Reactor Lecture 1 PDF

Dr.
Farah Talib Al-Sudani
Reactor Design Lectures

Notes
Department of Chemical Engineering
University of Technology
Third Year
.
[Introduction to Chemical Reaction Engineering ] | [Chapter-One]..University of Technology-Chemical Engineering Department-Dr.Farah Al-Sudani
1.Introduction
Chemical kinetics is the study of chemical reaction rates and reaction mechanisms. The
study of chemical reaction engineering (CRE) combines the study of chemical kinetics
with the reactors in which the reactions occur. Chemical kinetics and reactor design are
at the heart of producing almost all industrial chemicals.
It is primarily a knowledge of chemical kinetics and reactor design that distinguishes
the chemical engineer from other engineers. The selection of a reaction system that
operates in the safest and most efficient manner can be the key to the economic
success or failure of n chemical plant.
Design of the reactor is no routine matter, and many alternatives can be proposed for a
process. In searching for the optimum it is not just the cost of the reactor that must be
minimized. One design may have low reactor cost, but the materials leaving the unit
may be such that their treatment requires a much higher cost than alternative designs.
Hence, the economics of the overall process must be considered. Reactor design uses
information, knowledge, and experience from a variety of areas-thermodynamics,
chemical kinetics, fluid mechanics, heat transfer, mass transfer, and economics.
Chemical reaction engineering is the synthesis of all these factors with the aim of
properly designing a chemical reactor.
To find what a reactor is able to do we need to know the kinetics, the contacting
pattern and the performance equation. We show this schematically in Figure (1).
Figure (1). Information needed to predict what a reactor can do.

Much of this lectures deals with finding the expression to relate input to
output for various kinetics and various contacting patterns, or
output = f [input, kinetics, contacting] (1)
This is called the performance equation. Why is this important? Because with
this expression we can compare different designs and conditions, find which is
best, and then scale up to larger units.
2.Type of Reactors.
In chemical engineering, chemical reactors are vessels designed to contain chemical

reactions. The design of a chemical reactor deals with multiple aspects of chemical
engineering. Chemical engineers design reactors to maximize net present value for the
given reaction. Designers ensure that the reaction proceeds with the highest efficiency
towards the desired output product, producing the highest yield of product while
requiring the least amount of money to purchase and operate. Normal operating
expenses include energy input, energy removal, raw material costs, labor, etc.
U
There are a couple main basic vessel types:

A tank
A pipe or tubular reactor (laminar flow reactor(LFR))
Both types can be used as continuous reactors or batch reactors. Most commonly,
reactors are run at steady-state, but can also be operated in a transient state. When a
reactor is first brought back into operation (after maintenance or inoperation) it would
be considered to be in a transient state, where key process variables change with time.
Both types of reactors may also accommodate one or more solids (reagents, catalyst, or
inert materials), but the reagents and products are typically liquids and gases.
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There are three main basic models used to estimate the most important process
variables of different chemical reactors:
Batch Reactor
Continuous Stirred-Tank Reactor (CSTR)
Plug Flow Reactor (PFR)
Key process variables include

Residence time () , Volume (V) , Temperature (T) , Pressure (P) , Concentrations
of chemical species (C1, C2, C3, ... Cn) ,Heat transfer coefficients (h, U)
Chemical reactions occurring in a reactor may be exothermic, meaning giving off heat,
or endothermic, meaning absorbing heat. A chemical reactor vessel may have a cooling
or heating jacket or cooling or heating coils (tubes) wrapped around the outside of its
vessel wall to cool down or heat up the contents.
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2.1 Batch Reactor

Type of Reactor
Batch Reactor
Characteristics
Reactor is charged (i.e., filled) through the holes

at the top ; while reaction is carried out.
Nothing else is put in or taken out until the
reaction is done; tank easily heated or cooled by
jacket
Kinds of
Usage
Phases Present
1. Gas phase
1. Small scale production
2.Liquid
phase
2. Intermediate or one
shot production
3.Liquid Solid
3.Testing new process

that have not been fully
developed
4.Manufacture of
expensive products.
Advantages
Disadvantages
1. High conversion per 1. High operating

unit volume for one cost
pass
2. Product quality
2.Flexibility
of more variable than
operation-same
reactor with continuous
can
produce
one operation
product one time and a
different product the 3.Difficalty
of
next
large
scale
production .
3. Easy to clean
5.Pharmaceutical,
Fermentation
4
Figure(2) simple batch reactor .
Semi-batch reactors operate much like batch reactors in that they take place in a single stirred
tank with similar equipment . It modified allow reactant addition and/or product removal in time.
A semi-batch reactor, however, allows partial filling of reactants with the flexibility of adding more
as time progresses. Semi-batch reactors are used primarily for liquid-phase reactions , two-phase
reactions in which a gas usually is bubbled continuously through the liquid , and also for
biological and polymerization reaction.
U
2.2. Continuous-Flow Reactors

