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315 Alagbe

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Chemical Reaction Kinetics

2024/2025 Session

Dr. E. E. Alagbe
Department of Chemical Engineering
Covenant University, Ota.
Recommended Textbooks
i. Chemical Vapour Deposition – Advances, Technology and
Applications. Series in materials science and Engineering. Edited by
Kwang Leong Choy. CRC Press, 2019

ii. Elements of Chemical Reaction Engineering by H. Scott Fogler.


International Series in the Physical and Chemical
Engineering Sciences. 6th ed.
Wreathing Reactions
• The term "wreathing" is derived from the visual resemblance of the structures formed to a wreath, where one
component loops or wraps around another. Wreathing reactions refer to chemical processes in which a
compound or a structure "wraps around" or interacts with another molecule or ion in a way that forms a ring-like
or entangled structure. In wreathing reactions, molecules can interact and assemble to form complex, often
mechanically bonded, systems with diverse applications.

Wreathing reactions find use in molecular machines, supramolecular chemistry, and drug delivery systems. They
are done via two major routes:
- Physical Vapour Deposition (PVD)
- Chemical Vapour Deposition (CVD)
Physical Vapour Deposition (PVD)
Physical Vapor Deposition (PVD) is a vacuum-based coating process used to deposit thin films of material onto
a substrate. The process involves the physical transfer of material from a solid or liquid phase to a vapor phase,
and then back to a solid phase as a thin film. This technique is widely used in various industries to improve
properties like wear resistance, hardness, and corrosion protection.
The steps involved in the PVD Process are:
1. Material Vaporization: A source material (target) is vaporized either through heat (thermal evaporation) or by
bombarding it with high-energy particles (sputtering or arc evaporation).
2. Transport of Vapor: The vaporized atoms or molecules travel through a vacuum or low-pressure gas toward
the substrate (the object being coated).
3. Deposition on Substrate: When the vapor reaches the substrate, it condenses and forms a thin solid film. The
thickness of the film can range from a few nanometers to several micrometers, depending on the application.
4. Adhesion and Growth: The film adheres to the substrate and begins to grow layer by layer, creating a
uniform coating.
PVD Techniques
- Thermal Evaporation: The material is heated in a vacuum until it vaporizes and condenses on the substrate.
- Sputtering: A high-energy plasma is used to knock atoms from a target material, which then coat the substrate.
- Arc Vapor Deposition: An electric arc is used to vaporize the target material, which is then deposited on the
substrate.
- Electron Beam Evaporation: A focused beam of electrons is used to evaporate the target material.

Advantages of PVD
- High precision in thin film deposition.
- Strong adhesion of the coating to the substrate.
- Environmentally friendly, as it avoids the use of harmful chemicals.
- A wide variety of materials can be deposited, allowing for versatile applications.

Examples of PVD products and materials are semiconductor components, watches, jewellery, lenses, mirrors.
Substrates Vapours Used
Semiconductors Al, Ti, Cu
Watches TiN, Cr, Au
Cutting tools Ti, Al, N2
Optical coatings MgF2, SiO2
Chemical Vapour Deposition (CVD)
Chemical Vapor Deposition (CVD) is a process used to create solid material coatings, films, or structures on
substrates by means of chemical reactions in the vapor phase. In CVD, gaseous precursors (often called
reactants or "vapors") react or decompose on a heated substrate surface, forming a solid material layer. This
technique is widely employed in industries as it produces high-purity, uniform, and well-adhered films.
Chemical Vapor Deposition (CVD) is a versatile and widely used process for creating solid material coatings,
films, or structures on various substrates. Chemical Vapor Deposition is a vital technology for industries seeking
precise, high-quality material coatings, and it enables advancements in fields such as electronics, optics, and
renewable energy.

The steps involved in the CVD Process are:


- Introduction of Gaseous Precursors: Gaseous chemicals, known as precursors, are introduced into a reaction
chamber where the substrate is placed.
- Reaction on the Heated Substrate: The substrate is heated to a specific temperature, which causes the gas
molecules to react or decompose. The result of this reaction is the deposition of a solid material on the substrate
surface, while byproducts are often removed as gases.
- Deposition of Thin Film: The solid material accumulates on the substrate, forming a thin film. The properties
of this film can be controlled by adjusting factors like temperature, pressure, gas flow rates, and precursor types.
Advantages of CVD

- Produces high-purity, uniform, and conformal films.


