UNIT – I

1.1. GROUP THEORY - CONCEPTS

Symmetry Elements
Symmetry elements are defined as imaginary geometrical entities such
as points, lines and planes that are present in a molecule, about which when
symmetry operations are performed, the molecule presents an indistinguishable
configuration. The nature of symmetry elements present in any molecule
depends on its geometry.
What are indistinguishable configurations?
These are spatial arrangements which cannot be distinguished from
one another. The two configurations are alike in all respects (but are not
exactly identical) and it is difficult to predict if any change has been carried
out or not. However, they can be differentiated by introducing appropriate
suffixes in the form of numbers or letters. For example, configurations I and
II (Fig.1) are indistinguishable but for the suffixes 1 and 2 on the B atoms.

Fig. 1

Symmetry Operations
These are simple geometric operations such as reflection, rotation or
inversion which when performed on the molecule, give rise to an
indistinguishable configuration of the same molecule. Thus, the presence of
symmetry elements in a molecule can be identified by performing the
appropriate symmetry operations (Table 1).
Table 1: Types of symmetry elements and their corresponding
symmetry operations
Symmetry element Corresponding symmetry operation
Identity element (E) or (I) doing nothing (360° rotation)
Plane of symmetry () reflection
Centre of symmetry (i) inversion of all coordinates
Proper axis of symmetry (Cn) rotation through an angle of (360/n) about
an axis where n is the order of the axis
Improper axis of symmetry rotation through an angle of (360/n) about
(Sn) an axis followed by reflection about a plane
perpendicular to the original axis

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Identity Element (E)
The identity element is present in all molecules. Identity is the
operation of not doing anything. When a molecule is not operated upon by
any symmetry element, the system is left unchanged and the configuration of
the molecule is identical with the original configuration. Thus, the molecule
is said to possess the identity element. It is denoted by the symbol E. Though
it may appear that this element does not have any significance, its
mathematical relevance will be clear as we proceed further.
Plane of Symmetry ()
When reflection is carried out about an imaginary plane in a molecule
and if the molecule presents an indistinguishable configuration, the plane is
called a plane of symmetry. It is represented by . A molecule may have one
or several planes of symmetry or may not have any such plane. Let us identify the
symmetry planes present in molecules possessing different geometrics.
Note: All linear molecules have an infinite number of planes of symmetry.
AB2 (Bent)
All molecules of this type possess two planes of symmetry. An example
of such a molecule is H2O.
(i) One plane of symmetry passes through atom A and
bisects the line joining the two B atoms which are identical (Fig. 2).
But for the subscripts, the atoms B 1 and B2 in the two configurations
cannot be distinguished.

Fig. 2
(ii) The molecular plane: It is the plane in which the molecule
lies. When reflection is done about this plane, the molecule reflects
onto itself and presents an indistinguishable configuration.
Note: All planar molecules have the molecular plane as one of the planes
of symmetry.
AB3 (Planar)
A triangular planar molecule will have the following planes of symmetry.
(i) A molecular plane (since it is planar);
(ii) A plane passing through one of the B atoms (say B1) and A
which bisects the line joining the other two B atoms (B2 and B3).
Similarly, there are two other planes of symmetry, that is, a plane
passing through A and B2 which bisects the line joining B1 and B3, and
a third plane passing through A and B3 which bisects the line joining B1
and B2 (Fig. 3). An example of this type of molecule is BCl3.
2
 Fig. 3
Thus, a tetra atomic AB 3 planar molecule has four (1 + 3) planes of
symmetry.
AB3 (Pyramidal)
This type of molecule has three planes of symmetry. Each plane passes
through A and one of the B atoms (B1, B2 or B3) and bisects the line joining
the other two B atoms (Fig. 4). There is no molecular plane of symmetry. An
example of this type of molecule is NH3.

Fig. 4
AB4 (Square planar)
In a square planar molecule, the following planes of symmetry exist
(Fig. 5 and Fig. 6).

Fig. 5 Fig. 6
(i) A molecular plane (since the molecule is planar);
(ii) Two planes of symmetry exist, each passing through atom
A and bisecting the line joining the adjacent B atoms on either side.
(iii) Two diagonal planes each passing through A and the two
diagonally opposite B atoms.
Thus, such a molecule will possess a total of five (1+2+2) planes. An
example of this type of molecule is [PtCl4].
AB4 (Tetrahedral)
In a tetrahedral molecule, there is no molecular
plane. There are six planes of symmetry, each passing
through A and two B atoms (AB1B2, AB2B3, AB3B4, AB4B1,
AB2B4, AB1B3) (Fig. 7). An example of this type of
molecule is CH4.
Fig. 7
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AB5 (Pentagonal)
In a pentagonal molecule, the following planes of
symmetry exist (Fig. 8).
(i) Molecular plane;
(ii) Five symmetry planes each passing
through A and one of the B atoms and bisecting
the line joining adjacent B atoms on the opposite
face. Fig. 8
Thus, the molecule has a six (1 + 5) planes of
symmetry. This type of molecule is hypothetical.
AB5 (Trigonal bipyramidal)
A trigonal bipyramidal molecule has the following
planes of symmetry (Fig. 9).
(i) A plane of symmetry passing through A
and the three equatorial B atoms (B1, B2, B3);
(ii) Three planes of symmetry, each passing
through A, the two axial B atoms (B4 and B5) and
one equatorial B atom.
Thus, the molecule has four (1 + 3) planes of Fig. 9
symmetry. An example of such a molecule is PCl5.
AB5 (Square pyramidal)
In a square pyramidal molecule, the planes of
symmetry that exist are as follows (Fig. 10).
(i) Two planes of symmetry, each passing
through A and the axial B(B1) which bisects the line
joining adjacent B atoms on both sides;
(ii) Two diagonal planes of symmetry,
each passing through A, the axial B and the two Fig. 10
diagonally opposite equatorial B atoms.
Thus, the molecule has four (2+2) planes of symmetry. An example of
such a molecule is IF5.
AB6 (Octahedral)
In an octahedral molecule, the following planes of symmetry exist
(Fig. 11).
(i) Six planes passing through the opposite edges of the
octahedron;
(ii) Three planes passing through A and the
four equatorial B atoms and bisecting the line joining the
axial B atoms.
Thus, the molecule will have a total of nine (6+3)
planes of symmetry. An example of this type of molecule is
[Cr(CO)6]. Fig. 11
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Centre of symmetry (I)
When the coordinates (x, y, z) of every atom in a molecule are changed
into (x, y, z) and even after that, if the molecule presents an
indistinguishable configuration, then the point of origin (0, 0, 0) is called the
centre of symmetry of the molecule. That is, if an imaginary line is drawn
from an atom to the centre of the molecule and extended on the other side by
the same distance and meets a similar atom, the molecule is said to possess a
centre of symmetry or a centre of inversion. For example a cube, a sphere
and an octahedron possess a centre of symmetry whereas a triangle and a
pyramid do not.
Whenever diagonally opposite atoms are the same in a molecule, the
molecules will have a centre of symmetry and vice versa.
Proper axis of symmetry (Cn)
A proper axis of symmetry is defined as an imaginary axis present in a
molecule about which, when the molecule is rotated through an angle of
(360/n)°, the molecule presents an indistinguishable configuration. Here, n
represents the order of the axis and can take whole number values. When n = 2,
the axis is referred to as the C2 or the diad axis; when n = 3, the axis is
referred to as the C3 or the triad axis and so on.
The nature of Cn axis present in a molecule varies with its geometry.
All linear molecules, when rotated through any angle with respect to their
bond axis, present an indistinguishable configuration and hence possess an
axis of symmetry which is called the C axis. An example of this kind of
molecule is HCl.
AB2 (Bent)
Such a molecule has a C2 axis of symmetry (Fig. 12). An example of
this kind of molecule is H2S.

Fig. 12
AB3 (Planar)
Such a molecule possesses one C3 axis of symmetry and three C2 axes
of symmetry.

Fig. 13
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 An example of this kind of molecule is BCl3.

Fig. 14
AB3 (Pyramidal)
Such a molecule possesses only the C3 axis of symmetry.

Fig. 15
AB4 (Square planar)
This molecule has one C4 axis of symmetry and four C2 axes of
symmetry. The C4 axis is the imaginary line passing through A and
perpendicular to the molecular plane (Fig. 16).

Fig. 16
As already pointed out, this molecule has four C2 axes of symmetry.
Out of these, two pass through A and bisect the line joining adjacent B atoms
on both sides (Fig. 17).
The remaining two C2 axes pass through A and two diagonally
opposite atoms (Fig. 18). All the four C2 axes lie in the molecular plane and
are perpendicular to the principal C4 axis. An example of this type of

molecule is PtCl4.
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 Fig. 17 Fig. 18
Note: When a molecule has more than one Cn axis, the highest ordered
axis is referred to as the principal axis of symmetry.
AB4 (Tetrahedral)
This type of molecule has four C3 axes of symmetry and three C2 axes
of symmetry. For example, the axis passing through B1 and A is a C3 axis and
there are four such axes present in the molecule. (Fig. 19)

Fig. 19
Three C2 axes are present in the molecule; two are shown (Fig. 20). An
example, of this type of molecule is [Ni(CO)4].
AB5 (Pentagonal)
Thus type of molecule has one C5 axis of
symmetry and five C2 axes of symmetry. The C5 axis is
the imaginary line passing through A and is
perpendicular to the molecular plane (Fig. 21). Fig. 20

Fig. 21
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 The C2 axis is the imaginary line passing
through A and one of the B atoms (say, B1) in the
molecular plane and it bisects the line joining the two
B atoms (B3 and B4) on the opposite side. It lies in the
molecular plane (Fig. 22).
There are five such axes present in this molecule
and they are perpendicular to the principal C5 axis. Fig. 22
AB5 (Square pyramidal)
This type of molecule has a C4 axis. This is an imaginary line that
passes through A and the axial B atom (B5 in Fig. 23). It is perpendicular to
the square plane of the molecule. An example of this type of molecule is IF5.

Fig. 23 Fig. 24
AB6 (Planar)
This type of molecule has one C6 axis of symmetry and six C2 axes of
symmetry. The C6 axis is the imaginary line passing through A and is
perpendicular to the molecular plane (Fig. 24).
There are six C2 axes present in this molecule. Out of these, three are
imaginary lines that pass through A and two B atoms lying opposite to each
other (Fig. 25). That is, they pass through B1 – A – B4, B2 – A – B5 and
B3 – A – B6.

Fig. 25 Fig. 26
The remaining three C2 axes pass through A and bisect the line joining
two adjacent B atoms on both sides (Fig. 26). All the six C2 axes lie on the
molecular plane.
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AB6 (Octahedral)
This molecule has three C4 axes of symmetry,
four C3 axes of symmetry and six C2 axes of symmetry.
The C4 axis is the imaginary line passing though A
and two diagonally opposite B atoms. There are
three such axes present. They are, the lines passing
through B5 – A – B6, B2 – A – B3 (Fig. 27).
The C3 axis is the imaginary line passing
through A and the centres of the two triangles (two
faces of the octahedron) opposite to each other. Fig. 27
There are eight triangular faces in an octahedron
and hence four C3 axes are present in this molecule.
The C2 axis is the imaginary line passing through A and bisecting the
line joining the two adjacent B atoms on opposite sides. That is, it passes
through A and two opposite edges of the octahedron. Since there are twelve
edges in an octahedron, six C2 axes exist in the molecule.
Improper axis of symmetry (Sn)
When a molecule is rotated about an axis through an angle of 360°/n,
followed by reflection about a plane perpendicular to the originally chosen
axis, if it presents an indistinguishable configuration, it is said to possess an
improper axis of symmetry. This axis is represented by Sn. Molecules having
an improper axis of symmetry can be classified into two types.
 Molecules having both, an axis of symmetry (Cn) and a
perpendicular plane of symmetry ().
 Molecules having neither an axis of symmetry nor a plane of
symmetry but having only an
improper axis of symmetry (Sn).
An example for the first type is
BCl3 (Fig. 28). In this molecule, the
C3 axis is perpendicular to the molecular
plane. Rotation through 120° (C3)
followed by reflection about the
molecular plane gives an indistinguishable
configuration. Hence, the molecule is
said to possess an improper axis of Fig. 28
symmetry (S3). Hence the C3 axis is
also the S3 axis.
An example for the second type is, the staggered conformation of
ethane. Consider the end-on view (Newmann Projection) of the staggered
conformation of ethane (Fig. 29).

