Symmetryy Operation

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UNIT-I
LESSON: 1 SYMMETRY ELEMENTS AND SYMMETRY OPERATIONS
CONTENTS
1.0. AIMS AND OBJECTIVES
1.1. INTRODUCTION
1.2. IDENTICAL CONFIGURATION
1.3. EQUIVALENT CONFIGURATION
1.4. SYMMETRY OPERATION
1.5. SYMMETRY ELEMENT
1.6. ROTATION AXIS OF SYMMETRY (Cn )
1.7. PLANE OF SYMMETRY OR MIRROR PLANE ()
1.8. CENTER OF SYMMETRY OR INVERSION CENTER (i)
1.9. ROTATION-REFLECTION AXIS N-FOLD (Sn )
1.10. IDENTITY (E)
1.11. INVERSE OPERATIONS
1.11.1. INVERSE OF s And i
1.11.2. INVERSE OF ROTATION [Cn -1 ]
1.11.3. INVERSE OF Sn
1.12. LET US SUM UP
1.13. CHECK YOUR PROGRESS
1.14. LESSON - END ACTIVITIES
1.15. REFERENCES
The aim is to motivate and enable a comprehensive knowledge on symmetry elements
and symmetry operations to the students.
On successful completion of this lesson the student should have:
*
Understand the symmetry elements and symmetry operations.
1.1. INTRODUCTION
Symmetry is a very fascinating phenomenon in nature. It is found in geometrical figures
such as a cube, a sphere, an equilateral triangle, a rectangle, a square, a regular pentagon, a
regular hexagon etc. Its importance was recognized by eminent Greek philosophers Pythagoras
and Plato.
1.2. IDENTICAL CONFIGURATION
An identical configuration is the one which is not only indistinguishable from the original
one but also identical with it.
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2
1.3. EQUIVALENT CONFIGURATION
An equivalent configuration is the one which cannot be distinguished from the original
one but need not be identical with it.
1.4. SYMMETRY OPERATION
A symmetry operation is a movement of the molecule such that the resulting
configuration of the molecule is indistinguishable from the original.
1.5. SYMMETRY ELEMENT
A symmetry element is a geometrical entity such as a line or a space or a point about
which an operation of rotation or reflection or inversion is done.
1.6. ROTATION AXIS OF SYMMETRY (Cn)
It is also called rotational axis, if a rotation around an axis by 360/n results in a
molecule indistinguishable from the original. Examples are water (C2 ) and ammonia (C3 ). A
molecule can have more than one symmetry axis and the one with the highest number of n is
called the principal axis and takes the z-axis in a Cartesian coordinate system.
This axis of symmetry can be explained by taking the example of triangular planar boron
trichloride molecule. In boron trichloride molecule an axis of symmetry is located perpendicular
to the plane containing all the atoms. This is known as the C3 axis of symmetry. In general the
symbol for proper axis of symmetry is Cn where n is known as the order of the axis. The order of
the axis is given by the number of rotations by q, to get the identical configuration. n i s
2p
alternatively given by the formula n =
, where q is the minimum angle of rotation to obtain
q
the equivalent configuration. n has non- zero positive integral values. Boron trichloride molecule
has three C2 axes of symmetry in addition to the C3 axis (Fig.1.1). The C3 axis in this molecule is
known as principal axis. In general, if there are Cn axes of different orders in a molecule, the axis
with the highest order is referred to as the principle axis.
C2
Cl
B
Cl
Cl
(a)
3
C3
Cl
Cl
B
Cl
(b)
Fig.1.1.
(a). The C2 axis of symmetry in BCl3 molecule.

(b). The C3 principal axis in BCl3 molecule.
1.7. PLANE OF SYMMETRY OR MIRROR PLANE ()

If reflection through a plane leaves an identical copy of the original molecule it has a
plane of symmetry. Water has two of them: one in the plane of the molecule itself and one
perpendicular to it. A symmetry plane parallel with the principal axis is dubbed vertical (v ) and
one per perpendicular to it horizontal (h ). A third plane exists: if a symmetry plane bisects the
angle between two n-fold axes that are perpendicular to the principal axis the plane is dihedral
(d). A plane can also be identified by its plane (xz),(yz) in the Cartesian coordination plane.
C2
C2
sv
sv
O
H
H
Fig. 1.2. The reflection planes in water molecule.

1.8. CENTER OF SYMMETRY OR INVERSION CENTER (i)
A molecule has a center of symmetry when for any atom in the molecule an identical
atom can be found when it moves in a straight through this center an equal distance on the other
side. An example is xenon tetrafluoride but not cisplatin even though both molecules are square
planar.
This is a point such that any line drawn through it meets the same atom at equal distances
in opposite directions. All homo-nuclear diatomic molecules possess the centre of symmetry.
4
Fig.1.3 lists the molecules with centre of symmetry. This element of symmetry is also called S2
axis.
A particular symmetry element generates many symmetry operations. A Cn axis generates
a set of operations C n1 , C n2 , C n3 ,....., C nn . The C nn operation is equivalent to the identity operation.
H
C
Fig.1. 3. Diagram showing molecules with centre of symmetry.

1.9. ROTATION-REFLECTION AXIS N-FOLD (Sn )
It is also called improper rotational axis. Molecules with this symmetry element can
have a 360/n rotation around an axis followed by a reflection in a plane perpendicular to it
without a net change. An example is tetrahedral silicon tetrafluoride with three S3 axes and the
staggered conformation of ethane with S6 symmetry.
It is the line about which a rotation by a specific angle followed by reflection in a plane
perpendicular to the rotation axis is performed. Fig.1.4 shows the S6 axis in staggered from of
ethane.
H
H
H
H
C
C
H
s
C6
H
C
H
C
C
H
Fig.1.4. The S6 axis in staggered form of ethane.

1.10. IDENTITY (E)
This is a default symmetry element and every molecule has one.

1.11. INVERSE OPERATIONS
Suppose for a molecule we carry out an operation P followed by Q such that Q returns all
the atoms of the molecule to their original position then, Q is said to be the inverse of P. In such
cases,
QP = E =PQ
Algebraically we can express Q = P-1 , thus we can write P-1 P = E = PP-1 because an
operation and its inverse always commute.
1.11.1. INVERSE OF s And i
In the case of inversion and reflection, the carrying out of these operations in succession
leads to identity E, i.e. s.s = s2 = E and i.i= i2 = E. Hence in these cases, these operations
themselves are their own inverse that i = i-1 and s = s-1 .
1.11.2. INVERSE OF ROTATION [Cn-1 ]
In the case of rotation, simply carrying out an operation for the second time does not give
the original configuration. In Cn is the clockwise rotation by (2p/n)0 then Cn -1 is an anticlockwise
rotation by (2p/n)0 about Cn . Then, Cn -1 Cn = E.
For example, in NH3 molecule C 3-1C 3 = E .
C3
C3
C3-1
C3+
N
H1
H2
H3
Clockwise
rotation
Anti-clockwise
rotation
N
H2
H3
N
H1
H2
H3
H1
At the same time, for NH3 , C32 C31 = E

The above way of carrying out the symmetry operations successively is algebraically
represented as multiplication. If P and Q are two symmetry operations, PQ is a combined
operation of carrying out Q first and then P. By conversion, first operation is written at right. For
example, in the second case shown above for NH3 molecule, carrying out C2 first and then sv is
represented as sv C2 .
1.11.3. INVERSE OF Sn
As with Cn -1 , Sn-1 can be defined as rotation anticlockwise by (2p/n)0 followed by
reflection with perpendicular plane. We can prove for improper axis.
)(
S n-1 S n1 = C n-1s h C n1s h = E
C n1s = s C n1
Since
)(
) (
)(
S n-1S n = Cn-1s h Cn1s h = Cn-1s h s hCn1
= C n-1 s h s h C n1 = C n-1 EC n = C n-1C n = E

However, we can express Sn -1 interms of clockwise rotation about the same axis. We know that
Sn n= E when n is odd. Then
S nn -1 S n1 = E (n-even) Thus, S n-1 = S nn -1
S n2 n-1 S n1 = E (n-odd) Thus, S n-1 = S n2 n -1
1.12. LET US SUM UP

In this lesson, we:
Pointed out
Identical configuration
Equivalent configuration
Symmetry operation
Symmetry element
Rotation axis of symmetry (Cn )
Plane of symmetry or mirror plane ()
Center of symmetry or inversion center (i)
Rotation-reflection axis n-fold (Sn )
Identity (E)
Inverse operations
Inverse of s and i
Inverse of rotation [Cn -1 ]
Inverse of Sn

1.
2.
What is n improper axis of rotation? What are the operations generated byS5 ? How
many of these are the distinct operations of S5 ?
Prove the following:
a) S2 =I b) S 62 = C 3 and c) S nn = E
7
1.
2.
(a) Distinguish between

(1). Symmetry element and symmetry operations.
(2). Proper and improper rotation.
(b) Show that C2 (z) and s(xy) commute.
What is an inverse operation? Is this equivalent to any other combination of operations?
Give an example.
1.15. REFERENCES
1.
K.V. Raman, Group Theory and its applications to Chemistry, Tata McGraw-Hill
Publishing Company limited, New Delhi.
2.
B.R. Puri, L.R. Sharma and M.S. Pathania, Principles of Physical Chemistry, Millennium
edition, 2006- 2007.
3.
V. Ramakrishnan, M.S Gopinathan, Group Theory in Chemistry, Vishal Publications.
LESSON: 2 GROUPS AND THEIR BASIC PROPERTIES

CONTENTS
2.1. INTRODUCTION
2.2. GROUP
2.2.1. BASIC PROPERTIES OF A GROUP
2.2.2. ORDER OF GROUP
2.2.3. ABELIAN GROUP
2.2.4. NON-ABELIAN GROUP
2.2.5. ISOMORPHISM
2.3. SIMILARITY TRANSFORMATION AND CLASSES
2.3.1. SIMILARITY TRANSFORMATION
2.3.2. CLASS
2.4. GROUP MULTIPLICATION TABLE
2.4.1. IMPORTANT CHARACTERISTICS OF A GROUP MULTIPLICATION
TABLE
2.5. SYMMETRY CLASSIFICATION OF MOLECULES INTO POINT GROUPS:
2.6. DIFFERENCE BETWEEN POINT GROUP AND SPACE GROUP
2.7. LET US SUM UP
2.10. REFERENCES

The aim is to motivate and enable a comprehensive knowledge on groups and their basic
properties to the students.
*
Understand the groups and their basic properties.
2.1. INTRODUCTION
Having defined various symmetry operations in Lesson 1 we may now ask ourselves
whether it is possible to classify the molecules into Groups on the basis of the symmetry
elements they posses. Is it possible to define certain symmetry groups so that all molecules
belonging to a certain group have the same type of symmetry operations? Luckily, the answer is
Yes. This means that we can give an accurate description of the symmetry of any molecule by
knowing to which group it belongs.
2.2. GROUP
A group is a complete set of members which are related to each other by certain rules.
Each member may be called an element.
2.2.1. BASIC PROPERTIES OF A GROUP

Certain rules have to be satisfied by the elements so that they form a group. These rules
are the following:
1.
2.
The product of any two elements and the square of any element must be elements of
group (closure property).
There must be one element in the group which commutes with everyone of the elements
and leaves it unchanged.
The associative law of multiplication should be valid.
For every element there must be a reciprocal (inverse) and this reciprocal is also an
element of the group.
3.
4.
RULE 1
If A and B are the element of the group and if AB = C, C must be a member of the group.
Product AB means that we perform the operation B first and then operation A i.e., the sequence of
operations is from right to left. It should be noted that the other product BA need not be same as
AB. BA means doing A first and then performing the operation B later. Let BA = D. D must be a
member of the group by rule 1. Usually AB BA and so C D. However, there may be some
special elements A and B each that AB = BA. Then A and B are said to commute with each other
or the multiplication of A and B is commutative. Such a group where any two elements commute
is called an abelian group. H2 O belongs to an abelian group. The four symmetry operations for
H2 O are E, C2z, sv(xz) and sv(yz).The inter-relationships between these operations are given in the
group multiplication table (Table 2.1).
Table 2.1.
E
E
C2z,
C2z
sv(xz)
sv(xz)
sv(yz)
sv(yz)
C2z
C2z
sv(yz)
sv(xz)
sv(xz)
sv(xz)
sv(yz)
C2z
sv(xz)
C2z
sv(yz) sv(yz)
Note that each member is its own inverse. The product of any two operations is found
among the four members.
( )
E 2 = C 22 = s v'
=E
s v s v' = s v' s v = C2 ; C2 s v = s v C2 = s v' etc
All these are noted from the table.
10
RULE 2
Each group must necessarily have an element which commutes with every other element
of the group and leaves it unchanged.
Let A and B be the elements of the group. Let X be the element satisfying rule 2.
i.e. XA = AX = A and also XB = BX = B.
BA = BX2 A; BX2 = B = BE, where we have set X2 = E (identity)
It is clear BEn = B, n being any integer. This kind of element E which does not effect any
change when multiplied with any element is a unique element and is called an identity operation
E. For water, E, the identity operation satisfies this rule. It is so for all molecules.
RULE 3
Associative law of multiplication must be valid. This means ABCD is the same as (AB)
(CD), (A) (BCD) or (ABC) (D). ABC is the same as A(BC) or (AB)C.
For example, we have for water
C 2s v Es v' = (C 2s v ) Es v' = s v' s v' = E
C 2s v' Es v = C 2 s v' E s v = C 2s v s v' = C 2
Multiplication simply means successive application of the symmetry operations in the

order right to left.
RULE 4
Inverse of an element A is denoted by A-1 (this does not mean 1/A). It is simply an
element of the group such that A-1 A=E. In case of symmetry groups, A-1 is that element which
undoes or annuls the effect of A. For H2 O we have, for example, C2 C2 = E. Therefore C 2-1 = C 2
i.e., C2 is its own inverse. This is true of all other elements for H2 O. But this is not general. For
example, C 62 = C3 E . Therefore C 6-1 is not C6 .
2.2.2. ORDER OF GROUP
The total number of elements present in a group is known as the order of the group. It is
denoted by n.
Example:
1.
2.
Water molecule belongs to C2v group of order 4 because it contains 4 elements namely E,
C2z, sv and sv.
Ammonia belongs to C3v group of order 6 as it contains 6 elements namely E, C3 1 , C32 ,
sv(1), sv(2) and sv(3).
11
2.2.3. ABELIAN GROUP
A group is said to be abelian if for all pairs of elements of the group, the binary
combination is commutative. That is AB = BC; BC = CB and so on.
Example: The elements of C2v point group E, C2z, sv and sv form an abelian group as all the
elements of this group commute with each other.
2.2.4. NON-ABELIAN GROUP
A group is said to be non-abelian if the commutative law does not hold for the binary
combinations of the elements of the group, i.e., AB BA.
Example:
The elements of C3v point group E, C 3 1 , C3 2 , sv(1), sv(2) and sv(3) donot consecutive an
abelian group since the elements donot follow commutative law.
2.2.5. ISOMORPHISM
Two groups are supposed to be isomorphic if they obey the following rules.
1.
2.
3.
Both have same order and structure.

There is a one-to-one correspondence in all respects between the members of the two
groups. If A1 , B 1 , C 1 , D 1 and A2 , B 2 , C 2 , D2 are the members of the two isomorphic
groups, A1 corresponds to A2 , B1 corresponds to B2 and so on.
The relationship between the any two members of a group is exactly the same as the
relationship between the corresponding members of the other group.
Let us take the three groups listed below:
(i) E, C2
(ii) E, i
(iii) E, sh
All the three are isomorphic groups.
E = C 22 ; C 2 E = C 2
E = i 2 ; iE = i
E = s h2 ; s h E = s h etc.
2.3. SIMILARITY TRANSFORMATION AND CLASSES

2.3.1. SIMILARITY TRANSFORMATION
Let A and X be the elements of a group and let us define B such that
B = X-1 AX
12
B is called the similarity transform of A by X, or A is said to be subjected to similarity
transformation with respect to X. If A and B are related by a similarity transformation they are
called conjugate elements.
Take the NH3 molecule, for instance. Z axis is the C3 axis.
Z
s "'
N
Hc
120
C3Z
N
Hc
Ha
N
Ha
Hb
Hb
Hc
Hb
Ha
s"'
Z
N
Hc
Ha
C32Z
N
Ha
Hb
Hb
Hc
Fig. 2.1. Illustration of similarity transformation on NH3 .
1.
2.
3.
There are three reflection planes. These are usually designated as follows:
Plane formed by z-axis and NHa bond: s or sa or sv.
Plane formed by z-axis and NHb bond: s or sb or sv.
Plane formed by z-axis and NHc bond: s or sc or sv.
Let us prefer the designation s, s and s.

Let us perform a reflection (s) with respect to the plane formed by NHc and z-axis. Let
us perform s again. s2 = E.
Now let us find the similarity transform of C3 w.r.t. s, i.e., (s)-1 C3 s = ?
It is seen from the Fig. that (s)-1 C3 s = C 32 . Remember (s) = (s)-1 . Thus C3 and
C 32 are conjugate elements.
The following rules about conjugate elements are notable:

1.
2.
Every element is conjugate of itself because every element is the similarity transforms of
itself w.r.t. identity (E): E = E-1 and A = E-1 AE.
If A is the conjugate of B then B is the conjugate of A. This means that if A is the
similarity transform of B by X, B is the similarity transform of A by X-1 . We have
A = X-1BX
13
But (X-1 )-1 AX-1 = XA X-1 = X (X-1 BX) X-1
= (XX-1 ) B (XX-1 ) = B (associative law)
3.
If A is the conjugate of B and B is the conjugate of C, then A, B and C are mutually

conjugate.
2.3.2. CLASSES
A complete set of elements which are conjugate to one another is called a class of the
group.
Let us consider NH3 . Set us the coordinate system in such a manner that ZNHa is in the yz
plane. (Fig. 1) s is then syz. Without disturbing the NH3 molecule rotate the coordinate system
by 120 w.r.t z axis, i.e., subject the coordinate system to C3 . Now yz plane is ZNHb . syz is s, s
and s are equivalent. s becomes same as that of s if we change the coordinate system by a
symmetry operation (C3 ) of the point group. s and s are therefore in the same class.
Example:
Show that the three reflections of NH3 constitute a class. It is not difficult to show
-1
that C .C 3 = E . Hence, C32 = (C3 ) .
Let as perform the similarity transformation of s by C3 in NH3 .
2
3
C3-1s 'C3 = C32s 'C3 = s "
Thus s and s are conjugate. Similarly we can show that s, s and s are mutually
conjugate. Therefore s, s and s form a class.
2.4. GROUP MULTIPLICATION TABLE

Every group is characterized by a multiplication table. The relationship between the
elements of the binary combinations is reflected in the multiplication table.
Consider a water molecule. It has four symmetry elements, viz., E, C2 (z), sv (xz) and
sv (yz) (Fig.2.2).
14
sv (xz)
z
C2
O
H
H
sv '(yz)
Fig. 2.2. The Four symmetry elements of H2 O molecules

We can easily show that the product of any two symmetry elements is one of the four
elements of the group. Thus, for instance, C2 (z)sv (xz) = sv (yz). Proceeding this way the
symmetry operations of H2 O can be listed in a group multiplication table (GMT) (Table 2.2).
E
C2 (z)
sv (xz)
sv (yz)
C2 (z)
sv (xz)
sv (yz)
E
C2 (z)
sv (xz)
sv (yz)
C2 (z)
E
sv (yz)
sv (xz)
sv (xz)
sv (yz)
E
C2 (z)
sv (yz)
sv (xz)
C2 (z)
E
Table 2.2. Group multiplication table of the symmetry operations of H2 O molecule

2.4.1. IMPORTANT CHARACTERISTICS OF A GROUP MULTIPLICATION TABLE
1.
2.
3.
4.
5.
It consists of h rows and h columns where h is the order of the group.

Each column and row is labeled with group element.
The entry in the table under a given column and along given row is the product of the
elements which head that column and the row (multiplication rule is strictly
followed).
At the intersection of the column labeled by Y and the row labeled by X, we found
the element which is the product XY.
The following rearrangement theorem holds good for every Group Multiplication
Table.
Each row and each column in the table lists each of the group elements once and only
once. No two rows may be identical nor any two columns be identical. Thus each row and
each column is a rearranged list of the group elements.
2.5. SYMMETRY CLASSIFICATION OF MOLECULES INTO POINT GROUPS

Molecules can be classified into point groups depending on the characteristic set of
symmetry elements possessed by them. A molecular group is called a point group since all the
elements of symmetry present in the molecule intersect at a common point and this point remains
fixed under all the symmetry operations of the molecule. The symmetry groups of the molecules
are denoted by specific symbols known as Schoenflies notations.
15
Table 2.3. Some Molecular Point Groups

Point
Group
C1
C2
C3
Cs
C2v
C3v
Cv
C2h
D2h
D3h
D4h
Symmetry Elements
Examples
D6h
Td
Oh
C 6 H6
E,2C6 ,6C2 (^ to C6 ),3sv , 3sd, sh , C2 ,2C3 ,2S6 , 2S3 ,i
CH4
E, 4C3 ,3C2 ,3S4 (coincidence with C2 ),6sd
E,3C4 ,4C3 ,3S4 and 3C2 (both coincident with the C4 SF6
axes), 6C2 ,4S6 , 3sh , 6sd
E
CHFClBr
E,C2
H2 O 2
E,C3
C 2 H6
NOCl
E,sv
H2 O,CH2 =O, pyridine
E,C2 ,2sv
NH3 ,CHCl3 ,PH3
E,C3 ,3sv
HCl, NO,CO
E,C,sv
trans CHCl=CHCl
E,C2 , sh , i
CH2 =CH2 ,naphthalene
E,3C2 , 3s, i
BF3 (trigonal planar)
E,2C3 , 3C2 (^ to C3 ),3sv , sh , 2S3
E,C4 , 4C2 (^ to C4 ),2sv , 2sd, sh , C2 , S4 (coincidence with [PtCl4 ]2- ( s q u a r e
planar)
C4 ), i
2.6. DIFFERENCE BETWEEN POINT GROUP AND SPACE GROUP

Symmetry operations do not alter the energy of the molecule. Further in all the above
operations the centre of the molecule is not altered as none of the operations involve a total
translational movement of the molecule. Whatever happens to the molecule, the centre (point) is
not changed. At least one point is fixed. Hence these are classified as point group operations.
In case of crystals operations such as screw rotations and glide plane reflections can be
additionally specified. Screw rotation involves a rotation with respect to an axis and then a
translation in the direction of the same axis. Glide plane reflection is a reflection in a plane
followed by a translation along a line in that plane. These are particular to crystals and the
classification comes under what is known as space group. Note that here even the centre changes.
Thus in short, in point group, there is at least one point (centre) which is not altered after all
operations while in space group it is not possible to identify such a stationary point.
2.7. LET US SUM UP
In this lesson, we:
Pointed out
Group
Basic properties of a group
Order of group
Abelian group
Non-abelian group
16
Isomorphism
Similarity transformation and classes
Group multiplication table
Symmetry classification of molecules into point groups
Difference between point group and space group

1.
2.
Explain why a set of numbers cannot form a group by the process of division.
Explain why the set of integers between 0 and do not form a group under the process of
multiplication.

1.
2.
Construct the multiplication table for the C3v point group to which NH3 molecule
belongs.
Draw the structure of three distinct isomers of C2 H2 Cl2 and determine their point groups.
Which of them is polar?
2.10. REFERENCES
1.
2.
edition, 2006- 2007.
3.
17
UNIT-II
LESSON 3: REDUCIBLE AND IRREDUCIBLE REPRESENTATIONS
CONTENTS
3.1. INTRODUCTION
3.2. REDUCIBLE REPRESENTATION
3.3. IRREDUCIBLE REPRESENTATION
3.4. GRAND/GREAT ORTHOGONALITY THEOREM (G.O.T.)
3.5. CHARACTER TABLES FOR POINT GROUPS
3.6. CALCULATION OF CHARACTER VALUES OF REDUCIBLE REPRESENTATION
PER UNSHIFTED ATOM FOR EACH TYPE OF SYMMETRY OPERATION
3.6.1. IDENTITY (E)
3.6.2. INVERSION AT THE CENTRE OF SYMMETRY (i)
3.6.3. REFLECTION IN A SYMMETRY PLANE (s)
3.6.4. PROPER ROTATION Cn
3.7. DETERMINATION OF TOTAL CARTESIAN REPRESENTATION T3N
3.8. DETERMINATION OF DIRECT SUM FROM TOTAL CARTESIAN
REPRESENTATION
3.9. LET US SUM UP
3.12. REFERENCES

The aim is to motivate and enable a comprehensive knowledge on reducible and
irreducible representations to the students.
*
Understand the reducible and irreducible representations.
3.1. INTRODUCTION
The set of matrices corresponding to the symmetry operations of a group is called its
representation. Representations can be classified into (a) Reducible representations (reps) and
(b) irreducible representations (irreps).
3.2. REDUCIBLE REPRESENTATION
Let A, B, C Be the matrices which form the representation of a group and let X be the
similarity transformation matrix of this group such that
18
X-1 AX = A
----- (1)
X-1 BX = B
----- (2)
X-1 CX = C
----- (3)
Then, if X is the proper transformation matrix, we have

a1'
0
a2'
X-1AX = A' =
a3 '
a4'
----- (4)
The new matrix A is now blocked out along the diagonal into smaller matrices a1 , a2 ,
a3, a4, etc., with the off-diagonal elements equal to zero. Similarly, we have
b1'
0
b2'
X-1BX = B' =
b3'
b4'
----- (5)
This is expressed by saying that the given sets of matrices form a reducible
representation (rep).
3.3. IRREDUCIBLE REPRESENTATION
If it is not possible to find a similarity transformation which will reduce the matrices A,
B, C ... to block-diagonalized form, the representation is called an irreducible representation
(irrep).
3.4. GRAND/GREAT ORTHOGONALITY THEOREM (G.O.T.)
This is the most important theorem of group theory. It concerns the matrix elements
which constitute the irreps of a point group. Mathematically it is stated as follows:
G (R )
i
G j (R ) m ' n ' =
*
mn
h
li l j
d ij d mm 'd nn '
----- (6)
19
Here Gi and Gj are the ith and jth irreps of a point group of order h with dimensions li and lj,
respectively; Gi (R)mn is the mnth matrix element corresponding to the symmetry operation R
belonging to the ith irrep and Gj (R)mn, is the complex conjugate of the mnth matrix element
corresponding to the symmetry operation R belonging to the jth irrep. The ds are the well known
Kronecker deltas which have the following property:
1, i = j
1, m = m'
1, n = n'
d ij =
; d mm ' =
; d nn ' =
0, i j
0, m m'
0, n n'
----- (7)
The summation is performed operations R of the molecule. If the matrix elements are
real, then
Gi (R) mn = Gj (R)mn
----- (8)
The following three cases arise for the G.O.T. assuming that the matrix elements are real:
1. For two different irreps, i
G (R )
i
mn
j, m=m and n=n,
G j (R )mn = 0
----- (9)
2. For the same irrep i=j, m m and n n,

Gi (R )mn G j (R )m'n' = 0
----- (10)
3. For an irrep I and for m=m, n=n,
[G (R ) ]
mn
----- (11)
= h li
In practice, we do not use the G.O.T. in the form given above but in a slightly different
form involving the characters of the irreps.
3.5. CHARACTER TABLES FOR POINT GROUPS
For practical purposes, it is sufficient to know only the characters of each symmetry class
of a point group to which a molecule belongs. A character table lists the characters of all the
symmetry classes for all the irreps of a group. Character tables for the C2v and C3v point groups
are given in Tables 3.1 and 3.2.
Table 3.1. Character table for C2v point group
C2v
I
A1
A2
B1
B2
E
1
1
1
1
C2 (z)
1
1
-1
-1
sv (xz)
II
1
-1
1
-1
Table 3.2. Character table for C3v point group
sv (yz)
1
-1
-1
1
III
z
Rz
x, Ry
y, Rx
IV
x2 ,y2 ,z2
xy
xz
yz
20
C3v
I
A1
A2
E
E
1
1
2
2C3
II
1
1
-1
3sv
1
-1
0
III
IV
z
x2 +y2 ,z2
Rz
(x,y)(Rx ,Ry ) (x2 - 2 ,xy)(xz,yz)
The character tables can be obtained from the properties of the irreps given above. We
can explain the character table by dividing it into four sections I, II, III, IV.
Section I. In the top row, the Schoenflies symbol for the point group is given. This
section also lists the Mulliken symbols for the different irreps. Symbols A and B are used to
label one dimensional irreps and E and T to label two dimensional and three-dimensional irreps,
respectively. The nomenclature E should not be confused with the identity operation. A is used
when the character for the rotation about the principal axis is +1 and B when it is -1. In other
words, A stands for symmetric and B for antisymmetric to such rotation. For a molecule having
a centre of symmetry, the subscripts g and u are used to label the irreps that are respectively
symmetric and antisymmetric to inversion through the centre of symmetry. Subscripts 1 and 2 are
used to label the irreps that are resoectuvekt symmetric and antisymmetric to reflection in a
vertical plane s v . The superscripts are used it denote the irreps that are respectively symmetric
and antisymmetric to reflection in a horizontal plane s h .
Section II. This section gives the characters for all the symmetry operations of different
irreps. The characters of the identity operation for the one-dimensional, two-dimensional and
three- dimensional irreps are, respectively, 1, 2 and 3.
Section III. It gives the transformation properties of the Cartesian coordinates x,y,z and
rotations Rx , Ry , Rx about these axes.
Section IV. It gives the transformation properties of the binary products of Cartesian
coordinates xy,yz,zx etc. and the squares of the coordinates x2 , y2 , z2 , x2 + y2 , x2 + y2 +z2 etc. The
Cartesian coordinates, their squares and binary products, etc., listed in sections III and IV are
referred to as the basis functions on which the symmetry operations operate.
3.6.
CALCULATION
OF
CHARACTER
VALUES
OF
REDUCIBLE
REPRESENTATION PER UNSHIFTED ATOM FOR EACH TYPE OF
SYMMETRY OPERATION
The contribution to c (R ) per unshifted atom for all symmetry operations R can be
worked out in the following manner.
3.6.1. IDENTITY (E)
In this case, all three vectors remain unchanged for every unshifted atom as shown in Fig
3.1 where x=x, y=y and z=z. The transformation matrix therefore, includes diagonal elements:
21
+1
+1
+1
Then c (E ) per unshifted atom is +3.
z'
z
E
y'
x'
Fig. 3.1
3.6.2. INVERSION AT THE CENTRE OF SYMMETRY (i)

