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STATISCAL THERMODYNAMICS
The relationship between the microscopic description of individual molecules and the
macroscopic properties of a collection of molecules is a central concept in statistical mechanics.
Statistical thermodynamics or statistical mechanics provides a link between quantum mechanics
(or wave mechanics) and classical thermodynamics. Classical thermodynamics deals with
macroscopic properties of matter and describes the behavior of large number of molecules in
terms of properties such as pressure, volume, temperature, composition, etc. Quantum
mechanics, on the other hand, deals almost exclusively with matter at microscopic level. Neither
classical nor quantum mechanics is able to calculate the macroscopic properties of matter form
the microscopic structures of individual molecules.
The discipline which deals with the computation of the microscopic properties of matter from the
data on microscopic properties of individual atoms (or molecules) is called statistical mechanics
or statistical thermodynamic
Type of statistics: Different physical situation encountered in nature are described by three types
of statistics, viz., the Maxwell –Boltzmann (Or M-B) statistics, the Bose-Einstein (or B-E)
statistics and the Fermi-Dirac (or F-D) statistics. The M-B statics, developed long before the
advent of quantum mechanics, is also called classical statistics whereas the Bose –Einstine
statistics and the Fremi-Dirac statistics are collectively called quantum statistics.
(i) In M-B statistics, 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 boltzons or
maxwellons.
(ii) In B-E statistics, the particles are indistinguishable and any number of particles may occupy a
given energy level. This statistic is obeyed by particles having integral spin, such as hydrogen
(H2) deuterium (D2) helium -4 (4He) and photons. Particles obeying B-E statistics are called
bosons.
(iii) In F-D statistics, the particles are indistinguishable and any number of particles may occupy
a given energy level. This statistic is obeyed by particles having half- integral spin, e.g., the
proton electrons, helium -3(3He) and nitric oxide (NO). Particles obeying F-D statistics are
fermions.
Aim of statistical mechanics
DISTINGUISHABLE AND INDISTINGUISHABLE PARTICLES
Since, each particle some coordinate system which specifies its position. Thus, on the basis of
these coordinates, the particles are classified into two categories–
Distinguishable: If any two particles does not have the same coordinate system, then they are
distinguishable. In solid state, the position of particle is fixed. Let x, y, z are the coordinates of
any one particle but no other particle can have this coordinates. Since the position of each
particle is fixed.
Indistinguishable: If any two particles have the same coordinate systems, then they are said to be
indistinguishable. In gaseous state, the position of particle is not fixed. They can collide, thus at
one time one particle can x, y, z coordinates and at another time the other particle can have the
same coordinates (x, y, z)
In statistical Mechanical, all investigations are confined to isolated system only.
Isolated system: In this system there is no transfer of matter or energy to or from the system.
Thus, in an isolated system-
(a) The total number of particles is constant i.e., N.

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∑𝑛𝑖=0 𝑛𝑖 = N …(1)
Here =, ni = no. of particles in i the energy level.
(b) The total energy, E, of the system is constant i.e., E
∑𝑛𝑖=1 𝐸𝑖 = E …(2)
Here, E1 = energy of the ith energy level.
The constancy of the total no. of particles implies that
dN = ∑ 𝑑𝑛1 = 0
And the constancy of the total energy implies that
dE = ∑ 𝐸1 𝑑𝑛1 = 0
Thermodynamic Probability
Consider a system of N distinguishable particles occupying energy level 𝜖0 , 𝜖1, 𝜖2 etc. The total
number of arrangements for placing no particles in the ground state energy level, 𝜖0 , 𝑛1 particles
in the first excited state 𝜖0 , 𝑛1 particles in the second excited state level 𝜖2 and so on. The term
thermodynamic probability W, is for such an arrangement is given by
𝑁! 𝑁!
W (N) = 𝑛 !𝑛 !𝑛 !…𝑛 ! = 𝜋 !
1 2 3 𝑖 𝑛𝑖
When N = ∑ 𝑛𝑖(Total no. of particle) Here n1 is the total number of particles in the ith state.
Here, ni = occupancy number
Example: Calculate the no. of ways of distributing 20 identical objects with the
arrangements 1, 0, 3, 5, 10, 1
20!
Solution: W = 1!0!3!5!10!1! = 9.31 ×108
Example: Suppose there are 5 distinguishable particles and total energy is 5E, then in how
many ways we can distribute these particles? Find out all the possible ways.
Solution: Let the 5 distinguishable particles a, b, c d and e.
Thus, the possible arrangements for the 5 energy levels are-

5E e
4E e
3E e e
2E de d e
E abcd c d cd bcd
0 abcd ab abc abc ab a
Total 0+5E 5×E 0 + E + 2×2E 0+E+4E 0+2E+3E 0+2×E 0+3×E+2×E
Energy = 5E = 5E = 5E = 5E = 5E = 5E = 5E

No. of ways (thermodynamic probability) W in each case-

𝑁!
(1) W = 𝑁 !𝑁 !𝑁 !𝑁 !𝑁 !𝑁 !
0 𝜖 2𝜖 3𝜖 4𝜖 5𝜖
5!
𝑊1 = 4!0!0!0!0!1! 0! = 1
𝑊1 = 5
5!
(2) 𝑊2 = 2!5!0!0!0!0!
𝑊2 = 1
5!
(3) 𝑊3 = 2!1!2!0!0!0!
𝑊3 = 30

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5!
(4) 𝑊4 = 3!1!0!0!1!0!
𝑊4 = 20
5!
(5) 𝑊5 = 3!0!1!1!0!0!
𝑊5 = 20
5!
(6) 𝑊6 = 2!2!0!1!0!0!
𝑊6 = 30
5!
(7) 𝑊7 = 1!3!1!0!0!0!
𝑊7 = 20
Total number of ways = 𝑊1 +𝑊2 +𝑊3 +𝑊4 +𝑊6 +𝑊7
= 5+1+30+20+20+30+20 = 126
Degeneracy: The presence of multiple states at a given energy is referred to as degeneracy and
the total number of energy states in energy level is called as degeneracy of the energy level.
Degenerate states have equal energies always.
Macro state and micro states: The number in each energy level is said to give a macrostate and a
specification of total number of particles in each energy state give microstate.

The first energy level has four energy states and we have 2 particles in 1st energy state, 2 un
second energy state, and rest two in third and fourth energy state. Then we are specifying
microstate to the corresponding energy level.
Note: If we also specify which particle in which box, then or interchanging the particles,
microstate remains same but microstate changes.
In last illustration there were 7 microstates and 126 microstate corresponding to these
microstates
Thermodynamic Probability in presence of degeneracy energy state.
Let g1 = degeneracy of an energy level n1 = number of particles in that energy level.
Then,
The number of ways of distributing these distinguishable n1 particles in gi different energy state
is = 𝑔𝑖𝑛𝑖
And the no. of ways of distributing total N particles in different energy levels is-
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𝑁!
= 𝜋𝑛 !
𝑖
Since, thermodynamics probability is multiplicative
Thus, total no. of ways/total probability
THE BOLTZMANN DISTRIBUTION
Using the Maxwell-Boltzmann statistic,
Consider a system of N distinguishable particles occupying energy levels 𝜖0 , 𝜖1, 𝜖2 etc. The total
number of arrangements for placing n0 particles in the ground state energy level 𝜖0 , 𝑛1 particles
in the first excited state 𝜖1, 𝑛2 particles in the second excited state energy level 𝜖2 and so on.
The term thermodynamic probability W. is for such an arrangement is given by
𝑁! 𝑁!
W (N) = 𝑛 !𝑛 !𝑛 !…𝑛 ! = 𝜋 !
1 2 3 4 𝑛𝑖
If 𝑔𝑖 is degeneracy correspond to ith level, then
𝑛
𝑔𝑖 𝑖
W = N! π 𝑛 !
𝑖
Taking in of both the sides
In W = In N! + ∑𝑖 𝑛𝑖 In 𝑔𝑖 - ∑𝑖 𝐼𝑛 𝑛𝑖 !
Using stirling approximation
In W = (N In N–N) + ∑𝑖 𝑛𝑖 In 𝑔𝑖 - ∑𝑖 𝐼𝑛 𝑛𝑖 + ∑ 𝑛𝑖
= N in N-N + ∑𝑖 𝑛𝑖 In 𝑔𝑖 - ∑𝑖 𝐼𝑛 𝑛𝑖
(∵ ∑𝑛𝑖 = 𝑁)
In W = N In N - ∑𝑖 𝑛𝑖 In 𝑔𝑖 - ∑𝑖 𝐼𝑛 𝑛𝑖
Differentiating, by keeping N and 𝑔𝑖 constant, we get
d In w = ∑𝑖 𝐼𝑛 𝑔𝑖 𝑑𝑛𝑖 -∑𝑖 𝐼𝑛 𝑛𝑖 𝑑𝑛𝑖 - ∑𝑖 𝑑 𝐼𝑛 𝑛𝑖 = 0
𝑑𝑛
Now, ∑𝑖 𝑛𝑖 𝑑 𝐼𝑛 𝑛𝑖 → ∑𝑖 𝑛𝑖 𝑛 𝑖 → ∑𝑖 𝑑𝑛𝑖 = 0
𝑖
Hence, d In w = ∑ 𝐼𝑛 𝑔𝑖 𝑑𝑛𝑖 - ∑ 𝐼𝑛 𝑛𝑖 𝑑𝑛𝑖
∴ for most probable distribution
d In w = 0 …(1)
𝐼𝑛 𝑔𝑖
∴ ∑𝑖 𝑛 𝑑𝑛𝑖 = 0
𝑖
Using the two conditions of a closed system
∑ 𝑑𝑛𝑖 = 0 …(2)
∑ 𝜖𝑖 𝑑𝑛𝑖 = 0 …(3)
Multiplying equations 2 and 3 by the arbitrary constant α and β subtracting these form equations1.
We get
𝑔
∑𝑖(𝐼𝑛 𝑖 − α − β𝜖𝑖 ) 𝑑𝑛𝑖 = 0
𝑛𝑖
This method is known as lagrange’s undetermined multiplicative principle
Since, 𝑑𝑛𝑖 ≠ 0
𝑔
∴ In 𝑔1 –α – β𝜖𝑖 = 0
2
∴ 𝑛𝑖 = 𝑔1 𝑒 α – β𝜖𝑖
Here, 𝑛𝑖 is the number of particles corresponding to the most probable distribution. α and β are
langrange’s undermined constants.
1
Β = 𝐾𝑇
As,
∑ 𝑛𝑖 = N
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∴ 𝑒 −𝛼 ∑ 𝑔𝑖 e𝛽𝜖𝑖 = N
𝑁
𝑒 −𝛼 ∑ 𝑔 e𝛽𝜖𝑖
𝑖
𝑛𝑖 𝑔𝑖 e𝛽𝜖𝑖
∴ = ∑ 𝑔𝑖 e𝛽𝜖𝑖
𝑁
1
Substituting β = 𝐾𝑇
𝑛
The 𝑁𝑖 is the fraction of number of particles present in the ith energy level.
Similarly, The ration of no. of particles in two energy level i and j with energies 𝜀𝑖 and 𝜀𝑗 of
degeneracy gi and gi respectively is
𝜀
𝑛𝑖 𝑔𝑖 𝑒 𝛽 𝑖
= 𝜀
𝑛𝑗 𝑔𝑗 𝑒 𝛽 𝑖
1
Substituting β = 𝐾𝑇
𝑛𝑖 𝑔 𝑘𝑇
= 𝑔 𝑖 (𝑒 (𝐸𝑖 −𝐸𝑗) )
𝑛𝑗 𝑗
This is known as Boltzmann distribution Law.
Example: A system of N particles has among others, two energy levels with 𝑔1 = 2, 𝑔2 = 3, 𝑈1 =
41.84 𝑘𝐽 𝑚𝑜𝑙 −1 and 𝑈2 = 58.58 𝑘𝐽 𝑚𝑜𝑙 −1. Calculate the ratio of the number of particles in the
two energy states at 1000K.
𝑛 𝑔 𝜀 −𝜀 𝑔 𝑈 −𝑈
Solution: 𝑛2 = 𝑔2 exp [− 2𝑘𝑇 1 ] = 𝑔2 exp [− 2𝑅𝑇 1 ]
1 1 1
3 (58580−41840)𝐽𝑚𝑜𝑙 −1
exp [− ] = 0 ∙ 201
2 (8∙314𝐽𝐾 −1 )(100𝐾)
Practice Problem 1: Calculate the relative Boltzmann poplution of two energy level at 298K if the
difference in energy levels is 500𝑐𝑚 −1ration of degeneracy is 1
Ans. 0 ∙ 0892

