Reactor design and analysis

cture 1 (A) – Kinetics of chemical Reactio

Instructor
Awad ALSHEBANI
Email: [email protected]

Lectures: Wednesday 12:00 – 16:00 (Every Month)

Lectures: Thursday 12:00 – 16:00 (Every Month)

WhatsApp: 0916591986 (Available: Sunday 10:00 – 12:00)

 First lecture1
Reaction Kinetics & Data Analysis

Chemical Reaction Engineering

 Objectives

Learning Outcomes

Text Book & Course description

 Objectives and
Expected outcomes
 How student measure rates of reactions
 How the rate depends on amounts of reactants
 How to calculate amount left or time to reach a given
amount
 How long it takes to react 50% of reactants
 How rate constant changes with temperature
 Link between rate and molecular scale processes

 Will have the ability to analyze information and interpreting

data.
 Learn how to calculate kinetics and thermodynamics parameters
(activation energy) from kinetics data.
 Will have the ability to demonstrate an understanding of
chemical kinetic properties and analyzing of data.
 References and
other information
H.S. Fogler, Elements of chemical reaction
engineering, Fourth Edition, 2005, Prentice–Hall

O. Levenspiel, Chemical reaction engineering,

Third Edition, 1999, John Wiley & Sons

R. Smith, Chemical process design and integration,

2005, John Wiley & Sons
 Course
1) Description
General information
1 Reactor Design and
Title of course
Analysis - CHE603
2 Dr. Awad Emhemmed
Course coordinator
ALSHEBANI
3 Department or division
Chemical Eng. Depart.
that offers the course
4 Scientific departments
Chemical Eng. Depart.
related to the course
5 Teaching hours during
Numbersemester Lectu
of hours per week: 3 UnitsExerc
Labor - 32 Hours
Tot 4
3 - 1
res
6 Language of teaching atory
English ises
language al
7 Academic year / Semester Second year /3th
level Semester
8 Date of accreditation of XXXXXXXXX
the course
RKDA
emical Reaction Kinetics- What is it
 Chemical Kinetics is the study of the rate at which a chemical
process occurs
 Besides information about the speed at which reactions occur,
kinetics also sheds light on the reaction mechanism (exactly how
the reaction occurs).
We will now study:
 Our goal: is to understand chemical reactions at the molecular level.
 Kinetics: the study of how fast chemical reactions occur
 Speed of a reaction: is measured by the change in concentration
with time.

of
Important factors which affect rates of reactions: y nd
u d
 reactant concentration st ns a r
s: tio cc u
 temperature t ic eac y o
i ne l r the
 action of catalysts K ica ich
a l em w h
 surface area i c ch by
e m f s
h o
 C es nism
pressure of gaseous reactants or products
at a
 Chemical Reaction Kinetics - Why?

 How fast a reaction can take place?

 What steps or pathways are involved in any chemical reaction?
 How complete is the chemical reaction?
 What are the two major factors controlling the outcome of chemical
reactions?
 Chemical thermodynamics
 Chemical kinetics
Kinetics Concept Map
Reaction Rate

Rxn Movie

Rates of reactions
can be determined by
monitoring the change in
concentration of either
reactants or products as a
function of time.
Reaction
Rate

i
‫تحذف‬
Reaction
Types
Rate of reaction rate
Instantaneous rate : rate at a specific
time
Average rate : ∆[A] over a specific time
interval
Initial rate : instantaneous rate at t = 0
Note: Rates and rate laws are not based on
stoichiometry!! They must be determined
experimentally.
Reaction
Rate
Reaction
Rate
Reaction Rate example
Example 1 Reaction Rate
Examples
Example 2 Reaction Rate
Examples
Reaction Rate
Examples

Exercise
Average vs. instantaneous rxn rate ‫تحذف‬
 Exercises on
Reaction Rate
Exercise 1

Exercise 2

Exercise
Reaction Rate and stoichiometry
 tr y?
m e
Reaction Rate and stoichiometry io
o ich
S t
t is
ha
W

What its uses?

 Reaction Rate and stoichiometry

The ratio is 1:1

Reaction Rate and stoichiometry
 Exercise OnReaction Rate and stoichiometry

Exercise 1

Exercise 2

Exercise 3

Exercise 4
 Factors That Affect Reaction Rates
 Physical State of the Reactants: (Molecules must mix to collide)
 In order to react, molecules must come in contact with each other. If the
reaction is happening between a solid and a liquid it will react only on the
surface.
 The more homogeneous the mixture of reactants, the faster the molecules
can react.

 Reactants Concentration:
 As the concentration of reactants increases, so does the likelihood that
reactant molecules will collide. (molecular collisions are required for
reactions to occur)

 Temperature: (molecules must collide with sufficient energy to react).

 At higher temperatures, reactant molecules have more kinetic energy, move
faster, and collide more often and with greater energy.

