Surface Chemistry and Catalysis 2.

Unit II

SURFACE CHEMISTRY AND CATALYSIS

Introduction - Terminologies in surface chemistry - Difference between adsorption and absorption

—Enzymes - Kinetics of Enzyme Catalysed Reaction Or Michaelis and Menten equation - Factors A

CHAPTER 2: Surface Chemistry

INTRODUCTION

Surface Chemistry is closely related to interface and colloidal science. Surface

chemistry is important in many criticalchemical processes, such as enzymatic reactions at
biological interfaces found in cell walls and membranes, in electronics at the surfaces and
interfaces of microchips used in computers, and the heterogeneous catalysts found in the
catalytic converter used for cleaning emissions in automobile exhausts.
DEFINITION
Surface science is the study of chemical phenomena that occur at the interface
of two phases (solid–liquid interfaces, solid–gas interfaces, solid–vacuum interfaces,
and liquid-gas interfaces). (or)
It is defined as the study of chemical reactions at interfaces.
2.1
2. Chemist

TERMINOLOGIES IN SURFACE CHEMISTRY

 Adsorbate: The substance which gets adsorbed on any surface is called adsorbate.

 Adsorbent: The substance on the surface of which adsorption takes place is called
adsorbent.

 Adsorption: The process whereby molecules of gases or liquids adhere

chemically to the surface of a solid.

(Eg.) Occlusion of Hydrogen gas on Palladium where palladium is adsorbent and

hydrogen gas is adsorbate.
1Adsorbent - the gas adsorbed
on the surface of solids

Adsorbent - the solid where

adsorption takes place

Figure 2.1 : Adsorption Process

 Desorption: The removal of the adsorbed substance from a surface is

called desorption.

 Interface: The plane which separates anytwo phase is generally called an interface.

 Absorption: When the molecules of a substance are uniformly distributed

throughout the body of a solid or liquid. This phenomenon is called absorption.

 Sorption: The phenomenonin which adsorption and absorption occur

simultaneously is called sorption.

 Occlusion: When adsorption of gases occurs on the surface of metals it is

called occlusion.
Surface Chemistry and 2.3
Adsorption Desorption Absorption

Adsorbant
Chemisorption Physisorption

Figure 2.2 : Occlusion Process

 Positive adsorption: When the concentration of solute adsorbed on the solid

adsorbent surface is greater than in the bulk it is called positive adsorption.

(Eg.) Concentrated solution of KCl is shaken with blood charcoal, it shows

positive adsorption

 Negative adsorption: When the solvent from the solution may be absorbed by
the adsorbent so that the concentration of the solute decreases and the
concentration of solution increases than the initial concentration and it is called
negative adsorption.

(Eg.) Dilute solution of KCl isshaken with blood charcoal it showsnegative

adsorption.

Enthalpy or heat of adsorption

Amount of heat evolved when 1 mole of an adsorbate gets adsorbed on the surface of
an adsorbent is called Molar Heat or Molar Enthalpy of Adsorption.

DIFFERENCE BETWEEN ADSORPTION AND ABSORPTION

Absorption
Adsorption

Figure 2.3 : Illustration of Absorption and Adsorption

2. Chemist

S.No. ABSORPTION ADSORPTION

1. It is a bulk phenomenon It is a surface phenomenon
2. It is a slow process It is a fast process
3. Substance uniformly distributed Higher concentration of molecular
throughout the surface species in the surface than in the bulk
4. Attainment of equilibrium takes Equilibrium attained easily
time
5. Eg.: Ammonia adsorbed in Eg.: Ammonia adsorbed in water
charcoal

TYPES OF ADSORPTION

Physical Adsorption Chemical Adsorption

Figure 2.4 : Illustration of Physical and Chemical Adsorption

d d
r
e o
r
b
o
s b
d
e
s Temperature
Temperature
Figure 2.5 : Amount of gas adsorbed vs temperature
Surface Chemistry and 2.5
S.No Physical adsorption or Chemical adsorption or Chemisorption
Physisorption
1. Caused by intermolecular Caused by chemical bond formation
vanderwaal’s forces
2. Not specific in nature Highly specific in nature

3. Reversible in nature Irreversible in nature

4. Multimolecular layers are formed Unimolecular layers are formmed on the

on the adsorbed surface surface
5. Heaat of adsorption is less (20 to 40 Heat of adsorption is large (80 to 240
KJ/mole) KJ/mole)
6. No activation energy is required High activation energy is required

7. Depends on nature of gas. Easily Depends on nature of adsorbent and

Liquefiable gases are adsorbed adsorbate
easily
8. Occurs at low temperature Increases with increase in temperature

9. Increase in pressure increase High pressure is favourable. Decrease in

adsorption pressure does not cause desorption

Adsorption of Gases on Solids

In adsorption of gases on solid surface, the solid surface is called the adsorbent and
the gas adsorbed is called adsorbate. The extent of adsorption depends on many factors.

Absorbed
Gas Molecules

Solid
Surface

Solid

Figure 2.6 : Adsorption of gases on solids

2. Chemist

2.2 FACTORS AFFECTING THE EXTENT OF ADSORPTION

(i) Nature ofAdsorbent

The adsorption depends on the type of adsorbents used. When the adsorbent is
highly porous the rate of adsorption increases. Activated carbon, metal oxides like
aluminum oxide, silica gel and clay are commonly used adsorbents. The rate of
adsorption can be increased by activation process. It helps in enhancing the pores in the
adsorbent Eg. charcoal adsorbs 0.011 gms of CCl4 at 24°C and activated charcoal
adsorbs 1.48 gm of at 24°C.
Activation of adsorbent

During activation, the adsorbent is heated in steam to about 1500°C. Heating drives
out all impurities and leads to a lager free surface for adsorption. It can be done in 3 given
ways

 By making the surface of adsorbent rough.

 By heating the adsorbent in vacuum so that the water vapour present in pores
leave those pores.

 By increasing the surface area of adsorbent

(ii) Surface area ofadsorbent

Increase in surface area of the adsorbent increases the adsorption of gases andthe
extent of adsorption depends on two factors
 Greater the surface area greater the adsorption-Increase in surface area increases
the number of adsorbing sites.
 Larger the porositygreater the adsorption-Finely divided and highly porous
materials acts as good adsorbents.

Eg. Charcoal and silica gel (excellent adsorbents).

(iii) Nature of Gases

The amount of gas adsorbed by a solid depends on the nature of the gas.
Easilyliquefiable
gases like HI, NH3, CI2, SO2 etc., are adsorbed more easily then the permanent gases like
H2, N2, and O2 etc. Physical adsorption is non-specific in nature, so any gas will be
adsorbed on the surface under any given conditions of temperature and pressure.
Chemisorption is specific in
nature so only those gases which forms chemical bonds will be adsorbed.
Surface Chemistry and 2.7
The nature of gas depends on two factors:

 Critical Temperature (maximum temperature above which the gas cannot be

liquefied). Liquefactions of gases depend on critical temperature. When the
critical temperature is more the gases will be liquefied and more adsorption
occurs.

 Van der Waal’s forces: Easilyliquefiable gases possess greater Vander Waal’s
forces than permanent gases, so they are adsorbed more readily.
(iv) Exothermic Nature
Heat of adsorption is defined as the energy liberated when 1 g mol of a gas is
adsorbed on a solid surface. Increase in temperature increases the kinetic energy of the gas
molecules and it results in more number of collisions of gas molecules over the adsorbent
surface.
(v) Pressure
When pressure is increased then the rate of adsorption increases initially. The
extent of adsorption is expressed as x/m where ‘x’ is amount of adsorbate; ‘m’ is mass of
adsorbent when the dynamic equilibrium is established between free gas and the adsorbed
gas. But after some time it reaches appoint where no more adsorption occurs and at this
point adsorption is independent of pressure.

