UNIT-1

INTRODUCTION

All chemical process is aimed at production of a desired product economically from the
given the raw materials, it is the 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. The step in which the raw materials are converted into the 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.
Primarily 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. It states that the 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]

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-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

Ester formation from organic acids and alcohols in presence of sulphuric acid is a
liquid phase reaction.
H2SO4
C2H5OH + CH3COOH === CH3COOC2H5 + H2O
Ehanol acetic acid ethyl acetate

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

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 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

Ex: Decomposition of cyclobutane is a unimolecular reaction.

H2C ----CH2
-------2C2H4

H2C---- CH2
Cyclobutane ethylene

Decomposition of hydrogen iodide is a bimolecular reaction which involves the

collision of two molecules

2HI (g) ---------I2 (g) + H2 (g)

Oxidation of NO to NO2 is a trimolecular /termolecular reaction which involves

collision of three molecules.
2 NO + O2 -------.2NO2

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---------------CH3OH + 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 ---------- 2NO2 + ½ O2

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A reaction of which the sum of orders with respect to reactants participated in reaction is
two is called second order reaction.

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:

The rate of a reaction may vary from a large value to zero. In ionic reactions such as
those occur on photographic film, or in high temperature combustion reactions, the rate is
extremely fast.

There are number of ways of defining the rate of reaction example 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 & so on.

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

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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 + rR= +( 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.

For homogenous systems, the possible factors that affect the rate of reaction are
temperature, pressure and composition, they are interdependent factors and pressure is
determined for the given temperature and composition of a phase.

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

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Rate equation:

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.

Multiple reactions are classified as

1. Series reaction: A-----R -------S

2. Parallel reaction: R
* Competitive reaction: A

* Side by side reaction: A------- R

B------- S

3. Series-parallel reaction: A + B------ R (parallel w.r.t B)

R + B----- S (series w.r.t A, R and S)

Concentration dependency of a rate equation:

For determining the concentration-dependent term of a rate equation, temperature of the
system is kept constant. Before finding the form of a concentration-dependent term in a
rate expression first different types of reactions are to be distinguished.

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, which is one of the reactants that is disappearing as a result of
reaction.

The rate of disappearance of A , -r A depends upon the temperature and composition . For
many reactions it can be written as the product of the reaction rate constant and the
function of concentrations of various species involved in the reaction.

-rA=Rate of reaction w.r.t A =k f (CA, CB, …)

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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)…

where k is the reaction rate constant

nA, nB…are the powers of concentrations of reactants A,B,… on which the rate of the
reaction depends ( not necessary nA=A, nB=B)

The algebraic equation that relates -r A 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.

Also a rate equation is represented by equivalent measurable quantity to the concentration

ex: partial pressure of the reacting materials.
In case of gas phase reaction rate is given by -rA=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.

Rate constant:

The rate constant of a reaction is a 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. It is also known as specific constant. The k depends upon
the units of concentration and time.

The unit of concentration is mol/ l & the unit of time is s.

i.e., ((mol/l.s)/ (mol/l) n) = (s) -1. (mol/l)(1-n) since -rA=k. (CA) n
Then the 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

Reaction Mechanism:

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Reaction mechanisms refer to the step or series of steps by which the initial reactants
interact in the process of forming products.

A reaction usually does not occur in the single step, it may be 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. Always the slowest step
controls the rate of a reaction and also determines the form of the overall rate equation.

Elementary & Non elementary reactions:

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
Representation of an elementary reaction:

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 -r A=-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

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i.e., the stoichiometric equation reflects only the initial and final states of the reaction
system involved. Also it failed to describe the mechanism of reaction in detail & hence
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

The rate equation, by analogy with the elementary reaction may be written as

-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.

Representation of a non-elementary reaction:

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)

the non-correspondence indicates the development of a multistep reaction scheme/ model

to explain its kinetics.

To know the kinetics of non-elementary reactions, assume that the overall reaction is the
result of a series of elementary reactions that involve the formation and subsequent
reaction of the intermediate species, which cannot be measured or observed as they are
present in very minute quantities and thus left undetected. Hence to know the kinetics it is
necessary to develop the reaction mechanism &also test it.

