There three (3) important factors

1) External mass transfer (from bulk phase to the external surface of the catalyst)
2) Internal mass transfer (from the external surface to the interior part of the catalyst)
3) Chemical reaction (on the active surface of the catalyst)

Either one or a combination of the above factors may control the overall rate of reaction (the
slowest step)

Reaction control

There three (3) steps which can control a chemical reaction

a) Adsorption of reaction onto the active surface

b) Surface reaction
c) Desorption of product from the active surface

Either one or a combination of the above factors may control the overall rate of reaction (the
slowest step)

For example, for a simple reaction

N ⇌C

The mechanisms involved

Adsorption: N +S⇌ N .S (1)

k N for foward rate constant∧k −N for reverse rate constant

Surface reaction: N . S+ S ⇌C . S +S (2)

k S for foward rate constant ∧k −S for ℜ verse rate constant

Desorption: C . S ⇌ C +S (3)

k C for foward rate constant∧k−C for reverse rate constant

Assuming the surface reaction control the overall rate of reaction

r S=k S C N . S C V −k −S CC . S C V
 C C. S CV
(
r S=k S C N .S C V −
KS )
kS
KS=
k −S

Assuming (1) and (3) are fast and at equilibrium

r A =k N PN C V −k −N C N . S

k N P N C V =k −N C N . S

CN.S
K N=
PNCV

C N . S =K N P N CV

For desorption

C . S ⇌C +S

r C =k C C N . S−k−C P C C .V

PC C . V
K C=
CC . S

PC C .V
C C .S =
KC

Site balance

C t=C V +C N .S +C C . S

C C. S CV
(
r S=k S C N .S C V −
KS )
PC C2V
(
r S=k S K N PN C − 2
V
KSKC )
 PC
2
r S=k S CV K N P N − ( K N KS KC )
C V =C t −C N . S−C C .S

PC CV
¿ C t−K N PN C V −
KC

PC C V
C t=C V + K N PN C V +
KC

PC
C t=C V 1+ ( KC
+ KN PN )
2
PC
C 2t =C2V 1+( KC
+ K N PN )
2 C 2t
C =
V 2
P
( 1+ C + K N P N
KC )

PC

r S=
k S K N C2t P N − ( K N KS KC )
2
PC
( 1+
KC
+K N PN
)

At equilibrium

r S=0

Therefore

PC
P N=
K N K S KC

PC
K e=
PN
 PC
it is a ratio of
PN

K e =K N K S K C

PC

r S=
(
k X P N−
Ke )
2
P
( 1+ C + K N P N
KC )
k X =k S K N C2t

Therefore the order of reaction changes according to P N and PC

k X ( PN)
If P N ≫ PC than r S= 2 under what circumstances?
( K N PN)

r S=k Y P−1
N

Now derive rate equation based on

a) adsorption rate limiting

b) desorption limiting
 Do this exercise in class.
Consider for the following reaction in which an inhibitor (I) is included

C ⇌ B+ P

Write rate equation if the following steps is rate limiting

a) adsorption
b) Surface reaction
c) desorption

Adsorption rate equation

C+ S ⇌C . S

k A for foward rate constant ∧k −A for reverse rate constant

CC.S
(
r A =k A PC CV −
KA )
Surface reaction rate equation

C . S ⇌ B . S+ P

k S for foward rate constant ∧k −S for reverse rate constant

PP CB. S
(
r S=k S C C .S −
KS )
Desorption rate equation

B . S ⇌ B+ S

k D for foward rate constant∧k −D for reverse rate constant

PB C V
(
r D=k D C B . S−
KD )

Rate of adsorption of inhibitor onto the surface

I+S ⇌ I .S

CI.S
(
r I =k I P I CV −
KI )
C I . S=P I C V K I

Rate equation if Adsorption is rate limiting process

CC.S
(
r A =k A PC CV −
KA )
At steady state r C =r A=r S =r D

If adsorption is limiting then k A is smaller than k S and k D

Need to eliminate C V and C C .S in the rate terms because these parameters are immeasurable.