- Can deposit a wide range of materials, including metals, oxides, nitrides, and carbides.
- Allows for excellent control over film thickness and composition.
- Can be applied to complex geometries and high-aspect-ratio structures.
Types of CVD
1. Pressure (sensitive and require higher vacuum)
- APCVD (Atnospheric Pressure CVD) -
- LPCVD (Low Pressure CVD) operates at reduced pressures compared to traditional atmospheric CVD,
typically in the range of 0.1 to 1 Torr. This lower pressure improves the uniformity and step coverage of the
deposited films, making LPCVD ideal for producing high-quality films of materials like silicon nitride and
polysilicon. Common vapors used in LPCVD include dichlorosilane (SiH₂Cl₂) and ammonia (NH₃).
- UHCVD (Ultra High CVD) -

2. Stimulus (Temperature)
PECVD (Plasma Enhanced CVD) uses plasma to initiate chemical reactions, allowing deposition to occur at
lower temperatures (100°C to 400°C). This is especially useful for coating heat-sensitive materials, such as
polymers or microelectronic components. PECVD is widely employed for depositing thin films of dielectric
materials like silicon nitride or silicon dioxide. Gases like silane (SiH₄), methane (CH₄), and nitrous oxide (N₂O)
are commonly used in this technique.
PICVD
3. Source
- ALD Atomic Layer Deposition where the precursor gases are introduced one at a time as opposed to all at the
same time. That is, gaseous precursors are introduced in a sequential, self-limiting manner, enabling atomic-
scale precision in film deposition. ALD is used when extremely thin, uniform coatings are needed, such as in
advanced semiconductor manufacturing or nanotechnology. Precursors like trimethylaluminum (TMA) and
water vapor (H₂O) are commonly used in ALD to deposit materials like aluminum oxide (Al₂O₃)
4. Others
- MOCVD (Metalorganic CVD) uses metalorganic compounds serve as precursors. These compounds, which
combine metal and organic elements, decompose on the substrate to create metal-containing films. MOCVD is
critical in the production of compound semiconductors, such as gallium arsenide (GaAs) and gallium nitride
(GaN), materials essential for the fabrication of LEDs and high-speed electronic devices. Vapors like
trimethylgallium (TMGa) and arsine (AsH₃) are commonly used in MOCVD.
- HWCVD (Hot Wire CVD) uses a hot filament is used to decompose the gaseous precursors, allowing
deposition to occur without the need for high substrate temperatures. This technique is commonly used in the
production of thin-film solar cells and diamond films, with gases such as silane (SiH₄) and methane (CH₄)
frequently used.
Applications of CVD
• Semiconductors – solar panels, Ics, and phones
• Abrasion resistant materials
• Corrosion resistant materials
POLYMER REACTIONS
Poly (Greek) means many while Mer (Greek) means part. Therefore, polymers are large molecules made up of
simple repeating units. They are made from simple molecules (monomers) via a polymerization process. The
molecular weights of polymers range from several thousands to several million atomic units. Hence, polymers
are usually represented by structural units in enclosed brackets.

Figure 1: structures of some monomers and their polymers


Monomers are either monofunctional (having one functional group) or difunctional (having 2 functional
groups). Examples of difunctional monomers include ethylene glycol (EG), p-hydroxybenzoic acid while
examples of mono-functional monomers are ethanol and benzoic acid.
Terminologies in polymer science

Degree of polymerization: is the total number of structural units with the end groups included. It covers both
the molecular weight and chain length.
Homopolymers: polymers formed from a single monomer.
Copolymers: are formed from two or more monomers. If distributed randomly, the resulting polymer is called a
random copolymer, in alternating fashion (alternating copolymer) and they are called bloc copolymer if the
monomers are distributed in blocks.
Cross-linked polymers: can either be linear or branched polymers.
Thermoplastic polymers: are polymers that can melt and flow when dissolved in solvents.
Polymerization Processes
Addition polymerization
In this process, the resulting polymers contain the same atoms as the starting monomers in its repeating units.
Most chain reactions are addition polymerization.

Condensation Polymerization
Here, the polymers formed have fewer atoms because byproducts are formed during the polymerization process.
Most step-reaction are condensation polymerization processes

Other classification of polymerization reactions


a.Step-reaction/step-growth:
This process describes the products of a random union of monomers, usually in a step-wise manner, to form
dimers, trimers and higher species.

b. Chain-reaction/chain-growth:
This process involves the successive linking of monomers to form a growing chain. It involves 2 specific kinetic
steps of initiation and propagation.

c. Ring-opening polymerization: this process can either be step- or chain-reaction


Chain reactions may also proceed with an anion (B:-) to initiate ring-openingpolymerization of a cyclic
monomer.
Polymer Nomenclature
The IUPAC recommends polymer names be derived from the base unit, according to the following steps;

i. the smallest base unit or constitutional repeating unit (CRU) is identified


ii. the lowest possible numbers are assigned to the subsequent groups on the backbone
iii. the name is written in parenthesis (brackets) and prefixed with poly eg

