KYAMBOGO UNIVERSITY

FACULTY OF SCIENCE

DEPARTMENT OF CHEMISTRY

MASTER OF SCIENCE IN CHEMISTRY

MCH 7103 Advances in Physical Chemistry

Academic Year: 2022-2023

Semester: One

Task: Course Work

Topic: Interpretation of experimental chemical kinetic data

Lecturer: Dr Nyende David Livingstone

Date of submission: 20/11/2022

GROUP ONE

STUDENT NAME REGISTRATION NUMBER STUDENT NUMBER

SSENKABIRWA DENIS 22/U/GMCH/708/PE 2200800708
EGONYU FRANCIS 22/U/GMCH/185/PE 2200800185
KALIBBALA SAM 22/U/GMCH/251/PE 2200800251
OMARIA JAMES 22/U/GMCH/643/PE 2200800643
MUGANGU K NICHOLAS 22/U/GMCH/397/PE 2200800397
UWAMARIA SCOVIA 22/U/GMCH/754/PE 2200800754
BASEMERA DOREEN 22/U/GMCH/ /PE 2200800130

2
 Contents

Chapters Page No.

1. Kinetics of Fast Reactions 1-10

2. Collision Theory of Reaction Rates 11-24
3. Reactions Mechanism 25-37
4. Chain reactions 38-59
5. Homogeneous and Heterogeneous Catalysis 60-75
6. Enzyme Catalysis 76-82
7. Acid –Base catalysis 83-87
8. Reactions in Solutions 88-97
9. Sample questions 98
10. References 99
 3

Chapter 1

Kinetics of Fast Reactions

1.1. Introduction: In the study of chemical reactions, two important factors

must be considered: (i) How far the reaction will proceed? (ii) How fast will
the reaction occur?
The first aspect forms the subject of ‘chemical equilibria’ where initial
and final states of the system are considered and time required for the system
to proceed from the initial to the final state is not important. The second aspect
is concerned with the study of rates of reactions and is dealt under the subject
of ‘chemical kinetics’.
Chemical kinetics is thus concerned with the progress of the reaction as
a function of time. Further, the influence of various factors such as
temperature, pressure, solvent etc., on the rates of reaction is also investigated.
Such a comprehensive study of the rate of any reaction and the factors
affecting it provides a general method of determining the mechanism of the
reaction.
There are many different types of chemical reactions, and a wide
variety of experimental techniques may be used to investigate them. Majority
of kinetic investigations should be concerned with reactions whose rates can
be measured easily, without the use of special methods. During recent years,
due to the development of new techniques, one can study reactions that are
difficult to study by conventional methods. Some reactions are slow which
proceed slowly and their rates can be measured by conventional methods.
However, the rates of many reactions are too fast to be measured by
conventional methods. The term ‘fast’ is a relative one but generally means
that the reaction is fast relative to the time of mixing and observation by
conventional methods. These conventional methods cannot be applied to
reactions which go to equilibrium in a few seconds of less.
The reasons why conventional techniques lead to difficulties for very
rapid reactions are as follows:
(i) The time that it takes to mix reactants or to bring them to a specified
temperature may be significant in comparison to the half life of the reaction.
An appreciable error therefore will be made because the initial time can not
be determined accurately.
(ii) The time it takes to make a measurement of concentration may be
significant compared to the half life.
 4

1.2. Techniques for the study of fast reactions: Special analytical methods
and experimental techniques are used for studying fast reactions. A few of
them are described as follows:

1.2.1. Flow Method:

Generally, the kinetic study of a reaction involves the initiation of the
reaction by mixing the reactants and following the progress of the reaction
through monitoring the concentration change of a species by titration or by
following a change in physical property of the system as a function of time.
A fast reaction, whose life is less than a second would be completed
and the rate measurement could not be obtained. If a method involving the
mixing of the reactant solutions is to be used to study the rate of fast reaction,
then the following two conditions must be met:
1. The time of mixing must be much less than the reaction time.
2. A method of making measurements must be found.

In 1923, Roughton and Hastridge first developed the flow technique which
satisfied these conditions for fast reactions in solution. The principle of the
method is that the two solutions that are to react together are placed in separate
containers and allow to mix thoroughly into mixing chamber in times as short
as 10-3 sec. The mixed solution then flows into an observation tube. At various
points along the observation tube, the composition of the solution is
determined by optical, thermal, or other methods. It is possible to make
observation in a few milliseconds after mixing.
Each position along the observation tube corresponds to the lapse of a
definite time interval t after mixing is given by:
𝑥.𝑎
𝑡=
where x cm is the distance along the tube from the mixing chamber, a cm2 is
the cross-sectional area of the tube, and f cm3 s-1 is the total flow rate.
By observing the change in composition at several points in the
observation tube, the concentration-time plots can be obtained. A schematic
figure of this method, known as continuous method is given in Figure 1.1. The
rates of reactions with half-lives of a few milliseconds can be studied by this
method.
The extent of reaction can be determined by the measurement of light
absorption, if the absorption spectrum of the product differs from that of the
reactant. The spectrophotometric equipment can be set up with beam of light
passing through the solution at a point “down–stream” from the point of
mixing.
 5

Fig. 1.1: Constant flow apparatus with movable spectrophotometer

If experiments are performed with different rates of flow, values of light

absorption at this one particular point provide data from which a plot of extent
of reaction verses time can be prepared. With observation points at several
positions, the same data can be accumulated at one particular flow rate.
Various factors must be considered while using flow method.
(i) Method of driving the fluid.
(ii) Mixing chamber and the efficiency of mixing.
(iii) Nature of fluid flow in the observation tube.

One of the first reactions studied using this method was the reaction
between Fe3+ and CNS- in aqueous solution. The rate law is:
𝑎
𝑟𝑎𝑡𝑒 = 𝑘2 [𝐹𝑒 3+ ][𝐶𝑁𝑆 − ] [1 + + ]
[𝐻 ]
where k2 is the second order rate constant and a is an empirical constant which
is related to the dependence of reaction rate on pH. At 250C, the rate constant
k2 is 127.1 mol -1s-1 .
The continuous flow method has disadvantage of requiring large
volumes of reactant solutions. Further, flow methods can also be used to study
irreversible reactions.

Stopped flow method: In this method, the flow of the reaction mixture is
suddenly stopped and the rate at which the system reaches equilibrium can be
followed by measuring the concentration change of the reactant or a product
 6

as a function of time at a fixed position in the observation tube away from the
mixing chamber by a fast response device usually UV-visible spectroscopy.
The schematic figure of a typical stopped flow apparatus is given in Figure
1.2.

A-Lamp, B- Photomultiplier R1, R2-Reservoirs for reactant solutions, S1, S2-Syringes for reactants,
S3- Stopping Piston, V1, V2, V3, V4, V5 –Valves, P- Point of observation, M-Mixing Chamber, C-
Oscillioscope.

Fig.1.2: Stopped flow method with optical detection

In this figure, R1 and R2 are the reservoirs for the reactants. S1 and S2
represent the syringes to force the reactants into the mixing chamber. P is the
observation point where the concentration changes are monitored. S 3 is the
stopping piston to stop the flow of the fluid. If concentration changes are
monitored optically then an oscilloscope is triggered at the point of stopping
the flow of the liquid in the observation tube and the concentration change
with time can be recorded.

Quenched flow method: In this method, after rapid mixing, the flowing
reactants get discharged into a quenching solution to arrest the reaction. At
this instant, the concentration as a function of time can be measured using
chemical procedure like titration, to determine the extent of reaction.
The decomposition of carbonic acid is another fast reaction, which can
be studied using flow technique.
H2CO3  H2O + CO2
In a flow apparatus, by mixing a solution of NaHCO3 with a solution of
HCl gives carbonic acid.
 7

NaHCO3 + HCl  H2 CO3 + NaCl

The decomposition reaction can be followed by measuring the pH (pH<8).
The initial solutions contain an indicator the color of which gets changed
because of the change in pH during the course of a reaction. The rate law is
𝑑[𝐻 𝐶𝑂 ]
− 2 3 = 𝑘2 [𝐻2 𝐶𝑂3 ]
At 180C, the rate constant k2 has been 12.3 s-1 which corresponds to a half life
of 0.056 second.
For the kinetics investigation of fast reactions, it becomes necessary to
overcome two problems. In the first place, the reaction has to be initiated and
in the second, its time course has to be observed. In flow techniques, the
classical principle of initiating a reaction by mixing the reactants has been
extended. In the remaining techniques, new principles are used for the
initiation of the reaction.

1.2.2. Relaxation method: Flow techniques are not suitable for the study of
reactions occurring in less than 10-3 second. Relaxation techniques are used
to study some of the faster reversible gaseous and solution reactions.
Kinetic study based on the measurement of rate of attainment of
equilibrium is known as relaxation method. In this method, the reaction is
allowed to reach equilibrium under controlled conditions. The state of
equilibrium is then suddenly changed by rapid change of the physical
parameters (electric field intensity, temperature or pressure). The time, called
relaxation time (τ) which is necessary to cover a certain fraction of the path
towards its new equilibrium, is measured. The system tries to cover this path
quite rapidly to reach the new equilibrium. This movement to equilibrium
(known as relaxation), i.e., the rate of reaction from non-equilibrium state to
the equilibrium state can be measured by a “fast” physical method. Usually
photometric method is used. Two important requirements of the method are:
1. The physical parameter required to disturb the equilibrium must be
changed very quickly. The time taken for the change must be of the
order of half life time of the reaction.
2. The analytical method used (spectrometry or conductometry) must be
capable of responding very quickly to the changes in the reaction
mixture.
Consider a reaction of first order in both directions: A ↔B
where k1 and k2 are the rate constants of forward and backward reactions.
Suppose the equilibrium is suddenly displaced to the right. Let a0 and
b0 are the original concentrations of A and B respectively and concentrations
in the new equilibrium positions are ae and be respectively. The concentrations
 8

at time t are a and b. If the initial displacement from the new equilibrium
position is x0 and x is the displacement at time t, then,
𝑥 = 𝑎 − 𝑎𝑒 = 𝑏𝑒 − 𝑏 …..(1.1)
The overall rate of the forward reaction leading to a state of new equilibrium
position, i.e., the rate of relaxation, is
𝑑𝑥
− = 𝑘1 𝑎 − 𝑘2 𝑏 …….(1.2)
Substituting the value of a and b from equation (1.1) in equation (2.2), we
get,
𝑑𝑥
− 𝑑𝑡 = 𝑘1 (𝑥 + 𝑎𝑒 ) − 𝑘2 (𝑏𝑒 − 𝑥)
𝑑𝑥
− 𝑑𝑡 = (𝑘1 𝑎𝑒 − 𝑘2 𝑏𝑒 ) + (𝑘1 + 𝑘2 )𝑥 ……(1.3)
At equilibrium, the rates of two opposing reactions become equal, i.e.,
(𝑘1 𝑎𝑒 = 𝑘2 𝑏𝑒 )
𝑑𝑥
Hence, − = (𝑘1 + 𝑘2 )𝑥 ……(1.4)
Rearrangement of equation (1.4) gives:
𝑑𝑥
− = (𝑘1 + 𝑘2 )𝑑𝑡
𝑥
On integration, we get:
−𝑙𝑛𝑥 = (𝑘1 + 𝑘2 )𝑡 + 𝐶……(1.5)
When t=0, x=x0 and C=-ln x0. Hence,
𝑥
𝑙𝑛 ( 0 ) = (𝑘1 + 𝑘2 )𝑡 …..(1.6)
Equation (1.6) shows that the rate of relaxation depends on two rate constants.
Thus, the overall first order constant
𝑘 = 𝑘1 + 𝑘2 …..(1.7)
So, equation (1.6) becomes:
𝑙𝑛 ( 𝑥 ) = 𝑘𝑡
or 𝑥 = 𝑥0 𝑒 −𝑘𝑡 …..(1.8)
Here, x0 signifies the departure from equilibrium concentrations
immediately after the initial conditions are changed.
The rates of relaxation processes are defined by relaxation time. Relaxation
time is a quantity which is the inverse of the sum of the rate constants.
1 1
𝜏= =
(𝑘1 + 𝑘2 ) 𝑘
Equation (1.8) can be written as:
𝑥 = 𝑥0 𝑒 −𝑡/𝜏 …..(1.9)
Thus, by measuring x/x0 at different intervals of time, τ is obtained.
From τ, the value of rate constant can be evaluated.
 9

Determination of relaxation time:

There a number of experimental techniques for the determination of
relaxation time. Some of these are high electric, magnetic fields or ultra sonic
vibrations (used for times smaller than 10-5 seconds) and temperature jump
and pressure jump methods (used for times larger than 10-5). However,
temperature jump and pressure jump methods are mostly used.
In temperature jump method, a temperature change of about 100C in 10-6
second is created by a discharge of high voltage condenser (100KV) through a
small quantity of solution. The increase in temperature causes a change in
equilibrium constant. For a finite but small temperature jump, δT, the
equilibrium constant changes according to the equation,
𝐾 ∆𝐻 0𝛿𝑇
𝑙𝑛 =−
𝐾 𝑅𝑇
where ∆H is the standard enthalpy difference between products and reactants.
0

This method has been used to study the measurement of the rate of reaction.
𝐻+ + 𝑂𝐻− → 𝐻2 𝑂
The concentration in the observation tube, i.e., extent of the reaction can be
determined by using some property of the reaction mixture like color
intensity, conductance, etc.
In the pressure jump method, the reaction mixture is enclosed in a
pressure vessel sealed with a thin metal disc. A pressure of about 50-100
atmosphere is applied to this. The metallic disc is punctured and the pressure
is reduced to that of atmospheric pressure. The decrease in pressure changes
the equilibrium constant K.
The sensitivity of a reaction to pressure depends on the change in volume
∆V and is represented quantitatively by the equation:
0

𝜕𝑙𝑛𝐾 ∆𝑉 0
=−
𝜕𝑃 𝑇 𝑅𝑇
The electric field jump technique is applicable for reactions which are
associated with a change in dipole moment. Example is dimerization of
carboxylic acids in non polar solvents.

1.2.3. Flash Photolysis method: This method is useful in the study of atoms
and radicals that have only a short life time before reacting.
In this method, the reactant system is first irradiated with an intense
flash of light in visible or UV region to produce a measurable change of
concentration in the system. The flash must be of a short duration which is
 10

usually of the order of few microseconds (10-3 – 10-4 s). The subsequent
chemical changes are followed by spectral methods.
Thus, when iodine vapor is illuminated with light of appropriate wave
length, the dissociation reaction occurs.
I2 + hν  2I
The absorbed photon is represented by hν, where h is Planck’s constant 6.62
x10-27erg.sec and ν is the frequency of the light in second-1. Rapid
recombination of iodine atoms occurs in a non-photochemical reaction. The
reaction consumes the iodine produced by the photochemical dissociation
reaction. Under steady illumination with light of moderate intensity, steady
state
2I I2
is established with only a very small fraction of iodine dissociated to atoms.
This steady state results from equality of rates of photochemical dissociation
of iodine molecules and non photochemical dissociation of iodine molecules
and non-photochemical recombination of iodine atoms.
If illumination occurs as a very brief and very intense flash, an
appreciable number of iodine atoms can be produced, their recombination can
be directly observed after the flash. In actual experiments, the peak intensity
of a flash may be build up in 10-5 sec and their decay over a period of 4 x 10-
4
sec, or less. After light intensity from the flash has decayed, light of low
intensity can be used in a spectro photometric arrangement to follow the
increase in concentration of molecular iodine.
This method, called flash photolysis, gives valuable information
regarding rates of very fast reactions. The technique has been used for study
of reactions in solution as well as those in gas phase.
The exact form of apparatus use d i n flash photolysis experiment depends to a
large extent on the nature of the problems but a typical one is shown in Figure 1.3.
The reactants are placed in a cylindrical quartz vessel 50 cm long and 2
cm in diameter which is mounted next to the photolytic flash tube. The latter
is a quartz tube of about the same length as the reaction vessel which is filled
with a rare gas, often krypton. The light emitted by the flash tube is a
continuum extending over the whole of the visible range and well into the
infrared and ultraviolet on which are superimposed the broadened atomic
spectral lines of the rare gas. The reaction vessel and flash lamp are mounted
in a hollow cylindrical whose inner surface is coated with magnesium oxide,
which has high reflectivity towards light of most wavelengths. A blank of
condensers connected to the electrodes is charged up to the required voltage
and then discharged by applying a triggering pulse to a small central electrode
 11

or to a spark gap in series with flash tube. The duration time of the photolysis
flash depends on the energy to be dissipated. Usually, a short pulse of high
intensity with energies per flash ranging from 2 to 2000 J in a time interval of
one to hundred micro second is applied.

Fig.1.3: A Flash Photolysis Apparatus

Advantages of flash photolysis:

1. Flash photolysis method has the advantage of covering largest range of
reaction times compared to other fast reaction techniques.
2. The various methods used for studying fast reactions other than flash
photolysis deals with reactions of molecular or ions in ground state.
However, flash photolysis method is useful for investigation of
reactions of “excited state” as absorption of light leads to their
formation. These “excited state” species decompose to give reactive
products like free radicals, atoms which cannot only interact among
themselves but can react with other molecules like solvent to give
complicated reaction schemes involving different products.

Applications:
(1) Gas phase reactions: A mixture of chlorine and oxygen is flashed. The
radiation causes dissociation of the Cl2 to chlorine atoms. After this,
other reactions follow:
𝐶𝑙2 → 2𝐶𝑙
2𝐶𝑙 + 𝑂2 → 2𝐶𝑙𝑂
2𝐶𝑙𝑂 → 𝐶𝑙2 + 𝑂2
 12

The ClO was produced very quickly, and its presence and rate of
disappearance were followed by taking a series of absorption spectra (one per
experiment) at times up to 10 milli second after the initial flash. Later, using
a faster flash, the rate constant can be measured for the addition of chlorine
atom to oxygen, which is found to be third order with a rate constant of 6 x
1014 mole-2 cc2 sec-1, where N2 is the principal third body.

(2) Liquid phase reactions: The reactions between ferrous ion and
methylene blue can be studied by flash photolysis.
 13

Chapter 2

Collision Theory of Reaction Rate

2.1. Classical Collision Theory: According to the classical collision theory,
molecules must collide to react and the rate of a chemical reaction is
proportional to the number of reacting molecules i.e.,
𝑅𝑎𝑡𝑒 ∝ 𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑐𝑜𝑙𝑙𝑖𝑑𝑖𝑛𝑔 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠 𝑝𝑒𝑟 𝑙𝑖𝑡𝑟𝑒/𝑠𝑒𝑐𝑜𝑛𝑑
In this theory, rate depends on the product of concentration terms. Consider a
reaction where molecule A combines directly with a molecule B to form AB,
i.e,
𝐴 + 𝐵 → 𝐴𝐵.
Suppose there are four molecules each of A and B in a box. Then, one
molecule A can collide with any of four B molecules. Hence, it has four
opportunities for collision. The same is the case for each of the four A
molecules, making 16 possible collisions in all. Therefore, assuming the
reaction rate is proportional to the number of collisions i.e. collisions per
second. Thus, the rate of reaction is proportional to the product of the
concentration, i.e,
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 ∝ [𝐴][𝐵] ……(2.1.1)
The chance of collision is equal to NA NB where NA and NB refer to the
number of moles of A and B respectively. If the volume of the vessel is
assumed to be constant, the chance of collision of reactant molecules is
proportional to the product of the concentration of reactants.
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑓𝑜𝑟𝑚𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝐴𝐵 = 𝑘𝑟 [𝐴][𝐵] …..(2.1.2)
where kr is specific rate constant.
𝑑𝑛
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 = − = 𝑍AB 𝑒 −𝐸/𝑅𝑇 ….. (2.1.3)
where ZAB refers to the number of bimolecular collisions per second per cc
and E the activation energy. The number of collisions of molecule A with that
of B per second per cc in a bimolecular mixture will be given as:
1 1 1⁄2
2 [8𝜋𝑘𝑇 (
𝑍𝐴𝐵 = 𝑁𝐴 𝑁𝐵 𝜎𝐴𝐵 − )] ….. (2.1.4)
𝐴 𝐵
where NA,NB = number of molecules of A and B in one cc
σ +σ
σAB = average diameter equal to the molecular diameter ( 𝐴 𝐵) which is
called the distance of closet approach of effective molecular diameter.
k is Boltzmann constant, T is absolute temperature and mA and mB are the
reduced masses of A and B molecules.
The reduced mass m is equal to the ratio of molecular weight (M) and
Avogadro’s number (N) i.e., m=M/N.
On substituting Eq. (2.1.4) in to (2.1.3), we obtain
 14

1⁄2
− = 𝑁 𝑁𝐵 𝜎 𝐵 [8𝜋𝑘𝑇 ( − )] 𝑒 −𝐸/𝑅𝑇 ..… (2.1.5)
𝑑𝑡 𝑚𝐴 𝑚𝐵
From the fundamental postulate of chemical kinetics, we have
𝑑𝑛
− = 𝑘𝑟 [𝐴][𝐵] ….. (2.1.6)
where kr is the specific rate constant.
As the concentrations of reactants A and B are equal to N A and NB, Eq.
(2.1.6) becomes:
𝑑𝑛
− =kr 𝑁𝐴𝑁𝐵 ..… (2.1.7)
𝑑𝑡
From equations (2.1.6) and (2.1.7), we get,
1 1 1⁄2
2 [8𝜋𝑘𝑇 (
𝑘𝑟 = 𝜎𝐴𝐵 − )] 𝑒 −𝐸/𝑅𝑇 ..… (2.1.8)
𝐴 𝐵
or 𝑘𝑟 = 𝐴/ 𝑇 1⁄2 𝑒 −𝐸/𝑅𝑇 ….. (2.1.9)
1 1 1/2
where 𝐴/ = 𝜎 𝐵 [8𝜋𝑘 ( − )] ….. (2.1.10)
On taking the logarithm of Eq. (2.1.9), we obtain
𝑙𝑛𝑘𝑟 = 𝑙𝑛𝐴/ + 21 𝑙𝑛𝑇 − 𝑅𝑇𝐸
…..(2.1.11)
On differentiating this equation with respect to T, we get
𝑑 𝐸 𝑅𝑇
𝑟
= = + ..… (2.1.12)
𝑑𝑇 𝑅𝑇 𝑅𝑇 2 2𝑇
1
In most cases 2𝑇 is small as compared to E/RT2. Thus, Eq. (2.1.12) will
becomes:
𝑑 ln 𝑘𝑟 𝐸
=𝑅𝑇 2 𝑑𝑇
If the reaction involves two identical molecules,
𝐴 + 𝐴 → 𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠
Then,
𝑑𝑛
− 𝑑𝑡 = 𝑘𝑟 [A] [A] = 𝑘𝑟 N2A
The value of collision number may be given as:
1⁄2
2 2 𝜋𝑘𝑇
𝑍𝐴𝐴 = 4𝑁𝐴 𝜎 ( )
𝑚𝐴
𝜋𝑘𝑇 1⁄2
and 𝑘𝑟 = 4𝜎 2 ( ) 𝑒 −𝐸/𝑅𝑇 ….. (2.1.13)
𝐴
1⁄2
2 𝜋𝑅𝑇
or 𝑘𝑟 = 4𝜎 ( ) 𝑒 −𝐸/𝑅𝑇 = 𝑍𝑒 −𝐸/𝑅𝑇 ……(2.1.14)
𝐴
(where k=R/N and reduced mass m= M / N where N is Avogadro’s number
and R is gas constant)
 15

The collision number, Z, may be thus defined as “the number of

collisions per second when there is only one reactant molecule per ml of the
gas.”

Failures of the theory: This theory fails in a number of cases such as:
(i)The bimolecular polymer polymerization of ethylene occurs at a rate which
is slower by a factor of 5× 10-4 than the theoretical value calculated from
simple collision theory [(Eq. 2.1.14)]
(ii)The polymerization of 1:3 butadiene proceeds at a rate which is slower by
a factor of 10-4 than the value calculated from Eq. (2.1.14)
(iii)The reaction between ethyl alcohol and acetic anhydride vapors occurs at
a rate which is slower by a factor 10-5 than the value calculated from simple
collision theory [Eq. (2.1.14)]
(iv)The chain reaction proceeds at a very fast rate which is much higher than
the value obtained from equation (2.1.14).

2.2. Modified Collision Theory: Under standard conditions, the number of

colliding molecules calculated from kinetic theory of gases is of the order of
magnitude of 1032 molecules per litre per second. Hence, if collisions were the
only requirement for reactions, all gaseous reactions should proceed at
practically the same explosive rate. However, for the same reactant
concentration at the same temperature, 3000C, the decomposition rate of
gaseous HI is 4.4x10-3 mole/litre/hour, while the decomposition rate of
gaseous dinitrogen pentaoxide is 9.4 x 105moles/litre. This suggests that
collision between molecules cannot be the only factor involved in determining
the rate of a reaction. So, simple collision theory is modified. According to
modified theory:
(1) The collisions between all molecules do not lead to chemical reaction.
(2) The collisions between such molecules which possess energy of
activation lead to the chemical reaction. So, if the energy of the
colliding molecules is less than activation energy, no reaction occurs.
If the energy of the colliding molecules is equal to or greater than
activation energy, reaction occurs. Thus, equation (2.1.14) becomes:
𝑘𝑟 = 𝑃𝑍𝑒 −𝐸/𝑅𝑇 ……(2.2.1)
where P is the probability factor or steric factor for such effects which
decreases or increases the speed of reactions. The value of P varies from 1 to
10-8.
 16

Weaknesses of the collision theory:

(i) The values of P could not be correlated to the characteristics of
reacting molecules.
(ii) Sometimes, abnormally high rates of reaction are observed which
could not be explained by this theory.
(iii) When a simple collision theory is applied to reversible reactions, a
logical weakness is observed. For example, for the following
reversible reaction:
𝑥 + 𝑦 ↔ 𝑥𝑦
The rate constant for the forward reaction is given by:
𝑘1 = 𝑃1𝑍1 𝑒 −𝐸⁄𝑅𝑇 …..(2.2.2)
and the rate constant for the backward reaction is given by:
𝑘2 = 𝑃2𝑍2 𝑒 −𝐸⁄𝑅𝑇 …..(2.2.3)
𝑘
But, 𝐾= 1 ……(2.2.4)
2
Substituting equations (2.2.2) and (2.2.3) in equation (2.2.4), we get,
−𝐸⁄𝑅𝑇
𝐾=𝑃𝑍 − ⁄ = 𝑃 𝑍 𝑒 −(𝐸1 −𝐸2 )/𝑅𝑇 ……(2.2.5)
2𝑒 2
From thermodynamics, the value of equilibrium constant is given by,
𝐾 = 𝑒 −∆𝐺/𝑅𝑇
But, We know that ∆𝐺 = ∆𝐻 − 𝑇∆𝑆 (Gibbs-Helmholtz equation)
So, 𝐾 = 𝑒 −(∆𝐻−𝑇∆𝑆)/𝑅𝑇 = 𝑒 ∆𝑆/𝑅 𝑒 −∆𝐻/𝑅𝑇 …..(2.2.6)
Comparison of equations (2.2.5) and (2.2.6) gives,
𝑃 𝑍1 −(𝐸1 −𝐸2 )/𝑅𝑇
𝑒 = 𝑒 ∆𝑆/𝑅 𝑒 −∆𝐻/𝑅𝑇 …..(2.2.7)
2 2
But, 𝐸1 − 𝐸2 = ∆𝐻 (change in energy)
So, equation (2.2.7) becomes:
𝑃1𝑍1 −∆𝐻/𝑅𝑇
𝑒 = 𝑒 ∆𝑆/𝑅 𝑒 −∆𝐻/𝑅𝑇
2 2
𝑃1 𝑍1
or = 𝑒 ∆𝑆/𝑅 …..(2.2.8)
𝑃
If dimensions of the reactants and products are roughly of the same sizes,
then Z1=Z2. Hence, equation (2.2.8) can be simplified as:
𝑃1
= 𝑒 ∆𝑆/𝑅 …..(2.2.9)
𝑃 2
But, simple collision theory does not give any physical explanation of
relationship (2.2.9) of the probability factor with entropy change.