2.2.1 Continuous-Stirred Tank Reactor CSTR
Type of Reactor
Characteristics
Kinds of Phases
Present
1. Gas phase
2. Liquid phase
3. Liquid Solid
Continuous-Stirred Tank Reactor CSTR
Run at steady state ,the flow rate in must equal the mass flow
rate out, otherwise the tank will overflow or go empty
(transient state).
The feed assumes a uniform composition throughout the
reactor, exit stream has the same composition as in the tank.
The reaction rate associated with the final (output)
concentration.
Reactor equipped with an impeller to ensure proper mixing.
Dividing the volume of the tank by the average volumetric flow
rate through the tank gives the residence time, or the average
amount of time a discrete quantity of reagent spends inside the
tank.
Usage
1. When agitation
is required
2. Series
configurations for
different
concentration
streams
Advantages
Disadvantages
1. Continuous operation
2. Good temperature control
3. Easily adapts to two phase
runs
4. Simplicity of construction
5.Low operating (labor) cost
6. Easy to clean
1. Lowest conversion
per unit volume, very
large reactors are
necessary to obtain
high conversions
2. By-passing and
channeling possible
with poor agitation
Some important aspects of the CSTR:
It is economically beneficial to operate several CSTRs in series. This allows, for

example, the first CSTR to operate at a higher reagent concentration and therefore a
higher reaction rate. In these cases, the sizes of the reactors may be varied in order
to minimize the total capital investment required to implement the process.
U
Figure (3) Flow sheet for the manufacture of nitrobenzene from benzene using
a cascade of CSTR
2.2.3. Tubular Reactor (PFR)
Type of Reactor
Tubular Reactor (PFR)
Characteristics
Kinds of
Phases
Present
1.
Primarily
Gas
Phase
Consists of a long cylindrical tube or many short reactors in a tube

bank.
Operated at steady state.
The rate is very high at the inlet to the PFR.
No radial variation in reaction rate (concentration) and the reactor is
referred to as a plug-fiow rcactor (PFR).
Concentration changes with length down the reactor
As the concentrations of the reagents decrease and the concentration
of the product(s) increases the reaction rate slows.
A PFR typically has a higher efficiency than a CSTR of the same
volume. That is, given the same space-time, a reaction will proceed to a
higher percentage completion in a PFR than in a CSTR.
Usage
1. Large Scale
2. Fast Reactions
3. Homogeneous Reactions
4. Heterogeneous Reactions
5. Continuous Production
6. High Temperature
Advantages
Disadvantages
1. High Conversion
per Unit Volume
1. Undesired thermal
gradients may exist
2. Low operating
(labor) cost)
2. Difficult temperature
control
3.Good heat
transfer
3. Shutdown and
cleaning may be
expensive
4.Hot spot occur for
exothermic reaction
Other types
Reactor
of
reactors:-
Catalytic
reactors(packed
bed
and
Fluidized-bed
Type of Reactor
Paced bed Reactor (fixed-bed,PBR)
Characteristics
is essentially a tubular reactor that is packed with solid

catalyst particles.
Kinds of Phases
Usage
Present
1. Gas-Soli phase
2. Liquid-Solid
Heterogeneous
phase
reaction
3. Gas-Liquid Solid
Advantages
Disadvantages
Most reaction gives

the highest conversion
per weight of catalyst
of
any
catalytic
reactor.
1. Difficulties with temperature

control.
2. Catalyst is usually troublesome to
replace
3. Channeling of the gas or liquid flow
occurs, resulting in ineffective use of
part of the reactor bed
Figure(4) Packed bed Reactors
Type of Reactor
Fluidized-bed Reactor
Characteristics
Is analogous to the CSTR in that its contents.

Heterogeneous reactor, are well mixed.
Kinds of Phases
Present
1. Gas-Solid phase
2. Liquid-Solid
phase
3. Gas-Liquid
Solid phase
Usage
1.Heterogeneous
reaction
2. reactor can
handle large
amounts of feed
and solids
Advantages
Disadvantages
1.Good mixing
2. temperature is relatively
uniform throughout
3. Catalyst can be
continuously regenerated with
the use of an auxiliary loop
4. good temperature control
1. Bed-fluid mechanics
not well known
2. Severe agitation can
result in catalyst
destruction and dust
formation
3. Uncertain scale-up
Figure(5) Fluidized-bed
Reactors
3.Classification of Chemical Reaction
it classify according to
Five traditional types of chemical reactions are
1. Decomposition reactions: single compound decomposes to two or more other
substances,decomposition of calcium carbonate by heating it.
CaCO3(s) ---> CaO(s) + CO2(g)
2. Combination reactions (Synthesis reactions)
3. Single-replacement reactions (Displacement reactions):copper displaces silver
from an aqueous solution of silver nitrate is an example of a single-replacement
reaction.
Cu(s) + 2 AgNO3(aq) ---> Cu(NO3)2(aq) + 2 Ag(s)
4. Double-replacement reactions (Metathesis reactions):Precipitation
one type of double-replacement reaction. An example is
reactions
are
AgNO3(aq) + NaCl(aq) ---> AgCl(s) + NaNO3(aq)

