School of

Institute of Chemical and Food

Technology Engineering

Lecture Note - VI
Catalysis and Catalytic Reactor Engineering
(Basics of Catalysis and Surface Reactions )
(Reading Material- Chapter 10 and 11 of H. Scott Fogler)

Nigus Gabbiye Habtu (PhD),

Associate professor of Chemical, Environmental and Process Engineering
Basics of heterogeneous Catalysis in multiphase
systems

➢ What will happen on bluk phase???

➢ What will happen in catalyst pore???
➢ What will happen on the catalyst surface???
2
 What is Catalyst???
▪ “A catalyst accelerates a chemical reaction without affecting the
position of the equilibrium.” A definition that is still valid today is
due to Ostwald (1895):

▪ While it was formerly assumed that the

catalyst remained unchanged in the
course of the reaction, it is now known that Catalytic cycle
the catalyst is involved in chemical
bonding with the reactants during the
catalytic process.

▪ Thus catalysis is a cyclic process: the reactants are bound to one

form of the catalyst, and the products are released from another,
regenerating the initial state.
3
 What is Catalysis???
– Catalysis is the occurrence, study, and use of catalysts and catalytic

processes

– Catalysis is an action by catalyst which takes part in a chemical

reaction process and can alter the rate of reactions.

▪ Because a catalyst makes it possible to obtain an end product by a

different pathway (e.g. a lower energy barrier), it can affect both the
4
4
yield and the selectivity.
▪ In theory, an ideal catalyst would not be consumed, but this is
not the case in practice. Owing to competing reactions, the
catalyst undergoes chemical changes, and its activity becomes
lower (catalyst deactivation).
▪ Thus catalysts must be regenerated or eventually replaced.

▪ Apart from accelerating reactions, catalysts have another

important property: they can influence the selectivity of
chemical reactions.

▪ The suitability of a catalyst for an industrial process depends

mainly on the following three properties:
– Activity
– Selectivity
– Stability (deactivation behavior)
5
• Catalysis-based processes represent more than 90% of current
chemical processes and generate 60% of today's chemical
products[see HANDBOOK OF HETEROGENEOUS CATALYSIS Volume-1,].

▪ In addition to traditional roles in the chemical and petroleum

industries, catalysts are of growing importance in fields
ranging from fuel cells, green chemistry(Environmental
protection), nanotechnology, and biorefining/biotechnology
and energy to pharmaceuticals and the processing of high
performance materials.

▪ The development and use of catalysts is a major part of the

constant search for new ways of increasing product yield and
selectivity from chemical reactions

6
Development of Important Industrial Catalytic
Processes

7
Development of Important Industrial Catalytic Processes

Production of Liquid Fuels!!!

8
Development of Important Industrial Catalytic Processes

NO N2
CO O2 CO2
CxHy H2O

9
 What is Catalysis???
– Catalysis is an action by catalyst which takes part in a chemical

reaction process and can alter the rate of reactions, and yet itself

will return to its original form without being consumed or

destroyed at the end of the reactions???

▪ Ostwald recognized catalysis as a ubiquitous phenomenon that

was to be explained in terms of the laws of physical chemistry.

Consider this reaction

With catalyst active site (X1 and X2), partially

poised and thermally deactivated
1a
1b

1c
1d
1e 10
 Observations/remarks of such reaction

1. In absence of poising and/or thermal deactivation, the catalytic

concentration of active sites X1 and X2 do not suffered consumption.
Then, the catalyst does not appear explicitly in the overall reaction

2. At least one reactant must be chemisorbed in any heterogeneous

catalytic events ( 1a to 1c). For example, if only one reactant be
chemisorbed and the co-reactant from gas phase

Co- reactant
3. Various form of deactivation [poising, thermal deactivation] conspire to
deny catalyst immortality. The life is dependent on the cycle time

4. Deactivation can be minimized by using catalyst promoters

11
Example of catalytic process

➢ Homogeneous catalysis

➢ Heterogeneous catalysis

12
Three key aspects of catalyst action
➢ Taking part in the reaction
• it will change itself during the process by interacting
with other reactant/product molecules

➢ Altering the rates of reactions

• in most cases the rates of reactions are increased by the
action of catalysts; however, in some situations the
rates of undesired reactions are selectively suppressed

➢ Returning to its original form

• After reaction cycles a catalyst with exactly the same
nature is ‘reborn’
• In practice a catalyst has its lifespan - it deactivates
gradually during use 13
▪ Catalyst forms complex with reactants/products, controlling
the rate of elementary steps in the process. This is evidenced
by the facts that

• The reaction activation energy is altered

• The intermediates formed are different from those formed in
non-catalytic reaction
• The rates of reactions are altered (bothdesired and undesired
ones)
▪ Reactions proceed under less demanding conditions
• Allow reactions occur under a milder conditions, e.g. at
lower temperatures for those heat sensitive materials

14
Catalysis action - Reaction kinetics and mechanism
• Catalyst action leads to the rate of a reaction to change: This is
realised by changing the course of reaction (compared to non-catalytic
reaction)

→ This means , the catalyst changes the reaction path by lowering its
activation energy and consequently the catalyst increases the rate of
reaction. 15 15
 Conversion of graphite to diamonds is a thermodynamic favor
process (G -ve ).
C (graphite)  C (diamond)
Kinetics makes this reaction nearly impossible (Requires a
very high pressure and temperature over long time)

Reaction path for conversion of A + B into AB

• Activation Energy : The energy required to overcome the
reaction barrier. Usually given a symbol Ea or ∆G≠
• The Activation Energy (Ea) determines how fast a reaction occurs, the
higher Activation barrier, the slower the reaction rate. The lower the
16
Activation barrier, the faster the reaction
 Fundamental Catalytic Phenomena and Principles