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 Fig. 29
Rotation about the C–C bond through an angle of 60° followed by
reflection about a perpendicular plane at the centre of symmetry gives an
indistinguishable configuration. Hence the C–C bond axis is the S6 axis.
Associated Operations of Sn
Rotation about an axis through an angle of (360/n)° followed by
reflection about a perpendicular plane can lead to an indistinguishable
configuration but not the original configuration. However, by repeating the
two processes many times, the original configuration can be arrived at. The
number of times the process has to be repeated to get the original
configuration is referred to as the associated operations of the Sn axis. The
total number of associated operations of the Sn axis depends on whether n is
even or odd. An assumption is made that Cn and n commute which is true in
most cases.
Example: Associated operations of the S2 axis
Mathematically, the associated operations of the S2 axis are represented
as follows.
;
Associated operations of the S4 axis
Mathematically, the associated operations of the S4 axis are represented
as follows.
;

Therefore, they can be listed as C2, and E.

Associated operations of the S4 axis
They are represented as,
;

;
Thus, an even-ordered improper axis of symmetry is associated with n
number of operations where n is the order of the axis. It is interesting to note
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that the associated symmetry operations of the Sn axis (where n is even)
include the associated symmetry operations of the Cn/2 axis. That is, the Cn/2
axis is also the Sn axis when n is even.
Associated operations of the S3 axis
Mathematically, the associated operations are represented as,
;

;
Thus, the S3 axis is associated with six symmetry operations.
Associated symmetry operations of the S5 axis
The associated operations are represented as,
;

;
Thus, the S5 axis is associated with 10 symmetry operations. In
general, the Sn axis of odd order is associated with 2n number of symmetry
operations. The associated operations of the odd ordered Sn axis include the
associated operations of the Cn axis. This indicates that the Cn axis of odd
order is also the Sn axis of the same order.
Horizontal planes (h), Vertical Planes (v) and dihedral planes (d)
The various symmetry planes present in molecules of different shapes
have already been discussed in detail. These planes can be classified into
three types-horizontal planes (h), vertical planes (v) and dihedral planes (d).
Horizontal planes (h)
Horizontal planes are those planes that are perpendicular to the
principal axis of the molecule. For example, in the BCl3 molecule, the C3 axis
is the principal axis. It passes through boron and is perpendicular to the
molecular plane. Hence, the molecular plane becomes the horizontal plane as
it is perpendicular to the principal axis.
Vertical Planes (v)
Planes containing the principal axis are referred to as vertical planes.
For example, in the water molecule, the principal axis is the C2 axis passing
through oxygen. Both the molecular plane and the other plane passing
through oxygen and bisecting the line joining the two hydrogen atoms
contain the C2 axis and are thus referred to as vertical planes.

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Dihedral planes (d)
Planes bisecting two C2 axes are referred to as dihedral planes. For
example, the planes that exist in the staggered conformation of ethane are
dihedral planes.

Product of Symmetry Operations

The product of any two symmetry operations is also a symmetry
operation. The product depends on the order in which the symmetry operations are
carried out. Generally, the order in which symmetry operations are performed
is represented from right to left.
For example, if the symmetry operation A is carried out first followed
by B, it is represented as B  A.
Determination of the Product of Symmetry Operations
The product of symmetry operations can be determined either by
choosing a point with its respective coordinates (Method 1) or an appropriate
molecule (Method 2) or through a matrix (Method 3). All these methods can
also be extended to determine the product of more than two symmetry
operations.
Method 1
Let a symmetry operation A be performed on a point with its
coordinates as x1, y1, z1. Let the transformed coordinates be x2, y2, z2. Now, if
a second symmetry operation B is performed on x2, y2, z2, let the resultant
coordinates be x3, y3, z3. A single symmetry operation C has to be identified
which can directly transform x1, y1, z1 to x3, y3, z3 which is the product of the
symmetry operations A followed by B performed on the point as shown
below.

For example, consider a rotation by 180° about the x axis followed by a

rotation by 180° about the z axis.

The effect is the same as a single rotation by 180° about the y axis.
Limitation: The limitation of this method is that it cannot be applied to
products involving higher ordered proper axis of symmetry (Cn).
Method 2
A molecule that has both the symmetry operations for which the
product has to be determined, is chosen. The desired symmetry operations are
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performed one after another in the respective order and the new configuration
is obtained for the molecule. Now, a single symmetry operation which can
directly transform the molecule from configuration I to configuration III has
to be identified which is the product of the two symmetry operations. For
example, to find the product of C3(z) followed by v1. Consider the ammonia
molecule since it contains both C3 and v.

Fig. 44
v1 is the plane passing through nitrogen and the hydrogen on the left
and v2 is the plane passing through nitrogen and the hydrogen at the back.
v1  C3(2) = v2

Commutative Symmetry Operations

Two symmetry operations A and B are said to be commutative when
the product of these two symmetry operations remains the same irrespective
of the order in which they are carried out. That is,
AB=BA=C
To find out whether xz and xy are commutative, the two binary
products xz  xy and xy  xz are determined. If the products are the same,
then these two operations are said to be commutative.

Therefore, xy  xz = C2(x).

Since xz  xy = xy  xz = C2(x), these two operations are
commutative.

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Group Postulates and Types of Groups
1. Two elements of a group combine to give the third element of
the group.
2. An element combines with itself to form another element of the
group.
3. Every group consists of one element which commutes with all
the elements and leaves them unchanged. This element is known as the
identity element E.
4. Every element of the group obeys the associative law of
combination.
If A, B & C are three elements of the group then (AB)C = A(BC).
5. Every element has an inverse or reciprocal which is also an
element of the group. The element and the inverse combine to give the
identity element.
6. Addition or multiplication of a symmetry operation can be the
combination process of the elements of a group.
Multiplication table, subgroups and classes
The elements of group can be listed in a table known as the
multiplication table. This table reveals the different relations between the
elements of a group.
(eg.) symmetry operations of water.
E C2'  v'
E E C2' v v'
C2' C2' E v' v
v v v' E C2'
v' v' v C2' E
Subgroups
Any subset of a collection of elements which forms a group is called a
subgroup. The elements of a sub group should obey the following conditions.
1. The elements should satisfy all the rules of the group.
2. If g is the order of the group and s is the order of sub group
then g/s is a natural number.
(eg.) consider H2O.
The subgroups in this molecule can be identified using the multiplication
table for H2O molecule, there are 4 subgroups.
(1) E (2) E & C2' (3) E & v (4) E & v'
Classes
1. Two elements A and B in a group form a class if they are
conjugate to each other.

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2. Conjugate elements are related by the equation X1AX = B where
X is another element of the group.

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Similarity Transformation
If A & X are the two elements present in the P then X-1 AX = B is the
similarity transform of A by X. X is known as the similarity transform
element.
X is known as the similarity transform’ element. The similarity
transform” of one element by another may be used to find whether a set of
elements form a class.
(eg) H2O the similarity transform of a particular operation is obtained
with all the operations as follows
; ; ;

belongs to a separate class since similarity transformation of with

all the operations generates .
It is found that the other operations of water molecule also belong a
separate classes. In every group the identity operation belongs to a separate
class since it commutes with all the symmetry operations (a) every operation
in an Abelian group belongs to a separate class.
Types of groups
A group in which all elements commute is called an abelian group. If A
& B are two elements of an Abelian group, AB = BA.
(eg) set of symmetry operations of water molecule.

A group is said to be non-Abelian if all the elements do not commute

with one another. (eg) Phosphine

different configuration do not commute.

i) A group is said to be cyclic if all the elements of a group can be

generated from one element.
ii) A, A2, A3, ...,An form the elements of cyclic group with A 11 as the
identity element, n refers to the total no of elements and is called the
order of the group. (eg) Trans -1, 2-dichloro cyclic propane H2O2
symmetry operations of these molecules form cyclic group of order two

Order of the group

It is defined as the number of elements in a group. The order is
denoted by the letter ‘n’ (eg). The group contains
 The order is 4.

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Symmetry Elements and Point Groups
Group
A group is defined as any set or collection of elements which obey a
certain set of mathematical rules and are related to each other by certain
rules. The elements could be numbers, matrices, vectors, roots of an equation
or symmetry elements. For example,
 All positive and negative whole numbers together with zero
form a group under the combining operation of addition.
 Elements 1, 1, i, i (where i= ) form a group under
multiplication.
 All powers of two ..., 2 2, 21, 20, 21, 22,... form an infinite group
under multiplication.
Mathematical Rules for the Formation of a Group
The elements of any group must obey the following rules.
 The combination of any two members of a group and the square
of every member of a group should also be a member of that group (this is
known as the closure property). Let A and B be the members of a group
under the multiplication operation. If A multiplied by B gives C, A
multiplied by A gives D, and B multiplied by B gives G, then C, D and G
should also be members of the group. (C, D and G can also be the same as
A or B).
 The group must contain one and only one identity element (E)
which has the property AE = EA = A for all elements of the group.
 The associate law of combination should hold good. (i.e) A(BC)
= (AB)C.
 The inverse of every element should also be a member of the
group. The inverse of any element X is denoted by X1 which when
combined with the element itself results in the identity element. It can be
represented by the following equation.
X1X = XX1 = E
Let the inverse of  be 1 Therefore, 1 = E according to the
definition. Since it has already been proved that 2 = E, 1 = .
Similarly, we can prove that the inverse of i is i itself, and C2 is C2 itself.
But the inverse of C3 is since =E. In general, the inverse of any Cn is
(Cn) and the inverse of any Sn is (Sn) when n is even and (Sn)2n1 when n is
n1 n1

odd.
Definition and Classification of Point Groups
A point group is a collection of the symmetry elements present in a
molecule that obeys the mathematical rules for the formation of a group.
During the application of various symmetry operations in a molecule, the
centre of mass does not shift and therefore all the axes, points and planes of
17
symmetry of the molecule intersect at one common invariant point (center of
mass) and hence the term point group is used. The point groups are
represented by Schoenflies symbols. Table 2 summarises the various point
groups and their corresponding symmetry elements.
Table 2: Point groups and their symmetry elements
Point
Symmetry Elements
group
C1 E
Cs E, 
Ci E, i
C2 E, C2
C3 E, ,
C4 E, , ,
C5 E, , , ,
C6 E, , , , ,
C2v E, C2, v1, v2
C3v E, , , v1, v2, v3
C4v E, , , , v1, v2, v3, v4
C5v E, , , , , 5v
C6v E, , , , , , 6v
Cv E, C, infinite number of v
C2h E, C2, h, i
C3h E, , , h, ,
C4h E, , , , h, ,
C5h E, , , , , h, , , ,
C6h E, , , , , h, , , i, ,
D2 E, C2, 2  C2
D3 E, , , 3  C2
D2h E, C2, 2  C2, 2h, 2v, S2 = i
D3h E, , , 3C2  C3, h, , ,i
D4h E, , , , 4C2  C4, h, 4v, , ,i
D5h E, , , , , 5C2  C5, h, 5v, , , ,
D6h E, , , , , , 6C2  C6, h, 6v,
, , i, ,

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 Dh E, C, infinite number of C2, h infinite number of , i
D2d E, 2d, 3 mutually  C2, ,
D3d E, , , 3C2  C3, 3d, , ,i
D4d E, , , , 4C2  C4, 4d, , , ,
D5d E, , , , , 5C2  C5, 5d, , , , ,i
D6d E, , , , , , 6C2  C6, 6d, ,
, , , ,
S4 E, C2, ,
S6 E, , , , ,i
Td E, 8C3, 3C2, 6S4, 6d
Oh E, 6C4, , 8C3, 6C2, 3h, 6d, I, 8S6, 6S4
Ih E, , , 20C3, 15C2, 15d, 20S6, , i,

The point groups C1, Cs and Ci are generally referred to as low

symmetry point groups as they have either one or two symmetry elements.
The Cn point groups have the Cn axis as the only symmetry element.
However, n number of associated symmetry operations of the Cn axis are
present in the Cn point groups. The Cnh point groups have an additional h
along with the Cn axis. The Cn axis can generate n number of associated
operations and the combination of Cn and h generate n number of symmetry
elements corresponding to the Sn axis thus accounting for 2n symmetry
operations.
E, , , ------ , h, , , ------, or
The Cnv point groups contain the Cn axis and nv. The Cn axis can
generate n symmetry elements and an additional n number of vertical planes
thus accounting for 2n symmetry elements (E, , , ------, , nv).
Dn point groups contain, in addition to the Cn axis, a set of nC2 axes
perpendicular to it. n number of associated operations of the Cn axis and n
number of C2 axes perpendicular to the Cn axis together account for the 2n
symmetry elements of this group.
Dnh point groups have a h in addition to a set of Dn group elements,
that is, Cn and n perpendicular C2 axes. The presence of h and nC2 axes
perpendicular to Cn automatically implies the presence of n v. Cn axis and h
can generate n number of Sn symmetry elements. Thus there are 4n number of
symmetry elements present in this group.
Dnd point groups have the Cn axis, nC2 axes perpendicular to it and n
number of vertical planes. Such groups are additionally associated with n
19
 number of symmetry operations of the S2n axis. Thus, a total of 4n symmetry
elements are present in the point group.
Symmetry axes of special point groups like Td and Oh are illustrated in
the following figures.

