Surface Chemistry and Catalysis 2.

Unit II

SURFACE CHEMISTRY
AND CATALYSIS
Introduction - Terminologies in surface chemistry - Difference between adsorption
and absorption - Types of adsorption - Adsorption isotherm- Freundlich Adsorption
Isotherms- Langmuir Adsorption Isotherm - Contact Theory (or) Mechanism of
Heterogeneous Catalysis - Kinetics of Surface Reaction - Kinetics of Bimolecular
Reaction (Langmuir-Hinshelwood) - Types of Adsorption Isotherm - Application
of Adsorption- Terms - Mechanism of Catalytic Reaction- Criteria (or) Characteristics
for Catalyst Types of Catalysis - Homogeneous Catalysis - Heterogeneous Catalysis-
Catalytic Poisoning and Promoters Application of Catalysis- Biological Catalyst—
—Enzymes - Kinetics of Enzyme Catalysed Reaction Or Michaelis and Menten
equation - Factors Affecting Enzyme Activity

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
2.2 Chemistry
y

TE
ERMINOLO
OGIES IN
N SURFACE
E CHEMIS
STRY

Adsorrbate: The suubstance whicch gets adsorb

rbed on any suurface is calleed adsorbate..

Adsorrbent: The suubstance on thhe surface off which adsorrption takes place
p is calledd
adsorb
bent.

Adsorrption: The prrocess wherebby moleculess of gases or liiquids adhere chemically too
the surrface of a soliid.

(Eg.) Occlusion
O off Hydrogen gas
g on Palladiium where paalladium is addsorbent andd
hydrog
gen gas is adssorbate.
1Ad
dsorbent - the gas adsorbed
on
n the surface off solids

Adsorbent - the solid wherre

adsorption ta
akes place

Figure 2.1 : Adsorption Prrocess

Desorrption: The removal off the adsorbeed substancee from a surrface is

called desorption.

ace: The planne which sepaarates any twoo phase is gennerally called an
Interfa a interface.

Absorrption: Whenn the moleculees of a substannce are uniform

mly distributeed throughoutt
the bod
dy of a solid or
o liquid. Thiis phenomenoon is called abbsorption.

Sorptiion: The phennomenon in which

w adsorptiion and absorpption occur siimultaneouslyy
is calleed sorption.

usion: When adsorption of

Occlu o gases occcurs on the suurface of meetals it is
called occlusion.
Surface Chemistry and Catalysis 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 is shaken with blood charcoal it shows negative 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

2.4 Chemistry
y

S.No. ABSOR
RPTION ADSOR
RPTION
1. It is a bulk phennomenon It is a suurface phenom
menon
2. It is a slow proccess It is a faast process
3. Su
ubstance unifoormly distribuuted Higher concentration of molecular
th
hroughout the surface species in the surfacee than in the buulk
4. Attainment
A of equilibrium
e takkes Equilibrium attained easily
tim
me
5. Eg
g.: Ammoniia adsorbed in Eg.: Am
mmonia adsorbbed in water
ch
harcoal

TY
YPES OF ADSORPTI
A ION

Physical
P Addsorption Cheemical Adso orption
Figure 2.4 : Illustration off Physical and Chemical
C Adso
orption

e
d d
b
e r
b o
r s
d
o
s
d

Temperature
Temp
perature
Figure 2.5 : Amount of
o gas adsorbed
d vs temperature
Surfface Chemis
stry and Cattalysis 2.5

S.N
No Physical ad
dsorption or Chem
mical adsorpttion or Chem
misorption
Physisoorption
1. Caussed by intermoleccular Causedd by chemical bond formation
vand
derwaal’s forcees
2. Not specific
s in natture Highlyy specific in naature

3. Reveersible in naturre Irreverrsible in naturee

4. Multtimolecular layyers are formeed Unimoolecular layerss are formmedd on the

on th
he adsorbed suurface surfacee
5. Heaaat of adsorptioon is less (20 too 40 Heat of adsorption iss large (80 to 240
KJ/m
mole) KJ/moole)
6. No activation
a enerrgy is requiredd High activation
a enerrgy is requiredd

7. Depeends on naturee of gas. Easilyy Depends on natuure of adsoorbent and

Liqu
uefiable gasees are adsoorbed adsorbbate
easily
8. Occu
urs at low temp
mperature Increasses with increaase in temperaature

9. Increease in prressure incrrease High pressure

p is favoourable. Decreease in
adsorption pressurre does not caause desorptionn

Adsorption of Gases on Solids

In adsorpption of gases on solid surfface, the solidd surface is caalled the adsorrbent and thee
gas adsorbed
a is called adsorbbate. The exteent of adsorpption dependss on many facctors.