PARTITION FUNCTION
According Boltzmann distribution law,
𝑛2 𝑔 𝑒 −𝜖1 𝑘𝑇
= ∑ 𝑔𝑖 𝑒 −𝜖1 𝑘𝑇
𝑛1 𝑖
The factor in denominator ∑ 𝑔𝑖 𝑒 −𝜖1 𝑘𝑇 is called partition function denoted by q. It is always a
number and has no units.
𝑛2 𝑔𝑖 𝑒 −𝜖1 𝑘𝑇 𝑒 −𝜖1 𝑘𝑇
Thus, = → 𝑛1 = 𝑛𝑔1
𝑛 𝑞 𝑞
thus partition function is the sum of the probability factor for different energy levels or ‘the
number of ways in which energy of a system is distributed among the molecules constituting the
system.’
q = ∑ 𝑔𝑖 𝑒 −𝜖1 𝑘𝑇
Here the term 𝜖 represents the total energy of the molecules such as translation. (𝜀1 ), rotation
(𝜀𝑟 ), vibrational (𝜀𝑣 ), electronic (𝜀𝑒 ), and zero point energy (𝜀𝑜 ) is
𝜀 = 𝜀1 + 𝜀𝑟 + 𝜀𝑣 + 𝜀𝑒 + 𝜀𝑜 + 𝜀𝑛𝑢𝑐.
Also the statistical wt factor is defined as
𝑔 = 𝑔1 + 𝑔𝑟 + 𝑔𝑣 + 𝑔𝑒 + 𝑔𝑜 + 𝑔𝑛𝑢𝑐.
Thus partition function becomes
/𝑘𝐽
q = ∑(𝑔1 + 𝑔𝑟 + 𝑔𝑣 + 𝑔𝑒 + 𝑔𝑜 + 𝑔𝑛𝑢𝑐. ) × 𝑒 −[𝜀1 + 𝜀𝑟 + 𝜀𝑣 + 𝜀𝑒 + 𝜀𝑜 + 𝜀𝑛𝑢𝑐. ]

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Or,q=∑ 𝑔𝑖 𝑒 −𝜖𝑖 /𝑘𝑇 × ∑ 𝑔𝑟 𝑒 −𝜖𝑟 /𝑘𝑇 × ∑ 𝑔𝑣 𝑒 −𝜖𝑉 /𝑘𝑇 × ∑ 𝑔𝑒 𝑒 −𝜖𝑣 /𝑘𝑇 × ∑ 𝑔𝑜 𝑒 −𝜖𝑜 /𝑘𝑇 ×
∑ 𝑔𝑁 𝑒 −𝜖𝑁 /𝑘𝑇
q = 𝑞1 × 𝑞𝑟 × 𝑞𝑣 × 𝑞𝑒 × 𝑞𝑜 × 𝑞𝑛𝑢𝑐.
Thus net partition function is the product of the separate partition function in respect of different
types of energies associated with the molecules.
This relationship demonstrates that the total molecular partition function is simply the product of
partition functions for each molecular energetic degree of freedom. Using this definition for the
molecular partition function, the final relationships of interest are.
𝑁
𝑄𝑡𝑜𝑡𝑎𝑙 = q 𝑇𝑜𝑡𝑎𝑙 (distinguishable)
1
𝑄𝑡𝑜𝑡𝑎𝑙 = 𝑁! 𝑞 𝑁𝑇𝑜𝑡𝑎𝑙 (in)
Physical significance of q:
1. It indicates how the particles are distributed among the various energy levels.
2. It reflects the diversity of energy state of the molecules of a system.
3. It determines the relative population of any two quantum states p and q by the ration 𝑛𝑃 /𝑛𝑞 .
𝑛𝑃 𝑔
= ( 𝑔𝑃 ) 𝑒 −(𝜖𝑃 −𝜖𝑞)/𝑘𝑇
𝑛𝑞 𝑞
Effect of temperature on partition function (q):
Partition function increases on increasing temperature.
Case(I):Assuming all the energy levels to be non-degenerate i.e., degeneracy 𝑔1 = 1
∴ q = ∑ 𝑔𝑖 𝑒 −𝑒𝑖 /𝑘𝑇 (here, 𝑔𝑜 , 𝑔1 , 𝑔2 =1)
−𝑒𝑜 /𝑘𝑇 −𝑒1 /𝑘𝑇 −𝑒2 /𝑘𝑇
q=𝑒 +𝑒 +𝑒 +…
𝐸0 (energy of ground state) = 0
∴ q =1 𝑒 −𝑒1 /𝑘𝑇 +𝑒 −𝑒2 /𝑘𝑇 + …
Two conditions are possible
At very low Temp. At very higher high temp
T →0 K T →∞ K
−𝑒1 /𝑘𝑇 −𝑒2 /𝑘𝑇
q=1+𝑒 +𝑒 +… q = 1 + 𝑒 −𝑒1 /𝑥 +𝑒 −𝑒2/𝑥 + …
−𝑧 −𝑧
q = 1 + 𝑒 + 𝑒 +… q = 1 + 𝑒 −0 + 𝑒 −0 +…
q = 1 + 1 + 1 +…
q=1 q=∞
Case (II): Assuming all the energy level degenerate.
∴ q = 𝑔0 𝑒 −𝜖𝑛/𝑘𝑇 + 𝑔𝑖 𝑒 −𝜖𝑖 /𝑘𝑇 …
At very low Temp. At very higher high temp
T →0 K T →∞ K
q = 𝑔0 + 𝑔1 𝑒 −𝜖𝑛/0+ 𝑔2 𝑒 −𝜖2 /𝑘𝑇 … q = 𝑔0 + 𝑔1 𝑒 −𝜖𝑛/∞+ 𝑔2 𝑒 −𝜖2 /∞ …
q = 1 + 𝑒 −𝑧 + 𝑒 −𝑧 +… q = 𝑔0 + 𝑔1 + 𝑔2 + ⋯
q=1 q=∞
generalizing,
limq
T→0K = 1or 𝑔0 (depending whether the energy state is degenerate or non-degenerate)
Lim q
T →∞ K = ∞
Special case to evaluate q: suppose all the energy levels are non-degenerate i.e., degenerate of all
energy level = 1 and the energy difference between the energy levels is uniform (E).

