Cre Slides Mids

Chemical Reaction
Engineering-CHE356
Dr. Rabya Aslam

Institute of Chemical Engineering and Technology
University of the Punjab, Lahore 54590
rabya.icet@pu.edu.pk 1
July, 2021
Course contents
▪ Introduction to chemical reaction engineering

▪ Kinetics of homogeneous reactions
▪ Interpretation of reactor data for single and multiple reactions.
Integral method and differential method of analysis for constant
volume and variable volume batch reactors.
▪ Design of homogeneous reactors: Batch, Mixed flow, Plug flow
reactors, Comparison of single reactor, multiple reactor systems in
parallel/series.
▪ Design of heterogeneous reactors: Rate equations for
heterogeneous reactions. Catalyst deactivation and regeneration.
Design of fixed bed and fluidized bed catalytic reactors.
2
Course contents
Kinetics of homogeneous reactions: Rate of reaction, variables affecting
the rate of reaction, order of reaction, rate constant; searching for a
mechanism of reaction, activation energy and temperature dependency,
Interpretation of batch reactor data for single and multiple reactions.
Integral method and differential method of analysis for constant volume
and variable volume batch reactors. Search for a rate equation.
Design of homogeneous reactors: Batch, Mixed flow, Plug flow reactors,

Comparison of single reactor, multiple reactor systems in parallel/series.
Temperature and pressure effects, Adiabatic and non-adiabatic operations.
Design of heterogeneous reactors: Surface phenomenon and catalysis,

adsorption/desorption isotherms, Heterogeneous reaction systems, Rate
equations for heterogeneous reactions, Determination of rate controlling
steps. Kinetics of solid catalyzed reactions. Catalyst deactivation and
regeneration. Design of fixed bed and fluidized bed catalytic reactors.
3
Recommended books
▪ Levenspiel, O. 1999. Chemical reaction engineering. 3rd ed. Wiley
& Sons, Inc., Singapore.
▪ Fogler, H.S. 2006. Elements of chemical reaction engineering. 4th
ed. Prentice-Hall.
▪ Froment, G.F.; Bischoff, K.B.; De Wilde, J. 2011. Chemical
reactor analysis and design. 3rd ed. John Wiley & Sons, Inc.
▪ Missen, R.W.; Mims, C.A.; Saville, B.A. 1999. Introduction to
chemical reaction engineering and kinetics. John Wiley & Sons,
Inc., New York.
▪ Smith, J.M. 1981. Chemical engineering kinetics. 3rd ed. McGraw-
Hill Int. Book Co., Singapore.
4
Course objectives
The objective of this course is to give the understanding

of designing of commonly used chemical reactors. This
course will provide in-depth knowledge of the
application of laws of thermodynamics and reaction
kinetics for the economical design of chemical reactors.
Students will learn how can a chemical engineer

develop a rate expression and design an
industrial reactor.
5
Course Learning Outcomes
1. Explain chemical reaction engineering related

terminologies
2. Develop the rate equation with concentration and
time data using integral and differential methods.
3. Derive the performance equations of ideal batch and
flow reactors to size the ideal reactors
(homogeneous and heterogeneous system).
4. Evaluate the combination of reactors’ system to
minimize the volume.
6
Chemical reaction engineering
Typical chemical process
7
Reaction engineering
Chemical reaction engineering tries to answer to the
following types of questions:
▪ What are the optimum operating conditions for a reaction

system to carry out one or more desired reactions?
▪ What is the optimum reactor design, i.e., size, type,
energy considerations, and configuration of the reactor
system?
▪ Is there a need of a catalyst? If yes, how to develop and
design of an optimum industrial catalyst?
8
Catalysis and reaction engineering
Principle of
Chemical
reaction
engineering
9
What is Chemical Reaction
chemical reaction is said to be taken place when a detectable
number of molecules of one or more species have lost their
identity and assumed a new form by a change in the kind or
number of atoms in the compound and/or by a change in structure
or configuration of these atoms.
Thus a chemical reaction is responsible for a chemical change that

may be happened by any of the following processes
▪ Decomposition
▪ Combination
▪ or isomerization
In this classical approach to chemical change, it is

assumed that the total mass is neither created nor
destroyed when a chemical reaction occurs. 10
Rate of a chemical reaction
The rate of consumption of a reactant species is defined as
the change in number of moles of the reactant species per
unit volume of the reaction mixture per unit time.
Negative sign
indicates that rate is 1 𝑑𝑛𝐴 Perfectly dC=
decreasing with time (−𝑟𝐴 ) = − ⋅ mo
𝑉 𝑑𝑡 general
and required as dnA is
negative for a reactant Volume of
reaction mixture
▪ Not general
▪ Applicable when volume of the reaction mixture
dC A
(−rA ) = − is constant during the course of reaction
dt ▪ It may be true for liquid phase reactions or for
constant density gas phase reactions
The volume of a gas also changes due to changes in operating

conditions (temperature and pressure) in addition to changes in
11
number of moles
Rate of a chemical reaction
▪ The rate of a chemical reaction is usually based on the limiting
reactant
▪ On the similar basis, a rate may be defined for the formation of
a product species
▪ For the reaction:
aA + bB → cC + dD
or
(−rA ) (−rB ) rC rD
= = =
a b c d
▪ This minus sign is to show rate of consumption of a reactant

