Module-1

Introduction
• Chemical process – production of desired product economically from the given
the raw materials,
• Result of the unit operations and the unit processes which are performed at the
correct sequence starting from the raw materials to the formation of products.
• decides the economics of the overall process.
• Equipment in which the reactants are converted into useful product is referred to
as a reactor.
• Design of the reactor properly for given reactions and given process conditions is
the main aim and the design activity utilizes the information and knowledge of
thermodynamics, chemical kinetics , fluid flow, heat transfer, mass transfer
and the economics.
• two factors are to be considered for any reaction
1. whether the reaction is feasible or not and if feasible ,
2. what is the maximum possible extent of a reaction and the time required for a
given reaction for a specific extent of reaction.
• The first part is concerned with the thermodynamics and the second one is
dealt with the Kinetics.
• Thermodynamics provides us the information about the feasibililty of a reaction
i.e., whether the reaction will occur or not under the given set of the
conditions, heat absorbed or liberated during the course of the reaction i.e.,
heat of a reaction and the maximum possible extent of a reaction.

• Kinetics is a study of rates at which the reactions occur and the effect of
parameters such as the temperature, pressure and the reactant
concentration / composition on the reaction rates.
It provides the information about the reaction mechanism, speed of a reaction
and the type of the rate reaction which is used in the design of a reactor.
But is not concerned with the chemical nature of the changes taking place.
All the kinetic work is based on the LAW OF MASS ACTION proposed by Guldberg and Waage
in 1867.
rate of a reaction is proportional to the product of the activities of each reactant, each activity
being raised to the power to the number of molecules of that reactant taking part , as indicated by the
reaction equation
For the reaction aA +bB--------- products
Rate is proportional to ( activity of A)a X (activity of B) b

• For the practical purposes the term activity is replaced by concentration,

From this law of mass action the concept of order of reaction was developed.

• Reaction rate= -d[A]/dt= + d[P]/dt= k[A]

• [A]= concentration of reactant A at time t
• [P]= concentration of product A at time t
• -d[A]/dt= rate of decrease of [A]
• -d[P]/dt= rate of increase of [P]
Classification of the Chemical reaction:

1. Reactions are classified depending upon the number of phases involved as homogeneous and heterogeneous
reactions.

• A homogeneous reaction is one which takes place in only one phase, i.e., all the reacting materials , products
and catalyst (if any ) will all be present within a same phase (one phase).

Ex: Oxidation of nitrogen oxide to nitrogen dioxide with air, is a gas phase reaction
NO+ ½ O2--------NO2
• A heterogeneous reaction is one which involves the presence of more than one phase i.e., in heterogeneous
reactions at least one of the reactants, catalyst or products is present in phase different from the remaining
components of the reacting system.
Ex: Oxidation of sulphur to sulphur trioxide using vanadium pentaoxide catalyst is a heterogeneous reaction as
SO2 , O2 and SO3 are gaseous while V2O5 is a solid material.
V2O5
SO2 + ½ O2 -------- SO3
2. Reactions are classified based on their catalytic activities, i.e., catalytic & non-catalytic reactions.
Catalytic reactions are those reactions which does not involve the use of catalyst to enhance the rate of a
reaction /speed of a reaction.
Ni
Ex : C2H4 + H2 --------- C2H6
ethylene Heat ethane

Hydrogenation of ethylene is a catalytic reaction which makes use of nickel catalyst.

• Non catalytic reactions are those reactions which does not involve the use of catalyst.
Oxidation of NO to NO2 is a non- catalytic reaction.
NO + ½ O2 ----------- NO2
• 3. Reactions are also classified based on the molecularity of a reaction i.e., based upon the number of
molecules that take part in the reaction( in rate determining step) such as unimolecular, bimolecular &
termolecular reactions
4. Reactions may be classified based upon based upon the heat effect (based on as they give off or absorb heat
to from the surroundings) as exothermic and endothermic reactions.