Causes of the weakness of the collision theory:

Following are the main causes for the weakness of simple collision theory:
(1) This theory is based on classical mechanic, which is very crude and
needs modification.
 17

(2) The internal motions of the reactants are not considered.

(3) Numerical calculations are usually made in terms of elastic hard
spheres, which are the cases only for ideal systems.

2.3. Theory of Reaction Rate: In 1935, Eyring and collaborators has

replaced the older collision theory. In this theory, a reaction is considered in
terms of the changes in the potential energy of the reactants as they approach
each other from infinite separation and then separate as different and
distinguishable product molecules when they return to a state if zero potential
energy. This theory is known as the transition state theory or theory of
absolute reaction rates because it uses fundamental physical properties such
as dimensions, vibrational frequencies, and masses etc. of the reacting
molecules to calculate the rates of chemical reaction.
This theory can be treated in two stages: (a) The formulation of the rate
equation using statistical mechanics to describe the equilibrium between
reactants and the activated complex and (b) Formulation of the rate equation
in terms of thermodynamics state functions characterizing the transition state
complex and the reactants.

2.3.1. Statistical mechanical Derivation of the Rate Equation: In this

theory, there are various postulates:
(i) In order for any chemical reaction to take place, it is necessary that the
reactants, possessing sufficient energy must approach one another to form the
activated complex. These complexes will be in equilibrium with the reactants.
𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 ↔ [𝐴𝑐𝑡𝑖𝑣𝑎𝑡𝑒𝑑 𝑐𝑜𝑚𝑝𝑙𝑒𝑥]
(ii) Activated complex is regarded as a normal molecule in every respect
except that in addition to having three translational degrees of freedom, it has
a forth degree of freedom along the reaction co- ordinate.
(iii) Activated complex decomposes along the fourth degree of freedom to
form the products. Then, the rate of the reaction is given by the rate of
decomposition of activated complex which is to be calculated.
[𝐴𝑐𝑡𝑖𝑣𝑎𝑡𝑒𝑑 𝑐𝑜𝑚𝑝𝑙𝑒𝑥] → 𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠
It is assumed that the activated complex has one vibration degree of
freedom less than a normal molecule.
Thus, the above postulates can be written as:
𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 ↔ [𝐴𝑐𝑡𝑖𝑣𝑎𝑡𝑒𝑑 𝑐𝑜𝑚𝑝𝑙𝑒𝑥] → 𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠
The activation energy of a reaction is defined as the additional energy
which the reacting molecules should acquire before forming the intermediate
activated complex for the reaction. This is shown in the Figure 1 for
endothermic reaction.
 18

Fig.2.1: Activation energy required for the formation of activated

complex.

In Fig. 2.1, there is a small initial fall in the potential energy of the
reactants which is due to the approaching of the reactant molecules close to
one another before reacting to yield the activated complex. Similarly, there is
small final rise in the energy of the products which is due to the falling apart
of the molecules after the reaction. The activation energy of the back reaction
may be defined as the additional energy which the product molecules should
acquire before forming the activated complex.
It is clear from figure 2.1 that the activation energy of the backward
reaction is less than that of the forward reaction. This is because of the fact
that the product possess higher energy than the reactants i.e., the reaction has
been assumed to be endothermic. If a reaction is exothermic, the reverse thing
is there, i.e., the products possess less energy than the reactants and the
activation energy of the back reaction will be higher than that of the forward
reaction.
Consider a bimolecular reaction between a molecule of A and a
molecule of B.
𝐴 + 𝐵 → [𝐴𝐵]≠ → 𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠 …..(2.3.1)
where [AB]≠ is the activated complex and its concentration will be calculated
by using simple statistical mechanics.
The rate of the reaction is equal to the rate of decomposition of the
activated complexes. Therefore,
 19

Rate of reaction = frequency of crossing the energy barrier x concentration

of activated complex at the top of energy barrier x probability of crossing the
barrier. …..(2.3.2)
The frequency of crossing the barrier means the number of activated
complexes crossing the energy barrier per unit time. This is given as:
ū
𝐹𝑟𝑒𝑞𝑢𝑒𝑛𝑐𝑦 𝑜𝑓 𝑐𝑟𝑜𝑠𝑠𝑖𝑛𝑔 𝑡ℎ𝑒 𝑏𝑎𝑟𝑟𝑖𝑒𝑟 = (2.3.3)
where ū is the mean velocity of the activated complex in a length  in the
reaction co- ordinate at the top of energy barrier.
From the kinetic theory of gases, along a single direction, the average
velocity ū is given by:
kT
ū = √(2πm) …..(2.3.4)
Substituting equation (2.3.4) in (2.3.3), we get:
kT 1
𝐹𝑟𝑒𝑞𝑢𝑒𝑛𝑐𝑦 𝑜𝑓 𝑐𝑟𝑜𝑠𝑠𝑖𝑛𝑔 𝑡ℎ𝑒 𝑏𝑎𝑟𝑟𝑖𝑒𝑟 = √( ). (2.3.5)
2πm δ
The concentration of activated complexes means the number of
activated complexes per unit volume in the length  which can
be represented as C≠ i.e.,
𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑎𝑐𝑡𝑖𝑣𝑎𝑡𝑒𝑑 𝑐𝑜𝑚𝑝𝑙𝑒𝑥 = 𝐶 ≠ …...(2.3.6)
The activated complex is treated as a normal molecule in which one of
the vibrational degree of freedom is replaced by translational motion in the
reaction coordinate. The value of this translational partition function along the
length in reaction coordinate is given by,
1⁄
(2πmkT) 2δ
𝑇𝑟𝑎𝑛𝑠𝑙𝑎𝑡𝑖𝑜𝑛𝑎𝑙 𝑝𝑎𝑟𝑡𝑖𝑡𝑖𝑜𝑛 𝑎𝑙𝑜𝑛𝑔 𝑙𝑒𝑛𝑔𝑡ℎ δ = …..(2.3.7)
where h is the Planck’s constant, k the Boltzmann constant and m is the
effective mass of the activated complex in the reaction co-ordinate.
Equation (2.3.7) also gives the probability of activated complex at the
top of energy barrier. That is,
1⁄
(2πmkT) 2δ
𝑃𝑟𝑜𝑏𝑎𝑏𝑖𝑙𝑖𝑡𝑦 𝑜𝑓 𝑐𝑟𝑜𝑠𝑠𝑖𝑛𝑔 𝑡ℎ𝑒 𝑏𝑎𝑟𝑟𝑖𝑒𝑟 = …..(2.3.8)
Substituting the equations (2.3.3), (2.3.6) and (2.3.8) in the expression
(2.2.2), we get,
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 = 𝑇ℎ𝑒 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑏𝑟𝑒𝑎𝑘𝑖𝑛𝑔 𝑢𝑝 𝑜𝑓 𝑡ℎ𝑒 𝑎𝑐𝑡𝑖𝑣𝑎𝑡𝑒𝑑 𝑐𝑜𝑚𝑝𝑙𝑒𝑥𝑒𝑠
1⁄
kT 1 (2πmkT) 2δ 𝑘𝑇
or 𝑅𝑎𝑡𝑒 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 = √(2 ). . 𝐶 ≠. = 𝐶 ≠. …..(2.3.9)
where kT/h is known as the universal frequency having the dimensions of
time-1. The value kT/h depends only on the temperature and is independent
of the nature of the reactants and the type of the reaction.
 20

If kr is the specific reaction rate, the rate of formation of activated

complex is given by:
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑓𝑜𝑟𝑚𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑎𝑐𝑡𝑖𝑣𝑎𝑡𝑒𝑑 𝑐𝑜𝑚𝑝𝑙𝑒𝑥𝑒𝑠 = 𝑘𝑟 𝐶𝐴𝐶𝐵 …..(2.3.10)
where CA and CB are the concentrations of A and B respectively.
For steady reaction,
Rate of formation of activated complexes = Rate of decomposition of
activated complexes.
Therefore, equations (2.3.9) and (2.3.10) give
𝑘𝑇
𝑘𝑟 𝐶𝐴𝐶𝐵 = 𝐶 ≠ .
ℎ
𝐶 ≠ 𝑘𝑇
or 𝑘𝑟 = . …..(2.3.11)
𝐶 𝐴 𝐶𝐵 ℎ
Applying the law of mass action to the first equilibrium:
A+ B ↔ [AB]≠
we obtain,
≠
𝐾≠ = …..(2.3.12)
𝐶𝐴 𝐶𝐵
where K is the equilibrium constant and C≠ is the concentration of activated
≠

complexes.
From equations (2.3.11) and (2.3.12) we get,
𝑘𝑇
𝑘𝑟 = 𝐾 ≠ . …..(2.3.13)
From statistical mechanics, the value of equilibrium constant K ≠ in
terms of partition function is given by:
𝜃≠
𝐾≠ = 𝑒 −∆𝐸0 ⁄𝑅𝑇 …..(2.3.14)
𝐴 𝐵
where A and B are the partition function of the reactants A and B.
θ≠ is the partition function of the activated complex [AB≠] and E0 is
the change in the zero point energy in passing from the reactants to the
activated complex state i.e., heat of activation.
Substituting the value of K≠ from equation (2.3.14) in equation (2.3.13),
we obtain
𝑘𝑇 𝜃 ≠
𝑘𝑟 = . 𝜃 𝜃 . 𝑒 −∆𝐸0 ⁄𝑅𝑇 …..(2.3.15)
𝐴 𝐵
From equation (2.3.15), the specific rate of a reaction can be calculated from
the physical properties of the reacting substances.
By comparing equation (2.3.15) with the Arrhenius equation,
𝑘𝑟 = 𝐴𝑒 −∆𝐸0 ⁄𝑅𝑇
the frequency factor A is given by:
𝑘𝑇 𝜃 ≠
𝐴 = . …..(2.3.16)
ℎ 𝜃𝐴𝜃𝐵
 21

The partition functions depend on the translational degree of freedom of the

molecules and the activated complex and on the internal degrees of freedom.

2.3.2. Thermodynamical Formulation of Reaction Rate: The equations of

the theory of absolute reaction rates can be expressed in terms of
thermodynamical functions instead of partition functions. In this case, the
equilibrium between reactants and activated complexes may be expressed in
terms of partition functions as well as in thermodynamical functions.
Consider the general reaction
𝐴 + 𝐵 → [𝐴𝐵]≠ → 𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠
The equilibrium constant for the reaction: A + B ↔[AB]≠ may be given by
equation (2.3.14). Comparison of equation (2.3.14) with equation (2.3.15)
gives:
𝑘𝑇
𝑘𝑟 = 𝐾 ≠ . …..(2.3.17)
≠
The equilibrium constant K is related to the free energy of formation
G of the activated complex by the equation:
≠

−∆𝐺 ≠ = 𝑅𝑇𝑙𝑛𝐾 ≠ …..(2.3.18)

But, according to Gibbs –Helmholtz equation:
∆𝐺 ≠ = ∆𝐻≠ − 𝑇∆𝑆 ≠
So, equation (2.3.18) may be written as:
−(∆𝐻≠ − 𝑇∆𝑆 ≠ ) = 𝑅𝑇𝑙𝑛𝐾 ≠ ….(2.3.19)
[−(∆𝐻 ≠ −𝑇∆𝑆 ≠ )]
or 𝑙𝑛𝐾 ≠ =
≠ ≠
or 𝐾 ≠ = 𝑒 [−(∆𝐻 −𝑇∆𝑆 )]⁄𝑅𝑇 …..(2.3.20)
Substitution of equation (2.3.20) in equation (2.3.17) gives:
𝑘𝑇 ≠ −𝑇∆𝑆 ≠ )/𝑅𝑇
𝑘𝑟 = 𝑒 [−(∆𝐻
𝑘𝑇 ≠ ≠
or 𝑘𝑟 = 𝑒 −∆𝐻 /𝑅𝑇 𝑒 ∆𝑆 /𝑅 …...(2.3.21)
This equation was derived by Wyne –Jones and Eyring in 1935.
H≠ is the heat of activation which is not experimentally measured
quantity. So, in equation (2.3.21), it is replaced by Eexp, which can be
measured experimentally and is known as experimental energy of activation.
We know that
𝑑𝑙𝑛𝐾 ≠ ∆𝐸≠
= …..(2.3.22)
where E is the increase in energy in passing from the initial state to the
≠

activated state.
Taking logarithm of equation (2.3.17), w get
𝑙𝑛𝑘𝑟 = ln 𝑘 − 𝑙𝑛ℎ + 𝑙𝑛𝑇 + 𝑙𝑛𝐾 ≠
Differentiation of above equation, we get
 22

𝑑𝑙𝑛𝑘𝑟 1 𝑑𝑙𝑛𝐾 ≠
= + …..(2.3.23)
Substituting equation (2.3.22) in equation (2.3.23), we get
𝑑𝑙𝑛𝑘𝑟 1 ∆𝐸 ≠ 𝑅𝑇+∆𝐸≠
= + 2
= …..(2.3.24)
We know that
𝐸𝑒𝑥𝑝 = 𝑅𝑇 + ∆𝐸 ≠ …..(2.3.25)
But, ∆𝐻≠ = ∆𝐸 ≠ + 𝑃∆𝑉 ≠ …..(2.3.26)
Substituting equation (2.3.26) in equation (2.3.25), we get
𝐸𝑒𝑥𝑝 = 𝑅𝑇 + (∆𝐻 ≠ − 𝑃∆𝑉 ≠ ) …..(2.3.27)
When equation (2.3.27) is applied to uni molecular reactions, to reactions in
solution and to the reactions in gas phase different equations are obtained.

2.3.3.Unimolecular Reactions: For uni molecular reactions, the change in the

number of molecules as the activated molecule is formed is zero. Therefore,
V≠ is zero. Thus equation (2.3.27) becomes,
𝐸𝑒𝑥𝑝 = 𝑅𝑇 + ∆𝐻 ≠
or ∆𝐻≠ = 𝐸𝑒𝑥𝑝 − 𝑅𝑇 …..(2.3.28)
Substitution of equation (2.3.28) in equation (2.3.21) gives,
𝑘𝑇 ∆𝑆 ≠ −(𝐸𝑒𝑥𝑝 −𝑅𝑇)
𝑘𝑟 = 𝑒 𝑅 𝑒 𝑅𝑇
ℎ ≠
∆ −𝐸 𝑒𝑥𝑝
𝑘𝑇
or 𝑘𝑟 = 𝑒 𝑅 𝑒 .…..(2.3.29)

2.3.4. Reactions in solution: In these cases, V≠ is zero. Therefore, equation

(2.3.27) becomes,
𝐸𝑒𝑥𝑝 = 𝑅𝑇 + ∆𝐻 ≠
or ∆𝐻≠ = 𝐸𝑒𝑥𝑝 − 𝑅𝑇
Substitution of this in equation (2.3.21), we get,
𝑘𝑇 ∆𝑆 ≠ −(𝐸𝑒𝑥𝑝 −𝑅𝑇)
𝑘𝑟 = 𝑒 𝑅 𝑒 𝑅𝑇
ℎ
∆ ≠ −𝐸𝑒𝑥𝑝
𝑘𝑇
or 𝑘𝑟 = 𝑒 𝑅 𝑒 .…..(2.3.30)

2.3.5. Reaction in gas phase: We know

𝑃∆𝑉 ≠ = ∆𝑛≠ 𝑅𝑇 ……(2.3.31)
where n≠ denotes the increase in the number of molecules when the activated
complex is formed from the reacting species.
Substituting equation (2.3.31) in equation (2.3.27) we get,
𝐸𝑒𝑥𝑝 = 𝑅𝑇 + ∆𝐻 ≠ − ∆𝑛≠ 𝑅𝑇
 23

or ∆𝐻 ≠ = 𝐸𝑒𝑥𝑝 + 𝑅𝑇(∆𝑛≠ − 1) .…..(2.3.32)

So, equation (2.3.21) becomes:
≠)
𝑘𝑇 −[𝐸𝑒𝑥𝑝 +𝑅𝑇(∆𝑛 −1] ∆𝑆 ≠
𝑘𝑟 = 𝑒 𝑅𝑇 𝑒 𝑅
ℎ
−𝐸𝑒𝑥𝑝 ∆ ≠
𝑘𝑇 ≠ −1)
or 𝑘𝑟 = 𝑒 𝑒 𝑅 𝑒 −(∆𝑛 .….(2.3.33)
For bimolecular reaction in gas phase, n≠ is -1. Therefore, equation
(2.3.33) becomes:
− 𝑝 ∆ ≠
2 𝑘𝑇
𝑘𝑟 = 𝑒 𝑒 𝑅𝑇 𝑒 …..(2.3.34) 𝑅

Thus, equation (2.3.21) is the general thermodynamical formation of reaction

rate. Equation (2.3.29) is applicable to unimolecular reaction, equation
(2.3.30) is applicable to reaction in solution, equation (2.3.33) is applicable to
reaction in gas phase and equation (2.3.34) is applicable to bimolecular
reaction in gas phase.

2.3.6. Comparison of Collision Theory and Absolute Reaction Rate

Theory: From equation (15), we have
−
𝑘𝑇 𝜃 ≠
𝑘𝑟 = ( ) 𝑒 𝑅𝑇 …..(2.3.35)
ℎ 𝜃𝐴𝜃𝐵
Replacing E0 by E, the energy of activation, we get,
−𝐸
𝜃≠
𝑘𝑟 = ( 𝑘𝑇
ℎ 𝜃
) 𝑒 …..(2.3.36)
𝐴𝜃𝐵
𝑘𝑇 𝜃≠
If 𝐴= ( ). .…..(2.3.37)
𝜃𝐴𝜃𝐵
Then, equation (2.3.36) can be written as:
−𝐸
𝑘𝑟 = 𝐴𝑒 𝑅𝑇 …..(2.3.38)

2.3.7. Reaction between Atoms: The value of A can be calculated by using

equation (2.3.37) for a reaction between two atoms A and B.
3⁄
(2𝜋𝑚𝐴 𝑘𝑇) 2
𝜃𝐴 = …..(2.3.39)
From thermodynamics, we have
3⁄
(2𝜋𝑚𝐵 𝑘𝑇) 2
𝜃𝐵 = …..(2.3.40)
3
(2𝜋𝑚 𝑘𝑇) ⁄2 8𝜋 2𝐼𝑘𝑇
𝜃≠ = ℎ
[ ℎ ] …..(2.3.41)
where I is the moment of inertia and its value is given by:
𝐼 = 𝜎 2 [𝑚 ] …..(2.3.42)
𝐴 +𝑚𝐵
where σ is the mean diameter of the activated complex.
 24

Substituting equations (2.3.39), (2.3.40), (2.3.41) and (2.3.42) in

equation (2.3.37), we get
3⁄
(2𝜋𝑚 𝐵 𝑘𝑇) 2 8𝜋 2 (𝑚 𝑚 )𝜎 2 𝑘𝑇
𝐴 𝐵
ℎ3 ℎ 2 (𝑚 𝐴 +𝑚 𝐵 ) 𝑘𝑇
𝐴= 3
⁄ ⁄
.
(2𝜋𝑚 𝐴 𝑘𝑇) (2𝜋𝑚 𝐵 𝑘𝑇)
ℎ3 ℎ3
1⁄
(𝑚𝐴 +𝑚𝐵 ) 2
or 𝐴 = [8𝜋 𝑘𝑇] 𝜎2
𝐴 𝐵
1⁄
( 𝑁𝑚𝐴 +𝑁𝑚𝐵 ) 2
or 𝐴 = [8𝜋 𝑁𝑚 )(𝑁𝑚 ) 𝑁𝑘𝑇] 𝜎 2
𝐴 𝐵
1⁄
( 2
or 𝐴 = [8𝜋 )(𝑀
𝑅𝑇] 𝜎 2 …..(2.3.43)
𝑀𝐴 𝐵)
where R=Nk and M= mN
Comparison of equation (2.3.43) with equation (2.1.8) of section 2.1 of
this chapter shows that both are identical. Thus, both the statistical and
collision the theories lead to the same result provide the reactants are both
atoms.

2.3.8. Reaction between Molecules: The partition function θ of a molecule

can be represented as:
𝜃 = 𝑞𝑇 𝑞𝑅 𝑞𝑉 …..(2.3.44)
where t, r and υ are the numbers of degree of freedom.
Consider a reaction between two non-linear molecules A and B
containing a and b atoms respectively. Then,
𝜃𝐴 = 𝑞3𝑇 𝑞𝑅3 𝑞𝑉3𝑎−6 …..(2.3.45)
𝜃𝐵 = 𝑞3𝑇 𝑞𝑅3 𝑞3𝑏−6
𝑉 …..(2.3.46)
≠ 3 3 (3𝑎+3𝑏)−7
and 𝜃 = 𝑞 𝑇 𝑞𝑅 𝑞𝑉 …..(2.3.47)
The activated complex has one vibrational degree of freedom less than
a normal molecule.
Substituting equation (2.3.45), (2.3.46) and (2.3.47) in equation
(2.3.37), we get
3 3 (3𝑎+3𝑏)−7 5
(
𝐴=( ) 3 3 3𝑎−6
ℎ (𝑞 𝑇𝑞𝑅 𝑞𝑉 ) 𝑞 3𝑇𝑞 3𝑅𝑞 3𝑏−6
𝑉 )
= ℎ
. 𝑞 3𝑇𝑞𝑅3 …..(2.3.48)
We know that A=PZ. So, comparison of equation (2.3.48) with this
equation gives:
𝑘𝑇 𝑞 𝑘𝑇 𝑞 𝑞
𝑃𝑍 = .𝑞 𝑞𝑅
= . . …..(2.3.49)
𝑇2 𝑅
𝑘𝑇 𝑞
But, 𝑍= .
𝑇
 25

𝑞
Therefore, 𝑃= 5 ……(2.3.50)
𝑅
At ordinary temperature, qυ is unity and qR may be about 10-100 in the
case of complex molecules. Thus, the value of (qυ/qR) is 10-1 to 10-2, so that
(qυ/qR)5 is 10-5 to 10-10.
Thus, the value of P is 10-5 to 10-10. On the basis of collision theory,
such reactions should proceed more slowly than calculated. This is actually
observed in both gas phase and in solution.
Thus, the absolute reaction rate theory gives physical significance of
the probability factor.

2.3.9. Transmission Coefficient: It is not necessary that every activated

complex is converted into one of the reaction product. To allow for this
possibility, an coefficient known as transmission co-efficient K is introduced
in equation (15).
𝑘𝑇 𝜃≠
𝑘𝑟 = 𝐾 (
ℎ 𝜃𝐴𝜃𝐵
) 𝑒 −∆𝐸0 /𝑅𝑇 …...(2.3.51)
For most of the reactions, the transmission co-efficient is unity
suggesting thereby that every activated complex becomes a product.
However, for some reactions, the value of K has been found to be less than
unity. For example, (i) in bimolecular atom recombination in the gas phase
and the reverse decomposition of atomic molecules and (ii) in reactions, where
there is a change from one type of electronic state to another.

2.3.10. Entropy of Activation: From equation (2.3.21), we have

𝑘𝑇 ≠ ≠
𝑘𝑟 = 𝑒 −∆𝐻 /𝑅𝑇 𝑒 ∆𝑆 /𝑅
This equation can be compared with the collision theory expression,
−𝐸
𝑘𝑟 = 𝑃𝑍𝑒 ⁄𝑅𝑇 …..(2.3.52)
So, we get,
−𝐸 𝑘𝑇 −∆𝐻 ≠ /𝑅𝑇 ∆𝑆 ≠ /𝑅
𝑃𝑍𝑒 ⁄𝑅𝑇 = 𝑒 𝑒
ℎ
But, 𝐸 = ∆𝐻 ≠
So,
≠ 𝑘𝑇 −∆𝐻 ≠ /𝑅𝑇 ∆𝑆 ≠/𝑅
𝑃𝑍𝑒 −∆𝐻 /𝑅𝑇 = 𝑒 𝑒
ℎ
𝑘𝑇 ≠
or 𝑃𝑍 = 𝑒 ∆𝑆 /𝑅
𝑘𝑇 ≠ /𝑅
Therefore, 𝑃=𝑍 𝑒 ∆𝑆 …..(2.3.53)
Thus, the probability factor P is related to the entropy of activation S≠.
 26

2.3.11. Advantages of Thermodynamic Formulation over Absolute

Theory of Reaction Rates:
(i) Thermodynamic formulation provides a quantitative treatment of
the steric factor P in bimolecular recations (equation (2.3.53))
(ii) Thermodynamic formulation (2.3.21) is not restricted to
bimolecular processes but is equally applicable to the rate constants
of unimolecular and termolecular processes.
(iii) Thermodynamic formulation (2.3.21) can be applied to reactions in
solution.
 27
Chapter 3

Reactions Mechanism

3.1. Introduction: The study of chemical kinetics is one of the principal

methods for discovering the mechanism of a reaction. The mechanism of a
reaction tells us the precise position of the atoms as a function of time, in the
reactant molecules, as they are converted into products. Thus, the mechanism
of reaction refers to the step or series of steps by which the initial reactants
interact in the process of forming products.
Most of the chemical reactions take place by a sequence of steps. Each
one of the steps is called an elementary process. The slowest elementary
process in a sequence is called the rate determining step. After characterizing
the product (or products), the mechanism of the reaction is determined by
considering all the possibilities that are consistent with the experimental
observations.
Examples of some simple reactions are discussed in the following
sections.
3.2. Reactions where First Step is Rate-Determining one:
3.2.1. Reaction between NO2 and F2 :
2𝑁𝑂2 + 𝐹2 → 2𝑁𝑂2 𝐹 …..(3.2.1)
The stoichiometric equation reveals that the reaction between NO2 and F2 may
be of third order, but experimental data indicate that the reaction is actually of
second order, first order in NO2 and first order in F2.The most likely
mechanism for the reaction may be put as follows:
𝑘1
𝑆𝑡𝑒𝑝 1: 𝑁𝑂2 + 𝐹2 → 𝑁𝑂2 𝐹 + 𝐹 (𝑠𝑙𝑜𝑤)
𝑘
2
𝑆𝑡𝑒𝑝 2: 𝐹 + 𝑁𝑂2 → 𝑁𝑂2 𝐹 (𝑓𝑎𝑠𝑡)
The first step is slow and is the rate-determining step. Therefore, the
rate is of second order and can be written as:
Rate = k [NO2] [F2] ….. (3.2.2)
By using steady-state approximation for the reaction in Eq. (3.2.1), the
same rate law can be determined. Here, F is the intermediate. On writing the
differential equation and equating it is zero, we get
𝑑[𝐹]
= k1 [NO2 ] [F2 ] − k2 [F] [NO2 ] = 0 ….. (3.2.3)
[𝐹] = 𝑘𝑘1 [𝐹2] ….. (3.2.4)
2
The rate of disappearance of NO2 may be given as follows:
𝑑 [𝑁𝑂2 ]
− = k1 [NO2 ] [F2 ] + k2 [F] [NO2 ] ….. (3.2.5)
On substituting [F] from equation (3.2.4) into equation (3.2.5), we obtain
 28

𝑑 [𝑁𝑂2 ] k
− = k1 [NO2 ][F2 ] + k 2 [NO2 ] ( 1 ) [F2 ] = 2k1 [NO2 ][F2 ]
2
1 𝑑 [𝑁𝑂2]
or − = k1 [NO2 ][F2 ] ….. (3.2.6)
The various steps of the above reaction have been found to show the
agreement of the mechanism with the stiochiometry with the order of reaction.