SOURCE NAME IUPAC NAME

polyethylene Poly(methylene)
Polytetrafluoroethylene Poly(difluoromethylene)
Polystyrene Poly(1-phenylethylene)
Poly(acrylic acid)
Poly(α-methylstyrene)
Poly(1-pentene)
LASER CLADDING
A laser produces a very narrow light beam useful in many technologies and instruments. Laser is an acronym for
Light Amplification by Stimulated Emission of Radiation. Laser cladding is an advanced surface engineering
technique that involves re-conditioning a substrate by material deposition onto the substrate using a laser as a
heat source. The process melts the material being added (typically in powder or wire form) and fuses it to the
surface of a base material. This highly controlled technique allows for precise modifications and enhancement of
surface properties such as wear resistance, corrosion resistance, and hardness.
Principles of Laser Cladding
Laser cladding is a surface modification process where a material is deposited onto a substrate using
a laser as the energy source. The precision, low heat input, and ability to control the deposition
make laser cladding suitable for repairing worn-out parts, enhancing surface properties (such as
hardness or corrosion resistance), and even for additive manufacturing applications.
The key principles of laser cladding involve material deposition, precise heat control, and
metallurgical bonding. Here’s an outline of the fundamental principles:
1. Material Deposition: In laser cladding, a cladding material (usually in powder or wire form) is fed
into the laser beam's path. This material can be metallic, ceramic, or a composite and is selected
based on the desired surface properties (e.g., wear resistance, corrosion resistance). Products from
these processes include gear teeth, biomedical implants, and pump shafts.
2. Laser Heating: A high-energy laser beam is focused onto the substrate surface, rapidly heating it.
The laser provides localized and controlled energy, creating a melt pool on the surface of the
substrate. Examples include ship propeller blades, cutting tools, and engine cylinder bores.
3. Simultaneous Melting of Cladding Material and Substrate: The cladding material is melted by the
laser beam as it reaches the substrate. Simultaneously, the substrate’s surface also melts slightly,
promoting bonding between the cladding layer and the substrate. This forms a metallurgical bond,
ensuring the coating adheres to the surface. Examples are jet engine components, mold tools, and
rail lines.
4. Controlled Cooling and Solidification: After the material melts and bonds to the substrate, it
rapidly cools due to the controlled localized heat input of the laser. This fast cooling can result in a
refined microstructure, often improving mechanical properties like hardness and wear resistance.
Hydraulic piston rods, agricultural tools, and industrial rollers.
5. Dilution Control: The laser cladding process is designed to minimize the dilution of the cladding
material with the substrate material. This helps maintain the desired properties of the cladding
layer, such as its composition and hardness. Examples are landing gear components, valves in
petrochemical plants, and boiler tubes.
6. Precise Control and Automation: One of the key advantages of laser cladding is the precise
control over process parameters like laser power, scanning speed, and feed rate of the cladding
material. This allows for accurate control of the clad layer's thickness, quality, and overall geometry,
making it highly customizable. Products from these process include bladed disks for aerospace,
mining equipment, and transmission components.
7. Layer-by-Layer Deposition: Laser cladding can be used to deposit multiple layers of material to
achieve the desired thickness or specific properties, making it ideal for applications requiring a thick
coating or specific surface enhancements. Products from this process are engine casing (aerospace),
wear plates in construction, and orthopaedic implants.
Key Techniques of Laser Cladding
1. Direct Energy Deposition (DED): This process feeds powder or wire material directly into the laser’s focal
point, where it is melted and deposited onto the substrate. It’s widely used for repairing components or building
layers in additive manufacturing.

2. Blown Powder Cladding: The powder material is delivered through nozzles into the laser’s path and fused
onto the surface. This method is particularly efficient for coating larger surface areas with minimal material
wastage.

3. Wire-fed Cladding: A wire is melted by the laser to create coatings or build parts, making it more suited for
specific applications where solid feedstock is preferred over powder.
Additive Manufacturing
Additive manufacturing (AM), commonly known as 3D printing, is a process that builds objects layer by layer
from digital models, as opposed to traditional manufacturing, which involves subtracting material from a solid
block (subtractive manufacturing) or molding materials (formative manufacturing). AM uses materials such as
plastics, metals, ceramics, and composites, making it versatile across various industries. Examples of products of
AM are drone frames, prosthetics, vehicle spare parts, especially obsolete/outdated parts, eyeglass frames, ..etc.
The advantages of additive manufacturing include
i. design freedom, allowing the creation of complex geometries that are difficult or impossible with traditional
methods, such as internal lattice structures.
ii. enables customization, which is particularly useful in industries like healthcare (for prosthetics) and
aerospace (for lightweight parts).
iii. AM reduces material waste, as only the necessary material is used and
iv. it accelerates prototyping by allowing rapid parts production directly from digital models.
AM challenges include
- slower production speeds for large-scale manufacturing;
- limited material selection compared to traditional methods; and
- the need for post-processing to achieve desired surface finishes or mechanical properties.
Types of reactions
• Homogeneous reactions
• Heterogeneous reactions
• Reversible reactions
• Irreversible reactions

22
Homogeneous & Heterogeneous Reactions
INTRODUCTION TO HOMOGENEOUS AND HETEROGENEOUS
REACTIONS

Homogeneous Reactions: Reactions where reactants and products are in the same phase
(solid, liquid, or gas).
Heterogeneous Reactions: Reactions that occur at the interface between different phases
(e.g., solid-liquid, gas-solid).