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

1. 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. ,

2. Ionic intermediates: Electrically charged atoms, molecules or fragments of

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

3. 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.

4. Transition complexes: they are the unstable forms of molecules, unstable

association of molecules which decompose to give products or by further collision

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 return to the molecules in the normal states, such unstable formed are called transition
complexes.

Reactions involved with the intermediates are classified into 2 types:

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

Here the propagation step, the intermediate is not consumed but acts as catalyst for
converting reactant into product.
Hence the intermediate before getting destroyed can catalyze the long chain of reactions.

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

Mechanism of non-elementary reactions:

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To verify the rate expression with the experimentally found, following rules are to be
followed:

1. If any component I takes part in more than one reaction than its net rate of change
is equal to the sum of the rates of change of component I in each of the
elementary reactions in which it is participated.

ri, net= ∑ ri
all elementary
reactions participated.
2. As the intermediates are highly reactive they have very short life time and they
are present in very small quantities, hence the rate of formation is taken as zero.
i.e., net rate of formation of A*=rate of formation of A* - rate of disappearance of
A*.
rA*=0
This is called the steady state approximation.

In elementary reactions also, two types of intermediates are present.

Type 1: An unobserved and unmeasured intermediates X * usually present at such a low

concentration that its rate of change in the reaction system is taken as zero.
So it is assumed that Cx* is small,
d Cx*/dt= 0

Type 2: Whenever homogeneous catalyst with initial concentration C o is present in two

forms i.e. one as a free catalyst C & in combination with the reactant to form active
intermediate X * then the accounting for catalyst gives

[Co] =[C] + [X *] or d X*/dt= 0 or the intermediate is in equilibrium with the reactants

k1
A +C X where A is reactant, C is catalyst & X is intermediate
k2
K=k2/k1= [X] / [A][C]

Temperature dependency of a rate equation:

For many reactions, particularly elementary reactions the rate of reaction can be written
as the product of concentration dependent term and temperature dependent term.

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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, all the reactions proceeds instantaneously which not
the actual practice is. 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

It has been verified empirically to give the temperature behavior of most reaction rate
constants within the experimental accuracy over the fairly large temperature ranges.
From, the kinetic theory gas, the factor e-E/RT gives the fraction of the collision between
molecules that together have this minimum energy .Activation energy is determined
experimentally by carrying out the reaction at several different temperatures. On taking
the natural logarithm of the Arrehenius equation
lnk= lnko - E/RT i.e., on plotting lnk v/s 1/T gives the straight line with slope equal to
–E/R

ln k slope=-E/R

1/T X 103
From the data of reaction rate constant as a function of temperature value of E can be got.
E can also be evaluated by measuring the rate constants k 1 & k2 at temperatures T1 & T2
respectively.
lnk1= lnko-E/RT1 and lnk2= lnko-E/RT2
lnk2- lnk1 = -E/RT2 + E/RT1

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ln(k2 /k1) = -E/R(1/T2 - 1/T1) =E/R(1/ T1 -1/T2)
Suppose if concentration dependency of the rate of reaction is not known but rate of
reaction v/s temperature data is available for concentrations, and then E can be evaluated
from the plot of ln r v/s 1/T

Note: Basic thumb rule says that for every 10 0C rise in temperature the rate of reaction
doubles.

Significance of Activation energy:

Always the reacting molecules must acquire discrete minimum energy before the end
products are formed. Thus the reactants must pass throu’ the energy rich or activated state
before they can react. The quantity of energy required by the reactants to overcome this
activated state or energy barrier is known as the activation energy. Difference between
the energies of reactants and products is the heat of reaction.

Exothermic Reaction

In an exothermic reaction in which the change in enthalpy between the change in

enthalpy between the products and reactants is positive.

Endothermic Reaction

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 Even in an endothermic reaction in which
the change in enthalpy between the products and the reactants is negative, there must be
an input of energy to start the reaction.