3.2.2. Reaction between NO2 and CO at Low Temperature: The reaction

between CO and NO2 at lower temperatures is as follows:
NO2 + CO → NO + CO2
This reaction follows the rate law
𝑑[𝑁𝑂2 ]
− = 𝑘 [NO2 ]2 ….. (3.2.7)
Equation (3.2.7) shows that the concentration of CO is not involved in the rate
determining step. The mechanism is given as follows:
𝑘
1
𝑆𝑡𝑒𝑝 1: 𝑁𝑂2 + 𝑁𝑂2 → 𝑁𝑂3 + 𝑁𝑂 (𝑠𝑙𝑜𝑤)
𝑘
2
𝑆𝑡𝑒𝑝 2: 𝑁𝑂3 + 𝐶𝑂 → 𝑁𝑂2 + 𝐶𝑂2 (𝑓𝑎𝑠𝑡)
The first step has been slow and is the rate determining step, thus we get,
𝑑 [𝑁𝑂2 ]
− = 𝑘1 [NO2 ]2
Applying the steady-state approximation to NO3, we get
𝑑 [𝑁𝑂3 ]
= 𝑘1 [NO2 ][NO2 ]– 𝑘2 [NO3 ][CO] = 0
𝑑𝑡
or k1 [NO2]2 = k2 [NO3] [CO] ….. (3.2.8)
The overall rate of disappearance of NO2 is given by
𝑑 [𝑁𝑂2 ]
− = 2𝑘1 [NO2 ][NO2 ]– 𝑘2 [NO3 ][CO]
𝑑𝑡
Substituting the value from equation (3.2.8), we get
𝑑 [𝑁𝑂2 ]
− == 2𝑘1 [NO2 ]2 − 𝑘1 [NO2 ]2 = 𝑘1 [NO2 ]2
𝑑𝑡
Thus, the rate of the reaction is independent of carbon monoxide
concentration.

3.2.3. Decomposition of Ozone:

2 𝑂3 → 3𝑂2 …..(3.2.9)
The observed first order differential rate law was found to be
𝑑 ]
−2. = 𝑘1 [𝑂3 ] …..(3.2.10)
𝑑𝑡
The rate law in equation (3.2.10) indicates that the above reaction is not a
single step reaction and one molecule of ozone is involved in the rate-
determining step. The following mechanism was proposed.
 29
𝑘
1
𝑆𝑡𝑒𝑝 1: 𝑂3 ↔ 𝑂2 +𝑂 (𝑠𝑙𝑜𝑤)
𝑘
2
𝑆𝑡𝑒𝑝 2: 𝑂3 + 𝑂 → 2𝑂2 (𝑓𝑎𝑠𝑡)
Thus, the suggested mechanism leads to the observed rate law:
𝑑 ]
− 2 . 𝑑𝑡 = 𝑘1 [𝑂3 ] …..(3.2.10)
Applying the steady state approximation to oxygen atom, we get
𝑑[𝑂]
= 0 = 𝑘1 [𝑂3 ] − 𝑘2 [𝑂][𝑂3 ]
𝑑𝑡
𝑘
or [𝑂] = 1 …..(3.2.11)
𝑘2
The rate of disappearance of O3 is given by:
𝑑[𝑂 ]
− 3 = 𝑘1 [𝑂3 ] + 𝑘2 [𝑂][𝑂3 ] …..(3.2.12)
Substituting [O] from equation (3.2.11) to equation (3.2.12), we obtain,
𝑑[𝑂3 ] 𝑘
= 𝑘1 [𝑂3 ] − 1 𝑘2 [𝑂3 ] = 2𝑘1 [𝑂3 ] …..(3.2.13)
2
𝑑 ]
or − . = 𝑘1 [𝑂3 ]
2 𝑑𝑡
which is identical to the observed rate law.

3.3. Reactions where the first step of the mechanism is a fast equilibrium
which produces an intermediate and this intermediate thus reacts slowly
in the rate-determining step:
The following reactions are the examples where the first step is a fast
equilibrium reaction followed by a rate determining step.

3.3.1. Ammonium Cyanate-Urea Reaction: The reaction of ammonium ion

and cyanate ion in aqueous solution is:
NH4+ + OCN+ → OC(NH2)2 (Urea) …. (3.3.1)
𝑑[𝑈𝑟𝑒𝑎]
The rate law is: = 𝑘[𝑁𝐻4+][𝑂𝐶𝑁 − ]] …. (3.3.2)
The postulated mechanism consistent with the rate law is:

As the second step is the rate-determining one, we get

𝑑[𝑈𝑟𝑒𝑎]
= 𝑘2 [NH4 OCN] …. (3.3.3)
From the fast equilibrium reaction, we get
k1 [NH4+] [OCN-] = k-1 [NH4OCN]
 30

𝑘1 [𝑁𝐻4 𝑂𝐶𝑁]
𝐾𝑒𝑞 = =
𝑘−1 [𝑁𝐻4+ ][𝑂𝐶𝑁 − ]
and [NH4OCN] = keq [NH4+] [OCN-]
Thus Eq. (3.3.3) become as follows:
𝑑[𝑈𝑟𝑒𝑎]
= k2 Keq [NH4+] [OCN-] =k [NH4+] [OCN-]
which is the experimentally observed rate law.
The mechanism can be depicted as follows:

3.3.2. Nitric Oxide-Oxygen Reaction:The reaction between nitric oxide and

oxygen may be as follows:
2NO + O2 → 2NO2
This follows the rate law
𝑑 [𝑂2 ]
− = k [NO]2 [O2] … (3.3.4)
There are two possible mechanisms, both of which are consistent with
the rate law.
First mechanism:

As the second step is the rate-determining step, the rate of reaction may
be as follows:
𝑑 [𝑂2 ]
− = 𝑘2 [𝑁2𝑂2 ][𝑂2 ] … (3.3.5)
From step 1, which is fast at equilibrium we have
 31

𝑘 [𝑁2𝑂2 ]
Keq = 𝑘 1 = [𝑁𝑂]2
−1
or [N2O2] = Keq [NO]2
Hence, the rate equation in equation (18) becomes:
𝑑 [𝑂2]
− = 𝑘2 K eq [NO]2 [𝑂2 ] = 𝑘[NO]2 [𝑂2 ]

where k= k2 Keq
It is experimentally observed that the reaction rate decreases with an
increase in temperature. This can be explained from the rate equation. It is
evident that the constant k consists of two constants k2 and Keq. k2 increases
with temperature. However, Keq decreases appreciably with rise in
temperature as the reaction is exothermic in nature. Thus, the value of the
product k2Keq becomes less with increase of temperature.

Second mechanism: An alternative mechanism which also gives a rate

equation consistent with the rate law is:

… (3.3.6)
As the second step is slow, the overall rate of reaction will be given by:
𝑑 [𝑂2]
− = 𝑘2 [𝑁𝑂][𝑂𝑂𝑁𝑂] ..… (3.3.7)
From step 1, we have, [OONO] =Keq [NO] [O2]
Hence
𝑑 [𝑂2]
− = 𝑘2 K eq [NO]2 [𝑂2 ] = 𝑘[NO]2 [𝑂2 ] ….. (3.3.8)

3.3.3. Hydrogen-Iodine Reaction: The reaction between H2(g) and I2(g)

𝐻2 (𝑔) + 𝐼2 (𝑔) ↔ 2𝐻𝐼(𝑔)
follows the rate law:
1 𝑑 [𝐻𝐼]
. = 𝑘[𝐻2 ][𝐼2 ]
2 𝑑𝑡
The postulated mechanism is:

Step 2 is the rate-determining step, so we get

 32

1 𝑑 [𝐻𝐼]
. = 𝑘[𝐻2 ][𝐼]2 …..(3.3.9)
From equilibrium step 1, we obtain
𝑘 [𝐼]2
𝐾𝑒𝑞 = 𝑘 1 = [𝐼2 ]
−1
2
or [I] = Keq [I2]
Hence, equation (3.3.9) becomes:
1 𝑑 [𝐻𝐼]
. = 𝑘2 𝐾𝑒𝑞 [𝐻2 ][𝐼2 ] = 𝑘[𝐻2 ][𝐼2 ] …..(3.3.10)
which is the required rate law.

3.4. Reactions involving more than two elementary processes with at least
one slow step:
Let us consider some reactions where more than two elementary
processes are involved in the mechanism with at least one slow step:

3.4.1. The mechanism of Acid catalyzed hydrolysis of Methyl Acetate: The

acid hydrolysis of methyl acetate takes place as:

The possible rate expression is:

𝑑[𝐶𝐻3 𝐶𝑂𝑂𝐶𝐻3 ]
− = 𝑘[𝐶𝐻3 𝐶𝑂𝑂𝐶𝐻3 ][𝐻+ ][𝐻2 𝑂] … (3.4.1)
The hydrolysis involves water, but its concentration in the reaction
mixture is quite large, so the variation of the rate of reaction with change in
water concentrations cannot be detected. Thus, the rate of reaction for the acid
hydrolysis of methyl acetate depends linearly on the [CH3COOCH3] and [H+]
and was found to be of first order, with the first order rate constant equal to
k[H+]. The experimental rate expression is:
𝑑[𝐶𝐻3 𝐶𝑂𝑂𝐶𝐻3 ]
− = 𝑘[𝐶𝐻3 𝐶𝑂𝑂𝐶𝐻3 ][𝐻+ ] … (3.4.2)
The following mechanism which is consistent with the rate expression
has been proposed:

Step I:
 33

Step II:

Step III:

Step IV:
 34

The rate of the formation of products would be equal to the rate of the
third, slow step.
𝑑[𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠]
= 𝑘3 [𝐼𝑛𝑡𝑒𝑟𝑚𝑒𝑑𝑖𝑎𝑡𝑒 𝐼𝐼𝐼] ..… (3.4.3)
From equilibrium step 1, we have
[𝐼𝑛𝑡𝑒𝑟𝑚𝑒𝑑𝑖𝑎𝑡𝑒 𝐼]
𝐾𝑒𝑞 =
[𝐶𝐻3 𝐶𝑂𝑂𝐶𝐻3 ][𝐻+ ]
or [𝐼𝑛𝑡𝑒𝑟𝑚𝑒𝑑𝑖𝑎𝑡𝑒 𝐼] = 𝐾𝑒𝑞 [𝐶𝐻3 𝐶𝑂𝑂𝐶𝐻3 ][𝐻 + ] …..(3.4.4)

Applying steady-state approximation, we obtain

𝑑[𝐼𝑛𝑡𝑒𝑟𝑚𝑒𝑑𝑖𝑎𝑡𝑒 𝐼𝐼]
= 𝑘2 [𝐼𝑛𝑡𝑒𝑟𝑚𝑒𝑑𝑖𝑎𝑡𝑒 𝐼][𝐻2 𝑂] − 𝑘3 [𝐼𝑛𝑡𝑒𝑟𝑚𝑒𝑑𝑖𝑎𝑡𝑒 𝐼𝐼] = 0
𝑑𝑡
or
𝑘2
[𝐼𝑛𝑡𝑒𝑟𝑚𝑒𝑑𝑖𝑎𝑡𝑒 𝐼𝐼] = [𝐼𝑛𝑡𝑒𝑟𝑚𝑒𝑑𝑖𝑎𝑡𝑒 𝐼][𝐻2 𝑂] …..(3.4.5)
3
Substituting the value of [Intermediate II] in equation (3.4.3), we get
𝑑[𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠] 𝑘
= 𝑘3 2 [𝐼𝑛𝑡𝑒𝑟𝑚𝑒𝑑𝑖𝑎𝑡𝑒 𝐼][𝐻2 𝑂] …..(3.4.6)
3
Substituting the value of [Intermediate I] from equation (3.4.4) to equation
(3.4.6), we get
𝑑[𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠] 𝑘2
= 𝑘3 𝐾𝑒𝑞 [𝐶𝐻3 𝐶𝑂𝑂𝐶𝐻3 ][𝐻 + ][𝐻2 𝑂]
3
or
𝑑[𝑃𝑟𝑜𝑑𝑢𝑐𝑡] 𝑞
= (𝑘2 𝑘3
. 𝑘3 [𝐻2 𝑂]) [𝐶𝐻3 𝐶𝑂𝑂𝐻][𝐻 + ] …..(3.4.7)
If
𝑘𝑒𝑞
𝑘 = (𝑘2 . 𝑘 [𝐻 𝑂])
𝑘3 3 2
equation (3.4.7) becomes,
𝑑[𝑃𝑟𝑜𝑑𝑢𝑐𝑡]
= 𝑘[𝐶𝐻3 𝐶𝑂𝑂𝐻][𝐻 + ] …… (3.4.8)
which is of same as equation (3.4.2).

3.4.2. Hypochlorite-iodide reaction:

Mechanism 1: For the reaction,
𝐼 − + 𝑂𝐶𝑙− → 𝑂𝐼 − + 𝐶𝑙−
The rate expression was
𝑑 [𝑂𝐼− ]
= 𝑘 / [𝐼 − ][𝑂𝐶𝑙− ] …..(27)
But, when the measurements are carried out at various [OH-], a more complete
rate law was found to be
 35

𝑑 [𝑂𝐼− ] [𝐼 − ][𝑂𝐶𝑙 − ]
=𝑘 𝑂 −
…..(28)
Negative dependence of rate on [OH-] makes one to postulate the
existence of a reaction step, which results in the formation of OH-.The
possible reaction could be
𝑂𝐶𝑙− + 𝐻2 𝑂 ↔ 𝐻𝑂𝐶𝑙 + 𝑂𝐻 −
HOCl so produced should take part in rate determining step involving
iodide ion. The possible reaction may be as follows:
𝐼 − + 𝐻𝑂𝐶𝑙 → 𝐻𝑂𝐼 + 𝐶𝑙−
HOI in alkaline medium would exist as hypoiodite ion, in accordance
to the reaction
𝑂𝐻− + 𝐻𝑂𝐼 ↔ 𝐻2 𝑂 + 𝑂𝐼 −
As this reaction involves reaction between H+ and OH-, it should be fast
and almost complete. Therefore, the reaction between I- and OCl- may be
involving a three step mechanism.
𝑆𝑡𝑒𝑝 1: 𝑂𝐶𝑙− + 𝐻2 𝑂 ↔ 𝐻𝑂𝐶𝑙 + 𝑂𝐻−

If the second step has been the rate determining step, the rate of reaction
would be given as:
𝑑 [𝑂𝐼 − ] [𝐻𝑂𝐼]
𝑅𝑎𝑡𝑒 = = = 𝑘2 [𝐼 − ][𝐻𝑂𝐶𝑙]
𝑑𝑡 𝑑𝑡
From reaction step 1, we get
[𝑂𝐶𝑙 − ]
[HOCl] = K eq = −
Hence, the reaction rate may be written as:
𝑑 [𝑂𝐼− ] [𝐼 −] [𝑂𝐶𝑙 − ]
= 𝑘2 𝐾𝑒𝑞 [ −
…..(29)
𝑑 [𝑂𝐼− ] [𝐼 ] [𝑂𝐶𝑙− ]
−
Or 𝑑𝑡
= 𝑘 / [𝑂𝐻 −]
A rate equation which is exactly the same as obtained experimentally
with k equal to k2 Keq.

Mechanism 2: An alternative mechanism, which also gives rate equation

similar to that obtained experimentally would involve the following three
steps.
 36

𝑆𝑡𝑒𝑝 2: 𝐻𝑂𝐶𝑙 + 𝐼 − → 𝐼𝐶𝑙 + 𝑂𝐻 − (𝑠𝑙𝑜𝑤)

𝑆𝑡𝑒𝑝 3: 𝐼𝐶𝑙 + 2𝑂𝐻 − → 𝑂𝐼 − + 𝐶𝑙 − + 𝐻2 𝑂 (𝑓𝑎𝑠𝑡)
As the second step is slow, the overall rate of formation of OI - would
be governed by this step. Hence,
𝑑 [𝐼𝑂 − ]
= 𝑘2 [I − ][HOCl]
From step 1,
[𝑂𝐶𝑙 −]
[HOCl] = 𝐾𝑒𝑞 = −
−
𝑑[𝐼𝑂 ] [𝐼 −][𝑂𝐶𝑙 − ]
Thus, = k2 Keq −
…..(30)
[
Both the mechanisms give the same rate equation, suggesting thereby
that the rate expression cannot distinguish between these two mechanisms.
Thus, it is necessary to look for other evidences.

3.4.3. Reaction of Acetone with Iodine: When a dilute solution of iodine in

acidic aqueous acetone is kept for some time, mono iodo ethane is formed.
The reaction is represented as follows:
𝐻+
𝐶𝐻3 𝐶𝑂𝑂𝐶𝐻3 (𝑎𝑞. ) + 𝐼2 (𝑎𝑞. ) → 𝐶𝐻3 𝐶𝑂𝐶𝐻2 𝐼(𝑎𝑞. ) + 𝐼 − (𝑎𝑞. )
The overall order of the reaction is two and a possible rate expression is:
𝑑[𝐼 ]
− 2 = 𝑘[𝐻 + ][𝐶𝐻3 𝐶𝑂𝐶𝐻3 ] …. (31)
A mechanism consistent with the rate law can be put as follows:

Step 1:
(rapid, at equilibrium)

Step 2: (slow)

Step 3: (fast)
 37

In this mechanism, the rate-determining step 2 does not involve iodine,

which is in agreement with experiment.

3.4.4. Reaction between CO and Cl2 to form Phosgene:

Cl2 + CO → COCl2
It follows a rate expression
𝑑[𝐶𝑂𝐶𝑙2 ]
= 𝑘[𝐶𝑂][𝐶𝑙2 ]3/2 …. (32)
The possible mechanism consistent with the rate law is:

As step 3, being the rate determining step, gives the rate law
𝑑[𝐶𝑂𝐶𝑙2 ]
= 𝑘3 [𝐶𝑂𝐶𝑙][𝐶𝑙2 ] .… (33)
The steps 1 and 2 are fast at equilibrium, we can write:
𝑘1 [𝐶𝑙]2
𝑘−1
= [𝐶𝑙
2]
1⁄
𝑘1 2
[𝐶𝑙] = ( [𝐶𝑙2 ]) …. (34)
−1

= [𝐶𝑙] …. (35)
𝑘−2 [𝐶𝑂]
𝑘2 𝑘 𝑘1 1/2
or [𝐶𝑂𝐶𝑙] = [𝐶𝑙][𝐶𝑂] = .( [𝐶𝑙2 ]) [𝐶𝑂] …. (36)
−2 −2 −1
Substituting the value of [COCl] in equation (33), we obtain
𝑑[𝐶𝑂𝐶𝑙2 ] 𝑘 3 𝑘2 𝑘1 1/2 𝑘3𝑘2 𝑘1 1/2
= ( [𝐶𝑙2 ]) [𝐶𝑂][𝐶𝑙2 ] = /
[𝐶𝑂][𝐶𝑙2 ]3/2 =
−2 −1 −2 −1

𝑘[𝐶𝑂][𝐶𝑙2 ]3/2 ---

(37)
𝑘3𝑘2 𝑘 /2
where 𝑘= 1/2
𝑘−2 𝑘−1
Equation (37) shows that the proposed mechanism is consistent with
the rate law.

3.5. Reactions where all the steps have comparable rates: All the
mechanisms discussed above have been treated mathematically to yield a rate
expression for the reaction. The assumption made was that one step was
slower than the others and it governed the rate. However, in many reactions
 38

in which all steps of the mechanism proceed at comparable rates, no such

assumption can be made.
However, another simplified assumption may provide us with a simple
tool to obtain a rate expression from the mechanism. This is Bodenstein steady
(or stationary) state approximation. The assumption involved in steady state
hypothesis is that the concentration of very reactive intermediates remain very
low and effectively remain constant compared with the reactant concentration.
The following steps are used for calculating the rate law in terms of stable
species.
1. The highly reactive species are first selected in the mechanism.
2. The differential rate laws are thus written down for the highly reactive
intermediates.
3. The change in the concentrations of the intermediates with time is
assumed to be zero. Therefore, the differential rate laws of reactive
intermediates are put equal to zero and concentrations of reactive
species are calculated in terms of the stable species.
4. Steady state concentrations of the intermediate, calculated in step 3 is
substituted in the required expression to get the experimental rate law.

The steady state approximations can be successfully applied to the thermal

decomposition of N2O5 where all the steps proposed in the mechanism have
comparable rates.

3.5.1. Thermal decomposition of N2O5: The decomposition of dinitrogen

pentoxide is a first order gas reaction.
2N2O5 → 4NO2 + O2
which has the rate law
𝑑[𝑂2 ]
= 𝑘[𝑁2 𝑂5 ]
The following mechanism is given which gives the above rate law.

:
NO3 and NO molecules are reactive intermediates having small
concentrations. Their concentrations can be calculated by steady-state
approximations.
 39

𝑑[𝑁𝑂3 ]
= 0 = 𝑘1 [𝑁2 𝑂5 ] − 𝑘−1 [𝑁𝑂2 ][𝑁𝑂3 ] − 𝑘2 [𝑁𝑂2 ][𝑁𝑂3 ] − 𝑘3 [𝑁𝑂][𝑁𝑂3 ]
𝑑𝑡
or [𝑁𝑂3 ] = ….. (3.5.1)
𝑘−1 [𝑁𝑂2 ]+ 𝑘2 [𝑁𝑂2]+ 𝑘3 [𝑁𝑂]
𝑑[𝑁𝑂]
and = 0 = 𝑘2 [𝑁𝑂2 ][𝑁𝑂3 ] − 𝑘3 [𝑁𝑂][𝑁𝑂3 ]
𝑘2
[𝑁𝑂] = [𝑁𝑂2 ] ..… (3.5.2)
3
Substituting the value of [NO] in equation (3.5.1), we get
𝑘1 [𝑁 𝑂5 ]
[NO3 ] =
(𝑘−1 + 2𝑘2 )[𝑁𝑂2 ]
Now, the reaction rate is given by the rate of production of oxygen, hence
𝑑[𝑂2 ]
= k 2 [NO2 ] [NO3 ] ..… (3.5.3)
On substituting the value of [NO3] in equation (3.5.3), we obtain
𝑑[𝑂2 ] 𝑘 𝑘 [𝑁 𝑂 ] 𝑘 𝑘 [𝑁 𝑂 ]
= (𝑘 1 2 2 5 ] [𝑁𝑂2 ] = 𝑘 2 2 5 = 𝑘[𝑁2𝑂5 ]..… (3.5.4)
− ) 2 −

where 𝑘=𝑘
−1 + 2𝑘 2
Equation (3.5.4) is of the same form as the experimental rate law. It is
difficult to prove the existence of an intermediate. However, spectroscopic
studies and also the use of radioactive tracers can sometimes provide direct
proof. As intermediates are very unstable, ordinary analytical techniques
cannot be applied for their detection.
 40

Chapter-4

Chain reactions

4.1.Introduction: A chain reaction is one in which the products of the

reaction carry on the reaction as a part of reacting molecules and thus a long
series of self repeating steps is started.

4.2. Distinguishing Features of Chain Reaction or Characteristics of

Chain reaction:
(i) The rates of chain reactions are affected by exposure of the reaction
mixture to radiation of a certain wavelength. In this process, one of
the reactants might absorb a photon, for example, from incident sun
light which leads to dissociation.
(ii) The probability factor P of chain reactions is generally greater than
unity. That is, if the value of P is very large, the reaction chain may
occur.
(iii) Sometimes, the chain reactions possess very high speed, which may
lead to explosion. The transition from steady reaction rate to
explosion usually occurs when some parameters such as pressure or
composition is very abrupt.
(iv) In all non-chain processes, the highest rate is observed at the
beginning and the rate of reactants falls off with time. Whereas chain
reactions begin at zero rate. Then, it rises to maximum and then falls
off with time as shown in Figure 4.1. In Figure 4.1, curve 2 indicates
a very rapid increase of rate in which very high values are attained
which corresponding to an ignition. Such reaction system may
momentarily reach very high temperatures and possibly cause
explosion. Curve 3 represents a much slower chain reaction in which
the maximum rate is not reached until after a considerable time
interval, but the maximum rate is maintained for an appreciable
period before slowly falling off. Curve I represent a typical non
chain reaction.
(v) As the chain reactions begin at zero rate, it requires enough time so
that the rate of the reaction could be detected experimentally. This
time interval is called the induction period. This induction period
is regarded as the striking feature of chain reactions. In the oxidation
of hydrogen sensitized by NO2 or NOCl induction period of 2-3
minutes are observed during which no detectable pressure change
 41

occurs and after which either an explosion or a slow reaction may

occur.