Low Pressure High

Figure 2.7 : Rate of adsorption

3. ADSORPTION OF SOLUTE FROM SOLUTIONS

The process of adsorption of solutes on solid surface can take place from solutions.
For example the activated animal charcoal adsorbs colouring matter present in sugar
solution and clarifies the sugar solution. It also has the capacity to adsorb acetic acid and
oxalic acid from water thereby reducing the concentration of acids in water.
There are two (or more) components present in a solution namelysolute and solvent.
The solute may be present in the molecular or ionic form. The extent of adsorption from
solution
2 Chemist
depends upon the concentration of the solute in the solution, and can be expressed by
the Freundlich Isotherm.

x
 k c(1n)
m
x 1
log  log k  log C
(or) m n
where, x- is the mass of the solute adsorbed,
m -is the mass of the solid adsorbent,
c -is the concentration of the solute in the solution &
n -is a constant having value greater than one,

k -is the proportionality constant.

The value of k depends upon the nature of solid, its particle size, temperature, and
the nature of solute and solvent etc. It the graph is plot between x/m against c which gives
a straight line which is similar to Freundlich adsorption isotherm.

FACTORS AFFECTING ADSORPTION OF SOLUTES FROM

SOLUTION

Nature of adsorbent
Adsorption ofsolute from solution is highlyspecific. Adsorption depends mainlyon
nature of adsorbent.
Temperature
Adsorption from solution decreases with rise in temperature.
Concentration of solute
Adsorption fromsolution decrease with decrease in concentration of solution.eg
charcoal adsorbs water from dilute KCl solution whereas charcoal adsorbs KCl from
concentrated KCl solution.
4. ADSORPTION ISOTHERM
The process of adsorption is usuallystudied through graphs know as adsorption
isotherm. It is the graph between the amounts of adsorbate (x) adsorbed on the surface of
adsorbent (m) and pressure (P) at constant temperature.
Surface Chemistry and 2.

Adsorbent + Adsorbate Adsorption

Adsorption isotherm shows the amount of molecules adsorbed on the solid surface as
a function of the equilibrium partial pressure at constant temperature.

Adsorp tion Isotherm

X/m
Saturation Pressure

P PS

Figure 2.8 : Adsorption Isotherm

A plot of x/m vs P is plotted to obtain adsorption at constant temperature, Ps is

called the saturation pressure.

FREUNDLI H ADSORPTION ISOTHERMS

In 1909, Herbert Freundlich gave an expression representing the isothermal

variation of adsorption of a quantity of gas adsorbed by unit mass of solid adsorbent with
pressure.Freundlich adsorption isotherm is an empirical relation between the concentration
of a solute on the surface of an adsorbent to the concentration of the solute in the liquid
with which it is in contact. The isotherm is given as:
1
x  
 k  p n  [ n > 1]
m
x 1
(or) log  log k  log P
m n
where x – is mass of adsorbate,
m – is mass of adsorbent,
P – is the equilibrium pressure of
adsorbate, K & n – areconstants.
2.1 Chemist
At low pressure, extent of adsorption is directly proportional to pressure:
x 1
p
m
At high pressure, extent of adsorption is independent of pressure:
x 0
p
m
At intermediate value of pressure, adsorption is directly proportional to pressure
1
raised to power  n value is greater than 1.
n

x
p(1/ n)
m
To remove proportionality a proportionality constant ‘k’ is used which is known as
adsorption constant and we get

x
k 1
 
m pn 
The above equation is known as Freundlich Adsorption equation.

Plotting of Freundlich Adsorption Isotherm

x
k 1
 
m p n 
Taking log both sides of equation, we get,
x 1
log  log k  log P
m n

The equation is comparable with equation of straight line, y = m x + c where, m

represents slope of the line and c represents intercept on y axis. Plotting a graph between
log (x/m) and log p, we will get a straight line with value of slope equal to 1/n and log k
as y-axis intercept.
Surface Chemistry and 2.1

195 K

244 K
X 273 K
m
P

b
Q
a
1
log X
m Slope = n
log K (intercepted)

log p

Figure 2.9 : log (x/m) vs. log p graph

Limitation of Freundlich Adsorption Isotherm

1. Freundlich equation is purely empirical and has no theoretical basis.
2. The equation is valid only upto a certain pressure and invalid at higher pressure.
3. The constants k and n are not temperature independent, they vary with temperature.

4. Frendilich’s adsorption isotherm fails when the concentration of the adsorbate is very
high.

LANGMUIR ADSORPTION ISOTHERM

In 1916, Irving Langmuir proposed another adsorption Isotherm which explained

the variation of adsorption with pressure

AB A
st
1 layer

Surface Surface

Figure 2.10 : Equilibrium between tree molecule and adsorbed molecules

2.1 Chemist
Assumptions of Langmuir Isotherm

Langmuir proposed his theory by making following assumptions.

(i) Surface is energeticallyuniform. Fixednumber ofvacant or adsorptionsites are

available on the surface of the solid.
(ii) All the vacant sites are of equal size and shape on the surface of adsorbent.
Each site can hold maximumof one gaseous molecule and a constant amount of heat
energy isreleased.
(iii) Heat of adsorption is constant throughout the surface and it ranges from 0 to 1.
(iv) Dynamic equilibrium exists betweenadsorbed gaseous molecules and the free
gaseous molecules.

(v) Adsorption is monolayer or unilayer.

Derivation

Langmuir Equation depicts the relationship between the extent of adsorption and
pressure. Langmuir proposed that dynamic equilibrium exists between adsorbed gaseous
molecules and the free gaseous molecules. Using the equilibriumequation,
equilibriumconstant can be calculated.

A(g)B(s) Adsorption
□ AB
Desorption

where A(g )  is unadsorbed gaseous molecule

B(s)  is unoccupied metal surface and

AB  is adsorbed gaseous molecule

According to Kinetic theory,
Rate of forward reaction = Ka [A]
[B] Rate of backward reaction = Kd
[AB]
At equilibrium, Rate of forward reaction is equal to Rate of backward reaction
Ka [A] [B] = Kd [AB]
A new parameter ‘’ is introduced.
Surface Chemistry and 2.1

Let  be the number of sites of the surface which are covered with gaseous
molecule and (1–è) be the fraction of surface unoccupied by gaseous molecule. Rate of
forward direction depends upon two factors, number of sites available on the surface of
adsorbent, (1 – ) and pressure, P.
Rate of forward reaction  P (1  )

Rate of adsorption  P (1  ) or

Rate of adsorption  Ka P (1  )

Rate of backward reaction or rate of desorption depends upon number of sites

occupied by the gaseous molecules on the surface of adsorbent.
Rate of desorption   (or)

Rate of desorption = Kd 

At equilibrium, rate of adsorption is equal to rate of desorption.

Ka P (1  )  Kd 

The above equation can be written in terms .

Ka P  Ka P  Kd 

Ka P  Ka P  Kd 

Ka P  ( Kd  Ka P)

Ka P

(Kd  Ka P)

Divide numerator and denominator on RHS by Kd , we get

Ka
P
 Kd
Kd Ka
Kd  Kd P
K
a
But K 
Kd
2.1 Chemist
Substituting in the above equation we get

KP
  1  KP

This is known as Langmuir Adsorption Equation.

