Advanced Reaction Engineering

HETEROGENEOUS CATALYSIS AND

CATALYTIC KINETICS

Lecture -7
By Dr. Eng. Hundessa D. Demsash
Heterogeneous Catalytic system
The Characteristics of Heterogeneous Reactions
Heterogeneous Reactions
 requires the presence of at least two phases
CaCO3( s ) 
 CaO( s )  CO2( g )
Fe2O3( s )  3C( s )  12 O2( g ) 
 2 Fe( s )  CO2( g )  2CO( g )

ZnS( s )  32 O2( g ) 
 ZnO( s )  SO2( g )
C( s )  H 2O( g ) 
 CO( g )  H 2( g )
Heterogeneous Reactions
 classified as catalytic and non catalytic
The difference between catalyzed and non- catalyzed reactions is that the
catalyst (say S), while participating in one or more of the elementary steps, is
regenerated at the end of each reaction cycle. Reaction,
S
A  B  P
catalyzed by S, may have the following detailed mechanism:
A  S  AS

B  S  BS

AS  BS  P  2 S

A  B  P
Iron in the presence of oxygen reacts to form iron oxide which is not
a catalytic reaction 2 Fe  3 O 
2 2
 Fe O 2 3
Here Fe is a reactant.
Now consider Fe  N 2  3H 2  2 NH 3  Fe acts as Catalyst
General Characteristics of heterogeneous reactions

 At least two phase exists:-

 govern inter phase heat and mass transport
and these becomes one of the important

Hence Rate is
reactions parameter
The reaction rate will depend upon

complex
 the contact b/n two phases

 factors of con.- temp.- and pressure

 Diffusion step :- one or more reactants and products

must be transported from their phase
  The complication of the rate equation
- the rate equation will incorporate mass transfer
terms in addition to the usual chemical kinetics
term
 The contacting patterns for the two phase
system
Rate Equation for Heterogeneous Reactions
• for heterogeneous reactions, the rate equation accounts
for more than one process /steps/, namely, movement
of material from phase to phase i.e., account of physical
transport and chemical reaction
to be the rates of change for
r1 , r2      rn transforming the reactants to
the products.
 The overall rate

a) If the reaction steps are observed to occur in

series
at steady-state condition, all these steps will proceed in the same rate and

r overall  r1  r2          rn
b) If the reaction steps take place in parallel and all the parallel
steps are independent of each other,
n
roverall   ri
l 1
C) If the steps are vary Since in the process, various rates
are involved which vary from step to step.
Often we come across one step creating the major resistance to
the overall change
 In such cases, we consider the overall rate of reaction is
equal to the rate of the slowest. i.e., the step which has the
smallest rate constant (Rate controlling) and this can be
considered alone.

• Attention!! when the rates are to be compared or

combined, they should be defined in the same manner /unit

The rates of mass transfer step

dn  
r m 1 A  1 mol



S dt m2 s 




Where S =Surface Area

Catalysts and Catalysis

• A Catalyst is a substance that affects the rate

of chemical reaction but emerges from the
process unchanged.
• Catalysis is the occurrence, study, and use of
catalysts and catalytic processes.

8
 Catalysis

May/23 2011 Spring 5

Role of Catalysis in a National Economy
• 24% of GDP from Products made using catalysts (Food,
Fuels, Clothes, Polymers, Drug, Agro-chemicals)
• > 90 % of petro refining & petrochemicals processes use
catalysts
• 90 % of processes & 60 % of products in the chemical
industry
• > 95% of pollution control technologies
• Catalysis in the production/use of alternate fuels (NG,DME,
H2, Fuel Cells, biofuels…)
Three Scales of Knowledge Application
 porous carrier
(catalyst
support)

bed of
catalyst
particles
reactants substrate product

reactor reaction desorption

adsorption
products
catalyst support

active
site
 2D & 3D Tools, Fabrication &
Flowsheet CAD Solids Microscale Design Assembly Materials of
Synthesis Modeling Modules Construction
Microprocess
Components
Multiscale
Process Transport
Micro Systems
Engineering Component Engineering
Simulation & Integration
Control Flow Optimization Multi-scale
Systems Patterns Transport
Micro Process Plant