Activation energy & temperature dependency:

High E
Low E

ln k

Slope= -E/R

1/T
1. ln k v/s 1/T gives large slope for large E & small slope for small E.
2. Reactions with high E are very temp. sensitive, the more temperature sensitive is
the rate of reaction.
3. Reactions with low E are relatively temperature insensitive, for reactions with low
E change in temperature does not give remarkable difference in reaction rate, so
rate of reaction does not change very much.
4. Change in temperature from T1 to T2 say T2> T1 results in small changes in ln k
for low E indicating that the reaction with low E is relatively temperature
sensitive. For large E , the change in temperature from T1 to T2 results in large
change in ln k indicating that the reaction with large E is very temperature
sensitive.
5. A given temperature is more temp. sensitive at low temperature than at high temp.
the reaction rate changes rapidly at low temperature compared to the change in
reaction at high temperature for a given temperature change.

Arrehenius equation was derived from the thermodynamics.( from vantoff equation)

Temperature dependency from the Collision theory:

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The collision theory is based on the concept that 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 .This leads to the
rate expression based upon the frequency of molecular collisions and the fraction of
collisions that are effective.

Consider bimolecular collisions of unlike molecules:

the 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
-E/RT
=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
(s) (cm3)
Collision rate in molecules/( s) (cm3) = 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 } N /10 { 8π kB T ( 1/MA + 1/MB)}1/2. CA.CB. 103 .e-E/RT
2 6

N
3 1/2 -E/RT
-rA ={(σA + σB)/2 } N/10 { 8π kB T ( 1/MA + 1/MB)} . CA.CB.e --------------(1)

Rate of bimolecular type reaction is given by,

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

Compare equations (1) and (2)

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

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

this is in the form k= k10. T1/2 . e-E/RT --------------------------------(3)
where k10 = {(σA + σB)/2 } N/103{ 8π kB( 1/MA + 1/MB)}1/2

equation (3) describes the temperature dependency of the reaction rate constant from the
collision theory. To the equation (3) apply logarithm on both the sides
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

Similarly for the like molecules / identical molecules,

A +A --------- products
Same procedure is applicable, & proved that k= k10. T1/2 . e-E/RT

So 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

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 1. there exists an equilibrium between the activated complex and the reactants at
all times and that the rate of decomposition of complex is same for all
reactions and is given by k BT/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 is given by

CAB* / CA. CB --------------------------------------------------(2)
CAB* = Kc*. CA. CB
Then the rate expression will be kBT/h. Kc*. CA. CB.------------(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

17
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) ).
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:

Consider an elementary reversible reaction of type

k1
A R
k2
the equilibrium constant varies with the temperature
i.e., k1
A R; - rA=- k1CA

K2
R A; rA= k2CR

At equilibrium, - rA=- k1CA + k2CR but - rA=0 at equilibrium

Therefore, k1CA = k2CR or k1/ k2 = CR/ CA;
k1/ k2 =k = equilibrium constant

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

18
In general , k α e- E/RT

Comparision of Theories:

Reaction rate got 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.

Consider the Arrehenius theory k α e- E/RT = k = k01. e- E/RT

Taking log on both sides of (1) and differentiate w.r.t T
d (ln k) = ln k01 + ln Tm + (- E/RT )
d (ln k)/dT = m/T + E/RT2  (mRT +E)/RT

mRT <<E for most reactions , mRT can be neglected.

dlnk/dT=E/RT = k α e- E/RT
Arrehenius law /equation is a good approximation to the temperature dependency of both
collision and transition state theories.

Interpretation of Batch reactor data:

19
The rate of reaction is always characterized by rate equation; it may be the result of
theoretical considerations or the result of simple empirical curve-fitting procedure. In all
the cases 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:

20
This is 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.

Analysis of total pressure data obtained in a constant volume system:

For isothermal gas reactions the number of molecules of material changes during the
reaction. A general expression which relates the changing total pressure (π) of the system
to the changing concentration / partial pressure of any of the reaction components for
given initial conditions and any reaction stoichiometry.