Physical roperties Chemical roperties

(Surface Area, Pore (Oxidation State,
Structure, Pore Acidity, Surface
Density, pore Composition)
volume) Catalyst
Design

Catalytic Properties
▪ (Activity and Selectivity)
▪ Frequency factor,
▪ dispersion

• Catalyst design is an optimized combination of interdependent

mechanical, chemical/physical, and catalytic properties
17
 General requirements for a good catalyst
❑ Activity – It is a measure of how fast one or more reactions
proceed in the presence of the catalyst. Activity can be defined in
terms of kinetics or from a more practically oriented viewpoint. Being
able to promote the rate of desired reactions Catalyst

Stability

❑ This shows, there are three possibilities for expressing catalyst activity, i. e., as:
– Reaction rate
– Rate constant k
– Activation energy Ea

18
➢ Comparison of catalyst activities
 Turnover Frequency TOF:- as a measure of catalyst activity
▪ The turnover frequency TOF quantifies the specific activity of a catalytic center for a
special reaction under defined reaction conditions by the number of molecular reactions
or catalytic cycles occuring at the center per unit time.
▪ For heterogeneous catalysts the number of active centers is derived usually from
sorption methods
TOF= number of product molecules formed per unit area per
sec(molecules.cm-2.sec-1)

TOF= number of product molecules formed per active site

per sec(molecules.sec-1) only if active site is known.
TON= Turnover Number :- The turnover number specifies
the maximum use that can be made of a catalyst for a
special reaction under defined conditions
Table : TOF values for the hydrogenation
of cyclohexene (Example) TON = TOF[time-1] . lifetime of the
Catalyst [time]

▪ For industrial applications the TON

is in the range 106–107.

19
 ❑ Selective - Being to promote only the rate of desired reaction and
also retard the undesired reactions (e.g. selective oxidation of NO to NO2 in the
presence of SO2). It is expressed by the ratio of the amount of desired product to
the reacted quantity of a reactant eed A

Example: Reactions
of synthesis gas

20
 ❑ Stability:- The chemical, thermal, and mechanical stability of a
catalyst determines its lifetime in industrial reactors. Catalyst stability is
influenced by numerous factors, including decomposition, coking, and
poisoning. Catalyst deactivation can be followed by measuring activity or
selectivity as a function of time.

❑ Morphology: The external morphological characteristics of a

catalyst, i.e. its form and grain size, must be suited to
the catalytic corresponding process.
• Pressure drop is an important parameter to select catalyst size
and shape Rings < beads < pellets < extrudates < crushe

21
❑ Mechanical Strength: The mechanical strength of a catalyst is demonstrated by its
resistance to crushing, resistance of the grains to attrition through rubbing, which
produces fines and can cause an increase in the pressure drop in a catalytic bed.

❑ Thermal Characteristics: High thermal conductivity of the catalytic mass leads to

reduced temperature gradients within the grain, as well as in the catalytic bed,
▪ A high specific heat permits a catalytic cracking catalyst to carry a large thermal load
from the combustion of coke back to the endothermic cracking reaction, where it is
usefully consumed.

❑ Regenerability: All catalysts age; and when their activities or their selectivity's have
become insufficient, they must be regenerated through a treatment that will return part or all
of their catalytic properties. The most common treatment is burning off of carbon, but
scrubbing with suitable gases is also frequently done to desorbe certain reversible poisons;

❑ Reproducibility: Reproducibility characterizes the preparation of a catalyst as much

as the catalyst itself; it is of concern to industrial users who want to be assured of the quality
of successive charges of catalyst; and it also preoccupies the various rngineers responsible
for developing the catalyst from the laboratory on to industrial manufacture.

22
 Types of Catalysts & Catalytic Reactions
• The types of catalysts
– Classification based on the substances from which a catalyst is made
• Inorganic (gases, metals, metal oxides, inorganic acids, bases etc.)
• Organic (organic acids, enzymes etc.)
– Classification based on the ways catalysts work
• Homogeneous - both catalyst and all reactants/products are in the
same phase (gas or liq)
• Heterogeneous - Heterogeneous catalysis involves systems in which
catalyst and reactants form separate physical phases.
– Classification based on the catalysts’ action
• Acid-base catalysts
• Enzymatic
• Photocatalysis
• Electrocatalysis, etc.
23
 Classification of Catalysts:
❑ The numerous catalysts known today can be classified according to various
criteria: structure, composition, area of application, or state of aggregation.

➢ Classifications of catalysts according to the state of aggregation

in which they act.

▪ In supported catalysts the catalytically active substance is applied to a support

material that has a large surface area and is usually porous.
▪ By far the most important catalysts are the heterogeneous catalysts.
▪ The market share of homogeneous catalysts is estimated to be only ca. 10–15 %
24
 Classification of Catalyst

➢ Homogeneous catalysts, such as They enhance the reaction

organic and inorganic acids and rate, but their effect is
bases, as well as metal complexes, v limited to the reaction
enzyems are dissolved in reaction kinetics
media.

➢ Heterogeneous catalysts, are Form a separate (solid) phase

typically metals and metal oxides, but
many other materials have been found
to possess a catalytic effect (e.g.,
zeolites, activated carbon and other
alumina silicates).
in a chemical process. Mass
v and heat transfer effects thus
often become prominent in
heterogeneous catalysts.

➢ Heterogeneous catalysts are the dominant ones in the chemical industry,

mainly because they are easier to recover and recycle.

➢ A catalyst helps to facilitate close contact between reacting molecules

and thus lowers the activation energy.