Abs
sorbed
Gas Molecules
M

Solid
Surface

Solid

Figure 2.6 : Adso

orption of gasees on solids
2.6 Chemistry

2.2 FACTORS AFFECTING THE EXTENT OF ADSORPTION

(i) Nature of Adsorbent

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 of adsorbent

Increase in surface area of the adsorbent increases the adsorption of gases and the
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 porosity greater 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. Easily liquefiable
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 Catalysis 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: Easily liquefiable 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
2.8 Chemistry

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
(or) log = log k + log C
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 highly specific. Adsorption depends mainly on nature
of adsorbent.
Temperature
Adsorption from solution decreases with rise in temperature.
Concentration of solute
Adsorption from solution 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.
Surfface Chemis
stry and Cattalysis 2.9

Adsorbent + Addsorbate Adsorption

Adsorptio on isotherm shows
s the am
mount of molecules adsorbeed on the solid surface as a
functtion of the equ
uilibrium parttial pressure at
a constant tem
mperature.

Adsorp
ption Isotherm
m

X/m
S
Saturation Prressure

P PS

Figure 2.8 : Adsorption Iso

otherm

A plot off x/m vs P is plotted

p to obbtain adsorption at constannt temperaturre, Ps is calledd
the saturation
s prressure.

FR
REUNDLIC
CH ADSOR
RPTION IS
SOTHERM
MS

In 1909, Herbert
H Freunndlich gave ana expression representing the isothermmal variation of
adsoorption of a qu
uantity of gas adsorbed by unit
u mass of solid
s adsorbennt with pressuure.Freundlichh
adsoorption isotherrm is an empiirical relation between the concentrationn of a solute ono the surfacee
of ann adsorbent tot the concenntration of thee solute in the liquid with which it is inn contact. Thee
isothherm is given as:
a

⎛1⎞
x ⎜ ⎟
= k ⋅ p⎝n ⎠ [ n > 1]
m

x 1
(or) log = log k + log P
m n
wherre x – is maass of adsorbbate,
m – is maass of adsorbbent,
P – is the equilibrium pressure
p of addsorbate,
K & n – are co
onstants.
2.10 Chemistry

At low pressure, extent of adsorption is directly proportional to pressure:

x
∝ p1
m
At high pressure, extent of adsorption is independent of pressure:
x
∝ p0
m
At intermediate value of pressure, adsorption is directly proportional to pressure raised
1
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

⎛1⎞
x = k ⋅ p⎜⎝n ⎟⎠
m
The above equation is known as Freundlich Adsorption equation.

Plotting of Freundlich Adsorption Isotherm

⎛1⎞
x ⎜ ⎟
= k ⋅ p⎝n ⎠
m

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 Catalysis 2.11

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

2.12 Chemistry

Assumptions of Langmuir Isotherm

Langmuir proposed his theory by making following assumptions.

(i) Surface is energeticallyuniform. Fixed number ofvacant or adsorption sites 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 maximum of one gaseous molecule and a constant amount of heat
energy is released.
(iii) Heat of adsorption is constant throughout the surface and it ranges from 0 to 1.
(iv) Dynamic equilibrium exists between adsorbed 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 equilibrium equation, equilibrium constant can be calculated.
Adsorption
A(g)+B(s) 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 ‘θ’ is introduced.
Surface Chemistry and Catalysis 2.13

Let θ 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 – θ) and
pressure, P.
Rate of forward reaction ∝ P (1 − θ)

Rate of adsorption ∝ P (1 − θ) or

Rate of adsorption = Ka P (1 − θ)

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 ∝ θ (or)

Rate of desorption = Kd θ

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

Ka P (1 − θ) = Kd θ

The above equation can be written in terms θ.

