Reaction and Biochemical Module: Prepared By: 1. Samson Zeru (MSC) 2. Tesfahun Asha (MSC) 3. Feven Hagereselam (MSC)

REACTION AND BIOCHEMICAL MODULE 2022
SCHOOL OF CHEMICAL AND BIO ENGINEERING

PROCESS, ENERGY AND ENVIRONMETAL ENGINEERING
CHAIR
REACTION AND BIOCHEMICAL MODULE
PREPARED BY:
1. SAMSON ZERU(Msc)
2. TESFAHUN ASHA(Msc)
3. FEVEN HAGERESELAM(Msc)
NOV, 2022
DIRE DAWA, ETHIOPIA

Module Description:- The module consisted of three courses. Two of them concerns
about reaction kinetics and chemical reactor design. The third course concerns about bio-
processing and bioreactor design.
Rationale and objective of the module:- Different chemical and bio-processing

industries require different type of reactors for different purposes to obtain a desired product.
That is why this module is included in the study program.
The module has the following objectives;
 introducing students with preliminary reaction kinetics

 designing of reactors for single and multiple reactions on both isothermal and non
isothermal basis
 demonstrate how important parameters necessary for reactor design, such as reaction
constant and order, can be obtained from experimental data.
 apply reaction kinetic concepts on biochemical processes and design bioreactor
Module Competency:- After completion of this module the students will be expected of
having the following expertise and skills. Students will
 be equipped with basic and practical skills of reaction kinetics for different systems
 identify the effect of different operating conditions and reactor types on the reaction
kinetics .
 apply thermodynamic and kinetic tools for analysis of reactions
 able to select specific reactor type and design chemical reactor
 Understand fundamentals of microbiology, enzyme kinetics and their industrial
applications thereby select and optimize a bioreactor.
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Contents
PART ONE ..............................................................................................................................VI
CHEMICAL REACTION ENGINEERING, I ........................................................................VI
1. Introduction to homogeneous chemical reaction kinetics ...................................................... 1
1.1. The Scope of Chemical Reaction Engineering ............................................................... 1
1.2. Classification of Reactions .............................................................................................. 1
1.2.1. Batch Reactor ........................................................................................................... 3
1.2.2. Continuous Flow Reactors........................................................................................ 4
1.3. Stoichiometric Relationship in Reaction ......................................................................... 6
1.3.1. Measurement of Concentration for the Batch Systems ............................................ 8
1.3.2. Measurement of Concentration for the Flow System ............................................. 10
1.4. Selectivity and Yield ..................................................................................................... 11
1.4.1. Selectivity ............................................................................................................... 11
1.4.2. Yield ....................................................................................................................... 11
2. Chemical Kinetics ................................................................................................................ 12
2.1. The Rate of Chemical Reaction .................................................................................... 12
2.2. Rate Equation ................................................................................................................ 14
2.3. Effects of Temperature on the Rate Constant ............................................................... 20
2.4. Reaction Mechanism ..................................................................................................... 23
3. Kinetics of Homogeneous Simple Reactions ....................................................................... 24
3.1 Variation of Concentration with Time in an Irreversible Batch Reactor ....................... 24
3.1.1 Isothermal Operations at Constant Volume............................................................. 24
3.1.2. Irreversible isothermal operations at change of volume during reactions .............. 30
3.2. Variation of Concentration with Reactor Volume in Flow Reactors ............................ 31
3.2.1. Plug Flow Reactors ................................................................................................. 31
3.3. Reversible Isothermal Reaction at Constant Volume ................................................... 33
3.3.1. First-Order Reversible Reaction ............................................................................. 33
4. Determination of Rate Equations from the Experimental Data ........................................... 35
4.1. Differential Methods ..................................................................................................... 36
4.2. Integral Methods ........................................................................................................... 36
4.3. Initial Rate Methods ...................................................................................................... 36
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4.4. Method of Half-Lives .................................................................................................... 37

4.5. Least-Square Methods ................................................................................................... 37
5. Kinetics of Homogeneous Complex Reactions ................................................................... 38
5.1. Variation of the Concentration with Time for Homogenous Complex Irreversible
Reactions in Batch Reactor .................................................................................................. 41
5.1.1. Simultaneous Reaction ........................................................................................... 41
5.1.2. Mixed - Order Reactions ........................................................................................ 42
5.1.3. Consecutive Reactions ............................................................................................ 44
5.1.4. Parallel or Concurrent Reactions ............................................................................ 45
5.2. Autocatalytic Reactions................................................................................................. 46
6. Kinetics of heterogeneous reactions .................................................................................... 47
6.1. Catalysts ........................................................................................................................ 47
6.2. Catalyst Properties......................................................................................................... 48
PART TWO ............................................................................................................................. 59
CHEMICAL REACTION ENGINEERING, II ....................................................................... 59
CHAPTER ONE ...................................................................................................................... 60
FUNDAMENTALS OF CHEMICAL REACTORS ............................................................... 60
1.1. Classification of Reactors.............................................................................................. 60
1.2 Reactor Design Concept ................................................................................................. 60
1.2.1 Steady-State Condition Concept .............................................................................. 61
1.2.2 Unsteady-State Condition Concept ......................................................................... 62
1.2.3. Ideal concept in the reactor ..................................................................................... 62
1.2.4. Calculation concept ................................................................................................ 62
1.3 Material and Energy balance .......................................................................................... 63
1.3.1 Material Balance ...................................................................................................... 63
1.3.2 Energy Balance ........................................................................................................ 63
CHAPTER TWO ..................................................................................................................... 66
IDEAL - BATCH AND SEMI - BATCH REACTORS DESIGN .......................................... 66
2.1. The Ideal Batch Reactor ................................................................................................ 66
2.1.1 Design of batch reactors .......................................................................................... 67
2.1.2 Numerical evaluation of integral ............................................................................. 70
2.1.3 Heat Effect on the batch reactors ............................................................................. 71
2.1.4 Available Technologies ........................................................................................... 75
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2.2 Ideal semi-batch reactor ................................................................................................. 77

2.2.1 Ideal semi-batch reactor design ............................................................................... 77
2.2.2 Energy Balance ........................................................................................................ 79
CHAPTER THREE ................................................................................................................. 80
STEADY STATE IDEAL PLUG FLOW REACTOR ............................................................ 80
3.1 Plug flow reactor design ................................................................................................. 81
3.2 Heat effect on the plug flow reactors ............................................................................. 83
3.3 Design principle and available technology for plug flow reactor .................................. 86
3.4 The effect of pressure in plug flow reactors ................................................................... 87
3.4.1 Pressure drop along the empty pipes in a gas flow reaction .................................... 88
3.4.2 Pressure drop across a packed bed .......................................................................... 91
3.5 Design of a fixed bed reactor ......................................................................................... 95
CHAPTER FOUR .................................................................................................................... 96
HEAT TRANSFER IN REACTORS ...................................................................................... 96
4.1 Temperature effect on the reactor .................................................................................. 96
4.2 Optimum temperature profiles for non-isothermic reactors ........................................... 97
4.3 Temperature effect in an adiabatic fixed - bed gas reactors ........................................... 99
4.4 Temperature effect in an auto thermal reactor ............................................................. 103
4.4.1 Design of an auto thermal adiabatic tubular reactor with external heat exchanger
tube between the product and the feed ........................................................................... 105
CHAPTER FIVE ................................................................................................................... 107
STEADY - STATE MIXED FLOW REACTORS ................................................................ 107
5.1 Single continuous stirred tank reactor design .............................................................. 107
5.1.1 Material balance of Continuous Stirred Tank Reactor .......................................... 108
5.1.2 Energy balance of continuous stirred tank reactor (CSTR) ................................... 112
5.2 Multiple - Reactor Systems .......................................................................................... 118
5.2.1 Design of plug Flow Reactors (PFR) in series ...................................................... 118
5.2.2 Plug flow reactors connected in parallel or parallel / series .................................. 119
5.2.3 Continuous stirred tank reactors (CSTR) in series ................................................ 119
5.2.4 Design of different types of reactors in series ....................................................... 127
5.3 Design of Recycle Reactor ........................................................................................... 129
PART- THREE ...................................................................................................................... 142
INTRODUCTION TO BIO-CHEMICAL ENGINEERING ................................................. 142
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CHAPTER 1 .......................................................................................................................... 143

BIOTECHNOLOGY AND BIOCHEMICAL ENGINEERING ........................................... 143
1.1. Introduction ................................................................................................................. 143
1.2. Application of Biotechnology ..................................................................................... 143
1.3. Biological Processes .................................................................................................... 143
1.4. Definition of fermentation........................................................................................... 145
1.5. Biochemical Engineering ............................................................................................ 145
CHAPTER 2 ENZYME KINETICS ..................................................................................... 148
2.1. Introduction ................................................................................................................. 148
2.2. Commercial Applications of Enzymes ........................................................................ 148
2.3. Simple Enzyme Kinetics ............................................................................................. 148
2.4. Evaluation of Michaelis-Menten Parameters .............................................................. 153
2.5. Enzyme Reactor with Simple Kinetics........................................................................ 156
2.6. Inhibition of Enzyme Reactions and Other influences on Enzyme Activity .............. 159
CHAPTER 3 ENZYME IMMOBILIZATION ...................................................................... 163
3.1. Introduction ................................................................................................................. 163
3.2. Immobilization Techniques ......................................................................................... 164
CHAPTER 4 INDUSTRIAL APPLICATIONS OF ENZYMES .......................................... 168
4.1. Introduction ................................................................................................................. 168
4.2. Carbohydrates.............................................................................................................. 168
CHAPTER FIVE ................................................................................................................... 174
CELL KINETICS .................................................................................................................. 174
5.1. Introduction ................................................................................................................. 174
CHAPTER 6 STERILIZATION........................................................................................... 182
6.1. Introduction ................................................................................................................. 182
6.2. Sterilization Methods .................................................................................................. 182
6.3. Thermal Death Kinetics .............................................................................................. 183
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PART ONE
CHEMICAL REACTION ENGINEERING, I
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1. Introduction to homogeneous chemical reaction kinetics

1.1. The Scope of Chemical Reaction Engineering
The subject of chemical reaction engineering initiated and evolved primarily to accomplish
the task of describing how to choose, size, and determine the optimal operating conditions for
a reactor whose purpose is to produce a given set of chemicals in a petrochemical application.
However, the principles developed for chemical reactors can be applied to most if not all
chemically reacting systems (e.g., atmospheric chemistry, metabolic processes in living
organisms, etc.)
The conversion process of any raw materials to products could pass through a number of
steps. For illustration see the following schematic approach:
The steps of conversion can be stated as:

Step 1. Physical preparation of raw materials ( Purification,Grinding etc.).
Step 2. Chemical process with partial conversion
Step 3. Separation of non-converted raw material l(obtained from step 2)
Step 4. Separation of unwanted and wanted products.
The steps of a chemical process can be simple or complex, depending upon the purity of the
raw material, the desired quality of the products etc. The main objective of the chemical
reaction process is to secure quality of the wanted products with a minimum cost of
production. In the chemical reaction process stated above, the steps 1, 3 and 4 are physical
treatments and are mainly carried out in unit operations. Step 2 is the chemical treatment,
which is carried out in the reactors. The cost of production depends on step 2.
1.2. Classification of Reactions

There is no specific guideline to classify reactions due to the complexity of the nature of the
reactions. In general, reaction can be classified as follows:
1
1. According to the number of phases involved in the reactions

I) Homogeneous Reaction
II) Heterogeneous Reaction
2. According to the type of reaction
 Simple
 Complex
 Catalyzed
 Noncatalyzed
3. According to the process nature of the reaction, i.e., whether the process of
reaction is:
 Reversible
 Irreversible
4. According to the conditions of the process of reactions,
 Isothermal
 Nonisothermal –
 Adiabatic
However, it should be well understood that one reaction may simultaneously belong to
classifications stated above. Example of reaction may be homogenous, simple, irreversible
etc.
a. The General Mole Balance
A mole balance is the basis for calculating and assessing the quantity of a particular
molecular species (reactant or product) in a given system volume of reaction. In the process
of balance, it takes a small volume of the reactor to observe what happens there in the small
interval of time. A material balance on any reactant species can be drawn up through the
following equations:
Conducting a mole balance on species j at any given instant of time which obeys the
following equation format.
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or expressed in mathematical form of equation,
where Fj,o - represents initial molar flow rates of species j, mol / time
Fj - represents final molar flow rates of species j, mol / time
Gj - represents rate of formation at which a component is formed or disappeared by reaction,
and it is given by the product of the reaction volume, V and the rate of formation of species j,
rj
The total rate of formation within the system volume would be the sum total of all the rates of
formation or by taking the appropriate limits and following the definitions of integral, it can
be expressed for the rate of formation of species j as:
In actual, the subject of mole balance is concerned with the evaluation of this integral
replacing Gj in equation (1.3.1). Thus, substituting equations (1.4.1) to (1.3.1) we get the
basic equation of the mole balance for any chemical species j that is entering, leaving,
reacting and or accumulating within any system volume, v.
Using this basis of equation, the design equation can be developed for various types of
industrial reactors. Of course one needs to find rj using chemical kinetics.
1.2.1. Batch Reactor

Batch reactor:- is a vessel used for chemical reaction that has no feed or effluent streams.
The reactor is well stirred and usually run either isothermally or adiabatically. The main
design variable is how much time the reactants are allowed to remain in the .reactor to
achieve the desired level of conversion.

In a batch reactor, no material is supplied to or withdrawn from the reactor during the
reaction. The amounts of individual components may change due to reaction, but not due to
flow in or out of the system. Therefore, for the species j, the mole balance equation (1.3.2)
can be expressed as:
The rate of formation of species j is uniform and is equal to the system average rate,
everywhere in the reaction, and therefore, we can take the rate of formation out of the integral
and can rewrite the equation of the mole balance in the form of:
And for the disappearance of reactant A,

A Product
Multiplying both sides of equation (1.5.1) by (-1), we get
1.2.2. Continuous Flow Reactors

Continuous flow reactors represent the largest group of reactor types by operational
classification. Several continuous flow reactors are used industrially. a. The continuous-
stirred tank reactor (CSTR) involves feeding reactants into a wellmixed tank with
simultaneous product removal. b. The plug flow reactor (PFR) consists of a long pipe or tube.
The reacting mixture moves down the tube resulting in a change in concentration down the
length of the reactor. c. In the recycle reactor part of the outlet stream is returned to the inlet
of the reactor. Although not a typical reactor classification by type, the recycle reactor allows
for continuous operation in regimes between CSTR and PFR conditions.
In this type of reactors, the chemical reactions occur while the reacting stream is flowing
through the reactor. The reaction is operated at steady-state and this means that the variables
such as concentration, temperature etc. at each point with in the system do not vary with time.
Thus equation (1.3.2) becomes,

A) Continuous Stirred Tank Reactor (CSTR)

In this type of reactors, due to continuous stirring, vigorous agitation takes place. As a
result, the contents are thoroughly mixed and the conditions throughout the reactor are the
same and equal to the conditions at the outlet. For the same reason, the rate of formation
is constant throughout the reactor. Therefore, the rate of formation can be taken out of
integral and the equation can be simplified as
Then the mole balance equation (1.6) becomes,
B) Plug Flow Reactor

In this reactor type, the content of the reactor is perfectly mixed in the radial direction. No
mixing takes place in axial direction. This condition provides the concentration,
temperature, rate of formation etc to vary continuously in the axial direction. Hence the
material balance has to be applied to a differential element of volume. This can be shown
in the Figure 1.2.
Figure 1.2. Plug flow reactor

The differential element of volume can be expressed in equation form as under:

1.3. Stoichiometric Relationship in Reaction

It can be seen that the changes in the composition of a reactor are of two types.
I) Advective change due to material brought into the system or removed from it.
II) The internal change due to chemical reactions.
Our interest is to study the structure of chemical reaction chain in the reaction chain of the
reactor system. To understand the phenomena, let us take a well-known reaction,
Such type of equations can have two alternative meaning: kinetic and stoichiometric
explanation. In a kinetic explanation, it implies that one molecule of N2 combines directly
with three molecules of H2 to form two molecules of NH3.In terms of stoichiometric
description of the reaction means that the number of nitrogen and hydrogen molecules
combine to form ammonia in the ratio 1:3. It is clear that if a reaction expression is true in a
kinetic sense, it is also true in stoichiometric sense, but the converse statement is not true.
The proportions 1:3 in the stoichiometric description are absolutely definite and an equation
such as 3N2 + 3H2 = 3NH3 is non-existent. The stoichiometric relationship explains to us how
many molecules of one species will be formed during a chemical reaction when a given
number of molecules of another species disappear, or in another word, it shows the variation
of the amount of individual species remaining during the course of reaction at time t.
Let us examine a typical chemical reaction, where the chemicals species present in the
reaction system be represented by the letters A1, A2 - - - - -- etc, assuming there are other
species present, represented by j = 1,2 - - - - - - S. A chemical reaction will not be split into
two sides of an equation, unless as in equation (a) above, are written on one side and is set
equal to zero as expressed below:
If we identify A1 with NH3; A2 with N2 and A3 with H2, then S=3 and the reaction (b) can
be expressed as:
Where υ1 =2; υ2 = -1 ; υ3 = -3 is called the stoichiometric coefficient of Aj in the reaction.

The species with positive stoichiometric coefficients are the product of the reaction and those

with negative stoichiometric coefficients are the reactants. The important thing to observe at
this point is that the meaning of the reaction equation is unchanged if it is multiplied by non-
zero constant. The reaction -2 NH3 + 1 N2 +3H2 = 0 is multiplied by (-1), the same reaction
with the decomposition of NH3, can be viewed from the other side.
Considering the following reaction,
As per stoichiometric law, it is true that the change in number of molecules are directly
related to the stoichiometric number, thus

1.3.1. Measurement of Concentration for the Batch Systems

In chemical reaction, the composition of the reaction mixture can be expressed in terms of
one variable, the molar extent or conversion of the reaction. The conversion X is the fraction
of a reactant that has been converted into products, in symbols:
or in other word the conversion of XA is the number of moles of A that have reacted per
mole of A fed to the system

A) Mole as a function of Conversion
Equation (1.11) expresses the changes in number of moles of j species as a function of main
(limiting) reactant (species A) conversion at any given time.
B) Concentration as a function of Conversion
The concentration of species j is the number of moles of j per unit volume, we get by
definition.
where Vf is the final volume.

In general, the concentration of species j for constant volume can be expressed as:
In general, the concentration of species j for variable volume can be expressed as:
(1.4)
For constant temperature and pressure equation (1.4), variable of volume becomes,
(1.5)
Therefore, concentration in a variable volume batch system under constant temperature and
pressure, can be expressed combining equation 1.11 and 1.5 becomes

(1.6)
1.3.2. Measurement of Concentration for the Flow System

The flow system used to describe stoichiometric relationships is given in Figure 1.3
Figure 1.3. Flow system
A) Molar Flow Rate as a function of Conversion for a Flow System

The total molar flow rate can be expressed as
B) Concentration as a function of conversion for a flow system

For constant volumetric flow rate
(1.24)

Note that the same concentration expressions are also obtained as those for a constant volume
batch system, equation (1.13).
For variable volumetric flow rate
(1.25)
1.4. Selectivity and Yield

1.4.1. Selectivity:- Selectivity can be defined in many ways, as illustrated below:
 Selectivity is the ratio of the moles of desired product formed per mole of undesired
product formed:
 Selectivity is the ratio between the amount of desired product P obtained and the key
reactant A converted.
 Selectivity is the ratio between the changes of mole of the main reactant in the main
reaction and the total main reactant mole changes in the process
1.4.2. Yield:- It refers to the amount of a specific product formed in a given reaction
process per mole of entering reactant.
It should be noted that both the selectivity and yield vary between 0 and 1. Both factors are
considered when complex reactions take place and where reactions are competing with each
other.