Alternate form of Langmuir Adsorption Equation

Langmuir adsorption equation can be written in an alternate form in terms of

volume of gas adsorbed. Let V be volume of gas adsorbed under given sets of conditions
of temperature
and pressure and Vmono be the adsorbed volume of gas at high pressure conditions so as to
cover the surface with a unilayer of gaseous molecule.

V
V
mono

Substituting the value of  in Langmuir equation

V
KP
Vmon  1  kP
o

1
(or) 1
kP
Vmono

in terms of pressure P we get, Langmuir Adsorption Equation in alternate form.

Thus, if we plot a graph between P/V vs P, we will obtain a straight line with
Slope = 1/Vmono and intercept =1/ KVmono.

Limitations of Langmuir Adsorption Equation

(i) The adsorbed gas has to behave ideally in the vapour phase. Langmuir
equation is valid under low pressure only.
(ii) Langmuir Equation assumes that adsorption is monolayer. But, monolayer
formation is possible only under low pressure condition. Under high pressure
condition the assumption breaks down as gas molecules attract more and more
molecules towards each other.
(iii) Another assumption is the surface of solid is homogeneous but in real solid
surfaces is heterogeneous.
Surface Chemistry and 2.1
(iv) Langmuir equation assumed that molecules do not interact with each other.
This is impossible as weak force of attraction exists even between molecules of
same type.
(v) In adsorption liquefaction of gases taking place, which results in decrease in
randomness but the value is not zero.
5. CONTACT THEORY (OR) MECHANISM OF
HETEROGENEOUS CATALYSIS (OR) ADSORPTION
THEORY
This theory postulated by Faraday in 1883. It explains the action of heterogeneous
catalysis. Heterogeneous catalysis has five steps.

Figure 2.11 : Mechanism of heterogeneous catalysis

(i) Diffusion of Reactant(s) to the Surface: The reactants diffuse to the surface of
the catalysts. Some of the reactant cross the barrier and enter the interior exposed
surface that includes paths and cracks on the external surface.
(ii) Adsorption of reactants: Bonds are formed as the reactant(s) are adsorbed
onto the surface of the catalyst. The ability for an atom or molecule to stick to
the surface is known as the Sticking Co-efficient.
(iii) Reaction: The reactants, when bound to the surface have a higher probability
of reacting with each other, and after the reaction, they forman intermediate
compound.
(iv) Desorption of products: The intermediate compound gets desorbed fromthe
surface, which again becomes available for adsorption for other molecules
2.1 Chemist
(v) Diffusion of Product(s): The intermediate compound then disintegrates to form
the final products and the products are then desorbed from the surface of the
catalyst.
Surface Chemistry and 2.1

For example,
1. Conversion of ethylene to ethane

Ethylene
Ni surface

Ethylene absorbed on
surface breaking  bonds

A (g)B (s)
N 2( g)3H 2(g) 2N 3(g) 
A  A ( a d s )B ( g )    B ( a d s )
A(a ds )B (a ds )r ds A B(ads)fast A B(g)
k  
A B
bP

Figure 2.12 : Conversion of ethylene to ethane

2. Haber–Bosch reaction
The original Haber–Bosch reaction chambers used osmium as the catalyst, less
expensive iron-based catalyst, which is still used today.

N 2 ( g)  3H 2 ( g)  2 NH3 (g)

The reaction mechanism, involving the heterogeneous catalyst, is believedto involve the
following steps:
1.
N2 (g)  N2 (adsorbed)
2.
N2 (adsorbed)  2 N(adsorbed)
3.
H2 (g)  H2 (adsorbed)
2.1 Chemist
4.
H2 (adsorbed)  2 H (adsorbed)
5.
N (adsorbed) + 3 H (adsorbed)  NH3 (adsorbed)
6.
NH3 (adsorbed)  NH3 (g)

6. KINETICS OF SURFACE REACTION

The kinetics of heterogeneously-catalyzed reactions might vary with the partial

pressures of the reactant gases above the catalyst surface which can be predicted by using
the Langmuir isotherm.

6.1 KINETICS OF UNIMOLECULAR DECOMPOSITION

Examples of unimolecular decomposition

1. Decomposition of NH3 to N2 and H2 on metal surfaces,

2. Decomposition of Phosphine on glass,

3. Decomposition of Formic acid on glass, Pt, Ag, Au, or TiO2.

Consider the surface decomposition of a molecule A , i.e. the

process

A(g)  A (adsorbed)  Pr oduct

Assumption

1. The decomposition reaction occurs uniformly across the surface sites. Molecule ‘A’
may be adsorbed and is not restricted to a limited number of specific sites.

2. The products are very weakly bound to the surface and, they can be easily deformed.

3. The rate determining step is the surface decomposition step.

According to Langmuir adsorption isotherm molecule ‘A’ adsorbed on the surface is in

equilibrium with the gas phase and the surface concentration is represented as:

bP
  (1 b P)
Surface Chemistry and 2.1
The rate of the surface decomposition is given by an

expression : Rate  k 

Substituting, θ , in the rate expression we get:

kbP
Rate 
(1 b P)

The reaction is expressed within two limits:

a. Low pressure limit: b  P 1(First order reaction with a first order constant k = k b
)

k  P
Rate 
(1 bP)

K P  K
Rate  b

K
So Rate □ k b  P as is constant.
b
Under low pressure ‘è’ is very small and rate is directly proportional to pressure

b. High pressure limit: b P 1 (Zero order reaction)

Rate  k b  P
(1 bP)

Rate  k
(1 bP)

Therefor
e
(1 + b  P) ~ b P and Rate ~ k

Under high pressure θ is almost unity.

2.2 Chemist

Rate ~ k (zero order)

Rate

Rate ~ kbP (first order)

Figure 2.13 : Graphical representation of unimolecular surface decomposition

6.2 KINETICS OF BIMOLECULAR REACTION (Langmuir-Hinshelwood)

Between molecular adsorbates.

Consider the reaction:
A(g )  A(ads)
B( g )  B(ads)

A(ads)  B(ads) rds  AB(ads) fast AB(g)

Assumption:
The surface reaction between the two adsorbed species is the rate determining step.
The rate of the reaction of the two adsorbed molecules for biomolecular surface will be
given by:
Rate = k A B
According to Langmuir adsorption isotherm:
b P
  (1 b
P)
where two molecules (A & B) are competing for the same adsorption sites then

bA PA
A  1 b P  b bBPB
A A B an B  1 b P  b P
PB A A B B

Substituting these into the rate expression gives:

Rate  k A B  k bA PA bB PB
1 b P  b P 2
A A B B
Surface Chemistry and 2.2
Condition

1. Reactant Aand B in first order then

bA PA 1 and bB PB 1

A & B are very low.

Hence, Rate  k bA PA bB PB  kPAPB

2. First order in A, but negative first order in B then

bA PA 1 bB PB
k bA PA
so Rate  k PA
A  0, B 1
b BP B PB


7. TYPES OF ADSORPTION ISOTHERM

Adsorption process is usually studied through graphs known as adsorption isotherm.

After saturation pressure Ps, adsorption does not occur anymore, as there are limited
numbers of vacancies on the surface of the adsorbent. At high pressure when all the sites
are occupied and
further increase in pressure does not cause any difference in adsorption process. At high
pressure, adsorption is independent of pressure. There are 5 different types of adsorption
isotherms and each of them has specific characteristics.
Monolayer
I

III II

Multilayer

IV
V
Condensation in pores/capillaries

Figure 2.14 : Illustration of different types of Adsorption Isotherm

 2.2 Chemist
Type I Adsorption isotherm is for very small pores or microporous adsorbents.
Adsorption occurs by filling of micropores and it mainly depicts Monolayer
adsorption. Eg. Adsorption of Nitrogen or Hydrogen on charcoal around 1800°C.