Micro Analyzers (GC,

Raw Materials & Integrated LC, MS, TOF)
Feedstocks Sensors

Chemistry & Catalyst Sampling Micro Process

Characterization Sensors Analytical
Catalysis
Reaction Reaction Pathways & Data handling & Micro PAT Systems
Kinetics Mechanisms Chemometrics Integration
1. Steps in a Catalytic Reaction I
o Main Interests

- ③Adsorption of reactant(s)
- ④Surface reaction
- ⑤Desorption of product(s)
☞ Determine the most slow (rate determining) step

May/23 2011 Spring 21

 Mechanism of Heterogeneous Catalysis:

1. Bulk Diffusion of reacting molecules to the

surface of the catalyst.
2. Pore Diffusion of reacting molecules into the interior
pores of the catalyst.

3. Adsorption of reactants (chemisorption) on the

surface of the catalyst.

4. Reaction on the surface of the catalyst

between adsorbed molecules.
16
5. Desorption of products.

6. Pore Diffusion of product molecules to the surface of

the catalyst.
7. Bulk Diffusion of product molecules.

17
 Steps in a Heterogeneous Catalytic Reaction
7. Diffusion of B
from external
1. Mass transfer of
surface to the bulk
A to surface
fluid (external
diffusion)

2. Diffusion of A from
pore mouth to 6. Diffusion of B
internal catalytic from pellet interior
3. Adsorption of A onto
surface to pore mouth
catalytic surface

5. Desorption of product B
from surface

4. Reaction on surface
Ch 10 assumes steps 1,2,6 & 7 are fast, so only steps 3, 4, and 5 need to be considered
1.Mass transfer through 2.Diffusion into-pores 3.Chemisorption
External boundary layer

4,5 Reaction and 6. Diffusion of products out 7.Mass transfer back to

Desorption of product of pores bulk fluid
19
Diffusion and Reaction in a Porous Catalyst
Effective Diffusivity: Bulk diffusion ( Large pore )and
Knudsen diffusion(small pore) Dk(cm2/s)=9.7 *103 r (cm) (TK/M)1/2

D c φpσ c
De =

where
Actual distance a molecule travels btw 2 points
τ = tortousity =
S hortest distance btw 2 points
Volume of void space
φp = pellet porosity =
Total volume( voids and solids)
σ c = Constriction factor, f(  )
11-Dec-18 Dr. Eng. Hundessa Dessalegn, SCBE,AAiT,AAU 21
11-Dec-18 Dr. Eng. Hundessa Dessalegn, SCBE,AAiT,AAU 22
11-Dec-18 Dr. Eng. Hundessa Dessalegn, SCBE,AAiT,AAU 23
Steps in a Catalytic Reaction
o Step 1 Overview: External Diffusion

DAB
Rate  kC (C Ab  C As ) wherek C 
δ
May/23 2011 Spring 22
1. Steps in a Catalytic Reaction III
o Step 1 Overview : External Diffusion 2

May/23 2011 Spring 23

 Steps in a Catalytic Reaction
o Step 2 Overview: Internal Diffusion

Rate  kr CAs For a large pellet, near the center

might not be used when reaction
⇒ Waste!!
May/23 2011 Spring 24
Steps in a Catalytic Reaction
o Step 3 : Adsorption
o Adsorption isotherms
A  S  AS
- Total molar concentration of active sites
Ct  C v  CAS  CBS
• adsorption as molecules (on nickel)
CO  S  CO S ☜ nondissociated adsorption
• adsorption as atoms (on iron)
CO  2S  CS  OS ☜ dissociated adsorption
☞ Depends on surface conditions

May/23 2011 Spring 25

 CO  S  CO S

11-Dec-18 Dr. Eng. Hundessa Dessalegn, SCBE,AAiT,AAU 28

11-Dec-18 Dr. Eng. Hundessa Dessalegn, SCBE,AAiT,AAU 29
11-Dec-18 Dr. Eng. Hundessa Dessalegn, SCBE,AAiT,AAU 30
11-Dec-18 Dr. Eng. Hundessa Dessalegn, SCBE,AAiT,AAU 31
11-Dec-18 Dr. Eng. Hundessa Dessalegn, SCBE,AAiT,AAU 32
11-Dec-18 Dr. Eng. Hundessa Dessalegn, SCBE,AAiT,AAU 33
11-Dec-18 Dr. Eng. Hundessa Dessalegn, SCBE,AAiT,AAU 34
11-Dec-18 Dr. Eng. Hundessa Dessalegn, SCBE,AAiT,AAU 35
Rate-Determining Step (RDS)
In a kinetics scheme involving more than one
step, it may be that one change occurs much
faster or much slower than the others (as
determined by relative magnitudes of rate
constants).