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1
Partition Function q = ∑ 𝑔𝑖 𝑒 −𝛽𝜖𝑖 (𝛽 = )
𝑘𝑇
Q = 1𝑒 −𝜖/𝑘𝑇 + 𝑒 −2𝜖/𝑘𝑇
+…
Since the energy difference is uniform

2 3
This can be written as q = 1 + 𝑒 −𝜀/𝑘𝑇 + (𝑒 −𝜀/𝑘𝑇 ) + (𝑒 −𝜀/𝑘𝑇 ) …
Let 𝑒 −𝜀/𝑘𝑇 = x
Then, q = 1 + x +x2 + x3 …
This is a geometric progression series.
1
∴ q = 1−𝑥
1
∴ q = 1−𝑒 −𝜀/𝑘𝑇
𝑁
∴ 𝑛𝑖 = 𝑞 𝑒 −𝜀/𝑘𝑇
𝑛𝑖
Fraction of no. of molecules in the ith energy state = 𝑁
𝑛𝑖
= 𝑒 −𝜀/𝑘𝑇 (1-𝑒 −𝜀/𝑘𝑇 )
𝑁
Where 𝜀𝑖 is the energy is ith level
Example: The vibrational frequency of I2 is 208cm-1. What is the probability of I2 populating the
n = 2 vibrational levels if the energy difference between the level is constant and 𝑔𝑖 = 1. Take the
temperature to be 298K.
Solution: Here, 𝑔𝑖 = 1 and the energy difference is uniform.
𝑛
∴ 𝑁2 = 𝑒 −𝜀2 /𝑘𝑇 (1-𝑒 −𝜀/𝑘𝑇 )
∈ ℎ𝑐𝑣̅ 6∙626 ×10−34 × 3×108 × 208
= 𝑘𝑇 = = 1 ∙ 0054
𝑘𝑇 1∙38×10−23 × 298
−𝜀/𝑘𝑇
𝑒 = 0 ∙ 3659
Now, 𝜖2 = 2𝜖
𝜖 2×𝜖
∴ 𝑁2 = 𝑁 = 2 × 1 ∙ 0054 = 2 ∙ 0108
𝑒 −𝜀2 /𝑘𝑇 = 0 ∙ 13388
𝑛2
= 0 ∙ 0848
𝑁
Factor affecting partition function q: Since q represents the partitioning / distribution of
molecules less.
1. Temperture: when T is low, particles are confined to low energy level and hence value of q is
accessible to molecules and hence value of q is high.
2. Energy difference: when energy different is less, more energy are accessible to molecules and
hence q is high, particles are confined to lower energy level and hence q is less.
Now, we will discuss the different types of partition function.
TRANSLATION PARTITION FUNCTION
Translation energy levels correspond to the translational motion of atoms or molecules in a
container of volume V. Rather than work directly in three dimensions, a one dimension model is
first employed and then later extended to three dimensions. From quantum mechanics, the energy
levels of a molecules. From quantum mechanics, the energy levels of a molecule confined to a box

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were to a box were described by the “Particle-in-a-box” model as illusted in figure. In this figure,
a particle with mass m is free to move in the domain 0≤ 𝑥 ≤ 𝑎, where a is the length of the box.

Particles in a box model for translational energy levels.

𝑛2 −ℎ2
Box is 𝐸𝑛 = 8𝑚𝑎2
−𝛽 2 ℎ2
And partition function is 𝑞𝑇.𝐼𝐷 = ∑∞
𝑛=1 𝑒 8𝑚𝑎2 …(1)
[∴ as degeneracy for ID-box is given as 𝑔1 = 𝑔2 = 𝑔3 …= 1]
Summation consists o an infinite number of terms.
Because numberous translation energy levels are accessible at room temperature, the summation
in Equation (1) can be replaced by integrate into with negligible error:
2 ∞ 2
qT = ∑ 𝑒 −𝛽𝛼𝑛 ≈ ∫𝑛=1 𝑒 −𝛽𝛼𝑛 dn …(2)
In this expression, the following substitution was made to keep the collection of constant terms
compact:
ℎ2
𝛼 = 8𝑚𝑎2 …(3)
The integral in Equation (2) is readily evaluated
∞ 2 1 𝜋
qT = ∫0 𝑒 −𝛽𝛼𝑛 dn √𝛽𝛼 …(4)
2
Substituting in for α, the translational partition function in one dimension becomes
2𝜋𝑚 1/2
[Link] = ( ℎ2 𝛽 ) a …(5)
The expression can be simplified by a defining the thermal de Broglic wavelength, or simply the
thermal wavelength, as follows:
1/2
ℎ2 𝛽
A = (2𝜋𝑚) …(6)
Such that
𝑎 2𝜋𝑚 1/2 𝑎 𝑎
[Link] = Λ = ( ) = (2𝜋𝑚)1/2 ℎ …(7)
𝛽 ℎ
Referring to Λ as the thermal wavelength reflects that the average momentum of a gas particle
ℎ
p is equal (𝑚𝑘𝑇)1/2 as Λ = 𝑃 .
The transitional degrees of freedom are considered separable; therefore, the three-dimensional
translational partition function is the product of one-dimensional partition functions for dimension:
𝑞𝑇.3𝐷 = 𝑞𝑇𝑥 𝑞𝑇𝑦 𝑞𝑇𝑧

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𝑎 𝑎𝑦 𝑎
= ( Λ𝑥 ) ( Λ ) ( Λ𝑧 )
1 3
= (Λ ) 𝑎 𝑥 𝑎 𝑦 𝑎 𝑧
1 3
= (Λ ) 𝑉
𝑉 𝑉
𝑞𝑇.3𝐷 = Λ3 = (2𝜋𝑚𝑘𝑇)3/2 h3 …(8)
where V is volume and Λ is the thermal wavelength. The translational partition function depends
on both V and T.
The increase in qT with volume reflects the fact that as volume is increased, the translational
energy-level spacing decrease such that more states are available for population at a given T.
Example: What is the translational partition function for A r confined to a volume of 1.00 L at
298K?
Solution: Evaluation of the translational partition function is dependent on determining the thermal
wave-length [Equation (6)]
1/2
ℎ2 𝛽 ℎ
Λ = (2𝜋𝑚) = (2𝜋𝑚𝑘𝑇)1/2
The mass of Ar is 6.63 × 10−26 kg. Using this value for m, the thermal wavelength becomes
6.626 × 10−34 𝐽𝑠
Λ = (2𝜋(6.63 × × 10−26 𝑘𝑔)1/2 (1.38 × 10−23 𝐽𝐾−1 )(298𝐾)1/2
The unit of volume must be such that the partition function is unit less. Therefore, conversion of
volume to units of cubic meters (m3) is performed as follows:
1𝑚 3
V = 1.00 L = 1000mL = 1000cm3 (100𝑐𝑚) = 0.001m3
The partition function is simply the volume divided by the thermal wavelength cubed:
𝑉 0.001𝑚3
𝑞𝑇.3𝐷 = Λ3 = (1.60 × 10−11 𝑚)3 = 2.44 × 1029
∵ A large number translational energy states are available at room temperature.
ROTATIONAL PARTITION FUNCTION
Diatomic
A diatomic molecule consists of two joined by a chemical bond.

Figure: Schematic representation of a diatomic molecule; consisting of two masses (m1 and m2)
joined by a chemical bond with the separation of atomic centers equal to the bond length r.
In treating rotational motion of diatomic molecules, the rigid rotor approximation is employed in
which the bond length is assumed to remain constant during rotational motion and effects such as
centrifugal distortion are neglected.
In the rigid rotor approximation, the quantum mechanical description of rotational energy levels
for diatomic molecules that the energy of a given rotational state E, is dependent on the rotational
quantum number J:
𝐸𝐽 = hcBJ (J +1) for J- 0, 1, 2… …(1)
Where J is the quantum number corresponding rotational energy level
The rotational constant is given by
ℎ
B = 8𝜋2 𝑐𝑙 …(2)

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Where Γ is the moment of inertia

Γ = 𝜇𝑟 2 …(3)
Γ is the distance separating the two atomic centres and μ is the reduced mass,
𝑚 𝑚
μ = 𝑚 1+ 𝑚2 …(4)
1 2
1 1
B∝ 1 ∝ 𝜇
Using the above expression for the rotational energy, the rotational partition function can be
constructed
qR = ∑𝐽 𝑔𝐽 𝑒 −𝛽𝐸𝐽 = ∑𝐽 𝑔𝐽 𝑒 −𝛽ℎ𝑉𝐽 (𝐽+1) …(5)
The above expression for the rotational partition function contain an addition term, gJ, that
represents the degeneracy is given by
gJ = (2J +1)
the degeneracy originates from the quantum number mJ
mJ = -J ….. 0…..+J
therefore rotational function partition is
qR = ∑𝐽(2𝐽 + 1)𝑒 −𝛽ℎ𝑐𝐵𝐽 (𝐽+1) …(6)
The spacing between translational levels were small relative to kT such that the partition function
could be evaluated by integration rather than discrete summation.
Energy level spacing between rotational energy states depends upon value B (rotational constant).
The rotational constant depends on the atomic mass, with an increase in atomic mass resulting in
a reduction in the rotational constant.
For I2 energy-level spacing are clearly much smaller than kT and integration of the partition
function is appropriate. However, for H2 the energy level spacing is greater than kT so that
integration would be inappropriate, and evaluation of the partition function by direct summation
must be performed.
With the assumption that the rotational energy –level spacing are small relative to kT, evalution of
the rotational partition function is performed with integration over the rotational states:
∞
𝑞𝑟 = ∫0 (2𝐽 + 1)𝑒 −𝛽ℎ𝑐𝐵𝐽(𝐽+1) 𝑑𝐽
Evaluation of the preceding integral is simplified by recognizing the following:
𝑑 −𝛽ℎ𝑐𝐵𝐽(𝐽+1)
𝑒 = 𝛽ℎ𝑐𝐵(2𝐽 + 1) 𝑒 −𝛽ℎ𝑐𝐵𝐽(𝐽+1)
𝑑𝐽
Using above relationship, the expression for rotation partition for can be written as
∞ ∞ −1 𝑑
𝑞𝑅 = ∫0 (2𝐽 + 1)𝑒 −𝛽ℎ𝑐𝐵𝐽(𝐽+1) 𝑑𝐽= ∫0 𝛽ℎ𝑐𝐵 − 𝑑𝐽 𝑒 −𝛽ℎ𝑐𝐵𝐽(𝐽+1) 𝑑𝐽
1 1 8𝜋 2 𝑙𝑘𝑇
𝑞𝑟 = 𝛽ℎ𝑐𝐵 = ℎ𝑐𝐵 = 𝜎ℎ2
𝑇
Also, 𝑞𝑟 = 𝑄 : 𝑄𝑟 = characteristic rotational temperature
𝑟

8𝜋 2 𝑙𝑘𝑇
𝑄𝑟 = 𝜎ℎ2
Symmetry Number: Symmetry number (symbol: 𝜎) of a molecule is the number of
indistinguishable configurations the molecule assumes when it is rotated once by an angle 360o.
For a homonuclear molecule ( e.g. H2, O2, N2, …), 𝜎 = 2 as the rotation by 180o produces
indistinguishable configuration from its original confinuration.
For ahetronuclear molecule (e.g HCl, HBr,…) 𝜎 = 1.

