CHE594 CHE594

INTRODUCTION TO CHEMICAL
REACTION ENGINEERING

Chemical Reaction
Engineering
SHARMEELA MATALI
Room : PA-A11-8C
Phone Number: 03-55436328/013-2990609
For notes, browse: ilearn portal
http://i-learn.uitm.edu.my

INTRODUCTION TO CHEMICAL
REACTION ENGINEERING
WHAT IS CHEMICAL REACTION
ENGINEERING?
Chemical Reaction Engineering (CRE)
is ..
the field that studies the rates and
mechanisms of chemical reactions and
the design of the reactors in which they
take place
.
Chemical reaction engineering is the
heart of virtually every chemical process.
It separates the chemical engineer from
other engineers.

Lets begin CRE.

What is a chemical reaction?

The change of a substance into a new substance
which has new/different chemical identity

i.e acid + metal a type of salt

2HCl + 2Mg 2MgCl + H2
2HCl + 2Na 2NaCl +H2
Mg(OH)2 + 2HCl MgCl2 + 2H2O

changes in physical effect i.e. emission of heat,

formation of precipitation, colour change, etc.

Chemical reaction process

In industrial chemical process, the

typical situation of chemical process
is shown below:

Classification of reactions
Generally, chemical reactions can be classified into homogeneous and
heterogeneous reactions.
1. Homogeneous reaction is a reaction that take place in one phase
alone. i.e. reaction between 2 gases, 2 liquids, 2 solids
NOx formation
NO (g) + O2 (g) NO2 (g)
Ethylene Production
C2H6 (g) C2H4 (g) + H2 (g)

2. 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
Coal combustion
C (s) + O2 (g) CO2 (g)
SO3(for sulphuric acid production)
SO2 (g) + 1/2 O2 (g) SO3 (g)

Vanadium catalyst (s)

Classification of reactionscont.

Classification of reactionscont.

Variables 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 heat and mass transfer can become
important.
E.g.: burning of coal briquette

Chemical Identity

Chemical species refers to any compound or element

with a given identity.

The identity of a chemical species is determined by

the kind, number, and configuration of that species'
atoms.

A chemical species is said to have reacted when it has

lost its chemical identity.

Three ways a chemical species can lose its chemical

identity:

decomposition

combination

isomerization

Chemical Identity

A chemical species is said to have

reacted when it has lost its
chemical identity.
Example of reaction:
1. Decomposition
2. Combination
3. Isomerization

Reaction rate

The reaction rate is the rate at which a species

looses its chemical identity per unit volume.
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 (mol/dm3/s) can be
expressed as either
the rate of Disappearance:
or as
the rate of Formation (Generation):

-rA
rA

Reaction rate

Reaction rate

Consider the isomerization

AB

rA = the rate of formation of species A per unit volume

-rA = the rate of a disappearance of species A per unit volume
rB = the rate of formation of species B per unit volume

Reaction rate

EXAMPLE:
AB
B is being formed at a rate of:
rB = 0.2 mole/dm3/s

Then A is disappearing at the same rate:

-rA= 0.2 mole/dm3/s
The rate of formation (generation of A) is
rA= -0.2 mole/dm3/s

Reaction rate

By definition, the reaction rate is the

increase in molar concentration of a
product of a reaction per unit time.
(EQ 2)

(EQ 3)

Reaction rate

Consider this reaction

4 moles of A reacted with 8 moles of B to

produce 4 moles of C and 4 moles of D

Reaction rate

If the rate of change is in number of

moles of component i due to reaction,
, the rate of reaction in various forms can
be defined:

based on unit volume of reacting fluid

(EQ 4)

based on unit mass of solid in fluid-solid

(EQ 5)
systems

A rocket engine, Fig. El.l, burns a stoichiometric

mixture of fuel (liquid hydrogen) in oxidant (liquid
oxygen). The combustion chamber is cylindrical, 75 cm
long and 60 cm in diameter, and the combustion process
produces 108 kg/s of exhaust gases. If combustion is
complete, find the rate of reaction of hydrogen and of
oxygen.