PP CB. S
(
r S=k S C C .S −
KS )
 rS
Since k S is big than =0 then
kS

P P CB .S
C C .S =
KS

PB C V
(
Eliminate C B . S by looking at the term in the r D=k D C B . S−
KD )
rD
Again since k D is big then =0
kD

PB C V
C B . S=
KD

Then

PP PB C V
C C .S =
KS KD

CC.S
(
Coming back to this equation r A =k A PC C V −
KA )
P P PB C V
(
r A =k A PC CV −
K A KS K D )
Then

P P PB
(
r A =k A C V P C −
K A KS K D )
At equilibrium K D K A K S =K e

C t=C V +C B . S +C C .S +C I . S

PB CV P P P B C V
C t=C V + + + PI C V K I
KD KS KD
 Ct
CV=
PP PB P B
+ + P I K I +1
K D KS KD

P P PB
(
r A =k A C V P C −
K A KS K D )
P P PB

r A=
(
k A C T P C−
Ke )
PP PB PB
+ + P I K I +1
K D KS K D

Initially with no products

P P=PB =0

k A CT ( PC )
r AO =
P I K I +1

k A CT y CO ( P¿ )
r AO =
y IO P ¿ K I +1

At low pressure

k A C T y CO ( P¿ ) ≪ 1

r AO ∽ P¿

At high pressure

k A C T y CO ( P¿ ) ≫ 1

k A CT y CO
r AO =
y IO K I

When surface reaction is rate-limiting

 PP CB. S
(
r S=k S C C .S −
KS )
We need to utilize the rates of adsorption and desorption to eliminate C C .S ∧C B .S because both are
immeasurable so assume

Express C C .S from adsorption equation by assuming adsorption constant k A is big

rA
=0
kA

CC.S
(
r A =k A PC CV −
KA )

C C .S =K A PC C V

As for desorption to solve C B . S

PB C V
(
r D=k D C B . S−
KD )
rD
=0
kD

PB C V
C B . S=
KD

Substitute in r S

PP CB. S
(
r S=k S C C .S −
KS )
PP PBCV
(
r S=k S K A PC C V −
KS KD )
PP P B
(
r S=k S K A PC − C
K S KD K A V )
K D K A K S =K e
 PB PP
(
r S=k S K A PC −
Ke )
CV

C t=C V +C B . S +C C .S +C I . S

PB CV
C t=C V + + K A PC C V + PI C V K I
KD

Ct
CV=
PB K B + K A PC + P I K I +1

1
Whereby K B=
KD

PB PP Ct
(
r S=k S K A PC − )
K e P B K B + K A PC + P I K I +1

Assuming the initial mixture containing 50 % C and the rest is inhibitor I. Therefore
PB =PP =0

(0.5 P ¿¿ ¿)
r S=k S K A Ct ¿
(K ¿ ¿ A 0.5+ 0.5 K I )P¿ +1¿

If pure C is used then

k S K A C t P¿
r S=
P¿ K A +1

Desorption is rate-limiting
We need to utilize the rate based surface reaction to eliminate C B . S and then C C .S from adsorption
equation because the terms are immeasurable so assume

PB C V
(
r D=k D C B . S−
KD )
From adsorption process

CC.S
(
r A =k A PC CV −
KA )
rA
=0
kA

C C .S =K A PC C V

PB C V
(
r D=k D C B . S−
KD )
rS
Since k S is big than =0
kS

PP CB. S
(
r S=k S C C .S −
KS )
PP C B . S
(
r S=k S K A PC C V −
KS )

K S K A PC CV
C B . S=
PP
 K S K A PC C V PB C V
r D=k D ( PP
−
KD )
PC P B
r D=k D K S K A ( − )
C
PP K e V

C t=C V +C B . S +C C .S +C I . S

K S K A PC C V
C t=C V + + K A PC CV + P I C V K I
PP

Ct
CV=
K S K A PC
+ K A PC + P I K I +1
PP

PC P B
r D=k D K S K A ( − )
C
PP K e V

PP PB Ct
(
r D=k D K S K A PC − )
K e K S K A PC
+ K A PC + PI K I +1
PP

PB PP Ct
(
r D=k D K S K A PC − )
K e K S K A PC + K A PP PC + PI P P K I + PP

In case of pure reactant at the initial rate

P P=PB =0 , PI =0

Ct
r D=k D K S K A ( PC )
PC (K ¿ ¿ S K A + K A P P )¿

Ct
r D=k D K S K A ( PC )
PC (K ¿ ¿ S K A ) ¿

r D=k D C t
 Catalyst deactivation
Deactivation:

 The catalyst loss of activity with time-on-stream

 The process is both of chemical and physical nature and occur simultaneously
 Inevitable, but can be slowed or prevented

