Lesson No-1

SOLIDS
Reality is for people who can't face science fiction

A solid is classified either as crystalline or amorphous. A crystalline solid shows

sharp melting point. An examination with microscope reveals well developed faces and
characteristic shapes in crystals. X-ray diffraction shows a crystalline solid to be possessing
a regular ordered structure composed of identical repeating units having the same orientation
throughout the crystal. The repeating unit is a group of one or more atoms, molecules or
ions. An ampuorous solid does not have characteristic crystal shape. When heated, an
amphorous solid melts over a temperature range. X- ray diffraction shows a disordered
structure.
The crystal systems
The faces of crystals and the planes within the crystal can be characterised by means
a set of three non coplanar axes. Let us consider the three non coplanar axes having
lengths a, b and c, which are cut by the plane ABC making intercepts OA, OB and OC.
If a,b,c are chosen as unit lengths, the lengths of the intercepts may be expressed as
OA/a, OB/b and OC/c.

Fig. 1 crystal axes intercepted by a crystal plane.

The reciprocals of these lengths will then be a/OA, b/OB, c/OC. It has been observed
that it is always possible to find a set of axes on which the reciprocal intercepts of crystal
faces are small whole numbers. Thus if h,k,l are small integers,
a b c
 h,  k,  l.
OA OB OC
The use of reciprocal intercepts (hkl) as indicies to define the crystal faces was
proposed by W.H.Miller and so these indicies are termed as Millers indicies. If a face of the
crystal is parallel to an axis, the intercept is at infinity and the Miller index becomes 1/  or
zero. The notation is also applicable to planes drawn within the crystal. The application of
Miller indices to some of the planes in a cubic crystal is illustrated in Fig.2.

Fig.2 Miller indices of planes in cubic lattice

1
 According to the set of axes used to represent their faces, crystals may be divided
into seven systems. These systems range from the completely general set of three unequal
axes (a, b, c) at three unequal angles ( ,  , r ) of the triclinic system, to the highly
symmetrical set of three equal axes at right angles of the cubic system. These are sum
marised in Table 1.
Table 1. The cubic systems of crystals

S.No.System Axes Angles Example

1. Cubic a b c     900 Rock salt

2. Tetragonal a  b; c      900 White tin

3. Orthorhonmbic a;b;c      900 Rhombic sulpher

4. Monoclinic a;b;c   r  900 ;  Monoclinics sulpher

5. Rhombohedral a b c    r Calcite

6. Hexagonal a  b;c     900 ; r  1200 Graphite

7. Triclinic a;b;c  ; ; r Potassium dichomate.

A crystal is considered to be consisting of elementary material units on a regular

array of points in space. This is called a lattice. An exmaple in two dimensions is shown in
Fig.3. The lattice points can be connected by a regular network of lines in various ways.

Fig.3 Two dimensional lattices with unit cells.

Thus the lattice is broken up into a number of unit cells. Some examples are shown
in the Fig.3. Each cell requires two vectors, a and b, for its description. A three dimensional
space lattice can be similarly divided into unit cells described by three vectors. If each point
in a space lattice is replaced by an identical atom or group of atoms the crystal structure of
the substance will be obtained. The lattice is an array of points. In the crystal structure each
point is replaced by a material unit. The positions of the atoms in unit cells are dentoed by
coordinates which are fractions of the unit cell dimensions. If a unit cell has sides a,b,c an

2
 1 1 1 a b c
atom at  , ,  would be at  , ,  relative to the origin (0,0,0) at a corner of the
 2 4 2  2 4 2
cell.
Bravais showed that all possible space lattices could be assigned to one of only 14
classes. The fourteen Bravais lattices are represented in Fig.4. These lattices provide
differents translational relations between points in an infinitely extended regular three
dimensional array.

Fig.4 The Fourteen Bravais lattices.

3
Symmetry properties in crystals :
The term symmetry in crystals has been used to refer to the arrangement of crystal
faces. Symmetry is described in terms of certain symmetry operations, which transform
the crystal into an image of itself. The symmetry operations are the result of certain symmetry
elements. The possible symmetry elements of finite figures such as crystals are, mirror
plane of symmetry, rotation axis symmetry, centre of symmetry, rotatory invension etc.
There are exactly thirty two possible combinations of these symmetry elements in crystals.
These combinations of symmetry elements define 32 crystallographic point groups which
determine the 32 crystal classes. The symbol for a crystal class is derived by writting down
the symmetry elements associated with the three important directions in the crystal.
The unit all of crystalline rock salt possesses the full symmetry of the cube, viz.,
three four fold axes, four 3-fold axes, six 2-fold axes, three mirror planes perpendicular to
the 4-fold axes, six mirror planes perpendicular to the 2-fold axes and a centre of invension
(Fig. 5).

Fig.5 Symemtry elements of Rock salt cubic crystal.

The crystal classes are the groups of symmetry operations. These groups are made
up of operations by symmetry elements which leaves at least one point in the crystal
inveriant. So these groups are termed as point groups. Since the crystal structure is
considered as an infinitely extended pattern in space, new types of symmetry operation,
which leave no point invariant, are applicable. The new symmetry operations involve
translations in addition to rotations and reflections. So these possible groups of symmetry
operations of infinite figures are called space groups. They may be considered to arise
from combinations of the 14 Bravais lattices with the 32 point groups. The space group
expresses the sum total of the symmetry properties of a crystal structure.

4
 Lesson No-2
X-RAY DIFFRACTION STUDIES
The Chemists have made their universe. If you don't like it, you must make your own

In 1912 while studies were carried on crystallography and behaviour of X-rays, it was
proposed that if the wavelength of X-radiation is comparable to the distance between atoms
in the crystal, a diffration pattern should result when X-rays are passed through the crystal.
Such result was observed when X-rays are passed through copper sulphate crystal and
the new science of X-ray crystallographly began.
The Bragg Treatment :
It was shown that the scattering of X-rays could be represented as a reflection by
successive planes of atoms in the crystal. Consider in Fig.6, a set of paraller planes in the
crystal structure and a beam of X-rays incidenting at an angle  . Some of the rays will be
reflected from the upper layer of atoms, the angle of reflection being equal to the angle of
incidence. Some of the rays will be absorbed, and some will be reflected from the second
layer, and so on with successive layers. All the waves reflected by different underlying
planes be in phase with one another. That particular condition is that the difference in length
of path between the the waves scattered from successive planes must be an integer numbe
of wavelength, n  .

Fig.6. Bragg scattering condition

If we consider the reflected waves at the point P, this path difference for the first two planes
is   AB  BC . Since triangles AOB and COB are congruent, AB  BC and   2 AB .
Therefore 8  2d sin  . The condition for reinforcement of Bragg reflection is thus,
n   2d sin  .
So, there are different orders of reflections specified by the values of n  1, 2,3..... .
The second order diffraction maximum from (100) planes may be regarded as a reflection
due to a set of planes (200) with half the spacing of the (100) planes.
Braggs (X-ray spectrometer) method :
A single crystal was mounted on the spectrometer, as shown in Fig.7, so that X-ray
beam was incident on one of the important crystal faces, (100), (110) or (111). The Bragg
spectrometer was arranged so that the reflected beam enters the ionization chamber, which
was filled with methyl bromide. The intensity of X-radiation was measured by the charge
built up on the electrometer.

5
 Fig. 7 Bragg X-ray spectrometer

The experimental data plotted in Fig 8. for NaCl and KCl crystals represents the
graphs drawn between intensity of scattered beam and twice the angle of incidence of
X-ray beam. As the crystal is rotated, successive maximum intensities of reflected radiation
was observed at angles which are conforming to the Bragg's equation. In these studies the
monochromatic X-radiation is obtained from a palladium target.

Fig 8. Bragg experimental data, Intensity vs.

2 (angle of incidence)

6
 The distance between the planes in a cubic lattice is given by,
a
d hkl 
(h 2  k 2  l 2 )

where dhkl is the distance between the successive hkl planes and 'a' is the lenngth of the
side of the cubic unit cell. Combining this equation with Bragg's equation, we set.

2
sin 2   2
(h 2  k 2  l 2 )
4a

So each observed value of sin can be indexed by assigning values to h k l for the
set of planes responsible for that reflection.
For a simple cubic lattice the following spacings are allowed.
221
hk l 100 110 111 200 210 211 220 300 etc.

h2  k 2  l 2 1 2 3 4 5 6 8 9 etc.

If the observed X- ray diffracted pattern from a simple cubic crystal was plotted as
intensity vs sin 2  , we should obtain a series of six equidistant maxima. Then the seventh

should be missing, since there is no set of integers ( h k l ) such that h 2  k 2  l 2  7 . After

that there would be seven more equidistant maxima, with the 15th one missing. Later
seven more equidistant maxima would be observed with the 23rd one missing etc.
Let us consider the (100), (110) and (111) planes of a simple cubic lattice represented
in Fig.9. A structure basing on this lattice would be obtained by replacing each lattice point

d100  a 1 1
d110  a d111  a
(100) 2 3
(110) (111)
(a)

Fig.9 Spacings in cubic lattices of simple cubic lattice

7
  1   
by an atom. If an X-ray beam strikes such a structure at the Bragg angle    sin   ,
  2a  
the X-rays scattered from the (100) planes will be exactly in phase with the rays from
successive (100) planes. A strong scattered X-ray beam may be called the 'first order
reflection from the (100) planes.' A similar result is obtained for the (110) and (111) planes.
With a structure based on simple cubic lattice, we should obtain a diffraction maximum
from each set of planes ( h k l ) , since for any given ( h k l ) all the atoms are included in
those planes.

Fig.10 shows a structure based on a body centerd cubic lattice. The (110) planes,
pass through all the lattice points as in the case at simple cubic lattice and so a strong first
order (110) reflections occurs. Howerer, in case of (100) planes, exactly mid way between
any two (100) planes, there lies another layer of atoms. When X-rays scattered from the
(100) planes are in phase, the rays scattered from interleaved planes will be retarated by
half a wavelength and hence will be exactly out of phase with the reflections from the (100)
planes. Therefore, the observed intensity will be the difference between the scattering
intensities from the two sets of planes. When all the atoms have identical scattering powers,
the resultant intensity will be reduced to zero due to destructive interference and no first
order reflections will appear.

1 1 1
d 200  a 2 d110  2 a d 222  . 3a
2 2 3
(b)

Fig.10 Spacings in body centred cubic lattice

But if atoms are different, the first order reflections will appear but with reduced
intensity. The (200) planes, situated at exactly half the distance between successive (100)
planes, provides the same first order reflection as the second order reflection from (100)
planes. In body centered cubic lattice all the atoms lie in the (200) planes and a strong
scattered beam is obtained. The same situation applies for the (111) planes and the
reflections from (111) planes are weak or extinguished. But the second order reflections
( n  2) from the (111) planes, i.e; the (222) planes will give strong reflections.
In the case of the face centered cubic structure Fig.11, the reflections from (100) and
(110) planes are missing and the reflections from (111) planes are very intense. So, the
second order reflections from the planes (100) and (110) i.e., (200) and (220) are intense
and give strong reflections.

8
 (c)

Fig 11. spacings in face centered cubic lattice.

From the above discussion, the ratios of the interplanar distances of different faces
in the three cubic lattices are :

1 1
Simple cubic lattice d100 : d110 : d111  1 : :
2 3

= 1 : 0.707 : 0.577

1 1 1
Body centered cubic lattice d 200 : d110 : d 222  : :
2 2 2 3

= 1 : 1.414 : 0.577

1 1 1
Face centered cubic lattice d 200 : d 220 : d111  : :
2 2 2 3

= 1 : 0.707 : 1.154

The general formula for interplaner spacing in a system of orthagonal axes with unequal
side lengths ( a  b  c ) can be represented as,

1 h2 k2 l2
  
d 2hkl a2 b2 c2

9
 The predicted pattern for three types of cubic lattices are as follows.(Table-2)

221
300
100

200

210

220

310
110

211

311
111
1k 2k 3k 4k 5k 6k 7k 8k 9k 10k 11k

Simple

Body

Face

Table 2. A typical X-ray diffraction pattern of a cubic system.

(Where k   | 4 a 2 )

In general for a body centred cubic lattice, all diffrations for which ( h  k  l ) is an even
integer do exist. But in case of face centred cubic lattice strong diffraction lines are observed
only from those planes for which the values of h, k and l are either all even or all odd.
However in case of simple cubic lattice diffractions are absent for the values of h  k  l
equal to 7, 15, 23 etc. Once the diffraction pattern is identified, it is possible to assign each
and everyline wtih the correct values of h , k , l . The cube edge length 'a' can be calculated
for the every measured value of '  ' by the equation,

 1
a (h 2  k 2  l 2 ) 2
2 sin hkl

If the idexing of the lines has been done correctly, the same value of 'a' will be obtained
from all the values of sin hkl . The observed diffraction pattern of sodium chloride revealed
that the unit cell is a face centred cubic type consisting of interpenetrating face centred
  
cubic array of Na ions and face centred cubic array of Cl ions. Each Na ion is
 
surrounded by six equidistant Cl ions and each Cl ion is surrounded by six equidistant
Na  ions. The (100) and (110) planes contain and equal number of both kinds of ions, but
 
the (111) planes consist of either all Na ions or all Cl ions. However in case of KCl

crystal, the scattering powers of K  ion and Cl ion are indistinguishable since they both
have an argon configuration with 18 electrons. So the first order reflections from (111)
planes are all together extinguished because of interference from the reflection of the
interlearved planes. The Bragg spetrometer method described above is generally applicable
but most crystal investigations used photographic methods to record the diffraction patterns.

The powder method :

The simplest technique for obtaining X-ray diffraction data is the powder method.
Instead of a single crystal with definite orientation to the X-ray beam, a mass of finely divided
crystals with random orientation is taken and experimental arrangement is made tube as

10
illustrated in Fig-12. The powder is contained in a thin walled capillary and is rotated in the
X-ray beam to obtain a possible orientation of the crystallites. Out of the many random
orientations of the little crystals taken in the capillary tube, there will be some crystals at
proper angle for X-ray reflection from each set of planes. For each set of planes, the reflected
beams outline a cone of scalltered radiation. This cone of scattered radiation intersects a
cylindrical film surrounding the specimen and gives rise to observed lines. On a flat plate
film the observed pattern consists of a series of concentric circles.

Fig.12. Experimental arrangement of the powder method.

A schematic representation of the powder pattern ofsodium chloride is given in Fig

13.
200
220

222

400

420
111

311

311

)))) )))
Fig 13. Diffraction pattern of sodium chloride.
Eachline of the powder diagram is assigned with a plane which is responsible for
obtaining that line. The distance x of each line from the central spot is measured carefully..
If the radius of the film is r, the circumference 2 r corresponds to a scattering angle of
3600. Then, x / 2 r  2 / 3600 . Thus we calculate  and from the value of  we can
calculate interplanar spacing.
Rotating crystal method :
The rotating crystal method is the most widely used techniques for precise structure
investigations. The crystal is mounted with a well defined axis perpendicular to the beam of
X-radiation. The film may be held in a cylindrical camera. As the crystal is rotated slowly,
successive planes pass through the orientation necessary for Bragg reflection, each
producing a shot on the film. Sometimes the data is recorded on a single film by oscillating

11
the crystal through a smaller angle. The spots formed on the film are indexed and their
intensities are measured. From this information the crystal, structure will be determined.

Crystal Structure Determination :

The Bragg's equation, viz., fixes the angle of scattering in terms of the
interplaner spacings, which are determined by the arrangement of atoms in the crystal
lattice. Let us consider a structure formed by replacing each points in a body centered
orthorhombic lattice by a diatomic molecule. If a set of planes is drawn through the black
atoms, another parallel but slightly displaced set can be drawn through the white atoms.
When the Bragg condition is satisfied, the reflections from all the black atoms are in phase.
Further the reflections from all the white atoms are in pahse. However, the radiation scattered
from black atoms is slightly out of phase from the radiation scattered from the white atoms.
Therefore intensity is diminished by interference. (Fig 13). The coordinates of a black

Fig 13. X-ray scattering from a typical structure.

12
atom may be taken as (0,0), in a two dimensional plane, and the coordinates of white atom
are ( x, y ) . Let us assume a plane ( h, k ) satisfies the Bragg condition. The phase difference
between these planes and those going through the white atoms is proportional to the
displacement of the white atoms. The phase difference Px , for the displacement x is
given by,

x /( a / h)  Px / 2 or

2 h x
Px 
a

The total phase difference for displacement in a, b and c directions for ( h k l ) plane
due to an atom at ( x, y , z ) in unit cell is given by,,

 hx ky lz 
P  2    
 a b c

Consequently, the expression for the resultant amplitude of the waves scattered from
the ( h k l ) planes by all the atoms in an unit cell is given by,,

 hx ky lz 
2 i    
F (h k l )   fj e  a b c
j

where fi is the amplitude of the wave scattered from the jth atom. The expression for
F ( h k l ) is called as the structure factor of the crystal. The structure factor expressions for
all the space groups have been tabulated in the literature.
Further the intensity of the scattered radiation is proportional to the square of the
absolute value of amplitude.
Fourier Synthesis :
It is the electrons in a crystal structure that scatter the X-rays. So, a crystal structure
examined by X-rays may be regarded as a periodic three dimensional distribution of electron
density. Such a density function can be expressed as a Fourier series and the electron
density in a crystal may be represented as,
 hx ky lz 
1 2 i    
 a b c
 ( x y z )   F (h k l ) e
V

where V is the volume of the unit cell. The summation is carried out over all values of
h, k , l so that there is one term for each set of planes ( h, k , l ), and so for each spot on the
X-ray diffraction diagram.

13
 Actually, the positions of the individual atoms are peaks in the electron density function,
with heights proportional to atomic numbers (number fo electrons). So a knowledge of
F ( h k l ) s enables to plot the crystal structure. Usually a trial structure is assumed and the
intensities are calculated by the help of the above mentioned equations. If these values
agree with the experimental observations at least approximately, the compulation of Fourier
series can be carried out by taking observed F ( h k l ) values and calculated phase values.

Binding in Crystals.
The binding of atoms in a crystal are assumed to be occurring by two different
theoretical approaches, viz., the bond model and the band model. The bond model is
referred as tight binding approximation and the band model is termed as collective electron
approximation.

14
 Lesson No-3
THE BOND MODEL
Is it true? Is it false?
Education does not cost ......It pays.

The Bond Model

It is considered that a solid is held together by chemical bonds and the different
types of bonds are mentioned below.
(i) The van der Waals bonds :
These bonds result because of forces between inert atoms or saturated
molecules. The crystals with this type of bonds are termed as molecular crystals
(Ex : Nitrogen, benzene, carbon tetrachloride). The forces operating among
the molecules are dispersion forces. The molecules tend to pack as closely as
their geometry permits.
(ii) The ionic bonds
In a crystal, the coulombic interaction between oppositely charged ions leads
to a regular three dimensional structure. The ionic bond is spherically
symmetrical and an ion will be surrounded by as many oppositely charged ions
as can be accommadated geometrically, provided that the requirement of overall
electrical neutrality is satisfied. For example, in rock salt, each positively charged
Na  ion is surrounded by six negatively charged Cl  ions and each Cl  ion is

surrounded by six Na ions.

(iii) The Covalent Bond

These bonds are the result of the sharing of electrons by atoms. A good example
is the structure of diamond. This structure is based on two interpenetrating
face centred cubic lattices. Each atom on one lattice is surrounded tetrahedrally
by four atoms of the other lattice. This arrangement constitutes a three-
dimensional polymen of carbon atoms. The C-C bond distance is 1.54A0 in
diamond which is same as the C-C bond distance ethane. Germanium, silicon
and greytin also crystalises in the structure similar to that of the diamond
structure. Further, ZnS , Agl , AlP and SiC also have the same structure as that
of diamond structure.
(iv) The intermediate type bonds
This type of bonds arise because of resonance between covalent and ionic
contributions or because of polarisation of one ion by oppositely charged ion.
The effect of polarisation is seen in the structures of silver halides. AgF , Ag Cl
and AgBr have the rock salt structure, but as the anion becomes larger it

becomes more strongly polarised by the small Ag ion.

15
 (v) The hydrogen bonds
In the crystal structure of ice each oxygen atom is surrounded tetrahedrally by
four hydrogen atoms at a distance of 2.76 A0.

(vi) The metallic bonds

The metallic bond is closely related to ordinary covalent electron-pair bond.
Each atom in a metal forms covalent bonds by sharing electrons with its nearest
neighbours. But these are more number of orbitals for bond formation than the
available electrons to fill these orbitals. So the covalent bonds resonate among
the available interatomic positions. In the case of crystals this resonance extends
through out the entire structure. So the empty orbitals permit a ready flow of
electrons under the influence of applied electric field, leading to metallic
conductivity.
The Band Model
The existence of electrons is responsible for the high thermal and electrical
conductivities exhibiled by metals. Based on the behaviour of electrons, three
classes of solids can be identified
1) Conductors, which offer a low resistance to the flow of electrons, when a potential
difference is applied.
2) Insulators which offer a very high resisstively for the flow of electrons, when a
potential differences applied.
3) Semiconductors, whose resistivities for the flow of electrons are intermediate
between those of typical metals and insulators.
Let us consider the crystal structure of sodium metal. The one dimensional structure
of sodium consists of arrays of sodium nucliei at their internuclear separation. The position
of each nucleus represents a deep potential energy well for the electrons. As these wells
are infinitely deep, the electrons arrange themselves into fixed positions on the sodium
nucleii, giving rise to 1s 2 2 s 2 sp 6 3s1 configuration which is similar to an isolated sodium
atom (Fig. 14. (a)). But the electrons can tunnel through these barriers and an electron

Fig.14 Energy levels in sodium

(a) isolated atom (b) section of a crystal.

16
on one nucleus slips through to occupy a position on neighbouring nucleus. So the sharp
1s energy level of an individual sodium atom is considered to be broadened into a band of
closely packed energy levels in crystalline sodium. A similar situation arises for the other
energy levels, each becomming a band of energy levels as shown in Fig.14(b).
Each atomic orbital contributes one energy level to the band. In the lower bands
(1s , 2 s, 2 p ) there are just enough energy levels to accommadate the number of available
electrons, so that the bands are completely filled. Even if an electric field is applied these
electrons in the filled band can not move because all the energy levels above them are
already occupied.
However the situation is different for the upper most band, viz., 3s, which is only half
filled. An electron in the interior of the 3s band cannot be accelerated because the energy
levels directly above are already filled. However electrons near the top of the filled zone
can readily move up into unfilled energy levels within the band. These energy levels overlap
the peaks of potential energy barriers and so the electrons in these top most energy levels
move quite freely through out the crystal structure. The free movement of electrons results
in good electrical conductivity for the metals.
Inspite of having the filled 3s orbitals, magnesium behaves as a metal. The reason
for this is that the lower energy levels of 3 p band overlap the top of the 3s band, providing
a large number of available empty energy levels. The way in which 3s and 3 p bands
broden as the atoms are brought together is shown in Fig.15

interatomic separation, A0

Fig.15 Approximate quantum mechanical calculation of the formation of energy

bands as atoms are brough together into a crystal in case of sodium.
In case of sodium at an interatomic distance of 4 A0 there is no energy gap between
3s and 3 p bands. However in case of diamond, there is a large energy gap between the
filled valence band and the empty conduction band. Thus conductors are characterised
either by partial filling of bands or by overlapping of top mostbands. On the other hand
insulators have completely filled lower bands with a wide energy gap between the top most
filled band and the lowest empty band. These models are represented in Fig.16.

17
 Fig. 16 Band models of solids

Semi Conductors

Semi conductors are of two types, viz., intrinsic semiconductors and impurity
semiconductors.
In an intrinsic semi conductor (Fig. 16(c)), the energy gap between the filled valence
band and the empty conduction band is so narrow that an appreciable number of electrons
can be raised into the conduction band from tha valence band by thermal excitation. This
process causes positive holes (p) in the valence band. These holes and the electrons will
both be mobile under an applied electric field and thereby contribute to the electrical
conductivity. Germanium with an energy gap of 0.72 ev and grey tin with 0.10 ev are examples
of intrinsic semiconductors at moderate temperatures. However the property of intrinsic
semiconduction will be shown by any solid at a sufficiently higher temperature.
Fig. 17 represents a section of the structure of a germanium crystal. Each line between
atoms denotes one electron in a covalent bond. But two such electrons are represented
since they are separated from the bonds. These electrons are the mobile electrons in
conduction band. The positive holes created because removal of electrons are also mobile
so when the electrons move in one directions the positive holes move in opposite direction
leading to conduction.

Fig.17 Donors produced by group V impurities in Germanium

18
 The model of the impurity conductor is shown in Fig.16(d). Since the energy gap
between the valence band and conduction band is very large, a pure and perfect crystal of
such a substance would be an insulator. However it is possible to introduce imperfections
into such a crystal so as to create empty levels closely above the valence bands, or filled
energy levels closely below the conduction band. Then electron can be promoted into
conduction band from the filled (donor energy levels. Similarly, electrons can be raised into
empty (acceptor) energy levels from the valence band creating mobile positive holes. So
the presence of impurity levels leads to appreciable concentration of charge. These
substances are called as impurity semiconductors.
In another example (Fig.17) a small concentration of arsenic has been dissolved in
the germanium structure. The assenic atom consists of one electron more than the
Germanium atom. So this extra electron cannot be accommadated in the quadricovalent
structure of Germanium. Therfore, it must go into a higher energy level which is denoted as
donor energy level (Fig. 16(d)). So the electrons from the donor levels of the arsenic are
thermally promoted to the conduction band. Hence Germanium doped with arsenic is a
good semiconductor in which the caniers of the charge are electrons. So it is called as n-
type semiconductor, because the charge carriers are negative electrons.
The Indium atom contains one electron less than that of Germanium atom. So
whenever Indium atom replaces Germanium atom an aceptor level is created. Hence in
case of Germanium doped with indium, when an electron is thermally excited from a normal
Ge-Ge bond into the acceptor level, a mobile positive hole in the valence band is created.
So germanium dopes with indium behaves like p-type semiconductor.
When a compound deviates from its chemical stoichiometry, it may behave like a
semiconductor. Normally in zinc oxide (ZnO) more Zn atoms present than oxygen atoms.
Similarly, Nickel oxide consists of more Oxygen atoms than nickel atoms. Such
nonstoichiometry is due to the inclusion of extra atoms in the interstitial sites or due to
vacancies caused by absence of atoms. So in case of zinc oxide the excess zinc act as
typical donor and leads to n-type semi conductivity. In nickel oxide the vacancies due to the
2
absence of Ni ions provide typical acceptor energy levels resulting in p-type
semiconductivity.
Defects in Solids
Even though it is considered that there is perfectly ordered arrangement of atoms in
the crystals, in reality all crystals show defects. These defects cause slight variation in heat
capacity, entropy and crystal density. But these defects profoundly alter the mechanical
strength, electrical conductivity, diffusion rate and catalytic activity. Imperfections in solids
are classified as point, linear and edge defects.
(i) Point Defects.
It was observed that gold diffuses through lead (at 3000C) at faster rate than diffusion
of sodium chloride in water. The studies revealed that this is due to the point defects in
crystals. One such defect is Frenkel defect, observed in case silver chloride crystal. Silver

chloride crystal consists of Ag ions which left their lattice sites and moved into interstitial
positions. The Schottky defect is shown in case of sodium chloride. This defect is due to a
pair of vacancies of opposite sign. These Frenkel and Schottky defects are termed as
intrinsic defects (Fig.18)

19
 (a) crystal with (b) Ideal crystal (c) crystal with
Frenkel defects Schottky defects
Fig. 18 Intrinsic point defects in crystals.
These defects do not alter the stoichiometry of the crystal. But they provide a
mechanism by which atoms can move within the crystal because an atom can move from
an occupied site to a vacancy.
The number of point defects in crystal can be evaluated with the help of statistics.
Let the amount of energy required to create a defect is E. Let the entropy change associated
with the mixing of defects and normal lattice sites, causing the disorder, is S . If n
imperfections are distributed among the total of N crystal sites the entropy of mixing is,

N!
S  k n
( N  n)! n!
where k is the Boltz manns constant.
From the expression for Helmholtz free energy represented as,

 A   E  T S
we can write that
N!
 A  nE  kT n
( N  n)! n !

A
But at equilibrium, 0
n
Applying Stirling approximation given by

1n X !  X ln X  X ,
 A  nE  kT (n N ! ln( N  n)! 1n n !)
 n E  kT ( N n N  N  ( N  n) ln ( N  n)
 N  n  n n n  n)

20
  nE  kT ( N  n N  N  n( N  n)  n  n ( N  n)  n  n n)
since ( N  n)  N
 nE  kT (n n ( N  n)  n n n)
( n is very small )
n
 nE  kT n n
N n

 A n
 E  k T ln  0
n N n
n
ln   E | kT
N n
and since n is very small,

n
 e E kT
N
As an example, when E is about 1 ev and T is 10000 K,

n
 105
N
Since a pair of vacancies are created in case of schottky defect, the final
expression for n well be,

n  N e E / 2 k T
For Frenkel defects,

n  ( N N | )1 2 e  E / 2 k T

where N | is the number of interstitial sites available.

The rapid irreversible deformation of solids when a stress is applied is known as

plastics deformation. The existence of inperfections or defects in the crystal are responsible
for this kind of plastics deformation (Fig 19).

Fig.19 structure of edge dislocation.

21
 The deformation shown in Fig. 19 is the result of inserting an extra plane of atoms
on the upper half. Another defect known as screw dislocation is represented in Fig.20. The
atoms are represented by cubes in the figure.

Fig.20 screw dislocation at the surface of a crystal

22
 Lesson No-4
THEORIES OF SPECIFIC HEATS OF SOLIDS
There is no complex subject. If studied with patience and intelligence it will not
become more complex

The specific heat of a substance is defined as the amount of heat required to raise
the temperature of one gram of the substance through 10C.

The specific heats of solids increase with rise of temperature and tend to zero as
absolute zero temperature is approached.

Dulong and Petit's law has been proposed for the behaviour of specific heats of
solids. The law is stated as follows:

"At room temperature, the product of specific heat and atomic weight is constant
for solid elements and is approximately equal to 6.4".

Atomic heat = specific heat  atomic weight = 6.4

But the experimental observations revealed this law is not entively true. The specific
heats of many elements exhibited variation with temperature. So it was concluded that
there is no set of conditions under which Dulong and Petit's law is applicable to all elements.

However, Boltzmann applied the classical kinetic theory and deduced the value of
atomic heat capacity of solids. The main assumption of this theory is, "An ideal solid is
composed of atoms vibrating about their respective equilibrium positions".

So the atom is considered as a simple harmonic oscillator and the energy is given
by,
E  kinetic energy + potential energy

p2 1
  m  02 x 2
2m 2
where p is the momentum given by mv ,

m is mass. 0 is natural frequency of oscillator and x is displacement.

So, the total energy of the solid is given by,

E  NE

23
 Where E is the mean energy of each atomic oscillator and N is Avagadro's number..
From statistical mechanics, it can be concluded that the number of atomic oscillators
dN lying between E and E  dE at temperature T is proportional to e  E / kT .

dN  e  E / kT
or
 P2 1 
   m w02 x 2  kT
 2m 2 
dN  constant  e  

The mean energy of each oscillator is given by,

 Ed N
0
E  

 dN
0

Substituting the values of E and dN in the above equation,

P 2 m w02 x 2
 P2 1 2 2

2 mkT

2 kT
P x   m w0 x  e e dpx dx
E   2m 2 
P2 m w02 x2
 
e 2 mkT e 2 kT dpx dx
P x
or

 P2  m w02 x 2
2
p  1 
 e 2 mkT dp x  m w02 x 2 e 2 kT dx
2m 
2
 
E 
 P2  m w02 x 2
 
 e 2mkT dpx  e 2 kT dx
 

using the standard integrals,

24
  1
2  u 2 1  2
 u e du   3 
0
4  

We have,

 P2
P 2  2mkT
 e dPx 1 1  12
2m   (2mkT )3 
2
 2m 4 kT
 P2  
 1 12 2
e 2 mkT dPx 2   (2mkT ) 
 2


and


1  m 02 x 2 2 kT
 m  02 x 2 e . dx

2

 m 02 x 2 2 kT
 e . dx


1
3 2
2 1 1  2 kT  
m 0 . 2 .  
2 4  m  02   kT
   
1
2
1  2 kT  2
2   
2  m  02 

So, the total value of E is given by

kT kT
E    kT
2 2
Since the oscillator can vibrate in the three mutually perpendicular directions, the
mean free energy of atom is given by,

E  3k T

The energy of 1 mole of the solid, consisting of Avagadro Number of atoms is given
by

E  3 Nk T

 3 RT

25
 Differentiating this equation with respect to T

 E 
 T   3 R
 V
So, Cv  3 R

 3  1.987
 5.94 cal per gram atom.
The above value 5.94 is nearly equal to, the value given by Dulong & Petit's law.
This is the derivation of the law of Dulong and Petit from kinetic theory.
Limitations of classical theory
(i) The results are not in accordance with the experiment.
(ii) The conclusion that specific heat is independent of temperature is not
acceptable.
Einstein theory of specific heat :
Einstein explained the theory of specific heats of solids by using the concept of
quantum theory. He assumed that each atom in a solid acts as a simple harmonic oscillator.
The energy of each oscillator is given by,

E  nh
Where n is an integer,, h is Planck's constant and is the frequency of the oscillator..
At equilibrium, the oscillators in a crystal will be distributed among the various allowed
energies according to the Boltzmann distribution law. This law states that the number of
atoms Nn with energy En each is related to the number of atoms N 0 with energy E0  0 is
given by the expression

Nn  N0 e  En / kT

 N0 e nh / kT

Since the total number of atoms is equal to the sum of the numbers in each energy
state,

N  N 0  N1  N 2  N 3  ......
Substituting the Boltzmann factor,

N  N 0  N0 . eh / kT
 N0 e 2h / kT
 ........

 nh

 N0  e kT
n 0

26
 The total energy due to the oscillations of atoms is obtained by multiplication of
energy En with number of atoms Nn and carrying out the summation

 E  E0 N 0  E1 N1  E2 N 2  ....

 O N0  h N1  2h N2  ....
2 h
h / kT
 O  h N0 e  2h N 0 e kT  ......

 N0  n h e nh / kT

n 1

So, the average energy of one dimensional oscillator is given by,



E
N0 h  n enh / kT

n1
E 
N N 0  e nh / kT

Let

e nh / kT y
So
e  nh / kT
 yn
Then,
 
 nh / kT
 e   y n  1  y  y 2  ......
n 0 n 0

1

1 y
Similarly,
 
 n e nh / kT
  n y n  ( y  2 y 2  3 y 3  .......)
n 1 n 1

 y (1  2 y  3 y 2  ....)

y

(1  y ) 2
So,
h y
E  (1  y )
(1  y )2

27
 h y

(1  y )

h eh / kT

1  e h / kT

Multiplying numenator and denominator with e h / kT ,

h
E  h / kT
e 1
But
2 3
h 1h  1h 
eh / kT
1       ....
kT 2  kT  6  kT 

h
But at high temperatures  1
kT
So higher powers of h / kT can be neglected.

h
eh / kT
 1
kT
Substituting in the expression for E ,

h
E   kT
h / kT
Since the atom has vibrations in all the three directions, the average energy is given
by

E  3 kT .
The total energy of one mole of atoms in given by,

 E  NE  3 Nk T

 3RT
The heat capacity,

E
Cv   3R  3  1.987  5.94 cal pergramatom
T
Limitations :
i) The value of frequency of the atomic oscillator can not be verified.
ii) Deviation from theory is observed at low temperature.

28
Debye Theory :
Debye assumed that the particles of the crystal make transverse and longitudinal
vibrations. The equation for Cv is given as
3
T 
Cv  464.4   cal mol 1 deg 1
 
at low temperatures.

Since  is constant for a substance, at low temperatures specific heat varies as

T 3.

29
 Lesson No-5
TRANSPORT PROPERTIES OF GASES
Where shall I start chemistry? Begin at the beginning and go on
till the end is reached and then stop

Transport Properties of Gases

According to the laws of thermodynamics the decrease in free energy of a process
lead to the sponteneity. However the rate at which such a process occurs is not considered
in the studies of thermodynamics because time is not factor in thermodynamics.
But the rates of transformation of various processes are also very in portant. Usually
the derivation of expressions for rates transformation requires the postulation of some
mathematical models based on structure of the system. The validity of the model is tested
with experimental data to judge the adequacy of the model.
Transport Properties :
Those processes in which some physicla quantity such as mass, energy,
momentum or electrical charge is transported from one region of a system to another
region of the system are termed as Transport processes.
Examples :
(i) Flow of heat through a metal rod.
(ii) Flow of electrical charge through a conductor
(iii) Flow of fluid through a pipe because of pressure difference
So, the flow is defined as the amount of physical quantity transported in unit time
through unit area perpendicular to the direction of flow. The 'flow' is proportional to the
gradient of some other physical property.

 T 
Heat Flow J z   kT  
 z 

kT is thermal conductivity, T is temperature

 
Electrical current Jz   k  
 z 

k is electrical conductivity, is electrical potential

P 
Fluid Flow Jz  C  
 z 

30
 C is frictional coefficient, P is pressure.

 C 
Diffusion Jz   D  
 z 

D is diffusion coefficient and C is concentration.

The above equations are the equations for the flow of property in z direction.
The general equation for Transport.

Let the number of molecules passing through unit area in unit time  n

Let the amount of physical property carried by each molecule  q

So, the amount of physical quantity transported in unit time across unit area, J .

 n q
Let the average velocity of each molecule in z direction  c .

Let the number of molecules in unit volume  n

So the number of molecules passing through unit area in unit time n n c .

So, the flow of the property J  n c q .