 Presence ore action of a Catalyst:

 reactants
When are in
Catalysts different
speed upphases, the more
reactions by finely divided the
changing a solid or liquid reactant,
mechanism of thethereaction.
greater Catalysts
the surface area
are per
notunit volume, the
consumed more contact
during it makesof
the course with other
the reactants, and the
reaction.
faster the reaction.
  The effect of surface area on reaction rate
Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

steel nail in O2 steel wool in O2

 Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

Collision
energy and
reaction rate

Other factor: reaction

trajectory (not all collisions
with sufficient energy
are productive)

1
 Rate Law or Rate Equation
Rate Law or Rate Equation: equation describing the relationship
between the reaction rate and concentration of a reactant or
reactants
Consider the following reaction
aA + bB products
Rate = k[A]m[B]n

Reaction orders and, thus, rate laws must

be determined EXPERIMENTALLY!!!
– Note: m ≠ a and n ≠ b
– Overall order = sum of individual orders
 Rate Law or Rate Equation
Recall
 Examples of Reaction Rate Law
Example 1: Determine Order and Initial Rate Law
experimentally
One can gain information about the rate of a reaction by seeing how
the rate changes with changes in concentration.
Examples of Reaction Rate Law
Kinetic Constant or Rate Constant
Example 1- Calculating a value for k using initial rate data k

The exponent in the rate law indicates how the

rate is affected by the concentration of each
reactant.
Kinetic Constant or Rate Constant
Example 2- Calculating a value for k using initial rate data k
c Constant or Rate ConstantCalculating a value for k
using initial rate data

The rate constant k

 Unit for k depends on the overall Calculating
of k
units

order of the reaction

n
tio
ac
?? re
? ? er
?
= ord
of d)
it on
k
un sec
&
st
fir
r(
Fo
Order of Reaction

Type of Order Reaction

Order of Reaction

????????
 Examples on Rate law, order of
Example
1
Reaction and kinetics Rate constant

Example
2
 Working out orders from experimental initial
rate data
Example
3
Order of Reaction
Example

1 2

3 4
Exercise
1

Order of Reaction

Exercise
2
Order of Reaction- Summary
Integral Rate equation of the First
Order Reaction

1 2

3 4
Integral Rate equation of the First
2
Order1 Reaction

3 4
ed Reaction Rate law –First Order of Reaction

A product
 Reaction Half-life for a First-
order
First Order Reaction

1 2

Half-life for a First- order: is

the time required for the
concentration of a reactant to
decrease to half of its initial
concentration

Example 1: Half-life for a First-

order

3
 Reaction Half-life for
a First- order
Example 2: Half-life for a First-
order
 Integral Rate equation of the Second
Order
1
Reaction
2

Half-life for a second- order

reaction
Example: Half-life for a second-
order

1 2

3
Summary

How???
Rate Analysis Methods
 Differential Method
The differential method of analysis deals directly with the differential rate
equation to be tested, evaluating all terms in the equation including the derivative
dCi/dt, and testing the goodness of fit of the equation with experiment.
fferential Method
Example-1
Differential Method
Example-2
ntegral Method
Example
Temperature and Reaction Rate
Rate Theory
Collision
Theory
Collision Theory Molecular Orientation and Effective
Collisions

1 2

COLLISION THEORY: a reaction

results
when reactant molecules, which
are properly oriented and have the
appropriate energy, collide
The necessary energy is the
activation energy, Ea
Not all collisions leads to a
reaction
• For effective collisions proper
3 orientation of the molecules must4
be possible
 Collision Theory

The molecules must collide in order to react, but

that’s not all—they must collide with sufficient
energy and the correct orientation (geometry) so
that the collisions are effective.
Transition State Theory
• During a chemical reaction, reactants do not suddenly
convert to products

• The formation of products is a continuous process of

bonding breaking and forming

• At some point, a transitional species is formed containing

partial” bonds

• This species is called the transition state or activated

complex

• The transition state is the configuration of atoms at the

maximum of the reaction energy diagram
• The activation energy is therefore the energy needed to
reach the transition state
• Note also that the transition state can go on to form
products or break apart to reform the reactants
Activation Ener
gy
 Activation Energy: Ea

Just as a ball cannot get over a hill if

it does not roll up the hill with
enough energy, a reaction cannot
occur unless the molecules possess
sufficient energy to get over the
activation energy barrier.
Activation Energy:
Ea

1 2

3 4
Arrhenius Equati
on
 Arrhenius Equati
on
Svante Arrhenius developed a mathematical
relationship between k and Ea:
where A is the frequency factor, a number that
represents the likelihood that collisions would
occur with the proper orientation for reaction.
Taking the natural
logarithm of both sides,
the equation becomes

y=mx + b
When k is determined
experimentally at several
temperatures, Ea can be
Arrhenius Equati
on
Temperature Dependence of the Rate Con
stant

k = A • exp( -Ea/RT)
)Arrhenius equation(
Ea : is the activation
energy (J/mol)
R : is the gas constant
(8.314 J/K•mol)
T : is the absolute
temperature
A :is the frequency
-Ea 1
factor
Ln k = + ln
- R T A
 Arrhenius Equati
on
• This is how the rate constant of a chemical reaction
varies with respect to temperature and other
variables.
where...
k= rate constant
Ea = Activation Energy in
(kJ/mole)
R = Gas Constant
T = Kelvin temperature
A = “Frequency Factor”-- a
constant indicating how
many collisions have the
correct orientation to lead
to products.
 Examples on Arrhenius
1
Equation 2

