1.

1 Catalysts

1.2 Steps in Heterogeneous

Catalytic Reactions

1.3 Rate Limiting Steps

1.4 Temperature Dependence

of Catalytic Reaction Rates

1.5 Langmuir-Hinshelwood
Kinetic

1.6 Designing Catalytic

Reactors

1.7 Deactivation of Catalyst

CHE505: REACTION ENGINEERING II 1

 Reactor  Pellet  Catalyst pore  Catalyst particle

Length of Scales

A reaction takes
place on the surface,
but the species
involved in the
reaction must get to
and from the
surface.

2
The overall process by which heterogeneous catalytic reactions
can be broken down into the sequence of 7 individual steps :

1. Mass transfer (diffusion) of the reactant (e.g. species A) from

the bulk fluid to the surface of the catalyst pellet  external
diffusion
2. Diffusion of the reactant from the pore mouth through the
catalyst pores to the immediate vicinity of the internal catalytic
surface  internal diffusion.
3. Adsorption of reactant A onto the catalyst surface.
4. Reaction on the surface of the catalyst (e.g. A  B).
5. Desorption of the products (e.g., B) from the surface.
6. Diffusion of the products from the interior of the pellet to the
pore mouth at the external surface  internal diffusion.
7. Mass transfer of the products from the external pellet surface
to the bulk fluid  external diffusion. 3
 Steps in Heterogeneous Catalytic Reaction........

1. External diffusion or  7. External diffusion or 
external mass transfer external mass transfer

2. Internal  6. Internal 
diffusion diffusion

3. Adsorption
5. Desorption
4. Surface reaction
4
Concentration Gradients in Catalytic Reactor

CAb = concentration of reactant

A in bulk fluid

CAs = concentration of reactant

A at external catalyst
surface

CAx = concentration of reactant

A within the pellet

CHE505: REACTION ENGINEERING II 5

STEPS INVOLVED ARE:

Reactant Ab in the bulk

of the flowing fluid must
migrate through a
boundary layer over the
pellet at the external
surface of the pellet.

It must then migrate

down pores within the
pellet to find surface
sites where it adsorbs
and reacts to form B,
r” = k”CAs
which then reverses the process to wind up in the flowing fluid,
where it is carried out of the reactor

CHE505: REACTION ENGINEERING II 6

CHE505: REACTION ENGINEERING II 7
1. EXPLAIN EACH PROCESS/STEP
INVOLVE IN HETEROGENEOUS
CATALYSIS REACTIONS OF A
POROUS CATALYST WITH AN
AID OF A DIAGRAM.

2. ILLUSTRATE EACH STEP

INVOLVE IN A
HETEROGENEOUS CATALYTIC
REACTION OF A NON-POROUS
CATALYST BY A DIAGRAM.
CHE505: REACTION ENGINEERING II 8
 1.1 Catalysts

1.2 Steps in Heterogeneous

Catalytic Reactions

1.3 Rate Limiting Steps

1.4 Temperature Dependence

of Catalytic Reaction Rates

1.5 Langmuir-Hinshelwood
Kinetic

1.6 Designing Catalytic

Reactors

1.7 Deactivation of Catalyst

CHE505: REACTION ENGINEERING II 9

 (and the concept of overall rate of reaction)

 Typically, rate limiting step is the rate of the slowest step in the
mechanism (slowest step among the 7 heterogeneous catalytic steps).

 This rate limiting step governs the overall rate of the reaction.

 Classification of steps
1. Mass Transfer/transport related steps (1,2,6 and 7)
2. Reaction Kinetic related steps (3,4 and 5)

10
 (and the concept of overall rate of reaction (cont..))

 Then there are two cases:

– Mass Transfer /transport limitations
– Reaction Kinetic limitations

 If any of steps 3, 4 or 5 is slower than steps 1,2,6 and 7, transport

or mass transfer or diffusion steps do not affect the overall rate of
the reaction. The reaction is said to be under reaction kinetic
limitation or reaction kinetic regime/region, and free from mass
transfer/transport limitation.

 If any of steps 1,2,6 or 7 is slower

than steps 3, 4 and 5, reaction
kinetics does not affect the overall
rate of reaction. The reaction is
said to be under mass
transfer/transport limitation or
mass transfer/transport
regime/region, and free from
reaction kinetics limitation.
11
 (and the concept of overall rate of reaction (cont..))