A general stoichiometric equation is

aA + bB + … = rR + sS +…

Initial number of moles at time t=0: NA0; NB0; …; NR0; NS0; …; Ninerts
Number of moles either reacted or formed at time t: ax, bx, …, rx, sx, …
Number of moles at time t : (NA0 – ax),( NB0 – bx),…,( NR0 + rx), (NS0 +sx),…. Ninerts
Initial number of moles at moles :N0= NA0+ NB0 +…+ NR0 + NS0 +…+ Ninerts
Total moles present at time t:
N= (NA0 – ax)+( NB0 – bx)+…+( NR0 + rx)+ (NS0 +sx)+…. +Ninerts
N= (NA0 + NB0 +…+ NR0 + NS0 +…+ Ninerts) + x( r+ s+….– a – b -…)
 N= N0 + x Δn { Δn = r+ s+….– a – b -…) -----------(1)
Assuming the ideal gas law for any reactant A in the volumeV
CA=pA/RT = NA/V = (NA0-ax)/ V ---------------------------------- (2)
Combining equation (1) & (2)

CA= NA0 /V - ax / V where x = (N-N0) / Δn

CA= NA0 /V - a (N-N0) / ΔnV or

pA = CART = pA0- (a / Δn)( π – π 0) with respect to reactant A , the eqution

gives the concentration or partial pressure of reactant A as a function of the total pressure
(π ) at time t , initial partial pressure of A (p A0), and the initial total pressure of the
system(π0)

Similarly for the product(R) the equation is as follow:

PR = CRRT = pR0 + (r / Δn)( π – π0)

21
One deviation is that if the precise stoichiometry is not known or more than one
stoichiometric equation is needed to represent the reaction then the total pressure
procedure cannot be used.

Fractional conversion:

Fractional conversion of any reactant is the fraction of reactant reacted or converted into
different form. Or simply the conversion of reactant is represented by symbol X

Consider A as reactant, and the conversion of A is represented by X A .Suppose it NA0 is

the initial amount of A in the reactor at time t=0 , and that N A is the amount present at
time t.
The conversion of A in the constant volume system is given by:
XA = Number of moles of A reacted / number of moles of A taken initially

XA= NA0 - NA = 1 - NA/V = 1 – CA/CA0

NA0 NA0 /V

dXA= -dCA/CA0
XA= NA0 - NA = 1 - NA
NA0 NA0
1- XA = NA/NA0 = NA = NA0 (1- XA) = NA = NA0 (XB) This equation is
applicable for both constant volume and variable volume reactions.

For constant volume reactions.

XA= NA0 - NA
NA0
XA= (NA0/V)- (NA/V)

(NA0/V)

XA=CA0- CA/CA0 = 1- (CA/CA0 )

== (CA/CA0 ) =1- XA ===CA= CA0 (1-XA)

dCA/dt = CA0 ( 1-dXA/dt)

-rA = -dCA/dt= -CA0(-dXA/dt) = CA0(dXA/dt)

Integral Method of analysis of data:

In this method a particular rate equation is integrated and compared with the predicted C
versus t curve with the experimental C versus t data. If the fit is not satisfactory, another
rate equation is assumed and tested. The integral method is useful for fitting the simple
reaction types corresponding to the elementary reactions.
Irreversible Unimolecular type first order reaction

Consider the reaction, A--------- products

22
 -rA = - dCA/dt= k CA Separating and integrating we obtain
CA t
- ∫ dCA/CA = k ∫ dt
CA0 0
-ln ( CA/CA0 ) = kt

in terms of conversion (XA),

XA= 1-( NA/NA0)= 1- ( NA/V)
(NA0/V)
XA= (1- CA/CA0 )
d XA = - d CA/ CA0 ======- d CA = d XA. CA0
But the rate expression is –rA= - d CA/dt = - kCA
-d CA/dt = - k CA0 (1-XA)
- d XA. CA0 = - k CA0 (1-XA)
dt
d XA = k (1-XA)
dt
On rearranging the terms and integrating both sides,
XA t
∫ dXA/(1- XA) = k ∫ dt
0 0
======== -ln (1- XA) = kt
Similarily,in terms of partial pressure (pA), (CA/CA0)= (pA/pA0) i.e., -ln (pA/pA0)= kt
which is in the form y=mx.
Thus by plotting the -ln (1- XA) or -ln ( CA/CA0 ) v/s t straight line is obtained from the
origin for this form of the rate equation.