5. Combustion reactions:
follows.
substance reacts with oxygen,butane burns in air as
2 C4H10(g) + 13 O2(g) ---> 8 CO2(g) + 10 H2O(l)
Also Oxidation-reduction reactions (Redox reactions).

phases involved:
o Homogeneous reaction : it takes place in one phase alone
o Heterogeneous reaction : multiple phases, reaction usually occurs at the interface
between phases.
Direction of reaction
o Irreversible Reaction : Proceeds in only one direction and continues in that

direction until the reactants are exhausted.
Example :
10
Heterogeneous reaction
Toluene-hydrogenation 6 5 3() + 2() 6 6() + 4()

Homogeneous reaction
Decomposition N2O N2O (g)+2O2(g) 2 N2(g) + O2(g)
Water gas shift reaction H2O (g)+CO (g) H2(g) + CO2(g)

o Reversible Reaction : Can proceed in either direction, depending on the
concentrations of reactants and products present relative to the corresponding
equilibrium concentration.
Example :
Homogeneous reaction
Ammonia synthesis 22() + 32() 23()
Thermal cracking of ethane : 2 6() 2 4() + 2()
Heterogeneous reaction
Ammonium chloride synthesis or decomposition
3() + () 4 ()
11
12
[Reaction Rate and Conceptes of Kinetics][Chapter

Kinetics][Chapter[Chapter-Two]..University
Two]..University of TechnologyTechnology-Chemical Engineering DepartmentDepartment-Dr.Farah AlAl-Sudani
1.Reaction Rate (Rate Law , 12
In homogeneous reaction , the reaction rate (rA) is defined as the change in

moles of component A(reactant consumed) or mole of product formed with
respect to time per unit volume of reaction mixture.
In solid-catalyzed reactions, the reaction rate ( rA ) is defined as the change in
moles of component A with respect to time per unit reaction surface area or
catalyst weight.
o rA = rate of formation of A per unit volume
o -rA = rate of a disappearance of A per unit volume
Batch Reactor
%%%%
=
%%
%%%
disappear
homogeneous reaction 2a

&
',,
,
=
disappear
'(
homogeneous reaction 2b
disappear
heterogeneous reaction 2(
(' ' -,

disappear
heterogeneous or homogeneous reaction
'(
2d

disappear
heterogeneous reaction 2e
0' ' -,

= + * =.
%%
%%%
&
%%%% .3
The rate of reaction per unit weight catalyst, -rA, (e,g., -rA), and thi rate of reaction per unit
volume, -rA, , are related through the bulk density ,(mass of solid /volume) of the catalyst
particles in the fluid media:
13

Tubular Flow Reactor
34*5
..4
36
Where * is the molal rate of flow component A into the volume element.
element
Rate of reaction rA is:

o a function of concentration, temperature, pressure, and the type of
catalyst (if any)
o independent of the type of reaction system (batch, plug flow, etc.) but
on the reaction chemistry
o an algebraic equation, not a differential equation
o Rate of reaction per unit weight of catalyst and rate of reaction per unit
volume is related through the bulk density of the catalyst particle in
the fluid media
Rate of reaction rA is an intensive quantity and depended on composition
(Concentration), and the energy of the material (Temperature
Temperature) . Energy of
the material mean the temperature (random kinetic energy of the
molecules), the light intensity within the system (this may affect the bond
energy between atoms), the magnetic
magnetic field intensity, etc. Ordinarily we
only need to consider the temperature
-rA= f {temperature
temperature dependent term,concetration dependent term}
= mole/m3.time
2.Conceptes of Kinetics
1. Stoichiometry.
Consider the general reaction; aA + bB cC + dD
on a per mole of A basisi.e

basis assume A is the limiting reactant :b
c
d
A + B C + D
a
a
a
b c d
where , , the Stoichiometric Coefficients ,
a a a

14
Molecules are lost and formed by reaction , and mass conservation requires
that amounts of species are related by Stoichiometry as:b
c
1 mole of A and of B consumed , while
a
a
mole of D formed or appear
Rate of reaction or disappearance of A =
d
mole of C and
a
789:
7; .=>7:
c
789:
Rate of formation of C ? @ A = ? A ; .=>7:
7
a
789:
d
Rate of formation of D ? B A = ? A 7; .=>7:
a
@
Also, Rate of formation of C ? @ A = C3D ? B A

3
Rate of formation of D ? B A = C D ? @ A
@
Then the reaction Stoichiometry ;
E&5
F
E&G
F
&H
F
&I
F
Examples (1),(2)
********************************************************************
2. Temperature Dependent Term of a Reaction Rate Law.