Fig. 3.2 shows the effect for each unshifted atom, where x = - x, y = -y, and z = -z.
Therefore, the matrix contains the following diagonal elements:
-1
-1
-1
Thus c (i ) per unshifted atom is -3.

z
x'
i
y
y'
x
z'
Fig. 3.2
22
3.6.3. REFLECTION IN A SYMMETRY PLANE (s)

The effect of any s on an unshifted atom is typically shown in Fig. 3.3, where x = x, y =
y and z = z. The transformation matrix, therefore,
+1
-1
+1
Thus c (s ) per unshifted atom is +4.
z'
z
s
y
y'
x
x'
Fig. 3.3
3.6.4. PROPER ROTATION Cn
Rotation is by (360/n)0 , usually about z axis. For the unshifted atom, the result is as
shown in Fig 3.4, where q = (360/n)0 . x =z, contributing +1 to c (C n' ) and x.y go to x, y
respectively.
z'
y
Cn
z
x
x'
y'
Fig. 3.4
3.7. DETERMINATION OF TOTAL CARTESIAN REPRESENTATION T3N

The total Cartesian representation T3N can be derived from the contribution c (R ) per
unshifted atom by simple arithmetic multiplication of c (R ) with the number of unshifted atoms
for every symmetry operation. Hence the calculation of T3N involves two steps (i) to count the
number of unshifted atoms for every symmetry operation. (ii) to calculate the contribution to
23
c (R ) for every unshifted atom in every type of symmetry operation. T 3N is also called the
reducible representation of the group for a particular transformation.
ILLUSTRATIONS
(i) For H2 0 molecule
This molecule belongs to C2v group. The number of unshifted atom for each symmetry
operation and the resultant T3N can be given as
C2v
sxz
syz
-1
C2
unshifted
atoms
T 3N
O
H
(ii) For POCl3 molecule

This molecule belongs to C3v point group. Since it is made of five atom, it will give
15 15 matrices. Using the method of unshifted atoms, the reducible representations can be
worked out as given below
C2v
2C3
3sv
O
unshifted
atoms
3
P
T 3N
15
Cl
Cl
Cl
Rotation by C3 1 or C32 leaves P and O unshifted. Reflection by any sv leaves P, O and one Cl
unshifted.
3.8. DETERMINATION OF DIRECT SUM FROM TOTAL CARTESIAN
REPRESENTATION
The direct sum of total Cartesian representation T3N can be determined using the
reduction formula.
24
ILLUSTRATION
(1) POCl3 molecule
The unshifted atoms and total Cartesian representation for this molecule which belongs to
C3v point group is given by
C 3v
unshifted
atoms
T 3N
2C 3
15
C3v
3sv
A1
2C3
A2
-1
-1
By applying reduction formula

1
[(1 15 1) + (2 0 1) + (3 3 1)] = 4
6
1
a( A2 ) = [(1 15 1) + (2 0 1) + (3 3 -1)] = 1
6
1
a(E ) = [(1 15 2 ) + (2 0 -1) + (3 3 0 )] = 5
6
a( A1 ) =
Therefore, the direct sum for total Cartesian representation is

T3N = 4A1 + A2 + 5E
(2) Reducible representation and direct sum for T3N for [PtCl4 ] 2[PtCl4 ] 2- belongs to D4h point group
Cl
Cl
Pt
Cl
Cl
D4h
2C4
C2
unshifted
atoms
T 3N
15
-1
-3
2C2'
2S4
sh
2sv
2sd
-1
-3
-1
2C2''
3sv
Using the character table for D4h point group and reduction formula, it can be shown that
25
T3N = A1g + A2g + B1g + B2g + Eg + 2A2u + B2u + 3Eu

3.9. LET US SUM UP
In this lesson, we:
Pointed out
Reducible Representation
Irreducible representation
Grand/great Orthogonality theorem (G.O.T.)
Character tables for point groups
Calculation of character values of reducible representation per unshifted atom for each
type of symmetry operation
Identity (e)
Inversion at the centre of symmetry (i)
Reflection in a symmetry plane (s)
Proper rotation Cn
Determination of total cartesian representation T3n
Determination of direct sum from total cartesian representation

1.
2.
Define reducible and irreducible representation.

Construct the C2v character table.
3.11. LESSON END ACTIVITIES

1.
2.
State and explain the Great Orthogonality Theorem. Use the conclusions obtained from
the Orthogonality theorem to construct the character table for C2v group.
Using the Great Orthogonality theorem to construct the character table for C3v point
group.
3.12. REFERENCES
1.
2.
edition, 2006- 2007.
3.
26
LESSON 4: GROUP THEORY AND VIBRATIONAL SPECTROSCOPY

CONTENTS
4.1. INTRODUCTION
4.2. GROUP THEORY AND NORMAL MODES OF VIBRATION OF POLYATOMIC
MOLECULES
4.3. INFRA-RED ABSORPTION AND RAMAN SCATTERING SPECTROSCOPY
4.4. DETERMINATION OF SYMMETRY PROPERTIES OF VIBRATIONAL MODES
4.5. SYMMETRY SELECTION RULES FOR INFRA RED RAMAN SPECTRA
4.6. MUTUAL EXCLUSION RULE
4.7. LET US SUM UP
4.10. REFERENCES

The aim is to motivate and enable a comprehensive knowledge on group theory and
vibrational spectroscopy to the students.
*
Understand the group theory and vibrational spectroscopy.
4.1. INTRODUCTION
Group theory is a very powerful tool at the hands of a chemist, a theorist and a
spectroscopist. It finds many applications the details of which are beyond the scope of this
lesson. Some important applications of group theory are listed below.
1. Construction of hybrid orbitals.
2. Construction of SALCs (symmetry adapted linear combinations of atomic orbitals).
SALCs are used in molecular orbital theory (MOT) of chemical bonding.
3. Determination of the irreducible to which the vibrational modes of molecules belong.
4. Determining which spectral transitions in infrared and Raman spectra are allowed or
forbidden.
5. Determining the selection rules for transitions in carbonyl compounds and other
chromophores. It is found that the former transitions are forbidden whereas the latter
are allowed.
6. Determining which molecules are polar or nonpolar.
4.2. GROUP THEORY AND NORMAL MODES OF VIBRATION OF POLYATOMIC
MOLECULES
Group theory helps in two aspects of vibrational spectroscopy.
27
(i)
(ii)
Firstly helps in the classification of the normal modes of vibrations according to the
irreducible representations of the point group of the molecule.
Secondly, it helps in qualitatively finding out Raman and IR spectral activity of the
fundamentals as well as overtone and combination bands.
The number of fundamental modes of vibrations can be worked out in the following
manner: Let us consider a molecule having N atoms. If we specify the position of each atom in
space with the coordinates x, y and z, then there will be 3N coordinates (degrees of freedom) for
the entire system. Since the molecule has translational, rotational and vibrational motion, these
3N coordinates (degrees of freedom) can be assigned to each type of motion as given below.
Motion
Degrees of freedom to describe the motion

Linear
3
2
3N-5
Translation
Rotation
Vibration
Non linear
3
3
3N-6
These degrees of freedom for vibrational motion are called the normal or fundamental
modes of vibration. Depending on the type of molecule, these normal modes may be active
either in IR or Raman or both. Example, the normal modes of vibration in H2 O and CO2
molecules.
A knowledge of the symmetry of vibrational modes in molecules will be helpful in

predicting whether these modes of vibrations will give rise to infrared or Raman spectrum or
both these spectra.
4.3. INFRA-RED ABSORPTION AND RAMAN SCATTERING SPECTROSCOPY
28
In infra-red spectrum, the sample is irradiated with infra-red radiation leading to
absorption of the radiation at frequencies corresponding to the absorptions give the vibrational
frequencies of that molecule. Thus, infrared technique is a direct measurement of the vibrational
frequencies which lie in infrared region.
In Raman spectroscopy, the molecules are irradiated with uv or visible radiation causing
perturbation of the molecule which in turn induces vibrational transitions. As a result, energy is
taken up from or given out to the incident radiation, which is scattered at a shifted frequency.
The differences in frequency between incident light and Raman scattered light correspond to
vibrational frequencies. Further in Raman spectroscopy, plane-polarized light is used as incident
light. The scattered light may be still polarized or depolarized. Hence, certain frequencies and
hence certain vibrational modes may be found to give polarized Raman light and others give
depolarized scattered light. Since in Raman spectroscopy a higher energy radiation than IR is
used, the resulting data would consist of a series of infra-red absorption lines and a series of
Raman scattered lines. These lines could be assigned to different vibrational modes only if the
symmetry properties of these modes are clearly understood.
4.4. DETERMINATION OF SYMMETRY PROPERTIES OF VIBRATIONAL MODES

The simple procedure for obtaining the representations of vibrational modes and hence
understanding their symmetry properties involve the following steps:
(i) Assign point group to the given molecule.
(ii) Deduce the reducible representation T3N for all the symmetry operations of the point group
using the relation
c xyz (R ) = U R c i (R )
------ (1)
Where c xyz (R ) = The character for the operation R in the reducible representation
U R = The number of unshifted atoms for the operation R

c i (R ) = The character for operation R per unshifted atom.
(iii) The reducible representation T 3N for the molecule is split into the various irreducible
representations of the point group by using the standard reduction formula
( h ) g c (R )c (R )
ai = 1
----- (2)
Rp
(iv) The irreducible representations T3N thus obtained correspond to the translational, rotational
and vibrational degrees of freedom. Thus T3N can be written as
T3N = Tx + Ty + Tz + Rx + Ry + Rz +Tvib
Tvib = T3N- [Tx + Ty + Tz + Rx + Ry + Rz]
29
ILLUSTRATIONS
(a) Water molecule:
(i) Water molecule belongs to C2v point group.
(ii) The symmetry elements of this point group are
E
C2v
s xz s yz
C2
O
syz
H
sxz
(iii) The reducible representation T3N for this point group is

C2v
C2
sxz
syz
T 3N
-1
(iv) This reducible representation is decomposed into various irreducible representations using
the standard reduction formula and by using the character table for this group.
C2v
C2
sxz
syz
A1
Tz
A2
-1
-1
Rz
B1
-1
-1
T x ,R y
B2
-1
-1
T y,R x
1
[1.9.1 + 1.(- 1).1 + 1.1.1 + 1.3.1] = 3
4
1
a A 2 = [1.9.1 + 1.(- 1).1 + 1.1.(- 1) + 1.3.(- 1)] = 1
4
a A1 =
30
1
[1.9.1 + 1.(- 1)(. - 1) + 1.1.1 + 1.3.(- 1)] = 2
4
1
= [1.9.1 + 1.(- 1)(
. - 1) + 1.1.(- 1) + 1.3.1] = 3
4
a B1 =
aB2
Thus T3N is given by

T3N = 3A1 + A2 + 2B1 + 3B2
(v) The sum of the irreducible representations of vibrational modes Tvib is related to T3N by the
relation
Tvib = T3N- [Tx + Ty + Tz + Rx + Ry + Rz]
Using the values of Tx , Ty , Tz , Rx , Ry and Rz in the character table for this groups , we get
Tvib = (3A1 + A2 + 2B1 + 3B2 ) (B1 + B2 + A1 + B2 + B1 + A1 )
Tvib = 2A1 + B2
Thus the three normal modes of vibration of water molecule belong to A1 and B2 representations.
Of these, those vibrations which belong to A1 symmetry are called totally symmetric vibrations.
SO2 molecule also has the same symmetry properties as water molecule and hence its sum of
representations of vibrational modes Tvib is also
Tvib = 2A1 + B2
(b) Ammonia Molecule
(i)
(ii)
This belongs to C3v point group

The various symmetry elements of this group are
E
C2v
s xz s yz
C2
N
(iii)
The reducible representation T3N using reduction formula, we get
T 3N
(iv)
2C3
12
3sv
By decomposing T3N using reduction formula, we get
31
T3N = 3A1 + A2 + 4E
(v)
A reference to the character for C3v group gives
Tx + Ty + Tz = A1 + E
Rx + Ry + Rz = A2 + E
Thus Tvib is obtained as
Tvib = 2A1 + 2E
Thus ammonia has four vibrational modes.
(c ) BF3 molecule
(i)
(ii)
This molecule belongs to D3h point group.

The various symmetry operations present are
E
2C3
3C2
s h 2S3
3sv
F
F
B
F
(iii)
The reducible representation T3N for BF3 molecule is
T 3N
(iv)
2C3
3C2
sh
2S3
3sv
12
-2
-2
This representation is decomposed by reduction formula to give

T3N = A1 + A2 + 3E+ 2A2 +E.
The symmetries of the translations (Tx, Ty, Tz) and rotations (Rx, Ry and Rz) as given by
the character table for D3h are
Translation
Rotation
(T x ,T y) : E"
(R x ,R y) : E"
T z : A 2"
R z : A 2"
32
Thus Tvib is given by
Tvib = 2A1 + 2E+A2
(d) By a similar treatment the Tvib for the following molecules are obtained as
Molecule
SO2
Symmetry T3N
C2v
3A1 + A2 + 2B1 + 3B2
Tvib
2A1 + B2
POCl3
C3v
4A1 + A2 +5E
3A1 + 3E
PtCl4 2-
D4h
A1g + A2g + B1g + B2g+Eg

+2A2u+B2u+3Eu
A1g+ B1g+
B2g+A2u+B2u+2Eu
RuO4
Td
A1 + E +T1 + 3T2
A1 + E +2T2
Knowing the symmetries of all the vibrational modes of a molecule, it is possible to

predict which of them will be active in the infra-red and Raman spectra. To do this we must have
knowledge of symmetry selection rules for two effects.
4.5. SYMMETRY SELECTION RULES FOR INFRA RED RAMAN SPECTRA

(A)
SELECTION RULE FOR IR
Consider a transition from the vibrational ground state of a molecule with wave function
y 0 to an excited vibrational state with wave function y i . The probability of such a transition Pi
occurring is given by
Pi = y 0 my i dt
Where m = dipole moment of the molecule (a vector)
dT =implies integration carried over all possible variables of the wave functions.
The vector m can be split into three components mx , my , mz along the three Cartesian
coordinates and one of the three integrals is given by
Pik = y 0 m ky i dt
(k = x, y, z )
Symmetry selection rules:

(i)
If one of the three integrals y 0 m ky i dt is non-zero, then that vibrational mode is
inactive. This occurs when the product y 0 my 1 is totally symmetric, u, the character of this
direct product function is +1 for all symmetry opera5tions of the relevant point group.
33
(ii)
If the integral y 0 m ky i dt is zero, the probability of that transition is zero. Then it is
said to be forbidden in infra-red.

How to find out symmetry of a particular vibration
The integral consists of three product functions. Of these
(i) y o , the ground state vibrational wave function, is always totally symmetric.
(ii) The symmetry properties of mk and those of a translational vector along the same axis Tk are
the same.
(iii) The symmetry properties of y i are the same as those of vibrational mode i.
Thus, if a vibrational mode has the same symmetry property as one of the translation
vectors, Tx , Ty , Tz for that point group, then a transition from the ground state to that mode (in
excited state) will be infra-red active.
(B) RAMAN SELECTION RULE
The probability of a vibrational transition occurring in Raman scattering is given by
Pi = y 0ay i dt
Where a = Polarizability of the molecule (a tenser)

The Raman effect depends upon a molecular dipole induced in the molecule by the
electromagnetic field of incident radiation. The induced dipole is proportional to the
polarizability (a) of the molecule, which a measure of the ease with which the molecular electron
distribution could be disterted. Since a, is a tensor, there are only six distinct components, viz,
[For vibrational transitions ajk = akj (where j,k = x,y,z )]
SELECTION RULE
For a vibrational mode to be Raman active one of the six integral of the form
a jky i dt 0
( j , k = x, y , z )
As in the case of IR, the above integral will be non-zero only if a jk has the same
symmetry as the mode described by the wave function yi. It is found that a jk has the same
symmetry properties as x2 , a xy as xy and so on)
Thus, a transition from the ground state to that mode would be Raman active, if a normal
mode has the same symmetry as one of these binary combinations of x,y and z.
Since the selection rules for infra red and Raman spectra have different physical bases;
there is no relationship between them. Thus an infra-red active mode might or might not be
Raman active or conversely.
34
4.6. MUTUAL EXCLUSION RULE
Consider a molecule which has a centre of symmetry. Point groups of molecules with
this element of symmetry have two sets of irreducible representations. The representations which
are symmetric with respect to inversion are called g representations. The representations which
are antisymmetric to inversion are called u representations.
Let us consider the inversion of a Cartesian coordinate x through the centre of inversion.
The coordinate x becomes x. Therefore all representations generated by x,y, or z must belong
to a u representation. On the other hand, the product of two coordinates x and y does not change
sign on inversion (-x.- y = xy). The product xy generates a g representation. All the other
quadratic or binary coordinates also generate the g representation. From these rules we can
conclude that in centrosymmetric molecules, the vibrational modes belonging to g symmetry
species are Raman active and the modes belonging to u symmetry species are IR active. This
rule is called the mutual exclusion rule. Another way of stating this rule is as follows:
If a molecule has a centre symmetry, then any vibration that is active in the IR is inactive
in the Raman and vice versa.
Therefore, we can infer that a molecule has no centre of symmetry if the same vibration
appears in both IR and Raman. Table1 lists the IR active and Raman active vibrational modes in
some centrosymmetric and noncentrosymmetric molecules.
CO2 , C2 H2 and N2 F2 possess centre of symmetry. It is seen from Table1 that the IR active
modes in these molecules are Raman inactive and vice versa. H2 O, NH3 , HCN and BF3 do not
have centre of symmetry. In BF3 the vibrational mode with symmetry species E is IR active and
Raman active. In H2 O, NH3 and HCN, all the modes are IR active and Raman active.
Table1
Molecule
Point
Group
Symmetry
Species
IR Active
Species
Raman Active
Species
CO2
C 2 H2
N2 F2
H2 O
NH3
BF3
HCN
Dh
Dh
C2h
C2v
C3v
D3h
Cv
A1g,A1u,E1u
2A1g,E1g,E1u, A1u
3Ag,Au,2Bu
2A1 ,B2
2A1 ,2E
A1 , 2E , A2
2A1 ,E1
A1u,E1u
E1u, A1u
Au,Bu
A1 ,B2
A1 ,E
A2 , E
A1 ,E1
A1g
A1g,E1g
Ag
A1 ,B2
A1 ,E
A1 , E ,E
A1 ,E1
4.7. LET US SUM UP

In this lesson, we:
Pointed out
Group theory and normal modes of vibration of polyatomic molecules
Infra-red absorption and Raman scattering spectroscopy
Determination of symmetry properties of vibrational modes
35
Symmetry selection rules for infra red Raman spectra
Mutual exclusion rule
1.
2.
How is mutual exclusion principle explained on the basis of symmetry of vibrational

modes?
Taking water as example, illustrate how the various vibrational modes form basis for
group representation?

1.
2.
Explain the selection rules in IR and Raman spectroscopy from symmetry point of view.
Show that the normal modes form the basis for irreducible representations with a suitable
example.
4.10. REFERENCES
1.
2.
edition, 2006- 2007.
3.
36
UNIT-III
LESSON 5: THE TIME-DEPENDENT AND TIME-INDEPENDENT
SCHRDINGER EQUATIONS
CONTENTS
5.1. INTRODUCTION
5.2. THE TIME-DEPENDENT SCHRDINGER EQUATION
5.2.1. ONE-DIMENSIONAL EQUATION FOR A FREE PARTICLE
5.2.2. OPERATORS FOR MOMENTUM AND ENERGY
5.2.3. EXTENSION TO THREE DIMENSIONS
5.2.4. INCLUSION OF FORCES
5.3. TIME-INDEPENDENT SCHRODINGER EQUATION
5.4. REQUIREMENTS OF THE ACCEPTABLE WAVE FUNCTION
5.5. BORNS INTERPRETATION OF THE WAVE FUNCTION
5.6. LET US SUM UP
5.9. REFERENCES

The aim is to motivate and enable a comprehensive knowledge on the time-dependent and
time- independent Schrdinger equations to the students.
*
Understand the time-dependent and time- independent Schrdinger equations.
5.1. INTRODUCTION
Classical mechanics applies only to macroscopic particles. For microscopic particles
we require a new form of mechanics, which we will call quantum mechanics.
Schrodinger formulated an important fundamental equation in 1926. Schrodinger argued
that if micro-particles like electrons could behave like waves, the equation of wave motion could
be successfully applied to them.
5.2. THE TIME-DEPENDENT SCHRDINGER EQUATION
5.2.1. ONE-DIMENSIONAL EQUATION FOR A FREE PARTICLE
The wave function of a localized free particle is the one given in eqn.
37
Y ( x, t ) =
A(k )exp[ikx - iw (k )t ]dk
----- (1)
For a free particle, the classical expression for energy is

2
p
E= x
2m
2 2
1 mv 2 = 1 m v
E
=
2
2 m
px 2 = m2v 2
p = mv
----- (2)
Replacing px by kh and E by hw we get

w=
hk 2
2m
----- (3)
2p h
h
Q
k
h
=
=
=
l 2p l
hw = h 2pu = hu
2p
Substituting this value of w in Eq. (1)
Y ( x, t ) =
hk 2
(
)
A
k
exp
i
kx
2m
-
t dk
----- (4)
Differentiating Y ( x, t ) with respect to t, we get
Y ih
hk 2
2
(
)
=
k
A
k
exp
i
kx
t
2m -
2m
t dk
----- (5)
Differentiating Y ( x, t ) twice with respect to x, we get
2Y
hk 2
2
(
)
=
k
A
k
exp
i
kx
2m
x 2
-
t dk
----- (6)
Combining Eqs. (5) and (6), we have

ih
Y ( x, t )
h2 2Y
=t
2m x 2
----- (7)
38
which is the one-dimensional Schrodinger equation for a free particle.
5.2.2. OPERATORS FOR MOMENTUM AND ENERGY

To obtain the operators for momentum and energy, Eq. (7) may be written as
1

ih Y ( x , t ) =
- ih - ih Y ( x, t )
2m
x
x
t
----- (8)
From a comparison of Eqs. (2) and (8), it may be concluded that the energy E and momentum
P can be considered as the differential operators.
E ih
and Px ih
t
x
----- (9)
operating on the wave function Y ( x, t ) . Eq. (7) is obtained even if the operator for P is taken as
in place of - ih .
ih
x
x
5.2.3. EXTENSION TO THREE DIMENSIONS

The one-dimensional treatment given above can easily be extended to three dimensions.
The three-dimensional wave packet can be written as
Y (r, t ) =
A(k )exp[i(k.r - wt )]dk
dk y dk z
----- (10)
Proceeding on similar lines as in the on-dimensional case we get the three-dimensional

Schrodinger equation for a free particle as
ih
Y (r, t )
h2 2
= Y (r, t )
t
2m
----- (11)
An analysis similar to the one made for one-dimensional system leads to the following operators
for energy and momentum
E ih
and P ih
t
----- (12)
5.2.4. INCLUSION OF FORCES

Modification of the free particle equation to a system moving in a potential V(r,t) can
easily be done. The classical energy expression for such a system is given by
p2
E=
+ V (r , t )
2m
----- (13)
39
Schrodinger then made the right guess regarding the operators for r and t as
r r and t t
----- (14)
Replacing E,p,r and t in Eq. (13) by their operators and allowing the operator equation to
operate on the wave function Y (r, t ) , we get
Y (r, t ) h 2 2
ih
= + V (r, t ) Y (r, t )
t
2m
----- (15)
which is the time-dependent Schrodinger equation for a particle of mass m moving in a

potential V(r,t). The quantity in the square bracket in Eq. (15) is the operator for the
Hamiltonian of the system.
In general, its solution will be complex because of the presence of i in the equation. The
equation cannot be relativistically invariant as it contains first derivative in time and second
derivative in space coordinates.
5.3. TIME-INDEPENDENT SCHRODINGER EQUATION

The time-dependent Schrodinger equation (15) describes the evolution of quantum
systems using time-dependent wave function Y (r, t ) .It completely neglects the time dependence
of the operators. If the Hamiltonian operator does not depend on time, the variables r and t of the
wave function Y (r, t ) can be separated into two functions y (r ) and f (t ) .
Y (r, t ) = y (r )f (t )
----- (1)
Substituting this value of Y (r, t ) in Eq. (15)
ih
Y (r, t ) h 2 2
= + V (r, t ) Y (r, t )
t
2m
and dividing throughout by y (r ) and f (t ) we get
1 df (t )
1 h2 2
ih
=
+ V (r ) Y (r )
f (t ) dt
y (r ) 2m
----- (2)
The left side of this equation is a function of time and right side function of space
coordinates. Sincet and r are independent variables, each side must be equal to a constant,
say E. This gives rise to the equations
1 df (t )
iE
=f (t ) dt
h
----- (3)
40
and
h2 2
+ V (r )y (r ) = Ey (r )
2m
----- (4)
Solution of Eq. (3) is straightforward and is given by

iEt
f (t ) = C exp
h
----- (5)
where c is a constant. The equation for y (r ) , Eq. (4), is the time- independent Schrodinger
equation or simply Schrodinger equation.
Since y (r ) determines the amplitude of the wave functiony (r, t ) , it is called the
amplitude equation. Equation (1) now takes the form
iEt
Y (r, t ) = y (r ) exp
h
----- (6)
The constant C is included in the normalization constant fory (r ) .

Significance of the separation constant, E, can be understood by differentiating y (r, t ) in
Eq. (1) with respect to time and multiplying by ih . Then
ih
Y (r, t )
= EY (r, t )
t
----- (7)
Multiplying both sides of Eq. (7) by Y * from left and integrating over the space coordinates
from - to . We get
Y * ih t Y (r, t ) = E
----- (8)
As the left side Eq. (8) is the expectation value of the energy operator, the constant E is the
energy of the system. The same can be understood from Eq. (4) as
-
h2 2
+ V (r )
2m
is the operator associated with the Hamiltonian of the system.

5.4. REQUIREMENTS OF THE ACCEPTABLE WAVE FUNCTION
The interpretation given to Y or Y 2 imposes certain restrictions on acceptable values
of Y .
41
2
A physical system is described by the probability density Y (r , t ) and the normalization

integral equation.
2
Y(r , t )
dt = 1
For the probability density to be unique and the total probability to be unity, the wave function
must be finite and single valued at every point in space.
The probability current density j, equation
j (r , t ) =
ih
Y Y * - Y * Y
2m
Another important parameter of the probability interpretation contains Y and Y . Hence Y has
to be continuous and Y must be finite.
The Schrodinger equation has the term 2 Y .For 2 Y to exist Y must be continuous.
For a wave function Y (r, t ) to be acceptable, Y (r, t ) and Y must be finite, single valued and
continuous at all points in space.
Any function that is finite, single valued and continuous can be taken as an acceptable
(well-behaved) wave function.
5.5. BORNS INTERPRETATION OF THE WAVE FUNCTION
The wave function Y (r, t ) has no physical existence, since it can be complex. Also it
cannot be taken as a direct measurement of the probability as (r,t) since the probability is real and
non-negative. However, Y (r, t ) must in someway be an index of the presence of the particle at
(r,t).
A universally accepted statistical interpretation was suggested by Born in 1926.He
interpreted the product of Y (r, t ) and its complex conjugate Y * as the position probability
density P(r,t).
P (r , t ) = Y * (r , t )Y (r , t ) = Y (r , t )
----- (1)
The quantity y (r , t ) dt is the probability of finding the system at timet in the small
2
volume of element dt surrounding the point r. When Y (r , t ) dt is integrated over the entire
space one should get the total probability, which is unity. Therefore
Y(r , t )
dt = 1
----- (2)
For Eq. (2) to be finite, Y (r, t ) must tend to zero sufficiently rapidly as r .Hence,
one can multiply Y (r, t ) by a constant, say N, so that NY satisfies the condition in Eq, (2).Then
42
Y (r , t ) dt = 1
----- (3)
The constant N is called the normalization constant and Eq. (3) the normalization
condition. Since the Schrodinger equation is a linear differential equation, NY is a solution of it.
The wave functions for which the integral in Eq. (2) does not converge will be treated depending
on the nature of the functions.
5.6. LET US SUM UP
In this lesson, we:
Pointed out
The time-dependent Schrdinger equation

One-dimensional equation for a free particle
Operators for momentum and energy
Extension to three dimensions
Inclusion of forces
Time- independent Schrodinger equation
Requirements of the acceptable wave function
Borns interpretation of the wave function

1.
2.
What are the requirements of an acceptable wave function?

Outline the Borns interpretation of the wave function.

1.
2.
Is the time dependent Schrodinger equation relativistically invariant? Explain.