In such a case, the overall rate, may be

determined almost entirely by the slowest step,
called the rate-determining step (rds).

The rate of the rds is infinitesimal when

compared to the rates of other steps.
36
Alternately the rates of other steps are infinite
compared to the rate of rds.
Desorption:
Desorption of a product could also be rate
controlling in a few cases.
Complexities:
• Theoretically more than one step can be rate
controlling.
• Too many possible mechanisms.

37
Alternately:

C =Molar conc. of active sites =

t
No. of active sites/unit mass
Avogadro's number

C v =Molar conc. of vacant sites =

No. of vacant sites/unit mass
Avogadro's number
39
C AS =Molar conc. of sites by
No. of sites by A/unit mass
A=
Avogadro's number

C v +C AS =C t

40
 Kinetics of surface reactions:
Langmuir-Hinshelwood Mechanism
Unimolecular:single molecular species A
adsorbs on surface,reacts and the product P
does not adsorb.
A( g)
→
A ads

→
p( g )
Reaction rate R=kθA surface coverage of
adsorbed gas

K A PA
θA =
1+K A PA
41
 Surface coverage related to gas pressure p
via Langmuir adsorption isotherm

kK A pA
R =
1+K A pA

Example : decomposition of NH3 on W surfaces rate 1st

order at low P while as pressure increases it changes to
zero order corresponding to saturation kinetics.

42
Limiting situations
High Pressures
Kp>>1 Rate independent of gas pressure p
zero order kinetics.
R  k Adsorption rate very large when p is high
Decomposition Step rds.
Low Pressures
Kp <<1 Rate depends linearly on gas pressure
p first order kinetics.
R  kK p Adsorption process is rate deter-
mining when p is low Decomposition
is fast.
43
The Adsorption Step

A  S  A S
rAD  k A PACv - k -AC AS  k A PACV  C AS / K A 
K A  k A / k A [atm -1 ]

@ equilibriu m : rAD  0 C AS  k A PACV

rAD / k A  0 C AS  k A PACV

Ct  CV  C AS  CV  K A PACV  CV (1  K A PA )
𝐶𝑡
𝐶𝑉 =
1 + 𝐾𝐴 𝑃𝐴
44
Langmuir Adsorption Isotherm
𝐶𝑡
𝐶𝑉 =
1 + 𝐾𝐴 𝑃𝐴

𝐶𝐴∙𝑆 = 𝐾𝐴 𝑃𝐴 𝐶𝑉

𝐾𝐴 𝑃𝐴
𝐶𝐴∙𝑆 = 𝐶𝑡
1+𝐾𝐴 𝑃𝐴

𝐶𝐴∙𝑆 𝐾𝐴 𝑃𝐴
=
𝐶𝑡 1 + 𝐾𝐴 𝑃𝐴
45
Langmuir Adsorption Isotherm

C A S C AS K A PA

CT
Increasing T Ct 1  K A PA

Slope=kA
Langmuir Adsorption
Isotherm

PA

46
 Steps in a Single-Site Catalytic Reactor

 C AS 
Adsorption A  S  A S  rA  rAd  k Ad  PACv  
 k A 

 CB S 
Surface Reaction A  S  B  S  rA  rS  k S C AS 
 k C 


BS  B  S  rA  rD  k D CBS  k B PBCB 

Desorption

Which step is the Rate Limiting Step (RLS)?

47
The Rate Limiting Step:
Which step has the largest
resistance?

Electrical analog to heterogeneous reactions

48
Collecting and Analyzing Data

Collecting information for catalytic reactor design

49