #
2. Nature of adsorbate
3. Surface area of Adsorbent !
4. Temperature
5. Pressure

• Nature of adsorbent and adsorbate :

The amount of the gas adsorbed depends upon the nature of the adsorbent and the gas (adsor-
bate) which is to be adsorbed."
Gases like SO , NH , HCl and CO which liquefy more easily are adsorbed more readily than the
2 3 2
permanent gases like H , N and O which do not liquefy easily. This is because the easily liquefi-
2 2 2
able gases have greater vander-waal’s or the molecular forces of attraction or cohesive forces.

As the critical temperatures of the easily liquefiable gases are more than the permanent gases, it
follows that higher the critical temperature of the gas (adsorbate), the greater the extent of ad-
sorption.

• Surface area of the adsorbent :

The extent of adsorption of gases by solids depends upon the exposed surface area of the adsor-
bent. It is well known that larger the surface area of the adsorbent, the large will be the extent of
adsorption under given conditions of temperature and pressure. It is for this reason that silica gel
and charcoal obtained from different animal and vegetable sources become activated because
they posses a porous structure and thereby render a larger surface.

• Temperature :
For a given adsorbate and a adsorbent, the extent of adsorption depends upon the temperature of
the experiment. As discussed earlier, adsorption usually takes place with the evolution of heat.
Therefore, according to the Le chatelier's principle, the decrease in temperature will increase the
adsorption and vice- versa. An example is that if the temperature of the coconut charcoal is low-
ered from –29 to –78 C, the amount of nitrogen gas adsorbed increases from 20 to 45 mL. under
the same pressure.

• Pressure :
For a given gas and a given adsorbent, the extent of adsorption depends on the pressure of the
gas. Adsorption of a gas is followed by a decrease of pressure. Therefore, in accordance with Le
chatelier's principle, the magnitude of adsorption decreases with the decrease in pressure and
vice-versa. The variation of adsorption with pressure at constant temperature is expressed graph-
ically by a curve known as adsorption isotherm.
Freundlich Adsorption Isotherm
#

x 1
Freundlich Adsorption Isotherm Equation => = K . Pn
m

Limitation of Freundlich Adsorption Isotherm

 #2. Colloids
Thomas graham (1861) classified substances into two categories on the basis of their rates of diffusion .

Crystalloids : They diffuse rapidly in solution and can rapidly pass through animal or vegetable
membranes, e.g:- urea, sugar, salts and other crystalline substances.
Colloids : They diffuse very slowly in solution and can not pass through animal or vegetable
membranes, e.g. starch, gelatin, silicic acid, proteins etc. Since this class of substances generally
exist in amorphous or gelatinous condition and hence the name colloid meaning "glue form". 


Note : - Actually every substance irrespective of its nature can be crystalloid or colloid under
suitable conditions. For example: 

(i)  NaCl though a crystalloid in water behaves like a colloid in benzene. 

(ii)  Soap is a colloid in water, while it behaves like a crystalloid in benzene. 

Table 1

TRUE SOLUTION COLLOID SUSPENSION

Nature Homogenous Heterogenous Heterogenous
Particle Size less than 1 nm 1 nm - 100 nm greater than 100 nm
Appearance Transparent Transluscent opaque
Filtration Not possible by normal Possible by ultra-filters but Possible by both
filter as well as ultra-filters not by normal filters
Sedimentation Don`t settle Settle only by Settle automatically
centrifugation

What are colloids ?

Colloids are the heterogenous mixture containing the particle in the size range of 1 to 100 nm ;
they are translucent in appearance , the component can`t be separated using ordinary filter .
The particle of colloids can settle down by centrifugation .

A dispersed phase : It is also known as discontinuous or inner phase. It consists of

discrete particles significantly larger than ordinary molecules and in this small particles
of solute is diffused in solvent. 

A dispersion medium : It is also known as continuous phase or outer phase : It is the
medium in which dispersed phase is present. This consists of continuously interlinked
molecules.

Colloidal solution ( Dispersion system ) = Dispersed phase + Dispersion medium

Colloidal Solution : If dispersion of a solid (dispersed phase) in a liquid (dispersion medium),

the resulting solution is called colloidal solution.
Sol : If dispersion of a solid in a liquid, solid or gaseous medium, the resulting solution is called sol. 

Solid aerosol: The dispersion of a solid (dispersed phase) in a gas( dispersion medium).
Liquid aerosol : If the dispersed phase is a liquid and the dispersion medium is a gas, the resulting sol is
called a liquid aerosol. 

Emulsion : When a liquid is dispersed in another liquid the resulting system is called an emulsion.
Gel : If colloidal system becomes fairly rigid, it is termed as a gel.