Xm

Ps
P

Figure 2.15 : Type I

Type IIAdsorption isotherm shows large deviation from Langmuir modelof

adsorption. They are most frequentlyencountered when adsorption occurs on nonporous
powders or macroporous adsorbents with unrestricted monolayer -multilayer adsorption.
The intermediate flat region in the isoth e 2H K2 (Cg O) l 3 H 2Mn (gO(2o ))S 2 2KC Hl (3 3Og )

rm corresponds to monolayer formation.

When 3r37oo0m Ctem2p.

H 2  O 2      N o r ea ct io n
2 H 2  O 2 Ptb lack 2 H2 O
R C O O R  H O2  R C OO H  R O H
 C H6 10 O 5 n + Hn 2 O   n C1 H2 2 O2 1
2 C H O  Hn O   n C H O
 6 10 5 n 2 12 2 2 1
n C H12 2 O2 11  n H O2   n C H12 2 O2
11 V  V ma [Sx ] [E S ]  K [E ] [x S]
0 K m [ S] 1 (K 2  K )3
[ E t] [x S]  [E ] [x S] 
[ES]  ( K 2 K 3 )/ K [1 E S]  ([ S]  K m
X [S ]
( V ) V ma x [ S ]
K mV ax [S ] 1
(V) [S]  [S ] 2 V m ax
1 K [ S]
R a te (v ) V m [S ] V [
S] m ax m
ax
[ES]  [ Et ]x [S ] /([ S ] K m 
[ E t][ S ]
[ ES ]  K
1 [S ] /K m
K m  (K 2  K
)3 K 1
[ES]  [E ] [S ]/ K m
 C 2 H C5 l  A lC l3 C H6 5C 2 H 5 H C l
R C O O R  H O  H ro HO  R OC O H  R O
H est er 2
2 K M n O +4 5 H C2 O2 4 + 3 H 2 SO 4   2 Mca Sntaly Ost 4 + K S2 O 4 8 H O2 + 1 0 CO2

the monolayer formation of the adsorbed les are complete, multilayer formation starts to
lA2 3O

molec
C2 H5 O H    C H 2 et hen Ce 2 
O2 S O 2  O 2  Pt  2 S O 3
C 2 H5 O H    C H C h3te H nao O l + H 2
C H O  H  +H  C H O  C H O

u
A OFes2 3

N 2  3 H 2  2HS  2N H 3

/ /// /
2 H 2 + O 2   tP  2 H O2
CO

c1a2nesug22 ar1 1 2 6g 1luco 2se6 6 fruc12tos6e

C H C3 O O C H2 5  +H  C H C3 O O H  C2 H O5 H
et hyl ace tate or OH  ac eticaci d etha nol
2 N a S2 O 3 O 2  A lcoh ol 2 N a S2
O 4 4 N O + 4 N H     4 N  6 H O
3 2 2 2
2 N O 2 4 N H 3   2   3 N 2 6 H O2
+
N H 2 N O2 H  N O2  H O2
N H 2 N O2  O H    H O2  N HN O 2
CIntoemrmpledixate
N H NO 2   N 2 O  O H 
Fe
□Mo 2 N H 3
2 A s H3   2 As  3H 2
catlyst

take place corresponding to the ‘sharp knee’ of the isotherms.

Eg: Iron (Fe) catalyst and Nitrogen (N
2
(g)) adsorbed at 1950°C on silica gel.f

Xm

Ps
P

Figure 2.16 : Type II

Type III Adsorption Isotherm also shows large deviation from Langmuir model.
This isotherm explains the formation of multilayer. They are characterized principally by
heats of adsorption which are less than the adsorbate heat of liquefaction.
Surface Chemistry and 2.2
Eg: Bromine (Br2) at 790°C on silica gel or Iodine (I2) at 790°C on silica gel.
2.2 Chemist

X
m

P Ps

Figure 2.17 : Type III

Type IV Adsorption Isotherm occur on porous adsorbents possessing pores in

the range of approximately 15-1000 angstroms (A). At lower pressure region of graph is
quite similar to Type II. This explains formation of monolayer followed by multilayer.

The intermediate flat region in the isotherm corresponds to monolayer formation.

The saturation level reaches at a pressure below the saturation vapor pressure. This
can be explained on the basis of a possibility of gases getting condensed in the tiny
capillary pores of adsorbent at pressure below the saturation pressure (PS) of the gas.
Eg. Adsorption of Benzene on Iron Oxide (Fe2O3) at 500°C and adsorption of Benzene on
silica gel at 500°C.

Xm

P Ps
Figure 2.18 : Type IV

Type V Adsorption Isotherm results from small adsorbate-adsorbent

interaction potentials similar to the Type III isotherms. However, Type V isotherms are also
associated with pores in the same range as those of the Type IV isotherms.
Eg: Adsorption of Water (vapors) at 1000°C on charcoal.
Surface Chemistry and 2.2

X
m

P Ps

Figure 2.19 : Type V

Type III and Type V isotherms do not have the ‘sharp knee’ shape implying
stronger adsorbate – adsorbate interactions than adsorbate-adsorbent interaction.
Type IV and V shows phenomenon of capillary condensation of gas.

Volume of
I II III IV V
gas adsorbed

P0
P0 P0 P0
P0 Pressure
Figure 2.20 : Different types of adsorption isotherms

8. APPLICATION OF ADSORPTION

Extensive application of adsorption is been listed below

(i) Production of high vacuum

In Dewar flasks activated charcoal is placed between the walls of the flask so that
gas
entering into the annular space gets adsorbed.

(ii) In Gas masks

Activated carbon is used in gas masks to adsorb poisonous gases (e.g. oxide of
sulphur,
NOx etc.) and purifies air for breathing.
2.2 Chemist

gas molecules

Activated Charcoal

Figure 2.21 : Adsorption of poisonous gases using activated charcoal

(iii) In desiccation ordehumidification

Certain substances can be used to remove water vapour or moisture present in the air.
Silica gel and alumina are used for dehumidification in electronic equipment.
(iv) In clarification of sugar

Sugar isdecolorized bytreating sugar solution with animalcharcoalpowder which

removes the colour producing substances.
(v) In paint industry

The paint should not contain dissolved gases as it inhibits the adherence capacity of
paint to the surface to be coated. The dissolved gases are therefore, removed by suitable
adsorbents. This is done by adding suitable liquids which adsorbs these films. Such liquids
are called wetting agents. Eg. Use of spirit as wetting agent in furniture painting..
(vi) Adsorption chromatography

Analytical method, in which molecules are separated according to their

adsorptive properties, where a mobile fluid phase is passed over an immobile solid
adsorptive stationary phase.
(vii) In adsorption indicators

Various dyes which possess adsorption property have been introduced as

indicators mainly in precipitation titrations. For example KBr is titrated with AgNO3
using eosin as an indicator
Surface Chemistry and 2.2
(viii) Heterogeneous Catalysis

In heterogeneous catalytic reactions adsorption of gaseous reactants on solid

catalyst occurs. The adsorption mechanism is responsible for the greater efficiency of the
catalyst in the finely divided state and helps us to understand the action of catalyst
promoters and poisons. eg,

1. Finelypowdered nickel is used for the hydrogenation of oils.

2. In manufacture of sulphuric acid finely divided vanadium pentaoxide (V2O5) is used in

the contact process.