The structures and concentration profiles of reactant near and

in a catalyst particle might look as illustrated in Figure 7-9.

For the reactant to migrate into the particle, there must be a

concentration difference between the flowing bulk fluid CAb, the
concentration at the external surface CAs, and the concentration
within the pellet CA(x).

We write the
concentration within the
pellet as CA(x), indicating
that it is a function of
position x, which will be
different for different
geometries, as we will
consider later

12
 How do we know whether the reaction rate is
reaction limited (reaction control) or external mass
transfer limited (external mass transfer control)??

First, let’s recall on mass transfer

coefficient…
CHE505: REACTION ENGINEERING II 13
Mass transfer correlations for gases....

If there is a concentration difference of A between two

locations 1 and 2, then
JA = kmA (CA1 – CA2)

JA is the mass transfer flux, [mol/s.m2]

km is the mass transfer coefficient, [mol/(s·m2)/(mol/m3), or m/s]

CA1-CA2, concentration difference [mol/m3].

JA
k mA 
(C A1  C A2 )

CHE505: REACTION ENGINEERING II 14

Mass transfer coefficient can be defined through the
Sherwood number:

[convective mass transfer rate] k mAl

Shl = Shl 
[diffusive mass transfer rate] DA

l is length and DA is the diffusion coefficient of A

Then kmA can be defined:

Shl D A
k mA 
l

CHE505: REACTION ENGINEERING II 15

Sherwood numbers for several geometries:

1. Flow over a flat plate

2. Flow over a sphere

3. Flow through a tube

4. Flow over a cylinder

5. Tube banks and packed spheres

6. Heat transfer

CHE505: REACTION ENGINEERING II 16

1. Flow over a flat plate

For flow over a flat plate of length L.......

 Flow is laminar if ReL < 105,

ShL  0.66 Re L Sc
1 1
2 3

 Flow is turbulent if ReL > 105,

ShL  0.036 Re 0.8 1

L Sc 3

CHE505: REACTION ENGINEERING II 17

1. Flow over a flat plate

 The Reynolds number is

μ is the velocity

v is the kinematic viscosity

DA the diffusivity of
 Schmidt SC number species A, both of which
have units of length2/time.

 For gases, SC =1

CHE505: REACTION ENGINEERING II 18

2. Flow over a sphere

 Important geometry in catalyst spheres, liquid drops, gas

bubbles, and small solid particles

 The characteristic length is the sphere diameter D


ShD  2.0  0.4 Re D  0.06 Re D3 Sc 0.4
1
2
2

 In the limit of slow flow over a sphere ShD = 2.0, and
this corresponds to diffusion to or from a sphere
surrounded by a stagnant fluid.

CHE505: REACTION ENGINEERING II 19

3. Flow through a tube

 the characteristic length is the tube diameter D

 Flow is laminar if ReD < 2100,

8
ShD 
3

 Flow is turbulent if ReD > 2100,

1
ShD  0.023 Re 0D.8 Sc 3

CHE505: REACTION ENGINEERING II 20

4. Flow over a cylinder

 The transition from laminar to turbulence depends on

position around the cylinder

 Flow is laminar if ReD < 4,

CHE505: REACTION ENGINEERING II 21

 For gasses, we usually
assume Schmidt
Number, Sc = 1

CHE505: REACTION ENGINEERING II 22

Mass transfer coefficient can be defined through the
Sherwood number:

[convective mass transfer rate] k mAl

Shl = Shl 
[diffusive mass transfer rate] DA

l is length and DA is the diffusion coefficient of A

Then kmA can be defined:

Shl D A
k mA 
l

CHE505: REACTION ENGINEERING II 23

 Is it reaction limited or mass transfer
limited??

To answer this question, we consider the simplest example:

a nonporous catalyst (where reactions occur only on the
external surface of the catalyst pellet)

CHE505: REACTION ENGINEERING II 24

ASSUMPTION AND CONSIDERATION.