Thermal Conductivity :
Let us suppose that two large metal plates are separated by distance Z. The upper
plate is at temperature T2 and the lower one is at T1 . There will be a steady downward flow
of heat at a constant rate because the molecules at the upper levels have a greater thermal
energy than those at lower levels.

To calculate the net energy flow in unit time through 1Cm 2 parallel to the x y plane,
we imagine a large number of horizonal layers in the gas. Each successive layer is at
slightly higher temperature than the one below it. The change in temperature with height is,
dT  T T2  T1
 
dz z Z 0

The lower plate is at the position, z  0 and the upper plate is at z  Z . The
temperature gradient, (T / z ) is constant.

So the temperature at any height z is given by

 T 
T  T1   z
 z 

Let the gas is monatomic with average thermal energy.

31
 3
E  kT .
2
Then the thermal energy of molecule at height z is

3
E  kT
2

3   T  
 k T1    z
2   z  

Let us consider an area of one sq. cm in a horizontal plane at a height z as represented

in Fig.1.

Fig.1. The position of horizontal planes separated by distance  .

The energy carried by a molecule depends on the temperature of the layer of gas at
which the gas molecule had its last collision with another molecule. Suppose that the
molecule travelled a distance  since its last collission before it makes another collission.
At heigh z, for the molecules comming down had their last collission at a height z   while
those comming up made their last collission at height z   . The molecule carry an amount
of energy appropriate to the height where the last collission occured.
So the downward flow of energy is,

1 3   T  
E (n c ) k T1    ( z   )
6 2   z  

The energy for upward low is

1 3   T  
E (n c ) k T1    ( z   )
6 2   z  

32
 1
The value indicate that only one sixth of the existing molecules travels in a particular
6
direction.

The net upward flow of energy is given by,

Jz  E   E 

1 3  T 
 nc k   (z    z  )
6 2  z 

1  T 
Jz   nc k   
2  z 
comparing the equation with empirical form

 T 
Jz   k T   , we get
 z 
1
kT n c k
2
3
Since Cv  k N 0 , we can write
2

1 n 
kT    Cv c 
3  N0 

VISCOSITY
Knowledge is experiment’s daught
Let us assume that a gas is confined between the two parallel flat plates sepa-
rated by a distance Z . Let us suppose that the gas between the plates is made up of a
series of horizontal layers. The layer next to the lower plate is immobile . As we move
upward each successive layer has a slightly larger component of velocity. At the height Z
the velocity be U.

This type of flow is known as laminar flow. The layer at the height z has a velocity in the
x direction given by..
u
uZ  z
z
At z  Z and u  

33
 u 

z Z

 u 
u z      z   
 z 

u
uz  .z
z

u
uz    . z   
z
y
x

Fig.3 Velocity of layers in a flowing gas

The molecules from the upper layers will bring extra x  momentum to the layer at
z . Those molecules which come from below will bring deficient x momentum. So there
will be net downward flow of momentum through the layer.

The downward momentum from the layer at z   to layer at z is given by,,

1   u 
mu z      nc m   z   
6  z 

Similarly, the momentum comming up is

1   u 
mu z     n c m  z   
6  z 

The net upward momentum

1   u 
 nc m  z    z  
6  z 
1   u 
  n c m 2  
6  z 
1 
 u 
  n c m .  
3  z 

But the amount of momentum transported.

 u 
Jz    
 z 

34
Where  is viscosity coefficient

1 
  n c m.
So, 3
1 
 c 
3
where  is the density of the gas.

DIFFUSION :-
In a mixtue of two gases, if the concentration is not uniform, the gases dif-
fuse into one another until the composition is unifrom. Let us assume that some of the
molecules of the given gas are painted with red colour. Then the gas is introduced into a
vertical tube. So the number n1 of red molecules per cubic centimeter is greater at one end
than the n of unpained molecules per cubic centimeter at the other end. However the value
‘ n ’ must be greater at the other end of this vertical tube. For each species the number of
molecules per unit volume at height z may be written as,

n1
n1  n01  z for red molecules
z
 n 
n  no    z for ordinary unpainated molecules .
 z 
where n01 and n0 are the molecules per cubic centimeter at heigh z  o
So, the number of red molecules crossing an area of 1sq.cm downwards in one second
is given by,

1
n1   c n1  z   
6
1  1 n1 
 c
6  no  z  z    
 

Because the molecules originate in the layer  z    .

similarly, the number of molecules comming up form below is given by,

1 1
n1   c n z  
6
1   n1  
 c  no1    z    
6   z  

So, the net flow upward is,

1   n1 
n1   n1    c   
3  z 
35
 1
1  n 
But as per the law of diffusion the upward flow is  D  
 z 

1 
where D1 is diffusion coefficient . So, in general the diffusion coefficient D  c .
3

Since the mean free path is inversely proportional to pressure, the diffusion coeficient
decreases with increase in pressure.
Irving langmuir discussed the important application of diffusion and meanfree path
in case of tungsten filament lamp and concluded that the presence of Argon in the bulb
lengthens bulb life enormously.

THEORY OF LIQUID STRUCTURE

Perfection is not an accident. It is the result of concerted efforts with many
failures.
In general the molecules of the liquids are more disorderly than those of crystalline
solid but less disorderly than those of a gas. It is known that when a crystal melts, the
accompanying change in entsopy is always positive. This implies that there is less order in
rspect of the arrangement of molecules, when a crystal melts. The liquid is thus intermedi-
ate between the complete order of crystalline state and the complete disorder of the gas-
eous state.
But the molar volume of almost all the substances increases by about ten percent on
melting. Also the entropy of melting is much smaller than entropy of vaporisation. These
facts suggest that liquids should posses the characteristics of orderly arrangement to a
certain extent.
Further it has been experimentally observed that the diffraction pattern of liquid ar-
gon, just above melting point, exhibited a few broad maxima and minima . Since the diffrac-
tion maxima and minima are absent in case of complete randomness in arrangement of
the molecules, it can be concluded that there is a partially ordered arrangement of atoms in
liquids. It indicates that there is a short range order in liquids.
Actually the X- ray diffraction pattern of liquids represent a time average pattern
resulting from the translational motion of molecules. In cae of solid argon there are twelve
nearest neighbours at a distance 3.82Ao . But just above melting point, the number of
nearest neighbouring atoms are 10.5 only and this number further decreases as the tem-
perature is increased.
Similarly the decrease in density on melting of the solid is explained on the basis of
the additional free volume which has been distributed as ‘vancancies’ in the more or less
close packed liquid lattice.
Based on the above facts, the Eyring hole theory of liquids was proposed by Henry
Eyring and his coworkers. According to this theory, a liquid may be considered to be com-
posite system of two significant structures, gases on one side and solids on the other side.
In a liquid some of the molecules have gas like character and the other molecules have

36
solid - like character. If we assume that all the free volume in a liquid is arranged in molecu-
lar - sized vacancies, then any molecule next to a vacancy can move into it, thereby acting
as a gas molecule. Similarly any molecule that is completely surrounded and has no va-
cancy next to it acts as a solid molecule.

If Vl and Vs are volumes occupied by liquid and the same amount of solid respec-
tively, then the extra volume Vl  Vs  will appear as the vacancies of molecular size and
are randomly distrubited in the liquid . So the mole fraction of molecules next to a vacancy
Vl
is Vl Vs  V This is the mole fraction of gas - like molecules . Similarly Vs represents
s

the mole fraction of solid like molecules.

So, any physical propery of a liquid may be considered to be the sum of a contribu-
tion from solid - like molecules and a contribution from gas - like molecules. Let us consider
the effect of temperature on the heat capacity of liquid argon. The heat capacity of argon
gas is 3R /2 or 2.98cal / OK and the heat capacity of solid argon is 3R or 5.96cal / OK
. Then, if we wish to predict the heat capacity of liquid argon at any given temparature, we
need to measure the molar volume VL at that temperature This enables to calculate the
CV value of the liquid from the equation.

Cv  5.96  Solid  like fraction  

2.98  gas  like fraction  .
Vs  Vl  vs 
 5.96   2.98  
Vl  Vl 
The agreement between experimental and predicted values is excellent.

37
 Lesson No-6
PHYSICAL METHODS FOR THE ELUCIDATION OF
MOLECULAR STRUCTURE
Those with gold or power or knowledge make the rules

Magnetochemistry is one of the most powerful techniques in achieving solutions to

chemical problems. The molecules of the substances, which are exhibiting magnetic prop-
erties, do have a permanent magnetic dipole moment. When these substances are placed
in magnetic field there will be contribution to the overall magnetic moment.

The force F, acting between two magnetic dipoles of pole strength m1 and m2,
separated by a distance r is given by
m1 m2
F 
r 2

where  is a constant characteristic of the medium and is denoted as magnetic permeabil-

ity.
The magnetic permeability of a medium represents the tendency of magnetic lines
of force to pass through the medium relative to the tendency of the same lines of force to
pass through air or vaccum. Usually the substances are classified according to the values
of  . For vaccum  is taken as 1 and for other media  may be greater or lessthan unity..
If  is lessthan one the substance composing the medium is termed as diamagnetic
substance . So a diamagnetic substance is less permeable to the magentic lines of force
than vaccum. It means that the magnetic lines of force prefers to travel through vaccum
rather than through the substance. When ‘  ’is greater than one the substance is said to
be paramagnetic substance. So the magnetic lines of force tend to pass through the sub-
stance rather than through vaccum.

Diamagnetic behaviour vaccum Paramagnetic behaviour

Fig 1. Behaviour of paramagnetic and diamagnetic substances.

Substances with large values of magnetic permeability, of the order of 103, are termed
as ferromagnetic substances.
Magnetic Susceptibility
The intensity of magnetisation ( I ) induced at any point in a body is directly propor-
tional to the magnetising field (H)
So I H
 or I  KH .
wherer K is known as the magnetic susceptibility of the medium. Since I is the
change in magnetic moment per unit volume on magnetisation, K is called as volume
susceptibility.
So, the mass susceptibility, i.e., The susecptibility per gram of the medium is given by
  K  where  is density of the medium,

So, the molar susceptibility, which is susceptibility per gram mole is given by  M   .M
where M is the molecular weight of the substance.
When a substance is kept in a magnetic field of strength H, the magnetic flux den-
sity inside the medium is given by ,

B  H  4 I
But
B  H
So  H  H  4 I
Or I
  1  4
H
  1  4 K
But
  K  or K   .
So
  1  4  . 
Or 1
     1
4

So, in case of diamagnetic substances,  <1 and therefore  is negative

Ex : Copper, graphite, antimony, bismutu.

In case of paramagnetic substances,  >1 and therefore  is positive

Ex : Aluminium. platinum
in case of ferromagnetic substances,  and  are very high ranging between 200 and
100000.

THEORIES OF PARAMAGNETISM.

The theory of paramagnetism proposed by Langevin is based on kinetic theory. He

assumed that the molecules of a paramagnetic substance are small permanent magnets.
When a magnetic field is applied, the molecules tend to orient with their magnetic axes in
the direction of the field. But such a orientation is opposed by the collissions due to the
thermal motion among molecules. As a result, there will be an equilibrium distribution of
the magnetic axes of the molecules with reference to the direction of the applied magnetic
field. The principles used in this derivation are as follows :

39
1) The number of molecules , which are oriented at an angle  with the direction
of the applied magnetic field H, is directly proportional to sin  . d . (Fig.2)
dN  sin  d
ii) The number of molecules dN , which are possessing a potential energy E, is
proportional to e  E kT .
E
dN  e kT .

where k is boltzmann constant.

If  m represents the molecular magnetic moment of the molecules in the magneticfield of
strength H, the potiential energy is given by,

E    H cos 

From the
above equations

Fig.2. Orientation of molecules in the applied magnetic frield.

M H cos
dN  C sin  e kT
d .

where C is a proportionality constant.

Since the possible orientations are in between 0 and  ,the total number of molecules,

N   dN
o
  M H cos
kT .
 C  sin e d .
o

Let M H
  and cos  x
kT
 sin  . d  dx
When
  0, x  1
   , x  1
So,
1
N   C  e x .dx
1
1
 e x 
 C 
  1
C 
 e  e  
 
40
Or
N
C 
e  e  


The magnetic moment component of each molecule in the direction of the mag-
netic field   M cos  .

So, the resultant magnetic moment of all dN molecules in the direction of the mag-
netic field   M cos  . dN .

So the total magnetic moment due to all N molecules in unit volume,


I  
o
M cos . dN .

 M H cos
kT . d .
  M cos C sin  e
0

Once again applying the assumption that,

M H
  ; cos  x ,
kT
1
I    M .C  x. e x .dx
1

   xe x   1 1  x
e 
   M .C        dx
      1 1 
1
 xe x e x 
  M C   2
    1

 M C.   1 

    e  e    e  e   
 

Substituting the value of C

  e  e   1 
I   M .N     
  e  e   
 1
  M .N  coth   
 
   2 2 5 
 M .N     .... 
3 45 945 

  M .N
3
M H
  M .N
3kT
41
 I
Volume susceptibility K 
H
M 2 N
K
3kT
P . Pascal has demonstrated that the magnetic susceptibility is an additive property and
hence  M can also be calculated by using atomic and bond contributions. The pascal’s
constants for a few atoms and bonds are mentioned in the following table !

Table. 1. Pascal’s constants for atoms or bond.

atomorbond pascalsconst.

H - 2.9 x 10-6
C - 6.0 x 10-6
N (open chain) - 5.5 x 10-6
N (ring) - 4.6 x 10-6
O (alcohol) - 4.6 x 10-6
O (ketone) - 1.7 x 10-6
C=C 5.5 x 10-5
N =N 1.85 x 10-5
C=N 8.2 x 10-5
Benzenesing 1.4 x 10-5

The Gouy method for measurement of magnetic susceptibility

This method is based on the fact that
the mass of the sample varies directly with the
magnetic field exerted on the sample The ar-
rangement of Gouy’s apparatus is
schemetically represented in Fig 3. The sub-
stance is taken in a long cylindrical tube and is
suspended from one arm of the microbalance.
The axis of the cylindrical tube is arranged to
be at right angles to the applied magnetic field
of strength in the range of 5000 to 15000
oersteads.

Fig 3. Gouy Balance

42
Then the magnitude of the vertical magnetic forces acting on the specimen of length
dx and volume dV is given by
1 H 2 y
dFx   K1  K 2  dV
2 x

where K1 and K 2 are the volume susceptibilites of sample and surrounding atmosphere
respectively and H y is the maximum field to which the sample is subjected. If A is the
area of cross section of the specimen, it can be written as, dV  A dx

So,
1 H 2 y
d Fx   1 2
K  K A . dx.
2 x

Integrating the above equation to obtain the total amount of vertical force acting on the
sample.

1
Fx   K1  K 2  A H 2  H 0 2 
2

where H o is the strength of the magnetic field at the upper end of the specimen, which is
negligible.

So, we can write that

1
Fx   K1  K 2  A H 2 .
2

But the vertical force Fx can be calculated by the microbalance. The specimen is weighed
first when the field is off and then when the field is on . Thus.

Fx   mg .

where g is the gravitational constant and  m is the apparent change in mass of the
sample on the application of magnetic field. From the above equations, It can be written
that,

1
m g   K1  K 2  A H 2
2
2m g
 K1  K 2  
AH2
2m g
K1  K 2 
AH 2

Or 2m. g
K1  K 2 
A. H 2

43
Multiplying both the sides of the above equation with M  , we get

K1 M M Z m . g 
M    K2  
  A .H 2 

where  M is molar susceptibility of the specimen and  is its density..

The molar susceptibility of metals, powder samples and liquids can be estimated
by this technique. However this method is unsuitable for investigation of gases.

Application of magnetic susceptibility of coordination compounds .

An atom, ion or a molecule which has one or more unpaired electrons has a result-
ant magnetic moment. So it is attracted into a magnetic field and is said to be paramag-
netic in nature. This magnetic moment, which is also termed as spin moment, is propor-
tional to the number of unpaired electrons. This magnetic moments is related to molar
magnetic susceptibility by
1
2
 3k  M .T 
   
 N 

where  is Bohr’s magneton k is Bolt z mann constant  M is molar, magnetic suscep-

tibility, T is temperature and N is Avagadro’s number.
But the magnetic moment on the basis of classical theory may be represented as

  g S  S  1

where g is Lande’s splilting factor and is equal to 2, S is the total spin of the unpaired

electrons and is equal to n 1 2 where n is the number of unpaired electrons.

n n 
 2   1
2 2 
So,
 n  n  2

1
2
 3k  M T 
Hence,  2   n  n  2
 N 
 2N
Or M  n  n  2 .
3kT

44
From the expressions for  and  M we can write the following table.

N. of unpaired electrons n   n  n  2

1 1.732
2 2.828
3 3.873
4 4.899
5 5.916
6 6.928

Magnetic susceptibility measurements have bean used in determing the number of un-
paired electrons in the coordination compounds. Therefore it becomes possible to assign
suitable strucuture to these coordination compounds. For example the magnetic moment
3 3
for the complex Co  NH 3 6  is zero and while that of Co F6  is 4.86. This indicates
3 3
that Co  NH 3 6  is having no unpaired electrons while Co F6  is having four unpaired
3
electrons. Similarly it can be proved that  Fe  CN 6  is having one unpaired electron and
2
 Fe F4  3 ion is having five unpaired electrons. It is also understood that  Ni  CN 4  is
3 3
having no unpaired electrons. In case of  Mn  CN 6  and Cr  CN 6  the measured
values of magnetic moment is 3.0 indicating the existence of two unpaired electrons in
each case.

45
 Lesson No-7
NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY
Life is a continual struggle against the tendency to produce entropy as well as to
combat against it.

The nuclei of some atoms and electrons possess the property called spin. In case of
electrons each electron is having a spin represented as 1 2 and so the spin angular momen-
tum of an electron is equal to
h 3
1
2  1 2  1 2

2
Units.

Even though many nuclei possess spin angular momentum the value varies form
nulcleus to nucleus. The simplest nucleus is that of the hydrogen atom, which consists of
one proton. The proton has a mass of 1.67  1027 kg. and a charge of 1.60  1019 C. and these
values are considered as the units of atomic mass and charge repectively. The proton has a
spin of 1 2 . Another particle which is also a constituent of all nuclei is the neutron. It is having

an unit of mass but no charge. However it has a spin of 1 2

If a nuclues is composed of ' p ' number of protons and ' n ' number of neutrons, its
total mass is  p  n  and the total charge is  p . But the total spin of the nucleus is the vector
addition of spins of protons  p  and neutrons  n 

But the laws governing the vector addition of nuclear spins are not known. However,
observed spins to the nuclei can be rationalised into some empirical rules.
(i) Nuclei with even numbers of protons and even number of neutrons have zero
spin. (eg : 4 He, 12C , 16
O)

(ii) Nuclei with both p and n odd have integal spin

(eg : 2 H , 14
N.  spin 1
10
B  spin  3)

(iii) Nuclei with odd mass ( n  p odd ) have half integral spin values.

 1
eg : ' H , 15 N  spin  
 2
17  5
O  spin  
 2

46
 The spin of the nuclues is given by the symbol I and is termed as nuclear spin
quantum number. The spin angular momentum of the nucleus is given by the expression spin
angular Momentum.
h
I M  I  I  1
2
 I  I  1 units.
This expression represents the spin angular momentum of nuclei and also that of
electrons if the appropriate spin quantum number of electron is inserted. The direction of the
orientation of the angular momentum vector is such that its compenents along a reference
direction are equal to all integral values or all half integate values.
So the components of spin angular momentum vector along z direction are given by,,

 I M Z  I , I  1,......0,.....   I  1 ,  I  For I integral 

1 1
 I M Z  I , I  1,....... ,  .....  I  for I half  integral 
2 2

So there are  2 I  1 number of components for spin angular momentum. All these
components are having same energy and hence they are termed as degenerate energy
levels. However such a degeneracy may be removed (lifted) if an external magnetic field is
applied. So the application of magnetic field results in the for mation of  2 I  1 number of
energy levels. In this case the reference direction is the direction of the applied magnetic field.
A charged spinning particle resembles a circular electric current. So it produces a
magentic dipole. In other words the spinning charged particle behaves as a tiny bar magnet.
The strength of this magnet is given by,

q
 IM
2m
q I  I  1 h

2m 2
qh
 I  I  1
4 m

where q are m and the change and mass of the spinning point charge under consideration.
But the nuclei and electrons are not point charges. So another numerical factor G is to be
included in the above equation and can be represented as,

G qh
  I  I  1 Joules tesla 1
4 m

For electrons the value of G is given by Lande splitting factor  g  and this value
depends on the quantum state of electrons. However nuclear G factors can not be calculated
47
theoretically. These values are to be determined experimentally only.
So, for electrons,
  g I  I  1

qh
were   and is termed as Bohr magneton. substituting the values of electronic change
4 m
1.60 10 c  and mass.  9.1110
19 31
Kg  in the expression for Bohr magneton,

  9.2731024 J T 1
Similarly nuclear magneton  N can be calculated by substituting mass and change of proton
in the expression for  and
 N  5.050  1027 J T 1.

So, for a nucleus of mass M and atomic number P , we can write

G mP . P
 . N I  I  1
M
 g N I  I  1

where m p is the mass of the proton. and so the factor g is characteristic vlave of each nucleus.
So the magnetic dipole have components along the direction of the applied magnetic field
governed by the  I M 2 valuels.

 Z   g   I M  Z (for electron )

 Z  g  N  I M Z (for nuclei)

Let us consider a nucleus with a spin I  1. . The angular momentum of this

nucleus is
h
IM  11  1 .
2
 2 units.
If we consider a semicircle with radius of
2 units, the vector arrow of I M can point so as to
have components in z direction as 1, 0, or  1. (Fig:1)

Fig1.
The three orientations of the spin angular menventent of the nucleus
with a spin quantum number I 1
48
Then the resulting magnetic dipole  z oriented in a magnetic field B z is schematically repre-
sented in Fig.2.
The  z values are represented as arrows alined in the

direction of applied field for  I M  Z  1 and opposite to

direction of applied field for  I M  Z   1 The state

 I M Z  0 has no net dipole along the field direction.

Fig. 2. Orientation of magnetic dipole in applied magnetic field.

When nuclear g factor is positive the three allowed spin energy levels of the nucleus
can be represented as shown in fig.3

Fig.3. The allowed energy levels of nuclues with I 1

Similarly two energy levels are allowed when the nuclear spin is 1 2 and the lower energy

1
level corresponds to  I M Z  as represented in fig .4:
2

1 ---------

2

1
 ---------
2

Fig.4. Orientation of dipole and energy levels in applied magnetic field.

Now it is evident that there is an interaction between the magnetic dipole of the nucleus
and the strength of the applied magnetic field. The extent of this interaction is the product of
the strength of the magnetic dipole and strength of the applied magnetic field along the z axis.

So,the interaction energy

E IM    Z B Z
Z

 g N  I M Z BZ
49
Now let us consider the difference in the energy values of the neighbouring energy levels as
mentioned below

E   E I M   E   I M 21 
 Z 
  g  N  I M  Z B Z  g  N   I M Z  1 B z 
 g  N . BZ Joules.

This can be expressed in frequency terms as H Z ,

E g N BZ
   HZ
h h

So, when a radiation of frequency mentioned as per the above equation is absorbed
by the nuclues, whcich is present in a magnetic field of strength B Z  in z direction  . the nucleus
will be promoted to next higher spin energy level.However the frequency of the radiation is
propertional to the strength of the applied magnetic field. Normally the strength of the applied
magnetic field is of the order of 1.5 Tesla for the spin spectral studies of nuclei and 0.33 tesla
for spin spectral studies of electrons. So let us calculate the approximate frequency of radia-
tion to be utilised in case of nuclei and electrons to arrive at a spectroscopic technique.

Assuming that a magnetic field of strength 1.4092 T is applied to a proton for which g
factor is 5.585 the freqvency of the radiation required for spectroscopic transition is,

E 5.585  5.05 1027 1.4092

  
h 6.63  1034
6
 60  10 H Z  60M H Z

Similarly, the frequency of required radiation for spectroscopic transition of electron

among spin energy levels, when placed in an applied magnetic field of strength 0.33 tesla is
9000 MH Z , i.e., the microwave region of the electromagnetic radiation.

In accordance with Fig.1 and Fig.4 the direction of the magnetic dipole of nucleus
is always oriented such that its component in the direction of the applied magnetic field is an
integral or half integral value depending upon the value of the spin quantum number. So,
always the direction of magnetic dipole and direction of applied magnetic field will make an
angle with each other. So the magnetic dipole will always be under the influence of a couple
inducing a precessional movement known as - larmor precession (Fig.5)
S
N

 BZ

S
N
Fig 5. The Larmor precession of a nucleus in the magnetic field.
50
The precessional frequency is given by

magnetic moment
   Bz
angular momentum
 BZ
 omega  
2  IM
g  N I  I  1 B z


2 I  I  1
2
g N BZ
 HZ


This precessional frequency is now found to be the same as the frequency of separation of
energy levels as discussed earlier.
From the above observation it is evident that the nucleus will absorb the radiation only
when the frequency of the radiation is equal to precessional frequency. This phenomenon is
known as reasonance since the absorbed radiation causes transition to next spin energy
level the spectral study concerned is termed as Nuclear Magnetic Resonance spectroscopy.
Similar behaviour among electron spin energy levels is known as Electron Spin Resonance
Spectroscopy.

So the experimental arrangement of a NMR Spectro meter consists of a radiation of

frequency 60 MHz incidenting upon the nuclei while the applied magnetic field is gradually
increased over a small range in region of 1.4092 T until absorption takes place when the
resonance condition is satisfied.
This absorption of radiation leads to the transition of the nucleus from one spin energy
level to another spin energy level. The probability of this transition depends upon the popula-
tion of the energy level from which transitions are taking place. The population distribution
among energy levels follows the Bolt Z mann distribution law. This law is denoted by..

N upper  E 
 exp  
N lower  kT 

where N lower is the number of nuceli present in the lower energy level and N upper is the
number of nuclei present in higher energy level, E is the energy difference between the two
energy levels, T is temperature and k is Bolt Z mann constant. In case of nuclear spin energy
levels and also electron spin energy levels E is extremely small.

 E nuclei  4  1026 J in 1.4092 T . field ,

 E electrons  6  1024 J in 0.33 T . field .

51
So, for nuclei, at T  300 K

N upper  4  1026 
 exp  21 
 exp  1  105 
N lower  4.2  10 
 1  1 05 

and for electrons , at T  300 K

N upper  6  1024 
 exp  21 
 exp  1  103 
N lower  4.2  10 
 1  1 03 

So in both the cases the ratio is very nearly equal to unity and so both the spin energy
levels have almost equal number of species concerned. Since the lower energy level is slightly
more populated transition to higher energy level takes place when radiation is absorbed. But
when the population becomes equal in both the energy levels the system is said to be satu-
rated and no net transitions takes place. However for the transitions to occur continuously the
energy of nuclei in the excited state should be transfered to surroundings or to other nuclei.
Such transfers of energy respectively are termed as spin lattice relaxation and spin - spin
relaxation. The time taken for a fraction 1 e  0.37 of the excess energy of nuclei in higher
energy level to be transfered to the surroundings (spin- lattice relaxation) or to other nuclei
(spin-spin relaxation) is termed as relaxation time.

These relaxation times have considerable effect on the width of the NMR spectral
lines. Normally a long relaxation time means a long life time for the nuclel in the excited
energy level. This indicates that in accordance with Heisenberg’s uncertainity principle there
will be a small uncertainity in the value of the excited state energy level. Thus for relaxation
time of 1sec, the Heisenberg’s uncertainity principle can be represented as,

h
E . t 
2
h
 or  E   1034 J
2  t

which is very small in comparision to the energy difference between the two nuclear spin
energy levels 10 J  in an applied field of strength 1.4092 T .
26

This uncertainity in energy corresponds to an uncertainity of 0.1 Hz in fre-

quency of the radiation associated with this transition. Since NMR spectrometers are not
capable of resolving lines closer than about 0.5 Hz apart, a line width of only 0.1 Hz repre-
sents a narrow spectral line. Similarly when  t  104 sec, the calculation results  v 1000 Hz
which is clearly a broad line when compared with the resolving power of the spectrometer.

52
 Lesson No-8
THE CHEMICAL SHIFT
Asking dumb questions is easier than correcting dumb mistakes

The resonance condition,

viz.,
E g  N BZ

h h

has been arrived by considering the behaviour of an isolated nuclues in an applied mag-
netic field. But, in reality the nuclei are associated with electrons in atoms and molecules.
When these are placed in the magnetic field the surrounding electron cloud tends to circu-
late in such a direction as to produce a field opposing the direction of the applied magnetic
field. This type of electronic circulation is termed as diamagnetic circulation and is repre-
sented schematically in

Fig .6
Since the diamagnetic circulation of surrounding electron density is opposing the
applied magnetic field, the effective field experienced by the nucleus is,
[ Beffective = Bapplied- Binduced.]
where Bapplied is the strength of applied magnetic field and Binduced is the mag-
netic field of electron cloud induced by the applied magnetic field. Since the induced field is
directly proportional to applied magnetic field.

Binduced   Bapplied,
Where  is a constant.
So,
Beffective = Bapplied  Bapplied
 B Z 1   

It is evident from the above equation that the nuclues is shielded from the applied
magnetic field because of diamagnetic electronic circulation. The amount of the shielding

53
will be constant for a given isolated atom but will change with electron density associated
with the atom in a molecule. So, in general

Bi  Bz  l   i 

where Bi is the field experienced by the nucleus whose shielding constant is  i. If we

consider the case of hydrogen atoms in methyl, alcohol it can be seen that the electron
density about the hydrrgen atoms in C  H bonds must be considerably higher than the
electron density about hydrogen atom in O  H bond, because the oxygen atom being elec-
tronegative draws the electron cloud more towards itself making the O  H hydrogen
defecient in electron density. So, the C  H proton is more shielded than the O  H proton,
i.e.,  CH   OH
Hence,
BCH  BZ 1   CH   BOH  BZ 1   OH 

thus the field experienced by the hydrogen nucleus of O  H bond is greater than the field
experienced by the hydrogen nuclues of C  H bonds . So, in order to have resonance with
a radiation of particular frequency O  H hydrogen requires a lower amount of applied
magnetic field than the C  H hydrogen.

The effect of the gradual increase of the magnetic field on the energy levels of
hydrogen nuclei of CH 3 group and O  H group in methyl alcohol is shown in

Fig.7
54
 It is evident that the hydrogen nucleus of O  H group experiences a greater magnetic field
than the hydrogen nuclei of CH 3 group at any given applied magnetic field. Since
E  g  N BZ , and the hydrogen nuclei of O  H experiences more field, the value of E
becomes equal to the energy of the radiation with which the sample is irradiated at a lower
magnetic field and so absorb radiation. However the hydrogen nuclei of CH 3 group, being
more shielded, experiences lower magnetic field and so come to resonance at a slightly
higher magnetic field. This is represented in the spectrum of methyl alcohol in fig.7 it self.
The smaller peak at lower magnetic field corresponds to the single hydrogen nucleus
of the OH group and the bigger peak at higher magnetic field corresponds to hydrogen
nuclei of CH 3 group. The ratio of the areas under larger peak and smaller peak is 3 :1
indicating that the larger peak is due to the absorption by three hydrogen nuclei of CH 3
group and the smaller peak corresponds to single hydrogen nucleus of O  H group. The
separation between these peaks is known as chemical shift. The chemical shift difference
between the OH and CH 3 signals of CH 3 OH is found to be 1.96 T . This chemical shift
difference depends upon the strength of the applied magnetic field and so depends upon
the operating conditions of the instrument. So as to overcome this difficulty chemical shift
is usually measured as the fraction of the applied field. Since the strength of applied mag-
netic field under the present study is 1.4092 T , the fraction of chemical shift will be
6

1.96  10 1,4092 or 1.39  106 or 1.39 p p m. But in usual practice a standard substance giv-
ing intense absorption is to be chosen as reference substance. Tetramethyl
silane, Si  CH 3  4 , consisting of twelve number of most shielded hydrogen nuclei is chosen
for this purpose and on  scale, its signal corresponds to zero.

BZ  reference   BZ  sample 
   106
BZ  reference 

The chemical shift is not merely because of the extent of electron cloud on the
nuclues but also because of electronic circulation induced due to applied magnetic field.
The diamagnetic electronic circulation in acetylene due to applied magnetic field reduces
the effect of the field at the hydrogen nucleus. It results in shielding and resonance will be
observed at higher field (Fig . 8)

Fig . 8

55
But in case of benzene the induced field has the same direction as the applied field in the
vicinity of hydrogen nuclei. So the hydrogen nuclei in benzene are deshielded and resonate
at low applied field (fig.9)

Fig.9

TMS has several advantages as a standard reference substance in NMR spectroscopy

i) The resonance is sharp and intense since all twelve hydrogen nuclei are
equivalent.
ii) resonance position is at very high field because of high shielding of
hydrogennuclei
iii) easily be separated from the sample after the experiment because of its low
boiling point.

A more convinient scale is  scale in which TMS resonance is at 10 and low field
resonances are measured in ppm . with decreasing numerical values Fig.10 shows both
 and  - scales and indicates the approximate resonance positions of some molecules
and groups.

Fig.11

56
 A small collection of available data is mention in table 2

SPIN-SPIN INTERACTION
No thing will be attempted if all possible objections must first be overcome
Let us consider two hydrogen nuclei labelled as A and X which are sufficiently
close to each other in a molecule of the solid substance. the component of spin angular
momentum of the hydrogen nucleus designated as A may be oriented in the direction of
the applied magnetic field or opposite to the direction of the applied magnetic field as repre-
sented in Fig.11

Fig .11

57
 It can be seen from the Fig.11 that the lines of force originating from A are opposing
the applied magnetic field at nucleus X when A is oriented in the direction of the field.
When A is oriented in opposite direction to the applied field the lines of force at X are in
the direction of the applied field and hence X experiences more field. Since the two direc-
tions of orientations for A are eqvually likely, the nucleus X will find itself in an applied field
BZ  BA or in BZ  BA with equal probability where BZ is the strength of applied field
and BA is the field due to the nucleus A at the nucleus X .Hence the X nuclei of the sample
show two different resonance positions in the spectrum resulting in a doublet. The two
signals of the doublet are separated by  B Z  BA    B Z  BA   2 BA on tesla scale. Similar
explanation can be extended for the effect of x on A causing the splitting of the signal of A
into doublet. This phenomenon is known as spin-spin interaction or coupling. But this effect
is very much smaller in case of liquids indicating the involvement of different mechanism.
Consisting of two hydrogen nuclei joined by a pair of bonding electrons. Let us
assume that electron (a) is associated wither nucleus designated as A and electron (x) is
associated with nucleus designated as X.

Fig .12
For an energetically stable molecule,
(a) The magnetic dipoles of electron and nucleus must be opposite to each other.
(b) The spins of the electrons present in the same or batyl must be opposite to
each other
So for a most stable state of the molecules the spins will be alternating in the order
nucleus (A) (  ) electron (a) (  ) electron ( x ) (  ) nucleus ( x ) (  ) as represented in fig
12. Since it resulted in opposite spins for nucleus (A) and nucleus (X), they are said to be
paired. So the paired configurations viz; the spins  or  , have lower energy than the
spin parallel configuration viz.,  ,  , as the spins of both the nuclei. However the en-
ergy difference between these two configurations is very small and is of the order of 1032
J. Hence both the configurations do occur with equal probability. The resulting four energy
levels of AX due to the spins of the two hydrogen nuclei, viz.,  ,  and  ,  are
represented in Fig.13. In this diagram, the upspin(  ) is designated as  and the down
spin (  ) as  .
58
 Fig. 13

Assuming that there is no coupling between A and X we can say that,

(i) the transition from

  

and   
corresponds to spin change of X only and these two transitions have identical en-
ergy resulting in a single spectral line at V X .

(ii) the transition from

  

and   
are having identical energy and corresponds to spin change of A only. So this tran-
sition results in a spectral line at VA .

When coupling occurs the stable configuration  ,  gets more stabilised whereas
the less stable configuration,  and  , gets more destabilized. The extent of stabiliza-
tion or destabilization is given by J/4 energy units. Now the two possible X transitions have
different energies. The energy of transition    is diminished by J/2 units whereas
the energy of transition    is enhanced by J/2 units. Hence one spectral line
J
appears above Vx . So two spectral lines will be resulted with a separation of J units and
2

59
this J is termed as coupling constant. Similarly the A transitions will also be split into identi-
cal doublet. Since all the spin states are equally likely likels the spectral lines of a doublet
have equal intensity. The value of J is independent of the strength of the applied magnetic
field and is expressed in Hz.
NMR spectrum of Ethylalcohol.

60
 Lesson No-9
APPLICATION OF NMR STUDIES IN STRUCTRUAL
ELUCIDATION
Zero is not zero but full. Full minus full is full. But is Reality for an expert

1) Structure of ethyl alcohol  CH 3CH 2OH  :-

This is A3 X 2 System

CH 3 TMS
OH CH 2

 Scale
O
1: 3 : 3 :1 1: 2 :1

Spectrum of ethyl alcohlo.

Ethanol is an example for A3 X 2 system. Where A is a CH 3 Protons of methyl

group. s and X is protons of methylene group. with coupling constant J Ax . We adopt
family tree method to explain the spectrum of ethanol as it is a much simpler approach. In
the bigining it was assumed that there is no coupling between A3 & X 2 . As a result of
which weget one line corresponding to each of intensity 3 and 2 units respectively.

When there is Coupling between A3 and X 2 , and , the A3 line splits into a doublet

of separation J AX and the intensity of each line is 1 1 2 units. Now each leg of the doublet

couples with the second X nucleus and splits into a doublet of separate J AX and the

intensity of line is 3 4 units. The innerline of each doublet will overlap because the cou-
pling is identical for both and so the spectrum appears as a triplet and the intensities are
in the ratio of 1: 2 :1. The Splitting of X 2 by coupling with, A3 proceeds in a similar fashion.

