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Chemical Reaction
Engineering
GATE & ESE
Content Sheet
Chemical Reaction Engineering 1

1 Introduction to Chemical Reaction Engineering 3
2 Ideal Reactors 15
3 Multiple-Reactor Systems 43
4 Recycle Reactor 56
5 Autocatalytic Reactions 59
6 Non-Isothermal Chemical Reactors 61
7 Non-Ideal Flow Reactors 66
8 Miscellaneous Topics 93
2.
1 Introduction to Chemical
Reaction Engineering
Chapter 1
Any process which causes chemical changes, or changes in molecular structure are dealt
with in chemical reaction engineering.
The general objective of chemical reaction engineering is to provide an overview of chemical
kinetics and reactor design at basic to the intermediate level. The subject will apply the
concept of reaction rate, then stoichiometry and equilibrium to the analysis of different
chemicals and biological reacting systems.
For example, derivation of the rate expression from the reaction mechanism or the concept
of equilibrium or steady state assumptions for certain reactions has been considered. This
course will consider the design of the reactors, by taking into account the chemical kinetics
as well as the mass and energy balance wherever necessary.
The broad goal of this course is to provide the theoretical and analytical background
to understand the chemical kinetics and the reactor design to tackle the complex
problem.
Chemical reactions are ubiquitous in nature. So, the chemical reactions will be constructed in
the form of the mathematical description. Mathematical description means that the physical
system is represented in a mathematical form that allows us to predict and understand the
view of different reactions and reactors.
Every chemical industrial process is designed to produce economically desired products
from different starting materials or a raw material. Explanation of this can be explained
by a simple example, let if you have a raw material and the raw material may not be
fed to the chemical reactor, then it means that it needs some physical separation, so it
will undergo some physical treatment steps, then it will be fed to the chemical reactors,
so chemical treatment steps. Once the chemical treatment is done or it is fed to the
chemical reactors the reactions would take place and it will produce the products,
the product may not be pure, so the products which will produce that again will go to
several physical treatment steps, so that it is again fed to the chemical treatments,
so this is recycle. This physical treatment step means once the product is produced
Introduction to Chemical Reaction Engineering

that has to be separated or some purification has to be done so that we can get the
finished products.
The physical treatments steps will not be covered in this subject, as this is covered in the
mechanical operation course, or the unit operation course, where most of the physical
treatment steps have been considered. In chemical treatment steps, it may be a simple
reactor or simple tank, simple mixing tank, although it is simple, but this is what makes
or breaks the process economically, so design of chemical reactors is not a routine matter
there are many alternatives, maybe available for a reactor design. The description of the
process is given in figure 1.
3.
Figure 1 : The steps involved in the production of economical product
In search of a reactor design, one must have to optimize the cost. In such cases, one design
may be superior with respect to the other design so the cost of the overall process has to
be considered while designing a chemical reactor. Design of the reactor is not a routine
matter, many alternatives may be proposed. For optimum design one must consider the
overall cost of the process. Reactor design gives the information from a variety of sources,
like thermodynamics it also uses the chemical kinetics, fluid mechanics, heat and mass
transfer and so on.
What is chemical reaction?

A chemical reaction is a process in which at least one species is transformed into chemically
different species.
Example: Consider combustion of methane, that is a very high exothermic reaction, methane
reacts with oxygen and it forms carbon dioxide and water vapor.
CH4 + 2O2 → CO2 + 2H2O
In the above reaction, the reactants are methane and oxygen and products are carbon
dioxide and water. In the reaction, the number and types of molecule may change. The
molecular or the number of molecules or the species have changed before and after the
reaction.
Figure 2 : Basic functioning of chemical reactor
4.
Figure 2 shows the basic functioning of a chemical reactor. In any process, the contacting
pattern means that when the reactants are fed into the reactor, how they contact, how they
flow inside the reactor, whether they are well mixed with each other or whether they are
segregated from each other, how they flow, what is the contacting pattern inside the reactor.
Similarly, if the reaction is very slow then the chemical kinetics or the rate of reactions will
tell what would be the chemical kinetics for those reactions. This information is needed to
know when a raw material is processed inside a reactor to obtain output and the relations
between the input and the output. The equations which would relate between the input and
output is known as the Performance Equation. Output is a function of input, kinetics and
contact pattern which is as Performance Equation.
Why is this performance equation important?
Performance equation is important to compare different designs and conditions and from
that the best condition and reactor can be found out that can be scaled up to the larger
units.
There are three idealized reactors:
1) Batch reactor
2) Plug flow reactor
3) Continuous stirring tank reactor
1.1 Chemical Reactors
Reactor is a vessel in which the reaction will be completely done without any changes of
characteristic properties of the vessel is called a chemical reactor.
y To designing the chemical reactor the following parameters are important
⚪ Kinetics - represents the process
⚪ Contacting patterns -flow behavior & pattern of reaction mixture.
⚪ Performances equations - It is the function of output, kinetics and contacting patterns.

y Type of phase
⚪ Homogeneous phase
⚪ Heterogeneous phase
1.2 Classification if reaction mixture

y Based on nature
⚪ Decomposition
When big molecules break in or more than smaller molecules.
A →B+C
⚪ Synthesis
When two or more than two molecules combine to form a bigger molecule.
A +B → C
5.
⚪ Isomerization
When a molecule’s structure changes without being decomposed and combined.
y Based on phase
⚪ Homogeneous reaction system – Reaction system in which only a single phase exists.
⚪ Heterogeneous reaction system: Reaction system in which more than one phase exists.
1.3 Kinetics of the reaction

y Rate of reaction ‘r’ - Rate equation is the dependency of the concentration with the rate
of the reaction. Mathematical representation of the reaction is known as the rate of the
reaction.
∑ ϑA
i i =0 → reaction equation
For a general reaction

A +B → C +D
ϑA A + ϑBB + ϑCC + ϑDD =0
Stoichiometric coefficient
( −a ) A + ( −b) A + ϑCC + ϑDD =0
aA + bB = cC + dD
Rate of reaction is directly proportional to the rate of change of moles of components.
dNi
rα
dt
where
dNi
is the change in then
umber of moles of reactant i with time
dt
The rate of reaction is defined on the basis of phase

Homogeneous phase
y Based on unit volume of reaction mixture .
1 dNi  mol 
r=  
V dt  m3 .s 
Heterogeneous phase
y Based on unit interfacial area of multiphase reaction mixture
1 dNi  mol 
r =  
S dt  m2 .s 
y Based on unit mass of solid catalyst in solid fluid catalytic reaction
1 dNi  mol 
r =  
W dt  kg.s 
6.
1.4 Homogeneous reaction system
y Relative rate of reaction
y aA + bB → cC + dD
−rA −rB rC rD
= = = = r
a b c d
Mole balance over chemical reaction
aA + b
B → cC + dD
( ) (
Feed NA0 → conversion inr eactor → NA product )
A0 ( 1 − X A )
NA N
=
where NA0 is the initial moles of reactant A, mol
NA is the final moles of reactant A, mol

is the initial moles of reactant A, mol
X A is the conversion of A Conversion (X)
Fractional amount of “A” reacted.
y It is defined only for one component.
y It depends on the stoichiometric coefficient.
y Stoichiometric coefficient is constant.
Dependent variables depending on independent variables.
XA = Fractional amount of “A” reacted.
Amount of ' A'reacted
XA =
Amount of ′A′ fed
Moles of ‘A’ reacted = NA0 .X A
NA N
= A0 X A − NA0

A0 ( 1 − X A )
NA N
=
Factor affecting the rate of reaction in homogeneous reaction:-

y Temperature
y Concentration
y Pressure (for gaseous reaction only)
r = f ( Temp , Conc. )
Hence, Power Law
αi
r= Kπ (Ci )
where
K is the rate constant which is a temperature dependent term.
7.
Ci Concentration of reactant ‘i’
‘ai’ is the apparent order of ‘i’.
The rate equation determines the rate constant and concentration of the ‘i’ component.
The rate equation indicates the formation of product and disappearance of reactant.
αi = ϑi ( of rxn rate determining step.
π = Product summation.
For any reaction
aA + bB → cC
(
r = K CαAA  CBαB )
α A = a , αB = b
1.5 Order of reaction (n)

The total number of molecules or atoms whose concentration determine the rate of reaction
is known as order of reaction.
Order of reaction = Sum of exponents of the conc. terms in rate law.
Key points
y Experimental Quantity.
y It can be zero, -ve or fraction value.
y The rate determining step is found only experimentally.
y It is denoted by “n”.
Overall order of the reaction a + b
1.6 Molecularity (M)

Molecularity is the sum of the number of molecules of reactants involved in the balanced
chemical equation. Molecularity of a complete reaction has no significance and overall

kinetics of the reaction depends upon the rate determining step. Slowest step is the rate-
determining step.
Key points:-
y Theoretical Quantity.
y Associates with elementary reactions only.
y It can’t be zero , -ve , fraction value.
y Express only 1 ,2 and 3 only.
Example : 2A + B → C
M = 2 + 1 = 3.
Molecularity is the sum of stoichiometric coefficient.
Rate of reaction depends on a number of parameters, the most important of which are
usually:
8.
y The nature of the species involved in the reaction
Many examples of types of very fast reactions involve ions in solution, such as the
neutralization of a strong acid by a strong base, and explosions. In the former case, the rate
of change may be dictated by the rate at which the reactants can be brought into intimate
contact. At the other extreme, very slow reactions may involve heterogeneous reactions,
such as the oxidation of carbon at room temperature. The reaction between hydrogen and
oxygen to form water can be used to illustrate both extremes. Subjected to a spark, a
mixture of hydrogen and oxygen can produce an explosion, but in the absence of this,
or of a catalyst such as finely divided platinum, the reaction is extremely slow. In such a
case, it may be wrongly supposed that the system is at equilibrium, since there may be no
detectable change even after a very long time.
y Concentrations of species
Rate of reaction usually depends on concentration of reactants (and sometimes of products),
and usually increases as concentration of reactants increases. Thus, many combustion
reactions occur faster in pure oxygen than in air at the same total pressure.
y Temperature
Rate of reaction depends on temperature and usually increases nearly exponentially
as temperature increases. An important exception is the oxidation of nitric oxide,
which is involved in the manufacture of nitric acid; in this case, the rate decreases as
T increases.
y Catalytic activity
Many reactions proceed much faster in the presence of a substance which is itself not a
product of the reaction. This is the phenomenon of catalysis, and many life processes and
industrial processes depend on it. Thus, the oxidation of SO, to SO3 is greatly accelerated
in the presence of V2O5 as a catalyst, and the commercial manufacture of sulfuric acid
depends on this fact.
y Nature of contact of reactants

The nature or intimacy of contact of reactants can greatly affect the rate of reaction. Thus,
finely divided coal burns much faster than lump coal. The titration of an acid with a base
occurs much faster if the acid and base are stirred together than if the base is simply
allowed to “dribble” into the acid solution. For a heterogeneous, catalytic reaction, the
effect may show up in a more subtle way as the dependence of rate on the size of catalyst
particle used.
y Wave-length of incident radiation
Some reactions occur much faster if the reacting system is exposed to incident radiation
of an appropriate frequency. Thus, the mixture of hydrogen and chlorine can be kept in
the dark, and the reaction to form hydrogen chloride is very slow; however, if the mixture
is exposed to ordinary light, reaction occurs with explosive rapidity. Such reactions are
generally called photochemical reactions.
9.
Chemical reaction based on number of steps
y Elementary reaction: The reaction which occurs is in single steps.
aA + bB → P
M= a + b
(
r = K CαA .CBβ )
Overall order of the reaction is α + β
y For elementary reactions, the apparent order of the component will be the same as the
stoichiometric coefficient.
y Molecularity and order of reaction are the same in the case of elementary reaction.
y Non-elementary reaction: The reaction which occurs in more than one step.
b
1. aA + B → P* P* (slow reaction)
2
b
2. P* + B
→C
3
2b
3. C + B
→D
3
4. Example
(
r = K CαA .CBβ )
b
n=a+
2
y Apparent order of components may or may not be the same as their stoichiometric coefficient.
y The non-elementary reaction may or may not be the same as the molecularity and order
of reaction.
Concentration (C)
The amount of component in mixture per unit volume.

Concentration of ‘A’ at any time ‘t’,
N
CA = A
V
where ‘V’ is the volume of the reactor.
Concentration of ‘A’ at any time t=0,
N
CA0 = A0
V0
NA NA0 ( 1 − X A )
C
= A =
V V
Reaction Rate Constant (K) :
10.
It is a strongly temperature dependent term.
From power low,
Unit of ‘K’ is
n
r = KCA
n
mol  mol 
3
= K  3 
ms  m 
1−n
 mol 
K =  3  s−1
 m 
For n = 0,
1
 mol 
K =  3 
 m .s 
For n = 1,
1
K =
s
For n = 2,
m3
K = .s
mol
There are some theories to finding the ‘K’
1) Arrhenius theory - The minimum energy required to break the old bond and to form new
bonds is called the activation energy.
K = Koe−E/RT
where

Ko = frequency or pre-exponential factor
E = Activation energy of the reaction
On integrating
K E 1 1 
lnln 2 =  − 
K1 R  T1 T2 
1.7 Why is there an activation energy?

The molecules need energy to distort or stretch their bonds in order to break them and
to thus form new bonds and as the reacting molecules come close together they must
overcome both steric and electron repulsion forces in order to react.
Activation energy and Temperature dependency

y From Arrhenius’ law a plot of In k vs. 1/T gives a straight line, with large slope for large E and
small slope for small E.
11.
y Reactions with high activation energies are very temperature sensitive; reactions with low
activation energies are relatively temperature-insensitive.
y Any given reaction is much more temperature-sensitive at a low temperature than at a high
temperature.
y From the Arrhenius law, the value of the frequency factor k0 , does not affect the temperature
sensitivity.
Q1 How fast the reaction will be at 600k than that of at 400k. if the activation
Cal
energy of the reaction is 9150 .
Mol
A E = 9150
Cal
× 4.18
J
= 38247
J
.
Mol Cal Mol
K E 1 1 
lnln 2 =  − 
K1 R  T1 T2 
38247  1 1 
=  − 
8.314  400k 600k 
 1 1 
= 4600.312  − 
 400k 600k 
K2 = 10 K1
Q2 Milk is pasteurized if it is heated to 63oC for 30 min, but if it is heated to 74oC

it only needs 15 sec. for the same result. Find the activation energy of this
sterilization process.
A To ask for the activation energy of a process means assuming an Arrhenius

temperature dependence for the process. Here we are told that
t1 = 30 min at a T1 = 336K
t2 = 15 sec at a T2 = 347K
Now the rate is inversely proportional to the reaction time,
1
or rate ∝ so,
time
12.
r2 K2 E 1 1 
lnln
= l nln
=  − 
r1 K1 R  T1 T2 
Or,
30 E  1 1 
lnln =  − 
0.25 8.314  336 347 
J
E = 422000 .
Mol
2) Collision Theory: Based on kinetic theory of gases:-

In the development of collision theory, the assumption is that all molecules had the
same average energy. However, all the molecules don’t have the same energy, rather
there is distribution of energies where some molecules have more energy than others.
This theory fails for unimolecular reaction.
K =K 0T1/2e−E/RT
K 1 T E 1 1 
lnln 2 lnln 2 +
=  − 
K1 2 T1 R  T1 T2 
3) Transition State Theory
Transition state theory (TST) provides a more accurate alternative to the previously
used Arrhenius equation and the collision theory. The transition state theory attempts to
provide a greater understanding of activation energy, EA , and the thermodynamic
properties involving the transition state. Collision theory of reaction rate, although
intuitive, lacks an accurate method to predict the probability factor for the reaction. The
theory assumes that reactants are hard spheres rather than molecules with specific
structures.
According to TST, between the state where molecules are reactants and the state where

molecules are products, there is a state known as the transition state. In the transition
state, the reactants are combined in a species called the activated complex. The theory
suggests that there are three major factors that determine whether a reaction will occur:
The concentration of the activated complex.
The rate at which the activated complex breaks apart.
The way in which the activated complex breaks apart: whether it breaks apart to
reform the reactants or whether it breaks apart to form a new complex, the products.
Based on statistical mechanics

K = Ko .T.e−E⁄RT
K2 T E 1 1 
lnln
= lnln 2 +  − 
K1 T1 R  T1 T2 
13.
In General
K = Ko TMe−E⁄RT
K T E 1 1 
lnln 2 M
= .lnln 2 +  − 
K1 T1 R  T1 T2 
M = 0, for Arrhenius Theory
1
M = , for Collision Theory
2
M = 1, for Transition State Theory.
The Determination of the rate equation is usually a two-step procedure; first the concentration
dependency is found at a fixed temperature and then the temperature dependence of the
rate constant is found, yielding the complete rate equation.
14.
2 Ideal Reactors
Chapter 2
The equipment by which information is obtained can be divided into two types:
1. Batch reactor
2. Flow reactor
2.1 Batch reactor

The batch reactor is simply a container to hold the contents while they react.
Such as:
a. The concentration of a given component.
b. The change in some physical property of the fluid, such as the electrical conductivity
or refractive index.
c. The change in total pressure of a constant-volume system.
d. The change in volume in a constant-pressure system.
The batch reactor is usually operated isothermally at constant volume.
The batch reactor is a relatively simple device adaptable to small-scale laboratory set-
ups, and it needs but little auxiliary equipment.
Principle applications of batch reactor

Is to conduct:
y Liquid-phase
y Liquid-solid reactions
Table 1: Advantages and disadvantages of batch reactor.
Advantages Disadvantages
Quick production changeover possible; use for Relatively high operating costs due to
substances produced on a small scale. long downtimes and high manpower
requirements.
Process steps upstream or downstream of the Quality differences between charges

reaction can also be performed in the reactor. because reaction conditions are only
partly reproducible.
Better process control than in continuous Limited temperature control capabilities,

operation if solid or highly viscous phases form especially with highly endo /exothermic
or are present. reactions.
Well-defined residence time.
2.2 Flow reactors

2.2.1 Continuous stirred-tank reactor (CSTR)
Ideal Reactors
A continuous stirred-tank reactor (CSTR) is normally used for liquid-phase reactions,

both in a laboratory and on a large scale. It may also be used, however, for the laboratory
15.
Chapter 2
investigation of gas-phase reactions, particularly when solid catalysts are involved, in which
case the operation is batch-wise for the catalyst. Stirred tanks may also be used in a series
arrangement (e.g. for the continuous copolymerization of styrene and butadiene to make
synthetic rubber).
Characteristics of CSTR
y The flow through the vessel(s), both input and output streams, is continuous but not
necessarily at a constant rate.
y The system mass inside each vessel is not necessarily fixed.
y The fluid inside each vessel is perfectly mixed (back-mix flow, BMF), and hence its properties
are uniform at any time, because of efficient stirring.
y The density of the flowing system is not necessarily constant; that is, the density of the
output stream may differ from that of the input stream.
y The system may operate at steady-state or at unsteady-state.
y The system may operate at steady-state or at unsteady-state. The fluid inside the vessel is
uniformly mixed (and hence elements of fluid are uniformly distributed), all fluid elements
have equal probability of leaving the vessel in the output stream at any time. Therefore, the
output stream has the same properties as the fluid inside the vessel. If there is a step-
change across the inlet in any property of the system that changes from inlet to outlet.
Applications of CSTR
y Liquid-phase reactions
y Gas-liquid reactions
y Gas – liquid reactions over suspended catalysts.
Table 2: Advantages and disadvantages of CSTR
Low operating costs, especially at Final conversions lower than in other basic reactor
high throughputs. types because of complete mixing (i.e., unreacted
starting materials can get into the product stream).
Consistent product quality due to High investment costs to implement continuous

reproducible process control. operation.
Wide range of possible flows.
2.2.2 Plug flow reactor

Characteristics of plug flow reactor:
Ideal Reactors
y Steady-state
y Maintenance of constant throughput
16.
Chapter 2
y Turbulent flow with plug flow velocity profile
y L/D ratio is sufficiently large
y D/Dp ratio is sufficiently large
y Low pressure drop
y Well-defined axial T-profile
y Negligible radial T-profile
y Prevention of further reaction following sampling.
A plug-flow reactor (PFR) may be used for both liquid-phase and gas phase reactions, and
for both laboratory-scale investigations of kinetics and large-scale production. The reactor
itself may consist of an empty tube or vessel, or it may contain packing or a tied bed of
particles (e.g., catalyst particles).
A PFR is similar to a CSTR in being a flow reactor, but is different in its mixing characteristics.
It is different from a BR in being a flow reactor, but is similar in the progressive change of
properties, with position replacing time. These features are explored further in this section,
but first we elaborate the characteristics of a PFR, as follows:
The flow through the vessel, both input and output streams, is continuous, but not necessarily
at constant rate; the flow in the vessel is PF.
y The system mass inside the vessel is not necessarily fixed.
y There is no axial mixing of fluid inside the vessel (i.e., in the direction of flow).
y There is complete radial mixing of fluid inside the vessel (i.e., in the plane perpendicular to
the direction of flow); thus, the properties of the fluid, including its velocity, are uniform in
this plane.
y The density of the flowing system may vary in the direction of flow.
y There may be heat transfer through the walls of the vessel between the system and the
surroundings.
Principle applications of plug flow reactor:
⚪ Homogeneous gas -phase reactions
⚪ Liquid -phase reactions
⚪ Gas-liquid reactions
⚪ Gas and liquid phase reactions over solid catalysts (PBR).
Table 3: Advantages and disadvantages of CSTR
Good conditions for temperature High degree of specialization, often with

control by heat transfer. complicated design and high investment costs.
No moving mechanical parts (suitable Relatively large pressure drops (depending on

Ideal Reactors
for high-pressure reactions). diameter etc).
17.
Chapter 2
2.2.3 Laminar- flow reactor (LFR)

A laminar-flow reactor (LFR) is rarely used for kinetic studies, since it involves a flow
pattern that is relatively difficult to attain experimentally. However, the model based
on laminar flow, a type of tubular flow, may be useful in certain situations, both in the
laboratory and on a large scale, in which flow approaches this extreme (at low Re). Such a
situation would involve low fluid flow rate, small tube size, and high fluid viscosity, either
separately or in combination, as, for example, in the extrusion of high molecular-weight
polymers.
Characteristics of LFR
The general characteristics of the simplest model of a continuous LFR, are as follows:
y The flow through the vessel is laminar (LF) and continuous, but not necessarily at constant
rate.
y The system mass inside the vessel is not necessarily fixed.
y There is no axial mixing of fluid inside the vessel.
y There is no radial mixing of fluid inside the vessel.
y The density of the flowing system is not necessarily constant.
y There may be heat transfer through the walls of the vessel between the system and the
surroundings.
2.3 Size comparison of single reactors

y The batch reactor has the advantage of small instrumentation cost and flexibility of operation
(may be shut down easily and quickly).
y It has the disadvantage of high labor and handling cost, often considerable shutdown time
to empty, clean out, and refill, and poorer quality control of the product.
y Hence we may generalize to state that the batch reactor is well suited to produce small
amounts of material and to produce many different products from one piece of equipment.
y On the other hand, for the chemical treatment of materials in large amounts the continuous
process is nearly always found to be more economical.
y Regarding reactor sizes, a comparison for a given duty and for ε = 0 shows that an element
of fluid reacts for the same length of time in the batch and in the plug flow reactor have
the same volume.
y Of course, on a long-term production basis we must correct the size requirement estimate
to account for the shutdown time between batches. Still, it is easy to relate the performance
capabilities of the batch reactor with the plug flow react.
Based on volume reactor system:-

y Constant volume reactor system
Ideal Reactors
y Variable volume reactor system
18.
Chapter 2
Analysis of batch reactor kinetic data
Rate equations can be obtained by two different procedures, one is the concentration
dependency which is found, first at fixed temperature and then at a temperature dependency.
Therefore, in the case of concentration dependency the condition is isothermal, so the
temperature is kept constant and the concentration has been varied to obtain the kinetics.
In the second case which is temperature dependent, in that case the concentration is fixed
and temperature is varied. On combining these two conditions the overall rate equation is a
function of temperature and concentration.
2.4 Constant volume reactor system

Here we are referring to the volume of the reaction mixture, and not the volume of the
reactor. Thus this term actually means a constant-density reaction system.
Most liquid-phase reactions as well as all gas-phase reactions occurring in a constant-
volume bomb fall in this class.
The volume of reaction mixture remains unchanged with respect to time. ( V = VO ).
NA N ( 1 − X A )
CA = CA = Ao
V V ( = Vo )
CA NAo ( 1 − X A )
= Valid for CVRS only.
In a constant-volume reaction system the measure of reaction rate of component ‘i’
become
N 
d i 
1 dNi  V  dCi
=ri = =
V dt dt dt
For the reaction A → B
For reactant ‘A’
dC
rA = A
dt
For product ‘B’
dC
rA = A
dt
p
For ideal gases, where C =
RT
1 dpi
rA =
RT dt
Thus, the rate of reaction of any component is given by the rate of change of its concentration
or partial pressure.
Ideal Reactors
19.
Chapter 2
Conversion (xa )
The fractional conversion, or the fraction of any reactant, say A, converted to something
else, or the fraction of A reacted away. We call this simply, the conversion of A, with the
symbol “XA”.
NA0 is the initial amount of A in the reactor at time t=0.
NA is the amount present at time t. than conversion of A in the constant volume system is
given by,
NAo − NA N ⁄V C
XA = =1- A =1- A
NAo NAo ⁄V CAo
Therefore,
dCA
dX A = −
CAo
Note: Conversion is defined only for the reactants not for the product.
For constant volume reactor system:
Kinetic equation for different order of reaction having one reactant only.
First order reaction:-