Exothermic reaction is the one in which heat is evolved.

Ex: The reaction between CO & H2 to produce methanol is exothermic reaction.
Cu
CO +2H2---------------CHOH + heat

• Endothermic reaction is the one in which heat is absorbed (heat will be supplied to the reacting system from
the surroundings for reaction to take place)
Al2O3
Ex: C2H5OH -------------C2H4 + H2O – heat
5. Reactions are classified based on the order of the reaction as first order reaction, second order reaction , third
order reaction , etc.,
A reaction of which overall order of reaction is one ( i.e., sum of orders with respect to participants in
reaction is unity) is called first order reaction.
Ex: Decomposition of Nitrogen pentaoxide is a first order reaction
N2O5 ---------- NO2 + ½ O2
• A reaction of which the sum of orders with respect to reactants participated in reaction is two is called
second order reaction.

Ex: Saponification of ester is a second order reaction

CH3COOC2H5 + NaOH------- CH3COONa + C2H5OH
Ethyl acetate Sodium acetate

Ex: for third order reaction is

2 NO (g) + H2 (g) -------------- N2O (g) + H2O (g)
6. Reactions are also classified as reversible and irreversible reactions based upon whether they proceed in one
or both the directions.

Reversible reactions are those in which the forward and the reverse reactions take place simultaneously.
Ex: Esterification reaction is a reversible reaction
H+
C2H5OH + CH3COOH === CH3COOC2H5 + H2O
Ehanol acetic acid ethyl acetate

Irreversible reactions are those which can proceed only in one direction.
Ex: Nitration of benzene is a irreversible reaction.
H+
C6H6 + HNO3 ---------C6H5NO2 +H2O
Benzene Nitrobenzene
Rate of a Reaction:
• Rate of a reaction may vary from a large value to zero.
• For ionic reactions such as those occur on photographic film, or in high
temperature combustion reactions, the rate is extremely fast.

• ways of defining the rate of reaction

• based on the unit volume of a reacting fluid for a homogeneous system, based
on unit mass of solid in case of fluid –solid systems
• For homogeneous systems, the rate of reaction is defined as the change in the
moles of reactant or product due to reaction per unit time per unit volume of
reacting fluid/ reaction mixture.

• The rate of reaction may be expressed either as the rate of disappearance of a

certain reactant or rate formation of certain product
Consider the irreversible reaction
aA + bB------ rR
Here, the reactants A and B are disappearing due to the reaction i.e., reacting and product R is being produced.

The rate of the reaction with respect to reactant A i.e., rate of disappearance of reactant A is given by
-rA= -1/ V ( dNA/dt)
= ((amount in moles of A disappearing)/(volume of fluid) X (time)), mol/l.s
NA is the moles of component A.

• For a constant volume reaction systems, V is constant, so

-rA= - ( d(NA/V) /dt) substitute CA= NA/V,
then, -rA= - ( dCA/dt)

similarily w.r.t products, rate of a reaction is expressed as + r R= +( dCR/dt)

Factors affecting the rate of reaction:

1. nature of reactants & products.

2. concentration of reactants
3. temperature of a system
4. pressure of a system
5. nature of catalyst
6. surface area of reactants
7. rates of the heat and mass transfer.
• Rate of reaction for homogeneous systems as a function of temperature and composition.

-rA= f[ temperature dependent terms, concentration dependent terms],mol/ l. s

Ex: A----------- R
-rA= k. (CA )α

-rA= ko.e-(E/RT). (CA )α

where,
• ko.e-(E/RT) - temperature dependent term
• (CA )α - concentration dependent term
• E - activation energy
• α - order of the reaction with respect to A
 Rate constant:

• measure of the rate of reaction( i.e., numerical measure of how fast the reaction occur) when all the reactants are at
unit concentration.
Rate of reaction = k X (function of concentration of reactants)

If the concentration are equal to unity then the rate of reaction = k

‘k’ is called the rate constant (specific constant).
The k depends upon the units of concentration (mol/ l) and time (s).