Td point group Oh point group

Table 3: Symmetry elements and point groups of molecules

Search of minimum
Complete list
S. symmetry elements for Point
Molecule of symmetry
No. identification of point group
elements
groups
Acetylene C axis is present (bond axis), E, C, C2,
1. Dh
H–C = C–H i is present h, v, i
Carbonyl C axis is present (bond axis)
2. Cv E, C, v
sulphide no i
3. Water One C2 axis is present (passes C2v E, C2(Z), v1,
O through O and bisects the v2
line joining the two H atoms.
H H No h, 2v present (molecular
plane and the plane passing
20
 Search of minimum
Complete list
S. symmetry elements for Point
Molecule of symmetry
No. identification of point group
elements
groups
through O and bisecting the
line joining the two H atoms).
One C2 axis present (it
passes through the centre of
Trans-
5. the molecule and is  to the C2h E, C2, h, i
dichloroethylene
molecular plane) h present
(molecular plane)
One C3 axis (passing through
nitrogen and the centre of
the triangle having fluorines
at the corners), h sent, 3v
Nitrogen
6. present (each passing through C3v E, C3, 3v
trifluoride
nitrogen and one of the
fluorine atoms and bisecting
the line joining the other 2
fluorine atoms)
One C3 axis (passing through
the C and Cl atoms and also
Methyl chloride through the centre of the
Cl triangle formed by joining
the three hydrogen atoms), E, , ,
7. C3v
C h absent, 3v present (each 3v
passing through C, Cl atoms
H H H and one of the H atoms, and
bisecting the line joining the
other two H atoms)
3C2 axes present (the
principal C2 axis bisects the
C=C bond and is  to the
molecular plane, the second
Ethylene
H
C2 axis passes through
H
C=Cbond and bisects the E, 3C2, h,
12. D2h
C C line joining the adjacent H 2v, i
on both sides, the third C2
H H
axis bisects the C=C bond
and is in the molecular
plane), h is the molecular
plane
14. Boron C3 axis present (passes through D3h E, , ,
trichloride B and is  to the molecular
3v, 3  C2,
plane), 3C2  to C3 present
(each C2 passes through B h, ,
and one of the Cl atoms and
21
 Search of minimum
Complete list
S. symmetry elements for Point
Molecule of symmetry
No. identification of point group
elements
groups
Cl
bisects the line joining the
B other two Cl atoms), h
present (molecular plane)
Cl Cl
C4 axis present (passing
through Pt and  to the
[PtCl4] molecular plane), four  C2 E, , ,
Cl Cl
axes also present (2C2 axes
passing through Pt and the C2, , 4C2
15. Pt
D4h
diagonally opposite Cl  C4, h, 43,
atoms, the other two C2 axes
Cl Cl
passing through Pt and , ,i
bisecting the line joining the
adjacent Cl atoms on both
C6 axis present (passes
E, ,
through the centre of the
molecule and is  to the ,
Benzene molecular plane), 6C2  to
,
H C6 (3C2 axes pass through
H 1 H the centre of the molecule ,
6 and bisect the line joining
18. 2 D6h , 6C2 
5
the adjacent H atoms on
4
3 both sides, the other three C6, h, 6v,
H H C2 axes pass through the
H S6, (
centre of the molecule and
the two opposite H atoms), h=S6), ,
h is the molecular plane,
, ,i
6v are present
Chlorobenzene One C2 axis present (it
Cl passes through Cl, C1 and
H
6
1 H C4 atoms), h absent, 2v
19. 2 present (the molecular plane C2v E, C2, 2v
5
3
and the plane passing
H
4
H through the Cl, C1 and C4
H atoms)
24. p-dichloro 3C2 axes present (principal D2h E, C2, h, 2C2
benzene C2 axis passes through the  C2, 2v, i
centre of the molecule and
is  to the molecular plane,
the second C2 axis passes
through C1 and C4, the third

22
 Search of minimum
Complete list
S. symmetry elements for Point
Molecule of symmetry
No. identification of point group
elements
groups
Cl
H
6
1 H C2 axis bisects the C2, C3
2 bond on one side and the C5,
5
3 C6 on the other), h is the
4
H H molecular plane
Cl
One C3 present (passes
through the C–C bond), 3C2
Eclipsed ethane
HH  to C3 (every C2 axis E, , ,
bisects one front and one
31. D3h 3C2  C3, 3v,
back H atom on both sides),
h is present (passing h, ,
HH HH
through the plane bisecting
the C–C bond)
One C3 present (passes
Staggered through the C–C bond), 3C2
ethane  to C3 (every C2 axis E, , ,
H H H bisects one front and one
32. D3d 3C2  C3,
back H atom on both sides),
3d (passing through the 3d, ,
H H
H front –CH and back –CH
and bisecting the two C2 axes)
Ferrocene One C5, 5C2  to C5 present E, , ,
42. (neither eclipsed (as before), h absent, v D5 , ,
nor staggered) absent
5C2C5

Transformation Matrices for Symmetry Elements

Transformation Matrix for Identity Element
Consider a vector having the coordinates (x1, y1, z1). When the
identity operation ‘E’ is performed on this vector, let the coordinates be
changed to (x2, y2, z2).

Since by definition, the identity operation should not change any

coordinates, x2 = x1, y2 = y1 and z2 = z1.
The new position of the vector can be defined in terms of the original
coordinates of the vector and the relationship between (x 2, y2, z2) and (x1, y1, z1)
can be expressed as a set of mathematical equations.
x2 = (1  x1) + (0  y1) + (0  z1)
y2 = (0  x1) + (1 + y1) + (0  z1)
23
 z2 = (0  x1) + (0  y1) + (1  z1)
These equations can be combined to give the following matrix equation.

The matrix is the transformation matrix for E since it

indicates the net quantitative effect of E on the vector. A 3  3 matrix is

obtained since we started with three components (also called the basis
elements) of a vector.
The above procedure gives an idea about the changes that have taken
place with respect to the original coordinates that results in new coordinates.
The character for the transformation matrix E,
E = sum of diagonal elements (from left top to right bottom)
= 3.
Transformation Matrix for Plane of Symmetry (Reflection)
Let xy performed on a vector (x1, y1, z1). The original coordinates
(x1, y1, z1) get transformed to (x2, y2, z2).
(x1, y1, z1) (x2, y2, z2)
During reflection along the xy plane, only the z coordinate gets
inverted. That is,
x2 = x1
y2 = y1
z2 = -z1
The new position of the vector is defined by the combination of the
original coordinates and this generates a set of mathematical equations.
x2 = (1  x1) + (0  y1) + (0  z1)
y2 = (0  x1) + (1  y1) + (0  z1)
z2 = (0  x1) + (0  y1) + (-1  z1)
These simultaneous equations can be combined to give the following
matrix equation.

24
 The matrix represents the position corresponding to the new

coordinates of the vector.

The matrix represents the position corresponding to the original

coordinates of the vector and corresponds to the transformation

matrix for the reflection xy.

xy = 1

Similarly, the transformation matrix for xz = and xy = 1,

and the transformation matrix for yz = and yz = 1.

Transformation Matrix for Centre of Symmetry

When inversion operation is performed on a vector (x1, y1 z1), it
changes to the vector with coordinates (x2, y2, z2).
(x1, y1, z1) (-x1, -y1, -z1) = (x2, y2, z2)
 x2 = -x1
y2 = -y1
and z2 = -z1
The relationship between (x 1, y1, z1) and (x2, y2, z2) can be represented
by a set of mathematical equations.
x2 = (-1)  x1 + 0  y1 + 0  z1
y2 = 0  x1 + (-1)  y1 + 0  z1
z2 = 0  x1 + 0  y1 + (-1)  z1
The corresponding matrix equation can be given as,

25
 The transformation matrix for i = and i = -3.

26
Transformation Matrix for Axis of Symmetry
Consider Figure 45. Let a vector have a magnitude ‘t’ and derive
an angle  respect to the x axis. Assume that is rotated about the z axis
in the clockwise direction through an angle of . The new vector ,
derives an angle ( - ) with the x axis. The z coordinates of the points do not
change and z2 = z1.

Fig. 31
From the figure, we can see that,
OM = x1 = r cos  OM' = x2 = r cos( - )
PM = y1 = r sin  P'M' = y2 = r sin( - )
Using the identities,
cos(A – B) = cos A cos B + sin A sin B
sin(A – B) = sin A cos B – cos A cos B
the relationship between (x2, y2, z2) and (x1, y1, z1) can be expressed as,
x2 = r cos  cos  + r sin  sin 
y2 = r sin  cos  - r cos  sin 
z2 = z1
Substituting for r cos  and r sin  as x1 and y1, we obtain,
x2 = x1 cos  + y1 sin 
y2 = -x1 cos  + y1 sin 
z2 = z1
Then, the new position of the vector can be expressed in terms of the
original coordinates as,
x2 = x1 cos  + y1 sin  + 0  z1
y2 = -x1 sin  + y1 cos  + 0  z1
z2 = 0  x1 + 0  y1 + 1  z1
27
These three simultaneous equations can be expressed in terms of a matrix
equation as follows,

The transformation matrix for C n where  = 360°/n (where n is the order of

the axis) is given by,

and Cnh = 2 cos  + 1

When n = 2,  = 360°/2 = 180° and the corresponding 3  3 matrix is given
by,

and C2 = 1.
When n = 3,  = 360°/3 = 120°, the 3  3 transformation matrix is given by,

and C3 = 0.
When n = 4,  = 360°/4 = 90°, the 3  3 transformation matrix given by,

C4 = 1.
Transformation Matrix for Improper Axis of Symmetry
The Sn operation involves rotation about an axis followed by reflection
about a plane perpendicular to that axis. The transformation matrix for S n can
be obtained by finding the product of the transformation matrices of C n(z)
and xy.
Sn = xy Cn(z)
Transformation matrix of

Sn =

28
 =

and Sn = 2, cos  = -1

Thus, this chapter has highlighted how various symmetry operations
can be represented using matrices. The products of symmetry operations can
be determined by the multiplication of the respective matrices. For example,

yz  xz =

Matrix Representation
A collection of such matrices corresponding to every symmetry
element present in a point group is referred to as the matrix representation of
a point group.
Characteristics of Matrix Representations
Matrix representations of point groups should obey the following
mathematical rules.
(i) The product of any two matrices and the square of any
matrix belonging to the point group, should also be a matrix that belongs to
the point group.
(ii) There should be one matrix, which when combined
with any other matrix, leaves that matrix unchanged.
(iii) Associative law should hold good.
(iv) The inverse of every matrix of the point group
should also be present in the representation for that point group.
Thus, the collection of matrices corresponding to each symmetry element of
a point group which obeys all the four mathematical rules for the formation
of a group, and produces a group multiplication table identical to that derived
from the symmetry operations is called a matrix representation of a point group.

Classification of Representations
Representations are classified into reducible and irreducible representations.
The definitions of these representations and the differences between them are
highlighted in Table 4.
Table 4: Reducible and irreducible representations
Reducible Representation Irreducible Representation
If dimensions of representations can Irreducible representations are those
be reduced either using the similarity representations whose dimensions
transformation method or the block cannot be reduced by any of the
factoring method, they are referred to mathematical methods like the block

29
 Reducible Representation
as reducible representations.
They can be expressed as a
combination of various irreducible
representations that are possible for
a group.
Reducible representations are derived
for the product or for the combination
of fundamental bases.
Irreducible Representation
factoring or the similarity transformation
methods.
They cannot be expressed as
combinations of any other representations.
Irreducible representations are derived
for fundamental bases.

The Great Orthogonality Theorem

The theorem is mathematically represented as follows.

where is a matrix element belonging to the m th row and the nth

column of a symmetry operation R in the i th irreducible representation.
is the matrix element belonging to the m'th row and the n'th column
of a symmetry operation R in the jth irreducible representation. 1i and 1j are
the dimensions of the ith and the jth irreducible representations and h is the
order of the group. It is necessary to take the complex conjugate of one factor
on the left side, whenever imaginary or complex numbers are involved.
ij = 0 if ij
and ij = 1 when i = j
Thus, six solutions are simultaneously introduced in the theorem by
the three s. If i = j, m = m', n = n', the above equation reduces to

=0 ...(1)

Similarly if i = j, m = m', n  n', the equation reduces to

=0 ...(2)

If i  j, m = m', n = n', then,

=0 ...(3)

If i = j, m = m, n = n', then,

...(4)

Equations (1), (2), (3) and (4) are simplified expressions of the
orthogonality theorem.
Consequences of the Orthogonality Theorem

30
(i) The sum of the squares of the dimension of all the IRs
that are possible for a point group should be equal to the order of the
group.

where l is the dimension of the ith representation and h is

the order of the group.