Relevance
Understanding these types of reactions is crucial for designing reactors, optimizing
reaction conditions, and scaling up from lab to industry.
SOLID/LIQUID/GAS PHASE REACTIONS
Homogeneous Reactions (Single-phase):
- Gas-Phase Reactions:
Example: Combustion of methane
- Equation: CH4 + 2O2 CO2 + 2H2O
- Used in power plants and engines.

- Liquid-Phase Reactions:
Example: Esterification of ethanol and acetic acid
- Equation: CH3COOH + C2H5OH CH3COOC2H5 + H2O
- Industrial production of esters for flavors, solvents.

- Solid-Phase Reactions:
Example: Thermal decomposition of calcium carbonate
- Equation: CaCO3 CaO + CO2
- Used in the cement industry.
Industrial Example: Gas-Phase Reaction (Combustion of Methane)
- Industrial Reactor:
- Large-scale furnaces or boilers.
- Methane combusted in a controlled oxygen environment.

- Key Parameters:
- Temperature control to prevent incomplete combustion.
- Efficiency is critical for minimizing pollutants (e.g., CO, NOx).
Heterogeneous Reactions

Heterogeneous Reactions:
Solid-Liquid Reaction:
Example: Dissolution of calcium carbonate in acid
CaCO3 + 2HCl CaCl2 + CO2 + H2O
Used in neutralizing acidic waste.

Gas-Solid Reaction:
Example: Oxidation of sulfur dioxide on a catalytic surface
- Equation: 2SO2 + O2 2SO3
- Used in the production of sulfuric acid via the contact process.
Liquid-Gas Reaction:
Example: Absorption of CO2 in NaOH solution
- Equation: CO2 + 2NaOH Na2CO3 + H2O
- Used in scrubbing flue gases in power plants.
HOMOGENEOUS AND HETEROGENEOUS CATALYSIS
Homogeneous Catalysis: Catalyst in the same phase as reactants.
Example: Acid-catalyzed esterification
Catalyst: H₂SO₄ in liquid phase.

Heterogeneous Catalysis: Catalyst in a different phase from reactants.


Example: Haber process for ammonia synthesis
Catalyst: Solid iron, reactants in gas phase.

Relevance in Industry:
Homogeneous: Easily mixed, but difficult to separate.
Heterogeneous: Easier to separate, widely used in refining, pollution control.
INTRODUCTION TO RATE EXPRESSIONS
Rate expressions describe how the rate of a chemical reaction depends on the concentrations of
the reactants. It is a mathematical representation of the rate of reaction as a function of the
concentrations of species involved. The general form of the rate expression is:

Where

The overall reaction order is the sum of m and n


Molecularity & Order of Reaction
Molecularity refers to the number of molecules participating in an elementary step of a reaction. It is
always a whole number and applies to individual steps in a mechanism, not the overall reaction.
- Unimolecular reaction: One molecule participates. + examples
- Bimolecular reaction: Two molecules participate. + examples
- Termolecular reaction: Three molecules participate. + examples

Order of Reaction refers to the powers to which reactant concentrations are raised in the rate
expression. It is an empirical concept, determined experimentally, and can be fractional or whole
numbers.
First-order reaction: The rate depends linearly on the concentration of one reactant.
Second-order reaction: The rate depends on either the square of the concentration of one reactant or
the product of two reactants.
First-Order Reaction
A reaction is first-order if the rate depends on the concentration of one reactant raised to the power of 1. The
general form of the rate expression for a first-order reaction is:

Where

The integrated form of the first-order rate law can be derived by separating variables and integrating to give,

to give

or

Where [A]0 = initial concentration of A


t = time
Similarly, the half-time, which is the time required for the concentration to decrease to half of its initial value, is given as,
Second-Order Reaction
For a second-order reaction, the rate depends on the concentration of one reactant squared or
on the product of two reactants. The rate expression is:
or

Consider a reaction, A B,
Integrating the rate law gives,

Such that,

The half-life for a second-order reaction is given as:


Class work

12
13
Estimation of Kinetic Parameters
Rate Constant (k)
The rate constant, k, is a key parameter in rate expressions, and it depends on temperature
according to the Arrhenius equation:

Where

Estimation of K
i. From the concentration-time data
ii. From the Arrhenius equation at different temperatures
The Arrhenius plot
−𝐸𝑎
Recall: 𝑘 = 𝐴𝑒 ൗ𝑅𝑇
To work with this eqn., experiments are carried out in different
temperatures and a plot of ln k versus T is generated.
𝐸𝑎
ln 𝑘 = ln 𝐴 −
𝑅𝑇
This is a straight line with
Intercept = ln K
Slope = -Ea/R

15
Activation Energy, E
This is the minimum energy a reacting specie must possess to cross the
barrier and form products. Low barriers would require low energy and
vice versa – with higher barriers demanding high reaction temperature.
When molecules collide, reactions occur with a fraction of collisions
having the minimum energy to cross the barrier.