Coupling to one A yields 1:1 doublet , to a second A yields a 1 2 :1: 1 2 triplet, and a third

A yields a 1 4 : 3 4 : 3 4 : 1 4 quartet, 1: 3: 3:1 lie (quartet) with a coupling constant J

repeated three times.

61
 The nuclei in the methyl group (or) the methylene group are said to be magnetically
and chemically equivalent. Magnetically and chemically equivalent protons don’t cause
any splitting of the signals amoung themselves. So we can neglet the coupling between
methyl hydrogen themselves or methylene hydrogen themselves and have considered only
the coupling between a methyl and methylene nucleus.
Thus we have a generalisation that group of equivalent nuclei (protons)splits a
neighbouring group into  n  1 lines and the intensities are inaccordance with the pascal’s
triangle

Intensities of signals in accordance with Pascels Triangle

No. Of protons No. Of signals Intensities

0 1 Singlet 1
1 2 doublet 11
2 3 triplet 1 2 1
3 4 quartet 1 3 3 1
4 5 quaintest 1 4 6 4 1
5 6 sextet 1 5 10 10 5 1
6 7 septet 1 6 15 20 15 6 1

But CH 3CH 2OH contains traces of acid imparities, the impure ethanol

CH 3CH 2OH A can exchange its. protons  H A  with other protons say  H B  present in
imparity. So the proton in OH group in continuously changing and doesn’t remain for
sufficient time. As a result there is no influence of H A on CH 2 group protons and vice
versa.

 CH 3CH 2OH B  H A

CH 3CH 2 OH A  H B 

As a result there is no Coupling between CH 2 Proton and OH proton.

In pure form of CH 3CH 2OH , there is coupling between CH 2 protons and OH
proton and as a result the quartet corresponding to methylene group is further split into 8
peaks with intensities 1:1: 3: 3: 3 : 3:1:1 . Similarly the singlet of OH group splits into a
triplet due to coupting with CH 2 protons. The entire NMR spectrum for ethanor is shown
below.

62
 TMS
OH CH 2 CH 3

1: 2 :1 1: 4 : 6 : 4 :1 1: 2:1
BZ

2) N,N - Dimethyl Formamide :-

O CH 3
 
C N
H CH 3
N , N  Dimethyl formamide

In this , two different chemical environments are present. Generally, we expect two
signals, one correspond to two CH 3 groups and other for aldehyde proton. Actually differ-
ent signals are found depending up on the external condition mainly upon the tamperature.

a) N ordinary temperature :-

O CH 3 O CH 3
 

CN


 C N
H CH 3 H CH 3 b

At room temperature a double bond in formed between carbon and nitrogen due to
conjugation. No free rotation of C  N bond takes place due to the presence of more strong
double bond.

The spectrum for N , N  dimethys formanide shows two non-equivalent methyl

group which absorb at different field strengths.

CH 3  CH 3 TMS
O CH 3
 CHO
CN
H CH 3 equal At room temp.

O
BZ

63
 At elevated temperatures the rapid rotation between C  N makes both the methyl
magnetically equivalent and only one signal is observed for both the methyl groups.

O CH 3 a 
 
C N
At 1200 c
H CH 3 b
TMS
Broad
spectrlum

BZ
At 1600 c
TMS

BZ

3) STYRENE :  HC  CH 2

C6 H 5 H
CC  Or 
H H

X H X Y X H
CC C C CC
H Y H H Y H
Trans. Vicinal Ge min al
J  12  18 H Z J  6  12 H Z J  1 3 HZ
For Styrene
HB J AB  17.2 H Z
J AC  10.2 H Z
C C
J BC  1.3H Z
HA HC

Normally three chemical environments are expected i.e., CH 2 , CH and ring pro-
tons. But infact 4 types of signals, out of which three are further split into more than one
signal are obtained and this can be explained on the basis of spin spin coupling.

Let the protons are labelled as H A , H B , & H C .

H A & H C are vicinal, protons with J AC  10.2 H Z

H A & H B are trans protons with J AB  17.2 H Z

H B & H C He are Geminal protons with J BC  1.3H Z

64
 A B C
J AB  17.2 J AB  17.2 J AC  10.2



J J AC  10.2 J BC  1.3 J BC  1.3

These three protons can couple with each other. The protons H A & H B are near to
the Benzenering where as H C is some what away. So H A , H B are more deshielded them
H C . Also H A is more nearer to benzene ring then H B , As result H A is more deshielded.
As a result the increasing order of field strengths at which the protons resonate is given by.
Because sheildion effect of H C is more,
H A  H B  HC

H A Couples with H B and given a ‘doublet with J AB  17.2 H Z . Then H A also

couples with H C as a result of which each singlet is split into a doublet with H AC  10.2 H Z .
Hence for H A weget two deletes. Similarly the proton H B couples with H A to give a
doublet with spacing J AB  17.2 H Z due to coupling of H B with H C each singlet splits into
doublet with J BC  1.3 H Z . Since J BC in so small each doublet is merged. A similar
phenome non is observed for the proton H C .

 The over all Spectrum of styrene is represented as

1) ring protons

HB HC TMS
HA

 BZ O
4) Acetophenone :-
O
O
 
C  CH 3 C  CH 3
H H HA H A1

H H HB H B1
H HC
TMS
Complicate
Spectrum
6 5 4 3 2 1

ortho metapara
65
 Spectrum of Acetophenone doesn’t obey  n  1 rule. We have a complicated spec-

trum. H A , H 1A protons are magnetically non-equivalent . Simillarly H B & H B1 are also mag-
netically non-equivalent because Coupling constant between ortho protons is different to
that of para protons. Here we observe three chemical environ ments for ring protons. The
ortho protons of the ring are deshidded and as a result they resonate at a law field. The
remaining three protons H B , H B1 , don’t interact with oxygen of  C  O group. We get a
three proton slight above the field of ortho protons. We get a singlet for methyl group at a
higher magnetic field.

O

5) Acetamide :- CH 3  C  NH 2 .
H
|
H  C  C  N
|
H o

In acetamide, the methyl protons adjacent to carbonyl group are deshideled due to
the presence of carbonyl oxygen atom. So we get a three proton singlet for CH 3 protons
at a lower fields than expected for normal alkyl group. Also a broad singnal corresponding
to  NH 2 protons is obtained, at a low field. As nitrogen is more electonegative the  NH 2
protons can be deshielded and resonate at a lower field. In this case, there is no conjuga-
tion as in the case of N,N-dimethyl formamide . As a result more number of conformers
are possible for acetamide . We Can’t say which proton of  NH 2 is nearer (or) which is far
a part from the oxygen. The probability is same for each proton. Hence the two protons
resonate at a same field and we get a broad band. This signal is also known as two protons
singlet

CH 3 TMS

 NH 2

BZ O

66
 Lesson. No-10
ELECTRON SPIN RESONANCE SPECTROSCOPY
The first and last thing required of genius is the love of truth

An electron spins about its axis, and since the electron has charge this rotation
produces magnetic dipole. The electron spin resonance method is concerned with the
study of the re-orientation of such magnetic dipoles by applying electromagnetic radiation
of a fixed frequency in the presence of a suitable magnetic field.

In ESR often called Electron Paramagnetic Resonance (EPR), electromagnetic

radiation (usually of microwave frequency) is absorbed by molecules, ions, or atoms pos-
sessing electrons with unpaired spins, i.e. electronic spin S  0.

In both ESR and NMR, the sample material is immersed in a strong static magnetic
field and exposed to an orthogonal low-amplitude high-frequency field. ESR usually re-
quires microwave-frequency radiation (GHz), while NMR is observed at lower radio fre-
quencies (MHz). With ESR, energy is absorbed by the sample when the frequency of the
radiation is appropriate to the energy difference between two states of the electrons in the
sample, but only if the transition satisfies the appropriate selection rules.

Most of materials in a bulk form at normal conditions have net zero electronic spin
and, thus, are ESR silent, but some are can provide an ESR signal.

Theory

In ESR spectroscopy there is splitting of energy levels and hence the frequency
capable of causing transitions between these levels is a function of the magnetic field
strength H.
We know that electron is a charged particle with anpular momentum and hence it
possesses a magnetic moment  . The magnetic moments can be detected by their inter-
actions with magnetic fields. In case of zero field, the magnetic moments of odd electrons
in a sample have randomised directions, but in the presence of a magnetic field H, the
electron moments are aligned parallel or antiparallel to the field giving rise to two energy
states.
For unpaired electrons, there are thus two energy levels, linear in H. The difference
between the two levels, at a particular value of field strength is given by :

E  hv  g  H 0 ______(1)

where h is Planck’s constant, v the frequency of radiation,  the Bohr magneton, H 0 the
field strength, and g the spectroscopic splitting factor. The quantity g is not a constant but
a tensor quantity. For a free electron g gas has the value of 2.0023. In many free radicals,
the g value of the odd electron is close to that of a free electron, but in metal ions g values
are often greatly different from the free electron value.

67
 In general the magnitude of g depends upon the orientation of the molecule con-
taining the unpaired electron with respect to the magnetic field. In a solution or in the gas
phase, g is averaged over all orientations because of the free motion of the molecules, but
in a crystal, movement is restricted. If the paramagnetic radical or ion is located in a per-
fectly cubic crystal site (e.g., an octahedral or teetotaler is said), the g value is independent
of the orientation of the crystal and is said to be isotropic. In a crystal site of lower symmetry
the g value depends upon the orientation of the crystal and is said to be anisotropic.

The ESR spectrum can be obtained by varying either the frequency or the field
strength. In practice it is simpler to vary the latter. The effect of magnetic moments of nuclei
on the ESR spectrum is known as hyperfine interaction and responsible for splitting of the
ESR line, giving rise to hyperfine structure. The magnitude of the splitting in called hyper-
fine coupling constant and usually expressed in gauss. A field strength of 3200 gauss will
provide a high sensitivity ESR signls.
Presentation of the Spectrum
The ESR spectrum can be represented by plotting intensity against the strength of
the applied field, but ESR spectra are commonly presented as derivative curves, i.e., the
first derivative (the slope) of the absorption curves is plotted against the strength of the
magnetic field. The two modes of presentation are easily inter converteble, and the rela-
tionship between the two kinds of spectra is illussirated in Fig. -1. In (a), a single absorption

Intensity
Intensity

Field Strength Field Strength

Intensity

Intensity

Field Strength
Field Strength

Fig .1 :- Comparison of Spectral Presentation as Absorption (a and c)

and Derivative (b and d) Curves.

peak with no fine structure is represented; (b) is the derivative curve that corresponds to
(a). The derivative curve crosses the abscissa at a maximum in the absorption curve, for
the slope changes sign at maximum Curve (c) is the absorption counterpart of curve (d).
Note that the shoulders in (c) never pass through a maximum and as a result the absorp-
tion peaks in (d) corresponding to these shoulders do not cross the abscissa. The number
of peaks and shoulders in the absorption curve can be determined from the number of
minima (marked with an asterisk in (d)) or maxima in the derivative curve.
Hyperfine Splitting in Some Simple Systems
When an unpaired electron comes in the vicinity of a nucleus with a spin I , an
68
interaction takes place which causes the absorption signal to be split into components.
The cause of this splitting in an isotropic system is the nuclear spin-electron spin coupling
arising mainly from the Fermi contact term.
This effect is simply illustrated by considering as an example a hydrogen atom
1
(I  for the proton). The EPR spectrum of a hydrogen atom in a solid matrix consists of
2
two peaks of equal intensity centered at g  2.0023. The two energy levels of a free electron
1 1
in a magnetic field are shown in fig. 2a with ms   aligned with the field and ms  
2 2
aligned opposed to the field. The spectrum of a free electron would consist of a single peak
corresponding to a transition between these levels. For each value of the electron spin
1
angular momentum number mI , can have values of  , giving rise to four different energy
2
levels (Fig. 2b).

Fig .2 :- (a) Energy States for an Electron in a Magnetic Field and (b) Effect
1
of a Nuclear Spin of 2
on These States.

From magnetic considerations, one expects that the interaction of a proton nuclear
1
moment corresponding to quantum number mg   will lead to a lower energy than the
2
1 1
interaction of moments of mI   and ms   . Similarly the interaction of the moment
2 2
1 1 1
from ms   and mI   will lead to a lower energy than interaction with mI   . The
2 2 2
energies of the levels are gives by

E  g  Hmg  Amg mI ___(2)

where A is referred to as the hyperfine coupling constant. Upon substitution of the proper
values of mg and mI one obtains the energies indicated in Fig. 2. The selection rules in EPR
are: mI  0 and mS   1. The two peaks in the spectrum correspond to the transitions

69
shown in Fig. 2b where mI does not change and mS   1. The energies for the two
1
transitions observed are then g  H  A, and the spearation between the two peaks (ex-
2
pressed in gauss or mc sec1 ) is just A , the hyperfine coupling constant. The splitting
1 1
indicated in Fig. 2 implies a positive value for A . If A were negative, mS  , mI   would
2 2
be the low energy state. In general the sign of A cannot be determined from a simple
spectrum.
The same argument can easily be extended to a single electron located on a nucleus
1
with spin I other than . For such a nucleus, the nuclear magnetic moment can take any
2
of the 2 I  1 values corresponding to the quantum numbers  I ,  I  1,..... I  1, I . As in the
1
example in Fig. 2, where I  , these orientations give rise to 2 I  1 different nuclear en-
2
ergy states (one for every value of mI ), and when each of these couple with the electron

 1
moments  mg    , 2 I  1 lines result. Since these energy differences are very small, all
 2
levels are equally populated and the components will usually be of equal intensity and equal
spacing.
The magnitude of the spliting, expressed in terms of coupling constant, A , de-
pends on the following factors: (1) the ratio of the nuclear magnetic moment to the nuclear
spin, (2) the electron spin density in the immediate vicinity of the nucleus and (3) an aniso-
tropic effect.
Hyperfine Splittings in Various Structures
An unpaired electron interacting with a nuclear spin I will give rise to 2 I  1 lines, all
of equal intensity and equal spacing, e.g., three lines are expected for an unpaired electron
on nitrogen, where I  1. We shall next consider the effect on the spectrum when the
electron interacts with, several nuclei. For simplicity, the species shall be assumed to be
rotating very rapidly in all directions, and orbital contributions shall be assumed absent. As
an example, the methyl radical will be discussed. As illustrated in Fig 3, addition of the
nuclear spin

Fig .3 :- Possible Nuclear Spin Arrangementsof

the Protons in a Methyl Radical.

angular momentum quantum numbers of the individual protons results in four different
values for the total nuclear spin moment. As indicated in Fig. 4, this gives rise to four
transitions  mI  0, ms  1 . Since there are three different ways to obtain a total of
70
 1 1 3 3
mI   or  (see Fig. 3), but only one way to obtain mI   or  , the former sys
2 2 2 2 -
tem is three times more probable than the latter and the observed relative intensities for the
corresponding transitions are in the ration 1:3:3:1.

Fig .4 :- The Four Transitions that Occur

in the ESR Spectrum of the
Methyl Radical (See Fig. 5 for the Spectrum).

In general, when the absorption spectrum is split by n equivalent nuclei of equal

spin I i , the number of lines is given 2nI i  1. When the splitting is caused by both a set of
n equivalent nuclei of spin I i and a set of m equivalent nuclei of spin I i the number of lines is

given by  2n I i  1  2n I j  1 .

The spectrum of the methyl radical illustrated in Fig. 5 contains the four peaks
expected from these considerations.

Fig .5 :- The Derivative Spectrum of the Methyl

Radical in a CH 4 Matrix at 4.2 K . From F. J. Adrian,
et. at., Advan. Chem. ser., 36, 50 (1962). .

Factors Affecting the Magnitude of The g Values

The value of g for an unpaired electron in a gaseous atom or ion, for which Russell-
Saunders coupling is applicable, is given by the expression:

J  J  1  S  S  1  L  L  1
g  1 ___(3)
2 J  J  1

 1 1
where J is the total angular momentum. For a free electron  S  , L  0, J   , the value
 2 2

71
of g  2.0 is easily calculated from equation (3). The actual value for a free electron is
2.0023 where the contribution 0.0023 is due to a relativistic correction. For the halogen
atoms in the gas phase, g values predicted by equation (3) have been found to agree
exactly with experimental values. No such agreement is found, however, when the un-
paired electron is placed in a chemical environment, either in a free radical, or in a transition
metal ion complex crystal lactice.
Anisotropy in the Hyperfine Coupling Constant
Only when the absorbing species is rotating rapidly in all directions or when it has
spherical symmetry is the g value found to be isotropic. These same considerations are
true for the hyperfine splitting constant. When the species is either rotating or spherically
symmetric, the coupling constant is isotropic, and the energy of the transition, E (excluding
fine splitting) is given by :

E  hv  g  H 0  Am1 ___(4)

When a radical is rigidly held in position, as in a solid matrix or in a crystal, the

electron may be subjected to magnetic anisotropies, this effect can lead to an anisotropy in
the hyperfine coupling constant. The anisotropy in the coupling constant has the same
angular dependence as the g value. Equation (4) can be rewritten to take account of anisot-
ropy in both g and A for an axial system:

1 2   1  
 3 3  3
 
E  hv   g  g    H 0  Am1   g   g    H 0  Am1  3 cos 2   1 ___(5)
  

where  is the angle between the direction of the magnetic field and the z axis, A is called
the isotropic coupling constant, and B is called the anisotropic coupling constant. It is seen
readily that for a freely rotating radical, equation (5) reduces to equation (4).

Experimental technique and principles

In general the basic requirements of an ESR spectrometer are :
(a) A source of microwave radiation.
(b) An absorption cell containing the sample under investigation.
(c) A.D.C, magnetic field which is so arranged as to be perpendicular to the
magnetic field component of the microwave radiation.
(d) A crystal or bolometer to detect resonance absorption.
(e) A recorder or cathode ray oscilloscope.
Fig .6 is a diagrammatic representation of an ESR spectrometer incorporating the
features (a) to (e). A klystron oscillator supplies energy of a fixed frequency which is fed by
a wave-guide to the resonant cavity. The cavity is located in a homogeneous magnetic
field, the field strength of which is varied slightly by employing subsidiary modulation coils.
The sample under investigation is placed at the point in the cavity where the micro-wave
magnetic field is a maximum. If the sample exhibits absorption, then the signal reflected by
the cavity is modified. The signal is detected by means of a crystal rectifier at the end of the

72
wave-guide, is then amplified, and fed to either an oscilloscope or a pen recorder. In the
case of the oscilloscope an absorption spectrum is observed on the cathode ray screen.
For electron spin resonance the resonant frequencies are given by equation
and when the values of h and  are substituted this becomes :

v  1.3997 gH ______(6)

Where v is given Mc/S. The frequencies employed in ESR work have ranged from
0.8 to 55,600 Mc/s. However, for the study of wide lines or weak signals, it is desirable to
work in the kilo-oersted range. If g is approximately two, it follows from the above equation
that the resonant frequency must fall in the microwave range. The microwave radiation is
generated by a klystron oscillator. Klystrons with a power output of the order of 50 mW are
available for the three main bands, namely 3.2 cm (the X-band), 1.25cm (the K-band), and
8 mm (the Q-band). ESR spectrometers are operated at constant frequency.

Fig 6.

Radiation is conveyed to the sample by means of a wave-guide, the dimensions of

which are critical for a given frequency. For example, the internal cross sectional dimen-
sions of the wave-guide for X-band are 0.400 and 0.900 inch. The wave-guide (system)
feeds the power into a cavity, which may be a short length of rectangular wave-guide.
Wave-guide and cavity are joined together by a flange as illustrated in Fig. and power from
the wave-guide is coupled into the cavity by means of a small hole in a diaphragm.

73
Applications
ESR spectroscopy is used to study a variety of substances. A few examples are
discussed here.
(1) Presence of organic and inorganic radicals which are formed as intermediates dur-
ing the course of some chemical reactions can be ascertained from the esr spec-
trum. Radicals with a very short life cannot be recovered or trapped, but can only be
detracted. Certain organic radical intermediates such as methyl radical may have a
planar or a tetrahedral geometry. This information is obtained from the magnitude of
the hyperfine splitting constant " a " due to the interaction of the unpaired electron
with 13C carbon.
(2) Many enzyme catalysed biological redox reactions proceed through distinct one
electron steps. The oxidation of ascorbic acid by hydrogen peroxide is catalysed by
peroxidases. These catalyse the reaction

H 2O2  2 H   2e  2 H 2O

where the two electrons needed are provided by the ascorbic acid. That this reac-
tion is not a one step, two electron transfer process is shown by the formation of
radical intermediates which have been detected by electron spin resonance tech-
nique. This shows that two ascorbic acid molecules supply one electron each to
H 2 O2 molecule and from ascorbic acid radicals which then decay to form the prod-
ucts.

(3) Odd electron molecules such as NO2 , NO, C 1O2 , etc, can be identified by gas phase
esr experiment.
(4) Transition metal complexes with incomplete 3d, 4d or 5d electron sub-shells can
be studied by this method. Copper forms a number of complex compounds in
which the oxidation state of copper may be either one or two. Many of these com-
plexes show a strong esr signal thereby proving the presence of Cu(II) (d9 system)
in them. Cu(I) complexes with d10 configuration show only a feeble esr signal.
(5) N-type semiconduction. Germanium and silicon atoms have four electrons in the
outer orbitals of their atoms which form four covalent bonds at very low tempera-
tures, If some impurities with five electrons such as arsenic are deliberately intro-
duced during crystallisation, these substances become highly conducting due to
the presence of extra electron. This is known as extrinsic conduction and is proved
by esr spectroscopy.

74
 Lesson No-11
THERMODYNAMICS
A man is exactly as great as the tide surfing beneath him

Thermodynamics is the study of the relationship between heat and other forms of
energy. Thermodynamics concern with the intercon version of one form of energy into
another form and the work obtainable form such conversions. The first law of thermody-
namics is concerned with energy changes and the second law specifies the direction of
such changes. The first law enables to calculate the changes accompanying chemical
reactions and the second law enables to predict whether a reaction is feasible or not.
Thermodynamics is primarily concerned with systems at equilibrium. Thermodynamics is
an exact science. So thermodynamics is based on precise definitions of various terms
used.
System and Surroundings
A system is the portion of the universe under study which is separated from the
reminder of the universe by real or imaginary boundaries.
The system may be subjected to an experimental or theoretical investigations.
The rest of the universe which may or may not interact by exchange of matter or
energy with the system under investigation is treated as surroundings.
In many instances, a known amount of an ideal gas confined in a cylinder fitted with
a frictionless piston is considered as the system.
If the system is immersed in a large thermostat, this thermostat is considered as
the surroundings. In thermostat large volume of liquid is maintained at constant tempera-
ture.
Three types of systems may be distinguished depending on the nature of the
exchange of matter or energy with the surroundings. In an open system both matter and
energy can be exchanged with the surrounding. (Ex : Reaction in an open vessel).
In a closed system only energy can be exchanged but not matter. (Ex : Reaction in
a closed glass container)
In an isolated system neither energy nor mass is exchanged with the surroundings.
(Ex : Reaction in a sealed container kept in Dewar flask).
A system can be characterised by certain observable properties of bulk matter.
These properties are referred as state variables or thermodynamic variables.
Thermodynamics is concerned with a study of systems in equilibrium. When the
temperature and pressure are uniform in every part of the system then the system is said
to be in equilibrium. The variables pressure (P) , volume (V) and temperature (T) are
called as state functions or thermodynamic properties. A state functions is defined as the
property of a system which does not depend on the path or manner in which a particular
state is reached.

75
 The following are the important properties of state function :
(i) when a system goes from state A (initial state) to the state B (finial state) the
change in the state function is obtained by subtracting the initial value from the final value.

E  EB  E A

(ii) Any infinitesimal change in state function can be expressed as an exact or com-
plete differential. Since V is a single valued function of P and T ,

V  f  P2 , T2   f  P1 , T1 

But for an infinitesimal change in V given by dV .

 V   V 
dV    dP    . dT .
 P T  T  P

(iii) Euler’s criterion of integratability should hold good for an infinitesimal change.

It E  f  x, y 

 E   E 
dE    . dx    . dy.
 x  y  y  x

 E 
Let   M
 x  y

 2 E  M 
then   .
x y  y  x

 E  2 E N 
and    N ; then    .
 y  x y x   x y

2 E 2 E
then 
x y y x

Work of Expansion.
When there is a change in volume against a constant external pressure, work done
by the system is referred as work of expansion or P-V work. When work was done on the
system, it is referred as work of compression .

Let a constant pressure Px acts on the piston fitted to a cylinder consisting of one
mole of an ideal gas. Then the force exerted on the piston is Px A where A is the cross
sectional area of the cylinder. Let the pressure exerted by the gas on the piston be Pg . If

76
Px  Pg an expansion takes place and if Px  Pg the gas is compressed. Px  Pg refers to
an equvilibrium situation. Let the piston be displaced through dh, an infinitesimal distance,
as a result of infinitesimal work,  w , of expansion against external pressure Px .

work done,  w  Px . A . dh

 Px . dV

Because A . dh is the volume swept by the piston in moving through a distance dh . If Px is

kept constant and there is a finite change in volume from v1 to v2 , the total work done is
given by,

 w  Px  dv
w  Px V2  V1 

 P V

when a process occurs in such a way that the properties of the system at every
instant remain uniform and the system is in equilibrium with the surroundings, the process
is said to be thermodynamically reversible. Each intermediate step in the change in state
from A to B is always an equilibrium situation.  Px  Pg and Tx  Tg  . So a reversible pro-
cess is considered as a succession of equilibrium steps. Another criterion of a reversible
process is that it should be capable of reversible in either direction by appropriate infinitesi-
mal changes in thermodynamic properties such as pressure and temperature. The exter-
nal pressure is kept at  Pg  dP  where dP is an infinitesimal change in pressure. The gas
does a work of expansion and its temperature decreases by an infinitesimal amounts.
Because the cylinder is in the thermostat, this thermostat ensures that the heat lost is
supplied to the gas so as to maintain its temperature constant.
Now the gas is in new equilibrium state and is infinitesimally different from the pre-
vious state. Once again the pressure is decreased by infinitesimally small amount dP . An
infinitesimally small amount work is done and the temperature decreases. The thermostat
provides the heat to the system to maintain the temperature constant and the system
acquires new equilibrium. By repeating this process patiently for infinite number of times it
is possible to bring about the finite change in volume of the system. This process is termed
as isothermal reversible process.
Suppose the piston in the cylinder is pushed back in one stroke effecting the same
change of volume in the gas. This process results in definite changes in pressure and
temperature. It is because enough time is not given to attain equilibrium. This kind of rapid
expansion in a finite interval of time is known as an irreversible process.
In a reversible adiabatic expansion process the temperature of the gas decreases
as there is no heat exchange between the system and the surroundings. Similarly in an
adiabatic compression process there is an increase in the temperature of the gas.

77
 The work of expansion is given by the product of the external pressure and the
volume change. As the external pressure approaches Pg the work of expansion increases.
Hence the maximum work is obtained when the external pressure is infinitesimally smaller
then the pressure of the gas. In a revisable expansion process the external pressure
Px  Pg  dP,

Hence  w  Px dV

  Pg  dP  dV

v2

Integrating  w    P  dP  dV
v1
g

v2

  Pg dV
v1

because dP dV is externally small.

For n moles of an ideal gas

Pg V  n RT , we have

v2
dV
Wher   n RT .
v1
V

V2
 n RT ln
V1

If the gas expands isothermally against constant external presser, the work done

W  Px V2  V1 

If the gas expands into vacuum the external pressure is zero, and so the workdone
is zero.

Let a system absorb a certain quantity of heat  q  from the surroundings. As a

result of this, the internal energy of the system is increased. The system is also able to do
work  w  on the surroundings. If E is the change in the internal energy of the system,
according to the frist law of thermo dynamics.

q  E  w.

The heat changes accompanying chemical reaction depend on whether the reac-
tions are carried out at constant volume or constant pressure. As the temperature is raised

78
the quantity of heat absored also changes. The variation in heat absorbed with variation in

temperature i.e., dq is called the heat capacity. This value depend up on whether the
dT
changes take place at constant presser (or) constant volume. So two heat capacities are
proposed. The heat capacity at constant presume C p is given by

d qp
Cp  ;
dT

But the heat absorbed at constant presser is enthalpy and is given by

H  E  P V

(or) q p  qv  P v

dH
So Cp 
dT

 H 
  
 T  P

The heat capacity at constant volume is defined as

d qv
Cv 
dT

dE
Cv 
dT

 E 
Cv   
 T v

Calculation of E , H , q and w for ideal gases:-

An ideal gas is chosen as a model system since well established equations are
available relating its thermodynamic properties, eg, the equation of state PV  n RT . Among
the four functions, E and H are state functions, where as q ans w being path functions,
their values are not fixed by the state of the system. The change in the state of the gas can
be brought about by (i) a constant pressure (isobaric) process (ii) a constant volume
(isochoric) process (iii) a constant temperature (isothermal) process and (iv) an adiabatic
 q  0  process.

Consider 1 mole of an ideal gas undergoing a change in state from A  P1 , V1 , T1  to

B  P2 , V2 , T1  . This change in state may be achieved by two different paths, (i) (path a and
b) and (ii) path c. fig1. isobaric process  dP  0, path a  . (1) The work done can be calcu-

79
lated but we know that

V2 V2

w   P1 dV  P1  dV .
V1 V1

 PV
1 2T2 
A ------- C

--------------
a

 b
c

D B  P2V2T1 

V1 V2
Volume
Fig. 11.1 Different pathways for calculation of
U ,  H , q and w for ideal gases.

Since the process is isobaric change in volume take place due to change in tem-
perature .

w  P1 V2  V1 

 RT R T1 
 P1  2  
 P1 P1 

 R T2  T1 

For n moles of an ideal gas

w  nR T2  T1 

2) The process is isobaric and so the heat absorbed is qP ; ie  H . Since

 H  C p dT , but

2 2

 dH   CP dT
1 1

 H  q p  C P T2  T1 

3) For n moles  H  nC P T2  T1 

80
4)  E  qP  w

 C P T2  T1   R T2  T1 

 Cv T2  T1  C p  Cv  R 

 E  Cv  T2  T1 

This can also be obtained from the of Cv for n moles

 E  n Cv T2  T1 

(ii) Isochoric process  dV  0, path b  .

Consider the change in state as represented by path (b) ie, from P1 V2 T2 to P2 V2 T1 .

This can be achieved by decreasing the pressure and temperature to P2 and T1 respec-
tively. However, these must be carried out reversibly such that Px  Pg and Tx  Tg .

(1) w   P dV  0 (Since
x dV  0 )
1

(2) The process is isochoric and so the heat absorbed  qv  E  is given by

2 T1

 dE 
1
C
T2
v dT

(or) qv  Cv T1  T2    Cv T2  T1  for n moles qv  n Cv T1  T2  . Here

T2  T , qv is negative ie, the heat is evolved by the system and absorbed by the surround-
ings

(3) E  q  w

  Cv T2  T1   0

(or)  E   Cv  T2  T1 

(4)  H  E  H  Pv   E  R T .

  Cv T2  T1   R T1  T2 

  Cv T2  T1   R T2  T1 

 H   C p T2  T1 
81
 (iii) Isothermal process  dT  O path c 

Here the change in state occurs from A  P1 , V1 , T1  to state B  P2 , V2 , T1  .

(1) The expansion process is carried out reversibly such that P2 is always equal
to Pg and Tx  Tg  T1 . Here Px and Tx refer to the external pressure and temperature re-
spectively of the surroundings. The subscript g, refers to these properties of the confined
gas.

Here the pressure is not constant as in (i) but at every stage Px  Pg  dP

The work of expansion, Wrev , is given by above equations

V2 P
Wrev  or  Wmax  RT1 ln  RT1 ln 1 . This work done is indicated by the shaded
V1 P2
area in above figure (1).

(2) The calculation of q becomes possible by using the equation E  q  w ;

For an ideal gas, its internal energy depends only on temperature and if it is constant E  0 .
Hence

V2 P
q  w  RT ln  RT ln 1
V1 P2

It will be noticed that for the isothermal process wrev  qrev . In an isothermal revers-
ible expansion of an ideal gas, a certain amount of heat, q is absorbed from the surround-
ings ( q  positive since V2  V1 ). and converted into an equivalent amount of work (w is
positive since V2  V1 )

(3) E  0 . This can be readily shown from the fact that E being state function.
E is independent of the path.

E  path c   E  path a   E  path b 

 Cv T2  T1   Cv T2  T1   0

(4) H  0. This can be shown as follows.

H  E    PV   E    RT 

 E  0  0

(or) H  path c   H  path a   H  path b 

 C p T2  T1   C p  T2  T1   0
82
 incendently it will be seen that

w  path c   w  path a   w  path b 

and q  path c   q  path a   q  path b 

V2
ie, w  path c   RT ln .
V1

w  path c   w  path b   R T2  T1   0

 R T2  T1 

Similarly
v2
q  path c   RT ln
v1

q  path a   q  path b 

 C p T2  T1   Cv T2  T1 

 R T2  T1  .

Problem : 2 moles of a monatomic gas   1.67  at 300K and 10 atm is allowed to

expand to 1 atm by
(a) a reversible isothermal process
(b) an irreversible isothermal process
(c) a reversible adiabatic process and
(d) an irreversible adiabatic process.

Calculate in each case the final temperature, final volume, w, q, E and H

 C 
( C p  4.968 cal deg mol) and Cv  2.981 cal deg mol,  r  P C 1.67.
 V 

(a) Reversible isothermal expansion. The final temperature is the same as the
initial temperature, ie, dT  0. Hence d E  0 and H  0. The final volume can be calcu-
lated by applying Boyle’s law. The initial volume

300
V1  2  0.0821   4.9261.
10

83
 P1 V1
The final volume is   10V1  49.26
P2

P1
wrev  q  n RT ln
P2

 2303  2 1.987  300 log 10  1

 2746 Cal.

(b) Irreversible isothermal expansion.

Hence the external pressure is kept constant at 1 atm and the gas expands irre-
versible under isothermal conditions.
Final temperature = initial temperature.

H  0 and E  0.

Final volume  10V

 n RT n RT 
w  P2  v2  v1   P2   
 P2 P1 

 P
 n RT 1  2 
 P2 

 P 1
 2  1.987  300  0.91  2  
 P1 10 

 1073 Cal.

 q  E  w  1073 Cal.

(c) Reversible adiabatic process.

Here q  0, and so E   w  n Cv T2  T1 

The final temperature can be calculated by using

 1 
 
 Constant.
  
TP

84
  1 
 
 P     0.401
T2  T1  1   300 10  .
 P2 

 119.1 k .

 E  2  2.981 119.1  300    1078.5 Cal.

w   E  1078.5 Cal.

 H  n C p T2  T1   2  4.968  180.9 

  1797.4 Cal.

Since the expansion has already occurred, the ideal gas law can be used to calcu-
late the final volume.

P1 V1 PV T P
 2 2 ; V2  2 . 1 . V1
T1 T2 T1 P2

119.1 10
 V2  . V1  3.972,
300 1

 V1  4.9261

 V2  3.97  4.926  19.551

(d) Adiabatic irreversible expansion :

q  0 and E   w  n Cv T2  T1 

The final temperature will be different from the value under reversible Conditions.
It can be calculated from eqn

  P2  
 Cv  R  P1  
T2  T1  
 CP 
 

T1  P 
  Cv  R 2 P 
Cp  1 

300
  2.981  1.987  0.1
4.968 

85
 T2  192 K .

The fall in temperature is then greater when the adiabatic process is carried out
reversibly .

 E  2  2.98 K 192  300    643.8 Cal

w   E  643.8 Cal

 H  n C p T2  T1   2  4.968  108 

  1073 Cal

The final volume, can be calculated.

192 10
(or) V2  . V1  6.4V1
300 1

V1  4.926

V2  6.4  4.926  31.531

Heat flows from a hotter to a colder body until they reach a common temperature. A
gas at high pressure spontaneously expands into a region of low pressure till the pressure
is uniform through out. Such processes occur by themselves without the aid of any exter-
nal agency. These are called spontaneous or natural processes. In all these cases the
system has a tendency to proceed towards an equilibrium state. However once this equi-
librium state is attained the system do not return to its original state.
So the Processes in which system Proceeds spontaneously from non equilibrium
to equilibrium condition is called thermodynamically irreversible. But a system approaching
an equilibrium state can be made to do work. The expansion of a gas from higer pressure
to low pressure can be used to push a piston. Water flowing down a hill may be made to
rotate a turbine. Similarly a spontaneous flow of heat from hotter to a colder region may be
make to do work by using heat engine. Based on the above discussion clausius slated the
second law of thermodynamics as
“ Heat will not flow from a colder body to a warmer body without the expenditure of
work”
The efficiency of a heat engine is defined as the fraction of the heat absorbed from
the higer temperature reservoir that can be converted to work.

work output w T T
E   2 1
heat input Q2 T2

Where T2 is the temperature of the source and T1 is the temperature of the sink.

86
 Further the efficiency can be written as,

Q2  Q1
E
Q2

where Q2 is the amount heat absorbed by the system in an isothermal reversible manner
from the source and Q1 is the amount of heat given by the system to the sink.

Clausices called the function  qrev as entropy. This function is a state function.
T
The increase in entropy, ds accompanying an infinitesimal reversible and isothermal change
is given by the ratio of  qrev , the heat absorbed in the reversible process and T , the abso-
lute temperature at which change takes place.

 q rev
ds  .
T

The units of entropy are cal deg 1 .

According to first law of thermodynamics.

 q rev  dE  PdV

Where dE is the increase in internal energy and PdV is the amount of work done because
of the absorption of an amount heat  q rev .

So,

TdS  dE  PdV .