To evaluate:
Reactor volume and volume in which reaction
takes place are identical. Thus,

H2O produced = 108 kg/s X (1 kmol/18 kg) = 6 kmol/s

Thus, H2 used = 6 kmol/s and O2 used = 3 kmol/s

Reaction rate

based on unit interfacial surface in two-fluid

systems or based on unit surface of solid in gassolid systems

(EQ 6)

based on unit volume of solid in gas-solid systems

(EQ 7)

based on unit volume of reactor, if different from

the rate based on unit volume of fluid
(EQ 8)

Reaction rate

In homogeneous systems the volume of fluid in the

reactor is often identical to the volume of reactor. In
such a case V and Vr are identical and Eqs. 4 and 8
are used interchangeably.
In heterogeneous systems all the above definitions
of reaction rate are encountered, the definition used
in any particular situation often being a matter of
convenience.
From Eqs. 4 to 8 these intensive definitions of
reaction rate are related by:

(EQ 9)

The Rate Law

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

Elementary reaction
Elementary reactions:
the rate of equation corresponds to a
stoichiometric equations
H2+I22HI
-rH2=k[H2][I2]

Consider a single reaction with stoichiometric equatio

The rate of disappearance of A is given by

Such reaction is called elementary reaction

Non-elementary reaction
Non-elementary reactions:
no direct correspondence between
stoichiometry and rate
When there is no direct correspondence between
stoichiometry and rate, then we have nonelementary reactions. The classical example of a
non-elementary reaction is that between hydrogen
and bromine,
which has a rate
expression:

Molecularity and Order of Reaction

The molecularity of an elementary reaction is the

number of molecules involved in the reaction,
and this has been found to have the values of
one, two, or occasionally three.
Note that the molecularity refers only to an
elementary reaction.
Let us say, materials A, B, . . . , D, can be
approximated by an expression of the following
type:

The molecularity
shows the power or
the order of the

Elementary reactions are often

represented by an equation
showing both the molecularity and
the rate constant. For example:
The rate of equation is:

Consider this reaction

Rate of equation that refers to B

Rate of equation that refers to D

Rate of equation that refers to T

But from stoichiometry point of view,

the equation will be

Hence,

A non-elementary reaction
is one whose stoichiometry
does not match its
kinetics. For example,

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

Kinetics Model for

Non-elementary Reaction

Testing of kinetic models

What is the possible reaction mechanism?

Temperature Dependent Term

of a Rate of Equation

Temperature dependency on Arrhenius Law

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

At the same concentration, but at two

different temperatures, Arrhenius' law
indicates that

It can be concluded that :

1.

From Arrhenius' law a plot of ln k vs 1/T gives a

straight line, with large slope for large E and
small slope for small E (slope = E/R).

2.

Reactions with high activation energies are

very temperature-sensitive; reactions with low
activation energies are relatively temperatureinsensitive.

3.

k0 does not affect the temperature sensitivity.

Activation Energy and Temperature

Dependency
The temperature dependency of
reactions is determined by the activation
energy and temperature level of the
reaction, as illustrated in Table 2.1

Milk is pasteurized if it is heated to 63 oC 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.
Answer :
Ea = 422 kJ/mol

WORK PROBLEMS: CHAPTER 1

1.1. Municipal waste water treatment plant. Consider a municipal
water treatment plant for a small community (Fig. P1.1). Waste water,
32 000 m3/day, flows through the treatment plant with a mean
residence time of 8 hr, air is bubbled through the tanks, and microbes
in the tank attack and break down the organic material

A typical entering feed has a BOD (biological oxygen demand) of 200

mg O2/liter, while the effluent has a negligible BOD. Find the rate of
reaction, or decrease in BOD in the treatment tanks.

1.3 Fluid catalytic crackers (FCC)

FCC reactors are among the largest processing units used in the
petroleum industry. Figure P1.3 shows an example of such units. A
typical unit is 4-10 m ID and 10-20 m high and contains about 50 tons
of porous catalyst ( = 800 kg/m3). It is fed about 38 000 barrels of
crude oil per day (6000 m3/day at a density = 900 kg/m3), and it
cracks these long chain hydrocarbons into shorter molecules.
To get an idea of the rate of reaction; lets suppose that the feed
consists of just C20 hydrocarbon:

If 60% of the vaporized feed is cracked in the unit, what is the rate
of reaction, expressed as r' (moles reacted/kg cat. s) and as r"'
(moles reacted/m3 cat. s)?

THE END OF
TOPIC