CHAPTER 1

INTRODUCTION TO
CHEMICAL REACTION
ENGINEERING

Prepared by:
SHAM 1
CONTENTS

 Classification of reaction

 Definition of reaction rate

 Elementary and non- elementary reactions
 Molecularity and order of reaction

 Temperature term of rate equation

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COURSE LEARNING OUTCOMES

Solve problems related to

Classify type of reactions temperature dependant equation,
Arrhenius’ Law

1 3

Define the reaction rate

CHEMICAL REACTION ENGINEERING (CRE)

• Study on the chemical kinetics with the reactor in which the

rxns occur.
• Chemical kinetics; tells how long it will take to achieve a
specified level of conversion and what products will be formed.
• Chemical reactors are the heart of the majority of industrial
chemical plant
• Operation in the safest and most efficient manner is the key to
the economic success or failure of a chemical plant.

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Typical Chemical Process
RAW MATERIAL

SEPARATOR

REACTOR

SEPARATOR

PRODUCT 5
Five Aspects Involved in Reactor Design

Mass
Transfer Fluid
Heat Mechanics
Transfer

REACTANT(S) PRODUCT
REACTOR

Reaction
Thermodynamics
Kinetics
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EXAMPLE OF CRE APPLICATION

Figure 1.1 : Gas-Liquid CSTR (left); batch reactor (right) 7

Figure 1.3 : Shell Cat-Cracker (left); All-riser Cracking FCC Unit (right)
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Catalytic Converter
• Reduce CO, NO gasses and unburned fuel.

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1.1 CLASSIFICATION OF REACTIONS
1.1.1 Types of Reactions
a. Homogenous and Heterogeneous
• Homogeneous » rxn which involve in one phase.
• Heterogeneous » rxn which involve more than 1 phase
and occurs at the interface between the phases.
 Example : CO2 absorption into alkali (gas-liquid); coal combustion
and automobile exhaust purification (gas-solid); coal liquefaction and
oil hydrogenation (gas-liquid-solid).
b. Irreversible and Reversible
• Irreversible » rxn which proceed in 1 direction and
continues until the reactant are consumed.
• Example :
A  B  C 10
 • Reversible » rxn which occurs in backward direction.
(depends on concentration of rxtants and products relative
to the corresponding equilibrium concentration)
• Example :
A  B  C
c. Endothermic and Exothermic
• Endothermic » rxn that absorbs heat.
• Exothermic » rxn that releases heat.

d. Molecularity
• Molecularity of rxn » the no of atoms, ions or molecules
involved (colliding) in a rxn step.
• Terms unimolecular, bimolecular and termolecular » rxn
involved, one, two or three atoms (or molecules) interacting
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 or colliding in any rxn step.
• The common example :
i. Unimolecular : Radioactive decay

92 U 238
 90Th 234
 2 He 4

ii. Bimolecular : Involving free radicals

Br  C2 H 6  HBr  C2 H 5 
iii. Termolecular : Almost non-exist

e. Single and Multiple

• Single stoichiometric equation and single rate equation
represent the progress for single rxns. Example :

A B  C
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• More than one kinetic expression to follow the changing
composition of all the rxn components to represent the
progress for single rxns. Multiple rxns may be classified :
i. Series of rxns
A RS
ii. Parallel rxns


R A R
A competitive and side by side

 S BS
iii. Complicated scheme : rxn proceeds in parallel with
respect to B, but in series with respect to A, R and S.
A B  R
RBS 13
1.1.2 Chemical Identity
• Chemical species: chemical component or element with a
given identity.
• A chemical species is to be reacted when it has lost its
chemical identity.
• The identity of a chemical species is determined by the kind,
number, and configuration of that species atoms.
• Three ways a chemical species can lose its chemical identity :
a. Decomposition (e.g. CH 3CH 3  H 2  H 2C  CH
) 2
b. Combination (e.g. N 2  O2  2 NO
)
c. Isomerization e.g. CH 3 CH 3
CH 2  C  CH 2CH 3  CH 3C  CHCH 3