Fig.4.1: Dependence of Rates of different reactions with time

(vi) The speed of chain reactions is retarded or accelerated by traces of

other substances. It may accelerate or retard the reaction. For
example, the rate of photosynthesis of phosgene is reduced
considerably by the presence of nitrosyl chloride.
(vii) The rate of chain reactions is affected by the material from which
the reaction vessel is made, its shape and the history. Generally, the
rate of chain reactions is reduced if the radius of the reaction vessel
is reduced. Under certain conditions, the rate of photochemical
reaction between hydrogen and chlorine is proportional to the square
of diameter of the cylindrical reaction vessel. At higher pressures,
those surface effects are much less marked and in some cases, a
chain reaction can not proceed in the absence of a surface.
(viii) Foreign gases which are chemically unchanged in a chain reacting
gas mixture often modify the reaction kinetics. At low pressures, the
action is frequently catalytic but at high pressures, they generally
exert a retarding action.
(ix) Generally, the chain reactions are rarely of simple order but have
integral orders which depend upon the vessel shape and other
experimental conditions.

4.3. Mechanism of Chain Reactions: Various mechanisms have been

suggested. Some of these are given below:
 42

4.3.1. Electron Mechanism: Bodensein, suggested this mechanism.

According to him, electrons act as chain carriers and are generated when
chlorine is exposed to light.
𝐶𝑙2 + ℎ𝑣 → 𝐶𝑙2+ + 𝑒 −
𝐶𝑙2 + 𝑒 − → 𝐶𝑙2−
𝐶𝑙2− + 𝐻2 → 2𝐻𝐶𝑙 + 𝑒 −
This mechanism could not be accepted because no ionization of chlorine was
detected when exposed to light.

4.3.2. Activation Mechanism: Again, this mechanism was suggested by

Bodenstein. According to him, chlorine molecules become activated when
exposed to light.
𝐶𝑙2 + ℎ𝑣 → 𝐶𝑙2∗
𝐶𝑙2∗ + 𝐻2 → 2𝐻𝐶𝑙∗
𝐻𝐶𝑙∗ + 𝐶𝑙2 → 𝐶𝑙2∗ + 𝐻𝐶𝑙
where * represent the activated substance.
In this mechanism, an activated molecule of hydrogen chloride can transfer
its energy to chlorine molecule but not to the hydrogen molecule. Thus, the
main draw back of this theory is that it could not explain transfer of energy
from hydrogen chloride to hydrogen.

4.3.3. Atoms and Radicals Mechanism: According to this theory, atoms and
radicals act as chain carries.
𝐶𝑙2 + ℎ𝑣 → 𝐶𝑙 + 𝐶𝑙
𝐶𝑙 + 𝐻2 → 𝐻𝐶𝑙 + 𝐻
𝐻 + 𝐶𝑙2 → 𝐻𝐶𝑙 + 𝐶𝑙
The presence of free atoms and free radicals in a reaction system can be
detected by various methods. So, this method is the most acceptable
mechanism.

4.4. Detection and Estimation of Atoms and Radicals in chain reactions:

The kinetics of a reaction can be studied by determining the
concentration of reactants and products. To study the kinetics of gas reactions,
atoms and radicals concentrations can be determined by the following
methods.

4.4.1. Metallic mirror method: In 1929, Paneth first detected the presence
of free radicals by metallic mirror technique by an apparatus shown in Figure
2. The method is based on the fact that the free radicals, such as CH3, C2H5
 43

etc., have tendency to form stable complexes with metals like Pb, As, Sb, Bi,
Hg and Zn etc.

Fig.4.2: Apparatus for metallic mirror method

The vapors from the liquid metals complex e.g., tetra methyl lead, are carried
over by an inert gas called carrier gas into a tube maintained at about 5000C,
at one position A by using a movable furnace. A lead mirror was formed near
A. When the furnace was moved to position B, a new mirror appeared near B
but that at A gradually disappeared. These observations were explained in the
following manner:
When first heating is done at A, the reaction
Pb(CH3)4 Pb + 4CH3
took place and the deposited lead formed a mirror. When heating was done at
B, the mirror formation was due to above reaction. The methyl radicals so
produced reacted with the mirror at A to tetra methyl lead, so mirror at A
disappeared. Later on, it was reported that even the vapors of acetaldehyde
when passed through the furnace could remove such metallic mirrors.

4.4.2. Spectroscopic Methods: Emission and absorption spectroscopy have

both been used for the detection and estimation of atoms and radicals in
reaction systems. When the reaction is accompanied by a flame, emission
spectra are used whereas absorption spectra are applied in studies using the
technique of flash photolysis, which yields very high concentrations of
radicals.
Indirect spectroscopic methods are also used for the identification of
radicals and atoms.
 44

4.4.3. Electron spin resonance spectroscopy: Atoms and free radicals,

which contain unpaired electrons, produce a splitting of energy levels in a
strong magnetic field. The atoms or radicals to be studied are introduced into
a quartz tube between the poles of a magnet, and at right angles to the broad
face of a waveguide. The power is provided by a magnetron or keystron. A
crystal detector is used to measure the absorption of radiation. Since the
intensity of absorption depends upon the number of unpaired electrons, the
method can be used for measuring radical concentrations. The region of
absorption varies for different species and hence the atoms and radicals can
be detected.

4.4.4. Mass spectrometry: This technique is used for the identification and
estimation of free radicals in reaction systems.

4.4.5. Trapping of free radicals: In this method, the reaction system is passed
over a surface that has been cooled, for example liquid air. The solid that
condenses is usually of vivid color, and then the technique like electron spin
spectroscopy (ESR), mass spectrometry etc. is used for the study. But, this
technique cannot be used for the determination of radical concentrations.

4.4.6. Chemical Methods: Various methods for the detection and estimation
of atoms and free radicals are based upon their high chemical reactivity. For
example, the introduction of metallic oxide into reaction system has been used
for the detection of hydrogen atoms. Hydrogen atom concentration can be
determined by introducing para-hydrogen into the reaction system and
following the rate of the reaction.
𝐻 + 𝑝 − 𝐻2 → 𝑜 − 𝐻2 + 𝐻
This method has disadvantage because the conversion is also catalyzed
by paramagnetic substances such as other radicals that may be present in the
reaction system.

4.5. Kinetics of Chain Reactions: There are approaches to the problem of

the mathematical representation of chain reactions.

4.5.1. Non steady Treatment: This method involves high mathematical

equations which are highly complicated.

4.5.2. Steady Treatment: According to this treatment, the concentration of a

free radical of intermediate or chain carrier is constant at any instant,
 45

𝑑 [𝑅 ]
=0
𝑑𝑡
where R is the free radical or intermediate or a chain carrier.
In all chain reactions, there is an initial slow step which gives rise to
active species which carry out subsequent steps. These active species are
called chain carriers and the initial reaction itself is called chain initiation step.
(i) 𝑀 →𝑅 𝑐ℎ𝑎𝑖𝑛 𝑖𝑛𝑖𝑡𝑖𝑎𝑡𝑖𝑜𝑛 𝑠𝑡𝑒𝑝
In the subsequent step or steps the chain carriers, formed in chain
initiation steps, react with other reacting substances to form intermediate
steps. These are called chain propagation or branching steps. In some cases,
new chain carriers are generated. These steps are called chain transfer steps.
(ii) 𝑀 + 𝑅 → 𝛼𝑅 + 𝑀/ 𝐵𝑟𝑎𝑛𝑐ℎ𝑖𝑛𝑔 𝑐ℎ𝑎𝑖𝑛 𝑠𝑡𝑒𝑝
α is the number of chain carriers formed from each R in propagation
step.
In the end when there are not enough molecules of reactants to be
converted to reaction products, active chain carriers are converted to non-
active molecular species. These steps are termed as chain termination steps.
(iii) 𝑅 + 𝑀 → 𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠
(iv) 𝑅 → 𝐷𝑒𝑠𝑡𝑟𝑢𝑐𝑡𝑖𝑜𝑛 𝑎𝑡 𝑠𝑢𝑟𝑓𝑎𝑐𝑒
(v) 𝑅 → 𝐷𝑒𝑠𝑡𝑟𝑢𝑐𝑡𝑖𝑜𝑛 𝑖𝑛 𝑔𝑎𝑠 𝑝ℎ𝑎𝑠𝑒
The chain carriers may be destroyed in two ways, either by colliding to the
walls of the vessel or by direct collision with other radicals within the gaseous
phase.
Applying the steady-state treatment to the radical R, we get:
𝑑𝑅
= 𝑘1 [𝑀] + 𝑘2 [𝛼 − 1][𝑅][𝑀] − 𝑘3 [𝑅][𝑀] − 𝑘4 [𝑅] − 𝑘5 [𝑅] = 0
𝑑𝑡
+
or [𝑅] = 𝑘 [𝑀] [𝑘 +𝑘 ]−𝑘 [𝛼−1][𝑀] …..(4.5.1)
3 4 5 2
The overall rate of the reaction is given by step (iii)
𝑣 = 𝑘3 [𝑅][𝑀] …..(4.5.2)
Substituting the value of [R] from equation (4.5.1) in equation (4.5.2), we
obtain
𝑣=𝑘 …..(4.5.3)
3 [𝑀]++[𝑘 4+𝑘 5 ]−𝑘 2 [𝛼−1][𝑀]

Chain Length: It is defined as the rate of the over-all reaction divided by the
rate of the initiation reaction.
 46

𝑅𝑎𝑡𝑒 𝑜𝑓 𝑜𝑣𝑒𝑟𝑎𝑙𝑙 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛

𝑐ℎ𝑎𝑖𝑛 𝑙𝑒𝑛𝑔𝑡ℎ =
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑐ℎ𝑎𝑖𝑛 𝑖𝑛𝑖𝑡𝑖𝑎𝑡𝑖𝑜𝑛 𝑠𝑡𝑒𝑝
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑖𝑛𝑖𝑡𝑖𝑎𝑡𝑖𝑜𝑛 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛(𝑖) = 𝑘1 [𝑀]
𝑇ℎ𝑒 𝑅𝑎𝑡𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑜𝑣𝑒𝑟𝑎𝑙𝑙 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 = 𝑣
where 𝑣=𝑘
3 [𝑀]++[𝑘 4 +𝑘 5 ]−𝑘 2 [𝛼−1][𝑀]
−
Therefore, 𝑐ℎ𝑎𝑖𝑛 𝑙𝑒𝑛𝑔𝑡ℎ = = …..(4.5.4)
𝑘1 [𝑀] 𝑘3 [𝑀]++[𝑘4 +𝑘5 ]−𝑘2 [𝛼 1][𝑀]
The reactions with slow termination steps possess long chain lengths
and these reactions become very fast in forming the products of the reaction.
For example, the hydrogen and chlorine combination reaction possesses a
chain length of 106.

4.6. Example of the Steady-State Treatment

4.6.1. Inorganic Reactions:

(a) Decomposition of ozone: The decomposition of ozone in the presence of

excess of oxygen was reported to be of second-order.
The mechanism for this decomposition is as follows:
(i) 𝑂3 ↔ 𝑂2 + 𝑂
The rate constants for forward and backward reactions are given by k 1
and k2 respectively. This is fast step.
(ii) 𝑂 + 𝑂3 → 2𝑂2
where k3 is the rate constant for this reaction. This second step is slow step so
it is rate determining step.
𝑑[𝑂3 ]
Thus, 𝑟𝑎𝑡𝑒 = − = 𝑘3 [𝑂][𝑂3 ] ……….(4.6.1)
From first step,
[𝑂][𝑂2 ]
𝐾𝑒𝑞 =
[𝑂3 ]
[𝑂3 ]
or [𝑂] = 𝐾𝑒𝑞 [𝑂 ] ………(4.6.2)
2
Substituting the value of [O] in equation (4.6.1) gives,
𝑑[𝑂3 ] [𝑂3 ]
− = 𝑘3 [𝑂][𝑂3 ] = 𝑘3 𝐾 𝑞 [𝑂3 ]
𝑑𝑡 [𝑂2 ]
𝑑[𝑂3] [𝑂3 ]2
or − =𝑘 …….(4.6.3)
2
 47

Thus, the rate is inversely proportional to the oxygen concentration

when sufficient oxygen is present, and is of second-order behavior when
oxygen is present in small concentration.

(b) Thermal Reaction between Hydrogen and Bromine: It was observed that
the reaction between hydrogen and bromine was not a simple bimolecular
process but the rate of such reaction can be expressed by the following
complicated empirical equation.
𝑑[𝐻𝐵𝑟] 𝑘[𝐻 ][𝐵𝑟 ]1/2
−= 2 2 …..(4.6.4)
[ 𝑟]
1+ 𝑚[𝐵𝑟
2]
where k and m are constants.
This reaction is initiated by the dissociation of bromine molecule to
atoms.
Chain initiation: (i)𝐵𝑟2 → 2𝐵𝑟
The dissociation is taking place to a small extent.
Chain propagation: The initiation reaction (i) is followed by a slow reaction.
(ii) 𝐵𝑟 + 𝐻2 → 𝐻𝐵𝑟 + 𝐻
and the rapid reaction (iii) 𝐻 + 𝐵𝑟2 → 𝐻𝐵𝑟 + 𝐵𝑟
Chain Inhibition: (iv) 𝐻 + 𝐻𝐵𝑟 → 𝐵𝑟 + 𝐻2
Chain breaking: (v) 𝐵𝑟 + 𝐵𝑟 → 𝐵𝑟2
The k1, k2, k3, k4 and k5 represents the specific rates of all the five reactions.
In this mechanism, the rate of formation of HBr is given by steps (ii) and
(iii). Hence,
𝑑[𝐻𝐵𝑟]
= 𝑘2 [𝐻2 ][𝐵𝑟] + 𝑘3 [𝐻][𝐵𝑟2 ]
𝑑𝑡
The rate of consumption of HBr is given by step (iv) as:
−𝑑[𝐻𝐵𝑟]
= 𝑘4 [𝐻][𝐻𝐵𝑟]
𝑑𝑡
Therefore, the net rate of formation of HBr will be given by,
𝑑[𝐻𝐵𝑟]
= 𝑘2 [𝐻2 ][𝐵𝑟] + 𝑘3 [𝐻][𝐵𝑟2] − 𝑘4 [𝐻][𝐻𝐵𝑟] …..(4.6.5)
The steady state equation for [H] and [Br] are
𝑑[𝐻]
= 𝑘2 [𝐻2 ][𝐵𝑟] − 𝑘3 [𝐻][𝐵𝑟2] − 𝑘4 [𝐻][𝐻𝐵𝑟] …..(4.6.6)
𝑑[𝐵𝑟]
= 2𝑘1 [𝐵𝑟2] − 𝑘2 [𝐻2 ][𝐵𝑟] + 𝑘3 [𝐻][𝐵𝑟2] + 𝑘4 [𝐻][𝐻𝐵𝑟] − 2𝑘5 [𝐵𝑟]2 …..(4.6.7)
As the concentrations of hydrogen and bromine atoms are relatively small,
it is, assumed that a stationary state is reached soon after the reaction has
 48

started. Therefore, the time derivative of atom concentration can be taken to

be zero over a short interval of time. It means,
𝑑[𝐻] 𝑑[𝐵𝑟]
=0 and =0
Applying this condition of stationary states to equations (4.6.6) and (4.6.7),
we get
𝑘3 [𝐻][𝐵𝑟2] + 𝑘4 [𝐻][𝐻𝐵𝑟] − 𝑘2 [𝐵𝑟][𝐻2 ] = 0 …..(4.6.8)
and 2𝑘1 [𝐵𝑟2] + 𝑘3 [𝐻][𝐵𝑟2] + 𝑘4 [𝐻][𝐻𝐵𝑟] − 2𝑘5 [𝐵𝑟]2 − 𝑘2 [𝐵𝑟][𝐻2 ] = 0 ..(4.6.9)
Equations (4.6.8) and (4.6.9) can be written as:
𝑘2 [𝐵𝑟][𝐻2 ] = 𝑘3 [𝐻][𝐵𝑟2 ] + 𝑘4 [𝐻][𝐻𝐵𝑟] …..(4.6.10)
𝑘2 [𝐵𝑟][𝐻2 ] = 2𝑘1 [𝐵𝑟 ] + 𝑘3 [𝐻][𝐵𝑟 ] + 𝑘4 [𝐻][𝐻𝐵𝑟] − 2𝑘5 [𝐵𝑟]2 …..(4.6.11)
2 2
Subtracting equation (4.6.10) from (4.6.11), we get
2𝑘1 [𝐵𝑟2 ] = 2𝑘5 [𝐵𝑟]2
1⁄
2 𝑘1 𝑘1 2 1⁄
or [𝐵𝑟] = [𝐵𝑟 ] or [𝐵𝑟] = ( ) [𝐵𝑟 ] 2 …..(4.6.12)
5 5
Substituting the value of [Br] from (4.6.12) in (4.6.10) we obtain
1⁄
2
𝑘2 (𝑘 ) [𝐵𝑟 ] 2 [𝐻2 ] − 𝑘3 [𝐻][𝐵𝑟 ] = 𝑘4 [𝐻][𝐻𝐵𝑟]
5 1
⁄2
or 𝑘2 ( ) [𝐵𝑟 ] [𝐻2 ] = [𝐻](𝑘3 [𝐵𝑟 ] + 𝑘4 [𝐻𝐵𝑟])
𝑘5 1⁄
𝑘1 2 1⁄
𝑘 ( ) [𝐵𝑟 ] 2[𝐻 ]
or [𝐻] = …..(4.6.13)
𝑘3 [𝐵𝑟2 ]+𝑘4 [𝐻𝐵𝑟]
Inserting the values of [H] and [Br] from equation (4.6.13) and (4.6.12)
in equation (4.6.5), we obtain the rate expression for the formation of
hydrogen bromide which is given by: 1 1
𝑘 ⁄2 1 𝑘 ⁄2 1
1⁄ 𝑘 ( 1 ) [𝐵𝑟 ] ⁄2 [𝐻 ] 𝑘 ( 1 ) [𝐵𝑟 ] ⁄2 [𝐻 ]
[ ] ⁄
𝑑𝑡
= 𝑘2 (𝑘 ) [𝐵𝑟 ] 2 [𝐻2] + 𝑘3 𝑘3 [𝐵𝑟 ]+𝑘4 [𝐻𝐵𝑟]
[𝐵𝑟 ] − 𝑘4 𝑘3 [𝐵𝑟 ]+𝑘4 [𝐻𝐵𝑟]
[𝐻𝐵𝑟]
5 1
𝑑[𝐻𝐵𝑟] 𝑘1 ⁄2 1⁄ 𝑘3[𝐵𝑟2] 𝑘4[𝐻𝐵𝑟]
or = 𝑘2 𝑟2 ] [ 2
] 1
𝑑𝑡 𝑘5 𝑘3[𝐵𝑟2]+𝑘4[𝐻𝐵𝑟] 𝑘3[𝐵𝑟2]+𝑘4[𝐻𝐵𝑟]3
1
𝑑[𝐻𝐵𝑟] 𝑘1 ⁄2 1 2𝑘 [𝐵𝑟 ]
𝑟2 ] ⁄ [ 2 ] 3 2
or 𝑑𝑡
= 𝑘2
𝑘5
𝑘3[𝐵𝑟2 ]+𝑘4 [𝐻𝐵𝑟]
Divide upper and lower terms by k3[Br2]
𝑘1 1⁄2 1
⁄
𝑑[𝐻𝐵𝑟] 2𝑘 2 ( ) [𝐵𝑟 2 ] 2 [𝐻2 ]
𝑘
=
𝑑𝑡 𝑘3 [𝐵𝑟 ] + 𝑘4 [𝐻𝐵𝑟]
𝑘3 [𝐵𝑟2 ]
1⁄
𝑘1 2 ⁄
𝑑[𝐻𝐵𝑟] ( ) [𝐻2 ]
or = 2𝑘2 𝑘 4 [𝐻𝐵𝑟] …..(4.6.14)
𝑘 3 [𝐵𝑟 2 ]
This equation is identical with the empirical equation (4.6.4).
 49

𝑅𝑎𝑡𝑒 𝑜𝑓 𝑜𝑣𝑒𝑟𝑎𝑙𝑙 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛

𝐶ℎ𝑎𝑖𝑛 𝑙𝑒𝑛𝑔𝑡ℎ =
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑖𝑛𝑖𝑡𝑖𝑎𝑡𝑖𝑜𝑛 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛
1
𝑘1 ⁄2 1
( ) [𝐵𝑟2] ⁄2 [𝐻2 ]
𝑘 1
𝐶ℎ𝑎𝑖𝑛 𝑙𝑒𝑛𝑔𝑡ℎ = 2𝑘2 5 𝑘 [𝐻𝐵𝑟]
𝑥
𝑘1 [𝐵𝑟2 ]
1+ 4
𝑘3 [𝐵𝑟2 ]
1 ⁄2
𝑘
2𝑘 ( 1 ) [𝐻 ]
or 𝐶ℎ𝑎𝑖𝑛 𝑙𝑒𝑛𝑔𝑡ℎ = 𝑘 [𝐻𝐵𝑟] 1
𝑘1 1+ 4 𝐵𝑟 2 ⁄2
𝑘 [𝐵𝑟 ]3 2

(c) Photochemical combination of hydrogen and bromine: The

photochemical combination of hydrogen and bromine is similar to the thermal
reaction discussed above. The initial reaction is brought about by light.
(i) 𝐵𝑟2 + ℎ𝑣 → 2𝐵𝑟
The rest part of the mechanism is similar to the thermal reactions.
(ii) 𝐵𝑟 + 𝐻2 → 𝐻𝐵𝑟 + 𝐻
(iii) 𝐵𝑟2 + 𝐻 → 𝐻𝐵𝑟 + 𝐵𝑟
(iv) 𝐻𝐵𝑟 + 𝐻 → 𝐻2 + 𝐵𝑟
(v) 𝐵𝑟 + 𝐵𝑟 → 𝐵𝑟2
From these equations, one can derive an equation analogous to equation
(11)
1⁄
2 ⁄
𝑑[𝐻𝐵𝑟] (𝑘 ) 𝑎 [𝐻2 ]
= 2𝑘2 5
𝑘 [𝐻𝐵𝑟] …..(4.6.15)
𝑘 3 [𝐵𝑟 2 ]
where Iabs is the intensity of radiation. This equation agrees with the
experimental data.

(d) Photochemical reaction of Hydrogen and Chlorine: The special

features of this reaction are:
(i) In case of hydrogen-bromine reaction, the quantum yield is less than
unity. But in the case of hydrogen-chlorine reaction, the quantum
yield is as high as 106.
(ii) The effect of oxygen affects the reaction after it has started. It is
found that the reaction is inversely proportional to the concentration
of oxygen.
(iii) The proposed equation for the rate of this reaction is as follows:
𝑑[𝐻𝐶𝑙] 𝑘𝐼[𝐻 [𝐶𝑙2 ]
= [𝑂 [
…..(4.6.16)
2 10
 50

where I is the intensity of light absorbed. This equation (4.6.16) implies

that the rate of the reaction would become infinite in absence of oxygen.
This equation holds good for an oxygen pressure above 0.04 mm. A more
accurate equation was later given as:
𝑑[𝐻𝐶𝑙] 𝑘𝐼[𝐻 ][𝐶𝑙 ]
= 𝑀[𝐶𝑙 ]+[𝑂 2][𝐻 ]+𝑁[𝐶𝑙
𝑑𝑡
2
…..(4.6.17)
2 2 2 2]
At very low pressure, equation (4.6.17) becomes:
𝑑[𝐻𝐶𝑙] 𝑘𝐼
= [𝐻2 ] …..(4.6.18)
Later on, Gobring gave the correct mechanism, which is:
(i) 𝐶𝑙2 + ℎ𝑣 → 2𝐶𝑙 Chain initiation
(ii) 𝐶𝑙 + 𝐻2 → 𝐻𝐶𝑙 + 𝐻
(iii) 𝐶𝑙2 + 𝐻 → 𝐻𝐶𝑙 + 𝐶𝑙
Reactions (ii) and (iii) are chain propagation
(iv) 𝐻 + 𝑂2 → 𝐻𝑂2
(v) 𝐶𝑙 + 𝑂2 → 𝐶𝑙𝑂2
(vi) 𝐶𝑙 + 𝑋 → 𝐶𝑙𝑋
Reactions (iv), (v) and (vi) are chain termination. In step (vi), X is any
substance which removes chlorine atoms.
Applying the steady state treatment to chlorine atoms, we get,
𝑑[𝐶𝑙]
= 2𝐼 − 𝑘2 [𝐶𝑙][𝐻2 ] + 𝑘3 [𝐻][𝐶𝑙2 ] − 𝑘5 [𝐶𝑙][𝑂2 ] − 𝑘6 [𝐶𝑙][𝑋] = 0…..(4.6.19)
This equation is simplified to,
2𝐼+𝑘3 [𝐻][𝐶𝑙2 ]
[𝐶𝑙] = …..(4.6.20)
𝑘2 𝐻 2 +𝑘5 𝑂 2 +𝑘6 𝑋
The rate of formation of hydrogen atom is given by,
𝑑[𝐻]
= 𝑘2 [𝐶𝑙][𝐻2 ] − 𝑘3 [𝐻][𝐶𝑙2 ] − 𝑘4 [𝐻][𝑂2 ] = 0…..(4.6.21)
𝑘3 [𝐻][𝐶𝑙2 ]+𝑘4 [𝐻][𝑂 2]
or [𝐶𝑙] = …..(4.6.22)
𝑘2 𝐻 2
By equating equations (4.6.20) and (4.6.22), we get,
𝑘2 [𝐻2 ](2𝐼 + 𝑘3 [𝐻][𝐶𝑙2 ]) = (𝑘2 [𝐻2 ] + 𝑘5 [𝑂2 ] + 𝑘6 [𝑋])(𝑘3 [𝐻][𝐶𝑙2 ] + 𝑘4 [𝐻][𝑂2 ])
…… (4.6.23)
2
If small term k4k5[H][O2] is neglected, equation (4.6.23) is simplified to:
[𝐻] = [𝐶𝑙 ][𝑋]+[𝑂 ][𝑘 [𝐻 ]+𝑘 [𝐶𝑙 ]+𝑘 [𝑋]]
…..(4.6.24)
𝑘3 𝑘6 2 2 2 𝑘4 2 3 𝑘5 2 4 𝑘6

The rate of formation of hydrogen chloride is given by step (iii).