▪ It has no mathematical importance, only a symbol
12
Various definitions of rate of a
chemical reaction
Based on unit volume H
of the reaction mixture s
Based on unit mass Het

in fluid-solid system sys
Based on unit surface of solid in fluid-solid

system or unit interfacial area in two fluid systems
Based on unit volume of solid

in fluid-solid system
Based on unit volume of reactor when different

from unit volume of the reaction mixture
13
Various definitions of rate of a
chemical reaction
Rates defined on various basis are interchangeable and
the following may be shown:
14
Relative values of rates of reactions
Rates of reactions vary in a wide range. Some reaction

are very fast and some reactions are extremely slow.
15
Why are we interested in rate?
▪ A higher rate of reaction means less processing time in a
batch reactor and smaller size of reactor vessel in a
continuous flow reactor (CSTR and PFR)
▪ As the residence time is dependent upon the rate, the
knowledge of rate is required for the design of a reactor
▪ We need an expression (rate equation) that describes the
rate of a given reaction
Rate equation cannot be found reliably from the reaction

stoichiometry or by any other theoretical means and therefore
rate expressions are always to be empirical, i.e., to be
discovered through experiments.
16
Classifications of reactions
Chemical reactions may be classified in several ways
1: Based on Mechanism
A=B
▪ Reversible
▪ Irreversible
▪ Consecutive A=B=C A=B
▪ Parallel A=C
A=D
2: Based on number of molecules involved
▪ Uni-molecular
▪ Bi-molecular
▪ Termolecular
17
3: Based on Operating Conditions
▪ Isothermal
▪ Adiabatic
▪ Non-adiabatic
4: Based on Order of Reaction
▪ Zero order
▪ First order -r=kC0
-r=k
▪ Second order
▪ Third order
▪ Fractional order
18
5: Based on Phases Involved
▪ Homogeneous
▪ Heterogeneous
▪ Catalytic
▪ Non catalytic/ autocatalytic
6: Based on Heat of Reaction
▪ Exothermic
▪ Endothermic
Nearly 90% of all industrial reactions involve

heterogeneous catalysis, i.e., they are heterogeneous
as well as catalytic 19
Stoichiometric coefficient
Stoichiometric coefficient (ν) is the number appearing
before the symbol for each compound in the balanced
equation for a chemical reaction.
For the reaction
aA + bB  cC + dD
ν
C+O2=CO2
a, b, c and d are the stoichiometric coefficients.
By convention:
▪ A stoichiometric coefficient for a reactant is negative
▪ A stoichiometric coefficient for a product is positive
▪ A stoichiometric coefficient for an inert, solvent, or
catalyst is zero. 20
Extent of a reaction
It is defined as the ratio of the initial moles of a component subtracted
from the moles of the component present at any time to the
stoichiometric coefficient of the component in the reaction.
aA + bB  cC + dD ni = ni 0 + i   𝜉=
0.5−1
1
=-0.5
N2+3H2=2NH3 Fi = Fi 0 +  i   
𝜉=
𝑛𝑖 − 𝑛𝑖0 change in moles of a species
𝜈𝑖
=
stoichiometric coefficient
ξ
Fi − Fi 0 change in molar flowrate of a species
 = =
i stoichiometric coefficient
ξ extent of a reaction in terms of change in moles
ξ′ extent of a reaction in terms of change in molar flowrate
νi stoichiometric coefficient of an ith species
21
Conversion or fractional conversion
Ratio of change in moles of a reactant (usually limiting
reactant) to the moles of the reactant fed.
For a reactant A: X = n A0 − n A = FA0 − FA = 1 − C A
XA
A
n A0 FA0 C A0
nA0 = initial moles of the reactant “A”, mol; nA = moles of “A” at
any time t (s), mol
FA0 = initial molar flowrate, mol·s−1,
FA = molar flowrate of A at any time t (s), mol·s−1,
CA = Concentration at time t, mol.L-1, and CA0 is initial
concentration.
For an irreversible and single (no side reaction) reaction, an
increase in the outlet conversion is an indication of higher rate
of the reaction 22
Relationship between extent of a
reaction and fractional conversion
For reactant A: n A − n A0
=
A
n A − n A0 n  n − n A n A0 
=  A0   = − A0  