The reaction occurs only on the external surface of a pellet -

only the external surface is reactive (e.g: non porous pellets)

Steady state assumption: there is no accumulation on the

surface:

[rate of transport to surface] = [rate of reaction at surface]

For a first-order irreversible reaction on a single spherical pellet

of radius R, the total rate of reaction on the external surface of
the pellet is:

4R 2 k mA (C Ab  C As )  4R 2 r"  4R 2 k " C As

CHE505: REACTION ENGINEERING II 25

 4R 2 k mA (C Ab  C As )  4R 2 r"  4R 2 k " C As

Transport

The rate of reaction on the pellet with surface area 4R is equal
2

to the rate of mass transfer from the bulk fluid to the surface

4R 2 k mA (C Ab  C As )  4R 2 k " C As C As k " k mA   k mAC Ab

k mA (C Ab  C As )  k " C As C As 
k mAC Ab
k mAC Ab  k mAC As  k " C As
k" kmA 
C Ab
k " C As  k mAC As  k mAC Ab C As 
 k" 
1  
 k mA 

CHE505: REACTION ENGINEERING II 26

Eliminate C As from the rate expression and solve for the rate to
yield
r"  k " C As
k " C Ab
r"   keff'' C Ab
 k" 
1  
 k mA 

The reaction rate has an effective rate constant:

k"
k ''

 k" 
eff

1  
 k mA 
CHE505: REACTION ENGINEERING II 27
 k"
LIMITING CASES: k ''

 k" 
eff

If k” << kmA, then.....

1  
 k mA 
k " C Ab
r"   k " C Ab Reaction limited
1   0

If kmA << k” then.....

r"  k mAC Ab
Mass transfer limited

28
 1.1 Catalysts

1.2 Steps in Heterogeneous

Catalytic Reactions

1.3 Rate Limiting Steps

1.4 Temperature Dependence

of Catalytic Reaction Rates

1.5 Langmuir-Hinshelwood
Kinetic

1.6 Designing Catalytic

Reactors

1.7 Deactivation of Catalyst

CHE505: REACTION ENGINEERING II 29

As the temperature is varied in a reactor, we should
expect to see the rate-controlling step vary.

CHE505: REACTION ENGINEERING II 30

At sufficiently low temperature, reaction rate is small
and overall rate is reaction limited.

As the temperature
increases, pore diffusion
becomes controlling and
at sufficiently high
temperature, external
mass transfer might
limit the process.

CHE505: REACTION ENGINEERING II 31

 1.1 Catalysts

1.2 Steps in Heterogeneous

Catalytic Reactions

1.3 Rate Limiting Steps

1.4 Temperature Dependence

of Catalytic Reaction Rates

1.5 Langmuir-Hinshelwood
Kinetic

1.6 Designing Catalytic

Reactors

1.7 Deactivation of Catalyst

CHE505: REACTION ENGINEERING II 32

 1915
Langmuir Isotherm

1927 
Kinetics of Catalytic 
Reactions

Cyril Norman Irving Langmuir
Hinshelwood 1881 ‐ 1957
1897 ‐ 1967 Nobel Prize 1932
Nobel Prize 1956

CHE505: REACTION ENGINEERING II 33

7 Steps of Heterogeneous Catalysis

CHE505: REACTION ENGINEERING II 34

 Adsorption

Surface Reaction

Desorption

 Determining the rate limiting step (is the adsorption rate or

surface reaction rate or desorption rate the rate limiting
step?)

 Developing/Postulate the overall rate law for the

heterogeneous reaction (assuming the reaction is free from
external mass transfer and internal diffusion limitations)

 Comparing the postulated overall rate law to experimental

data
CHE505: REACTION ENGINEERING II 35
 ADSORPTION

CHE505: REACTION ENGINEERING II 36

 WHAT IS ADSORPTION????

Adsorption is a physical or chemical phenomenon by

which the molecules present in a liquid or a gas attach to
the surface of a solid.

Surface means both external and internal surface

The substance on which surface adsorption occurs is

termed as the adsorbent, and the substance which
adsorbed from the bulk phase is known as the adsorbate

Depending on the force of attraction, adsorption is

mainly two types: (1) Physical adsorption (Physisorption)
and (2) Chemical adsorption (Chemisorption).

CHE505: REACTION ENGINEERING II 37

 WHY DOES SOLID SUBSTANCE ADSORB?

The adsorption phenomenon comes from the existence of non-

compensated forces of a physical nature on the surface of the
solid.