2. Chemical Kinetics
A chemical kinetics may be defined as that which deals with the velocity of a chemical
reaction (i.e., reaction rate) between the species involved in the reaction. In other words,
chemical kinetics is the phenomena to study the rate and mechanism of how one chemical
species is converted to another. Unlike chemical static’s, precise chemical kinetics principles
and data do not exist to permit a prior prediction. The behavior of chemical kinetics rests
largely upon the experiments conducted.
2.1. The Rate of Chemical Reaction

In a reaction, for a given number of molecules (e.g. mole) of a particular species have either
reacted or disappeared, to form a certain product. The rate at which a given chemical reaction
proceeds can be expressed in several ways. It can be expressed either in the rate of
disappearance of the reactants or in the rate of the formation of the products. For example, the
sucrose converts in the aqueous solution into glucose and fructose.
Let the symbol A represent the sucrose, the numerical values of the rate of reaction A − rA
can be defined as the number of moles of sucrose reacting (or disappearing) per unit time per
unit volume (mol/m3 .s) and is

The rate of reaction of species for homogeneous system in the batch reactor is formally
defined as the change in moles of a component with respect to time and per unit volume of
the reaction mixture,

2.2. Rate Equation

We have discussed that the rate expression must be determined experimentally. If it is found
by experiment, that the expression for the rate of reaction depends on the state of the system
mainly through temperature, pressure, and composition of the species, the rate can be
represented as,
(2.4)
These variables of temperature, pressure and composition are interdependent and given the
temperature and composition of the phase, the pressure can be determined through the
following relationship:
(2.5)
Where, k(T) is the proportional factor called rate constant or the specific reaction rate, which
is a function of temperature, surface effects, the concentration and nature of the catalysts etc.
Experiments show that there exists a simple relation between rate of reaction and
concentration.
(2.6)

Note here the dimensions of the rate constant depend upon the order of reaction. For
example, let us consider first-order reaction

It is proved that the order of reaction is unchanged for a change of parameter in expressing
the rate. That is any parameter equivalent to concentration can be used provided the order
remains unchanged. Thus, the rate expressions for reactions, which occur in the gaseous
phase may be stated in terms of either concentration or partial pressures.
In the above equation, rate of reaction has the same units whether concentration or partial
pressures are used. Therefore, it follows that c k and P k have precisely those dimensional

requirements on the left side of the each equations to equal the dimensions on the right side.
This can be demonstrated as,
As we have said the order of reaction is unchanged for a given reaction whatever are
parameters used, but this is not true for the rate constant. For example, consider the following
reaction, where the order is unchanged but the rate constant is changed

It is to be noted that the rate constant k is positive, therefore, the rate of reaction is positive.
However the rate of formation of a component is negative, when the component is consumed
and is positive, when the component is formed. Using this considerations, the relationship
between the rate of reaction and the rate of formation for a reaction can be shown as,

Example:-1. Consider the following liquid phase reaction

2.3. Effects of Temperature on the Rate Constant

According to the basic law of kinetics, the rate of reaction is expressed by the product,

(2.7)
The temperature, in principle, has an effect through a change in concentration and has the
exponents α , β ,............ and finally, through a change in the rate constant k. Experiment
shows that the possible change in the rate of reaction caused by the first two factors is
insignificant. Actually, the rate constant is more affected by the temperature and for that
reason, when the effect of temperature is considered on the rate of reaction, it can be implied
that it has the effect in the change in rate constant.
This dependency of rate constant on temperature, for an elementary process, follows the
Arrhenius equation, which is derived from the thermodynamics considerations,
(2.8)
where A is the frequency factor and E is the activation energy. Equation (2.7) can be written
(2.9)
In the logarithmic form, the equation (2.8) can be expressed as,
(2.10)
The temperature dependency of reaction will be influenced by the level of activation energy
and temperature, resulting the following conclusion.

Example:-2. At 500 K the rate of a bimolecular reaction is ten times the rate at 400 K. Find
the activation energy of this reaction and what is the percentage difference in rate of reaction
at 600 K
Using equation (2.8) the rate constant as a function of temperature is given
(1)
(2)
Dividing equation (2) by (1) gives
(3)
and simplifying equation(3)
The percentage difference of the rate at 600 K with that of 500 K calculated by

2.4. Reaction Mechanism

Another form of study of chemical kinetics is the mechanism of reaction. Mechanism of the
reactions is not as such considered in engineering discipline, rather it is in the domain of
chemists. Generally, there are two meanings for the reaction mechanism. They are,
i) Reaction Mechanism, means that the subject of studies of kinetics of particular

sequence of elementary reactions leading to the overall chemical change.
ii) Reaction Mechanism means about the detailed analysis of how the chemicals
bond in the reactants and rearrange them for the active complex of the reaction.
For our study purposes, we need to understand the science of reaction mechanism, as
explained under (i). In the reaction mechanism, it is necessary to apply the so-called science
of steady state treatment. The basic concept of this treatment is that there are many
intermediates, in the form of atoms and free radicals, that are present in very small amounts
when the concentration remain steady during the course of the reaction. These concentrations
are zero at the beginning of the reaction, but within a small fraction of a second, they rise to a
steady value. It is assumed that most of the kinetic measurements are appropriate to be taken
only after this steady state of concentration is achieved. Therefore, the rate equations of free
atoms and radicals become zero.

3. Kinetics of Homogeneous Simple Reactions

The Chemical Engineer needs the rate of reaction in order to design a reactor. The study of
the the rate of reaction is very important. This chapter deals specifically about the phenomena
of the rate of reaction in details.
Let us consider the first order irreversible reaction carried out in a batch reactor
To find the rate of reaction for this reaction we need to know the change of concentration
with time for already known rate constant k and that rate can be found out by using
experimental data. This can be done by:
 Measuring variation of concentration with time and recording the data

 Proposing the rate equation and deriving concentration as a function of time for a
batch reactor concentration as a function of volume for the flow reactor by using
integral or differential method.
 Inserting the experimental data to the proposed rate equation and checking the linear
relationship between concentration and time.
 If the experimental data fits the proposed equation then to find the order of reaction
and rate constant.
3.1 Variation of Concentration with Time in an Irreversible Batch Reactor
3.1.1 Isothermal Operations at Constant Volume

By isothermal operation, it is meant that the temperature of the reacting mixture is maintained
constant throughout the course of the reaction. By constant volume, it is meant that the
volume of the reacting mixture within the system remains constant throughout the course of
reaction. But for the volume of the reaction mixture to remain constant, it is necessary for the
mass density to remain constant.

1. Zero-Order Reactions
This occurs, when the rate of reaction is independent of the concentration of the reacting
species, the rate is said to be zero-order with respect to that species. This can happen under
two conditions. Either
(1) When the species are not participants in the reaction or,
(2) (2) When the species are supplied in such abundance that their concentration are
nearly constant during the reaction.
For example, in the NO oxidation to NO2, in the presence of excess O2, the rate becomes
zero-order with respect to O2 i.e. actual concentration dependency cannot be detected, and
apparently zero-order is presumed
In this form, the equation for zero-order reaction, prevails, where the concentration of the
reactant decreases with time linearly. Equation (3.2) can be used for experimental data of
concentration vs time to determine the order of reaction as well as k0.
If two reactants A & B are involved in the reaction, experiments can be carried out with A in
large excess, so that the rate equation is independent of CA. In this case the concentration of
B can be varied and its order can be determined

2. First-Order Reactions
Variation of Mole with Time
(3.4.3)
Variation of Conversion with Time
(3.4.4)
Half-life method
There is another parameter to determine the rate constant quantitatively by the application of
so-called half- life. The half-life is the time required for one-half of the reactant to undergo
reaction or the time taken for 50% reaction to occur (50% conversion).
(3.4.5)

3. Second-Order Reactions
Second-order reactions exist in two types.
(3.5)
(3.6)
The equation (3.6.) expresses the dependency of the concentration of the reacting substance
on time for the second-order reaction. It also shows that the dimension of the rate constant
includes the reciprocal concentration, which means that the numerical value of the rate

constant depends on the choice of concentration units. If the concentration is expressed in

moles per m3, then the rate constant dimension is
(3.6.1)
Substituting CA = CA0/2 in to equation (3.6), we obtain the half-life of the second-order

reaction as,
(3.6.2)
Equation (3.6.2) indicates that the half-life depends not only on the rate constant as it was for
the first-order reaction, but it is also inversely proportional to the first power of the initial
concentration.
(3.7)
Variation of mole with time
Consider the equation 3.6.

Substituting Cj = njVf and rearranging for constant volume, we get
(3.8)
4. Third order reactions

There exist three possible types of third order reactions
(3.9)
(3.10)

substituted in to the equation (3.10) as under,
(3.11)
5. Higher-Order Reactions
Since more often reactions of higher order than the third-order are particularly encountered,
we may sum up the dependency of concentration with time for the α thorder reactions. For
which let us consider the general reaction.
Where α = α th - order of the reaction. The rate equation can then be written as,
(3.12)
(3.13)
(3.14)
3.1.2. Irreversible isothermal operations at change of volume during

reactions
In certain reactions, the number of moles increases or decreases during the course of reaction
and the total moles are directly proportional to conversion.
This phenomena can be seen in the reaction,

(3.15)
For such type of reactions to occur, the volume must be decreased as the reaction progresses
in order to maintain the pressure of the reacting mixture to a specific value.
3.2. Variation of Concentration with Reactor Volume in Flow Reactors

There are two perspectives to define the rate namely, the rate is derived from the material
balance and the rate is expressed in terms of kinetics.
i) The first one depends mostly from the type of systems like batch or flow
reactors
ii) The second one depends on so many factors like concentration, pressure,
temperature etc. but does not depend on the type of systems.
Variation of concentration with reactor volume in flow reactors, where it is demonstrated for
two types of flow reactors namely plug and perfectly mixed flow types
3.2.1. Plug Flow Reactors
3.2.1.1. Liquid Phase Irreversible Reactions
(3.16)
for the volumetric flow rate is constant, FV,f = FV,0 naturally follows that

Here, the concentrations of species A may be expressed in terms of space time, θF which is
the time necessary to process one reactor volume of fluid based on entrance condition(or the
time it takes for the fluid to enter the reactor completely).
Space time is obtained by dividing reactor volume by the volumetric flow rate entering the
reactor, thus
(3.17)
Since , FV,f = FV,0 then equation (3.14) becomes
(3.18)
It is also possible here to express equation (3.15) in terms of residence time. Residence time, t
of an element of fluid leaving a reactor is the length of time spent by that element within the
reactor, thus
(3.19)
And for a change of volumetric flow rate
(3.20)
Note that for a constant volumetric flow rate residence time is identical to space time.
(3.21)
3.2.1.2. Gas Phase Irreversible Reactions

In this type of reaction, given under condition of isothermal and steady state operation, it is
found that negligible pressure drops across the plug flow reactor and under perfect gas
behavior.
i) No change in total number of moles

Such type of reactions are described as
and in such cases, the total molar flow rate, FT is independent of conversion and remaining
constant through out the reactors.
It can be represented that the relationship between molar flow rate and volume can be
expressed as,
(3.22)
ii) Change in the total number of moles
For those reactions, where change in total number of moles occur, the total molar flow rate as
well as the volumetric flow rate varies with the conversion. To understand the phenomena, let
us consider a first-order irreversible reaction,
A 2P
(3.23)
3.3. Reversible Isothermal Reaction at Constant Volume

In chemical reaction, it is rare to find the reaction achieves its full completion i.e., 100%
conversion or in another words, irreversible reaction is seldom found to happen completely,
but can happen to a certain tolerable approximation. Therefore, it can generally be stated that
most reactions which take place are reversible.
3.3.1. First-Order Reversible Reaction

Let us consider one reversible reaction, which is first-order in both directions.

(3.24)
(3.25)
(3.26)
(3.27)
Equation (3.27) cannot be integrated as it is, because it contains three variables. Therefore,
there is a need to reduce the variables into two. The following methods can be adopted to
reduce the variables.
i) Using Stoichiometric Relationships
ii) Using Conversion
iii) Using Extent of Reaction

4. Determination of Rate Equations from the Experimental Data

Determination of the rate equations can only be found through experimental data. This leads
to important experiments to be carried on to find the concentration dependency at a fixed
temperature for determining the order of the reaction. Thereafter to find the temperature
dependency for evaluating the rate constant to yield the complete rate equation for some
reaction parameters. The experimental methods used in kinetics may be classified into two
categories, namely chemical and physical.
i) In Chemical analysis, it is possible to determine directly the concentration
of one of the reacting substances or products against time(or more
specifically of residence time)
ii) In Physical Analysis, the physical change during the course of reaction is
measured.
Some of the physical methods are associated with the measurements of the pressure in
gaseous reaction diatometrically i.e., the measurements of the changes in the volume
produced by the reactions. The other methods are optical methods such as polarometry,
refractometry, colorimetry, conductometry, potentiometry, polarography and mass
spectroscopy. The advantages of application of physical methods, as a rule are their
measurement rapidity. They also make it possible to obtain a large number of experimental
data in a given time interval. The measurements can often be performed directly in reaction
vessel itself. Experimental data so obtained, are carried out in two types of equipments,
namely batch and flow reactors.
A) Batch Reactors
A batch reactor is a simple vessel. In it experimental data are measured against time. These
data are the change of concentration for a given component, the change of total pressure, and
change of volume etc. The experimental batch vessel is usually operated isothermally and at
constant volume. This is because it is easy to interpret the results of such measurement runs
and are used for obtaining homogenous kinetic data.
B) Flow Reactors
A flow reactor vessel is used primarily in the study of kinetics of heterogeneous reaction.
Raw Data obtained from the batch or flow reactor experiments are analyzed in one of the
following ways:
i) The differential method;

(ii) The integral method;

(iii) The initial rate method;
(iv) The half-life method;
(v) The least-square method;
For our study and application purposes, let us limit the above methods analyses in one of the
systems i.e., batch reactor systems.
4.1. Differential Methods

In this method, it requires differentiation of the experimental data to obtain a rate derived
from the experiment. Restriction for application for such method is that it should only be
applied for irreversible reactions with a single reactant.
(4.1)
to find k andα .(- dcA/dt) can be determined from concentration versus time data using one of
the methods such as graphical, polynomial, finite difference, non-linear least square analysis
etc.
4.2. Integral Methods

The integral method follows a trial and error approach to find reaction order. For successful
implementation of this method, first we start with an arbitrary form of rate equation. After
appropriate integration and mathematical manipulations, if the order we have assumed is
correct, the corresponding plot of a certain function –vs- time should be linear. Thus the data
are plotted, and if a reasonable good straight line is obtained, the rate is said to be
satisfactorily fitting the data.
4.3. Initial Rate Methods

In this method, a series of experiments is conducted at different initial concentration, and the
initial rate of reaction is determined for each test. The initial rate can be found by
differentiating the data and extrapolating to zero time. In other words, (say) the initial rates of
reaction are found by plotting the concentration-vs-time curve and finding the slopes at t = 0.
Following the rate law, the initial rate can be given as,
(4.2)
Taking the natural logarithm for both sides, we obtain

(4.3)
4.4. Method of Half-Lives

The general equation for half-life is
(4.4)
Taking the natural log of both sides, we get
(4.5)
4.5. Least-Square Methods

There are three techniques in use for the least-square method. They are Linearized, Non-
Linearized and Weighted Least-Squares. The method of least-squares can give the order of
the reaction with respect to all the components at once. That is why this method is effectively
used, when the rate law depends on the concentration of more than one species, frequency
factor, activation energy etc., especially if it is not possible to use the method of excess. The
Least-Square method requires having a series of measurements.

5. Kinetics of Homogeneous Complex Reactions

Chemical reactions that occur with more than one reaction in a single process to produce a
stable product are called complex reactions. These type of reactions are consisting of:
In a complex system, it may matter little, whether the reactant is totally converted or not. It is
of particular interest that the reactants are converted to the desired product. In another word,
the objective of a complex reaction is to establish wanted and unwanted products for any
reactant and using this relationship one can obtain selectivity and yield.
For example, in the air oxidation of ethylene, we get

The desired product is ethylene oxide, but complete oxidation leads to carbon dioxide and
water.
In such reactions, our interest is to maximize the formation of ethylene oxide and minimize
the formation of carbon dioxide and water. It can be well understood that the greater the
amount of CO2 and H2O formed, the greater will be the cost of separating the desirable
product, from the desired product, ethylene oxide.
Complex reactions are characterized by yield and selectivity and are defined as follows:
where D denotes desired product and U unwanted product

Let us consider the reaction,

The instantaneous selectivity will be
The behavior of kinetics of complex reactions is generally based on the principle of

independency and it postulates that if several reactions take place in a system, then each of
these reactions obeys the basic kinetic law and proceeds independently irrespective of the
other reactions.
Example 5.1. For the following reactions, find the formation of species A,B,C,D and E for
a batch reactor:

5.1. Variation of the Concentration with Time for Homogenous Complex

Irreversible Reactions in Batch Reactor
Conditions: Isothermal operation, perfectly mixed under constant volume
5.1.1. Simultaneous Reaction

In Simultaneous reaction, the reacting substances, instead of proceeding in one path to yield a
given set of products, also follow one or more other paths to give different products.
(5.1)
These reactions can be of many different types and can be distinguished with the following
categories:
i) Parallel reaction with a single reactant of equal reaction order, where n = m = p
ii) Parallel reaction with a single reactant but with different reaction order, where n ≠
m≠p
iii) Parallel reaction where more reactants are involved
(5.2)
First-Order Reaction
Let us consider a reaction, which is first-order in each step:

In the reaction, a substance X takes part simultaneously in two reactions resulting into the
formation of two products Y and Z. It is to be noted here that in general, k1≠ k2. Example of
such type of reaction is given as
The net rate of disappearance of X is equal to the sum of the rates at which X disappears
through the reaction (1) and (2); and that is given by:
(5.3)
Therefore, for a batch reactor, the material balance on species A for constant volume can be
given as,
(5.4)
Thus, we can deduce,
(5.5)
Separation of variables followed by rearrangement and integration gives us,
(5.6)
(5.7)
(5.8)
5.1.2. Mixed - Order Reactions

Let us consider the following reaction,

As per the rate laws, we get
(5.9)
(5.10)
Therefore, the sum of the rate of disappearance of A can be given as,
(5.11)
where α and β are positive order of the reaction. Thus, maximum desired product is obtained,
when the rate of formation of B is as high as possible compared to the rate of formation of C.
(5.12)
Case 1: when α > β
In this case the reaction order of the desired product is greater than the undesired product
order. Let α − β = n, a positive number, then the equation (5.12) is given as,
(5.13)
The ratio of the desired product to the undesired product will be high, if the reactant
concentration can be kept as high as possible. This can happen when: In gas phase run
without inerts and conducted under high pressure conditions. In liquid phase, dilution is
avoided.
Case 2: when β > α
That is where the order of the undesired product is greater than the order of the desired
product, β −α = n, is negative and then the equation (5.12) becomes,
(5.14)

In order for equation (5.14) to yield highest desired product, the reactant concentration should
be as low as possible. This may be affected by diluting the concentration of A with inerts.
Case 3: when α = β
(5.15)
Here, the selectivity is of zero order and is not influenced by the reactant concentration but
only can be influenced by the ratio of the rate constants.
Generally for reactions in parallel, the concentration level of reactants is the key to proper
control of product distribution. A high reactant concentration favors the reaction of higher
order, a low concentration favors the reaction of lower order, while the concentration level
has no effect on the product distribution for reaction of the same order. If all the above cases
are examined, the factor of the temperature influence is ignored. In other words, it can be said
that it occurs under isothermal conditions. When there is temperature sensitivity, in such case
the selectivity parameters can be determined from the ratio of the specific reaction rates,
(5.16)
Where A is the frequency factor and E is the activation energy.
Case 4: when EB > EC
For such cases, the rate constant of the desired product increases more rapidly with the
increasing temperature than the undesired product i.e., we obtain high rate of formation of B.
Thus, we apply high temperature to maximize selectivity.
Case 5: when EC > EB
Reactions should be carried out at low temperature up to the level, where the reaction can
proceed.
5.1.3. Consecutive Reactions

Reactions that proceed from the reactants to products not directly but through one or more
intermediate products are called Consecutive Reactions. They are of general type represented
as,