Reaction Rate Contestant.
k A (T )
Kinetic (reaction) Rate law ? A gives relationship between reaction rate

and concentration (is an algebraic equation that relates ? A to species
concentrations)
= J
K '
K L
, ( L( L '
K L
789:
7; .=>7:
rA = [k A (T )] [ f (C A , C B ,K)] ..5
15
kA(T) is the reaction rate constant

Strongly
trongly dependent on temperature
Depends
epends on whether or not a catalyst is present
NOT really a constant, but f(Ci)
The rate constant is described by Arrhenius equation :-
k A (T ) = Ae E RT 6
ln (k ) = ln ( A)
E1
7
R T
A Pre-exponential
exponential factor (frequency factor)
E Activation
ctivation energy (J/mol)
R Gas
as constant (8.314 J/molK,
J/mol 1.987 cal/mol K)
T Absolute
bsolute temperature (K)
Activation Energy
Activation energy has been equated with minimum energy that must be
possessed by reacting molecules before the reaction will occur.
Heat
Absorbed
Heat
Released
16
(2.1)Activation energy for exothermic and endothermic reaction.

Figure(2.1)Activation
At the same concentration but different two temperature Activation

Energy can be estimated as :
ln (r2 ) ln(k 2 ) E 1 1
=
=
ln(r1 ) ln (k1 ) R T1 T2 8
Figure (2.2) shows temperature dependency of the reaction rate
Example
Example
(4)
(5)
=example 3.1 from elemental

engineering , 4ed pag 95
of
chemical
reaction
*********************************************************************
17

3. Concentration Dependent Term of a Reaction Rate Law.
rA = [k A (T )] [ f (C A , C B ,K)].5
f (C A , C B ,K)
One of the most common general forms of this dependence is the product of
concentrations of the individual reacting species, each of which is raised to a power .
Reaction Order.
Elementary Reaction
A reaction order for which each
Stoichiometric coefficient as shown :-
specie
is
identical
to
its
aA + bB cC + dD
rA = kC Aa C Bb
o a and b represent the reaction order with respect to the reactant
A and B respectively ,
over all reaction order( n ) = a + b
o Reaction rate constant, k

shown :-
will vary with the order of the reaction as

18

A products
Order
Zero
Rate Equation
First
rA = kC A
s-1
Second
rA = kC A2
V.mol-1.s-1
Third
rA = kC A3
( V.mol-1 )2.s-1
nth order
Units
mol.V-1.s-1
rA = k
(concentration)1-n.s-1
rA = kC An
o Another example of elementary reaction ; reversible second

order :k1
2C 6 H 6
C12 H 10 + H 2
k2
CDCH2
rB = k1 C B2
Kc
where Kc equilibrium constant
All reversible reaction rate laws must reduce to the thermodynamic

relationship relating reacting species concentrations at equilibrium.
At equilibrium, the net rate of reaction is zero for all species involved
in the reaction rie = 0
kA
2A B + C
k A
Forward rate law

Backward or reverse rate law
rA = k AC A2
rA = k AC B CC
net rate law
rA,net = rA + r A = k AC A2 + k AC B CC
rA,net = 0 = k AC A2 + k AC B CC
Equilibrium condition
Equilibrium relationship
k AC A2 = k AC B CC
k A C B CC
=
= KC
k A
C A2
2 C B CC
Rate law in term Equilibrium relationship rA = k A C A
KC
Example (6)
19
Non-Elementary Reaction
Do not
reaction
follow
the
Stoichiometric
coefficients
for
the
overall
Homogeneous Reactions :
Gas-phase synthesis of phosgene,
CO + Cl 2
COCl 2
rCO = k CO CCO CCl3 /22 n=5.5
Decomposition of nitrous oxide
2N 2O
2N 2 + O2
rN2O =
k N 2 O C N 2O
1 + k CO2
n depended on CO2 concentration
Heterogeneous Reactions :
Heterogeneous reaction and corresponding rate law is the
hydrodemethylation of toluene (T) to form benzene (B) and methane (M)
carried out over a solid catalyst.
.
C6 H 5CH3 + H 2 cat
C2 H 6 + CH4
rT =
k PH 2 PT
1 + K B PP + K T PT
k=
mol toluene
kg cat .s.kPa 2
4. Molecularly Reaction.
The term molecularity refers to number of atoms, ions, or molecules
involved in the rate-limiting step of the reaction.
Unimolecular one reactant involved in reaction
Bimolecular two reactants must collide to react
Termolecular three reactants must interact for reaction to occur

20
5. Conversion , yield and selectivity

conversion, X, is defined as the fraction (or percentage) of the more
important or limiting reactant that is consumed. With two reactants A and
B and a nearly Stoichiometric feed, conversions based on each reactant
could be calculated.
X =
mole A reacted
mole A fed
.8
yield, Y, is the amount of desired product produced relative to the amount

that would have been formed if there were no byproducts and the main
reaction went to completion
Y=
moles of product formed

maximum moles of product, x = 1.0
6. Van't Hoff Equation.