Adsorbate
All the bonding requirements of the
constituent atoms of the material
Adsorbent

are filled by other atoms in the

Adsorbate

material.

However, atoms on the surface of

the adsorbent are not wholly
surrounded by other adsorbent
atoms and therefore can attract
adsorbates.

CHE505: REACTION ENGINEERING II 38

 Adsorption theory

H O
H O

H
H
H H O O O

Pt Pt Pt Pt Pt Pt Pt Pt Pt Pt Pt Pt Pt

CHE505: REACTION ENGINEERING II 39

 PHYSICAL ADSORPTION (PHYSISORPTION)

Physical adsorption is a phenomenon which takes place purely due

to the van der Waals forces of attraction.

It is a reversible phenomenon.

Because of very week force of

attraction, the physical adsorption
cannot bring to any change of
chemical structure of the adsorbent
and adsorbate

It can be compared with the

condensation of vapour of
liquids

CHE505: REACTION ENGINEERING II 40

 CHEMICAL ADSORPTION (CHEMISORPTION)

Chemical adsorption is adsorption which results from chemical bond

formation (strong interaction) between the adsorbent and the
adsorbate in a monolayer on the surface.

Example: Organic compound get adsorbed on the solid surface

with chemical bond formation.

CHE505: REACTION ENGINEERING II 41

42
ADSORPTION ISOTHERM
S = active site
A = atom; molecule; atomic combination
A.S = one unit of species A adsorbed on site S
Ct = total molar concentration of active sites
per unit mass of catalyst.
Cv = molar concentration of vacant sites
Pi = partial pressure of species, i in gas
phase (atm)
Ci.s = surface concentration of sites occupied
by species, i (g.mol/g.cat)

43
ADSORPTION ISOTHERM
S = active site
A = atom; molecule; atomic combination
AS = one unit of species A adsorbed on site S
Pi = partial pressure of species, i in gas phase (atm)

A  S  A S

Adsorption of A on a site S is represented by:

A A


44
 Adsorption of A and B on a site S is represented by:
A B A B


Site balance: Ct  Cv  C AS  C BS

Ct = total molar concentration of active sites per unit mass of catalyst.

Cv = molar concentration of vacant sites
Ci.s = surface concentration of sites occupied by species, i (g.mol/g.cat)

45
ADSORPTION ISOTHERM

Isotherms  the amount of gas adsorbed on a solid at

different pressures but at one temperature.

A model system was proposed then, the isotherm obtain

from the model is compared with the experimental data
shown on the curve.

If the curve predicted by the model agrees with the

experimental data, the model may reasonably described
what is occurring physically in the real system.

46
 Two models of Adsorption
Molecular/non-dissociative adsorption Dissociative adsorption

CO  S  CO  S CO  2 S  C  S  O  S

Rate of
attachment, rA Rate of attachment = k A PCO C ?
Rate of
Rate of detachment = k  A CCO  S ?
detachment, r-A
Adsorption
equilibrium K A  k A / k A is the adsorption equilibrium constant
constant, KA
Net rate of
rAD  k A PCO C  k  ACCOS
adsorption, rAd ?

 C 
rAD  k A  PCO C  COS 
 KA 
47
ADSORPTION MECHANISM

It is depend on the surface.

The equation can be considered as an elementary

reaction in order to determine the rate law.

Rate of attachment – molecules adsorb on vacant site,

the rate is proportional to the concentration of vacant
site, Cv.

Rate of detachment – detachment of molecules from the

surface, the rate is proportional to the concentration of
sites occupied by molecules

48
ADSORPTION MECHANISM

Net rate of adsorption = rate of attachment to the

surface – rate of detachment from the surface

Assumption to obtain Langmuir Isotherm:

Surface of catalyst

Adsorption system.

49
EXAMPLE (NONDISSOCIATED ADSORPTION)

Consider the adsorption of carbon monoxide molecule:

CO  S  CO  S

 The rate of attachment of carbon monoxide molecules to the

active site on the surface is proportional to the number of
collisions that these molecules make with a surface active site
per second.

 The collisions rate is proportional to the partial pressure, PCO.