K
A P
n=1
−dCA
-rA = = KCA
dt
CA −dC t
∫ CAo dt
A
∫
= Kdt
0
 dCA 
lnln   = Kt
 CA 
−Kt
CA = CAo e
This equation is called the kinetic equation for first order reaction.
Kinetic equation in terms of conversion.
Second order reaction

K
A P
n=2
−dCA
-rA = = KCA2
dt
CA −dC t
∫ CAo C 2
A
A
∫
= Kdt
0
Ideal Reactors
1 1
− = Kt
CA CAo
20.
Chapter 2
1 1
− Kt
=
CAo ( 1 − X A ) CAo
XA
= KCAo t
( 1 − XA )
KCAo t
XA =
( 1 + KCAo t )
Every reaction order which is greater than 1, can’t achieve the 100% conversion.
Zero order of reaction:-

K
A P
n=0
−dCA
-rA = = KCA0
dt
CA −dC t
∫ CAo C 0
A
A
0∫
= Kdt
CAo – CA = Kt
CAo.XA = Kt
Time required to achieve XA = 1
CAo
t=
K
Rate of change of XA,
dX A K
=
dt CAo
For nth order of reaction
−dCA
-rA = = KCAn
dt
CA −dC t
∫CAo C n
A
A
= Kdt
0 ∫
1 1
(n – 1 ) (=
t ) n−1 − n−1
K
CA CAo
This expression is valid for all order of reaction except 1.
Mole balance over chemical reaction
aA + bB → cC + dD
Ideal Reactors
21.
Chapter 2
Moles ofB r eacted
Moles of B reacted = × Moles of A r eacted
Moles of A r eacted
b
Moles of B reacted = × Moles of A reacted
a
Moles of B remaining = Moles of B initially fed – Moles of B reacted.
b
NB = NBo – × Moles of A reacted
a
b
NB = NBo − × NAo .X A
a
c 
Moles of C in Outlet = Moles of C initially +  × NAo .X A  Moles C formed .
a 
c
NC = NCo + × NAo .X A
a
d
ND = NDo + × NAo .X A
a
NA = NAo −NAo .X A
NA NAo −NAo .X A
=
V V
b
NBo − × NAo .X A
NB a
=
V V
c
NCo + × NAo .X A
NC a
=
V V
d
NDo + × NAo .X A
ND a
=
V V
NAo −NAo .X A
CA =
V
CA = CAo − CAo .X A
b
NBo − × NAo .X A
CB = a
V
b
CB = CBo − CAo .X A
a
c
NCo + × NAo .X A
CC = a
V
c
Ideal Reactors
CC = CCo + CAo .X A
a
22.
Chapter 2
d
NDo + × NAo .X A
CD = a ,
V
d
CD = CDo + CAo .X A
a
For constant volume reaction system

aA + bB → cC + dD
b
Mole of B reacted = Mole of A reacted
a
b
NBo .XB = N Ao .X A
a
NAo .X A NBo .XB
=
a b
Kinetic equation for bimolecular second order reaction:-

K
aA + bB P
n=2
−dCA
-rA = = KCACB
dt
CA = CAo (1-XA)
b
CB = CAo − CAo .X A
a
−dCAo ( 1 − X A )  b 
= K.CAo ( 1 − X A )  CBo − CAo .X A 
dt  a 
dX A  b 
CAo . = K.CAo ( 1 − X A )  CBo − CAo .X A 
dt  a 
dX A  b 
K ( 1 X A )  CBo − CAo .X A 
=−
dt  a 
C b 
= K ( 1 − X A ) CAo  Bo − CAo .X A 
 CAo a 
b 1
= = 1
a 1
dX A
= KCAo ( 1 − X A ) (M − X A )
dt
C
M = Bo
CAo
XA dX A t
Ideal Reactors
∫0 ( 1 − X ) (M − X )
A A
∫
= KCAodt
0
23.
Chapter 2
XA  1 1  t
∫ 0
 −
 ( 1 − X A ) (M − 1) ( M
 dX A =
− X A ) (M − 1)  0∫
KCAodt
1  XA dX A XA dX A 
(M − 1) 
 ∫ 0 ( 1 − XA )
− ∫ 0 (M
=
− X A ) 
KCAo t
− lnln ( 1 − X A ) − lnln ( 1 − 0 )  + lnln ( M

− X A ) − lnln ( M
− 0 )  =(M − 1)K
CAo t
( 1 − XA ) + lnln ( M
− X A ) −lnlnM ( − 1)K CAo t
=
M
 A 
lnln A − lnlnB
=
lnln   
 B 
 M − X A 
lnln  =  (M − 1) KCAo t M ≠ 1
M ( 1 − X A ) 
Case 1 :- It is not valid for M = 1,
CAo = CBo
NAo = NBo equimolar A&B
Valid only for NAo ≠ NBo
Case 2 :- Kinetic equation for equimolar A&B

K
A+B P

n=2
−dCA
-rA = = KCACB = KCA2
dt
For equimolar A&B CA = CB
2.5 Method of finding overall order of reaction

y Initial rate method
y Half life method
y Fractional life method
y Initial rate of reaction

The method of initial rates is a commonly used technique for deriving rate laws.
As the name implies, the method involves measuring the initial rate of a reaction. The
measurement is repeated for several sets of initial concentration conditions to see how
the reaction rate varies. This might be accomplished by determining the time needed to
exhaust a particular amount of a reactant (preferably one on which the reaction rate does
Ideal Reactors
not depend).
Example: A + B → P
24.
Chapter 2
Run [A] (M) [B] (M) [C] (M)
1 0.0100 0.0100 0.0347
2 0.0200 0.0100 0.0604
3 0.0200 0.0200 0.2776
The analysis of this data involves taking the ratios of rates measured where one of the
concentrations does not change. For example, assuming a rate law of the form
-rA = KCAαCBβ
(-rA)o = KCA0αCBoβ
The ratio of runs i and j generate the following relationship
ratei k [ A ]i [B]i
α β
=
rate j k [ A ]α [B]β
j j
So using runs 1 and 2

0.0347 k [0.01]1 [0.01]1
α β
=
0.0694 k [0.02]α [0.01]β
2 2
This simplifies to
α
1 1
=  
2 2
So clearly, α and the reaction is 1st order in A. Taking the ratio using runs 2 and 3
0.0694 k [0.02]2 [0.01]2
α β
=
0.2776 k [0.02]α [0.02]β
3 3
This simplifies to
β
1  1 
=  
4 2
By inspection, one can conclude that the reaction is second order in B. But if it is not so
clear (as it might not be if the concentration is not incremented by a factor of 2), the value
of β can be determined by taking the natural logarithm of both sides of the equation.
β
1 1
ln = ln  
4 2
On solving,
1 2
[ A ]i [B]i
rate = k
Ideal Reactors
So the rate law,

1 2
[ A ] [B]
rate = k
25.
Chapter 2
Q1 The decomposition of N2O5 is given as 2N2O5 4NO2 + O2 At initial concentra-

M.
tion of N2O5 =3.15M,the initial rate of reaction = 5.45 × 10-5
s
At the initial concentrations of N2O5 = 1.78M, the initial rate off
M
reaction = 1.35 × 10-5 .
s
Find out the rate constant “k” ?
A 5.45 × 10-5 = -K(CA0)n

1.35 × 10-5 = -K(CA0)m
n
5.45 × 10−5  3.15 
−5 = K  
1.35 × 10  1.78 
n
 3.15 
4.037 =  
 1.78 
n = 2.44
5.45 × 10-5 = -K(CA0)n
−1.44
−6 M
K = 3.315 ×10
s
−6 1
K = 3.315 ×10 1.44
sM

y Half life method:-

⚪ It is the time required to achieve 50% conversion of limiting reactants.
⚪ Half life of reaction only not for the reactant.
If one reactant
⚪ Time required to reduce the concentration to the half of its initial value. Reaction time
is t 1 .
2
nth order of reaction
Kinetic equation
1 1
(n – 1 )( Kt ) = − .
CnA−1 CnAo−1
At,t = t 1
2
Ideal Reactors
CAo
CA =
2
26.
Chapter 2
1 1
(n – 1 )(K t 1 ) = n− 1
− .
2  CAo  CnAo−1
 2 
 
2n−1 − 1 1−n
t1 = . CAo (i)
2 ( n − 1 ) K
 
t1 
 
 2
t 1 ∝ C1Ao
−n
(ii)
2
Equation (i) and (ii) are valid for all n order except 1.
y For 1st order reaction:-
C 
lnln  Ao  = Kt
 CA 
At,t = t 1 ,
2
C
CA = Ao
2
( ) = K. t 1
lnln 2
2
( ) 0.693
lnln 2

= t 1 =
2
K K
y Fractional life method
1 1
y (n – 1 )( Kt ) = n− 1
− n− 1 .
CA CAo
At,t = tf
CA = f.CAo
C
f= A
CAo
1 1
(n – 1 )( K tf ) = n− 1
−
( f.CAo ) CnAo−1
1−n
f − 1 1−n
tf = C
(n − 1) K Ao
2.6 Varying – Volume reactor
Varying – volume reactors are more complex than the simple constant-volume batch reactor.
Ideal Reactors
Consider a reaction aA + bB → cC + dD with inert
27.
Chapter 2
Initially, the total number of moles are

NT0 = NA0 + NB0 + NC0 + ND0 + NI0
Finally, the total number of moles are
NT = NA + NB + NC + ND + NI
From ideal gas law
pv = nRT
where p is the total pressure

v is the total volume
T is the total temperature
R is the gas constant
Initially,
p0 v 0 = nT0RT0 (1)
Finally,
pv = nTRT (2)
Dividing equation (2) and (1)
pv n T
= T (3)
p0 v 0 nT0RT0
Rearranging,
 N  T p 
V = V0  T     0 
 NT0   TT   p 
We know by the relation,
N
=A N
A0 − NA0 X A
b
N
=B N
B0 −   NA0 X A
a
c
N
=C N
C0 +   NA0 X A
a
 d
N
=D N
D0 +   NA0 X A
a
Ni =N
i0
Ideal Reactors
d c b 
NT = NT0 +  + − − 1 NA0
a a a 
28.
Chapter 2
b c d
A+ B
→ C + D
a a a
d c b
δ= + − −1
a a a
Therefore,
N=T NT0 + δNA0X A
Rearranging,
NT N
= 1 + δ A0 X A
NT0 NT0
NT
= 1 + δ y A0X A
NT0
NT
= 1+ ∈A X A
NT0
p   T 
V V0 ( 1 + εA X A )  0   
=
 p   T0 
In case of constant temperature and pressure
V V0 ( 1 + εA X A )
=
N − NT0
εA = T
NT0X A
V − V0
or X A =
V0εA
dV
or dX A =
V0εA
where εA is the fractional change in volume of the system between no conversion and the
complete conversion of reactant A. Thus,
= VX − VXA 0
1 =
A
εA =
VXA =0
To illustrate the fractional change in volume ( εA ) , consider an isothermal gas-phase reaction
A → 4R
Initially pure reactant A is feed into the reactor
Therefore,
4−1
ε=A = 3
1
We know that,
= NA N A0 ( 1 − X A ) (4)
Ideal Reactors
NA N ( 1 − X A ) 1 − X A
C=
A = A0 = CA0 (5)
V V0 ( 1 + εA X A ) 1 + εA X A
29.
Chapter 2
Thus,
CA 1 − X A
=
CA0 1 + εA X A
C
1 − A
CA0
XA =
C
1 + εA A
CA0
which shows the relationship between conversion and concentration for isothermal varying-
volume (or varying-density) systems.
The rate of reaction (disappearance of component A), is, in general
1 dN
−rA = − A (6)
V dt
Replacing V and NA0 , equation (6) becomes
CA0 dX A
−rA =

( 1 + εA XA ) dt
or in terms of volume,
C dV C d (lnln V )
A0
−rA = = A0
VεA dt εA dt
2.7 Different order of reactions

Zero-order reaction
For homogenous zero-order reaction the rate of change of any reactant A is
C d (lnln V )

= −rA A0= k
εA dt
Integrating,
CA0 V
lnln = kt
εA V0
εA
( + ∈A XA ) =
lnln 1 kt
CA0
For constant volume reaction
CA0X A = kt
Which shows that for zeroth order reaction, the reaction follows different kinetics of variable
volume reaction system and for constant volume reaction system for the same condition.
First order reaction

Ideal Reactors
For a unimolecular- type first order reaction the rate of change of reactant A is
30.
Chapter 2
CA0 d (lnln V )  1 − XA 
−rA= = kCA
= kCA0  
εA dt  1 + εA X A 
Replacing X A by V and integrating, the final expression is
 ∆V 
−lnln  1 −  = kt, ∆V = V − V0
 εA V0 
or
( − XA ) =
lnln 1 −k t
Which shows that for the first order reaction system, the kinetics in the case of constant
volume and variable volume reaction system are the same.
Second- order reaction

For a bimolecular-type second order reaction
2 A → R or A + B → products
Let CA0 = CB0
The rate of the reaction is
2
CA0 d (lnln V ) 2 2  1 − XA 
−r=
A = kCA = kCA0  
εA dt  1 + εA X A 
Replacing X A by V and integrating
( 1 + εA ) ∆V  ∆V 
+ εAlnln  1 −  =k
CA0t
V0εA − ∆V  V0εA 
Reactions of shifting order
In searching for a kinetic equation it may be found that the data are well fitted by one
reaction order at high concentrations but by another order at low concentrations. Let us
consider such a reaction as follows:
dCA kC
A → R with −rA =
− 1 A
=
dt 1 + k2CA
At high CA – the reaction is of zero order with rate constant k1 / k2
At low CA – The reaction is of first order with the rate constant k1
Now integrating the above equation
C
ln A0 + k2 (CA0 − CA ) =
k1t
CA
y The rate form of shifting order reaction and some of its generalizations are used to represent
Ideal Reactors
a number of widely different kinds of reactions.
31.
Chapter 2
y For example, in homogeneous systems this form is used for enzyme catalyzed reactions
where it is suggested by mechanistic studies.
y It is also used to represent the kinetics of surface-catalyzed reactions.
y In mechanistic studies, this form of equation appears whenever the rate controlling step
of a reaction is viewed to involve the association of reactant with some quantity that is
present in limited but fixed amounts; for example, the association of reactant with enzyme
to form a complex, or the association of gaseous reactant with an active site on the
catalyst surface.
Space time and space- velocity

Space time is the time required to process one reactor volume of feed measured at specified
conditions.
Space time is denoted by ' τ '
1
τ= [
= time ]
s
Space- velocity
Space velocity is the number of reactor volume of feed at specified conditions which can
be treated in unit time.
It is given as ' s '
1
s= time −1 
τ  
For better understanding, consider a space time of 10 min means that every 10 min one
reactor volume of feed at specified conditions is being treated by the reactor and space
r −1 signifies that 10 reactor volume of feed at specified conditions are fed into
velocity of 10h
the reactor per hour.
The value of the space time and space velocity depends on the temperature, pressure and
state chosen to measure the volume of material being fed to the reactor.
 moles of A entering 
1 CA0 V  volume of feed 
( volume of reactor )
τ= = =
s FA0  moles of A entering 
 
 time 
V (reactor volume )
τ = =
v0 volumetric feedr ate
Ideal batch reactor

In a batch reactor, composition is uniform throughout at any instant of time,
therefore accounting the whole reactor and material balance is done over reactant
Ideal Reactors
A concentration.
32.
Chapter 2
General material balance equation
Input = output + disappearance + accumulation
In a batch reactor, no input and output.
Therefore,
Disappearance = − Accumulation
Rate of loss of reactant A within the reactor due to chemical reaction =
− Rate of accumulation of reactant A within the reactor
Now, we know that
dX A
Disappearance of A by reaction moles/time = ( −rA ) V = NA0
dt
Rearranging and integrating,
XA dX
t =N
A0 ∫ A
0 ( −r ) V
A
(7)
Equation (1) can be simplified as

XA dX A CA dCA
t = CA0 ∫ 0 −rA
= − ∫ CA0 −rA
The general equation above shows the correlation showing the time required to achieve a
conversion X A for isothermal as well as for non- isothermal reactions.
Equation in case of:
1. Constant volume batch reaction
XA dX CA dC
t = CA0 ∫
0 −r
A
A
= −
CA0 −r
A
A
∫
for εA =0
2. Varying volume batch reactor

XA dX A XA dX A
t =N
A0 ∫
0 −r V ( 1 + ε X )
A 0 A A
= −CA0 ∫ 0 ( −rA ) ( 1 + εA XA )
Ideal Reactors
Figure 3: Graphical representation of the performance equation for the

batch reactors, isothermal or non-isothermal
33.
Chapter 2
Steady- state mixed flow reactor

In a mixed flow reactor the composition is uniform throughout and the concentration at the
exit of the reactor will be the same as that given in the reactor.
General material balance on reactant A.
Input = output + disappearance by reaction + accumulation
Accumulation =0
FA0 = v 0CA0 is the molar feed rate of component A to the reactor.
Input of A, moles/time = FA0 ( 1 − X A0
= ) FA0 , X=
A0 0
Output of A , moles/time =
= FA FA0 ( 1 − X A )
Disappearance of A by reaction, moles/time
 moles A r eacting 
= ( −rA ) V = ( time ) ( volume of fluid)  (
 volume ofr eactor )
 
Evaluating equation (7)
FA0X A = ( −rA ) V
which on rearrangement becomes
V τ ∆X
= = A
FA0 CA0 −rA
1 V VCA0 CA0 X A
τ= = = =
s v0 FA0 −rA
Note: X A and rA are measured at exit stream conditions, which are the same as the condition
within the reactor.
V ∆X A X − X Ai
= = Af
FA0 ( −rA )f ( −rA )f
VCA0 CA0 ( X Af − X Ai )
=τ =
FA0 ( −rA )f
C
For the special case of constant- density system X A = 1 − A
CA0
Performance equation can be written as
V X A CA0 − CA
= =
FA0 −rA CA0 ( −rA )
V C X C − CA
τ= = A0 A = A0
v −rA −rA
From the performance/ design equation the size of the reactor needed for a given duty or
Ideal Reactors
the extent of conversion in a reactor of given size can be found.
34.
Chapter 2
Figure 4: Graphical representation of the design equation for mixed flow reactor
For the first- order reaction becomes

XA C − CA
= kτ = A0 for εA
1 − XA CA
For varying density system
V V0 ( 1 + εA X A )
=
CA 1 − XA
=
CA0 1 + εA X A
Thus, for the first order reaction
X ( 1 + εA X A )
kτ A for any εA
1 − XA
Steady – state plug flow reactor

In a plug flow reactor the composition of the fluid varies from point to point along a flow
path; the material balance for a reaction component must be made for a differential element
of volume dV.
Input = output + disappearance by reaction + accumulation (8)
Input of A, moles/ time = FA
Output of A , moles/time = FA + dFA
Disappearance of A by reaction, moles/time = ( −rA ) dV
 moles of A r eactant 
=   ( volume of element )
 ( time ) ( volume of fluid ) 
Substituting in equation (8)
Ideal Reactors
( A + dFA ) + ( −rA ) dV
FA= F
35.
Chapter 2
d FA0 ( 1 − X A )  =
dFA = −FA0dX A
Therefore,
FA0dX A = ( −rA ) dV
For the reactor as a whole the expression is integrated,
The feed rate is constant, but rA is dependent on the concentration or conversion of material
VdV XAf dX A
∫ 0F
A0
= ∫ 0 −rA
Thus,
V τ XAf dX
= =
FA0 CA0 ∫ 0 −rA
If the feed on which conversion is based, subscript 0, enters the reactor partially converted,
subscript i, and leaves at a conversion designated by subscript f,
V XAf dX

FA0
= ∫
XAi −r
A
A
XAf dX
τ = CA0 ∫
XAi −r
A
A
For the special case of constant-density system

C
XA = 1 − A
CA0
dCA
dX A = −
CA0
XAf dX CAf dC
τ = CA0
0 ∫
−rA
A

=−
CA0 −r
A
A
∫
Figure 5: Graphical representation of the performance equation for plug flow reactors
Ideal Reactors
36.
Chapter 2
For zero-order homogeneous reaction, for constant density ε
kCA0V
kτ =
= CA0X A
FA0
First order irreversible reaction, A → product , for constant density system
( 1 + òA ) lnln 1
kτ =− ( − XA ) −ò A XA
Comparison between the batch reactor and plug flow reactor
y Performance equation of constant-volume batch reactor and plug-flow reactor are
identical.
y The space time ' τ ' for plug- flow is equal to the space time ' t ' of the batch flow reactor.
Mixed versus plug flow reactors

The ratio of sizes of mixed and plug flow reactors will depend on the extent of reaction, the
stoichiometry and the form of the rate equation.
Example: For ‘n’ order,
The rate of reaction is
1 dNA
−rA =
− =kCnA
V dt
where n varies anywhere from zero to three
In case of mixed flow reactors
C V C X
=τm  A0
=  A0 A (9)
 FA0 m −rA
In case of plug flow reactor
n
C V XAdX A 1 XA ( 1 + εA XA ) dXA
=τp  A0
=  CA0
 FA0 p
∫ =
0 −r
A
n− 1
kCA0 ∫ 0
( 1 − XA )
n (10)
Dividing equation (9) and (10), we get

  1 + ò X n 
 CnA0V  XA  A A
 
(
τ CnA0
−1
) m
 F 

 A0 m

  1 − X A  
m
= = (11)
(
τ CA0 )
n− 1  CnA0V   XA  1 + òA X A 
n 
p 
 FA0 p
 
 ∫ 0

 1 − XA 
 dX A 

p
with constant density, or ε =0 ,

On integration, equation (11) becomes,
Ideal Reactors
37.
Chapter 2
 X 
A
 
τ CnA0
−1
m
(
) n
 ( 1 − X A ) 
,n
≠1 m

= n− 1
τ CA0
p
( 
)
 ( 1 − X )1−n − 1 
A

 n −1 
p
or
 XA 
( τ C ) n− 1
A0
m
=
 
 1 − X A m
, n 1

=
( τ C ) n− 1
A0
p
−lnln 1( − XA ) p
Conclusion:
y For all the positive reaction orders, the volume required by the mixed flow reactor is larger
than that required by the plug flow reactor for the same conversion under constant reaction
conditions.
y The positive order of reaction conversion achieved by a mixed flow reactor is less than that
achieved by plug flow reactors of the same equivalent volume.
y For zeroth order reaction, volume required by a mixed flow reactor is the same as that of a
plug flow reactor for the same conversion.
y For zeroth order reaction conversion achieved by a mixed flow reactor is the same as that
achieved by the plug flow reactor of the same equivalent volume.
y For negative order of reaction volume required by plug flow reactor is greater than that of
mixed flow reactor for the same reaction.
y For the negative order reaction conversion achieved by a mixed flow reactor is more than
that achieved by plug flow reactors of the same equivalent volume.
y When conversion is small, the reactor performance is only slightly affected by the flow type.
The performance ratio increases very rapidly at high conversion.
y Density variation during reaction affects design.
2.8 Reactor design and analysis of performance

Reactor design embodies many different facets and disciplines, the details of some of which
are outside our scope. Here, we focus on process design as opposed to mechanical design
of equipment. Other aspects are implicit, but are not treated explicitly: instrumentation and
process control, economic, and socioeconomic (environmental and safe-operation). Reactor
design is a term we may apply to a new installation or modification.
Parameters affecting reactor performance: The term “reactor performance” usually refers to
the operating results achieved by a reactor, particularly with respect to fraction of reactant
Ideal Reactors
38.
Chapter 2
converted or product distribution for a given size and configuration; alternatively, it may
refer to size and configuration for a given conversion or distribution. In any case, it depends
on two main types of behavior.
(1) Rates of processes involved, including reaction and heat and mass transfer, sometimes
influenced by equilibrium limitations.
(2) Motion and relative-motion of elements of fluid (both single-phase and multiphase
situations) and solid particles (where involved), whether in a flow system or not.
At this stage, type (1) is more apparent than type (2) and we provide some
preliminary discussion of (2) here. Flow characteristics include relative times taken
by elements of fluid to pass through the reactor (residence-time distribution), and
mixing characteristics for elements of fluid of different ages: point(s) in the reactor
at which mixing takes place, and the level of segregation at which it takes place (as
a molecular dispersion or on a macroscopic scale). Lack of sufficient information
on one or both of these types is a major impediment to a completely rational
reactor design.
Interpretation of batch reactor data

A rate equation characterizes the rate of reaction, and its form may either be suggested by
theoretical considerations or simply be the result of an empirical curve-fitting procedure.
In any case, the value of the constants of the equation can only be found by experiment;
predictive methods are inadequate at present.
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.
Equipment by which empirical information is obtained can be divided into two types, the
batch and flow reactors. The batch reactor is simply a container to hold the contents while
they react. All that has to be determined is the extent of reaction at various times, and this
can be followed in a number of ways, for example:
y By following the concentration of a given component.
y By following the change in some physical property of the fluid, such as the electrical
conductivity or refractive index.
y By following the change in total pressure of a constant-volume system.
y By following the change in volume of a constant-pressure system.
y The experimental batch reactor is usually operated isothermally and at constant volume
because it is easy to interpret the results of such runs.
⚪ The flow reactor is used primarily in the study of the kinetics of heterogeneous reactions.
⚪ There are two procedures for analysing kinetic data, the integral and the differential
methods.
Ideal Reactors
39.
Chapter 2
Table 4: Comparison of differential and integral method
Differential method Integral method
In the differential method of analysis we In the integral method of analysis we guess

test the fit of the rate expression to the a particular form of rate equation and, after
data directly and without any integration. appropriate integration and mathematical
However, since the rate expression is a manipulation, predict that the plot of a certain
differential equation, we must first find concentration function versus time should
1 dN yield a straight line. The data are plotted, and
from the data before attempting
V dt if a reasonably good straight line is obtained,
the fitting procedure. then the rate equation is said to satisfactorily
fit the data.
The differential method is useful in more The integral method is easy to use and
complicated situations but requires is recommended when testing specific
more accurate or larger amounts of data mechanisms, or relatively simple rate
expressions.
the differential method can be used to The differential method is useful in more
develop or build up a rate equation to fit complicated situations but requires more
the data. accurate or larger amounts of data
Practice Questions
Q1 The performance equations for constant density systems are identical for:
(A) P.F.R and CSTR
(B) P.F.R and batch reactor
(C) P.F.R, batch reactor and PFR
(D) Batch reactor and CSTR
A (B)
Ideal Reactors
40.
Chapter 2
Q2 Study of chemical kinetics is the easiest in the case of which type of
reaction:
(A) Irreversible
(B) Reversible
(C) Surface
(D) Side
A (A)
Q3 In the first order reaction, the time required to reduce the concentration of
reactant from 1 mole/liter to 0.5 mole/liter will be _______________ that
required to reduce it from 10 moles/liter to 5 moles/liter in the same volume.
(A) More than
(B) Less than
(C) Same as
(D) Data insufficient, can’t be predicted
A (C)
Q4 An irreversible first order reaction is being carried out in a CSTR and PFR of
same volume. The liquid flow rates are the same. The relative conversion
will:
(A) Be more in CSTR than in PFR
(B) Be more in PFR than in CSTR
(C) Be same in both cases
(D) Depend on the temperature
A (B)
Ideal Reactors
41.
Chapter 2
Q5 Participation of ______________ is involved in the occurrence of a chemical

reaction.
(A) Protons
(B) Neutrons
(C) Electrons
(D) None of these
A Answer (C)
Q5 A photochemical reaction is ____________ light.

