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INTRODUCTION TO CHEMICAL

REACTION ENGINEERING AND


REACTION KINETICS

Dr Norhidayah Ideris
Level 6, Thermodynamic Lab
019-470 1439
Acknowledgement:
1. Norashikin Ahmad Zamanhuri
2. Norhasyimi Rahmat

What is Chemical Reaction Engineering?


Chemical reaction engineering (CRE) is the
discipline that quantifies the interactions
of transport phenomena and reaction
kinetics in relating reactor performance to
operating conditions and feed variables.

Expectation in Learning CRE


Chemical Kinetics
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
Reactor Design
deals with size of reactor
deals with type/configuration of reactor
involves consideration of heat and mass transfer.

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

Homogeneous vs Heterogeneous Reactions


Homogeneous 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)

Heterogeneous Reactions: 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)

Reaction Rate
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

Characteristics
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

Common Industrial & Lab Reactors


Batch Reactor
Flow Reactor
Continuous-Stirred Tank Reactor (CSTR)
Plug Flow Reactor (PFR)
Packed Bed Reactor (PBR)
Other Reactor Types
Membrane Reactor
Fluidized Bed Reactor

In industrial chemical process, the


typical situation of chemical process is
shown below:

Batch Reactor
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

Continuous-Stirred Tank Reactor

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

Tubular Reactor/Plug Flow Reactor


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

General Mole Balance Equation (GMBE)


INPUT Rate - OUTPUT Rate + Rate of GENERATION =
Rate of ACCUMULATION

F jO

Fj

+
Gj

Gj

dN j
dt

=
Fj

FjO
Control Volume = V
Gj = (rate of formation of j) V
= (rj)V

GMBE for Major Types of Reactors


Differential
Equation

Batch

dN j
(rj )V
dt

PBR

Integral
Equation

Nj

N jO

dN j
(rj )V

Fjo Fj
V
( rj )

CSTR
PFR

Algebraic
Equation

dF j
dV

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.

Rate of Equation
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]

sider a single[Ireaction
with stoichiometric equation
2]

e 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,

hich 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,

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

efinition of Reaction Rat


Simply put, reaction rates can be 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

efinition of Reaction Rat


The rate of a reaction can be expressed
as the rate of disappearance of a reactant
as the rate of appearance 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

Consider this reaction:


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

(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)

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)

olecularity or Order of Reactio


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

Kinetics Model for


Non-elementary Reactio
Testing of kinetic models

What is the possible reaction mechanism?

emperature Dependent Ter


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

Activation Energy and Temperature Dependency

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.

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