Van't Hoff equation relates equilibrium composition to temperature:
H ro d ln K eq ..10
d GRo / RT
=
=
dT
RT 2
dT
Van't Hoff equation
yield :
can be integrated from 298K to any temperature T to
H r
dT
2
298 RT
T
ln K eq = ln K 298 +
.11
Enthalpy change of reaction varies with temperature as:
H r (T ) = H ro (T298 ) + C p dT
T
T298
....12
An approximate estimate of equilibrium constant at any time , ignore the second

term in equation 12, then equation 11 became :
ln K eq = ln K 298
H r 298 1
1

R T 298
..13
For endothermic reactions, the equilibrium constant, Keq, increases with increasing
temperature. While for exothermic reactions, Keq and Xeq decreases with increasing
temperature.
21

Figure (2.3) show the variation of the concentration equilibrium constant and
equilibrium conversion as a function of temperature for an exothermic reaction.
reac
22

[Reactor Sizing and Design]

Design][Chapter[Chapter-Four]
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..University of TechnologyTechnology-Chemical Engineering DepartmentDepartment-Dr.Farah AlAl-Sudani
1. General Mole Balance Equation

Mole balance
lance on species j at any instance in time t ;
Volumn system V
rate of flow rate of generation rate of flow

rate of accumulati on
of j into system + of j in system by rxn of j out of system = of j within system
Fjo + G j Fj =
dN j
..4.1
dt
Fj0 = Entering molar flow rate of species j (mol/time)

Fj = Exiting molar flow rate of species j (mol/time)
Gj = Rate(total
(total rate) of generation(formation) of species j (mol/time)=r
(mol/time) j .V
V = Volume (e.g. m3)
rj = rate of generation(formation) of species j (mole/time.vol)
(mole/time
Nj = number of moles of species j inside the system Volume V (mole)
(
If rj varies with position in the system,
rj 6
V2
rj 4
rj 2
rj 3
rj1
V4
rj 5
V5
V6
G j ,1 = r j ,1V1
V3
i =1
i =1
G j = G j ,i = r j ,i Vi
V1
Let m , V 0
V
G j = rj dV
Then general mole balance:balance:

V
Fjo + r j dV Fj =
dN j
dt
4.2
From this general mole balance equation we can develop the design equations for
the various types of industrial reactors:
r
batch, semi-batch.
batch. and continuous-flow
continuous
reactors.
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REACTOR SIZING AND DESIGN
PART ONE
Batch Reactor
Isothermal Operation
o Operate under unsteady state

o Neither
either inflow nor outflow of reactants or products
If the reaction mixture is perfectly mixed so:
o Constant rate off reaction throughout the reactor volume
o Composition f (Position)
o Composition =f (time)
o Temperature f (Position)
o Temperature f (time)
ideal restrictions
Mole Balance
F j ,o = F j = 0
V
Fjo + rj dV Fj =
V
r j dV =
dN j
dN j
dt
...............................4.3
dt

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r jV =
dN j
..4.4
dt
Let's consider the isomerization of species A in a batch reactor
A B
As the reaction proceeds. the number of moles of A decreases and the number of
moles of B increases, as shown in Figure below
The time t necessary to reduce the initial number of moles NAo to a final number
of mole NA can be estimated as :
from equation 4.4
dN A
rAV = 4.4
dt
dt =
dN A
rAV
integrating with limits that at :

t = 0 NA = NA0 stat of reaction and at
t = t NA = NA
reaction time (end of reaction ) we obtain
N A0
t=
NA
dN A
rAV
..4.5
moles of A
moles of A
reacted or consumed = initially fed moles of A reacted

moles of A fed
at t = 0
moles of A
reacted or consumed = [N ] [ X ]
A0

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number of mole NA remain un-reacted after time t ,
moles of A
in reacter (remain) at
time t
moles of A
moles of A

= initially fed to reacted or consumed

the reactor at t = 0
[N A ] = [N A0 ] [N A0 ] [X ]
N A = N Ao (1 X )
X=
N Ao N A
N Ao
dN A
= rAV
dt
N Ao
Sub in equation 4.5 and 4.4
dX
= rAV
dt
N A = N Ao (1 X )
N A0
t=
NA
.4.6
Differential form
Batch Reactor Design Equation
m
dN A
r AV
t = N Ao
X (t )
dX
rAV
4.7
Integral form
Used in the Interpretation of
Lab Rate Data
Space time or Mean Residence Time= is the time necessary to process one reactor
mmmmmmmmmmmmmmmmmmm volume of fluid based on entrance conditions.
t B =t +t D