(A) Initiated by
(B) Accompanied with the emission of
(C) Catalyzed by
(D) used to convert heat energy into
A Answer (A)
Ideal Reactors
42.
3 Multiple-Reactor Systems
Chapter 3
Plug flow reactors in series
Consider N plug flow reactors connected in series, and let X1 , X2, ……… XN be the fractional
conversion of component A leaving reactor 1, 2, …… ..N
.
Material balance on the feed rate of A to the first reactor, the equation of ith reactor
Vi Xi dX
F0
=
Xi − 1 −r ∫
or for the N reactors in series
V N Vi V + V2 + V3 + … VN
= =
F0 i= 1 F∑
0
1
F0
X1 dX X2 dX XN dX XN dX
= ∫ X0 =0 −r
+ ∫ X1 −r
+ … ∫ XN− 1 −r ∫
=
0 −r
Hence, N plug flow reactors in series with a total volume V gives the same conversion as a
single flow reactor of volume V. In case of parallel arrangement of plug flow reactor V / F or τ
must be the same for each parallel line.
As observed, in plug flow reactors the concentration of reactant decreases progressively
through the system whereas, in case of mixed flow reactors the concentration drops
immediately to a low value. Because of this fact, a plug flow reactor is more efficient than
a mixed flow reactor for reactions where n>0.
Mixed flow reactors in series

Consider a system of N mixed flow reactors connected in series. The concentration is
uniform in each reactor is uniform, nevertheless, a change in concentration as fluid moves
from reactor to reactor.
For N constant density mixed flow reactors.
First order reactions
C V V C ( X − Xi−1 )
τi= 0 i= i= 0 i
F0 v −rAi
C V V C − Ci
τi= 0 i= i= i−1
F0 v kCi
Ci−1
or = 1 + kτi
Ci
Multiple-Reactor Systems
Space- time τ (or mean residence time t) is the same in all the equal-size reactors of
volume Vi . Therefore,
C0 1 C C C
= = 0 1 …… .. N−1= ( 1 + kτi )N
CN 1 − XN C1 C2 CN
Rearranging, the final equation is
43.
1/N
N  C0  
τNreactors = Nτi =   − 1
k  CN  
 
In the limit N → ∞ , this equation reduces to plug flow reactors

1 C
τp = ln 0
k C
Case 1: If all the tanks have same T

T
=1 T=
2 T=
3 T4      T=
N T
k=
1 k=
2 k=
3 k 4      k=
N k
CA0
CAN =
( 1 + τ1k ) ( 1 + τ2k ) ( 1 + τ3k ) ( 1 + τ3k ) ( 1 + τ4k ) ………… ( 1 + τNk )
Case 2: If all the tanks have same volume
V
=1 V=
2 V=
3 V4      V=
N Vi
τ1 =τ2 =τ3 =τ4      τN =τi
CA0
CAN =
( 1 + τ1k ) ( 1 + τ2k ) ( 1 + τ3k ) ( 1 + τ3k ) ( 1 + τ4k ) ………… ( 1 + τNk )
Case 3: If all the tanks have same volume and same temperature
V
=1 V=
2 V=
3 V4      V=
N Vi
T
=1 T=
2 T=
3 T4      T=
N T
CA0
CAN =
( 1 + τik )N
1
X AN= 1 − N
( 1 + τik )
Figure 6: Mixed flow reactor in series
44.
Below figure 7 gives insight of the performance equation of the single mixed flow reactors
and the mixed flow reactors in series.
Figure 7: Performance equation of the single and multiple mixed flow reactors in series
Comparative study of single mixed flow reactor and multiple flow reactors in series
1. For positive order of reaction, mixed flow reactor in series required less volume than
that of required by single mixed flow reactor for the same conversion.
2. For positive order of reactions, conversion achieved by mixed flow reactor in series is
higher than that of achieved by single mixed flow reactor of same equivalent volume.
Reactors of different types in series

Consider different types of reactors in series, such as mixed flow reactors followed by plug
flow reactor which in turn is followed by another mixed flow
Rate of reaction
V1 X1 − X0 V2 X2 dX V3 X1 − X0
=
F0
= , = ∫
,
( −r )1 F0 X1 −r F0 ( −r )1

Best arrangements of a set of ideal reactors (plug flow reactors, small mixed flow reactors
and large mixed flow reactors)
y For order of reaction n > 0 , the order of the reactors should be ordered so as to keep the
concentration of reactant as high as possible if the rate -concentration curve is concave
( n > 1 ) , and as low as possible if the curve is convex ( n > 1 )
y For n > 1 , the order of the reactors is plug, small mixed, large mixed.
y For n < 1 , the order of the reactors is large mixed, small mixed and plug.
y Examination of 1 / ( −rA ) vs. Cs a curve is a good way to find the best arrangement of units.
Best arrangements of a set of plug flow reactors and mixed flow reactors
y For n < 1 , early mixing is required
In this case, a mixed flow reactor is followed by a plug flow reactor.
45.
y For n > 1 , late mixing is required
In this case, a plug flow reactor is followed by a mixed flow reactor.
y For n = 1 , no effect of mixing
In this case, any arrangement is preferable.
Best arrangements of the set of small and large mixed flow reactors in series
y For order of reaction, n < 1 , early mixing is required
In this case a large mixed flow reactor is followed by a small mixed flow reactor.
y For order of reaction, n
> 1 , late mixing is required
In this case, a smaller mixed flow reactor is followed by a large mixed flow reactor.
y For order of reaction, n
= 1 , equal size mixed flow reactors in series.
Multiple reaction
Irreversible reactions in parallel –
Consider elementary reactions in which reactant A is decomposing into different
products.
Ak
1 →R

Ak
2 → S
The rates of change of the three components are given as
dCA
−rA = − =
1CA + k2CA =
k ( 1 + k 2 ) CA (1)
k
dt
dCR
k1CA = k1CA0 e ( 1 2 ) (2)
− k +k t
rR =
=
dt
dCS
k2CA = k2CA0 e ( 1 2 ) (3)
− k +k t
rS =
=
dt
Kinetics (k1 andk
2 ) in this case can be determined by using all the three above differential
equations
Equation (1) is the first order differential equation, Integrating equation (1)
C
( 1 + k2 ) t (4)
−lnln A =
k
CA0
Solving equation (2) and (3)
kC
CR 1 A0 1 − e ( 1 2 ) 
− k +k t
=
k 1 + k2  
kC
CS 2 A0 1 − e ( 1 2 ) 
− k +k t
=
k 1 + k2  
For determining the kinetics

Dividing equation (2) and (3)
46.
rR dCR k1
= =
rS dCS k2
CR − CR0 k1
= (5)
CS − C0 k2
Solving equation (4) and equation (5)
Kinetics can be determined.
Figure 8: Concentration – time curves for first- order parallel reaction
Irreversible reaction in series

Consider consecutive unimolecular reaction, first order elementary reaction
Ak
1 →R
k2 → S
The rate if reactions are as follows
dC
rA = A = −k1CA (1)
dt
dCR
rR = k1CA − k
= 2CR (2)
dt
dCS
rS =
= 2CR (3)
k
dt
Assuming that only reactant A is present with initial concentration of CA0 . Integrating
equation (1)
C
−lnln A =k1t or CA = CA0 e−k1t (4)
CA0
Substituting equation (4) in equation (2) for concentration of R
dCR
k1CA0 e−k1t (5)
+ k2CR =
dt
Equation (5) is first order differential equation
Solving by first- order linear differential equation of the form i.e.
47.
dy
+ Py =
Q
dx
By multiplying through with the integrating factor e∫
P dx
the final solution is
y e∫ ∫ P dx dx + constant

P dx

= ∫ Q e
Applying same method for solving equation (5)
 e−k1t e−k2t 
CR CA0k1 
= +  (6)
 k2 − k1 k1 − k2 
There is no change in total number of moles, the stoichiometry therefore is,
CA0 = CA + CR + CS (7)
Solving for concentration of S
 k2 k 
CS =
CA0  1 + e−k1t + 1 e−k2t  (8)
 k1 − k
2 k2 − k
1 
Thus, from equation(4) ,(6) and (8) it is clear that concentration varies with time, i.e
concentration is time dependent
Case 1:
k2  k
1
Equation (8) can be written as
(
CS CA0 1 − e−k1t
= )
which implies that concentration of S is governed by k1
Cases 2 :
k1  k
2
In this case equation (8) is
(
CS CA0 1 − e−k2t
= )
which implies that concentration of S is governed by k2
Case 3: k
1 =k
2
Rewriting equation (1) and (2)

dC
rA = A = −k1CA
dt
dCR
rR =
= k1CA − k
2CR
dt
As k1 = k
2
48.
dC
Therefore, = R k1 (CA − CR )
dt
dCR

=
dt
(
k1 CA0e−k1t − CR )
dCR
+ k1CR = k1CA0e−k1t
dt
Solving
CR = k1CA0e−k1t t
The maximum concentration of R and the time at which the concentration of R is maximum
dCR
Differentiating equation (6) and putting = 0
dt
On solving we get,
( 1 / k2 )
lnln k 1

= tmax = (9)
k2 − k 1 kloglog mean
Combining equation (9) and (6)
We get,
k2 / (k2 − k1 )
CR,max k 
=  1 
CA0  k2 
The determination of the kinetics of reaction Ak
1 →R
k2 → S is done by evaluating k1 and
k2 . This is done by determining by maximum concentration of the intermediate and the time
when the maximum is reached. Figure 9 the series reaction. A decreases exponentially, R
rises to a maximum and then falls and S as a final product, rises continuously. The greatest
rate of increase of S is attained when R is maximum.
Figure 9: Concentration – time curves for consecutive first- order series reaction
49.
First order reversible reaction –
Consider a reaction in which complete conversion cannot be achieved.
KC= K= equilibrium constant
dCR dCA dX A
= − = CA0 =− 1CA k2CR = k1 (CA0 − CA0X A ) − k
k 2 (CR0 + CA0X A ) (1)
dt dt dt
dCA
At equilibrium = 0
dt
Fractional conversion of A at equilibrium condition to be
CR0
+ X Ae
CRe CA0
Kc =
=
CAe 1 − X Ae
CR0
Let M =
CA0
Then,
CRe M + X Ae
Kc =
= (2)
CAe 1 − X Ae
and the equilibrium constant to be
k
Kc = 1 (3)
k2
Combining the above three equations we obtain, in terms of the equilibrium conversion
dX A k1 (M + 1)
= ( X Ae − X A ) (4)
dt M + X Ae
With conversion measured in terms of X Ae . Integration equation (4)
 X  C − CAe M+1
−lnln A
−lnln  1 − A  = =
k1t
 X Ae  CA0 − CAe M + X Ae
Second-order reversible reaction –
For the bimolecular, type second, order reactions.
50.
Let CA0 = CB0 and C=
R0 C=
S0 0
On integrating the rate for A and B are identical,
X − 2X ( Ae − 1)  1 
lnln Ae = 2k1  − 1  CA0t
X Ae − X A X
 Ae 
Parallel reaction
In case of multiple reactions, more than one rate expression is required. Multiple reactions
can be a combination of series or parallel reactions.
Consider a parallel reaction,
R is the desired product and S is the undesired product
The corresponding rate equation is:

dCR
rR =
= 1 CnA1 (1)
k
dt
ds
rs = k
= 2 CnA2 (2)
dt
rR dCR k2 n1 −n2
= = CA (3)
rS dCs k1
In case of ratio to be as large as possible
According to equation (3), the factors which decides maximizing the ratio are CA , k1 ,k2 ,n andn
2
. Among these factors, k1 ,k2 ,n1 andn
2 are all constants for a specific system at a given
temperature. Thus, only CA can be controlled.
51.
Table 5: Conditions for low and high CA
Low C A High C A
Mixed flow reactor. Batch/ plug flow reactor.
Maintaining high conversion. Maintaining low conversion.
Increasing inerts in the feed. Removing inserts from the feed.
Decreasing the pressure in the gas-phase Increasing the pressure in the gas-phase
systems. systems.
Conditions to determine the concentration of the reactant A

y If n1 > n2 , in other words the desired reaction is of higher order than the unwanted reaction.
Therefore, a batch or plug flow reactor would favor formation of product R and would
require a minimum reactor size.
y If n1 < n2 , in other words, the desired reaction is of lower order than the unwanted reaction.
Therefore, a mixed flow reactor is needed.
y If n1 = n2 , or the two reactions are of the same order.
rR dC1 k1
= = = constant . This implies that the product distribution is fixed by k2 / k1 alone
rS dC2 k2
and is unaffected by the type of the reactor used. In this case the kinetics of the reactions
can be changed to attain the desirable product.This can be done by changing temperature.
In multiple reactions, obtaining a favorable distribution of products can be obtained by
proper contacting patterns.
Different cases of multiple reactions with more than one reactant.
Case 1: Reactants A and B are added at the same time in noncontinuous operation.
In this case, both the reactants CA and CB should be of high concentration.
Case 2: Reactants A and B are added slowly in noncontinuous operation.
In this case, both the reactants CA and CB should be low.
Case 3: Reactant A is already present and B is added slowly.
In this case CA should be high and CB should be low.
Instantaneous fractional yield
Consider a parallel reaction

A + B → R (4)
A + B → S (5)
52.
Equation (4) is the desired reaction and equation (5) is the undesired reaction.
Consider the decomposition of reactant A, and let ϕ be the fraction of A disappearing at any
instant which is transformed into desired product R.
Thus, the instantaneous fractional yield of R.
formed  dCR
 moles ofR
ϕ  = 
 moles
o f
A r eacted  −dCA
ϕ is the instantaneous fractional yield of R, hence, ϕ will change with position in the
reactor.
To quantify the overall fractional yield of R, ϕ is defined as the fraction of all the reacted A
that has been converted into R or ϕ can be called as the overall fractional yield of R.
 allR formed  CRf CRf
ϕ =  = = in reactor
=ϕ
 all A r eacted  CA0 − CAf ( −∆CA )
ϕ in case of plug flow reactor, C changes progressively through the reactor
A
−1 CAf 1 CAf
ϕp
=
CA0 − CAf ∫ CA0
dCA
ϕ= ∫ ϕdCA
∆CA CA0
ϕ in case of mixed flow reactor, the composition is C everywhere
Af
For MFR: ϕm =
ϕevaluated at CAf
 dϕp 

ϕm = 
 dCA at CAf
Selectivity: Selectivity is defined as the ratio of moles of desired product formed to moles
of undesired material formed.
k
SR/S = 1 CnA1 −n2
k2
Case 1
n1 > n2
For maximum selectivity, high concentration of A is required.
Case 2
n1 < n2
For maximum selectivity, low concentration of A is required.
Case 3
n1 = n2
For maximum selectivity, independent concentration.
53.
Case 4
k
SR/S = 1 CnA1 −n2
k2
If E1 > E2
For maximum selectivity, high temperature is required.
Case 5
k
SR/S = 1 CnA1 −n2
k2
If E1 < E2
For maximum selectivity, low temperature is required.
Effect of temperature and pressure on reaction

Consider a reversible reaction
A ↔ B
The rate constant is k1 and k2
−r=
A k1CA − k2CB
The overall rate constant K
K
X Ae =
1+K
The Van’t Hoff equation is
dlnlnK
∆H
= 2
dT RT
On integration
k2 ∆H  1 1 
lnln
=  − 
k1 R  T1 T2 
Case 1: For endothermic reaction
∆H > 0
For an endothermic reaction as temperature increases, rate constant increases. Therefore
X Ae increases.
Case 2: For exothermic reaction

∆H < 0
For exothermic reactions as temperature increases, rate constant decreases. Therefore X Ae
decreases.
54.
Figure 10 : Effect of temperature on equilibrium conversion as predicted
by thermodynamics (pressure fixed)
What you should know:

Qualitative analyses (parallel and series reactions)
y Maximizing the reactor operation for single reactant systems.
y Maximizing the reactor operation for two reactant systems.
y Consideration of selectivity and yield.
y Algorithm for reactor design of multiple reactions
⚪ Mole balance.
y Net rates of reactions.
y Stoichiometry.
y Be able to write the set of equations for the system.
y Usually cannot be solved without computer programs.
y Be able to sketch the expected qualitative behaviour.
55.
4 Recycle Reactor
Chapter 4
In plug flow reactors, it is sometimes advantageous to return a part of the product stream
to the entrance of the reactor.
Let the recycle ratio R is defined as
Volume of fluid returned to ther eactor entrance
R =
volume leaving the system
The recycle ratio varies from zero to infinity.
For plug flow reactor, R = 0
Mixed flow reactor, R = ∞
Consider a plug flow reactor as a recycle reactor
V XA2 = XAf dX A
'
FA0
= ∫ XA1 −rA
(1)
'
where FA0 is the feed flowr ate of A if the stream entering the reactor
The flow entering the reactor includes both the fresh feed and the recycle stream.
'
FA0 = ( A which would enter in an unconvertedr ecycle stream) + ( A entering in fresh feed) (2)
=RFA0 + FA0 =( + 1) FA0 (3)
R
C
1 − A1
CA0 RX
X A1 = = A2 (4)
1 + εACA1 / CA0 1+R
Therefore,
FA1 FA0 + FA3 FA0 + RFA0 ( 1 − X Af )  1 + R − RX Af 
C=
A1 = = = CA0   (5)
v1 v 0 + Rv f v 0 + Rv0 ( 1 + εA X Af )  1 + R + RòA X Af 
From equation (4) and (5)
 R 
X A1 =   X Af (6)
R + 1
Replacing equation (6) in equation (1)
The performance equation for recycle reactors is
V XAf dX A
FA0
( + 1)
= R ∫  R 
  XAf
 R+1 
−rA
(7)
For plug flow reactor R = 0

V XAf dX A
FA0
( + 1)
= R ∫ 0 −rA
For mixed flow reactor R = ∞
Recycle Reactor
Integrating equation (7) for first order reaction
56.
Chapter 4
kτ  C + RCAf 
= lnln  A0 
R+1  (R + 1) CAf 
kCA0 τ CA0 (CA0 − CAf )
= −rA kC2
And for the second -order reaction, 2A → products, A=
R + 1 CAf (CA0 + RCAf )
Figure 11 : Representation of the performance equation for recycle reactor
Plug flow versus mixed flow reactor, no recycle –

y At low conversion the mixed reactor is superior to the plug flow reactor.
y At high enough conversions the plug flow reactor is superior.
The above two observation is different from n > 0 in which case the plug flow reactor is
always more efficient than the mixed flow reactor.
4.1 Semi-batch reactor

Semi-batch reactor is the combination of batch reactor and continuous flow reactor.
Design of equation of semi-batch reactor with continuous input and no output
Recycle Reactor
Figure 12: Semi-batch reactor in case of continuous input and no output
57.
Chapter 4
General equation : Molar flow input
= Output molar flow + Accumulation − Generation
dV dC
CA0
= ϑ0 CA + V A + ( −rA ) V
dt dt
Dividing by ' V '
CA0ϑ0 CA dV dCA
= + + ( −rA )
V V dt dt
Overallm
assb
alance
d ρV
ϑ0ρ0 =
dt
Assumption is the constant density is constant throughout
t V
∫ 0 ∫
ϑ0dt =
dV
0
ϑ0t = V
V
t=
ϑ0
dV
ϑ0 =
dt
dCA CA 1
+ + ( −rA ) = CA0
dt t t
For first order reaction
( −rA ) =
kCA
dCA CA 1
+ + kCA = CA0
dt t t
dCA  1  1
+  + k  CA = CA0
dt t  t
On solving the above differential equation
CA0  kt
=CA
kt 
e − 1 
 ( )
Recycle Reactor
58.
5 Autocatalytic Reactions
Chapter 5
A reaction in which one of the products of reaction acts as a catalyst is called autocatalytic
reaction.
Autocatalytic reactions rate is low at the start because a small amount of product is present,
it increases to a maximum as product is formed and then drops again to a low value as
reactant is consumed.
Consider a simple reaction
A + R → R + R
The rate of reaction is
dCA
−rA =
− =kCACR
dt
The total number of moles of A and R remains unchanged as A is consumed,
therefore,
C0 = CA + CR = CA0 + CR0 = constant
Thus, the rate of the equation becomes,
dCA
−rA =
− =kCA (C0 − CA )
dt
Rearranging and breaking into the partial fractions, we obtain
dCA 1  dCA dCA 
− −
=  +  =
k dt
CA (C0 − CA ) C0  CA C0 − CA 
On integration,
CA0 (C0 − CA ) C / CR0
ln = lnln R = C= ( A0 + CR0 ) kt
0 kt C
CA (C0 − CA0 ) CA / CA0
An autocatalytic reaction in a batch reactor progresses as shown in the figure

13, product R must be present to proceed the reaction. The reaction starts with
very less concentration of R, further the rate will increase once R is formed. The
rate of the reaction drops to zero when the reactant A is used up. Autocatalytic
reaction follows the parabolic profile with maximum occurs at a location where
the concentration of A and R are equal.
Autocatalytic Reactions
59.
Figure 13: Rate- concentration curve for autocatalytic reaction
Figure 14 : Arrangement of flow reactors in case of autocatalytic reaction