diffusion

(i) diffusion of reactants to surface;

adsorption (ii) adsorption of reactants to surface;
(iii) reaction on thesurface;
reaction
(iv) desorption of products from surface;
(v) diffusion of products away from
the surface.
diffusion

Figure 2.22 : Process of Heterogeneous Catalysis

(ix) In adsorption indicators

In many precipitation titrations many dyes are used as indicators which work on
the principle ofadsorption.
(x) In curing diseases

Some pharmaceutical drugs have the capacity to adsorb the germs on them and kill
them and protect us from diseases.
(xi) Lake test for aluminium

It is based on adsorption of litmus paper byAl(OH)3 precipitate

2.2 Chemist
(xii) Separation of inert gases

Due to the difference in degree of adsorption of gases by charcoal, a mixture of

inert gases can be separated by adsorption on coconut charcoal at different low
temperatures.
(xiii) In softening of hardwater

The use of ion exchangers for softening of hard water is based upon the principle
of adsorption chromatography. The ion exchange resins helps to remove hardness causing
ions from water and make it useful for industrial and domestic applications.
(xiv) Arsenic Poisoning

Colloidal ferric hydroxide is administered which adsorbs arsenic and removes it

from body by vomiting
(xv) Formation of stable emulsions in cosmetics and syrups etc.

(xvi) Froth floatation method

Used for concentration of sulphide ores is based on adsorption.

(xvii) In cleaning action of soaps and detergents

Adsorbed Surfactant lowers the interfacial tension between the fabric and the stain

Fat or Oil Stain Add Surfactant

fabric substrate fabric substrate fabric substrate

Stain does not desorb spontaneously

Mechanical agitation

Mechanical agitation

Fat or Oil Globule

Fat or Oil Globule

fabric substrate

Clean Fabric + adsorbed surfactant prevents re-adsorption of fat globule

fabric substrate

Figure 2.23 : Cleaning actions of soaps and detergents

Surface Chemistry and 2.2
(xviii) Application of adsorbents on pollution abatement

o Many pollutants, both natural and synthetic, are gaseous in nature and it need to
be effectively removed from the exhaust.
o Gaseous industrial pollutants include HCl, H2SO4, H2S, SOx, NOx, NH3,
Ethylene, Benzene, Ethanol, and HAP’s. Adsorption is a mass transfer process in
which a porous
solid comes in contact with a liquid or gaseous streamto selectively remove
pollutants or contaminates by adsorbing them onto the solid.
o The most common adsorbents used in industry are activated carbon, silica gel,
activated alumina (alumina oxide), and zeolite. Activated carbon is the most
common non-polar adsorbent. Polar adsorbents have a great attraction to absorb
moisture.
o Most industrial exhaust streams contain moisture the use of polar adsorbents
is significantly limited for air pollution control systems. There are two main
types of adsorption systems; fixed bed or continuous.

[1] Fixed Bed or Packed Bed Systems

These are quite simple devices. The fixed bed or packed bed reactors are most
commonly used for study of solid catalyst. Afixed bed reactor usually consists of a
cylindrical vessel packed with the adsorbent material (eg. activated carbon) and it contains
more surface area for adsorption. The contaminated or the polluted air enters the fixed bed
system at the side, where there is an exhaust distributor. The exhausted air exits the fixed
bed adsorber clean of pollutants or contaminates. Once the adsorbent is fully saturated
with adsorbate the system requires change- out of the spent materials, which is then packed
with new adsorbent material. The spent adsorbent will be thermallycleaned.
Advantages

1. Ideal plug flow behavior

2. Lower maintenancecost

Disadvantage

1. Plugging of bed due to coke deposition which results in high pressure drop.
2.3 Chemist

products and
unreacted materials to
separation

catalyst on
support

diffuser

reactants

Figure 2.24 : Fixed Bed Reactor Device

Vent
gas

Recirculating
Caustic Liquor Caustic M ake-up
Scrubbing
Tower

Cooler
“End of Pipe”
Chlorin Fixed Bed Reactor
Laden
Gas Liquid
Effluent
Recirculating Blowdown
(to drain or
Pump Stream and
recycle)
Optional
Preheater

Figure 2.25 : Schematic representation of fixed bed reactor

[2] Continuous Flow Reactor Systems

Continuous-flow reactors are almost always operated at steady state. These are more
complex and provide continuous operations. These systems provide in-situ desorption of
the adsorbates from the adsorbent. This can be done with superheated or saturated
steam. The adsorbate can be condensed, collected, and re-used in the process. There are
two adsorber
 Surface Chemistry and 2.3

units in the system. The gases are being adsorbed in one unit as the other unit is being
desorbed with steam. The exhaust from the desorbed bed can be condensed for solvent
reuse or other beneficial purpose.
Stirrer

Liquid Surface
Input Rate V

O utput Rate

Figure 2.26 : Continuous Flow Reactor

[3] Special Type of Continuous System (Zeolite Concentrator, or Rotary Concentrator)

A hydrophobic zeolite is designed in a monolithic rotor in which the contaminated air

flows. An integrated thermal oxidizer is used to provide desorption of the solvents from
the zeolite. They have wide acceptance in industrial air pollution control applications.

CHAPTER 3: Catalysis
A catalyst is defined as a substance which alters the rate of a chemical reaction, itself
remaining chemically unchanged at the end of the reaction. The process is called
catalysis.

3.1 INTRODUCTION

The word “catalyst” was introduced into science by the great Swedish chemist
Jons Jakob Berzelius (1779-1848) who also determined the atomic and molecular weights of
thousands of substances, discovered several elements including selenium, first isolated
silicon and titanium, and created the present system of writing chemical symbols and
reactions.
Catalysts are of immense importance in chemistry and biology. All enzymes are
catalysts that expedite the biochemical reactions necessary for life. (eg) Enzymes in saliva
accelerate the conversion of starch to glucose.

3.1.1 DEFINITION

The process by which a substance speeds up a chemical reaction without being

consumed or altered in the process.
2. Chemist
Surface Chemistry and 2.3

P
A B B
egin
x t Cycle Catalyst
Ne
Catalyst
Bonding
Catalysis Cycle Separation
Reaction
A B P
Catalyst aC talyst

A & B = Reactants
P = Product
Figure 3.1 : Catalysis Cycle

1. TERMS
1. Catalyst

A catalyst is a substance that decreases the activation energy of a chemical reaction

without itself being changed at the end of the chemical reaction
(or)

It is the small amount of substance which alters the velocity of reaction without
altering in any change in mass and composition at the end of the reaction.
2. Positive and negativecatalyst

Catalyst helps in altering the velocityof the reaction and the catalyst is called as
positive
catalyst.eg.MnO2 acts as catalyst in decomposition of KClO3 into KCl and O2.Some catalyst
have the capacity to retard the chemical reaction and they are called as negative catalyst
.eg Alcohol retards the conversion of chloroform to phosgene.
3. Auto Catalysis

If the products ofa reaction act as a catalyst for the reaction, it is referredto as
Eg autocatalysis
. RCOOR   H 2 O  RCOOH  R OH
Product + Catalysts
Reactants
positive feedback
2. Chemist
2. MECHANISM OF CATALYTIC REACTION
increasing energy

gas molecule

gas molecule
Adsorption of gas molecules on to catalyst
active sites. The molecules are chemically
bonde dto the catalyst

desorption of
product
Adsorption as separate atoms, individually
chemically bon ded to catalyst active sites
adsorbed product

Stepwise reaction on catalyst surface

Figure 3.2 : Mechanism of catalytic reaction

3. CRITERIA (OR) CHARACTERISTICS FOR CATALYST

(i) A catalyst remains unchanged in mass and chemical composition at the end of
the reaction qualitative and quantitative analysis show that a catalyst undergoes no
change in mass ofchemical nature. However, it may undergo a physicalchange.
Thus granular
manganese dioxide (MnO2) used as a catalyst in the thermaldecomposing of
potassium chlorate is left as a fine powder at the end to the reaction.
(ii) A small quantity of catalyst is generally
need d to almost unlimited reaction
produc
Sometimes a trace of a metal catalyst is required to affect very large amounts
of reactants. For example, one ten-millionth of its mass of finely divided
platinum is all that is needed to catalyse the decomposition of hydrogen
peroxide.