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To avoid more than one counting of indistinguishable configurations of a molecule during the
rotation by 360o, the partition function is divided by its symmetry number to give
𝑇
𝑞𝑟 = 𝜎𝜃
𝑟
8𝜋 2 𝑙𝑘𝑇
Thus, 𝑄𝑟 = 𝜎ℎ2 (σ is symmetry number)
Note: value of 𝜎 for some molecules.
(a) CO → 𝜎 = 1
(b) O2 → 𝜎 = 2
(c) CO2 → 𝜎 = 1
(d) H2S → 𝜎 = 2
(e) O3 → 𝜎 = 1
(f) SO2 → 𝜎 = 6
(g) SiH2 → 𝜎 = 12
(h) CHCl3 → 𝜎 = 3
(i) SF6 → 𝜎 = 24
(j) Al2Cl3 → 𝜎 = 4
(k) C6H6 → 𝜎 = 18
Note: For small molecules, (lighter molecules) at low T we can not solve the expression of
rotational partition function and thus we use , only
𝐽 (𝐽+1)ℎ
−
Q = ∑(2J +l)𝑒 8𝜋2 𝑙𝐾𝑇
𝐽 (𝐽+1)𝐵𝑟
Q = ∑(2J +l)𝑒 − 𝑇
If θr = T
−𝐽 (𝐽+1)
Then, Qr = ∑~ 𝐽=1(2𝐽 + 1)𝑒
When J = 0, Qr = 1
When J = 1
𝑄𝑟 = 1 + 3𝑒 −2 + 3𝑒 −2 + 3𝑒 −6 + ….
Exercise: what is the characteristic rotation temperature 𝜃𝑟 for 𝐻2 (g)? what is the value of the
molecular partition function for rotation at 3000K? The moment of inertia is 4.6 × 10−48 Kg m2
ℎ2
Solution: 𝜃𝑟 = 8𝜋2 𝑙𝐾
ℎ2 (6.626 × 10−34 )
𝜃𝑟 = 8𝜋2 𝑙𝐾 = 8𝜋2 × = 87.5k
10−48 ×1.38 × 10−23
𝑇 3000𝐾
𝑄𝑟 = 𝜎𝜃 = 2 ×87.5𝐾 = 17.14
𝑟

Exercise: Calculate the translational partition function a H2, molecule confined in a 100 ml flask
1298 K molecular wt. of H2 = 2.016.
(2𝜋𝑚𝑘𝑇)1/2
Solution: 𝑄𝑟 = ×V
ℎ3
= √𝑀3 𝑇 3 × V × 1.89 × 1026
= √2.0163 × 2983 × 100 × 10−4 1.89 × 1026
= 2.8 × 1026
An advanced Topic: The Rotational states of H2
Molecular hydrogen exists in two forms, one in which the nuclear spins are paired (para-hydrogen)
and one in which the spins are aligned (ortho-hydrogen). Because the hydrogen nuclei are spin ½
particles, they are fermions. The paul exclusion principle dictates that when two identical fermions
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inter-change position, the overall wave function describing the system must be antisymmetric (or
change sign) with interchange. The wave function in this case can be separated into a product of
spin and rotational components. The spin component of the wave function is considered first.

For para H2
The spin component of the wave function should be antisymmetric and given as
𝜓𝑠𝑝𝑖𝑛,𝑜𝑟𝑡ℎ𝑜 = α(A)β (B) - α(B)β (A)
𝛼 & β represents spin, A & B represent H-atoms.

For ortho Hydrogen,

The spin wave function should be symmetric. Three combinations of nuclear spin states meet this
requirement:
𝜓𝑠𝑝𝑖𝑛,𝑜𝑟𝑡ℎ𝑜 = {α(A)α (B),β(A)β(B), α(A)β(B)+β(A)α(B)}
Spin component of P–H2 is antisymmetric, that of O–H2 is symmetric.
Now consider the symmetry of the rotational component of the wave function, the symmetry of
rotational states is dependent on the rotational quantum number J. If J is an ever integer (J = 0, 2,
4, 6, …) the corresponding rotational wave function is symmetric with respect to interchange, and
if J is odd (J = 1, 3, 5, 7…) the wave function is antisymmetric. Because the wave function is the
product of spin and components.
1
𝑞𝑟 = 4 [1 ∑𝐽 =0,2,4,6…(2𝐽 + 1)𝑒 −𝛽ℎ𝑐𝐵𝐽(𝐽+1) + 3 ∑𝐽 =1,3,5…(2𝐽 + 1)𝑒 −𝛽ℎ𝑐𝐵𝐽(𝐽+1) ]
In above equation, the first term is brackets corresponds to para-hydrogen and the second term
corresponds to ortho-hydrogen.
This symmetry number is omitted in above equation because over counting of the allowed
rotational level has already been taken into account by restricting the summations to even or odd
J.
ROTATIONAL PARTITION FUNCTION
Polyatomic
The polyatomic molecule is not linear, then there are three no vanishing moments of inertia.

𝐼𝐴 ≠ 0, 𝐼𝑎 ≠ 0, 𝐼𝐶 ≠ 0
Therefore, the partition function that describes the rotational energy levels must take into account
rotation about all three axes.
√𝜋 1 1/2 1 1/2 1 1/2
Partition function, 𝑞𝑟 = (𝛽ℎ𝑐𝐵 ) (𝛽ℎ𝑐𝐵 ) (𝛽ℎ𝑐𝐵 )
𝜎 𝐴 𝐵 𝐶
The subscription on B in above equation indicates the corresponding of inertia as illustrated in
figure, and σ is the symmetry numbers. Also, rotational motion is considered to be rigid.
Exercise: Evaluate the rotation a partition functions for CH2O species at 298K. Assume that the
high temperature expression is value.

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Solution: CH2O is a nonlinear polyatomic. However, the symmetry of this molecule is such that
σ = 2 with this value for the symmetry number, the rotational partition function becomes
√2 1 1/2 1 1/2 1 1/2
qR = (𝛽ℎ𝑐𝐵 ) (𝛽ℎ𝑐𝐵 ) (𝛽ℎ𝑐𝐵 )
𝜎 𝐴 𝐵 𝐶
1/2
√𝜋 𝑘𝑇 3/2 1 1 1/2 1 1/2
= (ℎ𝑐 ) (𝐵 ) (𝐵 ) (𝐵 )
2 𝐴 𝐵 𝐶
3/2
√𝜋 (1.38 ×10−23 𝐽𝐾 −1 )(298𝐾)
= ((6.626 ×10−34 𝐽𝑠) (3.00 ×1010 𝑠−1 ))
2
1 1/2 1 1/2 1 1/2
(9.40 𝑐𝑚−1 ) (1.29 𝑐𝑚−1 ) (1.13 𝑐𝑚−1 ) = 713

VIBRATIONAL PARTITION FUNCTION:

The quantum mechanical model for vibrational degrees of freedom is the harmonic oscillator. In
this Figure. The energy levels of the harmonic oscillator are as follows:
𝐸𝑛 = hc𝑣̅ (n = 0, 1, 2,…)

Figure: The harmonic oscillator model. Each vibrational degree of freedom is characterized by
quadratic potential. The energy levels corresponding to this potential are evently spaced.
The energy of given level 𝐸𝑛 is dependent on the quantum number n.
𝑣̅ = vibrational frequency in in cm-1.
1
Here, 𝐸0 = 2 hc𝑣̅
𝐸0 ≠ 0
This residual energy is known as the zero-point energy and was discuss in detail the
quantum mechanical development of the harmonic oscillator. The vibrational partition function
using above energy expression can be written as

The sum can rewritten using the series identity:

Using in above vibrational partition function:

Now vibrational partition function without zero point energy i.e.

𝐸0 = 0
We get

Characteristic Vibrational Temperature:

ℎ𝑣
is a dimensionless quantity,
𝑘𝑇
ℎ𝑣
So , must have units of temperature
𝑘

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ℎ𝑣
i.e. 𝜃𝑣 = 𝑘
𝜃𝑣 = characteristic vibrational temperature, partition function with 𝐸0 = 0 can be written as
1
𝑞𝑣 = 1−𝑐 𝜃𝑣/1
And, partition function with 𝐸0 ≠ 0 will be ,
𝑒 −𝜃𝑣/2𝑇
𝑞𝑣 = 1−𝑒 −0𝑣/𝑇
Limiting cases for vibrational partition function expression
𝜃𝑉
(a) At very low temperature (𝑄𝑉 ≫ 𝑇) 𝑒 − 𝑇 will be very low.

