LHHW Models and The KSSA 1h6gbxo

Catalytic Kinetics:
Cycles and the LHHW Formalism

"A Catalyst is by definition a substance that increases the rate
of approach to equilibrium of a chemical reaction without being
substantially consumed in the reaction; a catalyst works by
forming chemical bonds to one or more reactants and thereby
facilitating their conversion. A catalyst does not significantly
affect the reaction equilibrium."1
"The definition of a catalyst rests on the idea of reaction rate

and therefore the subject of reaction kinetics is central,
1
providing the quantitative framework."
Common theme: Catalysis ≡ Kinetics
1 Gates, B.C. Catalytic Chemistry, Wiley (1990).
Reactions 1 © Michael T. Klein

Reaction Chemistry:
The Practice of Catalysis
Reaction: A → B + C
o o o o
Thermodynamics: ∆H R = ∆H f + ∆H f - ∆H f
B C A
Role of Catalyst: Increase the rate
Implications: Smaller vessels

Better selectivities (relative rates)

Reaction Coordinate Diagram
Motivates and Explains Catalysis
Homogeneous
E
A good catalyst
A
A poor catalyst
B+C
ξ
∆H R = E B + E C - E A is independent of catalyst
Kinetics of Heterogeneous
Catalytic Reactions
External Transport
Adsorption/Desorption
Internal Transport
Surface Reaction

Series and Parallel Events
in Catalytic Reactions
A
B
Steps 1,3,4,5,7 in series
1 7
Steps 2,3,4,5,6 in parallel
A ss Bss
2
As
Al 3
4
6
Bl
5
Bs

SITES AND ACTIVE CENTERS
"|" USED TO INDICATE A CATALYTIC SITE
Single Site Dual Site

A R = S A R S
Al Rl Sl Al 1 =Rl 1 Rl 2 Sl 2
Surface Intermediates, Active Centers

Adsorption
Physical adsorption Chemisorption
Adsorbent All solids Some solids
Adsorbate All gases below critical point Some chemically reactive

gases
Temperature range Low T Generally high temperature
Heat of adsorption Low, ~ ∆H liq High order, about enthalpy

of reaction
Rate and activation Very rapid, low E Nonactivated, low E;

energy activated, high E
Coverage Multilayer Monolayer and less
Reversibility Highly reversible Often irreversible
Importance For determination of surface For determination of surface

area and pore size concentration, rates of
adsorption and desorption,
estimates of active center
area, and elucidation of
surface-reaction kinetics
From Carberry, J. J. , Chemical and Catalytic Reaction Engineering
, McGraw Hill
Adsorption Isotherms
Langmuir Model:
Homogeneous solid surface
Energetics independent of coverage
Adsorbed species don't interact
Mass Action Steps:

A + l = Al
r a = k a C AC l rd = k dC Al

Adsorption Isotherms
The Equilibrium Isotherm:

ra = r d ka C AC l = k dC Al
or, with
C t = constant = C l + CAl
ΘA = CAl /C t = K AC A /(1 + KAC A)
1.0
0 order
ΘA
1st order
0
0 CA / CA 1
SAT
Extensions of Basic Idea
1. Multicomponent Systems
Θi = C il/C t = K iC i/(1 + ΣKjC j)
2. Dissociative Adsorption of "A"
ΘA = (K AP A) 1/2 /(1 + (K AP A) 1/2 + ΣKjP j)

Heterogeneous Rate Laws
Premises
Homogeneous Principles Valid
Surface Concentrations Relevant
Three Different Classes of (Equal) Rates

Heterogeneous Rate Laws
1. Adsorption A + l = Al
ra = k A(C AC l-C Al/K A)
2. Surface Reaction Al = Rl
rsr = k sr(C Al-C Rl /K sr)
3. Desorption Rl = R + l
rd = k R (C Rl /K R -C R C l)
K i = Adsorption Equilibrium Constant

(used by convention)
Site Balance: C t = C l + C A + C B + …
Steady State Solution
This General Rate Expression Reduced for Various

Rate Controlling Steps
Which May:
Not Exist
Change with T
Change with P

Rate Determining Step
1. The Usual Procedure
2. Requires that all other steps be in virtual

equilibrium
Two Common Cases:

1. Surface Reaction Controls
2. Adsorption/Desorption Controls

Surface Reaction Controlling
A R
r = k sr(C Al - CRl /K sr)
Θi = C il/C t = K iC i/(1 + Σ KjC j)
r = ksrC tKA(C A-C R /K)/(1 + KAC A + K R C R )
K = KsrKA/K R
Additional Examples
Bimolecular Reactions
A+B R+S
r = k srC tKAKB(C AC B-C R C S /K)/(1 + ΣKJC J) 2

0
1st -1
r init
CA

Additional Examples
Two-Site Mechanisms
Al1 + Bl2 Rl1 + S l2
r = ksrCAl1CBl2 =
k sr C t KAKBCACB/(1 + ΣKi1Ci)(1 + ΣKi2Ci2)