Note: Suppose if curve is obtained instead of straight line, and then try another rate form
because the first order reaction does not satisfactorily fit the data.

-ln (1- XA)

or
-ln ( CA/CA0 )
or Slope=k
-ln ( pA/pA0 )

For the first order reaction , conversion is independent of initial concentration.

Irreversible Bimolecular type second order reactions

23
Consider the reaction of type A + B -------------------- products

With the rate equation

-rA = - dCA/dt= dCB/dt = k CA. CB where CA0 # CB0
the amount of A and B that have reacted at any time t are equal and is given by CA0.

In terms of XA as , -rA = CA0 .dXA/dt = k(CA0 -CA0 XA) (CB0 -CA0 XA)---(1)

Note: CA= CA0(1-XA)

CB= CB0(1-XB) = CB0 - CB0 XB = CB0 - Breacted
but Breacted = Areacted ====== CB0 XB = CA0 XA
therefore, CB = CB0 - CA0 XA

Case (1) :
The initial molar ratio of reactants M= CB0 / CA0 ( M # 1)  CB0 = M. CA0
Substitute in(1) and separate CA0
-rA = CA0 .dXA/dt = k CA02 (1- XA) (M- XA) --------------(2)

Separating and integrating we obtain

XA t
- ∫ dXA/(1- XA) (M- XA) = CA0 k ∫ dt ----------------------(3)
0 0

Break into partial fractions ,

1/(1- XA) (M- XA) = A/(1- XA) + B/ (M- XA)

1= A(M- XA) + B (1- XA))

if XA =1, 1= A(M-1) == A = 1/(M-1)

if XA =M, 1= B(1-M) == B = 1/(1-M)

substitute A and B values in (3)

XA t
1/(M-1) ∫ [1/(1- XA) – 1/ (M- XA)]. dXA = CA0 k ∫ dt
0 0

XA
1/(M-1) [-ln(1- XA) + ln(M- XA)] = CA0 kt
0
1/(M-1) [-ln(1- XA) + ln(M- XA) -lnM] = CA0 kt

24
1/(M-1){ln[(M- XA)/M(1- XA)]}= CA0 kt
ln[(M- XA) / M (1- XA)] = CA0(M-1)kt but M # 1

ln[(M- XA)/M(1- XA)]

slope(M-1)CA0k

Suppose if CB0 is much more greater than CA0 , CB remains approximately

constant at all times . Therefore, second order reaction becomes pseudo first order
reaction.

Case 2:

A + Bproducts

where the rate equation is -rA=k CA.CB

the Molar ratio will be M=CB0/CA0
i.e., CB0= MCA0 i.e., the reactants are taken in their stoichiometric ratio.
At any time, constant ratio will be the same stoichiometric ratio i.e., CA = CB
-rA =dCA/dt = k CA2
dCA/ CA2 = k dt ---------(2)
Separating and integrating the equation (2) we obtain
CA t
2
- ∫ dCA/ CA = k ∫ dt
CA0 0
CA
{(- CA-2+1) / (-2 +1) } =kt
CA0
CA
[ 1/CA] =[ 1/CA – 1/ CA0] =kt
CA0
===============> 1/CA = 1/CA0 + kt It is in the form of y=mx +C
Case (3) :

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.
Hence the reaction is second order overall

25
 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
CB= CB0 – B reacted ( but B reacted = 2A reacted =2 CA0 XA)
CB= MCA0 – 2CA0XA ======= CA0 (M-2XA)
Substitute in the rate equation (1),

-CA0.dXA/dt = k (1-XA) CA0 (M-2XA)

-dXA/ (1-XA) (M-2XA) = k CA0 dt

Integrating the above equation, we obtain

XA t
- ∫ dXA/ (1-XA) (M-2XA) = k ∫ dt
0 0

Break into partial fractions,

1/(1- XA) (M- 2XA) = A/ (1- XA) + B/ (M- 2XA)