Ka P − Ka Pθ = Kd θ

Ka P = Ka Pθ + Kd θ

Ka P = ( Kd + Ka P)θ

Ka P
θ=
(Kd + Ka P)

Divide numerator and denominator on RHS by Kd , we get

Ka
P
Kd
θ=
K d Ka
+ P
K d Kd
Ka
But K =
Kd
 2.14 Chemistry

Substituting in the above equation we get

KP
θ=
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
θ=
Vmono

Substituting the value of θ in Langmuir equation

V KP
=
Vmono 1 + kP

1
(or) Vmono =1+
kP
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.
Surfface Chemis
stry and Cattalysis 2.15

(
(iv) Langm
muir equationn assumed thaat molecules do not interaact with eachh other. This iss
imposssible as weakk force of attraaction exists even betweenn molecules of
o same type.
(
(v) orption liquefaaction of gases taking placee, which resultts in decrease in
In adso i randomness
but thee value is not zero.
z
5. CONTACT
T THEORYY (OR) MECHANISM
M OF HETE
EROGENEOUS
CATALYS
SIS (OR) ADSORPT
A TION THEO
ORY
This theoory postulateed by Faradaay in 1883. Itt explains thee action of heterogeneouus
catallysis. Heterog
geneous catallysis has five steps.

Figuree 2.11 : Mechaniism of heterogeeneous catalysis

(
(i) Diffusion of Reacttant(s) to thee Surface: Thhe reactants diffuse
d to the surface of thee
catalyssts. Some of thhe reactant crross the barrieer and enter thhe interior exp
xposed surfacee
that inccludes paths and
a cracks onn the externall surface.
(
(ii) Adsorrption of reaactants: Bonnds are formeed as the reacctant(s) are adsorbed ontoo
the surrface of the caatalyst. The ability
a for an atom
a or moleecule to stick to
t the surfacee
is know
wn as the Sticcking Co-efficcient.
(
(iii) Reactiion: The reaactants, whenn bound to thhe surface haave a higher probability
p of
reactin
ng with each other,
o and afteer the reactionn, they formann intermediatte compound..
(
(iv) Desorp ducts: The inttermediate com
ption of prod mpound getss desorbed froomthe surfacee,
which again becomees available for
fo adsorptionn for other moolecules

(
(v) uct(s): The inntermediate coompound theen disintegratees to form thee
Diffusion of Produ
final prroducts and thhe products are
a then desoorbed from thhe surface of the
t catalyst.
2.16
6 Chemistry
y

For example,
e
1. Conversion
C of
o ethylene to ethane

Ethylene
Ni surface

Ethyle
ene absorbed ono
e breaking π bonds
surface

A (g)+B(s)
N 2( g)+3H 2(g) ⎯⎯→ 2N 3(g) →
A ( g ) ← ⎯ → A ( a d s )
B ( g ) ← ⎯ → B ( a d s )

A( a ds)+B(a ds) ⎯r⎯ds →A B(a ds) ⎯f ⎯ast⎯→ A B( g)

k θ θ
A B
θ=b⋅P

Figu
ure 2.12 : Conversion of ethyleene to ethane

2. Haber–Bosc
H ch reaction
The origiinal Haber–BBosch reactiion chambers used osmiuum as the caatalyst, less
expeensive iron-b
based catalysst, which is still
s used todday.

N 2 ( g) + 3 H 2 ( g) ⎯⎯
⎯
→ 2 NH3 (g)

The reacttion mechanissm, involving the heterogenneous catalysst, is believed to

t involve thee
follow
wing steps:
1. N2 (g) → N2 (adsorbed)
(
2. N2 (adsorbed)) → 2 N (adssorbed)
3. H2 (g) → H2 (adsorbed)
(
Surface Chemistry and Catalysis 2.17

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
θ=
(1+ b ⋅ P)
2.18 Chemistry

The rate of the surface decomposition is given by an expression :

Rate = k θ

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)

k ⋅b ⋅ P
Rate =
(1+ bP)

k
Rate =
(1+ bP)

Therefore

(1 + b ⋅ P) ~ b⋅ P and Rate ~ k

Under high pressure θ is almost unity.