𝑑[𝐻𝐶𝑙]
= 𝑘3 [𝐻][𝐶𝑙2 ] …..(4.6.25)
 51

Substituting the value of [H] from equation (4.6.24) in equation (4.6.25), we

get

𝑑[𝐻𝐶𝑙] 2𝐼𝑘2 𝑘3 [𝐻2 ][𝐶𝑙2 ]

𝑑𝑡
=𝑘 …..(4.6.26)
3 𝑘6 [𝐶𝑙2 ][𝑋]+[𝑂2 ][𝑘 2𝑘 4 [𝐻2 ]+𝑘 3 𝑘 5 [𝐶𝑙2 ]+𝑘 4 𝑘6 [𝑋]]

Dividing each term of equation (4.6.26) by k2k4 gives,

𝑑[𝐻𝐶𝑙] [2𝑘3 ⁄𝑘4 ]𝐼[𝐻2 ][𝐶𝑙2 ]

𝑑𝑡 = 𝑘3 𝑘 6 𝑘3 𝑘5 𝑘6 …..(4.6.27)
[𝐶𝑙 ][𝑋]+[𝑂 ][[𝐻 ]+ [𝐶𝑙 ]+ [𝑋]]
2 4 2 4 2
If last term of denominator (k6[X]/k2) is neglected and if
2𝑘3 [𝑋]𝑘3 𝑘6 𝑘3 𝑘6
𝑘= , 𝑀= , 𝑁=
𝑘4 𝑘2 𝑘4 𝑘2 𝑘4
Then, equation (4.6.27) becomes:
𝑑[𝐻𝐶𝑙] 𝑘𝐼[𝐻2 ][𝐶𝑙2 ]
𝑑𝑡
= 𝑀[𝐶𝑙 ]+[𝑂 ][𝐻 ]+𝑁[𝐶𝑙 ]
…..(4.6.28)
2 2 2 2
which is similar to equation (4.6.17).

Thermal reaction of Hydrogen and Chlorine: Thermal reaction takes place

above 2000C. If its mechanism is similar to photochemical reaction, then the
rate of reaction is derived in an analogous manner to give
𝑑[ 𝑙] ′ 𝑙
= …..(4.6.29)
𝑑𝑡 𝑚′ [𝐶𝑙 2 +[𝑂2 ]]([𝐻2 ]+𝑘
′′ [𝐶𝑙
2 ])
The difference between the two expressions (4.6.27) and (4.6.29) is that
2I is replaced by [Cl2]2 in equation (4.6.29). This change is due to the initiation
reaction which is
𝐶𝑙2 + 𝑋 → 2𝐶𝑙 + 𝑋
X can be any part of the surface of vessels.
As vessels can be of different shapes and sizes, surfaces can be of
different types. So, different results are obtained. Thus, thermal reactions are
complicated because initial decomposition of chlorine molecule may take
place on the surface.

4.6.2. Organic Decomposition: Most of the decomposition reactions organic

compounds follow simple kinetic laws. In decomposition of organic
substances, free radicals play an important role. It was assumed that the
initiating reactions are first order processes. If the reactions are in second-
order region under ordinary experimental decompositions, then the over-all
order will change.
 52

Following are some examples, in which over-all rate may be unit, one-
half or three-halves.

(i) First order kinetics:

The decomposition of ethane into ethylene and hydrogen is an example
of this case where over-all order of unity. It is assumed that (i) the initiating
reaction is of first order and (ii) the chain-terminating step is a reaction
between an ethyl radical and an hydrogen atom.
The mechanism for this is
(i) 𝐶2 𝐻6 → 2𝐶𝐻3 ∙
(ii) 𝐶𝐻3 ∙ + 𝐶2 𝐻6 → 𝐶𝐻4 + 𝐶2 𝐻5 ∙
(iii) 𝐶2 𝐻5 ∙ → 𝐶2 𝐻4 + 𝐻.
(iv) 𝐻 . + 𝐶2 𝐻6 → 𝐶2 𝐻5 ∙ + 𝐻2
(v) 𝐻 . + 𝐶2 𝐻5 ∙ → 𝐶2 𝐻6

The steady state equations for methyl radicals and for hydrogen atoms
are
𝑑[𝐶𝐻3 ∙ ]
= 2 𝑘1 [𝐶2 𝐻6 ] − 𝑘2 [𝐶𝐻3 ∙ ][𝐶2 𝐻6 ] = 0 …..(4.6.30)
𝑑[𝐶2 𝐻5 ∙]
= 𝑘2 [𝐶𝐻3 ∙ ][𝐶2 𝐻5 ∙ ] − 𝑘3 [𝐶2 𝐻5 ∙ ] − 𝑘4 [𝐻. ][𝐶2 𝐻6 ] − 𝑘5 [𝐻. ][𝐶2 𝐻5∙ ] = 0 …..(4.6.31)
𝑑 ]
= 𝑘3 [𝐶2 𝐻5 ∙ ] − 𝑘4 [𝐻 . ][𝐶2 𝐻6 ] − 𝑘5 [𝐻. ][𝐶2 𝐻5 ∙ ] = 0 …..(4.6.32)
𝑑𝑡
By adding equations (4.6.31), (4.6.32) and (4.6.33), we obtain,
𝑘5 [𝐻. ][𝐶2 𝐻5 ∙ ] = 𝑘1 [𝐶2 𝐻6 ]
𝑘 [𝐶 𝐻 ]
[𝐻] = 1 2 6∙ …..(4.6. 33)
5 2 5
Substituting this value of [H] in equation (4.6.32), we get
𝑘 𝑘4 [𝐶 𝐻 ] 𝑘 [𝐶 𝐻 ]
𝑘3 [𝐶2 𝐻5 ∙ ] − − 𝑘5 [𝐶2 𝐻5 ∙ ] = 0
𝑘5 [𝐶2 𝐻5 ]
1 2 6 𝑘5 [𝐶2 𝐻5 ]
1 2 6

or 𝑘5 𝑘3 [𝐶2 𝐻5 ]2 − 𝑘1 𝑘4 [𝐶2 𝐻6 ]2 − 𝑘1 𝑘5 [𝐶2 𝐻6 ][𝐶2 𝐻5 ] = 0…..(4.6.34)

Rearranging equation (4.6.34), we get,
𝑘3 𝑘5 [𝐶2 𝐻5 ∙ ]2 − 𝑘1 𝑘5 [𝐶2 𝐻6 ][𝐶2 𝐻5 ∙ ] − 𝑘1 𝑘4 [𝐶2 𝐻6 ]2 = 0…..(4.6.35)
By solving this quadratic equation, we get
𝑘 2
2 ∙ 2 2 1⁄
∙ (𝑘 1 𝑘 [𝐶2 𝐻5 ] + 4𝑘1 𝑘3 𝑘4 𝑘5 [𝐶2 𝐻6 ] ) 2
[𝐶2 𝐻5 ] = 1 𝑘5 [𝐶2 𝐻6 ] ± 2𝑘 𝑘
3 5
2 1⁄
𝑘1 𝑘5 𝑘1 𝑘 4𝑘 𝑘3 𝑘4 𝑘5 2
or [𝐶2 𝐻5 ∙ ] = [ ±( 2 + ) ] [𝐶2 𝐻6 ] …..(4.6.36)
4
 53

1⁄
2
or [𝐶2 𝐻5 ∙ ] = [ ±( + ) ] [𝐶2 𝐻6 ] …..(4.6.37)
2𝑘3 2𝑘2 𝑘3 𝑘 5
As the initiating reaction (i) has very high activation energy, so the
constant k1 is very small. So, the term (k1/2k3) can be neglected in comparison
with (k1k4/k3k5). Therefore, equation (4.6.37) becomes,
1⁄
∙ 𝑘1 𝑘4 2
[𝐶2 𝐻5 ] = ( ) [𝐶2 𝐻6 ] …..(4.6.38)
𝑘3𝑘 5
From step (iii) of the reaction mixture, the rate of production of ethylene
is given by
𝑑[𝐶2 𝐻4 ]
= 𝑘3 [𝐶2 𝐻5 ] …..(4.6.39)
Substituting the value of [C2H5] from equation (4.6.38) in equation
(4.6.39), we obtain
1⁄
𝑑[𝐶2 𝐻4 ] 𝑘1 𝑘3 𝑘4 2
=( ) [𝐶2 𝐻6 ] …..(4.6.39)
5
Therefore, the reaction is of first order.
Chain length of a reaction is defined as:
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑜𝑣𝑒𝑟𝑎𝑙𝑙 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛
𝐶ℎ𝑎𝑖𝑛 𝑙𝑒𝑛𝑔𝑡ℎ =
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑖𝑛𝑖𝑡𝑖𝑎𝑡𝑖𝑜𝑛 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛
1⁄
𝑘1 𝑘 3 𝑘 4 2
( ) [𝐶 𝐻 ] 1
2 6 𝑘3 𝑘4
𝐶ℎ𝑎𝑖𝑛 𝑙𝑒𝑛𝑔𝑡ℎ = 5
=( ) …..(4.6.40)
1 2 6 1 5

(ii) Three-halves Order Kinetics: An example for this is the decomposition

of acetaldehyde. To explain three-halves order of this reaction, it is assumed
that
(i) The initiation is of first order.
(ii) The chain terminating step is of a second-order reaction between
two radicals which will undergo a second-order propagation
reactions.
The proposed mechanism is:
(i) 𝐶𝐻3 𝐶𝐻𝑂 → 𝐶𝐻3 + 𝐶𝐻𝑂
(ii) 𝐶𝐻3 + 𝐶𝐻3 𝐶𝐻𝑂 → 𝐶𝐻3 𝐶𝑂
(iii) 𝐶𝐻3 𝐶𝑂 → 𝐶𝐻3 + 𝐶𝑂
(iv) 2𝐶𝐻3 → 𝐶2 𝐻6
The further reactions of radical CHO is ignored to avoid further
complications.
 54

The steady-state equation for the methyl and CH3CO radicals are given
by:
𝑑[𝐶𝐻3 ]
= 𝑘1 [𝐶𝐻3𝐶𝐻𝑂] − 𝑘2 [𝐶𝐻3 ][𝐶𝐻3𝐶𝐻𝑂] + 𝑘3 [𝐶𝐻3 𝐶𝑂] − 𝑘4 [𝐶𝐻3 ]2 = 0 …..(4.6.41)
𝑑[𝐶𝐻 𝐶𝑂]
and = 𝑘2 [𝐶𝐻3 ][𝐶𝐻3 𝐶𝐻𝑂] − 𝑘3 [𝐶𝐻3 𝐶𝑂] = 0 …..(4.6.42)
𝑡
By adding equations (4.6.41) and (4.6.42), we get
𝑘1 [𝐶𝐻3 𝐶𝐻𝑂] − 𝑘4 [𝐶𝐻3 ] 2 = 0
or 𝑘4 [𝐶𝐻3 ]2 = 𝑘1 [𝐶𝐻3 𝐶𝐻𝑂]
𝑘
or [𝐶𝐻3 ]2 = 1 [𝐶𝐻3 𝐶𝐻𝑂]
4
1
1
or [𝐶𝐻3 ] = (𝑘1) [𝐶𝐻3 𝐶𝐻𝑂] ⁄2 ……(4.6.43)
4
The rate of formation of methane is given by step (ii) of reaction mechanism.
This is
𝑑[𝐶𝐻4 ]
= 𝑘2 [𝐶𝐻3 ][𝐶𝐻3 𝐶𝐻𝑂] …..(4.6.44)
Substituting the value of [CH3] from equation (4.6.43) in equation (4.6.44),
we get
1
𝑑[𝐶𝐻4 ] 𝑘 1 ⁄2 1
= 𝑘2 ( ) [𝐶𝐻3 𝐶𝐻𝑂] ⁄2 [𝐶𝐻3 𝐶𝐻𝑂]
𝑑𝑡 𝑘4
1
𝑑[𝐶𝐻4 ] 3
or = 𝑘 2 ( 1) [𝐶𝐻3 𝐶𝐻𝑂] ⁄2 …..(4.6.45)
4
Thus, the reaction is of three-halves order.
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑜𝑣𝑒𝑟𝑎𝑙𝑙 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛
𝐶ℎ𝑎𝑖𝑛 𝑙𝑒𝑛𝑔𝑡ℎ =
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑡ℎ𝑒1 𝑖𝑛𝑖𝑡𝑖𝑎𝑡𝑖𝑜𝑛 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛
𝑘 ⁄2 3
𝑘 ( 1) [𝐶𝐻 𝐶𝐻𝑂] ⁄2
2 3
𝐶ℎ𝑎𝑖𝑛 𝑙𝑒𝑛𝑔𝑡ℎ = 𝑘1 [𝐶𝐻3 𝐶𝐻𝑂]
=
1⁄
1 2 1
𝑘2 ( ) [𝐶𝐻3 𝐶𝐻𝑂] ⁄2 …..(4.6.46)
1 4

(iii) One-half Order Kinetics: In order to explain the one-half order of

reaction, it is assumed that
(i) The initiation is of first order.
(ii) The chain terminating step is of a second-order reaction between
two radicals which will undergo first-order propagation reactions.
Therefore, the hypothetical scheme for the decomposition of acetaldehyde can
be written as:
(i) 𝐶𝐻3 𝐶𝐻𝑂 → 𝐶𝐻3 + 𝐶𝐻𝑂
(ii) 𝐶𝐻3 + 𝐶𝐻3 𝐶𝐻𝑂 → 𝐶𝐻4 + 𝐶𝐻3 𝐶𝑂
 55

(iii) 𝐶𝐻3 𝐶𝑂 → 𝐶𝐻3 + 𝐶𝑂

(iv) 2𝐶𝐻3 𝐶𝑂 → 𝐶𝐻3 𝐶𝑂𝐶𝑂𝐶𝐻3
The steady-state equation for the methyl and CH3CO radicals are given
by:
𝑑[𝐶𝐻3 ]
= 𝑘1 [𝐶𝐻3 𝐶𝐻𝑂] − 𝑘2 [𝐶𝐻3 ][𝐶𝐻3 𝐶𝐻𝑂] + 𝑘3 [𝐶𝐻3 𝐶𝑂] = 0 …..(4.6.47)
𝑑[𝐶𝐻 𝐶𝑂]
and = 𝑘2 [𝐶𝐻3 ][𝐶𝐻3 𝐶𝐻𝑂] − 𝑘3 [𝐶𝐻3 𝐶𝑂] − 𝑘4 [𝐶𝐻3 𝐶𝑂]2 = 0 …..(4.6.48)
𝑡
Addition of equations (4.6.47) and (4.6.48), we get
1⁄
𝑘1 2 1
or [𝐶𝐻3 𝐶𝑂] = ( ) [𝐶𝐻3 𝐶𝐻𝑂] ⁄2 ……(4.6.49)
4
The rate of formation of carbon mono oxide is given by:
𝑑[𝐶𝑂]
= 𝑘3 [𝐶𝐻3 𝐶𝑂] …..(4.6.50)
Substituting the value of [CH3CO] from equation (4.6.49) in equation
(50), we get
1
𝑑[𝐶𝑂] 1
= 𝑘3 ( 𝑘 ) 1
[𝐶𝐻3 𝐶𝐻𝑂] ⁄2 …..(4.6.51)
4
Thus, the reaction is of one-half order.
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑜𝑣𝑒𝑟𝑎𝑙𝑙 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛
𝐶ℎ𝑎𝑖𝑛 𝑙𝑒𝑛𝑔𝑡ℎ =
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑖𝑛𝑖𝑡𝑖𝑎𝑡𝑖𝑜𝑛 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛
⁄ 1⁄
𝑘3 ( ) [𝐶𝐻3 𝐶𝐻𝑂] 2 1⁄
2 1⁄
𝐶ℎ𝑎𝑖𝑛 𝑙𝑒𝑛𝑔𝑡ℎ = 𝑘4
[𝐶
= 𝑘3 ( ) [𝐶𝐻3 𝐶𝐻𝑂]− 2 …..(4.6.52)
𝑘4

(iv) Decomposition of butane: The mechanism for this reaction is:

(i) 𝐶4 𝐻10 → 𝐶𝐻3 + 𝐶3 𝐻7
(ii) 𝐶𝐻3 + 𝐶4 𝐻10 → 𝐶𝐻4 + 𝐶4 𝐻9
(iii) 𝐶4 𝐻9 → 𝐶𝐻3 + 𝐶3 𝐻7
(iv) 2𝐶𝐻3 → 𝐶2 𝐻6
As the CH3 radical is the principal chain carrier, the overall rate of
reaction is given by:
𝑑[𝐶 ]
− 4 𝑡 10 = 𝑘2 [𝐶𝐻3 ][𝐶4 𝐻10 ] …..(4.6.53)
The rate of initiation is equal to rate of termination. So,
𝑘1 [𝐶4 𝐻10 ] = 𝑘4 [𝐶𝐻3 ]2
1
1
or [𝐶𝐻3] = (𝑘 ) [𝐶4𝐻10 ] ⁄2
1
……(4.6.54)
4
Substituting the value of [CH3] in equation (4.6.53), we get
1⁄
𝑑[𝐶 ] 2 1
⁄
− 4 𝑡 10 = 𝑘2 ( 𝑘 ) 1
[𝐶4 𝐻10 ] 2 [𝐶4 𝐻10 ] …..(4.6.55)
4
 56

1⁄
𝑑[𝐶 ] 𝑘1 2 3
or − 4 𝑡 10 = 𝑘2 ( ) [𝐶4 𝐻10 ] ⁄2 …..(4.6.56)
4
Equation (4.6.56) agrees with the experimental data.

4.7. Autooxidation: The reactions which take place between molecular

oxygen and other substances are usually called autoxidations. These reactions
occur with very high velocities by releasing certain energy which is sufficient
to cause explosion. This can be explained as follows:
As oxygen has two unpaired electrons, it therefore acts as a diradical.
It means that two radical will be produced when oxygen reacts with other
substances. For example,
𝐻 + 𝑂2 → 𝐻𝑂 + 𝑂
In this reaction, one atom [H] gives rise to two radicals (O and OH). This type
of the reaction, in which there occurs an increase in the number of radicals, is
usually known as the branching reactions.
When such reactions take place to a considerable extent, there will be a
rapid increase in the total number of free radicals and, thus steady state
conditions do not hold good. Therefore, such reactions take place with very
high velocities by releasing certain energy which will be sufficient to cause
explosion.

4.7.1. Reaction mechanism of branching chains: In some cases, the reaction

mechanism involves branching chains. This type of reaction mechanism
which involves branching chain is termed as branching chain process.
Consider the following reaction mechanism:
(i) Chain initiation:
?→R
where R is the radical. The rate of such a reaction is given by:
𝑑[𝑅]
𝑣𝑖 = …..(4.6.57)
(ii) Chain branching:
𝑅 → 𝛼𝑅
where α is the number of chain carrier formed in each chemical act. The rate
of such a reaction is given by:
𝑑[𝑅]
𝑣𝑏 = = 𝑓𝑏(𝛼 − 1)[𝑅] …..(4.6.58)
where fb is the function of concentration of the reactant.
(iii) Product reaction:
𝑅 → 𝑃𝑟𝑜𝑑𝑢𝑐𝑡
The rate of such a reaction is given by:
 57

𝑑[𝑃]
𝑣𝑏 = = 𝑓𝑝[𝑅] …..(4.6.59)
where fp is the function of concentration of the product.

Chain-ending at surfaces:
𝑅 → 𝐷𝑒𝑠𝑡𝑟𝑢𝑐𝑡𝑖𝑜𝑛 𝑎𝑡 𝑠𝑢𝑟𝑓𝑎𝑐𝑒
The rate of such a reaction is given by:
𝑑[𝑅]
𝑣𝑠 = − = 𝑓𝑠 [𝑅] …..(4.6.60)
where fs is the function of breaking of the chains by a surface.

Chain-ending in gas phase:

This reaction is
𝑅 → 𝐷𝑒𝑠𝑡𝑟𝑢𝑐𝑡𝑖𝑜𝑛 𝑖𝑛 𝑔𝑎𝑠 𝑝ℎ𝑎𝑠𝑒
The rate of such a reaction is given by:
𝑑[𝑅]
𝑣 =− = 𝑓 [𝑅] …..(4.6.61)
where fg represents the factor for breaking of the chains by collisions in the
gas phase.
The steady state for R is given by:
𝑑[𝑅]
= 𝑣𝑖 + 𝑓 (𝛼 − 1)[𝑅] − 𝑓 [𝑅] − 𝑓 [𝑅] = 0 …..(4.6.62)
or [𝑅] = 𝑓𝑠+𝑓𝑔−𝑓 …..(4.6.63)
𝑏 (𝛼−1)
The rate of reaction is given by:
𝑑[𝑃]
𝑣= = 𝑓𝑣 [𝑅] …..(4.6.64)
Combining equation (4.6.63) and (4.6.64), we get,
− 𝑝
𝑣= )
…..(4.6.65)
𝑓𝑠 +𝑓𝑔 𝑓𝑏 (𝛼−1

Case I: When α=1, equation (4.6.65) becomes as:

𝑝
𝑣 = 𝑓 +𝑓 …..(4.6.66)
𝑠 𝑔
Thus, the rate of the reaction is finite and dependent upon the chain
length. Such carriers are said to be stationary.

Case II: When α >1, the last term fb(α-1) in equation (4.6.65) is positive.
Therefore, it is possible for the denominator of equation (4.6.65) to be zero if
the value of fb(α-1) is too large to balance fs and fg. It is only possible when
is large. It means than the number of free radicals produced is larger than
the number of free radicals destroyed. Thus, no stationary state is possible.
Such chains are known as non stationary chains.
 58

When fs + fg = fb (- 1), then becomes infinite. This condition at any

sets of conditions, for which fs + fg - fb (- 1) is zero, is known as an explosion
limit. When the concentration is changed beyond this explosion limit, the
steady state reaction may suddenly convert into an explosion.
An example is hydrogen- oxygen reaction in which explosion limits
exists.

4.7.2. Upper and lower explosion limits: The reaction between hydrogen
and oxygen proceeds at a measurable speed if the temperature is between 4500
and 6000 C. Below this range, the reaction becomes slow but above this range,
explosion takes place.
Consider a mixture of O2 and H2 in the ratio of 1:2 which is maintained
at a 5500C and at a pressure of about 2 mm. When the pressure is slowly
increased, the rate of the reaction also increases slowly, as shown in Figure
4.3. At a certain critical pressure of 50 mm or so the mixture explodes. The
exact value of this critical pressure will depend upon the size and shape of the
vessel. The limit at which it occurs is known as first explosion limit or lower
explosion limit.

Fig. 4.3: Variation of explosion limits with pressure

Now, the mixture of O2 and H2 are maintained at 200 mm pressure.

Again, the reaction proceeds at a steady rate. If the pressure is reduced, the
rate of the reaction is also reduced. But at about 100 mm the reaction mixture
explodes. Thus, there is a pressure region between 50 and 100 mm within
which explosion takes place. Above and below this pressure region, reaction
proceeds at a normal rate. The pressure limit of 100 mm at which the
explosion occurs is known as upper explosion limit or second limit.
 59

In Figure 4.3, there is a third limit of explosion which is at still higher

pressures. Here explosions are due to the rise in the temperature of the reaction
system. Such explosions are known as thermal explosions.
In Figure 4.4 shows the variation of explosion limits with the
temperature. It is observed from Figure 4.4 that explosion will take place at
all pressures above 600oC but no explosion will occur under any pressure
condition below 4600C.

Fig. 4.4: Variation of explosion limits with the temperature

4.7.3. Explanation of Explosion limits: At low pressures (2 mm), the

recombination of radicals will take at the surfaces. When the pressure is
increased, the rate of the recombination of radicals at surfaces will decrease.
Thus, fs decreases. This may happen to a limit when fs+ fg becomes as small
as fb(-1). When this limit is reached, explosion will take place. This is
explanation for the explosion limits.
When gases are maintained at higher pressure (200 mm), the
recombination of radicals will occur in the gas phases. When the pressure is
decreased, the rate of the removal of radicals in the gas phase is decreased; fg
is decreasing. This may happen to such a limit of pressure (100 mm) that the
fs + fg may become equal to fb(-1). This limit of pressure (100 mm) is known
as second pressure limit.
4.7.4. The Hydrogen-Oxygen Reaction: The simplified mechanism of this
reaction is:
(i) 𝐻2 → 2𝐻
(ii) 𝐻 + 𝑂2 → 𝑂𝐻 + 𝑂
(iii) 𝑂 + 𝐻2 → 𝑂𝐻 + 𝐻
(iv) 𝐻 + 𝑂2 + 𝑀 → 𝐻𝑂2 + 𝑀
(v) 𝐻𝑂2 → 𝑟𝑒𝑚𝑜𝑣𝑎𝑙 𝑎𝑡 𝑠𝑢𝑟𝑓𝑎𝑐𝑒
 60

(vi) 𝐻𝑂2 + 𝐻2 → 𝐻2 𝑂 + 𝑂𝐻
(vii) 𝑂𝐻 + 𝐻2 → 𝐻2 𝑂 + 𝐻
(viii) 𝐻 → 𝑟𝑒𝑚𝑜𝑣𝑎𝑙 𝑎𝑡 𝑠𝑢𝑟𝑓𝑎𝑐𝑒
(ix) 𝑂𝐻 → 𝑟𝑒𝑚𝑜𝑣𝑎𝑙 𝑎𝑡 𝑠𝑢𝑟𝑓𝑎𝑐𝑒
The reaction (ii) and (iii) are chain branching processes. The HO2 radical is
quite stable. This can diffuse to the surface and be removed. Another
possibility is that HO2 can react with hydrogen as shown in reaction (vi). This
reaction is important of higher pressure near third limit.
At the lower limit the important processes are (viii) and (ix) but the
reactions (iv), (v) and (vi) are not important.
Consider a reaction at low pressure. The steady state equation for
hydrogen atom is:
𝑣𝑖 − 𝑘2 [𝐻][𝑂2 ] + 𝑘3 [𝑂][𝐻2 ] + 𝑘7 [𝑂𝐻][𝐻2 ] − 𝑓8[𝐻] = 0 …..(4.7.1)
Reaction (iv) is not considered because at low pressure this reaction is
not important as mentioned above.
The steady state equations for oxygen atoms and for hydroxyl radicals
are:
𝑘2 [𝐻][𝑂2 ] − 𝑘3 [𝑂][𝐻2 ] = 0 …..(4.7.2)
𝑘2 [𝐻][𝑂2 ] + 𝑘3 [𝑂][𝐻2 ] − 𝑘7 [𝑂𝐻][𝐻2 ] − 𝑓9 [𝑂𝐻] = 0 …..(4.7.3)
In equation (4.7.1), vi is the rate of initiation reaction (i) and f8 is the
rate of coefficients for reaction (viii).
In equation (4.7.3), f9 is the rate coefficient for reaction (ix).
By adding equation (4.7.1) and (4.7.2), we get
𝑣𝑖 + 𝑘7 [𝑂𝐻][𝐻2 ] − 𝑓8[𝐻] = 0 …..(4.7.4)
By adding (4.7.2) and (4.7.3), we get
2𝑘2 [𝐻][𝑂2 ] − 𝑘7 [𝑂𝐻][𝐻2 ] − 𝑓9[𝑂𝐻] = 0 …..(4.7.5)
From equation (4.7.4), we have
𝑓8[𝐻] = 𝑣𝑖 + 𝑘7 [𝑂𝐻][𝐻2 ]
𝑣 +𝑘 [𝑂𝐻][𝐻2 ]
or [𝐻] = 𝑖 7 ……(4.7.6)
8
Substituting the value of (H) in equation (4.7.5), we obtain
𝑣𝑖 + 𝑘7 [𝑂𝐻][𝐻2 ]
2𝑘2 [ ] . [𝑂2 ] − 𝑘7 [𝑂𝐻][𝐻2 ] − 𝑓9 [𝑂𝐻] = 0
𝑓8
or 2𝑘2 𝑣𝑖 [𝑂2 ] + 2𝑘2 𝑘7 [𝑂𝐻][𝐻2 ][𝑂2 ] − 𝑘7 𝑓8 [𝑂𝐻][𝐻2 ] − 𝑓8 𝑓9 [𝑂𝐻] = 0
or 2𝑘2 𝑣𝑖 [𝑂2 ] = 𝑓8 𝑓9 [𝑂𝐻] + 𝑘7 𝑓8 [𝑂𝐻][𝐻2 ] − 2𝑘2 𝑘7 [𝑂𝐻][𝐻2 ][𝑂2 ]
or 2𝑘2 𝑣𝑖 [𝑂2 ] = [𝑂𝐻](𝑓 𝑓 + 𝑘7 𝑓 [𝐻2 ] − 2𝑘2 𝑘7 [𝐻2 ][𝑂2 ])
or [𝑂𝐻] = 𝑓 𝑓 +𝑘 𝑓 [𝐻 ]−2𝑘 𝑘 [𝐻 ][𝑂 ] …..(4.7.7)
8 9 7 8 2 2 7 2 2
At low pressures, the rate of the formation of water is given by reaction (vii).
𝑣 = 𝑘7 [𝑂𝐻][𝐻2 ] …..(4.7.8)
 61

Combining equation (4.7.7) and (4.7.8), we get

𝑣= [𝐻 ]−2𝑘 [𝐻 ][𝑂 ]
…..(4.7.9)
𝑓8 𝑓9 +𝑘7 𝑓8 2 2 𝑘7 2 2
In equation (4.7.9), the sum k7f8[H2] + f8f9 is related to the surface removal
processes. When the pressure is increased, the value of k7f8[H2]+f8f9
decreases. A limit may be reached when k7f8[H2]+f8 f9 becomes equal to
2k2k7[H2][O2]. Thus, the denominator becomes zero and so the rate becomes
infinite.