1= A(M- 2XA) + B (1- XA))

if XA =1, 1= A(M-2) == A = 1/(M-2)

if XA =M/2, 1= A( M-M) +B(1-M/2) == B = -2/(M-2)

substitute A and B values in (3)
XA t
1/(M-2) ∫ [1/(1- XA) – 2/ (M- 2XA)]. dXA = CA0 k ∫ dt
0 0
XA
1/(M-2) [-ln(1- XA) + -2ln(M- 2XA)] = CA0 kt
- 2 0

1/(M-2) [-ln(1- XA) + ln(M- 2XA) -lnM] = CA0 kt

1/(M-2){ln[(M- 2XA)/M(1- XA)]}= CA0 kt

ln[(M- 2XA) / M (1- XA)] = CA0(M-2)kt but M # 2

26
 ln[(M- 2XA)/M(1- XA)]
slope(M-2)CA0k

Case (4):

A + 2B ---------------- products

Since the reactants are taken in their stoichiometric ratio concentration

at any time will be the same ratio .

where the rate equation is -rA=k CA.CB ----------------(1)

the Molar ratio will be M=CB0/CA0 = 2

==========>CB0 = 2CA0

CB= CB0 – B reacted ( but B reacted = 2A reacted =2 CA0 XA)

CB= 2CA0 – 2CA0XA ======= 2CA0 (1-XA)

Substitute in the rate equation (1),

-CA0.dXA/dt = k CA0 (1-XA) 2 CA0 (1-XA)

XA t

27
- ∫ dXA/ (1-XA)2 = 2k CA0 ∫ dt
0 0

XA t
-2+1
-(1- XA) ] = 2 kCA0t ] XA/ 1- XA
(-2 + 1) 0 0

XA 2 kCA0t
-(1/(1- XA)) (-1) ] =2 kCA0t
0
XA
( 1/(1- XA)) ] = 2 kCA0t t
0
( 1/(1- XA)) - 1 = 2 kCA0t

XA/ 1- XA = 2 kCA0t

28
In terms of concentration,
dCA/ dt = k CA CB CB =2CA
2
dCA/ dt = 2k CA
Separate the variables
CA t
2
- ∫ dCA/ CA = 2k ∫ dt
CA0 0
CA t
-2+1
(- CA ) / (-2 +1) ] =kt ]
CA0 0
CA
[ 1/CA] =[ 1/CA – 1/CA0] =2kt
CA0
============== 1/CA = 1/CA0 +2kt It is in the form of y=mx +C

CA
{(- CA-2+1) / (-2 +1) } =kt
CA0
CA
[ 1/CA] =[ 1/CA – 1/CA] =kt
CA0
=============== 1/CA = 1/CA0 + kt It is in the form of y=mx +C

Empirical rate equations of nth order:

Consider the reaction A------- products

29
 When the mechanism of the reaction is not known , then attempt is made to fit the data
with an nth order rate equation of the form,
n
rA = - dC /dt = k C
A A
on separation and integrating
CA t
- ∫ dCA/ CAn = k ∫ dt
CA0 0
CA t
(-n + 1)
-CA
= kt ]
-n + 1
CA0 0
n-1 n-1
1/ (n-1) [1/ CA - 1/ CA0 ] = (n-1) kt n#1

Unit of k for nth order is (time)-1 (concentration) 1-n

By selecting the value of n k can be calculated .

The value of n which minimizes the variation in k is desired value of n .

Reactions with order n> 1 will not go to completion in finite time.

But the reactions with order n< 1 , rate forms predicts that the reactant concentration will
fall to zero and then become negative at some finite time.

CA1-n - CA01-n =(n-1)kt

And CA=0 at t greater than or equal to CA01-n /(1-n)k

Since real concentration cannot fall below zero , integration cannot be implemented
beyond time for n< 1.Also the observed fractional order will shift upward to unity as
reactant is depleted.