Poisoning

 Loss of activity due to strong chemisorption on the active sites due to impurities in
the feed system. An example, adsorption of basic compound onto an acid catalyst
 Geometrical effect- blocking an active site
 Electronic effect- alter the adsorptivity of other species, modify the chemical nature
of the active sites, formation of a new compound which result in alteration of
catalyst performance.
 Differences between poison and inhibitor in term of the strength of bond formed
 “Non-Selective” actives sites are uniform poison and chemisorption occurs in a
uniform manner. “Selective” the sites have distribution of the characteristic such as
strength, the strongest attacked first.
 Reversible and irreversible

Coking

 For catalytic reactions involving hydrocarbons side reaction on the catalyst surface leading to
the formation of carbonaceous residues (coke)
  15 to 20 % of catalyst weight
 Cover active surface or cause pore blocking
 Carbon from product of CO eg. 2CO →C +CO2 and coke from decomposition of hydrocarbon

CH4→ C + 2H2

Sentering

 The loss of active surface via structural modification of the catalyst

 Thermally activated process and physical
 Occurs in both supported metal catalyst and unsupported metal catalyst
 In supported metal catalyst- via agglomationn and coalescence of small metal crystallities
into larger ones thus lower surface to volume ratio.
 Additive can reduce the sentering such as BaO, CeO 2, SiO2 and ZrO2 improve the stability of
alumina.
 Sentering may also lead to reduction in pore opening or pore closure.

Kinetics of catalyst deactivation

The activity of a catalyst at timet , a (t) is expressed as

−r A (t )
a ( t )=
−r A ( t=0)

By combining rate equation and catalyst activity

−r A =a ( t ) k ( T ) fn(C A ,C B … … … … C P )

a ( t ) - catalytic activity, time dependent

k ( T ) – specific reaction rate constant- temperature dependent

C i – concentration of reactant, product and contaminant.

Since the catalyst decay is time dependent, so we can express it just analogous to rate
equation

−d a
rd = = p [ a ( t ) ] k d (T )h(C A , C B … … … …C P )
dt

k d – specific decay constant

h - Functionality of r d on reacting species concentration

pa ( t ) – Functionality of the activity term. Influenced by order of decay and causes of deactivation.
Sintering
−da
r d =k d a2=
dt

a=1 at t=0

1
a ( t )=
1+ k d t

k d follows the Arrhenius equation

Coking
Follow the empirical correlation

C c =A t n

C c Concentration of carbon on the surface and A and n are fouling or coking parameters which can
be functions of feed rate.

1
e.g. a ( t )=
1+ 7.6 t 1 /2

Poisoning
−da
rd = =k d C mP a n
dt

C P- poison concentration

If C P is constant then

−da
=k 'd an
dt

n≠1
1

a ( t )=[ 1−(1−n)k 'd t ] (1−n)

Case 1

A first order reaction A → B was carried out isothermally in a batch reactor. Derive an equation for
conversion x in term of t the catalyst deactivation was caused by sintering.
Second order

1
a ( t )=
1+ k d t

Reactor design equation

dx
N AO =−r A W
dt

Rate

−r A =ka (t)C A

C A=C AO (1−x )

N AO
¿ (1−x)
V

dx
N AO =ka(t)C AO (1−x) W
dt

dx N AO
N AO =ka(t) (1−x) W
dt V

dx W
= ka( t)(1−x )
dt V

dx dt
=k '
(1−x ) 1+k dt

x t
dx dt
∫ (1−x) =k '∫
o 0 1+ k d t

1 k'
ln = ln ⁡(1+ k d t )
(1−x) k d

1
x=1−
[ (1+k d t )
k
'

kd ]
External Mass Transfer Process
Even though a catalyst is active, its effectiveness depends on whether the reactant can reach its
surface (active sites) or not. The first step is the mass transfer of the reactant from the bulk phase to
the surface of the catalyst, external mass transfer.
 External mass transfer depends on

 Concentration/temperature gradient
 Physical properties of the fluid such as viscosity, density…
 Fluid velocity

If the concentration on the reactant on the surface is less than the concentration in the bulk phase
then the overall rate of reaction is less than the rate of reaction measured.

TB
TB
TS
TS

CB CB

CS CS

Endothermic Exothermic

Resistances to external mass Transfer

Consider a system whereby a reactant A flows over a catalyst pellet

CAb Boundary
layer

CAs
For a first order reaction
r As=k r C As

Under steady state condition, the number of mole of A, N A , transferred from

the bulk phase = the number of mole reacted on the surface. r As is in kmol/m2h

Therefore
N A =k g ( C Ab −C As )=r As =k r C As

kg
C As= C
k g + k r Ab
−1
1 1
r As=
[ +
kg kr ] C Ab

¿ k o C Ab

Therefore
−1
1 1
[
k o= +
kg kr ]
1 1 1
= +
ko k g kr

Where k o is the overall rate constant

There are two extreme cases, external mass transfer rate limiting or surface reaction is rate
limiting.

