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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:

• List types of chemical reactions.


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

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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Types of reaction 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

Combination Isomerization

reactant + reactant product • The molecule neither adds other


molecules to itself nor breaks into
• Two or more simple substances combine smaller molecules
to form a more complex substance • It just loses its identity through a
• Two or more reactants yielding one change in configuration
product is another way to identify a • Example:
synthesis reaction
• Example:

Rate of Reaction
The reaction rate is the rate at which a
species loses its chemical identity per
unit volume

Rate of Reaction
Can be expressed either as
1. The rate of disappearance of a
reactant
or
2. The rate of formation of a product

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Rate of Reaction Rate of Reaction


Consider species A: REACTANT PRODUCT
EXAMPLE 1
A B Given reaction as A B
• The rate of reaction, -rA is the number Therefore
of moles of A reacting (disappearing) rA = The rate of formation of species A per
per unit time per unit volume [e.g. unit volume
-rA = The rate of a disappearance of
mol/dm3.s]
species A per unit volume
rB = The rate of formation of species B per
• It is a function of concentration,
unit volume
temperature, pressure and types of -rB = The rate of disappearance of species
catalyst (if any) B per unit volume

Rate of Reaction Rate of Reaction


REACTANT PRODUCT REACTANT PRODUCT

A B A B

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

Rate of Reaction Rate of Reaction


• The Relative rates of reaction of the Consider the reaction
various species involved in a reaction can
be obtained from the stoichiometry of the
reaction. in which the rate of disappearance of A is 5 moles
aA + bB cC + dD of A per dm3 per second at the start of the
reaction. At the start of the reaction:
• The rate of reaction can be represented
by the rate of disappearance of a
1. What is -rA?
reactant [–rA or –rB] and the rate of 2. What is the rate of formation of A?
formation of a product, [rC or rD]. 3. What is -rB?
• They can be related by: 4. What is the rate of formation of B?
5. What is the rate of formation of C?
 rA  rB rC rD
   6. What is the rate of disappearance of C?
a b c d

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Rate of Reaction Rate of Reaction


1. -rA is the rate of disappearance of A 3. -rB is the rate of disappearance of B.
For every one mole of A that disappears, two
 rA  5mol / dm .s 3
moles of B disappear. Reactant B is
disappearing twice as fast as reactant A.
2. A is a reactant that is being used up therefore  rB  10 mol / dm3 .s
its rate of formation is negative

rA  5mol / dm3 .s 3. B is being used up therefore its rate of


formation is a negative number.

rB  10mol / dm3 .s

Rate of Reaction Summary


• For reactants the rate of disappearance
5. C is a product that is being formed three
times as fast as A is disappearing. is a positive (+) number.
Because C is a product is being formed, • For products the rate of disappearance is
its rate of formation is positive. a negative (-) number because they are
being formed and not disappearing.
rC  15mol / dm3 .s • For reactants the rate of formation is a
negative (-) number because they are
6. The rate of disappearance of C is -rC.
disappearing and not being formed.
Because C is a product, its rate of
disappearance, -rC, is a negative number • For products the rate of formation is a
positive (+) number.
 rC  15mol / dm3 .s

Rate Law
• The rate law or reaction rate
equation is an equation that tells us
how fast the reaction proceeds and
Rate Law 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
parameter

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Rate Law Rate Law


aA + bB  cC + dD
• The order of reaction with respect to a
• Based on Power Law Model, the certain reactant is defined, as the
reaction rate, -rA is given as power to which its concentration term
 
- rA  k(C A CB ) in the rate equation is raised.

k = specific reaction rate constant


CA and CB = concentrations of
component A and B (mol/L)
 and  = reaction orders

Rate Law Rate Law


Elementary Rate Laws vs Elementary Rate Laws vs
Non-elementary Rate Laws Non-elementary Rate Laws

A reaction follows an Elementary Rate • For NON-ELEMENTARY RATE LAW, the


Law if the REACTION ORDER of each rate equation cannot be determined by
REACTANT is identical with the looking at the stoichiometric coefficient.
stoichiometric coefficient of the reactant for
the reaction as written. • Additional information are needed from
Example: experimental works or literature to deduce
For reaction of 2NO + O2 2NO2 the rate law and the order of reaction
The rate law would be -rNO = k CNO2 CO2

Reaction rate constant Reaction rate constant


  Ea 
 
• Reaction rate constant, k determined by • At temperature T1, k ( T1 )  Ae 
RT1 

Arrhenius equation
  Ea    Ea 
  • At temperature T2,  
k  Ae  RT  k ( T2 )  Ae 
RT2 

where
Ea = activation energy (J/mol) • Taking the ratio to obtain,
R = gas constant (8.314 J/mol.K)  Ea  1 1 
T = temperature (K)     
 R  T1 T2  
A = frequency factor k 2 ( T2 )  k1( T1 )e
• Unit of k and A depends on overall reaction
order