50
EXAMPLE (NONDISSOCIATED ADSORPTION)

CO  S  CO  S

 Carbon monoxide molecules adsorb only on vacant sites and

the rate of attachment is proportional to the concentration of
vacant sites, Cv.

 Thus, the rate of attachment to the surface is proportional to

the partial pressure and the concentration of vacant sites

Rate of attachment  k A PCO C

51
EXAMPLE (NONDISSOCIATED ADSORPTION)

Rate of detachment - detachment of CO molecules from

the surface usually proportional to the concentration of
sites occupied by the adsorbed molecules (e.g., CCO.S).

Rate of detachment  k  ACCOS

Rate of adsorption is equal to the rate of molecular

attachment to the surface minus the rate of detachment
from the surface

rAD  k A PCO C  k  ACCOS

52
EXAMPLE (NONDISSOCIATED ADSORPTION)

Adsorption equilibrium constant

K A  k A / k A  CCOS 
rAD  k A  PCO C  
 KA 

kA  independent of temperature
k_A  increases exponentially with increasing temperature
KA  decreases exponentially with increasing temperature

53
EXAMPLE (NONDISSOCIATED ADSORPTION)

Site balance:

C t  C v  C CO  S

At equilibrium,

C CO  S  K A C v PCO

Solve CCO.S in terms of constant and partial pressure. Thus,

K A PCO C t
C CO  S 
1  K A PCO
54
EXAMPLE (DISSOCIATED ADSORPTION)

Consider the isotherm for carbon monoxide adsorbing as

atom

Two adjacent vacant active site are required

The rate of adsorption is proportional to the product of

partial pressure of CO and square of the vacant site
concentration.

The rate of desorption is proportional to the product of the

occupied site concentration.

55
EXAMPLE (DISSOCIATED ADSORPTION)

Thus, the net rate of adsorption:

rAD  k A PCO Cv2  k  ACOS CC S

 COS CCS 
rAD  kA  PCOCv 
2

 KA 

Site balance:
C t  C v  C C S  C O S

56
EXAMPLE (DISSOCIATED ADSORPTION)

At equilibrium,
k A PCO C v2  k  A C C  S C O  S

Consider CC.S = CO.S. Solve CO.S in terms of constant and

partial pressure. Thus

1
(K A PCO )
2
Ct
C O S  1
1  2(K A PCO )
2

57
 EXERCISE 1

Write a rate law and Langmuir isotherm based on the

adsorption reaction below:

a) I + S IS

b) W + S WS

58
Surface Reaction

59
SURFACE REACTION MODEL

The rate of adsorption of species A onto solid surface

A  S  A S

 C 
rAD  k A  PACv  AS 
 KA 

The reactant that has been adsorbed onto the surface

will react in a number of ways
 Single site
 Dual site
 Eley-Rideal mechanism

60
SURFACE REACTION MODEL

SINGLE SITE
MECHANISM

DUAL SITE
MECHANISM

ELEY-RIDEAL
MECHANISM

61
 SINGLE SITE MECHANISM

Surface reaction with single site mechanism

Only the site on which reactant is adsorbed is involved in

reaction
A  S  A S

The reaction mechanism is elementary in each step, thus

the rate law:

AS  B S A B

 C BS 

rS  k S  C AS  

 KS 
62
 DUAL SITE MECHANISM
Surface reaction may be dual site mechanism

The adsorbed reactant interacts with another site

(occupied/unoccupied ) to form the product.

Adsorbed A react with an adjacent vacant site to yield a

vacant site and adsorbed product site.

A S  S  B  S  S A B

 C BS Cv 

rS  k S  C AS Cv  

 KS 

63
 Reaction between two adsorbed species

A S  B  S  C  S  D  S  CC S C D S 

rS  k S  C AS C BS  

 KS 

B A C D

Reaction of two species adsorbed on different types of

sites S and S’
 C C  S 'C D  S 
A  S  B  S '  C  S ' D  S 
rS  k S  C AS C BS '  

 KS 

B A C D

64
 ELEY-RIDEAL MECHANISM

The reaction between an adsorbed molecule and molecule

in the gas phase

 CC S PD 
A  S  B( g )  C  S  D( g ) 
rS  k S  C AS PB  

 KS 

B D
A C

65
 EXERCISE 2

Based on surface reaction below :

i) Sketch the reaction on the conceptual model

ii) Write down the rate law of surface reaction

66
Desorption

67
DESORPTION

The products of the surface reaction adsorbed on the

surface are subsequently desorbed into the gas phase.