A n A0  n A0 A 
n A0 − n A
XA =
n A0
 n A0  X A n A0

 = − X A  
 =−
 A  A
23
Expansion factor
It is the fractional change in volume of the system between no

conversion and complete conversion of reactant A
V x A =1 − V x A =0
=
Vx A =0
V = V 0(1 +  .x A )
For constant density system
εA = 0 𝑉 = 𝑉0 + 𝑉0𝜀. 𝑥𝐴
V A = V A0
For variable density system(gas systems),
24
Expansion factor
V − V0
XA =
εV0
25
Class Activity
Find the expansion factor for following gas phase

reaction reactions
4−1
𝜀= 1
=3
What will be expansion factor, if 50 % inert are present in

the feed.
26
Class Activity
a. What is the expansion factor?

b. What is the expansion factor if feed composed of 50 percent inert?
c. What is the expansion factor if feed composed of 2/3 phosphine
and 1/3 inert?
4A=B+6C
A B C T
VXA=0 4 0 0 4
VXA=1 0 1 6 7
7−4
𝜀= 4
=3/4=0.75
27
Class Activity
a. What is the expansion factor?

b. What is the expansion factor if feed composed of 50 percent inert?
c. What is the expansion factor if feed composed of 2/3 phosphine
and 1/3 inert?
4PH3=P4+6H2
PH3 P4 H2 I T
VXA=0 4 0 0 4 8
VXA=1 0 1 6 4 11
11−8
𝜀= 8
=3/8=0.375
E=0.75*0.67 = 0.505 28
Class Activity
Find the expansion factor for following liquid phase

reaction reactions
?
29
Selectivity
It is the ratio of moles of the one (usually desired) product to
the moles of another (usually undesired) product.
A→ B
A→C
moles of B formed
Selectivit y of B =
moles of C formed
moles of C formed
Selectivit y of C =
moles of B formed
30
Yield
It is the ratio of moles of a certain product to the

maximum possible moles of that product which can be
formed.
Or
It is the ratio of moles of a certain product to the moles
consumed of the limiting reactant.
Or
It is the ratio of moles of a certain product to the moles
of the limiting reactant fed.
31
Limiting and excess reactant
▪ In a chemical reaction the reactant present in excess to that

required stoichiometrically is the excess reactant the other is
limiting reactant
▪ If the reactants are added in stoichiometric amounts, there is
no point using the concept of limiting or excess reactant
The choice of the limiting reactant is arbitrary and depends

on the cost (profit) considerations
32
Limiting and excess reactant
Can you mention any example of an industrial
process and indicate the limiting reactant?
What are the reasons for the choice of a particular
limiting reactant in your example?
Combustion of a coal
required excess air
33
Possibility of a reaction
▪ For a thermodynamically possible reaction means that

Gibbs free energy of reaction ∆Grxn is less than zero,
i.e., the reactants have higher free energy than the
products.
A useful criterion for knowing the possibility of

reaction occurrence is to know the standard state Gibbs
free energy of reaction, ∆Grxno. A reaction, however,
may not be feasible at the standard conditions but may
occur at the other conditions.
34
Possibility of a reaction
Value of ∆Grxno Possibility of Reaction Occurrence
Reaction is possible with very high
< ‒10 kcal/mol (‒41.8 kJ/mol)
equilibrium conversions
0 to ‒10 kcal/mol (‒41.8 Reaction is possible with moderately
kJ/mol) high equilibrium conversions
Reaction is possible at the other
process operating conditions but
0 to 10 kcal/mol (41.8 kJ/mol)
usually with low equilibrium
conversions
Reaction may be possible at the other
process operating conditions and if
> 10 kcal/mol (41.8 kJ/mol)
possible occurs with generally very
low equilibrium conversions
35
Reactor Design
36
Types of reactors
Chemical reactors may have wide variety of size, shape, flow pattern.
And operating conditions. Mainly these are classified on the basis of
1. Based on mode of operation
▪ Batch reactors
▪ Semi batch reactors
▪ Continuous reactors
2. Based on no. of phases involved
▪ Homogeneous reactors
▪ Heterogeneous reactors
3. Based on shape of reactor
▪ Tank reactors
▪ Tubular reactors
37
Types of reactors: Based on mode of operation

▪ Batch reactors
▪ Continuous reactors (MFR/ PFR)
38
Types of reactors: Based on mode of operation

▪ Batch reactors
▪ Continuous reactors (MFR/ PFR/ PBR/FBR)
39
Types of reactors: Based on phases involved
2. Based on number of phases involved