-rA=k. (CA) n
Rate constant = Rate of reaction/ (concentration of the reactants) n

i.e., ((mol/l.s) / (mol/l) n) = (s) -1. (mol/l)(1-n)

• unit of k will be, (time) n-1. (Concentration)(1-n)
• Where, n is the order of the reaction.
• For first order reaction, n=1 unit of k is (s)-1
• For second order reaction, n=2, unit of k is l. (s)-1. (mol)-1
• Single stoichiometric equation and single rate expression represent the
progress of a single reaction.

• i.e., A----------- R
• When more than one stoichiometric equation & more than one kinetic
expression is needed to follow the progress of reaction i.e., to follow
the changing composition of all the reacting components result in
multiple reactions.
Concentration dependency of a rate equation:
For determining the concentration-dependent term of a rate
equation, temperature of the system is kept constant.
Consider an irreversible reaction: aA + bB +… ------- rR + sS+
…

For describing the rate of reaction, the basis of calculation will

always be the limiting reactant (ex : species A).
The rate of disappearance of A , -rA depends upon the temperature
and composition .
Rate of reaction w.r.t A (-rA ) =k f (CA, CB, …)
• From the kinetic study , the dependence of rate of reaction on the concentration
of the reactants for many reactions is

• -rA=k . (CA )(nA). (CB ) (nB)…

• nA, nB…are the powers of concentrations of reactants A,B,… on which the rate
of the reaction depends
• The algebraic equation that relates -rA to the concentrations of species
participating in a reaction is called the kinetic expression, rate law or rate
equation. It gives the relationship between reaction rate and concentration.
• rate equation is represented by equivalent measurable quantity to the concentration ex: partial pressure of the
reacting materials.
• In the case of gas phase reaction rate is given by -r A=k . (pA )(n1). (pB ) (n2)
• The order w.r.t reacting component remains same/unchanged though any measurable quantity equivalent to
concentration, but only the value & units of k differs.
•
•
Reaction Mechanism:
• Reaction mechanisms refer to the step or series of steps by which the
initial reactants interact in the process of forming products.

• A reaction is represented by the overall stoichiometric equation but

rather takes place in a series of steps which adds up to the overall
equation and forms the mechanism of the reaction.
• Slowest step controls the rate of a reaction and also determines the
form of the overall rate equation.
• Kinetics classifies the reactions as elementary and non elementary reactions.
• The reactions in which the formation of product from the original reactants occurs
through a series of reaction steps are called as non elementary reactions.
• The individual reaction steps which contribute to the overall reaction are termed
as elementary reactions i.e., the reaction in which the molecules react exactly as
the stoichiometric equation. It is single step reaction
• For irreversible elementary reaction, aA + bB----- rR
• Rate equation is given by -rA= k. (CA )a. (CA )b
• Elementary reactions are represented by the equation showing the molecularity and the rate equation.
k1
• Ex: 2A--------2S, this represents the irreversible bimolecular second order reaction implying that the rate of
the reaction is -rA=-rS= k1. (CA )2 , where k1is the second order rate constant.
k1
The same equation cannot be represented as A--------S, since this will be shown as
-rA=-rS= k1. (CA ) which is not true , as the reaction is second order w.r.t A
•
• There are possible representations of stoichiometry for one particular equation which is elementary reactions,
but there is only one representation of rate of reaction. So, it is always necessary to specify the component in
the reaction to which the rate constant is referred.
Ex. Consider reaction, A + 2B------ 3R
Rate of reaction in terms of
Reactant A, -rA= kA.CA .(CB )2 ,
Reactant B, -rB= kB.CA .(CB )2 ,
Product R , -rR= kR.CA .(CB )2 ,
i.e., the rate of formation of R is three times the rate of disappearance
of A & the rate of disappearance of B is twice the rate of disappearance
of A.
• For non-elementary reactions there is difference between order and stoichiometric coefficients,
• since the net reaction is the overall effect of a series of elementary reaction i.e., the stoichiometric equation
reflects only the initial and final states of the reaction system involved.
• As mechanism cannot be explained, there is no direct relation between the order of reaction and reaction
stoichiometry for non-elementary reaction.