𝑒 −ℎ𝑣𝑎 /𝑘𝑇
𝑞𝑣 = 1−𝑒 −ℎ𝑣𝑎 /𝑘𝑇
Thus in the denominator 𝑒 −ℎ𝑣𝑎/𝑘𝑇 or 𝑒 −𝜃𝑣/𝑇 can be neglected in comparison to 1.
𝑞𝑣 = 𝑒 −𝜃𝑣/2𝑇
𝜃𝑉
(b) At very high temperature (𝑄𝑉 ≪ 𝑇) 𝑒 − 𝑇 will be low and 𝑒 −𝜃𝑣/𝑇 will be high
𝑒 −ℎ𝑣𝑎 /2𝑘𝑇
𝑞𝑣 = 1−𝑒 −ℎ𝑣𝑎 /𝑘𝑇
𝑒 −ℎ𝑣𝑎 /2𝑘𝑇
𝑞𝑣 = ℎ𝑣0
1−(1− +⋯ )
𝑘𝑇
𝑒 −ℎ𝑣𝑎 /2𝑘𝑇
𝑞𝑣 = ℎ𝑣0
1−(1− +⋯ )
𝑘𝑇
The rest of the terms can be neglected being very small.
𝑇
∴ 𝑞𝑣 = 𝜃 𝑒 −𝜃𝑉/2𝑇
𝑉
Example: For 𝐻2 gas at 300K, calculate vibrational 𝜃𝑉 and the vibration partition function
𝑄𝑣𝑖𝑏 given that the fundamental vibrational frequency of H2 molecule is 4405.3 cm-1.
ℎ𝑣 ℎ𝑐𝑣̅ 6.626 ×10−34 ×3× 108 ×4.4053× 102
Solution: 𝑄𝑣𝑖𝑏 = = = = 6338.3K
𝐾 𝐾 1.38× 108
1 1 1 1
𝑞𝑣𝑖𝑏 = 1−𝑒 −0/𝑇 = 1−𝑒 −6338.3/3000 = 1−0.1210 = 0.879 = 1.137
Example: Calculate the vibrational partition function for Br2 at 300K if the vibrational frequency
is 151.2cm-1
1
Solution: 𝑞𝑣 = 1−𝑒 −ℎ𝑣𝑛/𝑘𝑇
ℎ𝑣𝑛 ℎ𝑒𝜔 6.62 ×10−34 ×3× 1010 ×151.2
= = = 0.725
𝑘𝑇 𝑘𝑇 1.38× 10−23 ×300
1
𝑞𝑣 = 1−𝑒 −0.725 = 1.938
Electronic partition function:
Electronic partition levels correspond to the various arrangements of electrons in an atom or
molecule. The hydrogen atom provides an excellent example of an atomic system where the orbital
energies are given by
−𝑚𝑒 𝑒 4 1
En = = -109, 737 cm-1 𝑛2 (n = 1, 2, 3, …)
8𝜀02 𝑛2
Above equation shows that the energy of a given orbital in the hydrogen atom is dependent on the
quantum number n. Also, degeneracy correspond to each orbital is
𝑔2 = 2n2

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Figure: Orbitals energies for the hydrogen atom, (a) the orbital energies as dictated by solving the
Schrodinger equation for the hydrogen atom. (b) the energy levels shifted by the addition of 109,
737 cm-1 of energy such that the lowest orbital energy is 0
From the perspective of statistical mechanics, the energy levels of the hydrogen atom represent the
energy levels for the electronic energetic degree of freedom.
We will adjust the energy levels such that the energy associated with the n = 1 orbital is zero,
similar to the adjustment of the ground state energy of the harmonic oscillator to zero by
elimination of the zero-point energy. With this redefinition of the orbital energies, the electronic
partition for the hydrogen atom becomes
qE = ∑∞ 𝑛=1 𝑔𝑛 𝑒
−𝛽ℎ𝑐𝐸𝑛
= 2𝑒 −𝛽ℎ𝑐𝐸1 + 8𝑒 −𝛽ℎ𝑐𝐸2 + 18𝑒 −𝛽ℎ𝑐𝐸3 + …
−1 −1 −1
= 2𝑒 −𝛽ℎ𝑐(0𝑐𝑚 ) + 8𝑒 −𝛽ℎ𝑐(82,303𝑐𝑚 ) + 18𝑒 −𝛽ℎ𝑐(97,544𝑐𝑚 ) +…
−1 −1
= 2 + 8𝑒 −𝛽ℎ𝑐(82,303𝑐𝑚 ) + 18𝑒 −𝛽ℎ𝑐(97,544𝑐𝑚 ) +…
The magnitude of the terms in the partition function corresponding n ≥ 2 will depend on the
temperature at which the partition function is being evaluated.
Now defining the “electronic temperature” QE, in exactly the same way as the rotational and
vibrational temperatures were defined:
ℎ𝑒𝐸 𝐸
QE = 𝑘 𝑛 = 0.695𝑐𝑚𝑛−1 𝐾−1
With the definition of 𝐸1 = 0, the energy of the n = 2 orbital, 𝐸2 , is 82, 303cm-1 corresponding to
QE = 118,7421 k! This is an extremely high temperature. It shows that electronic degrees of
freedom are generally characterized by level spacing that are quite large relative to k.T. i.e.
∆𝐸𝑒 >>> kT. Therefore, only the ground electronic state is populated to a signification extent.
Now the terms corresponding to higher energy i.e., n ≥ 2 orbitals will extremely small that the
electronic partition function for the hydrogen atom is
𝑞𝑒 = 𝑔0 𝑒 −𝜃/𝑘𝑇 + small terms
𝑞𝑒 = 2 (1)2
𝑞𝑒 = 2 at 298 K
In general, the contribution of each state to the partition function must be considered, resulting in
the following expression for the electronic partition function:
𝑞𝐸 = ∑𝑛 𝑔𝑛 𝑒 −𝛽ℎ𝑐𝐸𝑛
The electronic partition function can be expressed as
𝑞𝑛 =
Where 𝜖𝑒 = electronic energy of molecule
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𝑔𝑛 = electronic statistical wt factor

In general
𝑔𝑛 = 2J + 1
Where J is the total angular momentum and its values are denoted by the symbols 𝑆1/2, 𝑆1/2, 𝑆3/2
Where subscript equal to J.
Thus,
𝑞𝑛 = ∑(2𝐽 + 1)𝑒 −𝐸𝑛/𝑘𝑇
The electronic energy levels are widely spaced, So we cannot solve the expression further. Thus,
𝑞𝑒 is found out by summation only.
𝑞𝑒 = 𝑔0𝑒 𝑒 −𝐸0 /𝑘𝑇 + 𝑔1𝑒 𝑒 −𝐸0 /𝑘𝑇 + 𝑔2𝑒 𝑒 −𝐸2 /𝑘𝑇 (∵ 𝜖0 = 0)
Special cases
1. Rare Gases (noble and inert gas) and alkali metals:
In these case, the energy difference between the ground state and next energy level is
very high and thus only ground state is accessible to molecules.
∵ 𝑄𝑒 = 𝑔0 e
2. Halogen:
In halogens, energy difference between ground state and the first excited state is not very
large. Thus, molecules can have some population in other energy level also.
𝑄𝑒 = 𝑔0 e+ 𝑔1 𝑒 −∈1 /𝑘𝑇
Exercise: The first excited state of chlorine atom, 2P1/2, lies at 0.11eV above the
ground state, 2P3/2 Calculate the electronic function of Cl atom at 1,000K.
Solution: For the ground state, 𝑔0 = 2(3/2) +1 = 4
For the first excites state, g = 2(1/2)+1 = 2
Hence, at 1,000K, 𝑞𝑒𝑙 = 𝑔1 𝑒 −∈1 /𝑘𝑇
(0.11 𝑒𝑉)(1.602 ×1019 𝐽/𝑒𝑉)
= 4𝑒 0 +2exp [ ]
1.38 × 1019 𝐽𝐾−1 ×1000𝐾
= 4 + 2(0.28) = 4.56
Nuclear Partition Function: The nuclear of an atomic can also partition among the
available nuclear energy levels and thus we have nuclear partition function.
𝑄𝑁 = ∑ 𝑔1 𝑒 −∈𝑛1 /𝑘𝑇
𝑤ℎ𝑒𝑟𝑒 ∈ 𝑛1 = nuclear energy of molecule
𝑔𝑛 = nuclear statistical wt factor
𝐼𝑛 𝑔𝑒𝑛𝑒𝑟𝑎𝑙 𝑔𝑛 = 21+1 (for one atom)
𝑤ℎ𝑒𝑟𝑒 1 = Total nuclear spin Quantum no.
𝑈𝑛𝑑𝑒𝑟 normal conditions, the nucleus remain in the ground state since the difference
between the ground state and next energy level is very high
∴ 𝑄𝑁 = 𝑔𝑛0 + 𝑔𝑛1 𝑒 −∈𝑛1 /𝑘𝑇 + 𝑔𝑛2 𝑒 −∈𝑛2 /𝑘𝑇 + ….
𝑄𝑁 = 𝑔𝑛0
𝑇ℎ𝑖𝑠 is the case of one atom for a molecule, we have many atoms and this has many nuclei
each nuclei has its own partition function.
𝑇ℎ𝑢𝑠 ,
𝑇𝑜𝑡𝑎𝑙 partition function of the molecule = product of all the individual function of the
nucleus partition function
𝑄𝑁 = π(21+1) where 1 is the nuclear spin quantum number of ith atom
Table: values of spin Quantum No. I for some elements

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Element 𝝉 (spin Quantum no.)