▪ Reactors for Liquid Phase
▪ Reactors for Gas phase
▪ Reactors for Gas/Liquid Phase
▪ Reactors for Gas/solid phase or liquid/solid phase
▪ Reactors for Gas/ Liquid/ Solid Phase
40
Types of reactors: Based on shape
3. Based on shape
▪ Tank reactors
▪ Tubular reactors
41
Fundamental Design Equation
Accumulation (mole/time) =
Input (mole/time) – output (mole/time) – Consumption (or +Generation) (mole/time)
42
Fundamental Design Equation
Accumulation of energy within reactor volume =

Energy in matter flow into reactor volume– Energy in matter flow out of reactor
volume– Energy transferred from surrounding to the reactor volume
43
Batch reactor-Homogeneous
Batch reactor
Semi-batch reactor
44
Batch reactor
▪ In the batch reactor, or BR, the reactants are initially charged into a
vessel, are well mixed, and are left to react for a certain period. The
resultant mixture is then discharged.
▪ This is an unsteady-state operation where composition changes with
time; however, at any instant the composition throughout the
reactor is uniform.
45
Batch reactor
This is the general equation showing the time required to achieve

a conversion XA for either isothermal or non-isothermal operation.
46
Isothermal Batch Reactor
Case1: If density of the fluid is constant
𝑋𝐴
𝑑𝑋𝐴
𝑡 = 𝑁𝐴0 න
(−𝑟𝐴 )𝑉
0
𝑋𝐴 𝑋𝐴
𝑁𝐴0 𝑑𝑋𝐴 𝑑𝑋𝐴
𝑡= න = 𝐶𝐴0 න
𝑉 (−𝑟𝐴 ) (−𝑟𝐴 )
0 0
𝐶𝐴 𝐶𝐴
𝑑(1 − ) CA
𝐶𝐴0 X A = 1−
𝑡 = 𝐶𝐴0 න C A0
(−𝑟𝐴 )
𝐶𝐴0
47
Case 2: If density of the reaction mixture is not constant
48
Graphical representation of the performance equations for batch reactors
A Levenspiel plot is a plot used

in chemical reaction engineering
1/(-rA)
to determine the required
volume of a chemical reactor. It
is named after the late chemical
or CA engineering professor Octave
Levenspiel.
Levenspiel Plot
49
Space time and space velocity
Space time (τ): It is the time needed to process one
reactor volume of feed measured at specified conditions
Space velocity (s): It is the number of reactor volumes
of feed at specified conditions treated in unit time. A
space velocity of 10 h‒1 means that ten reactor volumes
of the feed at specified conditions are processed in a
reactor per hour.
1
space time =
space veloicty
1 V volume of reactor
= = =
10 feed reactor volumes
s v0 feed volumetric flowrate 50
Batch reactor
Average Residence time: Batch reactors are reactors in
which the reactants are put in the reactor at time 0 and react
until the reaction is stopped. In a batch reactor, the space
time is the same as the average residence time.
51
Steady-state mixed flow reactor (MFR/CSTR)
The ideal steady-state flow reactor is

called the mixed reactor, the back-mix
reactor, the ideal stirred tank reactor,
the CSTR, or the CFSTR (constant
flow stirred tank reactor. It is a reactor
in which the contents are well stirred
and uniform throughout. Thus, the
exit stream from this reactor has the
same composition as the fluid within
the reactor.
52
CSTR
Introducing these three terms into general equation, we have
𝑋𝐴
𝑉 = 𝐹𝐴0
(−𝑟𝐴 )
53
CSTR
where XA and rA are measured at exit stream conditions, which are the same as the
conditions within the reactor. More generally, if the feed on which conversion is
based, subscript 0, enters the reactor partially converted, subscript i, and leaves at
conditions given by subscript f, we have
54
Mixed Flow Reactor
Type equation here.
𝑚𝑜𝑙𝑒
𝑖𝑛𝑝𝑢𝑡 𝑜𝑓 𝐴,
𝑡𝑖𝑚𝑒
= FA0 (1 − X A0 )
𝑚𝑜𝑙𝑒
out𝑝𝑢𝑡 𝑜𝑓 𝐴, 𝑡𝑖𝑚𝑒 = FA = FA0 (1 − X A )
V X A − X A0 − rA
=
FA0 − rA 55
at final conversion
mixed flow reactor
V X A − X A0
=
FA0 − rA
For XA0 = 0, we have
V XA
=
FA0 − rA
Also for constant density system,
56
mixed flow reactor: Levenspiel Plot
Graphical representation of the performance equations for mixed flow

reactor/CSTR
57
CSTR ( Class Activity)
A feed solution containing a reactant A (CA0 =1 kmol/m3) is fed to a
CSTR at a volumetric flow rate of 0.6m3 /min, and converted to
product (P) in the reactor. The reaction rate is 1.2 kmol/(min.m3).
Determine the reactor volumes of the CSTR required to attain a
fractional conversion (XA) of 0.95.
𝑋𝐴
𝑉 = 𝐹𝐴0
(−𝑟𝐴 )
𝑽 = 𝟎. 𝟒𝟕𝟓 𝒎𝟑
58
The following reaction
A B+C
was carried out in CSTR and the following data was recorded
X 0 0.2 0.4 0.5 0.6 0.8 0.9

(-rA)
100 70 20 20 20 16 8
(mol/dm3.min)
The entering molar flow rate of A was 100 mol/min.

