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Mechanisms of Catalytic Reactions

and Characterization of Catalysts

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What is a Catalyst ?

Catalyst is a substance that increases the rate


of the reaction at which a chemical system
approaches equilibrium , without being
substantially consumed in the process.

Catalyst affects only the rate of the


reaction,i.e.Kinetics.

It changes neither the thermodynamics of


the reaction nor the equilibrium composition.

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Chemical Reaction

Thermodynamics says NOTHING about the rate of a


reaction.

Thermodynamics : Will a reaction occur ?


Kinetics : If so, how fast ?

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Kinetic Vs. Thermodynamic

A reaction may have a large, negative DGrxn, but the


rate may be so slow that there is no evidence of it
occurring.

Conversion of graphite to diamonds is a


thermodynamic favor process (DG -ve ).
C (graphite) C (diamond)

Kinetics makes this reaction nearly impossible


(Requires a very high pressure and temperature over long time)

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Kinetic Vs. Thermodynamic

Reaction path for conversion of A + B into AB

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Activation Energy
Activation Energy : The energy required to overcome the reaction
barrier. Usually given a symbol Ea or G

The Activation Energy (Ea) determines how fast a reaction occurs, the higher
Activation barrier, the slower the reaction rate. The lower the Activation
barrier, the faster the reaction

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Activation Energy

Catalyst lowers the activation energy for both forward and


reverse reactions.

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Activation Energy

This means , the catalyst changes the reaction path


by lowering its activation energy and consequently
the catalyst increases the rate of reaction.

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How a Heterogeneous Catalyst works ?

Substrate has to be adsorbed on the active sites of the catalyst

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Absorption and Adsorption

H H H H H H H H H H H H H H H H H H
H HH H H H H
H H H
H H H
H H H
H H

H2 adsorption on H2 absorption
palladium palladium hydride

Surface process bulk process

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Adsorption

In physisorption
1. The bond is a van der Waals interaction
2. adsorption energy is typically 5-10
kJ/mol. ( much weaker than a typical
chemical bond )
3. many layers of adsorbed molecules may
be formed.

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Adsorption

For Chemisorption
1. The adsorption energy is
comparable to the energy of a
chemical bond.
2. The molecule may chemisorp intact
(left) or it may dissociate (right).
3. The chemisorption energy is 30-70
kJ/mol for molecules and 100-400
kJ/mol for atoms.

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Characteristics of Chemi- and Physisorptions

DE(ads) < DE(ads)


E(d) Physisorption Chemisorption

small minima large minima


weak Van der Waal formation of surface
attraction forces chemical bonds
CO
physisorption/
physisorption desorption chemisorption

atomic chemisorption
d

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Adsorption and Catalysis

Adsorbent: surface onto which adsorption can occur.


example: catalyst surface, activated carbon, alumina
Adsorbate: molecules or atoms that adsorb onto the substrate.
example: nitrogen, hydrogen, carbon monoxide, water
Adsorption: the process by which a molecule or atom adsorb onto a surface of
substrate.
Coverage: a measure of the extent of adsorption of a specie onto a surface

adsorbate
H H H H H H H H H coverage q = fraction of surface sites occupied
H H H H H

adsorbent

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Adsorption Mechanisms
Langmuir-Hinshelwood mechanisms:
1. Adsorption from the gas-phase
2. Desorption to the gas-phase
3. Dissociation of molecules at the surface
4. Reactions between adsorbed molecules

Two Questions:
Is the reaction has a Langmuir-Hinshelwood mechanism?
What is the precise nature of the reaction steps?
Cannot be solved
without experimental or computational studies
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Langmuir-Hinshelwood mechanisms

Example

The Reaction A2 + 2B = 2AB

may have the following mechanism


A2 + * = A2*
A2* + * = 2A*
B + * = B*
A* + B* = AB* + *
AB* = AB + *

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Adsorption Mechanisms

Eley-Rideal mechanism:
1. Adsorption from the gas-phase
2. Desorption to the gas-phase
3. Dissociation of molecules at the surface
4. Reactions between adsorbed molecules
5. Reactions between gas and adsorbed molecules

The last step cannot occur in a Langmuir-Hinshelwood


mechanism

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Eley-Rideal mechanism
Example
The reaction
A2 + 2B = 2AB

may have the following Eley-Rideal mechanism


A2 + * = A2*
A2* + * = 2A*
A* + B = AB + *

where the last step is the direct reaction between the adsorbed
molecule A* and the gas-molecule B.

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Eley-Rideal or Langmuir-Hinshelwood?
For the Eley-Rideal mechanism:
the rate will increase with increasing coverage
until the surface is completely covered by A*.
For the Langmuir-Hinshelwood mechanism:
the rate will go through a maximum and end up
at zero, when the surface is completely covered
by A*.

This happens because the step B + * = B*


cannot proceed when A* blocks all sites.
The trick is that the step B + * = B*
requires a free site.
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Catalyst Preparation

(1) Unsupported Catalyst


Usually very active catalyst that do not require high
surface area
e.g., Iron catalyst for ammonia production (Haber process)

(2) Supported Catalyst


requires a high surface area support to
disperse the primary catalyst
the support may also act as a co-catalyst
(bi-functional)
or secondary catalyst for the reaction
(promoter)

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Supported Catalyst

Highly dispersed metal on metal oxide

Nickel clusters

SiO2

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Molecules in Zeolite Cages and Frameworks

+ p-xylene

ZSM-5

Paraffins
Y-zeolite
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What is ZSM-5 Catalyst ?