Autocatalytic Reactions
60.
6 Non-Isothermal Chemical
Reactors
Chapter 6
Although isothermal conditions are most useful for the measurement of kinetic data, real
reactor operation is normally non-isothermal. Within the limits of heat exchange, the reactor
can operate isothermally (maximum heat exchange) or adiabatically (no heat exchange); recall
the limits of reactor behavior studied so far. Between these bounds of heat transfer lies the
most common form of reactor operation-the non-isothermal regime (some extent of heat
exchange). The three types of reactor operations yield different temperature profiles within
the reactor or an exothermic reaction. If a reactor is operated at non isothermal or adiabatic
conditions then the material balance equation must be written with the temperature, T, as
a variable. Since the reaction rate expression now contains the independent variable T, the
material balance cannot be solved alone. The solution of the material balance equation is
only possible by the simultaneous solution of the energy balance. Thus, for non-isothermal
reactor descriptions, an energy balance must accompany the material balance.
So far, we have dealt with isothermal chemical reactors and were able, by using only as
many species mass balances as there are independent reactions to relate reactor size, inlet
and outlet composition. However, even for isothermal reactors we need the energy balance
to determine what heat duty is necessary in order to keep the reactor isothermal. For non
isothermal reactors (adiabatic and nonadiabatic) the energy balance is needed together with
the mass balances in order to arrive at reactor design equations.
The energy balance is the principle of conservation of energy or the first law of thermodynamics
as applied to our reaction system.
The assumptions are:

y Homogeneous system.
y Gas is ideal.
y A Single reaction.
y Continuous flow reactors operating at steady state.
y Kinetic energy changes are negligible compared to those in internal energy.
y Potential energy changes are negligible compared to internal energy changes.
y Heat of reaction is approximately constant.
y Shaft work is negligible.
y Mixtures are ideal.
Non-Isothermal Chemical Reactors
y Constant means specific heat and density.
The conservation equation requires:
 Rate of   Rate of   Rate of   Rate of 
 − + =  (1)
 input   output   generation   accumulation 
Apply it to the energy, the control volume being the total volume of the reaction mixture in
the reactor.
The energy per unit mass of the inlet stream may have different forms are:
Total energy = Kinetic energy (K.E) + Potential energy (P.E) + Internal Energy (I.E)
61.
Chapter 6
 Energy   Kinetic   Potential   Internal   Other 

         
 per unit mass  =  energy per  +  energy per  +  energy per  +  energy per 
 of a stream   unit mass   unit mass   unit mass   unit mass 
         
Among others, energy forms may be surface energy (not important in homogeneous flow),
magnetic energy, electric energy, etc.Most often in chemical reactors changes in other energy
forms can be neglected since there are no magnetic or electric fields used.
Now the above equation modifies to:
 Rate of energy   Rate of energy input by   Rate of heat addition 
=
   + 
 input   flow of material streams   from the surroundings 
 Rate of energy   Rate of energy output by   Rate of work done 
=
   + 
 output   flow of material streams   by the system 
 Rate of energy input or output by 
  = (Mass flow rate ) (Energy per unit mass )
 flow of material streams 
In steady state, the overall mass balance indicates a constant mass flow rate
m
= in m out m
=  (kg / s)
 Rate of energy input by 
 =  (KE + PE + u) (2)
 m
in
 Rate of energy output by 

 =  (KE + PE + u) (3)
 m
out
 Rate of heat addition   KJ 

  = q   (4)
 from the surroundings   s 
The work done by the system consists of three parts:
 Rate of work 
 Rate of work   
   done by the   Rate of work 
 Rate of work   Rate of shaft   done to expel
    
  surroundings   done against 
 done by the  =  work done by  +  the outflow
− + 
 system   the system  into the
  to propel the   gravity or other 
       inflow into   body forces 
 surroundings

 
  the system   
 
p p
w w
s m
 =+    −m    + mg (hout − hin ) (5)
 ρ out  ρ in
Using eqs (2), (3), (4) and (5) in (1) we get
p p
 (u + KE + PE ) + q − m
0= m  (u + KE + PE ) + ws +m
   −m    (6)
in out
 ρ out  ρ in
62.
Chapter 6
 p   p  
m
  u + + KE + PE  −  u + + KE + PE   = q − w
s
 ρ out  ρ in 
  p  st
1 law
m
  ∆E + ∆   = q − w
s ← 
  ρ 
One can readily show that in chemical reactors:
Recall the definition of enthalpy.
Hence equation (6) becomes
 (Hout − Hin ) =−
m q w
 s (7)
In almost all chemical reactors there is no considerable shaft work leading to:
m (Hout − Hin ) =
q (8)
For booking purposes in chemical reactors, we represent

s s
mH
 out = ∑ j= 1
FH
j j ; mH
 in = ∑ F H
j= 1
jo jo (9)
 Partial molal enthalpy 

 
 Enthalpy per unit   Molar flow rate   of species j per mole of 
(Mass flow rate)   =  ∑
 mass of mixture  all species  of species j

  j at conditions of the 
 
 mixture 
We will here further assume:
 partial   molal 
 = 
 molal enthalpy   enthalpy 

While H f(T,P,
= composition), Hj f(T,P) .
j
~
Furthermore, for gases we will assume ideal gases

Hj = f(T) (ideal gas)
~
This means that molal enthalpies are functions of temperature only. Non-Isothermal Chemical Reactors
Note. This assumption must be deleted and the effect of pressure considered when dealing
with reaction systems such as: ammonia synthesis, high P polymerization, coal conversion,
etc.
This means that Ts – reference (standard) T
 ∂ Hj 
 ~  = Cp j T
 ∂T 



p

specific heat for j
(10a) Hj (T) =∆ H (Ts )
~ ~ fj
 
+ ∫CdT
Ts
pj

(10)
enthalpy of formation temperature correction
at standard conditions
63.
Chapter 6
With eq (9) and assumptions (7) and (8), the reactor energy balance can finally be written as:
s
 
∑ F H (T) − F
j= 1
j
~
j jo Hj (To ) =
~ 
q (11)
Where exit temperature is T, inlet temperature is To. The mass balance for any species j is
F=
j Fjo + υJX (12)
Using eq (12) to eliminate Fjo in eq (11) we get

s
   
∑ F H (T) − H (T ) + υ H (T )X  =q (13)
j j j o j j o
j= 1  ~ ~ ~ 
Using equation (10a) in eq (13) we get
 To

s T s  
j
=j 1 =
∑F ∫ C
pjdT + X
j 1

∑ υ j  ∆ Hfj + CpjdT  =
 ~ Ts 
∫
q (14)
To
 
Recall that by definition the standard heat of reaction is:
s

o
∆H=
R ∑ υ ∆H
j= 1
j
~
fj
Heat of reaction at temperature To is

s To
∆HR (To ) =∆HRo + ∑υ ∫C

j= 1
j p j dt
Ts
s T
∑ ∫ Fj CpjdT + X ∆HR (To ) =q

 

j= 1
 To
  (I) (III) (14.a)
(II)
Equation (14.a) can be interpreted in words as follows:

 Rate of heat   Rate of heat "absorption"   Rate of heating the reaction 
     
=  addition to   by reaction at temperature +  mixture at exit composition 
     
 the reactor   of feed   from feed to exit temperature 
i.e. change in enthalpy
caused by reaction⋅the rate of
reaction progress
(III) = (I) + (II)
Had we eliminated by eq (12) Fj in eq (11) we would obtain an equivalent equation to eq (14.a).

s T
∑F ∫ C
j= 1
jo pjdT + X ∆HR (T) =q (14.b)
To
64.
Chapter 6
 Heat needed to raise   Heat used by 
   
 inlet temperature to (Heat added)
 +  reaction at exit  =
 exit temperature T   temperature T 
   
In reaction engineering problems, additional assumptions are often made
S T
∑ ∫
ρ Q Cpm (T − To ) =Fjo CpjdT (constant mean specific heat and density can be used
j= 1 To
Under the assumptions (9) and (10), equations (14a) or (14b) are reduced to:
(15) ρQCpm (T − To ) + X ∆HR = q

(I) (II) (III)
Equation (15) is then often interpreted as the “heat balance”.
 Sensible heat 
   Heat absorbed 
 absorbed by flowing (Heat added)
 +  by reaction  =
 stream   
 
By interpreting term (II) as a “generation” term in an energy balance, disservice is done to
the clarity of the subject.
However, a user can use equation (15) as long as he recalls what the assumptions under
which it was formulated are and makes sure that they are satisfied.
Applications to ideal reactors
CSTR – The entire reactor is at temperature T. Hence eq (15) can be used as it is
 −∆H ) = q
ρ Q C (T − T ) − X(
pm o R
With the mass balance:

 Rj 
X =   V .
 υj 
 
PFR – Equation (15) as it stands is valid between inlet and outlet. However q then represents
the total rate of heat addition.
In order to solve the reactor problem we have the mass balance
dX  RJ 
= =  r
dV  υJ 
Where the reaction rate r is a function of extent X and temperature T at position V. Thus
we must apply eq (15) to a differential volume resulting in
dT dX
ρ Q Cpm + ∆HR =q v
dV dV
q v - rate of heat addition per unit reactor volume at position V.
65.
7 Non-Ideal Flow Reactors
Chapter 7
Not all tank reactors are perfectly mixed nor do all tubular reactors exhibit plug-flow
behavior. In these situations, some means must be used to allow for deviations from ideal
behavior. For non-first-order reactions in a fluid with good micromixing, more than just the
RTD is needed. These situations compose a great majority of reactor analysis problems and
cannot be ignored. For example, we may have an existing reactor and want to carry out a new
reaction in that reactor. To predict conversions and product distributions for such systems,
a model of reactor flow patterns is necessary. To model these patterns, combinations and/
or modifications of ideal reactors to represent real reactors. With this technique, a model
has been classified as being either a one-parameter model (e.g., tanks-in-series model or
dispersion model) or a two-parameter model (e.g., reactor with bypassing and dead volume).
The RTD is then used to evaluate the parameter(s) in the model. In addition, combinations
of ideal reactors to model a real reactor has also been described.
Flow patterns in real equipment show deviations from the ideal plug and mixed flow patterns.
The factors which are responsible for the non-ideal flow patterns in non-ideal flow:
1. Residence Time Distribution (RTD) of material which is flowing through the vessel
2. The tendency of the group of molecules to move about together is the state of segregation.
3. Earliness and lateness of mixing of material in the vessel.
The Residence Time Distribution (RTD) or The Age Distribution (E)

The fluid elements undergo channeling, recycling, and or creating stagnant regions in the
vessel. Because of this reason the element of fluid takes different routes through the reactor
may take different lengths of time to pass through the vessel. The distribution of these
times for the stream of fluid leaving the vessel is called the exit age distribution E, or the
residence time distribution RTD of fluid. E has the units of time−1 .
∞
∫ E dt = 1
0
Non-Ideal Flow Reactors
Figure 15 : The exit age distribution curve E for fluid for fluid flowing through the vessel, also called
Residence Time Distribution (RTD)
66.
E curves follow closed vessel boundary conditions. In this condition the fluid enters and
leaves the vessel one time, which means that there should be no flow or diffusion or upflow
eddies at the entrance or at the vessel exit.
The fraction of exit stream of age between t and t + dt is
The fraction younger than age t1 is
t1
∫ E dt
0
Whereas the fraction of material older than t1

∞ t1
∫ Edt=
t1
1− ∫ E dt
0
The E curve is the distribution needed that accounts for nonideal flow.
Tracer input experiment is subdivided into two experiments: Pulse input and step input
Figure 16 : (a) Pulse input (b) Step input
Pulse input experiment
Figure 17 : Depiction of pulse input tracer
67.
Mass balance at outlet
Amount of tracer leaving the reactor t & t + dt
dN = v 0c ( t ) dt (1)
Dividing by N0
dN v 0c ( t )
= dt (2)
N0 N0
dN
where is the fraction of tracer leaving the reactor between time t & t + dt
N0
For pulse input experiment
Exit age function
v 0c ( t )
= E ( t ) dt whereE
( t ) dt (3)
N0
where E ( t ) dt is the fraction of tracer leaving the reactor between time t & t + dt
dN
= E ( t ) dt (4)
N0
Integrating equation (1)
N0 dN ∞
∫ 0 N0
= ∫ E ( t ) dt (5)
0
On integration, result obtained

∞
∫ E ( t ) dt = 1
0
Other expression
dN = v 0c ( t ) dt (6)
Integration equation (6)
∫ dN = v ∫ c ( t ) dt
0
From equation (3)

c (t) ∞

E (t) 0 ∫
= c ( t ) dt
c (t)
E ( t ) = ∞
∫ c ( t ) dt
0
Moments of Residence Time Distribution (RTD)

nth moment of RTD
∞
∫ ( t ) dt
tn E
µn =
0
68.
Zeroth moment of RTD
∞
µ0 = ∫
( t ) dt
t0 E
0
∞
µ0 = ∫
( t ) dt
E
0
∞
1 which is equivalent to
µ0 = ∫ E ( t ) dt = 1 Area of E curve
0
First moment of RTD

∞
µ1 = ∫
( t ) dt
t1 E
0
∞
µ1 = ∫
( t ) dt
tE
0
t
µ1 =
∞
t = tE∫
( t ) dt
0
or,
∞
t =
∫ tE ( t ) dt
0
∞
∫ E ( t ) dt
0
Second moment of RTD

∞
t2 E
µ2 = ∫
( t ) dt
0
Second moment represents variance.

σ2 =µ 21
2 −µ
∞
=σ2 t2 E ∫
( t ) dt − t 2
0
Normalized time
Eθ is defined as the RTD function. The time is measured in terms of mean residence time
θ =t / t . Thus,
V Cpulse V
E= t=
E
 = Cpulse
θ
ϑ M M
ϑ
Eθ is used to measure when dealing with flow models.
∞
∫ E ( t ) dt = 1
0
69.
∞
∫ E ( t ) dt . dθ =1
0
∞
∫ E ( θ) . dθ =1
0
Step input experiment
Figure 18: Step input demonstration
Mass balance over tracer
F0 =
ϑ0C0 =
d Cstep  V
ϑ0Cstep +
( )
dt
where F0 is the molar flow rate (mol / s )
ϑ0 volumetric flow rate m3 / s ( )
Cstep concentration of tracer mol / m3 ( )
V
(
d Cstep )+ϑ
0 Cstep = ϑ0Cstep
dt

(
d Cstep ) + ϑ0 C ϑ0
= Cstep
step
dt V V

(
d Cstep ) + 1 C ϑ0Cstep
=
step
dt τ
70.
On solving
C=
step C0 1 − e− t/ τ( )
Figure 19: C and F curve in case of step input experiment
CA0
Area ∫ 0
t dCstep
C=
step C0 1 − e− t/ τ ( )
 t 
 1 −
dCstep = C0  0 −  −  e τ dt 
  τ 
 
t
C0 ∞ C0 −
∫ 0
t dCstep = ∫ 0 τ
t. e τ dt
C0  t −t 
∫ (e ) dt  
 
− t/ τ
=  τ e τ + τ 
τ  −1 

= C0 τ
CA0
Area ∫ 0
t dCstep= C0 τ
71.
Relation between E-curve and F-curve
Figure 20 : Graph depicting the relationship between the F and E curve
The total fraction of tracer left the reactor till time ‘t’
t
∫
F ( t ) = E ( t ) dt
0
dF ( t )
= E (t)
dt
The difference between the E(t) and F(t) is that E(t) is the fraction of tracer leaving the
reactor at time ‘t’ and F(t) is the fraction of tracer left the reactor till time ‘t’.
Residence time distribution (RTD) in case of plug flow and mixed flow reactor in case of
pulse input.
In case of plug flow reactors, there is no dead zone, no bypassing and no turbulence and
hence no RTD in case of plug flow reactors.
72.
Figure 21: RTD n case of Plug flow reactor
RTD in case of mixed flow reactor
Figure 22 : RTD in case of Mixed flow reactor
Mass balance over the tracer.

Input flow rate of the tracer = Output flow rate of the tracer + Accumulation of the tracer
concentration in the reactor.
d (C.V )
ϑ0 C ( t ) +
0= (7)
dt
where
ϑ0 is the volumetric flowrate m3 / s
mol
C(t) concentration of the tracer
m3
V is the volume of the reactor
73.
Manipulating equation (7)
dC
−ϑ0  C ( t ) = V 
dt
C dC t ϑ
∫ C0
−
C (t)

=
0 V∫
0
dt
C ( t ) = C0e− t/ τm
In terms of E(t)
C (t)
E ( t ) = ∞
∫ C ( t ) dt
0
C0e− t/ τm
E ( t ) = ∞
∫Ce
− t/ τm
0 dt
0
Solving,
e− t/ τm
E ( t ) =
τm
Figure 23: RTD depiction in mixed flow reactor
Case 1: Mixed flow reactor followed by plug flow reactor in series.

 ( t −τp ) 
−
 e τm 
 
E (t)  0 t < τp t < τp 
 τ m 
 
74.
Case 2: RTD for mixed flow reactor and plug flow reactor in parallel.
Figure 24: Mixed flow reactor and plug flow reactor in parallel arrangement and the resultant graph.
Figure 25: Mixed flow reactor in parallel arrangement and the resultant graph.
Figure 26 : Plug flow reactor in parallel arrangement and the resultant graph.
75.
Figure 27: Plug flow reactor in series arrangement and the resultant graph.
Figure28: Mixed flow reactor in series arrangement and the resultant graph.
7.1 Heterogeneous system

Catalyst
A catalyst is a substance that affects the rate of a reaction but emerges from the process
unchanged. A catalyst usually changes a reaction rate by promoting a mechanism for the
reaction.
76.
Figure 29: Reaction path in the presence of catalyst
A heterogeneous catalytic process involves more than one phase; usually the catalyst is a
solid and the reactant and product are in liquid or gaseous form. A heterogeneous catalytic
reaction occurs at or near the fluid-solid interface. The principle that govern heterogeneous
catalytic reactions can be applied to both catalytic and noncatalytic fluid-solid reactions.
The other two types of heterogeneous reactions involve gas-liquid and gas-liquid-solid
systems.
Factors responsible for the catalyst deactivation:
y Aging – which happens due to the gradual change in surface crystal structure.
y Poisoning – this is the irreversible deposition of a substance on the active site.
y Fouling or coking – which happens due to the deposit of the carbonaceous or other material
on the entire surface.
The catalytic reaction occurs when the reactant(s) must come in contact with the catalyst.
The reactant comes in contact with the catalyst by adsorption which can take place by
physical or chemical adsorption.
The type of adsorption that affects the rate of a chemical reaction is chemisorption. If a
catalytic reaction involves chemisorption, then it must be carried out within the temperature
range where chemisorption of the reaction is appreciable. In the case of a solid surface, the
reaction is not a catalyst over the entire solid surface but only at certain active sites. The
active sites are the points on the catalyst surface that can form strong chemical bonds with
an adsorbed atom or molecule.
77.
Steps in catalytic reaction
Figure 30 : Steps in Catalytic reaction
1. Mass transfer (diffusion) of the reactant(s) (e.g. species A) from the bulk fluid to the
external surface of the catalyst pellet (catalyst pellet is considered to be spherical
shape).
2. Diffusion of the reactant from the pore entrance (mouth) through the catalyst pores to
the immediate vicinity of the internal catalyst surface.
3. Adsorption of reactant A onto the catalyst surface.
4. Reaction of reactant A onto the catalyst surface.
5. Desorption of the product (e.g. B) from the surface.
6. Diffusion of the product from the interior of the pellet to the pore mouth at the external
surface.
7. Mass transfer of the products from the external pellet surface to the bulk fluid.
Explanation of the steps

Picture form notes
Mole balance equation
Molar rate of ' A ' in = Molar rate of ' A ' out + Disappearance of ' A ' - Generation of ' A '
dCA  dCA 
 2
 −DA dZ  πR =
 z

 −DA


dZ z+dz
πR2 = ( )
−rA'' ds
where ds= 2πR dz

 dCA dCA  2
 DA
dz
− DA ( )
''
 πR =−rA 2πR dz
dz z 
 z +dz
78.
dividing both the sides by πR2dz
d2CA 2
dz2 ( )
= −rA'' 
RDA
2
( )
d2CA = −rA'' 
RDA
dz2
For 1st orderr eaction
d2CA 2
dz2 ( )
= −rA'' 
RDA
, −rA'' =
k′′CA
d2CA 2
2
=k
′′CA 
dz RDA
Rearranging the above equation
d2CA 2
=k
′′  dz2
CA RDA
1 dNA 1 dN
We know that, −rA =− = kCA and −rA'' = − A =
k′′CA
V dt S dt
 dNA 
for same  − 
 dt 
(kCA ) = k
( ′′CA ) s
(kCA ) πR2=L k( ′′CA ) 2πRL
2k''
k=
R
d2CA kCA
=
dz2 DA
d2CA kCA
− 0
=
dz2 DA
k
2=
letm
DA
then,
d2CA
− m2 =
0
dz2
On solving
CA C1emz + C2e−mz (1)

=
Using boundary conditions
at z 0 ,
= = CA CAS
dCA
=z L ,
= CAS
dz
79.
solving,
e−mL
C1 = C2
emL
C e−mL
C1 = mLAS −mL
e +e
C
CA mL AS −mL e ( ) + e ( ) 
m z −L −m z −L
=
e +e  
emθ + e−mθ
coshθ =
2
CAScoshcoshm (z − L )
CA =
coshcoshm L
Thiele modulus mT or ∅
To describe the relationship between the diffusion and reaction rate in porous catalyst
pellets with no mass transfer limitations. The value of Thiele modulus is used for determining
the effectiveness factor for catalyst pellets.
∅ =mL
k
∅= L
DA
reaction rate
=∅ × Characteristicl ength
diffusionr ate
Volume
Characteristicl ength (L) =
Surface area
Shape Characteristic length
Cylinder R/2
Sphere R/3
Flat plate t/2
R – radius
t= thickness of slab
Consider following cases
Case 1: If ∅ is high

y Means that the reaction rate is high, signifying fast reaction.
y diffusion rate is low, signifying slow diffusion.
y Large characteristic length, means largest pore size
For this case, pore diffusion will be a rate controlling step.
80.
Case 2: If ∅ is low
y Means that the reaction rate is slow,
y Diffusion rate will be fast.
y Shortest pore size, means short characteristic length.
For this case, surface reaction will be the rate controlling step.
Effectiveness factor ( η)
Reaction rate withp
ore diffuson resistance
η=
Reactionr ate withoutp ore diffusion resistance
η1
−rA'' k′′CA n
=η =
( )
−rA'' k′′CnAs
s
forn
=0
η =1
For 1st orderr eaction
−rA'' k′′CA n CA n
=η = = <1
( )
−rA'' k′′CnAs
s
CnAs
(z − L )
coshcoshm
CA = CAs
coshcoshm L
CAs  CA0h m ( z − L ) dz
L
CA =
∫
0 coshcoshm L
L
∫
dz
0
CAs L
CA
Lcoshcoshm
L 0 ∫
coshcosh m ( z − L ) dz
L
CAs  sinhsinh m ( z − L ) 
CA =  
L  coshcosh mL  m 0
C tanhtanhm L
CA = As
mL
CAs tanhtanh ∅
CA =
∅
tanhtanh ∅
η=
∅
Case 1: If ∅ > 4
Which implies a fast reaction , slow diffusion and largest pore size.
Therefore,
81.
tanhtanh ∅
η=
∅
tanhtanh ∅ ≈ 1
1
η=
∅
( )
rA k′′CnAs η
−=''
1
( −r ) =
''
A k′′C
∅
n
As
1 1 1
r′′ ∝ ∝ ∝
∅ L R
''
r2 ∅1 L1 R1 dp1
= ''
= = =
r1 ∅ 2 L 2 R 2 dp2
This is the case of strong pore diffusion resistance.