Additional Examples
Rideal Mechanism
Al + B (g) Rl + S (g)
r = k srC tKAC AC B/(1 + ΣKiC i)

Additional Examples
Mole Change
l + Al Bl + Cl
r = k srC tKA(C A-C BC C /K)/(1 + ΣKiC i) 2

Kinetic Groups
Adsorption of A controlling kA
Adsorption of B controlling kB
Desorption of R controlling kR K
Adsorption of A controlling with dissociation kA
Impact of A controlling kA KB
Homogeneous reaction controlling k
A R A R+S A+B R A+B R+S
Without dissociation ksrKA ksrKA ksrKA KB ksrKAKB

With dissociation of A ksrKA ksrKA ksrKA KB ksrKAKB
B not adsorbed ksrKA ksrKA ksrKA ksrKA
B not adsorbed, A dissociated ksrKA ksrKA ksrKA ksrKA
Yang/Hougen tables from Froment, G. F. and K. B. Bischoff, Chemical

Reactor Analysis and Design, Wiley
Exponents of Adsorption Groups
Adsorption of A controlling without dissociation n=1

Desorption of R controlling n=1
Adsorption of A controlling with dissociation n=2
Impact of A without dissociation A + B R n=1
Impact of A without dissociation A + B R+S n=2
Homogeneous reaction n=0
A R A R+S A+B R A+B R+S
No dissociation of A 1 2 2 2
Dissociation of A 2 2 3 3
Dissociation of A
(B not adsorbed) 2 2 2 2
No dissociation of A
(B not adsorbed) 1 2 1 2

Driving-Force Groups
Reaction A R A R+S A+B R A+B R+S
pR pR pS pR pR pS
Adsorption of A controlling pA - pA - pA - pA-
K K KpB Kp B
pR p Rp S
Adsorption of B controlling 0 0 pB - pB -
KpA KpA
pR pA pR pR p Ap B p R
Desorption of R controlling pA -
K pS - k pA pB -
K ps - K
p p p p p p
Surface reaction controlling pA - R pA - R S p Ap B - R pA pB - R S
K K K K
pR pR pS
Impact of controlling 0 0 p Ap B - pA pB -
K K
(A not adsorbed)
p p p p p p
Homogeneous reaction pA - R pA - R S p Ap B - R pA pB - R S
K K K K
controlling

Replacement In the
General Adsorption Groups
(l + KApA + KBpB + KSpS + KR PR + KIpI )
Reaction A R A R+S A+B R A+B R+S
KApR KA pR pS KA pR KAp Rp S
Where adsorption of A is rate K K KpB KpB
controlling, replace K A pA by
KB pR KBp Rp S
Where adsorption of B is rate 0 0 KpA KpA
controlling, replace K S pS by
p p p
Where desorption of A is rate KKR pA KKR A KKRp Sp B KKR A B
controlling, replace KA pA by pS ps
KA pR KAp Rp S KA pR KAp RpS
Where adsorption of A is rate K K KpB KpB
controlling with dissociation
of A, replace KA pA by
Where equilibrium adsorption

of A takes place with
dissociation of A, replace KA pA KA pA KA pA KA pA
KApA byand similarly for
other components adsorbed
with dissociation
Where A is not adsorbed

replace KApA by 0 0 0 0
and similarly for other
components that are not
adsorbed
ADSORPTION/DESORPTION
CONTROLLING
• SURFACE REACTION IN VIRTUAL EQUILIBRIUM
Π ν il
KSR = i Cil
1. Al + Bl Rl + Sl with Adsorption of "A" controlling
r = kaA CA Cl – kd A CAl = k A' (CACl – CAl/KA)
CBl = KB CBCl 
CRl = KR CRCl
 4 eqn, 4 unknowns
CAl = C RlCSl/(CBlKSR) 
CSl = KS CSCl

Used instead of final adsorption isotherm
kACt (CA - CRCS /CBK)
r=
1+ CRCS KA + K C + K C + K C 
 CB K B B R R S S


Some Criteria for Parameter Estimation
1. Adsorption and Rate Constants be Statistically

non-negative
2. E* > 0 ln k ↓ with 1/ T ↑ (Arrhenius)
3. Exothermic adsorption ln k ↑ with 1/ T ↑
Confidence intervals may make negative-value containing

models acceptable.

Linearization of Model
kr KA(p A - p R pS /K)

rA = (1+ K p + K y = a + bpA + c pR + dp S
A A R pR + KSpS ) 2
pA - p R pS /K a = 1/ kKA c = KR / kKA

y= rA b = K A/ kKA d = KS / kKA
This allows linear regression. However, this suffers from lack o

statistical rigor--y not truly dependent variable.