That is,
where l1 = dimension of the first IR, l2 = dimension of the second IR and so
on.
(ii) The absolute square of the length of any character
representation is equal to the order of the group, provided the
representation is an irreducible representation. That is, the absolute square
of the character corresponding to the irreducible representation summed
over the symmetry operations of a point group should be equal to the
order of the group.
 | i (R) |2 = h
That is, | i (R1) |2 + | i (R2) |2 + ......... + | i (Ri) |2 = h
where i (R1) is the character corresponding to the symmetry element R 1 in
the ith IR and so on.
(iii) The product of any two character representations is zero
when the representations are irreducible representations. That is, the
character representations derived from the IRS of a group are mutually
orthogonal.

That is,

(iv) The characters corresponding to the conjugate elements

are the same in any IR. Since the transformation matrices of conjugate
elements are the matrix and its transpose, their character remains the
same. For example, consider the C3v point group. and are
conjugate elements.
= 2 cos 120° + 1 ( Cn = 2 cos  + 1)

= =0

= (2  cos 240°) + 1 = = 0.

(v) The total number of IRs that are possible for a point group
is equal to the total number of classes present in a point group. For
example, the number of classes for the C2 point group is 2. That is, C2
and E. Hence, the number of IRs = 2. Similarly, for the C 3v point group,

31
the number of classes is 3; E, 2C 3 and 3v. Hence, the number of IRs =
3.
D2h: 8 classes, 8 IRs
C8 : 2 classes, 2 IRs

32
Character Tables
A character table contains four main areas and gives information about the
following.
(i) The name of the point group with the possible
symmetry elements classified under appropriate classes.
(ii) The number of IRs possible for a point group.
(iii) The character corresponding to various classes of
symmetry elements for all the IRs that are possible for a point group.
(iv) The symmetry and corresponding fundamental
bases for every IR.
(v) The respective combined bases for the various IRs
of a point group.
For example, the character table for a C2V point group is given below.
Area
Area II Area I Area IV
III
C2V E C2(z) xz yz
A1 1 1 1 1 Z x2,y2,z2
A2 1 1 -1 -1 R(z) xy
B1 1 -1 +1 -1 y, Rx yz
B2 1 -1 -1 +1 x, Ry xz
From the character table, we can see that Area I contains the list of
symmetry elements possible for a point group with appropriate classes. It
also gives the respective characters of each IR possible for a point group and
is mainly derived from the orthogonally theorem. Area II contains the
Mulliken symbols which indicate the symetry of the various IRs that are
possible for a point group. In Area III, the corresponding fundamental bases
for the various IRs are listed. Area IV contains the combined bases for the
various IRs.
Construction of Character Tables
Area I of the character table can be derived using the orthogonality
theorem as given below.
(i) The total number of IRs of a group is equal to the
total number of classes present in the group in accordance with the
axiom derived from the orthogonally theorem which states that the
number of IRs is equal to the number of classes in the group.
(ii) The dimensions of the various IRs can be derived
using the following axiom derived from the orthogonality theorem, 

(iii) Using other axioms derived from the orthogonality

theorem,

33
 and

it is possible to derive characters corresponding to every symmetry

element of the group.
Area II of the character table can be derived based on following
conventions reported by Mulliken.
(i) One-dimensional representations are represented by
A or B, two-dimensional representations by E and three dimensional
representations by T.
(ii) One-dimensional representations which are
symmetric to the principal axis are represented by A and those which
are antisymmetric to the principal axis are represented by B.
(Symmetric the character is positive; antisymmetric the character is
negative).
(iii) If the representations are symmetric to i, a subscript
‘g’ is added; whereas, if the representations are antisymmetric to i, a
subscript u is added.
(iv) A subscript ‘1’ is added to representations which
are symmetric with respect to v and ‘2’ is added to those
representations which are antisymmetric with respect to v.
(v) Single prime (') is added as a superscript for those
representations which are symmetric to h and double prime (") is
added as a superscript for those operations which are antisymmetric to
 h.
Area III of the character table is derived by determining the influence of the
symmetry operations of a group on the various fundamental bases. Generally
and rotation about the x, y and z axes (R x, Ry, Rz) are considered as
fundamental bases.
Area IV of the character table consisting of product vectors is derived using
the direct product concept.
Character Table for the C2v Point Group
(i) The total number of IRs possible for a C 2V
point group is 4 since the point group contains 4 classes of symmetry
operations.
(ii) Let the dimensions of the four IRs be l 1, l2, l3
and l4. The order of the group is 4.
 =4

As the dimensions cannot be zero, =1

Therefore, all the four representations are one-dimensional representations.

34
(iii) Since the character corresponding to the
identity element is the dimension of the representation, in all the four
IRs, E = 1. The characters corresponding to C2(z), xz and yz will be (x1,
y1, z1), (x2, y2, z2), (x3, y3, z3) and (x4, y4, z4) respectively for the four
IRs.
(iv) The square of the character representation is
equal to the order of the group.
 12 + + + =4
where, i = 1, 2, 3 or 4 corresponding to the four IRs.
As xi, yi and zi cannot exceed the value 1,

 xi =  1, yi =  1 and zi =  1.
(v) To decide the sign of the characters (x i, yi,
zi), the expression

is used.

Substituting the characters from four different IRs of the group, we get
1  1 + (x1  x2) + (y1  y2) + (z1  z2) = 0
1  1 + (x1  x3) + (y1  y3) + (z1  z3) = 0
1  1 + (x1  x4) + (y1  y4) + (z1  z4) = 0
All these equations will be simultaneously satisfied when all the
characters are positive in the first IR, and in the remaining IRs, the
characters of two symmetry elements are positive, and the characters
of two IRs are negative.
Therefore, Area I of the C2V character table is
E C2(Z) xz yz
I 1 1 1 1
II 1 1 -1 -1
III 1 -1 1 1
IV 1 -1 -1 -1
The highlights of Area II are,
(i) Among the four one dimensional IRs, two are symmetric
(+ve character) with respect to the principal C 2 axis and are hence
labelled as A. The remaining two IRs that are antisymmetric with
respect to the principal C 2 axis (-ve character) are labelled as B
representations.
(ii) Representations that are symmetric to v(yz) are
indicated as A1 and B1 whereas representations that are antisymmetric
to v are labelled as A2 and B2 respectively.
The highlights of Area III are,

35
 The symmetry of the fundamental bases can be
determined by performing the symmetry operations of a group on them
and arriving at the corresponding characters using the following short
method.
R = Number of bases which do not change position and direction –
Number of bases which do not change position but reverse the
direction
Choosing as base,
E = 1 – 0 = 1
=1–0=1

=1–0=1

=1–0=1
 has A1 symmetry. Similarly it can be shown that has B1
symetry and has B2 symmetry. Choosing Rx as base,

E = 1
= –1

= –1

=1
Rx has B1 symmetry. Similarly, Ry has B2 symmetry and Rz has A2
symmetry.
Note: The character table of the C 2h group is similar to that of the C 2V
group except for the Mulliken’s symbols.
Character Table for the C3V Point Group
(i) The total number of IRs possible for the C3V point group is
three since this point group contains three classes of symmetry
operations.
(ii) Let the dimensions of the three IRs be l 1, l2 and l3, and the
order of the group be six.
 =6
As the dimensions cannot be zero, the only possible solution is
and = 4.
That is, l1 = l2 = 1 and l3 = 2.

36
 Thus, among the three IRs, two are one-dimensional representations
and one is a two-dimensional representation.
(iii) The character corresponding to the identity element in any
representation is the dimension of that representation.
 E = 1 for one-dimensional representations and E = 2 for two-
dimensional representations. The characters corresponding to the C 3
and v classes of the C 3V group will be (x 1, y1), (x2, y2) and (x3, y3)
respectively in the three IRs.

(iv) Since for a one-dimensional

representation of C3V point group, 12 + = 6 where (i = 1 and

2). xi and yi cannot exceed 1.
= 1 and =1
 xi = 1 and yi = 1.
For the two-dimensional representation of the group,
22 + =6

The possible solutions are, = 1 and =0

 x3 = 1 and y3 = 0.
(v) To decide about the sign of character, equation

is used. Substituting the characters of the one-

dimensional representations in the above equation we get,

(1  1) + (2x1  x2) + (3y1  y2) = 0
 x1 = x2 = +1, y1 = +1 and y2 = -1
Similarly, by considering a one-dimensional representation and a two-
dimensional representation, we have
(1  2) + (2x1  x3) + (3y1  y3) = 0
2 + 2x1x3 + 3y1y3 = 0
As x1 = +1, y1 = +1 and y3 = 0,
x3 = -1.
Hence Area I of the character table is,
E 2C3 3v
I 1 1 1
II 1 1 -1
III 2 -1 0
The highlights of Area II are,

37
(i) The one-dimensional IR symmetric to C 3(Z) and v is
labelled as A1 and the other one symmetric to C 3(Z) and antisymmetric to v
is indicated as A2.
(ii) The two-dimensional representation is labelled as E.
The highlights of Area III are
The symmetry of the fundamental bases [ and Rx, Ry, Rz] can be
determined by performing symmetry operations of a group and then arriving
at the corresponding characters using a short method. Choosing as the
base,
E = 1 – 0 = 1
=1–0=1

=1–0=1
 has A1 symmetry.
The X and Y axes are inseparable in the C 3V point group due to the C3
operation (since the new position of and can be expressed only by the
combination of original and ).
Thus, choosing and together as the base,
E = 2 – 0 = 2
= 2 cos 120° + 1 = –1

=1–1=0
 and together have ‘E’ symmetry. Similarly Rx and Ry
together have ‘E’ symmetry and Rz has A2 symmetry.

Direct Product and Correlation Tables

If XA+ XB(R) denote the character for operation R in the representation
A and B then the character of operation R into direct product representation
is given by
XAB(R) = XA(R)  XB(R)
The character of representation of a direct product are equal to the
product of the character of representation base on the individual functions.
The C3v character table is used to obtain the direct product reproduction.
A1A2, A r E, A2E & E2
C3v E 2C3 3v Direct product E 2C3 3v
A1 1 1 1 A1  A2 1 1 -1
A2 1 1 -1 E  E or E2 4 1 0
E 2 -1 0 A2  A2 1 1 1
A1  E 2 -1 0
38
 A2  E 2 -1 0

Projection Operators
The generating operator or the projection operator for the jth irrep is
defined as

... (1)
th
where lj is the dimensionality of the j irreduible representation. Though
equation 1ooks somewhat formidable, it is easy to use. Let us consider the
trans-1,3-butadiene molecule which belongs to C2h point group:

Denoting the 2pz orbital on carbon atom i by i, Equation 1 yields

= ... (2)

= ... (3)

= ... (4)

with similar results for 3 and 4.

Similarly, using 1 and 2, we obtain

... (5)

... (6)
Here we have ignored the numerical factors in front of the various
symmetry orbitals since we are interested only in their functional form.

39
 1.2. CHEMICAL KINETICS

Theories of Reaction Rates

An important theoretical problem in chemical kinetics is to interpret
the pre-exponential factor in the Arrhenius equation

We may realise that the distribution of energy among molecules is

brought about by the collisions that occur between them and that the rate of
reaction is determined by the frequency of these collisions and by factors
related to energy distributions. There were four main lines of approach to the
problem of the pre-exponential factor.
1. Treatment based on the kinetic theory of collisions.
2. Treatments based on thermodynamics but with an additional
hypothesis to explain reaction rates.
3. Treatments based on statistical mechanics again with an
additional hypothesis to explain rates.
4. Treatment based on molecular dynamics.

Transition State Theory

Postulates
1. As the reactant molecules approach each other there is
continuous series of changes in bond distance. These changes are
accompanied by energy changes.
2. The reactant molecules are transformed into an energy rich
intermediate called activated complex or transition state.
3. The activated complex may be formed by some loose
association or bonding of reactant molecules with necessary
rearrangement of valence bonds and energy. Or if it be a unimolecular
reaction the reactant molecule may produce the activated complex by
rearrangements of atoms and redistribution of energy.
4. The activated complex though unstable has transient existence.
It is treated formally as a definite molecule with an independent entity.
The activated complex is in equilibrium with the reactants. The potential
energy of activated complex is maximum.
Reactants activated complex
5. The activated complex decomposes into products
schematically, reactants activated complex products
6. The activation energy of reaction in the light of transition state
theory is defined as the additional energy which the reacting molecules
must acquire to form the activated complex.