16
Maxwell Boltzmann’s distribution of relative
velocities
For the reactant velocities,

Where kB = Boltzmann’s constant = 3.29 x 10-24 cal/molecule/K


m=reduced mass, g; U = relative velocity, m/s
T = absolute temp. K; e = Energy, kcal./molecule
E = kinetic energy, kcal/mol

17
If e is replaced with the kinetic energy eqn, then the Maxwell
Boltzmann’s eqn becomes,

In terms of energy per mole (rather than energy per molecule),


the eqn reduces to;

This function can be plotted at different temperatures from which


the fraction of collisions within a given energy range can be
deduced.

18
The energy distribution of the reacting molecules is then plotted as
a function of temperature, from which the fraction of collisions
between two energy levels are deduced.

19
The Trapezoidal Rule
The Trapezoidal rule is used to calculate the area under a curve and it is
written as:

𝑏
∆𝑥
න 𝑓 𝑥 𝑑𝑥 = 𝑓𝑓 + 𝑓𝑙 + 2 ෍ 𝑓𝑒𝑣𝑒𝑛 + 2 ෍ 𝑓𝑜𝑑𝑑
𝑎 2
𝑏−𝑎
Where ∆𝑥 = and N = number of rectangles
𝑁
Alternatively, the Simpson’s rule can be used.

20
Classwork
1. The decomposition of hydrogen peroxide 2H2O2 H2O + O2 follows first-order
kinetics with respect to hydrogen peroxide. The rate constant k = 0.03 min-1. Calculate the
concentration of hydrogen peroxide after 50 minutes if the initial concentration is 0.10 M
2. The reaction 2NO 2NO + O2 follows second-order kinetics with a rate constant of
1.0 M-1s-1. If the initial concentration of NO2 is 0.50M, calculate the concentration after 10
seconds.
Chain reactions
A chain reaction refers to a reaction mechanism where the steps involve a sequence of events
that regenerate reactive species (e.g., free radicals) that propagate the reaction. Chain reactions
are common in polymerization processes, such as polymeric isomerization, where long chains of
molecules undergo transformations or structural rearrangements.

Polymeric Isomerization:
Polymeric isomerization is a reaction in which a polymer undergoes structural rearrangement
without any change in molecular weight or chemical composition. These types of reactions are
typically controlled by the reaction kinetics and follow a mechanism involving initiation,
propagation, and termination steps.
1. Initiation Step:
The chain reaction starts with an initiation step where a reactive species (like a radical) is
formed, typically through external energy (e.g., heat, light, or a chemical initiator).

2. Propagation Step:
Once the chain is initiated, the reactive species attack polymer molecules, causing
isomerization. In this case, the polymer undergoes a structural rearrangement. The reactive
species is regenerated after each step, continuing the chain reaction.

3. Termination Step:
The chain reaction eventually ends when two reactive species combine or when the reactive
species reacts with an inhibitor, forming a stable product.
Kinetics of Polymeric Isomerization:
In chain reactions like polymeric isomerization, the overall rate of the reaction depends on the
rates of the initiation, propagation, and termination steps. The rate law can be complex and
depends on the concentration of the reactive species and the polymer substrate.
For a polymeric isomerization chain reaction, the rate expression may be written as:

Where;

The concentration of the reactive species is determined by the balance between the rates of
initiation and termination:
Kinetics of Heterogeneous Reactions
In heterogeneous reactions, reactants are present in more than one phase (e.g., solid-liquid, gas-solid).
The reaction kinetics in such systems are more complex due to the involvement of different phases.
Establishing kinetic parameters is challenging because transport phenomena (diffusion, adsorption)
often play a significant role alongside chemical reaction rates.
Basic Steps in Heterogeneous Reactions:
For a reaction occurring in more than one phase, several steps may occur in sequence:
1. Mass Transfer of Reactants to the Interface: Reactants in one phase (e.g., gas or liquid) must be
transferred to the surface of another phase (e.g., solid catalyst or another liquid phase).
2. Adsorption of Reactants: The reactants must adsorb onto the surface of a catalyst or another solid
material.
3. Surface Reaction: The adsorbed reactants undergo a chemical reaction on the surface.
4. Desorption of Products: The reaction products desorb from the surface.
5. Mass Transfer of Products: The products are transferred back into the bulk phase.

The rate of the overall heterogeneous reaction is often controlled by the slowest of these steps, which
can be either mass transfer (diffusion-limited) or the surface reaction (reaction-limited).
Rate Expressions for Heterogeneous Reactions

The rate expression for heterogeneous reactions depends on the limiting step. For example:

- Surface Reaction-Limited:
If the surface reaction is the rate-limiting step, the rate of reaction is proportional to the concentration
of adsorbed reactants:

Where θA is the surface coverage (the fraction of sites occupied by reactant A), and ksurface is the surface
reaction rate constant.

