CATÁLISIS

Bogotá D.C. – July 5 / 2020

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 Goals of today's class:
• Isotherms
• Langmuir-Hinshelwood kinetic mechanism
• Synthesizing a Rate Law, Mechanism, and
Rate-Limiting Step
• Deducing a Rate Law from the Experimental
Data

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 Steps in a heterogeneous catalytic reaction

Etapas de transporte
externo: (1) y (7)

Etapas de reacción
superficial: (3), (4) y (5)

Etapas de difusión
interna: (2) y (6)

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FUENTE: Fogler (2006)
 Langmuir isotherm
• Langmuir (1918) proposed a model that quantitatively described the volume of gas adsorbed onto an
open surface such as mica.
• This model may be classified as applying to localized adsorption of monolayer coverage, includes the
following assumptions:
1) All the surface of the catalyst has the same activity for adsorption, this is; it is energetically
uniform.
2) There is no interaction between adsorbed molecules. This means that the amount adsorbed has
no effect on the rate of adsorption per site.
3) All the adsorption occurs by the same mechanism, and each adsorbed complex has the same
structure.
4) The extent of adsorption is less than one complex monomolecular layer on the surface.

Irving Langmuir was an American metallurgical engineer, physicist and chemist known for his work in various
fields of chemistry and was awarded the Nobel Prize in Chemistry in 1932

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 Langmuir isotherm
• Associative Adsorption: the adsorbed molecules are in equilibrium with the gas phase.
A + S  A-S
where S = active site alone  vacant site, with no atom, molecule or complex adsorbed on it
A-S = species A chemically adsorbed on the site S

Some definitions are:

Pi = partial pressure of species “i" in the gas phase [atm or kPa]
Ci-s = surface concentration of sites occupied by species “i” [mol/g cat]
Ct = total molar concentration of active sites per unit mass of catalyst [mol/g cat]
Cv = molar concentration of vacant sites

JEAC FUENTE: Fogler, (2006)

 Langmuir isotherm

• Associative Adsorption: the adsorbed molecules are in equilibrium with the gas phase.
A + S  A-S

JEAC FUENTE: Fogler, (2006)

 Langmuir isotherm

Davis, E. (2003). Fundamentals of chemical reaction engineering.

USA: Mc Graw Hill

At low and high concentration of A respectively 

≈ , ∗ ≈1

JEAC Davis, E. (2003). Fundamentals of chemical reaction engineering. USA: Mc Graw Hill
 Langmuir isotherm

JEAC
Fogler. (2006). Elements of Chemical Reaction Engineering, 4ta - 2006
 Langmuir isotherm

• Dissociative Adsorption: Example, isotherm for carbon monoxide

disassociating into separate atoms as it adsorbs on the surface.
CO + 2S  C-S + O-S
It is easy to prove that:
∗ ∗ ∗
= ∗ −
,
Al equilibrium = 0, and for ∗ = ∗
/
, ∗ ∗
= /
= /
1+2 , ∗ 1+2 , ∗

by linearizing the equation:

/ /
1 2
Fogler. (2006). Elements of Chemical
= /
+
Reaction Engineering, 4ta - 2006 ∗ ∗ ,

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 Adsorption isotherms

JEAC Brunauer´s classification of adsorption isotherms

 Adsorption isotherms

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 Langmuir isotherm

HOMEWORK: When more than one substance is present, the adsorption isotherm equations are
somewhat more complex, but, the principle are the same.

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 Langmuir isotherm

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 LHHW model

The Langmuir-Hinshelwood–Hougen-Watson(LHHW) approach is one of the most commonly used way

of deriving rate expressions for fluid solid catalytic reactions. The advantages of this method are that:
(1) Rate derived by this method takes into account the adsorption/desorption process occurring over
the surface along with the surface reaction.
(2) Rate equation derived can be extrapolated more accurately to concentrations lying beyond the
experimentally measured values but, the principle are the same.

The chemical rate depends on: (1) chemisorption steps - (2) surface reaction steps - (3) desorption
steps.
In LHHW model development, the rate equation is first derived in terms of surface concentration of
adsorbed species and vacant sites. Then, these surface concentrations are related to the fluid or bulk
concentration that is directly measurable.

Cyril Norman Hinshelwood (Nobel Prize in Chemistry in 1956) – Irving Langmuir (Nobel Prize in
Chemistry in 1932)

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 LHHW model
• Superface reaction: A + S  A*S
∗
= ∗ −
1) Single site: A*S  B*S

∗
= ∗ − =

2) Dual site:

a) A*S + S  B*S + S

∗
= ∗ −

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 LHHW model

b) A*S + B*S  C*S + D*S

∗ ∗
= ∗ ∗ −

c) A*S + B*S’  C*S’ + D*S

∗ ∗
= ∗ ∗ −

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 LHHW model

3) Eley-Rideal: A*S + B(g)  C*S

∗
= ∗ −

• Desortion: C*S  C + S

= ∗ − =−

1
= ∗ − =

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 Rate limiting step

The Rate-Limiting Step

− ≡ = =

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 Derive a Rate Law for Catalytic rxn

• Assume pseudo-steady state hypothesis (rate of adsorption = rate of surface reaction = rate of
desorption)
• No accumulation of species on the surface or near interface
• Each species adsorbed on the surface is a reactive intermediate
• Net rate of formation of species i adsorbed on the surface is 0, ri·S=0
• One step is usually rate-limiting
• If the rate-limiting step could be sped up, the entire rxn would be faster
• Although reactions involve all 7 steps, only adsorption, surface reaction, or desorption will be
rate limiting
• The surface reaction step is rate limiting ~70% of the time!
• Steps to derive the rate law
• Select among types of adsorption, surface reaction, and desorption
• Write rate laws for each individual step, assuming all are reversible
• Postulate which step is rate limiting
• Use non-rate-limiting steps to eliminate the surface concentration terms that cannot be
measured

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 Derive a Rate Law for Catalytic rxn

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 Steps L-H kinetic mechanism

C6H5CH(CH3)2  C6H6 + C3H6

HOMEWORK

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 Algorithm: rxn mechanism – rate limit.

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 Algorithm: rxn mechanism – rate limit.

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 Irreversible surface reaction limited rate laws

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 Rate Law

Reducing a Rate Law from the Experimental Data:

It has already been studied

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 PROJECT

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