Heterogeneous catalysis

Lec 9 week 12
Comparison of homogeneous and heterogeneous
catalysts
Comparison of homogeneous and
heterogeneous catalysts
 Heterogeneous Catalysis:
Fundamentals
Individual Steps in Heterogeneous Catalysis
Heterogeneously catalyzed reactions are composed of purely
chemical and purely physical reaction steps.

For the catalytic process to take place, the starting materials must
be transported to the catalyst. Thus, apart from the actual chemical
reaction, diffusion, adsorption, and desorption processes are of
importance for the progress of the overall reaction.
Steps in catalytic reactions
 We will now consider the simplest case of a
catalytic gas reaction on a porous catalyst.
 In heterogeneous catalysis chemisorption
of the reactants and products on the
catalyst surface is of central importance,
so that the actual chemical reaction step
can not be considered independently from
adsorption and desorption steps.
The measured reaction rate, known as the
effective reaction rate, is determined by
the most strongly inhibited and therefore
slowest step of the reaction sequence.
This rate-determining step also
determines the reaction order.
 The Importance of Adsorption in
Heterogeneous Catalysis
For the moment, let us focus our attention on gas-phase reactions
catalyzed by solid surfaces.
For a catalytic reaction to occur, at least one and frequently all of the
reactants must become attached to the surface. This attachment is
known as adsorprion and takes place by two different processes:
physical adsorption (physisorption) and chemical adsorption
chemisorption.

Physisorption is the result of van der Waals forces, and the

accompanying heat of adsorption is comparable in magnitude to the
heat of evaporation of the adsorbate.
chemisorption, chemical bonds are formed between the catalyst
and the starting material. The resulting surface molecules are much
more reactive than free adsorbate molecules, and the heats of
adsorption are comparable in magnitude to heats of chemical
reaction.
both types of adsorption are exothermic.
 Comparison between physisorption and
chemisorption.

Physisorption is fast, and equilibrium is rapidly

reached, even at low temperature.
Chemisorption generally requires high activation
energies. The rate of adsorption is low at low
temperatures, but the process can be rapid at
higher temperatures.
The rate of both types of adsorption is strongly
dependent on pressure. Chemisorption leads
only to a monolayer, whereas in physisorption
multilayers can form.
The type of adsorption that affects the rate of a
chemical reaction is chernisorption
 Factors affect the extent of adsorption on the
catalyst surfaces:

(1) Nature of the adsorbate (gas) and

adsorbent (solid)
(2) Surface area of the solid adsorbent
(3) Effect of pressure on the adsorbate gas
(4) Effect of temperature
 Factors which affect the extent
of adsorption on the catalyst
surfaces:
The following are the factors which affect the
adsorption,
(1) Nature of the adsorbate (gas) and adsorbent
(solid)
(i) In general, easily liquefiable gases e.g., CO2, NH3,
Cl2 and SO2 etc. are adsorbed to a greater extent than
the elemental gases e.g. H2, O2, N2, He etc.

(ii) Porous and finely powdered solid e.g. charcoal,

fullers earth, adsorb more as compared to the hard
non-porous materials. Due to this property powdered
charcoal is used in gas masks.
 Factors which affect the extent
of adsorption on the catalyst
surfaces:
(2) Surface area of the solid adsorbent
(i) The extent of adsorption depends directly
upon the surface area of the adsorbent, i.e.
larger the surface area of the adsorbent,
greater is the extent of adsorption.
(ii) Surface area of a powdered solid
adsorbent depends upon its particle size.
Smaller the particle size, greater is its surface
area.