- Mass Transfer-Limited:
If the reaction is limited by mass transfer, the rate of reaction depends on how fast the reactants are
transported to the surface:

Where [A] is the concentration of reactant A in the bulk phase, and [A]surface is the concentration of A at
the surface.
Establishment of Kinetic Parameters:
The kinetic parameters for heterogeneous reactions are established through experimental
studies and depend on the reaction mechanism and limiting step. Some important parameters
include:
1. Rate Constants (k): These are determined experimentally by fitting the rate expressions to
reaction data.
2. Surface Coverage θA: For reactions involving adsorption, surface coverage is a key parameter
that depends on the equilibrium between adsorption and desorption.
3. Mass Transfer Coefficients (kmass): These coefficients are important when the reaction is mass
transfer-limited and depend on the system’s physical properties (e.g., diffusivity, film thickness).

The kinetics of chain reactions, such as polymeric isomerization, involve complex mechanisms
where initiation, propagation, and termination steps occur. For heterogeneous reactions, where
multiple phases are involved, the establishment of kinetic parameters requires understanding of
both surface reactions and mass transfer phenomena. These principles are key to designing and
optimizing chemical reactors for various industrial processes.
CHE315
2024/2025 SESSION
CATALYSIS

Dr. Edith Alagbe


Department of Chemical Engineering
Covenant University, Ota.
Catalysts are essential components in chemical reactions that accelerate reaction rates without being
consumed in the process. Their presence helps in reducing the activation energy needed for reactions,
allowing them to proceed at a faster pace or under milder conditions. They greatly affect the yield
and selectivity of reactions. Catalysts only impact the reaction rate and not the equilibrium.
Yield is the fraction of raw material converted to product while Selectivity refers to the preferred
products in a reaction where more than one product is possible.
Series and parallel reactions
Series Reactions
- Each reaction has a specific rate constant
- The overall yield of C depends on both rate constants

Parallel Reactions

- Each reaction pathway has its own rate constant


- The competition between the pathways will determine the
distribution of products B and C.
Types of Catalysts
Catalysts are classified broadly into two categories:

Homogeneous Catalysts: These catalysts are in the same phase (solid, liquid, or gas) as the reactants. They mix
uniformly with the reactants, which facilitates efficient interaction at the molecular level. Common examples
include acid and base catalysts in solution.

Heterogeneous Catalysts: These catalysts are in a different phase from the reactants, often solids interacting
with liquid or gas-phase reactants. Heterogeneous catalysts usually operate on the surface, where reactants
adsorb, react, and then desorb as products. They’re widely used in industrial processes due to ease of
separation and reusability.

Catalysts may further be classified as:

- Biocatalysts: Enzymes are a notable example of biocatalysts, which are proteins that catalyze biochemical
reactions. These catalysts are highly specific, operating under mild conditions, and are crucial for metabolic
processes in living organisms.

- Organocatalysts: These are small organic molecules that catalyze chemical reactions, often enhancing
stereoselectivity. They’re widely used in asymmetric synthesis, which is valuable in pharmaceutical
production.
- Photocatalysts: These are materials that change the rate of a chemical reaction on exposure to light.
Solid catalysts
Properties of catalysts
i. Surface area
ii. Porous structure
iii. Selectivity
iv. specificity

Classification of catalysts
a. Molecular sieves
b. Porous
c. Monolithic
d. Supported
e. Unsupported
Promoters may be added with catalysts to improve their activity.

Examples of solid catalysts are silica-alumina, Raney nickel, zeolite,


Mechanism of catalysis
Catalysts function by offering an alternative reaction pathway with a lower activation energy. This pathway
typically involves the formation of an intermediate compound or complex. Here are a few primary catalytic
mechanisms:

Adsorption and Surface Reaction: In heterogeneous catalysis, reactants adsorb onto the catalyst surface,
weakening bonds within the reactant molecules, which leads to easier bond breaking and new bond formation.

Acid-Base Catalysis: Involves acids or bases donating or accepting protons in homogeneous catalysis, which
lowers the reaction's activation energy, e.g., in reactions like esterification and hydrolysis.

Redox Catalysis: In redox reactions, the catalyst undergoes oxidation or reduction to facilitate the reactants’
transformation. Transition metals are often used here, as they can alternate between oxidation states to mediate
electron transfer.

Enzyme Catalysis: Enzymes use specific active sites that bind substrates and stabilize the transition state,
often through hydrogen bonding, ionic interactions, or van der Waals forces. This specificity is the concept of
‘lock-and-key’ or ‘induced fit’ model.
Reaction Catalysts
Catalysts Synthesis
Catalysts are synthesized using various techniques, often tailored to optimize properties such as surface area,
porosity, and active site accessibility.