Chapter 5

Homogeneous and Heterogeneous Catalysis

5.1. Introduction: In 1836, it was observed by Berzelius that the rate of

reaction is accelerated by the presence of a foreign substance. He gave the
name catalysis to this phenomenon and catalyst to the foreign substance.
However, later on, it was observed that catalyst could also retard the rate of
reaction.
 62

Thus, catalysis can be defined as a process in which the presence of

foreign substance could affect the rate of a reaction without being used up in
that reaction.
A catalyst is defined as the substance which can change the speed of
the reaction without being used up in that reaction and this phenomenon is
known as catalysis.

5.2. Types of catalysis: Catalysis can be divided into two classes:

Homogeneous Catalysis and Heterogeneous Catalysis

5.2.1. Homogeneous Catalysis: In homogeneous catalysis, the catalyst and

reactant are in same phase.
For example, for the manufacture of sulphuric acid, nitric oxide (NO)
gas catalyzes the reaction between sulphur dioxide and oxygen. In this case,
both the reactants (sulphur dioxide and oxygen) and the catalyst (nitric oxide)
are in the gaseous phase.
Example from liquid phase is inversion of cane sugar, which is
catalyzed by a mineral acid. In this case, the catalyst and reactant are in the
liquid phase.

5.2.2. Hetrogeneous Catalysis: In heterogeneous catalysis, the catalyst is

present in a different phase than that of reactants. For example, decomposition
of potassium chlorate in the presence of solid manganese dioxide (MnO 2).
The catalyst (MnO2) is present as a separate phase from the solid reactant
(KClO3).
Another example of heterogeneous catalysis is the decomposition of
hydrogen peroxide, which is catalyzed by colloidal solution of gold and
platinum. Hydrogen peroxide is a liquid reactant.
Similarly, combination of SO2 and O2 in presence of finely divided
platinum and manufacture of ammonia from nitrogen and hydrogen in
presence of iron are also examples of heterogeneous catalysis.

5.3. Criteria or Characteristics of Catalysis: Following are some general

characteristics of catalyzed reactions:

1. The catalyst remains unchanged in mass and chemical composition: The

catalyst remains unchanged in mass and chemical composition at the end of
the reaction though a change in its physical state, color etc., may occur. For
example, coarsely grained manganese dioxide used in the decomposition of
 63

potassium chlorate becomes finely powdered after the reaction. In a few cases
the shining surface of a catalyst is found to become dull or pitted.

2. Small amount of the catalyst is needed: Generally, a small quantity of the

catalyst is sufficient to change the rate of a reaction. For example, one gram
of copper in 109 liters can catalyze the oxidation of NaHSO3 by air.
This is true only in the case heterogeneous catalysis. However, in
homogeneous reactions, the rate is proportional to the concentration of
catalyst. For example, in the inversion of cane sugar, dilute acids act as
catalyst and the rate of inversion is proportional to the [H+] ion concentration.
Similarly, the rate of reaction catalyzed by hydroxyl ions (e.g. the conversion
of acetone to tri acetone alcohol) is proportional to the concentration of
hydroxyl ions.
In homogeneous catalysis, the catalyst becomes disabled during the
reaction and it is replaced when it has catalyzed the amounts of reactants
shown by the chemical reaction.

3. Effect on the equilibrium of a reversible reaction: In case of reversible

reactions, the catalyst does not influence the composition of reaction mixture
at equilibrium. It means that it affects the forward and backward reaction to
the same extent and the value of equilibrium constant remains unchanged.

4. Inability to start a reaction: A catalyst cannot start reaction but can only
decrease or increase its rate.

5. Specific nature of a catalyst: The action of a catalyst is highly specific in

nature. Thus, a particular substance can act as a catalyst only in a particular
reaction and not in all reactions. For example, MnO2 may catalyst the
decomposition of KClO3 and not of KClO4.
Another example is the catalytic decomposition of formic acid. When
decomposition is catalyzed by copper, it gives hydrogen and carbon dioxide
whereas products will be water and carbon monoxide, when catalysis is
alumina.
The catalytic action of enzymes is highly specific.

6. Nature of the products is unaltered by the presence of the catalyst:

Hydrogen and nitrogen always combine to give ammonia in the absence of
the catalyst. Similarly, sulphur dioxide and oxygen will always combine form
sulphur trioxide, whether a catalyst is present or not.
But this is not always true. For example,
 64

(i) CO and H2 combine to give three different products when three different
catalysts are used.
𝐼𝑛 𝑝𝑟𝑒𝑠𝑒𝑛𝑐𝑒 𝑜𝑓 𝑛𝑖𝑐𝑘𝑒𝑙 𝐶𝑂 + 3𝐻2 → 𝐶𝐻4 + 𝐻2 𝑂
𝐼𝑛 𝑝𝑟𝑒𝑠𝑒𝑛𝑐𝑒 𝑜𝑓 𝑐𝑜𝑝𝑝𝑒𝑟 𝐶𝑂 + 𝐻2 → 𝐻𝐶𝐻𝑂
𝐼𝑛 𝑝𝑟𝑒𝑠𝑒𝑛𝑐𝑒 𝑜𝑓 𝐶𝑟2𝑂3 𝐶𝑂 + 2𝐻2 → 𝐶𝐻3 𝑂𝐻
(ii) Similarly chlorination of toluene in the presence of a halogen carrier such
as iron or iodine and absence of sunlight gives ortho- and para-chloro toluene.
But, in the presence of sunlight or higher temperature, it gives benzyl chloride
i.e., chlorine is substituted in the side chain.

7. Optimum temperature: At a particular temperature, the efficiency of a

catalyst is most marked. This temperature is known as the optimum
temperature. The activity of an enzyme, which acts as a catalyst increases
exponentially with temperature. If the temperature is raised sufficiently, the
enzymes are coagulated and lose their activity. Generally, the activity of
enzymes is maximum between 350C to 450C.

8. Action of promoters: The addition of a small amount of foreign substances

which are not catalytically active, sometimes, increases the activity of the
catalyst. Such substances are called promoters.

9. Action of poisons: The activity of a catalyst is inhibited or completely

destroyed by the presence of even minute traces of certain substance called
catalyst poisons or anti- catalyst. For example, in the manufacture of
sulphuric acid by the contact process, a trace of As 2 O3 destroys the catalytic
efficiency of spongy platinum.

5.4. Theory of Homogeneous Reaction: A chemical reaction can take place

only when the reacting substance possess sufficient minimum energy which
is known as activation energy.
According to the theory of homogeneous catalysis, if reacting
molecules do not possess enough energy to undergo chemical reaction,
catalyst provides an alternative path in which lesser energy of activation is
required. For this, usually an intermediate compound is formed between
catalyst and one of the reactants. This compound formation requires less
energy than needed by the actual reaction. This compound is unstable and
gets decomposed to regenerate the catalysis with the simultaneous formation
of the desired product of the reactions. Figure 5.1 shows the effect of catalyst
on energy required for the chemical reactions.
 65

Fig. 5.1: Effect of catalyst on energy required for the chemical reactions.

The rate constant (k) of any reaction is related to energy of activation (Ea) by
the following Arrhenius equation:
𝑘 = 𝐴𝑒 −𝐸𝑎 ⁄𝑅𝑇 ……(5.1)
whereas for a catalytic reaction, Arrhenius equation can be written as:
𝑘𝑐 = 𝐴𝑒 −𝐸𝑐 ⁄𝑅𝑇 ……(5.2)
From these two equations, it is evident that if energy of activation Ec is
less than Ea, kc would be greater than k. Thus, a catalyzed reaction is having a
lower value of Ea than the unanalyzed reaction.
The various postulates of the theory of homogeneous catalysis are:
(i) The catalyst first forms an intermediate compound with the reactant which
is termed as substrate.
𝐴 + 𝑋 ↔ 𝐴𝑋
where A is the substrate and X is the catalyst, AX is the intermediate
compound. k1 and k2 are the velocity constants for the forward and backward
reactions.
(ii) The intermediate compound then reacts with other reactant molecule (B)
to form the product and catalyst.
𝑘3
𝐴𝑋 + 𝐵 → 𝐴𝐵 + 𝑋
This reaction is slow and is the rate determining step. Thus,
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 = 𝑘3 [𝐴𝑋][𝐵] …..(5.3)
(iii) The catalyst X which is regenerated in last step may further undergo steps
(i) and (ii) to form more and more of the products. Thus, the rate of
homogeneous catalytic reactions depends upon the concentration of catalyst
 66

X. So, the rate of the reaction increases with increase in the concentration of
catalyst. This can be proved as follows:
Applying steady state concept, the concentration of intermediate
compound [AX] is given by:
𝑑[𝐴𝑋]
= 𝑘1 [𝐴][𝑋] − 𝑘2 [𝐴𝑋] − 𝑘3 [𝐴𝑋][𝐵] = 0
𝑑𝑡
or 𝑘1 [𝐴][𝑋] = 𝑘2 [𝐴𝑋] + 𝑘3 [𝐴𝑋][𝐵]
or 𝑘1 [𝐴][𝑋] = [𝐴𝑋](𝑘2 + 𝑘3 [𝐵])
[
or [𝐴𝑋] = 𝑘 …..(5.4)
2 +𝑘 𝐵]
Substituting the value of [AX] in equation (5.3) we get,
𝑘 𝑘 [𝐴][𝑋][𝐵]
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 = 1 3 …..(5.5)
2 3
If k2 < < k3[B] then equation (5.5) becomes:
𝑘 𝑘 [𝐴][𝑋][𝐵]
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 = 1 3 = 𝑘1 [𝐴][𝑋] …..(5.6)
3
If k2 > > k3 [B] then equation (5.5) becomes:
𝑘 𝑘 [𝐴][𝑋][𝐵]
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 = 1 3 …..(5.7)
2
Thus, equation (5.6) and (5.7) proves that the rate of reaction depends upon
the concentration of catalyst although it is neither produced nor consumed in
the reaction.
Following are some examples which shows that catalysts are regenerated
at the end of reactions.
(i) The reaction between alcohol and sulphuric acid
𝐶2 𝐻5 𝑂𝐻 + 𝐻𝐻𝑆𝑂4 → 𝐶2 𝐻5 𝐻𝑆𝑂4 + 𝐻2 𝑂
Sulphuric acid is catalyst and C2H5HSO4 is an intermediate compound.
𝐶2 𝐻5 𝐻𝑆𝑂4 + 𝐶2 𝐻5 𝑂𝐻 → (𝐶2 𝐻5 )2 𝑂 + 𝐻2 𝑆𝑂4
The catalyst sulphuric acid is regenerated.
(ii) The catalytic action of nitric oxide for the manufacture of sulphuric
acid.
𝑂2 + 2𝑁𝑂 → 2𝑁𝑂2
NO is catalyst and nitrogen dioxide is intermediate compound.
𝑁𝑂2 + 𝑆𝑂2 → 𝑆𝑂3 + 𝑁𝑂
So, NO is regenerated catalyst.
5.4.1. Successes of this theory:
(i) This theory explains the mechanism of homogeneous catalysis.
(ii) This explains that the rate of homogeneous catalytic reaction
depends upon the concentration of catalyst.
(iii) The theory explains the specification of catalyst.
 67

(iv) This theory gives an adequate explanation of the change brought

about in the physical state of the catalyst in the course of a reaction.

5.4.2. Failure of this theory:

(i) This theory does not explain the mechanism of heterogeneous
catalysis.
(ii) This theory fails to explain the action of catalytic poisons and
activators.
(iii) The scope of the theory is limited as the formation of intermediate
compounds only possible in the case of homogeneous system when
the catalyst and the reactant are in one phase.

5.5. Theory of Heterogeneous Catalysis: This theory of heterogeneous

catalysis is based upon the phenomenon of adsorption. The action of
heterogeneous catalyst is due the presence of free valences on its surface. Due
to these free valances, reactant molecules undergo chemical reaction on the
surface of the catalyst.
Fig. 5.2 shows valencies in nickel catalyst. An atom within the body of a
catalyst is joined to the surrounding atoms and hence all of its valencies are
satisfied. However, atoms present on the surface of the catalyst possess free
valencies directed outward.
. . . .
. . . .
. . . .
…Ni –Ni–Ni–Ni…
| | | |
…Ni –Ni–Ni–Ni…
| | | |
…Ni –Ni–Ni–Ni…
. . . .
.. .. .. ..
Fig.5.2: Free valencies on the surface of nickel

The mechanism of heterogeneous catalysis involves various steps (Figure 5.3)

which are as follows:
(a) Diffusion: When the reactants are allowed to enter a reaction vessel
containing catalyst, the reactants molecules from gas or liquid phase undergo
diffusion on the surface of the catalyst (Fig. 5.3 A).
(b) Adsorption: The surface of the solid catalyst possesses some isolated
active centres having free unsatisfied valency forces. Due to these unsatisfied
valency forces on the catalyst surface, the molecules of the gaseous reactants
 68

get adsorbed in unimolecular thickness layer (Fig. 5.3 B). If reactants are
adsorbed in higher concentrations on the surface of the catalyst, then rate of
reaction is also increased. Adsorption is an exothermic process, so the heat of
adsorption decreases the need for energy of activation.
(c) Formation of activated complex: Due to adsorption, reacting
molecules are close to catalyst so they undergo interaction to form an activated
complex (Fig. 5.3 C). Whenever an activated complex is formed, it is
accompanied by an increase in its energy.
A B

Diffusion A B
│ │ │ │ │ │ │ │ │ │
-M-M-M-M-M- -M-M-M-M-M-
│ │ │ │ │ │ │ │ │ │
-M-M-M-M-M- -M-M-M-M-M-
│ │ │ │ │ │ │ │ │ │

A: Diffusion B: Adsorption

A…B A-B
. . +
│ │ . . │ │ │ │ │ │
-M-M-M-M-M- -M-M-M-M-M-
│ │ │ │ │ │ │ │ │ │
-M-M-M-M-M- -M-M-M-M-M-
│ │ │ │ │ │ │ │ │ │

C: Formation of activated complex D: Decomposition of activated complex

Fig. 5.3: Mechanism of heterogeneous catalysis

(d) Decomposition of activated complex: The activated complex is

associated with larger amount of energy than the reactants and the product.
So, it decomposes giving products, which leave the surface. (Fig. 5.3 D).
(e) Diffusion of the products: The molecules of reaction products diffuse
away from the catalyst surface. The fresh molecules may come on the surface
of the catalyst and react to form the desired products.
If both the reacting molecules are absorbed, product of the reaction leaves
the surface quickly so that the surface of the catalyst becomes available for
the adsorption of the fresh reacting molecules.

5.6: Explanation of mechanism of heterogeneous catalysis by absorption

Theory: The theory of heterogeneous catalysis can be easily explained by
 69

hydrogenation reaction of alkenes taking place on solid nickel surface. The

adsorption theory explains the following facts:
(i) Action of finely divided catalyst. On disintegration, the free surface area is
increased i.e., free valencies of active spots increase which are responsible for
the adsorption of reactant molecules. Thus, as active spots increase, activity
of catalyst also increases.
| | | | :
…Ni –Ni–Ni–Ni– :
| | | | on disintegration gives .…Ni….
…Ni –Ni–Ni–Ni– :
:
(ii) Action to rough surface of the catalyst. The rough surface of catalyst has
greater number of free valencies, so it is more effective than smooth one. The
edges corners, cracks and beaks on the surface are active centers and the
efficiency of the catalyst is mainly due to them.
(iii) Action of the promoters: Promoters are adsorbed on the surface of the
catalyst which causes discontinuity or uneven surface. This results in an
increase in the number of active centers which thereby causes greater
adsorption of reactant molecules on the interface between the promoter and
catalyst where free valencies are crowded. The increased adsorption means
greater concentration, hence higher rate of the reaction.
(iv) Action of poisons: If poison is adsorbed on the active spots of catalyst,
number of active centers available for the adsorption of the reacting molecules
decreases.
(v) Specific action of the catalyst: The extent of adsorption of the reactant
molecules on the catalyst surface and their subsequent conversion in to
products depend upon the chemical affinity of the catalyst for the reactant
molecule.

5.7. Theory of Heterogeneous Catalysis:

The quantitative treatment of the theory of heterogeneous catalysis was
given by Langmuir. A reaction taking place on a surface is supposed to consist
of four consecutive steps.
(i) Diffusion of gases to the surface
(ii) Adsorption of the gases on the surface
(iii) Reaction of the surface
(iv) Desorption and diffusion of product from the surface to the bulk.

The steps (i) and (iv) are very rapid so they do not play any role in the
overall rate determination process. The equilibrium between adsorption (ii)
 70

and (iv) is easily attained. Therefore, these two reactions also do not take part
in the overall rate determining process. Thus, it is only the step (iii), which
determines the overall rate and it is the concentration of the molecules on the
surface on which the reaction rate would depend.

5.7.1. Quantitative treatment of heterogeneous catalysis: Langmuir

concept of unimolecular film: Langmuir postulated that:
(1) The gases adsorbed by a solid surface are not able to form a layer more
than a single molecule in depth, i.e., adsorbed gas is unimolecular in thickness.
(2) There is equilibrium between the adsorbed gas and the gas in the bulk
phase, i.e., rate of condensation and rate of sorption of molecules will be
equal.
Suppose
𝜃 = 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑢𝑟𝑓𝑎𝑐𝑒 𝑎𝑟𝑒𝑎 𝑐𝑜𝑣𝑒𝑟𝑒𝑑 𝑏𝑦 𝑔𝑎𝑠 𝑎𝑡 𝑎𝑛𝑦 𝑖𝑛𝑠𝑡𝑎𝑛𝑡
(1-𝜃) = 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝑡ℎ𝑒 𝑏𝑎𝑟𝑒 𝑠𝑢𝑟𝑓𝑎𝑐𝑒 𝑎𝑣𝑎𝑖𝑙𝑎𝑏𝑙𝑒 𝑓𝑜𝑟 𝑎𝑑𝑠𝑜𝑟𝑝𝑡𝑖𝑜𝑛
𝑃 = 𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑔𝑎𝑠
If gas molecules collide with unit area of the surface, then the rate of
condensation of molecules at any time is proportional to the pressure P and
fraction of uncovered surface (1-). Thus,
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑎𝑑𝑠𝑜𝑟𝑝𝑡𝑖𝑜𝑛 = 𝑘1 (1 − 𝜃)𝑃 …..(5.7.1)
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑒𝑣𝑎𝑝𝑜𝑟𝑎𝑡𝑖𝑜𝑛 = 𝑘2 𝜃 …..(5.7.2)
where k1 and k2 are proportionality constants for the given system.
At equilibrium, two rates are equal. Then,
𝑘1 (1 − 𝜃)𝑃 = 𝑘2 𝜃
or 𝜃= …..(5.7.3)
𝑘2 +𝑘1 𝑃
𝑏𝑃
or 𝜃= …..(5.7.4)
𝑘 1+𝑏𝑃
where 𝑏= 1
2
b is known as Langmuir adsorption isotherm. Figure 5.4 shows graphical
representation of equation (5.7.3).
 71

Fig. 5.4: Langmuir adsorption isotherm

Limiting cases of equation (4):

(a) If the gas is slightly adsorbed either due to very low pressure or due to low
adsorption capacity of the surface, b is small. So, bP may be neglected in
comparison to unity and equation (5.7.4) is reduced to :
𝜃 = 𝑏𝑃 …..(5.7.5)
Thus, extent of adsorption is directly proportional to the pressure and
the reaction will behave as that of first order.
(b) If a gas is strongly adsorbed, the surface gets covered by monomolecular
thick layer of the gas, i.e., when b or P or both are large, then bP>>1, and
equation (5.7.4) becomes:
𝜃=1
Under these conditions, the reaction rate is constant or independent of
pressure and the reaction is kinetically of zero order.
(c) Equation (5.7.4) can rearranged as:
𝑏𝑃
1−𝜃 = 1−( )
1 + 𝑏𝑃
1
or 1 − 𝜃 = (1+𝑏𝑃 )…..(5.7.6)
If adsorption is strong, bP>>1, then
1
1 − 𝜃 = 𝑏𝑃 …..(5.7.7)
i.e., the fraction of the surface still available for the adsorption would be
inversely proportional to the pressure of the gas.
 72

5.8. Kinetics of heterogeneous reactions: The kinetics of unimolecular and

bimolecular surface reactions can be interpreted using Langmuiradsorption
isotherm.

5.8.1.Unimolecular surface reactions: In case of single reactant, at first,

chemisorptions takes place. Subsequently, on activation, it breaks up into
product. If A is reactant molecules and S is the surface atom of the solid, then
elementary process will be:
𝐴 + 𝑆 ↔ 𝐴𝑆
k1 and k-1 are the rate constants for the forward and backward reactions.
The activated complex AS then breaks into products.
𝑘
2
𝐴𝑆 → 𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠
k2 is the rate constant for this reactions.
Suppose θ is the fraction of the surface covered by A at any instant t and
pressure P. According to Langmuir adsorption isotherm, the reaction rate
should be:
𝑅𝑎𝑡𝑒 = 𝑟 = 𝑘2 𝜃 …..(5.8.1)
Applying steady state approximation for [AS], we get
𝑑[𝐴𝑆]
= 𝑘1 [𝐴][𝑆] − 𝑘−1 [𝐴𝑆] − 𝑘2 [𝐴𝑆] = 0 …..(5.8.2)
𝑘1 [𝐴][𝑆]
or [𝐴𝑆] = …..(5.8.3)
−1 2
If Cs is the total concentration of the surface site of the catalyst, then,
𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑣𝑎𝑐𝑎𝑛𝑡 𝑠𝑖𝑡𝑒𝑠 = [𝑆] = 𝐶𝑠 (1 − 𝜃)
and 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑜𝑐𝑐𝑢𝑝𝑖𝑒𝑑 𝑠𝑖𝑡𝑒𝑠 = [𝐴𝑆] = 𝐶𝑠
Substituting the values of [S] and [AS] in equation (5.8.3) gives,
𝑘1 [𝐴]𝐶𝑠 (1 − 𝜃)
𝐶𝑠 =
𝑘−1 + 𝑘2
+
or 𝜃=𝑘 [𝐴] 𝑘−1 +𝑘2
…..(5.8.4)
1
From equation (5.8.1), we can write
𝑟=𝑘 …..(5.8.5)
1 [𝐴]+𝑘−1 +𝑘 2
On inverting equation (5.8.5),we get
1 1 𝑘− +𝑘2
= + 𝑘
…..(5.8.6)
For the gaseous reactions, concentration term [A] can be replaced by
partial pressure. So, equation (5.8.6) becomes:
1 1 𝑘 +𝑘 1
= + −𝑘 2 . …..(5.8.7)
1
 73

A plot of 1/r against 1/PA would give a straight line having 1/k2 as the intercept
and [(k1 +k2)/ k2k1] as the slope.