Derive the time independent Schrodinger Equation.
5.9. REFERENCES
1.
R.K. Prasad, Quantum Chemistry, Wiley Eastern Limited, New Delhi.
2.
IRA N. Levin, Quantum Chemistry, Prentice-Hall of India private limited, New Delhi.
3.
G. Aruldhas, Quantum mechanics, Prentice-Hall of India private limited, New Delhi.
4.
edition, 2006- 2007.
43
LESSON 6: OPERATORS
CONTENTS
6.1. INTRODUCTION
6.2. ALGEBRA OF OPERATORS
6.2.1. ADDITION AND SUBTRACTION
6.2.2. MULTIPLICATION
6.3. COMMUTATOR OPERATOR
6.4. LINEAR OPERATOR
6.5. EIGENVALUES AND EIGENFUNCTIONS
6.6. BASIC POSTULATES OF QUANTUM MECHANICS
6.6.1. POSTULATE-I
6.6.1.1. RULES FOR SETTING UP A QUANTUM MECHANICAL
OPERATORS
6.6.1.2. SOME OPERATORS OF INTEREST
6.6.1.2.1. MOMENTUM OPERATOR
6.6.1.2.2. HAMILTONIAN OPERATOR
6.6.1.2.3. ANGULAR MOMENTUM OPERATOR
6.6.2. POSTULATE-II
6.6.2.1. SCHRODINGER EQUATION AS AN EIGENVALUE EQUATION
6.6.3. POSTULATE-III
6.6.4. POSTULATE-IV
6.6.4.1. STATIONARY STATES
6.7. AVERAGE OR EXPECTATION VALUES
6.7.1. UNCERTAINTIES IN POSITION AND MOMENTUM
6.8. LET US SUM UP
6.11. REFERENCES
The aim is to motivate and enable a comprehensive knowledge on operators to the
students.
*
Understand the operators.
6.1. INTRODUCTION
An operator is a symbol for transforming a given mathematical function into another
function. It has no physical meaning if written alone. For example, is an operator which in
itself does not mean anything, but if a quantity or a number is put under it, it transforms that
d
quantity into its square root, another quantity. Similarly,
is an operator which transforms a
dx
44
function into its first derivative with respect to x; for example
d
transform the function sin x
dx
into the function cos x.

In general, if A denotes an operator which transforms the function f(x) into the function
g(x), then we write A f ( x ) = g ( x ) . For example,
1.
2.
d
d
Let A be
, and f(x) = ax2 ; then A f ( x) =
(ax 2 ) = 2ax , i.e., g(x) = 2ax.
dx
dx
Let A be a. (i.e., multiplication by a) and f(x) = x2 + c, then

A f ( x ) = a.( x 2 + c ) = ax 2 + ac , i.e., g(x) = ax2 +ac.
6.2. ALGEBRA OF OPERATORS

Although operators do not have any physical meaning, they can be added, subtracted,
multiplied and have some other properties.
6.2.1. ADDITION AND SUBTRACTION
The addition or subtraction of operators yields new operators, the sum or the difference of
operators being defined by,
(A B ) f (x ) = A f (x ) B f (x )
d
For example, let A be loge and B be
, and f ( x ) be ; then,
dx
(A B ) f (x ) = log dxd x
= log e x 2
d 2
x
dx
( )
= log e x 2 x = A f ( x ) B f ( x )
6.2.2. MULTIPLICATION
Multiplication of two operators means operations by the two operators one after the other,
the order of operation being from right to left; for example, A B f ( x ) means that the function
f ( x ) is first operated on by B to yield a new function g ( x ) which is then operated on by A to
yield the final function h( x ) ,
A B f ( x ) = A B f ( x ) = A g ( x ) = h( x )
d
For example, let, A be 4x 2 , B be
,and f ( x ) = ax 2 , then,
dx
45
d
A B f ( x ) = 4 x 2
ax 3 = 4 x 2 3ax 2 = 12ax 4
dx
( )
The square of an operator means that the same operator is applied successively twice, i.e.,
A 2 f ( x ) = A A f ( x ) . For example,
2
d
d
Let A =
and f ( x ) = sin x , then A 2 f ( x ) = sin x
dx
dx
d d
d
(sin x ) = d (cos x ) = - sin x
sin x =
dx dx
dx
dx
Or
6.3. COMMUTATOR OPERATOR

For any two operators A and B , the difference A B - B A , which is simply denoted by
A B - B A or [A,B] is called commutator operator
If A and B commute then [A,B] = 0, where 0 is called the zero operator which means
multiplying a function with zero.
d
In the earlier example, where, A =
, B = 3 x 2 and f ( x ) = sin x ,the commutator is obtained as
dx
follows
[A, B ] f (x ) = [A B - B A ] f (x ) = (6 x sin x + 3x 2 cos x ) - 3x 2 cos x = 6 x sin x = 6 xf (x )

or
[A, B] f (x ) = 6 x
6.4. LINEAR OPERATOR
An operator is said to be linear if its application on the sum of two functions gives the
result which is equal to the sum of the operations on the two functions separately, i.e., if,
A [ f ( x ) + g ( x )] = A f ( x ) + A g ( x )
or
A cf ( x ) = C A cf ( x ) , C = constant
Example:
d
d
d
d
(i)
is a linear operator because
(
(
ax m + bx n ) =
ax m ) + (bx n )
dx
dx
dx
dx
(ii)
, square root, is not a linear operator because
f (x ) + g (x )
f (x ) + g (x )
46
6.5. EIGENVALUES AND EIGENFUNCTIONS
If an operator A operates on a well-behaved (i.e., finite, continuous and single-valued)
function f to give the same function but multiplied by a constant, then the constant is called the
eigenvalue of the operator and the function f is called the Eigenfunctions. The equation is
called eigenvalue equation. For example, if the function f = e - ax is acted upon by the
d
d - ax
operator , the result is
e
= - a (e - ax ) .
dx
dx
d
Therefore, (- a ) is the eigenvalue and e - ax is the eigenfunction of the operator .
dx
( )
6.6. BASIC POSTULATES OF QUANTUM MECHANICS

The fundamental postulates are four which are stated and explained below.
6.6.1. POSTULATE-I
Every physical property of a system (i.e. a particle or a system of particles) has a
corresponding mathematical (quantum mechanical) operator.
Physically measurable quantities of a particle are a position ( x ) , momentum ( p ) , kinetic
energy (T ) , potential energy (V ) , total energy (E ) , etc. The operators corresponding to these
quantities are given in table I.
Table-I. Quantum Mechanical OPERATORS Corresponding to Various Physical Quantities

Physical quantity
Position ( x )
Position (r )
x-Component of momentum ( p x )
momentum ( p )
kinetic energy (T )
x-Component of K.E. (Tx )
Quantum mechanical operator

x
r
h
2pi x
h
2pi
h2
- 2 2
8p m
-
h2
2
2
8p 2 m x
47
Potential energy (V )
V
Total energy (H )
-
h2
2
2 + V .
8p m
6.6.1.1. RULES FOR SETTING UP A QUANTUM MECHANICAL OPERATORS

(i) Write down the expression for the physical quantity in classical terms, i.e., in terms of
Cartesian coordinates of position ( x, y, z ) and momenta ( p x , p y , p z ) .
(ii) Replace these coordinates and momenta by their corresponding
operators (vide Table I above).
(iii) Operator for a coordinate of position (say x) is multiplication by that
variable x itself (i.e.x.).
(iv) Operators for a coordinate of momentum(say px ) is
h
.
2pi x
Take for example the kinetic energy (Tx ) of a single particle moving in one
direction(x).
2
p
1
2
Tx = mv x = x
2
2m
Therefore, the K.E. Operator
1 h
Tx =
2m 2pi x
=-
h2
2
2
8p 2 m x
----- (1)
p
Similarly, potential energy operator V ( x ) = V ( x ) . The total energy (H) is x + V ( x ) ;
2m
hence, the total energy operator
h2
d2
H =- 2
+ V (x )
2
8p m dx
----- (2)
48
6.6.1.2. SOME OPERATORS OF INTEREST
6.6.1.2.1. MOMENTUM OPERATOR
The kinetic, potential and total energies are derived from coordinates of momentum and
position. but how is momentum operator to be derived? This is done by using a more
fundamental property of electron wave itself. For an electron wave the wave function may be
represented by the function,
y = A exp( 2pix l )
----- (3)
Differentiating with respect to x,

dy
2pi
2pi
=
A exp( 2pix l ) =
y
dx
l
l
But by de Broglie relationship,

h
l=
px
Therefore,
dy
2pi
=
p xy
dx
h
or,
p xy =
h dy
2P i dx
----- (4)
Buty is a function which on being removed from the equation reduces it to a differential
operator,
h d
)
px =
2P i dx
The operator Px in the =x direction is
----- (5)
h d
h d
and in the negative x direction it is .
2pi dx
2pi dx
6.6.1.2.2. HAMILTONIAN OPERATOR

The operator corresponding to the total energy of a system, written as a sum of kinetic
and potential energies, is called Hamiltonian operator H . The total energy of a single particle

of mass m is
H=
p2
1
2
2
2
+ V ( x, y , z ) =
px + p y + pz + V
2m
2m
----- (6)
49
where V is written for V(x,y,z).
The corresponding operator will, therefore, be
1 2 2 2
px + py + pz +V .
2m
H=
But
h2 2
h
2
;
px =
=
4p 2 x 2
2pi x
similarly,
py
h2 2
h2 2
2
= - 2 2 and p z = - 2 2
4p y
4p z
Thus,
H =-
=-
h2 2
2
2
+
+
8p 2 m x 2 y 2 z 2

+ V
h2
2
+
V
8p 2 m
----- (7)
For a system of n particles,

h2
H =- 2
8p
m
i
i 2 + V
----- (7a)
where mi is the mass and i2 the Laplacian operator of the ith particle.
6.6.1.2.3. ANGULAR MOMENTUM OPERATOR
The angular momentum (L) is a very important physical quantity for rotating systems.
r
r
Classically, it is given by the vector product of position (r ) and linear momentum ( p ) ,
r r r
----- (8)
L=rp
r
r r
If i , j and k are unit vectors along x, y and z coordinates respectively, we have
r
r
r r
r = i x + jy + kz ,
and
r
r
r r
p = i p x + j p y +kp z
Therefore,
r
r
r r
r
r
r
L = i x + jy + kz i p x + jp y + kp z
r
r
r
= i ( yp z - zp y ) + j ( zp x - xp z ) + k (xp y - yp x )
Also, by definition,
r
r r
r
L = i Lx + j L y + k Lz
----- (9)
) (
where Lx , L y and Lz represent the three components of L. Replacing px , p y and pz by their

corresponding operators we obtain the operators for the three components of angular momentum.
50
Thus,
h

y - z
L x = ( yp z - zp y ) =
2pi z
y
h

L y = ( zp x - xp z ) =
z - x
2pi x
z
h

x - y
L z = (xp y - yp x ) =
2pi y
x
----- (10)
6.6.2. POSTULATE-II
The possible values of any physical quantity of a system (e.g. energy, angular momentum
etc) are given by the eigenvalues a in the operator equation,
)
Ay = a y
----- (11)
)
where A i s the operator corresponding to that physical quantity and y is a well-behaved
eigenfunction.
The eigenvalues and eigenfunctions for a system can be obtained by solving the operator
equation. While the Eigenfunctions and the operator may be real or complex, the eigenvalues
must be real because they represent observable physical quantities. Moreover, quantum
mechanical operators of interest, e.g. momentum, energy, etc., are Hermitian operators which
have been shown earlier to have real eigenvalues.
Consider, for example, the operator equation for momentum px (in one dimension),
h dy ( x )
)
p xy ( x ) =
= p xy ( x )
2pi dx
----- (12)
This is an ordinary differential equation whose solution may be easily obtained as

y ( x) = A exp( )2pip x x
----- (13)
where A is a constant. Now, any value of px is allowed that keeps the function y ( x ) well2pp x
= k , then the eigenfunction of
behaved, i.e., finite, single- valued and continuous. If we put
h
momentum operator becomes,
y = A exp( ikx )
----- (14)
with eigenvalues
px =
kh
2p
----- (15)
51
6.6.2.1. SCHRODINGER EQUATION AS AN EIGENVALUE EQUATION
A particularly important eigenvalue equation is the equation for energy of a system. The
operator for energy E (K.E+P.E) is the Hamiltonian operator. For a single particle in three
dimensions, the Hamiltonian is
h2
H = - 2 2 + V ( x, y, z )
8p m
----- (16)
The eigenvalue is,

H y ( x, y , z ) = Ey ( x, y , z ) or simply H y = Ey
i.e.
-
h2
2y + Vy = Ey
2
8p m
----- (17)
This is the familiar Scharodinger equation. It is a second order partial differential

equation which has to be solved in order to obtain expressions for the eigenfunctions,y , and the
observable quantity, energy (E), of the particle.
Since energy is a very important observable property of a system, and can often be
measured experimentally, a topic of major importance in the quantum chemistry is solving of
Schrodinger equation.
6.6.3. POSTULATE-III
The expected average (expectation) value of a physical quantity (M) of a system, whose state
function is y , is given by
y *Mydt
M =
y *ydt
----- (18)
)
where M is the operator for M.
)
)
It has to be noted that y is not necessarily an eigenfunction of M , though M has a set of
orthonormal eigenfunction (j i ) and y can be expressed as
y = aij i
i
Hence,
M = aij i * M aij i dt , if y is normalized

i
)
= ai * a j j i * Mj j dt
i
52
)
Mj j = l j j j
But
Therefore,
M = (ai * a j ) j i * l j j j dt
i
= (ai * a j )l j j i * j j dt
i
Since
* j j dt = 0 for i j , ( ji and j j are orthogonal)
= 1 for i = j , ( ji and j j are normalized)
M = ai * ai li or
i
2
i
li
This expression means that each measurement of M must give one of the eigenvalues
li (postulate-II) and the average of many such measurements is equal to M . Further, ai * ai or
2
ai represents the fraction of the total number of measurements that give the eigenvalue li ,
and a i
= 1 .0 .
Consider for example the expectation value of position, x, for a particle moving in one
dimension, which is given by
+
x=
xy *ydx = y * xydx
because the operator for x is just x, for which the order of applying is immaterial.
Similarly, the expected average value of momentum for the above system is,
+
h
dy
px =
y*
dx
2pi -
dx
----- (19)
and K.E.,
Tx = -
h2
d 2y
y
*
dx
8p 2 m -
dx 2
----- (20)
The limits of integration in each case will depend on the total length available for the
particles motion.
6.6.4. POSTULATE-IV
The time-dependent Schrodinger equation is given by,
53
)
ih y
Hy =
2p t
----- (21)
)
where H is the Hamiltonian operator, y is a function of position (x,y,z) as well
as time (t) and V is a function of position only.
Since this a partial differential equation involving both position and time variables, it can
be solved only by separating it into two differential equations, one containing position variable
and the other containing time variable only. This can be done if we assume that,
y = y (q, t ) = y (q ).j (t )
----- (22)
where q is the collective symbol for the three coordinates of position x, y and z; dropping q and t
for simplicity,
y = yf
Then,
y
y
=j
q
q
or
2y
2y
=
j
q 2
q 2
----- (23)
y
y
=y
t
t
----- (24)
and
Substituting equations (22),(23) and (24) into (21) and dividing the resulting equation by yj , we
get
h 2 2y ) 1
ih 1 j
.
----- (25)
- 2 . 2 + Vy =
8p m q
y 2p j t
and
ih j
----- (26)
= Ej
2p t
Equation (25) is the familiar Schrodinger equation, also called the amplitude equation of the type
)
Hy = Ey in which the function y ,the wave function, is found by solving the equation
Equation (26) has a solution,
2piEt
f = a exp
h
So the time dependent wave function y (q, t ) is given by,
----- (27)
54
2piEt
Y = ay exp
h
----- (28)
6.6.4.1. STATIONARY STATES

States for which Y is given by (28) are called stationary states. A stationary state does not
imply that the particle, or particles, of the system are at rest. It is stationary in the sense that the
2
probability density Y and the energy are independent of time as long as the state of the system
is being described by the function Y . The probability density is given by,
2
2piEt * *
2piEt
YY * = Y = ay exp .a y exp
= aa*yy * ------ (29)
h
2piEt
which is independent of time. Thus, we see that the factor exp is of no significance
h
and the essential part of the state function for a stationary state is the time-independent wave
function y .
A knowledge of stationary states is of prime importance in understanding chemical

problems. If the state of a system corresponds to one of these stationary states, every physical
property of the system e.g. energy, charge density, dipole moment, etc., will be independent of
time. Atomic and molecular spectra arise due to transitions between these stationary states
brought about by the action of radiation.
6.7. AVERAGE OR EXPECTATION VALUES
We can use the wave function to determine, in a state n, the average or expectation values
of any physical quantity, e.g., position, momentum, energy, etc. Consider, for example, the
position. Since the particle can be anywhere in the box, the result of a single measurement is
never precise; but the average of a series of measurements has some meaning. This average can
be computed by the formula,
L
2
npx
x = yx ydx = x sin 2
dx
L0
L
0
------ (30)
Let
npx
Lu
L
, or x =
, dx
du;
'
L
np
np
when x = 0, u = 0 and when x = L, u = np
u=
Therefore,
x=
2
L
np
Lu
np sin
0
L
u
du
np
------ (31)
55
np
2L
u sin
(np )
udu
------ (32)
Using the table of integrals

np
2 L u 2 u sin 2u cos 2u
x=
4
8 0
(np )2 4
=
2
(np ) sin (2np ) - cos (2np ) - 0 - 0 - 1
2 L (np )

2
4
8
8
(np ) 4

=L
2L
(np )
2
(
np )
L
2
------ (33)
Thus, quantum mechanical considerations show that the average value of the position of
the particle in any state (n) lies in the middle of the box, which is the same as that obtained from
classical point of view. This should not be surprising as the probability density curves (Fig. 1)
indicate that the probability of finding the particle at a distance d to the left of the centre is
exactly the same as that at the distance d to the right.
We can likewise calculate other quantities. A quantity of interest is x 2 .
2 2L
x =
L np
2
3 np
sin 2 u du
np
3
2 L u 3 u 2 1
u cos 2u
=
- - sin 2u
L np 6 4 8
4
0
56
2 L n 3p 3
np
-0

L np 6
4
- (0 - 0 - 0 )
n 2p 2 1
2 L
=
-
(np )
L np
4
6
L2
L2
=
3 2n 2p 2
= 1 - 2 2
2n p
------ (34)
6.7.1. UNCERTAINTIES IN POSITION AND MOMENTUM

Since the particle can be anywhere within the length L, the error (uncertainty) involved in
any single measurement of position, Dx = L . the momentum lies between
+
so, the uncertainty,
nh
2L
and
nh
;
2L
57
Dp x =
nh nh nh
- ,
=
2L 2L L
for
n = 1,
px =
h
L,
and the product

Dx.Dp x = h
------ (35)
which satisfy the Heisenberg uncertainty relation.

6.8. LET US SUM UP
In this lesson, we:
Pointed out
Algebra of operators
Addition and subtraction
Multiplication
Commutator operator
Linear operator
Eigenvalues and eigenfunctions
Basic postulates of quantum mechanics
Postulate-I
Rules for setting up a quantum mechanical operators
Some operators of interest
Momentum operator
Hamiltonian operator
Angular momentum operator
Postulate-II
Schrodinger equation as an eigenvalue equation
Postulate-III
Postulate-IV
Stationary states
Average or expectation values
Uncertainties in position and momentum

1.
2.
Prove that the Hamiltonian Operator for the total energy of a system is Hermitian
provided that the wave function is well behaved.
What are eigen functions and eigenvalues of an operator?

1.
2.
Outline the different postulates of quantum mechanics.

Write notes on
(a) Average or expectation values
(b) Uncertainity in position and momentum
58
6.11. REFERENCES
1.
2.
3.
4.
B.R. Puri, L.R. Sharma and M.S. Pathania, Principles of Physical Chemistry, millennium
edition, Vishal Publishing co.
59
UNIT-IV
LESSON 7: PARTICLE IN A ONE-DIMENSIONAL BOX
CONTENTS
7.1. INTRODUCTION
7.2. PARTICLE IN ONE DIMENSIONAL BOX
7.3. NORMALIZATION OF y
7.4. ORTHOGONALITY OF THE WAVE FUNCTIONS
7.5. PARTICLE IN A THREE-DIMENSIONAL CUBICAL BOX
7.4.1. SEPARATION OF VARIABLES
7.4.2. DEGENERACY
7.6. ONE-DIMENSIONAL SIMPLE HARMONIC OSCILLATOR (S.H.O)
7.5.1. ENERGY OF S.H.O
7.7. THE RIGID ROTOR (OR) ROTATOR
7.8. LET US SUM UP
7.11. REFERENCES

The aim is to motivate and enable a comprehensive knowledge on particle in a onedimensional box to the students.
*
Understand the particle in a one-dimensional box.
7.1. INTRODUCTION
Now consider the particle which is allowed to move in a limited space such a model,
usually called particle in a box model, serves as the simplest case for the treatment of bound
electrons in atoms and molecules.
7.2. PARTICLE IN A ONE-DIMENSIONAL BOX
This is the simplest quantum mechanical problem. Here a particle of mass m is confined
to move in a one-dimensional box of a length a, having infinitely high walls (Fig.1). It is
60
assumed, for the sake of simplicity, that the potential energy of the particle is zero everywhere
inside the box, that is
V (x ) = 0
----- (1)
Thus, inside the box the Schrodinger equation, viz.,
h2 2
d dx 2 + V ( x )y ( x ) = Ey ( x )
2m
takes the form
h2 2
d y dx 2 = Ey ( x )
2m
----- (2)
----- (3)
Our problem is solving this equation for energy E and the wave functiony ( x ) .
Mathematically, Eq.3 may be rewritten as
d 2y
+ 2mE h 2 y = 0
2
dx
----- (4)
d 2y
+ k 2y = 0
2
dx
----- (5)
or as
where k2 (= 2mE h 2 ) is a constant, independent of x.

Eq.5 is an ordinary second-order differential equation which has solution of the form
y = A cos kx + B sin kx
----- (6)
61
where A and b are constants. Before we proceed further, it should be pointed out that outside the
box where V ( x ) = , the Schrodinger equation (2) is
h2 2
d dx 2 + y ( x ) = Ey ( x )
2m
----- (7)
d 2y 2m
+ 2 (E - )y = 0
dx 2
h
----- (8)
or
This equation is satisfied if y is zero everywhere outside the box. This is another way of saying
that the particle cannot be found outside the box; it is confined within the box. This implies that
y must be zero at the walls of the box, i.e., at x=0 and at x=a. Since the postulate of quantum
mechanics requires that y must be a continuous function of y , we are forced to conclude that in
Eq. 6, A must be zero. Thus, the solution of Eq. 5 is of the form
----- (9)
y = B sin kx
Since y = 0 at x=0 and at x=a, we have
B sin ka = 0 or B sin ka = 0 or sin ka = 0 so that k = np a
----- (10)
where n(=0,1,2,3,4.......,)is the quantum number. Hence, the allowed solutions of Eq. 4 are
y y n = B sin (npx a ) ; (n=1,2,3, ......)
----- (11)
Notice that the n=0 value of the quantum number, though allowed, is not acceptable since
it implies that the wave function y is zero everywhere inside the box. This is not corre4ct since
the particle is taken to be inside the box, to begin with.
From eqs.4 and 9, we have
(2mE h ) = n p
2
or
a2
----- (12)
E = E n = n 2 h 2p 2 2ma 2 = n 2 h 2 8ma 2 ; n=1,2,3,........ (h = h 2p ) ----- (13)
Eq.13 gives the expression for the energy of the particle in a one-dimensional box. It
should be committed to memory. Since energy depends upon the quantum number n, which can
have any integral value, the energy level of the particle in the box are quantize.
Before we discuss eq.13 further, let us determine the coefficient b in the wave function
given by Eq. 11. This can be done by normalizing the wave function.
7.3. NORMALIZATION OF y
62
Since the total probability of finding the particle within the box is 1, therefore, according
to Borns interpretation of the wave function, the normalization of y requires that
a
2
n
dx = 1
----- (14)
Substituting the value of y n from Eq.11, we have

2
(B sin npx a ) dx = 1
----- (15)
0
a
or
B 2 sin 2 (npx a ) dx = 1
----- (16)
1
Since sin 2q = (1 - cos 2q ) , hence from Eqs. 14 and 16, we have
2
a
a
a
1
2npx
2
2 1
y
dx
=
B
dx
cos
dx

0 n
20
a
2 0
----- (17)
B 2 [a 2 - 0] = 1
----- (18)
Hence,
B = (2 a ) 2
----- (19)
Thus, the normalized wave functions for the particle in a one-dimensional box are
1
y n ( x ) = (2 a ) 2 sin (npx a ) ;
n=1,2,3,.......
----- (20)
A few normalized wave functions for a particle in a one-dimensional box are given in
Fig.2.
63
7.4. ORTHOGONALITY OF THE WAVE FUNCTIONS

We have shown in lesson 6 that eigenfunctions of a Hermitian operator corresponding to
different eigenvalues are necessarily orthogonal to each other, and that Hamiltonian is an
Hermitian operator.
For the problem of particle in a one-dimensional box, it can be demonstrated easily.
Let
y1 =
2
px
sin , and y 2 =
L
L
2
2px
sin
L
L
be the two normalized eigenfunctions corresponding to the two eigenvalues E1 a n d E 2

(characterized by quantum numbers 1 and 2 ). Then,
L
y 1y 2 dx =
0
2
nx
2px
sin sin
L0
L
L
(2 - 1)px - cos (2 + 1)px
L cos
2
L
L
=
dx
L0
2
(2 - 1)px - L sin (2 + 1)px

1 L
=
sin
(2 + 1)
L (2 - 1)
L
L 0
=
1
(0 - 0) = 0
L
64
7.5. PARTICLE IN A THREE-DIMENSIONAL CUBICAL BOX
Let us now consider the motion of a particle of mass m confined to a three-dimensional
cubical box with edges of length a and volume equal to a 3 . The potential is zero within the box
and is infinite outside the box and at its boundaries. The time- independent Schrodinger equation
for the particle is
h2 2
2
2
----- (21)
+
+
x 2 y 2 z 2 y ( x, y, z ) = Ey ( x, y, z )
2
m
Eq. 21 may be rewritten as

2y 2y 2y 2mE
+
+
+
y = 0
x 2 y 2 z 2 h
----- (22)
7.5.1. SEPARATION OF VARIABLES

Assuming that the wave function y is a product of three parts which separately depend on x,y, z,
we have
Hence,
y ( x, y, z ) = X ( x )Y ( y )Z ( z )
----- (23)
2y
2 X
=
YZ
x 2
x 2
----- (24)
2y
2Y
=
XZ
y 2
y 2
----- (25)
2y
2Z
=
XY
z 2
z 2
----- (26)
Substituting Eqs.24-26 in Eq.22 and dividing throughout by (2m h 2 )XYZ , we have
h 2 1 2 X 1 2Y 1 2 Z
+
+
+E =0
2m X x 2 Y y 2 Z z 2
----- (27)
We notice that the first term is a function of x only and is independent of y and z; the
second term is a function of y only and is independent of x and z and the third term is a function
of z only and is independent of x and y. The fourth term E is a constant. If energy E is written as
the sum of three contributions associated with the three coordinates, then Eq. 27 can be separated
into three equations. Thus, for instance, for motion along the X-axis (where X varies while Y
and Z remain constant), the second and third terms on the left hand side of Eq.27 remain constant
be Ex . Accordingly, we can write
h2 1 2 X
= Ex
2m X x 2
----- (28)
65
h 2 1 2Y
= Ey
2m Y y 2
----- (29)
h2 1 2Z
= Ez
2m Z z 2
----- (30)
where E = E x + E y + E z .
We see that each of the Eqs. 28-30 is of the form of Eq.3, the solution of which is given
by Eq.20, i.e., we have
1
X (x ) = (2 / a )2 sin (nx px a ) ; nx = 1,2,3...

2
E x = n x h 2 8ma 2
and
----- (31)
----- (32)
Similar solutions exists for Y(y) and Z(z). Hence
y ( x, y, z ) = X ( x )Y ( y )Z ( z ) = 8 a 3
E = Ex + E y + Ez
and
1
2
sin (n x px a )sin (n y py a )sin (n z pz a )
(n
=
2
x
+ n y + nz h 2
8ma
----- (33)
----- (34)
where nx , ny , nz =1,2,3,4,..........
7.5.2. DEGENERACY
It is seen from Eq.34 that the total energy depends upon the sum of the squares of three
quantum numbers. It is evident that groups of different states, each specified by a unique set of
quantum numbers, can have the same energy. In such a case, the energy level and the
corresponding independent states are said to be degenerate. Consider, for instance, the energy
level having energy = 14h2 /8ma2 . There are six combinations of nx ,ny and nz which can give this
value of energy:
nx
ny
nz
2
3
3
2
1
3
1
2
3
1
2
1
This energy level is, therefore, 6- fold degenerate, i.e., its degeneracy is equal to 6.
Proceeding in this manner we can calculate degeneracy of the energy levels of a particle in a
three-dimensional cubical box. The results are shown in Fig. 3.
66
7.6. ONE-DIMENSIONAL SIMPLE HARMONIC OSCILLATOR (S.H.O)

A diatomic vibrating molecule can be represented by a simple model, the so-called simple
harmonic oscillator (S.H.O). The force acting on the molecule is given by f = -kx, where x is the
displacement from the equilibrium position and k is a constant called the force constant. The
potential energy V(x) of this molecule is given by
x
V ( x ) = - f dx = kxdx =
0
1 2
kx
2
----- (35)
Eq. 35 is the equation of a parabola. Thus, if we plot potential energy of a particle

executing simple harmonic oscillations as a function of displacement from the equilibrium
position, we get a curve as shown in Fig. 4.
67
The vibrational frequency of the oscillator of mass m is given by

1
1 k 2
u=

2p m
----- (36)
It is more accurate to define the vibrational frequency as

1
1 k 2

u=
2p m
----- (37)
where m is the reduced mass of the diatomic molecule defined as

1
1
1
=
+
m m1 m 2
----- (38)
where m1 and m2 are the atomic masses of the two atoms.

