Reaction Kinetics

& Catalysis

Introduction

Lecture 1

PTK-IU 1
 Syllabus
Teaching and learning
Week Content Assessment
activities
Introduction of catalysis: homogeneous and - Lecture
1
heterogeneous catalysis - Class discussion
Kinetics: Rate equation, reaction mechanism,
- Lecture Quiz
2&3 adsorption/desorption, Langmuir adsorption
- Class discussion
isotherm and Langmuir–Hinshelwood Kinetics
- Lecture Homework
4 Reaction rate theory
- Class discussion
- Lecture Homework
5&6 Catalyst Characterization
- Class discussion
- Lecture
7 Solid catalysts Homework
- Class discussion
- Lecture
8 Kinetics of reaction on surfaces Quiz
- Class discussion
MIDTERM EXAM Written exam
- Lecture
9 Kinetics of reaction on surfaces (con’t) Quiz
- Class discussion
Catalysis in Practice: Synthesis Gas and - Lecture
10 Homework
Hydrogen - Class discussion
- Lecture
11 Oil Refining and Petrochemistry Homework
- Class discussion
- Lecture
12 Environmental Catalysis
- Class discussion
- Lecture
13 Modern catalysts Homework
- Class discussion
14-15 Project presentations
FINAL EXAMINATION Written exam
PTK-IU 2
 Textbooks & Grading
Textbooks:
❑ I. Chorkendorff, J.W. Niemantsverdriet, Concepts of Modern Catalysis and
Kinetics, 2017, John Wiley&Son.
https://drive.google.com/drive/u/2/folders/1iEGK0Fn7GGfQA9-zefLJPqEdCQDGOKTD

Grading:

Activity Percentage

Assignments, homework, learning

25%
activities, project (15%)
Mid-term exam 35%
Final exam 40%

PTK-IU 3
 Introduction to Catalysis

Lecture 1

PTK-IU 4
 Global Catalyst Market

$38.40Billion

$25.08Billion 6.5% / year

Catalyst Market Outlook To 2026: In-Depth Market Overview, Key Raw Material Categories
(Metal, Chemical Compounds), Product Type (Heterogeneous, Homogeneous), Application
(Polymers & Petrochemicals, Environmental), Regional Segmentation, Pricing Analysis,
Pipeline Analysis, Competitive Dynamics, M&A Insights, Segment Forecast, And Conclusion

PTK-IU https://www.ameriresearch.com/product/catalyst-market/ 5
 Catalysis in Industry
❑ Approximately 85–90% of the products of chemical industry
are made in catalytic processes.

❑ Catalysts are indispensable in:

▪ Production of transportation fuels in approximately 440 oil
refineries all over the world.
▪ Production of bulk and fine chemicals in all branches of
chemical industry.
▪ Prevention of pollution by avoiding formation of waste
(unwanted byproducts).
▪ Abatement of pollution in end-of-pipe solutions (automotive
and industrial exhaust).

PTK-IU 6
 What is Catalysis?
❑ Catalyst: is a substance that enables a
chemical reaction to proceed at a usually
faster rate or under different conditions (as at
a lower temperature) than otherwise possible.

❑ Catalysis: is the process of increasing the rate

of a chemical reaction by adding a substance
known as a catalyst.

https://www.merriam-webster.com/dictionary/catalyst
PTK-IU https://goldbook.iupac.org/terms/view/C00876 7
 What is Catalysis?
Catalysts are not consumed in the catalyzed reaction but can act repeatedly

Every catalytic reaction is a sequence of elementary steps, in which reactant

molecules bind to the catalyst, where they react, after which the product
detaches from the catalyst, liberating the latter for the next cycle.
PTK-IU 8
 The terms
ΔG < 0 : exergonic

ΔG > 0 : endergonic

ΔH < 0 : exothermic

ΔH > 0 : endothermic

PTK-IU 9
 Potential Energy Diagram
Potential energy diagram of a heterogeneous catalytic reaction, with
gaseous reactants and products and a solid catalyst.

Ea > ΔEcat

Exothermic step
ΔG < 0
ΔEcat

Endothermic step
Note that the uncatalyzed reaction has to overcome a substantial energy
barrier, whereas the barriers in the catalytic route are much lower.
PTK-IU 10
 Potential Energy Diagram
The Potential Energy diagram shows several important points, in terms of the
enthalpy changes in the course of the reaction:

▪ The catalyst offers an alternative path for the reaction, which is obviously more
complex, but energetically much more favorable.

▪ The activation energy of the catalytic reaction is significantly smaller than that
of the uncatalyzed reaction; hence, the rate of the catalytic reaction is much larger.