40
 E1 – activation energy of reactants
E2 – activation energy of products
Mathematical (Thermodynamic) Treatment of Transition State Theory
Conventional Transition State Theory (CTST)
The great value of CTST is that the resulting rate equation, although
simple, provides a framework in terms of which even quite complicated
reactions can be understood in a qualitative way. There are various assumptions
and approximations involved in this theory. The main assumptions of CTST are:
1. Molecular systems that have surmounted the col in the direction
of products can not turn back and form reactant molecules again.
2. The energy distribution among the reactant molecules is in
accordance with the Maxwell-Boltzmann distribution. Furthermore, it is
assumed that even when the whole system is not at equilibrium, the
concentration of those activated complexes that are becoming products
can also be calculated using equilibrium theory.
3. It is permissible to separate the motion of the system over the
col from the other motions associated with the activated complex.
4. A chemical reaction can be satisfactorily treated in terms of
classical motion over the barrier, quantum effects being ignored.
Derivations of the rate equations
The rate equation for a bimolecular reaction, derived by the methods of
conventional transition state theory is

... (1)

qA & qB  Partition functions of two reactants A & B.

qSpecial type of partition function for the activated complex.
The rate equation has been derived in a number of different ways.
Derivation 1
The first derivation is by Wynne & Eyring. It considers the equilibrium
between initial and activated states and then treats the motion through the col
as a very loose vibration.
41
 The equilibrium between two reactants A & B and the activated
complex X# may be expressed by the equilibrium

... (2)

where concentration equilibrium constant. This may be expressed in

terms of the partition functions,

... (3)

where E0–difference between the molar zero point energy of the activated
complexes and that of the reactants. This energy is the hypothetical
activation energy at absolute zero.
The partition function in the above expression must be evaluated
with respect to the zero point levels of the respective molecules.
If molecule A contains NA atoms & molecule B contains NB atoms, the
activated complex X contains NA + NB atoms.
If the complex is nonlinear,
rotational degrees of freedom = 3
vibrational degrees of freedom = 3(NA + NB) – 6
if linear, vibrational degrees of freedom = 3(NA + NB) – 5
One of these has a different character from the rest. Since it
corresponds to such a loose vibration that there is no restoring force the
complex can form products without any restraint. For this one degree of
freedom, the partition function is (1 – eh/kT)1.
The value of the function is calculated in the limit at which 
approaches zero. This is obtained by expanding the exponential and taking
only the first term,

... (4)

This expression (4) is included in q and the remaining product of

factors can be written as q.
Now, 3(NA + NB)–7 degrees of vibrational freedom (non-linear)
3(NA + NB) – 6 degrees of vibrational freedom (linear)

q = ... (5)

Now the equation (3) becomes

... (6)

42
On rearranging,

... (7)

frequency  is the frequency of vibration of the activated complexes in the

degree of freedom corresponding to their conversion into products.
The expression on L.H.S. of (7) is the product of concentration of
activated complex and frequency of their conversion into products. Therefore
it is equal to rate of reaction v. Hence

v = [A] [B] ... (8)

where are constants, equal to the rate constant k.

So v = k[A] [B] where ... (9)

... (10)

which is the CTST formula.

Derivation 2
In this derivation, the motion over the col is not expressed as a
vibrational motion as in derivation 1. It is considered as translational motion.
This figure shows a schematic representation of the top of the potential
energy barrier. Here all complexes lying within the arbitrary length  being
activated complexes.

Consider an arbitrary length  at the top of the potential energy barrier.

All complexes lying within this length are activated complexes. The arbitrary
length  can be considered as a one dimensional box of length .
43
 The translational partition function corresponding to the motion of a
particle of mass m in a one dimensional box of length  is

qt = ... (1)

Thus the total partition function q for the activated complexes may be
written as

q = ... (2)

where q is p.f for all the motions except that over the col.
Introducing (2) into (3) in I derivation (i.e.) consider

[X] = ... (3)

This again includes activated complexes moving in both the directions

and is therefore twice .
According to kinetic theory the average speed of particles moving
from left to right over the barrier is

... (4)

average speed – distance moved in unit time.

While crossing the barrier, by crossing the length , the particles of
activated complex moves over the col once. Therefore, by crossing the

distance in unit time, the particle moves over the col is .

This is the frequency with which the activated complex passes over potential
energy barrier in unit time. (i.e)

= ... (5)

The rate of reaction is the concentration of complexes given by (3),

multiplied by this frequency

... (6)

44
 ... (7)

rate constant, as obtained in deviation 1.

As  cancels out, its magnitude is irrelevant.

Derivations (1) and (2) appear at first sight to be different, but they are
basically the same. Derivation (1) regards the passage over the barrier as a
very loose vibration and derivation (2) regards the passage as a free
translation. If a particle is vibrating and the restoring force is reduced
gradually to zero, the vibration ultimately becomes a translation. The p.f for a

very loose vibration should become p.f for a translation. If

is substituted in , we get .

(i.e.) in equation ,

Applications of Conventional Transition State Theory

Reactions between Atoms
Consider a reaction between 2 atoms A and B to form the diatomic
molecule AB. It is assumed that the product molecule does not dissociate in
the first vibration and so each collision between A and B produces a product
molecule AB in the zero activation energy.
The activated complex AB has three degree of translational freedom
and two rotational freedom. If it were a normal diatomic molecule, it would
have one degree of vibrational freedom. But because it is an activated
complex this mode of vibration corresponds to decomposition and the
corresponding partition function is  omitted.
The partition function q with this omission is

... (1)

where
mA & mB - atomic masses
I - moment of Inertia of diatomic activated complex
The first term – contribution from the three degrees of translational freedom.
45
Second term – for rotation.

... (2)

where dAB = distance between the centres of the atoms in the activated
complex.
The atoms A and B have only translational degrees of freedom so that
the respective partition functions are

... (3)

... (4)

when the activation energy is E0, the rate constant is

... (5)

To convert into molar units, multiply by L, Avogadro constant

... (6)

Substituting the expressions for partition function in (6)

46
Reactions between Molecules
The equations for reactions between molecules are more complicated,
and a simplified treatment is first given by Bawn. The approximation was
made such that the partition function for a given type of energy has the same
value for each degree of freedom. In reality the values of the partition
functions do not vary greatly with the molecular masses, moment of inertia or
vibrational frequencies so that the procedure of treating them as equal does
not involve a great error.
The partition functions for simple translational, rotational and
vibrational degrees of freedom are written as qt, qr and qv respectively. For
reaction between two atoms
, ,
as the complex is linear.

The rate constant,

... (1)

Significance

The significance of the ratio is that when two atoms form an

activated complex, two degrees of rotational freedom are gained and three
degrees of translational freedom are lost.
If A & B are complex non linear molecules,

NA, NB –no of atoms in the molecules, the activated complex contains NA + NB

atoms.
If the species is normal molecule, it would have 3(NA + NB) – 6 degrees
of vibrational freedom. In the activated complex however one of these
corresponds to passage over the barrier and only 3(NA + NB) – 7 are to be
included in the partition function, which is thus

47
 The rate constant is

... (2)

Significance of this expression – when the molecules A & B form an

activated complex, there is a loss of three degrees of translational freedom
and three degrees of rotational freedom. At the same time there is a gain of
five degrees of vibrational freedom.
Comparing the equations (1) & (2) the ratios of pre-exponential factors
in two equations Am & Aa are

Reaction Coordinates
It is an abstract one dimensional coordinate which represents progress
along a reaction pathway. It is usually a geometric parameter that changes
during the conversion of one or more molecular entities.
The reaction coordinate plots are very useful in showing 1. whether a
reaction is endothermic or exothermic process 2. which reaction pathway is
faster & 3. which products are kinetic and thermodynamic controlled
products.
The reaction coordinates are chosen from a measurable coordinate
such as bond length, bond angle, a combination of bond length and bond
angle or bond order. The reaction coordinates are often plotted against energy
to show an energy profile of a reaction.

Potential Energy Surfaces

Activation energy can be determined using a potential energy surface,
in which potential energy is plotted against bond distances and bond angles.
The procedure commonly used today is to plot potential energy against
certain bond lengths. If the reaction occurs between 2 atoms only, the
potential energy curve is constructed by plotting energy against the distance
between the 2 nuclei. This is a two dimensional diagram.
If three atoms are involved as in the reaction A + B – C  AB + C the
system A ... B ... C requires 3 parameters to describe it. They are A – B, B – C
and A – C distances or 2 distances and an angle. When energy is plotted
against 3 distances or 2 distances and an angle, a four dimensional diagram
48
would be necessary for that, such a diagram cannot be constructed or
visualised. It is necessary to fix one parameter at a particular value. For eg,
the A – B – C angle might be fixed at 180° and a three dimensional model
can be constructed. The A – B – C angle may be fixed at another value and a
three dimensional surface can be constructed. Thus a series of 3-dimensional
diagrams can be constructed in each of which one parameter (i.e.) A – B – C
angle is fixed at a particular value. These diagrams would be sections through
the four-dimensional surface.
When the procedure of fixing the A – B – C angle is adopted, the
resulting potential energy surface is of the form shown in the diagram ( A)
(variation of potential energy with A – B and B – C distances for the A ... B ... C
system in which the A – B – C angle has been fixed).

Fig. A
On the left hand face, the B – C distance may be considered
sufficiently great. That means we are dealing only with the diatomic
molecule A – B. The curve shown on that face is thus the potential energy
curve for the molecule A – B and atom C has no effect on the energy of the
system. In that curve, point Q corresponds to classical ground state and point
R corresponds to dissociation of the molecule. Similarly on the right hand
face the potential energy curve is for the diatomic molecule B – C, because
the distance A – B is sufficiently great and atom A has no effect on the
energy of the system. The classical ground state of B – C is indicated by the
point P.

49
 The course of the reaction is represented by the motion of system on
potential energy surface from P to Q. The system travels along paths where
the energy is not high. The potential energy surface can be represented by the
perspective drawing and by the contour diagram. In these potential energy
surfaces, moving in from P or from Q, there are two valleys. From point P,
on moving in, is the reactant valley. From point Q, on moving in, is the
product valley. The two valleys meet at a col or saddle point. For the system
to pass from P to Q during the reaction, the system travels up the reactant
valley, reaches the col. passes over the col and then goes into the product
valley. The paths of steepest descent from the col into the reactant valley and
into the product valley is together called minimum energy path (MEP). The
actual reaction paths are not the same as this MEP.
A section of the minimum – energy path is known as potential energy
profile. The maximum point in this profile or (at the col in the potential
energy surface) is a position of maximum energy along the minimum energy
path (diagram B).
System in a small region around this maximum point are known as
activated complex and their state is referred to as transition states of the
reaction.
Potential energy surfaces for reactions involving more than 3 atoms are
hyper surfaces in multi-dimensional space. These surfaces can be constructed
only by holding all variables constant except 2. Therefore, in such reactions,
groups of atoms are treated as single particles. CH 3 + H2  CH4 + H is
treated as A + BC system.
Most of the work on potential energy surfaces has been done on
bimolecular system such as
H + H - H  H - H + H
The 3H atoms are labelled as ,  & . The rate of this reaction is
measured by measuring the rate of conversion of ortho-hydrogen to para-
hydrogen.
Frotz-London has discussed chemical reactions from the stand point of
molecular structure. He suggested that quantum mechanical methods can be
used to calculate the energies of reaction intermediates such as activated
complexes. Heitler and London have given quantum mechanical treatment of
the H2 molecule. The allowed energies of the H2 molecule are the sum and
difference of 2 integrals.
E=A+
A – Coulombic energy  Classical energy of system
  exchange energy
A electrons are indistinguishable, they are not localised on any
particular nucleus. They can be exchanged  is used.

50
 At internuclear distances A and  are –ve. E is lowest energy
corresponding to a stable state if E = A + .
For a triatomic species, from quantum mechanical treatment, E is
given by London equation as

Fig. B

Kinetic Isotope Effect

Isotope Effect
If an atom in a reactant molecule is replaced by one of its isotopes,
both the equilibrium constant of the reaction and the rates are altered. If there
is change in equilibrium constant of the reaction, the term equilibrium
isotope effect is used. If there is change in rate or rate constant of the
reaction, the term kinetic isotope effect is used. If a bond involving the
substituted atom is broken or formed during the reaction, the isotope effect is
very great. If the site of isotopic substitution is far from the seat of reaction,
then isotope effects are small. Thus by measuring isotopic effects, we can
find out whether a particular bond is involved directly in the rate-controlling
step of the reaction. If the bond containing the substituted atom is involved in
the rate-controlling step directly, then the isotope effect is primary isotope
effect. If the isotopic substitution has taken place at a bond not involved in
the rate controlling step, then it is called secondary isotope effect.
When an atom is replaced by its isotope, there is change in atomic
masses. Thus isotopic effects are due to change in atomic masses. When
there is a relatively large change in atomic mass, isotope effect is large. For
eg, isotope effect is large when an ordinary H atom is replaced by D or T, the
relative masses being in the ratio 1:2:3. When 12C is replaced by 13C, isotope
effect is only small, since the change in atomic masses is in the ratio 12:13.
However even very small isotope effects can provide valuable mechanistic
information.