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Reaction rate constant Reaction rate constant


• Activation energy, Ea is the minimum energy
 Ea  1  
that must be possessed by reacting
 R  T  k molecules before the reaction will occur.
 
k ( T )  Ae 

Ea  1 
ln k(T )  ln A    Slope = -Ea/R
R T ln k

1/T

Reaction rate constant Reaction rate constant

EXERCISE 1

• The initial stages of the gas phase


Reaction 2: Low Ea
reaction between ammonia and nitrogen
dioxide follow second-order kinetics.
Given that the rate constant at 600 K is
Reaction 1: High Ea 1.60 x 10-4 mol-1m3s-1 and at 716 K is 3.85
x 10-4 mol-1m3s-1. Calculate the activation
energy and the frequency factor.
1/T
(R = 8.314 J/mol.K)
k with higher Ea is more sensitive to
temperature than those with low Ea

Reaction Order

A+B  C+D -rA = k (CAaCBb )


 Based on Power Law Model, exponent of 
and  are called the REACTION ORDERS.
 The order of reaction is defined, as the
Reaction Order power to which its concentration term in the
rate equation is raised.
 Based on the equation above, the reaction is
α order with respect to reactant A, and β order
with respect to reactant B. The overall order of
the reaction, n is:
n=α+β 36

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Reaction Order Reaction Order


• Overall reaction order can be determined by
the unit of k mole mole
Reaction rate;  rA  but  conc.
vol.time vol
k  time 1 concentration 1n The reaction rate become;  rA 
conc.
• # n = order of reaction time

Reaction Order Rate Law k unit  


However;  rA  k C A C B
Zero -rA=kA mol/dm3.s
One -rA=kACA s-1 Rearrange the equation;  rA 
C
 k CA CB
t
Two -rA=kACA2 (dm)3/mol.s
Three -rA=kACA3 (dm3/mol)2.s-1 Differential equation;  rA   dC A  k CA C B 
dt

Reaction Order Reaction Order


Zero order of reaction
Rate
is
First order
dCA independent dCA dC A
• Rate law:  rA   k of the conc • Rate law:  rA    kCA   kdt
dt of reactant.
dt CA
dC A Rate
• Integrate:  CCAA0 dC A k 0t dt • Integrate:  C A
C
k 0t dt of reaction is
A0 CA proportional
to conc of 1
• 0th order: C A C A0 kt • 1st order: ln C A0  kt reactant.
CA

• Plot • Plot
m=–k C A0
ln
CA

Reaction Order Conversion


First order
dCA dC A • Conversion XA is the number of moles of
• Rate law:  rA    kCA 2   kdt
dt CA
2 a that have reacted per moles of a fed to
dC A the system:
• Integrate:  CAA0 k 0t dt
C Rate
of reaction is
CA 2 proportional XA 
moles of A reacted
1 1 to conc moles of A fed
• 2nd order:   kt squared.
CA CA 0
• For constant volume reaction system:
• Plot N AO  N A C AO  C A FAO  FA
1 XA   
N AO C AO FAO
CA

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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
Factors influence the of the substances that are reacting have to

rate of reaction
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.

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

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

Temperature Temperature
• At a lower temperature, no. of collisions • At a higher temperature, the no of
is lower because the particles are moving collisions is greater because the particles
more slowly. are moving more quickly.
• When a collision occurs, there is less • When a collision occurs, there is more
chance of a reaction taking place because chance of a reaction taking place because
the movement energy in the the movement energy in the particles is
greater.
particles is less.
• The higher the temperature, the higher the
average kinetic energy.

K.E = ½ mv2

Temperature Pressure
• Temperature is a measure of the average • If the substances involved
kinetic energy of the molecules. in the reaction are gases,
• When average kinetic energy is pressure will have an
equivalent to activation energy, much effect on reaction rate.
greater fraction of the molecules • Gases are readily
successfully react when they collide. compressible, so pressure
acts as a kind of
"concentration" for gases.
• Boyle's law that the
pressure  as the volume
of a gas 

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Catalysts Catalysts
• A catalyst is a substance that speeds up • How does a catalyst work?
a reaction without being used up itself 1) A catalyst provides a surface on which
• Example: the reaction can take place.
This increases no. of collisions between
• This reaction only occurs very slowly particles of substances that are reacting.
unless we add the compound 2) A catalyst lowers the activation energy
manganese oxide that acts as a catalyst This means that the particles can react
for this reaction. When the catalyst is with less energy than they needed before
added the reaction speeds up greatly but the catalyst was added. If we lower the
the manganese oxide never runs out. amount of energy needed for particles to
react, then more particles can react.

Catalysts

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