25
 Components of a Typical Heterogeneous Catalyst
– Active phase
• Where the reaction occurs (mostly metal/metal oxide)

– Promoter
• Textual promoter (e.g. Al - Fe for NH3 production)
• Electric or Structural modifier
• Poison resistant promoters Catalys
t
• Additive which improves catalyst properties Suppor
( activities, selectivity, catalyst life t
Active site
– Support / carrier
• Increase mechanical strength
• Increase surface area (98% surface area is
supplied within the porous structure) porous pore
solid
• May or may not be catalytically active
• High surface area oxide which disperses
and stabilizes the active phase

26
 Components of a Typical Heterogeneous Catalyst

Component Material Typ es Examples

Active Phase: metals noble metals: Pt, Pd; base metals: Ni, Fea
metal oxides transition metal oxides: MoO2, CuO
metal sulfides transition metal sulfides: MoS2, Ni3S2

Promoter:
textural metal oxides Al2O3, SiO2, MgO, BaO , TiO2, ZrO2
chemical metal oxides alkali or alkaline earth: K2O, PbO

Carrier or stable, high surface area Group IIIA, alkaline earth and transition
Supportb metal oxides, carbons metal oxides, e.g. Al2O3, SiO2, TiO2,
MgO, zeolites, and C arbon

27
 Active Catalytic Phases and Reactions
They Typically Catalyze

Active Phase Elements/Compounds Reactions Catalyzed

metals Fe, Co, Ni, Cu,Ru, Pt, hydrogenation, steam reforming, HC

Pd, Ir, Rh, Au reforming, dehydrogenation, ammonia
synthesis, Fischer-Tropsch synthesis

oxides oxides of V, Mn, Fe, complete and partial oxidation of

Cu, Mo, W, Al,Si, hydrocarbons and CO, acid-catalyzed
Sn, Pb, B reactions (e.g. cracking,isomerization,
alkylation), methanol synthesis

sulfides sulfides of Co, Mo, hydrotreating (hydrodesulfurization,

W, Ni hydrodenitrogenation,hydrodemetallation),
hydrogenation

carbides carbides of Fe, Mo, W hydrogenation, FT synthesis

➢ The key issue is the development of catalytic materials, which, in most cases,
consist of an active metal or a metal oxide deposited on a carrier/support material

28
 Solid Catalysts Support

• Some common solid support / carrier materials

– Alumina
 Other supports
• Inexpensive
➢ Active carbon (S.A. up to 1500
• Surface area: 1 ~ 700 m2/g m2/g)
• Acidic ➢ Titania (S.A. 10 ~ 50 m2/g)
– Silica ➢ Zirconia (S.A. 10 ~ 100 m2/g)
• Inexpensive ➢ Magnesia (S.A. 10 m2/g)
• Surface area: 100 ~ 800 m2/g ➢ Lanthana (S.A. 10 m2/g)
• Acidic Active site
– Zeolite
• mixture of alumina and silica,
• often exchanged metal ion present porous pore
solid
• shape selective
• acidic

29
 Typical Physical Properties of Common
Carrier (Supports)

Support/Catalyst BET area (m2/g) Pore Vol. Pore Diam. (nm)

Activated Carbon 500-1500 0.6-0.8 0.6-2

Zeolites (Molecular Sieves) 500-1000 0.5-0.8 0.4-1.8
Silica Gels 200-600 0.40 3-20
Activated Clays 150-225 0.4-0.52 20
Activated Al2O3 100-300 0.4-0.5 6-40
Kieselguhr ("Celite 296") 4.2 1.14 2,200

30
 Physical and Mechanical Properties:
Definitions and Specifications Support Materials
Property Definition/Specification

density
bulk density,  mass per unit vo l. of bulk catalyst, i.e., bed, packed dens ity
particle density,  mass per unit vo l. of pellet; also called appa rent density
solid density,  mass per unit vo l. of solid; also called skeletal or true density

pore volume, Vpore

macropore volume volume of macropores per unit mass (dpore > 50 nm)
mesopore vo lume volume of mesopores per unit mass (dpore of 3-50 nm)
micropore volume volume of micropores per unit mass (dpore < 3 nm)

pore size and size distr.

macropores ave rage size (diam.) and distribution for dpore > 50 nm
mesopores ave rage size (diam.) and distribution for dpore of 3-50 nm
micropores ave rage size (diam.) and distribution for dpore < 3 nm

surface area, Sint

meso and macropore SA SA o f pores with diameters of 3-5,000 nm
micropore surface area SA o f pores with diameters of less than 3 nm

catalyst particle size diameter and/or length of pellets/extrudates or hole size (pitch)
of monoliths

crushing strength
particle force necessary to crush particle in axial or radial direction
bulk displacement or percentage of fines ve rsus hydrau lic pressure

attrition percentage loss per time due to tumbling

31
 Applications of Catalysis: Industrial applications
• Almost all chemical industries have one or more steps employing catalysts
– Petroleum, energy sector, fertiliser, pharmaceutical, fine chemicals …

Advantages of catalytic processes

– Achieving better process economics and productivity
• Increase reaction rates - fast
• Simplify the reaction steps - low investment cost
• Carry out reaction under mild conditions (e.g. low T, P) - low energy
consumption
– Reducing wastes
• Improving selectivity toward desired products - less raw materials required,
less unwanted wastes
• Replacing harmful/toxic materials with readily available ones
– Producing certain products that may not be possible without catalysts
– Having better control of process (safety, flexible etc.)
– Encouraging application and advancement of new technologies and materials
32 32
 Applications of Catalysis: Environmental applications
– Pollution controls in combination with industrial processes
• Pre-treatment - reduce the amount waste/change the composition of
emissions
• Post-treatments - once formed, reduce and convert emissions
• Using alternative materials
…
– Pollution reduction
• gas - converting harmful gases to non-harmful ones
• liquid - de-pollution, de-odder, de-colour etc
• solid - landfill, factory wastes

• Other applications
– Catalysis and catalysts play one of the key roles in new technology development.