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At constant volume batch reactor

i.e constant density reaction mixture.
N
NAo = CAo * V then; equations 4.4 and 4.5 become ( Ci = i ) :
V
dC A
dt
rA =
dC A
..4.8.(Reaction Time)
C Ao r
A
t=
CA
Evaluation of Reaction Time Graphically:
From equation 4.7 plot

vs. X and evaluate the area under the curve
r
A
to estimate reaction time
1
rA
t = N Ao
X (t )
dX
rAV
Area
X
X1
t=
N Ao
* Area
V
Or
1
From equation 4.7 plot
vs. CA and evaluate the area under the curve
rA
to estimate reaction time
dC A
C Ao r
A
t=
1
rA
t = Area
Area
CA
CA
CA
CAo
Example

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Evaluation of Reaction Time Numerically:

Need rA = f (C A )
to size reactors or calculate reaction time
o For the reactions in which the rate depends only on the concentration of
one species then rA = f (CA)
First order and Irreversible :-
A B
rA = kC A
dC A
1 C A dC A
=
C Ao kC
k C Ao C A
A
t=
CA
1 C
t = . ln A
k C Ao
C A = C Ao e kt
Second order and Irreversible :-
A B
rA = kC A2
dC A
1 C A dC A
=
C Ao kC 2
k C Ao C A2
A
t=
CA
1 1
1
t =
k C A C Ao
CA =
C Ao
1 + C Ao kt
nth order and Irreversible :-
A B
kt =
rA = kC An
1
n +1
C An +1 C Ao
n +1
C A = C Ao 1 + (n 1)kC
1
n +1 1 n
Ao
Example
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Bimolecular Reactions
o when the rate law depends on more than one species , we must relate the
concentrations of the different species to eac2h other "as a function of
conversion rA = f ( X ) ". This relationship is most easily established with
the aid of a Stoichiometric table.
In formulating our stoichiornetsic table, we shall take species A component as
our basis of calculation (i.e.. limiting reactant) and then divide through by the
stoichiometric coefficient of A , in order to put everything on a basis of "pet mole
of A ".
Stoichiornetsic table presents the following information
o Column I: the particular species
o Column 2: the number of moles of each species initially present
o Column 3: the change in the number of moles brought about by reaction
o Column 4: the number of moles remaining in the system at time t
o Column 5: concentrations as a function of conversion of each species
Consider the general reaction;
Stoichiometry set up of equations with A as basis
b
c
d
A + B C + D
a
a
a
The rate law is :
a b CCc C Dd
rA = k A C AC B
K
C

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Constant Volume (Constant Density) V = V0

liquid-phase and some of gas phase reaction system fall into this category.
Stoichiometric Table Batch System
Specie
Initial
Change
NAo
NBo = NAo B
-(b/a)NAo X
NB = NAo[
B (b/a)X]
NCo = NAo C
+(c/a)NAo X
NC = NAo[
C +(c/a)X]
NDo = NAo D
+(d/a)NAo X
ND = NAo[
D +(d/a)X]
-NAo X
Remaining
NI = NAo
NA = NAo(1 X)
NI = NAo I
NTo = NAo i
Concentration
C A = C A 0 (1 X )
X
a
CC = C A0 C + X
a
C D = C A0 D + X
a
CIo
C B = C A0 B
NT = NTo +
NAoX
Where
i = Nio/NAo = Cio/CAo= yio/yAo

= (d/a) + (c/a) (b/a) - 1
Express table in terms of concentrations
Concentration (batch):
Ci =
Ni
V
CA =
N A N A0 (1 X )
=
= C A0 (1 X )
V
V0
CB =
N B N A0
b
b
=
B X = C A0 B X
V
V0
a
a
N D N A0
c
c
=
C + X = C A0 C + X
V
V0
a
a
N
N
d
d
C D = D = A0 D + X = C A0 D + X
V
V0
a
a
CC =
Mole balance equation and the rate law are coupled and then solved
Example
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Variable Volume (Variable Density, but with Constant T and P )

Individual concentration can be determined by expressing the volume for
batch system as a function of conversion using the equation of state:
PV=ZNTRT..at any time in the reaction

PoVo=ZoNToRToat any time =0;when reaction is initiated
Then,
N
V = V0 T
NT 0
T0
P0
Z 0
.4.9
Change in the total number of moles during reaction in gas phase reaction system,
but with constant temperature and pressure, and the compressibility factor will not
change significantly during the course of the reaction ,
N
V = V0 T
NT 0
Where
NT = NTo +
NAoX
= (d/a) + (c/a) (b/a) 1

= (change in total number of mole) / (mole of A reacted)
N
NT
= 1+ Ao X
NT 0
NT 0
y Ao =
N Ao
NT 0
N Ao
= y Ao 4.10a.
NT 0
Then
NT
= 1 + X
NT 0
N T N To
..4.10b
NT 0 X

