5.

Kinetics of heterogeneous reactions

Heterogeneous Reactions

 requires the presence of at least two phases

C ( s )  H 2 O ( g )   CO ( g )  H 2 ( g )

 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, it is regenerated at the end of each reaction cycle.

S
A  B   P
Reaction catalyzed by S, may have the following detailed mechanism:
A  S   AS

B  S   BS

AS  BS   P  2 S

A  B   P

2 Fe  3 O 2   Fe 2 O 3
Here Fe is a reactant. 2
Now consider Fe in the presence of N 2 and H 2
Fe  N 2  3 H 2
 2 NH 3
 Fe
In this case, Fe acts as Catalyst
General Characteristics of heterogeneous reactions

 At least two phases are found :-

 govern inter phase heat and mass transport and these
becomes important reactions parameter

The reaction rate will depend upon

Hence Rate is
 the contact b/n two phases

complex
 factors of con.- temp.- and pressure

 Diffusion step :- one or more reactants and products must be

transported from their phase
The rates of mass transfer step by diffusion, the flux of A to the
surface is given by,

1 dn A C  D
r   D  (C A , g  C A  S )   k g (C A , g  C A  S )
m S dt X X

where, D – molecular diffusion coefficient;

kg – mass transfer coefficient
 The rate of chemical reaction step
The reaction is of first-order with respect to A, and based on the unit
surface it can be given as,

1 dn A
r   ksC A  S
S dt

Where, ks – reaction rate constant based on unit surface

a)At steady-state, rm =r k g (C A , g  C A  S )  k s C A  S
kg
C AS  C A,g
kg  kS
 kg 1
r  ks. C A,g  1 .C A,g
kg  ks 1

ks kg
r   K overall C A,g

where
1
K overall 
1 ks  1 kg
b) If the mass transfer is the rate-controlling

C A,g  C A  S hence C AS  0

then
rmass transfer  r reaction   k g (C A , g  C A  S )   k g C A
,g
Catalysts and mechanism of reaction

Catalysts
 Catalyst is a material which initiates and enhances the rate of a
chemical reaction without being consumed by that reaction.
 The catalyst involves at least one phase which is not a net reactant,
yet its presence alters the speed of the reaction and its mechanism.
 While the catalyst very much participates in the reaction, yet it
does not itself appear in the overall reaction at the end, or on the
other hand, it does not enter into the Stoichiometry of the reaction.

1 V2O5
SO 2  O 2     SO 3
2
V 2 O 5  SO 2   V 2 O 4  SO 3
V 2 O 4  1 O 2   V 2 O 5
2
Advantage of Catalyst:
Changes the rate of reaction
Does not affect the equilibrium
Can only speed up a reaction that which is thermo-dynamically
possible
.
Has ability to alter yields and selectivity by speeding up some
reactions more than others

Al 2 O 3 CH 2  CH 2  H 2O

CH 3  CH 2  OH
Cu
CH 3  CHO  H2

Needs a larger surface area.

Lowers the potential energy barriers i.e., lowering the free

energy of activation.
 The reaction forms many
intermediates. A catalyst
lowers the energy of these
intermediates.

The activation energy is lower

with catalyst, so the reaction
proceeds faster.
Mechanism of catalytic reactions
 A gas phase reaction, which is catalyzed by solid surface
(catalyst) occurs on the surface of the catalyst.
 For such reaction to take place, at least one reactant must
become attached to the surface.
This attachment is known as adsorption.

CS

Catalyst surface Catalyst surface

Fig. Adsorption of substrate on active catalyst

  There are two types of adsorption, physical and
chemical adsorption.

Physical Adsorption
The force of attraction between the gas molecules and
the solid surface are weak,

The process is exothermic,

The heat of adsorption is relatively small,

The amount of gas physically adsorbed decreases rapidly

with the increasing temperature
Chemical Adsorption / Chemisorbtion /

 Affects the rate of chemical reaction,

 It involves a chemical bond,

 It is exothermic,

 The heat of adsorption is of the same magnitude as the

heat of chemical reaction
For a catalytic reaction to occur,
at least one reactant must be chemically
adsorbed (i.e., chemisorbed).