Case 2: If ∅ < 0.4
This implies the case of slow reaction, fast diffusion and shortest pore size.
This is the case of surface reaction is the rate controlling step (diffusion free case)
tanhtanh ∅ = ∅
η =1
Case 3: If 0.4 < ∅ < 4
In this case surface reaction and pore diffusion will be almost the same almost.
th
For n order reaction
∅ =
( −r )  L ''
A
s
1/2
2D ∫ ( −r ) dC
 CAs 
''
e A A
0 
De is the effective diffusivity
We know that, for nth order reaction
−r'' =
′′CnA
k
Therefore,
k′′CnAs  L
∅=
1/2
∫ ( )
 CAs 
n
2De 0 k′′CA dCA 
k′′CnAs  L
∅= 1/2

 k '' CnAs+ 1 
2De 
 ( n + 1) 
82.
k′′CnAs−1 (n + 1)
∅ = L

2De
Now, for strong pore diffusion resistance
1
η=
∅
'' 1
We know that, −rA = ′′CnAs
k
∅
n 1
= k′′CAs
k′′CnAs−1  (n + 1 )
L
2De
( n+ 1 )
2Dek′′ 1
−rA''
=  CAs2 
(n + 1 ) L
2Dek''true 1
kobs = 
(n + 1)true L
k''obs  CnAsobs
−rA'' =
Case 1: If ntrue > 1

(n + 1 ) ( 2 + 1)
Example :
=ntrue 2 ,
= nobs = = 1.5
2 2
(n + 1 ) ( 5 + 1)
ntrue 5 ,n
= = obs = = 3
2 2
ntrue > nobs
Case 2 : If ntrue = 1
( 1 + 1)
nobs = 1
=
2
For 1st order reaction, no effect of strong pore diffusion resisitance
Case 3 : ntrue < 1
( 0 + 1)
1
Example :n
= true 0 ,n
= obs =
2 2
( −3 + 1)
ntrue =
−3 , nobs =
−1
=
2
ntrue < nobs
Effective diffusivity
83.
DA σC ϕp
De =
τ
where
DA is the molecular diffusivity
σC is the constriction factor (for varying surface area)
ϕp catalyst porosity
τ tortuosity factor
y Porosity is defined as the ratio of volume of voids to the total volume of the catalyst.
y Tortuosity factor is the ratio of actual distance travelled by molecule to the shortest distance
between these points
Physical and chemical adsorption

y The solid surfaces are not smooth in the microscopic sense. There are irregular valleys and
peaks distributed all over the area. The regions of irregularity are particularly susceptible
to residual force fields. At these locations, the surface atoms of the solid may attract other
atoms or molecules in the surrounding gas or liquid phase. The surfaces of pure crystals
have non-uniform force fields because of the atomic structure in the crystal. Such surfaces
also have sites or active centers where adsorption is favored.
y Adsorption on solid surfaces may be divided into two categories, viz. physical and chemical
adsorption. Physical adsorption is non-specific and similar to condensation. The forces that
attract the fluid molecules to the solid surface are weak van der Waals forces. The physical
adsorption is also known as van der Waals adsorption.
y The heat evolved during physical adsorption is low, which usually lies between 2–25 kJ/mol.
The energy of activation for physical adsorption is also low (<5 kl/mol). Equilibrium between
the solid surface and the gas molecules is usually attained rapidly and it is reversible
because the energy requirements are small. Multiple layers of adsorbed molecules are
possible, especially near the condensation temperature. The extent of physical adsorption
decreases with increasing temperature. Physical adsorption is useful for determining the
surface area and pore size of solid catalysts.
y Chemical adsorption or chemisorption is specific. It involves forces which are much stronger
than physical adsorption. The amount of heat evolved in chemisorption is large (e.g., 50–500
kJ/mol), which is similar to chemical reactions.
y The name chemisorption was given by H. S. Taylor (1931). However, the concept of
chemisorption was proposed by Langmuir much earlier (in 1916). According to him, in the
interior of the solid material (i.e., the adsorbent), the atoms have their force field wholly
satisfied by the atoms which surround them. The atoms on the surface however are not
surrounded. These atoms have a residual force due to unshared electrons towards exterior.
This residual force-field leads to sharing of electrons with the striking gas molecules (i.e.,
the adsorbate).
84.
y A sort of covalent linkage is formed between the gas molecules and the atoms of the solid
at the surface. However, this linkage is not the same as the covalent bond that exists in a
chemical compound. In spite of the sharing of electrons with the gas molecule, the surface
atom remains bonded simultaneously with the other atoms in the crystal lattice.
y Langmuir observed that a stable film of oxide formed on tungsten wires in presence of
oxygen, which was not same as the normal oxide, WO3 in terms of its properties. This oxide
gave off from the surface upon desorption. This adsorbed compound was designated as
WO3 .
y Langmuir pointed out that because of the rapid falling-off of intermolecular forces with
distance, it is probable that the adsorbed layers are no more than a single molecule in
thickness. Langmuir (1918) proposed simple formulations for rates of adsorption and
desorption of gases on solid surfaces. These are also applicable to liquids.
y Unlike physical adsorption, chemisorption does not take place on all solids. It occurs with
some chemically reactive gases. Chemisorption usually occurs at high temperatures. The
surface coverage is limited to a monolayer. The process is often irreversible. Chemisorption
is used for finding the active centers of a catalyst.
y Chemisorption can be divided into two categories, viz. activated chemisorption and non-
activated chemisorption. In activated chemisorption, the rate of chemisorption varies
with temperature following Arrhenius law with finite activation energy. In some situations,
chemisorption occurs very rapidly which suggests that the activation energy is nearly zero.
This type of adsorption is called non-activated chemisorption. Both activated and non-
activated chemisorption may take place at different stages of an adsorption process. A
comparison between physical adsorption and chemisorption is presented in Table 6.
Table 6: Comparison between physical adsorption and chemisorption
Physical adsorption Chemisorption
All solids can be used as adsorbents. Some solids can be used as adsorbents.
All gases below their critical temperatures Some chemically reactive gases can act as
can act as adsorbates. adsorbates.
Occurs at low temperatures. Generally occurs at high temperatures.
Low heat of adsorption. High heat of reaction, which is of the order of

the heats of chemical reactions.
High rate. Both low and high rates are observed.
Low activation energy. Low activation energy for non-activated

chemisorption, and high activation energy for
activated chemisorption.
85.
Physical adsorption Chemisorption
Multilayer possible. Monolayer.
Highly reversible. Often irreversible.
Used for the determination of surface Used for the determination of active center
area and pore size. area and elucidation of surface reaction
kinetics.
Surface reaction mechanism

The surface reaction mechanism can be understood by mainly two mechanism:
y Eley- Rideal mechanism.
y Langmuir Hinshelwood mechanism.
The above two mechanisms are based on Langmuir adsorption isotherms.
The assumptions of the Langmuir adsorption isotherm.
y The surface of the adsorbent is uniform, that is, all the adsorption sites are equivalent.
y Adsorbent molecules do not interact.
y All adsorption occurs through the same mechanism.
y At the maximum adsorption, only a monolayer is formed: molecules of adsorbate do not
deposit on other, already adsorbed, molecules of adsorbate, only on the free surface of the
adsorbent.
Langmuir- Hinshelwood mechanism

For the reaction
A +B ↔ C +D
Let rAD = rate of adsorption (gmol/s.gm of catalyst)
rs = rate of surface reaction (gmol/s.gm of catalyst)
rD = rate of desorption (gmol/s.gm of catalyst)
CAS = concentration of adsorbed A on surface (g mol/gm of catalyst)
CBS = concentration of adsorbed B on surface (g mol/gm of catalyst)
CCS = concentration of adsorbed C on surface (g mol/gm of catalyst)
CDS = concentration of adsorbed B on surface (g mol/gm of catalyst)
Co = total concentration of active sites on surface (g mol/gm of catalyst)

Cv = concentration of vacant sites on surface (g mol/gm of catalyst)
CA = concentration of A in bulk gas phase (g mol/ cm3 )
Similarly CB , CC , CD are the concentration of B,C,D in the bulk gas phase respectively.
86.
Let the reaction follow the mechanism given below.
A + S ↔ A.S Adsorption of reactant A on surface vacant site S
.S
B + S ↔ B Adsorption of reactant B on surface vacant site S
A.S + B.S → C.S + D.S Surface reaction between adsorbed A and B
C.S → C + S Desorption of product C from surface creating a vacant site
D.S → D + S Desorption of product D from surface creating a vacant site
Among the various steps described, the slowest step controls the overall rate of reaction
and the other remaining steps are assumed to be at the near equilibrium conditions.
This approach greatly simplifies the overall rate expression, reducing rate constants and
equilibrium constants to be determined from experimental data. Further each step in this
method is assumed to be elementary and the number of sites is conserved in each step.
Therefore, the controlling step can be either of the following:
(1) Surface reaction
(2) Adsorption
(3) Desorption
Now total concentration of active sites on surface, Co , will be the summation concentration
of all sits on which either reactants or products are adsorbed and the concentration of
vacant sites.
Co = Cv + CAS + CBS + CCS + CDS
where Cv is the concentration of vacant sites
Case 1: Rate of surface reaction controlling

The surface reaction is the lowest step and is the rate controlling. According to the
mechanism, surface reaction occurs between adsorbed A and adsorbed B producing
adsorbed C & adsorbed D.
AS + BS ↔ CS + DS
The rate of surface reaction is given as
=rS k 's CCSCDS
SCASCBS − k
kS rate constant for forward surface reaction
k's rate constant for reverse surface reaction
 k' 
= ks CASCBS − s CCSCDS 
 ks 
 1 
= ks CASCBS − CCSCDS  (2)
 K 
ks
where ' = K
ks
87.
Now, since all the other steps are considered to be in equilibrium, therefore concentration
of adsorbed species can be obtained as follows:
For adsorption steps and desorption steps,
C
KA = AS
CA CV
C
KB = BS
CBCV
C
KC = CS
CCCV
C
KD = DS
CDCV
KA , KB , K
C ,K
D are adsorption equilibrium constants.
Then, the adsorbed phase concentrations can be written as:
=CAS K =ACACVCCS K
CCCCV
=CBS K
=
BCBCVCDS K
DCDCV
Substituting all these values in equation (1)
 1   K 
= BCBCV − C CCCV .KDCDCV  .
rS ks CASCBS − CCSCDS  = ks KACACV .K
 K   KS 
 2 K K 2 
=Or, rS ks KAKBCACBCV − C D CCCV CDCV  .
 KS 
 K K  2
=Or, rS ks KAKBCACB − C D CCCV CD  CV (3)
 KS 
Now, Co = CAS + CBS + CCS + CDS + CV
Co = K
A CA CV + K
BCBCV + K
CCCCV + K
A CA CV + CV
Co = CV [1 + KACA + KBCB + KCCC + KDCD ]
Co
CV = (4)
[1 + KACA + KBCB + KCCC + KDCD ]
For the reaction A + B ↔ C + D , at equilibrium, the overall equilibrium constant is
K = CCCD / CACB
All concentration corresponds to the equilibrium conditions in gas phase

(CCS / KCCV ) (CDS / KDCV ) CCSCDS KAKBC2V
K =  (5)
(CAS / KACV ) (CBS / KBCV ) CASCBS KCKDC2V
K K
Or, K = A B KS
KCKD
88.
C C
KS = CS DS .
CASCBS
Substituting, (4) & (5) in equation (3)
 1  C2o
rS K
SKAKB CACB − CCCD 
 ([1 + KACA + KBCB + KCCC + KDCD ])
2
 K
 1 
CACB − K CCCD 
SKAKB C2o
rS =K (6)
([1 + KACA + KBCB + KCCC + KDCD ])
2
The above rate expression can also be derived in terms of bulk partial pressure
Case 2: Rate is adsorption control
(a) Adsorption of A controlling.
Let adsorption of A be the slowest step so that adsorption of B, surface reaction and
desorption of C are at equilibrium.
Adsorption of A is given as
A + S ↔ AS
Rate of adsorption
= rAD K
AD CACV −K
DSCAS
 K 
=rAD K AD  CACV − DS CAS 
 KAD 
KDS
KA = Adsorption equilibrium constant for A
KAD
 1 
=rAD K
AD  CACV − CAS  (7)
 KA 
Now as other steps are in equilibrium
C C
KS = CS DS
CCSCDS
C
KB = BS
CBCV
C
KC = CS
CCCV
C
KD = DS
CDCV
CBS =K
BCBCV
CCS =K
CCCCV
CDS =K
DCDCV
89.
Substituting value in equation (7)
 1 KCKD CCCD 
=rAD K ADCV CA − 
 KACV KSKB CB 
 1 KCKD CCCD 
=rAD K ADCV CA − 
 KA KSKB CB 
 1 C C 
=rAD K ADCV CA − C D  (8)
 K CB 
K K K
K = S A B = Overall equilibrium constant
KCKD
Co = CAS + CBS + CCS + CDS + CV
K K C C C
= CV + C D  C D V + K BCBCV + KCCCCV + KDCDCV
KSKB CB
Manipulating the above equation
Co KCKD
CV =
KA CCCD
1+ + KBCB + KCCC + KDCD
K CB
Substituting the value of CV in equation (8)
C C 
CACB −  C D 
rAD = KADCo  K 
(9)
1 + KACA + KBCB + KCK CACB + KDCD
For a given catalyst Co is constant
C C 
CACB −  C D 
rD = KDCoK  K 
1 + KACA + KBCB + KCK CACB + KDCD
Eley-Rideal mechanism
The Eley Rideal mechanism depicts the reaction mechanism in which one reactant species
(A) is adsorbed while the second reactant species (B) is not adsorbed on the catalyst surface.
The reaction then occurs when the passing gas molecules of B in the gas phase directly
react with the adsorbed species A.
(1) A + S ↔ AS
(2) AS + B ( g ) ↔ P
Assuming that step (2), the reaction between adsorbed A and the gas phase B is irreversible
and the rate determining step, then the rate of reaction can be written as
r = KCASCB (10)
The concentration of adsorbed A can be given as CAS =K
A CA CV
90.
Now, Co = CAS + CV = KACACV + CV = CV ( 1 + KACA )
Co
CV =
1 + K A CA
K C C
CAS = A A o
1 + K A CA
Substituting value of CAS in equation (10)
KC K C C
=r KC
= ASCB o A A B
1 + K A CA
If the product are chemisorbed then the reaction may become reversible as shown below.
AS + B ( g ) ↔ PS
PS → P + S
Then the rate expression can be written as
=r KCASCB − KBCPS
The concentration of adsorbed product is CPS = KPCPCV
Co = CAS + CPS + CV = KACACV + CPCPCV + CV = CV ( 1 + KACA + KPCP )
Co
CV =
1 + KACA + KPCP
KACACo
CAS K
= =A CA CV
1 + KACA + KPCP
KPCPCo
CPS K
= =PCPCV
1 + KACA + KPCP
Substituting CAS and CPS in rate expression
 1 
r= K
CASCB −K
BCPS = K  CASCB − CPS 
 K 
 KACACo 1 KPCPCo 
r K  CB − 
 (1 + K C + K C ) K ( 1 + KACA + KPCP ) 
 A A P P
 KP 
 KACACB − CP 
K
Co 
r =K 
1 + KACA + KPCP
Where S is the vacant site on the catalyst surface

p is the partial pressure of species in gas phase, atm or kPa
For the reactant A in equilibrium.
Rate of adsorption at equilibrium = Rate of desorption at equilibrium
Rate of adsorption at equilibrium= (rAD ) k ACACS − k −ACAS
91.
kA
The ratio is the adsorption equilibrium constant.
k −A
Therefore,
C
(rAD )  CACS − AS 
=
 K 
Similarly for B
C
(rBD )  CBCS − BS 
=
 K 
92.
8 Miscellaneous Topics
Chapter 8
Mixing
The RTD tells us how long the various fluid elements have been in the reactor, but it does
not tell us anything about the exchange of matter between the fluid elements (i.e., the
mixing). The mixing of reacting species is one of the major factors controlling the behavior
of chemical reactors. Fortunately for first-order reactions, mixing is not important, and
knowledge of the length of time each molecule spends in the reactor is all that is needed to
predict conversion. For first-order reactions, the conversion is independent of concentration.
dX
(1 − X )
= k
dt
Consequently, mixing with the surrounding molecules is not important. Therefore, once the
RTD is determined, we can predict the conversion that will be achieved in the real reactor
provided that the specific reaction rate for the first-order reaction is known. However, for
reactions other than first order, knowledge of the RTD is not sufficient to predict conversion.
For reactions other than first order, the degree of mixing of molecules must be known in
addition to how long each molecule spends in the reactor. Consequently, we must develop
models that account for the mixing of molecules inside the reactor. The more complex
models of non-ideal reactors necessary to describe reactions other than first order must
contain information about micromixing in addition to that of macromixing. Macromixing
produces a distribution of residence times without, specifying how molecules of different
ages encounter one another in the reactor. Micromixing, on the other hand, describes how
molecules of different ages encounter one another in the reactor. There are two extremes
of micromixing.
(1) All molecules of the same age group remain together as they travel through the reactor
and are not mixed with any other age until they exit the reactor (i.e., complete segregation).
(2) Molecules of different age groups are completely mixed at the molecular level as soon
as they enter the reactor (complete micromixing).
For a given state of macromixing (i.e., a given RTD), these two extremes of micromixing
will give the upper and lower limits on conversion in a nonideal reactor. For single
reactions with orders greater than one or less than zero, the segregation model will
predict the highest conversion. For reaction orders between zero and one, the maximum
mixedness model will predict the highest conversion.
Fluid particles containing millions of molecules all of the same age. A fluid in which
the globules of a given age do not mix with other globules is called a macrofluid. A
macrofluid could be visualized as non-coalescent globules where all the molecules in
a given globule have the same age. A fluid in which molecules are not constrained to
remain in the globule and are free to move everywhere is called a microfluidic.
Miscellaneous Topics
There are two extremes of mixing of the macrofluid globules—early mixing and late
mixing.
The extremes of late and early mixing are referred to as complete segregation and
maximum mixedness, respectively.
93.
Segregation model
In a “perfectly mixed” CSTR, the entering fluid is assumed to be distributed immediately and
evenly throughout the reacting mixture. This mixing is assumed to take place even on the
microscale, and elements of different ages mix together thoroughly to form a completely
micromixed fluid. However, if fluid elements of different ages do not mix together at all, the
elements remain segregated from each other, and the fluid is termed completely segregated
. The extremes of complete micromixing and complete segregation are the limits of the
micromixing of a reacting mixture. In developing the segregated mixing model, we first
consider a CSTR because the application of the concepts of mixing quality are most easily
illustrated using this reactor type. In the segregated flow model, we visualize the flow
through the reactor to consist of a continuous series of globules.
These globules retain their identity; that is, they do not interchange material with other
globules in the fluid during their period of residence in the reaction environment, i.e., they
remain segregated. In addition, each globule spends a different amount of time in the reactor.
In essence, what we are doing is lumping all the molecules that have exactly the same
residence time in the reactor into the same globule. The principles of reactor performance
in the presence of completely segregated mixing were first described by Danckwerts and
Zwietering.
Because the fluid flows down the reactor in plug flow, each exit stream corresponds to a
specific residence time in the reactor. Batches of molecules are removed from the reactor at
different locations along the reactor in such a manner as to duplicate the RTD function, E(t).
The molecules removed near the entrance to the reactor correspond to those molecules
having short residence times in the reactor. Physically, this effluent would correspond to the
molecules that channel rapidly through the reactor. The farther the molecules travel along
the reactor before being removed, the longer their residence time. The points at which the
various groups or batches of molecules are removed correspond to the RTD function for the
reactor.
Because there is no molecular interchange between globules, each acts essentially as its
own batch reactor. The reaction time in any one of these tiny batch reactors is equal to the
time that the particular globule has spent in the reaction environment after exiting. The
distribution of residence times among the globules is given by the RTD of the particular
reactor.
Now that we have the reactor’s RTD, we will choose a model, apply the rate law and rate
law parameters to predict conversion as shown in the box above. We will start with the
segregation model. To determine the mean conversion in the effluent stream, we must
average the conversions of all of the various globules in the exit stream:
Maximum mixedness model

In a reactor with a segregated fluid, mixing between particles of fluid does not occur until
the fluid leaves the reactor. The reactor exit is, of course, the latest possible point where
94.
mixing can occur, and any effect of mixing is postponed until after all reaction has taken
place. We can also think of a completely segregated flow as being in a state of minimum
mixedness. We now want to consider the other extreme, that of maximum mixedness
consistent with a given residence time distribution. We return again to the plug-flow reactor
with side entrances, only this time the fluid enters the reactor along its length. As soon
as the fluid enters the reactor, it is completely mixed radially (but not longitudinally) with
the other fluid already in the reactor. The entering fluid is fed into the reactor through the
side entrances in such a manner that the RTD of the plug-flow reactor with side entrances
is identical to the RTD of the real reactor. The globules correspond to the molecules that
spend a long time in the reactor, while those at the far right correspond to the molecules
that channel through the reactor and spend a very short time in the reactor. In the reactor
with side entrances, mixing occurs at the earliest possible moment consistent with
the RTD. This situation is termed the condition of maximum mixedness. The approach
for calculating conversion for a reactor in a condition of maximum mixedness will now
be developed.
Adsorption/Desorption
y Adsorption is the sticking of gas molecules onto the surface of a solid all available surfaces
including that surface inside open pores.
y Increasing the pressure of gas over a solid causes increasing adsorption.
y Temperature dependent.
y Desorption is the removal of gas molecules from the surface of a solid all available surfaces
including that surface inside open pores.
y Decreasing the pressure of gas over a solid causes increasing desorption.
y Done at the same temperature as adsorption.
Adsorption
y When a gas or vapour phase is brought into contact with a solid, part of it is taken up and
remains on the outside attached to the surface.
y In physisorption (physical adsorption), there is a weak Van der Waals attraction between the
adsorbate and the solid surface.
y Useful to characterise porous materials allowing for the determination of specific surface
area, pore size distribution and pore volume.
Characteristics of physical adsorption

y Low heats of adsorption, no violent or disruptive structural changes.
y Can involve multiple layers of adsorbate, thus allowing for pore measurements.
y High temperatures tend to inhibit physical adsorption.
y Adsorption equilibrium is achieved quickly since no activation energy is generally required.
y Physical adsorption is fully reversible, allowing adsorbate to fully adsorb and desorb.
95.
Adsorption isotherms
An Adsorption Isotherm is obtained by measuring the amount of gas adsorbed across a wide
range of relative pressures at a constant temperature (typically liquid N2, 77K). Conversely
desorption Isotherms are achieved by measuring gas removed as pressure is reduced
The nature of gas sorption at a surface:

y When the interaction between a surface and an adsorbate is relatively weak only physisorption
takes place.
y However, surface atoms often possess electrons or electron pairs which are available for
chemical bond formation.
y This irreversible adsorption, or chemisorption, is characterized by large interaction
potentials which lead to high heats of adsorption. As is true for most chemical reactions,
chemisorption is usually associated with an activation energy, which means that adsorbate
molecules attracted to a surface must go through an energy barrier before they become
strongly bonded to the surface.
Physisorption vs chemisorption
Property Physisorption Chemisorption
Forces van der Waals Chemical bonding
(
ol −1
∆Hads kJm ) < 40 50-200
( ol −1
Ea kJm ) Rare 60–100
Isothermal Reversibility Complete Slow or none
Extent Multilayers Multilayers
Physisorption: Surface area and porosity are physical properties that impact the
quality and character of solid phase materials, Pore size distribution, Pore Volume etc.
Chemisorption - measures the number of surface active sites which are used to promote
a specified catalytic reaction. Critical parameters for chemisorption measurement are: the
area of the active element, metal dispersion, surface acidity, exposed proportion of the
active element.
Brunauer – Emmett – Teller (BET) Isotherm

y BET directly measures surface area & pore size distribution.

y BET theory deviates from ideal to actual analysis.
96.
Basic principle of BET
y BET is an extension of the Langmuir model.
y Kinetic behavior of the adsorption process.
y Rate of arrival of adsorption is equal to the rate of desorption.
y Heat of adsorption was taken to be constant and unchanging with the degree of coverage.
Assumption of BET
y Gas molecules behave ideally.
y Only 1 monolayer forms.
y All sites on the surface are equal.
y No adsorbate-adsorbate interaction.
y Adsorbate molecule is immobile.
y Homogeneous surface.
y No lateral interactions between molecules.
y Uppermost layer is in equilibrium with vapour phase.
The first and higher layer:

y Heat adsorption
y All surface sites have same adsorption energy for adsorbate
y Adsorption on the adsorbent occurs in infinite layers
y The theory can be applied to each layer.
Inert gas adsorption

y What can be measured using this technique?
⚪ Specific surface area
⚪ Pore size distribution
⚪ Heats of adsorption
y Who would be interested in such results?
y Everyone who needs to understand how pore structure affects material performance.
⚪ Surface area
y Affects dissolution rates.
y Affects electron/ion current density at electrode interface with electrolyte.
y Affects adsorption capacity.
y Represents surface free energy available for bonding in tabletting and sintering.
⚪ Pore size distribution
y Affects diffusion rates.
y Affects molecular sieving properties.

y Affects surface area per unit volume.
97.
Practice Questions
Q1 What is the unit of residence time distribution of RTD of fluid (E)?