Surface Chemistry and Catalysis 2.19

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) ⎯r⎯

ds
→ AB(ads) ⎯f⎯
ast
⎯ → 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 θA θB
According to Langmuir adsorption isotherm:
b⋅ P
θ=
(1+ b ⋅ P)
where two molecules (A & B) are competing for the same adsorption sites then
bA PA bBPB
θA = and θB =
1+ bA PA + bB PB 1+ bA PA + bB PB
Substituting these into the rate expression gives:

Rate = k θ A θ B = k bA PA ⋅bB PB
(1+ b P + b P )2
A A B B
2.20 Chemistry

Condition

1. Reactant Aand B in first order then

bA PA <<1 and bB PB <<1

θA & θB are very low.

Hence, Rate → k bA PA bB PB = k ′PA PB

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

bA PA <<1<< bB PB

kb P
= A A k ′PA
θA → 0, θB →1 so Rate
(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

Surface Chemistry and Catalysis 2.21

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.

X
m

Ps
P

Figure 2.15 : Type I

Type IIAdsorption isotherm shows large deviation from Langmuir modelof adsorption.
They are most frequently encountered when adsorption occurs on nonporous powders or
macroporous adsorbents with unrestricted monolayer -multilayer adsorption.
The intermediate flat region in the isoth e rm corresponds to monolayer formation. When
2H K2 (Cg )Ol 3+ H⎯ 2⎯Mn (gOo2 )⎯→⎯S) 2⎯→ 2KC Hl (+3 3Og )

3r37oo0m Cte mp. 2

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
K1
[ ES ] = [E ] [S ]/ K m
+ C 2 H C5 l ⎯ ⎯A Cl ⎯→l3 C H6 C5 2 H +5 H C l
R C O O R + H O ⎯ ⎯H+ ⎯or ⎯OH →− R CO O H + R O′ H
est er 2
2 K M n O +4 5 H C2 O2 4 + 3H 2 SO 4 ⎯ ⎯→ 2 Mca Sntaly Ost 4 + K S2 O 4+ 8 H O2 + 1 0 CO2

lA2 3O

C 2 H5 O H ⎯ ⎯ ⎯→ C H 2et =hen CΗe 2 + ΗO2

S O 2 + O 2 ⎯ ⎯Pt → 2 S O 3
CC 2 HH5 O OH ⎯ + H⎯ →⎯ C H⎯H+ C→3eth HCano OHl + HO 2 + C H O

the monolayer formation of the adsorbed molec u les are complete, multilayer formation starts to
A OFes2 3
N 2 + 3 H 2 ⎯ ⎯2HS → 2N H 3

/ /// /
2 H 2 + O 2 ⎯ ⎯tCOP → 2 H O2

c1a2 ne sug22 ar1 1 2 6g 1luco 2se 6 6 fruc 12tos 6e

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 eti c aci 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 + Ο ⎯ ⎯→ 4 N + 6 H O
3 2 2 2
2 N O 2 4+ N H 3 + Ο 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−
CInt oem rm ple edi xate
N H NO 2− ⎯ ⎯→ N 2O + O H −
Fe
Mo 2 N H 3
2 A s H3 ⎯ ⎯→ 2 As + 3H 2
ca taly st

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

X
m

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.
2.22 Chemistry
Eg: Bromine (Br2) at 790°C on silica gel or Iodine (I2) at 790°C on silica gel.
Surface Chemistry and Catalysis 2.23

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.

X
m

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.
2.24
4 Chemistry
y

X
m

P Ps

Figurre 2.19 : Type V

a Type V isotherms doo not have thee ‘sharp kneee’ shape imply
Type III and lying strongerr
adsoorbate – adsorrbate interacttions than adssorbate-adsorrbent interacttion.
V and V show
Type IV ws phenomenon of capillary condenssation of gass.