• For irreversible non-elementary reaction, aA + bB----- rR

• -rA= k. (CA ) α. (CB)β , α and β are orders w.r.t A and B which are found by experiment and α # a and β # b.
A non-elementary reaction is one whose stoichiometry does not match with its kinetics
Ex: Stoichiometry: H2 + Br2 ----------- 2HBr
• Rate = rHBr = k1. C H2. (C Br2)½
k2 + (C HBr / CBr2)
 3..

• Intermediates formed in the non-elementary reaction are of different types:

Free radicals: Free atoms or larger fragments of stable molecules that contain one or
more unpaired electrons are called free radicals. The unpaired electron is designated
by a dot in the chemical formula of a substance.
Ex: H. , CH3. ,

Ionic intermediates: Electrically charged atoms, molecules or fragments of

molecules are called ions (polar) intermediates
Ex: Na + , OH-, NH4+, I-,
Molecular intermediates:

Consider an example of molecule R in the series reaction: A------ R ------- S

In the above reaction if molecule R is highly reactive, its mean life time is very less
and its concentration in the reaction mixture is too small to measure. In such situation R
may not be observed and thus can be considered as the reactive intermediate

Transition complexes: they are the unstable forms of molecules, unstable association of
molecules which decompose to give products or by further collision return to the
molecules in the normal states, such unstable formed are called transition complexes.
•
1. Non-chain reaction – the intermediate formed in the first reaction then disappears as it
reacts further to yield the products.
Reactants--------- (Intermediates)*
(Intermediates)*------ products

2. Chain reaction – The intermediate formed in chain initiation step (first reaction) then
combines with reactant to yield product and more intermediate in the chain propagation
step and finally it gets destroyed in the chain termination step.

Reactant -------- (Intermediates)* ….initiation

(Intermediates)* + reactant ------- (Intermediates)* + product ….. propagation

(Intermediates)* --------- products ……termination

• For developing the reaction mechanism, first assume the model or
reaction mechanism, obtain the kinetic expression and check whether
the predicted rate expression corresponds to the experiment, if not
assume the new model.

Examples for the mechanisms are

1. free radicals with the chain reaction mechanism
2. Molecular intermediates with non-chain mechanism
3. Transition complexes with non-chain mechanism
 Temperature dependency of a rate equation:
For elementary reactions the rate of reaction can be written as the
product of concentration dependent term and temperature
dependent term.
ri= f1.( temperature dependent term). (Concentration dependent
term)
ri= f2( concentration)
It is the rate constant of the reaction that depends on the
temperature through rate constant.
• Arrehenius Law:
• Under the normal conditions the number of collisions between the
molecules of gases and the liquids are so high that if any collision between
reactant molecules led to the formation of the reaction product
• For any reactions to occur, it is necessary to break or weaken the bonds
between the atoms and the molecules of the reactants which require a
definite amount of energy.
• If the colliding molecules do not possess this energy, a collision between
them does not result in the formation of new molecule.
•
• Activitation energy: The minimum energy which the colliding molecules must
have in order to bring about a reaction. Or the energy barrier that the molecules
must overcome when the reaction system passes from one state to another.
• Lower the activation energy higher will be the rate at which reaction will proceed
& higher the value of activation energy lower will be the rate at which the reaction
proceeds.
• The reaction rate constant k , can be correlated by an equation :
• k= ko.e-(E/RT) The equation is known as the Arrehenius law.
• where, ko is the pre- exponential factor or frequency factor
• E is the activation energy, J/mol or cal/mol
• R is the gas constant=8.314J/(mol.K)=1.987 cal/(mol.K)
• T is absolute temperature, K
Temperature dependency from the Collision theory:

• before the molecules react, there must be collision between the

reactant molecules and only those collisions in which the colliding
molecules possess a certain minimum amount of energy are effective .
• Rate expression based upon the frequency of molecular collisions and
the fraction of collisions that are effective.
bimolecular collisions of unlike molecules:
rate of reaction for the given reaction , A + B-------------- products
will be
- rA= (collision rate in mol/l.s) X ( fraction of effective collisions)
fraction of effective collisions = fraction of collisions releasing energy
equal to or greater than E
collision rate of molecules in a gas can be found from the kinetic theory of of gases.
For bimolecular collisions of unlike molecules in a mixture of A and B from kinetic theory of gases,i.e.,
ZAB= {(σA + σB)/2 } nA.nB { 8π kB T ( 1/MA + 1/MB)}1/2

Substitute for nA= NCA/103 ; nB= NCB/103

Therefore, ZAB= {(σA + σB)/2 } N2/106{ 8π kB T ( 1/MA + 1/MB)}1/2 . CA.CB

Where,
σA , σB are the molecular diameters of molecules A and B respectively in cm.
σAB = (σA + σB)/2 is the average diameter ( collision diameter) in cm.
M is the mass of a molecule = ( molecular weight)/N in g
MA is the mass of molecule A= ( molecular weight of A)/N in g
MB is the mass of molecule B= ( molecular weight of B)/N in g
CA, CB are the concentrations of A and B in mol/l
N is the Avogadro’s number =6.023 X 1023 molecules / mole
nA, nB are the number of molecules of A and B /cm3
kBis the Boltzmann constant =R/N=1.3 X 10-16erg/K
ZAB = number of collisions of A and B
Collision rate in molecules/( s) (cm 3) = ZAB
Collision rate in mol/(l. s) = ZAB X 103
N
Therefore, Rate of a reaction (-rA) = ZAB X 103 .e-E/RT
N
-rA ={(σA + σB)/2 } N2/106{ 8π kB T ( 1/MA + 1/MB)}1/2. CA.CB. 103 .e-E/RT
N
-rA ={(σA + σB)/2 } N/103{ 8π kB T ( 1/MA + 1/MB)}1/2. CA.CB.e-E/RT --------------(1)

Rate of bimolecular type reaction is given by,

-rA =k CA.CB ---------------------(2)

Compare equations (1) and (2)

k CA.CB = {(σA + σB)/2 } N/103{ 8π kB T ( 1/MA + 1/MB)}1/2. CA.CB.e-E/RT
k = {(σA + σB)/2 } N/103{ 8π kB T ( 1/MA + 1/MB)}1/2. e-E/RT

k= k10. T1/2 . e-E/RT --------------------------------(3)

where k10 = {(σA + σB)/2 } N/103{ 8π kB( 1/MA + 1/MB)}1/2

k= k10. T1/2 . e-E/RT --------------------------------(3)

lnk= lnk10 + ½ ln T -E/RT
Differentiating the eqution w.r.t T
dlnk/dT= 1/2T +E/RT2 ,since the term 1/2T is small compared to
E/RT 2 , 1/2T is neglected
========= dlnk/dT= E/RT2
bimolecular reactions show that the temperature dependency of the
reaction rate constant is given by
K=k0T1/2.e-E/RT or K α T1/2.e-E/RT
• Collision theory is found to be satisfactory for number of bimolecular
gas phase reactions and also for reactions in solution involving simple
ions, but collision theory fails for unimolecular reactions.