Since

 E 
Cv   
 T  v

dE  Cv dT

So,

TdS  Cv . dT  PdV

or dT 1 RT
dS  Cv .  . . dV
T T V

dT dV
dS  Cv . R .
T V

87
 Integrating between the initial and the final states.

S2 T2 V2

 dS 
S1

T1
Cv . d ln T   R d ln V .
V1

T2 V
S  Cv ln  R ln 2
T1 V1

Since for an ideal gas

V2 PT
 1 2
V1 P2 T1

The above equation becomes

T2 T P
S  Cv ln  R ln 2  R ln 2
T1 T1 P1

T2 P
  Cv  R  ln  R ln 2
T1 P1

T2 P
 CP ln  R ln 2 .
T1 P1

At constant Pressure,

T2
S  CP ln
T1

dT
or dS  CP .
T

S for Phase change.

Whenever phase changes occur, (solid to liquid, liquid to vapor etc. ) the tempera-
ture remains constant as long as the two phases are present. Such transitions are accom-
panied by absorption of heat. So the entropy change for this process is given by,

H
S 
T

or Lf
S 
Tf

where L f is the latent heat of fusion and T f is the melting point temperature.

88
 Consider n moles of a solid being heated from T1 to its boiling point Tb . This overall
process can be represented as,

Solid T1  

S1
Solid T f 
L

S
f
 Liquid T f  
S
 Liquid Tb 
2 3

Lv

S
 Vapour Tb 
4

The total change in entropy is given by.

Tf Tb
dT Lf dT L
S   n CP  s   n  n  CP l . n v
T Tf   T Tv
T1 Tf

Irreversible Processes :-
For a reversible cyclic process,

 qrew
 T
O

For a cyclic process for which a part is irreversible.

 qrew
 T
 O

So r
 qrew 
 T
 O
i

‘ = ‘ refers to reversible process.

‘ < ‘ refers to an irreversible process.
The work done by a system in a reversible process is greater than that for a corre-
sponding irreversible process.

So,  wrev   w irr .

From first law of thermodynamics

 q  dE  PdV .

because  qrev
dS  ,
T

 qrev  T . dS

89
 So,
T dS   q.

T dS  dE  PdV

 dS  E ,V O

Or


 dS  E ,V O


where ‘ > ‘ applies to irreversible processes.

‘ = ‘ applies to equilibrium process.
‘ < ‘ refers to non spontaneous processes
Entropy of mixing
When two or more gases are brought into contact they mix spontaneously by diffu-
sion. Such a spontaneous process is accompanied by an increase in entropy.

Let nA moles of gas A and nB moles of gas B be mixed at constant temperature,

T and pressure P . The entropies of the gases before mixing are given by

S A  nA  CP  A .ln T  R ln P   SO  A 

S B  nB  CP  B .ln T  R ln P   SO  B 

where So refers to corresponding integration constant.

In the mixture, let the partial pressure of A be PA and that of B be PB , such that,

P  PA  PB .

After mixing the entropies of A and B are given by,,

 S A mix  nA  C P  A .ln T  R ln PA   SO  A 

 S B mix  nB  C P  B .ln T  R ln PB   SO  B 

The entropy change

Smix    S A mix   S B mix     S A  S B  

PA P
  nA R ln  nB R ln B .
P P

90
The mole fraction of A and B , x A and xB , are given by

PA PB
xA  and xB 
P P

Smix   nA R ln x A  nB R ln xB .

Or i
Smix   R  ni ln xi .
i 1

The entropy of mixing for a total of one mole of the mixture is. S  Smix .
n

i
S   R  x ln x
i 1
i i

91
 Lesson No-12
FREE ENERGY FUNCTIONS
Infinity in Computer iargon changed form 1038 to 104300 through 1075 and 10308. what is
real infinity? zero is not zero but full - It is not mathematics.

Entropy function is useful in predicting the spontaneity of a reaction, because, in an

irreversible process, the net change in entropy of the system and its surroundings is positive.
This criterion is incovenient because one has to have a knowledge of the properties of the
surroundings also, in addition to the properties of the system. Hence a modification of this
criterion, would be much helpful. A search for such a criterion resulted in the definition of
two more theromodynamic functions. These are the free energy functions of Helmholtz
and Gibbs, These functions are helpful not only as criteria of spontaneity, but also in predicting
maximum work.
The Helmholtz free energy is generally denoted by the symbol A and is defined by the
equation.

A  E  TS

The Gibbs free energy, generally represented by the symbol G,* is defined by the
equation.

G  H  TS

The equation for the free energy functions of Helmholtz and Gibbs involve only state
functions, namely, E , H , and S . Hence these two functions are also state functions and
their differentials are exact, i.e.,

 dA  0

 dG  0
B. The Gibbs free energy is given by the equation

G  H  TS

Substituting the value of H  E  PV

G  E  TS  PV

But since A  E  TS , it follows from that

G  A  PV
The change in Gibbs free energy, when a system changes from one state to another,
under isothermal conditions,

92
 G  G2  G1

  H 2  TS2    H1  TS1 

  H 2  H1   T  S 2  S1 

 G  H  T S

Hence for an infinitesimal change under isothermal conditions

dG  dH  T .dS

Similary, under isothermal conditions,

A  E  T S

and for an infinitesimal change

dA  dE  T .dS

Subtracting Equation  A from G from Equation

G  A  H  E

 P . V

since H  E  P.V

 G  A  P.V

or dG  dA  P.dV

Considering Equation

A  E  T . S

since in a reversible process, S   Qrev / T 

A  E  Qrev

But according to the first law equation

E  Qrev  Wrev

 A   Wrev

Thus in a reversible process, the decrease in Helmholtz free energy is equal to the
work done in that process. Hence the Helmholtz free energy is sometimes referred to as
the Work Function.

Since, in a reversible process, the decrease in Helmholtz free energy is equal to the
work done follows that
93
  G  Wrev  P.V

or  G  Wrev  P.V

i.e., in a reversible process, the decrease in Gibbs free energy is equal to the net work done
other than work of expanseion.

Differentiating Equation A  E  TS gives

dA  dE  T .dS  S .dT

But for a reversible process, T . dS  Qrev and Qrev  dE  P.dV . Therefore

dA   P.dV  S .dT

which is the equation for the total differential of the Helmholtz free energy.

Similarly, differentiating Equation G  H  TS

dG  dH  T .dS  S .dT

But dH  dE  P.dV  V .dP and T .dS  dE  P.dV

 dG  V .dP  S .dT

This equation represents the equation for the total differential of Gibbs free energy.

E. Under isothermal conditions, i.e., dT  0,

So,  dA T   P.dV

or  A 
   P
 V T

Similarly, since  dA V   S .dT

 A 
   S
 T V

Differentiating the above Equations with respect to T and N respectively

2 A  P   S 
     
V . T  T V  V T

i.e.,
 P   S 
    
 T V  V T

This equation represents one form of Maxwell’s Partial Relationship. Another form of

94
the relationship is derived from dG  vdP  sdT .

 dG T  V .dP

and
 dG  P   S .dT
From these two equations,

 G 
  V
 P T

and  G 
   S
 T  P

Hence

 2G  V   S 
    
P.T  T P  P T

or  V   S 
    
 T  P  P T

Equation (5.31) is the other form of the Maxwell’s Partial Relationship

Gibbs-Helmholtz Equation

According to Equation dG  vdP  sdT .

 dG  P   S .dT
Hence, if there are two states of the system, they can be represented as

 dG2  P   S2 .dT
and
 dG1  P   S1.dT
where G2 , S2 , and G1 , S1 are the Gibbs free energies and entropies of the final and initial
states respectively of the system.
Subtracting the above Equation one from the other

d  G2  G1     S2  S1  . dT

But G2  G1  G and S 2  S1  S . Hence

d  G  P  S .dT

95
 or    G  
   S
 T  P

But in an isothermal change

G  H  T S

   G  
 G  H  T .  
 T  P

This Equation is called the Gibbs-Helmholtz Equation. It enables one to calculate the
change in enthalphy of reaction, H , from a knowledge of change in Gibbs free energy and
the temperature coefficient of G.
A more convenient form of the Gibbs-Helmholtz Equation is obtained as follows :

d  G  1 d  G  G
  2
dT T T dT T

i.e.,    G / T   T .(  G / T  P  G
  
 T P T2

But

   G  
T   G
 T  P H
2
  2
T T

Hence

   G / T   H
   2
 T P T

or

   G / T  
   H
  1/ T   P

In a galvanic or voltaic cell, chemical energy is converted into electrical energy.

The electrical energy of a galvanic cell of E.M.F.E volts, is equal to n.F.E, where n is the
number of electrons involved in the reaction and F is the Faraday (nF is usually called the
quantity of electricity). Since the quantity of electricity is expressed in coulombs and the
E.M.F. in volts, the electrical energy is in the units, volts-coulombs (one volt-coulomb = one
joule).
The electrical energy of a galvanic cell was equal to the chemical energy expressed
96
as the enthalpy of the reaction  H  , taking place in the cell. The electrical energy of a
galvanic cell is equal to the chemical energy, expressed as the decrease in Gibbs free
energy  G  * .

Criteria of Equilibrium and Spontaneity

For a reversible process,

dA   P.dV  S .dT

is applicable. Hence at constant volume and temperature

 dAV ,T 0

That is , for any process, if the change in Helmholtz free energy at constant volume
and temperature, is zero, it can be said that the process is occurring in a reversible manner,

Similarly from dG  vdP  sdT it follows that for a process in which there exists an
equilibrium

 dG  P ,T 0

by dE   Pdv  sdT . So  dE v ,T  0

But for irreversible process.

Qirrev
dS 
T

so that
T .dS  Qirrev

where Qirrev represents the heatr taken in an irreversible manner. Bur

becasue dA  dE  Tds  sdT ; T .dS  dE  S .dT  dA

Hence
dE  S .dT  dA  Qirrev

But from the first law equation

Qirrev  dE  P.dV

 dE  S .dT  dA  dE  P.dV

or
 S .dT  dA  P.dV

 dA  P.dV  S .dT

97
 and
 dAV ,T  0
In a similar manner, it can be shown that

 dG  P ,T  0

So,  dAV ,T  0
and
 dG  P ,T 0

in which the ‘equal to’ sign applies to an equilibrium state (reversible process) and the ‘less
than’ sign applies to a spontaneous (irreversible) reaction. Similarly it can be written that

 dS  E ,V  0
in which the ‘equal to’ sign indicates a reversible process and the ‘greater than’ sign applies
to a spontaneous reaction.
Free Energy Changes in Ideal Gases
The free energy changes for isothermal processes involving ideal gases can be
calculated from Equation dA   Pdv  sdT

 dA T   P.dV

V2

   A T    P.dV
V1

where V1 and V2 are the initial and final volumes respectively. But for one mole of an ideal
gas, P  RT / V .

V2
RT
  A T   .dV
V1 V

V2
  RT 1n
V1

or
V1
 A T  RT . 1n
V2

In the case of Gibbs free energy, dG  vdP  sdT

 dG T  V , dP

98
 P2
  G T   V .dP
P1

where P1 and P2 are the initial and final pressures, For one mole of an ideal gas, V  RT / P;
therefore,

P2
dP
 G T   RT . P
P1

or
P2
 G T  RT .1n
P1

Since one mole of ideal gas is under consideration, in an isothermal process,

P1.V1  P2 . V2 . Hence it follows that for one mole of an ideal gas,

 A T   G T

99
 Lesson No-13
FREE ENERGY CHANGE ACCOMPANYING A
CHEMICAL REACTION
Why do you believe the sun will rise tomorrow. If at all yes, in which direction ?

Application of the law of chemical equilibrium to the reaction

A B  C  D

Gives the following equation

K
C . D
 A. B 
where K is the equilibrium constant and the concentrations refer to the equilibrium state.
The above reaction may be assumed to be occurring in a hypothetical box called the
van’t Hoff Equilibrium Box. It is supposed that (1) this hypothetical box has as many walls
as the total number of the reactants and products, and (2) one wall is premeable to one
component only. In the present case, since there are only two reactants and two products,
there four walls and each of these four walls is permeable to one of the reactants and
products. Further, it is also assumed that the equilibrium box is so large that the addition or
removal of one mole of the products or reactants does not affect the equilibrium. It is also
assumed that the reactants and products are ideal gases, to make the calculations simpler.
Considering two such equilibrium boxes, I and II Fig.1 in which there is equilibrium
between reactants and products, let PA , PB , PC , PD and PA , PB , PC , PD be the equilibrium partial
pressures of A, B, C and D in the boxes I and II respectively. The letters A, B, C and D
along with the arrows indicate the walls through which A, B, C and D can be introduced into
the box or removed from the box. Let us now carry out the following operations:

B B

A B  C  D A B  C  D
A A
C  I   II C
PA , PB , PC , PD PA , PB , PC , PD

D D
Fig .1 Vasit Hoff Equilibrium boxed
 one mole of A is removed from the box I and introduced into box II through the wall
permeable to A. The change in the Gibbs free energy in this process can be calculated
using the following equation

PA
dP
G A   RT . P
PA

or PA
G A  RT . 1n
PA

one mole of B is removed from box I and introduced into box II through the wall
which is permeable to B. The change in Gibbs free energy for this process is

PB
GB  RT .1n
PB

One mole of C is removed from box II and introduced into box I through the wall
permeable to C and the change in Gibbs free energy is

PC
GC  RT .1n
PC

One mole of D is removed from the box II and introduced into box I through the
wall permeable to D and the change in Gibbs free energy involved in this process is

PD
GD  RT .1n
PD

The total change in Gibbs free energy, G is equal to the sum of the terms
G A , GB , GC and GD . Hence

PA P P P
G  RT .1n  RT .1n B  RT .1n C  RT .1n D
PA PB PC PD

or
PA . PB . PC . PD
G  RT .1n
PA . PB . PC . PD

The above equation can be written as

PC . PD P . P
G  RT .1n  RT .1n C D
PA . PB PA . PB

But the systems are in equilibrium in the two boxes and hence the G should be
equal to zero.
 PC . PD P . P
 RT .1n  RT .1n C D
PA . PB PC . PD

or PC . PD P . P
 C D  KP
PA . PB PA . PB

where K P represents the equlilbrium constant.

The law of chemical equilibrium can be derived for a more general chemical reaction

aA  bB  cC  ...  lL  mM  nN  ...

where a, b, c, l m and n represent the respective numbers of moles, when the following
result will be obtained :

l m n
 PL   PM   PN 
a b c
 KP
 PA   PB   PC 
van’t Hoff Reaction Isotherm
Let us consider one equilibrium box, and the change in free energy involved in the
transfer of the reactants and products from an arbitrary partial pressure to the equilibrium
partial pressure, (Fig .2)
D

C PA e, PB e , PC e , PD e  A PA, PB, PC , PD

Fig .2

PA e, PB e , PC  e , PD  e  and PA, PB, PC , PD represent the equilibrium and arbitrary partial pressures,
respectively, of A, B, C and D. Four operations are carried out as and the total change in
the Gibbs free energy will be

PAe  PB e PC P
G  RT .1n  RT .1n  RT .1n  RT .1n D
PA PB PC  e  PD e 

PA e  . PB e  . PC . PD
G  RT .1n
PA . PB . PC e  . PD e
Rearranging the above equation.

PC  e  . PD e  PC . PD
G   RT .1n  RT .1n
PA e . PB e  PA . PB

PC  e  . PD e  PC . PD
  G  RT .1n  RT .1n
PA e  . PB e  PA . PB

But since PA e , PB e  , PC  e  and PD  e  are the equilibrium partial pressures of A, B, C and
D respectively, the first term on the right hand side of above equation is equal to the
equilibrium constant, K P .

So,
PC .PD
G  RT .1n K P  RT .1n
PA .PB

Considering a more general reaction

aA  bB  cC  ...  lL  mM  nN  ...

We will get

l m n
 PL  .  PM  .  PN  ...
G  RT .1n K P  RT .1n a b c
 PA  .  PB  .  PC  ...
in which

l m n
 PL e .  PM e .  PN e ...
KP  a b c
 PA e .  PB e .  PC e ...

the  PL e ,  PM e ,  PN e ..., and  PL  ,  PM  ,  PN  ... representing the equilibrium and arbitrary

partial pressures respectively. The second term can be written as RT .  n. 1n P, where
n represents the number of moles of the particular consitituent whose partial pressure is
P . The above equation can therefore be represented as

G  RT .1n K P  RT .  n.1n P (6.18)

The summation term in The above equation is such that it is positive for the products
and negative for the reactants. This equation is known as the van’t Hoff Reaction Isotherm.
Temperature Dependence of Equllibrium Constant-van’t Hoff Equation

The Vasit Hoff reaction isotherm is G  RT ln Kp  RT  n ln P. If arbitrary partial

pressure is 1atm. The second term becomes zero. Then the free energy change, is
replaced by G 0 , and is known as the Standard Gibbs Free Energy Change, because a
pressure of 1 atm for a gas represents its standard state. Hence

G 0  RT .1n K P

or
G0   RT .1n K P

Defferentiating the above equation (6.20) with respect to T


d G 0    R.1n K P  RT .
d 1n K P
dT dT

Multiplying both sides of the equation by T

T.

d G 0    RT .1n K  RT 2
d 1n K P
P
dT dT

or
T.

d G 0   G 0  RT 2
d 1n K P
dT dT

The Gibbs-Helmholtz equation for a standard state may be written as

T

d G 0   G 0   H
dT

where H 0 is the enthalpy change for the reaction carried out in the standard state.

Comparison of the above two Euations shows that

d 1n K P
RT 2 . H 0
dT

d 1n K P H 0
or 
dT RT 2

The above equation represents the variation of equilibrium constant of a reaction with
temperature and is known as the van’t Hoff Equation or van’t Hoff Reaction Isochore. For
ideal gases, the H 0 can be replaced by H .

d 1n K P H
So, 
dT RT 2

This Equation can also be written as

H
d 1n K P  . dT
RT 2
 H
  d 1n K P   . dT
RT 2

If H is independent of temperature, i.e., is constant over a range of temperature,

then

 K P 2 T2
H
 d 1n K P   RT 2
. dT
 K P 1 T1

 K P 2 H  1 1 
or 1n    
 K P 1 R  T2 T1 

where  K P 2 and  K P 1 are the equilibrium constants at T2 and T1 respectively..

This Equation enables us to calculate the equilibrium constant at a particular

temperature from a knowledge of its value at another temperature.

If H is dependent on temperature, its variation with temperature is given by the

kirchhoff’s equation

d  H 
 C P
dT

and since

CP     .T   .T 2

and
 2  2
H  H 0   .T  .T  .T
2 3

The Equation for Sd ln Kp may be written as,

 H 0    
 d 1n KP    RT    .T .dT
2
RT 2 R 3R 

H 0    2 I
 1n K P    .1nT  .T  .T  ... 
RT R 2R 6R R

where I is the integration constant, Multiplication of the above Equation by RT yields Equation

 2  2
RT 1n K P   H 0   .T 1nT  T  T  ...  I .T (6.33)
2 6

the above Equation contains two unknown quanities, H 0 and I , which can be
evaluated from a knowledge of C P and the equilibrium constants at two temperatures.
 For a definite change, This Equation will be

 K P 2 T2
 H 0    
 d 1n K P    RT 2
  
RT 2 R 3R
 .T  .dT

 K P 1 T1

 K P 2 H 0  1 1   T   2
or 1n K
 P 1

R
  
T T R
. 1n 2 
T 2 R
T2  T1  
6 R
T2  T12  
 2 1 1

Equation (6.35) should be used to calculate the equilibrium constant at a particular

temperature from a knowledge of the same at another temperature, provided, the variation
of H with temperature is known.
Chemical Potential
Many thermodynamic problems, concern with open systems involving mass changes.

Let us imagine an open system in which there are n1 , n2 , n3 ,... moles of components
1, 2, 3,...., and let the pressure and temperature of the system be P and T respectively. If
we say that X represents an extensive property, then

X  X  P, T , n1 , n2 , n3 ,....

Then the differential of the property, dX , will be

 X   X   X   X 
dX    .dP    .dT    .dn1    .dn2  ...
 P T , n1,n2 , ..  T  P , n1,n ..  n1 T , P , n ..  n2 T , P.n ..
2, 2 1

The above equation may be written as

 X   X   X 
dX    .dP    .dT     .dni
 P T , n1,n2 ,  T  P , n1,n , i
 n1 T , P , n,
2

The partial derivatives, which represent the variation of the function with respect to
the number of moles of any substance are known as Partial Molar Quantities. Thus

 X 
   X1
 n1  P , T , n , ....
2

and
 X 
   X2
 n2  P ,T ,n ....
1,
 If the function is the Gibbs free energy, G, then

 G   G   G   G 
dG    T ,n1 ,n2 , .... dP    . dT    . dn1    .dn2
 P   T  P ,n1 ,n2 , ....  n1  P ,T , n2 ,  n2  P ,T , n1,...

Hence  G  and  G 
   G1    G2
 n1 T , P, n2 ,  n2 T , P,n1 ,

where G1 and G2 are the partial molar Gibbs free energies of the components 1 and 2
respectively.
The partial molar Gibbs free energy is also known as the Chemial Potential and is
represented by the symbol  .

in general  G 
i    T, P
 n1 

Therefore The above equation may be represented as

 G   G 
dG    .dP    .dT  1.dn1   2 .dn2
 P T , n1, n2  T  P ,n1 ,n2

But since  G / P T  V , and  G / T  P   S respectively..

dG  V .dP  S .dT  1.dn1   2 .dn2

or
dG  V .dP  S .dT   i .dni
i

At constant temperature and pressure,

dG  1 .dn1   2 .dn2  ...

Since the chemical potentials are constant as long as the temperature, pressure and
composition of the system remain unchanged,
On integration.

n1 n2

G  1.  dn1   2 .  dn2  ...

0 0

or G  1 .n1   2 .n2  ...

It follows from Equation for dG that for an equilibrium state, the summation of the
terms obtained by multiplying the chemical potential by the change in the number of moles,
at constant temperature and pressure, should be equal to zero,
  1 .dn1  0

The chemical potential of the constituent of a mixture is given by the equation

 G 
 i  Gi   
 n1 T , P

But at constant number of moles, i.e., for a closed system,

 G 
V  
 P T

Differentiating the above Equations with respect to P and ni respectively

d 2G d i dV
 
dn1.dP dP dni

But according to the definition of partial molar quantity,  dV / dni  is equal to the partial
molar volume of the i th component, V i . Hence it follows

d i
V i
dP

But the equation of state for an ideal gas containing ni moles, is

Pi .Vi  ni .RT

or Vi  ni .RT / Pi

So that

dV
 RT / Pi
dni

and hence
d i RT

dPi Pi
or
dPi
d i  RT .
Pi

Hence i  i 0   RT .1n Pi

or in general
    0  RT .1n P

where  0 is the integration constant and is a constant at constant temperature. This Equation
presents the chemical potential of an ideal gas whose partial pressure is P .
Henry’s Law states that at a fixed temperature, the mass of a gas dissolved in a given
quantity of a solvent is proportional to its partial pressure. That is,

m  K. p

where m is the mass of the gas, p is the partial pressure and K is the proportionality
constant. It may also be written as

WB
 K . PB
WA

WB
and
MB
 K . PB
WA
MA

nB
 K  PB
nA

where WA , M A and nA represent the weight, molecular weight and number of moles,
respectively, of the solvent and WB , M B and nB are the corresponding values of these
quantities for the gas, PB is the pressure of the gas and K  is a constant. If the solution is
dilute, i.e., nA  nB , Equation (6.12) may be written as

nB
 K . PB
n A  nB

But the left-hand side of the above equation represents the mole fraction of the gaseous
solute in the solution, xB . Hence

xB  K . Ps

Thus, the solubility of a gas, expressed as mole fraction, is proportional to the pressure
of the gas.
Henry’s law may be stated as in a dilute solution, the vapour pressure of a solute is
proportional to its mole fraction.
Taking logarithns on both sides,
 so that on differentiation

d 1n xB  d 1n PB

or
d 1n PB
1
d 1n xB

Now, assuming that the solvent and solute of a solution are represented by A and B, at
constant temperature and pressure,

dG   A .dn A   B .dnB

But general differentiation gives

dG   A .dn A  n A .d  A   B .dnB  nB .d  B

Comparing the above Equations two it follows that

nA .d  A  nB . B  0

or
n A .d  A   nB .d  B

The relationship represented by Equation (6.121) is known as the Gibbs-Duhem equation.

Dividing both sides of by  nA  nB 

nA nB
.d  A   .d 
 nA  nB   n A  nB  B
or
x A .d  A   xB .d  B

where x A and x B are the mole fractions of A and B repectively..

Dividing both sides of equation by dx A ,

d A d B
xA   xB
dxA dxA

But since x A  1  xB  , dx A   dxB ,

d A d
xA  xB . B
dx A dxB

or
d A d B
xA  xB .
d 1n x A d 1n xB
 Assuming that the vapours of the two componets A and B behave like ideal gases,

 A   0 A   RT 1n PA

and  B   0 B   RT 1n PB

according to Equation (6.70). Hence

d  A  RT d 1n PA

and d  B  RT d 1n PB

Substituting these values of d  A and d  B .

d 1n PA d 1n PB
xA .  xB .
dxA dxB

or
d 1n PA d 1n PB

d 1n x A d 1n xB

This equation is called as the Duhem-Margules equation,

It follows that

d 1n PA

d 1n x A

so that d 1n PA  d 1n x A

or 1n PA  K1  1n x A  K 2

where K1 and K 2 are the integration constants. Extracting out the logarithms,

PA  K . x A

where K is a constant. When x A  1 , that is, for the pure solvent K  P 0 , where P0 is the
vapour pressure of the pure solvent .

PA  P 0 . xA

This Equation represents a general law known as Raoult’s law which may be stated
as : the vapour pressure of a solvent in a solution is directly proportional to the mole fraction
of the solvent.
Clapeyron - Clausius equation
The first element with which mankind got acquinted is carbon. It was is cave drawings
from Pre historic times in the form of soot.
Consider a system consisting of two phases of the same substance, e.g., solid-liquid,
solid-gas, or liquid-gas, in equilibrium at constant pressure and temperature. If a small
quantity of the substance is transferred from one phase to the other, the free energy of the
substance is the same in both phases.an appreciable transfer, from one phase to the
other, will not alter the equilibrium. In other words, at constant temperature and pressure if
an equilibrium exists between two phases of the same substance, the substance will have
the same molar free energy in both phases.
It can be extended to systems consisting of three phases as well as those containing
two or more components.
At equilibrium, and at constant temperature and pressure, it follows that if the
temperature and pressure are altered infinitesimally, such that the equilibrium is not affected,
then the change in free energy will be the same in both phases.

dGA  dGB

But in any phase change there is no other work done, except work of expansion.
Hence, substituting the values of dG as given by, we get

V A dP  S A dT  V B dP  S B dT

dP S  S A S
or  B 
dT VB  VA V

S and V being the changes in entropy and volume respectively for the transfer of one
mole of the substance from phase A to phase B. But S  H / T , where H is the change
in the enthalpy for the phase transfer. Therefore, it follows that

dP H

dT T V

The above is known as the Clapeyron equation and gives the variation of the equilibrium
pressure of any two phases with temperature.
For the evaporation of one mole of a liquid, the amount of heat absorbed is the molar
latent heat of evaporation, L. where one mole of a liquid is when evaporated, the change in
volume,  V , is equal to Vg  Vl ,Vg and Vl being the change in volume of the vapour and
liquid respectively. This V has always a constant value at a constant temperature and
therefore  S / V T can be substituted by S / V .

dP S
 
dT V
 But since Le is the molar latent heat of evaporation absorbed at the temperature, Tb
(the boiling point of the liquid)

dP Le

dT Tb . V

dP Le
or 
dT Tb Vg  V1 

This equation was first derived by Chaperone and later extended by Clausius and is
often referred to as Chapeyron - Clausius equation.

At temperatures which are not near the critical value, the volume of the liquid, V1  Vg
and hence it may be written as

dP Le

dT Tb . Vg

Assuming that the uapour behaves like an ideal gas, P . Vg  RT , or Vg  RT / P.

Substituting this value of Vg .

dP L .P
 e 2
dT RT

d 1n P 1 dP
But since  .
dT P dT

d 1n P L
 e2
dT RT

Integrating

P2 Le 1 1
1n     
P1 R  T2 T1 

This equation is the integrated form of the clapeyron - clausius equation.

 Lesson No-14
NERNST HEAT THEOREM
Evans boldy put 50 atm of ethylene in a cell with 25 atm of oxygen. The appara-
tus subsequently blew up, but luckily not before he obtained the spectra.
R.S. Mulliken chem . Rev . 69 (1969 ) 645

The first law of thermodynamics enables us to understand, that work can be com-
pletely converted into heat. This law introduced the thermodynamic functions, energy and
enthalpy. The second law, shows that heat cannot be completely converted into work and
there always exists an efficiency less than unity for any process. The first and second laws
enable us to calculate thermal data from a knowledge of the free energy data, because

from the integrated from of the van’t Hoff equation if the value of in G   RT 1n K p  at two
temperatures is known, the values of the two integration constants, H o and I can be
evaluated from the resulting simultaneous equations.
Further, calculation of thermal data from free energy data can also be done utilising
the Gibbs-Helmholtz equation.

   G  
G  H  T  
 T  p

The second term on the right-hand side of above equation can be calculated from
a knowledge of G at two temperatures. However, the calculation of free energy data from
thermal data is not possible from the two laws of thermodynamics studied till now. This
can be done only by utilising the third law of thermodynamic. But before we consider the
third law, let us consider the Nernst Heat Theorem.
From an examination of the Gibbs-Helmholtz equation, it will be evident that must
G be equalto H at T  0.
During a course of his investigations on the E.M.F’s of cells at low temperatures,
Richards found that, as the temperature is lowered, G becomes almost equal to H
and Nernst has suggested that G and H approach each other not only at T  0, but in

  G  / T  p approaches zero asymptotically Fig.1 The

the vicinity of absolute zero, i.e., 
mathematical expression from this is known as the Nernst Heat Theorem which is written
as

114
     G       H  
lim    lim   0
T 0  
 T  T  P
T 0
P


G
or
H

T
Fig 1:

But according to we know that,

  (G )    (H ) 
  P   S and   P C P
 T   T 

Hence , the heat theorem may be written as

lim S  0, and lim C P  0

T 0 T 0

Since gases and liquids do not exist at absolute zero, the heat theorem should be
applicable to solid systems only.
If we consider a general chemical reaction, A  B then it is known that,

 S B  C P( B )  S A  CP  A 
 T   , and  T  
 P T  P T

so that

 ( S )  C P
  
 T P T

Integration of above equation (9.3) gives

T
C P
` S   .dT  I 0 (9.4)
0 T

where I o is the integration constant. Since ( CP / T ) is known to be finite or zero,

and also since, according to the heat theorem S approaches zero as the temperature is

115
lowered, it follows that the integration constant, I o , should be equal to zero. Hence for solid
systems, one can write

T
C P
S   . dT
0 T

But since G  H  . TS

T
C P
G  H  T . .dT
0 T

The terms on the right-hand side of the above equation (9.6) involve only thermal
data, H and C P and therefore free energy data can be calculated from a knowledge of
thermal data utilising this equation.

H is given by Equation as
 2  3
H  H 0   .T  T  T
2 3

and

C P     .T   .T 2  ...

Substituting the values of H and C P in Equation for G ,

 2  3
G  H 0  T 1  1nT   T  T
2 3

But according to the heat theorem (  ( G / T ) P approaches zero at T  0 and this

can be so only when  is equal to zero. Hence

 2  3
G  H 0  .T  .T
2 3
and similarly

C P   .T   .T 2
and

 2  3
H  H 0  .T  .T
2 3

In this connection, it should be noted that the above treatment is based on the
assumption that Equation for 4CP is valid right down to absolute zero. This is not correct,
because at very low temperatures, the heat capacities of solids are proportional to T 3 .
Hence this part of the heat theorem may be considered as unsound. However, there is very
good agreement between the experimental values and the results obtained from the above
equations.
116
 Nernst has suggested that the heat theorem can be extended to gaseous system
also. Considering the reaction

A( s)  A( g ),

o
i.e., a process of sublimation, the variation of the vapour pressure of the solid, p , with
temperature is given by the Clapeyron-Clausius equation

d 1np 0 L
 s2
dT RT

where Ls is the molar latent heat of sublimation of the solid. But according to the Kirchhoff’s
equation

dLs
 C ' p
dT

where C ' p is the change in heat capacity, of the reaction at constant pressure, and is
equal to the heat capacity of the vapour minus the heat capacity of the solid. Integration of
above equation yields

T
Ls  Ls (0)   C ' p . dT
0

Substituting this value of LS in this equation

T
d 1np 0 Ls (0) 1
 2
  C ' p . dT
dT RT RT 2 0

or
T
LS (0) dT
1n p 0     RT 2 ,  C ' P . dT  i
RT 0

where i is the integration constant and is called the true chemical constant.

T T
LS (0) C ' p 1
 1n p 0    . dT  C ' p .dT  i
RT 0 RT RT 0

But we know that

T
LS (0) 1 L
  C 'P .dT  S
RT RT 0 RT

117
Hence we can white that
LS T C 'P
1n p 0    .dT  i
RT 0 RT

The application of van’t Hoff equation to the reaction

A( g )  B( g )
gives the equation

d 1n K P H g

dT RT 2

where H g represents the heat of the reaction.

Again, according to Kirchhoff’s equation

d ( H g )
 C Pg
dT
CPg being the change in heat capacity in the reaction. By analogy with the equation for ln
p0 .

T
H g CPg
1n K P    . dT  iR
RT 0 RT

The iR in above equation is the appropriate integration constant.

s
We have to calculate the change in the Gibbs free energy, G , when the reaction
A  s   B  s  occurs. This can be done by imagining that the reaction occurs in the ab-
sence of solid phase in an equilibrium box (see Fig 2).

A  s   A g   B  g 
A  g   B g   B s

Fig. 2

If PA0 and PB0 are the vapour pressures of the solids A and B and PA and PB are the
partial pressures of A and B in the equilibrium box, then

PA PB0
G S  RT 1n  RT 1n
PA0 PB

Rearranging the terms in above equation

 P0 P 
G S  RT 1n B0  1n B 
 PA PA 

118
or
 P0 
G S  RT 1n B0  1n K P 
 PA 

because PB and PA are the equilibrium partial pressures. Substituting the values of
0 0
ln pB , 1n pA
T
LS ( B ) C ' P ( B )
1n pB0     . dT  iB
RT 0 RT

T
LS ( A) C ' P ( A )
1n p 0A     . dT  i A
RT 0 RT
and
T
H g
1n Kp     C Pg . dt  iR
RT 0

We get

s
  Ls  B   Ls  A  H g
G  R 
 RT


T
 C     C     C  dt  i
P B P A
g
P


 iB  iR  
 RT
B
0 

or


G s   Ls  B   Ls  A  H g 
T C P  B   CP  A  C Pg
 RT  dT
0 T

 RT  iB  iA  iR 

Substituting the following values in Equation (9.26)

Ls  B   H B  g   H B  s  ; CP  B   CPg B   CPs  B 

Ls  A  H A g   H A s  ; CP  A  CPg A  CPs  A

H g  H B  g   H A g  ; CPg  CPg B   CPg A

we get
T
s s C Ps
G   H  T  . dT  RT  iB  i A  iR 
0 T
119
 Comparing the above equation with Equation for G which is applicable to a sys-
tem involving solids only, we see that

RT  iB  iA  iR   0
or
iB  i A  iR

Thus the integration constant of the expression for ln kp is equal to the difference
between the true chemical constants of A and B. Hence Equation for ln kp can be written
as
T
H g C Pg
1n K p       vi
RT 0 RT

where  v. i is equal to the sum of the true chemical constants of the products minus that
of the reactants. The values of the true chemical constants can be determined, theoreti-
cally, from vapour pressure and heat capacity data and from a knowledge of the true chemical
constants, 1n K p can be determined using Equation above. Thus, it is possible to evaluate
G from a knowledge of thermal data.

All the above equations are derived for a simple reaction. The term  v. i applies
for the gaseous species only.

Nernst Approximation Formula

The application of Equation for ln kp requires a knowledge of the vapour pressure
and heat capacity data down to aboslute zero, which is somewhat difficult. In view of this
difficulty , Nernst developed an approximation formula as detailed below.
For the reaction A  s   A  g  , the Clapeyron-Clausius equation is

dp 0 Ls

dT T Vg  Vs 

where Vg and Vs are the volumes of the vapour and solid respectively and p 0 is the vapour
pressure. Nernst suggested an emirical formula

 p0 
p 0 Vg  Vs   RT 1  
 pc 

where pc is the critical pressure. But

d 1n p 0 1 dp o
 0.
dT p dT

120
Substituting the value of  dp / dT  as given
0

d 1n p 0 1 Ls
 0 .
dT p T Vg  Vs 

Or

d 1n p 0 L 1
 s2 .
dT RT  p0 
 1  
 pc 

Nernst also proposed an empirical equation for Ls as

 p0 

Ls  Ls 0   aT  bT 2 1 

 
pc 
Hence

d 1n p 0 Ls  0  aT  bT 2

dT RT 2
and integration of above equation gives

Ls  0 a b
1n p 0   .1n T  .T  i
RT R R
where a and b are constants and i is the integration constant.
The integration constant in above equation should be approximately equal to the
true chemical constant and Equation this may be considered as an approximate equation.
From his experiments, Nernst concluded that the value of a is about 3.5 for a num-

 
ber of substances, so that a R is approximately 1.75. Equation So, the aobve can there-
fore be written as

Ls 0  b
1n p 0   1.75 1nT  . T  i
RT R
or

Ls  0 b
log p 0    1.75 log T  T C
4.57 T 4.57

i
The constant C in above equation appears to be equal to but in view of the
2.303
approximations, it is a new constant called the conventional chemical constant. The values
of C for some substances have been evaluated by Nernst, and are given in Table 1.