MENTOR :- JEETENDRA K ARYA MOB:- 7077 6066 22

 Depending upon whether the dispersed phase and the dispersion
cation medium
CLASSIFICATION OFare solids, liquids
COLLOIDS :- or gases, eight types of colloidal systems
on Physical are possible. A gas mixed with another gas forms a homogeneous
# Based on the physical state of dispersed phase & dispersion medium
f Dispersed mixture and hence is not a colloidal system. The examples of the
# Based on the nature of particles of dispersed phase
and various types of colloids along with their typical names are listed
sion # Based on the interaction of dispersed phase & dispersion medium
in Table 5.4.
m
Table
# 1. Based on the physical 5.4:
state of Typesphase
dispersed of Colloidal
& dispersionSystems
medium :-

Dispersed Dispersion Type of Examples

phase medium colloid

Solid Solid Solid sol Some coloured glasses and gem stones
Solid Liquid Sol Paints, cell fluids
Solid Gas Aerosol Smoke, dust
Liquid Solid Gel Cheese, butter, jellies
Liquid Liquid Emulsion Milk, hair cream
Liquid Gas Aerosol Fog, mist, cloud, insecticide sprays
Gas Solid Solid sol Pumice stone, foam rubber
Gas Liquid Foam Froth, whipped cream, soap lather

# 2. Based on the nature of particle of dispersed phase :-

try 134

Multimolecular Colloids
On dissolution, a large no. of atoms or smaller molecules aggregate together, where the
particle size ranges from 1 nm to 100 nm. These are called multimolecular colloids.
Eg :- Colloidal solution of Sulphur in water
Colloidal solution of Metals & Non-metals .
Colloidal solution of Metal sulphide & Metal hydroxide .
Macromolecular Colloids
Macromolecules or polymer in suitable solvent form a solution in which the particle size
range from 1 nm - 100 nm . These are called macromolecular colloids.
Eg :- Colloidal solution of Starch
Colloidal solution of Gelatin
Colloidal solution of Glue
Associated Colloids ( Micelles )
Substances which show electrolytic nature at low concentration but colloidal nature at high
concentration due to the formation of aggregates whose particle size ranges from 1 nm - 100
nm. These are known as associated colloids .
Eg :- Soap & Detergent
Soap = Na+ / K+ salts of higher fatty acids. Sodium stearate ( CH3(CH2)16COO- Na+)
Detergent = Sodium laurylsulphate ( CH3(CH2)11SO4- Na+ )

What is micelles ?
A micelle is an aggregate of surfactant molecules dispersed in a liquid colloid .

MENTOR :- JEETENDRA K ARYA MOB:- 7077 6066 22

 At low concentration :-
R-COONa ——> R-COO- + Na+
colloids

At high concentration :-
n R-COONa ——> (R-COO-)n + n Na+
micelles

# 3. Based on the interaction of dispersed phase & dispersion medium :-

Lyphobic or solvent-hating : When the dispersed phase has less affinity for the dispersion
medium, the colloids are termed as lyophobic. But when the dispersion medium is water,
they are given the name hydrophobic. Substances like metals, etc. which have particles of
size bigger than the colloidal particles or NaCl which has particles of size smaller than the
colloidal size, fall in this category. Such substances are brought into colloidal state with
difficulty. 

Lyophilic or solvent loving : When dispersed phase has a greater affinity for the
dispersion medium, the colloids are termed as lyophilic and when the dispersion medium is
water, they are given the name hydrophilic. They are also called natural colloids,
substances like proteins, starch and rubber etc. are grouped under this category. 


Difference between Lyophilic Colloids & Lyophobic Colloids :-

Table 1
LYOPHILIC LYOPHOBIC

Lyophilic means medium loving . Lyophobic means medium hating .

Dispersed particle are strongly attracted by Dispersed phase particle are not attracted by
Dispersion medium . Dispersion medium .

It is directly prepared . It is prepared by a special method .

It is more stable . It is less stable .

It is a reversible colloid . It is an irreversible colloid .

It can not be easily coagulated . It can be easily coagulated by the addition of

electrolyte .

Macromolecular colloids are Lyophilic in nature . Multimolecular colloids are Lyophobic in nature .

It mainly consists of Organic Polymer . It mainly consists of Inorganic colloids

Eg :- Starch , Glue, Gelatin etc Eg :- Sulphur sol , gold sol , metal sol etc

MENTOR :- JEETENDRA K ARYA MOB:- 7077 6066 22

# Methods of preparation of colloids :-

Preparation of lyophilic sols : …

Many organic substances like gelatin, starch, agar, egg albumin, glycogen etc dissolve readily
in water either in cold or on warming to give colloidal solutions directly. These are the
lyophilic colloids. For example :- sols of egg albumin or glycogen can be prepared by
dissolving 1-2 g of the finely ground substance in 100 mL of distilled water and then allowing
it to stand for two hours after constant stirring. After two hours, the solutions are filtered.

Preparation of lyophobic sols:

(i) By dispersion of coarse particles (Dispersion method). Here we start with bigger
particles and break them down to the colloidal size.
(ii) By inducing molecular particles to form large aggregates (condensation method). Here
we start with particles of molecular dimensions and condense them to the colloidal size.