Homogeneous Catalyst Synthesis

i. Metal Complexes: Transition metal complexes are frequently synthesized by coordinating a metal ion with
suitable ligands (organic or inorganic molecules that donate electrons). This coordination provides stability and
allows fine-tuning of the electronic and steric properties.

ii. Organometallic Catalysts: Synthesis involves bonding metal ions with organic groups. Techniques often
include oxidative addition and reductive elimination, where ligands are carefully selected to improve catalyst
reactivity and selectivity.
Heterogeneous Catalyst Synthesis

i. Precipitation and Co-precipitation: Involves the precipitation of metal ions as hydroxides or carbonates by
adding a base. These precipitates are then calcined to produce metal oxides. Co-precipitation allows the
formation of mixed oxides for more complex catalytic activities.

ii. Sol-Gel Method: Metal alkoxides or salts undergo hydrolysis and condensation to form a gel, which is then
dried and calcined to obtain a porous, high-surface-area catalyst. This method is widely used to synthesize
oxides and ceramics with controlled porosity.

iii. Impregnation: A porous support (e.g., silica, alumina) is soaked in a solution of the catalytic precursor, which
adsorbs onto the surface. After drying and calcination, the precursor is converted into an active catalytic phase.

iv. CVD (Chemical Vapor Deposition): This technique deposits thin films of catalyst onto a support by
vaporizing a precursor compound. It’s useful for synthesizing nanoparticles, often used in fuel cells and
electronic applications.
Enzyme Synthesis and Immobilization

i. Protein Engineering: For enzyme catalysis, techniques like genetic engineering and site-directed mutagenesis
modify enzyme structures to enhance stability, activity, or selectivity.

ii. Immobilization: Enzymes can be immobilized on solid supports like gels, resins, or beads. This stabilizes the
enzyme and makes it easier to recover and reuse.

Organocatalyst Synthesis

i. Amino Acid Derivatives: Many organocatalysts are based on amino acids (e.g., proline). Synthesis involves
modifying these structures to increase stereoselectivity for specific reactions, such as aldol or Mannich
reactions.

ii. Functionalized Polymers: Organocatalysts can be anchored to polymers, creating recyclable catalytic systems
that combine the benefits of homogeneous catalysis with easier recovery.
Steps in a catalytic Reaction
1. Mass transfer (diffusion) of the reactant(s) (e.g.,
species A) from the bulk fluid to the external surface
of the catalyst pellet, that is, the pore mouth.
2. Diffusion of the reactant from the pore mouth
through the catalyst pores to the immediate vicinity
of the internal catalytic surface
3. Adsorption of reactant A onto the catalyst surface
4. Reaction on the surface of the catalyst (e.g., A → B)
5. Desorption of the products (e.g., B) from the
surface
6. Diffusion of the products from the interior of the
pellet to the pore mouth at the external surface
7. Mass transfer of the products from the external
pellet surface to the bulk fluid
Rate-Limiting Steps
In heterogeneous catalysis, the steps involved are typically adsorption, surface reaction, and
desorption, and the slowest step within this sequence of reactions that controls the overall rate of the
reaction is called the rate-limiting step or rate-controlling step. Increasing the rate of this step would
increase the total reaction proportionately.
Each step can be considered as a resistance (similar in circuits), and the total rate of reaction
corresponds to the sum of the inverse of the resistances. This implies that the step with the greatest
resistance is rate-limiting. This suggests that if one step in the sequence is significantly slower than
the others, that step constrains the progress of the entire reaction. An example is the ammonia
synthesis reaction, where nitrogen adsorption on the catalyst surface is the rate-limiting step. This
creates a bottleneck, as only when nitrogen is adsorbed can it subsequently react with hydrogen to
form ammonia.
Identifying the rate-limiting step in catalytic processes is crucial for improving efficiency. If mass
transfer limits the reaction, altering the fluid velocity or reducing the catalyst particle size can
minimize these limitations. For surface reactions such as the RLS, optimizing catalyst surface
properties (e.g., increasing active site availability) can accelerate the reaction.
Overcoming rate-limiting steps in solid catalysis can be achieved by addressing the specific
factors limiting the reaction, such as mass transfer, surface reaction, or catalyst
deactivation.