H+ ½
H2 3
He4 0
C12 0
O16 0
O17 5/2
N14 1
N15 ½
Cl35 3/2

Exercise: Calculation the nuclear partition function for-

Solution: For C, I = 0
∴ 𝑄𝑁 = 21+1 = 2 × 0 +1 = 1
For ϴ, I = 0
∴ 𝑄𝑁 = 21+1 = 2 × 0 +1 = 1
For H, I = ½
1
𝑄𝑁 = 21+1 = 2 × 2 +1 = 1
For N, I = 1
𝑄𝑁 = 21+1 = 2 × 1 +1 = 3
∵ 𝑄𝑁 = π (21+1)

𝑄𝑁 = 96
Question: Calculation the nuclear partition function for CH3COOCOH3
Ans. +64
Canonical Ensemble Partition Functions: Suppose system consisting of N identical and
independent particles a, b, c ………...(i.e., there is no interaction between them).
Then total energy of the system is E
E = 𝜖1(a) + 𝜖2 (b) + 𝜖3 (c) + …..𝜖𝑁𝐴
The partition function 𝑄𝑐 is defined as (for gi = 1)
𝑄𝑐 = ∑ 𝑒 (−𝜖𝑘𝑇)
𝑄𝑐 = ∑ 𝑒 −𝜖1(𝑎)𝜖2 (𝑏)𝜖3 (𝑐)……………𝜖𝑁𝐴/𝑘𝑇
𝑘/𝑇 𝑘/𝑇
𝑄𝑐 = ∑ 𝑒 −𝜖1(𝑎) . ∑ 𝑒 −𝜖2 (𝑏) … … … … . . ∑ 𝑒 −𝜖𝑁𝐴𝑘/𝑇
𝑄𝑐 = qa. qb. qc………….qNA
Since each particle has the same set of energy levels because the molecules a, b, c are identical
and identical and their molecular partition function are identical, qa= qb = qc = ………….qNA.
∴ 𝑄𝑐 = qN or qN for distinguishable entities
𝑞𝑁 𝑄𝑁
𝑄𝑐 = 𝑁! or 𝑁! for indistinguishable entities
Relation Between Partition function and thermodynamic functions
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1. Internal Energy: If U is internal energy of the system Temperature T and Q is the partition
function of the particles in the system.
The expression of internal expression, we have
U = ∑𝑖 𝑁𝑖 𝜀𝑖
From the Boltzmann expression, we have
𝑁
𝑁𝑖 = 𝑞 𝑔𝑖 𝑒 −𝛽𝜀𝑖 ; (where 𝛽 = 1/kT)
𝑁
Hence , U = [∑𝑖 𝑞 𝑔𝑖 𝑒 −𝛽𝜀𝑖 ] 𝜀𝑖
From that fact that
𝜕𝑒 −𝛽𝜀𝑖
( ) = 𝜀𝑖 𝑒 −𝛽𝜀𝑖
𝜕𝛽
𝑉
We can write the above expression as
𝑁 𝜕𝑒 −𝛽𝜀𝑖 𝑁 𝜕 𝑁 𝜕𝑞
U = − 𝑞 ∑𝑖 𝑔𝑖 ( ) =𝑞 (∑𝑖 𝑔𝑖 𝑒 −𝛽𝜀𝑖 )𝑉 = − 𝑞 (𝜕𝛽)
𝜕𝛽 𝜕𝛽 𝑉
𝑉
𝜕 𝐼𝑛 𝑞
= −𝑁 ( )
𝜕𝛽 𝑉
𝜕 𝐼𝑛 𝑞 𝑑𝑇
U = −𝑁 ( ) −𝑁 ( 𝑑𝛽 )
𝜕𝛽 𝑉
Since T = 1 1/k𝛽, we have
𝑑𝑇 1 1
= 2 = = −𝑘𝑇 2
𝑑𝛽 𝑘𝛽 𝑘(1/𝑘𝑇)2
𝜕 𝐼𝑛 𝑞
Thus U = −𝑁𝑘𝑇 2 ( )
𝜕𝑇 𝑉
Exercise: Determine the total energy of an ensemble consisting of N particles that
have only two energy levels separated by energy hv.
Solution The energy level for the particles are illustrated in figure. To determine the
average, the partition function describing this system must be evaluated.
The partition function consists of a sum of two terms as follows.

q = 1 + 𝑒 −𝛽ℎ𝑣
The derivative of the partition function with respect of 𝛽 is
𝑑𝑞 𝑑
= 𝑑𝛽(1 + 𝑒 −𝛽ℎ𝑣 )
𝑑𝛽
Using this result, the total energy is
−𝑁 𝑑𝑞 −𝑁
E= (𝑑𝛽) = (1 + 𝑒 −𝛽ℎ𝑣 ) (ℎ𝑣 −𝛽ℎ𝑣 )
𝑞
Nhv𝑒 −𝛽ℎ𝑣 Nhv
= 1 + 𝑒 −𝛽ℎ𝑣 = 𝑒 −𝛽ℎ𝑣 + 1
In the final step of this example, he expression for E was multiplied buy unit in the form
of exp(𝛽ℎ𝑣)/exp(𝛽ℎ𝑣) to facilitate numerical evaluation.
Heat capacity: 𝑪𝑽
𝜕𝑙𝑛𝑄
∴ E = RT2 ( 𝜕𝑇 )
𝑣
𝜕𝐸 𝜕 𝜕𝑙𝑛𝑄
∴ (𝜕𝑇 ) = 𝜕𝑇
[𝑅𝑇 2 ( 𝜕𝑇 ) ]
𝑣 𝑣

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𝜕 𝜕𝑙𝑛𝑄
Or, 𝐶𝑣 = 𝜕𝑇 [𝑅𝑇 2 ( ) ]
𝑣 𝜕𝑇
𝜕 2 𝜕𝑙𝑛𝑄
𝐶𝑃 = 𝑅 + [𝑅𝑇 ( 𝜕𝑇 ) ]
𝜕𝑇 𝑣
3. Entropy
For a system containing N molecules at temperature T entropy is related with partition
function as-
𝐸
S = Nk In 𝑄 + 𝑇 for distinguishable particles
1 𝛿 𝑙𝑛 𝑄
Nk In 𝑄 + 𝑇 (𝑁𝑘𝑇 ( ) )
𝛿𝑇 𝑣
𝛿 𝑙𝑛 𝑄
Nk (In 𝑄 + 𝑇 ( ) ) for indistinguishable particles
𝛿𝑇 𝑣
𝛿 𝑙𝑛 𝑄
S = Nk (In 𝑄 + 𝑇 ( ) + 1)
𝛿𝑇 𝑣
Helmholtz free energy (A):
A = - NkT (In Q) for distinguishable particles
𝑄
A = - NkT (𝐼𝑛 𝑁 + 1) for indistinguishable particles
Gibbs free energy (G):
𝑄
G = -NkT (𝐼𝑛 𝑁 + 1) for indistinguishable particles.
Note: In statistical thermodynamics, generally all the calculation is for gases and for gases the
particles are indistinguishable.
Calculate of thermodynamic quantities for different system
1. For an ideal thermodynamic gas: For a monoatomic gas, all its degrees of freedom are
of translation motion only. Thus, here no rotational and vibrational motion is considered.
∴ Q = QTQrQvQeQn
The expression of partition function reduces to
Q = QTQr
Since, Qe = go and go = 1 for most the cases.
2𝜋𝑚𝑘𝑇 3/2
∴ Q=( )
ℎ2 𝑉
Using this partition function, we can calculate all thermodynamic properties→for N particles
as→
3
(a) Internal energy E = 2 NkT
3
(b) Heat capacity CV = 2 Nk
(c) Entropy
𝑘𝑇 2𝜋𝑚𝑘𝑇 3/2 5
S = Nk (𝐼𝑛 ( ) + 2)
𝑃 ℎ2
For 1 mole gas,
𝐼𝑛 𝑉 2𝜋𝑚𝑘𝑇 3/2 5
(molar entropy) = R ( 𝑁𝐴 ( ) + 2)
ℎ2
This equation is called as Sackur Tetrod equation.
(d) Helmholtz free energy
𝐼𝑛 𝑉 2𝜋𝑚𝑘𝑇 3/2
A = -NkT ( 𝑁𝐴 ( ) + 1)
ℎ2
(e) Gibbs free energy

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𝑘𝑇 2𝜋𝑚𝑘𝑇 3/2
G = -NkT 𝐼𝑛 𝑃 ( ℎ2 )
For a diatomic Gas:
In case of diatomic molecule, we have contribution from translation, rotational and vibrational
motions.
∴ Q = QTQRQvQeQN
Since the particles are independent i.e., there are no interactions between them. Thus all the there
motions are independent of each other. This means when we consider translational motion we
neglect rotational and vibrational motion and when we consider rotational motion, we neglect the
other motions.
2𝜋𝑚𝑘𝑇 3/2
QT = ( ) V
ℎ2
8𝜋 2 𝑙𝑘𝑇
QR = 𝜎ℎ2
8𝜋 2 𝑙𝑘𝑇
Qv = 𝜎ℎ2
Qe = g0e
Thus, we can calculation all the thermodynamic properties for N particles as:
(a) Internal energy:
3
For translation motion ET = 2 NkT
3
For rotational motion ER = 2 NkT
For vibrational motion Ev = NkT (at very higher T)
𝑅𝜃𝑉
Ev = 𝑒 𝜃𝑇 (at very low temperature)
For electronic motion Ee = 0
∴ Total internal energy = Er + ER + EV + Ee
3 7
Total internal energy at high temperature = 2 NkT + NkT +NkT = 2 NkT
(b) Heat capacity:
7
Total heat capacity at very high temperature = 2 Nk
(c) Entropy:
For translational motion
𝑉 2𝜋(𝑚1 +𝑚2 )𝑘𝑇 3/2 5
ST = Nk (𝐼𝑛 (𝑁𝐴 ) + 2)
ℎ2
For rotational motion
𝑇
SR = Nk In (𝜎𝜃𝑟 + 1)
For vibrational motion
𝑁𝑘𝜃𝑉
SV = 𝑇 (𝑒 𝜃𝑉/𝑇−1 ) – Nk In (1 − 𝑒 𝜃𝑉/𝑇 )
For electronic motion Se = Nk In g0e
∴ Total entropy S = Si + S + Sv + Se
(d) Helmholtz free energy (A)
For translation motion,
2𝜋 ( 𝑚1 + 𝑚2 )𝑘𝑇 3/2 𝑉𝑒
AT = NkT (𝐼𝑛 ( ) )
ℎ2 𝑁
For rotational motion