On the other hand, there are catalysts which need to be present in relatively large
amount to be effective. Thus in Friedel-Craft reaction,
C H  C H Cl  AlCl3  C H C H  HCl
6 6 2 5 6525

anhydrous aluminium chloride functions as a catalyst effectively when present to

the extent of 30 per cent of the mass of benzene. For the acid and alkaline
hydrolysis of an ester
2.3 Chemist
 

RCOOR  H O  H r OH  RCOOH  R OH

o

2
ester

the rate of reaction is proportional to the concentration of the catalyst (H+ or OH– )

(iii) A catalyst is more effective when finely divided In heterogeneous catalysis, the
solid catalyst is more effective when in a state of fine subdivision than it is used
in bulk. Thus a lump of platinum will have much less catalytic activity than
colloidal or platinised asbestos. Finely divided nickel is a better catalyst than
lumps of solid nickel.
(iv) A catalyst is specific in its action While a particular catalyst works for one
reaction, it will not necessarily work for another reaction. Different catalysts,
moreover, can bring about completely different reactions for the same substance.
For example, ethanol
(C2H5OH) gives ethene (C2H4) when passed over hot aluminium oxide,
O
C H OH Al2 3  CH  C   O
2 5 2
ethene
2 2 (Dehydration)

but with hot copper it gives ethanal (CH3CHO)

C H OH Cu  CH CHO +
H (Dehydrogenation)
2 5 3 2
ethanol

(v) A catalyst cannot, in general, initiate a reaction In most cases a catalyst speeds
up a reaction already in progress and does not initiate (or start) the reaction. But
there are certain reactions where the reactants do not combine for very long
period (perhaps years). For example, a mixture of hydrogen and oxygen, which
remains unchanged almost indefinitely at room temperature, can be brought to
reaction by the catalyst
platinum black in a few seconds.

H2  O2  roomtemp. No
reaction 2H2  O 2 Pt black

 2H2O

Thus it is now considered that the catalyst can initiate a reaction. According to
this view, the reacting molecules (in the absence of catalyst) do not possess
minimum kinetic energies for successful collisions. The molecules rebound from
collision without reacting at all
(vi) A catalyst should remain unchanged in mass and chemical composition during
Surface Chemistry and 2.3
end of the reaction.
2.3 Chemist
(vii) Catalyst can alter only the speed of the reaction but it should not affect the
equilibrium ofthe reaction.
(viii) Catalysts are more active at its optimum temperature. Change of temperature
alters the rate of a catalytic reaction as it would do for the same reaction without
a catalyst.
(ix) The catalytic activity can be altered by adding a small amount of foreign
substance. Such substances which catalyse the catalyst are called as promoters
and the substance which inhibits the reaction are called as catalytic poisons or
anti-catalyst.

4. TYPES OF CATALYSIS

Catalytic reactions can be broadly divided into the following types,

HOMOGENEOUS CATALYSIS

When the reactants and the catalyst are in the same phase (i.e. solid, liquid or gas)
it is said to be homogeneous.
Examples of Homogenous Catalysis

1. The depletion of ozone (O3) in the ozone layer of the Earth’s atmosphere by chlorine
free radicals (Cl ) is a an example where the reactant and product exist in gaseous
phase. Slow breakdown of manmade chlorofluorohydrocarbons (CFCs), release
chlorine free radical
into the atmosphere, which converts gaseous ozone to gaseous oxygen (O2).

2. Fischer esterification: Reaction of carboxylic acid with an alcohol involves the use
of sulfuric acid as the catalyst and is an example where everything is contained in a
liquid phase.

HETEROGENEOUS CATALYSIS

The catalytic process in which the reactants and the catalyst are in different phases is
known as heterogeneous catalysis.
Examples of Heterogeneous Catalysis

1. The catalytic converters in automobiles convert exhaust gasessuchas carbon monoxide

(CO) and nitrogen oxides (NOx) into more harmless gases like carbon dioxide
(CO2) and nitrogen (N2). Metals (solids) like platinum (Pt), palladium (Pd) and
rhodium (Rh) are used as the catalyst.
Surface Chemistry and 2.3
2. Manufacturing of sulfuric acid (H2SO4) involve solid vanadium pentoxide (V2O5) as
the catalyst to convert gaseous sulfur dioxide (SO2) into gaseous sulfur trioxide (SO3).

3. Catalytic hydrogenation of liquid Unsaturated hydrocarbons (alkenes) reacts with

gaseous hydrogen (H2) to produce liquid saturated hydrocarbons (alkanes) where
metals like platinum (Pt) and palladium (Pd) as the catalyst..

4. Haber Process

H 2 ( g )  3H 2 ( g)  2H 3 (g )

The catalyst is porous ironprepared byreducing magnetite, Fe3O4, with potassium

hydroxide (KOH) added as a promoter.

Positive Catalysis: When the rate of the reaction is accelerated by the foreign substance,
it is said to be a positive catalyst and phenomenon as positive catalysis. Examples of
positive catalysis are given below.

(i) Decomposition of KClO3

2 KClO3 MnO2 (S)

370o C  2 KCl  3O 2

Negative Catalysis: There are certain, substance which, when added to the reaction
mixture, ret ard the reaction rat e instead of increasing it. These are called
negative catalyst or inhibitors and the phenomenon is known as negative catalysis.

Some examples are as follows.

(i) Oxidation of sodium sulphite

2 Na 2SO 3  O 2 Alcohol  2 Na 2SO 4

(ii) Tetra Ethyl Lead (TEL) is added to petrol to retard the ignition of petrol
vapours on compression in an internal combustion engine and thus minimize the
knocking effect.
2.3 Chemist
5. AUTOCATALYSIS

When one of the products of reaction itself acts as a catalyst for that reaction
the phenomenon is called Autocatalysis.
In autocatalysis the initial rate of the reaction rises as the catalytic product is
formed, instead of decreasing steadily (Figure). The curve plotted between reaction rate
and time shows a maximum when the reaction is complete

Completion of reaction
Percentage reaction

Sigmoid Curve

Time

Figure 3.3 : Rate of autocatalytic reaction

A chemical reaction is said to have undergone autocatalysis, or be autocatalytic, if

the reaction product is itself the catalyst for that reaction.
Examples of Autocatalysis

(1) Hydrolysis of an Ester. The hydrolysis of ethyl acetate forms acetic acid
(CH3COOH) and ethanol. Of these products, acetic acid acts as a catalyst for the
reaction.

CH 3COOC2 H 5  H 2O  CH3COO  C2 H5OH

catalyst

(2) Oxidation of Oxalic acid. Whenoxalic acid is oxidised by acidifiedpotassium

permanganate, manganous sulphate produced during the reaction acts as a catalyst for
the reaction.
2 KMnO4 + 5H2C2O4 + 3H2SO4  2 + K2SO4  8 H2O +10 CO2
MnSO4
catalyst

(3) Decomposition of Arsine. The free arsenic produced by the decomposition of arsine
(AsH3) autocatalyses thereaction.