It is an abbreviation for (Zeolite Scony Mobile Number 5 )


First synthesized by Mobil Company in 1972
It replaces many Homogeneous Catalysts were used in
many petrochemical processes
ZSM-5 has two diameters for its pores : d1= 5.6 , d2= 5.4
Where as, Zeolite Y has a diameter = 7.4

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Properties ZSM-5

The ZSM-5 zeolite catalyst is used in the petroleum industry


for hydrocarbon interconversion.
ZSM-5 zeolite is a highly porous aluminosilicate with a high
silica/alumina ratio.

It has an intersecting two-dimensional pore structure.


The aluminum sites are very acidic.
The acidity of the zeolite is very high.
The reaction and catalysis chemistry of the ZSM-5 is due
to this acidity.

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Structure of ZSM-5

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Aromatic Isomerization

Observed by Haag and Co-workers P-Selectivity is


achieved due to the high diffusion coefficient of P-
Substituted Molecules Relative to that of Ortho or Meta.

A side reaction in homogenous solution phase


isomerization is the Bimolecular disproportionation of
Xylene.

This Can not occur when using zeolite such


as ZSM-5 since the pore size will not allow
for the bulky bimolecular transition state
necessary for disproportionation.
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+ p-xylene

ZSM-5

Compound Relative Diffusion


Coefficient
p-Xylene > 10000

o-Xylene 1
m-Xylene 1
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Zeolite Effective Diameter of Kdis/Kiso
Catalyst intracrystalline
Type Cavity (nm)
ZSM-5 0.60 1000
Mordenite 0.70 15000
ZSM-4 0.80 10000
HY > 1.2 > 45000
Selectivities of acidic zeolite for disproportionation and
isomerization of Xylene. The HZSM-5 Catalyst is preferred,
minimizing the bimolecular disproportionation reaction by
virtue of restricted transition state selectivity.
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Schematic diagram of product shape selectivity: Para-xylene
diffuses preferentially out of the zeolite channels

p-xylene m-xylene

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Acidity of the Catalyst Vs. Acid Sites

Theoretically,
As the Acid Sites increase the Acidity increases

Experimentally,
As the Acid Sites increase the Acidity decreases

How we can understand this behavior?

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Acidity of the Catalyst Vs. Acid Sites

Al is the Acidic Site


But,
B C N O F
Si is more electronegative than Al
Al Si P S Cl

Electronegativity Effect
H+

O O
Al Si Si
Al

Si Makes the release of the H+ faster since it attracts Electrons


toward it which make the proton away of it
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Acidity of the Catalyst Vs. Acid Sites

It is possible to conclude that:


the acid strength of a site will increase when there is a decrease
in the number of Al atoms in the Next Nearest Neighbor
position of the Al atom.

So, the strongest type of framework Bronsted site is


A completely isolated Al tetrahedron which have zero NNN or
(0NNN)

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Acidity Characterization of a Catalyst
Acidity of the catalysts can be assess by:

I. Temperature Programmed Desorption (TPD)


II. Fourier Transformation Infrared spectroscopy ( FTIR)
III. Induced Laser spectroscopy (IL)

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I. Temperature Programmed Desorption (TPD)

1. Pure carrier gas (typically helium) flows over the sample as the
temperature is raised to desorb the previously adsorbed gas e.g.
NH3

2. This characteristic "fingerprint" for each catalyst,used to determine:


the distribution of acid-site strength if ammonia is the sorbed gas,
or the distribution of basic sites if carbon dioxide is the sorbed gas.

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I. Temperature Programmed Desorption (TPD)

Temp.

Time(min)

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II. Fourier Transformation Infrared spectroscopy ( FTIR)

By this method we assess acidic site:


Bronsted acidic site or Lewis acidic site

For example: if pyridine is the probe molecule, It will give peaks at:
1. 1540 cm-1 for Bronsted site
2. 1450 cm-1 for Lewis site

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II. Fourier Transformation Infrared spectroscopy ( FTIR)

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II. Fourier Transformation Infrared spectroscopy ( FTIR)

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III. Induced Laser spectroscopy (IL)

To assess the acidity by IL:


1. Probed molecule has to be prepared in different acidic
concentration solutions
2. Life time measurements has to run onto each concentration
3. Calibration curve between life time Vs. concentration of the acid

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III. Induced Laser spectroscopy (IL)

y = 0.0814x + 1.12
Life time Vs. [HCl] R2 = 0.9627

2.2
2.1
Life time(ns)

2
1.9
1.8
1.7
1.6
1.5
1.4
4 5 6 7 8 9 10 11 12

[HCl]

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Conclusion

There is no single method that can be used to determine all


aspects of acidity for a solid i.e. nature, strength and the number
of acid sites

Each method measures only certain aspects and,therefore, the


application of many methods is desirable.

THE END

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End of the Catalysis and Catalysts

THANK YOU
References
1. A.Corma,Inorganic solid acids and their use in acid-catalyzed hydrocarbon
reactions. Chem. Rev.1995, 95, 559-614.
2. Bruce C. gates, Catalytic Chemistry.1992.
3. Zaki Seddigi, Characterization of the acidic properties of zeolite and their
catalytic behavior in the synthesis of MTBE. 1994.
4. Ali El-Rayyes, Study of the photochemical properties of some aromatic
compound on molecular sieves using a picosecond pulse laser system. 2001.
5. Keith Laidler, Chemical Kinetics, 1987.

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