121
 Table 1
ConventionalChemical Constants

Substance C Substance C

Methane 2.5 Ammonia 3.3

Hydrogen 2.2 Iodine 4.0
Nitrogen 2.6 Water 3.6
Oxygen 2.8 Alcohol 4.1
Chlorine 3.0 Benzene 3.1
Sulphur Dioxide 3.3 Acetone 3.7

In a similar menner, Nernst suggested that the variation of H g may be expressed

by the Equation (9.41).

H g  H 0g   n. 1nT   T 2

where H 0g is the integration constant,  and  are constants and  n refers only to the
gaseous reactants and products. The above equation is an approximate form. The equa-
tion for log K p would then be

H 0g 
log K p     n  1.75 log T  T   n.c  9.42 
4.57 T 4.57

g
Nernst approximated This equation further by substituting H g for H 0 and negelcting the
term involving  , so that

H g
log K p     n  1.75 log T   n.c
4.57 T

This equation is the Nernst approximation formula for gaseous reactions. Although
approximate, Equation gives values for K p which are in excellent agreement with those
obtained experimentally, especially for reactions in which  n, i.e., change in the number
of gaseous moles, is zero, e.g., water-gas reaction, and reactions involving dissociation of
hydrogen chloride, hydrogen bromide and hydrogen iodide.

122
 Lesson No-15
THIRD LAW OF THERMODYNAMICS
Knowledge is experiment’s daughter
Experiments are adapted to knowledge

The Nernst heat theorem led to a new generalisation, which was given the name
the third law of thermodynamics. In the heat theorem, it was seen that,

lim  C p  0
T 0

which means that, at absolute zero, all substances have the same heat capacity. Applica-
tion of quantum theory to the study of specific heats of solids have indicated that the heat
capacities of solids tend towards zero as the temperature approaches absolute zero and
that the ratio, C P / T , should have a finite value or should be equal to zero. These conclu-
sions have been established experimentally and hence it is possible to extend the heat
theorem as

lim C p  0
T 0

Further, according to the second postulate of the Nernst heat theorem, lim  S  0.
T 0

That is, at absolute zero all solid substances should have the same entropy. These obser-
vations led Planck to state the third law of thermodynamics as :
Every substance has a finite positive entropy which may become zero at absolute
zero and does so in the case of a perfectly crystalline solid.
Now using this third law, we can calculate the absolute entropies of substances,
because according to Equation
T
Cp
S  ST  S 0   . dT
0 T

where ST and S0 are the values of the entropy at temperatures T and 0 respectively. Ac-
cording to the third law, since S0 of perfectly crystalline solids is zero, the entropy of a
substance at any temperature T is given by
T
Cp
S  T . dT ,
0

and in order to find out ST , the above equation has to be integrated.

The third law includes the heat theorem, but it has an advantages over the heat
theorem, in that the integration constant C can be indirectly obtained from the heat capac-
ity data, whereas in the heat theorem, Nernst had to use approximation methods for this
purpose.

123
 The value of ST , using above equation is calculated as follows. The heat capacity
measurements are carried out to as low a temperature as possible and a plot of C P / T against
T is prepared. The curve BC represents the variation of C P with 1nT for the solid

E
D


CP C
1
B
B
A
ln T 
Fig. 3

and the curve DE represents that of the liquid. The points C and E correspond to the melt-
ing and boiling points of the solid and liquid respectively. The point B corresponds to the
lowest temperature upto which the measurements of C P can be carried out. The value of
the entropy between 00 K and the temperature corresponding to the point B is computed
from the Debye equation. Since.
T
ST   C P . d 1nT
0

or
T T
ST    C P  CV  .d 1n T   CV .d 1nT
0 0

But according to Lindemann and Magnus

3
2
C P  CV  a.T

T
2 3 2
  C
0
P  CV  d 1n T 
3
. aT 2   C P  CV 
3

so that
T
2
ST   CP  CV    CV .d 1n T
3 0

124
 At low temperatures  CP  CV  is very small and hence the first term on the right-
T
hand side of the above equation (9.50) can be neglected and the value of C V .d 1n T is
0

evaluated form the Debye equation

3
T 
CV  464.4  
 

where  is the characteristic temperature.

The integration of Equation for entropy is usually carried out graphically and can be
illustrated taking nitrogen as example . The lowest temperature upto which the vlaues of
C P could be determined was 100 K and the entropy between 00 K So 100 K is computed
form the Debye equation. The entropy form 100 K to 350.610 K is calculated by graphical
integration, i.e., by determining the area under the curve between the two temperatures.

Solid nitrogen undergoes a transition from one form into another at 35.610 K , the
heat of transition being 54.71 cal. Hence the entropy of transition is equal to  54.71 / 35.61 cal
deg 1 . The entropy from 35.610 K to 63.140 K , the melting point of nitrogen, is again com-
puted by determining the area under the curve between 35.610 K and 63.14 0 K . The molar
heat of fusion of nitrogen is 172.3 cal and hence the entropy of fusion is (172.3/63.14) cal
deg 1 . The curve DE represents the variation of C P with 1n T of liquid nitrogen and hence
the area under the curve between 63.140K and 77.320 K gives the entropy of liquid nitro-
gen. At the boiling point, 77.320 K, the amount of heat absorbed is 1332.9 cak mole-1 and
hence the entropy of vapourisation is equal to (1332.9/77.32) cal deg-1. The above results
can be summarised as

Entropy
cal deg 1

00K to 100K (from Debye equation) 0.458

100K to 35.610K (graphical integration ) 6.034
Transition at 35.610K, (54.71/35.61) 1.538
0 0
35.61 K to 63.14 K (graphical integration) 5.589
Fusion at 63.140K (172.3 / 63.14) 2.729
63.140K to 77.320K (graphical integration) 2.728
0
Vapourisation at 77.32 K, (1332.9/77.32) 17.239
Total entropy at 77.320K 36.31

The entropy of nitrogen gas at 77.320K is thus 36.31 cal deg-1. Since the standard
entropies of substances are used in the calculation of G ' s, the entropy of nitrogen gas at

125
1 atm has to be calculated assuming that the gas behaves ideally. This is achieved by
using the Maxwell’s partial relationship, in conjunction with an equation of state for a real
gas. So the entropy of gaseous nitrogen at 77.320 K is 36.33 cal deg 1 . The entropy of nitro-

gen from 77.32 K to 298 K  25 C  can be obtained by the integration of the Equation be-
0 0 0

tween the limits 77.320 K and 2980 K . However, this integration does not generally yield
accurate results and hence the calculation is done by statical methods and this yields
satisfactory results. The value obtained for nitrogen in this manner is 9.36 cal deg 1 so that
the entropy of nitrogen at 2980 K is 36.33  9.36  45.89 cal deg 1

Using this method, the standard entropies of a number of substances have been
determined and from a knowledge of the entropies of the sunstances taking part in a reac-
tion and H 0 , G 0 can be calculated from the equation.

G 0  H 0  T S 0
The validity of the third law of thermodynamics can be verified by comparing the
expreimentally observed values of G 0 with those calculated from a knowledge of H 0
and S 0 .

Applicability and Limitations of the Third Law

The third law is applicable not only to a single crystalline form of a pure substance
but also to all forms that are stable or metastable in this region, provided all the molecules
in each state are reduced toa single energy state.
Heat capacity data have shown that the third law does not hold good for supercolled
liquids and solid solutions. If a solid solution contains two constituents A and B, and if the
solution is assumed to be ideal, and if x A and xB represent the mole fractions of the two
constituents, then the change in free energy resulting from the transfer of x A moles of A and
xB moles of B from the pure solution is given as

G  x A .RT 1n xA  xB . RT 1n xB

But
   G  
    S
 T T

  S  x A . R 1n x A  xB .R 1n xB

Since x A and xB represent the mole fractions, (whose values are always less than
unity) the right-hand side of the above equation (9.52b) will be negative or S will be posi-
tive. Thus the entropy of a solid solution will not be zero 00 K . Since entropy is a measure
of the randomness of a state, it follows that there must be some randomness in the ar-
rangement of the atoms and molecules in a solid solution.
A part from the solid solutions, there are some other substances which do not obey
the third law. Two types of such substances are: (1) homonuclear diatomic molecules,
126
whose nuclei possess a resultant spin, and (2) heteronuclear molecules containing atoms
of almost same size. Hydrogen falls under the first category whereas carbon monoxide,
nitric oxide, nitrous oxide and ordinary and heavy water fall under the second category.
Hydrogen exists in two forms. namely the ortho-and para-forms, in which the nuclear
spins are parallel and antiparallel, respectively. The equilibrium amounts of these two forms
are dependent on temperature and the equilibrium is reached slowly in the absence of a
catalyst on which the material is absorbed atomically. Further, since hydrogen cannot be
cooled and solidified under equilibrium conditions, the solid at 00 K does not exclusively
consist of the molecules of para-form which posses the lower energy. Hence the solid at
00 K possesses a small molar entropy and provides an exception to the third law..
Considering nitric oxide as an example of heteronuclear molecules containing at-
oms of alsomt similarsizes, the most orderly one-dimensional array in the crystal may be
represented as :
NO - NO - NO - NO - NO - NO

Such an array will have minimum energy and zero entropy at 00 K . On the other hand, if
there is an inversion of some of the molecules to produce
NO - NO - ON - ON - NO - NO
it leads to a random distribution and increase in entropy.
The maximum value of entropy, assuming a completely random arrangement in the
crystal, would be R 1n 2, or 1.38 E.U . The S 00 values for NO, CO and N 2O based on spec-
troscopic and thermal data are: 0.66, 1.10 and 1.14 E.U., respectively. These values indi-
cate increasing deviations from orderly arrangements in the three solids.

127
 Lesson No-16
KINETICS INTRODUCTION
Time is an opportunity to learn, not to allow it drain

In Chemical Sciences there are two types of phenomena namely time independent
and time dependent reactions. Time dependent reactions are subclassified as chemical
15 3
dynamics and chemical kinetics. Time scales (10 to10 Sec) are considered as fast. But,
reactions which require a few days to 108 years are very slow.
Ex :HCl + NaOH  NaCl + H2O (difusion controlled very fast)
U238  Products ( very slow)
Chemical dynamics: The transfer of energy and rate of the reaction in terms of atomic
nucli and electrons is called chemical dynamics
Ex: - K + HCl  KCl + H
F2+H  HF + F
H2 + F  HF + H
These are studied by molecular beam instrument. Lasers can specifically activate a
C–H bond of an organic compound. The study of molecules and their kinetics also comes
in this stream.
Chemical Kinetics :
The study of rate and mechanism of a reaction in gaseous, solution or solid phases.
–10
Fe(III) + SCN  Blood red colour
CO(II) + SCN
–
 Blue
} fast

–
Cr(III) + SCN  Slow
–
Ag+ + Cl  Agcl 

Ba2++ + SO4
2–
 BaSO4  } fast

Thus in chemical kinetics there are fast and slow reactions. The fast reactions are
useful in qualitative analysis. Fast and those occurring to completion are used in quantitative
analysis.
The fundamental question why do molecules react is explained based on
thermodynamics. But, kinetics helps to make a slow reaction fast and a fast reaction slow.
Application of kinetics in different disciplines :
Physical Chemistry : Organic Chemists interested in rates of reactions initiated physical
chemistry which spread its wings. The reaction of gaseous, and liquid molecules of general
chemical interest are studied in physical chemistry.
Pharmacokinetics : The rate of absorption, transportation and excretion of drugs, in
biosystems. Here mechanism is essential to discover better drugs.
Bio-inorganic systems : The rate of complexation and adsorption / desorption at different
bio active sites for the action of antidotes for poisoning.
128
Organic synthesis : By changing the rate, a minor product can be made major and a
major product a minor one. The mechanism helps to choose different substituents for a
target molecule.

Rate law :

A rate law is a functional relationship between the speed and concentrations of reactants
with their exponents. It is a differential equation and the solution gives integrated form of
rate law

CH3COOC2H5 + H2O + H+  CH3COOH + C2H5OH

dp
v  = k [ CH3COOC2H5] [H2O] [H+]
dt

Molecularity : The number of species in the rate determining or rate limiting step.

A reaction may have several steps like in the radical reaction.

Ex 1 : Br2  Br..
Br + H2  HBr + H.
H + Br2  HBr + Br.. etc. } Rate determining

Slow
Ex 2 : A + H  AH  Ratedetermining.

fast
AH  Products

Ex 3 : B + D  X (fast)

Slow
X  P1
P1  P2
In Example (1), All steps are rate determing. In Example (2) the first step is rate-
determining. In Example (3) the 2nd step is rate-determining.
Order : The order of a reaction with respect to a reactant is the coefficient to which the
concentration is raised in the rate law.

dP
Ex :  k2 [ A]2 Order  2
dt
dP
 k 1 [ A] [ B ]2 [C ]1 Order , A = 1, B = –2, C = –1
dt

Total Order : The sum of the coefficients in the rate law corresponds to total order.

129
Rate constant : It is a constant with chemical significance and is calculated by observing
(monitoring) the change of concentrations of reactant, intermediate or product with time.
Example :

CH 3COOC2 H 5  H 2O  H   CH 3COOH  C2 H 5 OH

dp
rate law :  k s [CH 3COOC2 H 5 ] [ H 2O ] [ H  ] .
dt

At constant [ H  ]  kS [ H  ]  k2

dP
 k2 [CH 3COOC2 H 5 ] [ H 2O ]  pseudo 2nd order..
dt

A pseudo order (say 2) appears to be 2nd order but it may be a higher order one
under experimental conditions.

At constant [ H 2O]  k2 [ H 2O ]  k1

dP
 k1 [ CH 3COOC2 H 5 ]  pseudo 1st order reaction. Only when the component
dt
is more than 100 times, pseudo first order rate constant is reliable. Otherwise, a mixed
constant is obtained.

130
 Lesson No-17
COLLISION THEORY
Jaggery itself is sweet. It does not expect rice flow to be sweeter

The rate of the reaction interpreted by collision theory was restricted to gas phase
reactions. It doesnot consider reactions in solution phase
Necessary condition : In a bimolecular reaction collision is considered as a necessary
condition for formation of the products. But it is not a sufficient condition.
Basis : Molecules moving in random directions result in the products when collision occurs.
Assumptions : The molecules are hard and rigid spheres. The gas laws are applicable for
kinetics.
Ex : N2 + O2  2 NO ------(1)
H2 + Br2  2 HBr ------(2)
2HBr  H2 + Br2 ------(3)
In reactions (1) and (2) the molecules are of differented size. In reaction (3) the size is
same.
Physical model : The rate of a ( bimolecular gas phase) reaction at ordinary temperatures
and pressures depend upon the number of collisions in unit time and in unit volume i.e.,
frequency (ZAB). The frequency of collisions is very high and the rate constants calculated
were of the order 1029. But the experimentally found rate constants are in the range 10–3 to
   Ea  
1014. Hence energy factor  exp    was considered wherein only those molecules
  RT  
with an energy in excess result in product. Still, the rate of the reaction calculated from
collision theory was very high. A factor depending upon shape, steric hinderance etc., was
introduced. It is called pre-exponential or statistical probability) contribution.
Collision Theory :

A A
bA

0 sec 1 sec
Then molecule A collides with any molecule B coming in its --------
dB/2

dB/2

A 3 D representation is that it encounter with all molcules with in the cylinder of

d A  dB
radius
2
131
 
d A  dB .
2

bA
keep in before Mathematics

Mathematical Model :
In the mathematical model, classical mechanics, gas laws and principles of classical
kinetics are used.

Molecules A B

Mass mA mB

diameter(cm) dA dB

velocity(cm/sec) vA vB

vA is considered relative to vB.

Reduced mass : (  )

For the reaction A + B  P

 m A * mB 
the reduced mass is given by =   -----(12)
 m A  mB 

2 8  KT
Number of molecules of B = nB * d AB

Case i

Frequency of collisions of A with B =

2 8  KT
nA * nB * d AB ---------(13)

Case ii

For A + A  P

nA  nB ; mA  mB

The equation 13 reduces to

132
 mA * mA m
A + A  P and    A ------(14)
2mA 2

2 2 8 KT
Frequency  nA  d AA 
mA / 2

 KT
 n 2A * d AA
2
*4
mA

In this case the collisions are counted twice

 KT
 Z AA  2 n 2A * d AA
2
mA
The rate of reaction by experimental method is given as
(Rate)Exp = kS * [A] * [B]
kS is specific rate constant which can be experimentally determined. A and B are
concentrations. Similarly the rate by collision theory can be written as

  Ea 
( Rate)collision  P * Z AB * exp  
 RT 
All the quantities are only theoretical. If the theory is adequate and experiments are
of sufficient accuracy then (rate)Exp = (rate)Collision theory.

 2 8  kT    Ea 
Thus kS  P *  nA * nB * d AB *  * exp  
   RT 
 
This is because A and B become unity when molecular collisions in unit volume are
considered.
Validation of collision theory :
The collision theory is tested by comparing rate constants, frequency factor and
sometimes other conditions imposed in the theory.
For the reaction

H 2  I 2  2 HI

[ k s ]exp  3.5  10 7

[ k s ]collision theory  5.4  10 7

at 5560 K and dAB is 3.5  10 8 cm . Although the numbers 3.5 and 5.4 appear to be
7 .
different they are equal in the scale of 10

133
Failure of collision theory :

The Polymerisation reactions 1,3 – butadiene, ethylene have

[k s ]theoretical
 10 4
[k s ]exp erimental

The reaction of ethyl alcohol with acetic anhydide has the ratio 10–5. Thus collision theory
fails in such reactions.
The radical reactions like H2 with O2 (or) Cl2 are of very high magnitude than predicted.
Reasons for invalidity of collision theory :
d A  dB
The collision diameter dAB is not exactly equal to the average
2
Classical mechanies and gas laws are applicable only in ideal situation.
Realistic Picture of molecules :
Molecules are not like frozen mummies in Egypt. They are dynamic and like good
athlets. The electron density (or) potential (electrostatic) of even simple molecules is not
uniform. No doubt they have vibrational and rotational motion. The conformers are too many
and all of them are in dynamic motion.
Remedy :
Quantum chemistry and reaction dynamics. The activation energy part will be
improved by transision state theory.

Transition State theory

Necessary conditions :
1) The molecules come together. This is the same assumption as in collision theory.
2) Under the influence of an atom / molecule over other the bonds are loosened, broken
and new bonds are formed.
3) There is a stastical thermodynamic equilibrium between activated complex and
reactant molecules.
Physical model of transition state :

An activated complex ( ) is also like a normal molecule except that it has a higher
potential energy compared to reactants and products.

The reaction coordinate represents

the distance between reactants over
time. The activated complex has one

134
 more degree of freedom compared
to normal reactants.
For Example :
A + B  product
Molecule X#
Translational 3 3+1
Vibrational 3 2

The vibrational degree of freedom is used as the fourth translational degree of freedom
in moving the activated complex along reaction coordinate.
This physical model consists of three influencing factors namely the frequency of
movement of activated complex along the reaction coordinate, concentration of activated
complex ( X # ) and the stastical factor for fruitful formation of the product.

Rate = f * [X #] * P
XH

They involve respectively stastical thermodynamics, kinetic theory of gases, classical

thermodynamics and statistics.
Transistion state diagram :
Considering a reverse reaction
A  BC  X #  AB  C
#
The activation energy for a forward reaction is E f . That for the reverse reaction is

Er# . The difference ‘  ’ is, so small on Potential energy (P.E) scale that it is sufficient to
consider a single activated complex ( X # ) . When the distance between the reacting
molecules is greater than that possible for vander waal interactions (11) represents the
situation. When they approach the bond between B–C is loosened and a new one between
A and B is formed (12), (13) represents a transition state (TS ) which is an unstable
state.Before the formation of products (16) a state like (15) may be possible. Similarly for
the reverse reaction similar patterns are possible of course with a difference in (14).

A B.....C (11) R
A............B.....C (12)
A.......B......C (13)

A.......B......C (14)  TS

135
 A.......B...........C (15)

A–B C (16) P
The detection, identification and conformation of an intermediate or transistion state
(T.S) is possible by isolation as a compound, by a spectroscopic method or from
mathematical principles like eigen value analysis.
Mathematical model : The specific rate constant of a bimolecular reaction.

K#
A  B  K#  P (1)

can be theoretically calculated by mathematical model. Here one should be able to

compute kS without using any experimental parameter. From classical thermodynamics
and law of mass action.

[X# ]
K#  (2)
[A]*[B]
Where the terms in square brackets are concentrations. From kinetic theory of gases
and classical principles of chemical kinetics rate of formation of actirated complex is

dX #
 k s * [A] * [B] (3)
dt
From stastical thermodynamic principles the rate of decomposition of X# to produce

dX # K T
 B * [X # ] (4)
dt h
KB = Boltzmann constant
T = Temperature
h = Planck constant

X # is a transient species and hence study state hypothesis is applicable. It states

that rate of formation and rate of decomposition of a radical, unstable species (or) transient
one is equal.

 Equation (3) = eq (4)

KT
ks [ A] [ B]  *X#
h

KT [X #]
ks  * (5)
h [ A] [B]

Substituting (2) in (5)

136
  KT  #
ks   *K (6)
 h 

If K # , the equilibrium constant of activated complex can be caluclated from theoretical

principles without employing experimental quantities, only then prediction of rate constant
from transistion state theory is possible.

Derivation of K # from classical thermodynamics :

G #  H #  TS# (7)

G #   RT l n K # (8)

 RT l n K #  H #  TS# (9)

 H # S#
l n K#   (10)
RT R

  H #   S# 
K #  exp  . exp
 RT    (11)
1)
   R 

Substituting (11) in eq. (6)

K BT   H #   S# 
kS  * exp  * exp (12)
h  RT   
   R 

H # , S# and X# no doubt are obtained from experiment. Here the rate constant is
#
determined at least at two temperatures. But reaction dynamics gives H # and S
theoretically. So k S can be computed by transistion state theory.

Derivation of Ks from stastical thermodynamics :

The partition function obtainable from stastical thermodynamics is used to calculate

K#
Z AB  E 
K#  * exp  a  (13)
ZA * ZB  RT 

Where Z AB is the partition function of the molecule AB. ZA, ZB are those for the
reactants A and B. Ea , excess of activation energy over zero point energy..

137
 Substituting (13) in (6)

kT z AB  Ea
kS  * * exp (14)
h z A . zB RT

Hence kS can be computed from stastical thermodynamical principles.

d  X #  kT  # 
Derivation of  X (1)
dt h  

d X #
From the physical model  freq * [ X # ] * Prob (2).
dt
The frequency is equal to the ratio of velocity of activated complex along reaction
coordinate and the length through which it travelled.
From kinetic theory

kT
v
2 m
The probability is equal to the translational partition function and is equal to

Thus,

d [ X ] 1 kT  l
 *  X #  *  2 mkT .  (4).
dt l 2 m  h

kT
 *  X #  (5).
h
Limitations :
Transistion state theory also is not satisfactory for complex processes. It is due to
the limitations of classical theories, namely kinetic theory of gases, elementary theory of
probability and consideration of simple bimolecular reactions.
Remedy : Reaction dynamics & RRKM theory

138
 Lesson No-18

KINETIC ISOTOPE EFFECT

Experience is a wonderful thing. It enables you to recognize a mistake
when you make it again. (Back of a sugar packet)

When a heavier isotope is substituted for a normal one the thermodynamics and
kinetics of the reaction alters to a significant extent. The change (increase, decrease) in
rate constant is called kinetic isotope effect. It is divided into primary & secondary kinetic
isotope effects depending upon the bond cleaved and the isotope substituted. There is
another category called inverse kinetic isotope effect. It is used to support reaction
mechanism in terms of bond cleavage.
Primary Isotope effect :
When the isotopically substituted bond is same as that broken during the kinetics, it
is called primary isotope effect. Ex:- Isotopic substitution occurs for C–H. The bond that is
loosened or broken before (or) during formation of TS is also C–H. The energy profile of D–
or T–substituted compound is lower than the normal one. After the transition state both

EH #
ED#
#
ED
#
EH  EH # #
ED  EH

EH
ED
ED

(a) (b) (c)

the curves coincide. If ( E H  ED )  E #

H 
 ED# the rate constant should increase. In an
extreme situation where the activated complex has same energy for H and D substituted
KH
compound then K D is maximum i.e., around 7.0 (fig.c).

With isotopic substitution, vibrionic level is affected and it is shown on PE curve

(fig.b). In many reactions the bond is broken or loosened beyond Vander waal interaction
before transition state. This explains only energy of activation and not other factors governing
rate constant.
Applications :
Elucidation of Reaction mechanism of organic Reactions.
Secondary isotopic effect :
The isotopically substituted bond and that is broken are not same but they are on the
same carbon atom and hence  –effect

139
 Br OCOCH3
CH3COOH
C C C
CH3 CH3 CH3 CH3 H3C CH3
H H H

Here ‘D’ is substituted on C–H but the bond on the  atom is broken (C–Br) forming
carbonium ion.

Secondary –  isotope effect :

If the isotopically substituted bond is far (more than two carbon atoms) from the bond
broken then it is called  -category of secondary isotope effect. It is not directly useful to
elucid the mechanism. But it is used to understand hyperconjugation and related-
phenomenon.
Reverse isotope effect :

KH
When ( E H  ED )  E #
D 
 EH# the rate of the reaction decreases and K D is
less than one. It is referred as reverse isotope effect.

E
D#

EH#

(d)
EH

ED

Mathematical model :
The energies are represented by vibronic level and hence IR Spectrum gives indication
about bonding in activated complex.
1
EO  hvO (1)
2
h = Planck’s constant
vO = wave numbers
For Hydrogen and its heavier isotope D or T
1 1 1
EH  hvH ; E D  hvD ; EO#  h vO# ------- (2 to 4)
2 2 2

140
 Considering (1) and (4)

1 1
EO  EO#  h v0  h vO#
2 2
1
EO  EO# 
2

h vO  vO#  (5)

1  v# 
EO  EO#  h 1  O 
2  vO 

1
Since EO  h vO
2

1  v# 
EO  EO#  EO  1  O  (5)
2  vO 


1 force const
vO 
2 Reduced mass

 force const  #
vO#

 Reduced mass # 
 force const  # *
Reduced mass
vO forceconst forceconst  Reduced mass #
Reduced mass

If the force constants in the ground state and in the activated complex are nearer.

vO# Reduced mass


vO  Reduced mass #
The IR spectrum of activated complex (if possible) throws light on the bonding
characteristics like force constant.
Explanation of isotope effect from collision theory :
Inspite of the weakness of collision theory it sufficiently explains the positive isotope
effect when a heavier isotope is substituted for a normal one. The probability (P), frequency
of collision (f) and activation energy  Ea  are computable. But their accuracy is not very
high.

  Ea 
k  P . f . E xp   (1)
 RT 

141
   EH 
k H  PH . f H . E xp   (2)
 RT 

  ED 
k D  PD . f D . E xp   (3)
 RT 

kH P f   E H  ED 
 H . H . exp   (4)
kD PD fD  RT 

If probability for successful collision is same for H–and D–substituted compounds

and EH & ED are also approximately same then

kH f
 H (5)
kD fD

1
 frequency  (6)
Red .mass

and reduced mass for the same type of atoms reduces to mA/2

1
kH  Red .mass  H  Red .mass  D
 
kD 1  Red .mass H
 Red .mass D

mD
  2 1
mH

Thus collision theory explains the positive isotope effect.

Explanation of kinetic isotope effect from stastical thermodynamics and Transition
State theory :
The rate constant for isotopically labelled (D or T) and that hydrogen can be written
as :

kT Z H#  E 
kH  . exp  H  (1)
h ZH  RT 

kT Z D#  E 
kD  . exp  D  (2)
h ZD  RT 

Where EH is the energy of activation in excess over ZPE (Zero Point Energy). Z H# is
the partition function which can be caluclated from stastical thermodynamics.
142
 kH Z H# ZD   E  ED 
  . . exp  H  (3)
kD Z D# ZH  RT 


# #

The partition function terms can be equated for transistioin state Z H & Z D then
the ratio.

ZH
Z D is +ve, equal or very large.

Thus it explains primary, secondary and reverse isotope effects. In some cases
EH= ED and thus exponential term is one. The assumptions in physical as well as
mathematical models in explaining kinetic isotope effect are

* The collision diameter is equal to the average of individual diameters

 d A  dB 
 d AB  2 
 

* Probability of crossing activated state is same

PH  PD

Transistion state (TS) :

The energy of activation is same for H&D. Partition function is also same for H&D
Z H#  Z D# .

 kH 
Thus due to various assumptions the numerical values   from experiment and
 kD 
theory show the same trend but do not give same value.

Examples :

kH
1)  2
kD

k018 m018
2)  1.125 
k016 m016

k P 31
3)  1.03
k P 30

k105
4)  1.019
k103

143
 The kinetic isotope effect decreases significantly for element of heavy atomic weights
and thus difficult to experimentally determine it.
Problem 1 :

Caluclate the reduced mass for H 2  I 2  2 HI in gas phase. The atomic weights
are H = 1.0079, I = 126.90

mA . mB
 Reduced mass 
mA  mB

(2  1.0079) * (2  126.90)

(2  1.0079)  (2  126.90)

= 0.999915721

Amu (Atomic mass unit) :

N (Aragardo’s number)  6.023  10 23

1 1
Amu  
N 6.023  1023  1.6603  10 24 gms  1.6603  10 21 kgs

144
 Lesson No-19
SALT EFFECT ON RATE OF A REACTION
The Chemists are a strange class of people who seek their pleasure among
smoke and vapor, soot and flame, poisons and exotic materials.
Johann joachim becher, 1635-1682
Acta laboratorii chymica monacensis, 1669

Electrolyte : A compound which is completely ionised in water.

Ex : HCl. NaCl in water.
In media of very low dielectric constant (dioxane, dielectric constant = 6), an electrolyte
behaves as a weak electrolyte. Similarly, HCl in gas phase is covalent.
Indifferent electrolyte :
An electrolyte which is completly ionised but the cation and anion donot form any
complexes with reactants, activated complex etc. Perchlorate (ClO4–) was thought to be
least complexing agent. But now it is known that it forms a complex with cerium with a
stability constant of 74.
Acidity :

The acids generally used in kinetics are HCl, and HClO4. When the acidity is high (>
4M) acidity function (Hammett, Bunnett etc) are used. In normal scale PH or concentrations
are used.
Salt effect :
The change in rate (or) rate constant of a reaction between an ion and any other
species when increased or decreased with the concentration of an indifferent electrolyte.
The reaction may be between two ions, ion-dipole, ion-neutral molecule etc.
Primary Salt Effect : Consider the reaction between persulphate and iodide.

S 2O82  2 I   SO42  I 2 (1)

The change in the concentration of an indifferent electrolyte alters the activity coefficient.
It in turn changes the activity. Hence the rate or rate constant is altered.
Secondary Salt Effect :
K 
RNH 2  H   R N H 3 (2)

 k
R N H 3  CS2  P (3)

The first step is a pre-equilibrium. Here salt effect changes the concentration of reactive
  
species  R N H 3  . The next step (eq. 3) is the rate-determining. The effect of salt on ‘k’
 
now (rate constant) is indirect and hence it is called secondary salt effect.
Physical model :
Rate

k
ion  molecule  P
Salt : KCl , MgCl2 , K 2 SO4

As the concentration increases from very dilute (10–4) to 2M various physical models
have been proposed. Upto 10–3 Debye Huckel Equation holds good. When concentration is
greater than 10–2 Davis and Extended Davis Equations are used. At 0.1 to 1.0M SIT (Specific
Interaction Theory) is a recent one which explained unusual behaviour. Bierrum triple ions
  
 also explain electrochemical behaviour..
   

Mathematical model for salt effect :

Considering a bimolecular reaction which forms a complex in a pre-equilibrium step
followed by first order kinetic pattern resulting in a product ‘P’

K# k#
A B  X #
 P (1)

Ks

a X# f#
X#
K#   * (2)
a A . aB [ A] [ B ] fA . fB

Where ‘f ’ is activity coefficient on molal scale

f A . fB
X #  k # [ A] [ B ] * (3)
f#
From classical kinetics of first order reactions
dP
 k# [X #]
dt
K#
Where k # is specific rate constant for the reaction X #  P

Substituting (3) in (4)

dP f .f
 K # . k # [ A] [ B] . A B (5a)
dt f#

k#
If the pre-Equilibrium step is kinetically fast [ A  B  X # ] then X # is completly

formed. This holds good only when k # is very large. It happens when U(IV), Th(IV) react
with EDTA (K = 1023).

146
 K#
A B  P (5b)

Now
dP
for the reaction (5b) is
dt
dP
 k s [ A] [ B ] (6)
dt

dP
is same for both the schemes of approaches. Thus (5) and (6) are equal
dt
Therefore

fA * fB
kS  K # * k # * (7).
f#
Assumption : 1

If all the activities ( a A , aB , and a X # ) are equal to unity then k #  1 (8).

Assumption : 2
When the activity coefficients of each species is equal
From eq. (7)

kS  K # . k # Then it reduces to

kS  K # (10).

From (8) and (10)

KS  K #  k #  1

eq (7) reduces
f A . fB
K S  k0 .
f#
Taking logarithms on both sides

lnk Salt  lnk0  (ln f A  ln f B  ln f # ) (12).

Applying Debye Huckel theory for solutions of low ionic strength and for reactions
involving at least one ion.

 A * Zi2 * I
lnfi  (13).
1  *a* I
147
 Where A is a constant and depends upon the solvent, temperature etc and for water
at 250C, A = 0.51.

 is 0 . 329  108 for water..

a is the closest distance of approach of the two ions.

1 2
I is the ionic strength caluclated by the formula 2  Ci * Zi

Ci is the concentration of each ion

Z i is the charge on the corresponding ion.

If the structure of activated complex and those of reactants are similar and there is no
change in the total charge then

Z A  Z B  Z# (14)

 Z A2  Z B2  ( Z A  Z B ) 2   2 Z A Z B (15)

Substituting (15) in (13)

2* A* I
lnk Salt  lnk0  (Z A Z B ) (16)
1  *a I

Case - I : If 1    * a * I then eq (15) reduces to

lnk Salt  lnk0  2 * A * I ( Z A * Z B )

 lnk0  1*02 * I *(Z A * Z B )

lnk Salt
When log K Salt (Y ) is plotted against I (X )
the intercept of the straight line corresponds
to lnk0 and the slope corresponds to 1.02 ZA ZB.
lnk0 
I
Case-II : If  * a  1

2* A* I
lnk s  lnk0  (Z A * Z B )
  a *1  I

I
lnk s  lnk0  2 * A * (Z A * Z B )
1 I
lnk Salt
A plot of log K Salt with respect to I /1 I

would be a straight line with the slope

2 * A * (Z A * Z B ) I /1 I
148
Case- III :

2. A I
If 1 is negligable in comparison with  * a * I then (Z A Z B )
. a I

Here kS is independent of ionic strength.

Case : IV :

Under conditions where Ionic strength effect lnk Salt

is higher than that observed with I where a plot

lnkSalt ( y ) versus I becomes a straight line.

I

Reaction Reactant 1 Reactant 2 Z A ZB

CH 3 I  H 2O  P neutral neutral 0

CH 3 I  OH  P neutral anion –1

[CO ( NH 3 )5 Cl ]2  Cu ( I )  P cation cation 2

[CO ( NH 3 )5 Cl ]2  Hg 2  P cation cation 4

Generally, the rate constant data at different ionic

+3
+2
strengths (ln k ) versus I is analysed by two methods. +1
ZA ZB  0
log K Salt
The first one is drawing graphs between lnkSalt ( y )
–1
–3 –2
versus I ( X ) or I /1  I or I on different
I
graphs. Based on the best straight line and chemistry of kinetic pattern. Ionic strength
effect is interpreted.

From the figure log K Salt versus f ( I ) (function of Ionic strength) is a straight line
with slope equal to zero, positive or negative.

149
Reactants. A B
(a) Ion Ion b) Ion molecule
cation cation Molecule Ion
anion cation c) Ion dipole
cation anion d) Ion quadrapole
anion anion e) Ion octapole

The types of reactions considered in classical kinetics are limited Quantum

mechanical approach of kinetics and molecular descriptor method etc account for other
categories. Recently the interaction of proton (Hydrogen) of Benzene interacting with -
cloud of another Benzene molecule is caluclated to be of 0.5 to one kcal.

150
 Lesson No-20
SOLVENT EFFECT
It was easy for any second-rate scientist to do Frist-rate work.
It is very difficult now even for a first-rate scientist to do second -rate work.
p.a.m. Dirac, on the early days of quantum mechanics Directions in physics, 1978,p.7

It the reactants and activated complex are of similar structure and change, then the
rate of the reaction in gas phase and in presence of a solvent is same.

Then kSolvent  k gas

In the gas phase the molecules are free to move and hence collision theory, TS
and Quantum mechanics is applicable. In presence of the solvent which does not interact
with the reactants and activated complex then the motion of the molecules is restricted. If
the reactant is non-electrolyte then due to the obstruction of the solvent rate constant should
decrease. On the other hand because of greater contact time of reactants there is a chance
for increase in number of collisions and hence increase in the rate constant. The
compensating effect of these two opposing trends determines the overall change in ‘k’. If
k0 is the rate constant at infinite dilution of the solvent and ksolvent is the rate constant in a
specific solvent then

Where f is activity coefficient of solute. In order to understand the role of water or

solvent on chemical reactions the rate constants in gas phase are compared with those in
a single solvent (or) mixtures.