Zero Order Reaction:

30
A reaction is of zero order when the rate of reaction is independent of the concentration
of materials.

Reaction : A-------- products

-rA=-dCA/dt =kCA0
-dCA/dt =k
on integrating

CA t
- ∫ dCA = k ∫ dt
CA0 0
= CA0 –CA = kt in terms of concentration and the
units of k is conc/time.

CA = CA0 (1-XA)
CA0 - CA = CA0XA =kt (for t < CA0/k)

This is the integrated rate equation in terms of

conversion.
CA= 0 for t greater than or equal to CA0/k
Plot of CA0 - CA versus t yields a straight line passing through origin with slope =k

31
 CA0-CA
Slope =k

NOTE:
1. Reaction is zero order only in higher concentrations. If the concentration is
lowered reaction becomes concentration dependent, the order rises from zero.
2. In general , zero order reactions are those whose rates are determined by
factors such as intensity of radiation within the vat for photochemical
reactions or the surface available in certain solid catalysed gas reactions.

Overall order of irreversible reaction from the half life t1/2

32
 (Fractional life method)

Consider the irreversible reaction

α A + β B +… ----------------- products
Rate expression can be expressed as
-rA= -dCA/dt= kCA α.CB β …--------------(1)
Let the reactantas be taken in the stoichiometric ratios . Thus , reactants A and B at any
instant of time can expressed as
CB/CA =β/ α
b
And can be written as – rA = -dCA /dt = k CAa. (β/ α CA) …
b a+b+…
= k ( β/ α) …CA

In general , – rA = k1.CAn -----------------(2)

b
Where k1 = k ( β/ α) …and
n=a+b+…( overall order of the reaction)
substitute the equation (2) in (1)
-dCA/dt= k1.CAn separate the variables and integrate between the limits
CA t
n
∫ -dCA/ CA = ∫ k1. dt
CA0 0
CA t
-n+1
-CA
= k1t
-n +1
CA0 0

CA t
1-n
C A
= k1t
n -1
CA0 0

Therefore, CA1-n - CA01-n= (n-1)k1t

Half life is defined as the time required for the concentration of reactants to drop
to one half the original value.

i.e., at half life CA= CA0/2 substitute the same in the above equation ,

(CA0/2)1-n -(CA0)1-n= (n-1)k1t1/2

 CA01-n { (0.5)1-n – (1)1-n}

= t1/2
k1(n-1)

33
 OR

CA01-n { (2)n-1 – (1)1-n}

= t1/2
k1(n-1)
OR

ln(t1/2) = (1-n) lnCA0 + ln{ (2)n-1 – 1}

k1(n-1)

ln t1/2 n>1
n<1
n=1

ln CA0

Note:

1. Half life method requires making series of runs at a different initial

concentration and shows that the fractional conversion in a given time rises with
increased concentration for orders greater than one (X A increases with concentration at
n>1).
2. It will drop with increased concentrations for orders less than one (X A
decreases with concentration at n<1).
3. It is independent of initial concentration for reactions of first order (X A does
not depend on concentration at n=1).

Half life method can be extended to any fractional life method in which the concentration
of reactant drops to any fractional value F=CA/CA0 at time tF.

{ (CA/CA0)1-n – 1} CA01-n
tF =
k1(n-1)

t0.5 α 1/CA0n-1

n=0, t0.5 α CA0

n=1, t0.5 is independent of CA0
n=2, t0.5 α 1/CA0
n=3 t0.5 α 1/CA02

34
 For the first order reaction, dCA/dt= kCA

-ln(CA/CA0) = kt
CA= CA0/2; t= t1/2
-ln((CA0/2)/CA0) = k t1/2
-ln(0.5) = k t1/2
====== t1/2 = 0.693/k

For the second order reaction, dCA/dt= kCA2

1/CA = 1/CA0 + kt
CA= CA0/2; t= t1/2
2/ CA0 -1/ CA0 =k t1/2
====== t1/2 = 1/CA0k

For the zero order reaction, dCA/dt= k2

CA t
- ∫ dCA = k ∫ dt
CA0 0
CA0-CA=kt (where CA= CA0/2; t= t1/2)
CA0-CA0/2 =kt1/2
====== t1/2 = CA0/2k

Rate determining step:

A reaction usually does not occur in the single step and it may be
represented by the overall stoichiometric equation even though it takes place
in the series of steps which adds up to the overall equation.