In some cases the actual rates of reactions differ to a marked extent from
the rates calculated from theory. Hence, a deviation factor is considered
i.e., the probability factor ( P ) also known as the steric factor .
Steric factor is referred to as the ratio of observed rate constant to that
calculated from the collision theory.
P= k observed/ ktheory === k observed = P. ktheory
Temperature dependency from Transition
State Theory:
Transition state theory or absolute reaction rate theory gives more
detailed information for the transformation of reactants into products.
The fundamental postulate of the theory is that:
1. the reacting molecules must form unstable intermediate called
activated complex before being converted to products and there
exists an equilibrium between the activated complex and the
reactants at all times and that the rate of decomposition of complex
and is given by kBT/h where kB is the Boltzmann constant(1.380 X
10-16 erg/K) and h is the Planck constant (6.024 X 10-27erg.s)
• The activated complex is a molecule in the process of breaking or
forming bonds. In the activated complex, the atoms are linked
together with loose valence bonds. The activated complex has only
a transient existence.

• Bimolecular reaction between A and B is given by:

A + B------------ AB* ---------------- Products

Activated complex or
Transition state
• Rate of reaction is equal to the product of the concentration of the
activated complex and the frequency (rate) of the decomposition of
activated complex.
Rate = conc. of activated complex X frequency of the decomposition
of
activated complex

= CAB* X kBT/h ----------------------------------------(1)

Equilibrium constant Kc* for the formation of activated complex

== CAB* / CA. CB ------------------------(2)
• CAB* = Kc*. CA. CB
• Then the rate expression will be k T/h. K *. C . C ------------(3)
• Kc* can also be expressed in the thermodynamic terms.

ΔG* = -RT ln Kc* = ΔH* - TΔS*

ln Kc* = (TΔS* - ΔH*)/RT
Kc*= e(ΔS*/R - ΔH*/RT) = e(ΔS*/R) .e(- ΔH*/RT) --------------------------(4)
Where ΔG*, ΔH*, ΔS* are change sin free energy, enthalpy and entropy of activation.

Then the equation (3) becomes

Rate = kBT/h.( e(ΔS*/R) .e(- ΔH*/RT) ). CA. CB -----------------------(5)

Suppose if the velocity constant (reaction rate constant) of the reaction, the
experimentally obtained rate law is rate= k CA. CB -----------(6)
Compare equation (5) and (6)
Then, k= kBT/h.( e(ΔS*/R) .e(- ΔH*/RT) )
• k= kBT/h.( e(ΔS*/R) .e(- ΔH*/RT) ).
• But the factor e(ΔS*/R) is less temperature sensitive so it is assumed
as constant.
• Relationship between ΔH* and Arrehenius activation energy E for
liquids and solids are E= ΔH* -RT
• For gases: E= ΔH* -(molecularity -1) RT
• Therefore, the transition state theory predicts k α T e- E/RT which
describes the temperature dependency of reaction rate from k.
Temperature dependency from thermodynamics:
• For thermodynamics, the temperature dependency of equilibrium constant k is given by Vant Hoff
equation

d(ln k1/ k2)/dt = d( ln k)/dt = ΔH/RT2

d( ln k1)/dt - d( ln k2)/dt = ΔHR/RT2

if the heat of reaction can be considered as the difference between the same two forms of energy, ΔHR=
E1-E2
(since ΔHR = ΔH1- ΔH2 ; H=E + PV on substituting above form is got)

d( ln k1)/dt - d( ln k2)/dt = - E2/RT2 on comparing

d( ln k1)/dt = E1/RT2 ; d( ln k2)/dt = E2/RT2 on integrating
ln k1=- E1/RT + ln A1 == k1 = A1 e- E1/RT
ln k2= -E2/RT + ln A2 == k2 = A2 e- E2/RT

• In general , k α e- E/RT
Comparision of Theories:
• Reaction rate obtained from Transition state theory agrees more closely with the experiment whereas
the reaction rates predicted with the collision theory does not agree more closely with the experiment.

• Transition state theory is based on statistical mechanics whereas collision theory is based on kinetic theory
of gases.

• Transition state theory views that the formation of activated complex is very complex are very rapid
whereas collision theory views that the decomposition of activated complex is rapid.