(a) Time-1 (b) Length-1 (c) Time (d) Length. Time-1
A The residence time distribution RTD is Time-1

Explanation : The elements of fluid take different routes through the reactor
and therefore take different time to pass through the vessel. The distribution
of these times for the stream of fluid leaving the vessel is called the exit age
distribution E or the residence time distribution RTD of fluid. (Ref : Octave
Levenspiel)
Q2 The graph shows the exit age distribution curve E for fluid flowing through a
vessel. Find the area under the E curve.
t1 ∞
(a) ∫ 0
E dt = 1 (b) ∫ E dt = 1
0
∞
(c) ∫ t1
E dt = 1 (d) None of these
A Answer (b)
∞
The area under the curve is ∫ E dt = 1
0
The elements of fluid take different routes through the reactor and there-
fore take different time to pass through the vessel. The distribution of these
times for the stream of fluid leaving the vessel is called the exit age distri-
bution E or the residence time distribution RTD of fluid. (Ref: Octave Leven-
spiel)
t1 ∞ ∞
∫ E dt + ∫ E dt = 1 or ∫ E dt = 1
0 t1 0
98.
Q3 From the graph given below infer the relation between the Cstep curve i.e F
curve and residence time distribution curve i.e E curve in case of closed
vessel.
t dF t dE
(a) E= ∫ F dt (b) = E (c) F= ∫ E dt (d) =F
0 dt 0 dt
A (b) and (c)

Explanation: In a closed vessel if the inlet concentration of the tracer rises
from zero to unity, then the variation is found by Cstep vs time . The dimen-
sionless form of the Cstep is the F curve. Therefore the variation of the con-
centration with time is taken care by residence time distribution of the tracer
inside the closed vessel. The mathematical form is
dF t
dt
= E or F= E dt
0∫
Q4 Determine the necessary factors needed for the evaluation of the reactor
behavior in case of non-ideal flow reactors:
(a) The kinetics of the reaction.
(b) The RTD of the fluid in the reactor.
(c) Whether the fluid is a micro or macro fluid.
(d) All of these.
A (d)
Explanation: All the options are correct answers.
In case of non-ideal reaction:
99.
(a) T he kinetics of a reaction is to determine the behavior of the reaction tak-
ing place in the reactor at any time. The progress of any reaction can only
be determined by the kinetics of the reaction.
(b) In non-ideal reactions the residence time distribution is necessary to de-
termine the time taken by the reactant inside the reactor.
(c) Microscopic level means mixing of individual molecules and macroscopic
means mixing of lumps, groups, or aggregates of molecules. This involves
the concept of segregation in batch, plug and mixed flow reactor. Macro
and micro fluids follow different reaction mechanisms in different reac-
tors.
Q5 The exit age distribution for an ideal mixed flow reactor is defined by:
(a) A step function (b) A dirac delta function
(c) Exponential function (d) A linear function
A (c)
Explanation:
For an ideal CSTR,
 t
− 
e τ 
E(t) =
τ
Which is an exponential function.
Explanation:
As we know that in case of CSTR the concentration of the reactant/fluid in
the input stream is same as the concentration throughout the reactor.
Let us assume that an inert tracer has been injected at time t=0 into a CSTR.
Therefore, at t>0
In – out = Accumulation
dC
0- v C = V (1)
dt
At time t = 0
C= C0
On integrating equation (1)
t
−
C(t) = C0 e τ
100.
We know that
C (t)
E(t) = ∞
∫
C ( t ) dt
0
 t  t
−  − 
C0 e  τ
e τ 
=  t
=
∞ −  τ
∫ C0 e
0
 τ
dt
Q6 The residence time distribution (RTD) of an ideal plug flow reactor:

1 − tτ
t
(a) δ ( t − τ )
−
(b) E(t) = e (c) e τ (d) 0
τ
A (a)
Explanation
RTD in case of plug flow reactor and batch reactor is the same. All the atoms
leaving the reactors have the residence time.
The E function for plug flow reactor

Mathematically, this can be represented by Dirac delta function
E(t) = δ ( t − τ )
Q7 Two equal sized mixed flow reactors in series undergoes first order liquid
phase reaction for which the Damkohler number is 7 and initially 2 mol/m3 of
reactant is present. Final concentration of the reactant is______________
A 0.03125 mol/m3
Da = 7
For first order reaction Da = τ k
101.
2 MFRs in series
1 1
XA = 1 − 2 =1 − 2
( 1 + Kτ ) ( 1 + D
a)
1 1
XA = 1 − 2 = 1−
(1 + 7) 64
X A = 0.9843
CA
1− = 0.9843
CAO
CA= 2 × 0.0157
ol / m3
CA = 0.03125m
Q8 Three equal size CSTR are placed in parallel arrangement. The re-
actors operate at the same temperature , have identical feed rates.
If the overall conversion obtained is 80%, overall volume is 5L then
find the feed flow rate in the second reactor.
The reaction is A → B -rA = 0.4 C2A . CA0 = 6 mol/L
(a) 3.6 mol/s (b) 0.4 mol/s
(c) 1.2 mol/s (d) 10.8 mol/s
Sol: The overall conversion is 80%

Overall volume is 5 L
CA0 = 6 mol/L
The design equation for CSTR is
V X
= A
FA0 −rA
5 0.8
=
FA0 0.4 C2A .
5 0.8
=
FA0 0.4 CAO (1 − X A )2
2
5 0.8
=
FA0 0.4 × 6 (1 − 0.8)2
2
FAO = 3.6 mol/s.

In case of CSTR in parallel arrangement

F
FAO i = AO
n
Where n is the number of reactor
102.
Here n =3
Therefore,
3.6
FAO 2 =
3
FAo= 1.2 mol/s
Q9 A gas stream with 80 % A at 200 kPa enters a reactor with a volumetric flow
rate v0 of 2 m3/s at 400K. Calculate the entering molar flow rate, FAO.
(a) 96.22 mol/s (b) 48.11 mol/s
(c) 120.27 mol/s (d) 60.139 mol/s
Sol: (a)
3
Sol: P = 200kPa = 200 × 10 P a
y AO = 80% A = 0.8
3
v 0 = 2m /s
T = 400 K , R = 8.314 J/ mol . K
P y P
CAO = AO = AO O
RT0 RT0
(0.8) × 200 × 103
= = 48.11 mol /m3
8.314 ×400
FAO = v oCAO
= 2× 48.11
= 96.22 mol /s
Q10 A second order liquid phase reaction takes place in the plug flow reactor,
conversion obtained is 40%. Find the percentage conversion when the plug
flow reactor is being replaced by two CSTR in series, having the same space
time as that of a single plug flow reactor.
The initial concentration of A is 1 mol/m3.
Sol: 63.89%
ol / m3 − rA = K C2A
Sol: CAO 1m
=
XA dX A
PFR τ = CAO ∫ 0 −rA
103.
XA dX A
Kτ CAO = ∫ 0
( 1 − XA )2
XA 0.40 2 2
Kτ CAO = = = Kτ =
1 − XA 0.60 3 3
New system → Two CSTRs in series XCSTR = 0.6389
1
XCSTR = 1−
( 1 + Kτ )2
1
= 1− 2
 2
1 + 
 3
1
= 1−
 25 
 
 4 
Q11 The Damkohler number of the second order irreversible reaction taking
place in CSTR is 4. Find the conversion of the reactant A → B.
(a) .56 (b) 60.96 (c).6096 (d) 50.2
Sol: (c)
Sol: Da = 4= Kτ CAO [ for 2nd order reaction]
Design equation MFR
C x CAO xA
τ = AO A = 2
− r A k CAO ( 1 − xA )
2
xA
τ= 2
( − xA )
k CAO 1
x
Kτ CAO = A 2
( 1 − xA )
2
= 4 ( 1 − xA ) =
xA
= [ A ≤ 1]
xA 1.640 x
xA = 0.6096
104.
Q12 For the parallel reaction:
A+B k 1 → M rM = k1 C A1 CB1 (desired)
α β
A+B k 2 → N rN = k2 C A2 CB2 ( undesired)

α β
Consider α1< α2 , β1 > β2 select the scheme that will maximize SM/N
(a) (b)
(c) (d)
Sol: (d)
Solution – From the selectivity concept, M is desired and N is undesired (giv-
en)
α1< α2 , β1 > β2
α β
rM = k1 CA1 CB1
α β
rN = k2 CA2 CB2
roverall = k1/k2 CαA1 −α2 CBβ1 −β2
α1< α2 , β1 > β2
To get the desired product CA should be low CB should be high. (Based on the
overall order of the reaction). As we know that, In PFR the reactant concen-
tration varies from maximum concentration to the minimum throughout the
reactor. Therefore, PFR maintains a high reactant concentration. However,
in case of CSTR the reactant concentration in the inlet is equal to the outlet
concentration which is the lowest concentration value, and hence the low
reactant concentration in CSTR.
105.
Q13 The irreversible liquid phase reaction is carried out in an ideal PFR operat-
ing isothermally at steady state conditions. Each stream of reactant A and B
are fed to the reactor with equal volumetric flow rates and each stream has
a concentration of 20 mol/L. The conversion of reactant A is 80%, then find
the concentration of M in the product field.
dCM
A + B k 1 → M, desired = 2 C 2A CB1 , mol/L.min
dt
dCN
A+B k 1 → N, undesired = C 1A CB1 , mol/L.min
dt
(a) 7.62 (b) 2.64 (c) 5.36 (d) 0.4
Sol: (c)
Molar balance on the reactor

Rate of change of moles = Inlet – outlet – generation + disappearance of the
reactant
Rate of change of moles = Inlet – outlet – generation + disappearance of the
reactant
In = out
C´A v 01 + C´B v 02 = (CA+ CB )v (1)
Volumetric balance
v 01 + v 02 = v (2)
Therefore, CA + CB = 10+10 ( Equal concentration)
CMf = CA0XA
= 8 mol/L
CA = CA0(1-XA)
= 2 mol/L
Instantaneous fractional yield
M  dCM
ϕ  =
A
  dC M + dCN
M  2C2 C 2CA
ϕ   = 2 A B =
A
  2C C
A B + C C
B A 2C A +1
106.
In case of PFR
1 CAf
FP =
∆CA CA0 ∫ϕ dCA
Solving
FP = 0.67
= FP(CA0 – CA)
CM = 5.36 mol/L
Q14 An irreversible gas phase reaction 4A → 3B is conducted in PFR

under isobaric and isothermal conditions. The feed is 80% A and
the rest is inert. The conversion achieved in PFR is 80% and the
volumetric flow rate is 4L/min. If the reaction also takes place in
MFR with the same volume and the conversion then what should
be the volumetric rate in MFR.
The rate of reaction is -rA = 2CA
Sol: 1.72 L/min

4A → 3B
ϵA = δyA
=((3-4)/4) × 0.8
=-.20
PFR design model
XA
V
= CA0
∫ 0
dX A
(1)
v −rA
In case of gaseous phase
-rA = KCA0 (1-XA)/(1+ ϵAXA)
Solving for equation (1)
V = 2.8951 L
For MFR
V CA0 X A
=
v −rA
v = 1.72 L/min
107.
Q15 An irreversible liquid phase reaction A → B (-rA = 0.2 CA) is carried
out in an adiabatic, isothermal steady state condition. The reaction
took place in the arrangement shown below. Equal sized CSTRs are
in parallel arrangement with the PFRs of 20 L and 40L respectively.
Find the volume of a single CSTR.
(a) 242 L (b) 968 L (c) 60 L (d) 484 L
Sol: PFR in series condition. Conversion in N series PFR of “v” will give the same
conversion as of the PFR of total volume V.
PFR design equation
-rA =0.2 CA
XA
τ = CA0 ∫ 0
dX A / ( −rA )
On solving, we get
τ = 11.51 min
Total volume is 20+40= 60L
vA0,PFR= 5.21 L/min
vA0 = vA0,PFR + vA0,CSTR
vA0,CSTR =44.78 L/min
Design equation for CSTR in series
1
XA = 1- N
( 1 + kτ )
Here N=2
On solving τ = 10.81min
CSTR in series τ1 =τ2 = τ
V CSTR
= 484.0718 L
108.
Q16 An experiment is done in a closed chemical reactor. The graph given below
shows the concentration of the continuous response of a pulse input with
time ‘t’.
(A) What is the mean residence time of the closed chemical reactor
(a) 81 (b) 11.57 (c) 31.15 (d) 70
(B) The area under the curve of Cpulse vs. time
(a) 810 (b) 420 (c) 60 (d) 260
Sol: (A) Answer: (c)

(B) Answer: (d)
Calculation
The mean residence time is given by
t =
∑ t c ∆t
i i i
≅
∑ tc
i i
∑ c ∆ti i ∑c i
Therefore,
From the graph
0 × 0 + 10 × 4 + 20 × 6 + 30 × 6 + 40 × 5 + 50 × 3 + 60 × 2 + 70 × 0
=
0+4+6+6+5+3+2+0
=31.15 min
(b) Area under the curve
Note : That ∆t is constant i.e ∆t = 10min

Area = ∑ C∆t =
=(0+4+6+6+5+3+2+0) × 10
= 260
109.
Q17 Given below are the different conditions wherein CSTR operates. Match the
different conditions:
1) Ideal CSTR with dead volume
(a)
2) Ideal CSTR
(b)
3) Ideal CSTR with bypass volume
(c)
(A) (1) – (a), (2)- (c) , (3)- (b)

(B) (1) – (a), (2)- (b) , (3)- (c)
(C) (1) – (b), (2)- (a) , (3)- (c)
(D) (1) – (b), (2)- (c) , (3)- (a)
Sol: (D)
From the picture below the concept of bypass stream and dead volume is
clear.
110.

Q18 A first order liquid phase reaction -rA= 2 CA mol/m3.s takes place in a mixed
flow reactor under steady and isothermal conditions. The exit age distribu-
tion for the reactor is given by E(t)=δ(t-1) where E(t) varies with the dirac
delta function. Calculate the mean conversion of the reactant at the exit of
the mixed flow reactor.
Sol: Explanation: This is the case of microfluidic and the performance equation
of the mixed flow reactor is given by,
CA ∞  CA 
1- X A =
CAO
= ∫ 
0 C
 Edt
 A0 
For the first order reaction
CA = CA0 e-kt
Therefore,
CA
= e-kt
CAO
It is given that E(t) = δ(t-1), which is a dirac delta function.
Now the properties of this function is
Area under the curve
111.
∞
∫ 0
δ ( t − t0 ) dt =
1
Any integration with δ function

∞
∫ 0
δ ( t − t0 ) f ( t ) dt =
f ( t0 ) (1)
According to the question t0 is 1

And f(t) = e-kt
CA ∞
1- X A =
CAO
=
0 ∫
e−kt δ ( t − 1) dt
According to equation 1
−kt
1- X A = e 0
−.2×5
= e
= 0.135
X A = .864
Q19 The graph given below is the C-curve measured during a pulse tracer exper-
iment. C(t) is the concentration of the tracer measured at the reactor exit in
mol/liter at t min. Calculate the mean residence time in min
(a) 20 min (b) 3 min (c) 2 min (d) 3 min
Sol: (d)
∞
Explanation: t =
∫ tc ( t ) dt
0
=
∑ C t ∆t
i i i
=
∑ Ct
i i i
(1)
∑ C ∆t ∑C
∞
∫ c ( t ) dt
0 i i i i
T Ci ( t ) Ci ( t ) ti
0 0 0
2 10 20
112.
4 10 40
∑ C =20
i i ∑ Ct i i i = 60
Therefore, from equation (1) = t =

∑ Ct
i i i
= 60/20 = 3min
∑C i i
Q20 Three equal size CSTR are arranged in series with total space ( τtotal = in) .
6m
In CSTR, first order reaction A → R takes place with an initial concentration
of A is 30 mol/m3. Concentration of A is found in CSTR are 15,11 and 2 mol/m3
in three CSTRs. For this reaction, what will be the value of τplug (in secs) to
reduce concentration from 30 mol/m3 to 2 mol/m3.
Sol: 678 s
Explanation:
In the question given that, τtotal =6=360 s
For the first order reaction,
1
XA = 1 − 3
( 1 + kτ )
CA0 − CA 30 − 2
Now calculating,
= X A = = 0.933
CA0 30
1
0.933= 1 − 3 = 0.0040
( 1 + k × 360)
−1
k= 0.0040 s
Now from the design equation of CSTR,
For PFR,
τ dX A
CAO
= ∫( −rA )
Or
dCA
∫
−
τp =
( −rA )
2 dCA
−
τp = ∫ 30 ( −r )
A
113.
2
τp × k =−
lnln CA 30
τp × 0.0040 = −lnln 2 + lnln 30
τp =678 s
Q21 In the aqueous phase reaction,
rR = k 1C A
rs = k 2 C 2A
Feed enters as C A = 1 mol / lt and C S = 0.3 mol / lt into a MFR in series of
0 0
two MFR as τ1 =5 min and τ2 =20 min . Composition in the first reactor is

C A = 0.4 , CR = 0.2 and C S = 0.7 then find the concentration of R in the
1 1 1
second reactor (in mol/L)
Sol: Explanation:
Design equation in case of MFR,
(CAO − CA )
τ =
( −rA )
(CAO − CA )
τ =
k1CA + k2C2A
For 1st MFR

(C − CA1 )
AO
τ1 = Given 5 min
k1CA1 + k2C2A1
(C − CA1 )
AO
τ1 =
k1CA1 + k2C2A1
114.
( 1 − 0.4 )
5 = 2
k1 ( 0.4 ) + k2 ( 0.4 )
0.6
5 =
0.4 (k1 + 0.4 k2 )
k1 + 0.4 k2 =
0.3
Molar balance in R
In = out + Accumulation
C=R0 v ( A ) V
CR v + r
(rA ) V
CR0 − CR =
v
( A)V
r
CR0 − CR =
v
C − CR0
τ= R
( −rA )
CR − CR0
τ=
( −rA )
In 1st MFR
C − CR0
τ1 = R1
k1CA1
0.2 − 0
5=
k1 × 0.4
0.2 − 0
k1 =
5 × 0.4
k1 = 0.1
Same for S,
C −C
τ1 = s1 2 s0
k2CA1
0.7 − 0.3
5= 2
k2 ( 0.4 )
k2 = 0.5
C − CR0
τ1 = R1
k1CA1
For A
(C − CA2 )
A1
τ2 =
k1CA2 + k2C2A2
115.
(C − CA2 )
A1
τ2 =
k1CA2 + k2C2A2
(0.4 − CA2 )
20 =
( )
0.1(CA2) + 0.5 C2A2
x=0.1
therefore,
For R,
C − 0.2
τ2 = R1
k1CA2
CR1 − 0.2
20 =
0.1 ×0.1
CR1 = 0.4m
ol / lt
Q22 A reactant in liquid phase undergoes decomposition in a system of two MFR

in series. The volume of the second reactor is half of the volume of the first
reactor and volumetric flow rate in the two reactors are the same. Feed
concentration of A is 4 mol/m3 and mean residence time is 1 min in the first
reactor. Concentration in the reactor is 2mol/m3 and 1 mol/m3 in the first and
second MFR respectively. Find the order of the reaction.
(A) 0 (B) 2 (C) 1 (D) none of these
Sol:
Explanation:
Given:
V2 = 0.5 V1 , therefore τ2= 0.5 τ1
mol
CA0 = 4 3
m
mol
CA1 = 2 3
m
mol
CA2 = 1 3
m
=τ 60secsec
= 1m in
In the first reactor the mean residence time is 60 sec
Design equation of MFR

C − CA1
τ = A0
( −rA )
116.
C − CA1
A0
τ1 = n
k (CA1 )
4 − 2

τ1 = n
k (2)
1−n
( )
τk =
2
1−n
(2)
k=
60
τ2= 0.5 τ1
τ2 =30 sec
C − CA2
τ2 = A1 n
k (CA2 )
(2)1 n
−
2 − 1
30 × n
=
60 ( 1 )
1−n
(2)
= 1
2
(2)1−n =2
1−n =1
n=0
Q23 Choose the correct statements with respect to a catalyst added in the fol-
lowing reaction
A B+C
(A) Catalysts affect both the yield and selectivity of the reaction.
(B) Catalysts can either accelerate or slow the formation of the product.
(C) Catalyst changes the rate of the reaction.
(D) Catalyst affects the equilibrium.
Sol: (A), (B), (C)

Explanation: A catalyst can obtain the product by following the different
pathways to follow the lower energy barrier, therefore it can affect both the
yield and selectivity. Shown in figure:
117.
Figure : The alternate path of the catalyst
A catalyst can either speed up the reaction or slow it down.
A catalyst changes the rate of the reaction but does not affect the equilibri-
um.
Q24 A reaction took place in a CSTR, following first order kinetics where k= .8 s-1.
The molar flow in CSTR is 4 mol/s and the initial concentration of the reac-
tant CAO is 2 mol/m3. Calculate the volume necessary to achieve 75% conver-
sion in the reactor.
Sol: 7.5 m3
Explanation: The design equation of the CRST is
X
V =F AO
( −rA )
0.75
V= 4
( − 0.75)
0.8 × 2 1
= 7.5 m3.
Q25 What is the order of the following reaction and the unit of the -rA in S.I units
A → Bα + C γ
where
= α 2 and
= γ 1
(A) 3, m6. mol-2.s-1 (B) 2, mol2.m6.s-1
(C) 3, m9. mol-3.s-1 (D) 2, m9. mol-3.s-1
Sol: (A)
Explanation = order of the reaction , n = α + γ
n=3
the order of the reaction is 3
(concentration )1−n
The unit of the reaction is
time
118.
Unit of concentration = mol/m3
Time = seconds
n is the order
1− 3
 mol 
 3 
 m 
therefore, reaction
s
2
 mol 
−2  m3 
 3   
 m   mol 
or
s s
Q26 Concentration time curves for the elementary reversible parallel reaction is
given by the following graph. Determine the correct reaction.
(A) (B)
(C) (D)
Sol: (3)
The product R is irreversible with A, that means that the concentration of R
will increase and then decreases. On the other hand, product S is increasing,
it means no reversible reaction for S.
On the other options where the order of the reaction is 3, is not possible in
this case, because in the graph R and S are apart, which means lower order
of the reaction of A and R
119.
Q27 The reaction is given as:
k C2
A → B −rA = 1 A2
1 + k 2CA
The reactant A is very high, then find the order of the reaction
Sol: zero order

Explanation : in case when the reactant concentration is very high then,
k C2 k
1 A2 = 1 = zero order
−rA =
k2CA k2
Q28 Performance equation of any chemical reactor is a function of which of the

following:
(a) Output = f[Thermodynamic conditions, input, kinetics]
(b) Output = f[Input, kinetics, contacting]
(c) Output = f[Mechanical properties, thermodynamics conditions, kinetics]
(d) Output = f[Operating conditions, input, kinetics]
Sol: (b)
Explanation: The performance equation is:
Output = f[Input, kinetics, contacting]
Q29 The chemical A → B , -rA= k CA3 in a mixed flow reactor. The initial
concentration of the reactant A is 2mol/m3, then find the units of the rate
constant k
2 3 2
 mol  −1  m3  −1  mol  −1  mol 
(a)  3  . s (b)   s (c)  3  .
s (d)  3  . s
−1
 m   mol   m   m 
Sol: (b)
Explanation: Rate constant general equation is:
(time)-1 (concentration)1-n
Therefore, for n=3
2
 m3  −1
k=   s
 mol 
120.
Q30 In the given below , the variation of concentration (CA,CR and Cs) for three
species (A,R and S) with time, in an isothermal homogenous plug flow
reactor.
For 80% conversion of A is achieved in plug flow reactors, find the concen-
tration of R in the product stream. The initial concentration of A is 10mol/L.
The rate of reaction of R and S are
dCR
= 2 C 2A mol/L.min
dt
dC s
= 4 C A mol/L.min
dt
Sol: 5.80 mol/L

The figure in the question depicts:
R  dCR
ϕ  =
 A  dCR + dCS
M  2C2 CA
ϕ   = 2 A =
 A  2CA + 4 CA CA + 2
In case of PFR
1 CAf
FP =
∆CA ∫ CA0
ϕ dCA
121.
−1 CAf
FP =
( A0 − CAf )
C ∫ CA0
ϕ dCA
−1 2
FP =
( 10 − 2) ∫ 10
ϕ dCA
1 10
FP =
( 10 − 2) ∫ 2
ϕ dCA
−1 2
FP =
( 10 − 2) ∫ 10
ϕ dCA
−1 2 CA
FP =
( − 2)
10 ∫ 10 C

A +2
dCA
1 10 C
FP =
( − 2)
10 ∫ A dCA
2 C +2
A
Solving
FP = 0.7253
Therefore, CR = 0.7253 (8)
CR = 5.80 mol/L
Gate questions
(Gate 2015)
Q1 For which reaction order is the half-life of the reactant half of the full life-
time (time for 100% conversion) of the reactant?
(A) Zero order (B) Half order
(C) First order (D) Second order
A (A)
We know that for zero order reaction,
dCA
− = kCOA = k
dt
Where k = rate constant
CAO − CA =
kt
For, full life time CA = 0
t = CAO / K
and for half life

CAO
=CA C=
AO / 2, So t1/2
2k
So, t = 2t1/2
122.
Q2 An irreversible, homogeneous reaction A → products, has the rate expression:
2C 2A + 0.1C A
Rate = , where C A is the concentration
1 + 50C A
of A.
CA varies in the range 0.5 – 50 mol/m3.
For very high concentration of A, the reaction order tends to be:
(A) 0 (B) 1 (C) 1.5 (D) 2
A (B)
We have,
2C2A + 0.1CA
Rate =
1 + 50CA
(
ol / m3
0.5 < CA < 50 m )
ol / m3 )
For very high value of CA ( say 50m
0.1CA << 2C2A
and 50CA > 1
2C2A 1
So, =
rate = CA
50CA 25
So reaction order is one
Q3 Which of the following can change if only the catalyst is changed for a reac-
tion system?
(A) Enthalpy of reaction.
(B) Activation energy.
(C) Free energy of the reaction.
(D) Equilibrium constant.
A (B) is the correct answer.

123.
Q4 The impulse response to a tracer pulse experiment for a flow reactor is given
below:
In the above figure, c is the exit tracer concentration. The corresponding E

or Eθ (normalized E) curve is correctly represented by which of the following
choices? Here, θ is dimensionless time.
A (C) is the correct answer.
124.
Q5 An isothermal steady state mixed flow reactor (CSTR) of 1 m3 volume is used
to carry out the first order liquid-phase reaction A → products. Fresh feed
at a volumetric flow rate of Q containing reactant A at a concentration CA0
mixes with the recycled steam at a volumetric flow rate RQ as shown in the
figure below.
It is observed that when the recycle ratio R = 0.5, the exit conversion XAf =
50% When the recycle ratio is increased to R = 2, the new exit conversion (in
percent) will be:
(A) 50.0 (B) 54.3 (C) 58.7 (D) 63.2
A (A) is the correct answer.

