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CHAPTER 1
CHEMICAL KINETICS
REACTOR TECHNOLOGY
CKD 20002 1.1 The rate of reaction

1.2 The rate law

1.3 The relationship between
CHAPTER 1 reaction rates and temperature
CHEMICAL KINETICS
1.4 Principle of chemical kinetics

Objectives
Upon the completion of this chapter, students are
able to:

• State the importance of reactors in chemical

industries.
• List types of chemical reactions. Introduction
• List the factors that influencing a chemical
reaction.
• Differentiate between rate of reaction and rate
law.
• Demonstrate the calculation related to reaction
order, reaction rate constant, conversion and
activation energy.

Introduction Introduction
• Chemical kinetics is the study of reaction
rates in a chemical reaction Reaction?
• Important aspects in chemical reaction Occurs when a chemical species
The rate at which chemical reactions take place, lost its chemical identity and a
mechanism and rate limiting steps that control new compound forms
the reaction process

The sizing of chemical reactor to achieve Kind

production goals
Chemical
How material behave within reactor chemically Number
and physically
Identity
Configuration
How data from chemical reactors should be
recorded, processed and interpreted

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Introduction Decomposition
Reaction?
reactant product + by product
decomposition
• A more complex substance breaks down
into its more simple parts
3 ways • One reactant yields 2 or more products
combination
• Example:

isomerization

Decomposition Combination

Such this/ reactant + reactant product

• Two or more simple substances combine

to form a more complex substance
• Two or more reactants yielding one
product is another way to identify a
synthesis reaction
• Example:

Combination Isomerization

Such this/ • The molecule neither adds other

molecules to itself nor breaks into
smaller molecules
• It just loses its identity through a
change in configuration
• Example:

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Isomerization

Like this…

Rate of Reaction

Rate of Reaction Rate of Reaction

Consider species A:
The reaction rate is the rate at which a
species loses its chemical identity per A B
unit volume
• The rate of reaction, -rA is the number
of moles of A reacting (disappearing)
Can be expressed either as per unit time per unit volume [e.g.
1. The rate of disappearance of a mol/dm3.s]
reactant
• It is a function of concentration,
or
temperature, pressure and types of
2. The rate of appearance of a product catalyst (if any)

Rate of Reaction Rate of Reaction

REACTANT PRODUCT
Consider species A: EXAMPLE 1

A B Given reaction as A B
Therefore
• Independent of the reaction system
rA = The rate of formation of species A per
(batch, CSTR, plug flow, etc.) unit volume
-rA = The rate of a disappearance of
• Used to relate the rate of reaction, - rA, species A per unit volume
to the concentration of reacting species rB = The rate of formation of species B per
and to the temperature at which the unit volume
reaction occurs [e.g. -rA = k(T)CA]. -rB = The rate of disappearance of species
B per unit volume

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Rate of Reaction Rate of Reaction

REACTANT PRODUCT REACTANT PRODUCT

A B A B

• For reactants, the rate of disappearance is
a positive (+) number.
• For products, the rate of disappearance is
a negative (-) number because they are being
formed and not disappearing.
• For reactants, the rate of formation is a
negative (-) number because they are
disappearing and not being formed.
• For products, the rate of formation is a
positive (+) number.

Rate of Reaction Rate of Reaction

aA + bB cC + dD Consider the reaction

• The rate of reaction can be represented

by the rate of disappearance of a in which the rate of disappearance of A is 5 moles
reactant, such as –rA or –rB and the of A per dm3 per second at the start of the
rate of formation of a product, such as reaction. At the start of the reaction:
rC or rD .
• They can be related by: 1. What is -rA?
2. What is the rate of formation of B?
− rA − rB rC rD 3. What is the rate of formation of C?
= = = 4. What is the rate of disappearance of C?
a b c d 5. What is the rate of formation of A, rA?
6. What is -rB?

Rate of Reaction Rate of Reaction

1. -rA is the rate of disappearance of A 3. C is a product that is being formed three
times as fast as A is disappearing
− rA = 5 mol / dm .s 3 Because C is a product is being formed,
its rate of formation is positive.

2. For every one mole of A that disappears, two rC = 15 mol / dm 3 .s

moles of B disappear. Reactant B is
disappearing twice as fast as reactant A.
4. The rate of disappearance of C is -rC.
B is being used up therefore its rate of
Because C is a product, its rate of
formation is a negative number. disappearance, -rC, is a negative number