51
 The predominant factor in isotope effect is the zero point energy which
is strongly affected by atomic masses. When an atom is replaced by an
isotope there is no change in the classical potential energy surface. But there
are changes in vibrational frequencies. Due to the change in vibrational
frequency, there will be change in zero-point energy. The zero point energy
for H2 is 26.1 kJ/mol and that of O 2 is 18.5 kJ/mol. At relatively low
temperatures, including temperatures around room temperature, H 2 and O2
molecules are largely at their zero point levels. Thus at the initial state of the
reaction, H2 has 7.6 kJ/mol more zero point energy than a O 2 molecule.
Hence it tends to react more rapidly and its reactions will have a higher
equilibrium constant.
Primary Kinetic Isotope Effect
The treatment of equilibrium isotope effect can be carried out
satisfactorily whereas the treatment of kinetic isotope effect is very difficult
due to 2 main reasons.
1. The structure and properties of the activated complexes are
involved and for a detailed knowledge of these, it is necessary to
calculate a reliable potential energy surface. A reliable potential energy
surface can be calculated only for the simplest type of reactions.
2. Quantum-mechanical tunneling does not affect equilibrium
constants, but it has important influence on the rates of reactions
involving H atoms or its ions H + or H. As there is no satisfactory
treatment of tunneling, there is uncertainty, in kinetic isotope effects in
reactions involving H, H+ or H-.
Semiclassical Treatment
As a first approach to the problem of kinetic-isotope effect, it is
convenient to neglect quantum mechanical tunneling and procedures that do
so are referred to as semiclassical treatments. Such treatments are reasonably
satisfactory for atoms heavier than H. Even when H, H + or H- is involved,
neglect of tunneling may not introduce much error at higher temperatures, At
temperature below about 350 K, however tunneling becomes significant and
neglect of tunneling introduces much error in kinetic isotope effect.
A simplified semiclassical discussion of kinetic-isotope effect in hydrogen
atom transfer process is given first. Consider the abstraction reactions in
which H or D atom is transferred from one carbon atom to another.
R – H + R'  (R ... H ... R')  R + H – R'
R – D + R'  (R ... D ... R')  R + D – R'
a) The situation is simple if R and R' are much heavier than either
H or D. The partition functions for R – H and R – D are then
practically the same. Also the partition functions for the activated
52
 complexes (R – ... H ... R')  and (R – ... D – ... R')  are
same. To compare energy consider the vibrational frequencies. Also
the relevant vibrational frequencies in the activated complexes are
almost the same for the 2 forms. For eg, the symmetry vibrational
frequencies depend largely on the masses of R and R' and much less on
the central masses of H or D. As R and R' are same in the 2 activated
complexes, their symmetry vibrational frequencies are close to one
another. As R and R' are heavier than H or D, the central H or D is not
displaced.
The same is true for bending frequencies. The asymmetric vibrational
frequencies are neglected in the transition state theory. As the vibrational
frequencies are same, the zero-point energies for the activated complexes are
 much the same for H and D. The partition functions (where the main
distribution is from translational motion) for the two isotopic forms in the
initial state R – H or R – D and in the activated complexes R ... H ... R' &
R ... D ... R' are practically the same. Therefore, the rate constants will differ
only due to zero point energy difference in the initial state. The semiclassical
ratio is determined by this zero-point energy difference in the initial state.

b) If one of the radicals R or R' is much higher than the other,

Suppose that R' is a hydrogen atom,
R – H + H  (R ... H ... H)  R + H2
R – D + H  (R ... D ... H)  R + DH
In this case, symmetric vibration brings about displacement of the
central H or D atom and therefore symmetric vibrational frequencies of the 2
activated complexes differ from one another. Therefore there is a difference
between the zero-point levels in the activated complexes. This brings the

ratio less than 6.1. Quantum mechanical tunneling increases this ratio.

c) In unsymmetrical systems,
H – H + R'  (H ... H ... R')  H + H – R'
H – D + R'  (H ... D ... R')  H + D – R'
There is a difference between the zero point levels in the 2 activated

complexes and therefore the ratio is reduced.

Thus the semiclassical ratio is reduced if there is asymmetry in the

activated state, while it is increased, if there is quantum mechanical

53
tunneling. The ratio is different for transfer of H or D from a different atom
such as N, O or S.

54
Potential Energy Profiles

Potential energy curve of H2&D2, showing zero point levels

Secondary kinetic isotope effects

When the isotopic substitution involves an atom that is not at the end
of a bond that is broken or formed during the reaction, the effect is much
smaller than that of primary effect.
Secondary effects are largely due to changes in vibrational frequencies
in the reactants and activated complexes. Because these changes affect the
zero point levels and hence the activation energies.

55
 eg. SN1 substitution reactions.
The rates of these reactions are controlled by an ionization process
such as
#
+  
C X C - - - X  C+ +X

Initially the C atom is sp3 hybridized.

Finally the C atom is sp2 hybridized.
In the activated complex, hybridization is intermediate between sp3 and sp2.
Potential energy profile for SN1 reaction

Slow step is the ionisation of C – X bond. A small secondary isotope

effect is obtained when H is replaced by D at a position close to C – X bond.
The bending vibration frequencies are lower in sp2 hybridization than
in sp3. There is  a decrease in the frequencies when the activated complex
is formed. If an H atom attached to the carbon atom at the reaction centre is
replaced by D, the zero point energies in the reactant and in the activated
complex are lowered. However since the vibrational frequencies are lower in
the activated state, the H and D levels are closer together than in the initial

state. The result is small +ve kinetic isotope effect. ratio is 1.3 – 1.4.

Sometimes secondary kinetic isotope effects are interpreted in terms of

difference in inductive and steric effects for the isotopic forms. For eg, D
appears to be slightly more e - donating than H and to occupy somewhat less
space. This effect arises from anharmonicity of vibration and from the fact
that the amplitude of vibration of a C – D bond is less than that of a C – H bond.

56
Principle of Microscopic Reversibility and Detailed Balance
This principle relates to the behaviour of systems at equilibrium. It was
formulated by Tolman. The principle of microscopic reversibility at equilibrium
can be expressed as follows.
In a system at equilibrium any molecular process and the reverse of
that process occur on the average at the same rate.
The principle of detailed balance at equilibrium applied by Fowler
states that in a system at equilibrium each collision has its exact counterpart
in the reverse direction and the rate of every chemical process is exactly
balanced by the rate of the reverse process. These two principles can be
applied in CTST.
1. In terms of transition state theory, it follows from the
principles that when a system is at equilibrium the flow of systems
over a potential energy surface must be exactly balanced by a flow in
the opposite direction.
2. In particular the most probable path in one direction must
also be the most probable path in the opposite direction. The activated
state for a reaction in one direction must be the same as the activated
state in the other direction.
3. The rate of a reaction in one direction depends on the
increase in Gibbs energy in going from the initial state to the activated
state. Since the activated states must be the same in both the directions,
it follows that for an elementary reaction, the Gibbs energy difference
in the 2 directions must be equal. As Gibbs energy of activation is
equal in both the directions, the rate of the reaction is same in both the
directions. Thus for a reaction A + B C + D, at equilibrium
k1[A] [B] = k2[C][D]

Thus the ratio of the rate constants must be equal to the equilibrium
constant.
These principles must not be applied to reactions that are not
elementary and reactions which are not at equilibrium. Change in pH and
change in dielectric constant do not affect the rate constants in forward and
reverse directions in the same way. The forward and reverse reactions have
different dependences in these cases.

57
Application of the Principles of Microscopic Reversibility and Detailed Balance
For an elementary reaction, the equilibrium constant must be the ratio
of the rate constants in the forward and reverse directions. Thus consider the
process A+B Y+Z in which the reactions in the forward and reverse
directions are elementary.
The rates in the two directions are
and

If the system is at equilibrium, these rates are equal. Hence,

Example
Consider a reaction that occurs in two or more stages.
H2 + 2ICl I2 + 2HCl
This reaction occurs in 2 steps. At equilibrium the processes are
occurring at equal rates in the forward and reverse directions.
1. H2 + ICl  HI + HCl
2. HI + ICl  I2 + HCl
Thus at equilibrium
k1[H2] [ICl] = k-1 [HI] [HCl]
k2[HI] [ICl] = k-2[HCl] [I2]
The equilibrium constant for each reaction is thus

The product of these two equilibrium constants is

where Kc is the equilibrium constant for the overall reaction. For any
mechanism involving any no. of elementary and consecutive steps, the
overall equilibrium constant is the product of the equilibrium constants for
the individual steps. It is also the product of the rate constants for the
reactions in the forward direction divided by the product of the rate constants
for the reverse direction.

58
 If a reaction occurs by a composite mechanism and we measure a rate
coefficient k1 for the overall reaction from left to right and also measure a
rate coefficient k-1 for the overall reaction from right to left at the same

temperature, the ratio is not necessarily the equilibrium constant for the

overall reaction.
An example for a reaction where the ratio of the rate constants is not
the equilibrium constant, is given below. Consider the reaction system

The rate of consumption of A at the very beginning of the reaction

before any X and Z have accumulated is

k1, the first order rate constant. Similarly starting with pure Z, initial
rate of consumption of Z is measured. The rate constant is k-2. In general the

ratio is not equal to the equilibrium constant Kc. This is because the

initial rate constants measuring k1 and k-2 are not the rate constants that apply
when the system is at equilibrium. When the system is at equilibrium,

The net rate of consumption of A is

Introducing for [X] gives

59
 The first term is the rate of the reaction from left to right and the

corresponding rate constant is . Similarly, the rate constant from

right to left is . The ratio of these rate constants is equal to

the equilibrium constant. Thus if the rate constant that are measured for
forward and reverse directions are those that apply when the system is at
equilibrium, their ratio gives the equilibrium constant for the reaction. For a
system not at equilibrium, the rate constants intermixed away from equilibrium
may be very different from the equilibrium constant.

Gas-Phase Combustion
The gas-phase reactions between oxygen and various substances such
as hydrogen, CO, phosphorous and PH3 have a special characteristic under
some conditions of temperature and pressure. They occur in a normal way,
but a slight change in temperature or pressure may cause the reaction mixture
to explode. The reaction between PH3 and O2 was studied in detail and it was
noted that sometime a decrease in pressure at constant temperature caused a
steady reaction to change into an explosion. Under certain conditions an
explosion in a gaseous mixture is accompanied by an explosion wave which
means a sudden pressure change and this is called detonation.
H2 – O2 Reaction
The reaction between H2 and O2 is a good example where a steady
reaction changes into explosion.
1. A stoichiometric mixture of the 2 gases explodes spontaneously
at any pressure if the temperature is above about 600°C.
2. A stoichiometric mixture gives no explosion at any pressure if
the temperature is below about 460°C unless a spark is passed through
the mixture or a flame is introduced in the mixture.
3. Between 460°C and 600°C the stoichiometric mixture explodes
spontaneously at certain pressures but not at other pressures.
The schematic diagram for the behaviour of a stoichiometric mixture

of H2 and O2 at 500°C is shown below.