33 33
Important Heterogeneous Catalytic Processes
• Haber-Bosch process
– N2 + 3 H2 → 2 NH3
– Fe/Ru catalysts, high pressure and temperature
– Critical for fertilizer and nitric acid production

• Fischer-Tropsch chemistry
– n CO + 2n H2 → (CH2)n + n H2O , syn gas to liquid fuels
– Fe/Co catalysts
– Source of fuel for Axis in WWII

• Fluidized catalytic cracking

– High MW petroleum → low MW fuels, like gasoline
– Zeolite catalysts, high temperature combustor
– In your fuel tank!

• Automotive three-way catalysis

– NOx/CO/HC → H2O/CO2/H2O
– Pt/Rh/Pd supported on ceria/alumina
– Makes exhaust 99% cleaner
34
Summarizing what is happened on the catalysis

▪ What then is the area per gram available to the reaction? --

-- Specific surface area
▪ What fraction of the area is represented by the active
catalytic centers? ---- Surface coverage
▪ How rapidly will reactants establish themselves on these
center? ---- Adsorption/Chemisoption process
▪ At what rate is the product molecule released from the
catalyst site? ---- Desorption process
▪ What relationship exists between the surface concentration
of species and the measurable bulk-phase concentration?
--- Diffusion resistance
35
Heterogeneous Catalysis: Fundamentals

36
Heterogeneous Catalysis: Fundamentals

❑ Heterogeneously catalyzed reactions are composed of

1. Purely chemical (reaction rate) and
2. Purely physical (mass transfer rate) 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,
▪ Desorption processes are of importance for the
progress of the overall reaction.

37
 ➢ Consider the simplest case of a catalytic gas reaction on a porous
catalyst. The following reaction steps can be expected

1. Diffusion of the starting materials through the boundary layer to the

catalyst surface.
2. Diffusion of the starting materials into the pores (pore diffusion).
3. Adsorption of the reactants on the inner surface of the pores.
4. Chemical reaction on the catalyst surface.
5. Desorption of the products from the catalyst surface.
6. Diffusion of the products out of the pores.
7. Diffusion of the products away from the catalyst through the boundary
layer and into the gas phase.

A B
Bulk Fluid CAb

1. External Diffusion 7 . Diffusion of

Rate = kC(CAb – CAS) products from pore
mouth to bulk
External Surface
C
of Catalyst Pellet As
6 . Diffusion of
2. Defined by an products from interior
Effectiveness Factor to pore mouth
Internal Surface of Catalyst Pellet
3. Surface Adsorption
A + S <-> A.S A →B 5. Surface Desorption 38
4. Surface Reaction B. S <-> B + S
Catalyst Surface
❑ For example, the film diffusion resistance (1 & 7) can be suppressed by increasing the gas
velocity in the reactor(Hydrodynamics of multiphase reactors.). While the pore diffusion(2
& 6) can be minimized, by lowering the particle size of the catalyst shortens the diffusion
path, and the reaction rate increases until it is no longer dépendent on pore diffusion.

(Diffusion limited)

Regions of mass transfer-limited and reaction-limited

reactions(Figure 11-6, Fogler} )
39
❑ Assume that step 1 & 7 and 2 & 6 are very fast (rapid diffusion) for
the time being, so that

❑ Either step 3 or step 5 slow relative to actual surface reaction

(step 4)
o Therefore, the rate of adsorption and desorption become of
interest to supply reacting species to the surface reaction (step
4)------need highly porous material and lower particle size
❑ Adsorption and desorption are rapid relative to reaction between
adsorbed surface species----- surface reaction needs improve

❑ Since chemisorption is usually a necessary part of a catalytic

process, we shall discuss it before treating catalytic reaction rates.

40
Heterogeneous Catalysis: Fundamentals
a) Film diffusion region: the reaction is fast compared to diffusion in the film
layer and to diffusion in the pores.
b) Pore diffusion region: the reaction is fast compared to diffusion in the
pores, but slow compared to film diffusion.
c) Kinetic region: the reaction is slow compared to diffusion in the pores and
through the gas film.

Figure: Concentration–position curves

in the film diffusion (a), the pore diffusion
(b), and the kinetic region (c)

41
Heterogeneous Catalysis: Fundamentals
▪ Changing the temperature changes the ratio of reaction to transport rate.
▪ In the kinetic region, the reaction rate increases rapidly with increasing temperature, the
Arrhenius law.
▪ In the pore diffusion region, the reaction rate also increases according to the Arrhenius
law, but at the same time the concentration profile becomes steeper.
▪ In the film diffusion region, reff increases slowly with increasing temperature because the
diffusion has only a slight temperature dependence.

42
 Adsorption and dsorption is fundamental for catalysis

Physical adsorption: Van der Waals attraction between adsorbate and

adsorbent. The attraction is not fixed to a specific site and the adsorbate is
relatively free to move on the surface. This is relatively weak, reversible,
adsorption capable of multilayer adsorption
In physisorption
1. The bond is a Van Der Waals
interaction
2. Adsorption energy is typically 5-10
kJ/mol (<30 kJ/mol). ( much weaker
than a typical chemical bond )
3. Many layers of adsorbed molecules
may be formed.

➢ Physisorption is important for measurement of total particle area

(specific surface area, Pore volume and pore size distribution)

43
 • Chemical adsorption: Some degree of chemical bonding between adsorbate and
adsorbent characterized by strong attractiveness. Adsorbed molecules are not free to
move on the surface. There is a high degree of specificity and typically a monolayer
is formed. The process is seldom reversible.

