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Chemical Reaction Engineering II

Adsorption Influenced Reactions

N.H. Tioh

May 2017
1. Introduction Todays topics

Adsorption
Heterogeneous
Introduction Influenced
Reactions
Reactions
External Internal Diffusion Design of
Diffusion Limited Limited Multiphase
Reactions Reactions Reactor
Catalyst
Resistance
Deactivation and
Analysis
Regeneration
1. Introduction Todays topics

Searching for a Reaction Mechanism and


Deduce and synthesize a Rate Law
Consistent with Experimental Observation;
Langmuir-Hinshelwood-Hougen-Watson
algorithm
Evaluation of Rate Law Parameters
1. Introduction

Bulk gas phase

Boundary layer
1 7
External diffusion

pore 2
6 Internal diffusion

Adsorption
3
5
4 Desorption
Surface
reaction
1. Introduction
1. Introduction

1. Mass transfer (diffusion) of the reactant (A) from the bulk fluid to
the external surface of the catalyst pellet
2. Diffusion of the reactant from pore mouth through the catalyst
pores to the immediate vicinity of the internal catalytic surface
3. Adsorption of reactant A onto the catalyst surface
4. Reaction on the surface of the catalyst (A B)
5. Desorption of the products (B) from the surface.
6. Diffusion of the products from the interior of the pellet to the pore
mouth at the external surface
7. Mass transfer of the products from the external pellet surface to
the bulk fluid.
1. Introduction Revision

Dr Yap YH Chapter 3
1. Introduction Revision

Dr Yap YH Chapter 3
1. Introduction The Power Law Kinetic Model

For homogenous reaction (CRE 1), power law form of


rate equation is used.
Rate is a function of concentration.
a and b are the order of reaction and k is reaction
rate constant which is independent of concentration
and depends on temperature.
rA kC Aa CBb
The Power Law Kinetic Model can be used for solid
catalytic reactions
The major disadvantage is it ignores all factors
associated with adsorption and reaction mechanism
on the surface of the catalyst
1. Introduction What is LHHW

LHHW model is commonly used to derive rate


expressions for fluid solid catalytic reactions.
Advantages of this approach include:
o It takes into account the adsorption/desorption
process occurring over the surface
o Rate equation derived can be extrapolated more
accurately to concentration lying beyond the
experimentally measured values.
Assume all physical transport steps like mass transfer
from bulk phase to catalyst, diffusion of reactants
from pore mouth to pore excluded.
1. Introduction What is LHHW

Advantages of Langmuir-Hinshelwood-Hougen-
Watson (LHHW) approach include represent
adsorption influenced reactions
a b
kC C
-rA = A B

1+ KCA + KCB
Compare with Power Law Approach

rA kC C a
A
b
B
1. Introduction What is LHHW

Knowing the variables that affect the external diffusion


and internal diffusion step. Therefore it is easy for us to
determine whether external or internal diffusion is rate
limiting step.
Then, employing Langmuir-Hinshelwood-Hougen-
Watson (LHHW) approach to determine which of
adsorption, surface reaction or desorption is the rate
limiting step
Langmuir-Hinshelwood-Hougen-Watson (LHHW)
approach is an algorithm that systematically postulate
and verify the rate limiting step for a chosen reaction
mechanism
1. Introduction What is LHHW History

Hinshelwood employed the concept of Langmuir


isotherm to model adsorption influenced reactions
In which surface coverage are correlated with partial
pressure in the fluid phase by means of Langmuir
adsorption isotherm

-rA = kq q a b
A B
Fractional
occupancy of
adsorption
sites A
K pA A
kCAaCBb
qA = eq
-rA =
1+ Keq pA + Keq pB
A B
1+ KCA + KCB
Langmuir adsorption isotherm Langmuir Hinshelwood kinetic model
1. Introduction What is LHHW History

Hinshelwoods LH model express the rate in terms of


surface coverage only. Langmuir isotherm was
employed to relate with fluid concentration
Hougen and Watson improved upon LH model to
become LHHW model with the following improvement:
Express rate in terms of surface concentrations of
adsorbed species and free sites
Account for multisite and adjacent sites
Rate determining step can be identified

Langmuir isotherm Freundlich isotherm


1. .. LHHW approach Ammonia synthesis
Success
The synthesis of ammonia from hydrogen and nitrogen,

3H 2 + N 2 2NH 3
Mechanisms (over an iron catalyst)
H2 + 2S 2H S Rapid

N2
N2 S
+
+
S
S
N2 S
2N S
Rate-limiting
Adsorption-limited


reaction

NS + HS HN S + S
HN S + HS H2 N S + S Rapid
H2 N S + HS NH 3 S + S
NH 3 S + S NH 3 + S
1. .. LHHW approach CO and NO reaction