 Factors which affect the extent

of adsorption on the catalyst
surfaces:
(3) Effect of pressure on the
adsorbate gas
(i) An increase in the pressure
of the adsorbate gas increases
the extent of adsorption.
(ii) At low temperature, the
extent of adsorption increases
rapidly with pressure.
(iii) Small range of pressure,
the extent of adsorption is
found to be directly proportional
to the pressure.
(iv) At high pressure (closer to
the saturation vapour pressure
of the gas), the adsorption
tends to achieve a limiting
value.
 Factors which affect the extent
of adsorption on the catalyst
surfaces:
(4) Effect of
temperature
(i) As adsorption is
accompanied by
evolution of heat, so
according to the Le-
Chateliers principle,
the magnitude of
adsorption should
decrease with rise
in temperature.
 The important factors influencing the
reaction kinetics:

1) Adsorption is a necessary step preceding the

actual chemical reaction on solid catalyst
surfaces.
2) Heterogeneous catalysis involves Chemisorption,
which has the characteristics of a chemical
reaction in that the molecules of the starting
material react with the surface atoms of the
catalyst.
3) Catalyst surfaces have heterogeneous structures,
and chemisorption takes place preferentially at
active sites on the surface.
 Fundamental laws of adsorption
Adsorption
Adsorption is a process in which molecules from gas
(or liquid) phase land on, interact with and attach to
solid surfaces.
The reverse process of adsorption, i.e. the process in
which adsorbed molecules escape from solid
surfaces, is called Desorption.
Molecules can attach to surfaces in two different
ways because of the different forces involved.
These are Physisorption (Physical adsorption) &
Chemisorption (Chemical adsorption)

 Adsorption process
Adsorbent and adsorbate
Adsorbent (also called substrate) - The solid that provides surface for
adsorption
high surface area with proper pore structure and size distribution is essential
good mechanical strength and thermal stability are necessary
Adsorbate - The gas or liquid substances which are to be adsorbed on
solid
Surface coverage,
The solid surface may be completely or partially covered by adsorbed
molecules

Adsorption heat
Adsorption is usually exothermic (in special cases dissociated adsorption
can be endothermic)
The heat of chemisorption is in the same order of magnitude of reaction
heat;
the heat of physisorption is in the same order of magnitude of
condensation heat.
Adsorption Mechanism
 Adsorption Isotherms
Data relating adsorbed concentration (g/g of bed weight) to
equilibrium gas phase concentration (g/ml of stream) is
given in terms of adsorption isotherms.

Wads = f (P,T)

Three common types of isotherms:

Langmuir
Freundlich
BET
 Characterisation of adsorption system
Adsorption isotherm - most commonly used, especially to catalytic
reaction system, T=const.
The amount of adsorption as a function of pressure at set temperature
Adsorption isobar - (usage related to industrial applications)
The amount of adsorption as a function of temperature at set pressure
Adsorption Isostere - (usage related to industrial applications)
Adsorption pressure as a function of temperature at set volume.

V3>V2
P4>P3
V2>V1
P3>P2
T1 V4>V3
Vol. adsorbed
Vol. adsorbed

T2 >T1 P2>P1 V1

Pressure
T3 >T2
P1
T4 >T3

T5 >T4

Pressure Temperature Temperature

Adsorption Isotherm Adsorption Isobar Adsorption Isostere
 Langmuir Isotherm
The earliest model of gas adsorption suggested by Langmuir
(1916). The classical Langmuir model is limited to monolayer
adsorption. It is assumed that gas molecules striking the surface
have a given probability of adsorption. Molecules already adsorbed
similarly have a given probability of desorption. At equilibrium,
equal numbers of molecules desorb and adsorb at any time. The
probabilities are related to the strength of the interaction between
the adsorbent surface and the adsorbate gas.
 Langmuir Isotherm (contd)
Rate of adsorption, ra ka P(1 )