# Dispersion Method

1. Mechanical dispersion : The substance is

first finely powdered and a coarse suspension
is made by shaking the powdered substance
with the dispersion medium. This suspension
is then passed through a colloid mill consisting
of two discs, moving in opposite directions at
a very high speed (fig.I) The particles of the
suspension are subjected to a great shearing
force and break down to the colloidal
dimension.

2. Electrical Dispersion Bredig's arc method :

This is commonly used method for preparing
the colloidal solutions of metals. An electric
arc is struck between two metallic rods kept
under the liquid (dispersion medium). A
current of 10 amperes and a voltage of 100 to
300 volts is generally employed. The liquid is
kept cooled by surrounding it with a cooling
mixture. Tiny particles of the metal break
away from the roads and disperse in the liquid.
Gold, platinum, silver, copper and such other
metals can thus be obtained in the colloidal
form.

3. Peptization : The process of bringing a

precipitated substance back into the colloids
state is known as peptization. It is carried out
by the addition of an electrolyte.

MENTOR :- JEETENDRA K ARYA MOB:- 7077 6066 22

# Condensation Method

1. Oxidation : Sols of some non-metals are 1. Oxidation :

obtained by oxidation. 2 H2S + SO2 ——> 3 S + H2O
. Colloidal Sol 


2. Reduction : Sols of some metals are 2. Reduction :

obtained by the reduction of their salts. Gold 2AuCl3 + 3 HCHO + 3H2O —> 2Au + 3 HCOOH + 6HCl
sols are made by reduction of AuCl3 solution . Gold Sol

with reducing agents like tannic acid, HCHO,

H2O2, phosphorus, hydrazine etc.

3. Hydrolysis : This method is generally

employed for the preparation of sols of 3. Hydrolysis :
number of a hydroxides and hydrous oxides. FeCl3 + 3H2O ——> Fe(OH)3 + 3 HCl
Fe(OH)3 and Al(OH)3 sols are obtained by . Iron Sol

boiling solution of the corresponding

chlorides. 


PURIFICATION OF COLLOIDS :-
# DIALYSIS
# ELECTRO-DIALYSIS
# ULTRA-FILTRATION

Dialysis : This method is based on the fact that colloidal particles are retained by animal
membrane or a parchment paper while electrolytes pass through them. The sol is taken in a
parchment or cellophane bag, which itself is placed in running water in a trough. Gradually the
soluble impurities diffuse out leaving a pure sol behind. Dialysis is a slow process and it takes
several hours and sometimes even days for complete purification.

Electrodialysis : Dialysis can be fastened by applying an electric field if the substance

in true solution is an electrolyte. This process is then called electrodialysis. By means of
electrodialysis it is possible to get a colloid in pure state in short time, although the electric
current does not affect non-conducting impurities such as alcohol, sugar, etc.

Ultra filtration : This is a method not only for purification of the sol but also for
concentrating the sol. The pores of the ordinary filter paper are large enough for the colloidal
particles to pass through. But if the pores are made smaller the colloidal particles may be
retained on the filter paper. This process is known as ultra filtration. 


MENTOR :- JEETENDRA K ARYA MOB:- 7077 6066 22

# Properties of colloids :-

1. Colligative properties:

Colloidal particles being bigger aggregates, the number of particles in a colloidal solution
is comparatively small as compared to a true solution. Hence, the values of colligative
properties (osmotic pressure, lowering in vapour pressure, depression in freezing point
and elevation in boiling point) are of small order as compared to values shown by true
solutions at same concentrations.

2. Optical properties :

The scattering of white light by colloidal particles is

called Tyndal effect .This effect was first observed by
Faraday and later studied in detail by Tyndall and is
termed as Tyndall effect. The bright cone of the light is
called Tyndall cone .The Tyndall effect is due to the
fact that colloidal particles scatter light in all directions
in space. This scattering of light illuminates the path of
beam in the colloidal dispersion.

3. Mechanical properties :

The random & rapid zig-zag motion of dispersed phase

particle in a colloidal solution due to continuous collision of
dispersed phase particle and dispersion medium particles is
called Brownian Motion

4. Electrical properties :

The movement of sol particle under the influence of electric

field towards oppositely charged electrode is called
Electrophoresis .

Cataphoresis = If the sol discharges on cathode, then it is called Cataphoresis.

Anaphoresis = If the sol discharges on anode, then it is called Anaphoresis.

MENTOR :- JEETENDRA K ARYA MOB:- 7077 6066 22

What is peptisation and peptising agent ?
Conversion of freshly prepared ppt into colloidal solution is called peptisation .
The minimum amount of electrolyte required to prepare colloid from precipitate is
called peptising agent .

What is coagulation and coagulating agent ?

Conversion of colloids into suspension by adding of small amout of electrolyte is
called coagulation / flocculation .
The minimum amount of electrolyte required to prepare suspension from colloid is
called Coagulating agent .