The category of such reactions belongs to, for example, the hydrolysis of esters of
dicarboxylic acids.
With the consecutive reactions, the reaction path always ends in the final product (s) of the
reaction chain. In many cases, one of the intermediate products is the one desired.
First-Order Consecutive Reactions
Consider the following reaction,
The rate of disappearance of A is given as,
(5.17)
and the net rate of disappearance of B is given as,
(5.18)
Equation (5.17) may be integrated at once to give us,
(5.19)
When we substitute CA into equation (5.18) the following differential equation is obtained:
(5.20)
Equation (5.20) is a linear first-order differential equation. Which gives us the analytical
solution, with the stated initial condition at t = 0, CA = CA,0 and CB =CC = 0 as follows:
(5.21)
5.1.4. Parallel or Concurrent Reactions

Let us consider the reaction,
Whereby the combination of mass balance and application of rate laws gives

(5.22)
(5.23)
By integrating and rearranging equation (5.22), we get
(5.24)
Substituting CA in equation (5.22), followed by integration and rearrangement for the
condition CB = 0 at t = 0, we get
(5.25)
In the same manner, equation (5.23) can be integrated and rearranged to give
(5.26)
5.2. Autocatalytic Reactions

Autocatalytic reactions takes place as soon as some product has been formed, or in other
words the product of the reaction are either catalyzed or promotes further reaction of the
reactants. By nature autocatalytic reactions are different from other types of reactions, where
the rate at the start is low because very little amount of product is present which gradually
increases to maximum product formation and then drops again to a low value when the
reactant is consumed. Figure 4.1 shows a typical behavior of such reactions.
Figure 5.1. Typical rate-concentration curve for autocatalytic reaction

6. Kinetics of heterogeneous reactions

6.1. Catalysts
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 different molecular
path (―mechanism‖) for the reaction. For example, gaseous hydrogen and oxygen arevirtually
inert at room temperature but react rapidly when exposed to platinum.
Catalysis is the occurrence, study, and use of catalysts and catalytic processes. Commercial
chemical catalysts are immensely important. Approximately one-third of the material gross
national product of the United States involves a catalytic process somewhere between raw
material and finished product. The development and use of catalysts is a major part of the
constant search for new ways of increasing product yield and selectivity from chemical
reactions. Because a catalyst makes it possible to obtain an end product by a different
pathway (e.g. a lower energy barrier), it can affect both the yield and the selectivity.
Normally when we talk about a catalyst, we mean one that speeds up a reaction, although
strictly speaking, a catalyst can either accelerate or slow the formation of a particular product
species. A catalyst changes only the rate of a reaction; it does not affect the equilibrium.
Homogeneous catalysis concerns processes in which a catalyst is in solution with at least one
of the reactants. An example of homogeneous catalysis is the industrial Oxo process for
manufacturing normal isobutylalciehyde. It has propylene, carbon monoxide, and hydrogen
as the reactants and a liquid-phase cobalt complex as the catalyst.
A heterogeneous catalytic process involves more than one phase; usually the catalyst is a
solid and the reactants and products are in liquid or gaseous form. Much of the benzene
produced in this country today is manufactured from the dehydrogenation of cyclohexane
(obtained from the distillation of crude petroleum) using platinum-on-alumina as the catalyst:
Of these two types of catalysis, heterogeneous catalysis is the more common type. The simple
and complete separation of the fluid product: mixture from the solid catalyst makes
heterogeneous catalysis economically attractive, especially because many catalysts are quite
valuable and their reuse is demanded.

A heterogeneous catalytic reaction occurs at or very near the fluid-solid interface. The
principles that govern heterogeneous catalytic reactions can be applied to both catalytic and
noncatalytic fluid-solid reactions. These two other types of heterogeneous reactions involve
gas-liquid and gas-liquid-solid systems. Reactions between gases and liquids are usually
mass-transfer limited.
6.2. Catalyst Properties

Since a catalytic reaction occurs at the fluid-solid interface, a large interfacial area can be
helpful or even essential in attaining a significant reaction rate. In many catalysts, this area is
provided by a porous structure; the slolid contains many fine pores, and the surface of these
pores supplies the area needed for the high rate of reaction. The area possessed by some
porous materials is surprisingly large. A typical silica-alumina cracking catalyst has a pore
volume of 0.6cm3/g and an average pore radius of 4nm. The corresponding surface area is
300 m2/g.

Multiple choice questions
1. Which of the following deals with the study of rates at which chemical reactions
occur and the effect of various parameters on the rate?
a) Fluid Mechanics
b) Chemical Technology
c) Chemical Sciences
d) Chemical Kinetics
2. In which of the following reaction the rate of reaction is a function of rate constant
alone is?
a) Zero order reaction
b) Third order reaction
c) First order reaction
d) Second order reaction
3. Which of the following is the most suitable reactor for the pharmaceutical industry?
a) PBR
b) MFR
c) PFR
d) Batch reactor
4. If the conversion of a first-order liquid phase reaction occurring in a CSTR is 75%,
molar feed rate is 5 mol/min, the rate of the reaction is 5 mol/litre.min then the
volume of the reactor (in litre) is?
a) 0.33
b) 0.4
c) 0.75
d) 0.5
5. The rate constant of a first order reaction depends on the _____________
a) Temperature
b) Concentration
c) Time
d) Pressure
6. The catalyst in a first-order chemical reaction changes the _______________
a) Activation energy

b) Equilibrium constant
c) Heat of reaction
d) Heat of formation of the product
7. What is the unit of activation energy?
a) J/ mol
b) K
c) mol
d) mol.K
8. The performance equations for constant density systems are identical for
(A) P.F.R. and backmix reactor
(B) P.F.R. and batch reactor
(C) P.F.R. batch reactor and backmix reactor
(D) Batch reactor and backmix reactor
9. Study of chemical kinetics is the easiest in the case of __________ reactions.
(A) Irreversible
(B) Reversible
(C) Surface
(D) Side
10. The point selectivity of the product 'Y' in the reaction as shown in the bellow figure, is
equal to
(A) K1/K2
(B) K2/K1
(C) K1 - K2
(D) K2 - K1
11. Rate of a gaseous phase reaction is given by, . The unit of rate
constant is

A. (atm)-1
B. (hr)-1
C. (atm)-1.(hr)-1
D. atm.(hr)-1
12. For a reaction of the type, , the rate of reaction (- rx) is given by
A. (K1+K1)CX
B. (K1+K2+K3)CX
C. K1CV - K2CX
D. (K1-K2)CX
13. The rate constant of a chemical reaction increases by 100 times when the temperature is
increased from 4000K to 5000K. Assuming transition state theory is valid, the value of E/R is
A. 89870K
B. 92100K
C. 87640K
D. 86210K
14. Specific rate constant for a second order reaction
A. is independent of temperature.
B. varies with temperature.
C. depends on the nature of the reactants.
D. both (b) and (c).
15. For an isothermal variable volume batch reactor, the following relation is applicable for a

first order irreversible reaction.
A. XA = k . t
B.
C. -ln(1 - XA) = kt
D. εA . ln (1 - XA) = k . t
16. For a zero order chemical reaction, the
A. half life period is directly proportion to the initial concentration of the reac-tants.
B. plot of products concentration with time is a straight line through the origin.
C. products concentration increases linerarly with time.
D. all
17. When the density of the reaction mixture is constant in a chemical reaction, the ratio of
the mean residence time to space time is
A. > 1
B. < 1
C. 1
D. 0
18. A reaction in which one of the products of reaction acts as a catalyst is called a/an
__________ reaction.
A. catalytic
B. autocatalytic
C. photochemical

D. none of these
19. The half life period of a first order reaction is
A. always the same irrespective of the reaction.
B. independent on initial concentration of the reactants.
C. proportional to the initial concentration of reactants.
D. half the specific rate constant.
20. A high space velocity means that a given
A. reaction can be accomplished with small reactor.
B. conversion can be obtained with a high feed rate.
C. both (a) and (b).
D. none of these.
21. The rate of the chemical reaction A B doubles as the concentration of A i.e.., CA is
doubled. If rate of reaction is proportional to CAn, then what is the value of n for this
reaction?
A. 0.5
B. 1
C. 0
D. 2
22. For a homogeneous reaction of nth order, the dimension of the rate constant is given by
A. l/(time)n
B. (concentration)1 - n/(time)
C. (concentration)n - 1/(time)
D. none of these

23. What is the order of a chemical reaction whose rate is deter-mined by the variation of one
concentration term only?
A. zero
B. first
C. second
D. third
24. The reaction in which the rate equation corresponds to a stoichiometric equation, is called
a/an __________ reaction.
A. elementary
B. non-elementary
C. parallel
D. autokinetic
25. Arrhenious equation represents graphically the variation between the __________ and
temperature.
A. rate of reaction
B. frequency factor
C. rate constant
D. activation energy
26. The half life period of a first order reaction is given by (where, K = rate constant. )
A. 1.5 K
B. 2.5 K
C. 0.693/K

D. 6.93 K
27. Half life period of a chemical reaction is
A. the time required to reduce the concentration of the reacting substance to half its
initial value.
B. half of the space time of a reaction.
C. half of the residence time of a reaction.
D. none of these
28. For a first order chemical reaction, the rate constant
A. changes on changing the concentration units.
B. is not a function of the unit of time.
C. has unit of time-1.
D. none of these
29. A multiple reaction may be classified as a __________ reaction.
A. consecutive or side
B. parallel or side
C. mixed
D. all
30. Residence time for flow reactors is __________ the space time, for constant fluid density
A. double
B. triple
C. equal to
D. none of these.
31. Reaction rate of a first order reaction, which is half completed in 23 minutes will be

A. 0.03 sec-1
B. 0.03 min-1
C. 0.03 hr-1
D. 0.05 min-1
32. The half life period 't' of a zero order reaction, A P is equal to
A. CA0/2K
B. CA0/K
C. 0.693/K
D. 1/K
33. The first order gas phase reaction is conducted isothermally in batch mode.
The rate of change of conversion with time is given by
A.
B.
C.
D.
34. The extent of a reaction is
A. Different for reactants and products.
B. Dimensionless.
C. depends on the stoichiometric co-efficient.

D. All of the above.
35. For the reaction, A + B 2B + C,
A. rA = rB
B. rA = -rB
C. rA = 2rB
D. rA = rB/2
36. The ratio of moles of a reactant converted into the desired product to that converted into
unwanted product is called
A. operational yield
B. relative yield
C. selectivity
D. none of these
37. Batch process is preferred over continuous process, when the
A. product yields and quality can not be achieved in continuous process, because of
long residence time.
B. sales demand of product is not steady.
C. same equipment can not be used for several processes of the same nature.
D. all
38. _______________ is the fraction of a reactant that has been converted into products.
A) Conversion B) Concentration
C) Mole fraction D) Extent of reaction
39._________________ is the number of moles of per unit volume.
A) Conversion B) Concentration

C) Mole fraction D) Extent of reaction
40._______________ is the ratio of the moles of desired product formed per mole of
undesired product formed:
A) Yield B) Concentration
C) Conversion D) Selectivity
41.__________________ is the type of reactor that the content of the reactor is perfectly
mixed in radial direction and no mixing in axial direction.
A) Batch reactor B) Plug flow reactor
C) Continuous stirred tank reactor D) none
42. ___________________ is the type of reactor that the contents are thoroughly mixed and
the conditions throughout the reactor are the same and equal to the conditions at the outlet.
A) Batch reactor B) Plug flow reactor
C) Continuous stirred tank reactor D) none

PART TWO
CHEMICAL REACTION ENGINEERING, II

CHAPTER ONE
FUNDAMENTALS OF CHEMICAL REACTORS

A Chemical reactor is a vessel or a container into which a chemical reaction takes place. The
size of such reactor can be a laboratory beaker or an industrial reactor.
1.1. Classification of Reactors

Reactors can be classified in a variety of ways based on the size, method of operation and the
phase involved in the process, namely homogeneous and heterogeneous reactors. Generally
there are four basic forms of homogeneous chemical reactors which differ from each other in
their mixing pattern. These are:-
 The batch reactor (BR)

 The semi-batch reactor (SBR)
 The continuous stirred tank reactor(CSTR)
 The plug flow reactor (PFR)
In the above, all reactors are also named based on the thermal operations such as isothermal,
adiabatic and non-isothermal reactors. Most of the industries now a days are working with
heterogeneous catalytic reactors, some of them are:
 Fixed Bed Reactors

 Fixed Bed Gas Reactors
 Non-isothermal, Non-adiabatic Fixed Bed (NIHAF) Reactors.
 Fixed Bed Gas-Liquid Reactors.
 Trickle Bed Reactors
 Fixed Bed Bubble Reactors(FBBR)
Suspended Bed Reactors.
 Continuous Stirred-Tank Reactors(CSTR)
 Slurry Reactors
 Ebullated Bed Reactors
 Three Phase Transport Reactors
1.2 Reactor Design Concept

A complete reactor design involves two types of design namely process design and
mechanical design. The process design, which is done by chemical engineer, engages with
the size of the reactor; methods of operation and condition for the required output. On the

other side the mechanical design involves with specific matters relating to the equipment
design including structural and mixing equipment
In process design, a chemical engineer is involved in making decisions. Among others the
followings are considered:-:
Type of processing :- batch, semi-batch, continuous etc

Type and nature of the reacting system:- reactant and product; single and multiple
reactions; desired and undesired products; stoichiometry relationship; homogeneous
and heterogeneous; catalytic and non-catalytic; endothermic and exothermic;
irreversible and nonreversible; possibilities of equilibrium limitation etc
Type and size of the reactors:- batch reactor; continuous stirred tank reactor (CSTR); or
plug flow reactor (PFR); fixed bed reactor (FBR); fluidized reactor etc
Mode of operation:- single stage; multistage; thermal like adiabatic, isothermal, non-
isothermal etc Process condition:- T profile, P profile, feed (composition and rate),
product (composition and rate) etc
1.2.1 Steady-State Condition Concept

This is a condition, where at the operation the variables at each point within the system do not
vary with the time. Therefore, in the reactor the following variables remain unchanged with
the time.
 The concentration of the reactants and products.

 The reaction temperature
 The reaction rate
In steady-state condition, where the above compositions remain unchanged with time. Hence,
there is no accumulation.

Figure 1.1 Information needed to design a reactor
1.2.2 Unsteady-State Condition Concept

This is opposite to the steady-state condition i.e., the compositions change with time and
therefore, accumulations exist. This type of reactor is complicated to model and only used in
batch reactor.
1.2.3. Ideal concept in the reactor

The contents of the reactor are instantaneously and perfectly mixed i.e., ideally mixed, so that
the condition throughout the reactor remains the same.
1.2.4. Calculation concept

Consider the general equation,
Conversion
The conversion of species A in a reaction is equal to the number of moles of A reacted per
mole of A fed.
Since conversion is unit less, it can be used for many variables like moles, concentrations,
molar flow rate etc. As for example, we can see:
Batch process:
For constant density,
Continuous process:
To understand the concept of conversion, reaction,

Is carried out in a batch reactor under isothermal condition. This is illustrated in Figure 1.2.
The conversion obtained through time is calculated.
Figure 1.2 Schematic batch reactor
 For Irreversible reactions

The maximum value of conversion, , is that for complete conversion, i.e.,
 For Reversible reactions

The maximum value of conversion, , is the equilibrium conversion, i.e., .
1.3 Material and Energy balance
1.3.1 Material Balance

A material balance on a reactor constitutes an application of the law of conversation of mass.
A material balance may be set up for any molecular species taking part in the system, i.e., for
example, for a component j at any instant time t, may be formulated in the following manner:
1.3.2 Energy Balance

A similar word statement as of material balance can be used for energy balance, i.e the
application of the principle of conservation of energy leads to an energy balance which is in

Figure 1.3 Energy balance on an open system: HF – inflow of enthalpy; HE – outflow of

enthalpy; Q – rate of heat supply from the surrounding or withdrawn from the system.
In principle, all forms of energy, like heat, kinetic energy, potential energy, electrical and
magnetic field must be taken into consideration. In most reactor calculations, the terms with
thermal energy and work done on the surroundings are of the main importance. Hence,
leaving out the other effect, the energy balance for an open system in which reaction takes
place is
Or ( )
For batch process the enthalpy change should be expressed into two elements:
(i) The enthalpy changes with time due to the change in composition. In another word, the
energy change due to the heat of the reaction.
( )
(ii) The enthalpy changes due to the change of temperature
( )
Substitute equation 3 in to 2
( )
( )
( ) ( )

Is the general energy equation
Where TS = Surrounding (cooling, heating) temperature
A = Effective area for heat transfer
T = The temperature of the reaction mixture
∆HR = Heat of reaction
CP = the specific heat for the composition mixture
r = rate of disaperance of species
u = overall heat transfer coefficient
mT = the total mass of reaction mixture
In batch process where there is no in and out flow the energy balance equation yield to
( ) ( )
In continuous process where accumulation does not exist the energy balance equation
becomes
( )
( )
For continuous process
( )
Then the energy balance for continuous process is
( ) ( )
Where FT is the total molal feed flow rate and Cp is the total molal heat capacity of the
reaction mixture

CHAPTER TWO
IDEAL - BATCH AND SEMI - BATCH REACTORS DESIGN

2.1. The Ideal Batch Reactor
A Batch reactor generally consists of a closed vessel provided with a means of stirring and
where the temperature is controlled. Figure 2.1 shows such type of reactor.
Figure 2.1 Typical batch reactor
In batch reactor, no material is supplied to or withdrawn from reactor during the reaction. In
such type of reactor, the reaction proceeds quickly at first, because of high concentration of
all reactants and the composition is only a function of time. Figure 2.2 and 2.3 indicates the
character.
Figure 2.2 Variation of concentration with time in a batch reactor

Figure 2.3 Variation of conversion with time in a batch Reactor
Another characteristics of a batch reactor is due to the well mixing of the composition
throughout the vessel, the total mass of the reaction i.e., concentration and temperature are
identical over the reactor volume. This is shown in Figure 2.4.
Figure 2.4 the concentration inside the batch reactor
2.1.1 Design of batch reactors

In the process design of a batch reactor, we involve determination of the reaction time and or
the size of a reactor for a specified conversion. This information we can get it from the
material balance, noting that in batch reactor, no material enters or leaves the reaction
mixture during the course of reaction.
2.1.1.1 Material balance for batch reactor

General Material balance equation

Assumption ⅰ) no input and out put ∫
ⅱ) perfect mixed
For disappearance = -Generation ( )=
( )
∫ ∫ ( )
∫ ( )
is design equation for batch reactor
In terms of conversion, ( ) , ( ),
∫ ( )
,
∫ ( )
∫ ( )
, ∫ ( )
, -rA = kCA for first order
reaction
( ) ( )
( )
( )
∫ ( )
( )
∫ ( )
2.1.1.2 Total time calculation for batch reactor

When a process is carried out on a batch reactor the following time cycle will takes place
I). Preparation time tch, during which a reaction is made ready and fresh reactants are
charged.
II). Reaction time, tr, during which the reaction proceeds to the desired conversion.