▪ The overall changes in enthalpy and also in free energy for the catalytic
reaction equals that of the uncatalyzed reaction. Hence, the catalyst does not
affect the equilibrium constant for the overall reaction of A + B to P. Thus, if a
reaction is thermodynamically unfavorable, a catalyst cannot change this situation.
A catalyst changes the kinetics but not the thermodynamics.

▪ The catalyst accelerates both the forward and the reverse reaction to the same
extent. In other words, if a catalyst accelerates the formation of the product P from
A and B, it will do the same for the decomposition of P into A and B.

PTK-IU 11
 Potential Energy Diagram
There will be cases in which the combination of catalyst with reactants or products
is not successful:

▪ If the bonding between reactants and catalyst is too weak, there will hardly be
any conversion of A and B into products.

▪ If the bond between the catalyst and one of the reactants, say A, is too strong,
the catalyst will mostly be occupied with species A, thus, not allowing B to
form any product. Also, if both A and B form strong bonds with the catalyst, the
intermediate situation with A or B on the catalyst may be so stable that reaction
becomes unlikely.

▪ In the same way, the product P may be too strongly bound to the catalyst for
separation to occur. In this case, the product poisons the catalyst.

PTK-IU 12
 Catalysts
❑ Catalysts Can Be Atoms, Molecules,
Enzymes, and Solid Surfaces; or

❑ Catalysts come in a multitude of forms,

varying from atoms and molecules to large
structures as zeolites or enzymes.

PTK-IU 13
 Homogeneous Catalysis
In homogeneous catalysis, the catalyst and the reactants are in the
same phase.
Gas phase
the Cl atom is a catalyst

Liquid phase
[Rh(CO)2I2]− complexes is a
catalyst
PTK-IU 14
 Biocatalysis
Enzymes are nature’s catalysts

Schematic representation of an enzyme-catalyzed reaction. Enzymes often match the

shape of the substrates they bind to, or the transition state (TS) of the reaction they
catalyze. Enzymes are highly efficient catalysts and represent a great source of inspiration
for designing technical catalysts.
PTK-IU 15
 Heterogeneous Catalysis
• In heterogeneous catalysis, solids catalyze reactions of molecules in gas or
solution.
• As solids – unless they are porous – are commonly impenetrable, catalytic
reactions occur at the surface. In order to use the often expensive materials (e.g.,
platinum) in an economical way, catalysts are usually nanometer-sized particles,
supported on an inert, porous structure.
• Heterogeneous catalysts can be considered the workhorses of the chemical and
petrochemical industry.

Shaikh Tofazzel Hossain, Synthesis and Kinetic Study of CeO2 and SiO2 Supported CuO Catalysts for CO Oxidation, DOI:
PTK-IU 10.13140/RG.2.2.31499.80165 16
 Heterogeneous Catalysis

Difficult step: break O – O bond

Reaction cycle and potential energy diagram for the catalytic oxidation of CO by O2.
PTK-IU 17
 Ethanol adsorption on the surface of Al2O3
Adsorption H3C-CH2-OH
on Lewis
acid/base sites
Al3+ O= H3C-CH2 H2C=CH2

Ethylene O-
-OH
synthesis
H3C-CH2-OH Al3+ -OH Al3+ -OH
Adsorption
on OH sites
-OH
H2O
Al3+ -OH

H3C-CH2 H3C-CH2 (H3C-CH2)2O

Diethyl
ether O- OH
-OH
synthesis
Al3+ -OH Al3+ -OH

PTK-IU Phung et al., Journal of Catalysis, 311 (2014) 102–113 18

 Why is Catalysis important?
❖ Using catalyst  reducing reaction condition ~ reducing
cost
• Reactions in general can be controlled on the basis of
temperature, concentration, pressure, and contact time.
• Thermodynamic limitations.
• Catalysts accelerate reactions by orders of magnitude, thus,
enabling reactions to be carried out in the thermodynamically
most favorable regime, and at much milder conditions of
temperature and pressure.
• In this way, efficient catalysts – in combination with optimized
reactor and total plant design – are the key factor in reducing
both the investment and operation costs of chemical
processes.

PTK-IU 19
 Catalysis and Green Chemistry
• Technology is termed “green” if it uses raw materials
efficiently, such that the use of toxic and hazardous reagents
and solvents can be avoided, while formation of waste or
undesirable byproducts is minimized.
The noncatalytic route (called the epichlorohydrine process):

The catalytic route:

Ag
2 CH2 = CH2 + O2 2 (CH2CH2)O

PTK-IU 20
 Plastic waste to fuels

https://www.ecoideaz.com/innovative-green-ideas/convert-plastic-waste-to-petroleum 21
PTK-IU
 Bio-ethanol
process

https://pubs.rsc.org/en/content/articlelanding/2019/gc/c8gc02698j#!divAbstract
PTK-IU https://www.sciencedirect.com/science/article/abs/pii/S2213343718305360 22
 Flow scheme of the UOP/Eni Ecofining
process for the production of green diesel