Using the potential energy given by Eq.35, for one dimensional S.H.O., the Schrdinger
equation
h2 2
+ V y = Ey is represented as
2m
h2 d 2
2
2m dx
1 2
+ kx y ( x ) = Ey ( x )
2
----- (39)
Mathematically,Eq. 39 may be written as
d 2y 2m
1
+ 2 E - kx 2 y = 0
2
2
dx
h
Defining a and b as a = 2mE h 2

Eq. 40 becomes
and b = (mk )
----- (40)
1
h,
d 2y
+ a - b 2 x2 y = 0
dx 2
Defining a new variable x = b
----- (42)
x , the above equation becomes ( x = Xi )
d 2y a
+ - x 2 y = 0
2
dx
b
Eq. 42 has a solution of the form
----- (41)
----- (43)
68
y (x ) = f (x )e
-x 2
----- (44)
Using this solution, Eq. 42 becomes
d 2f
df a
- 2x
+ - 1f = 0
2
dx b
dx
----- (45)
Eq. 45 is identical in form to a well known second order differential equation, called the
Hermite equation,. viz.,
d 2f
df
- 2x
+ 2nf = 0
2
dx
dx
----- (46)
The Hermite equation has solutions which depend upon the value of n. These solutions are called
Hermite polynomials, Hn (x).i.e.,f (x) Hn (x).
The Hermite polynomial of degree n is defined as
( )
n e -x 2
H n (x ) = (- 1) e
n
x
n
x2
----- (47)
A few Hermite polynomials are given below:

H0 (x) =1
H3 (x) =8x 3-12x
H1 (x) =2x
H4 (x) =16x 4-48x2 +12
H2 (x) =4x 2-2

The normalized wave functions of the one dimensional S.H.O. are then written as
b 12
y n (x ) = n
2 n! p
2 22
e -x H n (x ) Where n= 0,1,2,3,........
----- (48)
The first three wave functions (with n= 0,1,2), the corresponding energy levels and the
2
probability functions y n for the S.H.O., are shown in Fig. 5.
69
7.6.1. ENERGY OF S.H.O

The energy of the S.H.O is obtained by comparing Eqs. 45 and 46, hence we find that
= 2n + 1
----- (49)
Substituting for a and b from Eq. 41, we have
(2mE h )
2
E = n +
2
or
From Eq. 36,
(mk ) h = 2n + 1
(k m )1 2
12
12
h (k m )
= 2pn
Combining Eqs. 51 and 52, we have

1
E E n = n + h (2pn )
2
= n + hn ;n=0,1,2,3,.....( h = h 2p )
2
----- (50)
----- (51)
----- (52)
----- (53)
The energy state with n=0 is the vibrational ground state with energy
E0 =
1
hn
2
----- (54)
70
This energy is called the zero point energy of the oscillator. Classical mechanics predicts
that the zero-point energy of the oscillator is zero whereas quantum mechanics predicts that the
zero-point energy is non-zero. The occurrence of the zero-point energy is consistent with the
Heisenberg uncertainty principle.
7.7. THE RIGID ROTOR (OR) ROTATOR
A diatomic molecule rotating about an axis perpendicular to the intermolecular axis and
passing through the center of gravity of the molecule constitutes an example of a rigid rotor, it
being assumed that the internuclear distance does not change during rotation. The kinetic energy
(K.E.) of the molecule is given by
1 2
----- (55)
Iw = L2 2 I
2
Where w is the angular velocity and I is the momentum of inertia of the rotating molecular. The
angular momentum L =Iw. If no force acts on the rotor, we can set the potential energy V=0.
Hence, the Hamiltonian is expressed as
K.E. T =
H = T + V = L2 2 I
----- (56)
The expression for L2 in spherical polar coordinates (r,q,f) is given by
1

1 2
L2 = -h 2
sin
q
+
q sin 2 q f 2
sin q q
----- (57)
The Schrdinger equation H y = Ey may thus be written as

1
2I
2 1
y
1 2y
sin q
+
- h
= Ey
q sin 2 q f 2
sin q q
----- (58)
The above equation may be written as

1
y
sin q
sin q q
q
1 2y 8p 2 I
+
+ 2 Ey = 0
2
2
h
sin q f
----- (59)
Eq. 59 contains two angular variables q and f. It can be solved by the method of separation of
variables, i.e., we look for a solution of the form
y (q , f ) = Q(q )F (f )
----- (60)
Substituting Eq. 60 into Eq. 59, we obtain

sin q
Q 8p 2 IE
1 2F
2
sin
f
=
sin q
+
Q q
q
F f 2
h2
----- (61)
71
We can set both sides of Eq.61 equal to a constant, say m2 , thereby obtaining two differential
equations each in one variable. These equations are:
2F
+ m 2 F = 0 and
f 2
1
y
sin q
sin q q
q
----- (62)
m2

Q = 0
+
b

sin 2 q

----- (63)
Where b = 8p 2 IE h 2
Eq.62 has the solution
F (f ) = N exp( imf ) , i = - 1
----- (64)
where N is the normalization constant.

This wave function is acceptable provided m is an integer. This condition arises because
F must be single-valued. Thus,
F (f ) = F (f + 2p )
----- (65)
It follows, therefore, that exp (2pmi) =1
----- (66)
Since
e x = cos x + i sin x (Eulers relation)
----- (67)
cos 2pm + i sin 2pm = 1
----- (68)
This can be true only if m=0, 1, 2, 3... etc. Let us now normalize the wave function F(f)
to determine the normalization constant N.
2p
*
F Fdf = 1
(0 f 2p )
----- (69)
0
2p
N 2 e imf e imf df = 1
Or
----- (70)
0
2p
Or
N 2 df = 1 , i.e., N2 (2p) =1 so that

0
N = (2p )
-1 2
----- (71)
Hence, the normalized wave functions become
F m (f ) = (2p )
-1 2
exp( imf ) ; m=0, 1, 2, 3...
----- (72)
We shall not attempt to give a complete solution of Eq.63 but will merely state that if
b=l(l+1) where l is the rotational quantum number, then this equation becomes a standard
72
mathematical equation whose solutions are known to be associated Legendre polynomials
m
Pl (cos q ) where l is either zero or a positive integer and l> m .
The normalized solutions are given by
12
2l + 1 (l - m )!
m
Q(q ) = Q l , m (q ) =
Pl cos q
(l + m )!
2
----- (73)
The energy eigenvalues of the rigid rotor are obtained as follows:

b = 8p 2 IE h 2 = l (l + 1)
----- (74)
Thus,
E=
l (l + 1)h 2
; l = 0,1,2,3 ...
8p 2 I
----- (75)
In spectroscopy it is customary to use the symbol J rather than l for the rotational quantum
number so that the rotational energy levels are given by the expression,
J ( J + 1)h 2
EJ =
; J = 0, 1, 2, 3 ...
8p 2 I
----- (76)
7.8. LET US SUM UP

In this lesson, we:
Pointed out
Particle in a one dimensional box

Normalization of y
Orthogonality of the wave functions
Particle in a three-dimensional cubical box
Separation of variables
Degeneracy
One-dimensional simple harmonic oscillator (S.H.O)
Energy of S.H.O
The rigid rotor (or) rotator

1.
2.
Derive an expression for the energy of a rigid rotor using the Schrodinger equation.
Calculate the degeneracy of the energy level with energy equal to i. 11(h2 /8ma2 ) and
ii 12(h2 /8ma2 ) for a particle in a cubical box.
73
1.
2.
Set up and solve the Schrodinger wave equation for a particle in a one dimensional box,
with potential energy zero inside the box. Normalize the wave function.
Set up the Schrodinger wave equation for a simple harmonic oscillator, and solve it for
the energy eigenvalues.
7.11. REFERENCES
1.
2.
3.
4.
74
UNIT-V
LESSON 8: THE SCHRODINGER EQUATION FOR HYDROGEN ATOM
CONTENTS
8.1. INTRODUCTION
8.2. ANGULAR FUNCTIONS
8.3. PROBABILITY DENSITY AND RADIAL DISTRIBUTION FUNCTIONS
8.4. THE MOST PROBABLE DISTANCE OF THE H-ATOM (OR H-LIKE SPECIES) 1S
ELECTRON
8.5. PHYSICAL INTERPRETATION OF THE HYDROGENIC ATOMIC ORBITALS
8.6. THE SCHRODINGER WAVE EQUATION FOR MULTI-ELECTRON ATOMS
8.6.1. TIME-INDEPENDENT PERTURBATION THEORY
8.6.2. APPLICATION OF FIRST-ORDER PERTURBATION THEORY TO
HELIUM ATOM
8.7. VARIATION METHOD
8.8. LET US SUM UP
8.11. REFERENCES

The aim is to motivate and enable a comprehensive knowledge on the Schrdinger
equation for hydrogen atom to the students.
*
Understand the Schrdinger equation for hydrogen atom.
8.1. INTRODUCTION
Hydrogen atom is the simplest of all atoms. It is a three-dimensional system and the
Schrodinger equation for this system is
where
H y = Ey
----- (1)
h2 2
H = + V ( x, y , z )
2m
----- (2)
and where the Laplacian operator in Cartesian coordinates is given by
75
2 =
2
2
2
+
+
x 2 y 2 z 2
----- (3)
The potential energy of interaction between the electron and the nucleus is given by
V (r ) = - Ze 2 4pe 0 r
----- (4)
Since this attractive potential has spherical symmetry depending only upon r, it is
convenient to express the Schrodinger equation in terms of polar coordinates (r,q,f), rather than
Cartesian coordinates (x,y,z). The Cartesian coordinates are related to polar coordinates (see
Fig.1) as follows:
x = r sin q cos f
y = r sin q sin f
z = r cos q
The Schrodinger equation for hydrogen atom in terms of polar coordinates becomes
1 r 2 y
r 2 r r
1

y
1
2y 2 m
Ze 2
y = 0 ----- (5)
+ 2
+
E
+
sin q
+ 2
q r sin 2 q f 2
h
4pe 0 r
r sin q q
where m is the reduced mass of the electron and the nucleus, that is, m = me mn (mn + me ) .
Assuming that V(r) is a function of r only, the above wave equation can be solved by separating
the variables:
y (r , q , f ) = R(r )Q(q )F (f )
----- (6)
where R(r) is the radial function which is a function of r only, and Q(q) and F(f) are angular
functions. Substituting Eq. 6 into Eq. 5 then we get an equation which can be separated into three
equations which are:
76
1 d r 2 dR b
2m
Ze 2
R = 0
R
+
E
+
4pe 0 r
r 2 dr dr r 2
h 2
1 d
dQ m 2 Q
+ bQ = 0
sin q
sin q dq
dq sin 2 q
or
d 2F
+ m2F = 0
df 2
----- (7)
----- (8)
-----(9)
where m and b are constants.

The complete solution of Eq. 5 comprises the solutions of Eqs. 7,8 and 9. The energy
values of hydrogen-like atoms are found to be given by
En = -
2p 2 Z 2 me 4
----- (10)
(4pe 0 )2 (n 2 h 2 )
These energy levels are the same as those obtained from the Bohr theory. The normalized
solutions of radial equation (9) are found to be
where
(2 Z na 0 )3 (n - l - 1)!
exp(- r 2 )r l L2nl++l1 (r )
Rn ,l (r ) = -
3
2n[n + l ] !
----- (11)
r = (2 Z na 0 )r and a0 = (4pe 0 )h 2 me 2
----- (12)
L2nl++l1 (r ) are the associated Laguerre polynomials defined as
Lsr (r ) =
d s e r d r r -r
r e
dr s dr r
----- (13)
where s=2l+1 and r = n+l and n=1,2,3,4,...... .

The number n is called the principal quantum number which determines the energies of
different atomic orbitals and the distances of the electron from the nucleus.
The probability of finding the electron between r and r+dr is given by the quantity
R*(r)R(r)r2 dr.
8.2. ANGULAR FUNCTIONS
The solution of Eq. 8 gives
1
(2l + 1)(l - m )! 2 m
Q l ,m (q ) =
Pl (cos q )
2(l + m )!
----- (14)
77
where Pl
(cos q ) are called associated Legendre polynomials defined as

1
Pl (cos q ) = l 1 - cos 2 q
2 l!
m 2
l+ m
(cos
d cos q
q -1
l+ m
----- (15)
In the above equation, the quantum number l (=0,1,2....) is the azimuthal quantum
number. It determines the shape of the atomic orbitals. The solution of Eq. 9 gives
F m (f ) =
1
2p
exp(imf )
----- (16)
where 1 2p is the normalization constant and m = 0,1,2,......... .... l is the magnetic

quantum number. This name is given to this quantum number because in the presence of the
external magnetic field, the states having different values of m have different energies. The
phenomenon of removal of degeneracy of an energy state by application of external magnetic
field is known as Zeeman effect, after P. Zeeman (1865-1943) who was the co-winner (with H.A
Lorentz) (1853-1928) of the 1902 Physics Nobel Prize. These Dutch physicists were honored for
their work on the influence of magnetism upon radiation phenomena.
To sum up, the solution of the radial equation (7) gives quantum numbers n and l. The
solution of the Q-equation (8) gives quantum numbers l and m, and the solution of the
F-equation (9) gives quantum number m. In other words, the quantum numbers n, l, and m
follow directly from the wave mechanical treatment.
8.3. PROBABILITY DENSITY AND RADIAL DISTRIBUTION FUNCTIONS
As mentioned before, the value of y in the Schrodinger wave equation is important since
y 2 gives the probability of finding an electron of a given energy (i.e., of known quantum
numbers) at a given distance from the nucleus. Thus, by determining y 2 at different distances
from the nucleus, it is possible to trace out a region of space around the nucleus where there is
high probability of locating the electron. Each such region of space, as already pointed out, is
called an orbital.
The probability of locating the electron at different distances from the nucleus can be
represented graphically by plotting probability (y 2 ) against the distance (r) from the nucleus of
the atom. However, electron probability distribution is generally expressed in the form of radial
probability distribution which means the probability of finding an electron within a small
radial space around the nucleus.
Let us suppose that the space around the nucleus is divided into a very large number of
thin concentric shells of thickness dr at a distance r from the nucleus. The volume of a spherical
shell between radii r and r + dr will be given by 4pr2 dr. The probability of finding electron
within this spherical shell will be given by 4pr2y 2 dr. The radial probability at a distance r from
the nucleus is thus given by the function, 4pr2y 2 dr. In this function, while the probability factor
y 2 decreases, the volume factor 4pr2 dr increases with increase in the value of r. The radial
78
probability distribution of the electron is thus obtained by plotting the function 4pr2y 2 against
the distance r from the nucleus.
The probability of finding an electron at zero distance from the nucleus is zero. The
probability increases gradually as the distance increases, goes to a maximum and then begins to
decrease. The peak of the curve gives the distance from the nucleus where the probability of
finding the electron is maximum. This distance is called the radius of maximum probability.
In the case of hydrogen atom, the radius of maximum probability is 0.529 A .

Bohrs model restricts the electron to a definite orbit at a fixed distance from the nucleus.
The wave mechanical model, however, gives merely the maximum probability of locating the
electron at a given distance from the nucleus. In the case of hydrogen atom, for instance,
according to Bohrs calculations, the electron under ordinary conditions always stays at a
distance of 0.529 A from the nucleus. According to the wave mechanical model, however, the
electron keeps on moving toward or away from the nucleus and the maximum probability of
locating it lies at a radius of 0.529 A from the nucleus.
8.4. THE MOST PROBABLE DISTANCE OF THE H-ATOM (OR H-LIKE SPECIES) 1S
ELECTRON
Consider the 1s orbital wave function of hydrogen atom given by
y 1s = 1 pa 03
-r
2
a0
----- (1)
where r is the distance of the electron from the nucleus. The probability density for an electron
in this orbital is given by
y 12s = 1 pa 03 e
-2 r
a0
----- (2)
It may be noted that y 1s2 is independent of q and f and hence the electron distribution in
1s orbital is spherically symmetrical. Graphically the plot of y 1s2 against r is as shown by curve a
in Fig. 2.
79
There is also another procedure for describing the electron distribution in an atomic
orbital. It consists in determining the probability of finding an electron in a spherical shell of
thickness dr at a distance r from the nucleus. This is called radial probability. The radial
probability distribution of electron is given by
P (r )dr = 4p 2y 12s dr
1
= 4pr 2 3 e - 2 r a0 dr
pa 0
----- (3)
The plot of P(r), i.e., of 4p 2y 12s against r is given by curve b in Fig.1. The maximum of
the curve is found by differentiating P(r) with respect to r and setting the derivative equal to zero,
i.e.,
dP(r ) 4 2r 2
= 3 + 2r e - 2 r a0 = 0
----- (4)
dr
a0 a0
It readily follows from Eq. 4 that r = a 0 . Q e -2 r a0 0
Thus, we find that the maximum radial probability density occurs at a distance a0 , the
Bohr radius. We, therefore, conclude that the most probable distance of the 1s electron from the
nucleus is precisely what has been predicted by the Bohr theory. As already mentioned, while
the Bohr model restricts the electron to a definite orbit at a fixed distance from the nucleus, the
wave mechanical model gives merely the maximum probability of locating the electron at a given
distance from the nucleus.
80
8.5. PHYSICAL INTERPRETATION OF THE HYDROGENIC ATOMIC ORBITALS
According to the Bohr theory, the angular momentum L of an electron in an orbital is
given by
L = n(h 2p ) ;
n=1, 2, 3, .....
----- (5)
However, according to wave mechanics, the value of L is given by

L = [l (l + 1)] h = [l (l + 1)]
12
12
(h
2p )
----- (6)
Thus , while according to the Bohr theory the ground state angular momentum is equal to
h/2p since n=1(i.e., it is finite), according to wave mechanics its value is zero(Since l=0).
Consider an electron of mass me moving about the nucleus at a distance r in an orbit with
velocity u. The centrifugal force which keeps the electron away from the nucleus is given by
me u 2 me2 u 2 r 2
L2
F=
=
=
r
me r 3
me r 3
----- (7)
Where L= me ur is the angular momentum of the electron.

In terms of atomic units frequently used in quantum mechanics, we said me as well as e
and h =1. Hence, in atomic units we can write Eq. 6 as
L2 = l (l + 1)
----- (8)
Substituting for L2 in Eq.7, we have
F = l (l + 1) r 3
----- (9)
The radial motion of an electron in an atom is controlled by the centrifugal force given by
Eq. 9 as well as by the coulombic force of attraction, viz., - Ze 2 r 2 (or - Z r 2 in atomic units).
For the atom to be stable,
l (l + 1) Z
----- (10)
- 2 = 0 or
r = l (l + 1) Z
r3
r
Eq.10 shows that , other things being equal, an electron in an orbital of high angular
momentum tends to stay farther from the nucleus then an electron in a state of lower angular
momentum. Fig. 3 shows the radial parts of the Hydrogenic wave functions for the principal
quantum number n = 3. We see that the higher value of l, the less likely it is to be found near the
nucleus. Thus, for a given value of n, the size of the orbit increases with increasing the azimuthal
quantum number, l.
81
8.6. THE SCHRODINGER WAVE EQUATION FOR MULTI-ELECTRON ATOMS

The Schrodinger wave equation cannot be solved exactly for atoms beyond hydrogen
atom in the Periodic table. The troublesome term is the interelectron repulsion term in the
Hamiltonian because of which the n-electron wave function cannot be split into n one-electron
wave equations. Hence, methods have been developed for the approximate solution of the multielectron Schrodinger wave equation. One of these methods is based on the time-independent
perturbation theory and the other, called the variation method. Involves the selection of a trial
wave function.
8.6.1. TIME-INDEPENDENT PERTURBATION THEORY
The Schrodinger wave equation to be solved is
H y = Ey
----- (1)
The Hamiltonian is decomposed into two parts as
H = H ( 0 ) + lH '
----- (2)
where H ( 0 ) is the unperturbed part and lH ' is the perturbation where l is the perturbation
parameter which measures the deviation of the problem of interest from the unperturbed system.
It is further assumed that
lH ' << H ( 0 )
----- (3)
In general, l is set equal to unity which means that perturbation is fully applied.
Associated with H ( 0 ) are a set of eigenvalues E1( 0 ) , E 2( 0 ) , ........, E n( 0 ) and the corresponding
eigenfunctions y 1( 0 ) ,y 2( 0 ) ,.......y n( 0 ) , i.e.,
H y n( 0 ) = E n( 0 )y n( 0 )
----- (4)
82
It is assumed that the eigenfunctions y n and the energy eigenvalues En of the total
Hamiltonian H can be expressed in the form of a power series of l :
y n = y n(0 ) + ly n(1) + l2y n(21) + l3y n(3 ) + ....
----- (5a)
E n = E n(0 ) + lE n(1) + l2 E n(21) + l3 E n(3 ) + ....
----- (5b)
The first term in Eq. 5a is the zeroth-order term, the second represents the first order
correction; the third represents the second-order correction, etc., to the unperturbed zeroth-order
term. The eigen functions y n(1) ,y n(2 ) ,.... and the eigenvalues E n(1) , E n(2 ) ,... are independent of l and
y n(1) ,y n(2 ) ,.... are so chosen that they are orthogonal to y n(0 ) which is assumed to be normalized.
Omitted details, When Eq. 5a and 5b are solved, the results to the first-order in l are:
y n = y n(0 ) + y n(1)
(0 )
=y n
< y n(0 ) H 'y m(0 ) >

(0 )
+ l
(0 )
(0 ) y m
En - Em
mn
----- (6)
E n = E n(0 ) + E n(1)
where
= E n(0 ) + l < y n(0 ) H 'y n(0 ) >
----- (7)
(0 )
E n(0 ) =< y n(0 ) H (0 ) y n(0 ) > H nn
----- (8)
It can be further shown that
and
E n(1) =< y n(0 ) H 'y n(0 ) >
----- (9)
E n(2 ) =< y n(0 ) H 'y n(1) >
----- (10)
E n(3 ) =< y n(0 ) H 'y n(2 ) >
----- (11)
E n(n ) =< y n(0 ) H 'y n(n -1) >
----- (12)
These equations show that the calculation of nth order energy requires a knowledge of
(n-1)th order eigenfunctions. Since the contribution of second order, third order, etc., terms goes
on successively decreasing, we are primarily interested in the first order correction.
8.6.2. APPLICATION OF FIRST-ORDER PERTURBATION THEORY TO HELIUM
ATOM
83
We shall solve the Schrodinger wave equation for the ground state of helium atom using
the first-order time- independent perturbation theory. In this case,
H y = Ey
----- (13)
H = H ( 0 ) + lH '
----- (14)
where the unperturbed Hamiltonian, H (0 ) , is given by

h2 2
Ze 2 1 1
+
H (0 ) = 1 + 22 2m
4pe 0 r1 r2
----- (15)
and the perturbation is the interelectron repulsion term :
H ' = e 2 4pe 0 r12
----- (16)
Here r1 and r2 are the distances of the two electrons from the helium nucleus of charge Ze, and
r12 is the interelectron distance. We shall use atomic units, a.u. (h = e = m m = 1 4pe 0 = 1) , so
that
2 2
1
H (0 ) = - 12 + 22 - +
----- (17)
2
r1 r2
----- (18)
H ' = 1 r
12
Since H ' << H (0 ) , it is pertinent to use perturbation theory.

Since H (0 ) is the sum of two one-electron Hamiltonians, the unperturbed wave function
y (0 ) (r1 , r2 ) can be written as the product of two Hydrogenic wave functions:
y (0 ) (r1 , r2 ) = y (0 ) (r1 )y (0 ) (r2 )
----- (19)
Where y (0 ) (ri ) is the wave function of the ith electron in a Hydrogenic atom with nuclear charge
= Ze. Thus,
(0 )
Z 3 - Zr1
(r1 , r2 ) = 3 e
pa 0
= Z3 p e
- Z r1 + r2
12
a0
Z 3 - Zr1
3 e
pa 0
(in a.u.)
a0
----- (20)
The unperturbed ground state energy, E 0(0 ) , is equal to the sum of the ground state energies
of two Hydrogenic atoms :
) (
E o(0 ) = - Z 2 2 + - Z 2 2 = - Z 2
----- (21)
84
The first-order correction to the ground-state energy is
E 0(1) =< y (0 ) H 'y (0 ) >
= y *(0 ) (r1 , r2 )H 'y (0 ) (r1 , r2 )dt 1 dt 2
----- (22)
Substituting the value of y (0 ) (r1 , r2 ) from Eq. 20 into Eq. 22, we obtain
E 0(1) =
Z6
p2
- 2 Z ( r1 + r2 )(1 r12 )dt 1dt 2
----- (23)
where the volume elements of the two electrons (in spherical polar coordinates are) :
dt 1 = r12 sin q1 dr1 dq1 df1
dt 2 = r212 sin q 21 dr21 dq 21 df 21
The evaluation of the interelectron repulsion integral (Eq.23) is rather tedious; it can be shown
that it is given by
E 0(1) = (5 8)Z
----- (24)
Notice that E 0(1) is positive, as was to be expected since the repulsion energy between two
electrons is always positive.
Adding Eqs. 21 and 24, we have
5
E 0 = E 0(0 ) + E 0(1) = - Z 2 + Z
8
5
= - Z 2 - Z
8
----- (25)
Re- incorporating the original units we find that
5 me 2
E 0 = - Z 2 - Z 2
8 2h
Recalling that the ground state energy of hydrogen atom is -
----- (25a)
1
a.u. or - me 4 2h 2 or -13.60eV,
2
we get for helium atom

5
E 0 = - Z 2 - Z (27.2 )eV = -2.75 a.u. = -74.80 eV

8
----- (26)
85
The experimental value is -2.904 a.u. or 78.986 eV. The agreement between the
theoretical and experimental values is not good. If the second-order and higher order
contributions are included, the agreement improves but is still not very good.
8.7. VARIATION METHOD
According to the variation method, also called the variation theorem, i f y is an
approximate wave function of a quantum mechanical system, an atom or a molecule, described
by the Hamiltonian H , then the energy eigenvalue of the system, approximately given by the
integral
< y H y >
E=
<y y >
y * H ydt
y *ydt
----- (1)
or, if y is normalized (so that <y /y >=1), by the integral

E E0
----- (2)
is an upper bound to the ground state energy, E0 , of the system, i.e.,

We shall not give the proof of the variation theorem here.
If the approximate wave function, also called the trial function, happens to be exact (true)
wave function, then
E = E0
----- (3)
However, this is seldom the case since we have no idea of the exact wave function, to
begin with. The application of the variation method involves the following steps:
(i)
(ii)
Choose a trial wave function y dependent on variable parameters.

Evaluate the integral < y H y >
(iii)
(iv)
Minimise the above integral with respect to the variable parameters.

The function y with the optimum value of the parameters is the best
approximation to the true wave function and the lowest value of < y H y > is the
nearest approximation to the true energy.
8.7.1. APPLICATION OF VARIATION METHOD TO HELIUM ATOM

The Hamiltonian for He atom (in atomic units) is
2 2 1
1
H = - 12 + 22 - + +
2
r1 r2 r12
----- (4)
86
where the symbols have their usual meanings. As a result of screening, each electron (1 and2)
shields the other from the nucleus so that the two electrons do not see the same nuclear
charge. Here it is natural to use a wave function with nuclear charge Z less than 2. That is, Z is a
variation parameter which we shall determine from the variational calculation. It is important to
remember that the Hamiltonian in Eq. 4 contains the exact value of Z = 2.The vibrational
parameter appears only in the trial wave function:
1
y (r1, r2 )
Z 3 2 - Zr1
e
=
p
Z 3 2 - Zr2
e

p
----- (5)
= (Z 3 p )exp[- Z (r1 + r2 )]
----- (6)
E =< y H y >
----- (7)
Substituting the value of H from Eq. 4 in Eq. 7,
E=-
1
1
1
1
1
< y 12 y > - < y 22 y > -2 < y y > -2 < y y > + < y
y >
2
2
r1
r2
r12
----- (8)
The Laplacian operator in spherical polar coordinates (r,q,f) is given by

2 =
1 2
1

1
2
r
+
sin
q
+
q r 2 sin 2 q f 2
r 2 r r r 2 sin q q
----- (9)
Since the trial function (Eq. 5) does not depend upon angles q and f, differentiations with
respect to q1, f 1, q2 and f 2 vanish so that for the first kinetic energy operator in Eq. 8 , we get
Z3
1
2
- < y 1 y >=
2
p
1 2 - Zr1
- Zr1
- 2 Zr 2
2
e
- 2r12 r1 r1 r1 e r1 sin q1dr1dq1df1 e 2 r2 sin q 2 dr2 dq 2 df2
----- (10)
The functions of r2 are not affected by differentiation. Carrying out the integrations
overall angles we obtain
2
1 2 e - Zr1
Z3
1
r1
4p 2 e - Zr1 - 2
- < y 12 y >=
2
r1
p
0
2r1 r1
2
r1 dr1 e - 2 Zr2 r22 dr2
----- (11)
The second integral, evaluated using the standard integral, is equal to 2!/(2Z)3 so that Eq.
11 becomes
87
(4Z ) - 12
3 2
2!
e
(2 Z )
- Zr1
- Zr12 e - Zr1
r
1
) dr
= - 2Z 3
) e (- 2Zr + Z r )e
- Zr1
2
1
- Zr1
dr1
= - 2 Z 3 - 2 Z r1e - 2 Zr1 dr1 + r12 e - 2 Zr1 dr1

0
0
2Z
Z 2 2! Z 2
+
= (- 2 Z 3 )=
2
(2Z )3 2
(2 Z )
----- (12)
Similarly, the second kinetic energy operator term in Eq. 8 gives -2Z. The fifth term, the
interelectron repulsion energy integral, is some what more tedious. So, we will not go into details
about its evaluation, merely stating that it evaluates to (5/8)Z. Combining all these contributions
Eq. 8 becomes
E = 2 Z 2 2 + 2(- 2 Z ) + (5 8)Z = Z 2 - (27 8)Z
----- (13)
Using the variation method, we minimize the energy with respect to Z, obtaining
E Z = 2 Z - 27 8 = 0,
where Z = 27 16 = 1.69
Substituting this value of Z in Eq. 13, we obtain the ground state energy of helium atom:
E0 = (27/16)2 - (27/8)(27/16) = -2.8476 a.u.
= - (2.8476)(27.21 eV)
= - 77.48 eV
[ Q 1 a.u. = 27.21 eV ]
----- (14)
This is much better than the first-order perturbation theory result, viz., - 74.80 eV, we
obtained in Eq. 26, the experimental value being 2.904 a. u., i.e., - 78.986 eV. in 1929, E.A.
Hyleraas, using a more complicated wave function and the concept of the so-called electron
correlation which stipulates that electrons try to avoid each other, obtained a result for the ground
state energy of helium which is very close to the experimental value.
8.8. LET US SUM UP
In this lesson, we:
Pointed out
Angular functions
Probability density and radial distribution functions
The most probable distance of the H-atom (or H-like species) 1s electron
Physical interpretation of the hydrogenic atomic orbitals
88
The Schrdinger wave equation for multi-electron atoms

Time- independent perturbation theory
Application of first-order perturbation theory to helium atom
Variation method

1.
Show that the following radial wave function of hydrogen atom is normalized.
32
R1, 0 (r ) = (2 a 0 ) exp(- r a 0 )
.
2.
Using the first order perturbation theory solve the Schrodinger wave equation for the
ground state energy of Helium atom.

