CATÁLISIS

Bogotá D.C. – July 1 / 2020

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 Goals of today's class:
• Step in a heterogeneous catalytic
reaction.
• Adsorption: physical and chemical.
• Isotherms.

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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)
 Individual steps in heterogeneous catalysis

Concentration–position curves
a) Film diffusion region: the reaction
is fast compared to diffusion in the
film layer and to diffusion in the
pores.
b) Pore diffusion region: the reaction
is fast compared to diffusion in the
pores, but slow compared to film
diffusion.
c) Kinetic region: the reaction is slow
compared to diffusion in the pores
and through the gas film.
FUENTE: Hagen (2006)
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 Individual steps in heterogeneous catalysis

a) Film diffusion region: reff increase slowly

with increasing temperature because the
diffusion has only a slight temperature
dependence.
b) Pore diffusion region: the reaction rate
also increases according to the Arrhenius
law, but the same time the concentration
profile becomes steeper .
c) Kinetic region: the reaction rate increases
rapidly with increasing temperature, as in a
homogeneous reaction obeying the
Arrhenius law.
FUENTE: Hagen (2006)

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 Adsorption

Kinetics and Mechanisms of Heterogeneously Catalyzed Reactions

1) Knowledge of the reaction order with respect to the reactants and

products is a prerequisite for studying the mechanism of the
reaction  Optimize the catalyst on a scientific basis.
2) The design of the reactor, including the size and shape of the
catalyst particles, depends directly on the reaction order of the
reactants and the thermodynamic conditions.
3) The influence of temperature on the reaction rate can give helpful
indications as to which is the slowest step of the total catalytic
process.

JEAC FUENTE: Hagen (2006)

 Comparison of types of adsorption

The most important factors

influencing the reaction kinetics:
1) Adsorption is a necessary step
preceding the actual chemical
reaction on solid catalyst surfaces.
2) Heterogeneous catalysis involves
chemisorption, which has the
characteristics of a chemical reaction
in that the molecules of the starting
material react with the surface atoms
of the catalyst.
3) Catalyst surfaces have
heterogeneous structures, and
chemisorption takes place
preferentially at active sites on the
surface.

𝑎𝑏𝑝𝐴
𝐶𝐴 = 𝑎 𝑝𝐴𝑛 𝐶𝐴 =
1 + 𝑏𝑝𝐴
JEAC FUENTE: Hagen (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

It is easy to prove that:

𝐾𝑒𝑞,𝐴 ∗ 𝑃𝐴 ∗ 𝐶𝑡 𝐾𝑒𝑞,𝐴 ∗ 𝑃𝐴
𝐶𝐴−𝑆 = 𝑜𝑟 𝜃𝐴 =
1 + 𝐾𝑒𝑞,𝐴 ∗ 𝑃𝐴 1 + 𝐾𝑒𝑞,𝐴 ∗ 𝑃𝐴

At low and high concentration of A respectively  𝜃𝐴 ≈ 𝐾𝑒𝑞,𝐴 ∗ 𝑃𝐴 𝜃𝐴 ≈ 1

Davis, E. (2003). Fundamentals of
chemical reaction engineering. USA: Mc
Graw Hill
by linearizing the equation:

𝑃𝐴 1 𝑃𝐴
= +
𝐶𝐴−𝑆 𝐾𝑒𝑞,𝐴 ∗ 𝐶𝑡 𝐶𝑡

Davis, E. (2003). Fundamentals of

chemical reaction engineering. USA: Mc
JEAC Graw Hill
 Langmuir isotherm

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

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:
2
𝐶𝐶−𝑆 ∗ 𝐶𝑂−𝑆
𝑟𝐴𝐷 = 𝑘𝐴 𝑃𝐶𝑂 ∗ 𝐶𝑣 −
𝐾𝑒𝑞,𝐶𝑂
Al equilibrium 𝑟𝐴𝐷 = 0, and for 𝐶𝐶−𝑆 = 𝐶𝑂−𝑆
1/2
𝐶𝑡 𝐾𝑒𝑞,𝐶𝑂 ∗ 𝑃𝐶𝑂 ∗ 𝐶𝑡
𝐶𝑣 = 1/2
𝐶𝑂−𝑆 = 1/2
1 + 2 𝐾𝑒𝑞,𝐶𝑂 ∗ 𝑃𝐶𝑂 1 + 2 𝐾𝑒𝑞,𝐶𝑂 ∗ 𝑃𝐶𝑂

by linearizing the equation:

𝑃𝐶𝑂 1/2 1 2 𝑃𝐶𝑂 1/2

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

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 Langmuir isotherm

Davis, E. (2003). Fundamentals of chemical reaction engineering. USA: c Graw Hill

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 Adsorption isotherms

JEAC Brunauer´s classification of adsorption isotherms

 Adsorption isotherms

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 Adsorption isotherms

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