There are five methods to form suspension :-

1. By Mutual Coagulation ( Physical method )
2. By Prolonged Dialysis
3. By Centrifugation
4. By Electrophoresis
5. By the addition of electrolytes

Coagulation Value / Flocculation Value :-

The minimum amout of an electrolyte required in mili-moles, which can coagulate 1 litre of
colloidal solution is called Coagulation Value .
Its SI unit is milimoles / litre which means Molarity .
NOTE :- Less is the coagulating value , more is the coagulating power .

HARDY-SCHULZE RULE :-

MENTOR :- JEETENDRA K ARYA MOB:- 7077 6066 22

 The systematic study of the effect of various foreign substances
rates of chemical reactions was first made by Berzelius, in 18
#3. Catalyst suggested the term catalyst for such substances.
The systematic study of the effect Substances, which substances
of various foreign alter the rate of rates
on the a chemical
of reactio
chemical reactions was first madethemselves remain
by Berzelius, chemically and quantitatively unchanged a
in 1835.
He suggested the term catalyst for such substances. as catalysts, and the phenomenon is kn
reaction, are known
catalysis. You have already studied about catalysts and its func
in Section 4.5.
What is catalyst and catalysis ?
A catalyst is a substance which Promoters
increases and
the poisons
rate of a reaction without itself
Promoters are substances
undergoing any permanent chemical change. Catalysis is the that enhance
process of the activity of a catalys
increasing
poisons decrease the activity of a catalyst. For example, in
the rate of a chemical reaction by adding
processafor
substance known
manufacture as a catalyst
of ammonia, .
molybdenum acts as a pr
for iron which is used as a catalyst.
NOTE : Inhibitors are sometimes referred to as "negative
Fe(s) catalysts" since they
N2(g) + 3H2(g) Mo(s) 2NH3(g)
decrease the reaction rate.
5.2.1 Catalysis can be broadly divided into two groups:
Homogeneous and
Catalyst can be broadly divided into (a) Homogeneous
Promoters catalysis
and Poisons :-
Heterogeneous
Promoters are substances that enhance theWhen the of
activity reactants
a catalystand thepoisons
while catalyst are in the same pha
decrease
Catalysis
activity of a catalyst. liquid or gas), the process is said to be homogeneous cataly
following are some of the examples of homogeneous cataly
For example, in Haber’s process for manufacture of ammonia, molybdenum acts as a
(i) Oxidation of sulphur dioxide into sulphur trioxide with d
promoter for iron which is used as a catalyst.
in the presence of oxides of nitrogen as the catalyst in t
chamber process.
NO(g)
2SO2(g) + O2(g) 2SO3(g)
The reactants, sulphur dioxide and oxygen, and the c
For example, in Catalytic Hydrogenation ofnitricalkynes to alkenes,
oxide, are all inBaSO4
the sameactsphase.
as a poison
for palladium . (ii) Hydrolysis of methyl acetate is catalysed by H+ ions fu
by hydrochloric acid.
HCI(l)
CH3COOCH3(l) + H2O(l) CH3COOH(aq) + CH
Both the reactants and the catalyst are in the same ph
(iii) Hydrolysis of sugar is catalysed by H+ ions furnis
Catalysis can be broadly divided into Homogeneous
sulphuricand Heterogeneous catalysis :-
acid.
H2SO4(l)
C H22O11(aq) + H2O(l) C6H12O6(aq) + C6H12O6
When the reactants and the catalyst are in the 12same phase (i.e.,
liquid or
Solution gas),
Glucose Fructo
the process is said to be homogeneous catalysis.
Solution
A catalytic process in which the catalyst and the reactants are in different phases is
Both the reactants and the catalyst are in the same ph
called heterogeneous catalysis. This process is also called contact or surface
(b) Heterogeneous catalysis
catalysis. The catalytic process in which the reactants and the catalys
(ii) Combination between dinitrogen and dihydrogen to form
different phases
ammonia in theispresence
known of asfinely
heterogeneous
divided iron incatalysis. Som
Haber’s proces
examples of heterogeneous
N2(g) + 3H
Fe(s) catalysis are given below:
(ii) Combination 2(g)
between 2NH 3(g)
dinitrogen and dihydrogen to
Homogeneous Catalysis (i) Oxidation Heterogeneous
of sulphur dioxide Catalysis
into sulphur trioxide
ammonia in the
The reactants presence
are in gaseous of finely
state divided
while the iron in Haber’s
catalyst p
is in th
presence
solid state.of Pt. Fe(s)
N2(g) + 3H 2(g)
Pt(s) 2NH3(g)
(ii) 2SOof2(g)
(iii) Combination
Oxidation between
ammonia 2SO 3(g)
into dinitrogen
nitric oxide andin thedihydrogen
presence
The reactants
platinum gauze are
in in gaseous
Ostwald’s state while the catalyst is
process.
ammonia
The reactant in theis presence
in gaseous of finely
state divided
while the iron in Habe
catalyst is
solid state.
solid state.
4NH
N2(g) (g) + 5O
3 + 3H 2(g) (g)
Pt(s)
Fe(s)
4NO(g)
2NH + 6H O(g)
(iii) Oxidation of ammonia 2 into 3(g)
nitric oxide
2
in the prese
Chemistry 128 The
The reactants
reactants
platinum are
gauzeare in gaseous
in gaseous
in Ostwald’s state while the catalyst
state while
process. is in th
the catalys
solid state.
solid state.
4NH3(g)of+ vegetable
Pt(s)
5O2(g) oils 4NO(g) + 6H2O(g)
(iv) Hydrogenation in the presence of finely divide
(iii) Oxidation
nickel as of ammonia
catalyst. into nitric oxide in the p
The reactants are in gaseous state while the catalyst is
platinum gauzeoils(l)
Vegetable
solid state. in Ostwald’s
+ H2(g)
Ni(s) process.
Vegetable ghee(s)
Pt(s)
4NH
One of the
(iv) Hydrogenation 3(g) of
+ vegetable
reactants 5O is2(g)
in liquid 4NO(g)
oilsstate +the
6H
andpresence
in the 2O(g)
other in finely
of gaseoud
state while the catalyst
nickel as catalyst. is in the solid state.
The reactants are in gaseousNi(s)state while the catalys
5.2.2 Adsorption
MENTOR :- JEETENDRA K ARYA Theory solid Vegetable
This theory
state. explains oils(l) +H 2(g)
the mechanism
MOB:- ofVegetable
7077 6066 22ghee(s)
heterogeneous catalysi
of Heterogeneous The old theory,
One of the reactantsknown as adsorption
is in liquid theory of catalysis, wa
(iv) Hydrogenation
Catalysis of vegetable oilsstate
in theand the otherofinfin
presence
that the reactants in gaseous state or in solutions, are adsorbe
g
Adsorption Theory of Heterogeneous Catalysis