Limiting Case of equation (5.8.7)

Case-I: In the rate expression
𝑘1 𝑘2 𝑃𝐴
𝑟=
𝑘1 𝑃𝐴 + 𝑘−1 + 𝑘2
when 𝑘 >> (𝑘1 𝑃𝐴 + 𝑘−1 ) ,
𝑟 = 𝑘1 𝑃𝐴…..(5.8.8)
Intergration of equation (5.8.8) gives,
2.303 𝑃
𝑘1 = 𝑙𝑜𝑔10 ( 𝑖)…..(5.8.9)
where Pi refers to the initial pressure of A and P its pressure at any time t. This
equation is of first order with respect to concentration of A.
𝑘1 𝑘2 𝑃 (𝑘1 /𝑘−1 )𝑘2 𝑃 𝐾𝑘2 𝑃
𝑟= = =
𝑘1 𝑃 + 𝑘−1 (𝑘1 /𝑘−1 )𝑘2 𝑃 + 1 𝐾𝑃 + 1
Case-II:
If 𝑘2 ≪ (𝑘1 𝑃𝐴 + 𝑘−1 ), the rate equation (5.8.7) becomes:
𝑘 𝑘− 𝑃+ +
𝑟= = = …..(5.8.10)
𝑘1 𝑃 𝐴+𝑘−1 (𝑘1 /𝑘 −1)𝑘2 𝑃 𝐴 1 𝐾𝑃𝐴 1
where K is absorption equilibrium constant. Equation (5.8.10) is identical to
Langmuir adsorption isotherm and can be analyzed as follows:

(a) At low pressure, i.e., KP A << 1. Thus,

𝑟 = 𝐾𝑘2 𝑃𝐴…..(5.8.11)
and the reaction would be of first order with respect to A.
(b) At high pressure, i.e., KPA >> 1. Thus,
𝑟 = 𝑘2 …..(5.8.12)
and the reaction rate would be independent of pressure and the reactions is of
zero order with respect to A.
Equation (5.8.11) and (5.8.12) can be explained by variations of rate of
reaction with pressure as shown in Figure 5.5.

5.9. Classification of catalyst:

5.9.1. Negative catalysis or inhibition: When presence of a catalyst decreases
or retards the rate of the chemical reaction, such catalysts are known as
negative catalysts or inhibitors and the phenomenon is called negative
catalysis or inhibition. For example:
(i) The presence of 1% alcohol retards the oxidation of chloroform into
phosgene.
 74
𝐶 𝐻 𝑂𝐻
2 5
4𝐶𝐻𝐶𝑙3 + 3𝑂2 → 4𝐶𝑂𝐶𝑙2 + 2𝐶𝑙2 + 2𝐻2 𝑂

(ii) The decomposition of H2O2 is retarded by the presence of acetanilide

or H2SO4 or H3PO4.
(iii) The presence of lead tetra ethyl, nickel carbonyl serves as anti knock
material in internal combustion engines.

Fig. 5.5: Variation of rate of reaction with pressure

Action of inhibitor: The inhibitor acts in two ways:

(a) Inhibitor deactivates or destroys the foreign substance present in the
reacting system as a positive catalyst. Thus, it does not involve directly in the
reaction and retards the reaction.
(b) Sometimes, an inhibitor operates by dislocating a step in a multi step
reaction. For example, addition of phosphate to a solution of H2O2 inhibits its
decomposition by combining with existing traces of ferric ions which catalyze
the decomposition of H2O2.

5.9.2. Catalytic Poisons or Anti catalysts: Some substances when present in

the reactants, decreases the efficiency of the catalyst. These substances are
called Catalytic poisons or anti catalysts. The effect is usually observed with
a solid catalyst and is of two types:
(a) Temporary poisoning: If the catalyst regains its activity when the
substance responsible for its poisoning is eliminated from the reactants, the
poisoning is regarded as temporary. For example, presence of water vapor or
oxygen acts as a temporary poison for iron, which is used as catalyst in
manufacture of ammonia?
 75

(b)Permanent poisoning: If the poisoned catalyst fails to regain its activity

even when the catalytic poisons are subsequently removed, the poisoning of
the catalyst is said to be permanent. For example,
(i) Carbon mono oxide acts as poison for iron catalyst in Haber’s process for
the manufacture of ammonia.
(ii) As2O3 acts as poison for platinized asbestos (catalysis) in Contact process
for the manufacture of sulphuric acid.
(iii) HCN acts as poison for colloidal platinum (catalysis) for the
decomposition of H2O2.
(iv) Bromine vapor acts as poison for nickel catalyst for hydrogenation of oils.

Action of the poisons: It is mainly due to adsorption of poisons on the active

spots of the catalyst and thus reducing the number of free active spots
available for the adsorption of the reacting molecules.

5.9.3. Autocatalysis: The process in which one of the products of reaction

acts as the catalyst is known as autocatalysis. For example,
(i) Hydrolysis of an ester is auto catalyzed by the acid which is the product
of the reaction.
𝑅𝐶𝑂𝑂𝑅 ′ + 𝐻2 𝑂 ↔ 𝑅𝐶𝑂𝑂𝐻 + 𝑅 / 𝑂𝐻
(ii) During titration of warm solution of oxalic acid by KMnO4 solution, the
first few drops take appreciable time before they are decolorized. Initially, the
reaction is very slow but after some time, the decolonization goes fairly rapid
as the Mn+2 ions, formed in the course of reaction, catalyze the reaction.
5𝐶2 𝑂4−2 + 2𝑀𝑛𝑂4− + 16𝐻 + → 2𝑀𝑛2+ + 10𝐶𝑂2 + 8𝐻2 𝑂
(iii) In the action of HNO3 on copper, NO2- ions produced during the reaction
act as catalyst.
3𝐶𝑢 + 8𝐻𝑁𝑂3 → 3𝐶𝑢(𝑁𝑂3 )2 + 4𝐻2 𝑂 + 2𝑁𝑂
Nitric oxide formed in the above reaction dissolved in water in the
presence of air to provide NO2- ions.

5.9.4. Mathematical Expression of Autocatalytic Reactions: Consider a

reaction involving the hydrolysis of methyl acetate, in which the product
acetic acid formed catalyses, the reaction.
𝐶𝐻3 𝐶𝑂𝑂𝐶2 𝐻5 + 𝐻2 𝑂 ↔ 𝐶𝐻3 𝐶𝑂𝑂𝐻 + 𝐶2 𝐻5 𝑂𝐻
Suppose a and b are the initial amounts of ester and acetic acid
respectively and x is the extent of reaction. Then, after time t, concentration
of ester will be (a-x) and that of acid will be (b-x).
According to the law of mass action,
 76

𝑑𝑥
= 𝑘𝑏(𝑎 − 𝑥) + 𝑘𝑥(𝑎 − 𝑥) = 𝑘(𝑎 − 𝑥)(𝑏 + 𝑥)
𝑑𝑡
− 𝑑𝑥
or (𝑎 𝑥)(𝑏+𝑥)
= 𝑘𝑑𝑡
On separating the variables, we get
1 1 1
[ + ] 𝑑𝑥 = 𝑘𝑑𝑡
(𝑎 + 𝑏) (𝑎 − 𝑥) (𝑏 + 𝑥)
Integration of above equation gives,
1
+
(𝑎 𝑏)
[𝑙𝑛(𝑏 + 𝑥) − 𝑙𝑛(𝑎 − 𝑥)] = 𝑘𝑡 + 𝐶 …..(5.9.1)
When time t=0, x=0, so
1 𝑏
𝐶 = (𝑎+𝑏) 𝑙𝑛 …..(5.9.2)
𝑎
Substituting the value of C from equation (5.9.2) in (5.9.1), we get
( 1 1 𝑏
[𝑙𝑛(𝑏 + 𝑥) − 𝑙𝑛(𝑎 − 𝑥)] = 𝑘𝑡 + (𝑎+𝑏) 𝑙𝑛
𝑎+𝑏) 𝑎
or 𝑘 = (𝑎+𝑏)𝑡 𝑙𝑛 𝑏(𝑏+𝑥) …..(5.9.3)
This relation has been experimentally verified. If the initial catalyst be
an acid other than acetic acid, then
𝑑𝑥
= 𝑘1 𝑏(𝑎 − 𝑥) + 𝑘2 𝑥(𝑎 − 𝑥) = (𝑘1 𝑏 + 𝑘2 𝑥)(𝑎 − 𝑥) …..(5.9.4)
𝑑𝑡
This on integration gives,
1 (𝑘 𝑏+𝑘 𝑥)
(𝑘1 𝑏 + 𝑘2 𝑥) = 𝑙𝑛 1 2 …..(5.9.5)
1
Equation (5.9.5) is also verified experimentally

5.9.5. Catalytic Promotors or Activators: Some substances are not catalysts

by themselves but when present with some catalyst, greatly enhance their
action. They are called catalytic promoters or activators. For example,
(i) Molybdenum acts as promoter for iron catalyst in Haber’s process for the
manufacture of NH3.
(ii) Copper acts as promoter for finely divided iron (catalyst) in Bosch process
of H2 from water gas.
(iii) HCl or water acts as promoter for AlCl3 for isomerization of
hydrocarbons.

Action of promoters: It is assumed that a loose compound is formed between

the catalyst and the promoter, which possesses an increased adsorption
capacity than that of pure catalyst only.
 77

Chapter 6
Enzyme Catalysis
6.1. Introduction: Enzymes are complex organic compounds which are
produced by living plants and animals. These enzymes have dimensions in the
 78

colloidal range (1000-100000A) and are very specific catalysts. Due to their
colloidal behavior in solutions, their kinetic behavior is similar to that of
heterogeneous process. So, enzyme catalysis is also known as “micro-
heterogeneous catalysis”. Some examples are:
(i) Inversion of cane sugar by invertase,
𝐶12 𝐻22 𝑂11 + 𝐻2 𝑂 → 𝐶6 𝐻12 𝑂6 (𝐺𝑙𝑢𝑐𝑜𝑠𝑒) + 𝐶6 𝐻12 𝑂6 (𝐹𝑟𝑢𝑐𝑡𝑜𝑠𝑒)
(ii) Conversion of glucose to ethanol by zymase,
𝐶6 𝐻12 𝑂6 → 2𝐶2 𝐻5 𝑂𝐻 + 2𝐶𝑂2

6.2. Comparison of enzyme catalysis and general heterogeneous catalysis:

(i) Nature of catalysis: Enzymes are non-living complex nitrogenous

compounds produced by living organism. They cannot be synthesized by
artificial means in the laboratory. Whereas, the general heterogeneous catalyst
may be occurring naturally or artificially produced substance.
(ii) Enzyme is consumed during the reaction: Enzymes are consumed
during the reaction which they catalyze. But, the general catalysts remain
unchanged chemically during the reaction process.
(iii) Presence of certain inorganic substances: Certain inorganic substances
such as ammonium salts are needed as food for the enzyme producing
bacteria. No such substances are required for the general catalysts.
(iv) Pressure of Co enzymes: Co enzymes are substances which are similar
in nature to the enzymes. These coenzymes are essential for the action of the
enzyme. In general heterogeneous catalysis, the presence of a promoter is not
always essential.

Table 1 shows some examples of enzymes, their source and the

reactions catalyzed by them.
Table 1: Examples of enzymes, their source and reactions
catalyzed.

Enzyme Source Reaction catalyzed

Zymase Yeast Conversion of glucose into alcohol
Lactic bacilli Curd Conversion of milk in to curd
Lipase Caster oil seed Conversion of cane sugar into glycerol
Phyalim Human mouth Conversion of starch into glucose
 79

6.3. Characteristics of enzyme Catalysis:

1. All enzymes are proteins and have common properties. They form colloidal
solutions and are of high molecular weight.
2. Enzymes are associated with every chemical reaction that occurs in the
living system.
3. Enzymes generally accelerate biochemical reactions by reducing the energy
requirement (activation energy).
4. Enzymes do not alter the amount or nature of the product.
5. Enzymes do not affect the amount of energy released or absorbed during
the reaction.
6. Enzymes are not destroyed by the reaction they catalyze and so can be used
again. However, a given molecule of an enzyme cannot be used indefinitely
because it is readily inactivated by heat or action of acid etc. Inorganic
catalysts are highly stable and can be used over again.
7. Very small amounts of enzymes are required to catalyze a reaction.
8. Enzymes catalyze biochemical reactions at very low temperatures.
9. Enzymes are specific in their action. An enzyme that can hydrolyze starch
is unable to hydrolyze cellulose. For this, another enzyme, cellulose, is
needed.
10. Most enzymes can work in either direction i.e., they are capable of
operating reversibly. That is, one and the same enzyme can catalyze the
breakdown as well as the synthesis of the substance.

6.4. Factors governing the rate of an enzyme reaction:

1. Effect of temperature: Most of the enzymes have maximum activity at the
body temperature (370C). This temperature is called the optimal temperature
(Figure 6.1). With gradual increase to about 500C, there is a slight decrease in
the rate of reaction. At temperature more than 570C, there is fast decrease in
rate of reaction. At 1000C, the enzyme is completely destroyed. At this stage,
there is an irreversible change in enzyme and thus its activity cannot be
restored. However, at extremely low temperature (00C-20C), the enzyme is
 80

completely inactivated temporarily but with the progressive rise in

temperature, its activity can be regained.

Fig. 6.1: Effect of temperature on the reaction rate of enzymes

2. Effect of pH: Enzymes are sensitive to change in pH in the reaction

medium (Figure 6.2). Every enzyme works best at a specific pH called the
optimal pH. Most of the enzymes exhibit maximum activity at or around
neutral pH. In excessive acidic or alkaline medium, they become inactive.
However, few digestive enzymes operate either in extreme acidic or alkaline
medium. For example, the stomach enzyme, pepsin, functions best at a pH of
2.0, whereas the pancreatic enzyme, trypsin, has an optimal pH of 8.0.
3. Effect of activators: Various enzymes cannot act on their own and require
some substances for their activation and for accelerationg the rate of reaction
(Figure 6.3). These substances are called activators. Certain ions such as Na+,
K+, Ca++, Mg++, Mn++ etc., are used as activators. The stomach enzyme, pepsin
is produced in the inactive form as pepsinogen by one type of cells in the
gastric glands. Pepsinogen is converted into the active form, pepsin, by HCl
secreted by certain other cells of the gastric glands. Similarly, when pancreatic
juice containing the inactive trypsinogen is poured into the duodenum, it
comes in contact with another enzyme, enterokinase, secreted by the mucosal
layer of the duodenum, which converts trypsinogen in to the active form
trypsin.
 81

Fig. 6.2: Effect of pH on the reaction rate of enzymes

Fig. 6.3: Effect of activators on the reaction rate of enzymes

4. Effect of inhibitors: Certain substances called inhibitors slow down the

rate of enzymatic reaction (Figure 6.4). For example, mercury and arsenic ions
inhibit the activity of a wide range of enzymes. Some antibiotics are also
effective inhibitors for bacterial growth since they hamper their protein
synthesis.
 82

Fig. 6.4: Effect of inhibitor on the reaction rate of enzymes

5. Concentration: The rate of reaction is approximately proportional to the

concentration of enzyme.

6.5. Kinetics of enzyme catalysis: Enzymes are the best known catalysts. The
kinetics of enzyme catalyzed reaction is explained by Henry’s theory.
According to him, enzyme first combines with reactant (substrate) to
form an enzyme substrate complex which remains in equilibrium with the
enzyme and substrate.
𝐸 + 𝑆 ↔ 𝐸𝑆
where E is the enzyme, S is the substrate and ES is an enzyme-substrate
complex. The rates of forward and backward reactions are denoted by k 1 and
k 2.
The enzyme substrate complex ES can decompose to form products
with simultaneous regeneration of the enzyme.
𝑘3
𝐸𝑆 → 𝑃 + 𝐸
where P is the product.
The rate of formation of the product may be given as:
𝑑[𝑃]
= 𝑘2 [𝐸𝑆]…..(6.5.1)
During the course of reaction, the concentration of the addition complex
ES remains almost constant. Thus, we have,
d[ES]
=0
dt
Assuming, steady state condition, we obtain,
𝑑[𝐸𝑆]
= 𝑘1 [𝐸][𝑆] − 𝑘−1 [𝐸𝑆] − 𝑘2 [𝐸𝑆] = 0
𝑑𝑡
𝑑[𝐸𝑆]
or = 𝑘1 [𝐸][𝑆] − (𝑘−1 + 𝑘2 )[𝐸𝑆] = 0…..(6.5.2)
The enzyme can exist either in the free form (E) or in the combined
form (ES). So, the total concentration of the enzyme (E)0 is given as:
[𝐸]0 = [𝐸] + [𝐸𝑆]…..(6.5.3)
So, [𝐸] = [𝐸]0 − [𝐸𝑆]
Substituting the value of [E] in equation (6.5.2) gives,
𝑘1 [𝑆]([𝐸]0 − [𝐸𝑆]) − (𝑘−1 + 𝑘2 )[𝐸𝑆] = 0
or [𝐸𝑆] = 𝑘 +𝑘 +𝑘 [𝑆]
−1 2 1
The rate of formation of product can be represented as:
 83

] 𝑘 ]
𝑅𝑎𝑡𝑒 = 𝑑𝑡
=𝑘 ….(6.5.4)
−1 +𝑘2 +𝑘 𝑆]
On dividing the numerator and denominator of equation (6.5.4) by k1,
we get,
𝑑[𝑃] 𝑘 [𝑆][𝐸] 0
𝑅𝑎𝑡𝑒 = = 2 ….(6.5.5)
𝑚
𝑘−1 +𝑘2
where 𝐾𝑚 = …..(6.5.6)
1
Km is known as Michaelis constant. It is having the dimension of
concentration.
The order of reaction in equation (6.5.5) depends on the concentration
of substrate.
At low concentration of substrate: If concentration of the substrate S is
much less than Km, then the rate would be given as:
𝑑[𝑃] 𝑘
= 2 [𝐸][𝑆]….(6.5.7)
𝑚
The rate of reaction will be of first order with respect to substrate and enzyme.
At high concentration of substrate: When concentration of the substrate S
is high, then the rate would be retarded and saturation will be obtained. Hence
]
= 𝑘2 [𝐸]0 ….(6.5.8)
𝑑𝑡
So, the rate of reaction would be of zero order with respect to substrate for a
given amount of enzyme.
If equation (6.5.5) is reversed, we get,
𝑅𝑎𝑡𝑒
= 𝑘 [𝐸] + 𝑘 [𝐸]𝑚 [𝑆] …..(6.5.9)
2 0 2 0

or = [𝑅𝑎𝑡𝑒] +𝑘 𝑚
…..(6.5.10)
𝑅𝑎𝑡𝑒 𝑚𝑎𝑥 2 [𝐸]0 [𝑆]
Thus, a plot of (1/Rate) verses (1/[S]) would be straight line having a slope
(Km/(Rate)max). The extrapolated intercept to (1/[S]) axis is equal to -1/Km.
The Michaelis constant Km is obtained by equation (6.5.6) if k-1 > k2.
Thus,
𝑘 1
𝐾𝑚 = −1 = …..(6.5.11)
1 𝑒𝑞
where Keq is the equilibrium constant for the formation of an enzyme-substrate
complex. Km is the dissociation constant of the complex which characterizes
degree of enzyme affinity for a given substrate. That is, higher the value of
Km, smaller would be the affinity.
From the equilibrium constant Keq, the free energy (∆G) can be
calculated by the equation:
∆G = −RTlnK eq
If equilibrium constant Keq is determined at different temperatures, the
enthalpy (∆H) and entropy (∆S) can also be evaluated using the relation:
 84

∆G = ∆H − T∆S

Chapter 7

Acid –Base catalysis

7.1. Various homogeneous catalytic reactions are catalyzed by acids and

bases. These reactions are known as acid –base catalysis. The real catalysts
are the H+ and OH- ions in acid and base catalysis respectively.

7.2. Types of Acid-base catalysis: There are three types of acid-base

catalysis.
 85

7.2.1. Specific hydrogen ion catalysis: These reactions are catalyzed by H+

ions only. For example, inversion of cane sugar, which is catalyzed by H+ ions
only.
𝐻+
𝐶12𝐻22 𝑂11 + 𝐻2 𝑂 → 𝐶6𝐻12 𝑂6 + 𝐶6𝐻12 𝑂6
The rate of this reaction is proportional to the concentration of hydrogen ions
present in the solution.
𝑑𝑥
= 𝑘𝐶𝐻 + 𝐶𝑐𝑎𝑛𝑒 𝑠𝑢𝑔𝑎𝑟
𝑑𝑡

7.2.2. Specific hydroxyl ion catalysis: These reactions are catalyzed by OH-
ions only. For example, the conversion of acetone into diacetone is catalyzed
by OH- ions only. −
𝑂𝐻
𝐶𝐻3 𝐶𝑂𝐶𝐻3 + 𝐶𝐻3 𝐶𝑂𝐶𝐻3 → 𝐶𝐻3 𝐶𝑂𝐶𝐻2 𝐶(𝐶𝐻3 )2 𝑂𝐻

7.2.3. Hydrogen and hydroxyl ion catalysis: These are the reactions in
which both H+ and OH- ions simultaneously act as catalysis. For example,
(i) Hydrolysis of ester is catalyzed
+
by H−+ as well as by OH-ions.
𝐻 𝑜𝑟 𝑂𝐻
𝐶𝐻3 𝐶𝑂𝑂𝐶2 𝐻5 + 𝐻2𝑂 → 𝐶𝐻3 𝐶𝑂𝑂𝐻 + 𝐶2 𝐻5 𝑂𝐻

(ii) Hydrolysis of nitrile is catalyzed by H+ as well as by OH- ions.

𝐻 + 𝑜𝑟 𝑂𝐻 −
𝑅𝐶𝑁 + 2𝐻2 𝑂 → 𝑅𝐶𝑂𝑂𝑁𝐻4

7.3. General Acid-Base catalysis: The reactions catalyzed by H+ ions are

influenced by undissociated acids and even cations of weak bases such as
NH4+ ions. Thus, all the substances which have a tendency to lose a proton
can function as catalysis.
Similarly, the reactions catalyzed by bases (OH- ions) are also influenced
by undissociated bases or even anions or weak acids such as CH3COO- ions.
Thus, all substances which have a tendency to gain a proton can function as
catalysts.
This discovery gives a new concept of acid –base catalysis known as
general acid –base catalysis.

Types of General Acid-Base catalysis: There are three types.

7.3.1. General acid catalysis: These reactions are catalyzed by hydrogen

ions, undissociated acid and cations of weak bases. Thus, general acid
 86

catalysis are the reactions which are catalyzed by any substance which has a
tendency to lose a proton. For example, iodination of acetone is catalyzed by
monochloro-acetic acid and its salt.
𝐶𝐻3 𝐶𝑂𝐶𝐻3 + 𝐼2 → 𝐶𝐻3 𝐶𝑂𝐶𝐻2 𝐼 + 𝐻𝐼
7.3.2. General base-catalysis: These reactions are catalyzed by hydroxyl
ions, undissociated bases and even anion of weak acids only. Thus, these
reactions are catalyzed by such substance which has a tendency to gain a
proton. For example, in solution decomposition of nitramide is catalyzed by
hydroxyl ions, acetate ions and H2O.
𝑁𝐻4 𝑁𝑂2 → 𝑁2 𝑂𝑂 + 𝐻2 𝑂
7.3.3. General acid –base Catalysis: These reactions are catalyzed by
hydrogen ions, hydroxyl ions, weak acids, weak bases, cations of weak acids
and bases. For example, mutarotation of glucose.

7.4. Mechanism of acid –base catalysis: In acid-base catalysis also, there is

formation of an intermediate complex which then dissociates to give products.
The mechanism of acid base catalysis can be explained by some examples.
(i) The catalyzed transformation of α-glucose into β-glucose:

where H+(I) is a proton supplied by acid catalyst, GH is the -Glucose, HGH+

is the intermediate complex which is unstable, HG is the - glucose and H+
(II) is removed by base catalyst.
(ii) Hydrolysis of Ethyl Acetate catalyzed by proton: This can be
represented as:
 87

(iii) Decomposition of acid base catalysis: Acid-base catalyzed reactions

take place by transfer of proton from an acid to a substance molecule (S) or
from substance molecule to the base. Hence the reaction between an acid HA
and substrate S may be written as:
𝑆 + 𝐻𝐴 ↔ 𝑆𝐻+ + 𝐴−
k1 and k2 are the rate constants of forward and backward reactions
respectively.
𝑆𝐻+ + 𝐻2 𝑂 → 𝑃𝑟𝑜𝑑𝑢𝑐𝑡
Immediately after the start of the reaction, SH + will attain a steady state
concentration. Hence,
𝑘1 [𝑆][𝐻𝐴] = 𝑘−1 [𝑆𝐻 + ][𝐴− ] + 𝑘2 [𝑆𝐻+ ]
𝑘 [𝑆][𝐻𝐴]
or [𝑆𝐻+ ] = − ……(7.4.1)
𝑘 −1 2
Considering the limiting cases:
Case I: If k2 ˃˃ k-1[A-], then
𝑘 [𝑆][𝐻𝐴]
[𝑆𝐻+ ] = 1 ……(7.4.2)
2
Under these conditions the reaction is acid catalyzed and overall rate of
the reaction would be equal to the rate of formation of products. Then,
𝑅𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑟𝑎𝑡𝑒 = 𝑘2 [𝑆𝐻+ ]
or 𝑅𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑟𝑎𝑡𝑒 = 𝑘1 [𝑆][𝐻𝐴]
Thus, the reaction rate is proportional to the concentrations of the substrate
and the acid (in molecular form)
Case II: If k2 ˂˂ k-1[A-], then
𝑘 [𝑆][𝐻𝐴]
[𝑆𝐻+ ] = 1 − ……(7.4.3)
−1
The overall rate is then given as:
𝑅𝑎𝑡𝑒 = 𝑘2 [𝑆𝐻 + ] …..(7.4.4)
Substitution of value of [SH+] from equation (7.4.3) in equation (7.4.4) gives,
𝑘 [𝑆][𝐻𝐴]
𝑅𝑎𝑡𝑒 = 𝑘2 1 − . ……(7.4.5)
−1
If HA dissociates as, 𝐻𝐴 ↔ 𝐻 + + 𝐴−
Then, the equilibrium constant Ka is given by
+ −
𝐾 = [𝐻 ][𝐴 ]
𝑎
[𝐻𝐴]
[𝐻𝐴] [𝐻 + ]
or − = …..(7.4.6)
𝑎
From equations (7.4.5) and (7.4.6), we get,
𝑘1 𝑘2 [𝐻 + ]
𝑅𝑎𝑡𝑒 = ( ) [𝑆] …..(7.4.7)
−1 𝑎
or 𝑅𝑎𝑡𝑒 = 𝑘 / [𝐻 + ][𝑆] …..(7.4.8)
 88

Hence, the reaction rate is proportional to [H+] even in the presence of HA

and A-. This is a simple case of specific acid catalysis.