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1.2 DEFINITION OF REACTION
1.2.1 Rate of Reaction
• Example of simple reaction :

aA  bB  cC  dD
• Rate of rxn (rA) » the no. of moles of A (N) reacting/
disappearing per unit time per unit volume (V) (mol/dm3·s).
where C = concentration
1 dN j dC j (N/V = C at const. vol.)
rj   
V dt dt + if j is a product
 if j is a reactant

• -rA can describe about how fast a number of moles of one

chemical species rxn to form another species. 15
  rA  
1 dN A


amount of A disappearing ,  mol 
V dt volumetime   3 
m s

• For heterogenenous rxn, (-r’A) = the no. of moles of A reacting

per unit time per unit mass of catalyst (mol/s·g catalyst).

. 1 dN A  amount of A disappearing   mol 

rA '    , 
W dt  mass of solid time   s  g catalyst 

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1.2.2 Rate Law
• Rate equation i.e. rate law ; function of the properties of the
rxtant and rxn conditions (concentration, T or catalyst).
• However, it is independent to the type of reactor in which the
rxn is carried out.
• Commonly, the rate law is influenced by the composition
(concentration) and the energy of material for homogeneous
rxn.
• The definition for energy of material is :
i. Temperature (random kinetic energy of molecules) or
ii. Light intensity within the system (effect the bond energy btw atoms) or
iii. Magnetic field intensity.

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• However, for the heterogeneous rxn, rate law is depend to heat
and mass transfers (surface area of catalyst).
• Function of rate law :
Temperature concentration

rA   k T   fn C A , CB 

where k = specific reaction rate/ reaction rate constant

• Example 1 : A  products
• The rate law is : rA  kC A
• Example 2 : A B  P
 rA  kC 1ACB1
• The rate law is : 18
1.2.3 Order of Reaction
• The order of a rxn refers to the powers to which the
concentrations are raised in the kinetic law.
• Example : A  B  C  D
 
• The rate law : rA  kC A CB
α = order with respect to rxtant A
β = order with respect to rxtant B
n = (α + β) order of rxn

• In general :

 rA  kC C ......C ,
a
A
b
B
d
D a  b  .....  d  n
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• Example : 2 A  3B  products
Reaction is 3rd
order with respect
Reaction is 2nd order
to species B
with respect to
species A  rA  kC C 2
A
3
B

• Thus, the overall order is 2 + 3 = 5

• Rate constants, dimension of k for the nth order :

k (unit )  time  concentration 

1 1 n

• Exercise :
Unit of k = s-1(mol/dm3)1-n
Zero-order (n = 0) = ________ 1st order (n = 1) = ________
2nd order (n = 2) = _________
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1.2.4 Relative Rate of Reaction
• If the rate is known with respect to one species, the coefficients
of the balanced chemical equation can be used to find the rates
with respect to the other species.
• For rxn :
aA  bB  cC  dD
• Note : Taken A species as basis of calculation.
b c d
A  B  C  D
a a a
• Every mole of A consumed, c/a moles of C produced or formed:
 rA  rB rC rD
  
a b c d
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• Thus, rate of formation of C = c/a x (rate of disappearance of A)
rc = c/a (−rA) and so on…

• Consider the combustion of propane :

C3 H 8 ( g )  5O2 ( g )  3CO2 ( g )  4 H 2O( g )

• Compared to the rate with respect to propane :

 Rate with respect to oxygen is five times faster
 Rate with respect to carbon dioxide is three times faster
 Rate with respect to water is four times faster

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• Exercise 1.1 :
The liquid –phase rxn :

2 A  B  2C
i. Write down the relative of rxn rate.
ii. State the rate law for the above rxn.
iii. What is the rxn rate of A and B if the rate of formation of
C = 4 mol/dm3s.