For Chemisorption
1. The adsorption energy is comparable to the energy of
a chemical bond.
2. The molecule may chemisorp intact (left) or it may
dissociate (right).
3. The chemisorption energy is 30-70 kJ/mol for
molecules and 100-400 kJ/mol for atoms.
4. Only a monomolecular layer of adsorbate appears
on the adsorbing medium

Figure: Adsorption of ethylene on a platinum surface to form chemisorbed

ethylidyne. 44
How catalyst initiate reaction? Different theories

❑ A reaction is not catalyzed over the entire solid surface but

only at certain active sites or centers.
▪ H.S. Taylor(1928) visualized these sites as unsaturated atoms
in the solids that resulted from surface irregularities,
dislocations, edges of crystals, and cracks along grain
boundaries.
▪ The active sites can also be thought of as places where highly
reactive intermediates (i.e., chemisorbed species) are
stabilized long enough to react.
❑ However, for our purposes we will define an active site as a
point on the catalyst surface that can form strong chemical
bonds with an adsorbed atom or molecule.
45
➢ Chemisorption is the type of adsorption that affects the rate of a
chemical reaction
➢ Optimum design and efficient utilization of catalysts require a thorough
understanding of the surface structure and surface chemistry of the
catalytic material. Chemical adsorption (chemisorption) analyses can
provide much of the information needed to evaluate catalyst materials in
the design and production phases, as well as after a period of use.

Adsorption Mechanism 46
❑ Since both types of adsorption are exothermic, raising the temperature
generally decreases the equilibrium quantity of adsorbate.
▪ 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.

❑ Chemisorption leads only to a monolayer, whereas in physisorption

multilayers can form.

❑ The surface also has a major influence on adsorption.

▪ In physisorption only the magnitude of the surface area is important,
▪ Chemisorption is highly specific. The type of surface has considerable
influence on chemisorption, with surface irregularities such as corners,
edges, and lattice defects playing a major role. In particular, raised areas,
generally atoms with free valences, are referred to as active centers.
47
 Adsorption On Solid Surface
• Summary.
– Molecules can attach to surfaces in two different ways because of
the different forces involved. These are Physisorption (Physical
adsorption) & Chemisorption (Chemical adsorption)

Physisorption Chemisorption
Force Van de Waal Chemcal bond
Number of adsorbed layers Multi Mono- layer
Adsorption heat Low (10-40 kJ/mol) High ( > 40 kJ/mol)
Selectivity(rate) Low High
Temperature to occur Low High
Heat of adsorption low = heat of fusion high,heat of reaction
(ca. 10 kJ/mol), (80–200 (600) kJ/mol),
always exothermic usually exothermic

48
 Adsorption On Solid Surface
• 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

T2 >T1 V1
P2>P1
Vol. adsorbed
Vol. adsorbed

Pressure
T3 >T2

P1

T4 >T3

T5 >T4

Pressure Temperature Temperature

Adsorption Isotherm Adsorption Isobar Adsorption Isostere

49
 Adsorption On Solid Surface
❑ Adsorbent and adsorbate
– Adsorbent - 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, q
The solid surface may be completely or partially covered by adsorbed molecules

number of adsorption sites occupied

q =
number of adsorption sites available
q = 0~1

50
 The Langmuir Model: Quantitative Treatment

❑ Langmuir postulate that the solid surface upon which adsorption occur is
homogeneous;
▪ i.e the surface is energetically uniform, so that the free-energy change
accompanying the adsorption of the first molecule or atom is identical to
the change associated with subsequent adsorption of that molecular or
atomic species.
▪ Upon adsorption, the adsorbed species do not interact with previously
adsorbed neighbors.
▪ The homogeneous surface simply fills without
interaction(concentration) effect, and the heat of adsorption is constant
throughout the range of surface occupied(fractional monolayer
coverage θ from 0 to 1).

51
 The Langmuir Model: Quantitative Treatment
❑ Adsorption is assumed to be proportional to that fraction of the
surface which is unoccupied, 1-θ, and the partial pressure p of
the adsorbing gas

Rate of adsorption

❑ Desorption is assumed to be proportional to that of the

concentration of the adsorbed gas ( fraction of the surface
occupied θ)

Rate of desorption

52
 ➢ For homogeneous surface assumption, the frequency factor (A)
and activation energy (E) is independent of surface coverage
At equilibrium, Adsorption = Desorption (rA = rD)

➢ This is a base for multilayer

adsorption and adsorption –
desorption kinetics

➢ Where θ is defined as V/Veq , the volume of gas physically adsorbed relative

to that volume adsorbed at multilayer saturation

➢ Example: Adsorption of CO on a catalyst surface (see

Fogler chapter – 10)

53
 θ
▪ A plot of the amount of CO adsorbed
per unit mass of catalyst as a function
of the partial pressure of CO.

PA(bar)
Figure: Langmuir isotherm for adsorption
of molecular carbon monoxide

▪ One method of checking whether a model (e.g.,

molecular adsorption versus dissociative adsorption)
predicts the behavior of the experimental data is to
linearize the model's equation and then plot the
indicated variables against one another. For example,
we may be arranged in the form

54
 Adsorption On Solid Surface (See Fogler-3rd edition)
• The Langmuir adsorption isotherm: Basic assumptions
• Surface uniform (Hads does not vary with coverage)
• Monolayer adsorption, and
• No interaction between adsorbed molecules and adsorbed molecules

– Case I - Single molecule adsorption: when adsorption is in a dynamic

equilibrium
A(g) + M(surface site)  AM
the rate of adsorption rads = kads (1-q) P A
the rate of desorption rdes = kdes q
at equilibrium rads = rdes  kads (1-q) P = kdes q
case I
rearrange it for q

let  B0 is adsorption coefficient

(kads / kdes ) P k ads
q= B0 =
1 + (kads / kdes ) B0 P k des

Cs B0 P
V/Veq = q= =
C 1 + B0 P 55
 Adsorption On Solid Surface
• The Langmuir adsorption isotherm (cont’d)
– Case II - single molecule adsorbed dissociatively on one site