Experimentation is more difficult while interpretation is simpler. The solvents

nitromethane, toulene, their mixtures are used as non-aqeous water immiscible solvents.
Water miscible solvents (methanol, ethanol, dioxone, DMSO, DMF, Sulpholane and Propylene
Carbonate) are used in binary (or) ternery mixtures. (H2O-Dioxane-DMF). Micelles (or)
cryptands in water mimic cells (or) protiens in bio-systems.
Mathematical model :

If the solute is non-electrolyte and the solution is dilute then.

MVi
ln fi  ( i   1 ) 2 (3)
RT

E
i  (4)
MV

151
 Where 1 internal pressure of pure solvent

MV = molar volume

 E = Internal molar energy

Substituting (3) in (2)

1
lnk Solv  lnk0 
RT
 MV A* ( A  1 ) 2  MVB * ( B   1 ) 2  MV# * ( #  1 ) 2  5

 i  1   i

Where k0 = rate constant in an ideal situation

Case (i)
Case (i) : If  A  1 ;  B  1 ;  #  1
lnko
then (5) becomes

lnk Solv  lnk0 (6)

solvents
X
If the solvent parameters are identical with those
of the species in the activated form then a plot of
lnk solv. Case (ii)
lnk Solv ( y ) versus the solvents runs parallel to X- axis. lnko

Case(ii) :  A  1 ;  B  1 ;  #  1
solvents
Eq. (5) becomes

 1 
lnk Solv  lnk0 
 RT
 MV A* 
( A  1 )2  MVB * ( B  1 ) 2 


A plot of log k Solv versus solvents is a straight line with positive slope. The intercept
corresponds to lnk0

Case (iii) :  A  1 ;  B  1 ;  #  1 Case (iii)

lnk solv.
1
 lnk Solv  lnk0 
RT

 MV# ( #  1 ) 2  (8)

A plot of lnk Solv versus the solvents shows that solvents solvents

have a negative effect here. This mathematical model explains experimentally

observed rate constants in different simple solvents i.e., rate const increases (or) decreases
(or) remains constant.

152
Solvent effect on ion-ion interaction :
The rate constant of ion-ion interactions in presence of a solvent at a constant ionic
strength is influenced by the ion-ion, solvent-solvent, salt-salt (unary) and ion-solvent, ion-
salt and solvent-salt (binary) interactions. At very low ionic strength, ion-salt contribution to
G is negligable but constant. The ion-ion interactions are of chemical nature if an inner
sphere complex is formed. G non-electrostatic (ion-ion) is thus another constant. It is
assumed that solvent has no considerable effect.
The free energy for the interactions is given as

G ion – Solvent = G ion – ion + G ion – Salt

interaction (electrostatic) (electrostatic)

+ G ion – Solv + G ion – ion

(electrostatic) (non–electrostatic) (1)

G ion–solvent = G 0 + G ion–solv (2)

The rate constant of ionic reaction in a solvent is given by

KB * T   G 
kSolv  exp   (3)
h  RT 
K B = Boltzmann constant.

KB * T G
Taking logarithms log k Solv  log  (4)
h RT
(2) and (4) gives

KB * T   G 0   G electrostatic 
log   (5)
h  RT 

 K *T  G0   G elec
 log RSolv   log B    (6)
 h RT  RT
The kinetics of ion-ion interactions in a solvent in presence of an indifferent electrolyte
comprises (consists) of Unary and Binary interactions. The Unary interactions are ion-ion,
salt-salt and solvent-solvent type. The binary interactions are ion-salt, ion solvent, and salt -
solvent.

Born Model In 1920, Born proposed a model to account for reactions of ions in a solvent.
The ion is a sphere of uniform charge and the solvent has same dielectric constant through
out the medium i.e., isoelectric medium.

The change in energy in transfering an ion into the solvated one is as follows.

Step 1 : The ion is nutralised and the change in energy is calculated as the work done based
on electrostatics.
153
Step 2 : The neutral species is dropped in to the solvent

The charge in energy was assumed to be zero

Step 3 : The neutral molecule is ionised and it is calculated as charge in free energy.

The dielectric constant or permitivity is the capacity of the medium to keep the ions a
part. It is achieved through partial neutralisation of the charges. The higher the dielectric
contant the greater will be its ionising power. NaCl is completely ionised in water ( DH 2O  77) .
HCl although completely ionised in water, it exhibits covalent charector in dioxane. On the
other hand, acedic acid is more ionised in formamdie (D>100) compared to that in the water.

The energy considerations in Born theory depend up on the radius of the ion, dielectric
constant of the solvent and other universal constants.

e2 1 z A zB
 Gion solvent  ele

4D0 DS d AB
 (2)

Ion - solvent effect on k in ion-ion interactions : In the kinetics of an ion-ion reaction in

a solvent at constant ionic strength, the change in free energy can be written as

(G )ion ion  ( G )el  (G ) non el (3)

where el = electrostatic interactions

non-el = Non electrostatic component reflecting chemical compound formation,

molecular complex (or) interaction between non ionic species.
Assuming non-electrostatic contribution is constant in a given solvent,

(G ) ionion  (G )ion solvent  ( G ) salt  solvent  ( G )ion d  (4)

Only at high concentrations (> 0.5n) the interaction between ion-ion is considerable.
Similarly that between salt can be considered constant.

(G )ion ion  ( G )constant  ( G )ion solvent  (5)

The first term on R:H.S is a constant. From Born theory (G )ion  solvent can be obtained
as in eqn (2). Taking logarithm of (1), we get

K BT G
lnk sol  l n   (6) where KB = Boltzmann's
h RT
constant
K BT 1
lnk sol  l n  (G)constant  ( G )ion  solvent   (7)
h RT
Substituting (2) we will get

 K T Gconstant  e2 1 Z Z
lnk solvent  l n B    . . A B  (8)
 h RT  4D0 DS d AB

154
 e2 1 Z Z
 lnk solvent  lnk0  . A B  (9)
4D0 DS d AB

where k0 = rate constant in absence of solvent effect

D0 = Dielectric constant of the solvent in vaccune

d AB = distance between the ions in activated complex

Z A , Z B are the charges on the ions

e = charge on the electron
DS = dielectric constact of the solvent under the experimental conditions.

A plot of lnk solvent (Y) vs 1/ DS (X) gives a straight line . log K solv

From the slope it is possible to calculate d AB . If the plot is a

good straight line the variation of rate constant with dielectric 1/ DS
constant of the solvent explains the effect.
Y
Case (i) : If Z A . Z B  0 i.e., for reactions involving ions
of same charge (cataion-cation or anion - anion) log K solv

e2 1 Z Z X
 lnk solvent  lnk0  . . A B  (10) 0 1/ DS
4D0 DS d AB
Y
It is a straight line decreasing of slope. From the intercept
lnk0 can be calculated. log K solv

Case (ii) : If Z A  0 or Z B  0 i.e., if one of the reactant is 0 X

1/ DS
neutral Z A Z B  0 .  lnk solvent  lnk0

Case (iii) : If one species is a cataion and the other anion Y

Z A Z B is -ve. i.e., < 0.
log K solv

e2 1 Z Z X
lnk solvent  lnk0  . . A B 0 1/ DS
4D0 DS d AB

Many simple reactions follow Born hypothesis. The icrease, decrease and constant
behaviour of rate constant with dielectric constant of the solvent is explained.
Limitations of Born theory:

1) d AB may not be accurately determined.

2) The ion is not a sphere of uniform charge

3) The medium (solvent) in presence of salt has different
dielectric constant in different regions.

4) Non-electrostatic forces may contribute to variation

155
Abraham Model carity
Ist solvation hydration 2no solvation hydration

-----------
----------- -----------
----------- -----------
-----------
----------- -----------
-----------
ion -----------
-----------
----------- -----------
-----------
----------- -----------
ion
----------- -----------
-----------
----------- -----------
-----------
ion
-----------
-----------
----------- -----------
----------- -----------
-----------
----------- -----------
-----------
ion -----------
-----------
-----------
-----------
----------- -----------
-----------
----------- -----------
----------- -----------
-----------
----------- -----------
-----------
-----------
-----------
----------- -----------
----------- -----------
----------- -----------
----------- -----------
-----------
-----------
-----------
Fig (11) Fig (12) Fig (13) Fig (15)
Fig (14)
Abraham Abraham
1 layer 2 layer
model model

D 1 D 2 D 3 ----

Dielectric continum

The limitation of Born model is that it does not consider the variation of dielectric
constant (permitivity) of the solvant near anion and away from it. Further it does not consider
the structure (dimer, ionisation, dipole) of the solvent. Abram proposed one layer and two
layer models to calculate the free energy of an ion in a polar solvent (water). Here contribution
of free energy to the (attractive repulsion) intractions. The cavity calculations are performed
by scaled partition theory from statistical thermodynamics. The ion solvation can be represented
as
Phase (i) : A cavity depending up on the size and shape of the ion (solute) is formed at
the surface of the solvant [fig (12)]

Phase (ii) : The ion is in the solvent at the surface Fig(13)

Phase (iii) : A solvation (hydration) shell is formed around the ion (fig 14) and is called
Abraham one layer model.
Phase (iv) : A second hydration layer is formed around the first solvated ion (fig 15). This
is called Abraham 2 layer model.

The dielectric constant near the ion in water is very low (4 to 6) and gradually increases
(10,20,35,50-----) and becomes equal to bulk very dilute solutions. If can be represented in a
2 - Dimensional figure (Fig 16)

Advantages : It explains the dielectric properties of ions in solvents of high dielectric constants
better than Born model

156
 Langenin Dipole theory :

field solute
g
in
ct

1 2
ra

(17)
te
in

 3
n
no

In
te
ra Self consistent
ct
in field method
g


Interaction

Langenin dipole model (LD) assumes solvent molecule can be approximated as a
dipole. In other models solvent is considered to be a point charge. Infact, now it is possible to
calculate charge (monopole), dipole, quardupole, octapole hexa-decapole of any molecule
from quantum chemistry. The solution free energy is calculated in early model by two different
approaches.
Non-interacting model :
The solute at the centre exerts a field on the dipole of the solvent. The analytical,
numerical and mathemetical methods are employed to calculate the free energy of solvation.
Interacting model :
Consider, for example, three solvent molecules around a solute. The effect of all
dipoles and solute except the one dipole of interest are considered each time. The free
energy is calculated in an iterative fashion. The repetition (iteration) is continued until a self
consistent field solution is obtained.
Cavity Shape :
Generally right from Born model, a spherical shape of a molecule assumed. Recently,
it is extended to elliptical one.

Now it is possible to calculate any shape and associated cavity and free energy terms.

Realistic picture of solvation :

The optimised geometry (conformer) is calculated from first principles (ab – initio)
quantum chemical calculations. It is not yet completely reliasabh for condensed (liquid and
solid) (or) interphases (gas-water, water-solid). The principles of molecular dynamics gives a
realistic picture. For a tetrapeptide, years of super computer time is required to perform MD
calculations.
157
 The alternate models are called supra molecular models. Here a fixed no.of water
molecules (256, 512, 1000, 20,000, 30,000) are considered in a periodic box of definite
dimensions. The size of the box can be extended. It accounts for the specific solute-solvent
interaction. But, the total free energy is in error.
Inplicit Models :
Born - monopole
onsagar-dipole
Cosmo models :
Conductor like screening model. In this model, solvents of very high dielectric constant
can be used for free energy calculations.
B layer : H - bonds
C layer : fault layer
D layer : Bulk (layer) zone

H
- -O
-- -
OH H- H
H ------- O
H
O H ---- - -- H
O
--- - -- H
O
---

H H
M
-- -

O H ------- O
-

H
O H
H
H O
H
---

H
-- -

H
---

O
----

------

O C
H H D
---

H
-- -

H
-

O
- -- - - -

158
Chemical solvation :

For solutes (ions) having co-ordination sphere, chemical solution occurs. This is a
strong interaction and the layer is called A-layer or zone. The Hydrogen of water forms
hydrogen bonds with other water molecules resulting in B-zone this is weaker compare with
those in A-zone. Now the Hydrogen in B-layer forms still loosely hydrogen bonding with water
molecules. This is called C-layer (or) fault zone. The succeeding layer is called bulk layer.
The size and extent of interaction depends upon the size and change etc of the solute. When
the solute can not form chemical solution like tetraphenyl ammonium, tetraethyl phosphine
etc. The interactions in the A-layer are called Non-chemical (or) electrostate. In some cases
one or more layers may be missing.

Physical model of ion-ion reaction :

The formation of outer sphere complex from aquated (or) solvated metal ion and
anion is a fast-step with the ions held together intact. There is no change of size,charge
and orientation. It is followed by the formation of an inner sphere complex or anion enters
into coordination sphere of metal ion. Double Sphere model where in two spheres are held
together explains these reactions and the effect of Solvent.

ZA ZB 

 M ( H 2O ) x  
fast
  x ( H 2O) y     M ( H 2O ) x  ...  X  ( H 2O) y  --- (1)
 
rA rB Z
 M ( H 2O) Z X ( H 2O ) Z 2  (2)

The rate constant are of the order of 1010 to 102. For Beryllium halides they are of the
order 102 and for Barium and mercury R  108 . Experimentally pulse radiolysis, fast-
reaction kinetic techniques like temperature jump are used.
Entropy :
For metal ions (or co-ordinate compounds) the number of solvent molecules
depend upon geometry. With increase in the dentisity of ligand, released number of
water molecules increase. For example with ammonia it is one, ethylene diamine-
two etc. If  n (change in no. of molecules ) is greater than zero, entropy increases.
Another important type of entropy operating is called cratic entropy, of course its
magnitude is small. It is due to restricted movement of electrostricted (hydrated) water
molecules. All the types of motion (translational, rotational etc.) are reduced.
Ion-dipole interactions :
Physical model :- Necessary conditions
The reactant should be an ion and the other a diople (Eg: Hydrolysis of Sucrose
in presence of a strong acid). The transition state has similar charge and shape like
reactant. The non-electrostatic froces are considered as constant.

( Gel ) ion-dipole is given by the Equation which holds good for ion-ion also.

Ne 2 1  Z 2 # Z A2 Z B 2 
( Gel ) ion  dip  .     (1)
8  Do DS  r# rA rB 
159
 A dipole has no charge ( Z B  0) and the charge on activated complex and reactant is
same.
Z#  Z A  Z

In fact  Z#  Z A  ZB 
 Ne 2  1  Z 2 Z 2 
( Gel )      
 8  DO  DS  r# rA  (2)

 Gel # 
   
Substituting it in lnk Solv l nkO  RT  (2a)
 

 Ne 2  Z 2 Z 2 
lnk Solv  lnkO 
1  1  
8 D . D  r  r  (3)
RT  O S  # 
A 

Case - I:

If r#  rA then a plot of lnkSolv against 1 D S is a Straight line with positive slope.

Case - II:

If the plot is a straight line but with negative slope it infers that r#  rA . It means that
activated complex has smaller radius compared to reactants. It is many a time impossible.
Therefore one concludes that the reaction is not between an ion and dipole or the model
fails.

lnk Solv lnk Solv

1 1
DS DS
Case - I Case - II

Knowledge Base (KB) : If the transistion state is more polar than reactant then 'K' increases
with decrease in dielectric constant.

If the dipole is properly orientated towards the ion then partial neutralisation of the
charge takes place.

Dipole - Dipole interaction :

Ex : (C2 H 5 )3 N  C2 H 5 I  (C2 H 5 ) 4 N  I 

160
Mathematical model :-

( Gel ) dipole-dipole kinetics is given by

N D 1   2 
  Gel  dipdip  .   (1)
4  DO 2 D  1  r 3 

 = dipole moment
considering the reaction

A B  X #  P

N  D  1   #2  A2  B 2 
    3  3  (2)
4 DO  2 D  1   r#3 rA rB 

Substituting this Equation into

  Gel # 
lnk Solv  lnkO   
 RT 

 N D  1  #2  A2  B 2  
 .  3  3  3 
then lnk  lnk   4 DO 2 D 1  r# rA rB  
Solv O
RT

D 1
A plot of lnk Solv versus is a straight line. The sign of the slope depends upon
2 D 1
relative magnitudes of  # ,  A and  B .

If activated complex is more polar then  #   A &  B then 'k' increase with increase
in 'D'.

Limitation :

 D 1 
  can be expanded as a power series.
 2 D 1 

D 1 1 3 3 3
   2
  
2 D 1 2 4 D 8 D 16 D 3

1 1
If 'D' is high 2
, 3 terms can be neglected
D D

D 1 1 3
 
2 D 1 2 4 D

1  D 1 
If a plot of lnk Solv versus is linear and also   is linear, it is difficult to resolve.
D  2 D 1 
161
 Lesson No-21
HAMMETT EQUATION
Now Read a few minutes a day, no worry
In future you will become a lead. Toil many hours everyday.
Yet you will have all worry; no way out at al.

In 1863 A.F.A cross of strasburg university studied the toxicity of alcohols to mammals
and found that toxicity decreases with chain length. In 1890, Hans. Hoss. Mayer from Zurich
attributed it to lipophilicity. In 1937. Louis Hammett proposed for the first time a quantitative
relationship between ionisation constant of substituted aromatic carboxylic acids (Bencoic
acid) (or) rate constants for the hydrolysis of esters and substituent constants.
Hammet model (Physical model) : The standard (model) reaction inuestigated was
O O
 

C  OH C O


  H (1)

The rate and ionisation data were carefully chosen from the literature with similar
temperature, ionic strength and medium. Ortho-derivatives are excluded. Simple electron
donating substituents (–OH, –NH2 etc) and electron withdrawing ( –NO2 ) were considered.
The mathematical model is
l og kSubstituted  l og kUnSubstituted * _____(2)

l og K Substituted  l og KUnSubstituted * ______(3)

Where '  ' is called reaction constant. It depends upon the type of the reaction and
standard model reaction. The range is –5 to +5. '  ' is the substituent constant and has
+ve, –ve or near zero values. Hamett Equation is a subset of LFER (Linear Free Energy
Relationships).
QSAR : Non-linear and multi Parametric Equations including linear LFER are termed as
QSAR.
BR : (Biological Response) and Drug action are important components of BR. Examples
EC50 : Effective concentration to reduce BR by 50%

LD 75 : Lethal dose (75%)

IC 25 : Inhibitive concentration (25%)

COOH COO

  H

162
 When the compounds considered had importance of sequence (amino acids,
nucleotides etc). It is called structure sequence relationships. If the response is a physical
When NMR, ESR data are used it is termed as structure response relationships.
Caluclation of  : By carefully selecting the ionisation constants or rate constants (k) from
the literature Hammett obtained  values (substituent constants) from the equation.

'  ' (reaction constant) is considered as 1.0. From the table (1) it is clear that different
substituent groups have variable effect on ionisation or rate constant and meta and para
position also influences it.

X K log K log K Sub  log KUnsub Comment

H 6.27  105  4.203  

e withdrawing

m  NO2 32.1  105  3.497 0.71

ve
P  NO2 3.7  105  3.435 0.76

e donating
0.14 ve
CH 2  CH 3 4.47  105  4.349

Heuristics :

If  is  ve then electron -withdrawing group.

If  is  ve then electron - donating group.

If  is nearer to zero ( 0.05) it is not having much effect.

Limitations :

1) Hammett equation cannot explain substituent effect in o-substituted compounds.

2) It fails for aliphatic compounds

Remedy :

Taft equation.

The substituent constant  is divided into m and  p (meta and para). Further

  ,  ,  R are also proposed.

163
Reaction constant  :

 K Sub 
  vs
The range of '  ' is –5 to +5. It is obtained as the slope of the plot of Y   log K
 O 

 K Sub 
X   log  for benzoic acid. (Fig-(1)).
 KO 

Case (i) :

If the range of the slope is 1  0.02(3) then the system adheres to Hammett equation.

Case (ii) : If the slope is far greater than one the substituents have more influence on
ionisaton constants than predicted by Hammett equation.

Benzoic 6
1.0
acid 1.0 6
l og K Sub 0.9 l og K Sub
KO 1  0.02(3) KO Slope > > > 1

l og K Sub (Benzoic 
Fig (2)
Fig (1) KO acid)

l og K Sub l og K Sub convex

P<<1 KO max
KO
same mechanisms

 
Fig (3) Fig (4)

concave min
l og K Sub different
me ch an isms
KO

 Fig (5)

164
 values for different compounds :

Compound  Value

+
NH3 2.90
H
ionising
2.23

OH

H2C–COOH

0.49

CH2CH2 COOH

0.21
COOH

1.0

Case (iii) : If the slope of the Hammett plot is far less than 1 then the substituents has less
influence on K or k. (Fig (3). These reactions indicate a linear trend in Hammett equation.
There are reactions where the trend is non-linear and is useful to probe into mechanism.

Case (iv) : If Hammet plot is non-linear and passes through a maximum then the reaction
follows same mechanism. (Fig (4))

Case (v) : If the trend is non-linear and exhibits a minimum then different substituents
(electron-donating and electron withdrawing) follow different rate laws.

Application :

Rational drug design.

The simple application of Hamett equation is to predict ionisation (or) rate constants
for reactions with different substituents. In drug design, material preparation and device
applications prediction is the first step. For Example : Glassco welcome, tripos etc.

165
Limitations of Hamett Equation :
1) Rate constant (or) Ionisation constant of ortho substituted aromatic compounds cannot
be explained.
2) It is not applicable to aliphatic compounds.
3) Polar effect cannot be decomposed into inductive and resonance effects.
4) Steric effect is not considered.

TAFT EQUATION
Taft proposed a model to over come the limitationso f Hammett equation.
Taft Model : Hamett equation + steric effect
Standard reaction : COOEt
Et
; RCOOR1
R, R1 : Et , Me, propyl...

It was found that in alkaline medium the hydrolysis of esters are influenced by all the
three factors namely polarity (P), conjugation (C) and steric (S).
 K Sub 
 log   P CS I
 K 0  alk

In acid medium; only two factors C and S predominates, while that due to polarisability
is negligable.

 K Sub 
 log   CS II
 K 0  acid

Substracting II from I

 K Sub    K Sub  
 log    log     P III
 K0  alk   K0  acid

Respecting Hamett Equation P  Taft *  Taft IV

Where Taft is taken as 2.48 to have the same scale for substituent constants as
that of Hamett.
From eq (3) and (4)  Taft values are tabulated.
Including the steric effect the Taft model is

logK Sub  logK 0  Taft *  Taft  s.Es V

S is a sensitivity factor which is taken as one in simple cases.

166
Application :

Case I : If a plot of logK Sub versus  Taft is linear and intercept is equal to logK 0  0.02 then
ES is negligable.

Case II : If the intercept is equal to log k0  constant where constant significant numerically
then steric effect also plays a role and is linear.
Case III : If the plot is non-linear then either higher order effects of substituent

logK Sub  logK 0   * ( a1  a2 2  a3 3 ))

are important or the steric effect is non-linear.

Case-IV :

logK Sub logK Sub  ES logK Sub

* * Es
Fig. (9) Fig. (10) Fig. (11)
From figures (9), (10) and (11), it is clear that polar contribution and steric contribution
are non-linear.

Prediction of PKa values :

knowing the substituent ('  ') values and respecting additivity model pKa can be
computed without performing experiment.

 m NO2  0.71 ;  p CH 3   0.13 ; PKa  4.20

 PKa  4.2  {2 * 0.71  0.13}  4.20  1.29  2.91

The experimental value is 2.96 and the difference

( PKa )calC  ( PKa )exp  2.91  2.96  0.05

Since the accuracy of experimentally determined pKa ' s are of the order 0.10 to
0.02, this is tolerable. Further pKa depends on temperature, medium etc and  values
are not available under all conditions.

167
 Lesson No-22
CHAIN REACTIONS
Recite, unstand, practice, trasmit, realise truth

Chain Reactions are characterised by high yied. The yild should be below the explosion
limits especially in the gaseous phase. If an intermediate in any of the elementary steps of the
reaction produces another intermediate which in turn results in the same or another
intermediate it is preferred as a chain reaction. They can be considered as a special case of
multistep consecutive reactions.

The chain carriers are atoms ( H 2  Cl2 reaction, H 2  Br2 reaction), radicals (theremal
decomposition of acetaldehyde, ethane etc.) or anions. The radicals are detected by
decolourisation, precipitation (polymer formation with acryl nitrile, emrcurous chloride from
Hg Cl2 ) or ESR technique. Still short lived species at pico and femto second level are detected
by flash photolysis or LASER technique.

Effect of External conditions on Chain Reactions :

Increase in pressure no doubt increases the probabiliy of collisions and thus should
increase the rate of the reaction. But the radicals (intermediates) formed also has the same
probability for recombination and thus termiantion of the chain occurs. The net relative rates
dictate the net result i.e., the rate of the reaction.

Temperature :

Increase in temperature sometimes leads to explosion.

Surface Area :

Increase in surface are and/or roughnessof the solid surface increases the adsorption
of reactants. If radical recombination also follows the same mechanism, it decreases the rate.
But generally powdered glass or silica are used for quenching. The scavangers (radicals) like
NO diminish the rate of the reaction. The stochiometry dictates overall molecularity of reactants
and products. It can be divided into several groups by ionic reactions. Each of them from the
kinetic point of view are considered as elementary reactions.

k
1
Br2  2 Br ________ (1) Initiation

k2
Br  H 2  HBr  H _____________ (2)

k3
H  Br2  HBr  Br ______________ (3) Propagation

k4
H  HBr  HBr  Br ______________ (4)

k5
Br  Br  Br2 ] ______________ (5) termination

168
 A chain reaction is characterised by initiation, propagation and termination. Br is
produced in step (1) which initiatates chan reaction by producing another intermediate H in
step (2). Two more Br are produced in steps (3) and (4), thus increasing the yild. Reaction
(5) is the termination step. Respecting the short half life of H and Br atoms, their rate of
change with time is zero.
d  Br 
  k1 [ Br2 ]  k2 [ Br ] [ H 2 ]  k3 [ H ] [ Br2 ]  k4 [ H ] [ HBr ]  k5 [ Br ]2
dt
= 0 ____________ (6)

d [H ]
  k2 [ Br ] [ H 2 ]  k3 [ H ] [ Br2 ]  k4 [ H ] [ HBr ]  0 _______ (7)
dt
(6) + (7)
2
k1 [ Br2 ]  k5 [ Br ]  0 ________ (8)

1/ 2
k  1/ 2
 [ Br ]   1  [ Br2 ] ________ (9)
k 
 5
From (7)

k2 [ Br ] [ H 2 ]  k3 [ H ] [ Br2 ]  k 4 [ H ] [ HBr ]  0

k2 [ H 2 ] [ Br ]
 [H ] 
k3 [ Br2 ]  k4 [ HBr ] __________ (10)

substituting [ Br ] from (9) in (10)

1/ 2
k  1/ 2
k 2 [ H 2 ]  1  [ Br2 ]
k 
[H ]   5 ___________ (11)
k3 [ Br2 ]  k4 [ HBr ]

d [ HBr ]
 k2 [ Br ] [ H 2 ]  k3 [ H ] [ Br2 ]  k4 [ H ] [ HBr ] _______ (12)
dt
Here, HBr is not short lived, but a product. So, its variation cannot be made equal to
zero.
substituting (9) and (11) in (12).

1/ 2
d [ HBr ]  k1  1/ 2
 k2 [ H 2 ]   [ Br2 ]  {k3 [ Br2 ]  k4 [ HBr ] }  [ H ]
dt k 
 5
substituting [H] from (11)
169
 1/ 2
k  1/ 2
1/ 2 k2 [ H 2 ]  1  [ Br2 ]
d [ HBr ] k  k 
 k2 [ H 2 ]  1 
1/ 2
[ Br2 ]  {k3 [ Br2 ]  k4 [ HBr ] }.  5
dt k  k3 [ Br2 ]  k4 [ HBr ]
 5

1/ 2
 k1  1/ 2
= k2 [ H 2 ]   [ Br2 ] . k3 [ Br2 ] 
 k5 
1/ 2
k  1/ 2
k2 [ H 2 ]  1  [ Br2 ] . k4 [ HBr ] 
k 
 5

1/ 2
k  1/ 2
k3 [ Br2 ] . k2 [ H 2 ]  1  [ Br2 ] 
k 
 5

1/ 2
k  1/ 2
k4 [ HBr ] . k2 [ H 2 ]  1  [ Br2 ] k3 [ Br2 ]  k4 [ HBr ]
k 
 5

1/ 2
k  1/ 2
2k3 [ Br2 ] k2  1  [ Br2 ]
k 
=  5
k3 [ Br2 ]  k 4 [ HBr ]

Dividing the Nu and De by R3 [ Br2 ]

1/ 2
k  1/ 2
2k 2  1  [ Br2 ] [ H 2 ]
d [ HBr ] k 
  5
dt k [ HBr ]
1  4
k3 [ Br2 ]

1/ 2
k [ Br2 ] [H2 ]
 1
k [1  Br ]
1 
[ Br2 ]

1/ 2
 k1 
where 2 k  
2 
 k

 k5 

170
 k4 1
 k
k3

This is first order with respect to H 2 and complicate order with respect to Br2 .

Chemical kinetics deals with the estimation of rate constants based on monitoring
concentration of reactant / product / intermediate. rate law is the mathematical representation
of variation of rate with concentration. It is an emperical model. Mechanism is developed
based on the law, identified intermediates or products and species guessed. The alternate
mechanisms are possibile in chain reactions and in many biological processes. Of the several
mechanisms one or more are in use till a final one is proposed. Under different conditions
(concentrations, temperature, micelles) the rate law will be different i.e., the order may be 1,
0.5 or 2.3 etc. Naturally for every rate law different mechanisms will be proposed. Instead of
starting with experimental data and arriving at mechanism and rate constants, the reverse is
possible.This is called simulation.

Thermal Decomposition of Acetaldehyde

Heating in absence of air is called Pyrolysis.

k
1
CH 3 CHO  CH 3  CHO .
k2
CH 3  CH 3 CHO  CH 4  CH 3CO .
k3
CH 3CO  CH 3  CO .
k4
CH 3  CH 3  C2 H 6 .

The steady state is applied for the radicals CH 3 and CH 3CO

d [.CH 3 ] 2
 k1 [CH 3 CHO]  k2 [.CH 3 ] [CH 3 CHO ]  k3 [CH 3CO]  K 4 [.CH 3 ]
dt
= 0 _________ (1)

d [CH 3CO]
  k 2 [.CH 3 ] [CH 3 CHO ]  k3 [CH 3CO ]  0 . ______ (2)
dt
Adding (1) and (2)
2
0  k1 [CH 3 CHO]  k4 [.CH 3 ] _______ (3)
2
 k1 [CH3 CHO]  k4 [.CH 3 ] _______ (4)

171
 1/ 2
k  1/ 2
 [.CH 3 ]   1  [CH 3 CHO] ______ (5)
k 
 4

d [CH 4 ]
 k2 [.CH 3 ] [CH 3 CHO ]
dt
1/ 2
d [CH 4 ] k  1/ 2
  k2  1  (CH 3 CHO ) [CH 3 CHO]
dt k 
 4

1/ 2
 k1  1
k
Let 2   k
 k4 

d [CH 4 ] 1 3/ 2
  k [CH 3 CHO ] _____ (6) fractional order in rate law..
dt

Thermal (only for exothermic reaction)

Explosion Chain Carriers

Gaseous products

Explosion Limits

Takes place at const T and pressure is lower

II expl. III expl.
Limit Limit

Rate 

III Pressure 
Ist explosion Limits
 II
T
I
 Steady State
P 

172
 Lesson No-23
PARELLEL AND CONSECUTIVE REACTIONS
"Mathematics is the art of giving the same name
to different things."
O / O  NaN ; inf / inf  NaN
inf  inf  NaN ; inf : Infinity ; NaN : Not a number

In - unimolecular reactions, if two different products are formed, it is referred a parellel

reaction.

Ex : 1 CH 3 CH 3
CH  OH 
 C O
CH 3 CH 3
P1
H 3C
Ex : 2
C  H  OH  H 3C  CH  CH 2
H 2C
P2
H

In bimolecular reactions there are two types. Both reactants are same yielding different
products.
Ex :3

A  B 
 P1

A  B 
 P2

OH OH
OH
NO2
+ HNO3 +

P1 NO2
P2
The other category is one of the two reactants is same but the products are different.

173
Ex : 4 A  B 
 P1

A  C 
 P2

NH 2 NH 2
Br Br
+ Br2

Br

NH 2 NH 2
Br Br
+ Br2
COOH COOH
Br

If one of the reactants is in large excess, it reducess to a Unimolecular reaction.

Concentration of Reactants And Products as a function of time.

R1
A  P1 (1)

R2
A  P2 (2)

dA
  k1[ A]  k 2 [ A] (3)
dt
dA
  ( k1  k2 ) [ A] (4)
dt


A  A0 exp  k1  k2 t  (5)

If there were a reaction A  products with the rate constant (k1  k2 ), then the rate
equation is (5) it self.
Concentration of P1

dP1
From (1)  k1 [ A0 ] (6)
dt
dP1
From eq n s (5) and (6),
dt

 k1 A0 exp  k1  k2 t  (7)

174
 
 dP1  k1 A0 exp  k1  k2 t dt 
Integrating,

 dP   k
1 1 
A0 exp  k1  k2 t dt 

 P1  k1 A0 exp
 k  k t 
1 2
 IC (8)
 (k1  k2 )

At t  0; P1  0

k1 A0
 P1   IC  0
 (k1  k2 )

k1 A0
 IC  (9)
(k1  k2 )

k1 A0 k A
 P1  exp ( k1  k2 t )  1 0 (10)
 (k1  k2 ) (k1  k2 )

k1 A0
(k1  k2 )
 
1  exp  k1  k2 t  (11)
1)

dP2
Similarly,  k2 [ A]
dt

k2
 P2 
k1  k2

A 0 1  exp  k1  k 2 t   (12)

P1 k P1 k
 1   1 (13)
P2 k2 P2 k2

P1 and P2 are products of parallel reactions.

Physical Meaning of (13)

The ratio of the concentration of products in a unimolecular parallel reaction depend
only on the ratio of corresponding first order rate constants. More important consequence
P1
is, A  
P2 doesnot depend upon initial concentration of reactant 0 or time of the reaction.

175
Application

1) It is used to calculate the ratio of k1 to k2 by analysis and estimation of concentration

of the product at the end of the reaction.
2) A Major product can be made minor or vice-versa by altering the experimental
conditions.

thalf A  P1

for the product P1 , its concentration is zero at t  0, t1  0, [ P1 ]  0

After 7 or 8 half lives, or at  time, let conc. of P1 be [ P1 ] 

Half of it is the concentration at t1/ 2 .

k1 A0
 From (11), P1  (k  k ) 1  exp  k1  k2 t
1 2
  
k1 A0
 P1   (14)
k1  k2

 P1  k1 A0
At t1/ 2  (15)
2 2  k1  k2 
Substituting this in (11)

 P1  k1 A0 k1 A0
 P1 t / 2
2

2  k1  k2 

 k1  k2   
1  exp  k1  k2 t1/ 2 
1

2

 1  exp  k1  k2 t1/ 2 
1

 exp  k1  k2 t1/ 2   2

1
  k1  k2 t1/ 2  ln  
2

ln (2)
 t1/ 2  (16)
k1  k2

The t1/ 2 for P1 and P2 is same and represented by equation (16). It depends on
sum of both rate constants.

176
 CONSECUTIVE REACTIONS

k1 k2
A  B  C

k1 , k 2 are first order rate constants. I : intermediate

A# : activatedcomplex
k1 k2
237 238 239 TS : Transition State
U  NP  Pu
2.3 min 2.4 days consecutive, Ist order,
unimolecular, irreversible
2. stage process
NH 2 NH 2 NH 2
Br Br Br
k1 k2
 

Br Br Biphasic reaction
3 state process

(Triphasic reaction)

OH OH OH OH
Br Br
Br Br

 Br2   
k1 k2 k3

Br Br Br

In the conventional kinetics, the rate constant k, activation energy E # , entropy of

activation S # , etc are calculated by monitoring the concentration of reactant or product.
By carrying out the reaction at different temperatures, thermodynamic parameters are
calculated.

Application :

In organic synthesis, the desired product with high yield is the target. At the same
time undesired compounds should be absent or should be to a minimum extent. It is achieved
by changing rate constants by external parameters like temperature, concentration of
reactants, catalysts etc.

177
 k1 k2
A BC

Mass balance eq n . A0  [ A]  [ B ]  [C ] (1)

A0  conc. of A at time  0

B0 , C0  0

Initial conditions : [ A]  0 at t  0

d [ A]
Rate Laws :   k1[ A] (2)
dt

d [ B]
 k1[ A]  k2 [ B ] (3)
dt

d [C ]
 k2 [ B ] (4)
dt

Objective : To calculate concentration of A,B,C as a function of time.

From (2). [ A]  A0 exp ( k1 t ) (5)

Method (a) Steady State

Method (b) Equilibrium.

If the interemdiate (B) has a very small half life, steady state can be applied. Steady
d[ B]
state hypothesis gives the equation  0 . i.e., rate of formation fo B and rate of
dt
decomposition are equal. In other words, the net concentration is zero at any point of time.

d[B]
 k1[ A]  k2 [ B ]  0
dt

 k1[ A]  k2 [ B]

k1
[ B]  [ A] (5)
k2

From (5) and (6).

178
 Dervation

k1
[ B]  A0 exp ( k1t ) (7)
k2

n d [C ]
From eq (4),  k2 [ B ]
dt

d [C ] k
  k2 . 1 A0 exp ( k1t ) (from (7))
dt k2

d [C ]
  k1 A0 exp ( k1t ) (8)
dt

  d [C ]   k1 A0 exp (  k1t ) dt

 [C ]  k1 A0  exp ( k1t ) dt

exp ( k1t )
 [C ]  k1 A0  I .C .
 k1

  A0 exp ( k1t )  I .C .

at t  0; [C ]  0

k1 A0
 0  I .C
 k1

 I .C  A0

exp ( k1t )
 [C ]  k1 A0  A0
 k1

[C ]  A0 {1  exp ( kt )}

If steady state does not hold good, equilibrium method is applied.