7.5. Effect of pH on reaction rate: As mentioned above, the rate constant of

a reaction catalyzed by H+ is proportional to H+ concentration, i.e.,
𝑘 = 𝑘𝐻 + [𝐻 + ]…..(7.5.1)
where kH+ is the catalytic coefficient of the hydrogen ions.
On taking logarithms of equation (7.5.1), we get
𝑙𝑜𝑔𝑘 = 𝑙𝑜𝑔𝑘𝐻 + + 𝑙𝑜𝑔[𝐻+ ]
or 𝑙𝑜𝑔𝑘 = 𝑙𝑜𝑔𝑘𝐻 + − 𝑝𝐻…..(7.5.2)
A plot of log k verses pH is a straight line having slope equal to -1.
For a reactions catalyzed by OH-
𝑘 = 𝑘𝑂𝐻 − [𝑂𝐻− ] = 𝑘𝑂𝐻 − + …..(7.5.3)
[𝐻 ]
-
kOH- is the catalytic coefficient of OH .
𝑘 = (𝑙𝑜𝑔𝑘𝑂𝐻 − + 𝑙𝑜𝑔𝑘𝑊 ) + 𝑝𝐻…..(7.5.4)
Hence, a plot of log k against pH is a straight line having a slope equal to
+1.
For reactions catalyzed by both acids and bases i.e., H+ and OH-, the rate
constant, k, is given as:
𝑘 = 𝑘0 + 𝑘𝐻 + [𝐻 + ] + 𝑘𝑂𝐻 − [𝑂𝐻 − ] ……(7.5.5)
At low pH conditions, the contribution of third term to the overall rate of
reaction is negligible. Hence, the plot of log k versus pH gives slope equal to
-1. At high pH, the second term will not contribute and hence log k versus pH
plots should have slope equal to +1. Actually for such reactions, log k versus
pH plots show a minimum which is given by,
1
(𝑝𝐻) 𝑚𝑖𝑛 = 2 [𝑙𝑜𝑔𝑘𝐻 + − 𝑙𝑜𝑔𝑘𝑂𝐻 − + 𝑝𝑘𝑊 ] ……(7.5.6)
Figure 7.1 shows the effect of pH on rate constants for various reactions
catalyzed by acids and bases.
 89

Fig. 7.1: The effect of pH on reaction rate for acid-base catalyzed

reactions. (a) inversion of sugar. Curve (b) hydrolysis of esters (c)
depolymerization of diacetone alcohol. (d) mutarotation of glucose.

7.6. Catalytic coefficient: The effectiveness of any acid –base catalyst can be
measured by catalytic coefficient.
The rate of reaction is affected by all the species present in the solution.
For a solution having a weak acid HA and its conjugate base, the rate constant
is given as:
𝑘 = 𝑘0 + 𝑘𝐻 + [𝐻 + ] + 𝑘𝑂𝐻 − [𝑂𝐻− ] + 𝑘𝐻𝐴 [𝐻𝐴] + 𝑘𝐴− [𝐴− ]
where k0 denotes the rate constant for the uncatalyzed reaction and other k ‘s
denote the catalytic coefficient for the species involved. This is general
equation for any acid –base catalysis.
For any reaction in aqueous solutions, the catalytic coefficients of H+ and
OH- are much larger than that of HA and A-. But in the acid catalysis, the first
stage of the reaction involves the transfer of proton from acid to the substrate
molecule. Therefore, the catalytic coefficient of an acid is related to the
protonating power and hence the strength of the acid. Further, the catalytic
coefficient of a base is related to the dissociation constant for the base, which
is inversely proportional to the ionization constant of the conjugate acid (Ka).

Chapter-8

Reactions in Solutions
 90

8.1. Introduction. Reactions in solution are more complex than that in gas
phase. When a solute molecule dissolves in a solvent, it enters into a loose
combination with a salvation shell of the surrounding molecules. Therefore,
kinetics of chemical reactions depend on the nature of this solvent shell.
Further, when a chemical reaction is occurring in a solution, the solvent is
generally present in large excess, so its concentration is assumed to be
constant during the course of the reaction. However, in some reactions,
solvent takes part in chemical reaction and is not generated at the end of the
reaction. In such reactions, solvent affects the rate of reaction. Mechanism of
such reactions is changed when the solvent is changed.
In case of solutions, collision theory indicates that the total number of
collisions in a solution is more as compared to that in a gas because in
solutions, molecules are much closer one another than in gases.
The reactions in the solution involve the following three stages: (i)
diffusion of reacting molecules towards each other, (ii) reaction between the
molecules with the formation of activated complex and (iii) diffusion of
products away from each other.

8.2. Application of Activated Complex Theory to Reactions in Solution:

Bronsted-Bjerrum Equation: The theory of activated complex is used to
study the role of solvent medium in chemical kinetics.
Consider a bimolecular reaction:
𝐴 + 𝐵 ↔ (𝑋 ≠ )…..(8.2.1)
where A and B are reactants and (X#) is an activated complex.
(𝑋 ≠ ) → 𝑅𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 …..(8.2.2)
So, the rate of reaction is given as:
𝑅𝑎𝑡𝑒 = 𝑣[𝑋 ≠ ] …..(8.2.3)
where [X#] is the concentration of activated complex.
According to the absolute reaction rate theory, the rate equation for this
reaction is
𝑘𝑇
𝑣 = ( ) [𝑋 ≠ ] …..(8.2.4)
where k is the Boltzmann constant, h is Planck’s constant, T is the reaction
temperature. [X#] is the concentration of activated complex.
The equilibrium constant K≠ for equation (8.2.1) is given as:
≠
𝐾≠ = 𝑎 …..(8.2.5)
𝐴 𝑎𝐵
where a’s are the activities of reactants A and B and of activated complex.
The equation (8.2.5) can be written as:
≠ 𝛾
𝐾 ≠ = [𝐴][𝐵] . 𝛾 ≠𝛾 …..(8.2.6)
𝐴 𝐵
 91

where square brackets denote concentration of species. γA, γB and γ≠ are the
activity coefficients of the initial reactants A, B and of the activated complex.
Rearrangement of equation (8.2.6) gives,
𝛾 𝛾
[𝑋 ≠ ] = 𝐾 ≠ [𝐴][𝐵] 𝐴 𝐵 …..(8.2.7)
≠
So, equation (8.2.4) becomes:
𝑘𝑇 𝛾 𝛾𝐵
𝑣 = ( ) 𝐾 ≠ [𝐴][𝐵] …..(8.2.8)
𝛾≠
The rate law depends on the concentrations of the reactants A and B,
i.e.,
𝑅𝑎𝑡𝑒 ∝ [𝐴][𝐵]
or 𝑅𝑎𝑡𝑒 = 𝑘𝑟 [𝐴][𝐵]…..(8.2.9)
where kr is rate constant.
Thus, from equations (8.2.8) and (8.2.9), we get,
𝑘𝑇 𝛾 𝛾𝐵
𝑘𝑟 [𝐴][𝐵] = ( ) 𝐾 ≠ [𝐴][𝐵] 𝛾≠
…..(8.2.10)
𝑘𝑇 𝛾𝐴 𝛾𝐵
or 𝑘𝑟 = ( ) 𝐾 ≠ …..(8.2.11)
≠
Equation (8.2.11) is the equation for reactions in solution. (kT/h) is known as
universal frequency having the dimension of time-1. The value of (kT/h)
depends only on temperature and is independent of the nature of the reactants
and types of reaction.
In the vapor phase, the activity coefficient of the reacting particles and
of the activated complex may be taken as equal to unity. The specific rate of
the reaction is thus in the vapor phase.
𝑘𝑇
𝑘0 = 𝐾 ≠ …..(8.2.12)
and in the liquid phase,
𝛾 𝛾
𝑘 = 𝑘0 𝐴 𝐵…..(8.2.13)
≠
This equation is known as Bronsted and Bjerrum equation for the reactions
taking place in an arbitrary medium. Here k0 is the reaction rate constants
under ideal conditions, i.e. at low pressure for gaseous state and in extremely
dilute solution in liquid phase reaction.

8.3. Influence of ionic strength of solutions on reaction rates: Salt Effects:

Since ions exert considerable electrostatic forces on each other, the kinetics
of reactions between ions deviates from such reactions which involve non-
electrolytes. Thus, electrostatic interactions cause the equilibrium properties
of ionic solution to deviate greatly from ideality. The velocity constants of
ionic reactions depend upon the charges of reacting ions and also the ionic
 92

strength of solution. Thus, the effect of electrolytes can be divided into two
main types:

(i) Primary kinetic Salt Effect: It refers to the effect of ionic strength
on the rate constant.
(ii) Secondary salt effect: It refers to the actual change in the
concentration of reacting ions by the addition of electrolytes.

8.3.1. Primary salt effect: The rates of reactions in solution are affected by
the presence of electrolytes whether they are reactants, products or an added
inert salt. Inert salt is a salt whose ions do not react with either the reactant or
product. This effect of inert salts in the reaction rate is called primary salt
effect. The effect of inert salts on the rates of reaction can be calculated by
transition theory.
Suppose that the reaction is between two ions, ion A with a charge of
ZA and B with a charge of ZB. It proceeds though an activated complex, (AB#)ZA
+Z
B. Thus,
≠
𝐴 𝑍𝐴 + 𝐵 𝑍𝐵 ↔ [𝐴𝐵 (𝑍𝐴 +𝑍𝐵 ) ] → 𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠 …..(8.3.1)
For the equilibrium between the reactants and activated complex, we may
write
≠
+
𝐾≠ = …..(8.3.2)
𝑎(𝐴 𝑍𝐴 )𝑎(𝐵 𝑍𝐵 )
Since we are dealing with ions, it is necessary to express the equilibrium
constant K≠ in activities rather than concentration. Equation (8.3.2) can be
written as:
≠ ≠
) +( )
( [ (𝑍 + ) ]
𝐾≠ = 𝛾(𝐴 𝛾 𝐵 )
. [𝐴 ][𝐵 𝑍 ]
…..(8.3.3)
𝑍𝐴 𝑍𝐵
≠ 𝑍𝐵 𝛾(𝐴 )𝛾(𝐵 )
or [𝐴𝐵 (𝑍𝐴 +𝑍𝐵 ) ] = 𝐾 [𝐴 ][𝐵 ]
≠ 𝑍𝐴
≠
…..(8.3.4)
𝛾(𝐴𝐵 (𝑍𝐴+𝑍𝐵 ) )
where a ‘s are the activities γ ‘s are the activity coefficients.
According to the transition state theory. 𝑍
≠ 𝑘𝑇 𝛾(𝐴 𝐴 )𝛾(𝐵 𝑍𝐵 ) 𝑘𝑇
𝑣 = [𝐴𝐵 (𝑍𝐴 +𝑍𝐵 ) ] ( ) = 𝐾 ≠ [𝐴 𝑍𝐴 ][𝐵 𝑍𝐵 ] ≠
…..(8.3.5)
𝛾(𝐴𝐵 (𝑍𝐴+𝑍𝐵) )
For a bimolecular reaction between A and B, the experimental rate of reaction
may be expressed as:
𝑣 = 𝑘[𝐴 𝑍𝐴 ][𝐵 𝑍𝐵 ] …..(8.3.6)
where k is the experimentally evaluated rate constant. Equating equations
(8.3.5) and (8.3.6), we get:
 93

𝐵 𝐵
𝑘𝑇 𝛾(𝐴 )𝛾(𝐵 𝐵≠)
𝑘[𝐴 𝑍𝐴 ][ 𝑍𝐵 ] = (𝐾 ≠ ℎ ) [𝐴 𝑍𝐴 ][ 𝑍𝐵 ] 𝛾(𝐴 ( )
)
𝐵
𝑘𝑇 𝛾(𝐴 𝑍𝐴 )𝛾(𝐵 𝑍𝐵)
or 𝑘 = (𝐾 ≠ ) ≠
𝛾(𝐴𝐵 (𝑍𝐴+𝑍𝐵 ) )
𝑍𝐴
𝛾(𝐴 )𝛾(𝐵 𝑍𝐵 )
or 𝑘=𝑘 …..(8.3.7)
0 ≠
𝛾(𝐴𝐵 (𝑍𝐴 +𝑍𝐵 ) )
𝑘𝑇 ≠
where 𝑘0 = 𝐾
This is known as Bronsted –Bjerrum equation. Taking the logarithm of
equation (8.3.7) gives:
≠
𝑙𝑛𝑘 = 𝑙𝑛𝑘0 + ln[𝛾(𝐴 𝑍𝐴 )] + ln[𝛾(𝐵 𝑍𝐵 )] − ln [𝛾(𝐴𝐵 (𝑍𝐴 +𝑍𝐵 ) )] …..(8.3.8)
The activity coefficient of the ion depends upon the ionic strength of the
solution which is defined as:
1
𝜇 = ∑ 𝑚 𝑖 𝑧 2𝑖
2
The term mi and zi are the molarity and charge of an ion i, and the summation
includes all the ions present in the solution.
The activity coefficient is related to the ionic strength of the solution by
Debye- Huckel’s limiting law:
𝑙𝑜𝑔𝛾𝑖 = −𝐴𝑧𝑖2√𝜇
where A is a constant, zi is the charge of an ion i and μ is the ionic strength.
For an aqueous solution at 250C the constant A= 0.509 then we have
𝑙𝑜𝑔𝛾𝑖 = −0.509𝑧𝑖2 √𝜇 …..(8.3.9)
Hence equation (8.3.8) becomes:
𝑙𝑛𝑘 = 𝑙𝑛𝑘0 − ln[0.509𝑧𝐴2 + 0.509𝑧𝐵2 − 0.509(𝑧𝐴 + 𝑧𝐵 )≠ ]√𝜇 …..(8.3.10)
or 𝑙𝑛𝑘 = 𝑙𝑛𝑘0 + 1.018 𝑧𝐴 𝑧𝐵 √𝜇 …..(8.3.11)
Equation (8.3.11) indicates that the rate constant of an ionic reaction in
solution should depend on the ionic strength. This is the kinetics salt effect.
Figure 8.1 shows the effect of ionic strength on reaction rates for various
reactions shown in Table 2.
Reactions between pairs of ions of like charge are usually accelerated
by increasing the ionic strength. The process is favored by high ionic strength
because of the favorable interaction of activated complex with its denser ionic
atmosphere (systems I, II and III).
Conversely, reactions between ions of unlike charge are usually slowed
down. This is because the cancellation of charge on complex formation is
unfavorable due to lessening of its interaction with the ionic atmosphere
(systems V, VI and VII).
 94

Table 2: Reactions represented in the graph

System Reactants 𝑠𝑙𝑜𝑝𝑒 ⁄𝑍𝐴 𝑍𝐵
2+ 2+
I [𝐶𝑜[𝑁𝐻3 ]5 𝐵𝑟] + 𝐻𝑔 +4
− −−
II 𝐶 𝐻2 𝐵𝑟𝐶𝑂𝑂 + 𝑆2 𝑂 +2
− −
III 𝐶 𝐻2 𝐶𝑙𝐶𝑂𝑂 + 𝑂𝐻 +1
IV 𝐶 𝐻2 𝐵𝑟𝐶𝑂𝑂𝐶 𝐻3 + 𝑆2 𝑂 −− 0
+ −
V 𝐻2 𝑂2 + 𝐻 + 𝐵𝑟 -1
2+ −
VI [𝐶𝑜[𝑁𝐻3 ]5 𝐵𝑟] + 𝑂𝐻 -2
VI I 2 +
𝐹𝑒 + 𝐶𝑜(𝐶2 𝑂 ) 3− -6

√μ
Fig. 8.1: Effect of ionic strength on reaction rates for various reactions

The rates of reaction between two uncharged molecules, or between an

ion and a molecule are usually only slightly affected by the addition of inert
salts.

8.3.2. Secondary salt effect: The secondary salt effect is involved in catalytic
reactions. The rate of reaction may change by changing the effective
concentration of the catalyzing species. The rate can also be altered by
changing the concentration of one of the reacting ions in the presence of
foreign electrolyte that changes the ionic strength of the solution. Thus, the
degree of dissociation of reacting electrolyte changes. This phenomenon is
independent of primary salt effect and is known as the secondary salt effect.
If the reactions are catalyzed by acids or bases, i.e., H+ or OH- ions, the
addition of inert salt affects the concentration of H+ or OH- ions. Since the rate
 95

of reaction is a function of the degree of ionization of acetic acid, it is

proportional to the concentration of H+ or OH- ions. Thus the rate constant
will be influenced by the salt concentration, i.e., rate constant would depend
on the ionic strength.
Consider the hydrolysis of cane sugar catalyzed by a weak acid.
𝑤𝑒𝑎𝑘 𝑎𝑐𝑖𝑑
𝐶12 𝐻22𝑂11 + 𝐻2 𝑂 → 𝐶6 𝐻6 𝑂6 + 𝐶6 𝐻6 𝑂6
The rate of reaction is proportional to the concentration of H+ ions, i.e.,
𝑘𝑒𝑥𝑝 ∝ [𝐻+ ]
or 𝑘𝑒𝑥𝑝 = 𝑘[𝐻+ ] …..(8.3.12)
The catalyst comes from the dissociation of weak acid. Thus
𝐻𝐴 ↔ 𝐻 + + 𝐴−
[𝐻 +][𝐴− ]. 𝛾 [ + 𝛾[𝐴− ]
and 𝐾= [ 𝛾[𝐻 ]
[ 𝐴] 𝛾
or [𝐻 + ] = 𝐾 𝐴− . 𝛾 [ 𝛾 ] −
[ +] [ ]
If the reaction is carried out at fixed ratio of ([HA] /[A-]) by making use
of buffer solution, then
𝛾[𝐻𝐴]
[𝐻+ ] = 𝐾 / . …..(8.3.13)
[𝐻+ ] [𝐴− ]
+
Substituting [H ] in equation (8.3.12), we get,
𝛾[𝐻𝐴]
𝑘𝑒𝑥𝑝 = 𝑘𝐾 / . …..(8.3.14)
𝛾[𝐻 + [ −]
𝛾[𝐻𝐴]
or 𝑘𝑒𝑥𝑝 = 𝑘0 . …..(8.3.15)
[𝐻 +] [𝐴 − ]

or 𝑙𝑜𝑔𝑘𝑒𝑥𝑝 = 𝑙𝑜𝑔𝑘0 + 𝑙𝑜𝑔 𝛾[𝐻𝐴] − 𝑙𝑜𝑔 𝛾[𝐻 +] − 𝑙𝑜𝑔 𝛾[𝐴−] …..(8.3.16)

For undissociated HA (solid), activity coefficient (γ) is equal to one so
log γHA is equal to zero.
The Debye –Huckel limiting law is,
−𝑙𝑜𝑔𝛾𝑖 = −𝐴𝑍𝑖2√𝜇 … . . ( 8 . 3 . 1 7)
where γi is activity coefficient of i ions of valency Z, μ is ionic strength and A
is constant which depends on the dielectric constant of medium and
temperature.
Using Debye –Huckel limiting law (equation (8.3.17) for each ion,
equation (8.3.16) becomes:
𝑙𝑜𝑔𝑘𝑒𝑥𝑝 = 𝑙𝑜𝑔𝑘0 + 1.018√𝜇 …..(8.3.18)
The equation (8.3.18) shows that kexp increases with an increase in the
ionic strength of the solution.
 96

8.4. Effect of pressure on rate of reactions in solution: Reaction rates are

determined from the reaction mixture which takes place at constant volume
(for gaseous reactions) or at constant pressure (for reactions in solution).
At normal pressures, the reaction rate for a reaction in the solution does
not depend upon the pressure. But at high pressures, changes in the reaction
rates have been observed which can be measured. The study of effect of
pressure on reaction rate provides valuable information regarding the
mechanism of a reaction.
Consider a reaction:
𝐴 + 𝐵 ↔ 𝐴𝐵 ≠
According to the activated complex theory, the rate constant k is related
to the equilibrium constant by:
𝑘𝑇
𝑘 = 𝐾 ≠ …..(8.4.1)
where K≠ is the equilibrium constant of the reaction between the reactants and
the activated complex.
Taking logarithm of equation (8.4.1), we get
𝑘𝑇
𝑙𝑛𝑘 = 𝑙𝑛 ( ) + 𝑙𝑛𝐾 ≠ …..(8.4.2)
Differentiating equation (8.4.2) with respect to pressure P at a constant
temperature, T, we get,
𝜕𝑙𝑛𝑘 𝜕𝑙𝑛𝐾 ≠
( ) =( ) …..(8.4.3)
𝑇 𝑇
For any reaction, the standard free energy change (∆G) of the reaction
is related to the equilibrium constant (K) by the equation:
∆𝐺 = −𝑅𝑇𝑙𝑛𝐾
For a process involving the reactants and the activated complex, it
becomes:
∆𝐺 ≠ = −𝑅𝑇𝑙𝑛𝐾 ≠ …..(8.4.4)
where ∆G≠ represents the standard free energy change for the formation of the
transition state, and K≠ is the corresponding equilibrium constant.
Equation (8.4.4) can also be written as:
∆𝐺 ≠ ∆𝐻 ≠ ∆𝑆 ≠
𝑙𝑛𝐾 ≠ = − =− + …..(8.4.5)
≠ ≠ ≠
where ∆G , ∆H , ∆S are the standard free energy, enthalpy and entropy
changes respectively for the formation of transition state.
We know that, ∆𝐻 ≠ = ∆𝐸 ≠ + 𝑝∆𝑉 ≠
∆𝐸 ≠ 𝑝∆𝑉 ≠ ∆𝑆 ≠
Therefore, 𝑙𝑛𝐾 ≠ = − − + …..(8.4.6)
Partial differentiation of equation (8.4.6) with respect to pressure, at
constant temperature gives:
 97

𝜕𝑙𝑛𝐾 ≠ ∆𝑉 ≠
( ) =− …..(8.4.7)
𝑇
The quantity ∆V≠ is the volume of activation because it represents a change in
the molar volume of the system, in going from the reactant to the transition
state.
Equation (8.4.7) shows that: (i) The rate constant of a chemical reaction
increases with increasing pressure when ∆V≠ < 0 (the volume of the activated
complex is less than the total volume of the reactants). (ii) The rate constant
decreases with increase in pressure when ∆V≠>0. (iii) The reaction rate is
almost independent of pressure when ∆V≠ is negligibly small.
From equations (8.4.3) and (8.4.7), we get,
𝜕𝑙𝑛𝑘 ∆𝑉 ≠
( ) =− …..(8.4.8)
𝑇
Integration of equation (8.4.8) gives:
≠
−𝑙𝑛𝑘 = − 𝑅𝑇 + 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡…..(8.4.9)
When the applied pressure P is zero, k =k0. Hence
≠
𝑙𝑛𝑘 = 𝑙𝑛𝑘0 − 𝑅𝑇
…..(8.4.10)
𝑘 𝑃𝑉 ≠
or 𝑙𝑛 ( ) = − …..(8.4.11)
0
Thus, according to the transition state theory, in any incompressible system,
the plot of ln (k/k0) versus applied pressure, P should be straight line passing
through the origin (Figure 8.2) .The value of ∆V≠ can be determined from the
slope –∆V≠/RT.

Fig. 8.2: Dependence of log (k/k0) on pressure P

This secondary salt effect can cause either an increase or decrease in
the rate constant and can be either larger or smaller than a primary salt effect.
 98

In some cases, both the primary and secondary salt effect occur, in which case
cancellation of effect may cause the reaction rate to appear to be independent
of the ionic strength.
It is concluded from experimental studies that the reactions are of the
following types:
(i) When ∆V≠ is negative: The rates of such reactions increase by increasing
the pressure. This occurs in those reactions where there is an increase in the
electrical charge in going from reactants to the transition state e.g., the
unimolecular SN1 solvolysis and reactions of alkyl halides with amines. Such
reactions are known as slow reactions.
(ii) When ∆V≠ is negligibly small: The rates of such reactions are almost
independent of pressure. This occurs in those reactions in which the transition
state possesses the same charge as the reactants e.g., reaction of hydroxyl ion
with primary alkyl halides (SN2). These reactions occur at normal rates.
(iii) When ∆V≠ is positive: The rates of such reactions decrease with an
increase in the pressure. This occurs in reactions between the two opposite
charged ions such that there is decrease in the charge in going from reactants
to the transition state. e.g.,
𝐶𝑜(𝑁𝐻3 )5 𝐵𝑟 2+ + 𝑂𝐻 − → [(𝑂𝐻)𝐶𝑜(𝑁𝐻3 )5 𝐵𝑟 + ] → 𝐶𝑜(𝑁𝐻3 )5 𝑂𝐻 2+𝐵𝑟 −
Such reactions are generally fast.

8.5. Influence of Solvent on Reaction Rates: It was observed that not all
reactions are influenced in the same manner by a series of solvents. For
example, decomposition of nitrogen pentoxide and hexaphenyl ethane takes
place at almost the same rate in a number of media. Whereas for the reaction
between ethyl alcohol and acetic anhydride, the solvent influences is almost
the reverse of that observed for the reaction of triethylamine and ethyl iodide.
A polar solvent may increase a process in which a polar substance is
the product and retard one in which a nonpolar substance is formed. For
example, in a reaction of triethylamine and ethyl iodide, the product is a salt,
hence more polar than the reactants; the rate is increased as the polarity of the
solvent increases. Whereas in the acetylation of alcohol, the product is less
polar than the reactants, and the solvent effect will be reversed.
If either the reactants or the activated complex interacts with the
solvent, there may be considerable effect on the reaction rate. The effect of
interaction with the solvent is to lower the potential energy of the substance
by an amount equal to the energy of salvation. If one or both the reactants are
solvated, while the activated complex is not, the decrease in potential energy
means the increase in activation energy so the reaction rate will be decreased.
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 If the activated complex is solvated, but the reactants are not, the lowering of potential
energy means an equivalent decrease in the energy of activation of the reaction. So,
the specific rate will be greater than the normal.

TRIAL QUESTIONS

1. Deduce the expression for first order kinetics. Show that the time for half
decomposition of a first order reaction is independent of the initial concentration of
the reactant. 2. Deduce the expression for second order kinetics where the two
reactants are same. Show that the time for half decomposition of a second order
reaction is dependent on the initial concentration of the reactant.
3. What is pseudo unimolecular reaction? By taking an example show that the specific
reaction rate of a pseudo unimolecular reaction follows first order kinetics.
4. What is homogeneous catalysis? Give an example of gas phase homogeneous cata-
lyst. Show that for homogeneous catalysis the rate of reaction is dependent on catalyst
concentration.
5. Write short notes on activation energy.
6. Deduce the expression for the rate of the bimolecular reaction by using collision
theory. Under what condition the reaction will follow i) first order kinetics ii) second
order kinetics.
References

1. Kapoor, K.L (2019) A Text book of physical chemistry, Mc Graw-Hill volume

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2. Peter Artikin, Julio de Paula, James Keeler(2019); Atkin’s physical chemistry
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reactions.
3. Arun Bahl, B.S Bahl, G.D Tuli (2014) Essentials of Physical Chemistry 6 th
Edition, New Delhi volume 5, Chemical Kinetics
4. Kapoor, K.L(2012) A Text book of physical chemistry, Dynamics of chemical
reactions, Statistical thermodynamics, macromolecules and irreversible
processes, Vol 5, MC Graw-Hill 5th edition
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