60
 If the pressure is below ~ 2 mm Hg, there is steady reaction, but if the
pressure is increased to 2 mm, an explosion occurs. If the pressure is initially
maintained at about 230 mm Hg, there is again a steady reaction. But if the
pressure is reduced, the rate decreases to an extremely low value until about
100 mm Hg pressure is reached. Then the mixture explodes. Thus at 500°C
there is a pressure region (2 mm to 100 mm Hg) within which there is
explosion but above and below this pressure region there is steady reaction.
The lower limit at which explosion occurs is 2 mm Hg called first limit and
the upper limit is 100 mm Hg called 2 nd limit. At still higher pressures, the
reaction rate becomes very high that the heat evolved causes a substantial
increase in temperature. This causes explosion beyond a high pressure limit
called third limit. Beyond the third limit as explosion occurs due to rise in
temperature, this explosion limit is called thermal limit and the explosion
under such conditions is called thermal explosion.
The explosion occurring between the second and first limits occur in
systems where there is no temperature rise. Such explosions are called
isothermal explosions. In H2 – O2 system, the explosion occurring beyond the
third limit is not a thermal explosion. But it is due to an increase in the
concentration of free radicals and not due to rise in temperature.
Chain branching mechanism
The kinetic behaviour of such systems can be explained by branched
chains suggested by Thompson and Hinshelwood.
When a pair of ordinary chain propagating steps occurs, there is no
change in the number of chain carriers. When a branching chain occurs, there
is an increase in the no. of chain carriers.
For eg., 1. H + O2  OH + O
2. O + H2  OH + H
In each of these reactions, 2 chain carriers are formed from one. These
two reactions are examples of chain propagating steps in branched chain
process.
Adding together these 2 reactions,
H + O2 + H2  2OH + H

61
 H atom is regenerated but 2 OH radicals are produced which can
undergo further reactions. When such chain branching occurs, the number of
atoms and free radicals in the system can increase extremely rapidly and an
explosion may result. Suppose each OH radical produced in the above pair of
processes undergoes the reaction,
3. OH + H2  H2O + H
then, each time the pair of reactions (1) & (2) occurs, reaction (3) occurs
twice, the overall reaction
H + O2  OH + O
O + H2  OH + H

Thus in the first cycle of reactions, one H atom produces 3H atoms

together with 2 molecules of water.  in 2 cycles 3H atoms produces 9H
atoms together with 6 molecules of H2O.
Thus after 50 cycles have occurred, nearly 1 mol of H 2O is formed and
as the reactions are very fast, 50 cycles can occur in a fraction of a second.
If we include chain initiation and chain termination processes in the
chain branching mechanism, the schematic and simplified mechanism is
1. ?  R chain initiation
2. R  R chain branching
3. R  Z + R reaction to give final product z and another radical
4. R  ? chain termination in surface
5. R  ? chain termination in gas phase
Reaction (1) is chain initiation where free radicals are formed.
Reaction (2) is chain branching process where free radical R undergoes an
elementary process with the production of more free radicals. Reaction (3) is
the reaction in which the radical reacts with a molecule to give the product
and a radical. Eg.,
HO + H2  H2O + H
HO2 + H2  H2O + OH
Reactions (4) and (5) are chain termination reactions. The rates of these five
reactions are

62
The steady state equation for R is

63
The rate of formation of the product Z is

In a branching chain reaction,  is > 1 (usually 2)  last term in the

denominator is +ve. If (fs + fg) = fb(  1), then the denominator is zero. Thus
[R] = infinite. Hence vz = infinity (in principle).
In reality, the rate becomes larger than infinity, as the radical
concentrations increase very rapidly so that steady-state conditions do not
apply. Thus fs + fg = fb(1) is the condition for an explosion limit.
fb(  1) – (fs + fg) is known as net branching factor . The relative magnitude
of fs + fg and fb(  1) depend on the concentrations of the various species. At
certain concentrations fs + fg = fb(  1) causing explosion. As the concentration
is changed, a steady reaction changes into explosion.
Dependence on nature of the reaction vessel surface and vessel dimensions
The first limit is very sensitive to the nature of the reaction vessel
surface and to the vessel dimensions. The 2nd limit does not change with the
nature of the vessel.
Removal of radicals (i.e.) radical recombination may occur primarily
in the gas phase (or) primarily at the surface.
At very low pressures the radicals have easy access to the surface of
the vessel. Because there are not many gas-phase molecules to collide with
the free radicals. Thus surface recombination is predominant. An increase in
pressure reduces the rate at which the radicals can reach the walls, undergo
surface recombination and get removed. The concentration of molecules
formed by recombination of the surface fs decreases. As a result fs + fg may
become as small as fb( - 1), when (fs + fg) = fb(  1) explosion occurs.
At higher pressures, as there are sufficient molecules for gas phase
recombination, removal of radicals occurs in the gas phase. The molecules
also hinder the radicals from diffusing to the walls of the vessel. Under these
circumstances a decrease in pressure leads to a decrease in the rate of gas
phase recombination. Thus fg-concentration of molecules formed by recombination
decreases. Hence fs + fg may become equal to fb(  1) causing explosion.
Thus only the lower limit depends on the surface recombination. The
first limit is sensitive to the nature and area of the surface. If the surface is
coated with a material which inhibits recombination, fs decreases and causes
explosion at a still lower pressure. Thus coating lowers the lower explosion
limit. Also, on increasing the size of the vessel, the radicals have to diffuse a
long way to reach the walls. Therefore recombination is slow, fs decreases
and causes explosion at a still lower pressure.

64
Elementary Reactions in Solution
When a reaction takes place in solution the solvent is usually present in
much larger amounts than the reactants. The solvent concentration therefore
remains unchanged during the course of the reaction. Therefore the effect of
solvent on rate of the reaction cannot be understood.
For many reactions, the stoichiometric equation does not involve the
solvent. That means, the solvent has an environmental effect, it only acts as a
medium. If the solvent is involved in the stoichiometric equation, then it
means that the solvent takes part in the chemical change and it is regenerated
at the end of the reaction. Then the solvent has chemical effect as well as
environmental effect.
Two types of investigations can be done to know the influence of
solvent on reactions in solution.
(i) If a reaction occurs both in solution and in the gas phase,
the influence of solvent on the reaction in solution can be understood.
Such reactions are very few. Eg. Thermal decomposition of N 2O5. The
rate constants, preexponential factors and activation energies are the
same in various solvents as in the gas phase. Thus a solvent plays a
subsidiary role. Reactions that occur in the gas phase as well as in
solution show similar behaviour in solution as in the gas and the reaction
is not affected by the solvent.
(ii) If a reaction does not occur in the gas phase the influence
of solvent on the reaction can be studied, by comparing the kinetics of
reactions in different solvents. Eg., reaction between triethylamine &
ethyliodide has been studied in 22 different solvents by Menschutkin. It
is found that k, A and Ea vary considerably from solvent to solvent. A
similar wide variation was found in the reaction between pyridine and
methyl iodide.
Factors determining reaction rates in solution
A reaction between 2 molecules in solution involves 3 steps:
1. Diffusion of the reactant molecules towards each other.
2. Actual chemical transformation and
3. Diffusion of the products away from each other.
In most of the reactions, chemical transformation is the slow rate
determining step. If diffusion step would be slow, the activation energy will
be lower (not greater than 20 kJ mol-1). Most of the chemical reactions have
high Ea values.
Activity Coefficients (Application of Transition state theory to reactions in
solution)
Transition state theory was applied to reactions in solution by Wynne-
Jones, Eyring, Evans & Bell. As it is difficult to formulate partition functions
for substances in the liquid solution, it is convenient to use CTST-thermodynamic
65
derivation which will involve activity coefficients in order to estimate the
rate constant of a reaction in solution.
Consider a reaction A + B X in which the reactants A & B are in
quasi equilibrium with the activated complex. Then the equilibrium constant
of the reaction is

Thus

where A = activity coefficient of A

B = activity coefficient of B
 = activity coefficient of X
In case the reaction takes place in gas phase, the activity coefficients
may be neglected because they will be closer to unity. For a reaction in
solution, the activity coefficient factors differ markedly from unity  they
have to be included.
According to CTST, the rate of reaction is directly proportional to the
concentration of the activated complex.


(or)

 the rate constant in solution

... (1)

In an ideal gaseous system A = 1, B = 1 and  = 1.

... (2)
Comparing the rate constants for reaction in solution and reaction in
gas phase.
(1)  (2)

... (3)

= activity coefficient factor

66
 This equation (3) relates the rate constant for a reaction in solution to
the rate constant of the same reaction in gas phase. Also this equation relates
the rate constant for a reaction in any solution to that in a very dilute solution
where substances behave ideally.
If rates in solution and in gas phase are to be equal, the activity
coefficient factor must be unity. This happens in an unimolecular reaction

A  X, where the activity coefficient factor is . If the reactant &

activated complex have similar structure, will be unity as A &  will

be closer. Then ks = kg.

Eg. Decomposition of N2O5 has equal rates in solution and in gas
phase. But when HNO3 or propylene dichloride is used, there is a complex
formed between the solvent and the reactant.  A decreases and the rate of
decomposition of N2O5 is low in these 2 solvents.

By applying the formula for reaction in solution, it

is found that the preexponential factor for a reaction in solution is

approximately 3 times that in the gas phase.
Influence of Solvation
Solvent effects can be studied in terms of extent of solvation of the
reactants and activated complex.
Consider the reaction between pyridine and methyl iodide.

H H H H
+ 
+
N +H C I N C I N C+I
H H H H
The products are separated ions and in the activated complex, there is
partial ionisation. In a polar solvent, such as nitrobenzene, there is more
solvation of the activated complex than of the reactants. The effect of
solvation is to lower the activity coefficient. Thus  is low compared to A

& B. As a result the rate is high, according to the equation .

A polar solvent solvates the activated complex more than the reactant if the
reactions involves formation of ions.
Consider the reaction

There is a decrease in polarity as the activated complex is formed.

A polar solvent therefore solvates the activated complex less than the reactants.
67
 The activity coefficients of the reactants will be lesser than for the
activated complex. Thus the rate is less. A polar solvent reduces the rate of
the reaction where there is decrease in polarity.
Influence of Ionic Strength
Ionic strength is defined as

I=

where ci is the concentration of each ion present in the solution and zi is the
charge number.
The rates of II order reactions between charged species are strongly
affected by ionic strength of the solution. When the reacting species are of
the same sign, an increase in ionic strength increases the rate. When the ions
are of opposite sign, the rate decreases with increasing ionic strength.
Consider the reaction

The rate of the reaction is expressed as

... (1)

where k0 is a constant at a given temperature.

yA – activity coefficient of reactant A
yB – activity coefficient of reactant B
yX – activity coefficient of the collision complex formed when A & B come
together.

The ratio is called kinetic activity factor.

It is found that the use of kinetic activity factor gives satisfactory

agreement with experiment.
According to Debye Huckel theory, the activity coefficient yi of an ion
is related to the ionic strength by the equation
log10yi = ... (2)
where Zi – charge number of the ion.
B is calculated from Debye Huckel equilibrium. Its value is approximately
0.51 dm-3/2 mol-1/2 for aqueous solutions at 25°C. In the second order reaction
A + B  products, the rate constant k is given by equation (1) as

Taking log10,
log10k = log10k0 + log10yA + log10yB – log10yX
substituting for log10y from (2),
68
 log10k = log10k0

= log10k0

= log10k0
= log10k0 + 2BZAZBI1/2
= logk0 + 1.02ZAZBI1/2 B = 0.51
1/2
= 1.02 ZAZB I

This is Bronsted-Bjerrum equation, where k0 is the rate constant

extrapolated to zero ionic strength.
Test of the equation
In media of varying ionic strength, the rates of ionic reactions are

measured. According to Bronsted Bjerrum equation, when is

1/2 -3
plotted vs I (mol dm ), a straight line is obtained with slope 1.02 ZAZB. The
slopes of the reactions can be theoretically calculated.
[Co(NH35Br]2+ + Hg2+, Slope = 1.02  ZAZB = 1.02  4
, Slope = 1.02  ZAZB = 1.02  2
[Co(NH3)5Br]2+ + OH-, Slope = 1.02  ZAZB = 1.02  (-2)
Lines are drawn with theoretical slopes. Experimentally, the rate
constants are determined by varying ionic strength and they are plotted.
These points lie close to the theoretical lines. This proves the Bronsted –
Bjerrum equation.
If one of the reactants is a neutral molecule, ZAZB is zero and the rate
constant should be independent of ionic strength. Thus a horizontal straight
line parallel to X-axis is expected. However, small effects are found for such
ion-dipole reactions.

69
(A) Co(NH3)5Br2+ + Hg2+
(B)

(C) CO(O2H5)N. + OH-

(D) [Cr(urea)6]3+ + H2O (open circle)
CH3COOC2H5 + OH- (closed circle)
(E) H+ + Br + H2O2
(F) Co(NH3)5Br2+ + OH-
(G) Fe2+ + Co(C2O4)3-
Solvent Dielectric Constant
The electrostatic forces between ions are much stronger than non
electrostatic forces.  in ionic reactions, the pre-exponential factors depend
on ionic charges. If the ions are of opposite signs, the frequency of collisions
is increased by attractive forces and the pre-exponential factors are abnormally
high. If the ions are of the same sign, the frequency of collisions is decreased
by repulsive forces and the pre-exponential factors are abnormally low.
The influence of solvent on the rates of reactions between ions is
explained based on electrostatic theory.
Double-sphere model of an activated complex
According to the double sphere model, the ions are considered to
remain intact as they approach each other in order to form double sphere
activated complex in which the centres of the ions are separated by a distance
dAB.
Consider 2 ions A and B. The charges on the ions are zAe and zBe where
zA & zB are the charge numbers and e is the elementary charge (1.602  1019
C). The solvent is regarded as a continuum with a dielectric constant .
Initially the ions are at infinite distance apart. Then the ions remain intact as
they approach each other to form the double sphere activated complex.
According to coulomb’s law when the ions are separated by a distance
x, the force acting between them is,

where  = dielectric constant of medium

0 = permittivity of the medium
The work done on the system in moving the ions together towards each
other through a small distance dx is dw.