2 AsH3  2 As  3H
catalyst 2
Surface Chemistry and 2.3
6. CATALYTIC POISONING AND

PROMOTERS Promoters

The activity of a catalyst can often be increased by addition of a small quantity of

a second material. This second substance is either not a catalyst itself for the reaction or it
may be a feeble catalyst.
A substance which, though itself not a catalyst, promotes the activity of a
catalyst is called a promoter. They are substances when added in small concentration can
increase the activity of a catalyst.

Example of Promoters

Molybdenum (Mo) or aluminium oxide (Al2O3) promotes the activity of iron

catalyst in the Haber synthesis for the manufacture of ammonia.
Fe
N2  3H2 □ 2NH3
Mo

In some reactions, mixtures ofcatalysts are used to obtain the maximum catalytic
efficiency. For example, in the synthesis of methanol (CH3OH) from carbon monoxide and
hydrogen, a mixture of zinc and chromium oxide is used as a catalyst.
CO + 2H  ZnO CH OH
2 3
Cr2O3

Explanation of Promotion Action

The theory of promotion of a catalyst is not clearly understood. Presumably:

(1) Change of Lattice Spacing. The lattice spacing of the catalyst is changed thus
enhancing the spaces between the catalyst particles. The absorbed molecules of the
reactant (say H2) are further weakened and cleaved. This makes are reaction go faster.

(2) Increase of Peaks and Cracks. The presence of the promoter increases the peaks
and cracks on the catalyst surface. This increases the concentration of the reactant
molecules and hence the rate of reaction.

The phenomenon of promotion is a common feature of heterogeneous catalysis.

2.3 Chemist

Covalent bond
much weakened and
cleaves readily

Distance between catalyst particles

Figure 3.4 : How the change of crystal lattice spacing of catalyst makes the reaction go faster.

CATALYTIC POISONS

Small amounts ofsubstances can reduce the activity of catalyst. If the reduction in
activity is reversible, the substances are called inhibitors. Inhibitors are sometimes used to
increase the selectivity of a catalyst by retarding undesirable reactions.
A substance which destroys the activity of the catalyst to accelerate a reaction
is called a poison and the process is called Catalytic Poisoning.

Examples of Catalytic Poisoning

(1) The platinum catalyst used in the oxidation of sulphur dioxide (Contact Process), is
poisoned by arsenicoxide (As2O3)

SO2  O2 2SO3

P t


As2O3

(2) The iron catalyst used in the synthesis of ammonia (Haber Process) is poisoned by H2S.

N2  3H2 2NH3

F e


H2S

(3) The platinum catalyst used in the oxidation of hydrogen is poisoned by carbon monoxide
2H + O Pt  2H O
2 2 CO 2
Surface Chemistry and 2.3

Types of Catalytic Poison

(i) Temporary Poisoning

Catalyst regains its activity when the poison is removed from the reaction

(ii) Permanent Poisoning

a. Catalyst cannot regain its activity even if the catalytic poison is removed.

b. Eg.AS2O3 poisons catalyst Pt permanently in manufacturing of SO3.

Explanation of Catalytic Poisoning

(1) The poison is adsorbed on the catalyst surface in preference to the reactants.
Even a monomolecular layer renders the surface unavailable for further
adsorption of the reactants. The poisoning byAs2O3 or CO appears to be of this
kind.

O O O

C C C

Figure 3.5 : Poisoning of platinum catalyst by carbon monoxide

(2) The catalyst may combine chemically with the impurity. The poisoning of iron
catalyst by H2S falls in this class

Fe  H 2S  FeS + H 2

7. ACID AND BASE CATALYSIS

A number of homogeneous catalytic reactions are known which are catalysed

by acids orbases, or both acids and bases. These are often referred to asAcid-Base
catalysts. Arrhenius pointed out that acid catalysis was, in fact, brought about by H+ ions
supplied by strong acids, while base catalysis was caused by OH– ions supplied by strong
bases.
2.4 Chemist

Many reactions are catalyzed by both acids and bases. Typical reactions catalysed
by proton transfer are esterification and aldol reaction. Catalysis by either acid or base
can be in two different ways (Specific catalysis and general catalysis).

Example

 Acid-specific (acid catalysis) — Decomposition of Sucrose into glucose and

fructose occurs in presence of sulfuric ac d
 Base-specific (base catalysis) — Addition of hydrogen cyanide to aldehydes
and ketones in the presence of sodium hydroxide

Examples of Acid-Base Catalysis

(1) Inversion of Cane Sugar:

C H O  H H  C H O  C H O
+

12 22 11 2 6 12 6 6 12 6
cane sugar glucose fructose

(2) Keto-Enol Tautomerism ofAcetone

:

(3) Decomposition of Nitramide :

NH2 NO2 +
  N2O  H2O
H

(4) Hydrolysis of an Ester : 

CH COOC +

H  H  CH COOH  C H OH
3 25 or OH 3 2 5
ethyl acetate ethanol
acetic acid

Mechanism of Acid-Base Catalysis

(a) In acid catalysis, the H+ (or a proton donated by Bronsted acid) forms an
intermediate complex with the reactant, which then reacts to give back the proton.
For example, the mechanism of keto-enol tautomerism of acetone is:
Surface Chemistry and 2.4

(b) In base catalysis, the OH– ion (or any Bronsted base) accepts a proton from the
reactant to form an intermediate complex which then reacts or decomposes to
regenerate the OH– (or Bronsted base). For example, the decomposition of
nitramide
3
by OH– ions and CH COO– ions may be explained as follows: By OH– ions:
NH NO  OH   H O  NHNO
2 2 2 2
Intermediate
Complex
NHNO  N O 
2
OH 
2

8. APPLICATION OF CATALYSIS

1. Catalytic Converters

A device incorporated in the exhaust system of a motor vehicle, containing a catalyst

for
converting pollutant gases into less harmfulones.
Catalytic converters are used for mitigating automobile exhaust emissions.
Catalytic converters are used within internal combustion engines fueled by either petrol
(gasoline) or diesel. It converts three harmful substances into harmless ones carbon
monoxide (a poisonous gas) into carbon dioxide, nitrogen oxides (cause acid rain and
smog) into nitrogen and oxygen, and hydrocarbons (cause smog and respiratory
problems) into carbon dioxide and water.
Catalytic converters consist of a stainless steelbox attached to the muffler and
containing ceramic beads or honeycomb coated with catalysts (Expensive metals like
platinum, Palladium, Rhodium are used. Alumina, Ceria can also be used when combined
with expensive metals.)
Eg: Consider the reaction

2 CO + 2   2 CO2  N2

Carbon monoxide and Nitrogen monoxide wil be adsorbed on the surface of catalyst
where they get adsorbed to catalyst and result in formation of carbon dioxide and nitrogen
which gets desorbed.
Catalytic converters can be affected by catalytic poison.
2.4 Chemist

Eg. Lead is a very good example for catalytic poisoning. It gets adsorbed to the honey
comb of expensive metals and inhibits the function of catalyst. Catalytic converter has
also forced the removal of lead from petrol.

Catalyst

N2

Process O2 Exhaust to
Exhaust NOx H2O Atmosphere
O2

NH3

4 NO + 4 NH3  2  4 N2  6H2O
2 NO2  4 NH3  2  3 N2  6H2O



Figure 3.6 : Basic Catalytic Converter

2. Petroleum Refining

(i) Fluid catalytic cracking: Breaking large hydrocarbon into smallerhydrocarbons.