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At complete conversion i.e X=1 , NT= NTf ; therefore ,
N Tf N To
NT 0
.4.11
= (change in total number of mole for complete conversion ) / (total moles fed)
Then the volume as a function of conversion :
V = V0 (1 + X ) .4.12
Concentration at variable volume or density
Specie
N
CA = A
V
N A0 (1 X )
V
N
CB = B
V
N B 0 ( B - (b/a) X )
V
N
CC = C
V
N Co ( C + (c/a) X )
V
N
CD = D
V
N D 0 ( D - (d/a) X )
V
N
CI = I
V
N Ao I
V
C A0 (1 X )
(1 + X )
N B0 ( B - (b/a)X )
Vo (1 + X )
C B 0 ( B - (b/a) X )
(1 + X )
N Co ( C + (c/a) X )
Vo (1 + X )
CCo ( C + (c/a)X )
(1 + X )
C D 0 ( D - (d/a)X )
(1 + X )
N A0 (1 X )
Vo (1 + X )
N D 0 ( D - (d/a)X )
Vo (1 + X )
N Ao I
Vo (1 + X )
C Ao I
(1 + X )
Example

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Non-Isothermal Operation
Chemical reactors can liberate or absorb very large amounts of energy , and the handling of
this energy is a major concern in reaction engineering. It is important to estimate the
temperature increase or decrease in an adiabatic reactor in which no heat is add or
removed, and exothermic reactor and also the composition of the reaction mixture at any
time.
Energy Balance
Heat Generated by
Reaction
H r (T ) (rAV )
Heat Addition and

Removal by wall
Q& = UA(Ta T )
Heat Accumulated by
Reaction
dT
V C p,i Ci
dt
T = reaction temperature K
Ta= wall temperature K
TR= reference temperature K
A = heat transfer area m2
Cpi = specific heat KJ/Kmol
U = overall heat transfer KJ/s.m2.K
H r =enthalpy change in the reaction per mole of Areacting
The number of moles of species i at any X is =
Then energy balance is :
N i = N A0 ( i + i X )
dT
H r (T ) ( rAV ) + UA(Ta T ) = C p ,i N i
dt
H r (T ) ( rAV ) + UA(Ta T ) = N A 0 ( i C p ,i + CpX )
dT
dt
.4.13
Energy and mole balance equations with the rate law are coupled and then solved

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Mole balance equation
N Ao
dX
= r AV
dt
H r is calculated as
T
H r (T ) = H ro (TR ) + C p dT
TR
The rate law is required as a function of temperature and composition

Variable Volume (Variable Density ,T and/or P)
"Variable T in non-isothermal"
The volume for batch system as a function of conversion as :-
N
V = V0 T
NT 0
T0
P0
Z 0
T P
V = V0 (1 + X ) 0
T0 P
Z 0
If the compressibility factor will not change significantly during the course of the
reaction Zo=Z
T P
V = V0 (1 + X ) 0
T0 P
Concentration at variable volume (density , T and/or P )
Specie
N
CA = A
V
N A0 (1 X )
V
N A 0 (1 X ) To
V o (1 + X ) T
N
CB = B
V
N B 0 ( B - (b/a) X )
V
N B 0 ( B - (b/a) X ) To
Vo (1 + X )
T
Po
C B 0 ( B - (b/a) X ) To
(1 + X )
T
Po
N
CC = C
V
N Co ( C + (c/a) X )
V
N Co ( C + (c/a) X ) To
V o (1 + X )
T
Po
C Co ( C + (c/a) X ) To
(1 + X )
T
Po
N
CD = D
V
N D 0 ( D - (d/a) X )
V
N D 0 ( D - (d/a) X ) To
V o (1 + X )
T
Po
C D 0 ( D - (d/a) X ) To
(1 + X )
T
Po
N
CI = I
V
N Ao I
V
N Ao I To
V o (1 + X ) T
Po
Po
C A0 (1 X ) To
(1 + X ) T
C Ao I To
(1 + X ) T
Po
Po
Example
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Adiabatic Operation of a Batch Reactor
A batch reactor is usually well mixed, so that may neglect the special variation in
temperature and species concentration .
Batch reactors operated adiabatically are often used to determine the reaction
orders, activation energies, and specific reaction rates of exothermic reactions by
monitoring the temperature-time trajectories for different initial conditions.
In adiabatic operation of a batch reactor Q& = 0
H r (T ) ( rAV ) = (C p ,i N i )
dT
dt
H r (T ) ( rAV ) = N A0 ( i C p ,i + CpX )
dT
dt
.4.14
Energy and mole balance equations with the rate law are coupled and then
solved:
C
X =
i
p ,i
(T To )
H r (T )
T = To +
H r (T )X
i C p,i + CpX
;Where To = initial temperature
Example