V
Volume of
gass adsorbed I II III IV V

P0 P0 P0 P0 P0
Pressure
Figure 2.20 : Differentt types of adsorrption isotherm
ms

8. APPLICAT
A TION OF ADSORPTI
A ION

Extensive applicationn of adsorptiion is been listed below

(i) Production
P n of high vacuum

In Dewarr flasks activaated charcoall is placed bettween the waalls of the flassk so that gass
enterring into the annular
a spacee gets adsorbeed.
(ii) In Gas massks

Activatedd carbon is useed in gas massks to adsorb poisonous gaases (e.g. oxidde of sulphur,,
NOxx etc.) and pu
urifies air for breathing.
b
Surface Chemistry and Catalysis 2.25

gas molecules

Activated Charcoal

Figure 2.21 : Adsorption of poisonous gases using activated charcoal

(iii) In desiccation or dehumidification

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 is decolorized 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
2.26 Chemistry

(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. Finely powdered 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 the surface;
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 of adsorption.
(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

Surface Chemistry and Catalysis 2.27

(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 hard water

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
Fat or Oil Stain Add tension between the
Surfactant fabric and the stain

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

2.28 Chemistry

(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 stream to 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 thermally cleaned.
Advantages

1. Ideal plug flow behavior

2. Lower maintenance cost

Disadvantage

1. Plugging of bed due to coke deposition which results in high pressure drop.
Surfface Chemis
stry and Cattalysis 2.2
29

products and
unrreacted materiaals
to separation

catalyst
on support

diffuser

reactants

Figure 2.24 : Fixed Bed Reacttor Device

Vent
gas

Recirculating
Caustic Liquor
C Caustic Ma
ake-up
Scrubbing
To
ower

Cooler
e”
“End of Pipe
Chlorine
e Fixed Bed Reacctor
Laden
Gas Liquid
Efffluent
Recirculating Blowdown
(to
o drain
Pump Stream andd
or re
ecycle)
Optional
Preheater

Figure 2.25 : Schematic representation

r of fixed bed reaactor

[2] Continuous Flow Reacctor Systemss

Continuo ous-flow reacctors are almoost always opperated at steeady state. Thhese are moree
compplex and prov vide continuoous operationns. These sysstems providde in-situ desoorption of thee
adsoorbates from the adsorbennt. This can beb done withh superheatedd or saturated steam. Thee
adsoorbate can bee condensed, collected, annd re-used inn the processs. There are two
t adsorberr
 2.30
0 Chemistry
y

unitss in the system

m. The gases are being adssorbed in onee unit as the otther unit is beeing desorbedd
withh steam. The exhaust from m the desorbeed bed can bee condensed for solvent reuse r or otherr
beneeficial purposee.
Stirrer

Liquid Surface
Inputt Rate V

Ou
utput Rate

Figure 2.26 : Co
ontinuous Flow
w Reactor

[3] Special Typ

pe of Continu
uous System
m (Zeolite Con
ncentrator, or
o Rotary Cooncentrator))

A hydropphobic zeolitee is designed in a monolithhic rotor in which

w the conntaminated airr
flow
ws. An integraated thermal oxidizer is used to providde desorptionn of the solveents from thee
zeoliite. They havee wide accepttance in indusstrial air polluution control applications.
a

CHAPTE
ER 3: Cata
alysis
A cata alyst is defined as a su
ubstance which
w alters the rate of a chemical reaction,
itself remaining
r chemically
c u
unchanged at the end of the reacction. The process
p is
calledd catalysis.

3.1 INTRODU
UCTION

The word d “catalyst” was

w introducced into sciennce by the greeat Swedish chemist Jonss
Jakob Berzelius (11779-1848) who
w also determ rmined the atoomic and moleecular weightss of thousandds
of suubstances, discovered seveeral elements including
i seleenium, first isoolated siliconn and titanium
m,
and created
c the prresent system
m of writing chhemical symbbols and reacttions.
Catalysts are of immennse importancce in chemistrry and biologyy. All enzymees are catalystts
that expedite
e the biochemical
b r
reactions neccessary for liffe. (eg) Enzym
mes in saliva accelerate
a thee
convversion of starrch to glucosee.