Two noxious automobile exhaust products, CO and NO, react to form environmentally
acceptable products

Success

Mechanisms (over copper catalyst)


Rapid

Surface- limiting
reaction
2. Application of LHHW

Weakness in assumptions:
Activity of surface (adsorption energy) toward
adsorption, desorption or surface reaction is
independent of coverage
Adsorption sites are essentially uniformly distributed
2. Application of LHHW Algorithm

LHHW algorithm:
1. Experimental observations
2. Postulate:
a) Postulate reaction mechanism, each is elementary
step (could be molecular or atomic adsorption,
single or dual site)
b) Write rate equations for each step
c) Assume a rate limiting step LHHW
d) Convert rate (limiting) equation into a form which
the concentration can be measured and compared
against the experimental observation
3. Test whether 1 == 2 ------> determine
postulated rate limiting step is correct
2. Application of LHHW

Two examples to show LHHW (Foglers Chp 10.3):


Decomposition of cumene

Isomerization of n-pentene to i-pentene


2. Application of LHHW Decomposition of cumene

Chemical equation:

C B + P
2. Application of LHHW Decomposition of cumene

Experimental observation:
2. Application of LHHW Decomposition of cumene

Postulate steps in LH kinetic mechanism:


1. Adsorption of cumene on the surface

kA
C + S C S
k-A

2. Surface reaction to form adsorbed benzene +


gas phase propylene

kS
C S BS + P
k-S

3. Desorption of benzene from surface



kD
B S B + S
k-D

In formulating the rate laws for each of the step, each of


the steps is assumed as an elementary reaction.
2. Application of LHHW Decomposition of cumene Adsorption

Adsorption of cumene:

C + S C S
kA

k-A

C
C

rAD kA PCCv k ACCS

CCS
Adsorption : rAD kA PCCv
KC
2. .. Decomposition of cumene Adsorption rate limiting

Assuming adsorption step is rate limiting:


This implies

kA kS and kA kD

CCS
Adsorption : rAD kA PCCv
KC

cannot be measured
and must be replaced!

We must derive a rate equation in which we can measure


and which we can compare against the expt. observation
2. .. Decomposition of cumene Adsorption is rate limiting

Since kS is big
For steady state operation:
kA kS and Since kD is big
kA kD rS rD rAD
r rAD rS rD
'
C kS

kD

kA

The surface reaction rate:


rS
0
PPCBS kS
PPCBS
rS kS CCS CCS
K S KS

The desorption rate: rD


0
rD kD CBS KB PBC kD
CBS KB PBC
2. .. Decomposition of cumene Adsorption is rate limiting

CBS KB PBC
substituting

PC PB PPC
CCS P BS CCS K B
KS KS
substituting

CCS K B PB PP
rAD kA PCCv rAD kA PC Cv
K C KS K C
(Rate equation for adsorption)
K S KC
substituting KP
KB
PB PP Partial pressure
rAD k A PC Cv equilibrium constant
KP
2. .. Decomposition of cumene Adsorption is rate limiting

The partial pressure equilibrium constant:


1. Can be derived from thermodynamic data

Gibbs free
R= ideal gas constant energy
T= absolute temperature

RT ln K P G

K S KC
KP
KB
Partial pressure
equilibrium constant
2. .. Decomposition of cumene Adsorption is rate limiting

Previous slide:
PB PP
rAD k A PC Cv
KP

From site balance: PPCBS


CCS
KS Ct
Ct Cv CCS CBS Cv
1 PB PP K B / K S K B PB
CBS K B PBCv

substituting

PB PP
PB PP k ACt PC
rAD k A PC Cv K P
KP rC' rAD
1 PB PP K B / K S K B PB
2. .. Decomposition of cumene Adsorption is rate limiting

Simplifying: PB PP Initially negligible


k ACt PC products are
rC' rAD K P present, thus PP
1 PB PP K B / K S K B PB = PB = 0

Therefore:
rC0
'
rAD0 kACt PC0

Initial partial pressure of cumene, PC0

If adsorption were rate-limiting, the two will be the same


So adsorption is not the rate-limiting step
2. .. Decomposition of cumene Surface Reaction

Surface reaction to produce adsorbed benzene and


gas phase propylene:

kS
C S B S + P(g)
k-S

P
C B

PPCBS
Surface reaction : rS kS CCS
KS
2. .. Decomposition of cumene Surface reaction rate limiting

Assuming surface reaction step is rate limiting:


This implies

kS k A and kS k D

PPCBS
Surface reaction : rS kS CCS
KS

cannot be measured
and must be replaced!

