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3/20/18

Heterogeneous catalysis

Heterogeneously catalyzed reactions are composed of purely


chemical and purely physical reaction steps.
For the catalytic process to take place, the starting materials
must be transported to the catalyst. Thus, apart from the
actual chemical reaction, are of importance for the progress
of the overall reaction:
- diffusion,
- adsorption,
- desorption processes.

For a catalytic gas reaction on a porous catalyst, the


following reaction steps can be expected:
1) Diffusion of the starting materials through the
boundary layer to the catalyst surface.
2) Diffusion of the starting materials into the pores
(pore diffusion).
3) Adsorption of the reactants on the inner surface
of the pores.
4) Chemical reaction on the catalyst surface.
5) Desorption of the products from the catalyst
surface.
6) Diffusion of the products out of the pores.
7) Diffusion of the products away from the catalyst
through the boundary layer and
into the gas phase.

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In heterogeneous catalysis chemisorption of the reactants and


products on the catalyst surface is of central importance, so that the
actual chemical reaction (step 4) can not be considered independently
from steps 3 and 5.
Therefore, these (3 to 5) steps must be included in the
microkinetics of the reaction.
In cases where the other transport processes discussed above play a
role, the term macrokinetics is used.
The measured reaction rate, known as the effective reaction rate, is
determined by the most strongly inhibited and therefore slowest step
of the reaction sequence. This rate-determining step also determines
the reaction order.

The effective reaction rate reff is influenced by many parameters:


- the nature of the phase boundary,
- the bulk density of the catalyst,
- the pore structure,
- the transport rate in the diffusion boundary layer.
If the physical reaction steps are rate determining, then the catalyst
capacity is not fully exploited.
If one wishes to determine the mechanism and to describe it exactly
in terms of rate equations, then one must ensure that only steps 3–5
are rate determining.

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Reaction rate

Plotting concentration against position in the


pore provides information about the
ratio of the reaction rate to the transport rate.
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.

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Chemi- and physi-sorption


Physical adsorption (physisorption) and chemical adsorption (chemisorption)
rules most of the catalytic reactions.
Physisorption is the result of van der Waals forces, and the accompanying heat
of adsorption is comparable in magnitude to the heat of evaporation of the
adsorbate.
In chemisorption, chemical bonds are formed between the catalyst and the
starting material. The resulting surface molecules are much more reactive than
free adsorbate molecules, and the heats of adsorption are comparable in
magnitude to heats of chemical reaction.
Since both types of adsorption are exothermic, raising the temperature
generally decreases the equilibrium quantity of adsorbate.
Physisorption is fast, and equilibrium is rapidly reached, even at low
temperature. Chemisorption generally requires high activation energies. The
adsorption rate is low at low temperatures, but the process can be rapid at high T.
The rate of both types of adsorption is strongly dependent on pressure.
Chemisorption leads only to a monolayer, whereas in physisorption multilayers
can form.

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Factors affecting reff

let us summarize 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.

Mechanisms for gas-phase

Bimolecular gas-phase reactions:

Are usually desribed with two approaches:


Langmuir–Hinshelwood Mechanism (1921)
Eley–Rideal Mechanism (1943)

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Langmuir–Hinshelwood Mechanism

This mechanism is based on the following assumption:


- both reaction partners are adsorbed without dissociation at
different free sites on the catalyst surface.
- This is then followed by the actual surface reaction between
neighboring chemisorbed molecules to give the product C,
adsorbed on the surface.
- In the final step the product is desorbed.

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Each of the above-mentioned steps can be rate determining, but here we


consider the case in which the surface reaction between the two adsorbed
molecules is the rate-determining step. On the basis of the relationship for
mixed adsorption, the following rate equation can be formulated:

Of the numerous boundary conditions that are possible, we will consider only
two in more detail here:
1) When both starting materials are only weakly adsorbed, then both KA and KB
<< 1 and the rate equation becomes reff = k’ pA pB and k’ = kKAKB. The reaction
is first order in both reactants and second order overall.
2) When A is weakly and B strongly adsorbed, KA <<1 << KB and the rate
equation reduces to

The reaction order is one with respect to A and minus one with respect to B.

Effect of pressure
Let us consider the reaction rate as a function of the partial pressure of component
A, that is, at constant partial pressure pB:
1) At low partial pressure pA, the product KA pA in the denominator of Equation is
negligible compared to (1 + KB pB) and it follows that

Thus the reaction rate in this case is proportional to pA.


2) The reaction rate reaches a maximum when QA = QB or KApA = KB pB.
3) At high partial pressure pA, the term (1 + KBpB) in the denominator of Equation
is negligible compared to KApA and it follows that

Hence the reaction order with respect to component A is -1.