The old point of view was that when the catalyst is in solid state and the reactions are
in gaseous state or in solutions, the molecules of the reactants are adsorbed on the
surface of the catalyst. The increased concentration of the reactants on the surface
influences the rate of reactions. Adsorption being an exothermic process, the heat of
adsorption is taken up by the surface of the catalyst, which is utilised in enhancing
the chemical activity of the reacting molecules. The view does not explain the
specificity of a catalyst.
The modern adsorption theory is the combination of intermediate compound
Adsorption
formation theory and the old adsorption theory. The catalytic activity of
is localised on
reacting molecules
the surface of the catalyst.
+ A +B

The mechanism involves five steps : Reacting

molecules
(i) Diffusion of reactants to the Catalyst
surface surface
of the catalyst.
having
Adso
reactin
free valencies
(ii) Adsorption of reactant molecules on the surface of the catalyst.
(iii) Occurrence Fig.
of chemical
5.3 reaction on the catalyst’s surface through formation of
Adsorption of Desorption of
an intermediate
reacting product molecules
(iv) Desorption of reaction products away from the catalyst
molecules, + A –Bsurface.
formation of
(v) Diffusion ofintermediate
reaction products
and away from the catalyst surface. 

Product
desorption of
Adsorption of
products Catalyst
reacting molecules Intermediate
A
+ A +B even in small quantities. It however, does not explain th
B
catalytic promoters and catalytic poisons.
Reacting
molecules
Important features of solid catalysts
Adsorption of
Catalyst surface having
(a) Activity reacting molecules
free valencies