III). Recovery time, td, during which the product is discharged and return to the normal
operating condition.
IV). Cleaning time, tcl , during which the reactor is cleaned.
The total time (cycle time), tc, is the time where one operating cycle of a batch reactor is
described
Product rate (p) or ( ̇ ), the amount of product obtained on one operating cycle
From stoichiometry
( )( )
( )( )( )
̇
For constant
For constant volume
Time of reaction can be represented by the shaded areas in the Figure 2.6

Figure 2.5 Levenspiel Plots to find the reaction time
2.1.2 Numerical evaluation of integral

ⅰ. Trapezoidal rule (two point)
[ ( ) ( )]
∫ ( ) ,
ⅱ. Simpson's one-third rule
∫ ( ) [ ( ) ( ) ( )]
ⅲ. Simpson's three-eight rules (four points)

∫ ( ) [ ( ) ( ) ( ) ( )
2.1.3 Heat Effect on the batch reactors

Generally, all chemical reactions are in principle accompanied by the evolution(exothermic)
or absorption (endothermic) of heat. Changes of temperature during reaction are common in
reactors. This happens deliberately (by heat exchange with the surroundings) or by the nature
of the reaction. The temperature changes due to the nature of reaction versus conversion and
is shown in the Figure 2.6. On the other hand, the effect of temperature versus time in batch
reactor is illustrated in the Figure 2.7.
Figure 2.6 Temperature versus conversion in adiabatic reactors
Figure 2.7 Effect of temperature versus time in a batch reactor
Consider a reaction
Carried out in batch reactor under non isothermal and constant volume system
( )

Flow rate low
( )
∫ ∫
( )
Since the reaction is carried out non isothermal the temperature at the reaction will vary at the
reaction preceded
Energy balance
Energy in + Energy out from the surrounding = Energy out + Eabs + Eaccumulation
̇ ( ) ̇ ̇ ̇ ( )
Case 1 Isothermal operation
( ) ( )
Case 2 Non isothermal
( ) ( )
Case 3 Adiabatic operation
( )
( )
Relating temperature with conversion and time for non-isothermal operation
Consider the following batch reaction
A) Material balance
( )

[ ( )( )]
B) Energy balance:- energy balance for non-isothermal operation
( ) ( )
( )
For adiabatic operation
( )
From material balance
[ ( )( )]
To find the reaction t
[ ( )( )
Runge kuta method for solving differential equation
Case 1: adiabatic operation
Let ( ), from material balance
( )
Given initial point to find the value of y for incremental change on

( )
The procedure is first obtain the k value on Runge Kuta method
( )

[( ) ( )]
[( ( )]
To calculate the new value of ( )
[ ]
( )
[( ) ( )]
[( ( )]
[ ]
To find the value of y for the next incremental the above procedure will be repeated by
replacing
Repeat the same procedure until you reach the desired value
Case 2: ( ), ( )
Given initial value Xo,
To find the value of y for the incremental change on
( )
[( ) ( ) ]
[( ) ( ) ]
[( ( ) ]
[ ]

To find the value of y for the next incremental change Xo, yo, zo will be replaced by X, y
and z and repeated the above procedure
2.1.4 Available Technologies

A batch reactor is usually implemented in the industry for small scale operation, mostly for
testing new products that have to be fully developed and for the processes that are difficult to
convert to continuous operations. The main advantage of batch reactor is high conversion
with a long time and the disadvantage counts to high labor cost per unit production and the
difficulty in obtaining large scale production. The equipment required to conduct a batch
operation is relatively simple and encompasses:
(A) Reactor
It is often a vertical cylinder with an elliptical bottom. The reactor should be constructed in
such a way that it can withstand vacuum and some internal pressure. The material used for its
construction is generally suitable for various reactionary processes. Most often used is a
glasslined steel vessel. This type of reactor is used especially for high corrosion materials.
Figure 2.8 shows the illustrations of a simple batch reactor working in the industry.
Figure 2.8 Industrial batch reactor
(B) Heat Exchanger
The heat exchanger can be located inside the reactor (coil, plates) outside it (conventional
heat exchanger) or could be manufactured together with the reactor wall (double jacket).
Figure 2.9 -2.10 illustrates different type of a reactor with heat exchange mechanism

Figure 2. 9 Batch reactor with double jacket
Figure 2.10 Batch reactor with external heat exchange
(C) Stirrer
Stirrer is used to mix the reactor contents uniformly so that the concentration remains the
same throughout the reactor
(D) Auxiliaries
Water, steam, or a heat transfer medium, electrical energy etc. can be used in the operation.

2.2 Ideal semi-batch reactor

The semi-batch reactor is a tank type operated on a non-steady flow basis. Semi-batch occurs
when some reactants are charged into the reactor at time zero, while other reactants are added
during the reaction. Figure 2.11 illustrates typical semi-batch reactor.
Figure 2.11 Semi-batch reactor
Semi-batch reactor is inevitable when:
I. It is essential to regulate the heat effect of high exothermic reaction. This can be achieved
through regulating the rate of addition of one of the reactants so that the energy evolution can
be controlled.
II. To minimize unwanted side products by maintaining low concentration of one of the
reactants, where it is possible to maximize the selectivity of the product especially in the
liquid phase reaction.
III. It is required to remove one of the products to increase the equilibrium of the reaction to
the application of Le Chatelier’s principle.
2.2.1 Ideal semi-batch reactor design

As always the case in reactor designing, we use martial balance. For the semi-batch reactor
design all the four terms in the general mass balance of equation (1.8) may have to be
considered.
If is the molar feed rate and is the withdrawal, the mass balance for the reactant A
after rearranging becomes

The above equation can be integrated with numerical procedure. Analytical integral is
possible for the case of the constants of the feed and exit rates of the feed composition;
density and additional criteria is that it must be a first-order.
Taking the relationship,
For constant densities along the constant flow rate ( ) the reaction volume also
will be constant

The linear differential equation, which can be integrated analytically. By doing so, we obtain
variation of concentration with time for a first-order reaction in semi-batch operation.
2.2.2 Energy Balance

CHAPTER THREE
STEADY STATE IDEAL PLUG FLOW REACTOR

The tubular reactor consists of a tube inside which the reaction medium flow i.e., where the
feed enters at one end of a cylindrical tube and the product stream leaves at the other end.
Figure 3.1 shows such type of reactor. In this reactor, the turbulent flow bears the greatest
resemblance of the plug flow and as such tubular reactors are interchangeable with the plug
flow reactors
In a plug flow reactor, there is no mixing in the axial direction i.e., in the line of direction of
flow. Ideally each element of the feeds would spend the same time in the reactor. Such type
of the reactors work in the steady state, where the conditions at any point in the reactor are
independent of time and the total mass flow through any cross section of the reactor is the
same. The concentration (composition) of the reaction mixture depends on the distance from
the inlet point resulting from the reaction. Figure 3.2 shows the characteristics of such type of
reactor
Figure 3.1 Tubular Reactor
Figure 3.2 Characteristics of a tubular reactor
Where: Z = Coordinate in the direction of flow L = Length of reactor

The plug flow reactor can be built in the widest diversity of forms, from a mile long pipe,
through which the reactants flow comparatively slowly to a short pipe in a high temperature
furnace, where the reaction mixture passes at near sonic velocity. If the reaction in a plug
flow reactor is conducted under the presence of a solid say a catalyst, we call such type as a
fixed-bed reactor. Again here, designing of a plug flow reactor simply means to find the size
(volume) of a reactor for a certain amount of conversion. This can be obtained by using
material and energy balances.
3.1 Plug flow reactor design

Consider an idealized model of the plug flow reactor shown in Figure 3.3. Since the
composition of the fluid varies from point to point along a flow path, it is necessary to study
the behavior in such reactor. For calculating the molar flow rate of the distribution of the
material balance, it has to be applied to a differential section of the reactor volume . Figure
3.3 illustrates the notation for a plug flow reactor
Figure 3.3 Characteristics of a plug flow reactor
Thus for species J, referring to Figure 3.3, the material balance of equation for volume dV
becomes

On the other hand, for reactant A
From stoichiometric relationship of molar flow rate and conversion
For flow reactors, there is a need to define important parameter called space time. Space time,
, θ F is the time necessary to process one reactor volume of fluid based on the entrance
conditions or the time it takes for the fluid to enter the reactor completely:
Note that the entering volumetric flow rate FV0 is measured at the entrance conditions.
Residence time, t, of an element of fluid leaving a reactor is the length of time spent by that
element within the reactor:
And for variable volumetric flow rate, change of density, constant temperature and pressure ,
the residence time in terms of conversion becomes

For constant volumetric flow rate and the number of moles of feed, then we have
Note that the integral at the right hand side of equation (3.5) also occurs in the design
equation of a reaction time in a batch reactor provided that the density is constant
To find the size (volume) of a reactor for a given feed rate and required conversion, it can be
conducted by using numerical or graphical method. Figure 3.4 illustrates graphical method to
find the size of a plug flow reactor
Figure 3.4 Graphical finding of the size of a reactor in Plug Flow Reactor
3.2 Heat effect on the plug flow reactors

The assumption of plug flow directs that the rate of temperature rise or fall along the reactor
due to the nature of the reaction. Figure 3.5 shows the characteristics of a plug flow reactor.

Figure 3.5 Characteristics of a plug flow reactor
Energy balance
There is no accumulation for steady-state process; hence we use equation for continuous
process as it is
However, slightly modification is essential to model the energy balance for plug flow reactor.
We know that the concentration eventually the rate of reaction continuously varies in the
axial direction through the reactor. To formulate the energy balance for such situation, we
shall divide the reactor into a number of sub volumes. For such condition, the energy balance
for plug flow reactor is
This equation is analogue to of batch reactor energy balance. The only change is in batch
reactor, where we speak in terms of change of time, but in plug flow, it is in terms of change
in volume.
(A) Isothermal Operation
In isothermal operation, the reaction temperature across the length of the reactor is constant
i.e.
The temperature necessary from the heat exchanger to cool or heat to maintain the isothermal
operation is calculated by using

This equation depicts that cooling / heating temperature medium is a function of both the rate
of reaction /conversion/ as well as the length of the reactor
(B) Non Isothermal Operation
In general when dealing with non-isothermal operation of a plug flow reactor, it is required to
calculate the reaction temperature and conversion as a function of volume of the reactor. To
this end, the material balance and energy balance should be applied simultaneously, namely
Energy balance
(C) Adiabatic Operation
Adiabatic reactor of plug flow is working without any addition of heat or removal. In another
words, it works without the use of heat exchanger. This simplified the use of selected
adiabatic reactors for most of the industrial production. This type of reactor may be
materialized by simple insulation of the reactor against loss of heat. Of course the rise and
fall of the temperature against loss of heat. Of course the rise and fall of the temperature leads
to unfavorable equilibrium with exothermic and endothermic reaction. This problem is solved
by using multi stage operation. Since there is no heat transfer in an adiabatic plug flow
reactor, the heat transfer equation becomes
Then the energy balance
Integrating and rearranging gives

3.3 Design principle and available technology for plug flow reactor
As an advantage plug flow reactor (PFR) is easy to construct and produces the highest
conversion per reactor volume among any of the flow reactors. This is the main reason to use
it especially in gas phase reaction at the industrial level. The main disadvantage of the PFR is
that the difficulty to control the temperature along the tube, as a result the so called well
known problem of hot spot can occur, when the reaction is exothermic. Because of this
problem, the tubes are usually very narrow to ensure a high surface/volume ratio for heat
transfer. Thus, in order to get adequate reactor capacity at an acceptable pressure drop, the
industrial reactors must contain several thousands of such tubes, built together in a single
shell in which the coolant is flowing. Figure (3.6) shows such an arrangement. The coolant
might be different or the same than that of the reaction mixture. This is arranged in different
flow systems based on the effect of heat of reaction. Depending on the heat effect of reaction,
plug flow reactors available in the industry are fairly distinct into two categories. The first
one belongs to the reaction of a temperature below 500oC containing a concentric tube system
to facilitate circulation of heat transfer fluid/coolant mediums which are usually a transfer
fluid water, steam, organic fluids, molten salts etc.
Figure 3.6 Industrial plug flow reactors tubes built together in several single shell (Ectracted
from H.S.Fogler)

3.4 The effect of pressure in plug flow reactors

During a chemical reaction, especially those involving a net increase or decrease in the total
number of moles, we have to look the effects of pressure on the rate law. We are interested to
see the resistance to gas flow when a gas is passing through a reactor. The resistance to the
gas flow is measured by the pressure drop across the reactor. Generally, in liquid phase
reaction, the concentration of the reactants is not affected by the change of total pressures;
hence, we ignore completely the effect of pressure drop of reaction when dealing with the
sizing of the chemical reactors. Contrary to this belief, in the gas phase reaction, the
concentration of the reacting species is proportional to the change of the total pressure.
Therefore, we should properly take into account the effect of pressure drop on the sizing of
chemical reactors.
To find the size of the reactor, by accounting pressure drop effect, we use similar procedure
as we did in plug flow reactor. The change comes only to insert the pressure effect in rate
law, stoichiometry relationship etc. accordingly whenever necessary. As for illustration, let us
take a first-order gas phase reaction, which is conducted in an isothermal plug flow reactor.
Our target is to find the size of the reactor, for this we follow the same path as we did in
designing any type of reactors.
1. Mole balance and design equation
2. The rate low

( )
3. Stoichiometry relationship
To observe the effect of the pressure drop on the reactor design, concentration of the reacting
species A is defined by

3.4.1 Pressure drop along the empty pipes in a gas flow reaction
The resistance to the gas flow is measured by the pressure drop along the pipe. Normally, the
pressure drop for gases flowing through the pipes without packing can be neglected.
However, pressure drop in empty pipes can be calculated by applying the normal pressure
drop correlations for the friction loss in the pipes. Consider the flow in pipes along the length
of the pipe as shown in the Figure 3.7.
Figure 3.7 Gas flow in the empty pipes.
The pressure drop along the pipes can be obtained using "Fanning Equation"
( )
Were D – pipe diameter, m
u – Average velocity
f – Fanning friction

G- , superficial mass velocity (kg/m2s)
= gas density kg/m3
The value of f is dependant on the pipe roughness at one hand and the Reynolds number on
the other, where the mass velocity, G is constant along the length of the pipe.
Recalling
and differentiating
For the reactor operating at steady-state condition, we have the mass flow rate as a constant.
And volumetric flow rate for change of density and assuming isothermal conditions, we have
and differentiating

Integrating with limit P = PO when L = O and assuming that f does not vary, we have
Neglecting the second term on the right hand side of the equation we obtain
In terms of volume, V = ACL, we can relate pressure to volume
The basic parameters to account pressure drop in the rate law for reactor design.

3.4.2 Pressure drop across a packed bed

Here we are very much interested to see the resistance to gas flow when a gas is passing
through a packed bed reactor. Figure 3.8 illustrate such a reactor.
Figure 3.8 Fixed bed reactor
The pressure drop across the bed is given with the so called 'Ergun equation'.
Where - porosity = volume of void/Total bed volume
1- - conversion factor = volume of solid/Total bed volume
Dp = Diameter of the particle in the bed
= Viscosity of gas passing through the bed
L = Length down the pipe
P = pressure
= Gas density
G= = Superficial mass velocity = Volumetric flow/Cross sectional are of

pipe
gc = Conversion factor

Ergun equation shows variation of pressure drop across the length of the reactor. This
equation can be modified for specific parameters. For an example if there is a need to
determine in terms of weight of particle such as catalyst weight. The equation can be applied.
The reactor volume and catalyst weight are related through the reaction.
The above equation shows variation of pressure drop against the weight of a catalyst.
Generally, Ergun equation can be used to solve in two cases:
Case 1 : As a constant gas density
Assuming that the gas density is constant at mean value, ρˆ , the equation (3.43)can be
written as
Integrating the above equation with limit P = Po at L = Lo, the pressure P at a distance L
down the tube of the reactor, we obtain

Then the variation of pressure drop as a function of the length of the pipes of the reactor as
In terms of weight of the particles /catalysts/
Case 2: As a variable Density
As the reactor operates under steady-state, the mass flow rate at any point down the pipe
/reactor/ is equal to the entering mass flow rate. Thus
Rearranging

In terms of particle /catalyst/ weight,
The above equation is a first order differential form of equation and shows pressure drop as a
function of conversion as well as weight of a particle/catalyst/.
For isothermal conditions,
For the condition that ε = 0 or neglecting ( ) and for isothermal operation
Using the above equation we can formulate in terms of particle /catalyst/ weight as,

3.5 Design of a fixed bed reactor

By a fixed bed reactor, it is meant a continuous flow-plug flow rector containing a particle,
most of the time a catalyst mass. Figure 3.9 shows such type of a reactor.
Figure 3.9 Fixed Bed Reactor
The fixed bed reactor is relatively easy to construct at a low cost. In designing such type of
reactor, one can take plug flow reactor design equation and then change the volume of reactor
by weight of catalyst as shown
Where ( ) refers to the unit catalyst weight i.e., per unit mass of catalyst.
The volumetric flow rate through the particle/catalyst bed is monitored and the weight of
catalyst, W for a specified conversion can be calculated. In another word, the weight of a
particle/catalyst is commonly used as a variable instead of length or volume of the reactor. Of
course, we have indicated that designing of a reactor is simply finding the size of a reactor for
specified conversion. Here we are not contradicting this principle, but to find the volume of a
reactor, we can calculate the same by using the relationship between the volume and the
catalyst weight. One has to remember here that the volume in a fixed bed includes both the
volume occupied by the particle/catalysts and the voids. In calculating the rate of reaction,
one has to consider its functionality, namely it is a function of concentration, pressure,
temperature etc.

CHAPTER FOUR
HEAT TRANSFER IN REACTORS

4.1 Temperature effect on the reactor
It is to be recalled that all chemical reactions in principle are accompanied by evolution or
absorption i.e., under this principle it is hard to assume a chemical reaction that has a reaction
heat of zero. Figure 4.1 shows schematic diagram of temperature change during reaction in a
batch and continuous operation. In consequence to this reaction process, in designing the
reactor, the heat effect should be accounted where the range and the working temperature
should be specified.
Figure 4.1 Temperature change during reaction for batch & continuous operation
For endothermic and exothermic reactions, the heat liberated or absorbed during the reaction
is controlled by the so called Heat Transfer Equipment with heat transfer fluid. Normally the
heat transfer fluid is water/steam. In general, we prefer to use water. If not, we move up or
down the list, but if we go further away from water, the more practical difficulties may be
encountered due to the reasons of cost, corrosion, specific & latent heat etc.
Figure 4.2 Batch reactors with (a) cooling and (b) with heating

It is to be clear that the heat absorbed or released by reaction can enormously change the
temperature of the reacting fluid, and this is controlled by the cooling or heating medium.
This cooling medium also affects the path, irrespective of whether it is strong or poor or
medium cooling. Figure 4.3 demonstrates such effect.
Figure 4.3 The effect of cooling on the temperature and conversion against the Length (L),
Volume (V) or Weight of a catalyst (W)
4.2 Optimum temperature profiles for non-isothermic reactors

Looking to the relationship between temperature, reaction rate and the size of the reactor, one
can see high temperature favors the high reaction rate and contrary to this, high temperature
requires high volume or reactor. The general shape of rate and length of the reactor versus
temperature plot is shown in Figure 4.4.
Figure 4.4 Relationship between the temperature, rate of reaction and the length
The above variables that influence the design and operating performance of a chemical
reactor can be termed as optimum variables. Since the temperature influences the conversion,
the rate of reaction, the size of a reactor, we set this as a core variable and should find the

optimum operating temperature. Optimum operating temperatures are those at which the
chemical reactor shows an economically justifiable maximum production rate per unit length
of reactor in terms of the desired product. Our target in the design of a reactor, is to find the
size of a reactor for a specified conversion. This is not also the end, we have further to
consider if it is possible to minimize the size of the reactor. This means we have to establish,
in what operational temperature range, a given reaction can be operated to have the maximum
conversion and a plausible rate of reaction within the small size (length) of the reactor.
Looking to the design equation,
The minimum volume will be achieved if the reaction rate is maximum at all positions in the
reactor. The optimum operating temperature at any given position will be that for which the
rate of reaction is maximum at any conversion level. Therefore, the related rate of reaction
corresponding to the conversion, temperature, ( ) is the basic information necessary to
determine optimum operating temperature.
Generally to determine the temperature sequence, which minimizes the reactor volume or the
time of the reaction for a given conversion at the same time achieving the maximum rate of
reaction at all positions in the reactor. Here, different cases may be analyzed for distinction
a) Optimum operating temperature for irreversible reaction

Consider the reaction,
The rate of disappearance of reactant A
Where f(XA) is usually a decreasing function of XA

b) Optimum operating temperature for reversible reaction

Consider the reversible reaction
This has the rate of reaction functionality as
The function g(XA) is always an increasing function since the concentration of product
increases with the conversion
4.3 Temperature effect in an adiabatic fixed - bed gas reactors

Gas/solid catalyzed reaction is carried out in a plug flow reactor, where the reactants are fed
continuously into one end of a tube and the reactor products flow out at the other end. During
the reaction, heat is liberated or absorbed. This happens in such manner that if an exothermic
reaction is run into an adiabatic fixed bed reactor, the temperature of the gas stream will
increase from the inlet towards the outlet. On the other hand in an adiabatic fixed bed reactor
of an endothermic reaction, the temperature of the gas stream will drop within the reactor
length.
Figure 4.5 demonstrates the change of the temperature and conversion across the length of a
fixed bed tube reactor.