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Examples of LH mechamism

1) Oxidation of CO on Pt catalysts
2 CO + O2 Þ CO2
2) Methanol synthesis on ZnO catalysts
CO + 2 H2 Þ CH3OH
3) Hydrogenation of ethylene on Cu catalysts
C2H4 + H2 Þ C2H6
4) Reduction of N2O with H2 on Pt or Au catalysts
N2O + H2 Þ N2 + H2O
5) Oxidation of ethylene to acetaldehyde on Pd catalysts
CH2=CH2 + O2 Þ CH3CHO

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Eley–Rideal Mechanism

In this mechanism only one of the gaseous reaction partners (e. g.,
A) is chemisorbed.
Component A then reacts in this activated state with starting
material B from the gas phase to give the chemisorbed product C. In
the final step the product is desorbed from the catalyst surface.

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In this case only the degree of coverage of the gas A is decisive


for the reaction kinetics, and on the basis of the Langmuir
isotherm, the following rate equation can be formulated:

If we observe the reaction rate as


a function of the partial pressure
of component A at constant pB,
we see that it follows the
isotherm for pA and eventually
reaches a constant final value

Reduction of CO2

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Oxidation of ammonia

This reaction is Pt catalyzed

Energetic aspect in catalysis

If a molecule is to enter a reactive state, it must undergo activated


adsorption on the catalyst surface. Hence the catalyst must chemisorb at
least one of the reaction partners, as seen in the LH or ER models.
The strength of adsorption of the molecules is decisive for effective
catalysis: neither too strong nor too weak binding of the reactants can
induce the required reactivity; a certain medium binding strength is
optimum.
Thus chemisorption and the associated energetic aspects play a
crucial role in understanding heterogeneous catalysis.
The active centers on the catalyst surface are probably the result of free
valences or electron defects, which weaken the bonds in the adsorbed
molecules to such an extent that a reaction can readily occur.

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Comparison of a
heterogeneously
catalyzed reaction with
the uncatalyzed
equivalent.

The three elementary steps on the catalyst surface are depicted


qualitatively together with the corresponding energies.

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For the catalyzed reaction a distinction should be made between the


apparent activation energy, starting from the ground state of the
gaseous molecule, and the true activation energy, relative to the
chemisorbed state. The latter, also known as catalytic activation
energy, is more important.

Sometimes the product or transition state being formed may be so


strongly bound on the surface that its desorption or further reaction is
hindered. In this case the catalyst is poisoned by the product and
becomes inactive.

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The chemisorption of gases on metals has been investigated in deep, and


the available data allow the catalytic properties of metals to be explained
well.
Experimentally determined, qualitative orders of catalytic effectiveness are
often found in the literature. For example, for the adsorption of
hydrocarbons:

For the strength of chemisorption on many metals, the following sequence


is given:

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The electronic structure of the metals is decisive for their catalytic


activity.
The transition metals, with their partially filled d orbitals, are
particularly good catalysts. These orbitals are responsible for the
covalent binding of gases on metal surfaces in chemisorption and
catalysis. Whereas transition metals have one or more unpaired d
electrons in the outer electron shell, the weakly chemisorbing main
group elements have only s or p electrons.
It is postulated that unpaired d electrons are necessary to hold the
chemisorbed molecules in a weakly bound state, from which they
can then be transferred into a strongly bound state.

Two fundamental types of chemisorption processes can be


distinguished:
– molecular or associative chemisorption, in which all bonds of the
adsorbate molecule are retained;
– dissociative chemisorption, in which the bonds of the adsorbate
molecule are cleaved and molecular fragments are adsorbed on the
catalyst surface

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Molecular chemisorption

Dissociative chemisorption

Dissociative chemisorption occurs mainly with molecules containing


single bonds, for example, the adsorption of H2 on nickel, in which the
hydrogen is adsorbed in atomic form on the surface.

Homework: draw the Epot vs. Distance plot

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Heterolytic chemisorption

CO adsorption

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Diatomic chemisorption

One of the first predictions made on the basis of steric effects was
that the ease of chemisorption of diatomic molecules should
strongly depend on the lattice dimensions of the metallic catalysts.
The reasoning was that for large interatomic distances, diatomic
molecules would have to dissociate to be completely chemisorbed,
while for closely packed lattices, repulsion effects would hinder
chemisorption.
This is exemplified by the cyclohexane dehydrogenation. It was
shown that only elements with interatomic distances between 0.248
and 0.277 nm catalyze the dehydrogenation of cyclohexane.

interatomic distances between 0.248 and 0.277


nm catalyze the dehydrogenation of cyclohexane

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BCC

HCP
Hexagonal close packing
FCC
Face-centered cubic

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Steric effects

Apart from energetic and electronic effects, steric (geometric)


effects also play an important role in chemisorption and
heterogeneous catalysis.
The porosity and the surface of solids must therefore also be
taken into account.
A steric factor means that a molecule has to be adsorbed on the
catalyst in such a manner that it fits properly on the surface atoms.
Only then can it be readily activated.
In enzymatic catalysis this “key/keyhole” mechanism, or lock
and key model, is so pronounced that the reactant molecule must
fit exactly to the geometry of the catalyst for reaction to occur.

Since steric factors are not important in all heterogeneously


catalyzed reactions, a distinction can be made between structure-
sensitive reactions, which react to changes in the surface structure,
and structure-insensitive reactions.
Numerous examples exist for both types of reaction, and we shall
distinguish between them on the basis of the parameters that
influence them

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