CS CA - S

Catalyst surface Catalyst surface Adsorption

Substrate, (A) + Active Site (S) Adsorption, CA-S
k A
PA + CS k A
CA-S
Adsorption of non reacting gas on the surface of
catalyst

There are several models to express Concentration of

adsorption of species on the site( catalyst)

The Langmuir Adsorption

Assumption
a. Out of the molecules striking the surface, only those that strike the bare
surface are considered for adsorption
b. There is no interaction between adsorbed molecules
c. All adsorption occurs by the same mechanism, to which all sites
are the same.
Finding Concentration of adsorbed Species
Consider when a single gas is adsorbed on the
surface,
A + S A-S
PA

CA-S
CS CS CS

Catalyst surface Catalyst surface

CT CT = CS + CA-S
Total sites = Occupied sites + Vacant sites
CT = CA - S + CS

Moles of A adsorbed
C AS 
Unit mass of catalyst

total moles of sites

CT 
unit mass of catalyst
When two gases are adsorbed on the surface,
A(g) + B(g) + S A-S + B-S

Catalyst surface
PA ,PB
CA-S
CB-S
CS CS CS
CS

Catalyst surface Catalyst surface

CT = CA - S + CB - S + CS
Moles of B adsorbed
CBS 
unit mass of catalyst
a) Single non –reacting gas adsorbed on the surface (catalyst)
kA
A + S k
A-S
Rate of attachment,  A
r  k A PA C s
attachment ,A

Rate of detachment,
r  k C
det achment ,A A AS
The net rate of adsorption is equal to the rate of molecular
attachment onto the surface minus the rate of detachment the
surface, thus
rA  k A PA C s  k  A C A  S
At equilibrium, the attachment and detachment rates are equal.
Therefore, k A PA C s  k  A C A  S

k A PA C s
C AS   K A , eq P A C S
k A
The total concentration of the sites on the site balance can be
given by,

C C C
T S AS
Substituting gives

C  C  K P C
T S A , eq A S

or
C
C  T
S 1 K P
A ,eq A
Substituting gives, Langmuir isotherm equation,
K A , eq P A C T
C AS 
1  K A , eq P A

 The parameters kA k-A and KA,eq are all a function of

Temperature
 Where kA k-A increases with increasing Temperature.
While KA,eq decreases with increasing Temp.
 The above equation at low values of PA is a straight line of
slope KA,eq and at high pressure it becomes flat.
 The equation also helps us to confirm whether adsorption is
Langmuir single –site isotherm, and which on rearrangement,
the equation shows linearity
 P 1 P
A A
 
C K C C
AS A , eq T T

b) Two gases adsorbed on the same surface

The rate of adsorption (attachment) of A,

r  k P C
attachment ,A A A S

The rate of detachment (desorption) of A,

r  k C
det achment ,A A AS
At equilibrium,
k A PA C S  k  A C A  S

kA
C AS  P A C S  K A , eq P A C S
k A

The rate of adsorption (attachment) of B,

rattachment , B  k B PB C S

The rate of detachment (desorption) of B,

rdet achment ,B  k B C B  S
At equilibrium
k P C  k C
B B S B BS
k
C  B P C  K P C
BS k B S B , eq B S
B
The total concentration of the sites on the site balance can be
given by,

CT  C S  C A S  C B  S
C  C  K P C  K P C
T S A , eq A S B , eq A S
 CT
CS 
1  K A , P A  K B , PB
eq eq

C  K P C
AS A , eq A S

K A , eq P A C T
C AS  (a)
1  K A , P A  K B , PB
eq eq

C  K P C
BS B , eq B S

K B , eq P B C T
CBS 
1  K A , P A  K B , PB (b)
eq eq
Equations (a) and (b) shows that, when more than one substance
is present in the system, the Langmuir adsorption isotherm
equation becomes some what more complex. The other
components present in the adsorption process would also appear
in the denominator as

K P ,
X , eq X

for reaction product or reactant or for a trace of impurity or

poison or inert that is chemisorbed.

K P ,
In , eq In
Hence

K P C
A , eq A T
C 
AS 1 K P  K P  K P  K P  .......
A , eq A B , eq B X , eq X In , eq In
Exercise 1
Consider a general reaction

A   B  C  In

where
In
is a chemically inert species for the reaction,

and, A,B,C and In are all appreciably adsorbed.

Find the expressions for C ,C , and C
AS BS C S
 Catalytic of heterogeneous reactions
Catalytic of heterogeneous reactions
 involve interphase mass transfer combined with
chemical reaction

 Gas-phase reactants are adsorbed onto a solid

surface, react, and the products are desorbed.
 Catalyst surface

Figure f. A plug-flow catalytic reactor at various zoom-in levels.