3.1.1 DEFINITION

The proccess by whicch a substancce speeds upp a chemicaal reaction without

w beingg
conssumed or alteered in the process.
p
2.30
0 Chemistry
y

P
A B Begin
B
Nexxt Cycle
Cataalyst Ca
atalyst
Bonding
Cattalysis Separattion
A B C
Cycle P
Cata
alyst Ca
atalyst
Reacction
A & B = Reactantss
P = Product
Figure 3..1 : Catalysis Cyycle

1. TERMS
T
1. Catalyst

A catalysst is a substannce that decrreases the acttivation enerrgy of a chem

mical reactionn
without itself beiing changedd at the end ofo the chemiccal reaction
(or)

It is the small
s amounnt of substannce which allters the veloocity of reacction without
alterring in any change
c in maass and compposition at thhe end of thee reaction.
2. Positive an
nd negativee catalyst

Catalyst helps
h in alterinng the velocitty of the reacttion and the catalyst
c is callled as positivee
catallyst.eg.MnOO2 acts as cataalyst in decom mposition of KClOK 3 into KCl
K and O2.S Some catalysst
havee the capacityy to retard thhe chemical reeaction and theyt are calleed as negativve catalyst .egg
Alcoohol retards th
he conversionn of chloroforrm to phosgenne.
3. Auto Catalysis

ducts of a reacction act as a catalyst

If the prod c for thee reaction, it iss referred to ass autocatalysiss
Eg. RCOOR′ + H 2 O ⎯⎯
⎯ → RCOO
OH + R′OH

Reactants Prroduct + Catallysts

positive
feedback
Surfface Chemis
stry and Cattalysis 2.31

2. MECHANIS
M SM OF CA
ATALYTIC REACTIO
ON
incre
easing energy

gas
s molecule

ga
as molecule
Adsorption
A of gas
s molecules on to catalyst
active
a sites. The molecules
m are che
emically
bondedd to the catalyst

desorption of
product
Adsorption as se
eparate atoms, inddividually
chemically bondded to catalyst acttive sites
adsorbed product

Ste
epwise reactio
on on catalyst surface
s

Fig
gure 3.2 : Mech
hanism of catalyytic reaction

3. CRITERI
IA (OR) CH
HARACTE
ERISTICS FOR CATA
ALYST

(
(i) A catalyst remains unchanged inn mass and chemical
c commposition at the
t end of thee
reactio
on qualitative and
a quantitatiive analysis shhow that a cattalyst undergooes no changee
in masss ofchemical nature.
n Howeever, it may unndergo a physsicalchange. Thus
T granularr
mangan
anese dioxide (MnO2) usedd as a catalystt in the thermaaldecomposinng of potassiuum
chloraate is left as a fine powdeer at the end to the reactiion.
(
(ii) A smalll quantity of catalyst is generally needeed to producee almost unlim mited reactionn
Somettimes a trace of a metal catalyst
c is reqquired to affeect very large amounts of
reactan
nts. For exammple, one ten--millionth of its
i mass of finnely divided platinum
p is alll
that is needed to catalyse the decompositio
d on of hydroggen peroxidee.

On thee other hand, there are cattalysts whichh need to be present

p in rellatively largee
amoun
nt to be effectiive. Thus in Friedel-Crafts
F s reaction,

C6 H6 + C2 H5Cl ⎯ A⎯ ⎯
lCl3
→ C 6H
5 2 5C H + HC
Cl

anhydro ous aluminiumm chloride fuunctions as a catalyst

c effecctively when present
p to thee
extent of 30 per cennt of the masss of benzene. For the acidd and alkaline hydrolysis of
an esteer
2.32 Chemistry
+ −
RCOOR + H O ⎯ ⎯ ⎯ ⎯→ RCOOH + R′OH
H or OH
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,
C H OH ⎯A⎯
l2O3
⎯ → CH = CΗ + Η O
2 5 2
ethene
2 2 (Dehydration)

but with hot copper it gives ethanal (CH3CHO)

C H OH ⎯⎯ Cu
→ CH CHO + H
2 5 3
ethanol
2 (Dehydrogenation)