We must derive a rate equation in which we can measure


and which we can compare against the expt. observation
2. .. Decomposition of cumene Surface reaction rate limiting

For steady state operation:

k S k A
r rAD rS rD
'
C k S k D
rAD

rD

rS

kA kD kS

The adsorption rate: Since kA is big


rAD
0
CCS kA
rAD k A PC Cv CCS KC PC Cv
KC

Since kD is big
The desorption rate: rD
0
rD kD CBS KB PBC kD
CBS KB PBC
2. .. Decomposition of cumene Surface reaction rate limiting

CCS KC PC Cv
PPCBS K B PB PP
rS k S CCS
rS k S PC K C Cv
KS
CBS K B PBCv KS

K S KC
KP
KB

PB PP
rS k S K C PC Cv
KP

RT ln K P G
2. .. Decomposition of cumene Surface reaction rate limiting

Previous slide:
PB PP
rS k S K C PC Cv
KP

From site balance: PPCBS


CCS
KS Ct
Ct Cv CCS CBS Cv
1 PB K B K C PC
CBS K B PBCv

substituting

PB PP
PB PP k S Ct K C PC
rS k S K C PC Cv KP
KP rS
1 PB K B K C PC
2. .. Decomposition of cumene Surface reaction rate limiting

Simplifying: PB PP Initially negligible


k S Ct K C PC products are
rS KP present, thus PP
1 PB K B K C PC = PB = 0

Therefore: r rS 0
' k S Ct K C PC 0

kPC 0
1 K C PC 0 1 K C PC 0
C0

If surface reaction were rate-limiting, the two will be the same


So surface reaction is probably the rate-limiting step
2. Application of LHHW Decomposition of cumene Desorption

Desorption of benzene:

B S B + S
kD

k-D

B
B

Benzene
PBC adsorption
Desorption : rD kD CBS equilibrium
K DB constant

1
KD =
K DB Desorption : rD kD CBS KB PBC
2. .. Decomposition of cumene Desorption rate limiting

Assuming desorption step is rate limiting:


This implies

k D k A and k D kS

rD k D CBS K B PBCv

cannot be measured
and must be replaced!

We must derive a rate equation in which we can measure


and which we can compare against the expt. observation
2. .. Decomposition of cumene Desorption is rate limiting

For steady state operation:

k D k AD rAD rS rD
r rAD rS rD
'
C k D k S kA

kS

kD

The adsorption rate: Since kA is big


rAD
0
CCS kA
rAD k A PC Cv CCS KC PC Cv
KC

The surface reaction rate: Since kS is big


rS
0
PPCBS kS CCS
rS kS CCS C BS K B
KS PP
2. .. Decomposition of cumene Desorption rate limiting

CCS
C BS K B
PP
PC PB
rD k D CBS K B PBCv rD k D K C K S Cv
CCS KC PC Cv PP K P

K S KC
KP
RT ln K P G KB
2. .. Decomposition of cumene Desorption rate limiting

Previous slide:
PC PB
rD k D K C K S Cv
PP K P

From site balance: C


CBS K B CS
PP Ct
Ct Cv CCS CBS Cv
1 PC K C K S / PP K C PC
CCS KC PC Cv

substituting

PB PP
PC PB k DCt K C K S PC
rD k D K C K S Cv KP
PP K P rD
PP PC K C K S K C PP PC
2. .. Decomposition of cumene Desorption rate limiting

Simplifying: PB PP Initially negligible


k DCt K C K S PC products are
rD KP present, thus PP
PP PC K C K S K C PP PC = PB = 0

Therefore: rC' 0 rD0 k DCt

-rC0

PC0

If desorption were rate-limiting, the two will be the same


So desorption is probably not the rate-limiting step
2. .. Decomposition of cumene Comparison of rate limiting steps

From experimental
observation:

From LHHW:
-rC0

Initial partial pressure of cumene, Initial partial pressure of cumene,


PC0 PC0

Therefore, cumene decomposition is likely to be surface-reaction-limited.


In fact, more than 75% of all heterogeneous reactions that are not
diffusion-limited are surface-reaction-limited.
2. .. Decomposition of cumene Rate limiting step

Rate limiting equation --> surface reaction:

k S Ct K C PC 0 kPC 0
r rS 0
'

1 K C PC 0 1 K C PC 0
C0

Steady state only !!!