Ref: J.A. Moulijn, M. Makkee, A.E. van Piepen, Chemical Process Technology, Wiley-Interscience (2013), 2nd Edition
PTK-IU https://www.truckinginfo.com/108188/honeywell-green-diesel-to-be-produced-from-bio-feedstocks-in-us-facility 23
 Atom Efficiency
The atom efficiency is the molecular weight of the desired
product divided by the total molecular weight of all products

PTK-IU 24
 E Factors
The E factor: the weight of waste or undesirable byproduct
divided by the weight of the desired product

Table. Environmental acceptability of products in different segments

of the chemical industry

PTK-IU 25
 Environmental Friendliness
• An environmental quotient EQ (to stress the environmental
impact): the E factor multiplied by an unfriendliness quotient,
Q, which assigns a value indicating how undesirable a
byproduct is.
• For example, Q = 0 for clean water, 1 for a benign salt as NaCl, and
100–1000 for toxic compounds.

• Catalytic routes that avoid waste formation are highly

desirable, and placing more weight on the economic value of
environmental acceptability will spark greater motivation
towards catalytic alternatives.
• Waste prevention is in principle much to be preferred over
waste remediation.

PTK-IU 26
 The Chemical Industry

PTK-IU 27
 The Chemical Industry
❑ The chemical industry produces a large range of base, middle,
and end products.
❑ The main subsectors are:
• Base chemicals, including organic and inorganic chemicals,
polymers and plastics, dyes and pigments.
• Specialty chemicals, such as paints and coatings, adhesives,
plastic additives, and also catalysts.
• Agricultural chemicals, for farming and food processing.
• Pharmaceuticals, including diagnostics, drugs, vaccines,
vitamins, etc., for humans or animals.
• Consumer products, such as soaps, detergents, cleaners,
toiletries, and cosmetics.

PTK-IU 28
 The Chemical Industry

https://www.chemistryviews.org/details/ezine/2098119/German_Chemistry_Success.html 29
PTK-IU
PTK-IU 30
PTK-IU 31
PTK-IU 32
PTK-IU 33
PTK-IU 34
 Scales of a “Catalyst”

The relevant length scales in catalysis range from the subnanometer domain of the
atomic and molecular level to the macroscopic domain of an industrial reactor.
PTK-IU 35
 Scales of a “Catalyst”
Microscopic
• Understanding reactions at the elementary level of the rupture of bonds
in reactants and the formation of bonds on the way to products is at the
heart of the matter and requires the most advanced experimental
techniques and theoretical descriptions available.
• This is the domain of spectroscopy, computational chemistry, and
kinetics and mechanism on the level of elementary reaction steps.
• The length scales of interest are in the subnanometer region.
• The key interests at this level are the size, shape, structure, and
composition of the active particles, and in particular their surfaces, and
how these properties relate to catalytic reactivity.
• This is the domain of catalyst preparation, characterization, testing on
the laboratory scale, and mechanistic investigations.
• Transport phenomena such as the diffusion of molecules inside pores
may affect the rate at which products form and become an important
consideration on this level.

PTK-IU 36
 Possible reaction mechanism on the surface of the HNO3 pretreated SFN for the
oxidation of m-cresol in the wet peroxide oxidation reaction: the surface of the as-
prepared SFN catalyst before HNO3 pretreatment (a), the surface of the as-prepared
SFN catalyst (b), esterification and catalytic wet peroxide oxidation degradation of m-
cresol on the SFN surface (c), and the catalytic cycle in the wet per

PTK-IU https://doi.org/10.1039/C6EN00177G 37
 https://doi.org/10.1039/B809030K
PTK-IU 38
 https://doi.org/10.1016/j.enconman.2015.07.033 39
PTK-IU
 Shape Selectivity − Zeolites

PTK-IU Ref: J.A. Moulijn, M. Makkee, A.E. van Piepen, Chemical Process Technology, Wiley-Interscience (2013), 2nd Edition 40
 Confinement and shape selectivity effects
FAU MFI FER

BENZE ~6
NE
Å

✓The catalytic behaviour is interpreted as an evidence of a main role of

confinement effects, which quite evidently favour the formation of diethyl
ether at low conversion and of aromatic hydrocarbons at high conversion
over medium pore cavities.
✓Shape selectivity and number of acid sites are also relevant parameters.
PTK-IU 41
 FER [001]
[001]

C2H5OH C2H4

[010]

MFI
[010]
[010]

C2H5OH

[100]