1.
2.
Using the variation method solve the Schrodinger wave equation for the ground state
energy of Helium atom.
Write the Schrdinger wave equation for Hydrogen atom in terms of polar coordinates.
Separate the resultant equation in three equations using the technique of separation of
variables. How do the quantum numbers n,l, and m emerge from the solution of the wave
equation.
8.11. REFERENCES
1.
2.
3.
4.
89
UNIT-VI
LESSON 9: THERMODYNAMICS AND NON-IDEAL SYSTEMS:
CHEMICAL POTENTIAL
CONTENTS
9.1. INTRODUCTION: CONCEPT OF CHEMICAL POTENTIAL
9.2. GIBBS- DUHEM EQUATION
9.3. SOME IMPORTANT RESULTS
9.4. VARIATION OF CHEMICAL POTENTIAL WITH TEMPERATURE
9.5. VARIATION OF CHEMICAL POTENTIAL WITH PRESSURE
9.6. CHEMICAL POTENTIAL IN CASE OF A SYSTEM OF IDEAL GASES
9.7. APPLICATION OF THE CONCEPT OF CHEMICAL POTENTIAL
9.7.1. CLAPEYRONCLAUSIUS EQUATION
9.7.2. INTEGRATED FORM OF CLAPEYRON-CLAUSIUS EQUATION FOR
LIQUID VAPOR EQUILIBRIUM
9 . 7 . 3 . A P P L I CATION
OF
CLAPEYRON-CLAUSIUS EQUATION
LIQUID VAPOR EQUILIBRIA
9.7.4. CLAPEYRON-CLAUSIUS EQUATION FOR SOLID VAPOR
EQUILIBRIUM
9.7.5. APPLICATION OF CLAPEYRON-CLAUSIUS EQUATION FOR
SOLID LIQUID EQUILIBRIA
9.8. LET US SUM UP
9.11. REFERENCES
FOR

The aim is to motivate and enable a comprehensive knowledge on chemical potential to
the students.
*
Understand the concept of chemical potential.
9.1. INTRODUCTION: CONCEPT OF CHEMICAL POTENTIAL

The thermodynamic properties, E, H, S, A and G are extensive properties because their
values change with change in the mass (or) the numbers of moles of the system.
In the derivation of various equations described earlier the change of was considered to be
due to change in temperature and pressure only.
90
A tactic assumption was made that the systems under consideration was a closed system.
(i.e.) there could be no change in the mass of the system.
However, if the case of an open system containing two or more components, there can be
change in the number of moles of various components as well.
In that case, an extensive property like G must be a function not only of temperature and
pressure but of the number of moles o the various components present in the system as well.
Let T and P be the temperature and pressure respectively, of a system and let n1 , n2 , n5
.ni be the respective number of moles of the constituents; 1, 2, 3,.i, then in view of what
has been said above, the Gibbs free energy, G, must be a function of temperature, pressure and
the numbers of moles of the various constituents (i.e.)
G = f (T, P, n1, n2, n3 ni)
------- (1)
Where n1 + n2 + n3 + + ni = total number moles = N (say)

Then, for a small change in temperature, pressure and the numbers of moles of the
components, the change in free energy dG will be given by the expression
dG
dG
dG
dG
dG
dG = dT + dP +
dn i +
dn 2 ..... +
dn i
dT P , N
dP T , N
dn 2 T , P , n1, n 2...ni
dn i T , P , n 2...ni
dn i T , P , n1, n 2..... ni
The quantity
is called partial molal
n
2 T , P, n , n .......n
1 2
i
more often, chemical potential (i) of the concerned component i. Thus,
= Gi = m i
n
2 T , P, n , n .......nj
1 2
free
energy Gi or
------ (3)
The term chemical potential was first introduced by Gibbs.

The physical significance of chemical potential easily follows from eqn (3). The chemical
potential of a given substance is, evidently, the change in free energy of the system that results on
the addition of one mole of that particular substance at a constant temperature and pressure, to
such a large quantity of the system that is no appreciable change in the overall composition of the
system.
Eqn (2) may be written as
dG
dG
dG =
dT +
dP + m dn + m dn + m dn
1 1
2 2
i i
dT P, N
dP T , N
------ (4)
Where 1, 2 j are chemical potential of the components 1, 2 and j, respectively.
91
If temperature and pressure remains constant then,
------ (5)
(dG) T, P = 1dn 1 + 2 dn 2 + .. j dn j
If a system has a definite composition having n1 , n2 .ni moles of the constituents

respectively, then on integrating eqn (5) we have
(G)
T, P, N
1, 2 j
------ (6)
= n 1 1 + n 2 2 + .. n j j
From eqn (6) chemical potential may be taken as the contribution per mole of each
particular constituent of the mixture to the total free energy of the system under conditions of
constant temperature and pressure.
It readily follows that for a total 1 mole of a pure substance, G = (i.e.) free energy is
identical with chemical potential.
9.2. GIBBS- DUHEM EQUATION
We know that the eqn (6)
(G)
T, P, N
------ (6)
= n 1 1 + n 2 2 + .. n j j
Shows that the free energy of a system at constant temperature and pressure can be
expressed as a sum of n terms for the individual components of the system.
Diffentiating eqn (6), we obtain
dG = 1dn 1 + n 1d1 + 2 dn 2 + n 2 d 2 + j dn j + n j d j
(or)
dG = (1dn 1 + 2 dn 2 + ....... j dn j ) + ( n 1d1 + n 2 d 2 + ........ n j d j )
------ (7)
But, according to eqn. (5)

(dG) T, P = 1dn 1 + 2 dn
+ .. jdnj
------ (5)
The first term on right hand side of (7) is equal to dG , at constant temperature and
pressure. It follows therefore that at constant temperature and pressure, for a system of a definite
composition
n1d1 + n2d2 + njdj = 0
(Or)
n i d i = 0
------ (8)
------ (9)
This simple relationship is known as Gibbs Duhem equation.

For a system having only two components ((e.g.) a binary solution) the above equation
reduces to
n 1d1 + n 2 d 2 = 0
------- (10)
92
(Or)
d1 = (-)
n2
d 2
n1
------ (11)
Eqn (11) shows that variation in chemical potential of one component affects the value
for the other component as well. Thus, if d1 is positive, (i.e.) if 1 increases then d2 must be
negative, (i.e.) 2 must decease and vice versa.
9.3. SOME IMPORTANT RESULTS
In a special case when there is no change in the number of moles of the various
constituents of a system, that is, when the system is a closed one, then, dn 1 , dn 2 , dn j are all
zero. In such a case, eqn (4)
dG =
G
G
dT +
+ 1dn 1 + 2 dn 2 + .. jdnj
T P , N
P T , N
------ (4)
Reduces to
dG =
G
G
dT +
T P , N
P T , N
------ (12)
It also follows from the expression G = H- TS
dG = dE + PdV + - TdS SdT ---- (A) TdS = dq = dE + PdV

Combining eqns A & B
That in a closed system
------ (B)
we get, dG = VdP + SdT
dG = VdP SdT
Hence, by equating coefficients of dT and dP in the above two equations, we get
G
= -S
T P, N
------ (13)
= V
p T, N
------ (14)
and
These results are important as they help us in deriving expressions for the variation of chemical
potential with temperature and pressure.
9.4. VARIATION OF CHEMICAL POTENTIAL WITH TEMPERATURE
93
The variation of chemical potential of any constituent (i) of a system with temperature
can be derived by differentiating eqn (3) with respect to temperature and eqn (13) with respect to
ni
G
= Gi = m i
n
i T , P, n1 , n .......nj
------ (3)
= -S
T P, N
------ (13)
The results are
and
2G
m
= i
ni T T P , N
------ (15)
S
2G
= -
n
n T
i
i
------ (16)
= -Si
T , P, n ,....n
1
j
Where Si , by definition, is the partial molal (or) molar entropy of the component i.
It follows from equations (15) and (16) that
m i
= -Si
T P , N
------ (17)
Chemical potential
Eqn (17) gives the variation of chemical potential i of any constituent (i) with
temperature. Since the entropy of a substance is always positive, hence, according to eqn (17),
the chemical potential would decrease with increase in temperature. This is illustrated in fig (1)
for a substance in solid, liquid and gaseous states. It is evident from this figure that at the melting
point (Tm), the chemical potentials of the solid and liquid phases are the same. Similarly, at the
boiling point (Tb); the chemical potentials of liquid and gaseous phases are the same. These
observations are extremely useful in the phase rule studies.
Gas
Solid
Liquid
Tm
Tb
Temperature
94
Fig.1. Variation of chemical potential with temperature.
9.5. VARIATION OF CHEMICAL POTENTIAL WITH PRESSURE

The variation of chemical potential of any constituent I with pressure may be derived by
differentiation eqn (3) with respect to pressure and eqn(14) with respect to n i ,
G
= Gi = m i
n
i T , P, n1 , n .......nj
------ (3)
W.r.t. P
and
G
=V
P T , N
------ (14)
W.r.t. n i
The results are
2 G m i
Pni P T , N
2G V
=V
i
n P n
i i T , P, n .....n
1
j
------ (18) And
------ (19)
Here Vi by definition, is the partial molal (or) molar volume of the component i. It follows from
the eqns. (18) (19) that
m i
------ (20)
= Vi
P T , N
Eqn. 20 gives the variation of chemical potential (i) of any constituent i with pressure.
9.6. CHEMICAL POTENTIAL IN CASE OF A SYSTEM OF IDEAL GASES
For
system
of
ideal
gases,
faster
development
of
equation
m i
= -Vi ----- (A) is also possible. In an ideal gas, PV = nRT . Consider now a system
P T , N
consisting of a number of ideal gases, let n1 , n2, be the number of moles of each constituent
present in the mixture. Then, in the ideal gas equation, n the total number of moles may be
replaced by (n1 + n2 + ).
Hence,
nRT
RT
------ (1)
V =
= (n1 + n2 + ....)
P
P
95
Differentiating equation (1) with respect to the ni , at constant temperature and pressure,
we have
V
ni
RT
= Vi =
P
T , P ,n1 ,n2 ....
------ (2)
RT
Substituting the value of Vi =
equation (A), we have
P
RT
m i
=
P
P T , N
------ (3)
For a constant composition of the gases and at a constant temperature, equation (3) ay
also be expressed in the form
dm i =
RT
dP = RTd ln P
P
------ (4)
Let pi be the partial pressure of the constituent i present in the mixture, since, each
constituent behaves as an ideal gas, therefore,
piV = ni RT
------ (5)
It follows from equation (5) and (1) that

n
------ (6)
pi = i P
n
Since ni and n are constants, therefore, on taking logarithms and then differentiating, we get
d ln pi = d ln P
------ (7)
Substituting in equation (4) we have
dm i = RTd ln pi
------ (8)
On integrating equation (8), we get

m i = m i0 ( P ) + RT ln pi
------ (9)
Where m i0 ( P ) is the integration constant, the value of which depends upon the nature of the gas
and also on the temperature. It is evident from equation (9) that the chemical potential of any
constituent of a mixture of ideal gases is determined by its partial pressure in the mixture.
If the partial pressure of the constituent i is unity, (i.e.), pi = 1, then
m i = m i0 ( P )
------ (10)
96
Thus, m i0 ( P ) gives the chemical potential of the gaseous constituent i when the partial
pressure of the constituent is unity, at a constant temperature. According to equation (5),
n
------ (11)
pi = i RT
V
n
Now i represents molar concentration (i.e.), the number of moles per unit volume of
V
the constituent i in the mixture. If this concentration is represented by Ci , then equation (11)
gives
pi = Ci RT
------ (12)
Introducing this value of pi in eqn. (9), we have

m i = m i0 ( P ) + RT ln (Ci RT )
= m i0 ( P ) + RT ln RT + RT ln Ci (Or)
1442443
cons tan t
mi = m
0
i (C )
+ RT ln Ci
------ (13)
Where m i0 (C ) is a constant depending upon the nature of the gas and the temperature.
If Ci = 1 , then,
m i = m i0 (C )
------ (14)
Thus m i0 (C ) represents the chemical potential of the constituent (i) when the concentration of the
n
constituent in the mixture is unity, at a constant temperature. Lastly, since i represents the
n
mole fraction ( xi ) of the constituent i in the mixture, equation (6) may be represented as
pi = xi P
------ (15)
Substituting this value of pi in equation (9), we have

m i = m i0 ( P ) + RT ln ( xi P )
------ (16)
= m i0 ( P ) + RT ln P + RT ln xi
1442443
cons tan t
m i = m i0 ( x ) + RT ln xi
------ (17)
Where, one quantity m i0 ( x ) is also a constant which depends both on the temperature the total
pressure. If xi = 1 then,
m i = m i0 ( x )
------ (18)
97
Thus, the quantity m i0 ( x ) represents the chemical potential of the constituent i when its mole
fraction, at a constant temperature and pressure is unity.
9.7. APPLICATION OF THE CONCEPT OF CHEMICAL POTENTIAL
The concept of the chemical potential has been used in deriving a number of important
generalizations such as the law of mass action the phase rule, the distribution law, the laws of
osmotic pressure etc.,
9.7.1. CLAPEYRONCLAUSIUS EQUATION
An equation of fundamental importance which finds extensive application in one
component, twophase systems, was derived by Clapeyron and independently by Clausius from
the second law of thermodynamics and is generally knows as ClapeyronClausius equation.
The two phases in equilibrium may be any of the following types:
(i) Solid and liquid, S
L at the melting point of the solid.
(ii) Liquid and vapor, L
V at the boiling point of the liquid.
(iii)Solid and vapor, S
V at the sublimation temperature of the solid
(iv) One crystalline form and another crystalline form as, for example, Rhombic and monoclinic
sulphur SR
SM at the transition temperature of the allotropic forms
Consider any two phase (say liquid and vapor) of one and the same substance in
equilibrium with each other at a given temperature and pressure. It is possible to transfer any
definite amount of the substance from one phase to another, in a thermodynamically reversible
manner, (i.e.), infinitesimally slowly, the system remaining in a state of equilibrium all along.
For example:
By supplying heat infinitesimally slowly to the system, it is possible to change any
desired amount of the substance from the liquid to vapor, phase at the same temperature and
pressure. Similarly, by withdrawing heat infinitesimally slowly from the system, it is possible to
change any desired amount of the substance from vapor to liquid phase with out change in
temperature and pressure.
Since, the system remains in a state of equilibrium, the free energy change of either
process will be zero.
We may conclude, therefore, that equal amounts of a given substance must have exactly
the same free energy in the two phases at equilibrium with each other.
Consider in general, the change of a pure substance from phase A to another phase B
in equilibrium with in at a given temperature and pressure.
A
B at constant temperature and pressure.
If GA is the free energy per mole of the substance in the initial phase A and GB is the
free energy per mole in the final phase B, then, since
98
GA = GB
Hence, there will be no free energy change.
(i.e.,)
G = GB GA = 0
If the temperature of such a system is raised, say from T to T + dT, the pressure will also
have to change. Say, from P to P + dP, in order to maintain the equilibrium. The relationship
between dT and dP can be delivered from thermodynamics.
Let the free energy per mole of the substance in phase A at the new temperature and
pressure be GA + dGA and that in phase B be GB + dGB. Since, the two phases are still in
equilibrium, hence,
GA + dGA = GB + dGB
------ (1)
According to thermodynamics,
Since
\
G = H TS
H = E + PV
G = E + PV TS
------ (2)
dG = dE + PdV + VdP TdS SdT
------ (4)
------ (3)
Upon differentiation,
The first law equation for an infinitesimal change may be written as

dq = dE + dw
------ (5)
If the work done dw is only due to expansion, then

dq = dE + PdV
------ (6)
Now for a reversible process,

dS =
dq
T
TdS = dq = dE + PdV
------ (7)
Combining equations 4 and 7, we have
dG = VdP = SdT
------ (8)
The equation (8) gives change of free energy when a system under goes reversible a
change of temperature dT and a change of pressure dP equation (8) for phase A may be written
as
------ (9)
dG A = V A dP - S A dT
99
and for phase B as
dGB = VB dP - S B dT
------ (10)
Since GA = GB, hence from equation (1),

dG A = dGB
------ (11)
V A dP - S A dT = VB dP - S B dT
(or)
dP S B - S A
=
dT VB - V A
------ (12)
------ (13)
It may be noted that that since VA and VB are the molar volumes of the pure substance in
the two phases A and B respectively, VB V A represents the change in volume when one
mole of the substance passes from the initial phase A to the final phase B. It may be
represented by DV . Similarly, SB SA being the change in entropy for the same process, may be
put as DS .
Hence
dP DS
=
dT DV
------ (14)
If q is the heat exchanged reversibly per mole of the substance during the phase
transformation at temperature T , then the change of entropy DS in this process is given by
q
DS =
T
dP
q
Hence
------ (15)
=
dT TDV
Thus
dP
q
=
dT T (VB - V A)
------ (16)
This is Clapeyron-Clausius equation. This equation, evidently gives change in pressure dP which
must accompany the change in temperature dT (or) vice verse, in the case of a system
containing two phases of a pure substance in equilibrium with each other.
Suppose the system consists of water in the two phases, viz., liquid and vapor in
equilibrium with each other at the temperature T (i.e.)
Water (liquid)
The
water (vapor)
q = molar heat of vaporization, DH V
VB = volume of one mole of water in the vapor state, say V g

V A = Volume of one mole of water in the liquid state, say Vl
Equation (16) therefore, taken the form
100
DH V
dP
=
dT T (Vg - Vl )
------ (17)
If the system consist of water its freezing point, then, the two phases in equilibrium will
be
water (solid)
(ice)
water (liquid)
Equation (16) may then be written as

DH f
dP
=
dT T (Vl - VS )
------ (18)
Where DH f is the molar heat of fusion of ice.

9.7.2. INTEGRATED FORM OF CLAPEYRON-CLAUSIUS EQUATION FOR
LIQUID VAPOR EQUILIBRIUM
The clapeyronclausius equation
dP
DHv
=
dT T (Vg - Vl )
------ (1)
as applied to liquid vapor equilibrium can be easily integrated.

The molar volume of a substance in the vapor state is considerably greater than that in the
liquid state. In the case of water, for example the value of Vg at 100 is
18 1670 =
30060 ml while that of Vl is only a little more than 18 ml. thus Vg-Vl can be taken as vg without
introducing any serious error. The Clapeyron equation (1) therefore, may be written as
dP DHv
=
dT TV g
------ (2)
Assuming that the gas law is applicable, (i.e.), PV = RT (Per mole)

Vg =
RT
P
------ (3)
Hence,
dP DHv P
DHv
=
=P
dT
R
RT
RT 2
------ (4)
(or)
dP DHv dT
=
2
P
R
T
------ (5)
101
(i.e.)
1 dP DHv
=
P dT RT 2
------ (6)
(or)
d (ln P ) DHv
=
dT
RT 2
------ (7)
Assuming that DHv remains constant over a small range of temperature, we have
d ln P =
DHv dT
R T2
------ (8)
DHv 1
+C
R T
------ (9)
\ ln P = -
(or)
log P = -
DHv 1
+ C
2.303R T
------ (10)
Where C and C are integration constants. Equation (10) is, evidently, the equation of a straight
DHv
1
line. Hence, the plot ln P against should yield a straight line with slope and
R
T
intercept = C. This enables evaluation of DHv . Equation (7) can also be integrated between limits
of pressure P1 and P2 corresponding to temperature T1 and T2 . Thus,
P2
T2
d (ln P) =
P1
DHv dT
R T1 T 2
------ (11)
P
DHv 1 2
\ ln 2 = P1
R T T1
------ (12)
DHv 1 1
-
R T1 T2
------ (13)
=+
(or)
DHv T2 - T1
R T1T2
2.303 log
P2 DHv T2 - T1
=
P1
R T1T2
------ (14)
------ (15)
The equation (15) is known as Clapeyron-Clausius equation.

9.7.3. APPLICATION OF CLAPEYRON-CLAUSIUS EQUATION FOR LIQUID
VAPOR EQUILIBRIA
102
Equation (13) can be used for calculating the molar heat of vaporization, DHv liquid if
we know the vapor pressures at two temperatures. Further, if DHv is known, vapor pressure at a
desired temperature can be calculated from the knowledge of a single value of vapor pressure at a
given temperature. It can also be used for calculating the effect of pressure on the boiling point of
a liquid. A few examples are given below:
1.
Calculation of molar heat of vaporization, DHv : The molar heat of
vaporization of
a liquid can be calculated if its vapor pressure at two
different temperatures is known.
Eg. 1: Vapor pressure of water at 95 and 100 are 634 and 760mm, respectively. Calculate
the molar heat of vaporization, DHv , of water between 95 and 100 .
Solution:
Substituting the given data in eqn (13) we have
ln
373k - 368k
760mm
DHv
=
= DHv = 41363 Jmol-1
-1
-1
634mm 8.314 JK mol (368k )(373k )
------ (12)
2.
Effect of temperature on vapor pressure of a liquid: If vapor pressure of
at one temperature is known, that another temperature can be
calculated.
a liquid
Eg 2: The vapor pressure of water at 100 is 760mm. what will be the vapor p r e s s u r e a t
95 ? The heat of vaporization of water in this temperature range is 41.27 KJ per mole
Solution: Substituting the given data in eqn (13) we have
ln
p2
41.27 10 3 Jmol -1
=
760mm
8.314 JK -1mol -1
373k - 368k
(368k )(373k )
p2 = 634.3mm
3.
Effect of pressure on boiling point: If boiling point of a liquid at one
known, that at another pressure can be calculated.
pressure is
Eg 3:
Ether boils at 33.5 at one atmosphere pressure. At what temperature will it
boil at
a pressure of 750mm, given that the heat of vaporization of ether is 369.86
Joules per
gram?
Solution: Substituting the given data in eqn (13), we have
ln
)(
750mm 369.86 Jg -1 74 gmol -1 T2 - 306 Jk

=
760mm
8.314 JK -1mol -1
(306.5k )(T2 )
T2 = 305.9K = 32.9
103
9.7.4. CLAPEYRON-CLAUSIUS EQUATION FOR SOLID VAPOR
EQUILIBRIUM
The clapeyronclausius equation for solid vapor equilibrium may be put as
DH S
dP
=
dT T (Vg - VS )
------ (1)
Where DH S stands for the molar heat of sublimation of the substance. Since the molar
volume of a substance is the gaseous state as very much greater than that in the solid, Vg - VS can
be safely taken as V g .
Eqn (1) can thus be easily integrated, as before to give the following expression:
log
DH S T2 - T1
P2
=
P1 2.303R T2T1
9.7.5. APPLICATION OF CLAPEYRON-CLAUSIUS EQUATION FOR

SOLID LIQUID EQUILIBRIA
The Clapeyron-Clausius equation (1) for solid liquid equilibrium cannot be integrated
easily since VS cannot be ignored in comparison with Vl . Also the laws of liquid state are not as
simple as those for gaseous state. However, this equation can be used for calculating the effect of
pressure on the freezing point of a liquid. This aspect will be discussed in chapter phase rule
equilibria and phase rule. Eqn (1) can also be used for calculating heat of fusion from vapor
pressure data obtained at different temperatures.
Eg: 1
The vapor pressure of ice water system at 0.0075 is 4.58mm and at 0 is
759.80mm of mercury. Calculate the molar heat of fusion of ice, given that the specific volumes
of ice and water at 0 are 1.0907cc and 1.0001cc, respectively
Density of mercury at 0 = 13.6gm per cc.
Solution:
dT
Vl
= 759.8-4.58 = 755.22mm=75.52cm Hg
= 75.52 13.6 981 dynes cm-2
= 0.0075-0=0.00750
= 18 1.001
VS
= 18 1.0907 cm3
dP
104
Since vapor pressure increases on decreasing the temperature will have a negative sign.
Substituting various values in eqn (1) we have
DH f
75.52 13.60 981 dynes cm -2
=
0.0075 K
273 18(1.0001 - 1.0907 )cm -3
Hence, DH f = 5.98 1010 ergs mol-1 (1 dyn cm = 1 erg)
=
5.98 1010 ergs mol -1

= 1429 cal mol-1
4.184 10 7 ergs cal -1
9.8. LET US SUM UP

In this lesson, we:
Pointed out
Concept of chemical potential

Gibbs- Duhem equation
Some important results
Variation of chemical potential with temperature
Variation of chemical potential with pressure
Chemical potential in case of a system of ideal gases
Application of the concept of chemical potential
ClapeyronClausius equation
Integrated form of clapeyron-clausius equation for liquid vapor equilibrium
Application of Clapeyron-Clausius equation for liquid vapor equilibria
Clapeyron-Clausius equation for solid vapor equilibrium
Application of Clapeyron-Clausius equation for solid liquid equilibria

1.
What is chemical potential?
2.
How does chemical potential vary with temperature and pressure? Derive the
Duhem equation.
Gibbs-

1.
2.
Derive Claperyon-Clausius equation in the form dP/dT= DHv /(TVg). Under what
conditions can this equation be integrated and how?
What are the applications of Claperyon-Clausius equation? Explain with examples.
9.11. REFERENCES
1.
J.C. Kuriacose and J. Rajaram, Thermodynamics, Shoban lal Nagin Chand
Delhi.
2.
& Co.,
B.R. Puri, L.R. Sharma and M.S. Pathania, Principles of Physical Chemistry,
Millennium edition, 2006-2007.
105
3.
Gurdeep Raj, Advanced Physical Chemistry, Goel Publishing House, Meerut.
106

FUGACITY
CONTENTS
10.1. INTRODUCTION: CONCEPT OF FUGACITY
10.2. FUGACITY AT LOW PRESSURES
10.3. DETERMINATION OF FUGACITY OF A GAS
10.4. CALCULATION OF FUGACITY AT LOW PRESSURE
10.5. FUGACITY OF A GAS IN A GASEOUS MIXTURE
10.6. FUGACITY OF A LIQUID COMPONENT IN A LIQUID MIXTURE
10.7. PHYSICAL SIGNIFICANCE OF FUGACITY
10.9. LET US SUM UP
10.12. REFERENCES

The aim is to motivate and enable a comprehensive knowledge on fugacity t o the
students.
*
Understand the concept of fugacity.
10.1. INTRODUCTION: CONCEPT OF FUGACITY

Making use of the free energy function G Lewis introduced the concept of fugacity for
representing the actual behavior of real gases which is distinctly different from the behavior of
ideal gases.
We know that variation of free energy with pressure at constant temperature is given by
equation Viz.
dG
=V
dP T
------ (1)
This equation is applicable to all gases whether ideal or non- ideal. If one mole of a gas is
under consideration, then V refers to molar volume. For an ideal gas, the above equation may be
written as
(dG )T
and for n moles as,
dP
= nRT
P
Q PV = RT
V = RT
------ (2)
107
(dG )T
= nRT
dP
= nRT (ln P )
P
------ (3)
Integration of equation (3) yields,

G = G * + nRT ln P
------ (4)
Where G * , the integration constant, is the free energy of n moles of ideal gas at temperature,
when the pressure P is unity. Equation (4), evidently, gives the free energy of an ideal gas at
temperature T and pressure P .
Integration of equation (3) between pressures P1 a n d P2 at constant temperature T ,
yields,
P2
P
dP
= nRT ln 2
P
P1
DG = nRT
P1
------ (5)
The corresponding equation for 1 mole of the gas would be

DG = RT ln
P2
P1
------ (6)
Equations (4) and (6) are not valid for real gases since V is not exactly equal to
RT
.
P
In order to make these simple equations applicable to real gas, Lewis introduced a new
function f is called fugacity function. It takes the place of P in equation (3), which, for real
gases, may be expressed as
(dG )T
= nRT ln
df
f
------ (7)
And equation (7) may be represented as

G = G * + nRT ln f
------ (8)
Where G * is the free energy of n moles of real gas at temperature T , when its fugacity happens
to be 1. Thus fugacity is a sort of fictitious pressure which is used in order to retain for real gases
simple forms of equation which are applicable to ideal gases. Equation (8), evidently, gives the
free energy of a real gas at temperature T and pressure P at which its fugacity can be taken
as f .
Equation (7) on integration between fugacities f1 and f 2 , at constant temperature T ,
yields,
DG = nRT ln
f2
f1
------ (9)
108
The corresponding equation for one mole of the gas would be

DG = RT ln
f2
f1
------ (10)
As discussed above, equations (9) and (10) are applicable to real gases.
Eg: 1
Calculate the free energy change accompanying the compression of 1 mole of a gas at 57
from 25 to 200 atm. The fugacities of the gas at 57 may be taken as 23 and 91 atm,
respectively, at pressure 25 and 200 atm.
Solution:
DG = RT ln
P2
P1
= 1mole (8.314 JK -1mol -1 ) 330 K ln
200 atm
= 5702.8 J
25atm
for more accurate value, we should use the equation involving fugacities. Thus,
DG = RT ln
f2
f1
= 1mole (8.314 JK -1mol -1 ) 330 K ln
91atm
= 3730.0 J
23atm
10.2. FUGACITY AT LOW PRESSURES

f
, where P is the actual pressure, approaches unity when P approaches zero,
P
since in that case a real gas approximates to ideal behavior. The fugacity function, therefore, may
be defined as
The ratio
lim it
P0
f
=1
P
Evidently, at low pressures, fugacity is equal to pressure. The two terms differ materially
only at high pressures.
10.3. DETERMINATION OF FUGACITY OF A GAS
Equation G = G * + nRT ln f for one mole of a gas, may be put as
G = G * + nRT ln f
------ (1)
109
Differentiation of eqn (1) with respect to pressure at constant temperature and constant
number of moles of the various constituents, (i.e.) in a closed systems, gives
dG
d ln f
= RT =
dP T
dP
------ (2)
since
dG
=V
dP T
it follows that
d ln f V
=
dP RT
------ (3)
Thus, at definite temperature, eqn (3) may be written as

------ (4)
RTd (ln f ) = VdP
Since one mole of the gas is under consideration, V is the molar volume of the gas.
Knowing that for an ideal gas,
V =
RT
P
------ (5)
The quantity a , defined as departure from ideal behavior at a given temperature, is given
by
a=
RT
-V
P
------ (6)
Eqn (6) is multiplied by dP throughout, we get

adP = RT
dP
- VdP
P
------ (7)
Combining equations (4) and (6), we have

RTd (ln f ) = RT
dP
- adP
P
Both sides dividing by RT

(or)
d (ln f ) = d ln P - a
dP
RT
------ (8)
110
Integrating eqn (8) between pressures O and P , we have
P
ln
f
1
=adP
P
RT 0
------ (9)
Now a is given by eqn (6), can be determined experimentally, at different pressures.