CS  C  S

The rate of desorption:

 PC C v 
rDC 
 k D  CC  S  

 K DC 

Desorption equilibrium constant is 1

reciprocal of adsorption K DC 
equilibrium constant. KC

68
EXERCISE 3

69
 EXAMPLE

The adsorption isotherm of A in the presence of

adsorbate B is:

K A PACt
C AS 
1 K A PA  K B PB

When the adsorptions of A and B are 1st order, the

desorption are also 1st order, and, both A and B are
adsorbed as molecules

70
RATE LIMITING STEP

The rates of adsorption, surface reaction and desorption

series are equal to one another at steady state.

Rate limiting or rate controlling is one of the particular

step in the series.

In determining the step limiting in overall rate of

reaction, Langmuir-Hinshelwood approach was used.

71
RATE LIMITING STEP

Langmuir-Hinshelwood approach

 Assuming a sequence of steps in the reaction.

 Choose the mechanisms either as molecular or atomic

adsorption and single or dual site reaction

 By assuming all steps are reversible, rate laws are

written for the individual steps

 Rate limiting steps is postulated. Steps that are not

rate limiting are used to eliminate all coverage
dependent terms.

72
STEPS IN A LANGMUIR HINSHELWOOD KINETIC
MECHANISM

 Adsorption  Surface Reaction  Desorption

There is no accumulation of reacting species on the

surface, therefore the rates of each step in the sequence
are all equal.
 r ' C  r AD  r S  r D

Cv or Cc·s in the rate law must be replaced with

measurable quantities.

73
STEPS IN A LANGMUIR HINSHELWOOD KINETIC
MECHANISM

 Adsorption Rate Limiting k A  kS , k D

 Surface Reaction Rate Limiting kS  k A , k D

 Desorption Rate Limiting k D  k A , kS

Please read further : Fogler’s pg 669--687

74
 EXERCISE 4

Question 3(a): Exam Q June 2012

The catalytic reaction of was carried out in a differential

reactor. The reaction is controlling by the surface reaction
and is irreversible. The surface reaction is reacted through the
Eley-Rideal mechanism, and the rate expression is rs=ksCA·SPB.
The adsorption and desorption step are reversible. Suggest
the reaction mechanism steps for the above reaction. Prove
that the overall rate law can be expressed as:

kPA PB (13 marks)

r 
'

1 K A PA  KC PC
A

75
 EXERCISE 5
t-Butyl alcohol (TBA) was produced by the liquid phase
hydration (W) of isobutene (I) over an Amberlyst-15 catalyst.
The system is normally a multiphase mixture of hydrocarbon,
water and solid catalyst. The reaction mechanism is:

Determine a rate law :

 If the surface reaction is rate limiting.
 If the adsorption of isobutene is limiting

76
ADDITION OF INERTS

Example: A → B (surface reaction rate limiting)

A  S  AS kP A
A S  B S  r A' 
1  K A P A  K B PB  K I PI
B S  B  S
I  S  I S

If KIPI >> 1, KA & KB,

kP A
 r A' 
K I PI

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ADDITION OF INERTS

The rate is reduced by species I. It shows that the inert

can strongly inhibit the reaction of A.

Inert blocks the sites on which A must adsorb to react

and lowers its coverage to a small value, therefore inhibit
the reaction

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TEMPERATURE DEPENDENCE

Specific reaction rate, k will follow an Arrhenius

temperature dependence and increase exponentially
with temperature.

  ER 
k R  k 0R exp 
 RT 

The adsorption of all species on the surface is exothermic.

The adsorption equilibrium constant, k, will decreases as
the temperature increases.

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TEMPERATURE DEPENDENCE

 Ej
K j  K j 0 exp 

 ER is the activation energy for surface reaction.
 RT  Ej is the heat of adsorption of species j.

Example: A → B (surface reaction limited)

kP A
 r A' 
1  K A P A  K B PB

As the temperature increases, KA & KB decrease resulting

less coverage of the surface by A and B.

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 EXERCISE 6

Question 2(b) April 2011

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