(ii) Catalytic reforming: Reforming crude oilto produce high quality gasoline component
(iii) Hydrodesulfurization: Removing sulfur compounds from refinery
intermediate products
(iv) Hydrocracking: Breaking large hydrocarbon molecules into smaller ones
(v) Alkylation: Converting isobutane and butylenes into a high-quality gasoline
component

(vi) Isomerization: Converting pentane into a high-quality gasoline component

3. Chemicals and petrochemicals

(i) Haber process for ammonia production

(ii) Styrene and Butadiene synthesis for use in producing synthetic rubber
(iii) Contact process for production of sulfuric acid

(iv) Ostwald process for production of nitric acid

Surface Chemistry and 2.4

(v) Methanol synthesis

(vi) Production of different plastics and synthetic fabrics

4. Other

(i) Fischer-Tropsch and Coal gasification processes for producing synthetic fuel
gases and liquidfuels

(ii) Various processes for producing many different medicine

9. BIOLOGICAL CATALYST——ENZYMES

Numerous organic reactions are taking place in the body of animals and plants to
maintain the life process. These reactions being slow remarkably catalysed by the organic
compounds known as Enzymes. All enzymes have been found to be complex protein
molecules. Thus: Enzymes are protein molecules which act as catalysts to speed up organic
reactions in living cells. The catalysis brought about by enzymes is known as Enzyme
Catalysis.
Each enzyme is produced in a particular living cell to catalyse a reaction occurring
in that cell. Many enzymes have been identified and obtained in pure crystalline state from
the cells to which they belong. However the first enzyme as prepared by synthesis in the
laboratory in 1969.
Enzymes are substances found in biological systems that act as catalyst for
specific biochemical process. Enzymes are usually protein or steroid which is synthesized
in the living cells of animals and plants. Enzymes catalyze reactions inside organism.
Enzymes possess a incredible capacity to carry out complex chemical reactions like
hydrolysis, oxidation, reduction etc.
Eg.(i) Amylase is an enzyme which breaks down starch into glucose.

C6H10O5 
n
+ nH2O  nC12H22O11

(ii) Diastase converts starch to maltose and maltase converts maltose to glucose

2  C6 H10 O5  n  nH 2O  nC12 H22O11

nC12H22O11  nH2O  nC12 H22O11
2.4 Chemist

Enzymes speed up reactions by lowering activation energy. Many enzymes change

shape when substrates bind. This is termed as “induced fit”. Enzymes have active sites.
The enzyme active site is the location on the enzyme surface where substrates bind, and
where the chemical reaction catalyzed
Uncatalyst
Reaction
energy
barrier energy Catalyst Reactio
n
barrier
E2
E2
Free energy

reactants reactants
G
G

products products

course of reaction course of reaction

Figure 3.7 : Rate of free energy vs course of reaction

Enzymes do not

 Change the equilibrium constant for a reaction

 Change ΔG for a reaction
 Convert a nonspontaneous reaction into a spontaneous reaction.

KINETICS OF ENZYME CATALYSED REACTION OR MICHAELIS

AND MENTENEQUATION

Consider the enzyme catalyzed reaction:

Surface Chemistry and 2.4

Step 1: Formation of enzyme substrate complex

Step 2: Decomposition of enzyme substrate complex

It can be expressed as follows:

Vmax [S]
V0 
K m [S]

where the terms V0, Vmax and [S] and there is a constant Km, which is known as Michaelis
constant.

Rate of formation of ES = k1 [E]×[S]

Rate of breakdown of ES = (k2 + k3) × [ES]

At steady state, the formation and the breakdown are equal. This steady state would
onlybe temporary.

k1 [E]×[S] = (k2 + k3) × [ES]

Rearranging the above equation :

[ES]  K1 [E] x[S]

(K  K )
2 3

(or) [ES]  [E] x[S]

(K2  K3 ) / K1

But Km (K2  K3 ) and substituting in above equation and we get

 K
1

[ES]  [E] [S] / Km

2.4 Chemist
The total amount of enzyme equals the free and that bound to substrate

[ET] = [E] + [ES]

[E] = [ET]  [ES]

Substitute the value of E
[E] x[S]
[ES] 
([S]  Km

[Et][S]
K
Then [ES] 
1[S] /
Km

This simplifies to:

[ES]  [Et] x[S] / ([S] Km 

Multiplying both sides bythe kinetic constant k3 gives the velocity of the

reaction V = k3 × [ES] = k3×[ET] ×(([S] ([S] + KM )

and substituting Vmax for k3×[ET] leads to the familiar form of the Michaelis Menten Equation:
X[S]
VV
max [S]  K

The above equation is called Michaelis –Menton equation. This equation is

applicable to enzyme catalysed reaction having a single substrate. Aquantitative estimation
of initial rate of reaction, maximumvelocity and substrate concentration is combined
through a constant called Michaelis constant.
Case 1: First order reaction-When concentration of substrate is low.

If Km >> S then s is neglected and then the equation becomes

Rate (v) = Vmax ×[S] | (KM)
Case 2: Zero order reaction-When concentration of substrate is high.
Surface Chemistry and 2.4

If Km << S then Km is neglected and equation becomes

Rate (v) = Vmax ×[S] | [S] so Vmax = Constant

Case 3: If Km = [S] then

Rate (V)  Vmax [S] 1 V


[S]  [S] 2 max

Reciprocating the above equation

1 Km [S]
Rate (v) Vmax [S]

Vmax [S]

Rearranging the above equation:

1 Km [S]
Rate (v) Vmax [S]

Vmax [S]

The above equation is similar to an equation of straight line y = mx + c. Agraph is

plotted between 1/rate and 1/[S] we get a straight line.

0.15

0.10
1/V

0.05

0.1 0.0 0.1 0.2 0.3

1/[s]
Figure 3.8

where slope = Km /Vmax and Intercept =1/Vmax

2.4 Chemist
FACTORS AFFECTING ENZYME ACTIVITY
a. Enzyme Concentration
 If we keep the concentration of the substrate constant and increase the
concentration of the enzyme, the rate of reaction increases linearly. (That is if
the concentration of enzyme is doubled, the rate doubles.)
 This is because in practically allenzyme reactions the molar concentration of the
enzyme is almost always lower than that of the substrate.

b. Substrate Concentration
 If we keep the concentration of the enzyme constant and increase the
concentration of the substrate, initially, the rate increases with substrate
concentration, but at a certain concentration, the rate levels out and remains
constant.
 So at some point, increasing the substrate concentration does not increase the
rate of reaction, because the excess substrate cannot find any active sites to
attach to.

c. Temperature
 For enzyme-catalyzed reactions, like all chemical reactions, rate increases
with temperature. However, enzymes are proteins, and at higher temperatures
proteins become denatured and inactive. Thus, every enzyme has an optimum
temperature.
 Optimum temperature - the temperature at which enzyme activity is highest-
usually about 25oC40oC.

d. Effect of pH
 Small changes in pH can result in enzyme denaturation and loss of catalytic activity.
 Because the charge on acidic and basic amino acid residues located at the active
site depends on pH. Most enzymes only exhibit maximum activity over a very
narrow pH range.
 Most enzymes have an optimum pH that falls within the physiological range of
7.0- 7.5.
 Notable exceptions are the digestive enzymes pepsin and trysin.
 pepsin (active in the stomach) - optimum pH of 1.5

 trypsin (active in the small intestine) - optimum pH of 8.0

  