These values of a are then plotted against corresponding pressures, as shown in fig.
The area under the curve between pressure e=0 and any given pressure P , yields the value of
P
the integral adP , as illustrated by the shaded portion in fig.
negative
positive
Plot of a =
+ve area
pressure 'P'
-ve area
RT
- V vs. P for the determination of fugacity of the gas
P
Incorporating this value in eqn (9) the fugacity f can be evaluated at any given
pressure p of the gas.
Since a of the departure from ideal behavior, can be both positive as well as negative,
the area under the curve (with respect to the pressure axis) can be both positive as well as
negative. Thus, the fugacity of the gas can be both less than or more than the pressure. As is
P
evident from fig the area and hence the value of
a (dP) is positive at low pressure and negative

0
at high pressures. Hence, in accordance with eqn (9) fugacity f of the gas would be less than
the pressure p at low pressures and more than the pressure at very high pressures. This is
borne out by the data given in the table (1) for nitrogen gas at various pressures at 0 .
Fugacity of nitrogen gas at various pressures at 0

Pressure atmosphere
Fugacity atmosphere
111
50
100
200
400
800
1000
48.9
96.7
194.2
424.4
1191
1834
Fugacity of hydrogen gas at various pressures at 0

Pressure atmosphere
25
50
100
200
500
1000
Fugacity atmosphere
25.4
51.5
106.1
225.8
685
1899
It may be recalled that for hydrogen and helium PV is greater than RT for all pressures
at ordinary temperatures. Hence fugacity in these gases always remains greater than the pressure.
This is borne out by the data in table (2) for fugacity of hydrogen gas at 0 .
112
10.4. CALCULATION OF FUGACITY AT LOW PRESSURE
It has been found that the experimental value of a at low pressure assumes almost
constant value. Under such conditions, therefore, eqn
P
f
1
=a (dP )
P
RT O
f
P
ln = a
P
RT
ln
Becomes
------ (1)
Now at low pressure, since gases tend to be ideal,

or
f =p
f
=1
P
------ (2)
Making use of the fact that ln x is approximately equal to x - 1 when x approaches unity we
have,
ln
Hence,
f
f
= -1
P P
f
f
= 1 + ln
P
P
P
=1-a
RT
=
------ (3)
------ (4)
PV
RT
------ (5)
Hence,
f =
P 2V
RT
------ (6)
This equation is useful in calculating fugacity at moderately low pressures.

Eg:
For a VanderWaals gas, express the fugacity as a function of V, T, R and the
VanderWaals constants.
113
Solution:
From eqn
RTd ln ( f ) = Vdp --- (i) for one mole of the gas Integrating eqn (1)
RT d ln ( f ) = Vdp
------ (ii)
It is advisable to change the variable on the right hand side of the eqn (ii) by resorting to
integration by parts. Accordingly,
VdP = PV -
------ (iii)
Vdp
Now, for one mole of the VanderWaals gas,

P=
RT
a
- 2
V -b V
------ (iv)
(Where V is the molar volume) hence, from eqns (ii), (iii) and (iv),
a
RT
RT ln f = PV -
- 2 dV = RT - RT ln(V - b) - dV + C
V - b V
------ (v)
Where C is the integration constant.

To evaluate C, we recall that f p as p o .
Also,
as
po
at constant temperature T ,V a
so
that (V - b ) V a n d
1
0 .Hence,
V
RT ln P = RT - RT ln V + C = RT - RT ln (RT / P ) + C
= RT - RT ln RT + RT ln P + C
\ C = RT ln RT - RT
QP = 0
------ (vi)
Substituting for C in eqn (v), we get

a
RT ln f = PV - RT ln (V - b ) - + RT ln RT - RT
V
RT
a
= PV - RT + RT ln
-
(V - b ) V
------ (vii)
------ (viii)
Rearranging the Vander-Waals equation, after expansion, neglecting the term ab /V 2 and later
the term a / V 2 as well, we obtain
114
PV - RT =
RTb
a
V -b V
------ (ix)
Hence, ln f = b /(V - b) + ln RT /(V - b) - 2a / RTV this is the required expression for fugacity.
10.5. FUGACITY OF A GAS IN A GASEOUS MIXTURE
Remembering that for one mole of a pure substance, the free energy (G) is identical with
the chemical potential m eqn (dG )T = nRTd (ln f ) c for one mole of
dm i = RTd (ln f i )
------ (1)
and eqn G = G * + nRT ln f may be written as

*
m i = m i + RT ln f i
------ (2)
Where m i is the chemical potential of the gaseous component i at its unit fugacity.
10.6. FUGACITY OF A LIQUID COMPONENT IN A LIQUID MIXTURE
The eqn
*
is valid not only for the fugacity of a gas in gaseous mixture but also for the fugacity of a pure
liquid in a liquid mixture. This easily follows from the following discussion.
As is well known, in the case of phase equilibria, the chemical potential of any given
component is the same in all phases. Thus if there are three phases a, b, and c containing a
component i then at equilibrium,
m i (a ) = m i (b) = m i (c)
Consider, for example, a liquid i in equilibrium with its vapor. The chemical potential of
the liquid, ( m i ) l = ( m i ) g
Now according to the eqn G = G * + nRT ln f chemical potential of a vapor and a gas
may be written as
( m i ) g = ( m * i ) g + RT ln f i
------ (1)
(m )
Where as before i g is the chemical potential of the vapor (when its fugacity is equal to
1. therefore, chemical potential of a liquid may, evidently, be written as
( m i ) l = ( m * i ) l + RT ln f i
------ (2)
115
Where ( m *i ) l stands for the chemical potential of the liquid when its fugacity is equal to
1. It follows from the above discussion that the fugacity of a pure liquid would be the same as
that of its vapor in equilibrium with it, at a given temperature.
10.7. PHYSICAL SIGNIFICANCE OF FUGACITY
In order to understand the physical significance of the term fugacity, consider a system
consisting of liquid water in contact with its vapor water molecule in the liquid phase will have a
tendency to escape into the vapor phase by evaporation, while those in the vapor phase will have
a tendency to escape into the liquid phase by condensation. At equilibrium, the two escaping
tendencies will be equal. It is now accepted that each substance in a given state has a tendency to
escape from that state. This escaping tendency was termed as fugacity.
10.9. LET US SUM UP
In this lesson, we:
Pointed out
Concept of fugacity
Fugacity at low pressures
Determination of fugacity of a gas
Calculation of fugacity at low pressure
Fugacity of a gas in a gaseous mixture
Fugacity of a liquid component in a liquid mixture
Physical significance of fugacity

1.
2.
Explain the term fugacity. How is it related to chemical potential?

Explain why the fugacity of Helium or Hydrogen is always more than the pressure.
116
1.
How can you determine the fugacity of gas using (i) Graphical method and (ii)
From
equations of state?
2.
What is the physical significance of fugacity? How does fugacity vary with
temperature?
10.12. REFERENCES
1.
Delhi.
& Co.,
2.
3.
117

ACTIVITY
CONTENTS
11.0.
11.1.
11.2.
11.3.
11.4.
11.5.
11.6.
AIMS AND OBJECTIVES

INTRODUCTION: CONCEPT OF ACTIVITY
ACTIVITY COEFFICIENT
TEMPERATURE COEFFICIENT
REFERENCE STATES OR STANDARD STATES
RATIONAL AND PRACTICAL APPROACHES
DETERMINATION OF ACTIVITY OF SOLVENT
COLLIGATIVE PROPERTIES
11.7. LET US SUM UP
11.10. REFERENCES
AND
SOLUTE
FROM

The aim is to motivate and enable a comprehensive knowledge on activity to the students.
*
Understand the concept of activity.
11.1. INTRODUCTION: CONCEPT OF ACTIVITY

It may be pointed out that since the absolute value of free energy (or) chemical potential
is not known, it is impossible to evaluate of a substance. This difficulty has been overcome by
referring all free energy and chemical potential measurements for any given substance to a
standard reference point. Let m i be the chemical potential of a substance i in pure state and let
f i be its fugacity
\ Equation
May then be put as

*
------ (1)
Let m i be the chemical potential of the same substance in some other state. Then
*
------ (2)
The difference between chemical potential of a substance in any state and that in the pure
state is given by
118
f
0
m i - m i = RT ln i0 Or
fi
f
0
m i = m i + RT ln i0
fi
------ (3)
We may introduce here a new term, activity a and define it as

a=
f
f0
------ (4)
fi
0
fi
------ (5)
or for a substance i , as
a=
Activity of a substance in any given state is thus defined as the ratio of the fugacity of the
substance in that state to the fugacity of the same substance in the pure state.
The equation 3, therefore, reduces to
0
m i = m i + RT ln a
------ (6)
Let a system consisting of one mole of a substance change from a state in which its
chemical potential (or) free energy, both being identical since we are dealing with one mole of
the substance is m i , to another state in which its chemical potential is m 2 , the change in chemical
potential Dm , is then given by
Dm = m 2 - m1 = m 0 + RT ln a2 - m 0 + RT ln a1
or
a
Dm = RT ln 2
a1
)
------ (7)
Comparing the above equation with that for an ideal gas, viz.
P
DG = Dm = RT ln 2
P1
------ (8)
It is evident that in the case o real gases, activity replaces pressure. Thus activity of a gas
like fugacity, serves as a thermodynamic counter part of a gas pressure. In case of solutions it
serves as a counter part of concentration of the solute in the given solution.
11.2. ACTIVITY COEFFICIENT
For an ideal gas, activity is numerically equal to its pressure (i.e.) a = P For real gases,
however, activity is only proportional to its pressure (i.e.) a P or a = gP where g is known as
the activity coefficient
Eg:
119
The activity of 2.5 moles of a substance changes from 0.05 to 0.35. What would be the
change in its free energy at 27 ?
Solution: The change of free energy for one mole of a substance is given by the relation
a
DG = RT ln 2
a1
a
\ For n moles, DG = nRT ln 2 = (2.5 mol) (8.314 JK -1mol -1 ) (300K) ln 0.25
a
0.05
1
= 12133.65 J
11.3. TEMPERATURE COEFFICIENT
Temperature coefficient of a chemical substance is defined as the ratio of rate constants of
a reaction at two different temperatures separated by 100 C. The two temperatures are generally
taken as 350 and 250 C.
Thus, the temperature coefficient is expressed as
Temperature coefficient =
k 350
0
k 25
In general the temperature coefficient is expressed as

Temperature coefficient =
k t + 10 0
kt
Where kt is the specific rate of the reaction at t0 C and kt + 10 is the specific rate of the
same reaction at t+100 .
11.4. REFERENCE STATES OR STANDARD STATES

It may be emphasized again that there is no means of finding absolute values of free
energy (G) or Chemical potential (m) of any substance. It is necessary, therefore, to make such
measurements with reference to the value obtained for some convenient though arbitrary
reference state called standard state.
The standard state for a gas at any given temperature is defined as that state in which
the fugacity of the gas is unity. Since a = f/f0 , it follows that if f0 = 1, a = f. Evidently, the
standard state for a gaseous component is such that
fi = ai =1
The standard state for a liquid is the pure state of the liquid at one atmosphere pressure
at any given temperature. In this state of the liquid, f = f0 and a = 1.The standard state for a liquid
component I in a liquid solution is the pure state of the component such that ai = 1.
120
The standard state for a solid is the pure state of the solid at one atmosphere pressure at
any given temperature. In this state, its activity a = 1.
11.5. RATIONAL AND PRACTICAL APPROACHES
The concentration of a solution is usually expressed as mole fraction, molality or
molarity. The standard state chosen depends on the concentration unit used. If the choice is
mole fraction, it is referred to as the rational system, whereas if molality or molarity (practical
units) are used it is called the practical system.
(A) RATIONAL SYSTEM
If the mole fraction of the solute, x2 , is taken as the measure of the concentration of the
solute, Henrys law being applicable to solutes, f2 = K x2 , where K is the Henrys law constant.
It is therefore desirable to choose the standard state for the solute in such a way that in a dilute
solution, the activity becomes equal to the mole fraction of the solute. Thus it is desirable that
a2
1 as x2 0
----- (1)
x2
The fugacity- mole fraction relationship over the entire range of mole fraction, 0 to 1, can
be represented as the solid line in Fig1. For the very dilute solution as x2 0 , it is seen that the
actual curve merges with the Henrys law line.
Since a 2 = f 2 f 20 , Eq. 1 can be written as
121
a
f
Lim 2 = Lim 2 = 1
----- (2)
x x 0 x
2 x x 0 f 2 x 2
Since Henrys law is also applicable to the solute, in the very dilute solution,
Lim [f2 /x2 ] for solid line = limiting slope = K. For Henrys law line (dotted) x 2 0 .
f2'
=K.
Lim
x x 0 x
2
Therefore
Lim[ f 2 x 2 ] = Lim f 2 x 2 = K
x x 0
x x 0
'
----- (3)
Since f2 = Kx2 , eqn. (3) can be written as
f
Lim 2 = 1
x2 0 Kx
2
----- (4)
If equations 2 and 4 should hold good simultaneously f2 0 =K, the Henrys law constant for
this solute. From Fig. 1., it is seen that this state can be found by extrapolating the dotted line to
a concentration x2 = 1. From Henrys law f2 =Kx2 , it is seen that when x2 = 1, f2 = k. This
fugacity is taken as the standard fugacity for the solute. It should be noted that the standard
fugacity (f2 0 ) is a hypothetical quantity and is not equal to the fugacity (f2 ) of the pure solute.
The standard state for the solute is chosen as the hypothetical liquid solution at the given
temperature and 1 atm total pressure, in which the mole fraction of the solute is unity and yet it
behaves ideally, obeying Henrys law. If this law is obeyed over the entire range of composition
(x2 = 0 to 1).
Kx 2
a 2 = f 2 f 20 = f 2 K =
= x2
----- (5)
K
Thus as x 2 1 , a2 becomes unity. The activity at any other concentration will be equal
to x2 , the mole fraction of the solute. If the activity of the solute, a2 = f2 /f2 is plotted against x2 ,
the curve obtained (Fig.2) is similar to the one in Fig.1, since each value of the fugacity is
divided by the same constant, f2 0 . For an ideal solution, the slope of the curve should be unity
(Fig.2.). The activity of the pure solute, a2 is seen to be different from a2 0 . For any mole
fraction, xj the activity coefficient gx is aj /xj. In Fig.2, Y=a2 and since the slope of the dotted line
is unity,
xj =X. Thus gx =Y/X.
For a solution behaving ideally over the whole range of concentration, the activity will
always be equal to its mole fraction. For non-ideal solutions, the standard state has no reality and
it is preferable to define the standard state in terms of a reference state. It is seen from Fig.2 that
the activity coefficient gx becomes unity as x 2 0 . It is thus possible to choose the infinitely
dilute solution as the reference state, such that as x2 0 , n x 1 or a 2 x 2 .
122
(B) PRACTICAL SYSTEM

Molality is more widely used to express concentrations than mole fraction. In very dilute
solutions, molality is proportional to mole fraction. Henrys law is valid under these conditions
(i.e.) f2 =Km2 . If f2 is plotted against m2 , the Henrys law constant, K, can be obtained from the
limiting slope of the curve (I) (Fig.3.). The choice of the standard fugacity should be such that as
a
m2 0, 2 1 or
m2
a
f
Lim 2 = Lim 0 2 = 1
m2 0 m
2 m2 0 f 2 m2
----- (1)
Under such limiting conditions, Henrys law is valid (i.e.) f2 =Km2 or
f
Lim 2 = 1
m2 0 Km
2
----- (2)
For the same region (m2 0 ) of the solid line curve (Fig.3) equations 1 and 2 should
hold good simultaneously. This is true when f2 0 =K. In Fig.3., this condition is realized by
finding the fugacity corresponding to m2 =1. The interpolation is done on the Henrys law plot
(dotted line) since this law is obeyed by ideal systems under all conditions. The standard state of
the solute is the state, which has the fugacity that the solute in a solution of unit molality would
123
have, if Henrys law is obeyed at this concentration. With increasing dilution, a solute
approaches ideal behavior specified by the Henrys law. However it is misleading to say that the
standard state of the solute is the infinitely dilute solution. In such a case f2 =0. If f2 0 =0, the
activity at any finite concentration a2 = f2 /f2 0 , would be infinite.
A curve similar to that in Fig.3 can be obtained by plotting activity, a2 of the solute
against molality, m2 (Fig. 4). Since the mole fraction scale has limits of 0 and 1, the choice of x2
=1 as a standard state, is quite natural. Theoretically molality has no upper limit, but in practice
the upper limit is the solubility of the substance.
124
The choice of standard state, m2 0 = 1 mole/kg is arbitrary. The standard state is the
hypothetical 1 molal solution obtained by extrapolating the Henrys law line to m2 =1.
If the concentration of the solute is expressed in molarity (c) the standard state is chosen
as the hypothetical state obtained when Henrys law plot is extrapolated to c2 = 1 mol/l.
11.6. DETERMINATION OF ACTIVITY OF SOLVENT AND SOLUTE FROM
COLLIGATIVE PROPERTIES
VAPOUR PRESSURE MEASUREMENTS
(A) SOLVENT
The activity of a constituent, j, in solution is given by fj /fj0 , where fj is its fugacity in the
solution and fj0 is the value at the standard state (pure liquid at the same temperature as the
solution and at 1 atm total pressure). If the vapour pressures are sufficiently low, ideal behaviour
may be assumed; The fugacities may therefore be replaced by the respective partial pressures
(i.e.)
a j = p j p 0j
----- (1)
Since the effect of external pressure on activity is negligible, Eq. can also be written as
a j = Pj p j
----- (2)
125
Here pj is the partial vapour pressure of the solvent in equilibrium with the solution in
which its activity is aj, and p is the vapour pressure of the pure solvent at the same temperature
and 1atm pressure i.e. at the standard state. This method is useful in determining the activity of
the solvent in aqueous solutions, mixtures of organic liquids etc. If the mole fraction or the
concentration of the solvent is known, the activity coefficient of the solvent can be calculated.
(B) SOLUTE
If the solute is completely miscible with the solvent, the standard state is chosen as the
pure liquid. The activity may be determined by using Eq.
a j = Pj p j
If the solute is sufficiently volatile to permit the determination of its vapour pressure over
the solution. For dilute solutions it is preferable to use the infinitely dilute solution as the
reference state. The activity is proportional to its fugacity, the value of the proportionality
constant depending on the standard state used or reference state used. If 1/k is the proportionality
constant for the chosen reference state, a2 =f2 /k. In dilute solutions, as x 2 0, [a 2 x 2 ] 1 or
f 2 = a2 k = x2 k as x2 0
For a dilute solution f2 = p2 , the partial pressure of the solute. Hence
a2 p2 k
----- (1)
The value of k can be obtained by utilizing the fact that at high dilutions, the activity of
the solute, a2 * is equal to the mole fraction x2 *. If p2 * is the partial pressure under this condition,
a 2 * = x 2 * = p 2 * k or k = p2 * x2 *
----- (2)
The activity of the solute a2 , in the given solution is given by Eq.1. Substituting for k,
a2 =
p2
= p2
k
p2 *
x
*
2
----- (3)
The activity coefficient (g x )2 being a2 /x2 , from Eq. 3.
a2
= (g x )2
x2
p2

x
= 2
p2 *
x2 *
----- (4)
A graphical evaluation of k is possible, by plotting p2 /x2 against x2 and extrapolating it to

x2 = 0. Once k is known, by using Eq. 3 the activity can be calculated. From Eq. 4 the activity
coefficient can be calculated.
126
11.7. LET US SUM UP

In this lesson, we:
Pointed out
Concept of activity
Activity coefficient
Temperature coefficient
Reference states or standard states
Rational and practical approaches
Determination of activity of solvent and solute from colligative properties
1.
2.
Define activity and activity coefficient.

What are the applications of activity concept to solutions?

1.
Explain briefly the rational and practical approaches of activity.
2.
How can you determine (i) the activity of solvent from colligative properties (ii) the
activity of solute.
11.10. REFERENCES
1.
Delhi.
& Co.,
2.
3.
LESSON 12: THERMODYNAMICS AND NON-IDEAL SYSTEMS: THIRD

LAW OF THERMODYNAMICS
CONTENTS
12.1. INTRODUCTION: THIRD LAW OF THERMODYNAMICS
12.3. NERNST HEAT THEOREM
12.4. CONSEQUENCES OF THE NERNST HEAT THEOREM
12.5. THIRD LAW OF THERMODYNAMICS: PLANKS FORMULATION
12.6. STATEMENT OF LEWIS AND RANDALL
12.7. UNATTAINABILITY OF ABSOLUTE ZERO
12.8. THERMODYNAMIC QUANTITIES AT ABSOLUTE ZERO
12.9. APPLICATIONS OF THIRD LAW OF THERMODYNAMICS
12.10. THERMODYNAMIC PROBABILITY AND STATISTICAL
THERMODYNAMICS
12.10.1. DERIVATION OF THE BOLTZMANN ENTROPY EQUATION
127
12.11. APPARENT EXCEPTIONS
12.12. LET US SUM UP
12.15. REFERENCES

The aim is to motivate and enable a comprehensive knowledge on third law of
thermodynamics to the students.
*
Understand the third law of thermodynamics.
12.1. INTRODUCTION: THIRD LAW OF THERMODYNAMICS

In the earlier development of chemical thermodynamics, the difficult task was to ascertain
a quantitative relation between DG and DH in a chemical reaction and to find out DG from
thermal data (i.e.), DH . A preliminary discussion will now be given which will deal with this
problem thereby ultimately leading to the Nernst heat theorem and third law of thermodynamics.
12.3. NERNST HEAT THEOREM
Nernst postulate for a process in a condensed system that the value o f d
(DG )
dT
approaches zero asymptotically as the absolute zero is approached.

In other words it means that DG and DH curves meet each other at a short region above
the absolute zero and run coinciding with each other upto absolute zero. This behavior is being
shown by full lines and not by dotted lines (Fig. 1).
Fig. 1. Variation of DG and DH with change of temperature.

The dotted lines curve reveals that the two values, DG and DH not only become equal to
each other at absolute zero but their approach to each other becomes rapid and not gradual.
128
The mathematical expression of Nernsts postulate may be expressed analytically as

Lt
d
(DG )=T Lt0 (DH ) = 0
T 0 dT
----- (1)
This mathematical expression expresses the Nernst heat theorem.

12.4. CONSEQUENCES OF THE NERNST HEAT THEOREM
We know second law of thermodynamics that
d (DG )
= - DS
dT P
and
d (DH )
= DC P (Kirchoffs equation)
dT P
When we set up the conditions demanded by the Nernst heat theorem, we get
Lt
T 0
DS = T Lt0 DC P = 0
------ (2)
The significance of the equation (2) is that the entropy change tends to approach zero and
the difference between the heat capacities of products and reactants also tends to approach zero
as the temperature is lowered towards the absolute zero. This is the statement of Nernst heat
theorem.
Nernst heat theorem holds good only in the case of solids. Since no gas exists at
Nernst heat theorem cannot apply to gases. It can also not be applied to liquids.
0K.
12.5. THIRD LAW OF THERMODYNAMICS: PLANKS FORMULATION

The absolute value of entropy of a pure solid (or) a pure liquid approaches zero at 0K.
Lt
T 0
------ (1)
DS = 0
If equation (1) is assumed correct, Nernst equation (2) follows immediately for
Lt
Lt
T 0
(- DS )=
dDG
=0
T 0 DT
------ (2)
pure solids and liquids. Planks formulation is also consistent with the treatment of entropy
which is introduced in statistical mechanics. Plank statement asserts that S 0 K is zero for only
pure solids and liquids whereas Nernst assumed that his theorem was applicable to condensed
129
phases, including solutions. According to plank solutions at 0 K have positive entropy equal to
entropy of mixing.
12.6. STATEMENT OF LEWIS AND RANDALL
Lewis and Randall modified the statement of the third law of thermodynamics as follow.
Every substance has positive entropy but at the absolute zero the entropy may become zero, and
it dose so become in the case of perfect crystalline substance.
From the point of view of a chemist it is the most practical tool for calculating free
energy. Consider for example the transition
S (rhombic, 0 K)
S (monoclinic 0 K)
DS 0 K from heat capacity measurement is zero. Hence, both rhombic and monoclinic sulphur are
assigned zero entropy at 0 K. Thus no difficulty is involved for calculating absolute entropy of
sulphur at a temperature T.
12.7. UNATTAINABILITY OF ABSOLUTE ZERO

It is impossible to attain absolute zero in a finite series of operations. For example, if we
consider entropy change at constant pressure
(or)
dS =
DQP C P
=
dT
T
T
Lt
Lt
------ (1)
dS
P
= =
T 0 dT T 0 T
------ (2)
Equation (2) shows the entropy of any substance should tend towards infinity as T
approaches absolute zero. Since this cannot happen clear no infinite series of processes lead to
absolute zero.
12.8. THERMODYNAMIC QUANTITIES AT ABSOLUTE ZERO

(i) Equivalence of G and H
Since S 0 for any substance is zero, according to Lewis and Randall statement, is follows
that for any substance
G0 K = H 0 K - TS 0 K = H 0 K (or)
G0 K = H 0 K
------ (1)
130
(ii) DC P in a chemical transformation
From Gibbs-Helmholtz equation
dDG
DG = DH + T
dT P
------ (1)
dDG
Q - DS =

dT P
DG - DH
dDG
=
T
dT P
Lt
Lt
DG0 K - DH 0 K
dDG
=0
=
T
T 0 dT T 0
------ (2)
Q DG0 K - DH 0 K = 0
A close examination of (eqn. 2) shows that the result comes out to be an intermediate form
0
at
0
T=0.
To resolve an indeterminate expression we may apply the mathematical rule of
differentiating numerator and denominator with respect to independent variable T. Thus we
have
Lt
dDG dDH
-
=0
dT
T 0 dT
------ (3)
(or)
Lt
Lt
dDG
dDH Lt
=
=T 0 DC P
d
T
d
T
T 0
T 0
------ (4)
It follows then
Lt
T 0
DC P = 0
many investigations D have shown that DC P does approaches zero at T approaches zero.
(iii). Limiting value of Cp and Cv
For a reversible temperature change in a substance at constant pressure,
DQ p C p dT
=
dS p =
T
T
On integrating at constant pressure
131
dS = S =
0
C p dT
T
+ S0
Where S 0 is integration constant. An examination of equation (2)

Lt
Lt
DG0 K - DH 0 K
dDG
=0
=
T
T 0 dT T 0
T
Shows that if C p has a finite value at T = 0. Integral
C p dT
will not give a finite value since

T
the denominator T approaches zero. Hence S would not be finite. But according to Lewis and
Randall statements, S must be finite at all temperature. Hence T Lt0 C P = 0 following is an
0
analogous procedure, it can be shown that T Lt0 C P = 0 .

12.9. APPLICATIONS OF THIRD LAW OF THERMODYNAMICS
The third law of thermodynamics is used to calculate the absolute entropy of the solids,
liquids and gases at different temperatures and the entropy changes of chemical reactions and
other processes.
Let us describe these one by one.
1. DETERMINATION OF ABSOLUTE ENTROPY OF SOLIDS
It is useful in calculating the absolute entropies of pure substance at different temperature
by using thermal data.
dT
We know dS = C p
, this on integrating between temperature limits 0 and T K
T
becomes as follows
T
ST - S 0 = C p d ln T
0
On setting up the condition demanded by the third law (i.e.)., S 0 = 0 at T = 0. We get

T
ST = C p d ln T
------ (1)
Where ST = absolute entropy of the solid at temperature T. One can calculate the integrant in eqn.
(1) graphically by plotting C p against T (or) C p against ln T and the area of curve so obtained
gives the value of integrant (i.e.), ST between T = 0 to any desired temperature (Fig. 2).
132
Fig. 2. Determination of absolute entropy

2. EVALUATION OF ABSOLUTE ENTROPIES OF LIQUIDS AND GASES
In all these cases we generally start from the crystalline (solid) state of a given substance
at absolute zero when its absolute entropy is taken as zero and then supplying heat to this solid; it
can be converted into the required state of the substance at a given temperature.
The sum of the entropy changes involving these conversions will give the value of
absolute entropy of the specific substance at the given temperature. In all these calculations, the
absolute entropy at 0 o K has been taken to be zero.
When we have to calculate the absolute entropy of a liquid, the following steps are
involved.
(1). First of all measurements are made on the solid form at the melting point. The entropy of the
solid at this temperature (DS1 ) is given as follows.
Tm
DS1 =
(C )
p
(C )
p s
dT
T
------ (1)
is the heat capacity of solid.
(2). The integrant in eqn. (1) can be obtained graphically. Changing one solid into the liquid state
at the melting point Tm. The entropy of this process (entropy of fusion) is given by
DS 2 =
Where
DH f
DH f
Tm
------ (2)
is the molar heat of fusion of the substance.
(3). Heating the liquid from its melting point (Tm) to this boiling point (Tb). Te entropy involved
in this case is given by
133
Tb
DS 3 =
(C )
p l
dT
T
------ (3)
Where (C p )l is the heat capacity of the substance in the liquid state. This can be evaluated by
plotting (C p )l vs ln T between temperature Tm and Tb and noting the area below the graph as
described before.
(4). Changing the liquid into the gaseous state at the temperature Tb. The entropy involved here
DS 4 is the entropy of vaporization and is given by
DS 4 =
DH v
Tb
------ (4)
Where DH v is the heat of vaporization per mole of the substance.