Catalysis in Series
r1 r2
A1 → A2 → A3
A1 strongly held, A 2 weak, A 3 not at all
Independent Rates:
r1 = k 1 K1 A1/(1+ K1 A1) ~
– k1
r2 = k 2 K2 A2 /(1+ K2 A2) ~
– k2 K2 A2
@ Max of A2 0 = r 1 - r 2 ⇒ k1 = k 2 K2 A2
k1
or A 2 | Max =k K
2 2
Coupled Rates
In reality, with coupling,

k2 K2 A2
r2 = k 2 K2 A2 /(1+K 2 A2 + K 1 A1 ) ~
– K1 A1
k 1   K1 
A2 MAX =    A1
k 2  K 2 
or
C
A2 MAX
I
= K 1 A1 >>1
A2 MAX
• Gain in selectivity due to coupling

• This is thermodynamic in nature
Analytical Rate Laws Derived from Mechanism
BEFORE Use In Reactor Model
A Heterogeneous Chemistry (A  B) Example
A + l ⇔ Al
Al ⇔ Bl
Bl ⇔ B + l
l0 ( A − B / K )
rA =
 1 1 1   1 1 + K sr   1 1 + K sr 
 + +  + +  KAA +  + K B
 K A ksr k A Kk B   K A k sr Kk B   K A ksr Kk A  B
surface rxn control adsorption control
desorption control
l0 k A ( A − B / K )
l k K (A− B / K) l k K( A − B / K ) rA =
rA = 0 sr A rA = 0 B K
1 + K A A + KBB 1 + K A A + KK B A 1 + A B + KBB
K

Steady State Solution
A=R
dCAa/dt = r a
dC Al /dt = 0 = r a - rsr
dC Rl/dt = 0 = r sr - rd
dC R/dt = r d
C t (C A-C R /K)
r=
 1 1 1   1 1+K sr   1 + 1+K sr  K C 

  K k + k + Kk  +  K k + Kk K
 A CA
+  K sr k A  R R 
 A sr A R  A sr k R 
 K Ak sr 

Derivation of Rate Laws: Useful Tools
The Steady State Approximation
k2

Derivation of Rate Laws: Useful Tools

Estimation of Relaxation Time

Summary of Relaxation Time Issues

Closer Look at the Relaxation Time








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Catalytic Kinetics:

Cycles and the LHHW Formalism

"The definition of a catalyst rests on the idea of reaction rate

Common theme: Catalysis ≡ Kinetics

1 Gates, B.C. Catalytic Chemistry, Wiley (1990).

Reactions 1 © Michael T. Klein

Role of Catalyst: Increase the rate

Implications: Smaller vessels

Reactions 2 © Michael T. Klein

Reactions 4 © Michael T. Klein

Reactions 5 © Michael T. Klein

"|" USED TO INDICATE A CATALYTIC SITE

Single Site Dual Site

Surface Intermediates, Active Centers

Reactions 6 © Michael T. Klein

Physical adsorption Chemisorption

Adsorbent All solids Some solids

Adsorbate All gases below critical point Some chemically reactive

Temperature range Low T Generally high temperature

Heat of adsorption Low, ~ ∆H liq High order, about enthalpy

Rate and activation Very rapid, low E Nonactivated, low E;

Coverage Multilayer Monolayer and less

Reversibility Highly reversible Often irreversible

Importance For determination of surface For determination of surface

Mass Action Steps:

Reactions 8 © Michael T. Klein

The Equilibrium Isotherm:

Θi = C il/C t = K iC i/(1 + ΣKjC j)

2. Dissociative Adsorption of "A"

ΘA = (K AP A) 1/2 /(1 + (K AP A) 1/2 + ΣKjP j)

Reactions 10 © Michael T. Klein

Homogeneous Principles Valid

Surface Concentrations Relevant

Three Different Classes of (Equal) Rates

Reactions 11 © Michael T. Klein

K i = Adsorption Equilibrium Constant

This General Rate Expression Reduced for Various

Reactions 13 © Michael T. Klein

1. The Usual Procedure

2. Requires that all other steps be in virtual

Two Common Cases:

Reactions 14 © Michael T. Klein

r = k sr(C Al - CRl /K sr)

Θi = C il/C t = K iC i/(1 + Σ KjC j)

r = ksrC tKA(C A-C R /K)/(1 + KAC A + K R C R )

r = k srC tKAKB(C AC B-C R C S /K)/(1 + ΣKJC J) 2

Reactions 16 © Michael T. Klein

Al1 + Bl2 Rl1 + S l2

k sr C t KAKBCACB/(1 + ΣKi1Ci)(1 + ΣKi2Ci2)

Reactions 17 © Michael T. Klein

r = k srC tKAC AC B/(1 + ΣKiC i)

Reactions 18 © Michael T. Klein

r = k srC tKA(C A-C BC C /K)/(1 + ΣKiC i) 2

Reactions 19 © Michael T. Klein

Surface Reaction Controlling

A R A R+S A+B R A+B R+S

Without dissociation ksrKA ksrKA ksrKA KB ksrKAKB

Yang/Hougen tables from Froment, G. F. and K. B. Bischoff, Chemical

Adsorption of A controlling without dissociation n=1

Surface Reaction Controlling

A R A R+S A+B R A+B R+S

Yang/Hougen tables from Froment, G. F. and K. B. Bischoff, Chemical

Reaction A R A R+S A+B R A+B R+S