CHE594

Chemical Reaction Engineering

TOPIC 1

INTRODUCTION

SITI WAHIDAH BINTI PUASA

PHONE NO: 03-55436327
011-32338927
Reference: Fogler 4th Edition, Levenspeil
3rd Edition

CHE594: CHEMICAL REACTION ENGINEERING

CHEMICAL
REACTION??

CHE594: CHEMICAL REACTION ENGINEERING

A process in which at least one new

substance is produced as a result of
chemical change
The
change
of
a
substance into a new
substance which has
new/different chemical
identity

CHE594: CHEMICAL REACTION ENGINEERING

Reaction occurred.
How??

Color change
Formation of a solid (precipitate) within
a clear solution
Evidence of a gas
Evolution or absorption of heat

CHE594: CHEMICAL REACTION ENGINEERING

Reaction type??
Combination reaction A + B AB
Decomposition reactions AB A + B

Displacement reactions

AB + C AC + B

Metathesis reactions (double-replacement reactions)

AB + CD AD + CB
Combustion reactions reaction with oxygen

CHE594: CHEMICAL REACTION ENGINEERING

A component/species can lose its chemical

identity. HOW??
Decomposition
Molecule is broken down into smaller
molecules, atoms, fragment

Combination
Molecule/atom to combine with other
molecule/atom
Benzene react with propylene to form
cumene
Isomerization
Molecules change in configuration
i.e.

CHE594: CHEMICAL REACTION ENGINEERING

In industrial chemical process, the typical

situation of chemical process is shown
below:

CHE594: CHEMICAL REACTION ENGINEERING

Based on unit volume

of reacting fluid
Based on unit mass of
solid
in
fluid-solid
system
Based
on
unit
interfacial surface in
two-fluid systems or
based on unit surface
of solid in gas-solid
systems
CHE594: CHEMICAL REACTION ENGINEERING

Based on unit volume of

solid in gas-solid systems

Based on unit volume of

reactor, if different from
the rate based on unit
volume of fluid

CHE594: CHEMICAL REACTION ENGINEERING

Defined as speed of reactions

Some reactions can
treatment plants

be

very,

very

slow

i.e.

Sewage

Some reactions can be very, very fast i.e. Reactions in

rocket engines
The rate of a reaction can be expressed
as the rate of disappearance of a
reactant or as the rate of appearance
of a product

CHE594: CHEMICAL REACTION ENGINEERING

CHE594: CHEMICAL REACTION ENGINEERING

CONCENTRATION
OVER TIME

RATE LAW/
RATE OF EQUATION

CHE594: CHEMICAL REACTION ENGINEERING

Reaction rate is defined as changes in concentration

over time

dCi
rate Unit SI is mol L-1s-1
dt

Reaction rate can be quantified

in
terms
of
disappearing
reactant or appearing product

CHE594: CHEMICAL REACTION ENGINEERING

aA +bB cC + dD
For relative rate of reactions, various species that involved in
reaction can be obtained from stoichiometric coefficient:

rA rB rC rD

a
b
c
d

CHE594: CHEMICAL REACTION ENGINEERING

Consider this reaction..

A+ 2B C + D
4 moles of A reacted with 8 moles of B to produce 4
moles of C and 4 moles of D

CHE594: CHEMICAL REACTION ENGINEERING

The rate of equation/ the rate law is an algebraic equation

that depends on reacting materials and reaction conditions.
It is independent of the type of reactor (batch or
continuous).

k is rate constant which is temperature dependent.

CHE594: CHEMICAL REACTION ENGINEERING

CHE594: CHEMICAL REACTION ENGINEERING

HOMOGENEOUS

HETEROGENEOUS

CHE594: CHEMICAL REACTION ENGINEERING

Homogeneous reaction is a reaction that

take place in one phase alone. i.e.
reaction between 2 gases, 2 liquids, 2
solids

Heterogeneous reaction is a reaction

that that requires the presence of at
least 2 phases (or more) to proceed at
certain reaction rate. i.e. reaction
between gas and liquid, gas and solid,
liquid and solid

CHE594: CHEMICAL REACTION ENGINEERING

Variable factors that affect rate of reaction..