Equilibrium Treatment g
A rou
a ss ing th
P
0.1 0.025
max
A B  C C
fast slow

A0  1.0

0.025 0.1 B A
A  B  C B

179
 0.1
In the first reaction, rate constant of A  B is high,
A C
so it is a fast reaction. Hence we obtain a max for B in the
0.02
graph. But B  C is slow hence C is less in the graph.

From (2) [ A]  A0 exp ( k1t ) (9)

B
n is concentration B A
The above eq as a function of time.
C
dB
From (3)  k1 [ A]  k2 [ B ] (10)
dt
substuting (9) in (10)

d [ B]
 k1 A0 exp ( k1t )  k2 [ B ]
dt

d [ B]
  k2 [ B ]  k1 A0 exp (  k1t ) (11)
1)
dt

dy
This is of the form  f ( x). y  g ( x)
dx

A0
Solving (11), [ B ]  k1 {exp ( k1t )  exp ( k 2t )} (12)
k2  k1

from mass balance eq n ,

A0  [ A]  [ B]  [C ]

 [C ]  A0  [ A]  [ B]

k1 A0
 [C ]  A0  A0 exp (k1t )  { exp ( k1t )  exp ( k 2t )}
k2  k1

or [C ]  A0  A0 exp ( k1t )  [ B ] (13)

k1 A0
or [C ]  A0  A0 exp (  k1t )  { exp ( k1t )  exp ( k2t )} (14)
k2  k1

 k1 
 A0  1  exp (k1t )  { exp ( k1t )  exp ( k2t )}
 k2  k1 

180
  k2 exp (k1t )  k1 exp (k1t ) k1 exp (k1t )  k1 exp (k 2t ) 
or [C ]  A0 1   
 k2  k1 k2  k1 

 k exp (k 2t )  k2 exp (k1t ) 

 A0 1  1  (15)
 k2  k1 
When steady state hypothesis is not applicable for the intermediate product (B),
dB
 0 is not valid. Then concentrations of B and C are calculated using the same method
dt
as applied for A  products.
Concentration of B as a function of time is a first order differential equation. This has
a unique solution and [B] is given by equation no. (12). Similarly, concentration of C is
obtained by respecting the mass balance equation A0  [ A]  [ B ]  [C ] and substituting
the values for A and B.
Unimolecular

Monophasic
Biphasic
A P
ABC
A  P (equil )

Triphasic
Stoichiometry Molecularity
(related to entire A  B  C D
(related to rate
reaction) determing step) Bimolecualr ABP

Pseudo unimolecular
B0   A0
Trimolecular A P

A BC  P

(i) A  B  C It is a sequential plus parallel reaction.


fast renders as
(ii) A  B  C where A  B or A  C

(iii) A  B  C It is an opposing reaction, need not be at equilibrium.

(iv) A B  C

(v) A B  C

181
 R1 R
(vi) A  B  C Biphasic, unimolecular, Sequential, Parallel, opposing
R2 R k4
 5 
R6

Energy level diagram for A  B  C .

182
 Lesson No-24
ACID - BASE CATALYSIS
Let noble thoughts come to us from all sides

Catalysis : A catalyst is a species which increases the rate of reaction. Formerly it was
considered that the catalyst doesnot participate in the main reaction. But now there are several
evidences to show that it participates in one of the elementary steps. Generally a complex is
formed. The alternate path in the presence of a catalyst has lower activation energy compared
to unvatalysed reaction

2 H 2O2 (aq)  2 H 2O (l )  O2 ( g ) E uncatalysed

E k E catalysed
Uncatalysed 76 1 E
–
I 57 2000 Distance

Uncatalysed 8 1015

since E and K are related by exponential equation, a small decrease in E (activation

energy)
Homogeneous and Heterogeneous Catalysis
If the reactants and the catalyst are in the same phase, it is referred as homogeneous
catalyst.

Ex : Ester  H 2O  H   products
When the reactants are in one phase and the catalyst in another, it is referred as
heterogeneous catalysts.
Ex : Hydrogenation reactions.

Pd / Pt / Rh
Ethylene  H 2   Pr

When Hydrogen ion ( H # ) or hydroxyl ion (OH  ) catalyses the reaction, it is called
acid base catalysis.

Specific Acid Catalysis : If proton or H 3O  obtained from a strong acid,

( HClO4 , HCl , HNO3 ), it is called specific acid catalysis. Similarly if OH  or  ( H 2O)n OH 

obtained from an alkali ( NaOH , KOH ) or tetraphenyl ammonium hydroxide

 Ph 
 Ph  N  Ph  OH It is called as specific base catalysis.
 
 Ph 
183
General Acid-Base Catalysis :

The hydrogen ion H # or hydroxyl ion, OH comes from a weak acid or base. It may be
a Brownsted acid ( H . A) or a Lewis acid.

Skrabal Diagram :

It is a plot of variation or rate with pH .

O

CH 3  C  OEt  H 2O  H   P

dp
 k [ester ] [ H 2 O] [ H  ]
dt
[ H 2O]  excess
1
 k [ester ] [ H  ]  constant
Mechanism :

O H O
  
R  C  OR  O  R  C  O  R1
1 (1)

H H H
Step 1 : Proton transfer
Step 2 :

O O
 
R  C  O  R1  R  C   O  R1  O  R1 (3)
H H
H
O O
(2)
H H H H
Nucleophilic attack by water
O O
  
R  C  R  C  H3 O (4)
HO
O

H H O

H H

Step (1) is a proton transfer from H O to O of C  O  R1 . The positive charge is distributed
3

O
over OH . In the second step, carbonium ion (due to polarisation of C  O of )  reacts
R C
with the nucleophile H 2O (lone pair of electrons on O). The intermediate species decomposes
184
to R  OH by bond deavage. In step 4, proton is transferred to H 2O resulting in carboxylic
acid.

Evidences are obtained from 18 O NMR experiments and variation of rate with isotope
‘D’
Skrabel Diagram :

k1
S  H   SH  (1) fast, complete

k1
SH   P (2)  K  high

[ SH  ]
K1  (3)
[S ] [H  ]

dP
 k1 [ SH  ] 
dt

 k1 K1 [ S ] [ H  ] (4)

 K H [S ] [H  ]

RH = Rate constant for specific acid catalysis.

dP
dP
dt
 dt  k H [ H  ] (5) [S ]
[S ]

k H  k1 K1
[H ]
Case (i) k H  k1 K1

(Acid catalysed)  log k H  log k1  log FH

id
log RH Ac
 log k1  P H
[ H  ]  0.1
1.0
[H  ] [OH  ] is negligible PH
0.1

Case (ii) : S  OH   SOH

R2
(Base Catalysis) SOH  P
185
 dP [SOH ]
 k2 [ SOH ] K2 
dt [ S ] [OH ]

 k 2 K 2 [ S ] [OH  ]

Kw
 k2 K 2 [ S ]
[H  ] Alkali

dP
Kw
 dt  k2 K 2
[S ] [H  ] log Rob

dP
 log dt  log (k2 K 2 Kw)  P H
[S ]

Case (iii) : Uncatalysed Reaction

S P

k Un Catalysed
3 P
S  log Robsv

k observed = k3

dP
 k3 [ S ] PH
dt
log kobsv  log k3

  dP  
  dt  
log      log k0  log k H [ H  ]  log kOH [OH  ]
 [S ] 
 
d
Acid

y se
at al
Cat

eC
alys

[H  ] [OH  ]
Ba s
ed

Un Catalysed

186
3 Types : Acid Catalysed
Base Catalysed
Un Catalysed

Acid Catalysed Un Catalysed Base Catalysed

[H  ]
t.
Ca
id
Ac

Un Cat


[H ]

187
Minimum of Skrabel equation :

kobsv  kO  k H [ H  ]  kOH [OH ] (1)

kW
 kO  k H [ H  ]  kOH . (2)
[H  ]

 kobsv
The minimum occurs when 0
[H  ]

 kobsv k  k 
 
 k H  OH  2W  0
 [H ] [H ]

extremum (min/max)

kOH . KW
 kH 
[ H  ]2min

1
 k .K  2

 [ H ]min   OH W  (3).
 kH 

Application of Skrabel equation :

kobsv at [ H  ]min corresponds to

log Robsv
the lowest possible k with p H . It

may be the limit below which it is [ H  ]min

not possible to probe with variation in H  .

PH
K
R  H   RH  (1)

k2
RH P (2)

[ RH  ]
K  (3).
[ R] [ H  ]

Mass Balance equation : CH 3COOH

If p H  pKa, then the ionised [CH 3COO  ] and [CH 3COOH ] are exactly 50% : 50%

[CH 3COOH ]  [CH 3COO  ] 100%

188
 It PH   pKa, then CH 3COOH CH 3COO  [CH 3COOH ]  [CH 3COO  ]

99.999% 0.000.1% 100%

At equivalence point in a titration
9.0 4
PH   PKa 0% 100% 100%

LH (CH 3COOH )
L(CH 3COO  )

R0  [ RH ]  [ R] (4)

(neglecting charges)
PKa

L LH

Except in nuclear reactions, mass balance holds good for all the species. A species
may be reactant, product etc.

[ RH ]
From (3) ; [ R]  (5)
K .[ H  ]

Substituting (5) in (4),

[ RH ]
RO  [ RH ] 
K [H  ]

 1 
 [ RH ] 1  
 K [H  ] 

 K [ H  ]  1
 [ RH ]   
 K [ H ] 

RO K [ H  ]
 [ RH ]  (6)
K [H  ]  1

From equation (6), [ RH  ] concentration can be calculated from a knowledge of

equilibrium constant.

189
 RO is the initial concentration. H  is the p H where RH is needed. Experimental
determination of RH is possible only if ion selective electrode (ISE) is available.

dP
 k 2 [ RH  ] (7)
dt

Substituting (6),

dP R . K . [H  ]
 k2 . O  (8)
dt K (H ]  1

Case (i) :

It K [ H  ]  1 i.e., K is very high (complex with high formation constant.

Ex : Ca 2 EDTA (or )

[ H  ] is high (acid solution)

If K [ H  ]   1, then (8) reduces to

dP k2 . RO . K [ H  ]

dt K (H  ]

 k . RO (just like uncatalyseel reaction) (9)

Case (ii) If 1   K [ H  ]

dP k 2 RO . K [ H  ]

dt !

 k 2 RO K [ H  ] (10)

Equation (8) takes into account ionised and unionised forms.

(ii)

 
Explains uncatalysed and catalysed H reactions.

General Acid Catalysts

COOH COOH

 CH 3COOH
O CH 3 H

O
catalysed by both acid & baseds

190
 observed
expected
H OH 

b c

P H fig (1)

The hydrolysis of acetyl salicylic acid is catalysed both by strong acid and strong
base. The expected skrabel diagram is given in fig (1). But the actually observed one contains
additional features (b, c). This is due to general acid -base catalysis.
If a weak acid is also present, the hydrogen ion obtained from it has the same catalytic
effect. If hydrogen ion from weak acid catalyses, it is termed as general acid catalysis.
catalysis

kobsv  kuncatalysed  k H [ H 1 ]  kOH [OH  ] ,

 k HA [ H  ]  k BOH [OH  ] .

kobsv  kuncat  } uncatalysed

Robsv
kH [ H  ] 
kOH [OH  ]  } specific

k HA[ H  ]  general acid [H  ]

k [OH  ] dot of time
BOH 
general base
Redox catalysis :

Metal ion in different oxidation states (Cr (VI ) Cr ( III )) , (Co ( II ), Co ( III )) etc., forms
a redox couple. Co-ordinated metal ion has altogether different properites compared to
simple metal ion couple. For example, the standard potential of [ Fe [CN )6 ]3 [ Fe [CN )6 ]4
is 0.3 compared to [ Fe [OP )3 ]3 [ Fe (OP )3 ]2 is 1.08. Fe ( III ) / Fe( II ) potential is 0.77. If a
pair of co-ordinated metal ions in different oxidation states participate in the reaction,
catalysing it, then it is called redox catalysis. [ Fe(OP )3 ]3 prepared by adding OP (ortho
phenanthroline) to Fe3 has different properties from that obtained by the oxidation of
[ Fe(OP )3 ]2 .

Hydrogenation, synthesis of polyfines etc. are catalysed by redox catalysts. Some of

the important pairs are from Rhodium (Rh), Pd complexes in addition to those of Co, Fe
and sometimes Z n . Enzyme catalysis is unique and specific for a reaction in vivo (reactions
occuring in biosystems). The same reaction may not be equally efficient, may not occur at
all in vitro (the same reaction in a Petri dish even when the enzyme is isolated). The third
one is to study the interested reaction or similar ones on a computer (in silico). Drug design,

191
drug discovery and functioning of the drug are studied with model compounds both in vitro
and in silico. A model compound is one which resembles a part, fragment or residue of a
bio molecule. PAHS (Poly aromatic hydrocarbons) and PCBs (Poly chlorinated biphenyls)
are toxic and carcinogenic. Their activity is very complex but partially understood through
classical chemistry (radius ratio rules, ionisation potential) and now advanced parameters
like electrostatic potential.

192
 Lesson No-25
FAST REACTIONS
Knowing more and more of less and less
knowing less and less of more and more

 Time of monitoring the reactant / product or intermediate far less than t 1 2

 The reaction is far away from equilibrium, i.e., the reverse reaction doesnot occur
or its rate constant is very small.

Fast reactions can be thought of as if order=1 and t 1 2  1 Sec. Here time of mixing
is comparable to t 1 2 in the classical sense.

Fast reactions
Mixing  Flow methods

Monitoring  Computer interface Oscilloscope

Pen recorder.
Reaction at Pressure jump
equilibrium  Relaxation
Temp
A slow reaction can be made fast, by increasing temperature and / or increasing
concentration of rectants.
Slow Reactions :

S 2 O8   2 I  
 2 SO4   I 2

Stoichiometry is 1 : 2 ; order = 2 and the product is monitored by titrimetry and

spectroscopy.

H COO   I 2 
 I   CO2   H 2O

Pseudo first order reaction and the reactant is monitored.

H
CH 3COO C2 H 5  H 2O 
 CH 3 COO  C2 H 5 OH

Molecularity = 2 Order = (Psedo first order)

193
Fast Reactions

10 5
   
i) H 2O   H  OH
1011

Forward reaction – First order, k1  10 5

Backward reaction – Second order, k2  1011 .

ii) Fe( II )  OP 
 Temp . jump

Fe( III )  5CN  

 Stopped flow .

Kinetics system

Equilibrium Near equilibrium

Relaxation

Chart : Categories of reactions based on the scale.

Relation between k (rate constant) and k (equilibrium constant)

k1
k1 = rate const of forward rean

A  
 P
k 1
k 1 = rate const of backward rean.

Concentration

time A P Mass balance eqn

0 A0 0 [ A]0  [ A]0 (1)

t [ A] [ P] [ A]0  [ A]   P  (2)

 [ A]eq [ P]eq [ A]0  [ A]eq  [ P]eq (3)

i) If the reaction is irreversible, A  P , then at t  ,

A0  0 ; P  A0 .

ii) A  P, i.e., system at equilibrium, then at t  , [ A]eq  [ P]eq and

A0  [ A]eq  [ P]eq .

194
 If more than 7 or 8 half lives, are over then t is  .

At equilibrium,
rate of forward reaction = rate of reverse reaction,

k1 [ A]eq  k 1 [ P ]eq (4)

k1 [ P ]eq
 (5)
k 1 [ A]eq

Application :

k1
If K is known or monitored K 
k 1

k1
k1 is measured, then k1 
K

K
k 1 is measured, then k1  k
1

Else k1 , k 1 cannot be estimated.

This is the first equation relating thermodynamic concepts with kinetic theories.

Ex : Rate constant of reverse reaction in

H 2O  H   OH 

Continuous Flow System :

Syringe 1
observation tong tube

Syringe 2

Mixing chamber

The two reactants are added very fast with two syringes, in pulse or continuous
mode. The mixing of solutions in the mixing chamber is also fast. Thus addition and mixing
will be completed is less than a few milliseconds. The solution where the reaction continues
flows through (long) observation tube. At different lengths, ( l ) of the tube, the response of
reactant/product/intermediate is monitored. If v is the velocity of the movement of the

195
 l
solution, then ' t ' is calculated as l / v . t
v

Advantages :
1) Mixing is fast.
Application:
Applicable to irreversible reactions.
Limitation :
Very large volumes are required (20 litres in 1920's).
Stopped Flow Spectrometer :
The mixing chamber is now connected to another chamber with a stopping piston.
The solution coming out of the mixing chamber is suddenly stopped. The response is
monitored over a few seconds.

Stopper flow

stopping piston.

Application :
Irreversible reactions.
Limitation : Not applicable for system at equilibrium
Remedy : Relaxation methods.
Advantage : Very small amount of the reactant is sufficient. So, useful for enzyme reactions.

Example :
no. of points

0.087 M Pyridine Absorbance (NP) = 500
A
2  104 M acetic anhydride.

0 sec t  1 sec
P H ,   1, T  250 C

At Millisecond level, the uncertainity in response is high which is reflected as zig-

zag profile. NP = 500 is to reduce the error in rate constants.

Relationship between k , [k1, k 1 ] (For equilibrium) :

k1
Model : A  P (1)
k 1

196
A0  [ A]  [ P] (2)

dA
  k1 [ A]  k1 [ P] (3)
dt
From (2), [ P]  A0  [ A]

dA
  k1 [ A]  k1 { A0  [ A]} (4)
dt

  [ A] {k1  k 1}  k1 [ A]0 (5)

dA
  ( k1  k1 )  [ A]  k1 [ A]0 (6)
dt

Equation (6) is a first order differential equation.

k1  e xp {  k1  k1 t}
[ A]t  [ A]0 (7)
k1  k1

At time t  , exp ()  0, [ A]  [ A]eq

k 1
 [ A]eq  [ A]0 (8)
k1  k 1

[ P]eq  A0  [ A]eq (9)

From (9) & (8),

k 1
[ P]eq  A0  [ A0 ]
k1  k 1

[ k1  k 1  k1 ]
 A0
k1  k 1

k 1
 A0 (10)
k1  k1

[ P]eq k1
   K (11)
[ A]eq k 1

k1  K . k1 (12)
k 1
k 1  (13)
K

197
Relaxation :
k1
Time constant ( ) for A  P
k 1

T1 , T2 aretemperatures T2  T1

T  T2  T1  50 C to 300 C

T in  sec .
equilibrium time is 2–10 minutes.
Relaxation time in sec, millisec,  sec .
T2 T2 [ Aeq ]*

n
T1 T2

atio
 R ela

turb
k1 k1* ns
e
xation 
spo

Por
Re  sec
k1 k *1 T1 T1
T1 [ A]eq
* 10min
[ A]eq [ Aeq ] (equilibrium)
ing
mix

[ P]eq [ Peq ]*
time
[ A]eq  [ Aeq ]*  x (1) x may be  ve

[ P ]eq  [ Peq ]*  x (2) x may be  ve

A0  [ A]eq  [ P]eq , A0  [ Aeq ]*  [ Peq ]* .

dA
  k1[ A]  k 1 [ P] (3)
dt
All equilibrium,

dA
  0
dt
 k1[ A]eq  k1 [ P]eq (4)

[ P ]  A0  [ A] eg (5)

substituting (5) in (3)

dA
  k1 [ A]eq  k1[ A0  [ A]eq ] (6)
dt

dA
  k1 [ A]eq  k1[ P ]eq (7)
dt
substituting (1) and (2) in (7),

198
 dA
  k1 {[ Aeq ]*  x }  k 1 { [ Peq ]*  x} (8)
dt

  k1 [ Aeq ]*  k1 [ Peq ]*  (k1  k 1 ) x (9)

  ( k1  k1 ) x .

When the temperature is suddenly raised to T2 from T1 within a few microseconds,

the new equilibrium will be attained a little slowly. The equilibrium constant K and rate
constants k 1 and k 1 will be perturbed depending upon H 2 : of the reaction. It can be

considered k1[ Aeg ]*  k1 [ P ]*eq .

d [ A]eq
  ( k1  k1 ) x (10)
dt
d [ A]eq dx
 (11)
dt dt

d [ A]eq d {[ Aeq ]*  x}

dt dt

d [ Aeq ]* dx
  (12)  [ Aeq ]*
dt dt 1
e

The change of concentration ([ Aeq ]*) is small

within the range of relaxation time (seconds-milli sec).

[ A]eq
d [ A]*eq
Thus  0
dt
d [ A]eq dx
Eq n (12) becomes, 
dt dt
From (10) and (11),

dx
  (k1  k 1 ) x (13)
dt

Integrating eq n (13)

x  x0 exp (  k1  k1 t ) (14)

x
or  exp (  k1  k1 t )
x0

199
 x
or ln x   ( k1  k 1 ) t
0

1
Relaxation time, ,
e

1 
or ln     ( k1  k1 ) t
e 
1
or  t(1 e )   (15)
k1  k1

 is called relaxation constant in first kinetics.

It is the time for x0 to fall by e times i.e.,

x 1 ln(2)  x 1
 ,  t1 2 .   
x0 e k1  k 1  x0 2

1
 ln     1
e

   k1  k 1  t1 e   1

1
  t1 e
 k1  k1 

200
 Temperature jump

Spectrophoto
Modular T– temp
metre

T– jump

Window
Source
---------------------
---------------------
---------------------
---------------------

Mono Photo
chromator Quartz cell multiplier

Glass - 400 - 700 Photo cell

Quartz - 200 - 400 (single beam/
double beam)

The fast reactions can be monitored, by T–jump or P-jump instruments. T–jump

consists of mainly two modules, spectrophotometer and high energy source to implement
T–jump.
Spectrophotometer : The essential components are source, monochromator, T–jump
cell, photomultiplier and a computer.
The source is a tungsten lamp if one is interested in visible region. The light is made
monochromatic by passing it through a prism. The light now is absorbed by the solution
when it passes through the specially designed cell. Then, the remaining radiation is sent to
photomultiplier tube. The signals are processed in the computer.

Spark plug
Cell

High Capacitor
Voltage

10 kv  40 kv
100 kv

T–jump : A high voltage source with electrolytic capacitors and others generates 10–40
KV(kilo volts) with a small current. It will be connected to a capacitor through electron
circuit and spark plug. The other end of spark plug is connected to the reaction cell. When
the spark plug is closed through the computer signal a clock is on. The synchronisation
between the spark and clock will be in micro second range.

(Ferric – Thiocyanate reaction) :

201
 2.5 ml of Fe( III )  2.5 ml of SCN such that overall conc. is 5.0  103 M

NaCl O4  0.2 

HCl  0.1  Hcl O4

It was monitored at wavelength = 480nm

t in minutes ln ( x ) [ A]*eq  x  [ A]eq

0.05 1.57
0.10 1.50
0.20 1.39
0.60 0.70
0.70 0.30

Necessary conditions for temp.Jump

If A  P is near equilibrium, and it is not possible to separate them into two reactions
d lnk H d lnk p V
and  2
or  ).
dT RT dT RT 2

Application :

1) Metal complex formation in aqueous and non - aqueous solutions.

Ex : Fe  III   SCN

Fe  II   O  Phen

2)  H   OH  . By using high voltage pulsed laser, the temp.

Rate contants H 2O 

change can be 10  30 in nano seconds. Instead of a capacitor of high voltage cable is
used, application of voltage is possible in fraction of microseconds.

Pressure - Jump

 d lnk  V
Necessary condition    
 dP T RT 2

The reaction is sensitive to volume (volume change).

202
 Pressure Jump
Test/Sample Reference
Pressure Cells
Jump conductivity
1c m 3 K C l
M g SO4
Fig. 1
(Monitoring)
50 Khz
3
Cells are 1cm
Oscilloscope Fig. 2

Pressure jump is utilised for volume sensitive reactions

Pressure Jump Bronze or cu Kerosine is pumped at high

metallic sheet pressure at 150 atm

Auto clave 150 atm

Kerosine 
 1 a tm
Fig. 3 tim e Fig. 4
*
C

conc. C

tim e  
 Fig. 5
Some reactions like micelle formation, hydrolysis or complex formation  Be SO4  or

vanadyl sulphate etc. are sensitive to changes in volume. Such reactions are studied by
pressure jump technique to calculate rate constants using time constant  Z  . It
consists of two modules i.e., P  jump unit and monitoring (conductivity) unit.
Conductivity Cell :
venadyl sulphate etc. are sensitive to changes in volume. Such reactions are studied by
pressure jump technique to calculate rate constants k1 , k1 , using time  Z  . It consists to
two modules i.e.,   jump unit and monitoring (conductivity) unit.

Conductivity Cell :

Two identical conductivity cells of capacity 1cm3 made up of special material are used
to withstand 150 atm pressure. The reference cell is filled with Kcl or Mg SO4 for which
there is no relaxation. The two cells are connected to an oscilloscope measuring the
frequency at 150 KHz.
Pressure Jump Unit :-
An autoclave filled with Kerosine is the essential part of P  jump unit. The monitoring
module (fig-2) will be within the unit in Fig -3. A metallic sheet made up of copper or bronze
covers the autoclave. When the pressure increases to a pre-set value (50-60 atm), the

203
diaphragm brusts and simultaneously a timer 30 is on. The relaxation is followed with a
computer interface.

The concentration of the species goes to C * and during relaxation it falls off
exponentially (fig.5) Be SO4 .

R1

Be   SO4  
 Be H 2O SO4
  Be SO4

R 3

k3  185  25
k 2  285  10

The transformation of l to ll is formation of an outer sphere complex. It is known that it

contains one water molecule.

Example :
k1

H 2O    
 H  OH __________ (1)
k 2

forward reaction is 1st order, reverse reaction is of second order.

d  H 2O eq
  k1  H 2 oeq  k2  h   OH    0 __________ (2)
dt eq eq

K1  H 2 oeq  R2  H   OH   _________ (3)

eq eq

 H 2 o *   H 2 o eq  x
*
H    H    x _________ (4)
    eq

OH *  OH   eq  x

*
d  H 2O  * * *
  k1  H 2o   k2  H   OH   _________ (5)
dt

204
 sub (4) in (5) ,

d  H 2O eq  x
dt

  k1  H 2O eq  x  
 k2  H    x
eq OH    x _________ (6)

eq

d  H 2O eq dx
    k1  H 2O eq  R1 x
dt dt



 eq eq  eq 

 k 2   H   OH    x   H    OH eq   x 2 
 

dx
   k1 x  R2 x   H    OH    ________ (7)
dt  eq eq 

 d  H 2O eq 
   0 from  2  
 dt 
 


dx
dt 
  x k1  k 2   H     k2  OH  
 eq  eq  ________ (8)

Integrating

x  x0 exp   k1  k 2  H    k 2 OH   t 
 eq eq 

ln
x
x0 
  k1  k 2  H    k 2 OH   t
eq 
1
 k1  k2  H    k2 OH   ________ (9)
t eq eq

Q) Relaxation time is 37  sec, at 298 K and P H  7.

If PKW  14.01, calculate R1 and K . (eq. constant )

1
 k1  k 2  H    k 2 OH  
t eq eq

k1
 K  k1  k2 K
k2

1 1
or   k2 K  k 2  H    k 2 OH  
37  sec 37  106 eq eq

205
 OH    H  
K    
 H 2O 
Kw

 H 2O 

1014.01
  1.75  1016.
55.6


1
37  106

 k2 K   H  
eq
  OH  
eq   H 

eq
 OH  
eq
 Kw

 k2  K  2 Kw 

 k2 1.75 1017  2 107 

1
 k2  16
37 10  2  107

 1.35 1011

k1  k2 K

 1.35  1011  1.75  10 16

 2.43 10 5

If p H  3 , autoionisation of water can be neglected.

Similarly if p H  10, auto-ionisation of water can be neglected.

If p H is in the range 5-8, quadratic equation is to be solved.

206
 Lesson No-26
ELECTRO CHEMISTRY
Who comeout first gets the credit, careful person
is left out (Gentleman research)

Electro Chemistry deals with the spontaneous and non-Spontaneous chemical

reactions which occur or generate energy in the form of electromotive force (EMF). The
simplest application is potentiometric titration of Fe (II) with dichromate or permanganate
and AgNo3 with NaCl or KI. The spontaniety is made use in galvanic cells which is a source
of Energy. Electrolytic cells function under the influence of external Emf.
Electrochemical Cell
finat
e

Half Cell-1 Half Cell-2 Galvanic Cells Electrolytic cells

Electrode 1 Electrolyte 1 Electrode 2 Electrolyte 2

Metal (S)/Metal salt (aq.C1)

cu(s)cu++ (aq. 0.05)
Fig. (1)

Metal (S)/Semi solid salt (C1)

Ag (S)/Agcl(S), KCl (aq.)
Fig. (2)

Metal (S)/gas (fugacity), HCl (C1) - NHE

Fig. (3)

Pt
Metal (S)/ion Fe (II), Fe (III), (C1,C2)
Fe. (ii)
Fe. (iii)
Fig. (4)

Zn (S)  Zn (aq)  2e

zn [Zn (aq)][e 2 ]
K
znso4 Fig. (5) Zn (S).

207
 Cu  2e   Cu (S)
cu
cuso4
Fig. (6)
Half Cell :
A half cell consists of an electrode and a salt along with a reversible ion. The state of
the metal and salt are represented in the parentheses and the concentration is recorded for
aqueous solution. A vertical bar separates the electrode with the electrolyte.
There are mainly four types of half cells. Normal hydrogen electrode is a primary
standard electrode and the potential of any half cell is measured with respect to it. Now a
days calomel electrode, Ag/AgCl electrode commercially available are used.

Galvanic Cell :
The Spontaneous reaction is used in the galvanic cell as a source of Emf (energy).

In Galvanic Cells, the electrode reaction is spontaneous ie.,  G<O (or) E0>O (or) K
is significant (>104). LHE (Left Hand Electrode)

e-
e-

e- - EMF : 0.76 Volts

e
zn
znso4

Zn (S)  Zn (aq)  2e

[Zn (aq)][e]2
K
[Zn (S)]

The activity of the solid is deemed as unity and Eqn -1 reduces to K  [Zn (aq)] .
At LHE Oxidation takes place and generally it is considered as anode (anodic
oxidation). It is a thumb rule or heuristic. The electrons travel towards the electrode and
pass through the circuit.
RHE : (Right hand Eletcrod)

e-

e- - Cu   2e   Cu (S)
e
cu EMF : 0.34 Volts
cuso4

Copper electrode is called here as cathode and reduction takes place (Cathodic
Reduction). The electrons needed are considered as if they are sucked through the Cathode.
combining the two cells.

208
 e- e-

e- e-

Zn cu zn
Cn

The contact between the two cells is through a salt bridge and the flow of current is
as shown in fig.
e- e-

E0 = E0LHE + E0RHE
= 1.1 Volts
 G = -RT ln K
= -nFE
= -2 x 96496 x 0.34 =  15 koal.
 G = -2 x 96, 499x1.1

Electrolytic cell
e- e-

e- e-

Anode cu e- zn e- Cathode

The reaction in the electrolytic cell is non-spontaneous since E0 = -1.1 volts (or)
 G>O. However under the influence of EMF, the reaction takes place. But, still the oxidation
occurs at anode and the reduction at the cathode.

In the electrolytic cell also, oxidation takes place at anode ie LHS cell.

Ex : (a) Fe3+ + Reduced cytochrome  Fe2++oxidised cytochrome calculate Equilibrium

constant ? E = 0.50 volts at 250C.
(b) What is the EMF if concentration of Fe(iii) to Fe(ii) is an 1000:1 ratio and the two
forms of cytochrome are at 0.0001 m.
209
 Anode, Oxidation Cathode, Reduction
2
Cu ( s)  Cu  2e Zn 2  2e  Zn ( s)
E 0 Cu ( s ) / Cu ( s)   0.34 0
Ered   0.76

The cell reaction is Cu ( s )  Z n2  Cu 2  Z n ( s )

E 0   0.34  ( 0.76)   1.10

So the reaction is not feasible

But under the influence of external source, a battery, this reaction is possible

The flow of e both in Galvanic the electronic cells are

e e

e e

But the flow of current is in the

opposite direction.

Cell reaction represented as equillibrium,

Ecell  ELHC  ERHC

210
 Galvanic Electrolytic

 0.76  0.34 1.10 –0.76 + (–0.34) –1.10

Process represented as
Oxidation

ECell  ELHC  ERHC ECell   0.34  (0.76)   1.10

 0.76  ( 0.34)  1.10

Process represented as
reduction

ECell  ERHC  ELHC ECell   0.76  (0.34)   1.10

 0.34  ( 0.76)  1.10

(a)  G = -nFE

= -RTlnk

nFE 1 x 96,496 x 0.5

logK  
RT 2.303 x 8.314 x 298

= 8.45
K = 2.8 x 108

0 RT
(b) E  E  lnk
nF

0.059
E0  log k
n

Fe (III) 1000 [cytochrone] oxi

 ; 1
Fe (II) 1 [cytochrone] Re du
[Fe 2t ] [cyt]oxi
 0.50  0.059 Log
[Fe3t ] [cyt] Re d
1
 0.50  0.059 Log x1
1000
 0.0.67742

211
EMFs of different systems :
Persulphate - 1.8
Ce (IV) - 1.4
Permanganate - 1.3
Potassium dichromate - 1.0
Fe (II) - 0.7

1
H2 (g)  H (aq)  e  0.0
2

Application : Potentiometric titrations of reductant with oxidising species

Persulphate
In organic Chemistry; ferri cyanide a mild Cel (iv)
Mn (III)
oxidising agent is employed to get intermediate Cr (iv)
products of interest with Ce(IV), persulphate etc
oxidation will be complete.

Reduction Potentials :

Xe (VIII)  Xe (VI) 3.0

o3  o2 2.07
F2  F 2.87
3 2
Co  Co 1.81
H2 0.00

Na  Na  2.71
Li  e  Li  3.05

Energy manifests (occurs) in different forms.

Thermodyanics G, H , S (W ) 0
Gravity g
Quantum Chemistry Potential energy, KE
Photo Chemistry Photon
Statistical Thdynamics Between molecules
Dispersion, Dispersion energy
ElectroChemistry Emf
BioChemistry Bioenergy
The +ve or –ve charges are only a convenient form of expressions energy. So, it
can be beamed (thought) as condensed form of energy of varying magnitudes.
Sometime passing through imaginary boundary. The polarised, induced polaried
dispersion energies, although small it magnitudes, play a predominant role in
biosystoms.

212
 Lesson No-27
CONCENTRATION CELLS
Wrong frame work- all conclusions are erronean.
Correct frame work but inadequate knowledge one cannot
distinguish between truth and falsehood

Concentration Cells without transference

They belong to the category wherein there is an energy (charge) transfer but not
mass transfer. The other one is concentration cells with transference, in which mass
transfer is also there along with energy transfer.
Concentration cell without transference consists of two complete cells connected
through a salt bridge (or) any separation boundary. The left hand side cell has NHE (LHE)
combined with a secondary standard Ag/Agcl electrode (RHE). As usual at LHE oxidation
takes place and RHE reduction.
LHC : - It consist of two elecrode systems (LHE and RHE)

Step 1 : H2(g, 1 atm)/HCl (aq, a1) Agcl (s)/Ag(s) (1)

The electrode reactions are

1
LHE : H2 (g)  H (aq, a1)  e (2)
2
The thermodynamic Equilibrium constant

aH  (aq,a1 ) * a e
K 12
a (3)
H2

 (aH )1 (4)

At LHE, Oxidation (release of electrons) takes place and this electrode is anode.
(anodic oxidation). The activity of the gas at unit fugacity (Pressure) and that of electron
are considered as unity.

RT
ELHE  E 0  ln (a  )1 (5)
F H

Since number of electron change is equal to one. The cell reaction at the other electrode
(RHE) is

AgCl ( S )  e   Ag ( S )  Cl  ( aq, a1 ) (6)

a Ag ( S ) * (a Cl )1
K RHE  (7)
a Agcl ( S ) * ae

213
  a cl  1
(8)

ERHE  E 0  RT n (acl )1 (9)

The total cell reaction is (2) + (6)

1
H 2 ( g )  Agcl ( S )  H  (aq, a1 )  Ag ( S )  Cl  (aq, a1 ) (10)
2
The overall equilibrium constant

K  (a  )1 (a  )1 (11)
1)
H cl

which is a product of (3) & (7)

RT
ELHC  E 0  l n (aHCl )1 (12)
F
Step 2 :

The RHC (Right hand Cell) is similar to LHC except the activity of HCl is a2

H2 (g)/HCl (aq, a2) Agcl (s)/Ag(s) (12)

Following the same logic of Step (1)

K  (a ) (a  ) 2 (13)
H 2 cl

RT
ERHC  E 0  l n (aHCl ) 2 (14)
F
Step 3 :
The RHC is reversed and connected to LHC
LHC//Reverse (RHE)

H2(g,1atm)/HCl(aq,a1) Agcl (S)/Ag(s) // Ag(s) Agcl(s) (15)

LHC Reserve RHC

The symbol vertical double bar (II) indicates no mass transfer takes place. Thus, it
is a cell without transference. The Overall cell reaction and K and E can be written as
follows.
RT
 E LHE  E 0  ln (aHCl )1
F

214
 RT
ERHC  E 0  ln (aHCl ) 2
F
ECell  ELHE  ERHE (16)

 0 RT 
ln (aHCl )1  E ln (aHCl ) 2 
RT
0 
E   (17)
F  F 
RT (aHCl ) 2
ECell  ln (18)
F (aHCl )1

Eqn. (18) represents the total Emf of a cell without transference. It is immaterial
whether the reference electrode is NHE (Normal Hydrgen Electrode) or any another cell
since E0 is cancelled.