Improve Mass Transfer Limitations Optimize Internal Diffusion (Pore Diffusion)


- Increase Catalyst Surface Area: Use catalysts with higher - Increase Catalyst Porosity: Utilize highly porous materials or
surface areas (e.g., nano-structured or porous materials) to mesoporous catalysts that allow reactants to penetrate deeper
increase the exposure of reactants to active sites. into the catalyst structure, facilitating access to active sites
within the pores.
- Enhance Mixing: Improve reactor mixing through mechanical
agitation or optimizing flow rates. Increased mixing reduces - Design Catalyst with Optimal Pore Size: Balance the pore size
boundary layer thickness around catalyst particles, improving to allow adequate diffusion of reactants while maintaining
reactant access to the catalyst. structural stability. For smaller molecules, mesopores (2–50 nm)
may be effective, while for larger molecules, macropores (>50
- Reduce Particle Size: Smaller catalyst particles increase the
nm) are typically more suitable.
external surface area and shorten the diffusion pathway, helping
to overcome external mass transfer limitations. However, - Temperature Optimization: Raising the temperature can
excessively small particles may lead to high-pressure drops in increase the diffusion rate, but it must be done carefully to
packed beds. avoid catalyst sintering or deactivation.
- Use Fluidized-Bed Reactors: These reactors help improve
mass transfer by suspending catalyst particles in the reactant
stream, enhancing contact and mixing.
Increase Reaction Kinetics for Surface Reaction
Limitations Manage Catalyst Deactivation
- Increase Active Site Density: Modify the catalyst - Regeneration and Decoking: For catalysts that
composition or structure to increase the density of deactivate due to fouling (e.g., carbon deposits),
active sites on the surface, enhancing the probability of establish a regular regeneration cycle to remove coke
reactant interaction with the catalyst. deposits, often through controlled oxidation or steam
- Optimize Catalyst Composition: Use promoters or treatment.
dopants (e.g., alkali metals or rare earth elements) that - Use of Resistant Catalyst Materials: Design catalysts
enhance the catalyst material's intrinsic activity, from materials resistant to sintering, poisoning, and
improving the surface reaction rate. fouling (e.g., using metal oxides instead of metals prone
- Temperature Control: Ensure the reaction temperature to sintering at high temperatures).
is optimal for the desired surface reaction. Higher - Continuous Catalyst Replacement: In processes like
temperatures typically accelerate reaction rates but can moving-bed or fluidized-bed reactors, catalyst particles
also increase the risk of catalyst deactivation. can be continuously regenerated or replaced to maintain
consistent activity.
Kinetics of Heterogeneous Catalysis
The kinetics of heterogeneous reactions involve studying In the surface reaction step, the adsorption of one or
the rates and mechanisms of reactions where the reactants
exist in different phases, such as a gas reacting on a solid more reactants on the surface precedes the reaction.
surface or a liquid reacting at the interface of a solid Eg
catalyst. Unlike homogeneous reactions, where all reactants
are in the same phase, heterogeneous reactions often
involve complex factors that influence reaction rates, The rate of adsorption of species A onto a solid
including diffusion, adsorption, surface area, and surface site
temperature.

After a reactant has been adsorbed onto the surface,


that is, A · S, it can react in several ways to form the
reaction product.
1. Single site adsorption
Single site adsorption involves the
adsorption of a single reactant on
the surface that would either
decompose or react on the surface This mechanism also follows the
to form products. Since it is an Langmuir-Hinshelwood mechanism
elementary reaction, the rate is and the rate is given as:
given as:
𝑘𝐾𝐴 𝐶𝐴 𝑘𝐾𝐴 𝐴
𝑟= =
1 + 𝐾𝐴 𝐶𝐴 1 + 𝐾𝐴 𝐴
Adsorption may be considered to
proceed by the Langmuir isotherm
given as:
𝐾𝐶
𝜃=
1+𝐾𝐶
2. Reaction between 2 adsorbed species

The corresponding rate eqn. is:

Langmuir-Hinshelwood: In this mechanism, both


reactants adsorb onto the surface, and the reaction
The reaction follows a Langmuir-Hinshelwood occurs between adsorbed species. The rate depends
mechanism eg where ammonia adsorbs onto the on the surface coverage and the adsorption
platinum surface before decomposing. The rate equilibrium.
expression is:

Where, r =the rate of reaction,


KA, kB, = adsorption constants, and
CA, CB = concentrations of reactants A, B
• of reactants.
3. Eley-Rideal mechanism
In this mechanism, only one reactant adsorbs, and the reaction
occurs when a reactant from the gas or liquid phase collides with
the adsorbed species. The rate may depend only on the
concentration of one reactant in the bulk and the coverage of the
adsorbed species.

The rate is given as:

𝑟 = 𝑘𝐶𝐴 𝜃𝐴
Where
k = rate constant for the surface
reaction
CA = concentration of A
θ = fraction of the surface covered by A
Example 1
The decomposition of ammonia (NH3 ) on a platinum catalyst can be described by the reaction:

Given that the reaction follows a Langmuir-Hinshelwood mechanism where ammonia adsorbs onto the
platinum surface before decomposing. With a rate expression,

Calculate the rate of decomposition of ammonia.

Hint:
Example 2
Ethylene (C2H4 ) is hydrogenated to ethane (C2H6 ) on a nickel catalyst:

If the reaction follows the Langmuir-Hinshelwood mechanism where both ethylene and hydrogen
adsorb on the catalyst surface before reacting. From the rate expression given below, calculate the rate
of ethylene hydrogenation.

Given:

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