Figure 4.5 Temperature and Conversion behaviors for Exothermic (a) and Endothermic (b)
reaction in adiabatic reactors
In an exothermic reaction, the heat generation along the tube is uneven and at the beginning
of the reaction it can exceed Tmax so that the reactor is unworkable. To avoid such events, the
tube has to be very narrow. Using narrow tube ensures a high surface/volume ratio for heat
transfer. In order to get adequate reactor capacity at an acceptable pressure drop, one can use
in the industry several thousand tubes built together in a single shell in which the coolant is
flowing.. The energy exchange with the surrounding is obtained by circulating or perhaps
boiling, or a fluid in the space between the tubes. The most important problem in the design
of such multi tube reactor is to answer the questions such as that how large the tube diameter
should be? How many tubes are necessary? These questions are required to be answered for
achieving a given production.
If the reaction temperature exceeds Tmax before the desirable conversion, then the following
methods may be applied to extend the conversion to the desired level.
A) Using indirect heat exchanger

In this method, as illustrated in the figure 4.6, the beds are sub-divided into two or more so
that each bed does not exceed Tmax. Here the product in the first bed gets cooled by using
heat exchanger to bring the inlet temperature under control and then passed on to the second
bed. In this way it can be continued until it reaches the desired conversion. There is a critical
temperature, known as initiation temperature, where the reaction rate becomes so low that it
does not effectively start reacting before entering to the next reaction vessel. For such

reasons, the reactant temperature is raised to the desired temperature, by letting hot gas from
the product mixture of each bed. The initiation temperature can be determined from the
kinetics of the reaction, and the feed temperature must always be kept above to this.
Figure 4.6 Multi tube Fixed bed reactor
Figure 4.7 Cooling to the desired, temperature by using indirect heat exchanger in fixed bed
reactors
B) Direct cooling or quenching between two or more beds
This is used mostly in the case of high exothermic reaction, i.e., for too high temperatures and
it is not useful through the usage of indirect heat exchangers. Here one of the reactants is
injected in cold stage into the reaction stream between consecutive beds. Figure 4.8 shows
such methods.

Figure 4.8 Indirect interstages cooling of an exothermic reaction in an adiabatic reactor.
Figure 4.9 Direct cooling between beds in fixed bed reactor.
C) Stepwise Quenching
This is similar to the previous method, but the difference is that instead of sub-dividing the
beds, it will be carried out in the beds placed differently and by using perforated tubes.
Disadvantage of this method over the previous one is that it is somewhat sloppy and it is
difficult to design for. Figure 4.10 depicts such a method.

Figure 4.10 Stepwise quenching of the fixed bed reactor.
D) Adding an inert gas or an excess of one of the reactants to the reactor feed.
The addition of inert gas or excess reactant is used as heat sunk by adsorbing high exothermic
heat. The reduced temperature in the reaction plays advantageous role in increasing the
conversion. Such method has disadvantages over the other methods because of its
requirement of a larger size of the reactor to accommodate both the reaction mixture and the
inert or excess reactant.
4.4 Temperature effect in an auto thermal reactor

It is understood that when exothermic reactions are conducted, there is enormous heat
liberated to the surroundings. This heat might be used for preheating the reactant or for other
industrial uses. Usually the inlet temperature of the reactant is low when we compare with the
reaction temperature. Most of the time to bring the inlet reactant to the required reaction
temperature one must heat before inletting to the reactor with hot product stream from the
reactor. This phenomenon is used in the auto thermal reactor. A reactor system, in which the
reacting mixture is used to pre heat the feed (reactant) is called auto thermal reactor. Based
on the range of reacting temperature auto thermal reactors are working into two ways.
i) Reactor with external heat exchanger tube between the product and the feed.
Here two separate units are installed namely the heat exchanger and the reactor. The feed is
sent to get energy by counter current heat exchanger. The heated feeds are then sent to the
reactor to take reaction. It is to be noted here that the feed will not be preheated if no

conversion takes place. Figure 4.11 illustrates schematic diagram of such a system together
with the path of temperature
Figure 4.11 External heat exchanger tube between the product and the feed.
ii) Reactor with internal heat exchanger tube between the product and the feed
The auto thermal behavior of a fixed bed adiabatic reactor in which the reacting mixture
preheats the feed can take place in a single tube or multi-tube reactor. Here the heat
exchanger is an integral part of the reactor. Figures 4.12 show the schematic diagram of
internal heat exchanger for a single and multi-tube reactors together with temperature
distribution.

Figure 4.12 A single tube adiabatic reactor with heat exchanger between the reaction product
and the feed
4.4.1 Design of an auto thermal adiabatic tubular reactor with external

heat exchanger tube between the product and the feed
The main task here is to know the relationship between the temperature rise in the heat
exchanger and the inlet temperature of the reactor. We have to consider separately the heat
exchanger and the reactor part.
The left side of the above equation is simply the temperature rise in the heat exchanger, T FR -
TF H This temperature rise of the feed stream is the heat taken up in the heat exchanger and is
equal to the right side of the equation. This also can be translated as the temperature rise in
the reactor multiplied by the factor KA/ FTCP . In practice this factor is often greater than 1.
The right side of equation simply implies the heat production by conversion. Both terms can
be plotted separately as a function of the reactor inlet temperature T FR, which in this case is

the main variable. Figure 4.13 shows the schematic diagram, where the points of intersection
between the two equations represent possible points of operation of the system.
Figure 4.13 Heat removal and heat production against inlet temperature of the reactor.
Heat production curve is influenced by the quantity of space time or residential time.
Assuming the volume of a reactor for a single operation is fixed, the space time is inversely
proportional to the flow rate. The heat production curves reach a horizontal level at high
temperatures, where the conversion is complete. This level depends on the residence time in
the reactor.

CHAPTER FIVE
STEADY - STATE MIXED FLOW REACTORS

5.1 Single continuous stirred tank reactor design
This type of reactors consists of a vessel into which there is a continuous flow of reactants
and from which the products are derived. The contents of the vessel reactor are assumed to be
"perfectly mixed" so that the conditions in terms of composition and temperature throughout
the reactor remains the same and are equal to the condition at the outlet. Figure 5.1
demonstrates schematically such type of reactors. Such type of reactor has variety of names,
but for the sake of clarity and reference, we shall use the name, continuous stirred tank
reactor and abbreviated as CSTR.
Figure 5.1 Continuous operated ideal tank reactor
Figure 5.2 further depicts schematic diagram of concentration versus volume of a reactor.
From the figure, it is observed that the concentration of the reactant, while entering the
reactor is aggressively mixed so that it reaches the outlet for getting the optimum output from
the concentration.
In this system, since the reactant in the reactor are all at the exit concentration level, the
converted reactant conversion are very low and hence very low reaction rate takes place and
at the same time low conversion results. To have higher conversion, one needs a larger
volume of reactor and this is one of the disadvantages of such reactor

Figure 5.2 Concentrations versus volume of a reactor in CSTR
5.1.1 Material balance of Continuous Stirred Tank Reactor

As always, the reactor design is to find the size of the reactor for the specified conversion and
for that purpose, this is done by taking the material balance
In CSTR, the system reaches a steady - state, when the composition do not vary with time,
i.e., dt/dnj = 0. Hence taking rate of reaction out of the integrate
For disappearance of reactant A, it becomes

Recalling for flow reactors, conversion XA can be given as,
The design equation for the size of a reactor for a specified conversion as
The design equation can be further modified for intermediate conversion,
Table 5.1 Design equations of reactors
Equation of CSTR graphical representation

Figure 5.3 Graphical representation of design equation for CSTR
It is to be noted that the volume of PFR is much lesser than the volume of CSTR for the same
conversion. To find the size of a reactor for a variable flow system, we can use the
relationships for the total conversion as,
And the total concentration at any point in the reactor is equal to

Taking first - order reaction
As we have mentioned that in the designing of a reactor, the most important consideration is
to find the size of a reactor for a specified conversion. In order to find the size of a reactor for
higher order of reaction, sometimes, there is a need also to find the conversion.
Let us consider for the first - order reaction.
For the second order reaction

Here we can observe that while calculating conversion, it poses a problem to find whether the
reaction is third-order or above or fraction, unless we do not use numerical or graphical
method for solving the problem. Therefore, to obtain conversion, it can easily be computed
by using graphical method.
Let us take n - order of reaction
The rate of reaction such operation
The design equation of CSTR is
For isothermal condition, let
Then, the above equation can be written
5.1.2 Energy balance of continuous stirred tank reactor (CSTR)

Here, we consider the application of the energy balance equation of. The continuous flow
reactor in discussion, is considered to be the Open System as shown in the Figure 5.4

Where Qr - rate of heat removal by the outflow of the products
Qg – Rate of heat production by reaction
Qt – rate of heat removal heat transfer
To – Feeding temperature
Ts – cooling or heating temperature (surrounding temperature)
K – Overall heat transfer coefficient
A – Heat transfer area
Figure 5.4 Sketches of the function of a CSTR
Though we have said that in the CSTR, the contents are well mixed and the temperature is
uniform throughout the reactor, it does not mean that the reaction temperature is constant
throughout the process.

5.1.2.1 Isothermal CSTR

Isothermal operation occurs when the feed temperature is identical to the temperature of the
mixture inside the CSTR. This can be maintained either by applying or removing heat to or
from the reactor by external heat exchanger. This can be effected by the application of a
heating or cooling jacket (Fig 5.5a), or by a coil placed inside the reactor (Fig.5. 5b). This are
depicts in Figure 5.5 a /b.
In the case of isothermal, i.e., when the temperatures of the reacting mixture entering and
leaving the reactor are equal, T0 = T1, the energy balance reduces to
Figure 5.5 Addition or removal of heat in a CSTR, a) heating or cooling jacket; b) a coil
placed inside the reactor
5.1.2.2 Non isothermal CSTR

A CSTR is operated non isothermally i.e., the heat generated (or absorbed) due to reaction is
only partially removed (or added) with the consequence that the feed stream absorbs (or
yields) the untransferred heat, thus raising (or lowering) the reactant-stream temperature. By
assuming the specific heat of the reaction does not depend on the temperature and the
composition, and that the heat of reaction is independent of temperature, the energy balance
can be written as

The reaction temperature T is obtained graphically by combining heat production and heat
removal as a function of temperature into one graph.
The heat production curve shows different characteristics based on the batch and flow
process. In the case of batch exothermic reaction, the temperature will rise as the reaction
proceeds, and the production of heat increases. When the reactant is depleted, then the
reaction slows down and the heat of production ceases. Figure 5.6a shows such a phenomena.
On the other hand, the heat production curve for continuous process like CSTR have the
sigmoid shape as indicated in the Figure 5.6b. The shape is different due to the opposing
effects of increased rate constant and diminished concentration of reactants. During the
reaction, the temperature rises and causes to attain high value of the rate constant and as a
result the curve must flatten off. The rate of heat removal as well as heat transfer is virtually
linear function of temperature as shown in the Figure 5.6c.
Figure 5.6a Heat production rate as a function of temperature in batch process

The reaction temperature in a steady state must have a value which satisfies the equation.
This can be obtained, for example, by combining the two curves Qg and QR / Qt into one
graph. At an intersection of a heat production curve and a heat removal line, indicating that
the steady operation would be possible at the corresponding temperature Figure 5.11
demonstrates such a phenomena. From the Figure 5.11, one can see the possibilities of
several solutions and is therefore known as the multiplicity of steady states.
Figure 5.6b Heat production rate as a function of temperature in continuous process (CSTR)
Figure 5.6c Heat removal / Heat transfer function in a CSTR

Figure 5.7 Heat production / Heat removal versus temperature in a CSTR The steady state is
to occur in the CSTR, the energy balance will have an equation
This conditional equation guarantees the fulfillment of the steady state. If this equality does
not hold in exactness, the reactor is not at steady - state and the reaction temperature will
change with time. Thus the steady states at different locations are represented by points of
intersection of the heat production curve with the heat removal line, plotted as a function of
the reactor temperature. The positions of such points are, therefore, dependent on the values
of the variables which appear on both Qg and QR or Qt.
5.1.2.2 Adiabatic CSTR

As always our target is to find the size of a reactor and since the reactor is operating
adiabatically, the reaction temperature changes with conversion, where we must relate
conversion from the energy and material balance. Conversion from energy balance expressed
under equation (5.20.1) for adiabatic conditions is reduced to,
Substitution for concentration gives
Or for complete conversion, it becomes

Substituting we get the relation between conversion and temperature as given by energy
balance.
5.2 Multiple - Reactor Systems

In minimizing the negative factors of a single system reactor, sometimes it may be desirable
to use a series of reactor, with the exit stream from the first serving as the feed to the second,
and so on. Reactors may be connected in one type of reactors or of different types. Some of
the advantages of multiple reactor system are to enhance the conversion, yield and to control
the heat effect in the reaction.
Generally, we can have two types of reactors connected in …
Plug flow reactors connected in series and or in parallel. …

Continuous stirred tank reactor (CSTR) connected in series.
5.2.1 Design of plug Flow Reactors (PFR) in series

Multiple plug Flow Reactors are used for such cases as to boost the selectivity of multiple
reactions, high pressure reactions, and for high heat of reactions etc. Our aim is to find the
appropriate size of the reactor for specified conversions, for which we consider N plug flow
reactors connected in series as shown in the Figure 5.8.
Figure 5.8 Plug flow reactors connected in series
Let be the conversion of components A leaving the reactor

Based on the material balance of the feed rate of A to the first reactor using PFR design
equation, we find for the nth order of multiple plug flow reactors, which are objectively used
to boost the selectivity of multiple reactions, high pressure reactions, for high heat of
reactions etc.
Or for the N reactors in series, we obtain the equation
Thus N plug flow reactors connected in series with total volume VT gives the same
conversion as a single plug flow reactor of volume V.
5.2.2 Plug flow reactors connected in parallel or parallel / series

Such connection could be efficient, if the time in each reactor is the same, i.e.,
To achieve this condition, we can treat the whole system as a single plug flow reactor of
volume equal to the total volume of the individual units if the feed is distributed in such a
manner that the fluid streams which meet in the connection having the same composition.
5.2.3 Continuous stirred tank reactors (CSTR) in series

One of the disadvantages of a single continuous stirred tank reactor is that the reactant in the
reactor is all at the exit concentration level, i.e., very low concentration. Cognizant to this low
reaction rate, results low conversion, large holding time and large reactor volume. To produce
a higher conversion in a smaller reactor volume a number of CSTR should be installed.
A series (cascade) reactor enables a fraction of the reaction to proceed in each reactor, so that
each reactor handles a fraction of conversion as well as heat liberated/absorbed. Series
reactors are normally arranged to flow automatically under gravity by having the reactors
installed at progressively lower levels as shown in the Figure 5.9.

Figure 5.9 Gravity flow through a series of CSTRs.
To design a cascade reactor, we have to get answers of the following questions:
 How many reactors should be in the series?

 What would be the volume of each?
 Do the reactants should be fed to the first only or distributed over more than one
reactor?
The answers for the above questions are based on the conditions such as concentration,
temperature and required conversion. Generally, if the conditions are not so forced, it is
preferred to have a minimum number of reactors and in equal size reactors arrangement. Here
it is worth to notice that, there may be situations when different size reactors may be
employed, which could be useful, particularly if the heat dissipation is a problem. Changing
the size of the first reactor would change the heat generation in it and this might be used to
overcome heat transfer problems in the initial stages. The heat generation could then be
increased in the later reactors where heat removal is lesser of the problem.
5.2.3.1 Design of equal size CSTRs in series

Tank reactors are usually employed for liquid reaction and in most cases, it is assumed that
the density of the reaction is constant. Consider a system of N tank reactors connected in
series as shown in the Figure 5.10. Even though in each mixed reactor, the concentration is
uniform, there is nevertheless a change in concentration as fluid moves from reactor to
reactor.

Figure 5.10 change of concentration/conversion in each reactors.
Using the CSTR design equation we can write for each reactor
Assuming the first - order reaction for the condition that T, ρm = constant equation becomes
Separating the equation for each reactor, we get

Taking the basis, volumetric flow rate and eventually the space time, residence time and the
temperature are being the constants
In such type of cascade reactor, concentration, reaction rate and conversion are changed in
every reactor in the form of discrete as shown in the Figure 5.11.

Figure 5.11 Concentration and conversion as a function of volume of the reaction in cascade
reactor
Recalling the space time
And we can use this equation for n, numbers of reactors, we have
Therefore the total space time for the cascade may be written
As the numbers of reactors approach infinite, then
And then the space time will be

Figure 5.12 conversion as a function of number of reactors in Cascade for VR = Constant.
General conclusion would be,
i) When VR cascade = Constant and , then
i.e. conversion in cascade reactor is going to be equal to conversion in PFR
ii) when XA = constant and then
5.2.3.2 Design of different size CSTR in series

Due to the nature of the reactants, which involves the mixing behavior, heat effect,
conversion ability etc., there is a need to set up a reactor of different size. In designing of a
different size CSTR, there is also a need to evaluate the following considerations:
(i) To find the outlet concentration/conversion from a given reactor system

(ii) (ii) To find the best set up to achieve a given conversion
A) The required conversion in a given system
The best method to find the outlet composition in various sizes of a reactor, is graphical
method using (-rA) versus CA curve. consider the following CSTR's in series as shown in the
Figure 5.13.

Figure 5.13 Different size of CSTR's in series.
For the negligible density change, we assume FV0 = FV. Taking material balance design
equation and noting that ε = 0, we may write for the first reactor as,
By plotting (-rA) versus CA, we can find for each reactor, different slope of 1/ θFn. Let us draw
a curve (-rA) versus CA for component A. Knowing CA0 we draw a line of slope i.e

Figure 5.14 Graphical methods to find out the concentration of different size of reactors.
Our target always is to have a total minimum size of the reactors connected in series for a
specified conversion. Graphical method is used to depict this phenomena. Consider two set
up models of reactors having small and big size of reactors. The question arises for the
specified outcome conversion that whether there is a size advantage, simply by having two
alternative setups as shown in the Figure 5.15

Figure 5.15 Graphical method to find minimum total size of reactors for different models
arrangement.
5.2.4 Design of different types of reactors in series

Each reactor has advantage and disadvantage for certain process. Combining reactors might
bring size reduction, increasing yield, achieving high conversion, and sink the heat effect etc.
Considering the design equations of plug flow and perfectly mixed reactor and the
geometrical nature of the reactors, one can observe the size of reactor in plug flow is much
smaller than CSTR. This is shown in the Figure 5.16.
Figure 5.16 Size /volume comparison of PFR and CSTR

Figure 5.17 Graphical representations for reactors in series.

5.3 Design of Recycle Reactor

Sometimes, one may be forced to use recycle ratio, when the reaction is autocatalytic, or
when it is necessary to use excess reactants and the recirculation is of unconverted reactants
nature, or to promote certain selectivity, or to use it in biochemical operations. In designing
such type of reactors, we may follow the same procedures as we have done so far and then
small modifications may be carried out to suit the purpose. Figure 5.18 demonstrates such
type of reactors.
Figure 5.18 Typical recycle reactor
The general material balance equation for plug flow across the reaction gives,
Now, we have to define some of the parameters, which are difficult to quantify, namely FA1
and VA1, and change by measurable quantities. The recycled stream is drawn off at point C
and merged with the fresh feed at point B. The recycle ratio can be defined as
For special case, where, the volumetric flow is constant and no conversion takes place in the
recycle stream

To safeguard the operation, the concentration of A in the recycle would be that of the fresh
feed, thus
Two types of conversions are existing in the recycle reactors namely, the overall conversion
and the conversion per pass. The conversion per pass at the stream intersection B can be
defined indirectly by using the definition of concentration, and hence
Rearranging gives
Again to balance on the stream intersection B, we have
The total molar flow rate and volumetric flow rate to the overall conversion can be defined as

The intermediate conversion in terms of measurable quantities
For constant density operation, we may also modify the above equation in terms of
concentration as
From this Figure 5.18, one can examine the operating conditions for high or low recycle rate.
Equation (5.19) shows a plug flow reactor performance approaches for low recycle and
contrary to that for total recycling of a mixed reactor. These phenomena can be demonstrated
mathematically for a recycle reactor as shown in the Figure 5.19.