One Faraday in electrochemistry is equivalent to the product of charge of electron

and Avagardo number ie., it corresponds to the charge of one mole of electrons.

F  E  Na

= 6.02214 x 1023 x 1.602176 x 10-19

= 9.64853 x 104
For one Faraday of current the reactions taking place in the cell without transference
are
(i) One mole of Ag is transferred from left to right
(ii) One mole of AgCl(s) left to right

(iii) Half mole of H2 (g) from left to right

(iv) One mole of HCl from C1 to C2 where (C = Concentration)

The concentrations of HCl in the two compartment are large such that the transfer
doesn't affect the net concentration. Although the phenomenon doesn't involve the actual
mass transfer, energy transfer is reflected in emf.

Cells with Transference :

W hen two hydrogen electrods are

anode Cathode
connected, one gets both cell with transference + -
and cell without transference. If the activity of HCl Oxidation Reduction
is unity the net cell potential is zero and M2
correspond NHE's. When there is a hinderance
for the movement of ions by separation, it
corresponds to cell without transference. On the
other hand, if a porous membrane is present, it Hcl
Hcl (a2)
results in cell with transference. The cell in fig. (1) (a1)
corresponds to a system where in it is reversible

215
with respect to a cation (Hydrogen ion). The
processes taking place are as follows.
Step 1 :
1
LHE H 2 ( g )  H  (aq, a1 )  e (1)
2
1
RHE H  (aq, a1 )  e  H 2 (g ) (2)
2
Step 2 :
Let t+ (or tH+) is the transference (transport) number of a cation. For one mole of
electrons (one Faraday) passing through the circuit, t+ equivalents of hydrogen ion is moving
from left to right. It can be represented as
t H  ( aq, a1 )  t H  ( aq, a2 ) (3)

Step 3 : t_ is the transference number of anion (Cl) and for one faraday of current t_
equivalents of chloride is moving from right to left.
t [Cl  ]a1  t Cl  a2 (4)
Step 4 : Combining the Equilibria (1) to (4)
1 1
H 2 ( g )  H  (aq, a2 )  H  (aq, a1 )  H 2 ( g )  t H  (aq , a2 )  t H  (aq , a1 )
2 2
The assumption is t+ & t- is equal to unity and the Equation of

i  o  RT ln ai

Where  's are the chemical potentials.

Step 5 : The relation between  G and EMF is valid even where there is a transference
provided the transport Phenomenon is included.


H
(a1 )   0
H

 RT ln a
H 1


H
(a2 )   0
H
 
 RT ln a
H 2


Cl
(a1 )   0
Cl 

 RT ln a 
Cl 1


Cl
( a2 )   0
Cl 
 
 RT ln a
Cl 2

It is resonable to assume that 0 of cation is same as well as that of (Cl-)

a 
 G  RT ln  1  (6)
 a2 

216
considering the transport number  G = -nFE

RT (a2 )
E  t ln (7)
F (a1)
If a  is the mean activity coefficient of HCl
a 2   aHcl
RT (a)2
Equation (7) becomes E  2t ln (8)
F (a)1

Case - I : If t  = 1 then (8) reduces to

RT (a) 2
E2 ln
F (a)1

This corresponds to a cell without transference.

Case - II : If t  =0 (or) (a  )2 , (a  )1 then

E=0
The cell has zero EMF when the HCl is at unit activity corresponding to NME.
Relation ship between E and log K : -
From principles of thermodynamics and electrochemistry

RT
E  E0  lnk (or )
nF
E  E 0 1
 lnk (12)
RT / F n n=1
EE0 EE0 n=2
A plot of against lnk gives a straight line of
RT / F RT / F
slope 1
n where 'n' is the number of electron change.
lnk
Applications :
Chemical compounds can be synthesised to get a desired equilibrium constant
with metal ions (or) EMF. It renders a thermodynamically infesible reaction possible (or)
Vice versa. The oxidising (or) reducing power can be increased (or) decreased.
C1
A  A  a Spon tan eous reaction
G
B  B   Equilibrium A C
E**
C  C   a Non  Spon tan eous reaction A1
B 1

217
 Lesson No-28
DETERMINATION OF EO (STANDARD POTENTIAL)
If information from one source, it is plagarism.
But information from more than one source it is information fusion

The standard potential of a half cell (redox couple), cell where in it is reversible with
respect to a cation H+ (or) anion (cl-) can be determined by different means. The first one
is combining any two half cells and measuring the emf at any molarity (more accurately
molality). The other one is to measure emf at different ionic strengths and extrapolating to
zero ionic strength.
A hydrogen electrode is combined with AgCl cell and the emf is given as

Pt/H2(g)/HCl (aq, a) AgCl(s)/Ag (1)

Ka a (2)
H cl

RT
E  E0  ln a  a  (3)
F H cl

If Hcl is at unit activity Eqn. (2) becomes E = E0. Since the potential of NHE is Zero,
the potential measured itself is standard potential (E = ELHE+ERHE) (E = O + ERHE)

Case (ii) : - The activity of an ion is the product of molality, and activity coefficient. In dilute
solutions molality becomes equal to molarity and '  ' tends to 'f'.

a m * (4) a m *
H H H Cl Cl  Cl

From (2) &(3)

RT
E  E0  ln m  .  . m  .   (5)
F H H Cl Cl

For Uni-Univalent electrolyte (HCl, NaCl etc) mH   mCl and the mean activity
coefficient, if it sufficiently represents that of cation and anion

   
H Cl

Then Eqn. (5) becomes

RT
E0  ln m2 *  2
F

2 RT 2 RT
E  E0  ln m  ln  (6)
F F

218
 2RT
Case (iii) : - A plot of E versus ln m results in a straight line with intercept = E  ln 
0

If   is known E0 is calculated
Intercept =
Algorithm : Measure EMF of the cell at different molalities
2RT
E0  ln 
at different molalities E F

Data : - E : [ E1 , E2  ENP ]1 ;

m : [m1 , m2  mNP ] 1 ln (m)
Plot (m,E), least squares (E, ln m)
2RT
Intercept = E  ln 
0

Calculate E0

Case iv : - If  is not available then it can be assumed that ln    m (9)

2 RT 2 RT
(6) and (9) gives E  E  ln m  ( m )
0
(10)
F F

2 RT 2 RT
E ( m)  E0  ln m (11)
1)
F F

A plot of a vector of E values (emf) versus a vector of ln m results in a straight line

of intercept E0.
Intercept = t -0
Determination of activity coefficient :
2RT
E m
Considering the Equation (6) F

2 RT 2 RT
ln   E 0  ln m  E (15)
F F ln m
 E 0  E 
ln     ln m (16)
 2 RT / F 

Case (v) : - For a single measurment of EMF with a given 'm' ln   is calculated

Case (vi) : - If a number of EMF measurments are made at different molalities a least
square fit of E (y) versus ln (m) (X) gives a straight line of intercept
Intercept =
2RT 2RT
E0  ln  t ln 
F E F

 E0 is known, ln   can be calculated.

ln (m)

219
Effect of Complexation on Redox system
Complexation of a metal ion in different oxidation states results in varying magnitude
of stability constant. For example, the standard potential of Fe(III)  Fe(II) couple is 0.77.

Fe3  e  Fe2 (1)

RT
E  E0  ln K (2)
F
RT [ Fe2 ]
 E0  ln
F [ Fe3 ]

RT [ Fe3 ]
 E0  ln
F [ Fe2 ]

Fe( III )
E  0.77  0.059 log10 (3)
Fe( II )

1 2 102 Fe( III )

The concentration of Fe(III) is much less than Fe(II) (10 ; 10 )
101 Fe( II )

102
Then = 0.77 + 0.06 * log
101

= 0.71

A mixture of Fe(II) of concentration 10-1 and Fe(III) of concentration 10-2 is prepared

If phosphoric acid (or) Pyrophosphate is added Fe(III) is complexed and concentration

of uncomplexed Fe(III) drastically decreases. Hence

106
 0.77  0.06 log
101

 0.77  0.30

 0.47

220
Ferricyanide - Ferrocyanide Couple : - [ Fe(CN ) 6 ] / [ Fe(CN ) 6 ]

The potential (EMF) of Ferriyanide-Ferrocyanide is around 0.35 and it can be

explained by considering the compleation of cyanide with ion in +2 and +3 oxidation states.
Respecting additivity of free energy change and hypothetical thermodynamic equilibria nearly
represent the truth . The following cycle is considered.

G

Fe3  e  Fe 2  G1   F  E 0 I

Fe2  6CN   [ Fe(CN )6 ]4  G2   RT ln  II II


 Fe3  6CN   [ Fe(CN ) 6 ]3 
3  G3   RT ln  III III
[ Fe(CN ) 6 ]  e  [ Fe(CN ) 6 ]4 


The desired cell equilibrium is obtained as I + II – III.

[ Fe(CN )6 ]3  e   [ Fe(CN )6 ]4

 G   RT lnk

and G   nFE

G  G1  G2  G3 (4)

nFE   nFE 0  {RT ln  II }  {RT ln  III } (5)

RT RT
E  E0  ln  II  ln  III
F F

RT
E  E0  ln  II  ln  III  (6)
F

E 0 , the standard E MF of reduction potential of Fe III  Fe II in aqueous solution

a + 250 is 0.77.

log  II  24.0 log  III  31

 0.77  0.06 log 10  II  log 10  III 

 0.77  0.06 * (24  31)

 0.35

221
 If - the stability of complex in the higher oxidation state is larger than that in the lower
oxidation state
Then - The potential decreases.
IF - the stability of the complex in the lower oxidation state is larger than that in the
higher oxidation state sidered.
THEN - the potential of the redox couple increases.

Applications :

1) An oxidant can be made a reductant with respect to a species.

2) Thermodynamically feasible reaction can be made infeasible and vice versa.

[ Fe(OP)3 ]3
[ Fe(OP)3 ]2 

Ortho-Phenanthrouline forms a stronger complex with Fe( II ) with a stability

constant of log10  III  14.3

Substituting in Equation (6)

= 0.77 + 0.06 (21.3 – 14.3)

= 1.19

222
 Lesson No-29
PHOTO CHEMISTRY
Even if one is wrong it is forgorten soon if ever noticed,
it is ignored if not, gives a way for a newer finding

Photosynthesis in plants and vision in humans are explained by the principles of

photochemistry. There two essential phenomena are gifts of Nature to mankind. Science
enabled to understood details of the process. But there are no artificial counterparts ready
to use. However, liquid crystal display and photomedicine are fruit of science which find
industrial applications in clinical treatment and disgnosis.
Photo physical process : In monoatomic gases absorption of radiation excites an atom to
an excited state.
There is only one mechanism whereby it comes back to the normal state.
S*
S*

S
S

However, even in polyatomic system or in condensed phases (or in solvent or aqueous

solution), there are several other processes contributing to energy balance.
Whenever a system absorbs radiation several processes occur. If the excited molecule
gives products, it is called primary process. There are several techniques of audit viz.,
1) Mass balance.
2) Charge
3) Energy balance and
4) Photon balance
The time scale of some of the processes in photochemistry are given below.

Time Scales (SCC)

Electronic excitation 10-16 to 10-15

Fluorescence 10-12 to 10-6
Inter system Crossing (ISC) 10-12 to 10-4
Photosynthesis 10-6 to 10-1

223
 PHOTO CHEMISTRY
Absorption

Primary
S  hv  S *

Excited state absorption

S *  hv  S **

T *  hv  T **

EMISSION

S *  S  hv2  Flourescence

Deactivation with emission

S *  M  S  M  hv3

T *  M  T  M  hv4

Deactivation without emission

S *  M  S  M  heat

T *  M  T  M  heat

EXIMER formation

S *  S *  ( SS ) *

Energy Pooling

S *  S *  S **  ( S )

Electronic Energy Exchange

( S *)1  ( S ) 2  ( S )1  ( S *) 2

(T *)1  (T ) 2  (T )1  (T *) 2

224
 Lesson No-30
FLUORESCENCE
Middle age belief Angles pushed the planets around heavens.
Newton Intertia Kept them proving Theory of Relativity
Mass bends space

If the excitation source (U V Lamp, Sunlight, etc.) is removed and emission of radiation
persists for nanoseconds, then it is called flourescence. It is considered as a fast conversion
of absorbed energy into emission radiation. It excludes radiationless transfer.
Phosphorescence :
If the excitation source is removed and emission of radiation continues for fraction of
a second, and rarely hours, it is referred as phosphorescence. Here, there will be an initial
delay for the start of emission.
Fluorescence or Phosphorescence is explained by
1) Jabonowski diagram
2) Potential Energy (PE) plot and
3) Spectrum (absorption and emission)
Step 1 :

The molecule absorbs the radiation and it goes from S0 (electronic level) to one of
the vibronic levels of excited state S1. It results in the absorption spectrum.

R*
S=1

P.E

S=0

absorption Inter nuclear

distance.

Fluorescence
Spectrum
absorption
Intensity Spectrum

225
Step 2 :
The excited molecule collides with neighbouring ones and tries to transfer the energy
it absorbed. If the difference in energy of vibronic levels are small (unlike in water), then it
steps down the vibronic ladder until it reaches the electronic level of the excited state.
Now, the energy difference between the electronic level of S1 and vibronic levels of S0 is
high enough that other molecules cannot absolb.

R* Radiation less

(R*)

Step 3 :

A spontaneous emission from S1 to one of the vibronic levels of S0 resulting in

fluorescence spectrum.

(R*)
fluorescence

Step 4 :
Other radiationless transfers, dessipation of energy as heat etc., take place so that
all the molecules will be in the ground state. These are all exponential process.
Ex :

Why the frequency of fluorescence is smaller than excitation frequency and intensity
is also smaller?
The energy is dissipated during the stepping down of the electron in the vibronic ladder
of S1 state. Since the fluorescence spectrum arises due to the difference of energy of
S1 and S 0 states, the frequency at which a molecule gives fluorescence is lower
compared to the frequency of absorption.
The intensity of fluorescence depends upon the medium i.e., solvent molecules in
solution phase or ambient (laboratory) conditions. The vibronic levels of solvents widely
differ, and hence the amount of energy lost during interaction of solute with the solvent
changes. However, always the intensity of fluorescence is lower than corresponding
absorption spectrum.
Ex : Fluorescein, anthracene, naphthalene, etc.

226
 PHOSPHORESCENCE

Step :- (1) Absorption after excitation S o 

 S1 ______(1)

(2) Descending down vibronic level in S1 state (radiation less transfer) are same
both for fluonscence and phorphonsence. ______(2)

(3) At the point of intersection of the profiles of S1 and T1 , the energy is same.
Further, when the geometries of the two states are similar, the electron
jumps from S1 to T1 . It is called ISC (Inter system crossing). ______(3)

(4) The electron will descend down the vibrionic ladder of T1 till it reaches the

electronic level. Since, ET1   E S1  , it functions as a reservoir for the

energy. Now the electron has to go down from S1 to S0. It is forbidden.
However even in Inter system crossing, the rule is partially violated. ____(4)

(5) There is a slow leakage of energy that is, electron jumps from T1 to S0.

227
 Thus the frequency and intensity of phosponoscence spectra are lower than
even fluorosence spectra ______(5)
(6) The electron in the vibronic levels of so loses energy by heat, radialionless
transfer etc. ______(6)

(3) & (6) represent

Intersystem crossing

E(T1)  E(S1) to come back

E (osin) - type fluortcence :- E(osin) in presence of the deoxygenated glycerol (or)

ethyl acohol exhibits fluorosence. But the delay is noticeable compared to normal fluores-
cence. It is called   phosphoroscence, while normal phosphoroscence is known as
  phosphoroscence.

Step (1) Excitation :- S o  hv 

 S1

Setp (2) :- Descending down the vibronic ladder S1 .

Step (3) :- Inter system crossing  S1  

 T1  .

Step (4) :- Descending down vibronic level of T1 , is similar to

phosphonscence.

Step (5) :- When E  T1   E  S1  , delayed flourorcence is possible. By collision,

with other molecules the electron in T1 goes up the vibronic ladder..
At the point of intersection of PE curves, the electron goes back to
S1 from T1 . This is also inter system corssing (setp (6))

228
 Step(6) :- ISC T1  
  S1 

Step (7) :-  S1  
 . Like in the fouoroscence (with an exception) the electron
descends the vibronic ladder of S1.

Step (8) :- Fluorosence.   S 0   h 2

 S1  
The transition from S1 to S 0 renults is fluorosence . The delay is due
to steps (3)   (6) compared to the normal fluoroscence.
Step (9) :- The electron looses the energy in the from of heat, radiation less
transfer etc.
P (yrin) - type fluorcence :
In the case of P(yrin), Phenanthrene etc, another type of delayed fluorseence is
observed.
Steps (1) to (5) are common to ecosin type fluorscence.

Step (6) when E  S1  is not equal to E  T1  there is no possibility for I.S.C.

Here it is invokved (thought) that 2 triplet states interact resulting in
an eximer X. The eximer dissociates giving rise to S1 & S 0 states.

Step (7) S1  S 0  h 5 like fluoroscence

+ X#

S1 T1 T1

and X#

e going to the ground state S1

from the vibronic levels S0

229
 Lesson No-31
STERN-VOLMER EQUATION
Mother nature never published her results

Stern Volmer equation is developed for the quantum yield of a photochemical process
in presence and absence of a quenching substance. A quenching substance is a compound
which decreases or makes a fluorescent substance, non-fluorescent.

Step 1 : S  hv  S * (1) Vabs  I abs

(velocity of (Intensity of
absorption) absorption)
S *  S  hv f

Fluorescence:

v f  R f . [ S *]

Where vf = rate of fluorescence/velocity of fluorescence.

[ S *] = concentration at time t.
Internal Conversion (Non-radiative transfer)

S*  S

vIC  RIC [ S *] (3)

Internal conversion is a transition between electronically excited state S 1 and that of

the ground So.

S1
S2

Inter System Crossing (Non-radiative transfer) :

S* vISC  k ISC [ S *] (4)

There is no change in multiplicity.

If change of S* is zero, i.e., steady state is applicable.

230
 d [ S *]
Mathematically, 0 (5)
dt

 I abs  k f [ S *]  k IC [ S *]  k ISC [ S *]  0

The steady state is applicable to S* , if the intesity of excitation source is large and
absorption by the system is low.


 I abs  k f  k IC  k ISC  [S *] (6)

ISC : Inter system crossing .

At point of intersection, E S1  ET 1 .

abs. (2)

flu.
(1)
Phos. ISC
Intensity
Phos.
Relaxation.

hours

Quantum Yield :
The quantum yield in a photochemical process is defined as the number of primary
photochemical events divided by the intensity of absorption of light. From the kinetic
point of view, it is the ratio of rate of each of the photochemical events to the intensity of
light.

vf
 f  (7)
I abs

 f : Quantum yield of fluorescence

v f  Rate of fluoresecent phenomena.

k f [S *]
 f  (8)
(k f  k IC  k ISC ) [ S *]

231
 kf
 f  (9)
(k f  k IC  k ISC )

Equation (9) represents that quantum yield of fluorescence is a constant and depends
upon the magnitudes of rate constants k f , k IC and k ISC . It doesn’t depend upon intensity
of the source or concentration of excited molecules or even concentration of the substance.

f 1
  0 (10)
kf k f  k IC  k ISC

Whose 0 is called fluorescence time constant.

Quantum Yield In Presence of A Quenching Substance:

It is denived to explan the effect of quenching substance on the efficiency of
fluorcecence in absence of quenching substance. This equation explain the quantum
effciency, rate of flueroscence  f   & time constant   of the fluoroscence.
Step-1 :- When the intensity of the source (excitation) is high the fluoroscence is
low. The following equation holds good. The equation finds use in determining the rate
constant of fluoroscence rcactions. K fQ  

Denticity [Re(bipy)3 ]2

(bidentate)
Bipyridine

Ruthenium this bipyridine cation

This complex has a very strong charge transfer (CT) & the CT band is strong,
which is observed at 450nm.
The quenching is followed at 600mm.

K
fQ
(i) S *  h 
S * S *  Q   (10)
 S  Q 

(ii) S* IC  fQ  k fQ  S * Q  ____(11)

(iii) S* ISC  abs  I abs

(iv)  S  h 2
S * 

232
 Fluorescence in presence of a quencher or quenching subst.

2,21  bipyridene forms a tris complex with Ruthenium (II). It as a strong metal to
ligand charge transfer band at 450nm. Here aqua iron (II) has quenching effect on the
excited state of Ruthenium complex and the emission is monitored or observed at 600nm.
Here there is a red shift.
In presence of a quenching substance (Q), the rate of decrease of fluorescence.

fQ K
S *  Q   SQ _____(10)

 fQ  K fQ  S * Q  _____(11)

K fQ :- Rate constant of fluorscence in presence of a quencher or quenching substance.

The photon aider steps are sarre as those without quincher except emission.

Emission  K IC  S *  K ISC  S *  K f  S *  K fQ  S * Q  _____(2)

Applying the steady state hypothesis.


I abs  K IC  K ISC  K f  K fQ  Q   S *  _____(3)

 fQ  Quantum efficiency of fluoroscence.

Excitation, emission process in presence of quencher

Rate of fluorosence
 fQ 
Iabs from source

K fQ  S *
 _____(4)
K IC  K ISC  K f  K fQ Q S *
 fQ 1
  fQ  _____(5)
K fQ K IC  K ISC  K f  K fQ Q 
Time constant for flouroscence in presence

In absence of the quenching substance,   f  is equal to

 Kf 
=  f  K  K  K  _____(16)
 IC ISC f 

f 1
f   _____(17)
Kf K IC  K ISC  K f

233
Divide (17) by (15)

1
17  f K IC  K ISC  K f
 
15   fQ 1 _____(18)
K IC  K ISC  K f  K fQ Q 

f K IC  K ISC  K f  K fQ Q 
 _____(19)
 fQ K IC  K ISC  K f

K fQ Q 
 1  _____(20)
K IC  K ISC  K f

f
 1  K fQ . Q  .  f _____(21)
 fQ

1 1
  K fQ . Q  _____(22)
 fQ f

Eqn (22) is the stern volmer equation in the presence of quenching substance.

Assuming y  C  mx

1
A polt of  fQ against cone of quencling substance gives a straight line of intercept

1
 f & slope K fQ .

Applications :-

1. Stern volmer equation is employed to esti-

mate the rate constant of fluorescence &
time constant of fluorscence by monitoring
the florescence at different times.

Limitation:-
1. Steady state hypothesis limits the derivation. Otherwise for the forward & other
active reverse process separate equations are to be derived.

234
 Lesson No-32
GROTHUS DRAPER LAW
Mathematics is clear thinking, of one has clear thinking,
he has mathematical bent of mind

In photochemical events, only that part of radiation that is absorbed is responsible for
the primary process. The other part of the energy is accounted by thermal means, and
other side reactions.
Einstein Law of Photochemical Equivalence :
For every primary photochemical event one quantum of radiation (photon) is absorbed.
It doesnot mean that every photon absorbed results in a photochemical reaction.
It lead to the concept of quantum yield, since the efficiency of photochemical reaction
range between 10–5 and 10+5. Rarely, it is equal to 1.

Limitation : When molecules are exposed to high intensity radiation or LASERS, it has
been observed that the rate, is proportional to square of intensity of absorption. It is explained
by a biphotonic process wherein two photons are absorbed.

Case (i) S  2hv  S * *

Case (ii) S  hv  S *; S *  hv2 

Case (iii) S1  T  hv3  etc.

Beer - Lambert’s Law for Photochemistry :

It
Io
Lens Filter
source Ia

Fluorescence Spectrum of I2 :

I2 is exposed to filtered mercury lamp. The excitation latres place to B 3

04 electrone
level. The vibronoil level is v  25, J  34 . The resorcence fluorescence is observer
only from initially excited level. The two lines compound to  J   1 transition.

235
 Photo current (amp x 109

560
570 P (35) 25-3 R (33) 25-3 wave length nm

In presence of the, quenchis takes place, emission occurs from other vibranic or
rotated levels.
Photo current x 1010

27-3 24-4 26-1 R (33) 25-3 24-3 23-3

P (35)

Beer Lambert's Law :

Source
Lense Filter

236
 I 0  Intensity of incident radiation at a particular frequency  .
I E  Intensity of transmitted radiation.

E  Extinction coefficient (molar absorptivity coefficient).

C  Concentration in molarity (moles / litre).

l  Path length of the spectrophotometric cell (cuvette).

Io
Absorbance . A  log I  E.C.l
t

A  Absorbance at a wavelength  corresponding to a frequency)

It
 100  % transmission
I0

Species S1 S2 S3      SN ST

Concentration C1 C2 C3      CN CT

Extinction coeff E1 E2 E3      EN ET

Absorbance A1 A2 A3      AN AT

Appling Beers law for a number of species above,

A  E C l  E2 C 2 l 2       E N C N l N

A  A1  A2       AN

This is called extended Beer's law for multiple

solutions. For a single species the graph observed is
For a multispecies,
In Photochemistry of gaseous and solution phase reactions. Beer tambert's law is
applied for absorbance concentration.
In the gareous phase, conc. is expressed in Torr, pressure units and the equation
Io
employed is I  exp  E.C.l  . _____(1)
t

In solution phase, it is a practice to employ the logarthmic form ie

Io
A  log  E.C.l _____(2)
It

237
 Thus a plot of absorbance at a chosen wave length (maximum absorbance) Vs
concentration is a straight line with zero intercept & slope corresponding to E .

It is true only when the concentration is expressed in moles / lit. Another useful
It
measure is % transmittance given by  100 which can be converted into absorbance
Io
or vice versa.
Beer's law for multiple species :-

It there are N species, each with a concentration C N and extinetion coefficients

EN , then the total absorbance at a given frequency is

A  E1C1l2  E2C2l2       E N C N l N .

N
ie A   Ai
i 1

Here the assumption is that each species, follows Beer's law at the specified wave-
length. This is rarely realisable. However, if different species follow linear trends but with
different slope & intercept, the calibration curve looks like.

This graph is known as PIECE WISE LINEAR

CALIBRATION CURVE. A

Non linear Calibration Curves :-

Conc
When the speeceis follows a quadratic (or) exponentiae (or) cubic trend, the cali-
bration curves are

Non Linear Calibrations :-

quadratic
Cubic
Exponential

Beer's law in Matrix Notation :-

 E1  C1 
Conridinng E.C as column veetors, E   E2  , C  C2  .
 
 E3  C3 

238
 ET   E1 , E2 , E3 

 C1 
E .C . i   E1 , E2 , E3  C2  l  E1 C1 l  E2 C2 l  E3 C3 l  A
T

 C3 

Experimental Setup:-
Mercury vapour lamp Sodium Vapour lamp or Tungsten lamp etc. are used as a
source in normal spectrophotometers. The light rad" will be passed through a lens then, a
grating (or) prism (or) diode array will be used to obtain monochromatic light of desired
frequency or frequency range. Lasers, now result in pointed source of high intensity without
interference from other regions. Now the radiation passes through the reaction system
contained in a glass cell. The transmitted light (or) absorbed will be measured by a photo-
cell (or) complicated electronic circuits.

E1  h 1  1Photon

h E E
 No. of Photons  
 E1 h

E1  P.t

E P.t
 No. of Photons  
h h

No of moles of photons 
no of Photons
N

moles of subs tan ce

   coust
moles of photous

h  6.626  10 34 J
sec
C  2.997  10 8 m
sec
N  6.023  10 23 mole  1
P  J
 power  sec
t  sec
  m etres

No of moles of photon and  the energy of a single photo is the product of Plank's coustant
and freq. of radialion.

239
 hc
E1  h  ____(1)

For a total energy of E Einseins, the no of photons are

E E  .E
 No of photous   
E1 h hc

In photochemical experiments, the system is exposed to an excitation source of

power P for a time interval t .

Thus E  P. t

E P.t  .P.t
Hence no of photons   
h hc hc

To define quantum efficiency, no photons are expressed as no. of moles of pho-

tons, which is equal to the ratio of no of photons; to Avagadro no.
moles of subst reacted
 
No of moles of photons

The units of  are thus dimensionless,  being a constant

 in presence & obsence of Quenching substances:

 
From stern volumer equation, I abs  k IC  k ISC  k F  k fQ [Q ] [ S *] --------- (1)

If there is no internal convession & the quenching substance is absent.

I abs   k ISC  k F  [ S *] --------- (2)

k F is called rate constant for radialive process ( kr ) and knr as non radialive process
( K nr )

The total rate constant for the fluoresence;

ktotal  knr  kr -----------(3)

and total = Time const. for the total process is given by

total  1/ K tot

Problems :
1#. Integrated absorption data shows that quantum yield for fluoroscence from zero
level of benzene is   0.25 . The time constant for the total rate is 128 N.Sec.
What would be the fluorosence lifetime of benzene excited to this state if there
were no internal converssion
240
Solution:

If there is I.C; ktot  kr  knr

kr
f 
knr  k r  is defined either in terms of the subst reacted rate const. Hence
K f  Kr

k nr  k r k
 1/  f   nr  1
kr kr

knr
1/ 0.25  1/  f  1
kr

knr
4  1  knr  3 kr ------- (4)
kr

ktot  knr  kr  3 kr  kr  4 kn

1 1
ktot    4 kr
 t 128

kr  1 1 1
4  128 hence [ r  kr  1
 512 nano see ]

4 128

2#. Quantum yield of a photochemical reaction when a sample of 4-heptanone was

irradiated for 100 sec with 313 nm radiation with a power output of 50 W under
condition of total absorption. It was found that 2.8 millimoles of C2 H 4 formed what
is the quantum yield of ethene?

Sol : t  100 sec No. of photons absorbed

P.t
  313 nm 
h

 P. st
P  50 W 
hc
[C2 H 4 ] formed  2.8  10 3 moles
 ?

313  109  50  100

P 
6.6  1034  2.998  108

n n
No of moles of photons  N  6.022  1023  0.013087

241
 C2 H 4  formed 2.8  101
    0.21396
no of moles of photon 6.013087

3# In an expt, to measure the quantum efficiency of a photo-chemical reaction, the

substance is exposed to 498 nm light from 100W source for 45min. The intensity of trans-
mitted light is 40% of intensity of incident light. As a result of irradiation, 0.344 moles of
absorbing subtance is decomposed. Calculate the quantum efficiency.

  490 10 9 m

P  100W t  45  60  sees

Transmitted light = 40% I 0

(sub) decomposed = 0.344 moles

Abs. light = (100 – % T) I 0 = 60% I 0 = 0.6 I 0 .

490  109  100  45  60

No of photons  6.66  1023
h .c

6.66 1023
No of moles of photons =  1.106
6.022  1023

Moles of subst decomposed 0.344

    0.51807
no . of moles of photons 1.106  0.6

4#. In a photo chemical reaction; A  2 B  C . The quantum efficiency at 500nm is

2.1  102 mole Einstein 1 . After exposure of 300 millimoles of A, 2.28 millimoles of
B is found. How many photons are absorbed by A.
Step :
A 2B + C
Initial 300 m.moles 0
t 
A reacted 1.14 mmoles 2.28 mole  300  1.14

moles of a reacted 1.14  103

  2.1  102  
moles of photons no.of ph

1.14  103
n photons  2
 5.4286  106
2.1  10

No of photons  moels  N   6.023  1023

 3. 2691  1018 photons
242
 Lesson No-33
PHOTOCHEMICAL EQUILIBRIUM
Truth, knowledge and Nature are infinite

hv370 nm 
2 NO2  2 NO  O2 P
n 2 H n3  n  3 2 n  0

Box–1

hv
 Dimer
H

v f  R f  I abs

vr  Rr  [ Dimer ]

At equilibrium, v f  R f  I abs  Rr  [ Dimer ]

Rf
[ Dimer ]  I abs
Rr

When I abs . is constant , [ Dimer ]  constant

Box–2

hv
2SO2  O2  2SO3

Box–3

243
 Teacher teaches you. He won't help in examination.
Books are a medium. They do not accompany you.
What you have graspe alone helps you.

If either or both reactions of an equilibrium process happens to be a photochemical

then it is called photochemical equilibrium. It differs from conventional thermal equilibria in
that energy is given to the system by light. In the thermal equilibria it may be heat, mechanical
work, bond making, bond breaking etc. When the system attains photochemical equilibrium,
the additional energy due to the exposure by the source is converted into heat.

hv 370 nm
Ex : 1) 2 NO2  2 NO  O2
H

The forward process is photochemical, while the reverse is a thermal (non-

photochemical). As the reaction proceeds, the pressure of the system increases (since
 n  0 ). The products NO and O2 retort the reaction, when added to the system at
equilibrium. For quantum yield calculation, thermal reaction is to be taken into consideration,
and it is found to be 2.0
Ex : 2 : The dimerisation of anthracene is also a photochemical reaction with a thermal
reversible step.

 Dimer

At equilibrium, if the intensity of the source is kept constant, concentration of the

 kf 
dimer is a constant,   . It doesn’t depend upon the monomer concentration. For 100
 kr 
rise of temperature,

kf 1.1
  0.39
kr 2.8

And experimental value was 0.34. It indicates the influence of non-photochemical

processes.
hv1
Ex : 3) 2SO2  O2  2SO3
hv2

For the oxidation of SO2 , to SO3 there is no dark reactions (non-photochemical/

thermal). Here equilibrium constant is independent between 50  8000 C .

244
 Photosensitisation
The reaction of H 2 with O2 or CO with H 2O , N 2 , H 2 , etc. do not take place or occur
at infinitesimally small rate. The presence of a catalyst like an atom  Hg  , molecule  O3 
or compound (porphorin) etc. undergo photochemical primary process and induce the
chemical reactions otherwise not possible. These species are called photosensitisers and
the reaction photosensitisation.

A mixture of H 2 and O2 is saturated with mercury vapour and exposed with uv light
for a short time. The excited Hg atom forms a triplet state by inter system crossing  ISC 
and produces H. radicals. If it is with oxygen excited, oxygen radicals are founed. They
oxidise the reductant.

Hg  Hg *
Hg *  3Hg
Hg *  H 2  Hg  H .  H

Hg *  H 2  Hg H  H

Hg *  O2  1O2
1
O2  R  P

Ex : Formation of formaldelyde.
Photo Dynamic Theory (PDT).
A high intensity beam of laser is sent to the site of tumour through an optical fibre, the
drug administered reaches the turnour site and gets excited by laser.

P (orphoryn )  hv  P *  3 P )
3
P  tumor  partially oxidised product
Absorption spectrum of chlorophyl


 Ch  hv  Ch *

1
CO2  H 2O  (C6 H12 O6 )  O2
6

380 700


245
 For photochemical reaction, the activation energy is 38 k cal/mole at 700nm of excited
source. For dark reaction, the corresponding energy is 112 k cal.
Photolysis :

Ex : 1) CH 3COCH 3  CH 3CO  CH 3

(CH 3CO.)  (CH 3CO)2

CH 3CO.  CH 3 .  C2 H 6  CO

 1
Photolysis is the decomposition of a compound accomparied by a photochemical or
photoprimary process. The decomposition of acetone is activated at 310-313 nm. The
primary step is production of radicals followed by dimerisation. The final step results in the
product ethane. Since there is no chain reaction, the quantum yield is approximately one.
Here, C–C bond breakage is crucial.

Ex : 2) NH 3  NH 2  H (excitation wave length : 160 to 220nm)

Ammonia decomposes to NH 2 and various products including hydrazene. The low

quantum yield is due to third body collision. The yield increase from 0.15 at 200C to 0.50 at
4000C when exposed to light of 214nm. Further the yield decreases with increase in pressure.

HHH HHH

246
 Question Bank

Chemical Kinetics :
1. Discuss collision theory of reaction rates. What are the limitations of this theory?
2. Discuss in detail the transition state theory of reaction rates. In what way this theory
is superior to the rate of chemical reactions.
3. Using the equations of the theory of absolute reaction rates obtain expression for
entropy of activation and energy of activation and state their significance.
4. Describe the effect of dielectric constant on the rate of reaction.
5. Explain primary and secondary salt effects.
6. Derive an expression for the rate of a consecutive reaction
7. Discuss the kinetics of chain reactions. Explain Explosion limits.
8. Describe the kinetics of opposing reactions involving unimolecular steps.
9. Explain briefly the elementary ideas of Lineal Free Energy Relationships (LFER’s)
in the study of rate of reactions.
10. Write a note on Hammett equation.
11. Write a note on Tuft equation.
12. Give a brief account of mechanism of homogenous catelysed reactions
13. Give an account of acid-base catalysis.
14. Discuss briefly (a) Redox-catalysis (b) Euyyme catalysis
15. Discuss briefly theories of heterogenous catalysis.
16. Give a detailed account of study of fast reactions using flow and relaxation meth-
ods.
17. Give an account of theories of electrolytes. What is Delye-Onsaygar equation. Ex-
plain the terms.

Photochemistry :
1. State and explain laws of photochemistry
2. Write notes on
(i) Intersystem Crossing and Internal Conversion
(ii) Photosensitization and Photochemical equilibrium
(iii) Photolysis with examples.

247
3. Explain Fluoroscence and Phosphorescence
4. Write notes on stern-volumer equation
5. What is quantum yield. Account for the high quantum yield of Photochemical com-
bination of Hydrogen and Chlorine.

Electrochemistry :
1. What are Electrochemical cells.? What is the difference between Electrolytic and
galvanic cells.
2. Explain the effect of complexation on Redox Potential.
3. What are concentration cells? Derive an expression far Electrode Potential of a
concentration cell without transference.
4. What is liquid-Junction Potential? How it will be eliminated?
5. Derive Debye Huckle limiting law.
6. Explain EMF method to determine the activity coefficient of an electrolyte.
ESR Spectroscopy :
1. Explain the origin of Hyperfine splitting in ESR spectrum.
2. Discuss the principles and applications of ESR studies to the structure of free radi-
cals.
3. Explain the Principle and experimental techniques involved in ESR studies.

248