Catalyst surface Catalyst surface

Catalyst surface

Catalyst surface Catalyst surface

 In Catalytic of heterogeneous reactions
Inside, things are much more complicated:

reactants must diffuse through the catalyst pores,

 adsorb on its surface,

 travel to the active site,

 react there, and

desorbs back to the gas phase

In every gas/solid catalytic cycle, at least one of the reactants must at

some point be adsorbed chemically (Chemisorbed) on the catalyst
surface.
Catalyst in heterogeneous reactions
 Most are in a form of porous

 are supplied as cylindrical pellets with lengths and

diameters in the range of 2–10 mm

 More complex shapes and monoliths can be used when

it is important to minimize pressure drop

 The pores are structure in micro – and macro- porous

Internal surface
area in the pores

Fig. Structure of Pores catalyst

 Internal
Process
Reactant in the bulk

X
Catalyst
Particle
Pores

 The internal surface area, accessible through the pores, is

enormous, up to 2000 m2 per gram of catalyst.

 The internal surface area accounts for most of the catalytic

activity.
Steps in Pores Catalytic Reaction
Consider Reactant A react on the surface of catalyst to give
product B (A S B)  

Gas film
S-porous catalyst
A(g) 1

2
3
8
7 X
9 4,5,6
4,5,6
B(g)

External Internal
General overview of the above steps of pores catalytic
reaction

1.Bulk transport of the reactants to the vicinity of a

catalyst particle

2. Mass transfer across a film resistance from the bulk

gas phase to the external surface of the porous
catalyst

3. Transport of the reactants into the catalyst particle

by diffusion through the pores

4. Adsorption of reactant molecules onto the internal

surface of the catalyst.
 5. Reaction between adsorbed components on the
catalytic surface of the pellet.
6. Desorption of product molecules from the surface
to the pores

7. Diffusion of product molecules out of the pores to

the external surface

8. Mass transfer of the products across a film

resistance into the bulk gas phase.

9. Bulk transport of products to the reactor outlet.

Caution
All these steps can influence the overall
reaction rate
Summary of the steps of porous catalyst reaction
(A S B)
  

S-porous catalyst
Product, B 7 Pores
catalyst -S
6
1 2
Reactant, A
X 3,4,5

X- catalytic
External Internal Active Site

S
Fig. Events in the porous catalyst reaction ( A   B )
The catalytic reaction can be summarized of the overall
rate of reaction, which comprises the following steps;
Step1. Mass transfer of the reactant (Species A) from the bulk to
the external surface of the catalytic pellet.

Step 2. Transportation of the reactant (A) to the internal surface

of the catalyst particle
.

Step 3. Adsorption of reactant (A) onto the catalyst surface

Step 4. Reaction on the surface of the catalyst

Step 5. Desorption of the product (B) from the catalyst surface

Step 6. Transportation of the product (B) to the external surface

of the pellet.
Step 7. Mass transfer of the product (B) from the external pellet
surface to the bulk fluid
We can classify the above steps into two
categories:
Transporting Processes (Steps 1, 2, 6 and 7),
which mainly takes place by diffusion. These are
external and internal processes
Chemical Reaction Processes (steps 3, 4 and 5)
include adsorption, surface reaction and
desorption. These are called Catalytic Chemical
Reaction
Chemical reaction processes
A) Adsorption
rA  k A PA C s  k  A C A  S
is already explained in Chemical adsorption
B) Surface reaction
Once a reactant has been chemically adsorbed on to surface,
there are different ways surface reaction to produce a product.
A –S B –S
The net rate of surface reaction r k C k C
s s As s Bs
Surface reaction mechanism
Single-site mechanism
Dual-site mechanism
A –S1 + S2 B –S2 + S1
A - S1 + B-S2 C-S1 + D-S2
Eley-Rideal mechanism
In this mechanism, a reaction between an adsorbed
molecule and a molecule in the gas phase takes place,
which can be shown as,
B(g) + A-S C-S + D(g)
 C) Desorption
The product of surface reaction attached on the surface are
subsequently desorbed into the gas phase. Hence

B - S B(g) + S

The net rate of desorption becomes,

r D  k D C B  S  k  D PB C S