1. What is the volume of CSTR necessary to achieve conversion of 40
%.
%.
%.
59
Submit the activity solution till 28th Oct before 9.00 AM
A B+C
𝑋𝐴
𝑉 = 𝐹𝐴0
(−𝑟𝐴 )
60
Plug Flow reactor (PFR)
Plug flow/piston flow is an ideal flow reactor in which no back mixing
occurs. The concentrations of both reactants and products in the plug
flow reactor varies continuously along the flow direction, but are
uniform in the direction perpendicular to flow.
This ideal steady-state flow reactors is variously known as the plug

flow, slug flow, piston flow, ideal tubular, and unmixed flow
reactor. Mostly it is referred as the plug flow reactor, or PFR. It is
characterized by the fact that the flow of fluid through the reactor is
orderly with no element of fluid overtaking or mixing with any
other element ahead or behind. Actually, there may be lateral
mixing of fluid in a plug flow reactor; however, there must be no
mixing or diffusion along flow path.
61
Plug Flow reactor (PFR)
C1 C2 C3
62
Isothermal Plug Flow reactor/tubular reactor
In a plug flow reactor the composition of the fluid varies from point to point
along a flow path; consequently, the material balance for a reaction component
must be made for a differential element of volume dV.
63
Plug Flow reactor
Introducing these three terms in general equation
(1)
Also
Putting value of dFA in eq. 1.
For the reactor as a whole the expression must be integrated. Now FA0, the feed rate, is
constant, but –rA, is certainly dependent on the concentration or conversion of materials
64
Plug Flow reactor
These equations allows the determination of reactor

size for a given feed rate and required conversion
65
Levenspiel plot for Plug Flow reactor
Graphical representation of the performance equations for PFR
66
Packed Bed reactor (PBR)
Also called as Fixed bed reactor (FBR). It is a
heterogeneous reactor where catalyst particles are
arranged in a reactor vessel forming a bed of solid
particles.
Particles are packed either directly in the shell or
packed in tubes where tubes are arranged within the
shell. In the latter case, it is a multitubular fixed bed
reactor.
The multitubular reactor is commonly used when an
exothermic or endothermic reaction is to be carried
out and heat energy has to be added or removed
from the contents of the reaction mixture.
In the usual case, the reactants enter from the top
and products leave at the bottom and the reactor is
assumed to follow the plug flow characteristics.
67
The principal difference between reactor design calculations
involving homogeneous reactions and those involving fluid-solid
heterogeneous reactions is that for the: latter, the reaction takes
place on the surface of the catalyst. Consequently, the reaction
rate is based on mass of solid catalyst. W, rather than on reactor
volume, V.
For a fluid-solid heterogeneous system, the rate of reaction of a
substance A is defined as
68
In the three idealized types of reactors just discussed (the perfectly
mixed batch reactor. the plug-flow tubular reactor (PFR) and the
perfectly mixed continuous stirred rank reactor (CSTR), the
design equations (i.e.. mole balances) were developed based on
reactor volume.
The derivation of the design equation mole balance for (PBR) will
be carried out in a manner analogous to the development of the
tubular (PFR) design equation. To accomplish this derivation,
we simply replace the volume with the catalyst weight W.
69
70
dFA
= (−rA )
dW
d ( FA0 (1 − X A ))
= dW
− rA
XA
W dX A
FA0
= 
0
(− rA )
71
Summary
72
Summary
Mole balances on species A in four common reactors are as follows:
73
Comparison of BR, MFR, PFR
74
Assignment 2 (02 Marks)
For zero, first and second order liquid and gas phase
reactions, write down the design equations for
1. Batch reactors
2. Plug flow reactors
3. Mixed flow reactors
Submit till 2nd Nov 2020
75
Kinetics of homogeneous reactions
Introduction to
the rate equation
76
Rate equation
A rate equation characterizes the rate of
reaction.
The algebraic equation that relates rate to the species
concentrations is called the kinetic expression or rate law.
Rate equation may either be suggested by theoretical

considerations or simply it can be the result of an empirical
curve-fitting procedure of experimental data.
In any case, the value of the constants of the rate equation