PTK-IU Ref: T.K. Phung et al., Appl. Catal. A, 493 (2015) 77–89 42
 Scales of a “Catalyst”
The mesoscopic level is that of shaped catalysts in the form of extrudates,
spheres, or monoliths on length scales varying from millimeters to
centimeters, and occasionally even larger.
Typical points of interest are porosity, strength, and attrition resistance
which enable catalysts to survive the conditions inside industrial reactors

Various catalyst shapes

PTK-IU 43
 Solid catalysts
Top companies
producing catalysts
1) Haldor Topsoe
2) UOP
3) Axens
4) Johnson Matthey
5) Criterion
6) Süd-Chemie
7) Albemarle
8) Grace Davison

https://www.oilandgasmiddleeast.com/article-9496-top-10-catalysts-companies
PTK-IU 44
 Three-way catalysts
Three-way catalysts (TWC) are designed to
simultaneously convert three pollutants to
harmless emissions:
Carbon Monoxide (CO) → Carbon Dioxide (CO2)
Hydrocarbons (HC) → Water (H2O)
Oxides of Nitrogen (NOx) → Nitrogen (N2)
A three-way catalyst can cut CO, HC and NOx by
over 99% if the air to fuel ratio is accurately
controlled. Three-way catalysts will only give
full conversion of each of these three pollutants
in a gas stream containing a stoichiometric ratio
of CO and NOx.

https://matthey.com/en/products-and-services/emission-control-
PTK-IU technologies/mobile-emissions-control/three-way-catalysts 45
 Monolith Reactors − Automotive Emission Control
❑ Monolith reactors are conceptually the simplest structured reactors and
they are most widespread.
❑ Monoliths are continuous structures consisting of narrow parallel
channels (typically 1–3 mm diameter).

PTK-IU Ref: J.A. Moulijn, M. Makkee, A.E. van Piepen, Chemical Process Technology, Wiley-Interscience (2013), 2nd Edition 46
Monolith Reactors − Automotive Emission Control

PTK-IU DOI: 10.1016/j.cherd.2014.03.009 47

Monolith Reactors − Automotive Emission Control

PTK-IU DOI: 10.1016/j.cherd.2014.03.009 48

Monolith Reactors − Automotive Emission Control

PTK-IU DOI: 10.1021/ie100738q 49

 Scales of a “Catalyst”
• The macroscopic level is that of reactors, be it a 10 cm test reactor in a
laboratory or a 50-m high reactor vessel in an industrial plant.
• The catalyst forms the heart of the reactor.
• Catalysis as a discipline is only one of many other aspects of reaction
engineering, together with, for example, the design of efficient reactors
that are capable of handling high pressure, offer precise control of
temperature, enable optimized contact between reactants and catalyst,
and removal of products during operation.
• The mass and heat transport properties of reactants and products
through the catalyst bed are as important.
• For the catalyst, matters as mechanical stability, sensitivity to trace
impurities in the reactant feed, and degradation of the particles (e.g., due to
exposure to high temperatures) are essential in addition to intrinsic
properties as activity and selectivity.

PTK-IU 50
 Fluid Catalytic Cracking

Ref: J.A. Moulijn, M. Makkee, A.E. van Piepen, Chemical Process Technology, Wiley-Interscience (2013), 2nd Edition
PTK-IU https://www.sciencedirect.com/topics/materials-science/faujasite 51
 Fluid catalytic cracking: recent developments on
the grand old lady of zeolite catalysis

PTK-IU DOI: 10.1039/C5CS00376H 52

 BASF introduces portable FCC catalyst
addition system in Europe

Full design package of

catalyst in macroscopic level

https://www.hydrocarbonprocessing.com/news/2016/09/basf-
introduces-portable-fcc-catalyst-addition-system-in-europe
PTK-IU 53
 Reactor Types
Reactors for solid-catalyzed gas phase reactions.

PTK-IU Ref: J.A. Moulijn, M. Makkee, A.E. van Piepen, Chemical Process Technology, Wiley-Interscience (2013), 2nd Edition 54
 Reactor Types
Reactors for solid-catalyzed gas/liquid reactions.

PTK-IU Ref: J.A. Moulijn, M. Makkee, A.E. van Piepen, Chemical Process Technology, Wiley-Interscience (2013), 2nd Edition 55
 Time Scales in Catalysis
• The activation and breaking of a chemical bond inside a
molecule occurs in the picosecond regime;
• completion of an entire reaction cycle from complexation
between catalyst and reactants through separation from the
product may take anywhere between microseconds for the
fastest enzymatic reactions to minutes for complicated
reactions on surfaces.
• On the mesocopic level, diffusion in and outside the pores,
and through shaped catalyst particles may vary between
seconds and minutes
• Residence times of molecules inside entire reactors may vary
from seconds to infinity. This happens if reactants end up in
unwanted byproducts such as coke, which stay on the catalyst.

PTK-IU 56
PTK-IU 57
PTK-IU 58