Figure 5.19 Graphical representation of design equation for recycle reactor
MULTIPLE CHOICES
1. With increase in temperature, the equilibrium conversion of a reversible exothermic

reaction
(A) Decreases (C) Remain unaffected
(B) Increases (D) Decreases linearly with temperature
2. Which of the following is true for fluidized catalytic beds?
A) There is no pressure drop
B) They come under the category of batch reactors
C) The bulk density is a function of the flow rate through the bed
D) They cannot be used for multi-phase chemical reactions
3. Which of the following is the most suitable reactor for the pharmaceutical industry?
A) PBR C) PFR
B) MFR D) Batch reactor
4. Which of the following is NOT a part of reactor design?

A) Flow rates of the reactant and product streams
B) Method of operation
C) Type of the reactor
D) Size of the reactor
5. Which of the following is true for the rate law of a reversible reaction?
A) Rate law can be written only in terms of concentrations
B) It reduces to irreversible form when product concentration is zero
C) It satisfies thermodynamic relationships at all times
D) Rate law can be written only in terms of partial pressures
6. Which of the following does the concept of material balance based upon?
A) Conservation of mass
B) Conservation of energy
C) Conservation of momentum
D) Conservation of volume
7. The equation of material balance (final condition + sum of output) is equal to which of the
following?
A) Initial condition – sum of inputs
B) Initial condition – sum of inputs
C) Sum of inputs – initial condition
D) None of mentioned
8. A reaction is , if 2 moles of A and 4 moles of B entered the system, what is

the number of moles of C formed
A) 2 C) 6

B) 4 D) 8
9. The design equation for Batch reactor in differential form is _______
A)
B)
C)
D)
10. The design equation for Batch reactor in integral form is _____
∫
a)
∫
b)
∫
c)
∫
d)
11. Constant volume batch reactors are the widely used industrial batch reactors.
a) True
b) False
12. Determine the rate law for first order reaction at constant pressure with 60% A
in the initial reaction mixture and reduces by 15% in 4 minutes.
A) C)
B) D)
13. Increase in temperature for an endothermic reaction ____
A) Decreases equilibrium conversion

B) Increases equilibrium conversion
C) Does not affect equilibrium conversion
D) Initially decreases and then increases equilibrium conversion
14. The point of intersection of energy balance and material balance curves for exothermic
irreversible reactions, wherein instability is witnessed is stated as ____
A) Pour point C) Flash point
b) Boiling point D) Ignition point
15. For a gaseous reaction carried out in 25 litre PFR with 5molA/lit and space time 3 mins.
Calculate the conversion attained if reaction kinetics is given as follows
( )
A) 0.45 C) 0.95
B) 0.65 D) 0.98
16. Find the conversion of a 25 litre PFR if a gaseous feed of pure A (2 mol/lit, 150 mol/min)
is decomposed, kinetics are as follows.
( )
A) 0.89 C) 0.45
B) 0.92 B) 0.68
17. For a constant volume system, the size of batch reactor is _______________ PFR.
A) Smaller than C) Same as
B) Larger than D) Cannot be compared
18. A liquid phase reaction occurring in adiabatic PFR has a heat of reaction -120000 J/molK.
Specific heat of the stream is 10000 J/molK. The temperature difference for complete
conversion to be achieved is ___

A) 560 K C) 12 K
B) 8.33 K D) 83.33K
19. The conversion achieved for the liquid phase reaction occurring in an adiabatic PFR with
a heat of reaction -100 kJ/molK, specific heat of the stream being 100 J/molK and the
temperature difference being 800K is ___
A) 0.65 C) 0.90
B) 0.75 D) 0.80
20. Which is a WRONG characteristic for batch reactor?
A) Suitable to be used to test a new reaction process
B) Products vary with different batches
C) Can be operated under steady state.
D) The volume can be changed during reaction.
21. What assumptions are made when modeling an ideal tubular reactor (PFR)?
A) Steady state and no radial variations
B) Plug flow and liquid systems
C) Gas flow and steady state
D) Adiabatic system
22. Which equation is used in arriving at the design equation for a batch reactor?
A)
B)
C)
D)
23. Which is correct in terms of reaction rate for A+ 2 B  3/2 C?

A) C)
B) D) ( )
24. Which is WRONG about reactor arrangement for a 2nd order reaction?
A) In order to achieve the same conversion, a single CSTR needs larger volume than two
CSTRs in series.
B) A PFR can be approximated by a large number of CSTRs in series.
C) PFRs in series is always identical with a single one with the same total volume
D) Two CSTRs in parallel performs worse than a single CSTR with identical total volume.
25. Under which condition, PFR may need bigger volume than CSTR?
A) First order liquid reaction
B) Zero order liquid reaction
C) Adiabatic condition for exothermic reaction
D) Endothermic reaction with catalysts
26. For a batch reaction, which of the following CANNOT derive equation ?
A) Second order liquid reaction
B) First order gas reaction
C) Isobaric gas reaction:
D) Rigid reactor for gas reaction
27. What assumption is compulsory when studying an IDEAL CSTR?
A) Steady state C) Perfect mixing
B) Adiabatic operation D) Constant volume
28. In an ideal PFR. at steady state conditions
A) The composition of reactants remains constant along a flow path

B) The conversion of the reactant varies from point to point along a flow path
C) There is no lateral mixing of fluid
D) There may be diffusion along the flow path
29. An exothermic reaction takes place in an adiabatic reactor. The product temperature
__________ reactor feed temperature.
A) Is always equal to
B) Is always greater than
C) Is always less than
D) May be greater or less than
30. A first order irreversible reaction, A → B is carried out separately in a constant volume as
well as in a variable volume reactor for a particular period. It signifies that __________ in the
two reactors.
A) Both conversion as well as concentration is same
B) Conversion in both will be the same but concentrations will be different
C) Both the conversion as well as concentrations will be different
D) None of these
31. Exothermic reactions are best carried out in
A) A CSTR C) A plug flow reactor followed by CSTR
B) CSTR in series D) CSTR followed by a plug flow reactor
32. For nearly isothermal operation involving large reaction time in a liquid-phase reaction,
the most suitable reactor is a __________ reactor.
A) Stirred tank C) Batch
B) Tubular flow D) Fixed bed
33. The combination of ideal reactors among the following is ____

A) Plug flow reactor and batch reactor
B) Batch reactor and mixed flow reactor
C) Plug flow reactor and mixed flow reactor
D) Batch reactor only
34. Which one of the following combinations gives the highest conversion for second order
reaction?
A) PFR followed by smaller CSTR followed by a bigger CSTR
B) PFR followed by bigger CSTR followed by a bigger CSTR
C) Smaller CSTR followed by PFR followed by a bigger CSTR
D) Bigger CSTR followed by a PFR followed by smaller CSTR
35. For a PFR, the area under the curve gives ____
A)
B)
C)
D)
35. Which of the following is NOT a part of reactor design?
A) Size of the reactor
B) Type of the reactor
C) Flow rates of the reactant and product streams
D) Method of operation
36. For a mixed flow reactor operating at steady state, the rate of reaction is given by
A) ( ) ( )
B) ( ) ( )

C) ( )
D) ( )
37. An existing MFR is to be replaced by the one 4 times larger than it. Find the new
conversion if a homogeneous liquid phase reaction with reaction kinetics as follows.
with 30% conversion.

A) 0.67
B) 0.45
C) 0.53
D) 0.92
38. How should the two MFR’s of unequal size be connected in series to maximize
production for a first order homogenous reaction?
A) Smaller MFR followed by larger MFR
B) Larger MFR followed by smaller MFR
C) Any arrangement
D) MFR’s should not be connected in series
39. How should a PFR and MFR be connected to maximize production from a first order
reaction?
A) MFR followed by PFR
B) PFR followed by MFR
C) Any arrangement
D) MFR and PFR should not be connected
40. Best arrangement of reactors for a reaction whose rate-concentration curve that rises
monotonically.
A) Plug, Large MFR, Small MFR

B) Plug, Small MFR, Large MFR
C) Large MFR, Small MFR, Plug
D) Small MFR, Plug, Large MFR
41. Four MFR’s are operated in series the total space time is 5 minutes. If it is replaced by a
single PFR, What will be the space time? First order reaction with rate constant 2 min -1,
concentration reduces from 50 to 10 mol/m3.
A) 0.805 C) 0562
B) 0.123 D) 0.439
42. Effect of flow type on reactor performance when the conversion is small.
A) No effect C) Very small
B) Cannot be determined D) Very large
43. Space time is defined as ____
A) Time required to process unit volume of feed
B) Time required for the reaction to occur
C) Time required to produce unit volume of product
D) Time to process the entire volume of feed entering

PART- THREE
INTRODUCTION TO BIO-CHEMICAL
ENGINEERING

CHAPTER 1
BIOTECHNOLOGY AND BIOCHEMICAL ENGINEERING
1.1. Introduction
Biochemical engineering is concerned with conducting biological processes on an industrial
scale. This area links biological sciences with chemical engineering. The role of biochemical
engineers has become more important in recent years due to the dramatic developments of
biotechnology.
1.2. Application of Biotechnology

Biotechnology can be broadly defined as Commercial techniques that use living organisms,
or substances from those organisms, to make or modify a product. In recent years, the term
biotechnology is being used to refer to novel techniques such as recombinant DNA and cell
fusion.
Recombinant DNA allows the direct manipulation of genetic material of individual cells,
which may be used to develop microorganisms that produce new products as well as useful
organisms. The laboratory technology for the genetic manipulation within living cells is also
known as genetic engineering. A major objective of this technique is to splice a foreign gene
for a desired product into circular forms of DNA (plasmids), and then to insert them into an
organism, so that the foreign gene can be expressed to produce the product from the
organism.
Cell fusion is a process to form a single hybrid cell with nuclei and cytoplasm from two
different types of cells in order to combine the desirable characteristics of the two.
The applications of this new biotechnology are numerous, as listed in Table 1.1. Previously
expensive and rare pharmaceuticals such as insulin for diabetics, human growth hormone to
treat children with dwarfism, interferon to fight infection, vaccines to prevent diseases etc…
1.3. Biological Processes

Industrial applications of biological processes are to use living cells or their components to
effect desired physical or chemical changes. Biological processes have advantages and
disadvantages over traditional chemical processes. The major advantages are as follows:
1. Mild reaction condition: The reaction conditions for bioprocesses are mild. The typical
condition is at room temperature, atmospheric pressure, and fairly neutral medium pH. As a

result, the operation is less hazardous, and the manufacturing facilities are less complex
compared to typical chemical processes.
Table 1. Application of biotechnology
2. Specificity: An enzyme catalyst is highly specific and catalyzes only one or a small
number of chemical reactions. A great variety of enzymes exist that can catalyze a very wide
range of reactions.
3. Effectiveness: The rate of an enzyme-catalyzed reaction is usually much faster than that of
the same reaction when directed by no biological catalysts. A small amount of enzyme is
required to produce the desired effect.
4. Renewable resources: The major raw material for bioprocesses is biomass which provides
both the carbon skeletons and the energy required for synthesis for organic chemical
manufacture.
Disadvantages of biological Processes

1. Complex product mixtures: In cases of cell cultivation (microbial, animal, or plant),
multiple enzyme reactions are occurring in sequence or in parallel, the final product mixture

contains cell mass, many metabolic by-products, and a remnant of the original nutrients. The
cell mass also contains various cell components.
2. Dilute aqueous environments: The components of commercial interests are only
produced in small amounts in an aqueous medium. Therefore, separation is very expensive.
Since products of bioprocesses are frequently heat sensitive, traditional separation techniques
cannot be employed. Therefore, novel separation techniques that have been developed for
analytical purposes, need to be scaled up.
3. Contamination: The fermenter system can be easily contaminated, since many

environmental bacteria and molds grow well in most media. The problem becomes more
difficult with the cultivation of plant or animal cells because their growth rates are much
slower than those of environmental bacteria or molds.
4. Variability: Cells tend to mutate due to the changing environment and may lose some
characteristics vital for the success of process. Enzymes are comparatively sensitive or
unstable molecules and require care in their use.
1.4. Definition of fermentation

Traditionally, fermentation was defined as the process for the production of alcohol or lactic
acid from glucose
Yeast
C6H12O6 2C2H5OH +2CO2
Enzy
C6H12O6 2CH3CHOHCOOH
A broader definition of fermentation is an enzymatically controlled transformation of an
organic compound.
1.5. Biochemical Engineering

The recombinant DNA or cell fusion technologies have been initiated and developed by pure
scientists, whose end results can be the development of a new breed of cells in minute
quantities that can produce a product. Successful commercialization of this process requires
the development of a large-scale process that is technologically viable and economically
efficient.
For example, in a laboratory scale of 100 mL, a small Erlenmeyer flask on a shaker can be an
excellent way to cultivate cells, but for a large-scale operation of 2,000 L, we cannot make

the vessel bigger and shake it. We need to design an effective bioreactor to cultivate the cells
in the most optimum conditions. Therefore, biochemical engineering is one of the major areas
in biotechnology important to its commercialization.
To illustrate the role of a biochemical engineer, let's look at a typical biological process
(bioprocess) involving microbial cells. Raw materials, usually biomass, are treated and mixed
with other ingredients that are required for cells to grow well. The liquid mixture, the
medium, is sterilized to eliminate all other living microorganisms and introduced to a large
cylindrical vessel, bioreactor or fermenter, typically equipped with agitators, baffles, air
spargers, and various sensing devices for the control of fermentation conditions. A pure strain
of microorganisms is introduced into the vessel. The number of cells will start to multiply
exponentially after a certain period of lag time and reach a maximum cell concentration as
the medium is depleted. The fermentation will be stopped and the contents will be pumped
out for the product recovery and purification. This process can be operated
either by batch or continuously.
Figure 1.1 Typical biological process

To carry out a bioprocess on a large scale, biochemical engineers need to work together
with biological scientists:
1. to obtain the best biological catalyst (microorganism, animal cell, plant cell, or
enzyme) for a desired process.
2. to create the best possible environment for the catalyst to perform by designing the
bioreactor and operating it in the most efficient way.
3. to separate the desired products from the reaction mixture in the most economical way.
The preceding tasks involve process design and development, which are familiar to
chemical engineers for the chemical processes. Similar techniques which have been
working successfully in
chemical processes can be employed with modifications. The basic questions which need
to be asked for the process development and design are as follows:
1. What change can be expected to occur?
To answer this question, one must have an understanding of the basic sciences for the
process involved. These are microbiology, biochemistry, molecular biology, genetics, and
so on. Biochemical
engineers need to study these areas to a certain extent.
2. How fast will the process take place?
If a certain process can produce a product, it is important to know how fast the process
can take place. Kinetics deals with rate of a reaction and how it is affected by various
chemical and physical conditions.
3. How can the system be operated and controlled for the maximum yield?
For the optimum operation and control, reliable on-line sensing devices need to be
developed. On-line optimization algorithms need to be developed and used to enhance the
operability of bioprocess and to ensure that these processes are operated at the most
economical points.
4. How can the products be separated with maximum purity and minimum costs?
For this step, the downstream processing (or bio separation), a biochemical engineer can
utilize various separation techniques developed in chemical processes such as distillation,
absorption,
extraction, adsorption, drying, filtration, precipitation, and leaching. In addition to these
standard separation techniques, the biochemical engineer needs to develop novel
techniques which are suitable to separate the biological materials.

CHAPTER 2
ENZYME KINETICS
2.1. Introduction
Enzymes are biological catalysts that are protein molecules in nature.They are produced by
living cells (animal, plant, and microorganism) and are absolutely essential as catalysts in
biochemical reactions.
A major function of enzymes in a living system is to catalyze the making and breaking of
chemical bonds. Therefore, like any other catalysts, they increase the rate of reaction without
themselves undergoing permanent chemical change.
The catalytic ability of enzymes is due to its particular protein structure. A specific chemical
reaction is catalyzed at a small portion of the surface of an enzyme, which is known as the
active site.
Enzyme reactions are different from chemical reactions, as follows:
 An enzyme catalyst is highly specific
 The rate of an enzyme-catalyzed reaction is usually much faster than that of the same
reaction when directed by non-biological catalysts.
 The reaction conditions (temperature, pressure, pH, and so on) for the enzyme reactions
are very mild.
 Enzymes are comparatively sensitive or unstable molecules and require care in their use.
2.2. Commercial Applications of Enzymes

large-scale chemical synthesis of enzymes is impractical if not impossible. Enzymes are
usually made by microorganisms grown in a pure culture or obtained directly from plants and
animals. The enzymes produced commercially can be classified into three major categories.
1. Industrial enzymes: such as amylases, proteases, glucose isomerase, lipase, catalases, and
penicillin acylases.
2. Analytical enzymes: such as glucose oxidase, galactose oxidase, alcohol dehydrogenase,
hexokinase, muramidase, and cholesterol oxidase.
3. Medical enzymes: such as asparaginase, proteases, lipases, and streptokinase.
2.3. Simple Enzyme Kinetics

Enzyme kinetics deals with the rate of enzyme reaction and how it is affected by various
chemical and physical conditions. Kinetic studies of enzymatic reactions provide information

about the basic mechanism of the enzyme reaction and other parameters that characterize the
properties of the enzyme The rate equations developed from the kinetic studies can be applied
in calculating reaction time, yields, and optimum economic condition, which are important
in the design of an effective bioreactor.
Assume that a substrate (S) is converted to a product (P) with the help of an enzyme (E) in a
reactor as
S Enzym P
(2.1)
If you measure the concentrations of substrate and product with respect to time, the product
concentration will increase and reach a maximum value, whereas the substrate concentration
will decrease as shown in Figure 2.1 The rate of reaction can be expressed in terms of either
the change of the substrate CS or the product concentrations CP as follows:
The rate of reaction can be expressed in terms of either the change of the Substrate C or the
s
product concentrations C as follows:
p
r ⁄ (2.2)
s
r ⁄ (2.3)
s

In order to understand the effectiveness and characteristics of an enzyme reaction, it is

important to know how the reaction rate is influenced by reaction conditions such as
substrate, product, and enzyme concentrations.
If we measure the initial reaction rate at different levels of substrate and enzyme
concentrations, we obtain a series of curves like the one shown in Figure 2.2. From these
curves we can conclude the following:
1.The reaction rate is proportional to the substrate concentration (that is, first-order reaction)
when the substrate concentration is in the low range.
2.The reaction rate does not depend on the substrate concentration when the substrate
concentration is high, since the reaction rate changes gradually from first order to zero order
as the substrate concentration is increased.
3. The maximum reaction rate r is proportional to the enzyme concentration within the
max
range of the enzyme tested.
Henri observed this behavior in 1902 (Bailey and Olli’s, p. 100, 1986) and proposed the rate
equation
r = (2.4)
s
Where r and Km are kinetic parameters which need to be experimentally determined. Eq.
max
(2.4) expresses the three preceding observations fairly well. The rate is proportional to Cs
(first order) for low values of Cs, but with higher values of Cs, the rate becomes constant
(zero order) and equal to rmax. Now let's see the kinetic mechanism which supports the above
equations.
Brown (1902) proposed that an enzyme forms a complex with its substrate. The complex then
breaks down to the products and regenerates the free enzyme. The mechanism of one
substrate-enzyme reaction can be expressed as
One of the original theories to account for the formation of the enzyme-substrate complex is
the ―lock and key‖ theory. The main concept of this hypothesis is that there is a

topographical, structural compatibility between an enzyme and a substrate which optimally

favors the recognition of the substrate as shown in Figure 2.3.
Figure 2.3. Lock and key theory for the enzyme-substrate complex.
The reaction rate equation can be derived from the preceding mechanism based on the
following assumptions:
1.The total enzyme concentration stays constant during the reaction, that is, C = C + C
E0 ES E
2. The amount of an enzyme is very small compared to the amount of substrate. Therefore,
the formation of the enzyme-substrate complex does not significantly deplete the substrate.
3. The product concentration is so low that product inhibition may be considered negligible.
In addition to the preceding assumptions, there are three different approaches to derive the
rate equation:
1. Michaelis-Menten approach
It is assumed that the product-releasing step, Eq. (2.6), is much slower than the reversible
reaction, Eq. (2.5), and the slow step determines the rate, while the other is at equilibrium.
Since eqn 2.5 is reversible reaction and assumed it is in equilibrium
By substituting Eq. (2.8) into Eq. (2.7), the rate of reaction can be expressed as a function of
C and C , of which C cannot be easily determined. If we assume that the total enzyme
s E E
contents are conserved, the free-enzyme concentration C can be related to the initial enzyme
E
concentration C
Eo
the initial enzyme concentration. By substituting Eq. (2.8) into Eq. (2.9) for C and
E
rearranging for C , we obtain
ES

Substitution of Eq. (2.10) into Eq. (2.7) results in the final rate equation
Eqn 2.11 which is known as Michaelis-Menten equation and is identical to the empirical
expression Eq. (2.4). K in Eq. (2.11) is known as the Michaelis constant. In the Michaelis-
M
Menten approach, K is equal to the dissociation constant K or the reciprocal of equilibrium
M 1
constant Keq as
2. Briggs-Haldane Approach
The change of the intermediate concentration with respect to time is assumed to be

negligible, that is, d(C )/dt= 0. This is also known as the pseudo steady-state (or quasi-
ES
steady-state) assumption in chemical kinetics and is often used in developing rate expressions
in homogeneous catalytic reactions.
Assume that the change of C with time, is negligible compared to that of C

ES 𝑆 ESP
or C .
P
Substitution of Eq. (2.16) into Eq. (2.15) confirms that the rate of product formation and that
of the substrate consumption are the same, that is,
Again, if we assume that the total enzyme contents are conserved,
Substituting Eq. (2.9) into Eq. (2.16) for C , and rearranging for C
E ES

Substitution of Eq. (2.17) into Eq. (2.14) results
Example 2.1
When glucose is converted to fructose by glucose isomerase, the slow product formation step
is also reversible as:
Derive the rate equation by employing
(a) the Michaelis-Menten and
(b) the Briggs-Haldane approach. Explain when the rate equation derived by the Briggs-
Haldane approach can be simplified to that derived by the Michaelis Menten approach.
2.4. Evaluation of Michaelis-Menten Parameters

In order to estimate the values of the kinetic parameters, we need to make a series of batch
runs with different levels of substrate concentration. Then the initial reaction rate can be
calculated as a function of initial substrate concentrations. The results can be plotted
graphically so that the validity of the kinetic model can be tested and the values of the kinetic
parameters can be estimated.
The most straightforward way is to plot r against C as shown in Figure 2.2. The asymptote
S
for r will be r and K is equal to CS when r = 0.5 r .