Fig. 5.3 The activity of a catalyst depends upon the strength of che
Adsorption of Desorption of
to a large
extent. The reactants must get adsorbed
reacting product molecules
strongly on to the catalystA to become active. However,
molecules, + A –B
formation of not get adsorbed so strongly B that they are immobilised
Product
intermediate and reactants are left with no space on the catalyst’s s
desorption of
products Catalyst
adsorption. It has been found that for hydrogenation re
Intermediate
catalytic activity increases from Group 5 to Group 11 m
even in small quantities. It however, does not explain the action of
maximum activity being shown by groups 7-9 eleme
Activity and Selectivity
catalytic promoters and catalytic poisons.
periodic table (Class XI, Unit 3).
Important features of solid catalysts
Pt
Activity (a) Activity 2H 2(g) + O2(g)
Selectivity 2H2O(l)
The activity of a catalystThe activity
dependsof upon
a catalyst
(b) depends
the Theupon
Selectivity the strength
selectivity of chemisorption
of a catalyst is its ability to direct
to a large extent. The reactantsa musttoget
reaction adsorbed
yield a reasonably
particular product.
strength of chemisorption to a large extent. The
strongly on to the catalyst to selectivity of However,
become active. a catalyst is
they its ability to direct a react
must
It will direct single product
not getthrough different
adsorbed a particular
so strongly product.
that they are immobilisedForandexample,
other starting with H2 an
catalyst. reactants are left with using
no space on the catalysts,
different catalyst’s surface
we getfordifferent products.
adsorption. It has been found that for hydrogenation reaction, the
catalytic activity increases from Group 5 to Group 11 metals with
(i) CH2=CH2 + H2 + Ni ——> activity
maximum CH3—CH 3
being shown by groups 7-9 elements of the
(ii) CH2=CH2 + H2 + Pt ——> CH —CH Unit 3).
periodic table (Class
3
XI,
Pt
3
2H2(g) + O2(g) 2H2O(l)
(iii)CH2=CH2 + H2 +(b) Pd ——> CH3—CH3
Selectivity
Thus,
The selectivity of a catalyst is its it can to
ability bedirect
inferred that the
a reaction action of a catalyst is high
to yield
a particular product.inFor example, starting with
nature, i.e., a given substanceH and CO, and
can act as a catalyst
22 only in a
2
MENTOR :- JEETENDRA K ARYA
using different catalysts, we get different products. MOB:- 7077 6066
reaction and not for all the reactions. It means that a substa
acts as a catalyst in one reaction may fail to catalyse anothe
 as synthesised for catalytic selectivity.
Zeolites are being very widely used as catalysts in petrochemical
Zeolitesfor
industries are being very
cracking widely used as
of hydrocarbons andcatalysts in petrochemical
isomerisation. An important
industries for cracking of hydrocarbons and isomerisation. An important
zeolite catalyst used in the petroleum industry is ZSM-5. It converts
zeolite catalyst used in the petroleum industry is ZSM-5. It converts
alcohols directly into gasoline (petrol) by dehydrating them to give a
alcohols directlycatalysis
Shape-Selective into gasoline (petrol) by dehydrating them to give a
Zeolites
mixture of hydrocarbons.
mixture of hydrocarbons.
aluminosilicates
• The catalytic with
reactionthree thatdimensional
dependsorganic upon network
the pore of silicates
structure of in
the which
catalyst
e
me Enzymes
Enzymes are
are complex
complex nitrogenous
nitrogenous organic compounds
compounds whichwhich are are and the
is some
produced silicon atoms are replaced by aluminium atoms giving
sis produced size ofby
aluminosilicates by living
theliving with
reactant plants
three
and
plants and
product
and animals.
dimensional
molecules
animals. TheyThey
network
is calledare of actually
silicates
shape-selective
arezeolites
actually protein protein
in which
catalysis
Al–O–Si
molecules framework.
of high The
molecular reactions
mass taking
and form place in
colloidal solutionsdepend in upon
water.
some
molecules
• size silicon
Zeolites areatoms
of high molecular
good aremass replaced
shape-selectiveand form by aluminium
colloidal
catalysts solutions
because atoms
in water. giving
the and shape of reactant and product molecules asofwell
their ashoneycomb-like
upon
They
They are
Al–O–Si very effective
are framework.effectiveThe catalysts;
reactions
catalysts; catalyse
catalyse taking numerous
numerousplace in reactions,
zeolites
reactions, especially
depend
especially upon
the
those
structures.
pores and
connected cavities
withof of
naturalthe zeolites.
processes. They are
Numerous found in
reactions naturethat as well
occur
those
the sizeconnected
and shape with natural
reactant processes. Numerous
and product reactions
molecules that
as occur
well as upon
as synthesised for catalytic selectivity.
the pores and cavities of the zeolites. They are found in nature as network
in
in• the
the They
bodies
bodies are of
ofmicroporous
animals
animals andandaluminosilicates
plants
plants to to with
maintain
maintain the three
the
life dimensional
life process
process are arewell of
catalysedZeolites
catalysed silicates are
by enzymes.being
enzymes.
infor which very
The
Thesome widely
enzymes
enzymes
silicon used
are,
are, as
thus,
atomsthus,catalysts
termed
termed
are in
replaced petrochemical
as biochemical
as biochemical
by aluminium atoms
as synthesised catalytic selectivity.
industries
catalysts
catalysts for
and cracking
the of
phenomenonhydrocarbonsis known and as isomerisation.
biochemical
biochemical An important
catalysis.
catalysis.
givingand
Zeolites are the
Al–O–Si phenomenon
being framework.
very widely is known
used asascatalysts in petrochemical
zeolite Many catalyst
enzymes used
have in theobtained
petroleum industry is ZSM-5. It living
converts
• Many
industries enzymes
Zeolites for havebeen
cracking
are being been
of obtained
hydrocarbons
very widely
ininpure
used pure
and
as
crystalline
crystalline state
isomerisation.
catalysts in
from
state from
An living
important
petrochemical
alcohols
cells. directly
However, the into
first gasoline
enzyme was (petrol)
synthesised by dehydrating
in the laboratory them in to
1969. give aindustries
cells.
zeolite However, the first in
enzyme was synthesised in the islaboratory Itinconverts
1969.
mixture
The forcatalyst
cracking
of
following used
hydrocarbons.
are some of theexamples
of hydrocarbons
the petroleum industry
andofisomerisation.
enzyme-catalysed ZSM-5.
reactions:
The
alcohols following are some
directly into of the examples
gasoline (petrol) of byenzyme-catalysed
dehydrating reactions:
them
e
•(i)(i) Inversion
An important
Inversion of cane
of cane
zeolite
sugar:
sugar:
catalyst