(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 temp.
→ No reaction
2H2 + O 2 ⎯P⎯ ⎯→ 2H2O
t black

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 end of
the reaction.
Surface Chemistry and Catalysis 2.33

(vii) Catalyst can alter only the speed of the reaction but it should not affect the equilibrium
of the 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 gases such as 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.
2.34 Chemistry

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 iron prepared by reducing 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

MnO2 (S)
2 KClO3 ⎯⎯o ⎯ → 2 KCl + 3O 2
370 C

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⎯ ⎯→ 2 Na 2SO 4

lcohol

(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.
Surface Chemistry and Catalysis 2.35

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 ⎯⎯
→ CH3COOΗ + C2 H5OH
catalyst

(2) Oxidation of Oxalic acid. Whenoxalic acid is oxidised by acidified potassium permanganate,
manganous sulphate produced during the reaction acts as a catalyst for the reaction.
→ 2 MnSO 4 + K2SO4 + 8 H2O +10 CO2
2 KMnO4 + 5H2C2O4 + 3H2SO4 ⎯⎯
catalyst

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

→ 2 As + 3H2
2 AsH3 ⎯⎯
catalyst
2.36 Chemistry

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 Cr2O3 3

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.

Surface Chemistry and Catalysis 2.37

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 arsenic oxide (As2O3)

SO2 + O2 ⎯ ⎯ 2SO3
Pt

→
As2O3

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

N2 + 3H2 ⎯ ⎯ 2NH3
Fe

→
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
2.38 Chemistry

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 or bases, 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.
Surfface Chemis
stry and Cattalysis 2.39

Many reaactions are caatalyzed by both

b acids andd bases. Typiical reactionss catalysed byy
protoon transfer arre esterificatiion and aldoll reaction. Caatalysis by eitther acid or base
b can be inn
two different
d wayys (Specific caatalysis and general catalyssis).

Exam
mple

Acid-sp
pecific (acid catalysis)
c — Decompositio
D on of Sucrosee into glucosee and fructosee
occurss in presence of
o sulfuric aciid
Base-sspecific (basee catalysis) — Addition of
o hydrogen cyanide
c to alldehydes andd
ketonees in the preseence of sodium
m hydroxide..

Exam
mples of Accid-Base Ca
atalysis

( Inversion
(1) n of Cane Suggar:

C H O + H ⎯H⎯→ C H O + C H O
+

12 222 11 2 6 122 6 6 12 6
cane sugar
s glucoose fructosee

( Keto-Eno
(2) ol Tautomerissm ofAcetonee :

( Decompo
(3) osition of Nitrramide :
+
N 2 ⎯H⎯→ N2O + H2O
NH2 NO

( Hydrolysis of an Esterr :
(4)
H+
CH COOC
C H ⎯ ⎯−→ CH COOH
C + C H OH
3 2 5 or OH 3 2 5
ethhyl acetate e
ethanol
acetic acid

Mecchanism of Acid-Base
A Ca
atalysis

I acid catallysis, the H+

(a) In + (or a protonn donated byy Bronsted accid) forms ann intermediatee
c
complex with the reactannt, which then reacts to give
g back the proton. For example, thee
m
mechanism of keto-enol taautomerism of
o acetone is:
2.40
0 Chemistry
y

alysis, the OH
(b) IIn base cata H– ion (or anyy Bronsted baase) accepts a proton from
m the reactannt
t form an in
to ntermediate coomplex whichh then reacts or decomposes to regeneerate the OH––
( Bronsted
(or d base). For example, thhe decompossition of nitrramide by OH– O ions andd
C 3COO– io
CH ons may be exxplained as follows:
fo By OH
O ions:
–

N + OH − ⎯⎯
NH NO ⎯ → H O + NHNO−
2 2 2 2
Intermediate
Complex
NHNO− ⎯⎯
⎯ → N O + OH −
2 2