can only be found by experiment; predictive methods are
inadequate at present.
77
Reaction order and Rate Laws
▪ Homogenous reaction – one phase reaction
▪ Heterogeneous reaction – more than one phase
▪ Irreversible reaction:
▪ Reversible reaction:
78
Relative rates of reaction
79
Relative rates of reaction
80
Elementary rate laws
The stoichiometry coefficients are the same as the individual reaction
order of each species.
81
Non-Elementary rate laws
The stoichiometric coefficients are not the same as the individual
reaction order of each species.
Then the reaction is said to be 2nd order in A, 1st order in B, and 3rd
order overall.
82
Non-Elementary rate laws
The stoichiometric coefficients are not the same as the individual
reaction order of each species.
Then the reaction is said to be 2nd order in A, 1st order

in B, and 3rd order overall.
83
Reversible Reactions
At equilibrium, r =0. Thus,

net
K = thermodynamic equilibrium constant 84

Rate equation-homogeneous systems
Rate of reaction mainly depend on two parameters

1. Concentration of reactant/reactants
2. Temperature
The determination of the rate equation is usually a two-
step procedure; first the concentration dependency is
found at fixed temperature and then the temperature
dependence of the rate constants is found, yielding the
complete rate equation.
85
Rate equation
Equipment by which empirical information is obtained can

be divided into two types, the batch and flow reactors.
Extent of reaction is determined by considering variation
in following parameters
▪ By following the concentration of a given component.
▪ By following the change in some physical property of the fluid,
such as the density, electrical conductivity or refractive index.
▪ By following the change in total pressure of a constant-volume
system.
▪ By following the change in volume of a constant-pressure
system.
86
Class Activity: Expressing concentration as function of conversion
V=V0=constant
87
CONSTANT-VOLUME BATCH SYSTEMS
88
89
How to write the mole fraction?

90
aA +bB cC + dD
Equilibrium conversion= X
Initial moles of A = NA0
Initial moles of B = NB0
Initial moles of C = NC0
Initial moles of D = ND0
A +b/aB c/aC + d/aD

Final moles of A : NA = NA0 – XNA0
Final moles of B : NB = NB0 – (b/a)XNA0
Final moles of C : NC = NC0 + (c/a)XNA0
Final moles of D : ND = ND0 + (d/a)XNA0
Total moles : NT = NT0 – XNA0( 1+ b/a – c/a –d/a) = NT0 – XNA0(z)
Mole fraction of A : xA = NA/NT

91
92
Flow reactors: Calculation of concentration as function of
conversion
aA +bB cC + dD
Equilibrium conversion= X
Initial moles of A = FA0
Initial moles of B = FB0
Initial moles of C = FC0
Initial moles of D = FD0
A +b/aB c/aC + d/aD

Final moles of A : FA = FA0 – XFA0
Final moles of B : FB = FB0 – (b/a)XFA0
Final moles of C : FC = FC0 + (c/a)XFA0
Final moles of D : FD = FD0 + (d/a)XFA0
Total moles : FT = FT0 – XFA0( 1+ b/a – c/a –d/a) = FT0 – XFA0(z)
Mole fraction of A : yA = FA0/FT 93

Home Assignment
For following reaction
or
A + 3B C
Find concentration correlations as function of

conversion for toluene, MCH and H2.
94
Finding the kinetic data
▪ To find out the kinetic data , batch reactor is usually
operated isothermally and at constant volume because
it is easy to interpret the results of such runs.
▪ This reactor is a relatively simple device adaptable to
small-scale laboratory set-ups, and it needs little
auxiliary equipment or instrumentation.
▪ Thus, it is used whenever possible for obtaining
homogeneous kinetic data.
▪ The flow reactor is used primarily in the study of the
kinetics of heterogeneous reactions.
95
Analysis of kinetic data
Various methods are employed for data analyses such as:
1. Integral method
Most common
2. Differential method
3. Initial-rate method
4. Half-life Method
In the integral method of analysis we guess a particular form of rate equation
and, after appropriate integration and mathematical manipulation, predict that
the plot of a certain concentration function versus time should yield a straight
line. The data are plotted, and if a reasonably good straight line is obtained, then
the rate equation is said to satisfactorily fit the data.
In the differential method of analysis we test the fit of the rate expression to the
data directly and without any integration. However, since the rate expression is
a differential equation, we must first find (l/V)(dNldt) from the data before
attempting the fitting procedure.
96
Analysis of kinetic data
▪ There are advantages and disadvantages to each method. The
integral method is easy to use and is recommended when testing
specific mechanisms, or relatively simple rate expressions, or
when the data are so scattered that we cannot reliably find the
derivatives needed in the differential method.
▪ The differential method is useful in more complicated situations
but requires more accurate or larger amounts of data.
▪ The integral method can only test this or that particular
mechanism or rate form; the differential method can be used to
develop or build up a rate equation to fit the data.
In general, it is suggested that integral analysis