3 4
Maxwell–
Boltzmann
Distributions
 Maxwell–Boltzmann Distributions

• Temperature is defined as
a measure of the average
kinetic energy of the
molecules in a sample.
• At any temperature there is
a wide distribution of
kinetic energies.
• As the temperature • If the dotted line
increases, the curve represents the activation
flattens and broadens. energy, as the
• Thus at higher temperature increases,
temperatures, a larger so does the fraction of
population of molecules molecules that can
has higher energy. overcome the activation
energy barrier.
Temperature vs. Energy of Activation
1

2
Reaction Coordin
ate Diagrams
 Energy Diag
rams

Exothermi Endothermi
c c
(a) Activation energy (Ea) for the forward reac 50 kJ/mol 300 kJ/mol
tion
150 kJ/mol 100 kJ/mol
(b) Activation energy (Ea) for the reverse reac
tion -100 kJ/mol +200 kJ/mol

(c) Delta H
Reaction Coordina
te Diagrams

2
Reaction Mechani
sms
 Reaction Mechanisms
and Rate law
The sequence of events that describes the actual process by which reactants
become products is called the reaction mechanism.
• Reactions may occur all at once or through several discrete steps.

• Each of these processes is known as an elementary reaction or elementary

process.
The overall progress of a chemical reaction can be represented at the molecular
level by a series of simple elementary steps or elementary reactions.
The sequence of elementary steps that leads to product formation is the
reaction mechanism.
Reaction Mecha
nisms
 Rate Laws and Rate Det
ermining Steps
Writing plausible reaction mechanisms:
• The sum of the elementary steps must give the overall balanced equation for
the reaction.
• The rate-determining step should predict the same rate law that is determined
experimentally.

The rate-determining step is the

slowest step in the sequence of steps
leading to product formation.
Reaction Mech
anisms
 Rate Laws of Elementary Steps
 Since this process occurs in one single step, the stoichiometry can
be used to determine the rate law!
 Law of Mass Action: The rate of a simple (one step) reaction is
directly proportional to the concentration of the reacting substances.

 The molecularity of a process tells how many molecules are involved in the
process.
 The rate law for an elementary step is written directly from that step.

• Notice that the coefficients become the exponents.

 Reaction Inter
mediates
Intermediates are species that appear in a
reaction mechanism but not in the overall
balanced equation.
An intermediate is always formed in an early
elementary step and consumed in a later
elementary step.
Elementary step: NO + NO 2 2

+ Elementary NO N2O2 2NO2

Overall reactio
step: 2NO
+ O2 + O 2NO2
n: 2
 Multistep Mechani
sms
 In a multistep process, one of the steps will be
slower than all others.
 The overall reaction cannot occur faster than this
slowest, rate-determining step.
Example of Slow&
Fast Reaction
Mechanisms
 Rate Laws for Multistep M
• Let’s look echanisms
at another example…

2NO(g) + Br2(g) 2NOBr(g)

• The experimentally determined rate law is

…
Rate = k[NO]2[Br2]
• Consider the following mechanism…

Step 1: NO(g) + Br2(g) k1 NOBr2(g) (fast

)
k-1
Step 2: NOBr2(g) + NO( 2NOBr(g) (slow
g) k2 )
• The rate law is based on Step
2:
Rate = k2[NOBr2][NO]
 Slow
Initial
Step

2 3
 Slow
Initial
Step

2
Fast Initial
Step

3
1 5

4 6
2
Examples on Reaction Mechan
isms and Rate law
Examples on Reaction Mechan
isms and Rate law
Examples on Reaction Mechan
isms and Rate law
Examples on Reaction Mechan
isms and Rate law
Rate Laws for
Multistep
Reactions
Rate Laws for Multistep
Mechanisms

2
1

3
4
Catalyst
s
Catalysts

2 3
Catalysts
Catalysts and Reaction Rates

2
Heterogeneous Catalysts
2

3
Examples of Catalysts: Eny
mes
 Enzymes

• Enzymes are catalysts in

biological systems.
• The substrate fits into the
active site of the enzyme
much like a key fits into a
lock.
Enzyme Catalysts
2

3
 Enzyme Catalys
ts

Another example…Nitrogen gas cannot be used

in the soil for plants or animals. Nitrogen
compounds, NH3, NO2–, and NO3– are used in the
soil.
The conversion between N2 and NH3 is a process
with a high activation energy (the N≡N triple
bond needs to be broken). Nitrogenase, an
Other Examples of Cataly
sts
1