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Equilibrium Conversion
The highest conversion that can be achieved in reversible reactions is the
equilibrium conversion XEB. For endothermic reactions, the equilibrium
conversion increases with increasing temperature up to a maximum of 1.0.
For exothermic reactions, the equilibrium conversion decreases with increasing
temperature
Figure ( ) show the variation of the concentration equilibrium constant as a
function of temperature for an exothermic reaction the corresponding equilibrium
conversion XEB as a function of temperature.
Figure ( ) show the variation of the concentration equilibrium constant and

equilibrium conversion as a function of temperature for an exothermic reaction.
To determine the maximum conversion that can be achieved in an exothermic
reaction carried out adiabatically, we find the intersection of the equilibrium
conversion as a function of temperature ,with temperature conversion
relationships from the energy balance
X EB =
C
i
p ,i
(T To )
..4.15
H r (T )
Graphical solution of equilibriurn

and energy balance equations to
obtain the adiabatic temperature
and the adiabatic equilibriurn
conversion XEB.
Example
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Reactor Lecture 1 PDF

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Dr.

Farah Talib Al-Sudani

Reactor Design Lectures

Figure (1). Information needed to predict what a reactor can do.

In chemical engineering, chemical reactors are vessels designed to contain chemical

There are a couple main basic vessel types:

Continuous Stirred-Tank Reactor (CSTR)

Plug Flow Reactor (PFR)

Key process variables include

[Introduction to Chemical Reaction Engineering ] | [Chapter-One]..University of Technology-Chemical Engineering Department-Dr.Farah Al-Sudani

2.1 Batch Reactor

Reactor is charged (i.e., filled) through the holes

3.Testing new process

1. High conversion per 1. High operating

[Introduction to Chemical Reaction Engineering ] | [Chapter-One]..University of Technology-Chemical Engineering Department-Dr.Farah Al-Sudani

2.2. Continuous-Flow Reactors

Continuous-Stirred Tank Reactor CSTR

[Introduction to Chemical Reaction Engineering ] | [Chapter-One]..University of Technology-Chemical Engineering Department-Dr.Farah Al-Sudani

Some important aspects of the CSTR:

It is economically beneficial to operate several CSTRs in series. This allows, for

[Introduction to Chemical Reaction Engineering ] | [Chapter-One]..University of Technology-Chemical Engineering Department-Dr.Farah Al-Sudani

2.2.3. Tubular Reactor (PFR)

Tubular Reactor (PFR)

Consists of a long cylindrical tube or many short reactors in a tube

[Introduction to Chemical Reaction Engineering ] | [Chapter-One]..University of Technology-Chemical Engineering Department-Dr.Farah Al-Sudani

Paced bed Reactor (fixed-bed,PBR)

is essentially a tubular reactor that is packed with solid

Most reaction gives

1. Difficulties with temperature

Figure(4) Packed bed Reactors

[Introduction to Chemical Reaction Engineering ] | [Chapter-One]..University of Technology-Chemical Engineering Department-Dr.Farah Al-Sudani

Is analogous to the CSTR in that its contents.

[Introduction to Chemical Reaction Engineering ] | [Chapter-One]..University of Technology-Chemical Engineering Department-Dr.Farah Al-Sudani

3.Classification of Chemical Reaction

AgNO3(aq) + NaCl(aq) ---> AgCl(s) + NaNO3(aq)

substance reacts with oxygen,butane burns in air as

2 C4H10(g) + 13 O2(g) ---> 8 CO2(g) + 10 H2O(l)

Also Oxidation-reduction reactions (Redox reactions).

o Irreversible Reaction : Proceeds in only one direction and continues in that

Toluene-hydrogenation 6 5 3() + 2() 6 6() + 4()

Water gas shift reaction H2O (g)+CO (g) H2(g) + CO2(g)

Thermal cracking of ethane : 2 6() 2 4() + 2()

[Introduction to Chemical Reaction Engineering ] | [Chapter-One]..University of Technology-Chemical Engineering Department-Dr.Farah Al-Sudani

[Reaction Rate and Conceptes of Kinetics][Chapter

1.Reaction Rate (Rate Law , 12

In homogeneous reaction , the reaction rate (rA) is defined as the change in

[Reaction Rate and Conceptes of Kinetics][Chapter

Tubular Flow Reactor

Rate of reaction rA is:

Consider the general reaction; aA + bB cC + dD

on a per mole of A basisi.e

[Reaction Rate and Conceptes of Kinetics][Chapter

Rate of reaction or disappearance of A =

Also, Rate of formation of C ? @ A = C3D ? B A

Then the reaction Stoichiometry ;

2. Temperature Dependent Term of a Reaction Rate Law.

Kinetic (reaction) Rate law ? A gives relationship between reaction rate

kA(T) is the reaction rate constant

The rate constant is described by Arrhenius equation :-

(2.1)Activation energy for exothermic and endothermic reaction.

At the same concentration but different two temperature Activation

Figure (2.2) shows temperature dependency of the reaction rate

=example 3.1 from elemental