As there is no effect of external recycling on MFR, since MFR is itself a back
mix reactor with ∞ Dispersion number.
Q6 A catalyst slab of half-thickness L (the width and length of the slab>> L) is

used to conduct the first order reaction A → B. At 450 K, the Thiele modulus
for this system is 0.5. The activation energy for the first order rate constant
is 100 kJ/mol. The effective diffusivity of the reactant in the slab can be
assumed to be independent of temperature, and external mass transfer
resistance can be neglected. If the temperature of the reaction is increased
to 470 K, then the effectiveness factor at 470 K (up to two decimal places)
will be ______.
Value of universal gas constant = 8.314 J/mol.K
A .72 T1
= 450 K
= φ1 0.5 =EA 100 kg / mol
Order of the x/c is =1 It is given that DAB ≠ f (T)
T2 = 470 K E470 K = ?
125.
K1
φ1 =L (i)
DAB
−100
Ea/RT −
×103 /8.314×450
=K1 e= e
= 2.465 × 10−2 s−1
So by equation (i)
2.465 × 10−12
0.5 = L
DAB
DAB
= 9.86 × 10−12 L2
K2
At 470 φ2 =L
DAB
3
−Ea /RT
=K2 e= e−100×10 /8.314×470
K2
= 7.689 × 10−1251
7.689 × 10−12
φ2 =L
9.86 × 10−12
φ2 =1.13
tan hφ tan h1.13
=E = = 0.718
φ 1.13
E = 0.718
126.
Q7 Consider two steady isothermal flow configurations shown schematically as
Case I and Case II below. In case I, a CSTR of volume V1 is followed by a PFR
of volume V2, while in Case II a PFR of volume V2 is followed by a CSTR of
volume V1. In each case, a volumetric flow rate Q of liquid reactant is flowing
through the two units in series. An irreversible reaction A → products (order
n) takes place in both cases, with a reactant concentration CA0 being fed
into the first unit.
Choose the correct option:

CIA CIA
(A)  f > 1 for n = 1 (B) II f = 1 . for n = 1
CA CA
f f
C l
Af
C l
Af
(C) < 1 for n = 1 (D) = 1 for n > 1
C 
f
CIA
f
A (B) In the given arrangements,
There is no effect of mixing on first order reactio Hence, (B) is the correct
answer.
Final outlet concentration CAf will be the same inoth cases.
127.
Gate 2016
Q1 For a non-catalytic homogeneous reaction A → B, the rate expression at 300

10C
( )
K is −rA = A , mol m−3 s −1 where CA is the concentration of A (in mol /
1 + 5C A
m3). Theoretically, the upper limit for the magnitude of the reaction rate (– rA
in mol m–3 s–1, rounded off to the first decimal place) at 300 K is _______.
A Upper limit of reaction of reaction rate will be at

CA = CA0
10 CA0 CA0 (10)
− rA
⇒= = = 2
1 + 5 CA0  1 
CA0  + 5
 CA0 
Q2 The variations of the concentrations (CA, CR and CS) for three species (A, R
and S) with time, in an isothermal homogeneous batch reactor are shown in
the figure below.
Select the reaction scheme that correctly represents the above plot. The
numbers in the reaction schemes shown below, represent the first order
rate constants in units of s‒1.
A (C) is the correct answer.
128.
Q3 Hydrogen iodide decomposes through the reaction 2HI ⇋ H2 + I2. The value of
the universal gas constant R is 8.314 J mol‒1K‒1. The activation energy for the
forward reaction is 184000 J mol‒1. The ratio (rounded off to the first deci-
mal place) of the forward reaction rate at 600 K to that at 550 K is _______.
A 28.5
From Arrhenius law,
 k2  E  1 1 
ln =   − =where T1 550K
= & T2 600K
 k1  R  T1 T2 
k  18 4000  1 1 
So ln  2 
=  − 
 k1  8.314  550 600 
Ans ⇒ k2 =
28.5 k1
Q4 The liquid phase reversible reaction A ⇋ B is carried out in an isothermal

CSTR operating under steady state conditions. The inlet stream does not
contain B and the concentration of A in the inlet stream is 10 mol/lit. the
concentration of A at the reactor exit, for residence times of 1 s and 5 s are 8
mol/lit and 5 mol/lit, respectively. Assume the forward and backward reac-
tions are elementary following the first order rate law. Also assume that the
system has constant molar density. The rate constant of the forward reac-
tion (in s‒1, rounded off to the third decimal place) is______.
A rA k1 CA − k2 CB
For reaction given, rate equation can be representing as, −=
C AO ⋅ X A C AO ⋅ X A
For MFR,
= τm = CA =−
CA0 (1 X A ) and CB =
CAO .X A
(−rA ) k1 CA − k2CB
XA
So , τm =
k1 (1 − X A ) − k2 X A
So, for case – I
0.2
=1 = ⇒ 4k1 − k2 1 (I)
k1 (1 − 0.2) − k2 (0.2)
For case – I
τm 1 sec
= ⇒ =CA 8 mol l
8
X A =1 − =0.2
10
129.
For case – II
=τm 5 sec ⇒ =CA 5 mol 
5
X A =−
1 =0.5
10
For case – II
0.5
=5 = ⇒ k1 − k2 0.2 (II)
k1 (1 − 0.5) − k2 (0.5)
On solving equation (I) and (II)
k1 = 0.2667 sec−1
Q5 A liquid phase irreversible reaction A → B is carried out in an adiabatic CSTR

operating under steady state conditions. The reaction is elementary and
follows the first order rate law. For this reaction, the figure below shows
the conversion (XA) of A as a function of temperature (T) for different values
of the rate of reaction ( in mol ms ) denoted by the numbers to the left of
each curve. This figure can be used to determine the rate of the reaction at a
particular temperature, for a given conversion of A.
The inlet stream does not contain B and the concentration of A in the inlet
stream is 5 mol/m3. The molar feed rate of A is 100 mol/s. A steady state
energy balance for this CSTR results in the following relation: T=350+25 XA
where T is the temperature (in K) of the exit stream and XA is the conver-
sion of A in the CSTR. For an exit conversion of 80 % of A, the volume (in m3,
rounded off to the first decimal place) of CSTR required is?
A From the equation,

T = 350 + 25 XA
130.
At XA = 0.8
T = 350 + 25 x 0.8 = 370 K
So, from curve at XA = 0.8 & T =370 K
10 mol
⇒ − rA = 3
m .s
Vm X
= A
FA0 −rA
For MFR,
FA0 .X A 100 × 0.8
= Vm = = 8m3
(−rA ) 100
Q6 A porous pellet with Pt dispersed in it is used to carry out a catalytic reac-

tion. Following two scenarios are possible.
Scenario 1: Pt present throughout the pores of the pellet is used for catalys-
ing the reaction.
Scenario 2: Pt present only in the immediate vicinity of the external surface
of the pellet is used for catalysing the reaction.
At a large value of Thiele modulus, which one of the following statements is
TRUE?
(A) S
ince the reaction rate is much greater than the diffusion rate, Scenario 1
occurs.
(B) S
ince the reaction rate is much greater than the diffusion rate, Scenario
2 occurs.
(C) S
ince the reaction rate is much lower than the diffusion rate, Scenario 1
occurs.
(D) S
ince the reaction rate is much lower than the diffusion rate, Scenario 2
occurs.
A Explanation: Thiele modulus is given by,

Intrinsic reactionrate
ϕ × CharactersticLength
pore diffusionrate
So, for Large value of the Thiele modulus, the reaction rate will be high.
Since the reaction rate is much greater than the diffusion rate, Scenario 2
occurs. Hence, (B) will be the correct answer.
131.
Q7 A CSTR has a long inlet pipe. A tracer is injected at the entrance of the pipe.
The E-curve obtained at the exit of the CSTR is shown in the figure below.
Assuming plug flow in the inlet pipe, the ratio (rounded off to the second
decimal place) of the volume of the pipe to that of the CSTR is _______.
It is obvious, there is delay so, it can be assumed to be PFR & CSTR in series
so, the delay is equal to τP (space time of PFR) So here delay is 5 min
⇒ τP = 5 min
And we know that, for CSTR
− t/ τm
e
E(t) =
τm
1
At t = 0 E (0) =
τm
1
So at t = 5 E(0 − 5)
= = 0.05 ⇒ τ=
m
20 min
τm
A τp
=
5
= 0.25
τm 20
132.
Gate 2017
Q1 The following reaction rate curve is shown for a reaction A → P. Here, ( −rA )
and x A represent reaction rate conversion, respectively. The feed is pure A
and 90% conversion is desired.
Which amongst the following reactor configurations gives the lowest total
volume of the reactor (s)?
(a) CSTR followed by PFR (b) Two CSTR in series
(C) PFR followed by CSTR (d) A single PFR
A (A)
The performance equation for PFR
XA
τ V Dxa
=
CAO
=
FAO ∫
0
−rA
Hence the volume required for the reactor for given conversion is
xA
dX A
V = FAo ∫
0
−rA
1
Which is the area under the curve? − versus X A
rA
The performance equation for given conversion is
X
V = FAo A
−rA
Which is the volume of rectangle drawn on the graph between

1
− versus X A conversion for the given reaction.
rA
133.
The following options give the following volumes:
Set up0 Volume
CSTR followed by PFR Area of rectangle from 0 to 0.5 and area under curve
form 0.5 to 1
Two CSTRs in series Area of two rectangles (from 0 to 0.5 and 0.5 to 1)
PFR followed by CSTR Area under curve from 0 to 0.5 and area of rectangle
form 0.5 to 1
A single PFR Area under the curve
It’s clearly shown the combination of CSTR followed by PFR hence answer is
option (A).
Q2 The flowing liquid second order reaction is carried out in an isothermal CSTR
at steady state A → R ( −rA ) =
0.005C 2A mol / m3 .hr Where, CA is the concentra-
tion of reactant in the CSTR. The reactor volume is 2 m3, the inlet flow rate
flow rate is 0.5 m3/hr and the inlet concentration of the reactant is 1000
mol1/m3 the fractional conversion, rounded to 2 decimal places is ______.
A 0.80
For a CSTR the performance equation can be written as
V / Fo
= T=
/ CAo X A / rA
V / Vo= T= CAo. X A / −rA
(2 / 0.5) = (CAo X A ) / (0.005C2A )
=4 (C Ao X A ) / (0.005C2Ao (1 − X A )2 )
134.
Q3 Reaction A → B is carried out in a reactor operating at steady state and 1
mol/s of pure A at 4250C enters the reactor. The outlet stream leaves the
reactor a 3250C. The heat input to the reactor is 17 kW. The heat of reaction
at the reference temperature of 250C is 30 kJ mol. The specific heat capaci-
ties (in kJ/mol.K) of A and B are 0.1 and 0.15, respectively, The molar flow
rate of B leaving the reactor, rounded to 2 decimal places, is _____mol/s .
A 0.6.
A → B
Suppose X be the conversion of reactant
T1
= 4250 C, ∆=
Hx 30 kJ / mol
= 30000J / mol
=Q 17
= kW 17000J,
= T2 3250 C
Trpf= 250 C, FAo= 1 mol / sec, FA= (1 − x)FAo
=CPA 0.1kJ
= / mol, CPB 0.15kJ
= / mol, FB x FAo
Heat balance gives
(
FAo CPA T2 − Trpf )
( )
= FA CPA T2 − Trpf + FBCPB T2 − Trpf ( )
1 × 0.1(425 − 25)
= 0.1 (1 − x) (325 − 25) + x (0.15) (325 − 25)40
a 30 (1 − x) + 45 x
=
X = 0.6
=FB F= Ao X 0.6(1)
= 0.6 mol / sec
Q4 The C-curve measured during a pulse tracer experiment is shown below, in

the figure C (t) is the concentration of the tracer measured at the reactor
exit in mol/liter at time t seconds.
The mean residence time in the reactor, rounded to 1 decimal place, is
_____S.
A 1.0
The data can be drawn from the diagram is as follows:
C (t) t t. C (t)
0 0 0
135.
1 1 1
0 2 0
Mean residence time = ∑ t. C / ∑ C = (0 + 1 + 0) / (0 + 1 + 0) = 1s
Q5 The reversible reaction of t butyl alcohol (TBA) and ethanol (EtOH) to eth-
ylt-buty ether (ETBE) is:
TBA + EtOH → ETBE + H2O
The equilibrium constant for this reaction is KC = 1. Initially, 74 g of TBA is
mixed with 100g of aqueous solution containing 46 weight % ethanol. The
molecular weights are : 74 g /mol for TBA. 46 g/mol for EtOH, 102 g/mol for
ETBE, and 18 g/mol for water. The mass of ETBE at equilibrium rounded to 1
decimal place is _____g.
A
20.4
Let x mole of ETBE present of equilibrium mass of EtOH = 46 g mass water =
54 g
46
Mole of EtOH = = 1 mol
46
54
Mole of water = 3 mol
18
TBA + EtOH  +water
At t= 1 1 0 3
At equilibrium 1−x 1−x x 3+x
(3 + x) (x)
=Kc = 1
(1 + x) (1 − x)
X = 0.2
Mole of ETBE = 0.2
Moles of ETBE = 0.2 (102) = 20.4 gm
136.
Q6 The following gas phase reaction is carried out in a constant volume isother-
mal batch reactor
A + B → R +S
The reactants A and B as well as the product S are non condensable gases.
At the operating temperature, the saturation pressure of the product R is 40
kPa. Initially, the batch reactor contains equimolar amounts of A and B (and
no products) at a total pressure of 100 kPa. The initial concentrations of the
reactants are C= A.0
C=B.0
12.56 mol/m3. The rate of reaction is given by
( −r ) =
A
0.08C A
CB mol/m3.s The time at which R just starts condensing,
rounded to 1 decimal place, is ____.
A 4
A +B+R+ S
Let m moles of A and B present initially in the reactor
Initially m,m 0, 0
After time t, m − xm,m − xm mx mx
Total moles after time t = t = mx + mx + m − mx + m − mx = 2m
(mx ) Pt Pt x
Partial pressure of R at time t = = = PR
2m 2
At Pr = 40 kPa . R will start condensing
100(x)
Here, Pt = 100 kPa, PR = 40 =
2
x = 0.8
C=
A CAo (1 − X)
= 1.25 (1 − 0.8)
CA = 2.5 mol / m3
CA dCA
Batch reactor t = ∫CA0 0.08C2A
1  1 1  1  1 1 
=t  =
−   − =  ⇒ t 4 sec
0.08  CA CA  0.08  2.5 12.5 
 0 
137.
Gate 2018
Q1 For a chemical reaction, the ratio of rate constant at 500K to that at 400K is
2.5. Given R = 8.314 J mol-1K-1, the value of activation energy (in kJ/mol) is:
(A) 10.5 (B) 12.0 (C) 15.2 (D) 18.4
A (C)
By Arrhenius Law,
k2 E 1 1  ln (k2 / k1 )
ln =−  −  ∴ E =− × RE =15.236k
J / mol
k1 R  T1 T2   1 1 
 − 
 T1 T2 
Q2 Liquid phase isomerization of o-xylene to p-xylene using a zeolite catalyst

was carried out in a CSTR. Three sets of kinetic data at different tempera-
tures and stirring speeds were obtained as shown below.
Set A Set B Set C
Temperature(K) 500 500 500 600 600 600 700 700

700
Stirring 1000 2000 1000 2000 3000 1000 2000

speed(rpm) 3000 3000
Reaction rate 0.020 0.025 0.037 0.047 0.069 0.078

(mol L-1s1) .025 0.047 0.086
The operating condition at which the reaction rate is not controlled by ex-
ternal mass transfer resistance is:
(A) T = 500 K ; rpm = 3000 (B) T = 600 K ; rpm = 1000
(C) T = 700 K ; rpm = 1000 (D) T = 700 K ; rpm = 2000
A (A)
It is clear from the figure for after 2000rpm, despite an increase in rpm 3,000
no change in reaction rate. Hence at these conditions external mass transfer
is not controlling .
138.
Q3 A CSTR and a PFR of equal volume are connected in series to carry out a
first order, isothermal, liquid phase reaction A → P . The rate constant is
0.2 s-1. The space-time is 5 s for both the reactors. The overall fractional
conversion of A is __________(rounded off to third decimal place ).
A CSTR − ( 1)
τ XA
= 1 =
X A1
τk
C A0 −γ A kCA 1 − xA
0
(1
)
X A1 τk 5 × 0.2
= = x A1 = τA1 0.5
⇒=
1 − x A1 1 + τk 1 + 5 × 0.2
PFR-2
τ x dx 1 x dxA
=∫ xAAA A =∫xAA2 τ
C A0 1 −γ A kCA0 1
( 1 − xA ) k
x
−ln ( 1 − xA )]XA1 2=0.5 5 × 0.1 =
= ( )
−ln 1 − xA2 + ln ( 1 − 0.5 ) 1.69314
= ( )
−ln 1 − xA2 0.18394 =
1 − x A2 x A2 =
0.8160
Q4 The elementary second-order liquid phase reaction A + B → C + D is carried

out in an isothermal plug flow reactor of 2 m3 volume. The inlet volumetric
flow rate is 10 m3/hr. The initial concentrations of both A and B are 2 kmol/
m3. The rate constant is given as 2.5 m3 kmol-1 h-1. The percentage conversion
of A is______.
A Exp : C=
A0 C=
B0
3
2 kmol / m= 3 / hr; V
v 10m
3 2m 3
= 2m
= ;k 2.5 m2 / kmol.h=
∴ τ V=
/v
10 m3 / hr
τ dX dX A tkCA
0.2hr
= ∫ 2A =
= ∫ XA = o
C A0 kCA KCA0 ( 1 − X A )
2
1 + tkCA0
0.2 × 2.5 × 2 1
= = = X A 0.5X
= A 50%
1 + 0.2 × 2.5 × 2 2
139.
Q5 A set of standard stainless-steel pipes, each of internal diameter 26.65mm
and 6000 mm length, is used to make a plug flow reactor by joining them
in series to carry out degradation of polyethylene. Seven such pipes are
required to obtain a conversion of 66% at 450K. The minimum number of
standard 8000 mm long pipes of the same internal diameter to be procured
for obtaining at least 66% conversion under the same reaction conditions is
_______.
A Exp.
=L1 6000
=mm 6
=m d1 26.65 mm
Total volume (of same size) PFR ( VT ) = ∑i=1 vi
a
VT= 7 × V1
( )
2
v 1 = πd21 L
1 = π × 26.65 × 10−3 × 6 = 0.13387 m3 ∴ VT = 7 × V1
VTh = 0.09371l m3
Type II.
L2 = 8000 mm, d2 = 26.65 mm V2 = πd22 L
2 ,
26.65 × 10−3 m
d2 = , VT =
n × V2
( )
2
V2 = π × 26.65 × 10−3 3
× 8 = 0.0178498m
Both cases operating condition are same VT1 = VT2

VT1
nV2 = VT ⇒ n = = 5.25. ∴ n ≈ 6
V2
Minimum number of reactor type 2.
140.
Q6 Hydrogenation of benzene is to be carried out using Ni (density = 8910 kg/
m3) as catalyst, cast in the form of non-porous hollow cylinders, as shown
below. The reaction occurs on all the surfaces of the hollow cylinder. During
an experiment, one such cylinder is suspended in the reactant stream. If the
observed rate of reaction is 0.39 mol (m2 of catalyst surface )-1 min-1 , then
the rate of reaction in mol (kg of catalyst)-1 min-1 is _________(rounded off to
three decimal places).
A π 2
Exp: Vol of catalyst,
= D − d2 L
V ( )
4
=D 0.025m
= , d 0.02
= mL m.ρ 8910 kg m3
0.025
=
π
V=
4
( )
0.0252 − 0.022 × 0.025 v = 4.4178 × 10−6 m 3
kg
Weight of catalyst ω = ρat × v = 8910 × × 4.4178 × 10−6 m3
m
ω =0.03936 kg
Surface area of catalyst
π
( ) ( )
S = πDL + πdL + 2 D2 − d2 = π (D + d) L + 0.5 D2 − d2 
4  
=
 ( )
π ( 0.025 + 0.02) × 0.025 + 0.5 0.0252 − 0.022  S =
3.88772 × 10−3 m
2
π 2
( 2
)
[if we neglect 2 D − d Then, S may be a little smaller.]
4
γ'A ω = Sγ'A
S '
γ'A = γA
ω
141.
3.88772 × 10−1 m2 mol
= × 0.39 2
0.03936 kg of catalyst m catalyst surface
mol
ÿ Å =0.03852
Y
kg of catalyst
π 2
[If you neglect 2
4
(D − d2 ) circular disc area γÿA =0.03510 ]
Q7 In a laboratory batch setup, reaction of P over a catalyst was studied at

various temperatures. The reactions occurring are P → 2Q;P → R
At the end of one hour of operation, the batch contains xP , x Q and xR mole
fractions of P, Q and R components respectively. The mole fractions of
product components ( x Q and xR ) were found to vary linearly with tempera-
ture as given in the figure.
If the yield of Q based on reactant P consumed (YQ) at 25oC was found to be

0.40, then the value of YQ at 60oC is ________rounded off to second decimal
place).
A Exp. Yield of Q ( YQ ) =
roduct Q formed ( YQ )
Desiredp
SpecificR consumed ( XPT )
eactantP
@T
= 25°C
142.
GATE 2019
Q1 The desired liquid –phase reaction

D + E k 1 → F rF =
k 1CD2 CE0.3
Is accompanied by an undesired side reaction
D + E k 2 → F rG =
k 2 CD0.4 CE1.5
Four isothermal reactor schemes (CSTR: ideal continuous–stirred Tank re-
actor; PFR: ideal plug flow reactor) for processing equimolar feed rates of D
and E are shown in figure. Each scheme is designed for the same conversion.
The scheme that gives the most favourable product distribution is:
Sol: C
rF k CD2 CE0.3 k1 ( 2−0.4) (0.3−1.5)
= 1 0.4 1.5 = ( ) CD CE
rG k2CD CE k2
rF k1 CD1.6
=
rG k2 CE1.2
For favourable product distribution, CD= high and CE= low
Q2 For the first order reaction in a porous spherical catalyst pellet, diffusional
effects are most likely to lower the observed rate of reaction for:
a. Slow reaction in a pellet of small diameter,
b. Slow reaction in a pellet of large diameter
c. Fast reaction in a pellet of small diameter
d. Fast reaction in a pellet of large diameter
Sol: D
For a spherical catalyst particle
1  1 1 

= ε  − 
MT  tanh2MT 3MT 
Where,
k′′
MT = L
De
For a strong pore diffusion,
MT = high
143.
R k′′
MT = = high
3 De
( reaction)
k′′ = high fast
R= large (large pellet diameter)
Q3 The elementary, irreversible, liquid-phase, parallel reactions 2A->D and 2A-

>U, take place in an isothermal non-ideal reactor. The C-curve measured in a
tracer experiment is shown in the figure, where C(t) is the concentration of
the tracer in g/m3 at the reactor exit at time t (in min).
The rate constants are k1=0.2 Litre/ (mol min) and k2=0.3 litre/ (mol min).
Pure A is fed to the reactor at a concentration of 2 mol/litre. Using the seg-
regated model, the percentage conversion in the reactor is ……………..( round
off to the nearest integer).
Sol: −rA= k1C2A + k2C2A= (0.2 + 0.3) C2A= 0.5C2A

For a segregated model:
α
X= ∫ x ( t ) e ( t ) dt
0
E(t):
C (t)
E(t)= α
∫ C ( t ) dt
0
α 6
∫ C ( t ) dt = ∫ C ( t ) dt
0 0
= Area under the entire triangle
= are of triangle (t=0-1)+area of the triangle (=1-6)

Area of triangle t=0-1
1 5
Area1= × 5 × ( 1 − 0) =
2 2
Area of triangle t=1-6
1 25
Area2= × 5 × (6 − 1 )=
2 2
5 25
Total area= Area1+Area2= + 15

=
2 2
α
∫ c ( t ) dt = 15.9m
3
in / m
0
144.
c (t)
E (t) =
15
To evaluate c(t) as a function of time
Y=mx+c
( 5 − 0)
C(t)= t + 0n[ for 0 < t < 1]
( 1 − 0)
Or c(t)=5t 0<t<1
For 1<t<6
Y=mx+c
(0 − 5)
C(t)= t+c
(6 − 1)
C(t)=-t+c
At t=6, c(t)=0
0=-6+c
Or c=6
C(t)=-t+6
C(t) as a function of time
C(t)=5t 0<t<1
C(t)=-t+6
For 0<t<1
c (t) 5t
E(t)= α =
∫ c t dt 15
( )
0
For 1<t<6
c (t) (6 − t )
E(t)= α =
15
∫c ( t ) dt
0
For a second order reaction,