The
used
The invertase
invertase
in the
enzyme petroleum
enzyme
converts industry
converts
cane sugar
cane
istosugar
give a.
ZSM-5
Enzymes
mixture into of
are complex
hydrocarbons.
glucose and fructose.
nitrogenous organic compounds which are
is produced into glucose
by living andplants
fructose. and animals. They are actually protein
e Enzymes of
molecules arehigh complex
molecular nitrogenous
mass and form organic compounds
colloidal solutions in whichwater.are
s Enzyme
produced
They Catalysis
are very byeffective
living plants
catalysts; and animals.
catalyse numerous They reactions,
are actually especiallyprotein
molecules
those of high
connected with
(ii) Conversion molecular
naturalinto
of glucose mass
processes. and
ethyl alcohol:form
Numerous colloidal solutions
The reactions
zymase enzyme in
that occur water.
in(ii)the
Biochemical
They Conversion
are catalysts
of of
very glucose
converts
bodies effective
animals are
glucose known
catalysts;
into into
ethyl
and as
catalyse
alcohol
plants enzymes
ethyltoand carbonThe
alcohol:
numerous
maintain and the zymase
phenomenon
reactions,
dioxide.
the life process enzyme is known as
especially
are
those converts
biochemical
catalysed connected
C6Hby glucose Zymaseinto ethyl alcohol and carbon dioxide.
with
catalysis.
enzymes. natural
The2Cenzymesprocesses. Numerous
are, thus, termed as biochemical
reactions that occur
12O6(aq) 2H5OH(aq) + 2CO2(g)
catalysts
in the C Hand
bodies 12O6(aq)
6Glucose
theanimals
of phenomenon
Zymase
2Cand
2H
Ethyl is known
plants as biochemical
to maintain
5OH(aq) + 2CO2(g)
alcohol the life catalysis.
process are
catalysed
• Many
(iii)
Enzymes enzymes
Conversion
Glucose
are
by enzymes.complex
of have
starch The
beennitrogenous
enzymes
obtained
Ethyl
into alcoholin
maltose:
organic
are,
The pure thus,compounds
termed
crystalline
diastase enzyme
which
state fromare
biochemical
asconverts produced by
living
catalysts
cells.
(iii)livingHowever,
starch and
intothe
plants
Conversion the
and phenomenon
offirst enzyme
animals.
maltose.
starch into was
maltose:is known
synthesised asin biochemical
The diastase the laboratory
enzyme converts catalysis.
in 1969.
The• They following
Many
starch are are some
enzymes
actually
into have ofbeen
protein themolecules
examples
obtained
Diastase of
in
of enzyme-catalysed
pure crystallinemass
high molecular reactions:
state from
and living
form colloidal
2(C 6H 10O5)maltose.
n(aq) + nH2O(l) nC 12H22O11(aq)
cells. However,
(i)solutions
Inversion in the
of
Starch cane
water. first enzyme
sugar: The was synthesised
invertase
Diastase enzyme
Maltose in the laboratory
converts cane in 1969.
sugar
2(C6H 10O5)n(aq) + nH2O(l) nC H22O11(aq)
The following
into glucose are some
and of the
fructose.
(iv) Conversion of maltose into glucose: The examples of12enzyme-catalysed
maltase enzyme converts reactions:
Starch Maltose
maltose into
(i) Conversion glucose. The invertase
(iv) Inversion ofofcane sugar:
maltose into glucose: Theenzyme
maltaseconverts
enzyme cane sugar
converts
into
C12glucose
H22O
maltose 11(aq)
into and
+ H2fructose.
O(l)
glucose.
Maltase
2C6H12O6(aq)
Maltose Maltase Glucose
(ii) Conversion
C12H22O11(aq)of + glucose
H2O(l) into ethyl 2C6Halcohol:
12O6(aq)
The zymase enzyme
(v) converts
Decomposition of urea into
glucose into ethyl alcohol ammonia and carbon dioxide: The
and carbon dioxide.
Maltose
enzyme urease Zymase Glucose
catalyses this decomposition.
(v) C6H12O6(aq)of of
(ii) Decomposition
Conversion 2C into
urea HUrease
5OH(aq) + 2CO
ammonia 2(g) carbon
and The zymase The
dioxide:enzyme
NH2CONH2(aq) glucose
+ H2O(l)2 into ethyl alcohol:
2NH3(g) + CO 2(g)
enzyme
converts urease
Glucose glucose catalyses
intoEthylthis
ethyl decomposition.
alcohol
alcohol and carbon dioxide.
(vi) In stomach, theZymasepepsin enzymeUrease converts proteins into peptides
(iii) Conversion
NH CONH
C6H2in
while 12O 2(aq)
of
6(aq)
intestine, +the
starchH2into
O(l)
2C maltose:
2H5OH(aq)
pancreatic The
2NH diastase
+3(g)
2CO
trypsin + CO (g) enzyme
2(g) 2
converts proteinsconverts
into
starch
amino
(vi) In into maltose.
acids by
stomach, Ethyl
thehydrolysis.
pepsin alcoholconverts proteins into peptides
enzyme
Glucose Diastase
(iii) 2(C6in
(vii) while H10intestine,
Conversion
ConversionO5of
)nof
(aq)
milk+into
nH
starch O(l)
the2into
curd: It is annC
pancreatic
maltose: 12H22O
trypsin
enzymatic
The (aq)
converts
diastase
11 proteins
reaction brought
enzyme into
converts
about
amino by lacto
acids
starchStarch
into bacilli enzyme
by hydrolysis.
maltose. present in curd.
Maltose
Mechanism of enzyme catalysis
(iv) Conversion of maltose
(vii) milk intointo glucose:
curd: It is an
Diastase The maltase reaction
enzymatic enzyme converts
brought
2(C6H10O5)n(aq) E++nH 2O(l) nC H22O11Surface
12131 (aq) E Chemistry
maltose
about byinto
lactoglucose. S E – S
bacilli enzyme present in curd. + P centres on the surface
Starch Maltase Maltose enzyme particles. Th
C12H22O11Active
(iv) Conversion (aq) site
of maltose 2C6H12O
+ H2O(l) into glucose: 6(aq)
The maltase enzyme molecules of the reacta
Pconverts
131 Surface Chemistry
Maltose Glucose (substrate), which ha
maltose into glucose.
(v) DecompositionE +of ureaS into ammonia
Maltase E S and carbon
E +
dioxide: Thecomplementary shape,
C12H22urease
enzyme O11(aq) catalyses 2C6H12O6(aq)
+ H2O(l) this decomposition. into these cavities just lik
P a key fits into a lock. O
Maltose Urease Glucose
NH2CONH2(aq) + H2O(l) 2NH3(g) + CO2(g) account of the presence
(v) Decomposition
Enzyme
of urea
Substrate into ammonia and
Enzyme-Substrate Enzyme carbon dioxide:
Products The
active groups, an activate
(vi) In stomach,
enzyme urease the pepsin
(catalyst) catalyses
enzyme converts
(reactants) this decomposition.
complex
proteins into peptidescomplex is formed whic
while in intestine, the pancreatic Urease trypsin converts proteins into then decomposes to yie
NH2CONH Mechanism of2NH 3(g) + CO2(g)
2(aq) + 5.4:
H2O(l)
Fig. enzyme catalysed reaction
amino acids by hydrolysis. the products.
(vi) In stomach,
MENTOR
(vii) of the
:- JEETENDRA
Conversion milkpepsin
Kinto
ARYAcurd: Thus,
enzyme
It is an the enzyme-catalysed
converts
enzymatic proteins reactions
reaction may
intobrought be considered
peptides
MOB:- 7077 6066 22 to procee
in two steps.
while by
about in intestine,
lacto bacilli the pancreatic
enzyme present trypsin
in curd.converts proteins into
Gold Number is a term used in colloidal chemistry.
It was first used by Richard Adolf Zsigmondy.
Covering up of lyophobic particle by lyophilic particles is known as its protective action
and such colloids are called protective colloids.

