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 be very, very slow i.e. Sewage

treatment plants

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
 NON-
ELEMENTARY
ELEMENTARY

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 correspondence between

stoichiometry and rate, then we have non-elementary
reactions

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, non-
chain 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

rA
1 dN A
rA2
C A0 CA t1
V dt
2
dN A rAVdt
NA t
rA1 C A0 CA t1
1

dN
N A0
A rAV dt
0 Same result = same final concentration

N
N A0 rAVt
A

N A 1
N rA2

C A0 C A
1
t2

rA
A0

V t rA1
C A0 C A
1
t1

1
rA C A0 C A
t rA2 t1

rA1 t2

CHE594: CHEMICAL REACTION ENGINEERING

 E
rA kCA rA2 k 2 k0 e RT2
E

k k0e RT rA1 k1 k e E RT1
0

rA2 E
RT2
E RT2 E RT1
For same final concentration e
ln ln
E RT1 ln e


rA
e
rA2
1
k 2C A
rA2
rA1 k1C A ln E E ln e
rA RT1 RT2

rA2
1
k2

rA1 k1 rA2 E 1 1
ln
rA R T1 T2
1

CHE594: CHEMICAL REACTION ENGINEERING

CHE594: CHEMICAL REACTION ENGINEERING