2. .. Decomposition of cumene Addition of inert component

What if we add an inert component in the feed:


1)The inert would not participate in the reaction


2)But will occupy sites on the catalyst surface.
C + S kA
C S
k-A
kS kAC rADC rADI rD
I + S IS
kS kAI ~ ~ 0

C S BS + P
kS
kAC kAI kD
k-S kS kD

kD
B S B + S
k-D

Homework: check whether you get:


PB PP

k PC
rS KP
1 PB K B KC PC K I PI
2. .. Decomposition of cumene Addition of inert component

What would be affected?

CCS
rADC k AC PC Cv
KC

C I S
rADI k AI PI Cv
KI K B PB PP
rS k S PC K C Cv
KS
PP CBS
rS k S CC S
KS

rD kD CBS K B PBCv
2. .. Decomposition of cumene Addition of inert component

K PP
rS k S PC K C B B P Cv
KS

C
rADC k AC PC Cv C S rADC rADI rD CCS KC PC Cv
KC ~ ~ 0
k AC k AI k D
C CI S K I PI Cv
rADI k AI PI Cv I S
KI
CBS K B PBCv
rD k D CBS K B PBCv

Ct Cv CCS CBS CI S

PP
Cv Ct CCS CBS CI S k PC B P
rS KP
1 PB K B K C PC K I PI
2. Application of LHHW

Two examples to show LHHW:


Decomposition of cumene

Isomerization of n-pentene to i-pentene


2. Application of LHHW Isomerization of n-pentene to i-pentene

The n-pentane adsorbs onto the platinum, where it is


dehydrogenated to form n-pentene. The n-pentene desorbs
from the platinum and adsorbs on the alumina, where it is
isomerized to i-pentene, which then desorbs and subsequently
adsorbs onto platinum, where it is hydrogenated to form i-
pentane.

Focus on this
isomerization
step in this study
2. Application of LHHW Isomerization of n-pentene to i-pentene

Form of catalyst:
2. Application of LHHW Isomerization of n-pentene to i-pentene

Experimental observation:
In the form of :

PI
k PN
rN' rS K P

1 PN K N K I PI
2. Application of LHHW Isomerization of n-pentene to i-pentene

1. Postulate steps in LH kinetic mechanism:


1. Adsorption of n-pentene on the surface

2. Surface reaction of single adsorbed site


Dual-site
mechanism

3. Desorption of i-pentene from surface


2. Application of LHHW Isomerization of n-pentene to i-pentene

2. Assume a rate limiting step:


Surface reaction:
(as 75% of hetero. reactions are surface reaction limited)
CV CI S

rS k S CV C N S
KS

3. Find concentration for adsorbed and vacant species:

rAD / kAD 0 rD / kD 0

CNS PN K NCv
PC
CIS I v Ct C CNS CIS
KD
2. Application of LHHW Isomerization of n-pentene to i-pentene

4. Derive the rate law:


CV CI S k S Ct2 K N PN 1
P

rS k S CV C N S KP
KS rS
1 K N PN K1P1 2

PI
k PN
rN' rS K P

1 PN K N K I PI
2

5. Compare with experimental observation:


P Not matching, even for other steps
k PN I
KP Propose other reaction
rN rS
'

1 PN K N K I PI mechanisms !!
2. Application of LHHW Isomerization of n-pentene to i-pentene

1. Postulate steps in LH kinetic mechanism:


1. Adsorption of n-pentene on the surface

2. Surface reaction between adsorbed n-


pentene with vacant site Single-site
mechanism

3. Desorption of i-pentene from surface


2. Application of LHHW Isomerization of n-pentene to i-pentene

2. Assume a rate limiting step:


Surface reaction:
(as 75% of hetero. reactions are surface reaction limited)
CI S
rS k S C N S
KS

3. Find concentration for adsorbed and vacant species:

rAD / kAD 0 rD / kD 0

PC
CNS PN K NCv CIS I v Ct C CNS CIS
KD
2. Application of LHHW Isomerization of n-pentene to i-pentene

4. Derive the rate law:


k S Ct2 K N PN 1
P
CI S

rS k S C N S rS KP
KS 1 K N PN K1P1

P
k PN I
rN rS
' KP
1 PN K N K I PI

5. Compare with experimental observation:


P Match !!
k PN I Seems like the
rN rS
' KP
1 PN K N K I PI proposed reaction
mechanism is correct
2. Application of LHHW Isomerization of n-pentene to i-pentene

There is more than one steps are rate-limiting?