What is gold number ?

Gold no. is defined as the minimum amount of dried protective sol ( lyophilic / stable sol )
that will prevent the coagulation of 10ml Gold sol ( lyophobic sol / Unstable sol ) on the
addition of 1ml of 10% NaCl Solution.
OR
It is defined as the minimum amount of dried lyophilic colloid ( protective colloid ) in
milligrams which prevent the lyophobic colloids ( unstable colloids ) of 10ml gold solution
by the addition of 1ml 10% NaCl solution.
OR
It is defined as the minimum amount of protective colloid in milligrams which change the
colour from red to violet of 10ml gold solution by the addition of 1ml 10% NaCl solution.

Coagulation of gold sol is indicated by colour change from red to blue/purple when
particle size just increases. More is the gold number, less is the protective power of
the lyophilic colloid since it means that the amount required is more.

NOTE :- Smaller the gold number , Higher is the protection power.

Protective Gold
Colloids Number
Gelatin 0.005-.01
Haemoglobin 0.03-0.07
Egg Albumin 0.15-0.25
Potato Starch 20-25
Gum arabic 0.15-0.25
Caseinate 0.01-0.02
Sodium Oleate 1-5
Dextrin 125-150

MENTOR :- JEETENDRA K ARYA MOB :- 7077 6066 22

NOTES