(5). Heating the gaseous from Tb to the required temperature (i.e.), 25 o C
entropy involved in this process, DS 5 is given by
298.15
DS 5 =
(C )
p
Tb
dT
T
(298.15 K). The
------ (5)
where (C p )g is the heat capacity of the substance in the gaseous state at constant pressure. Thus
the absolute entropy of the gas at 25 o C ST is equal to the sum of the all the entropies listed
above that is
Tm
Tb
298.15
dT DH f
dT DH v
dT
ST = DS1 + DS 2 + DS 3 + DS 4 + DS 5 = (C p )
+
+ (C p )l
+
+ (C p )
T
Tm
T
Tb
T
0
0
Tb
s
g
(3). CALCULATION OF FREE ENERGY CHANGES THE REACTIONS
We know the simplified form of Gibbs-Helmholtz eqn. is
DG = DH - TDS
------ (1)
If the reactants and products are in their standard states equation (1) may be written as follows
DG 0 = DH 0 - T DS 0
The standard entropy changes may be determined experimentally while the values of standard
entropy changes may be obtained from the literature incorporating these values in eqn. (1) the
standard free energy of a reaction may be easily calculated.
Ex:
Calculate the standard free energy change DG 0 of the following reaction
CO ( g ) +
1
O2 ( g ) CO2 ( g ); DH o = -282.84kJ
2
134
Solution:
In this case DH o = -282.84kJ = - 282840 J.
The value of DS 0 is given by the expression.
DS 0 = S 0 products - S 0 reac tan t
The standard entropy of CO2 ( g ) is 213.80 JK -1mol -1 while the values for CO (g) and O
(g) are 197.90 and 205.01 JK -1mol -1 respectively.
Hence,
DS 0 = S 0 [CO2 ] - S 0 [CO ] + S 0 [O2 ]

= 213.80 (197.90 + 102.50) = - 86.60 JK -1mol -1
DG 0 = DH 0 - T DS 0
= - 282840 (298 K) (- 86.60 JK -1 )
= - 257033.2 J.
12.10. THERMODYNAMIC PROBABILITY AND STATISTICAL

THERMODYNAMICS
12.10.1. DERIVATION OF THE BOLTZMANN ENTROPY EQUATION
The Boltzmann entropy equation, viz., S = k ln W is probably the most famous equation
in statistical thermodynamics. Its derivation is naturally simple and appealing. Before we derive
it, we must distinguish between two kinds of probabilities, viz., mathematical probability and
thermodynamic probability.
Mathematical probability is a ratio of the number of case favorable to the occurrence of an
event to the total number of equally probable cases. This probability always lies between 0 and 1.
Thermodynamic probability is the number of microstates corresponding to a given macro state
when we are dealing with the distribution of molecules amongst an extremely large number of
energy levels. This probability W is a very large number, tending to be infinite.
Boltzmann suggested that entropy can be related to the thermodynamic probability W as
S = f (W )
------ (1)
Consider two systems A and B whose entropies and microstates (also called
complexions) are S A and S B , W A andWB , respectively, when the two systems are combined,
------ (2)
S = S A + SB
By definition, the probability of a thermodynamic state is proportional to the number of
complexions (macro states) required to achieve it. Mathematically, we know that the total
probability is the product of the probabilities of the independent events. This is also true of the
complexions. Hence,
W = W A WB
------ (3)
135
S A + S B = f (W AWB )
and
------ (4)
This relationship suggests that entropies are additive and probabilities are multiplicative.
This can be true only if S is a logarithmic function of W , (i.e.),
S = k ln W
------ (5)
This can be Boltzmann entropy equation. Eqn. (5) gives the quantitative definition of entropy of
disorder. In equation (5) W is defined as the total number of different ways in which a given
system in the specified thermodynamic state may be realized.
12.11. APPARENT EXCEPTIONS
Entropies calculated using the third law is called thermal entropies. However, the
statistical entropies, calculated by the method of statistical mechanics are more rigorous. It is
found that the thermal entropies are somewhat smaller than the statistical entropies, the deviation
ranging from .1 to 4.8 JK -1mol -1 . We thus conclude that entropies of substance (such as H2 , D2 ,
CO, NO, N2 O, H2O, etc.) are not zero at 0 K, as the third law formulates, but are finite. These
entropies are called residual entropies. The existence of residual entropy in a crystal at 0 K is
presumably due to the alterative arrangements of molecules in the solid. Such arrangements are
Fig. for CO and N2 O:
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
OC
OC
OC
OC
CO
NNO
NNO
NNO
NNO
NNO
NNO
NNO
NNO
NNO
NNO
NNO
ONN
ONN
ONN
ONN
NNO
(a)
(b)
Fig. Alternative molecular arrangements (a) perfect crystal (b) actual crystal
Since both the arrangements are equally likely, from the Boltzmann entropy equation (5),
S = k ln W , with W = 2 N A (where N A is Avogadros number), we find

that
S = k ln 2 N A = N A k ln 2 = R ln 2
= (8.324 JK -1mol -1 ) (2.303) (0.3010) = 5.76 JK -1mol -1
Since the residual entropies are found experimentally to be less than this value, it is
evident that the two alternative orientations of the CO and N2 O molecules in the solid state at 0 K
are not completely random.
For H2 and D2 , too, thermal entropies at 0 K are less than the corresponding statistical
entropies. The calculation of the statistical entropy assumes that there exists an equilibrium
between ortho and para H2 at all temperatures. The DS mix of ortho H2 and para H2 is found to be
136
18.37 JK -1mol -1 in the vicinity of 0 K. When this value is added to the thermal entropy
(calculated from heat capacity measurements), the arrangement with the statistical entropy is
very good.
In this lesson, we:
Pointed out
Third law of thermodynamics

Nernst heat theorem
Consequences of the Nernst heat theorem
Third law of thermodynamics: Planks formulation
Statement of Lewis and Randall
Unattainability of absolute zero
Thermodynamic quantities at absolute zero
Applications of third law of thermodynamics
Thermodynamic probability and statistical thermodynamics
Derivation of the Boltzmann entropy equation
Residual entropy

1.
2.
State third law of thermodynamics.

Explain the relation between probability and third law.

1.
Explain the Nernst heat theorem. How does it lead to the enunciation of the third l a w o f
thermodynamics?
2.
Write short notes on
(a) Thermodynamic quantities at absolute zero
(b) Statistical meaning of third law and its apparent exceptions.
12.15. REFERENCES
1.
Delhi.
& Co.,
2.
3.
137
UNIT-VII
LESSON 13: QUANTUM STATISTICS
The aim is to motivate and enable a comprehensive knowledge on quantum statistics to
the students.
*
Understand the quantum statistics.
13.1. INTRODUCTION
Statistical thermodynamics is concerned with the calculation of quantities such as heat
capacity, entropy, etc., in terms of atomic and molecular parameters. The discipline which deals
with the computation of the microscopic properties of matters from the data on the microscopic
properties of individual atoms or molecules is called statistical mechanicals or statistical
thermodynamics.
13.2. PROBABILITY
The word is commonly used to indicate the like hood of an event taking place.
For example: - suppose a coin is flipped or tossed only two results are possible, i.e.., either the
head or the tail will show up.
The probability of the head showing up is this does not mean that if a person tosses a
coin 10 times or tosses10 coins. The chance of getting head is 5.
The probability of any event occurring is given by
Number of cases favoring a given occurrence
C
Probability = ------------------------------------------------------- = -----Total number of equality possible cases
r
13.3. TYPES OF STATISTICS
Different physical situations encounter in nature are described by three types of statistics,
Viz., the MaxwellBoltzmann or (M-B) statistics, the BoseEinstein or (B-E) statistics and the
FermiDirac or (F-D) statistics.
The MB statistics, developed long before the advent of quantum mechanics, is called
classical statistics whereas; the B- E and FD statistics are collectively called quantum statistics.
The characteristics of the three types of statistics are summarized as follows.
1) In M-B statistics: -
138
The particles are assumed to be distinguishable and any number of particles may
occupy the same energy level. Particles obeying M-B statistics are called
boltzmannons or maxwellons.
2) In B-E statistics:The particles are indistinguishable and any number of particles may occupy a
given energy level. This statistics is obeyed by particles having integrated spin,
such as hydrogen H2 deuterium D2 , nitrogen N2 , Helium 4 (He4 ) and photons.
Particles obeying B-E statistics are called bosons.
3) In F-D statistics:The particles are in distinguishable but only one particle may occupy a given
energy level. This statistics is obeyed by particles having halfintegrated spin.
Example: The protons, electrons, helium 3(He3 ) and nitric oxide (NO) particles
obeying F-D statistics are called fermions.
13.4. THERMODYNAMIC PROBABILITY (W )
Consider a system of N distinguishable particles occupying energy levels
e 0 , e 1 , e 2 ...... etc., the total number of arrangements for playing n0 particles in the ground state
energy level e 0 , n1 particles in the first excited energy level e 1 , n2 particles in the second excited
energy level e 2 and so on, is known as the thermodynamic probability, W of the given macro
state. It is in general a very large number.
Our problem is to determine W (i.e.) to determine how many microstates correspond to
a given macro state.
It can be shown that W is given by
W=
N!
N!
=
n1!n2 !n3 !.......n j ! ni !
------ (1)
Where N = ni
In eqn (1) N is the total number of particles and the summation is over all the energy
levels. It is possible to realize a given energy level in more than one way (i.e.) more than one
quantum state has the same energy. When this happens, the energy levels is said to be
degenerate. Let g i be the degeneracy (or) multiplicity of the energy level e i . This means that if
there is one particle in the i th energy level, there are g i ways of distributing it. For two particles
in the i th level, there are g i2 possible distributions. Thus, for ni particles in the i th level there
n
are g i possible distributions. Hence the thermodynamic probability for the system of N
i
particles is given by
139
n
g i
W = N ! i Constant
i ni !
------ (2)
13.5. BOLTZMANN EXPRESSION FOR ENTROPY

Boltzmann suggested that entropy can be related to the thermodynamic probability W as
S = f (W )
------ (1)
Consider two systems A and B whose entropies and microstates (also called
complexions) are S A and S B ,W A andWB , respectively, when the two systems are combined,
S = S A + SB
------ (2)
By definition, the probability of a thermodynamic state is proportional to the number of

complexions (macro states) required to achieve it. Mathematically, we know that the total
probability is the product of the probabilities of the independent events. This is also true of the
complexions. Hence,
W = W A WB
S A + S B = f (W AWB )
And
------ (3)
------ (4)
This relationship suggests that entropies are additive and probabilities are multiplicative.
This can be true only if S is a logarithmic function of W , (i.e.),
S = k ln W
------ (5)
This can be Boltzmann entropy equation. Eqn. (5) gives the quantitative definition of entropy of
disorder. In equation (5) W is defined as the total number of different ways in which a given
system in the specified thermodynamic state may be realized.
13.6. STIRLINGS APPROXIMATION
The derivation
Consider the figure where ln x is plotted against x . In addition the figure also contains
steps both above and below the smooth curve with the values equal to ln 1 , ln 2 , ln 3 etc. The area
under the smooth curve from x = 1 to x = N is given by eqn (1)
N
ln xdx = N ln N - N + 1
------ (1)
Now, the same area can be approximated by adding up the areas of the rectangles formed
by these steps. If we choose the rectangles whose tops lie above the curve, we find for the area
ln 2 + ln 3 + ..... + ln N
= ln(2 3 ........ N )
140
= ln N !
lnx
------ (2)
3
x
On the other hand if we choose the rectangles below the curve, we get
ln 1 + ln 2 + ln 3 + ..... + ln( N - 1)
= ln[1 2 3 ........ ( N - 1)]

= ln( N - 1)! = ln N !- ln N
------ (3)
1 2 .......( N - 1) N N !
=
( N - 1)!= 1 2 .......( N - 1) =
N
N
The correct value of the area lies between those given by eqn (2) and (3). Thus,
N ln N - N + 1 ln N !
(Actual area) (Top rectangle)
ln N !- ln N
N ln N - N + 1
(Bottom rectangle)
(Actual area)
------ (4)
(Or)
ln N ! N ln N - N + 1 + ln N
= ln N !( N + 1) ln N - N + 1
------ (5)
Combining (4) and (5) we have

N ln N - N + 1 ln N ! ( N + 1) ln N - N + 1
------ (6)
Now, if N is very large ( 10 23 ) , we can neglect unity as compared with N without

appreciably affecting the calculated value for the upper and the lower limits of ln N ! with this
approximation, the upper and the lower limit become identical and therefore,
ln N != N ln N - N
141
The check:
ln N !
N ln N - N
Error
102
103
104
105
363.7
5912.1
82,108.9
10,51,999
360.5
5907.8
82,103.4
10,51,293
-0.8%
-0.07%
-0.007%
-0.0006%
Note: Each additional power of W in N decreases the % error by roughly a factor of 10.
Therefore % error is entirely negligible for N 10 23 .
13.7. STATE OF MAXIMUM THERMODYNAMIC PROBABILITY (Equilibrium State)
The state of maximum thermodynamic probability is also the state of maximum absolute
probability and it is also the equilibrium state.
W =
N!
ni !
------ (1)
Taking logarithms on both sides

ln W = ln N !- ln ni
------ (2)
ln W = N ln N - N - (ni ln ni - ni )
------ (3)
(Or)
We would like to adjust the ni to make ln W (and hence W ) a maximum while keeping constant
the total number of particles
N = ni
------ (4)
Diffentiating the eqn (4)

dN = dni = 0
------ (5)
(Since N is constant)
Similarly,
d ln W - d
=
dni
dni
=
(n
ln ni - ni ) = 0
d
(ni ln ni - ni )
dni
142
= - (ln ni + ni
1
- 1)
ni
dni Cross multiply
(Or)
d ln W = - ln ni .dni = 0
------ (6)
Now the restriction given in eqn (5) has to be incorporated into eqn (6). This is done by
using Lagranges multiplies a . Multiplying eqn (5) by a we get,
adN = adni = 0
------ (7)
d ln W - adN = - (ln ni + a )dni = 0
------ (8)
(6)- (7)
[In getting the right hand side of eqn (8) we have subtracted term by term to right hand side of
eqn (6)]
(Or)
(ln n
+ a )dni = 0
Since dni represent the variations in ni and hence are not necessarily zero, eqn (8)
requires the coefficient to be equal to zero.
(i.e.)
(ln ni + a ) = 0
(Or)
ln ni = -a (or ) ni = e -a
But
N = ni
------ (9)
\ N = e -a = se -a
\ ni = e -a =
ni =
N
s
N
s
------ (10)
Eqn (10) says the state and maximum thermodynamic probability is one with equal
number of particles in each one of the s aspects
13.8. MAXWELL-BOLTZMANN DISTRIBUTION LAW
If we consider our investigation to a closed system of independent particles, it would
meet the following two requirements
143
(i)The total number of particles is constant (i.e.)
N = ni = Constant
------ (1)
(i
i)The total energy U of the system is constant
U = ni e i= Constant
------ (2)
The constancy of the total number of particles implies that

dN = dni = 0
------ (3)
The constancy of the total energy implies that
dU = dni e i = 0
------ (4)
It is well known that a system of N distinguishable particles occupying energy levels

of e 1 , e 2 etc. The total number of arrangements for planning no particles in the ground state
energy level e 0 , n1 particles in the first excited level e 1 and so on is known as thermodynamic
probability W is given by
W =
N!
n0 ! n1!n 2 !.........ni !
------ (5)
On taking logarithms on both sides of eqn (5), we get

ln W = ln N !-(ln n0 !+ ln n1!+ ln n2 !+......)
= ln N !- ln ni !
------ (6)
Stirlings formula can be used for the factorial of large numbers (i.e.)
ln N != N ln N - N
ln ni = ni ln ni - ni
------ (7)
ln n != n ln n - n = n ln n
i
-N
------ (8)
------ (9)
Combining eqns (7), (8), & (9) we get
ln W = N ln N - N - ni ln ni + N
ln W = N ln N - ni ln ni
Differentiating and bearing in mind that N is constant, we get
------ (10)
144
dn ln W = - ln ni dni - ni d ln ni
------ (11)
Now,
n d ln n = n
i
dni
= dni = 0
ni
------ (11a)
Hence at equilibrium,
d ln W = - ln ni dni = 0
------ (12)
Eqn (12) gives the change in ln W which results when the number of particles in each
energy level is varied. If our system were open, then ni would vary without restriction and the
variation would be independent of one another. It would then be possible to solve eqn (12) by
setting each of the coefficients of the dni in eqn (12) equal to zero. However our system is not
open but closed and since N is constant, the value of dni are not independent of one another,
as is seen from eqn (11a). Again, the energy of the system is constant too. How, then can we
solve eqn (12) subject to the constraints of eqn (1) and (2)?.
The desired solution is obtained by applying the method of Lagranges undetermined
multipliers. Multiplying eqns (3) & (4) by the arbitrary constants a and b respectively and
subtracting the eqn (12) we get,
d ln W - adN - bdU = - (ln ni + a + be i )dni = 0
------ (13)
As the variables ni , dni ..... are independent of each other, so that the eqn (13) is to hold good,
then the summation must be zero
ln ni + a + be i = 0
------ (14)
Q dni 0
(Or)
(Or)
ln ni = -(a + be i )
- (a + be )
i
n =e
i
- be
i
n = e- a e
i
------ (15)
This equation is known as Maxwell- Boltzmann distribution law.

For complete generality, it is now necessary to make extension of this distribution law. In
deriving eqn (15), assumption is made that each energy level is said to be non-degenerate. It is
possible that there may be a number of quantum levels of almost identical energies, and for this,
a statistical weight factor g i is introduced for level e i . Hence the eqn (15) becomes as
n = g e- a e
i
i
- be
------ (16)
145
(or)
Where
(or)
e
- i
n = g e - a e KT
i
i
1
b =
KT
------ (17)
e
- i
n = g e - a e KT
i
i
Q ni = N
e
- i
\ N = g e - a e KT
i
------ (18)
------ (19)
Dividing eqn (17) by (19) we obtain

e
- i
n
g e - a e KT
i = i
e
N
- i
- a e KT
gi e
------ (20)
This is the general form of MaxwellBoltzmann distribution law.

13.9. EVALUATION OF LAGRANGES UNDETERMINED MULTIPLIERS
Evaluation of a :
We now proceed to determine a and b , we know that
N = g e
i
Since
- a - be
------ (1)
N = ni
e- a =
N
- be
i
gi e
------ (2)
Defining a quantity q called partition function, as
q = g e
i
- be
------ (3)
146
We obtain
e- a =
N
q
------ (4)
Accordingly, the Boltzmann distribution law becomes

- be
i
Ng e
i
n =
i
q
Partition function q is a quantity of immense importance in the statistical

thermodynamics. We shall see presently that by evaluating the partition function for a system we
can calculate the value of any thermodynamic function for that system.
Evaluation of b :
The constant b , can be evaluated as follows
g ni
We know that [ W = N ! i constant]
n!
i
ln W = ln N !+ (ni ln g i - ln ni !)
------ (1)
Applying Stirlings approximation to ln N and ln N !, we have

= N ln N - N + (ni ln g i - ni ln ni + ni )
i
= N ln N + ni ln g i - ni ln ni
i
------ (2)
Taking log of equation

- be
i
Ng e
i
n =
i
q
------ (20)
We have
ln ni = ln N - ln q + ln g i - be i
Substituting this value into eqn (2), we get

ln W = N ln N + ni ln g i - ni (ln N - ln q + ln g i - be i )
i
= N ln N + ni ln g i - N ln N + N ln q - ni ln g i + be i ni
i
= + N ln q + b U
Substituting this result into the Boltzmann equation
------ (3)
147
S = K ln W = NK ln q + Kb U
------ (4)
From the combined statement of the first and the second laws of thermodynamics, we know that
for a simple system,
dU = TdS - PdV
------ (5)
At constant volume ( V = constant; dV = 0 )
dU = TdS
1
S
\
=
V V T
------ (6)
------ (7)
Differentiating eqn (4) with respect to U at constant V , we get
NK S
S
b
+ Kb + KU
q U V
U V
U V
=
NK dq b
b
+ Kb + KU
q db U V
U V
------ (8)
Also, from eqn

- be
i
q = g e
i
i
dq
Uq
=db
N
------ (8a)
------ (9)
Substitution of eqn (9) in eqn (8) results in cancellation of the first and the last terms, giving
= Kb
U V
------ (10)
Comparing eqns (7) and (10), we find that

b =
1
KT
Hence, from eqn (8a) the molecular partition function q becomes
ei
q = g e KT
i
i
-
------ (11)
148
And the Maxwell- Boltzmann distribution equation (eqn 2a) becomes
e
- i
Ng e KT
i
n =
i
q
------ (12)
From eqn (12) we can easily obtain the ratio of the populations, (i.e.) the number of particles in
any two energy levels e i and e j . Thus,
n
i
n
j
(e - e )
i
j
g
i
KT
=
e
g
j
-
------ (13)
13.10. BOSE-EINSTEIN STATISTICS

In Maxwell- Boltzmann distribution, particles are distinguished from one another. It
means that if two particles interchange their positions or energy states, a new microstate or
complex ion would arise.
But in Bose Einstein statistics one considers the particles to be indistinguishable (i.e.) on
interchanging. The two particles between two energy states, no new microstate or complex ion
will arise.
Let us consider four particles distributed between two cells x and y . (i.e.) three in x
and one in y . If these four particles are distinguishable as assumed in Boltzmann statistics.
Four complex ion or microstates would arise. On the other hand, if four particles are
distinguishable as assumed in Bose Einstein statistics. Only one complex ion or microstate would
arise.
Cell
X
abc
abd
Cell
Y
W=4
acd
bcd
aaa
a
W=1
Suppose that cell is further divided into four compartments by portions, the sections are
representing the energy states. The possible distributions for these are shown in fig. (2). There
will be 20 possible distributions for three particles in cell x and four ways of distributions of
one particle in cell y . Therefore, the total possible distributions for three particles in a cell x
and one particle in cell y will be 4 20 = 80 .
Let us now attempt a general expression of the microstates under such conditions.
149
Suppose there are ni particles with energy e 1 in which there are g states of energy. We
shall need ( g - 1) positions to place the ni particles in g sections, each sections corresponding
to an energy state. It means that g is the degeneracy of the level. Now the question arises how
to distribute ni particles into g sections without any restriction. Then the permutations of ni
particles and ( g - 1) partitions simultaneously will be given by (ni + g - 1)! . However this also
includes permutations of ni particles amongst themselves and also ( g - 1) particles amongst
themselves because both these groups are internally indistinguishable. Hence the actual number
in which ni particles may be allocated in g states is given by
aa
Cell: Y
a
a
W = 20
aa
a
a
a
a
aa
aa
aa
aa
aa
aa
aaa
aa
aa
aa
aaa
aa
aaa
aaa
Cell: X
a
a
a
a
W=4
(ni + g - 1)!
ni !( g i - 1)!
------ (1)
As in the case of Maxwell- Boltzmann statistics, we assume that in the present case also
the total number of particles is constant and the total energy of the system is also constant.
(i.e.)
N = ni = Constant
------ (2)
U = ni e i= Constant
------ (3)
Thus, the thermodynamic probability W for the system of N particles (i.e.) the
number of ways of distributing N particles among various energy levels is given by
150
W=
(ni + g i - 1)!
Constant
ni !( g i - 1)!
------ (4)
Taking logarithm on both sides of eqn (4) we get
ln W = (ln ni + g i - 1)! - ln ni !- ln( g i - 1)!+ Constant
------ (5)
Here, too, since ni a n d g i are very large numbers, we can invoke Stirlings
approximation viz. ln x!= x ln x - x , neglecting unity
Compared to ni and g i , we get,
ln W = (ni + g i ) ln ni + g i -ni + g i - ni ln ni + ni - g i ln ni + g i
ln W = (ni + g i ) ln(ni + g i ) - ni ln ni i - g i ln ni
------ (6)
Where we have set ni + g i - 1 = ni + g i and g i -1 = g i . Since ni is very large, it can be treated as

a continuous variable.
Differentiation of eqn (6) with respect to ni and setting the differential equal to zero
gives for the most probable thermodynamic state of the system.
ln W = [ln ni - ln(ni + g i )] ni = 0
(or)
ni
ln
ni = 0
ni + g i
------ (7)
From eqns (2) and (3)
N = ni = 0
------ (8)
U = e i ni = 0
------ (9)
Applying the method of Lagranges undetermined multipliers (a & b ) to eqns (8) and (9)
respectively we get
ni
ln
+ a + be i dni = 0
ni + g i
Each term of the summation is equal to zero
ni
+ a + be i dni = 0
ln
ni + g i
151
Since the variations ni are independent of one another, (ni 0) it means that the
expression within the square bracket would be zero. Hence,
ln
ni
+ a + be i = 0
ni + g i
ln i + 1 = a + be i
ni
a + be
i
i + 1 = e
n
i
(or)
ni =
i
(a + be )
i -1
e
This equation is known as Bose-Einstein law of distribution.

13.11. ENTROPY OF BOSE-EINSTEIN GAS
Unlike in the case of Maxwell-Boltzmann statistics, in both Bose- Einstein and FermiDirac statistics the indistinguishability of particles is assumed right in the beginning and the
distribution laws described. Hence, no correction needs to be made at a latter stage. This is
evident from the following derivation of the expression for the entropy of a Bose-Einstein gas.
The thermodynamic probability of a Bose-Einstein system is
W=
(ni + g i - 1)!
Constant
ni !( g i - 1)!
------ (1)
Maximization of W leads to the Bose-Einstein distribution law
ni =
Now,
i
(a + be )
i -1
e
S = K lnWmax
------ (2)
------ (3)
Substituting eqn (1), after neglecting unity in comparison to g i , into eqn (3) gives
S = K (ln ( g i + ni )!i - ln g i !- i ln ni !)
i
Application of Stirlings approximation results in

S = K {( g i + ni ) ln ( g i + ni ) - ( g i + ni ) - g i ln g i + g i - ni ln ni + ni }
i
152
or
g + ni
S = K ni ln i
i
ni
g + ni
+ g i ln i
gi
n
S = K ni ln i + 1 + g i ln1 + i
g i
ni
from equation (2) ln i + 1 = a + be i

ni
n
\ S = K ni (a + be i ) + g i ln1 + i
g i
i
S = K n a + be + g ln1 +
i
i
i
i
Let us now denote
g
n
i
g
i
n
i
------ (4)
ni
as Z . Thus the argument of logarithm in equation (4) becomes
gi
(1+ Z ) 1 z . The function (1+ Z ) 1 z
approaches, the base of natural logarithm, as its limit when Z

approaches zero. If g i N i , it follows that Z will be small. Accordingly we can say that
g
i
n ni
1 + i
e , since for higher translational energy levels Z will be small. Thus,
g
i
S = Kni a + be + ln e
i
or
S = nKa + Kbe + nk
)
------ (5)
Equation (5) is identical to that obtained from Boltzmann statistics after correcting the latter for
the indistinguishability.
13.12. FERMI-DIRAC STATISTICS
In the Boltzmann or in the Bose-Einstein statistics, no restriction was made to the number
of particles present in any energy state. But in applying Fermi-Dirac statistics to particles like
electrons, the Paulis exclusion principle is taken into consideration; (i.e) two electrons (particles)
in an atom cannot possess the same energy level. In simple words, it implies that not more than
one particle can be assigned to a particular energy state.
153
In the example consider earlier (in Bose Einstein statistics), in which four particles were
distributed in two cells, three in the cell x and one in y , one will have a distribution as in
figure.
Cell: X
a
a
a
a
a
a
W=4
a
Cell: Y
a
a
W=4
When one applies the Fermi- Dirac statistics the total number of possible arrangements,
with the restriction that one particle can only occupy a compartment is ( 4 4) (i.e.) 16.
( ni g i )
g
Consider that the ni particles are distributed among the g i states
where i , as
before, is the degeneracy of the i th energy level. Imagine that the particles are distinguishable.
This implies that the first particle may be placed in any one of the g i states and for each one of
these choice, the second particle may be placed in any one of the remaining ( g i - 1) states, and so
on. Thus the number of arrangements is given by the expression
Number of arrangements =
gi!
( g i - ni )!
Since, however the particles are indistinguishable, the above expression has to be divided
by the possible number of permutations of ni particles, viz, ni ! . Hence, the number of
arrangements of ni particles in the i th energy level is given by the expression
gi!
[ni !( g i - ni )!]
Thus, the thermodynamic probability W for the system of N particles (i.e.) the
number of ways of distributing N particles among the various energy level is given by
W=
gi!
Constant
ni !( g i - 1)!
------ (1)
Taking logarithms of both sides of eqn (1) we have

ln W = [ln g i !- ln ni !- ln( g i - ni )!+ ] + Constant
i
Applying stirilings formula to evaluate the factorial
------ (2)
154
ln N != N ln N - N
ln W = g i ln g i - g i - (ni ln ni - ni ) - [( g i - ni ) ln( g i - ni ) - g i - ni )]
= g i ln g i - g i - ni ln ni + ni - ( g i - ni ) ln( g i - ni ) + g i - ni
= g i ln g i - ni ln ni - ( g i - ni ) ln( g i - ni )
------ (3)
Differentiating eqn (3) with respect to ni
1
d ln W = - ni + ln ni - ( g i - ni )
- ln( g i - ni ) dni ------ (4)
( g i - ni )
ni
[ln n
- ln( g i - ni )]dni
------ (5)
The maximum value of W is obtained by equating d ln W to zero
[ln n
- ln( g i - ni )]dni = 0
------ (6)
But
dN = dni = 0
------ (7)
adN = adni = 0
dU = e i dni = 0
------ (8)
bdU = e i bdni = 0
Multiplying eqn (7) by a and eqn (8) by b and adding to eqn (6) we get,
[ln n
- ln( g i - ni ) + a + be i ]dni = 0
------ (9)
Each term of the summation is equal to zero (Q dni 0 )

Since the variation ni are independent of one another, hence
[ln n
- ln( g i - ni ) + a + be i ]dni = 0
(Q dni 0 )
[ln ni - ln( g i - ni ) + a + be i ] = 0
ln
(or)
ni
= -a - be i ;
g i - ni
(or)
g - n
i = e (a + be i ) ; (or)
i
ni
n
i = e - a - be i
g -n
i
i
g
(a + be )
i +1
i=e
n
i
155
(or)
gi
n =
i
(a + be )
i +1
e
This is known as Fermi-Dirac distribution.