rB = − 10 mol / dm 3 .s − rC = − 15 mol / dm 3 .s

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Rate of Reaction
5. A is a reactant that is being used up
therefore its rate of formation is negative
rA = − 5 mol / dm 3 .s
6. -rB is the rate of disappearance of B
− rB = 10 mol / dm 3 .s
Rate Law
Rate Law
• It is algebraic equation determine from
the experiments observations and gives
the rate of reaction as a function of
reacting species concentration and
temperature.
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Summary
• For reactants the rate of disappearance
is a positive (+) number.
• For products the rate of disappearance is
a negative (-) number because they are
being formed and not disappearing.
• For reactants the rate of formation is a
negative (-) number because they are
disappearing and not being formed.
• For products the rate of formation is a
positive (+) number.
Rate Law
• The rate law or rate equation is an
equation that tells us how fast the
reaction proceeds and how the reaction
depends on the concentration of the
chemicals species involved.
• It is an equation which links the reaction
rate with concentrations or pressures of
reactants and constant parameters.
• Known as ‘Kinetic expression’
Rate Law
• For example given the reaction of
A+ B → C + D
• Based on Power Law Model, the
reaction rate, -rA is given as
α β
- rA = k(C A C B )
where
k = specific reaction rate constant
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Rate Law
α β
- rA = k(C A C B )
• CA and CB is function of concentrations of
component A and B (mol/L)
• The exponent of α and β are called the
reaction orders
• The order of reaction with respect to a
certain reactant is defined, as the power to
which its concentration term in the rate
equation is raised
Rate Law
EXAMPLE:
Given the reaction as A + 2B → C
CASE 1
1. If stated the reaction follows ELEMENTARY
RATE LAW, then the rate law and order of
reaction can be obtained from the
stoichiometric coefficient.
2. Therefore the rate equation is -rA = kCA1CB2.
3. The reaction order with respect to A would be
1 and with respect to B would be 2, the total
reaction order would be 2+1=3
Factors influence the
rate of reaction
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Rate Law
A reaction follows an ELEMENTARY RATE
LAW if the REACTION ORDER of EACH
REACTANT is IDENTICAL with the
STOCHIOMETRIC COEFFICIENT of THE
REACTANT for the reaction as written.
Example:
• For reaction of A + B C+D
The rate law would be -rA = k CA CB
• For reaction of 2NO + O2 2NO2
The rate law would be -rNO = k CNO2 CO2
Rate Law
EXAMPLE:
Given the reaction as A + 2B → C
CASE 2
1. If stated the reaction obeys a NON-
ELEMENTARY RATE LAW, therefore the
rate equation cannot be determined by
looking at the stoichiometric coefficient.
2. Additional information are needed from
experimental works or literature to deduce the
rate law and the order of reaction
Factors influence the
rate of a reaction
• Collision theory → explain how different
variables change the rate of reaction.
• For a reaction to take place, the particles
of the substances that are reacting have to
collide. If they collide, with enough
energy then they will react.
• The minimum amount of kinetic
(movement) energy that two particles need
if they are going to react when they collide
is called the activation energy.
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Factors influence the Physical State

rate of a reaction
• The physical state (solid, liquid or gas) of a
Physical reactant is also an important factor of
state
the rate of change
Concent
• Same phase (aqueous solution), thermal
Catalyst
ration motion brings them into contact
Reaction • Different phases, the reaction is limited to
rate
the interface between the reactants
• Reaction can only occur at their area of
Tempera
contact
Pressure
ture

Physical State Physical State

• This means that the more finely divided a
solid, the greater its surface area per unit
volume, and the more contact it makes with
the other reactant, thus the faster the
reaction
The perimeter of the large The perimeter around
chip is 12 units. The acid each chip is 4 units, but
particles can only collide there are 9 of them so the
with the edge of the chip total perimeter is 4 x 9 =
36 units. Notice how the
acid in the second
diagram can reach what
used to be the centre of
the large chip.

Concentration
• Molecules must collide in order to react
• More concentrated the reactants, the
greater the no. of molecules in any given
volume
• Therefore, the greater the no. of molecular
collision that result in greater successful
reaction
Temperature
• When we increase the reaction
temperature, the particles move more
quickly. This has two effects:
1) More collisions take place
2) When a collision occurs, there is
more chance that the collision will lead to a
reaction, because the amount of energy is
more likely to be greater than the min
amount of energy needed (activation
energy, Ea)

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Temperature
• At a lower temperature, no. of collisions
is lower because the particles are moving
more slowly.
• When a collision occurs, there is less
chance of a reaction taking place because
the movement energy in the
particles is less.
Temperature
• Temperature is a measure of the average
kinetic energy of the molecules.
• When average kinetic energy is
equivalent to activation energy, much
greater fraction of the molecules
successfully react when they collide.
Catalysts
• A catalyst is a substance that speeds up
a reaction without being used up itself
• Example:
• This reaction only occurs very slowly
unless we add the compound
manganese oxide that acts as a catalyst
for this reaction. When the catalyst is
added the reaction speeds up greatly but
the manganese oxide never runs out.
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Temperature
• At a higher temperature, the no of
collisions is greater because the particles
are moving more quickly.
• When a collision occurs, there is more
chance of a reaction taking place because
the movement energy in the particles is
greater.
• The higher the temperature, the higher the
average kinetic energy.
K.E = ½ mv2
Pressure
• If the substances involved
in the reaction are gases,
pressure will have an
effect on reaction rate.
• Gases are readily
compressible, so pressure
acts as a kind of
"concentration" for gases.
• Boyle's law that the
pressure ↑ as the volume
of a gas ↓
Catalysts
• How does a catalyst work?
1) A catalyst provides a surface on which
the reaction can take place.
This increases no. of collisions between
particles of substances that are reacting.
2) A catalyst lowers the activation energy
This means that the particles can react
with less energy than they needed before
the catalyst was added. If we lower the
amount of energy needed for particles to
react, then more particles can react.
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Catalysts