• Transition state theory views that the decomposition of activated complex is slow and is rate determing
whereas the collision theory views that the formation of activated complex is slow and rate controlling.
• From all the theories simple form of rate constant for
temperature dependency is
• k α Tm.e- E/RT = k01 Tm.e- E/RT ( 0 ≤ m ≤ 1)------- (1)
• Exponential term is temperature sensitive than Tm.
Interpretation of Batch reactor data:

• The rate of reaction is always characterized by rate equation ( based on theoretical

considerations or the result of simple empirical curve-fitting procedure)
• The values of constants of the equation is found only by the experiment.
• The determination of rate equation is a two step procedure: first the concentration
dependency is found at the fixed temperature and then the temperature
dependence of the rate constants is found, yielding the complex equation.

• Equipments can be classified into two types based on their empirical information;
they are the batch reactors and the flow reactors.
• The batch reactor is one in which the container holds the contents while they
react. All that is determined is the extent of reaction at various times, and it
follows in a number of ways such as:
1. By following the concentration of the reactants.
2. By following the change in some physical property of the fluid, such as electrical
conductivity or the refractive index.
3. By following the change in total pressure of a constant –volume system.
4. By following the change in volume of a constant-pressure system.
• Experimental batch reactor is usually operated isothermally and at constant
volume since it is easy to interpret the results of such runs. This is a simple reactor
used for obtaining the homogeneous kinetic data.
• The flow reactor is used primarily in the study of the kinetics of heterogeneous reactions.
• Majority there are two procedures for analyzing the kinetic data:
• One is the integral method and the other is the differential method.
•
• In integral method of analysis, a particular form of rate equation is a assumed and after appropriate
integration and the mathematical manipulation, graph of concentration function versus time is plotted to get a
straight line. If the straight line obtained for the plotted data is reasonably good then the rate equation is said
to be satisfactorily fit the data.
•
• In the differential method of analysis first check the fit of the rate expression to the data directly and without
any integration. Since the rate expression is a differential equation, first find the (1/V) (dN/dt) from the data
before attempting for the fitting procedure.
•
• In both the methods there are several advantages and disadvantages i.e.,

• The integral method is easy to use and is recommended when testing specific mechanisms or relatively
simple rate expressions or when the data are so scattered that we cannot reliably find the derivatives needed
in the differential method.
• The differential method is useful in more complicated situations but requires more accurate or larger amounts
of data.
• The integral method can only test this or that particular mechanism or rate form; the differential method can
be used to develop or build up a rate equation to fit the data.
Constant Volume Batch Reactor:

• also known as constant density reaction system .Most liquid phase reactions as well gas-phase reactions occurring
in a constant – volume bomb.

• In the constant volume system the measure of reaction rate of component i becomes,

• ri =(1/V)(dNi/dt) = d(Ni/V)/dt = dCi /dt for ideal gases C= p/RT

• ====== ri = (1/RT) (dpi/dt)

• Rate of reaction of any component is given by the rate of change of its concentration or partial pressure.

• For the gases reaction with the change in number of moles, the simplest way to find the reaction rate is to follow
the change in total pressure (π) of the system.
 Interpretation of batch reactor data
Integrated rate expression depends on the stoichiometry as well as the kinetics
A + 2B-------- products is a first order w.r.t both A and B. ( second
order reaction overall)
Rate expression is -rA=k CA.CB ---------------------(1)
Molar ratio will be M=CB0/CA0 # 2 i.e., CB0 = MCA0( the reactants are
taken in their stoichiometric ratio).
-rA = -rB
1 2
-CA = -CB ==========> CB = 2CA
1 2
• Apply the partial fraction method
Empirical rate equations of nth order:
• Consider the reaction A------- products
Zero Order Reaction:
• A reaction is of zero order when the rate of reaction is independent of the concentration of materials.

• Reaction : A-------- products

END