13.13. ENTROPY OF FERMI-DIRAC GAS
The thermodynamic probability of a Fermi-Dirac system is
W =
gi!
Constant
(g i - ni )!ni
------ (1)
Maximization of W leads to the Fermi-Dirac distribution law
ni =
Now,
i
(a + be )
i +1
e
------ (2)
S = K lnWmax
------ (3)
Substituting eqn (1), after neglecting unity in comparison to g i , into eqn (3) gives
S = K ln g i !-(ln ( g i + ni )!i - i ln ni !)
i
Application of Stirlings approximation results in

S = K {( g i ln g i - g i - ( g i - ni )) ln ( g i - ni ) + ( g i + ni ) - ni ln ni + ni }
i
or
g - ni
S = K ni ln i
i
ni
g - ni
- g i ln i
gi
n
S = K ni ln i - 1 - g i ln1 - i
g i
ni
from equation (2) ln i -1 = a + be i

ni
n
g
\ S = K ni (a + be i ) - i ln1 - i
ni
g i
i
156
S = K n a + be - ln1 i
i
Let us now denote
(1 - Z )
g
n
i
g
i
n
i
------ (4)
ni
as Z . Thus the argument of logarithm in equation (4) becomes
gi
1
. The function (1 - Z ) z approaches, the base of natural logarithm, as its limit when Z
approaches zero. If g i N i , it follows that Z will be small. Accordingly we can say that
g
i
n ni 1
1 - i
, since for higher translational energy levels Z will be small. Thus,
g
e
i
1
S = Kni a + be - ln
i
e
S = nKa + Kbe ' - nk
or
------ (5)
Equation (5) is identical to that obtained from Boltzmann statistics after correcting the latter for
the indistinguishability of particle.

In this lesson, we:
Pointed out
Probability
Types of statistics
Thermodynamic probability (W )
Boltzmann expression for entropy
Stirlings approximation
State of maximum thermodynamic probability (equilibrium state)
Maxwell- Boltzmann distribution law
Evaluation of Lagranges undetermined multipliers
Bose-Einstein statistics
Entropy of Bose-Einstein gas
Fermi-Dirac statistics
Entropy of Fermi- Dirac gas

1.
2.
Derive the expression of Bose-Einstein statistics.

Derive Stirlings approximation.
157
13.16. POINT FOR DISCUSSION
1.
2.
Maximizing the thermodynamic probability of a macro state and invoking Lagranges

undetermined multipliers derive the expression for Maxwell- Boltzmann statistics.
Derive the expression for Fermi-Dirac statistics.
13.17. SOURCES
1.
J.C. Kuriacose and J. Rajaram, Thermodynamics, Shoban lal Nagin Chand & Co.,
Delhi.
2.
edition, 2006-2007.
3.
UNIT-VIII
LESSON 14: PARTITION FUNCTION
The aim is to motivate and enable a comprehensive knowledge on partition function to
the students.
*
Understand the partition function.
14.1. INTRODUCTION: DEFINITION AND JUSTIFICATION OF NOMENCLATURE
The partition function may be defined as the sum of the probability factors for different
energy states or more conveniently it can be stated as the way in which the energy of a system
partitioned among the molecules constituting the system.
It is expressed as
Q ( or ) q = S g i e
ei
kT
where gi is the statistical weight factor and is equal to the degree of degeneracy, (i.e.), the number
of super- imposed energy levels k is the Boltzmann constant and equals to the ratio of the gas
158
constant R to the Avogadros number, e I is the energy of the quantum state in excess of the lower
possible value and T is the temperature on Calvin scale.
14.2. MICROCANONICAL AND CANONICAL ENSEMBLES
MICROCANONICAL ENSEMBLE
It is a collection of a large number of essentially independent assemblies each of which
possesses the same energy E, volume V and the number of systems N. For sake of simplicity, it
is assumed that all the systems are of the same type. Such an ensemble in which the individual
assemblies are separated by rigid and well insulated walls so that E,V and N for a particular
assembly are not affected by the presence of other assemblies.
CANONICAL ENSEMBLE
It is defined as a collection of a large number of independent assemblies, having the same
temperature T, volume V, and number of identical system, N. As all the assemblies possess the
same temperature, T, it means that one could bring them in thermal contact with each other and
also a large heat reservoir at the same temperature T. Thus, in canonical ensemble, systems can
exchange energy but not particles. The canonical ensemble in which the individual assemblies
are separated by rigid, impermeable but conducting walls.
14.3.
RELATION BETWEEN THE TOTAL PARTITION FUNCTION

MOLECULE AND THE SEPARATE PARTITION FUNCTION
OF
Consider a set of energy levels, represented by e i with degeneracies. The partition

function is defined by
ei
------ (1)
q = g e KT
i
i
If we substitute translational energies into this equation, we obtain the translational
partition function qtrans . If we substitute rotational or vibrational energies, we get q rot or q vib .
Actually there is only one partition function for a molecule, namely, the one obtained by putting
into the equation (1) all combinations of allowed energies and their corresponding
degeneracies.Thus
-
qtot =
tot
allenergy
levels
e tot
KT
------ (2)
Now,
e tot = e tr + e rot + e vib + e elec
Most of the time zero (if all energies measured with respect to ground electronic level)
g tot = g tr g rot g vib g elec
And
159
\q =
g rot g vib g elec e
tr
( e tr +e rot +e vib +e elec )

KT
allenergy
value
qtot = g tr g rot g vib g elec.e
e tr
KT
.e
e rot
KT
.e
e vib
KT
.e
e elec
KT
e
e
e
e
- tr
- rot
- vib
- elec
qtot = g tr e KT g rot e KT g vib e KT g elec e KT

allrot
allvib
allelec
.alltra
levels
levels
levels
levels
Define
q tr =
tr
e tr
KT
tra
levels
q rot =
rot
e rot
KT
e vib
KT
allrot
levels
q vib =
g vib e
allvib
levels
q elec =
g elec e
e elec
KT
allelec
levels
14.4. RELATION BETWEEN MOLECULAR PARTITION FUNCTION (q) AND

CANONICAL PARTITION FUNCTION (Q)
Consider a system of N non- interacting molecules. The Hamiltonian for such a system is
the sum of separate term for the individual molecule and there will be no interaction terms.
H = H 1 + H 2 + ............ + H N 1
------ (1)
The energy of such a system is the sum of the energies of all the N individual molecules
E i = e 1( i ) + e 2( i ) .......... + e N( i )
------ (2)
160
Where, e 1(i ) is the energy of molecules 1 in a system with total energy ET . The canonical partition
function is defined as,
Q=
ei
KT
------ (3)
Where the sum is over all the energy levels i of the system. Now
(i )
(i )
g = g1 .g 2 ........g N
i
(i )
------ (4)
(2) and (4) in (3)
(i )
e ( i ) + e 2( i ) ..... e N( i )
- 1
KT
(i )
(i )
Q g1 g 2 ..... g N e
g1
(i)
e 1( i )
.e
KT
-
(i)
(i) - e 2
g 2 e
i
KT
(i)
(i) - e N
.... g N e
i
KT
If all the molecules in the system are of the same kind, it is no larger necessary to distinguish
their energy levels and \ equation (5) reduces to
(i)
(i)
- e1
Q = g 1 .e
KT
i
(i)

(i) - e 1
g 2 e
i
KT
Or
(i )
(i ) - e
Q = g1 .e
KT
i
Now, since the molecular partition function is defined as
q = g
i
(i )
e (i )
.e
KT
Our last equation becomes
Q = qN
14.5. TRANSLATIONAL PARTITION FUNCTION ( qtrans )
(i)

(i) - e 1
.... g 2 e
i
KT
161
For a particle of mass m, moving in an infinite three-dimensional box of sides, a, b and c,
assuming that the potential is zero within the box, the energy levels obtained by the solution of
the Schrdinger equation are given by the expression:
q tr =
tr
e tr
KT
------ (1)
all tr
levels
But
e tr =
h2
(nx 2 + ny 2 + nz 2 )
2
8ma
------ (2)
Assuming the vessel to be cubical

e tr =
nx 2 h 2 ny 2 h 2 nz 2 h 2
+
+
8ma 2 8ma 2 8ma 2
------ (3)
(3) in (1)
q tr =
tr , x
g tr , y g tr , z e
nx 2 h 2
8 ma 2 KT
ny 2 h 2
8 ma 2 KT
nz 2 h 2
8 ma 2 KT
all tr
levels
Or
nx 2 h 2
2
q tr = g tr , x e 8 ma KT
all tr , x
levels
ny 2 h 2
8 ma 2 KT
g tr , y e
all tr , y
levels
q tr = q tr , x q tr , y q tr , z
nz 2 h 2
8 ma 2 KT
g tr , z e
all tr , z
levels
------ (4)
qtr , x = qtr , y = qtr , z

Let us evaluate qtr , x
q tr , x
nx 2 h 2
2
= g tr , x e 8 ma KT
all tr , x
levels
Where g tr , x =1
Since the translational energy levels for all practical purposes, are continuous, the summation in
the above definition can be replaced by integration.
162
qtr , x = e
nx 2 h 2
8 ma 2 KT
.dn x
Standard integral=
-ax
e
=
0
1
2
2a
1
2
Thus
qtr , x =
1
2
1
2
- h2
2 e 8 ma KT
qtr , x
1 8 ma 2 KT 2 8 mKT 2
=
=
a
2
2
h2
4
h
1
2
2 mKT
q tr , x =
a
2
4h
------ (5)
Substituting (5) in (4) and remembering that all the individual comments are equal, we have
q tr
2 mKT 2
3
=
a
2
4h
(Or)
3
2
2 mKT
q tr =
V
2
4
h
PV = RT ; V =
RT
P
14.6. ROTATIONAL PARTITION FUNCTION ( q rot ) - DIATOMIC MOLECULESRIGID ROTORS
The simplest system that undergoes rotational motion is a diatomic molecule. The
rotational energy levels of a rigid diatomic rotor (i.e., a rotor whose internuclear distance
remains fixed during rotation), obtained by solving the Schrdinger wave equation are,
163
rot
e J
KT
------ (1)
J = 0
Where
eJ =
J ( J + 1)h 2
2I
J = 0,1,2..
and g J = (2 J + 1) [degeneracy or statistical weight of the Jth level]
\ q rot =
( 2 J + 1 ). e
J ( J +1) h
2 IKT
------ (2)
J =0
For quantum mechanical rigid rotor equation (2) has to be evaluated partially to get q rot .
If, however, we assume the rotation energy levels to be almost continuous (which will be
true for large diatomic molecule at fairly high temperatures) the summation in equation (2) can
be replaced by integration.
q rot =
( 2 J + 1) e
J ( J +1) h 2
2 IKT
dJ
Now, J (J+1) = J2 + J
d [J ( J + 1)]
= 2 J + 1 or
dJ
d [J ( J + 1)] = (2 J + 1)dJ
\ Equation (3) becomes,
q rot
h2
2 IKT
J ( J + 1 ). d [ J ( J + 1 )]
Recall:
- ax
rot
1 - ax
dx =
e
-a
0
- 2 IKT
=
h 2
- J ( J +1)h
2 IKT
------ (3)
164
2 IKT
h2
q rot =
For homonuclear diatomic molecule expression for the partition function becomes,
2 IKT
sh2
q rot =
where s is called the symmetry number has a value of 2.
14.7.
VIBRATIONAL PARTITION
HORMONIC OSCILLATOR
FUNCTION:
DIATOMIC MOLECULES
For diatomic molecule vibrating as a simple harmonic oscillator (S.H.O), the vibrational
energy levels, obtained by the solution of the Schrdinger wave equation are given by
E vib = V +
1
hn
2
------ (A)
where n is the vibrational frequency and V is the vibrational quantum number which has the
values V = 0,1,2,3,.......
The energy levels are non-degenerate, (i.e.) the degeneracy, g is unity.
q = S i g i e - be i
------- (B)
using equations A and B the vibrational partition function of the diatomic molecule is given by
q vib =
gV e
eV
KT
V =0
where, e V = (V + 1 )hn
2
n =
1
2p
V = 0,1,2..
gV = 1 :
q vib =
1 .e 0
Let,
hn
=x
KT
(V + 1 ) h n
2
KT
------ (1)
165
+ 1 )x
2
e - (V
q vib =
Term by term,
=e
=e
-x
-x
+e
-3
2x
+e
-5
2x
+ .....
(1 + e - x + e -2 x + .....)
-x
Since,
(1 + e - x + e -2 x
e 2
+ .....) =
1 - e-x
-x
We have,
Or
qvib
e 2
=
1 - e-x
q vib =
- hn
1- e
2 KT
- hn
KT
14.8. ELECTRONIC PARTITION FUNCTION

Though it is possible in principle to solve the Schrdinger equation for the electronic
states and energies of a molecule, it is more convenient to obtain this information from the
spectroscopic data. For most of the molecules, the excited electronic energy levels lie so for
above the ground state compared with kT (a typical excited state value being greater than
2eV 3 10 -19 J ) that all the molecules may be considered to be in the ground state at ordinary
temperatures. Thus, contributions to the electronic partition function arising from excited
electronic states may be neglected. The electronic partition function is given by
qele
q ele = g ele , 0 e
e elec
KT
ele
allelectro nicenergylevels
e ele , 0
KT
+ g ele ,1 e
e ele ,1
Taking the lowest level as our reference level that is,
KT
------ (1)
166
e ele , 0 = 0
we have,
q ele = g ele , 0 1 + g ele ,1 e
e ele , 1
KT
------ (2)
There is no general formula for the e ele . The series is added term by term using spectroscopically
observed electronic energies.
For nearly all diatomic molecules, e ele 1 is very much greater than KT at room
temperature and therefore all terms in equation (2) after the first term contribute negligibly
(unless the temperature is 10,000 K ). Therefore,
q ele = g ele
,0
------ (3)
For most diatomic molecules the ground electronic level is non-degenerate (ie)
q ele = g
= 3 due to spin
degeneracy. Another exception is NO, which has an odd number of electron g ele , 0 = 2 ,
ele , 0
= 1 an important exception is O2 . For O2 , g
ele , 0
due to the two possible orientations of the spin of the unpaired electron.
14.9. LET US SUM UP
In this lesson, we:
Pointed out
Introduction
Justification of nomenclature
Microcanonical and canonical ensembles
Relation between the total partition function of a molecule and the separate partition
function
Relation between molecular partition function (q) and canonical partition function (q)
Translational partition function ( qtrans )
Rotational partition function ( q rot ) - diatomic molecules-rigid rotors
Vibrational partition function: diatomic molecules hormonic oscillator
Electronic partition function

1.
2.
Derive an expression for the molecular translational partition function of an ideal gas.
The fundamental vibrational frequency of F2 is 2.761013 HZ. Calculate the vibrational
partition function of F2 at 250 c?
14.11. POINT FOR DISCUSSION

1.
2.
Derive an expression for the molecular rotational partition function of an ideal gas.
Derive an expression for the molecular vibrational and electronic partition function of an
ideal gas.
167
14.12. SOURCES
1.
J.C. Kuriacose and J. Rajaram, Thermodynamics, Shoban lal Nagin Chand & Co.,
Delhi.
2.
edition, 2006-2007.
3.
168
LESSON 15: HEAT CAPACITY OF SOLIDS

CONTENTS
13.0.
13.1.
13.2.
13.3.
13.4.
13.5.
13.6.
13.7.
AIMS AND OBJECTIVES

INTRODUCTION
PROBABILITY
TYPES OF STATISTICS
THERMODYNAMIC PROBABILITY (W )
BOLTZMANN EXPRESSION FOR ENTROPY
STIRLINGS APPROXIMATION
STATE OF MAXIMUM THERMODYNAMIC PROBABILITY
(Equilibrium State)
13.8. MAXWELL-BOLTZMANN DISTRIBUTION LAW
13.9. EVALUATION OF LAGRANGES UNDETERMINED MULTIPLIERS
13.10. BOSE-EINSTEIN STATISTICS
13.11. ENTROPY OF BOSE-EINSTEIN GAS
13.12. FERMI-DIRAC STATISTICS
13.13. ENTROPY OF FERMI-DIRAC GAS
13.17. REFERENCES

The aim is to motivate and enable a comprehensive knowledge on heat capacity of solids
to the students.
*
Understand the heat capacity of solids.
15.1. INTRODUCTION
In 1819, Dulong and Petit found that at constant pressure, the molar heat capacity at
constant volume of most of the solid elements at room temperature was given by
CV 6calK -1 mol -1
In order to rectify this problem, two theories of heat capacities were developed. The first
by Albert Einstein in 1907 and the second (which is a modification of the Einstein theory) by
peter Debye in 1912.
15.2. THE EINSTEIN THEORY OF HEAT CAPACITY
169
Einstein made the following assumptions in consulting his theory of heat capacities of
mono atomic crystals.
1. The atoms in a crystal lattice undergo small oscillations (vibrations) about their
equilibrium configurations. In fact, an ideal crystal can be considered as a system of N
non- interacting particles (i.e.) atoms.
2. Each atom vibrates independently of the others and has three independent
vibrational
degrees of freedom. Thus the crystal may be treated as a system of 3 N
independent and
distinguishable harmonic oscillations.
3. There are no electronic, translational or rotational modes of motions in a mono
crystal.
atomic
Using assumptions 2 & 3, the molar vibrational partition function of the crystal can be
written as
QVib = ( q vib ) 3 N
------ (1)
e N
- i
From eqn Q = exp KT = q N
Q=Molar partition function; q = Molecular partition function
ln QVib = 3 N ln qVib
(or)
Where
(- )
QE
3 NQE
=
- 3 N ln1 - e T
2 T
------ (2)
E is the characteristics Einstein temperature for the vibration.
QE =
hn
K
Where n is the vibrational frequency of the oscillator. Thus the internal energy of an
ideal Einstein crystal is given by
d ln QVib
U = KT 2
dT
3
3 NK QE
= Nhn +
QE
V , N 2
e T -1
QE
(Or)
U - U 0 = 3RT
T
QE
e T -1
------ (4)
170
Where U 0 is the zero point-energy

3 Q
3
= Nhn = R E . Hence the molar heat capacity
2
2
QE
2
e T
QE
C = 3R
2
V
T QE
e T - 1
in
------ (5)
Experimentally it is found that at temperature approaching zero, CV approaches zero and

the limit of high temperatures, CV approaches the Dulong-Petit value of
3R (i.e.) (6CalK -1 Mol -1 ) .Einstein theory predicts these limiting values CV of quite successfully.
Thus as,
T
0
QE
QE
e T -1 = e T
------ (6)
So that
QE
2
QE
T
0 C = 3R
e T =0
V
T
Again as T
,
------ (7)
QE
1
QE
e T
+
So that
T
T lim
it 0
QE
QE
e T
C 3R
3R
2
V
T
Q
E

1+
-1
------ (8)
The above results are illustrated in Fig.1 for a number of metallic and non- metallic
crystals.
171
Fig.1. Temperature-dependence of CV for monotomic solids

Einstein theory however is not successful in predicting the CV values in the lower and
intermediate temperature ranges. The values predicted by it are lower than those actually
observed.
15.3. DEBYE THEORY OF HEAT CAPACITY

According to Debyes theory the crystal is treated as a macromolecule containing L
atoms, for which there are (3L - 6) vibrational modes. Since 6 3L ,this assembly can be taken
to have 3L vibrational modes. The frequencies of such vibrational range from n 0 (ground state)
to a maximum valuen max .
This limit arises when the wavelength of the oscillations is of the same order as the inter
atomic distances. Debye considered the solid to be a continuous elastic medium. The vibrations
of the atoms could be regarded as the elastic waves propagated through the medium.
The vibrational motion of the atoms can be considered to be similar to sound waves
propagated through this elastic medium. The vibrational energy is quantized and in order to
calculate the total energy of vibration it is necessary to know the number of vibrations at each
value of the allowed frequency (energy). This number, a function of the frequency (i.e.) f (n ) is
known to be proportional to n 2 (from the elastic theory of solids).
f (n ) = a n 2
------ (1)
172
In eqn (1) a is the constant of proportionality. Considering a narrow range of
frequency dn , the number of vibrations is f (n ) dn . The frequency ranges from n 0 (equal to
zero) to n max (Debye cut off frequency) and the energy levels of the vibrating solid are closely
spaced. Hence the total modes of vibration in the crystal can be evaluated by integration and
equated to 3L .
The total vibrational energy of the crystal is equal to the average energy of an oscillation
of frequency n multiplied by the number of oscillations at that frequency. This must be
summed up or integrated over all the ranges of allowed frequenciesn 0 andn max .
n
max
f (n )dn = 3L
n
0
max
2
a n dn = 3L
n
0
------ (2)
Evaluating this integral,

a =
9L
3
n max
f (n ) =
------ (3)
9L
3
n max
------ (4)
Q dn = n , a n 2 n = 3L , a = 9 L
3
3L
3L
n max
U has already been calculated (Einstein heat theory). Since n 0 is equal to zero.
max
U=
U f (n )dn
------ (5)
0
max
Since CV =
hn
e
hn
KT
-1
9 L n 2 dn
3
n max
------ (6)
dU
, on differentiating eqn (6) with respect to temperature,
dT
CV =
dU
d
=
dT dT
max
hn
2
9 Ln dnKT
KT
(e
hn
KT
- 1)n
3
max
------ (7)
173
hn
e KT
9 R max hn 2
n 2 dn

3
2
KT hn
n
max 0
e KT - 1
------ (8)
hn
has the dimensions o temperature and whenn = n max , the temperature
K
hn max
hn
corresponding to
is called the Debye characteristic temperature q D .Since
is
KT
KT
dimensionless, it can be replaced by u ,
The quantity
U max =
Since
hn max q D
=
KT
T
qD =
hn
hn
KT
;u=
=n =
u
K
KT
h
dn =
KT
dU
h
And so
2
KT 2 KT
KT 2
n 2 dn =
dU =
u
u du
h
h
h
Equation (8) can thus be written as
CV =
9R
3
KT 3
u
h
e u u 2 KT 2
u du
(e u - 1) 2 h
(or)
3
h T
= 9 R
KT q D
3
U max u 2 e u KT 3
2
u du

u
2
h
0 (e - 1)
(or)
T
= 9 R
q
D
(or)
qD
3
3
4 u
h KT T u e du

KT h 0 (e u - 1) 2
174
T
= 9 R
q
D
qD
T u 4 e u du
u
2
0 (e - 1)
------ (9)
The high and low temperature limits of CV (V ) can be obtained
u2
4
u
1
+
u
+
+ .......
4 u
2!
u e du
=
2
2
u
(e u - 1) 2
u +
+ .......
2!
Since u is small this reduces to
T
If T >> q D , CV (V ) 9 R
q
D
u4
or u 2
2
u
q
3 D
T
u 2 du

0
q
Q u 2 = hn = D
KT
T
dU =
hn q D
=
KT
T
T
\ CV (V ) = 9 R
q
D
3
1 q 3
D
3 T
CV (V ) 3R
The Debye formula has the same high temperature limit as the Einstein equation. At very
4p 4
q
and the value of the integral become
low temperature D
and is independent of T .
T
15
3
T
. The Debye equation for very low
The heat capacity varies under these conditions with
q
D
3
temperatures is thus CV = a T (Debye-T-cubed law). This law is used to calculate CV at very
low temperatures and to extrapolate the experimental results from the lowest accessible
175
temperature to the absolute zero. Since CV (V ) is a function of
T
for all solids should fall on a curve
q
D
T
only, a plot of CV against
q
D
(Fig. 2).
Fig. 2. The Debye curve for atomic heat capacity
T
is
q
D
is approximately 300. At temperatures near 300 K Dulong
From Fig. 2 it is seen that CV (V ) attains the classical value of 3R when

approximately one, (i.e.) when q
D
and Petits law holds good for carbon, q
is 1860 K and for other light elements also q being

D
T
is small and CV (V ) value falls on the ascending portion of the curve (i.e.) the value is
q
D
less than 3R . A higher value for CV is reduced only at high temperatures.
large,
15.4. PLANCK DISTRIBUTION LAW FOR BLACK BODY RADIATION

In the derivation of Plancks radiation formula, we will consider a small cavity in an
opaque material as a theoretical model of a black body. Suppose the cavity has volume V and it
is full of electromagnetic radiation at temperature T .An electromagnetic wave of frequency n
hn
and velocity C consists of particles called photons of energy hn , momentum
.
c
176
The cavity in an oppose material is assumed to be having a large number of photons, each
one of them is indistinguishable from the other. The assembly of photons in the cavity may be
compared to the assembly of gas molecules in vessels. Therefore, the assembly of photons is
supposed to constitute a gas known as photon gas.
The photon gas possess the following properties
1.
Photons are particles of rest mass zero
2.
Unlike the gas molecules the photons may be created and destroyed. In this case we
have dni 0 . This is strictly in accordance with the Bose Einstein statistics
because the
number of photons is not fixed in the cavity due to their absorption
and re-emission by the
walls of the cavity.
3.
There are two possible spin states which are associated with the photons of spin 1.
In other words the photon possess two allowed modes, the number of allowed
states
or modes per unit volume for the photons with momentum lying in the
range P to dP will lie
2
within a cell of volume 4pP dP .Therefore, the total
number of eigen states will be given
by
g ( p )dP =
2.4pP 2 dP
h3
V
------ (1)
For a photon,
P=
h hn
=
l
c
------ (2)
Differentiating equation (2), we get

dP =
hdn
c
------ (3)
On substituting equations (3) in (1), we get

g (n )d (n ) =
8pVP 2 hdn
c
h3
8pVh 2n 2 hdn
c
h 3c 2
8pVn 2
dn
c3
QP =
h 2n 2
hn
, \ P2 = 2
c
c
------ (4)
Equation (4) represents the total number of Eigen states which are lying in the frequency
range n andn + dn . Substituting eqn (4) in the Bose Einstein distribution law, we get
177
i
(a + be )
i -1
e
g (n )d (n )
n2
n
dn =
= 8pV 3
e
e
c
i
i
KT
KT
e
-1
e
-1
ni =
(or)
dn
n2
= 8pV 3
V
c
n
e
i
e KT - 1
------ (5)
The left hand side of the equation (5) represents the number of photons per unit volume.
When it is multiplied by hn , the energy of photon gives density Endn in the specified range.
On substituting E = hn , we get
En d n =
8phn 3
c3
n
hn
e KT - 1
------ (6)
Equation (6) is the Planck distribution law for black body radiation. Endn is also known as the
spectral energy density at the frequency n .
15.5. LET US SUM UP
In this lesson, we:
Pointed out
Introduction
The Einstein theory of heat capacity
Debye theory of heat capacity
Planck distribution law for black body radiation

1.
2.
For Al, QE = 240K, Calculate Cv for Al on the Einstein model at (a) 50K and (b) 240K
For I2 at 10K, Cv = 4.02JK-1 mol-1 . Calculate (a) QD and (b) Cv of I2 at 12K.
178
1.
Discuss the salient features of the Einstein theory of the heat capacity of monoatomic
crystals. How did Debye modified it? Show the results of the
Einstein
and
the
Debye theories on a plot and comment briefly.
2.
Explain briefly the heat capacities of solids.
15.8. REFERENCES
1.

Delhi.
& Co.,
2.
3.

Symmetryy Operation

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Understand the symmetry elements and symmetry operations.

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(a). The C2 axis of symmetry in BCl3 molecule.

1.7. PLANE OF SYMMETRY OR MIRROR PLANE ()

Fig. 1.2. The reflection planes in water molecule.

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Fig.1. 3. Diagram showing molecules with centre of symmetry.

Fig.1.4. The S6 axis in staggered form of ethane.

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This is a default symmetry element and every molecule has one.

At the same time, for NH3 , C32 C31 = E

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S n-1 S n1 = C n-1s h C n1s h = E

S n-1S n = Cn-1s h Cn1s h = Cn-1s h s hCn1

= C n-1 s h s h C n1 = C n-1 EC n = C n-1C n = E

1.12. LET US SUM UP

1.13. CHECK YOUR PROGRESS

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(a) Distinguish between

V. Ramakrishnan, M.S Gopinathan, Group Theory in Chemistry, Vishal Publications.

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LESSON: 2 GROUPS AND THEIR BASIC PROPERTIES

2.0. AIMS AND OBJECTIVES

Understand the groups and their basic properties.

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2.2.1. BASIC PROPERTIES OF A GROUP

s v s v' = s v' s v = C2 ; C2 s v = s v C2 = s v' etc

All these are noted from the table.

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C 2s v Es v' = (C 2s v ) Es v' = s v' s v' = E

C 2s v' Es v = C 2 s v' E s v = C 2s v s v' = C 2

Multiplication simply means successive application of the symmetry operations in the

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Both have same order and structure.

2.3. SIMILARITY TRANSFORMATION AND CLASSES

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Fig. 2.1. Illustration of similarity transformation on NH3 .

Let us prefer the designation s, s and s.

The following rules about conjugate elements are notable:

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If A is the conjugate of B and B is the conjugate of C, then A, B and C are mutually

C3-1s 'C3 = C32s 'C3 = s "

2.4. GROUP MULTIPLICATION TABLE

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Fig. 2.2. The Four symmetry elements of H2 O molecules

Table 2.2. Group multiplication table of the symmetry operations of H2 O molecule

It consists of h rows and h columns where h is the order of the group.

2.5. SYMMETRY CLASSIFICATION OF MOLECULES INTO POINT GROUPS

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Table 2.3. Some Molecular Point Groups

2.6. DIFFERENCE BETWEEN POINT GROUP AND SPACE GROUP

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2.8. CHECK YOUR PROGRESS

2.9. LESSON - END ACTIVITIES

V. Ramakrishnan, M.S Gopinathan, Group Theory in Chemistry, Vishal Publications.

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3.0. AIMS AND OBJECTIVES

Understand the reducible and irreducible representations.

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Then, if X is the proper transformation matrix, we have

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j, m=m and n=n,