Rate of desorption, rd kd 1-

At equilibrium, ka P
air
ka P kd adsorbate
where,
Wads = the mass of gas adsorbed at pressure P;
W
Wads
ads
CP
CP Wmax = the mass of gas which covers the entire
adsorbing surface with a monolayer;
W
Wmax
max
11CP
CP P = the partial pressure of interest in the gas phase;
= coverage;
C = a constant for the gas/solid combination = ka/kd;
ka = the adsorption rate coefficient;
kd = the desorption rate coefficient.
 Langmuir Isotherm (contd)
Some physisorption and most chemisoption
processes follow this isotherm. It is the one One can obtain the two
with the best theoretical basis, which constants by linearization
assumes that adsorption is limited to one of the isotherm: take the
monolayer on the surface. reciprocal and rearrange

Wads CP P 1 P

Wmax 1 CP Wads CWmax Wmax

S = 1/Wmax
P/Wads

C
J = 1/CWmax
0
P P
 Langmuir Isotherm (contd)
It is particularly suited to represent binary and ternary systems.

Wi bi Pi
i n
Wi ,max 1 bi Pi
i
 Assignment
Define the Langmuir
Isotherm
in case of liquid
phase.
 Freundlich Isotherm

The Fruendlich isotherm model is valid for heterogeneous

surfaces, monolayer coverage. Common for most
adsorption work since it fits almost all data. It is
empirical in nature, although some theoretical foundations
do exit.
 Freundlich Isotherm
The expression Wads = KF P 1/n
(KF and n are experimentally determined parameters)

When n = 1, the reaction is linear and called

n>1 partitioning.
When n > 1, the reaction is said to be favorable as
n=1 the incremental change in amount sorbed decreases
with increasing concentrations.
Wads While n < 1 is called unfavorable because the
n<1 reverse is true.
Most natural adsorbents exhibit either linear or
favorable adsorption.
The Langmuir and Fruendlich models for n < 1 are
concave downwards, so both models can be
P calibrated to similar data..
 Freundlich Isotherm (contd)
Wads = KF P 1/n lnWads = lnKF + 1/n lnP

n>1

n=1
Wads log ln Wads 1/n
n<1

ln KF

P ln P
Freundlich Isotherm Parameters
Available for a wide variety of organic vapors on
various activated carbon types Wads = KF P 1/n
Brunauer-Emmett-Teller (BET) Isotherm

Brunauer, Emmett and Teller (BET) developed

several models for gas adsorption on solids
which have become the effective standard for
surface area measurements.
BET isotherm is valid for multiple layers on
homogeneous surfaces.
 Brunauer-Emmett-Teller (BET) Isotherm
The assumptions underlying the simplest BET isotherm are:
1. Gas adsorbs on a flat, uniform surface of the solid with a uniform
heat of adsorption due to van der Waals forces between the gas
and the solid.
2. There is no lateral interaction between the adsorbed molecules.
3. After the surface has become partially covered by adsorbed gas
molecules, additional gas can adsorb either on the remaining free
surface or on top of the already adsorbed layer. The adsorption
of the second and subsequent layers occurs with a heat of
adsorption equal to the heat of liquefaction of the gas.

multi-layers adsorption
 BET Isotherm (contd)
Work for almost any type of data on the adsorption of gases on solids. It describes
every type of isotherm including the linear, and Langmuir isotherms. The theoretical
basis is sound.

For single component the equation is,

CP

P for n Wads
P0 P 1 C 1
P0

Cx 1 ( n 1) x n nx n 1

(1 x ) 1 (C 1) x Cx n 1 for finite n P

Note that n is the number of adsorbed monolayers, and x = P/P0. Where, P is the
actual partial pressure of gas in the stream and P0 is the vapor pressure of the pure
gas.
Note: The BET simplifies to the Langmuir when relative pressure x < 0.01 and C >100 (Valsaraj et al.,
 BET Isotherm (contd)
To obtain the parameters in the BET equation, one needs to linearize the
equation:
1 P (C 1) P 1

Wads ( Po P ) CWmax Po CWmax

1 P S
Wads ( Po P ) S = (C-1)/CWmax C 1
J
J = 1/CWmax 1
Wmax
SJ
P/Po
The most common isotherm models [Dastgheib and Rockstraw, 2002]