A-B(g) + M(surface site)  A-M-B

the rate of A-B adsorption rads=kads (1-qA )(1-qB)PAB=kads (1-q )2PAB

the rate of A-B desorption rdes=kdesqAqB =kdesq2 q=qA=q

A B
at equilibrium rads = rdes  kads (1-q )2PAB= kdesq2 A B
rearrange it for q

case II
(kads / kdes ) PAB
q=
1 + (kads / kdes ) PAB
k ads
B0 =
Let.  k des Cs ( B0 PAB )1/2
q= =
C 1 + ( B0 PAB )1/2

56
• The Langmuir adsorption isotherm (cont’d)
– Case III - two molecules adsorbed on two sites
A(g) + B(g) + 2M(surface site)  A-M + B-M
o the rate of A adsorption rads,A = kads,A (1- qA- qB) PA A B

o the rate of B adsorption rads,B = kads,B (1- qA- qB) PB

o the rate of A desorption rdes,A = kdes,A qA
case III
o the rate of B desorption rdes,B = kdes,B qB
at equilibrium rads ,A = rdes ,A and  rads ,B = rdes ,B
 kads,A(1-qA-qB)PA=kdes,AqA and kads,B(1-qA-qB)PB=kdes,BqB
Cs , A B0, A PA Cs , B B0,B PB
rearrange it for q qA = = qB = =
C 1 + B0, A PA + B0,B PB C 1 + B0, A PA + B0,B PB

are adsorption coefficients of A & B. kads ,A kads ,B

B0 ,A = and B0 ,B =
kdes ,A kdes ,B

57
 Adsorption On Solid Surface
• The Langmuir adsorption isotherm (cont’d) A B
A A B

case III

case I case II Cs ,A B0 ,A PA
qA = =
C 1 + B0 ,A PA + B0 ,B PB
Cs B0 P Cs ( B0 PAB )1/2
q= = q= = qB =
Cs ,B
=
B0 ,B PB
C 1 + B0 P C 1 + ( B0 PAB )1/2
C 1 + B0 ,A PA + B0 ,B PB
k ads k ads kads ,A kads ,B
B0 = B0 = B0 ,A = and B0 ,B =
k des k des kdes ,A kdes ,B
Adsorption
Adsorption Cs ,A B0 ,A PA
A, B both strong qA = =
Strong kads>> kdes kads>> kdes C B0 ,A PA + B0 ,B PB
B0>>1 B0>>1 Cs ,B B0 ,B PB
qB = =
Cs C
<< kq = s → 1
C B0 ,A PA + B0 ,B PB
Weak k << k
ads q = →1
des kads des A strong, B weak
C C q A = C s , A / C → 1
B <<1
0 B0<<1
A weak, B PB
weak q B = Cs ,B / C = ( B0 ,B / B0 ,A )
Cs Cs PA
q = = B0 P q = = ( B0 P)1/2 q A = Cs ,A / C = B0 ,A PA
C C
q B = Cs ,B / C = B0 ,B PB 58 5
8
 Adsorption On Solid Surface
• Langmuir adsorption isotherm Cs
Cs B0 P Strong adsorption kads>> kdes q = →1
case I q= = C
C 1 + B0 P Weak adsorption kads<< kdes Cs
q = = B0 P
Cs ( B0 PAB )1/2 C
case II q= =
C 1 + ( B0 PAB )1/2
Cs , A B0, A PA
qA = =
C 1 + B0, A PA + B0, B PB

Amount adsorbed
mono-layer
Case III
large B0 (strong adsorp.)
Cs , B B0, B PB
qB = =
C 1 + B0, A PA + B0, B PB moderate B0
small B0 (weak adsorp.)

Pressure

▪ Langmuir adsorption isotherm established a logic picture of adsorption process It fits many
adsorption systems but not at all
▪ The assumptions made by Langmuir do not hold in all situation, that causing error
▪ Solid surface is heterogeneous thus the heat of adsorption is not a constant at different q
▪ Physisorption of gas molecules on a solid surface can be more than one layer

59
 Adsorption On Solid Surface
• Other adsorption isotherms
Many other isotherms are proposed in order to explain the observations
• The Temkin (or Slygin-Frumkin) isotherm
– Assuming the adsorption enthalpy H decreases linearly with surface coverage
From ads-des equilibrium, ads. rate  des. rate
rads=kads(1-q)P  rdes=kdesq
Langmuir

H of ads
Temkin
B0 P b1eQs / RT P
q=  qs =
1 + B0 P 1 + b1eQs / RT P q
where Qs is the heat of adsorption. When Qs is a linear function of
qi. Qs=Q0-iS (Q0 is a constant, i is the number and S represents the surface site),

the overall coverage

1 1 [b1eQs / RT P RT  1 + b1P 
q =  q s dS =  dS = ln 
0 0 (1 + b e s
1
Q / RT
P i  1
1 + b P exp(- RT ) 
i

When b1P >>1 and b1Pexp(-i/RT) <<1, we have q =c1ln(c2P), where c1 & c2 are
constants 60
 Adsorption On Solid Surface
• The Freundlich isotherm
– assuming logarithmic change of adsorption enthalpy H with surface coverage
From ads-des equilibrium, ads. rate  des. rate
rads=kads(1-q)P  rdes=kdesq

H of ads
Langmuir

Freundlich

B0 P b1eQi / RT P
q=  qi = q
1 + B0 P 1 + b1eQi / RT P

where Qi is the heat of adsorption which is a function of qi. If there are Ni types of surface sites,
each can be expressed as Ni=aexp(-Q/Q0) (a and Q0 are constants), corresponding to a
fractional coverage qi,
i qi Ni 0 [b1eQ / RT P / (1+ b1eQ / RT P)] aeQ/Q0 dQ
the overall coverage q= =
 iN
i
 Q/Q
 dQ
ae
0
0

the solution for this integration expression at small q is:

lnq=(RT/Q0)lnP + constant, or

as is the Freundlich equation normally written, where c1= constant,

1/c2=RT/Q0 q = c1 p1 / C2

➢ Freundlich isotherm fits, not all, but many adsorption systems.