1.2.5 Elementary & Non-Elementary Reaction

• The exponents in the rate law are generally unrelated to the
chemical equation’s coefficients.
• Note : Never simply assume the exponents and coefficients are
the same!
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• The exponents must be determined from the results of
experiments.
• In general, the rxn’s mechanism is the series of simple rxns
called elementary processes.
• For any rxn shows equal rxn orders of its rxtants with the
stoichiometric coefficients in its stochiometric equation
» this rxn follow elementary process.
• Thus, the rate law of an elementary process can be written
based on its stoichiometric equation.
Examples :
Stoichometric : A  2B  C  D

Rate Law : rA  kC AC 2

B
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• Non-elementary rxns is no direct correspondence btw
stoichiometry and rate » stoichiometry does not match its
kinetics.
• Examples :
Stoichometric :
H 2  Br2  2HBr
Rate Law :
k1 H 2 Br2 
1/2

rHBr 
k 2  HBr  / Br2 
• This nonmatch show a multisteps rxn model have to be
developed to explains the kinetics.

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• In order to explain the non-elementary rxn, assume the
sequence of elementary rxn is occurred but we can not
measure or observe the intermediates.
• Thus, we need to observe only the initial rxtants and final
products appear in a single rxn formed »they only present in
very minute quantities.

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1.3 TEMPERATURE DEPENDENT TERM OF A RATE EQUATION
– ARRHENIUS’S LAW
1.3.1 Parameters Affect
• For many rxns, the rate expression can be written as a
product of a temperature-dependent term and a composition
dependent term :

 rA   fn1 (T ) fn2 (C )

 rA  k (T )   fn2 (C ) 

k : determination of Determination of
activation energy rxn order
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• Rate constant (k) is strongly depend on temperature.
• Thus, for the temperature-dependent term, k , the correlated
equations are:
Temperature
dependent term
Ea
  
 rA  k (T ) C A  kC A  Ae RT
CA
1.3.2 Arrhenius’ Law
• In general, the Arrhenius equation shows "the dependence of
the rate constant, k, of chemical rxns on the temperature T
and Ea :
Ea

k (T )  A e RT

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• where: A = pre-exponent/ frequency factor
Ea = activation energy, J/mol or cal/mol
R = gas constant = 8.314 J/molK = 1.987 cal/molK T=
absolute temperature, K

• The equation known as Arrhenius’ Law » molecules need

energy to distort/ stretch their bonds so that they break them
and thus form new bonds.

E
A -no of collision

k  Ae RT
e  E / RT -probability that
the collision will
result in a reaction

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 k A T   Ae  E / RT

 Activation energy is a measure of the minimum energy that

the reacting molecules must have in order for the reaction
to occur (energy required to reach transition state).

Transition state k - no of collision that

result in a rxn

A -total no of collision
Energy barier
probability that
e  E / RT - the collision will
result in a rxn

Reactants Products
• The Arrhenius equation can be put in standard slope-intercept
form by taking the natural logarithm.
• A plot of ln k versus (1/T) gives a straight line with slope
= Ea/RT

ln k  ln A  Ea / RT or
ln k  ln A  ( Ea / R )  (1 / T )
   
y  b  m x

Figure 1.4 : Arrhenius Plot

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• Rxn with high Ea are very temperature sensitive and rxn with
low Ea are relatively temperature-insensitive.
• For any given rxn, the temperature more sensitive at low
temperature than at very high temperature.

Temp sensitive
 E ⬆, k ⬆, -r = ⬆

Temp insensitive

The larger the

activation energy,
the more
temperature
sensitive k and thus
the reaction rate. 32
• The Ea can be related to the rate constant at two temperatures :

 E  1 1  k E  1 1
k (T )  ko (T ) exp      ln    
or
 R  To T   ko R  To T 

• As a rule of thumb, for every 10°C rise in temperature causes rxn rate to
double.
• However, this is true only for a specific combination of
activation energy and temperature.
• For example, if the Ea is 53.6 kJ/mol, the rate will double only if
the temperature is raised from 300 K to 310 K.

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Exercise 1.2 :
The rate of reaction constant of a first order is 0.0025 s -1 at 298 K.
Calculate the rate of reaction constant at 350 K if the activation
energy for the reaction is 77.8 kJ/mol.

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