should be attempted first, and, if not successful,
the differential method can be tried.
97
Integral method of kinetic data analysis
▪ The integral method of analysis always puts a particular

rate equation to the test by integrating and comparing
the predicted C versus t curve with the experimental C
versus t data.
▪ If the fit is unsatisfactory, another rate equation is
guessed and tested.
▪ It should be noted that the integral method is especially
useful for fitting simple reaction types corresponding to
elementary reactions.
98
Integral method of kinetic data analysis: constant-volume
batch reactor
Case 1: Irreversible Unimolecular-Type 1st Order Reactions (in
terms of concentration)
Suppose it’s a first-order rate equation of the following type,
Separating and integrating between CA0 at time = 0 and CA at time

t, we obtain
y=mx+c
Y=-ln(Ca/CA0)
X=t
C=0
Slope=m = k 99
batch reactor
100
Case 1: Irreversible Unimolecular-Type 1st Order Reactions
A plot of -In (CA/CAo) vs. t gives a straight line through the origin for
this form of rate of equation.
If the experimental data seems to be better fitted by a curve than by a

straight line, try another rate form because the first-order reaction does
not satisfactorily fit the data.
101
Case 1: Irreversible Unimolecular-Type 1st Order Reactions (in
terms of conversion)
Suppose that NAo is the initial amount of A in the reactor at time t = 0, and that
NA is the amount present at time t. Then the conversion of A in the constant
volume system is given by
Differentiating above equation, we obtain
Thus in term of conversion, rate expression for 1st order unimolecular irreversible
reactions can be written as
Inserting values of dCA and CA we have
102
A plot of In (1 - XA) vs. t gives a straight line through the origin for this
form of rate of equation.

103
batch reactor
y=mx+c
Y=-ln(1-X)
X=t
intercept=0
Slope=m = k
104
Should be a straight line
t
Test for the first-order rate equation 105
A plot of In (1 - XA) or In (CA/CAo) vs. t gives a straight line through

the origin for this form of rate of equation.

106
Class Activity: Analyzing Batch reactor data using integral method
Reactant A decomposes in a batch reactor
The composition of A in the reactor is measured at

various times with results shown in the following
table. Check whether the data follows first order
rate equation or not? If yes, find rate constant k.
Batch reactor
Reactant A
n=1 Suppose n=1
107

rate equation or not? If yes, find rate constant k.
Slope, k = 0.0726 min-1
−𝑟𝐴 = 0.0726𝐶𝐴
108

rate equation or not? Ig yes, find rate constant k.
Data does not follows first order

kinetics
109
Case 2: Irreversible bimolecular-Type 2nd Order Reactions
or
Based on stoichiometric equation, rate equation can be written as
On integration, we get y=mx+c

y=mx+c 1/CA=kt+1/CA0
XA/(CAO(1-XA))=kt
Y=1/CA
Y= XA/(CAO(1- X=t
XA))= C=1/CA0
X=t Slope=m = k
C=0
Slope=m = k 110
or

Test for the 2nd-order rate equation
111
Case 2a: Irreversible bimolecular-Type 2nd Order Reactions
−𝑟𝐴 = 𝑘𝐶𝐴𝐶𝐵
on separation and applying integration above eq. becomes
112
Case 2a: Irreversible bimolecular-Type 2nd Order Reactions
−𝑟𝐴 = 𝑘𝐶𝐴𝐶𝐵
𝐶𝐴 = 𝐶𝐴0 − 𝐶𝐴0𝑋𝐴 𝑀 = 𝐶𝐵0/𝐶𝐴0
𝐶𝐵 = 𝐶𝐵0 − 𝐶𝐴0𝑋𝐴
−𝑟𝐴 = 𝑘(𝐶𝐴0 − 𝐶𝐴0𝑋𝐴)(𝐶𝐵0 − 𝐶𝐴0𝑋𝐴)
113

Test for the 2nd-order rate equation
114
Case 3: Zero Order Reactions
A reaction is of zero order when the rate of reaction is independent
of the concentration of materials; thus
Integrating and noting that CA can never become negative
Which means that the conversion is proportional to time.