In
homogeneous
systems
the
temperature,
pressure,
and
composition are obvious variables
In heterogeneous, the problem
becomes more complex. Material
may have to move from phase to
phase during reaction; hence, the
rate of mass transfer can become
important

CHE594: CHEMICAL REACTION ENGINEERING

CHE594: CHEMICAL REACTION ENGINEERING

ELEMENTARY

NONELEMENTARY

CHE594: CHEMICAL REACTION ENGINEERING

Elementary reactions: the rate of equation corresponds to a

stoichiometric coefficients

H2+I22HI
-rH2=k[H2][I2]
Consider a single reaction with stoichiometric equation:

A+ B R
The rate of disappearance of A is given by
-rA = kCA CB

Such reaction is called ELEMENTARY REACTION

CHE594: CHEMICAL REACTION ENGINEERING

Elementary reactions are often represented by an equation

showing both the molecularity and the rate constant
For example:

The rate of equation is:

CHE594: CHEMICAL REACTION ENGINEERING

Consider this reaction

Rate of equation that refers to B

Rate of equation that refers to D

Rate of equation that refers to T

CHE594: CHEMICAL REACTION ENGINEERING

Non-elementary reactions: no direct correspondence between

stoichiometry and rate
When
there
is
no
direct
stoichiometry and rate, then
reactions

correspondence
between
we have non-elementary

The classical example of a non-elementary

reaction is that between hydrogen and
bromine,

Rate of

expression

CHE594: CHEMICAL REACTION ENGINEERING

Non-elementary reaction always involve intermediate and

multiple reactions

However, it is difficult to quantify the concentration of

intermediate since it exists only for few minutes

Types of intermediate can be grouped into

free radicals, ions and polar substances,
molecules, transition complexes, nonchain reactions and chain reactions
CHE594: CHEMICAL REACTION ENGINEERING

CHE594: CHEMICAL REACTION ENGINEERING

For many reactions, and particularly elementary reactions,

the rate expression can be written as a product of a
temperature-dependent term and a composition dependent
term, or

This is practically well presented by Arrhenius Law

k0: frequency or pre-exponential factor
E: activation energy of the reaction
T: temperature

At the same concentration,

but
at
two
different
temperatures,
Arrhenius'
law indicates that:
CHE594: CHEMICAL REACTION ENGINEERING

The temperature dependency of reactions (k) is

determined by the activation energy and temperature
level of the reaction
Example problem:
Milk is pasteurized if it is heated
to 63C for 30 min, but if it is
heated to 74C it only needs 15
s for the same result. Find the
activation
energy
of
this
sterilization process.

CHE594: CHEMICAL REACTION ENGINEERING

Consistent unit!!

Change temp. in
Kelvin

Insert EQ. 1
and 2

CHE594: CHEMICAL REACTION ENGINEERING

1 dN A
V dt
dN A rAVdt
rA
NA

dN
A

rA1
t

N A 1
rA

V
t
1
rA C A0 C A
t

A0

t1
2

A0

CA

t1

Same result = same final concentration

N A0 rAVt

A0

CA

rAV dt

N A0

rA2

1
C A0 C A
rA2
t2

1
rA1
C A0 C A
t1
rA2
rA1

t1
t2

CHE594: CHEMICAL REACTION ENGINEERING

 rA kCA
k k0e

rA2

k 2 k0 e RT2

rA1 k1 k e E RT1
0

RT

For same final concentration

rA2
rA1
rA2
rA1

k 2C A
k1C A

k2
k1

rA2
ln
rA
1

rA2
ln
rA
1

RT2

E RT2 E RT1
e

ln

E RT1 ln e

ln e
E
E
RT2
RT1

rA2
ln
rA
1

E 1 1

R T1 T2

CHE594: CHEMICAL REACTION ENGINEERING

CHE594: CHEMICAL REACTION ENGINEERING