1 1
When external mass transfer is big k g ≫k r and «
k g kr

kg
C As= C
k g + k r Ab

C As ≈ C Ab

Under this circumstances, the measured rate is the actual rate of reaction
(reaction is rate limiting)
When the rate of reaction is higher than the rate of mass transfer
k r≫ k g

1 1
≫
kg kr

kg
C As= C
k g + k r Ab

C As ≈ 0

Evaluation of mass transfer rate coefficient, k g

There are many correlations to determine the mass transfer coefficient

Frossling equation
1 1
Sh=2+0.6 R e 2 S c 3

k g dp
Sh=
D AB

ν
Sc=
D AB

When the fluid is stationary Sh=2

From Frossling equation it is obvious that k g depends on fluid physical properties, velocity
and pellet size.

Consider for this rate of reaction

 −1
1 1
r A= +
k g kr[ ] C Ab

which k r ≫ k g

To increase r A need to increase C A and / or k g. For most gas and liquid phase reaction

Sh≫ 2
1 1
2 3
Sh=0.6 R e S c
1 1
k gd p
=0.6 R e 2 S c 3
D AB

U dp
ℜ=
ν
1 1
D AB U dp ν
k g=0.6 ( )( ) ( )
dp ν
2
D AB
3

2 1

( )( )
3
D AB U 2
k g=0.6 1 1
6
ν d 2p

( )
3
D AB
1
influenced by temperature and pressure, Diffusivity increases with temperature for
6
ν
3
both gas and liquid. Kinematic viscosity also increases with temperature, ν ∝T 2 for gas and
it decreases exponentially for liquid.

()
2
U
1 –this term indicates the influence of fluid flow and the pellet size.
2
d p

Consider for a case whereby k g ≫k r

−r A =k r C AB

k r ≠ f ( pellet ¿ velocity)
 1

The plot of −r A vs
()U2

d
1
2
p
can be used to determine, which factor is rate limiting
Surface
reaction

−r A
External
diffusion

1
U
( )
dp
2

The above facts are important in conducting experiment to determine the kinetic
parameters.d p is based on diameter of a spherical shape pellet based on equal area. For a
cylindrical shape with length, Lc and radius r c

dp 2
4π ( )
2
2
=2 π r c Lc +2 π r c

1
Or d p=( 2 r c Lc +2 r 2c ) 2

Chilton-Colburn Correlation
Correlation to determine the mass and heat transfer coefficients.

For mass transfer, j D

k g ρ 23
j D= Sc
G

ρ−¿liquid density

G- Liquid mass velocity

μ
SC = – Schmidt No
ρD
μ- viscosity

D-Diffusivity

Correlation

Mass Transfer
ε - bed voidage

For gas

0.357
ε jD = 3< ℜ<2000
ℜ0.357

Liquid

0.250
ε jD = 0.310 55< ℜ< 1500
ℜ

0.35< ε <0.75

1.09
ε jD = 2 0.0016< ℜ<55
ℜ3

Heat Transfer
C p μ 23 2
h h
j H=
( C G )( )
p k
=
Cp G
Pr 3

μ- viscosity

C p –specific heat capacity

k -heat conductivity

h-heat transfer coefficient

Pr-Prandalt No

When heat of radiation can be ignored, (T < 400 oC) and for d p ≤6 mm

j H ≈ jD
Under a steady state condition, the amount of heat released is equal to the amount of heat
transferred.

Therefore

k g ( C Ab−C As ) (−∆ H )=h ( T s −T b )

Replace k g∧h in terms of

j H ∧ jD

kg ρ μ 2
j D=
G ρD ( ) 3

2
h Cp μ
j H=
( C G )( )
p k
3

G ( C Ab −C As ) C p G j H ( T s −T b )
2
j D (−∆ H )= 2
μ Cp μ
( )
ρ
ρD
3
( )k
3

Or
2
Cp μ 3
−∆ H k
( T s−T b ) = ρC
p μ
ρD
( )( ) jD
jH
( C Ab−C As)

2
Cpμ 3

( )
k
μ
ρD
- Le =Lewis no = Pr : Sc

2
Cpμ 3

For most gases

k
μ
ρD
( ) ≈ 1 and

j H ≈ jD

Therefore

−∆ H
( T s−T b ) = ρC ( C Ab−C As )
p
 −∆ H
The temperature difference depends on concentration and the ratio of
ρC p