e.g. Adsorption and surface reaction

Proposed mechanisms Rate law

N S
N+S
kN
rN*S kN PNC k-NCNS kSCNS 0
k N

N S
kS
I S rN' rS kSCNS
I+S rI*S kSCNS kICIS k-I PC
I 0
kI
I S
k I

The net rate of the adsorbed species (i.e. active intermediates) is zero
2. Application of LHHW Isomerization of n-pentene to i-pentene

kN PNC kSCNS k-I PC kSk N PN k-I


CNS CIS I
PI C
k-N kS kI kI k-N kS kI
kN kS
r rS kSCNS
' r rS
'
PNC
k-N kS
N
N

Site balance
Ct = CNS + CIS + C C = Ct - CNS - CIS

kN PNC kSk N PN k-I


C Ct PI C
k-N kS kI k-N kS kI
Ct kN PN kSk N PN k-I
1 PI
C k-N kS kI k-N kS kI
2. Application of LHHW Isomerization of n-pentene to i-pentene

Ct kN PN kSk N PN k-I
1 PI
C k-N kS kI k-N kS kI

Ct kN PN kSk N PN k-I
1 PI
C k-N kS kI k-N kS kI
Ct
C
k N PN kSk N PN k-I
1 PI
k-N kS kI k-N kS kI

Replacing Cv in the rate law


k N kS 1
rN' rS PNCt
k-N kS k N PN kSk N PN k-I
1 PI
k-N kS kI k-N kS kI
2. Application of LHHW Isomerization of n-pentene to i-pentene

k N kS 1
r rS
'
PNCt
k-N kS kSk N PN k-I
N
k N PN
1 PI
k-N kS kI k-N kS kI

k N kSCt PN
r rS
'

k-N kS kN
N
1 kS k-I
1 PN PI
k-N kS kI kI

k N kSCt PN
r rS
'

k-N kS kN
N
1 kS k-I
1 PN PI
k-N kS kI kI
2. Application of LHHW Isomerization of n-pentene to i-pentene

k N kSCt PN
r rS
'

k-N kS kN
N
1 kS k-I
1 PN PI
k-N kS kI kI

The adsorption constants are defined as the ratio of their respective rate
constants
k k
K I -I and K N N
kI k-N


k k C PN
rN rS N S t
'

1 kS 1 1
K N PN K I PI

k-N kS
1
k-N
2. Application of LHHW Isomerization of n-pentene to i-pentene


k k C PN
rN' rS N S t
1 kS 1 1
K N PN K I PI

k-N
kS
1
k-N

For surface-limiting step, the surface specific reaction constant, kS is very


small than the rate constant for the desorption of normal pentene, k-N.
kS
1
k N

kPN
r rS
'

1 K N PN K I PI
N
2. Application of LHHW Summary

LHHW algorithm:
1. Experimental observations
2. Postulate:
a) Postulate reaction mechanism, each is elementary
step (could be molecular or atomic adsorption,
single or dual site)
b) Write rate equations for each step
c) Assume a rate limiting step LHHW
d) Convert rate (limiting) equation into a form which
the concentration can be measured and compared
against the experimental observation
3. Test whether 1 == 2 ------> determine
postulated rate limiting step is correct
3. Significance of LHHW

Why LHHW?
Process engineers use it as LHHW incorporates all
steps

Clarification
Just because the mechanism and rate limiting
step fit the rate data does not imply that the
mechanism is correct

How to prove whether the mechanism is correct?


Spectroscopy experiment
3. Significance of LHHW Conclusion

When deriving rate equation for limiting step:


1. It is always based on elementary reaction (for
each step)

2. Use P for gas phase and C for adsorbed


concentration

3. Remember to put in equilibrium constant

4. Always substitute concentration that you cannot


measure

5. We are interested in the scalar unit, not vector of


the rate limiting step. Negative r is not necessary
3. Significance of LHHW Conclusion

Worry:
1. You dont have time to try all the postulated
mechanism
It will usually be given or hinted

2. Adsorption, surface, desorption, which is rate


limiting?
Almost 75% of reactions are surface-reaction limited

3. If L-H surface reaction, which one to choose?


Guideline (next page)
3. Significance of LHHW Conclusion

Cumene decomposition
PP
k S Ct K C PC B P kPA PB
KP r 'N
rS
1 PB K B K C PC
1 K1PA K 2 PB 2

Rules of thumb to decide which surface mechanism


1. Species having concentration in the denominator
Species are adsorbed onto the active sites

2. Square term in the denominator


Dual-site mechanism

3. Species having concentration in the numerator


Reactants will form active intermediate
3. Significance of LHHW Conclusion

Rules of thumb to decide which surface mechanism


4. Minus term in numerator
Reversible reaction

5. Multiple adsorption group in denominator


Multiple type of active sites