Consider a general reaction mechanism: Ex:

In which the several steps proceeds as follows:

Step 1: Initiation. -
Step 2: Propagation -

35
Step 3: Propagation -
Step 4: Termination -

And one of the steps is the slowest step; it controls the rate of a chemical
reaction and also determines the form the form of the overall rate equation.

Here, the propagation step continues as the intermediate is not consumed but
acts as a catalyst for converting the reactants into the products, hence the
intermediate can also catalyze the long chain of reactions before getting
destroyed (CHAIN REACTIONS).

Integral Method of Analysis of Data:

36
For determining the order of the reaction, assume the reaction order and integrate the
differential equation, if the assumption is correct the plot of concentration function v/s
time has to be linear.

If not assume the new value for the reaction order. This method uses a trial and error
procedure to determine the reaction order. This method is often used to evaluate rate
constants at different temperatures to determine the activation energy when reaction order
is known.

This method always put a particular rate equation to the test by integrating and comparing
the predicted concentration versus time data and if the fit is unsatisfactory, another rate
equation is suggested and the procedure is as follows:

1. In the constant volume system, the disappearance of the reacting component is of

the form:
rA = - dCA/dt = f(K,C) = k f ( C) = -dCA/dt

2. Separating the variables,

-dCA/ f(C ) = K dt
Now f ( C ) may be expressed in terms of concentration CA

3. Integrating relation between the limits CA to CA0

CA t
 -dCA/ f(CA) = K  dt =kt
CA0 0

This concentration function is proportional to time so the plot of LHS versus t

gives a slopes K

Slope=K
CA
 -dCA/ f(CA)
CA0

4. From experiment determine the numerical values for the above integral and plot
these at their corresponding times.

37
 5. If the straight line is obtained, our assumption is correct, if not assume different
function f (CA) and repeat the procedure.

In integral method of analysis of rate data appropriate concentration function

corresponding to a particular rate equation that is proportional to the time (linear with
time)

Differential method of analysis of Data:

In this method we test the fit of the rate expression to the data directly and without any
integration. However, since the rate expression is a differential equation we must first
find [(1/V)dN/dt] from the data before attempting the fitting procedure.

The procedure is as follows:

1. Hypothesize the mechanism and from it obtain a rate equation

-rA= -dCA/dt = f (K, C) = kf (C)

2. From the experiment obtain concentration –time data and plot them.
3. Draw a smooth curve through these data’s.
4. Determine the slope of these curves at suitably selected concentration values by
drawing the tangents to the curve at suitably selected concentrated values and the
slopes represent the rates of the reaction at that selected concentration.

CA1
Slope = r1 = - (dCA/dt)

CA

5. Evaluate f( C ) for each of the selected concentrations.

6. Plot a graph of - ( dCA/dt) i.e., -rA v/s f (C ) . If a straight line obtained passes
through the origin then the rate equation is consistent with the data (assumed rate
equation is correct) if not assume another data.

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 Slope=K
-rA

f (C )

Difference between the integral and the differential method:

In case of the integral method of analysis of data, particular form of the rate equation is
assumed, then the integration and the mathematical manipulations is performed finally
plot the concentration versus time to obtain the straight line.

Where as in case of the differential method of analysis, particular form of rate equation is
assumed to fit the rate equation to the data directly without any integration.

1. Integral method is easy to analyze the fit of the data whereas the differential
method is a complex method.
2. Integral method is useful for testing relatively simple rate expressions whereas the
differential method is useful for testing more complicated rate expressions.
3. Integral method is useful whenever the experimental data is limited or less
accurate but differential method is useful only when more accurate and large data
are available.
4. Integral method can only test a particular form of the rate equation whereas the
differential method can be used to develop the rate equation to fit the data.

In general, it is always suggested that the integral method is being attempted first and if
not successful then differential method be tried.

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