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𝑇
AR = - NkT In 𝜎𝜃𝑟
For vibrational motion
𝑁𝑘𝜃
Av = 2 𝑣 In (1 − 𝑒 𝜃𝑉/𝑇 )
For electronic motion
Ae = NkT In g0e
∴ Total Helmholtz free energy A = Ai + Av + Ac
(e) Gibbs free energy (G)
For transitional motion,
2𝜋 ( 𝑚 + 𝑚 )𝑘𝑇 3/2 𝑘𝑇
1 2
GT = -NkT In ( )
ℎ2 𝑃
For rotational motion,
𝑇
GR = -NkT In 𝜎𝜃𝑟
For vibrational motion
𝑁𝑘𝜃
Gv = 2 𝑣 In (1 − 𝑒 𝜃𝑉/𝑇 )
For electronic motion
Ae = NkT In g0e
∴ Total Gibbs free energy = GT + GR + Gv + Ge
QUANTUAM MECHANICAL EXPLANAION OF SYMMETRY NUMBER AND HEAT
CAPACITY OF HYDROGEN GAS.
Symmetry characteristics of Wave Functions:
We have following facts about the symmetry characteristics of the wave functions
involved in the total wave function.
 Translational wave function depends only upon the coordinates of the centre of mass of
the molecule, and thus this wave function is not affected by the exchange of two identical
nuclei, i.e., translational wave function is symmetric under the exchange of two identical
nuclei.
 Vibrational wave function depends upon the magnitude of r–req and thus this wave
function is also unaffected under the exchange of two identical nuclei, i.e., the vibration
wave function is symmetric under the exchange of two identical nuclei.
 Most of molecules in the ground electronic state have the symmetric electronic wave
function.
 The rotational wave function have the same symmetry characteristics as those of the
angular function of the hydrogen atom.
𝜓𝑟 are symmetric for even value of rotational quantum number J
𝜓𝑟 are antisymmetric for odd values of rotational quantum number J
A nucleus with spin quantum 1has a total of 2l + 1 spin states. These states are
represented by the magnetic spin quantum number which can have values of
+ 1, +(1- 1), ….., -(1-1), -1
For example, for a proton (1=1/2) the two state are
𝑚𝑙 = +1/2, known as α spin. Its wave function is represented by the symbol α.
𝑚𝑙 = -1/2, known as β spin. Its wave function is represented by the symbol β.

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A diatomic molecule involving identical nuclei with spin quantum number 1. Has a total
of (2l +1)2 nuclear wave functions. Of these wave functions, we have
(2l+1) (2l)/2, i.e. l(2l + l) wave functions are antisymmetric.
And (2l+1)2 - (2l+1), i.e. (1 + l) (2l + l) wave functions are symmetric.
From example, in hydrogen molecule we have
Three symmetric nuclear spin wave functions. These are αα, ββ and (1 / √2) (αβ + βα)
One antisymmetric nuclear spin wave functions.
Diagrammatic Display of Symmetries of Wave Functions
The above characteristics about the various wave function may depicted as follows.

Factor Deciding Symmetry of Total Wave Functions

The symmetric/antisymmetric characteristic of the total wave is decided by the proper coupling
of rotational and nuclear wave function. We can have the following combinations.
1. For bosons, the total wave function has to be symmetric. This possible when l(2l + 1)
antisymmetric nuclear spin functions couple with antisymmetric rotational wave
functions for which rotational quantum number J has odd values. (l + 1) (2l + 1)
symmetry nuclear spin functions couple with symmetric rotational wave functions for
which rotational quantum number J has even values.
2. For fermions, the total wave function has to be antisymmetric. This is possible only when
l (2l + 1) antisymmetric nuclear spin functions couple with symmetric rotational wave
functions for which rotational quantum number J has even values. (1 + 1) (2l + 1)
symmetric nuclear spin functions couples with antisymmetric rotational wave functions
for which rotational quantum number J has odd values.
Expressions of partition function
For bosons, we have
𝑞𝑟.𝑛 = (1 + 1) (2l +1) ∑𝐽(𝑒𝑣𝑒𝑛)(2𝐽 + 1)𝑒 −𝜃𝑟 𝐽(𝐽+1)/𝑇 + 1(2l + 1) ∑𝐽(𝑜𝑑𝑑)(2𝐽 + 1)𝑒 −𝜃𝑟 𝐽(𝐽+1)/𝑇 …(1)
For fermions, we have
𝑞𝑟.𝑛 = (1 + 1) (2l +1) ∑𝐽(𝑜𝑑𝑑)(2𝐽 + 1)𝑒 −𝜃𝑟 𝐽(𝐽+1)/𝑇 + 1(2l + 1) ∑𝐽(𝑒𝑣𝑒𝑛)(2𝐽 + 1)𝑒 −𝜃𝑟 𝐽(𝐽+1)/𝑇 …(2)
From the above expressions, it is obvious that the combined rotational and nuclear partition
function cannot be factored into 𝑞𝑟. and 𝑞𝑛 . However, if 𝜃𝑟 /T ≤ 0.20 for mononuclear diatomic
molecules, this factorization is possible since.
∑ 𝑖 (2𝐽 + 1)𝑒 −𝜃𝑟 𝐽(𝐽+1)/𝑇 = ∑ 𝑖 (2𝐽 + 1)𝑒 −𝜃𝑟 𝐽(𝐽+1)/𝑇
(𝑒𝑣𝑒𝑛) (𝑜𝑑𝑑)
1 −𝜃𝑟 𝐽(𝐽+1)/𝑇 1 ∞ 1
= 2 ∑ 𝑖 (2𝐽 + 1)𝑒 = 2 ∫0 (2𝐽 + 1)𝑒 −𝜃𝑟 𝐽(𝐽+1)/𝑇 = 2𝜃
(𝑎𝑙𝑙) 𝑟

With this, eqs (1) and (2) can be written as

𝑇
𝑞𝑟.𝑛 = (2l+1)2 2𝜃
𝑟
In which 𝑞𝑛 =(2l+1)2 and 𝑞𝑟 = 𝑇/2𝜃𝑟 .
For heteronuclear diatomic molecules 𝑞𝑟 = 𝑇/𝜃𝑟 .
The factor2 in the denominator of Eq. (3) is known as symmetry number.
KITNETIC THEORY OF GASES
1. The Kinetic Gas Equation
Postulates of an ideal gas Equation
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 A gas consists of a large number of very small special tiny particles, which may be
identified with the molecules.
The molecules of given gas are complete identical in size, shape and mass.
 The volume occupied by the molecule is negligible in comparison to the total volume of
the gas.
 The molecule are in rapid motion which is completely random. During their motion,
collide with one another and with the sides of the vessel. The pressure of gas is due to the
collisions of molecules with the sides of the vessel.
 The molecule are perfectly elastic, i.e., there occurs no loss of energy when they colloide
with on another and with the vessel.
 The laws of classical mechanics, in particular Newton’s second law of motion, are
applicable to the molecules in motion.
 There is no force of attraction or repulsion among the molecules, i.e., they are moving
independent of one another.
 At any instant, a given molecule can have energy ranging from a small value to a very
large value, but the average kinetic energy remains constant for a given temperature. i.e.,
the average kinetic energy is proportional to the absolute temperature of the gas.
2. Derivation of the kinetic Gas Equation
Imagine a cube of edge-length l, containing N molecule, each having a mass of m.
The velocity u1 of any molecule may be resolved into three-component velocity
designated as ux, uy and uz.
The component velocities are related by the expression
𝑢12 = 𝑢𝑥2 + 𝑢𝑦2 + 𝑢𝑧2 …(i)
Considering the x-component motion of molecule, we will have
Momentum of molecule before collision with the side ABCD = 𝑚𝑢𝑥
Momentum of molecule after collision with the side ABCD = −𝑚𝑢𝑥 .