61
 Adsorption On Solid Surface
• Summary of adsorption isotherms

Name Isotherm equation Application Note

Cs B0 P
Langmuir q= = Chemisorption and Useful in analysis of
C 1 + B0 P physisorption reaction mechanism

Chemisorption Chemisorption
Temkin q =c1ln(c2P)

Easy to fit
Freundlich q = c1 p 1 / C2 Chemisorption and adsorption data
physisorption
P / P0 1 c -1
= + ( P / P0 ) Useful in surface
BET V ( 1 - P / P0 ) cVm cVm Multilayer physisorption area
determination

62
Surface Reaction: Mechanism of Surface Catalyst Reaction

63
Surface Reaction: Mechanism of Surface Catalyst Reaction

64
Surface Reaction: Mechanism of Surface Catalyst Reaction

65
 The Rate-Limiting Step

❑ When heterogeneous reactions are carried out at steady state, the

rates of each of the three reaction steps in series (adsorption,
surface reaction, and desorption) are equal to one another:

❑ In most cases, one particular step in the series is usually found

to be rate limiting or rate-controlling. That is, if we could make
this particular step go faster, the entire reaction would proceed at
an accelerated rate (Reading assignment).

66
 Physical Adsorption on Solid Surface
• BET (Brunauer-Emmett-Teller) isotherm
– Many physical adsorption isotherms were found, such as the types II and III, that the
adsorption does not complete the first layer (monolayer) before it continues to stack
on the subsequent layer (thus the S-shape of types II and III isotherms)
– Basic assumptions
• the same assumptions as that of Langmuir but allow multi-layer adsorption
• the heat of ads. of additional layer equals to the latent heat of condensation
• based on the rate of adsorption=the rate of desorption for each layer of ads.
the following BET equation was derived

P / P0 1 c -1
= + ( P / P0 )
V ( 1 - P / P0 ) cVm cVm

Where P- equilibrium pressure

P0 - saturate vapour pressure of the adsorbed gas at the temperature
P/P0 is called relative pressure
V - volume of adsorbed gas per kg adsorbent
Vm - volume of monolayer adsorbed gas per kg adsorbent
c - constant associated with adsorption heat and condensation heat

Note : for many adsorption systems c=exp[(H -H )/RT], where H is adsorption heat of 1st layer &
1 L 1

HL is liquefaction heat, so that the adsorption heat can be determined from constant c.
67
 Physical Adsorption on Solid Surface
• Comment on the BET isotherm
– BET equation fits reasonably well all known adsorption isotherms
observed so far (types I to V) for various types of solid, although there
is fundamental defect in the theory because of the assumptions made
(no interaction between adsorbed molecules, surface homogeneity and
liquefaction heat for all subsequent layers being equal).
– BET isotherm, as well as all other isotherms, gives accurate account of
adsorption isotherm only within restricted pressure range. At very low
(P/P0<0.05) and high relative pressure (P/P0>0.35) it becomes less
applicable.
– The most significant contribution of BET isotherm to the surface
science is that the theory provided the first applicable means of
accurate determination of the surface area of a solid (since in 1945).
– Many new development in relation to the theory of adsorption
isotherm, most of them are accurate for a specific system under
specific conditions.
68
 Physical Adsorption on Solid Surface
Use of BET isotherm to determine the surface area of a solid
– At low relative pressure P/P0 = 0.05~0.35 it is found that
P / P0 1 c -1
= + ( P / P0 )  ( P / P0 ) P / P0
V ( 1 - P / P0 ) cVm cVm V (1- P / P0 )

Y = a +b X
P/P0
• The principle of surface area determination by BET method:
P / P0
A plot of against P/P0 will yield a straight line with slope of equal to (c- 1)/(cVm)
V (1- P / P0 )
and intersect 1/(cVm).

For a given adsorption system, c and Vm are constant values, the surface area of a solid
material can be determined by measuring the amount of a particular gas adsorbed on
the surface with known molecular cross-section area Am,
Vm - volume of monolayer adsorbed gas molecules calculated from the plot, L
Vm
As = Am N m = Am  6.022  1023 VT,P - molar volume of the adsorbed gas, L/mol
VT , P Am - cross-section area of a single gas molecule, m2

* In practice, measurement of BET surface area of a solid is carried out by N2

physisorption at liquid N2 temperature; for N2, Am = 16.2 x 10-20 m2
69
 Physical Adsorption on Solid Surface
• Five types of physisorption isotherms are found over all solids
I
– Type I is found for porous materials with small pores e.g. charcoal.
It is clearly Langmuir monolayer type, but the other 4 are not

II

– Type II for non-porous materials

amount adsorbed

III
– Type III porous materials with cohesive force between adsorbate
molecules greater than the adhesive force between dsorbate
molecules and adsorbent
IV

– Type IV staged adsorption (first monolayer then build up of additional

layers)
V – Type V porous materials with cohesive force between adsorbate
molecules and adsorbent being greater than that between
1.0
adsorbate molecules
relative pres. P/P0
70
 – Type I is found for porous materials with
small pores e.g. charcoal. It is clearly Langmuir
Type I Isotherm monolayer type.

– the potential field of force from the neighboring

walls of the pores will overlap causing an
increase in the interaction energy between the
solid surface and the gas molecules.

– This will result in an increase in adsorption,

especially at low relative pressures.

– These isotherms are thus characterized by a

plateau that is almost horizontal and parallel to
the pressure axis. The adsorption at higher
relative pressures being small and tending to
level off.