115
Case 3: Zero Order Reactions CA can never become
negative
Which means that the conversion

is proportional to time.
116
Case 3: Zero Order Reactions
As a rule, reactions are of zero order only in certain concentration ranges-
the higher concentrations. If the concentration is lowered far enough, we
usually find that the reaction becomes concentration-dependent, in which
case the order rises from zero.
Should be a linear line
Test for the zero-order rate equation 117

The composition of A in the reactor is measured at various times

with results shown in the following table. Find a rate equation to
represent the data using integral method.
118
For solution, pls see attend the class lecture.
119
120
Slope = k = 0.034 L/(mol. min)

Thus rate eq.
(-rA) = 0.034 CA2 121
Class Activity
− rA = 2
0.0145C A
Slope = k = 1 x 10-5 m3/(mol. min)

Thus rate eq.
(-rA) = 1 x 10-4 CA2
122
Class Activity
(-rA) = 1 x 10-5 CA2
t = 5 hr = 300 min
Thus CA = 200 mol/m3
CA 200
X =1− =1− = 0 .6
C A0 500
123
Differential Method of data analysis
The differential method of analysis deals directly with the differential
rate equation to be tested, evaluating all terms in the equation
including the derivative dC/dt, and testing the goodness of fit of the
equation with experiment.
Steps to be followed are
▪ Plot the CA vs. t data, and then carefully draw a smooth curve to
represent the data. This curve most likely will not pass through all
the experimental points.
▪ Determine the slope of this curve at suitably selected concentration
values. These slopes dC/dt = (-rA), are the rates of reaction at these
compositions.
▪ Now search for a rate expression to represent this (-rA) vs. CA data,
either by
a) picking and testing a particular rate form, (-rA) = k f(C)
b) testing an nth-order form (-rA) = kCAn
124
Differential Method of data analysis
y = mx + c
(-rA) = kCAn
log(−rA ) = n log C A + log k
Intercept = log k
125
Class Activity: Differential Method of data analysis

represent the data using differential method and integral method.
126
For solution, pls see the lecture notes.
Step-1: Plot concentration Vs time data
127
Step-1: Take tangents
min
128
log(− rA ) = log k + n log C A
129
Step-1: Plot log (-rA) vs log (CA)
log(− rA ) = log k + n log C A

log( − 𝑑𝐶𝐴 /𝑑𝑡) = log 𝑘 + 𝑛 log 𝐶𝐴
130
Class Activity

represent the data using differential method and integral method.
Use integral and Differential

methods to find rate equation
131

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Chemical Reaction

Dr. Rabya Aslam

▪ Introduction to chemical reaction engineering

Design of homogeneous reactors: Batch, Mixed flow, Plug flow reactors,

Design of heterogeneous reactors: Surface phenomenon and catalysis,

The objective of this course is to give the understanding

Students will learn how can a chemical engineer

1. Explain chemical reaction engineering related

Typical chemical process

▪ What are the optimum operating conditions for a reaction

Thus a chemical reaction is responsible for a chemical change that

In this classical approach to chemical change, it is

The volume of a gas also changes due to changes in operating

▪ This minus sign is to show rate of consumption of a reactant

Based on unit mass Het

Based on unit surface of solid in fluid-solid

Based on unit volume of solid

Based on unit volume of reactor when different

Rates of reactions vary in a wide range. Some reaction

Rate equation cannot be found reliably from the reaction

Nearly 90% of all industrial reactions involve

It is the fractional change in volume of the system between no

Find the expansion factor for following gas phase

What will be expansion factor, if 50 % inert are present in

a. What is the expansion factor?

a. What is the expansion factor?

Find the expansion factor for following liquid phase

It is the ratio of moles of a certain product to the

▪ In a chemical reaction the reactant present in excess to that

The choice of the limiting reactant is arbitrary and depends

▪ For a thermodynamically possible reaction means that

A useful criterion for knowing the possibility of

1. Based on mode of operation

1. Based on mode of operation

2. Based on number of phases involved

Accumulation of energy within reactor volume =

This is the general equation showing the time required to achieve

A Levenspiel plot is a plot used

The ideal steady-state flow reactor is

Introducing these three terms into general equation, we have

Type equation here.

Also for constant density system,

Graphical representation of the performance equations for mixed flow

X 0 0.2 0.4 0.5 0.6 0.8 0.9

The entering molar flow rate of A was 100 mol/min.

This ideal steady-state flow reactors is variously known as the plug

Putting value of dFA in eq. 1.

These equations allows the determination of reactor

Graphical representation of the performance equations for PFR

Submit till 2nd Nov 2020

Rate equation may either be suggested by theoretical

In any case, the value of the constants of the rate equation

Then the reaction is said to be 2nd order in A, 1st order

At equilibrium, r =0. Thus,

K = thermodynamic equilibrium constant 84

Rate of reaction mainly depend on two parameters

Equipment by which empirical information is obtained can

How to write the mole fraction?

A +b/aB c/aC + d/aD

Mole fraction of A : xA = NA/NT

A +b/aB c/aC + d/aD

Mole fraction of A : yA = FA0/FT 93

Find concentration correlations as function of