... (1)

As x decreases by dx, the –ve sign is included.

70
 The work done on the system in moving the ions together from infinite
distance (x = ) to form the double sphere activated complex in which
x = dAB is given by integration of (1).

If the ions are of same sign, the work done is +ve.

If the ions are of opposite sign, the work done is –ve.
This work is the electrostatic contribution to Gibbs energy of
activation when 2 ions form an activated complex.

L = Avogadro number
The total molar Gibbs energy of activation is the sum of electrostatic
and non electrostatic contributions.

 by RT,

( )

Taking natural log,

This equation can be written as

k0 is rate constant in a medium of infinite dielectric constant, in which

the electrostatic force have become zero.
According to this equation, the logarithm of rate constant of a reaction
between ions varies linearly with the reciprocal of the dielectric constant.
This equation has been tested by carrying out a reaction to occur in a series of
mixed solvents of varying dielectric constant. This relationship is obeyed
reasonably although there are deviations at low dielectric constant.

71
 Reaction between bromoacetate and thiosulphate ions in aqueous

medium. For ions of same sign log kr decreases as increases.

Significance
1. Calculation of dAB

The slope of the line obtained by plotting is . As

all other terms except dAB are known in this slope, dAB can be calculated from
experimental slope. In a number of cases, the values obtained in the order of
a few hundred picometers are reasonable.
2. Preexponential Factors
The electrostatic contribution to entropy of activation,

As

72
 In equilibrium  = 78.5 and = 0.0046 k-1 over a

considerable temperature change. When dAB is taken as 200 pm, then

.
For each unit of ZAZB, entropy of activation should decrease by 41 JK -1
mol-1. As pre-exponential factor is proportional to or .

Pre-exponential factor 

 10-2 when ZAZB = 1

 for ions of same sign, for each unit of ZAZB, the pre-exponential
factor and the rate should decrease by 10 2 times. For ions of opposite signs,
for each unit of ZAZB, the rate increase by 102 times.
Electrostriction (or) Solvent Binding
The solvent molecules in the neighbourhood of an ion are acted upon
by strong electrostatic forces. As a result, the freedom of motion is restricted
for the solvent molecules. Thus there is a reduction in entropy. This effect is
known as solvent binding or electrostriction. The reduction in entropy is
greater if the charge is larger.
(a) If the ions bear single positive charges, the activated complex
bears a double positive charge, if it is a double sphere activated complex.
As the reactant species are ions, there is some loss in entropy in the
initial state. In the activated state, there is much loss of entropy since the
charge is greater.  there is loss of entropy when the activated complex is
formed. S0 is –ve.
Eg. CH2ClCOO- + OH-
(b) If the reacting ions are of opposite signs, there is only less
charge on the activated complex, than on the reactant molecules. This is
because the activated complex is a double sphere. Consequently there is
decrease in electrostriction and there is increase in entropy when the
activated complex is formed. Thus S0 is +ve.
Eg. [Cr(H2O)6]3+ + CNS-
Effect of Pressure (Concept of volume of activation)
Generally, the reaction rates of gaseous reactions are determined at
constant volume and those of reactions in solution at constant pressure.
At normal pressures, the rate of a reaction in solution phase does not
depend on the pressure. But at high pressure considerable changes in the
reaction rates have been reported.
For any reaction, the standard free energy G0 is related to the
equilibrium constant (K) by the equation,
73
 G0 = RT ln K ... (1)
Hence for the reaction involving reactants and activated complex,
Reactants activated complex
the change in standard free energy is
G0 = RT ln K ... (2)
G0 = standard free energy of activation
= G0 of activated complex – sum of G0 of reactants
K = equilibrium constant for the above equation
Differentiating equation (2) w.r.t. P at constant T, we get

... (3)

Now G = H – TS
G = E + PV + TS
dG = dE + PdV + vdP – TdS – sdT
Since dq = dE + PdV = TdS
dG = VdP
At constant, dT = 0
(dG)T = VdP

=V

Hence for a change under standard state,

= V

(i.e.) = V ... (4)

Substituting (4) in (3)

= V ... (5)

V - volume of activation

V = molar volume of activated complex – sum of molar volumes of
reactants.
= V  Vreactants
The rate constant (k) of the reaction is related to K as follows

k=

ln k = ... (6)

74
Differentiating equation (6) w.r.t. P at constant temperature,

= ... (7)

from (5)

= substitute in (7)

= ... (8)

Integrating (8)

ln k =

when p = 0, k = k0
ln k0 = constant

Hence ln k = ln k0 ... (9)

The plot of ln k vs P (applied pressure) is a straight line, with slope

= .

V =  slope  RT


Thus volume of activation is determined graphically.

There may be different cases of equation.

75
Case 1
When V is negative
From equation (9), the rate constant k will increase with increase in P.
This is seen in those reactions where an increase in electrical charge takes
place in going from reactants to activated complex.
Eg. First order SN1 solvolysis and reactions of alkyl halides with amines.
These type of reactions are known as slow reactions.
Case 2
V is negligibly small

The factor in equation (9) will be too small to be neglected.

Hence
ln k = ln k0 = constant
(i.e.) reaction rate (k) is almost independent of pressure. This happens in
those reactions in which the activated complex possesses the same charge as
the reacting species.
Eg. SN2 reaction between OH and primary alkyl halides
OH- + R – X  [HO- ... R – ... X]  HO – R + X-
Such reactions occur at normal rates.
Case 3
When V is positive
According to equation (9), ln k will decrease with an increase in P.
This arise in those reactions involving oppositely charged ions such that the
charge decreases from reactants to transition state. For eg.,
[Co(NH3)5Br]2+ + OH-  [HOCO(NH3)5Br]+  [Co(NH3)5OH]2+ + Br-
These type of reactions are generally fast.
Significance of V
1. For reactions between opposite ions
In such reactions, oppositely charged reacting ions  transition state
 products.
The transition state will have weaker electrical field, resulting into
release of the solvent molecules from its coordination which give rises
to +ve V and S values.
2. For reactions between ions of same sign charges
In such reactions the transition state will have stronger electrical field
than that of reacting ions. This causes a decrease in volume and also a
loss of degree of freedom and hence causing a decrease of entropy
(i.e.) S = -ve.
3. Establishing the mechanism of reactions
The V has been used for establishing the mechanism of reactions by
providing the concept about the nature of transition state.
76
Catalysis by Enzymes
Enzymes are biological catalysts. They are more specific than by acids
and bases. Some enzymes show absolute specificity.
Lower degree of specificity is shown by proteolytic enzymes which
catalyze the hydrolysis of peptide linkage provided that certain structural
conditions are satisfied in the neighbourhood of the linkage. This is known as
group specificity.
Some catalysts catalyse the reactions of one stereo chemical form and
not the other. They are known to have stereo chemical specificity. Eg. The
proteolytic enzymes catalyse the hydrolysis of peptides made from amino
acids in the L configuration.
The enzymes are proteins associated with nonprotein substances
(known as coenzymes or prosthetic group) that are essential to the action of
the enzyme.
The catalytic activity of enzymes is due to a relatively small region of
the protein molecule. This region is referred as active centre.

Influence of Substrate Concentration

Single substrate enzyme catalysis
1. The rate varies linearly with the substrate concentration at low
concentrations (I order).
2. Becomes independent of [sub] at high concentration (zero
order).

Fig. A: This type of behaviour is explained by Michaelis Menten.

Mechanism
E+S ES (ES – addition complex)

ES E+P
Applying steady state principle
77
 k1[E] [S] – k-1[ES] – k2[ES] = 0 ... (1)
In enzyme reactions [subs] >> [E]. Only a small proportion of the
substrate is bound to the enzyme.
Hence
[E0] = [E] + [ES]
[E] = [E]0 – [ES]
substitute in (1)
k1([E]0 – [ES]) [S] – k-1 ES – k2[ES] = 0
k1[E]0 [S] – k1[ES] [S] – (k-1 + k2) [ES] = 0
k1[E]0 [S] = (k1[S] + (k-1 + k2)) [ES]

[ES] = ... (2)

v = k2[ES] ... (3)

= ... (4)

 by k1

u=

v=  Michaelis Menten equation ... (5)

where km =  Michaelis constant

when [S] is small

v=

Kinetics of reaction is first order w.r.t. [sub]

when [S] >> km,
 = k2[E0]
Kinetics of reaction is zero order.
The enzyme is then saturated with substrate and a further increase in
[S] has no effect on the rate.
Equation (5) can be rewritten as

v= ... (8)

where
V = k2[E]0

78
 V is limiting rate at high substrate concentration. It is often known as
maximal velocity.
when [S] = km, (8) becomes

v= ... (9)

This is shown in Figure (A).

The Michaeli’s constant km can be determined from a plot of v versus
[S], by finding the concentration of substrate that gives one half of the
limiting rate.

Consider the equation (8) v = , reciprocal of it is .

Plot of vs gives straight line with intercept and slope.

Line weaver – Burk Plot

V & km can be calculated from this plot. If [E 0] is known k2 can also be

calculated.
Eadie plot
If Michaelis – Menten equation (8) can be put in the form
vkm + v[S] = V[S]
 by [S],

... (10)

A plot of versus v gives slope and intercept.

 by km,

79
slope m =

intercept =

Eadie Plot

Example of Mechanism

E+S

Here, there are two products.

1. Y-formed by the breakdown of the Michaelis complex ES.
2. This breakdown gives second intermediate ES'.
3. This 2nd intermediate breaks down into enzyme and second
product Z.
Applying steady state treatment (rates of formation of both Y & Z)

v= ... (11)

This is of the form as (8) with

V= ... (12)

and

80
 km = ... (13)

when k3 >> k2,

equation (11) reduces to

In this case the intermediate ES' exists only at very low concentrations
and can be neglected so that the mechanism reduces to the simple one
intermediate mechanism.

In general, v = where kc is known as catalytic constant. This

equation applies to mechanisms having any number of sequential

intermediates ES  ES'  ES"  so on.

Kinetics of processes in micellar systems

The kinetics of micellar reactions are governed by electrostatic and
hydrophobic interactions between micelles and reactants, transition state
complexes and products. If any of the reaction species interacts with
micelles, then the presence of micelles will affect the reaction rate. Micelle-
catalyzed reactions are somewhat similar to enzyme-catalyzed.
In the simplest case, where we assume that the surfactant does not
complex with (i.e., solubilize) the substrate S, except when the former is in
the form of micelles M and that complexing between the substrate and the
micelle is in a 1:1 stoichiometric ratio, we can symbolize the formation of a
reaction product P as

where k0 is the rate constant for the reaction of the substrate in the bulk phase
and km is the rate constant for the reaction of the substrate in the micelle. The
overall rate constant for the reaction kp is then given by the expression

where f0 is the fraction of the uncomplexed substrate and fm is the fraction of

the complexed substrate. the equilibrium constant K for the interaction
between substrate and micelle, usually called the binding constant, is then
given by the relation

from which

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Since

and

Hence,

If we assume that [M] is given by the expression

where c is the total concentration of surfactant and N is the aggregation

number in its micelles, then the expression for the overall rate constant
becomes

Since the overall rate constant for the reaction kp and the rate constant
for the reaction in the absence of micelles k0 are readily obtained from kinetic
data, a plot of 1/(k0  kp) versus [1/c  CMC], which should be a straight line
with slope = N/K(k0  km) and intercept = 1/(k0  km), allows the calculation of
km, the rate constant for the substrate complexed with the micelles and K, the
binding constant of the substrate to the micelle.

EXERCISE
1. Identify the symmetry elements and assign the point group in
trans-dichloroethylene.
2. Write a short note on direct product?
3. What is meant by a class of a group?
4. State and explain great orthogonality theorem.
5. Deduce the character table for C2v point group.
6. Explain the application of CTST to reaction kinetics.
7. Write briefly about the potential energy surfaces.
8. What is meant by primary and secondary kinetic isotope effect?
9. Derive Bronsted Bjerrum equation.
10. Deduce Michaelis Menten equation.
11. Discuss the mechanism of H2 – O2 explosion reaction.
12. State the principle of microscopic reversibility.

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