1 XA
= kt
CA ( 1 − X A )
o
XA
= kCoA t
1 − XA
kC0A t
XA =
1 + kC0A t
0.5 × 2 × t t

= XA =
1 + 0.5 × 2 × t ( t)
1 +
145.
α
XA = ∫X 0
A ( t ) E ( t ) dt
1 6
= XA ∫X 0
A ( t ) .E ( t ) dt + ∫ 1 XA ( t ) .E ( t ) dt
1 t 5t 6 t (6 − t )
= XA ∫ . dt +
0 ( 1 + t ) 15 1 (1 + t )
. ∫
15
dt
5 1 t2 6 6 t 1 6 t2
X A =
15 ∫ 0 (1 + t )
dt +
15 ∫ 1 (1 + t )
dt −
15 ∫ 1 (1 + t)
dt
1 1 t2 6 t 6 t2
X=
A [ 5
15 ∫ 0 (1 + t )
dt + 6 ∫
1 (1 + t )
dt − ∫
1 (1 + t )
dt
Evaluating them differently,

t2
∫ (1 + t )
dt let u =+
t 1 du =
dt
2
(u − 1 ) u2 − 2u + 1  1 
∫ u
du = ∫ u  u ∫
du=  u + − 2  du

du
∫ udu + ∫ u
− 2 du ∫
2
u
+ lnu − 2u
2
2
( t + 1)
+ lnln ( t + 1) − 2 ( t + 1)
2
2
t2 ( t + 1)
∫ =
(1 + t )
dt
2
+ lnln ( t + 1) − 2 ( t + 1)
Evaluate
t
∫ ( t)
1 +
dt l etu
= t + 1
(u − 1 ) du
∫ u
dt = ∫
1 du − ∫ u
u − lnlnu
=
t
∫ (1 + t )
dt = t + 1 − ln ( t + 1)
Evaluate
t2  ( t + 1)2 
1
5 ∫ =
0 (1 + t )
dt 5 
 2
+ lnln ( t + 1) − 2 ( t + 1) 

146.
  ( 1 + 1)2   ( 0 + 1)2 

= 5   ( + 1) − 2 ( 1 = 1)  − 
− lnln 1 ( + 1) −2 (0 + 1)
+ lnln 0
 2 2 
   
=5 [ −1.3068 =0.5 + 2] =5 × 0.1932 =0.966
Evaluate
6 t
6 ∫ 1 (1 + t )
dt= 6 t + 1 − lnln ( t + 1) 
6 [5.054 − 1.3068] =
22.4832
Evaluate
6 t2  ( t + 1)2 
∫ 1
=
(1 + t )
dt 
 2
+ lnln ( t + 1) − 2 ( t + 1) 

=[12.446-(-1.30680]=13.7528
Evaluate
1
XA = [0.966 + 22.4832 − 13.7528]
15
X A = 0.6464
Percentage conversion of the reactor = 64.64%
Q4 A first–order irreversible liquid phase reaction A->B (k=0.1 min−1 ) is carried
out under isothermal, steady state conditions in the following reactor
arrangement comprising an ideal CSTR( continuous stirred tank reactor) and
two ideal PFRs (Plug flow reactor). From the information in the figure, the
volume of the CSTR (in litre) is ………………. (Rounded off to the nearest
integer).
Sol: Analysis of plug flow reactor:

N plug flow reactors in series with a total volume V gives the same conver-
sional as a single plug flow reactor of volume V.
That is, conversion of two PFR’s of volume 60L and 40L will give the same
conversin as a PFR of volume 100L.
For a PFR, 1st order reactor,
C0
kτ =lnln A
CA
1 C0
τ = lnln A
k CA
147.
1  1m
ol / l 
τ = ln  
0.1  0.5 mol / l 
τ =6.93m
in
V
τ = 6.93 min
=
FA0
V = V1 + V2 = 100L
V
FA0 = = 14.43 mol/l
6.93
Flow through plug flow reactor train =14.43 mol/l
Flow through CSTR= (100-14.43)= 85.57 l/min
Analysis of CSTR
C0A − CA
kτ =
C0A
1 − 0.5
kτ = 1
=
0.5
1 1
τ= = min= 10m in
k 0.1
VCSTR
= 10m
in
FA0, CSTr
L
VCSTR 85.57
= × 10min
min
VCSTR = 855.7 min
Q5 The elementary liquid phase reactions

A
=k1 0.4m in−1 →B
= k2 0.1min−1 → C
Take place in an isothermal ideal CSTR. Pure A is fed to the reactor at a
concentration of 2 mol/litre. For the residence time that maximizes the exit
concentration of B, the percentage yield of B, defined as
net formation rate ofB

( × 100 ), is ………. (rounded off to the nearest integer)
consumptionr ate of A
Sol: For irreversible series reaction in a CSTR

1 1
τm,opt= = = 5min
k1k1 0.4 × 0.1
Now at τm,opt
148.
CA 1 1 1
= = =
CA0 1 + k1 τm 1 + 0.4 × 5 3
1 2
= CA = CA0 mol / l
3 3
4 8
And, CR = CA0 = mol / l
9 9
8  8
Net formation rate of B= F( CB − CB0 )= F  − 0 = F  
9  9
2
Net consumption rate of A= F( CA0 − CA ) = F(2- )
3
 net formationr ate ofB 
Yield=   × 100
 net consumptionr ate of A 
8
F 
 9  × 100 =
66.67%
Yield=
4
F 
3
149.
Q6 The elementary irreversible gas phase reaction A->B+C is carried out
adiabatically in an ideal CSTR operating at 10 atm. Pure A enters the CSTR at
a flow rate of 10mol/s and a temperature of 450 K. Assume A,B and C to be
ideal gases.
The specific heat capacity at constant pressure (CPi) and heat of formation
( Hi0 ) of component I (i=A, B, C), are:
CPA= 30 J/(mol K)
CPB= 10 J/(mol K)
CPC= 20 J/(mol K)
H0A = -90 KJ/mol
HB0 =-54 KJ/mol
HC0 =-45 KJ/mol
E 1 1
The reaction rate constant k(per second)=0.133 exp {  − } where
R  450 T 
E=31.4 kJ/mol and universal gas constant R=0.082 L atm/(mol K)= 8.314
J(mol K). The shaft work may be neglected in the analysis, and specific heat
capacities do not vary with temperature. All heats of formation are referred
to 273K. The reactor volume (in litres) for 75% conversion is …………
(rounded off to the nearest integer)
Sol: P=10 atm

E 1 1
K(sec-)= 0.133 exp{  − 
R  450 T 
E=31.4 kJ/mol; R=8.314 J/mol.K
WS= 0 (no shaft work)
XA= 0.75
Energy balance on a reactor
ÿ ÿ ÿ ÿ
 −=
Q Ws ∑ out
ηi hi − ∑ ηihi + ε ∆Hr
in
η − ηA
X A = A0
ηA0
10 − ηA
0.75 =
ηA0
ηA =2.5
ηi − ηi0
=ε = 7.5
γi
150.
Energy balance
ÿ ÿ ÿ ÿ
 −=
Q Ws ∑ out
ηi hi − ∑ ηihi + ε ∆Hr
in
 J 
=0 7.5m
ol ×10 × ( T − 273 ) K + 7.5 × 20 × ( t − 273 ) + 2.5 × 30 × ( t − 273 ) 
 mol.K 
kJ mol
− 10 × 30 × ( 450 − 273 ) + 7.5 × ( −9) × ×1000
mol kmol
( T − 273) [75 + 150 + 75) − 53100 − 67500 =
0
120600
( T − 273) =
300
T = 675K

For a CSTR, with change in no. of moles due to reactor
X ( 1 + εA X A )
kτ = A
( 1 − XA )
=VX − VXA 0
1=
εA = A
VXA =0
For A-> B+C
2−1
ε=
A = 1
1
X A = 0.75
E  1 1 

= k 0.133 exp   − 
R
  450 T 
KJ J KJ

= E 31.4
= ; R
8.314
= K 8.314 = .K and T 675K
mol mol kmol
 KJ 100mol 1  1 1 
k sec−1
= ( 
)
0.133 exp 31.4
mol
×
lmol
× × − 
8.314 kmol.K  450 675  
= 0.133 exp (2.7976) = 2.1818
k=2.1818 sec-1
151.
Q7 Consider the reactor–separator-recycle process operating under steady
state conditions as shown in the figure. The reactor is an ideal continuous
stirred tank reactor, where the reaction A+B->C occurs. Assume that there is
no impurity in the product and recycle streams. Other relevant information
is provided in the figure. The mole fraction of B (xB) in the reactor that mini-
mizes the recycle rate is …………………….. (rounded off to two decimal)
Sol: Overall material balance

A+B ->C
ηA0= 100 kmol/h
ηB0= 100 kmol/h
At point A (before entering reactor)
Mole A: 100+ ηR,A
Mole B: 100 + ηR,B
Mole C: 0
At point B (at the reactor exit)
Mole A: ηR,A
Mole B: ηR,B
Mole C:100 kmol/hr
For minimum recycle ratio:
Rate of reactor of B= (100+ ηR,B)- ηR,B = 100 kmol/hr
And mole fraction of A= mol fraction of B
Moles B consumed= (-rA)V
100 kmol/hr= [103,xA. xB. Kmol/hr m3] [10m3]
xA=xB
100=104. xB2
100 −2
xB2= 4 = 10
10
xB=0.1
152.
GATE 2020
Q1 In a laboratory experiment, a unit pulse input of tracer is given to an ideal

plug flow reactor operating at a steady state with recycle ratio, R=1. The exit
age distribution E(t) of the tracer at the outlet of the reactor is measured.
The first four pulses observed at t1,t2,t3 and t4 are shown below.
In addition, use the following data and assumptions:
y R is defined as the ratio of the volume of fluid to the entrance of the rector
to the volume leaving the system.
y No reaction occurs in the reactor.
y Ignore any dead volume in the recycle loop.
If the space time of the plug flow reactor is τ seconds, which one of the
following is correct?
A. t1=τ t2=3τ t3=3τ t4=4τ
τ 3τ
B. t1 == t2 τ t3 = t4 = 2τ
2 2
τ τ τ
C. = t1 = t2 = t3
2 4 16
τ 2τ 4τ
D. t1 = t2 = t3 = τ t4 =
3 3 3
Sol: B
At steady state Fi=F (Flow in= flow out)
Fo= Fi + RF
Fo= Fi + RFi
kF i (R + 1)
o F
=
vol of fluid returned to fluid enterance
( ratio ) =
R Recycle
Volume leaving the systme
R=RF
Space time of theP FR
τ =
reactor volume
volumetric feedr ate
VPFR
τ = .
Fi
V VPFR
τ′ = PFR
F0 Fi (r + 1)
V τ
τ′ = PFR = τ
2Fi 2
153.
For ideal PFR, first phase of tracer shows up at the exit of after τ
In case of the recycle reactor will show up at τ/2, i.e at the outlet
T1- first pulse---- τ/2
T2- second pulse---- 2 τ/2
T3- third pulse-------- 3τ/2
T4- fourth pulse---- 4τ/2=2
Q2 The square of Thiele modulus. MT is given by

L2k
MT =
Deff
Where L is the characteristic length of the catalyst pellet, k is the rate
constant of a first order reaction, and Deff is the effective diffusivity of the
2
species in the pores. MT is a m
easure of
time scale ofp ore diffusion
A.
time scale ofr eaction
rate of pore diffusion
B.
rate of reaction
time scale ofr eaction
C.
time scale ofp ore diffusion
rate ofr eaction
D.
rate of externalm ass transfer
Sol: A
Q3 An irreversible gas phase reaction 2P→ 4Q+R is conducted in an isothermal

isobaric batch reactor. Assume ideal gas behaviour. The feed is an equimolar
mixture of the reactant P and an inert gas. After complete conversion of P
the fractional change in volume is …………..( round off to 2 decimal places).
Sol: 2P->4Q+R
Basis:
2 mol P
V − VXP
εA =
= XP 1 = 0
VXP =0
154.
XP=0 XP=1
P 2 0
I 2 2
Q 0 4
R 0 1
Total 4 7
7−4 3
εA = = = 0.75
4 4
Q4 The decomposition of acetaldehyde (X) to methane and carbon monoxide

follows a four-step free radical mechanism. The overall rate of decomposi-
tion of X is
1/2
 k1  3/2
=−rX k2 =  CX koverallC3/2
X
 2k3 
Where, k1, k2 and k3 denote the rate constants of the elementary steps, with
corresponding activation energies (in KJ/mol) of 320, 40 and 0, respectively.
The temperature dependency of the rate constant is described by the Arrhe-
nius equation. CX denotes the concentration of acetaldehyde. The rate con-
stant for the overall is Koverall. The activation energy for the overall reaction
(in KJ/mol) is…………..(round off to nearest integer)
Sol:  k1  2 23
1
=−rX k
2 =  CX overallC3/2
k x
 2k3 
1/2
 k 
2 1 
koverall = k
 2k3 
=E1/RT 1/2
−E −E /RT A e
[ Aoverall e overall /RT ] = A2e 2  1 −E3/RT
2e
Comparing LHS and RHS
 E1 E3 
 −E2− 2 + 2 
e−Overall = e 
E1 E2
−E
overall =−E2 − +
2 2
155.
320
−E
overall =−40 − +0
2
kJ
−E
overall −200
=
mol
−E
overall =
200K
J / mol
Q5 Consider the gas phase reaction N2O4 ↔ 2NO2 occurring in an isothermal and
isobaric reactor maintained at 298 K and 1.0 bar. The standard Gibbs energy
change of the reaction at 298 K is . The standard states are those of pure
ideal gases at 1.0 bar. The equilibrium mixture in the reactor behaves as an
ideal gas. The value of the universal gas constant is 8.314J/mol K. If one
mole of pure N2O4 is initially charged to the reactor, the fraction of N2O4
that decomposed into NO2 at equilibrium is:
A. 0 B. 0.17 C. 0.38 D. 1
Sol: N2O4 ↔ 2NO2

° J
∆G298 5253
=
mol
°
−∆G298
lnlnk
a =
RT
 J   1   1 
lnln ka =  −5253 × mol.K  ×  
 mol   8.314   298K

−2.12
lnlnk
a = −2.12=
. ka e= 0.12
c
∏
Ka ( T ) = a γi
i= 1 i
2
aNo2
Ka ( 298K ) =
aN204
For ideal gas mixture:
a=i p=
i Pyi
2
pNo2 (Py )2
ka ( 298K
= ) = NO2
PN2O4 (PyN2O4 )
2
yNO2
ka ( 298K ) = (P )

yN2O4
P= 1bar (givn)
And Ka=0.12
156.
2
yNO2
0.12=
yN2O4
N2O4 ↔ 2NO2
Initial At equilibrium
N2O4 1 1-y
NO2 0 2y
2
 2y 
 
1+ y 4y 2 4y 2
0.12= = =
1 − y  ( 1 + y ) ( 1 − y ) 1 − y2
1 + y 
 
2 2
0.12-0.12 y = 4y
2
Or, 4.12 y = 0.12
Y= 0.0291
Y=0.17
Q5 An elementary liquid phase reversible reaction P↔Q is carried out in an ideal

stirred tank reactor (CSTR) operated at steady state. The rate of consump-
tion of P, -rP(in mol li) , is given by
−rP = CP − 0.5CQ
Where, CP and CQ are the concentrations of P and Q respectively.
The feed contains only the reactant P at a concentration of 1 mol/litre, and
the conversion of P at the exit of the CSTR is 75% of the equilibrium
conversion. Assume that there is no volume change associated with the re-
action, and the temperature of the reaction mixture is constant throughout
the operation. The space time (in minutes) of the CSTR is ………………(round
off to 1 decimal place).
Sol: P ↔Q
k
KC = P
k −P
( −rP =) kPCP − kPCQ

kP=1
kP=0.5 Elementary reactions
Also, P ↔ Q
157.
P Q
Initial 1.0 0
At equation (1-xP) xPc

CQe x
KC = Pe
=
CPe ( 1 − xPe )
xPe xPe 2
=KC = 2 ; =
( Pe )
1 − x ( Pe ) Pe
1 − x +
x 2 +1
2
xPe =
3
Actual conversion of P in the CSTR
xP = 0.75xPe
32 1
xP =
=
43 2
For a CSTR
C − CP
τ = P0
( −rP )
CP0= 1mol.L
CP= 0.5 mol/L, CQ= 0.5 mol/L
−rP = CP − 0.5CQ
1  1    1 1  1  mol 
−rP =  − 0.5    =  −  =  
2  2    2 4  4  L.min 
 1
1 − 2  mol / l 1 / 2
=τ = = min 2 min
1 mol 1/4
.min
4 L
τ= 2min
158.
Q6 An exothermic, aqueous phase, irreversible, first order reaction. Y->Z is
carried out in an ideal continuous stirred tank reactor (CSTR) operated ad-
iabatically at steady state. Rate of consumption of Y (n mol /litre minute)is
given by
6500
−
−rY =109 e T C
Y
Where, CY is the concentration of Y (in mol/litre). And T is the temperature of

the reaction mixture (in K). Reactant Y is fed at 50 C. Its inlet concentration
is 1.0 mol/litre and its volumetric flow rate is 1.0 litre /minute.
In addition use the following data and assumptions:
y Heat of the reaction =-42000J/mol.
y Specific heat capacity of the reaction mixture=4.2 J/gK.
y Density of the reaction mixture=1000g/litre.
y Heat of the reaction , specific heat capacity and density of the reaction
mixture do not vary with temperature.
y Shaft work is negligible.
If the conversion of Y at the exit of the reactor is 90% the volume of the
CSTR (in litre) is …………….. (Round off to 2 decimal places).
Sol: Energy balance at steady state:

ÿ
 −W
Q s ( Total enthalpy out through exit stream) −
ÿ
( Total enthalpy in through inlet stream) + ε ∆Hr
(
 = 0 adiabatic
Q )
Ws = 0 Shaft work is 0 .
Assume 50°C (inlet stream temperature) as reference
Total enthalpy in through inlet stream Hi = 0J .
Total enthalpy out through exit stream= F0CP ( T − 50)
 L g J
=  1 × 100  × 4.2 × ( T − 50) K
 min K  g.K
=H0 4200 ( T − 50) J / min
ηio ηi ε
0.1 (0.0.1-1)/-1=0.9
Z 0 0 0.9 mol/min
159.
mol
ηi0= 1L / ×1 = 1mol / min
L
90%conversion of Y(given)
η − ηY 1 − ηy
= = Y0 =
X Y 0.9
ηA0 1
ηy =0.1
Substituting values in equation

ÿ
 − W= H − H + ε∆H
Q s 0 i 0
=0 4200 ( T − 50) − 0 + 0.9 ( −42000)

4200 ( T − 50) = 0.9 × 42000
0.9 × 42000
T − 50
= = 9
4200
T = 59°C = 332K
Rate of reaction of Y at T=59°C
6500
−
109 e (
59+273)
(- γ Y ) = (0.1)
mol
(- γ Y ) =
0.314 .min
L
For a CSTR
C X
τ = A0 A
( −rA )
Here,
CY0X Y
τ=
( −rA )
 mol  1

= τ 1  ( 0.9) × (L.min / mol )
 L  0.314
τ =2.866min
V
τ=
F0
V = 2.866L

160.
Q7 The liquid phase irreversible reactions Pk
1 → QPk
2 → R
are carried out in an
ideal continuous stirred tank reactor (CSTR) operating isothermally at
steady state. The space time of the CSTR is 1 minute. Both the reactions are
first order with respect to the reactant P and k1 and k2 denote the rate
constant of the two reactions. At the exit of the reactor, the conversion of
reactant P is 60%, and the selectivity of Q with respect to R is 50%. The
value of first order rate constant k1 (in
minute−1 ) is ………… ( correctu p to decimal place ) .
Sol: rQ = k1CP
rR = k2CP
and , ( −rP ) = k1CP + k2CP = (k1 + k1 ) CP
rQ k1CP k1
SQ/R= 0.5= = = ……
rR k2CP k2
k1
k2
= = 2k1
0.5
For an ideal CSTR,
C0X
τ= P P
( −rP )
CP0 − CP
= XP
CP0
C
1 − P0 = XP
CP
CP
= ( 1 − XP )
CP0
CP
CP0 =
( 1 − XP )
Placing the values,
 C X  1 
τ = P P   
 ( 1 − XP )   ( −rP ) 
 C X  1 
τ = P P   
 ( 1 − XP )   (k1 + k2 ) CP 
 XP   1 
τ =  
 ( 1 − XP )   (k1 + k2 ) 
161.
 XP   1 
τ =  
 ( 1 − XP )   (k1 + 2k1 ) 
1  XP 
τ=  
3k1  ( 1 − XP ) 
=τ 1and
= XP 0.6
1  0.6  1  0.6 
= 1 min =  
3k1  1 − 0.6  3k1  0.4 
1  0.6  −1
k1 =   min
3  0.4 
in−1
k1 = 0.5m
Q8 A catalytic gas phase reaction P->Q is conducted in an isothermal packed

bed reactor operated at steady state. The reaction is irreversible and second
order with respect to the reactant P. The feed is pure P with a volumetric
flow rate of 1.0 litre/minute and concentration of 2.0 mol/litre.
In addition, use the following assumptions:
� The reactant and product are ideal gases
� There is no volume change associated with reaction
� Ideal plug flow conditions prevail in the packed bed
When the mass of catalyst in the reactor is 4 g, the concentration of P meas-
ured at the exit is 0.4 mol/litre. The second order rate constant (in
litre2g −1mol −1minute−1 ) is ………… ( correctu lace ) .
pto one decimalp
Sol: W
=
XP
∫ ( −r )
dXP
FP0 0 '
P
XP dXP XP dXP
W =F
P0 ∫ ( −r ) = (F C )∫
0 '
P
P0
0 k CP2
XP dXP
= (F CP0 ) ∫ 0
k CP0 ( 1 − XP ) 
2
F XP dXP
= ∫
kCP0 0
( 1 − XP )2
X
F  1  P
=  
kCP0  1 − XP 0
162.
F  1 
=W  − 1 .
kCP0  1 − XP 
F  1 − 1 + XP 
W=  
kCP0  ( 1 − XP ) 
FX
W = 0 P
kCP ( 1 − XP )
FX
k = 0 P
WCP ( 1 − XP )
L mol mol
=F 1= ; CP0 2= ;CP 0.4
min L L
CP0 − CP 2 − 0.4
=XP = = 0.8
CP0 4
W=49
L 1 L 0.8
k=1
min 49 2m ol 1 − 0.8
L2
k= 0.5
g catalyst .m
ol.m
in
163.

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Chemical Reaction

Chemical Reaction Engineering 1

Introduction to Chemical Reaction Engineering

What is chemical reaction?

Figure 2 : Basic functioning of chemical reactor

1.1 Chemical Reactors

Introduction to Chemical Reaction Engineering

1.2 Classification if reaction mixture

1.3 Kinetics of the reaction

For a general reaction

The rate of reaction is defined on the basis of phase

where NA0 is the initial moles of reactant A, mol

NA is the final moles of reactant A, mol

Introduction to Chemical Reaction Engineering

Factor affecting the rate of reaction in homogeneous reaction:-

1.5 Order of reaction (n)

1.6 Molecularity (M)

chemical equation. Molecularity of a complete reaction has no significance and overall

Introduction to Chemical Reaction Engineering

The amount of component in mixture per unit volume.

Introduction to Chemical Reaction Engineering

1.7 Why is there an activation energy?

Activation energy and Temperature dependency

Q2 Milk is pasteurized if it is heated to 63oC for 30 min, but if it is heated to 74oC

A To ask for the activation energy of a process means assuming an Arrhenius

2) Collision Theory: Based on kinetic theory of gases:-

Introduction to Chemical Reaction Engineering

Based on statistical mechanics

2.1 Batch reactor

Principle applications of batch reactor

Table 1: Advantages and disadvantages of batch reactor.

Process steps upstream or downstream of the Quality differences between charges

Better process control than in continuous Limited temperature control capabilities,

Well-defined residence time.

2.2 Flow reactors

A continuous stirred-tank reactor (CSTR) is normally used for liquid-phase reactions,

Table 2: Advantages and disadvantages of CSTR

Consistent product quality due to High investment costs to implement continuous

Wide range of possible flows.

2.2.2 Plug flow reactor

Table 3: Advantages and disadvantages of CSTR

Good conditions for temperature High degree of specialization, often with

No moving mechanical parts (suitable Relatively large pressure drops (depending on

for high-pressure reactions). diameter etc).

2.2.3 Laminar- flow reactor (LFR)

2.3 Size comparison of single reactors

Based on volume reactor system:-

y Variable volume reactor system

2.4 Constant volume reactor system

First order reaction:-

Second order reaction

Zero order of reaction:-

For constant volume reaction system

Kinetic equation for bimolecular second order reaction:-

− lnln ( 1 − X A ) − lnln ( 1 − 0 )  + lnln ( M

Case 2 :- Kinetic equation for equimolar A&B

2.5 Method of finding overall order of reaction

y Initial rate of reaction

1 0.0100 0.0100 0.0347

2 0.0200 0.0100 0.0604

3 0.0200 0.0200 0.2776

So using runs 1 and 2

So the rate law,