MAX M MAX

Therefore, the Michaelis-Menten equation is usually rearranged so that the results can be
plotted as a straight line.
An equation of the form of Eq. (2.32) was given by Langmuir. The Langmuir plot will result
in a straight line, and the slope will be equal to 1/ r . The intercept will be K /r , as
MAX M MAX
shown in Figure 2.5.
Similarly, the plot of 1/r versus 1/C will result in a straight line according to Eq. (2.33), and
S
the slope will be equal to K /r . The intercept will be 1/r , as shown in Figure 2.6. This
M MAX MAX
plot is known as Lineweaver – Burkplot.

The plot of r versus r/C will result in a straight line with a slope of -K and an intercept of
S M
r , as shown in Figure 2.7. This plot is known as the Eadie-Hofstee plot.
MAX
In conclusion, the values of the Michaelis-Menten kinetic parameters, r and K , can be

MAX M
estimated, as follows:
1. Make a series of batch runs with different levels of substrate concentration at a constant
initial enzyme concentration and measure the change of product or substrate concentration
with respect to time.
2. Estimate the initial rate of reaction from the C or C versus time curves for different initial
S P
substrate concentrations.
3. Estimate the kinetic parameters by plotting one of the three plots explained in this section
or a nonlinear regression technique. It is important to examine the data points so that you may

not include the points which deviate systematically from the kinetic model as illustrated in
the following problem.
Example
From a series of batch runs with a constant enzyme concentration, the following initial rate
data were obtained as a function of initial substrate concentration.
Evaluate the Michaelis-Menten kinetic parameters by employing the Langmuir plot, the
Lineweaver-Burk plot, the Eadie-Hofstee plot, and nonlinear regression technique. In
evaluating the kinetic parameters, do not include data points which deviate systematically
from the Michaelis Menten model and explain the reason for the deviation.
2.5. Enzyme Reactor with Simple Kinetics

A bioreactor is a device within which biochemical transformations are caused by the action of
enzymes or living cells.
1. Batch or Steady-State Plug-Flow Reactor
The simplest reactor configuration for any enzyme reaction is the batch mode. A batch
enzyme reactor is normally equipped with an agitator to mix the reactant, and the pH of the
reactant is maintained by employing either a buffer solution or a pH controller. An ideal batch
reactor is assumed to be well mixed so that the contents are uniform in composition at all
times. Assume that an enzyme reaction is initiated at t = 0 by adding enzyme and the reaction
mechanism can be represented by the Michaelis-Menten equation.

This equation shows how C is changing with respect to time. With known values of r
S MAX
and K , the change C of with time in a batch reactor can be predicted from this equation.
M S
In a plug-flow enzyme reactor (or tubular-flow enzyme reactor), the substrate enters one end
of a cylindrical tube which is packed with immobilized enzyme and the product stream leaves
at the other end. The long tube and lack of stirring device prevents complete mixing of the
fluid in the tube. Therefore, the properties of the flowing stream will vary in both longitudinal
and radial directions.
Eq. (2.37) can also be applied to an ideal steady-state plug-flow reactor, even though the
plug-flow reactor is operated in continuous mode. However, the time t in Eq. (2.37) should be
replaced with the residence time τ in the plug-flow reactor, as illustrated in Figure 2.10.
In a plug-flow enzyme reactor (or tubular-flow enzyme reactor), the substrate enters one end
of a cylindrical tube which is packed with immobilized enzyme and the product stream leaves
at the other end. The long tube and lack of stirring device prevents complete mixing of the

fluid in the tube. Therefore, the properties of the flowing stream will vary in both longitudinal
and radial directions.
Eq. (2.37) can also be applied to an ideal steady-state plug-flow reactor, even though the
plug-flow reactor is operated in continuous mode. However, the time t in Eq. (2.37) should be
replaced with the residence time τ in the plug-flow reactor, as illustrated in Figure 2.10.
The substrate balance of a CSTR (see Figure 2.11) can be set up, as follows:
Input - Output +Generation = Accumulation
For the steady-state CSTR, the substrate concentration of the reactor should be constant.
Therefore, dC S/dt is equal to zero. If the Michaelis Menten equation can be used for the rate
S
of substrat consumption (r ), Eq. (2.39) can be rearranged as:
S
Eq. (2.40) can be rearranged to give the linear relationship:
Michaelis-Menten kinetic parameters can also be estimated by running a series of steady-state

CSTR runs with various flow rates and plotting C versus (C τ)/(C - C ).
S S SO S

2.6. Inhibition of Enzyme Reactions and Other influences on Enzyme

Activity
A modulator (or effector) is a substance which can combine with enzymes to alter their
catalytic activities.
An inhibitor is a modulator which decreases enzyme activity. It can decrease the rate of
reaction either competitively, noncompetitively, or partially competitively.
1. Competitive Inhibition
A competitive inhibitor has a strong structural resemblance to the substrate, both the inhibitor
and substrate compute for the active site of an enzyme.
The formation of an enzyme-inhibitor complex reduces the amount of enzyme available for
interaction with the substrate and, as a result, the rate of reaction decreases. A competitive
inhibitor normally combines reversibly with enzyme.Therefore, the effect of the inhibitor can
be minimized by increasing the substrate concentration, unless the substrate concentration is
greater than the concentration at which the substrate itself inhibits the reaction.
2. Derivation of enzyme kinetics for competitive Inhibition
The mechanism of competitive inhibition can be expressed as follows:
If the slower reaction, the product formation step, determines the rate of reaction according to
the Michaelis-Menten assumption, the rate can be expressed as:

The enzyme balance gives
From the two equilibrium reactions
where K and K are dissociation constants which are the reciprocal of the equilibrium
S I
constants. Combining the preceding four equations to eliminate C , C , and C C yields
E ES EI
Therefore, since K is larger than K , the reaction rate decreases due to the presence of
MI S
inhibitor according to Eqn Eq. (2.48). It is interesting to note that the maximum reaction rate
is not affected by the presence of a competitive inhibitor. However, a larger amount of
substrate is required to reach the maximum rate.\
Noncompetitive Inhibition
In noncompetitive inhibition, the binding of the inhibitor reduces enzyme activity, but does
not affect the binding of substrate.
These inhibitors bind non covalently to sites other than the substrate binding site. Inhibitor
binding does not influence the availability of the binding site for substrate. Binding of the
substrate and the inhibitor are independent of each other and inhibition cannot be overcome
by increasing substrate concentration.

Derivation of enzyme kinetics for noncompetitive Inhibition

The mechanism of noncompetitive inhibition can be expressed as follows:
Since substrate and inhibitor do not compete for a same site for the formation of enzyme-
substrate or enzyme-inhibitor complex, we can assume that the dissociation constant for the
first equilibrium reaction is the same as that of the third equilibrium reaction, as
The rate equation can be derived by employing the Michaelis-Menten approach as follows:
Therefore, the maximum reaction rate will be decreased by the presence of a noncompetitive
inhibitor, while the Michaelis constant K will not be affected by the inhibitor.
S
Effect of pH
The rate of an enzyme reaction is strongly influenced by the pH. The optimum pH is different
for each enzyme. For example, pepsin from the stomach has an optimum pH between 2 and
3.3, while the optimum pH of amylase, from saliva, is 6.8.
Effect of Temperature

The rate of a chemical reaction depends on the temperature according to Arrhenius equation
as
The temperature dependence of many enzyme-catalyzed reactions can be described by the

Arrhenius equation. An increase in the temperature increases the rate of reaction, since the
atoms in the enzyme molecule have greater energies and a greater tendency to move.
However, the temperature is limited to the usual biological range. As the temperature rises,
denaturation processes progressively destroy the activity of enzyme molecules. This is due to
the unfolding of the protein chain after the breakage of weak (for example, hydrogen) bonds,
so that the overall reaction velocity drops. For many proteins, denaturation begins to occur at
45 to 50°C.
Effect of Shear
Enzymes had been believed to be susceptible to mechanical force, which disturbs the
elaborate shape of an enzyme molecule to such a degree that denaturation occurs.
The mechanical force that an enzyme solution normally encounters is fluid shear, generated
either by flowing fluid, the shaking of a vessel, or stirring with an agitator. The effect of shear
on the stability of an enzyme is important for the consideration of enzyme reactor design,
because the contents of the reactor need to be agitated or shook in order to minimize mass-
transfer resistance.

CHAPTER 3
ENZYME IMMOBILIZATION
3.1. Introduction
What is Enzyme Immobilization?
The term immobilized enzyme refers to enzymes physically localized in a certain defined
region of space with retention of their catalytic activities, which can be used repeatedly and
continuously.
What immobilized enzymes?

An immobilized enzyme is one whose movement in space has been restricted either
completely or to small limited region.
Why to Immobilize Enzymes?
Advantages
 Protect from degradation and deactivation.
 Reuse of enzymes for many reaction cycles.
 Ability to stop the reaction rapidly by removing the enzyme from the reaction
solution.
 Enhance stability of a product.
 Easy separation of the product from the enzyme.
 Product is not contaminated with the enzyme.
Disadvantages
 High cost for isolation and purification and recovery of active enzymes.
 It affects the stability of enzymes.
 Certain immobilization protocols offer serious problems with respect to the
diffusion of the substrate to have access to the enzyme.
 Only few Industries are using immobilized enzymes.
 The catalytic properties of some are reduced or completely lost due to
immobilization on support or carrier.
Ideal carrier matrix for immobilization
Carrier: The carrier or matrix allows the exchange of medium (containing substrate or
product) to which an enzyme molecule confines.
The characteristics of the matrix are paramount important in determining the performance of
the immobilized enzyme system.
Ideal carrier properties

 Inertness
 Physically strong and stable by resisting compression

 Cost effective
 Regenerable
 Reduction in product inhibition
3.2. Immobilization Techniques

Immobilization techniques can be classified by basically two methods, the chemical and the
physical method.
1. Physical Method
A. Adsorption
the simplest immobilization method Enzymes can be adsorbed physically on a surface-active
adsorbent by contacting an aqueous solution of enzyme with an adsorbent.
Advantages of adsorption
 The procedure of immobilization is simple.
 It is possible to separate and purify the enzymes while being immobilized.
 The enzymes are not usually deactivated by adsorption.
 The adsorption is a reversible process.
Disadvantages
 The bonding strength is weak.
 The state of immobilization is very sensitive to solution pH, ionic strength, and
temperature.
 The amount of enzymes loaded on a unit amount of support is usually low.
Substrates for adsorption are

 Charcoal (catalse)
 Aluminium hydroxide
 Titanium dioxide
 Silica

 Calcium Phospphate (α-amylase)

 Cellulose (Subtilisin)
 Cellophane (glutaraldehyde)
B. Entrapment:
Enzymes can be entrapped within cross-linked polymers by forming a highly cross-linked

network of polymer in the presence of an enzyme.
Advantage
 There is no chemical modification of the enzyme, therefore, the intrinsic
properties of an enzyme are not altered.
Disadvantage
 Enzyme deactivation during the gel formation.
 Enzyme leakage.
The most commonly employed cross-linked polymer is the polyacrylamide gel system.
C. Micro encapsulation:
Enzymes can be immobilized within semipermeable membrane microcapsules. Capsule is

made up of nitro cellulose or nylon Effectiveness depends upon the stability of enzymes.

Advantages
 Cheap and simple method
 Large quantity of enzymes can be immobilized by encapsulation
Disadvantage
 Pore size limitation
 Only small substrate molecule is able to cross the membrane
2. Chemical Method
A. Covalent bonding
 Involves the formation of covalent bonding between the enzyme and support
 Widely used method of enzyme immobilization
Chemical groups in enzyme that form covalent bonds with the support are: -
 Amino acid
 Hydroxyl groups
 carboxyl groups
 phenol rings
Advantages
 Strong linkage of enzyme to the support
 No leakage
 A variety of support with different functional groups available
Disadvantages
 Chemical modification of enzyme leading to conformation loss
 Enzyme inactivation by changes in the conformation when undergoes reactions at
active sites
B. cross linking
 Covalent bonding between various groups of enzymes via polyfunctional reagents

 No matrix or support are involved
 Commonly used polyfunctional reagents are Glutaraldehyde, diazonium salt
 It is cheap
 Widely used in commercial preparations
 Polyfunctional reagent can denature the enzyme
Application of immobilized enzymes

CHAPTER 4
INDUSTRIAL APPLICATIONS OF ENZYMES
4.1. Introduction
The applications of enzymes can be classified into three major categories:
 industrial enzymes
 analytical enzymes and
 medical enzymes
4.2. Carbohydrates
Carbohydrates are defined as polyhydroxy aldehyde or ketones or compound which give
them on hydrolysis. Carbohydrates constitute a major class of naturally occurring organic
compounds, including sugars, starches, and celluloses. Carbohydrates are classified into three
major groups:
 Monosaccharides
 diasaccharides and
 polysaccharides
Monosaccharides are the simplest carbohydrate units. disaccharides contain two or more of
these simple mono saccharide units, and polysaccharides contain hundreds or thousands of
them.
Monosaccharides
The basic carbohydrate molecules are simple sugars, or monosaccharides, which are
polyhydroxy aldehyde, polyhydroxy ketone, and their derivatives.
All simple monosaccharides have the general empirical formula, (CH2O)n, where n is the
whole number ranging 3 to 8.
All monosaccharides can be grouped into two general classes as:
1. aldoses: contain a functional aldehyde grouping (-CHO), or

2. ketoses: contain a functional ketone grouping (>CO)
As indicated in Table 4.1, sugars can be further subclassified according to the number of
carbons: trioses, tetroses, pentoses, and hexoses. The number of possible optical isomers for a
compound can be determined by the formula 2Ʌn where n stands for the number of
asymmetric carbons. In chemistry, isomers are molecules or polyatomic ions with identical
molecular formulae — that is, same number of atoms of each element — but distinct
arrangements of atoms in space.
Glyceraldehyde, the simplest carbohydrate, exists in two isomeric forms that are mirror
images of each other:
Glucose (or dextrose) is one of aldohexoses which has two isometric forms (Figure 4.1): D
and L. The D form predominates in the nature. Glucose is the most common and most
important hexose and is found in sweetest fruits and in blood sugar.

In solution, very few sugar molecules exist with free aldehyde or ketone functional groups.
Aldehydes and hydroxyls in a sugar molecule can react in a solution so that the H from the
OH at the fifth carbon joins the aldehyde and the O from the same OH bonds to the first
carbon.
Disaccharides
Two sugars can link to each other by losing water from OHs to form disaccharides. The
important disaccharides are sucrose, lactose, maltose, and cellobiose, which all have the same
molecular formulas, C12H22O11 Sucrose and lactose are the most abundant and most
important disaccharides of natural origin. Maltose and cellobiose are repeating units of
polymeric starch and cellulose, respectively. Disaccharides may hydrolyze to form two
monosaccharide molecules.
Sucrose

Also known as table sugar. Both anomeric carbons of glucose and fructose are tied together in
the glycosidic linkage; thus neither ring can open, and sucrose is not a reducing sugar.
Maltose
Maltose is repeating units of starch and can be obtained by the hydrolysis of starch using the
diastase enzyme. Further hydrolysis of maltose yields two molecules of glucose.
Cellobiose
Cellobiose is stereoisomer of maltose, is obtained by the partial hydrolysis of cellulose.
Maltose and cellobiose are both reducing sugars, since the right rings may open to react, as
reducing agents. A stereoisomer is a form of isomerism in which molecules have the same
molecular formula and sequence of bonded atoms but differ in the three-dimensional
orientations of their atoms in space.
Polysaccharides
Polysaccharides contain hundreds or thousands of carbohydrate units. Polysaccharides are not

reducing sugars, since the anomeric carbons are connected through glycosidic linkages. We

will consider three kinds of polysaccharides, all of which are polymers of glucose: starch,
glycogen, and cellulose.
Starch
Starch is a polymer consisting of D-glucose units. Starches (and other glucose polymers) are
usually insoluble in water because of the high molecular weight. There are two forms of
starch: amylose and amylopectin.
Amylose consists of long, unbranched chains of glucose (from 1000 to 2000 molecules)
connected by α (1→4) glycosidic linkages.
Amylopectin consists of long chains of glucose (up to 10Ʌ5 molecules) connected by

α(1→4) glycosidic linkages, with α(1→6) branches every 24 to 30 glucose units along the
chain.
Amylose consists of long, unbranched chains of glucose (from 1000 to 2000 molecules)
connected by α (1→4) glycosidic linkages.
Glycogen
Glycogen also known as animal starch, is structurally similar to amylopectin, containing both
α(1→4) glycosidic linkages and α(1→6) branch points. Glycogen is even more highly
branched, with branches occurring every 8 to 12 glucose units.

Glycogen is abundant in the liver and muscles; on hydrolysis it forms D-glucose, which
maintains normal blood sugar level and provides energy.
Cellulose
Cellulose is a polymer consisting of long, unbranched chains of D-glucose connected by α
(1→4) glycosidic linkages; it may contain from 300 to 3000 glucose units in one molecule.
Cellulose is the most important structural polysaccharide, and is the single most abundant
organic compound on earth. It is the material in plant cell walls that provides strength and
rigidity; wood is 50% cellulose. Cellulose is important industrially, from its presence in
wood, paper, cotton, cellophane, rayon, linen, nitrocellulose (guncotton), photographic films
(cellulose acetate), etc.

