What is Chemical Reaction Engineering?

Chemical reaction engineering (CRE) is the

discipline that
in relating reactor performance to
operating conditions and feed variables.

 deals with how fast a reaction proceeds (reaction

rates)
deals with mechanism of reaction,
deals with the effects of P,T, composition and
catalysts on reaction rates

deals with size of reactor

deals with type/configuration of reactor
involves consideration of heat and mass transfer.

 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

Homogeneous vs Heterogeneous Reactions

reactions that occur in a
single phase (gas or liquid)
NOx formation
NO (g) + O2 (g) NO2 (g)
Ethylene Production
C2H6 (g) C2H4 (g) + H2 (g)

reactions that require the

presence of two distinct phases
Coal combustion

C (s) + O2 (g) CO2 (g)

SO3(for sulphuric acid production)
SO2 (g) + 1/2 O2 (g) SO3 (g)
Vanadium catalyst (s)

The reaction rate is the rate at which a species looses its

chemical identity per unit volume.
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. Consider species A: (rA; -rA; -rA)

rA

= the rate of formation of species A per unit volume

-rA

= the rate of a disappearance of species A per unit v

volume

-rA

= the rate of disappearance of species A on a per

mass of catalyst basis- for a catalytic reaction

Consider species j:
rj is the rate of formation of species j per unit volume. It is the
number of moles of species j generated per unit volume per unit
time.
rj is a function of concentration, temperature, pressure, and the
type of catalyst (if any)

rj is independent of the type of reaction system (batch, plug flow,

etc.)
rj can be also be function of position and can very from point to
point

 Continuous-Stirred Tank Reactor (CSTR)

Plug Flow Reactor (PFR)
Packed Bed Reactor (PBR)

Membrane Reactor
Fluidized Bed Reactor

, the typical
situation of chemical process is shown below:

Batch Reactor
mainly used for small
scale operation
suitable for slow reactions
mainly used for liquidphase reaction
charge-in/clean-up times
can be large

CSTR
steady state operation;
used in series
good mixing leads to
uniform concentration and
temperature
mainly used for liquid
phase reaction
suitable for viscous liquids

PFR
suitable for fast
reaction
gas phase reaction
temperature control is
difficult
there are no moving
parts
CHARACTERISTICS OF COMMON REACTOR

F jO

Fj

+
Gj

Gj

dN j
dt

=
Fj

FjO

Control Volume = V
Gj

= (rate of formation of j) V
= (rj)V

Differential
Equation

Batch

dN j
(rj )V
dt

dF j
dV

PBR

Integral
Equation

Nj

N jO

dN j
(rj )V

Fjo Fj
V
(rj )

CSTR
PFR

Algebraic
Equation

dFj
rj '
dW

Conc. changes with time

but is uniform within the
reactor. Reaction rate
varies with time.
Conc. inside the reactor is
uniform. rj is constant.
Exit conc = conc inside
reactor.

Fj

rj

Remarks

(r )

F jO

dF j

Fj

F jO

dFj
(rj ' )

Concentration and hence

reaction rates vary
spatially.

 The rate of equation/ the rate law is an

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

k is rate constant which is temperature dependent

the rate of equation corresponds to a

stoichiometric equations
H2+I22HI

-rH2=k[H2][I2]

Consider a single reaction with stoichiometric equation

The rate of disappearance of A is given by

Such reaction is called elementary reaction

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

 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

A non-elementary reaction is one

whose stoichiometry does not
match its kinetics. For example,

reaction always involve

However, it is difficult to quantify the concentration of
intermediate since it exists only for few minutes.

Types of intermediate can be grouped into

 Simply put, reaction rates can be defined as speed of reactions.

Some reactions can be very,
i.e. Sewage treatment plants
Some reactions can be very,
i.e. Reactions in rocket engines
The rate of a reaction can be expressed as the rate of
of a reactant or as the rate of
of a product

 The rate of a reaction can be expressed

as the rate of
of a reactant
as the rate of
of a product

Reaction rate is defined as changes in concentration over

time

Unit SI is mol L-1s-1

dCi
rate
dt

Reaction rate can be quantified in terms of disappearing

reactant or appearing product.

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

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

 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

based on unit mass of solid in fluid-solid systems

(EQ 4)

(EQ 5)

 based

on unit interfacial surface in two-fluid systems or

based on unit surface of solid in gas-solid systems

based on unit volume of solid in gas-solid systems

(EQ 6)

based on unit volume of reactor, if different from the

rate based on unit volume of fluid
(EQ 7)

(EQ 8)

In
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
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 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 reaction

 Testing of kinetic models

What is the possible reaction mechanism?

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

The temperature dependency of reactions is

determined by the activation energy and temperature
level of the reaction, as illustrated

These findings are summarized as follows:

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 temperaturesensitive; reactions with low activation energies are relatively
temperature-insensitive.

3.

k0 does not affect the temperature sensitivity.

Example 1
Milk is pasteurized if it is heated to 63oC 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.

Example 2
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.

Example 2
A human being (75 kg) consumes about 6000 kJ of food per day.
Assume that the food is all glucose and that the overall reaction is

Find man's metabolic rate (the rate of living, loving, and laughing) in
terms of moles of oxygen used per m3 of person per second.