– Type I is common to chemisorption, although

some physical adsorptions such as those in
highly microporous active carbons and in carbon
molecular
➢ The fact that the adsorption in Type I isotherms does not increase continuously as in Type II
isotherms but attains a limiting value shown by the plateau is due to the pores being so narrow
71
that they cannot accommodate more than a single molecular layer.
Type II Isotherms
▪ These isotherms correspond to multiplayer
Monolayer physical adsorption. They generally show a
capacity
rather long linear portion, a feature that is not
strictly compatible with the requirements of the
BET equation

the point at which

the monolayer is
completed

▪ Type IV isotherms are obtained for solids containing pores in

Type IV Isotherm
the mesopore range. The shape of the Type IV isotherm
follows the same path as the Type II at lower relative
pressures until its slope starts decreasing at higher
pressures.

▪ At the saturation vapor pressure, the isotherm levels off to a

constant value of adsorption. This portion of the isotherm,
which is parallel to the pressure axis, is attributed to filling of
72
the larger pores by capillary condensation
 ▪ The most significant characteristics of these isotherms is that they show adsorption-
desorption hysteresis, which means that the amount adsorbed is always greater at any
given relative pressure along the desorption branch than along the adsorption branch.
▪ This type of isotherm is generally obtained in the case of oxide gels and several porous
carbon materials that have larger-sized pores. These adsorption isotherms have led to the
development of the theory of capillary condensation

▪ Adsorption-desorption isotherms of water vapor on PVDC charcoal before and after degassing
at 1000°C. (Source: Bansal, R.C., Dhami, T.L., and Prakash, S., Carbon, 16, 389, 1978
73
Type III Isotherms ▪ Type III and Type V isotherms are characterized by
being convex to the pressure axis. Although in Type III
isotherms the convexity continues throughout the

▪ nonporous or highly isotherm

microporous adsorbents,
▪ The convexity of the isotherms is suggestive of the
cooperative adsorption, which means that the already
adsorbed molecules tend to enhance the adsorption of
other molecules. It implies that the adsorbate-
adsorbent interactions are of less importance than the
adsorbate-adsorbate interaction

Type V Isotherms ▪ In Type V the isotherm reaches a plateau at fairly high

relative pressures, often at p/po equal to or higher
than 0.51 in the multiplayer region

▪ The weak adsorbate-adsorbent interactions result in

small adsorption at lower relative pressures
▪ mesoporous or
microporous adsorbents
for the adsorption 74
 ❑ Basic of adsorption is derived from Potential theory of adsorption
▪ It is based on the idea that at the surface of the solid adsorbent, the adsorbed molecules of
the gas or vapor are compressed by the forces of attraction acting from the surface to a
distance into the surrounding space.
▪ Because the forces anchoring a molecule to the surface
Gas phase decay with distance, a multimolecular adsorbed film may

Adsorptio be regarded as lying in an intermolecular potential

n space gradient.
▪ The force of attraction at any given point in the adsorbed
film can be conveniently measured by the adsorption
potential e, which is defined as the work done by the
adsorption forces in bringing a molecule from the gas
Adsorbent phase to that point.

▪ For an idealized, energetically homogeneous surface, all

the points equidistant from the surface will have the
same potential e and will, therefore, form an
equipotential plane.

▪ The broken lines in the figure represent planes connecting points of equal potential. The value of
the adsorption potential e of the parallel equipotential planes decreases as their distance from
the surface increases and falls to zero at the maximum distance.

10/05/2021 75
Physical and chemical water and wastewater treatment by Nigus Gabbiyev(PhD)
 Types of Deactivation
• Poisoning
o The catalyst surface is slowly modified by chemisorption
on the active sites by materials which are not easily
removed.
o If reversibly adsorbed ---- removed by changing operating
condition
o If irreversibly adsorbed – need chemical treatment to
activated the catalyst surface
• Fouling
o Caused by a deposition and a physical blocking of the
surface by cracking products

e.g.

• Sintering:
• It is caused by exposure of the catalyst to extreme
conditions such temperature.
76
Coking (formation of deposits)
coverage of the surface by coke or carbon from
undesired reactions of hydrocarbon reactants,
intermediates, and products
• Mechanical damage/Attrition
•

77
 Major types of deactivation in heterogeneous Catalysis
Source: J.A. Moulijn et al.

1. Models for crystalline growth due to

sintering by movements of atoms

➢ A: migration;
➢ A‘: volatilization;
➢ B: migration of particles

78
 Three limiting cases of Poisoning
(from E.E. Petersen, Exp. Methods in Catalysis)

79
Important Heterogeneous Catalytic Processes
• Haber-Bosch process
– N2 + 3 H2 → 2 NH3
– Fe/Ru catalysts, high pressure and temperature
– Critical for fertilizer and nitric acid production

• Fischer-Tropsch chemistry
– n CO + 2n H2 → (CH2)n + n H2O , syn gas to liquid fuels
– Fe/Co catalysts
– Source of fuel for Axis in WWII

• Fluidized catalytic cracking

– High MW petroleum → low MW fuels, like gasoline
– Zeolite catalysts, high temperature combustor
– In your fuel tank!

• Automotive three-way catalysis

– NOx/CO/HC → H2O/CO2/H2O
– Pt/Rh/Pd supported on ceria/alumina
– Makes exhaust 99% cleaner
80
❑ Industrial aspects of catalyst deactivation
▪ Life time of catalysts
▪ Loss of activity and possibly selectivity
▪ Interruption of process operation for either
replacement or regeneration of catalysts leads
+ Loss of time for production
+ Loss of investment
❑ The field of heterogeneous catalysis is highly
interdisciplinary in nature, requiring the cooperation:
▪ Between chemists and physicists,
▪ Between surface scientists and reaction engineers,
▪ Between theorists and experimentalists,
▪ Between spectroscopists and kineticists,
▪ Between materials scientists involved with catalyst
81
synthesis and characterization