CHAPTER FIVE
CELL KINETICS
5.1. Introduction
Understanding the growth kinetics of microbial, animal, or plant cells is important for the
design and operation of fermentation systems employing them. Cell kinetics deals with the
rate of cell growth and how it is affected by various chemical and physical conditions. Unlike
enzyme kinetics, cell kinetics is the result of numerous complicated networks of biochemical
and chemical reactions and transport phenomena, which involves multiple phases and multi
component systems.
During the course of growth, the heterogeneous mixture of young and old cells is
continuously changing and adapting itself in the media environment which is also
continuously changing in physical and chemical conditions. As a result, accurate
mathematical modeling of growth kinetics is impossible to achieve. Because the model may
contain many parameters which are impossible to determine.
The simplest model is the unstructured, distributed model which is based on the following
two assumptions:
1)Cells can be represented by a single component, such as cell mass, cell number, or the
concentration of protein, DNA, or RNA. This is true for balanced growth, since a doubling of
cell mass for balanced growth is accompanied by a doubling of all other measurable
properties of the cell population.
2) The population of cellular mass is distributed uniformly throughout the culture. cell
suspension can be regarded as a homogeneous solution. heterogeneous nature of cells can be
ignored. cell concentration can be expressed as dry weight per unit volume.
Besides the assumptions for the cells,

 medium is formulated so that only one component may be limiting the reaction rate.
All other components are present at sufficiently high concentrations, so that minor
changes do not significantly affect the reaction rate.
 Fermenters are also controlled so that environmental parameters such as pH,
temperature, and dissolved oxygen concentration are maintained at a constant level.

Culture medium or growth medium is a liquid or gel designed to support the growth of
microorganisms.
growth medium, also called Culture Medium, or Nutrient Broth, solution freed of all
microorganisms by sterilization (usually in an autoclave, where it undergoes heating under
pressure for a specific time) and containing the substances required for the growth of
microorganisms such as bacteria, protozoans, algae etc…
Approach to modelling growth

Various models can be developed based on the assumptions concerning cell components and
population.
First, let us define the terminologies use for microbial growth.

If we mention the cell concentration without any specification, it can have many different
meanings. It can be the
 number of cells,
 wet or dry cell weight per unit volume
𝑪 𝑿 = Cell concentration, dry cell weight per unit volume
𝑪 𝑵 = Cell number density, number of cells per unit volume
𝝆 = Cell density, wet cell weight per unit volume of cell mass
Wet cell weight: -refers to the weight of cell including its contained water. The cells in a
sample can be separated from the broth and weighed while they are wet.
Dry cell weight: - refers weight of the cells after drying.

Accordingly, the growth rate can be defined in several different ways, such as:
𝒅𝑪𝑿/𝒅𝒕 = Change of dry cell concentration with time
𝒓x = Growth rate of cells on a dry weight basis
𝒅𝑪𝑵/𝒅𝒕 = Change of cell number density with time / Growth rate of cells on a number basis
𝜹 = Division rate of cells on a number basis, d log2 /
It appears that 𝒅𝑪𝑿/𝒅𝒕 and 𝒓𝑿 are always the same, but this is not true. The former is the
change of the cell concentration in a fermenter, which may include the effect of the input and
output flow rates, cell recycling, and other operating conditions of a fermenter. The latter is
the actual growth rate of the cells. The two quantities are the same only for batch operation.
The growth rate based on the number of cells and that based on cell weight are not
necessarily the same because the average size of the cells may vary considerably from one
phase to another. When the mass of an individual cell increases without division, the growth
rate based on cell weight increases, while that based on the number of cells stays the same.
However, during the exponential growth period, which is the phase that we are most
interested in from an engineer's point of view, the growth rate based on the cell number and
that based on cell weight can be assumed to be proportional to each other. Sometimes, the
growth rate can be confused with the division rate, which is defined as the rate of cell
division per unit time. If all of the cells in a vessel at time t = 0 ( = ) have divided once
after a certain period of time, the cell population will have increased to 𝑪𝑵 x 2.
If cells are divided n times after the time t, the total number of cells will be
and the average division rate is
and the division rate at time t is

Therefore, growth rate defined as the change of cell number with time (slope of CN vs t
curve), while division rate is the slope of log2 vs t curve. Note that the division rate is
constant during the exponential growth period, while the growth rate is not.
5.2 Growth Cycle for Batch Cultivation
Once you inoculate unicellular microorganism into a fresh sterilized medium and measure the
cell number density with respect to time, you may find six phase of growth.
A. Lag phase: A period of time when the change of cell number is zero.
B. Accelerated growth phase: The cell number start to increase and the division rate increases
to reach maximum.
C. Exponential growth phase: The cell number increases exponentially as the cell start to
decrease.
D. Decelerated growth phase: After the growth phase reach a maximum, it is followed by
the deceleration of both growth rate and division rate.
E. Stationary phase: The cell population will reach a maximum value and will not increase
any further.
F. Death phase: After nutrient available cells are depleted, cells will start to die and the
number of viable cells will decrease.

A. Lag Phase
 Change of cell number is zero or negligible.

 cells may grow in size (mass)
 length of a lag period depends on many factors such as
 type and age of microorganisms
 size of the inoculum (long lag period is occurs if MOs are inoculated from
a medium with low nutrient concentration to high concentration, or if a
small amount of cells are inoculated into a large volume)
 culture conditions
 size of medium (quantity)
B. Accelerated growth phase
Cell growth begins, division rate increases gradually and reaches a maximum value.
C.Exponential growth phase
 Cells have adjusted to their new environment and multiply rapidly

 Increase in cell mass and cell number with time exponentially
 Period of balanced growth, in which all the components of a cell grow at the same
rate.
growth = 2N or CN = 2NCN0
Where

CN0 = initial number of cells
CN = final number of cells
N = number of generations
Growth rate and specific growth rate
The rate of cell population increase at any particular time is proportional to the number
density (C ) of cell present at that time:
N
-1
Where the constant 𝝁 is known as specific growth rate [hr ].
 Specific growth rate is different from growth rate that
 growth rate is the change of the cell number density with time, while
specific growth rate is the change of the natural log of the cell number density with time
Comparing Eq. (5.4) and Eq. (5.6),
Therefore, the specific growth rate is equal to ln2 times of the division rate, 𝛿.
Cell number concentration at exponential growth

If is constant with time during the exponential growth period, Eq. (5.6) can be integrated
from time t1 to t as
To give
where No is the cell number concentration at t1, when the exponential growth starts. Eq.
(5.9) shows the increase of the number of cells exponentially with respect to time.
Doubling time
The time required to double the population, called the doubling time (td ), can be estimated
from Eq. (5.7) by setting CN = 𝟐CN o and solving for t0= 0:
The doubling time is inversely proportional to the specific growth rate and is equal to the
reciprocal of the division rate.
Factors Affecting the Specific Growth Rate

Substrate Concentration
One of the most widely employed expressions for the effect of substrate concentration on is
the Monod equation, which is an empirical expression based on the form of equation
normally associated with enzyme kinetics or gas adsorption:
Where
 Cs is concentration of limiting substrate in the medium

 Ks is system coefficient

Fig. Dependence of the specific growth rate on the concentration of the growth limiting
nutrient:
The value of 𝐾𝑆 is equal to the concentration of nutrient when the specific growth rate is half
of its maximum value ( ).
Product Concentration
As cells grow they produce metabolic by products which can accumulate in the medium. The
growth of microorganisms is usually inhibited by these products.
Other Conditions
The specific growth rate of microorganisms is also affected by
 medium pH,
 temperature, and
 oxygen supply.
 The optimum pH and temperature differ from one microorganism to another.
D. Death phase
If incubation continues after stationary phase, cells may remain alive and continue to
metabolize or they may die= death phase
Death occurs either because of
 depletion of the cellular reserves of energy/exhaustion of essential nutrient, or

 accumulation of toxic products.
In some cases, the organisms not only die but also disintegrate, called cell lysis Rate of cell
death generally slower than that of exponential growth.

CHAPTER 6
STERILIZATION
6.1. Introduction
Most industrial fermentations are carried out as pure cultures in which only selected strains
are allowed to grow.
If foreign microorganisms exist in the medium or any parts of the equipment, the production
organisms have to compete with the contaminants for the limited nutrients.
Therefore, before starting fermentation, the medium and all fermentation equipment have to
be free from any living organisms, in other words, they have to be completely sterilized.
6.2. Sterilization Methods

Sterilization of fermentation media or equipment can be accomplished by destroying all
living organisms by means of
 heat (moist or dry),

 chemical agents,
 radiation (ultraviolet or X-rays),
 and mechanical means (sonic or ultrasonic vibrations).
Another approach is to remove the living organisms by means of filtration or high-speed

centrifugation.
Sterilization by using Heat
Heat is the most widely used means of sterilization, which can be employed for both liquid
medium and heatable solid objects. It can be applied as
 dry or
 moist heat (steam).
The moist heat is more effective than the dry heat, because the intrinsic heat resistance of
vegetative bacterial cells is greatly increased in a completely dry state. As a result the death
rate is much lower for the dry cells than for moist ones. The heat conduction in dry air is also

less rapid than in steam. Therefore, dry heat is used only for the sterilization of glassware or
heatable solid materials.
Sterilization by using chemicals
Chemical agents can be used to kill microorganisms as the result of their oxidizing or
alkylating abilities. However, they cannot be used for the sterilization of medium because the
residual chemical can inhibit the fermentation organisms. Chemical agents are frequently
employed for disinfection that commonly implies the treatment to remove or reduce the risk
from pathogenic organisms.Some of the major antimicrobial chemical agents are
 phenol and phenolic compounds

 alcohol
 halogens
 detergents,
 dyes etc…
Sterilization by radiation
Many cellular materials absorb ultraviolet light, leading to DNA damage and consequently to
cell death. Wavelengths around 265 nm have the highest bactericidal efficiency.
However, ultraviolet rays have very little ability to penetrate matter. Therefore, their use is
limited to the reduction of microbial population in a room where sterility needs to be
maintained, such as hospital operating rooms or clean chambers in a laboratory.
X-rays are lethal to microorganisms and have penetration ability. However, they are
impractical as sterilization tools due to their expense and safety concerns.
Sterilization by sonic or ultra sonic vibration
Sonic or ultrasonic waves of sufficient intensity can disrupt and kill cells. This technique is
usually employed in the disruption of cells for the purpose of extracting intracellular
constituents rather than as a sterilization technique.
6.3. Thermal Death Kinetics

Steam (or moist heat) is used almost universally for the sterilization of fermentation media.

The destruction of micro-organisms by steam (moist heat) at specific temperature can be

described as a first-order chemical reaction provided if we considerer loss of viability not
destruction.
The thermal death kinetics may be represented by the following equation:
-dN/dt = kd N (6.1)
Where,
N, is the number of viable organisms present,
T, is the time of the sterilization treatment
kd, is the reaction rate constant of the reaction, or the specific death rate per time.
On integration of equation (i) from t=0’ to t=t, we have the following expression :
Nt/N0 =e-kdt (6.2)
where
No is the number of viable organisms present at the start of the sterilization treatment,
Nt is the number of viable organisms present after a treatment period, t.
On taking natural logarithms, equation (6.2) is reduced to:
ln(Nt/N0) = - kd t (6.3)
Equation 6.2 shows the exponential decay of the cell population. The temperature
dependence of the specific death rate kd can be assumed to follow the Arrhenius equation

QUESTIONS
1. A competitive inhibitor of an enzyme is usually

A. a highly reactive compound
B. a metal ion such as Hg2+ or Pb2+
C. structurally similar to the substrate.
D. water insoluble
2. The types of inhibition pattern based on Michaelis Menten equation are
A. competitive
B. non-competitive
C. uncompetitive
D. all of the above
3. The rate-determining step of Michaelis Menten kinetics is
A. the complex formation step
B. the complex dissociation step to produce product
C. the product formation step
D. Both (a)and(c)
4. Given an enzyme with a Km = 10m M and Vmax = 100 m mol/min. If [S] = 100 m
M, which of the following will be true?
A. A 10 fold increase in Vmax would increase velocity 10 fold y
B. A 10 fold decrease in Km would increase velocity
C. Both (a) and (b)
D. A 10 fold increase in Vmax would decrease velocity 20 fold
5. Which of the following statements is true for enzymatically catalyzed reaction?
A. The activation energy of the reaction is lowered so that a larger proportion of the
substrate qualifies to overcome it
B. Additional substrate molecules are energized to overcome the activation energy of
the reaction
C. The activation energy of the reaction is increased, thus decreasing the likelihood
that any substrate molecules will overcome it
D. The activation energy of the reaction is lowered so that a fewer substrate
molecules can overcome it
6. The enzyme inhibition can occur by

A. reversible inhibitors
B. irreversible inhibitors
C. Both (a) and (b)
D. None of these
7. Non-competitive inhibitor of an enzyme catalyzed reaction
A. decreases Vmax
B. binds to Michaelis complex (ES)
C. both (a) and (b)
D. can actually increase reaction velocity in rare cases
8. An enzyme and a reactant molecule maintain relationship as
A. a temporary association
B. an association stabilized by a covalent bond
C. one in which the enzyme is changed permanently
D. non complementary binding
9. The plot used for determining the value of Vmax is
A. Lineweaver Burk plot
B. Langmuir plot
C. Eadie Hofstee plot
D. all of these
10. A noncompetitive inhibitor of an enzyme-catalyzed reaction
A. increases KM and increases Vmax
B. increases KM and reduces Vmax
C. reduces KM and increases Vmax
D. reduces KM and reduces Vmax
11. The immobilized enzyme produced by micro encapsulation technique provides
A. an extremely large surface area
B. smaller surface area
C. high amount of solvent
D. relatively smaller surface area
12. Which of the following is considered as a disadvantage to the adsorption method of
immobilization?
A. It is possible to separate and purify the enzymes while being immobilized
B. The enzymes are not usually deactivated by adsorption

C. The adsorption is a reversible process

D. State of immobilization is very sensitive to solution pH, ionic strength and
temperature
13. During the enzymatic reaction of an immobilized enzyme, the rate of substrate
transfer is
A. equal to that of substrate consumption
B. more than that of substrate consumption
C. lesser than that of substrate consumption
D. is nothing to do with the substrate consumption
14. The immobilized technique involving chemical method is
A. covalent bond formation dependent
B. non-covalent bond formation dependent
C. both (a) and (b)
D. ionic bond formation dependent
15. For glucose isomerization by immobilized enzyme, the reactor generally used is
A. CSTR
B. plug flow
C. packed bed
D. fluidized bed
16. The most commonly employed cross-linked polymer is the
A. polyacrylamide gel
B. collagen
C. celluloses
D. cation exchange resin
17. Which of the following is not the correct answer?
A. Immobilized enzyme may show selectively altered chemical properties
B. Immobilized enzyme may show selectively altered physical properties
C. Immobilized enzyme may simulate the realistic natural environment where the
enzyme come from the cell
D. None of the above
18. Which of the following is not a physical method of immobilization?
A. Adsorption
B. Entrapment

C. Micro encapsulation
D. None of these
19. The intraparticle mass transfer resistance can affect the rate of enzyme reaction, if
enzymes are immobilized by
A. copolymerization or microencapsulation
B. crosslinking using multifunctional reagents
C. adsorption
D. all of the above
20. Which of the following mainly serve to convert starch into high fructose corn syrup
(HFCS)?
A. α-amylase
B. Gluco-isomerase
C. Gluco-amylase
D. all of these
21. which of the following is a form of starch which consists of long, unbranched chains
of glucose (from 1000 to 2000 molecules) connected by α (1→4) glycosidic linkages.
A. Amylopectin
B. Amylose
C. Glycogen
D. D-glucose
22. Stationary phase is described as
A. no further increase in the cell population after a maximum value
B. deceleration of growth and division rate after the growth rate reaches a maximum
C. acceleration of growth and division rate after the growth rate reaches a maximum
D. deceleration of growth and division rate after the growth rate reaches a minimum
23. In the accelerated phase, cell starts to
A. increase and the division rate increases to reach a maximum
B. decrease and the division rate increases to reach a maximum
C. increase and the division rate decreases to reach a maximum
D. None of the above
24. The monod model predicts that the specific growth rate
A. will increase with the concentration of the growth limiting substrate until it
reaches a maximum value

B. will decrease with the concentration of the growth limiting substrate

C. will increase with the concentration of the growth limiting substrate
D. does not depend on growth limiting substrate
25. In the death phase
A. nutrients available for the cells are depleted and begin to die
B. the number of viable cells will increase
C. nutrients available for cells are replenished and start to multiply
D. none of the above
26. The maximum specific growth rate of an organism depends on
A. medium composition
B. temperature
C. pH
D. All of these
27. Bacterial growth curve is obtained by plotting
A. number of cells versus time
B. number of spores versus time
C. log of number of cells versus time
D. log of number of cells survived versus time
28. Population doubling time, td can be expressed as (where μ is the specific growth rate.)
A. log2/μ
B. ln2/μ
C. μ/ln2
D. μ/log2
29. In the stationary phase
A. growth is proportional to death
B. growth rate is equal to death rate
C. growth rate is lesser than death rate
D. no co-relation exist between death rate and growth rate
30. The specific death rate of an organism can be expressed as
A. ln 2/D
B. D/ln2
C. D.ln2
D. 2.0.3/ln2

31. The del factor (Δ) increases as the final number of cells
A. decreases
B. increases
C. zero
D. constant
32. Sterilization can be carried out by
A. heat
B. radiation
C. chemical agents
D. all of these
33. The mechanical means of accomplishing sterilization of fermentation
media/equipment is
A. ultrasonic
B. radiation
C. chemical agents
D. none of these
34. The moist heat is more effective than the dry heat because the intrinsic heat resistance
of vegetative cells is greatly
A. increased in a dry state
B. decreased in a dry state
C. increased in a wet state
D. decreased in a wet state
35. The destruction of microorganisms by steam may be described as
A. first order chemical reaction
B. zero order chemical reaction
C. second order chemical reaction
D. none of these

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REACTION AND BIOCHEMICAL MODULE 2022

SCHOOL OF CHEMICAL AND BIO ENGINEERING

DIRE DAWA, ETHIOPIA

Rationale and objective of the module:- Different chemical and bio-processing

The module has the following objectives;

 introducing students with preliminary reaction kinetics

DDUIOT, SCBE, PEEC Page I

DDUIOT, SCBE, PEEC Page II

4.4. Method of Half-Lives .................................................................................................... 37

DDUIOT, SCBE, PEEC Page III

2.2 Ideal semi-batch reactor ................................................................................................. 77

DDUIOT, SCBE, PEEC Page IV

CHAPTER 1 .......................................................................................................................... 143

DDUIOT, SCBE, PEEC Page V

CHEMICAL REACTION ENGINEERING, I

DDUIOT, SCBE, PEEC Page VI

1. Introduction to homogeneous chemical reaction kinetics

The steps of conversion can be stated as:

1.2. Classification of Reactions

1. According to the number of phases involved in the reactions

DDUIOT, SCBE, PEEC Page 2

or expressed in mathematical form of equation,

1.2.1. Batch Reactor

DDUIOT, SCBE, PEEC Page 3

And for the disappearance of reactant A,

1.2.2. Continuous Flow Reactors

DDUIOT, SCBE, PEEC Page 4

A) Continuous Stirred Tank Reactor (CSTR)

Then the mole balance equation (1.6) becomes,

B) Plug Flow Reactor

Figure 1.2. Plug flow reactor

DDUIOT, SCBE, PEEC Page 5

1.3. Stoichiometric Relationship in Reaction

Where υ1 =2; υ2 = -1 ; υ3 = -3 is called the stoichiometric coefficient of Aj in the reaction.

DDUIOT, SCBE, PEEC Page 6

Considering the following reaction,

DDUIOT, SCBE, PEEC Page 7

1.3.1. Measurement of Concentration for the Batch Systems

DDUIOT, SCBE, PEEC Page 8

A) Mole as a function of Conversion

where Vf is the final volume.

DDUIOT, SCBE, PEEC Page 9

1.3.2. Measurement of Concentration for the Flow System

Figure 1.3. Flow system

A) Molar Flow Rate as a function of Conversion for a Flow System

B) Concentration as a function of conversion for a flow system

DDUIOT, SCBE, PEEC Page 10

1.4. Selectivity and Yield

DDUIOT, SCBE, PEEC Page 11

2.1. The Rate of Chemical Reaction

DDUIOT, SCBE, PEEC Page 12

DDUIOT, SCBE, PEEC Page 13

2.2. Rate Equation

DDUIOT, SCBE, PEEC Page 14

DDUIOT, SCBE, PEEC Page 15

DDUIOT, SCBE, PEEC Page 16

DDUIOT, SCBE, PEEC Page 17