8. APPLICAT
A TION OF CATALYSI
C IS

1. Catalytic Converters
C

A device incorporated
i d in the exhausst system of a motor vehiclle, containingg a catalyst forr
convverting pollutaant gases intoo less harmful ones.
Catalytic converters area used for mitigating
m auutomobile exhhaust emissioons. Catalyticc
convverters are useed within interrnal combustioon engines fuueled by eitherr petrol (gasolline) or diesell.
It connverts three harmful
h substtances into haarmless ones carbon
c monoxxide (a poisonnous gas) intoo
carbon dioxide, nitrogen
n oxiddes (cause accid rain and smog) into nitrogen
n andd oxygen, andd
hydrrocarbons (caause smog andd respiratoryy problems) innto carbon diooxide and waater.
Catalytic converters coonsist of a staiinless steelboox attached too the muffler and
a containingg
ceram
mic beads or honeycomb coated
c with catalysts
c (Exppensive metalls like platinumm, Palladium
m,
Rhoddium are used
d. Alumina, Ceria
C can alsoo be used wheen combined with w expensivve metals.)
Eg: Consider
C thee reaction

⎯ → 2 CO2 + N2
2 CO + 2 ΝΟ ⎯⎯

Carbon monoxide
m andd Nitrogen monoxide
m willl be adsorbedd on the surfaace of catalysst
wherre they get ad
dsorbed to cattalyst and resuult in formatioon of carbon dioxide
d and nitrogen
n whichh
gets desorbed.
Catalyticc converters can be affeccted by catalyytic poison.
Surface Chemistry and Catalysis 2.41

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 + Ο2 ⎯⎯
→ 4 N2 + 6H2O
2 NO2 + 4 NH3 + Ο2 ⎯⎯
→ 3 N2 + 6H2O

Figure 3.6 : Basic Catalytic Converter

2. Petroleum Refining

(i) Fluid catalytic cracking: Breaking large hydrocarbon into smaller hydrocarbons.
(ii) Catalytic reforming: Reforming crude oil to 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

2.42 Chemistry

(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 liquid fuels

(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.

( C6 H10O5 )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
Surfface Chemis
stry and Cattalysis 2.4
43

Enzymes speed up reacctions by low wering activation energy. Many

M enzymess change shapee
whenn substrates bind.
b This is termed
t as “in
nduced fit”. Enzymes
E havve active sitess. The enzymee
activve site is the lo
ocation on thhe enzyme surrface where substrates
s binnd, and wheree the chemicaal
reacttion catalyzed d
Uncatalyst
Reaction
energy
barrier energgy Catalyst
barrier Reaction
n
E2
Free energy

E2

reactants reactants
s

ΔG ΔG

produc
cts products

course of reaction course of reacttion

Figure 3.7 : Rate of freee energy vs co

ourse of reactio
on

Enzyymes do not

• Change th
he equilibrium
m constant forr a reaction
• Change ΔG
Δ for a reacttion
• Convert a nonspontanneous reactionn into a spontaaneous reactiion.

KINETI
ICS OF EN
NZYME CATALYSED
D REACTIO
ON OR MIC
CHAELIS
AND MENTEN EQUATION
E N

Considerr the enzymee catalyzed reaction:

r
2.44
4 Chemistry
y

Stepp 1: Formatiion of enzym

me substrate complex

Stepp 2: Decomposition of en
nzyme substtrate complex
ex

It can be expressed as
a follows:

Vmax [S]
V0 =
K m +[S]

wherre the terms V0, Vmax andd [S] and theere is a constant Km, whicch is known as Michaeliis
consstant.

Rate of formation
f off ES = k1 [E]×
×[S]

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

At steady
y state, the foormation andd the breakdoown are equall. This steadyy state wouldd
onlybe temporary
y.

k1 [E]×[S]] = (k2 + k3) × [ES]

Rearrang
ging the abovve equation :

[ES] = K [E] x[S]

(K + K )
1
2 3

[E] x[S]
(or) [ES] =
K2 + K3 ) / K1
(K

But Km = (K2 + K3 ) and substituuting in abovve equation and

a we get
K
1

[ES] = [E]] [S] / Km

Surface Chemistry and Catalysis 2.45

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 by the 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 = Vmax
[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, maximum velocity 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.
2.46 Chemistry

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

max
[S] + [S] 2

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

Surface Chemistry and Catalysis 2.47

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