Change of momentum of the molecule in a single collision with the side ABCD = [𝑚𝑢𝑥 ].
𝑢 𝑚
The total change of momentum per unit time due to such impacts is 2𝑚𝑢𝑥 ( 2𝑙𝑥)= 1𝑥
The area of the wall is l2. Hence the pressure exerted due to the Collison of x-component
velocity of single molecule with the side ABCD is
𝑚2 /1 𝑚2
Px = 𝑥1 = 𝑉𝑥 … (2)
Where V is the volume of the vessel.
Since each molecule will exert similar pressure, the total pressure exerted on the wall
ABCD will be
𝑚 𝑁
P = ∑𝑁 2
𝑖=𝑖 𝑃𝑖𝑥 = 𝑉 ∑𝑖=𝑖 𝑢𝑖𝑥 …(3)
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Defining the mean square speed as

1
𝑢𝑥̅̅̅̅̅
2
= 𝑁 ∑𝑁 2
𝑖=𝑖 𝑢𝑖𝑥 …(4)
We can write
𝑚𝑁
P = 𝑉 𝑢𝑥̅̅̅̅̅ 2
… (5)
Since the directions x, y and z are equivalent will also have
𝑢𝑥̅̅̅̅̅
2
= 𝑢𝑦̅̅̅̅̅
2
= 𝑢𝑧̅̅̅̅̅
2
…(6)
But from eq. (1) we have
𝑢2̅ = 𝑢𝑥̅̅̅̅̅
2
= 𝑢𝑦̅̅̅̅̅
2
= 𝑢𝑧̅̅̅̅̅
2
…(7)

From eq. (6) and (7) we have

1
𝑢𝑥̅̅̅̅̅
2
= 𝑢𝑦̅̅̅̅̅
2
= 𝑢𝑧̅̅̅̅̅
2
= 𝑁 𝑢2̅ …(8)

Substituting this in eq. (5) we get

𝑚𝑁 1 1
P= ( 𝑢2̅ ) or P = 𝑚𝑁𝑢2̅ …(9)
𝑉 3 3

Kinetic Energy of 1 mole of gas:

From kinetic gas equation

1
PV = 3 𝑚𝑛 𝑣 +2 (m.n = M total mass of gass)
1
PV = 3 𝑀𝑣 +2 (multiply and divide by 2 on RHS)
2
PV = 3 𝑀𝑣 +2
2 1 3
PV = 3 K.E → (𝐾. 𝐾 = 2 𝑚𝑣 +2 ) → K.E. = 2 PV
From ideal gas equation PV = RT for 1 mole

3
∴ KE = 2 PV … (10)
R = universal gas constant KE∝ T
Thus Kinetic energy 1 molecule:
3
∵ Kinetic energy for 1 mole = 2 RT

3 𝑅 𝑇
∴ KE for molecule = 2 (𝑁 ) (𝑁𝐴 = Avogadro’s number)
𝐴
3
KE = PV
2
… (11)
−23
KE∝ T K = Boltzmann constant (1.38 ×10 𝐽/𝐾 )
Thus kinetic energy for 1 molecule also depends on temperature.
Degree of freedom
The degrees of freedom of a molecule are defined as the independent number of
parameters required to describe the state of the molecule completely. Each molecule has

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3N degree of freedom. Where N is total number of atoms of 1atm is 1mole of molecular

formula.
It is of three types.
(i) Translational degree of freedom: Each molecule has three translation degree of
freedom along three axes x, y, z.
Monoatomic gases He, Ne-, Ar etc. poses only 3 translational degree of freedom. They
have no rotational or vibrational degree of freedom.
(ii) Rotational degree of freedom:
All linear molecule, such as CO2, C2H2, HCl has 2 rotation degrees of freedom.
Non linear molecule, such as H2O, NH3, CH4, H2S etc has 3 rotational degrees of
freedom.
(iii) Vibrational degree’s freedom:
For linear molecule (CO2, C2H2) = 3N –5
For non-linear molecule (H2O, NH3, CH4)
Note:
(i) Rotational degree of freedom present only in liquid & gases.
(ii) In solid state molecule possess only vibrational degrees of freedom. Translation &
rotational motion in solids converted into vibrational motion.
Principle of Equipartition of Energy:
According to the law of equipartition of energy, the total energy of a molecule is divided
equally amongst the various degrees of freedom of molecule.
Therefore:
1 1
(i) Energy of translation for each DOF = 2 𝑘𝑇 = 2 𝑅𝑇
1 1
(ii) Energy of rotation for each DOF = 2 𝑘𝑇 = 2 𝑅𝑇
(iii) Energy of vibration for each DOF = 𝑘𝑇 = 𝑅𝑇
Thus if n1, n2 & n3 are the translational, rotational and vibrational degrees of freedom, the
total energy
1 1
= n1 2 + n2 2 + n3 kT

Exercise: Estimate Cv (molar heat capacity of constant volume) for

(i) HCl (ii) He (iii) CO2 (iv) NH3 (v)CH4
Solution:(i) HCl-linear diatomic molecule.
3
Translation DOF = 3& ∴ 𝐸𝑇 = 𝑅𝑇
2
1
Rotational DOF = 2 (linear) ∴ 𝐸𝑇 = 2× 𝑅𝑇 = RT
2
Vibrational DOF = 3 × 2 – 5 = 1 𝐸𝑇 = RT
3 7
∴ Total energy = 2 𝑅𝑇 + RT + RT → u = 2 RT
𝑑𝑢 7 𝑑𝑇 7
∴ (𝑑𝑇 ) = 2 R (𝑑𝑇) → 𝐶𝑣 = 2 R
𝑣 𝑣
(ii) For He:
Only 3 Translational DOF
1 3
∴ u = 3 × 2 RT = 2 RT

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𝑑𝑢 3 𝑑𝑇 3
∴ (𝑑𝑇 ) = 2 R (𝑑𝑇) → 𝐶𝑣 = 2 R
𝑣 𝑣
(iii) For 𝐶𝑂2− linear:
3
Transaction DOF = 3 ∴ 𝐸𝑇 = 2 𝑅𝑇
Rotational DOF = 2 ∴ 𝐸𝑅 = 𝑅𝑇

Vibrational DOF = 3 × 3 – 5 = 1 𝐸𝑉 = 4RT =4

3 13
∴ Total energy (u) = 4𝑅𝑇 + RT + 2 RT 𝐸𝑉 = RT
2
13 𝑑𝑇 13
∴ 𝐶𝑣 = R (𝑑𝑇) → 𝐶𝑣 = R
2 𝑣 2
(iv) 𝑁𝐻3 − 𝐵𝑒𝑛𝑡
3
Transaction DOF = 3 𝐸𝑇 = 2 𝑅𝑇
3
Rotational DOF = 3 𝐸𝑅 = 2 𝑅𝑇
Vibrational DOF = 3 × 4 × 6 = 6 𝐸𝑉 = 6RT
3 3
∴ Total energy (u) = 𝑅𝑇 + 2 RT + 6RT 𝐸𝑉 = 9RT
2
𝑑𝑢 𝑑
∴ (𝑑𝑇 ) = (𝑑𝑇 9𝑅𝑇) → 𝐶𝑣 = 9R
𝑣 𝑣
(v) For CH4:
3
Transitional DOF = 3 𝐸𝑇 = 𝑅𝑇
2
3
Rotational DOF = 3 𝐸𝑅 = 2
𝑅𝑇
Vibrational DOF = 3 × 5 − 6 = 9 𝐸𝑉 = 9RT
3 3
u = 2 RT + 2 RT + 9 RT u = 12RT
𝑑𝑢 𝑑
∴ (𝑑𝑇 ) = (𝑑𝑇 12𝑅𝑇) → 𝐶𝑣 = 9R
𝑣 𝑣
Note: At room temperature the contribution of vibrational energy towards total energy is 20%
(or 0.20) for each vibrational DOF.
Exercise: Justify the following question
Considering CO2 as an ideal gas, equipartition theorem predicts its total energy as 6.5 KT
Solution: CO2 is linear molecule.
Translation energy = 3; , Rotational DOF = 2; Vibrational DOF = 3 × 3 -5 = 4
3
Total energy 𝑅𝑇 + 𝑅𝑇 + 4 𝑅𝑇 = 6.5 RT per mole
2
𝑅 𝑇
For 1 molecule: 𝐸𝑇𝑜𝑡𝑎𝑙 = 6.5 (𝑁 ) → 𝐸𝑇𝑜𝑡𝑎𝑙 = 6.5KT[𝑁𝐴 = Avogadro number]
𝐴
Distribution of molecular velocities (Maxwell’s and Maxwell Boltzmann’s Distribution Law
of Molecular velocities)
Due to collisions between molecules, velocity as well as direction of the movement, also changes.
Thus their kinetic energies as well as, velocities are redistributed. Hence, the molecule, move with
different velocities and their kinetic energies are also different. Boltzmann, gave the following
expression, for the distribution of energy between molecules.
𝑁𝜖
𝑁
= 𝑒 −𝜖𝑘𝑇 …(1)
0

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Here, 𝑁0 is the total number of molecules and 𝑁𝜖 is the number of molecules having energy, more
than a reference point 𝜖, k is Boltzmann constant and T is absolute temperature.
In 1860, J.C Maxwell gave a law, by using the theory of probability, which is known as Law of
Distribution of molecular velocities. According to this law, velocities of the molecules are
distributed from zero to a great range. By using Boltzmann’s equation and probability theory.
Maxwell derived a simple expression, which show that the actual distribution depends on
temperature and molecular weight of the gas. The mathematical expression of the Maxwell’s
distribution law is:
𝑑𝑛 𝑀 3/2 2
= 4𝜋 (2𝜋𝑅𝑇) 𝑒 −𝑀𝑐 / 2𝑅𝑇𝑐 2 𝑑𝑐 …(2)
𝑛
Velocities are between c and (c + dc). Where dc. (Represents a very small difference). M,
molecular weight R gas constant, T absolute temperature and e is base of natural logarithm
equation (2) can also be written as
1 𝑑𝑛 𝑀 3/2 2
P = 𝑛 𝑑𝑐 = 4𝜋 (2𝜋𝑅𝑇) 𝑒 −𝑀𝑐 / 2𝑅𝑇𝑐 2 𝑑𝑐 …(3)
Where P = Probability of the molecule, whose velocity is between c and (c +dc)
Equation (3) is known as Maxwell’s distribution law of Maxwell Boltzmann distribution law
of molecular velocities.

1 𝑑𝑛
Distribution of molecular velocities is shown by (figure), where, fraction of molecules, i.e.
𝑛 𝑑𝑐
probability (P) is plotted against co-ordinate axis and velocities of the molecule c, on the abscissa,
three different curves I, II and III are obtained at three different temperatures T1, T2 and T3
respectively, (T3 > T2 > T1). This type of curve at constant temperature is known as distribution
curve. Following observation can be made from the curve in:
Following observation can be made from the curve in:
(i) The number of molecules have very low and very high velocities is very low.
(ii) For every curve probability or fraction of those molecules whose velocity is more than
zero increases, with increasing value of velocity c, probability increases and reaches a
maxima and then readily decreases. As velocity c. increases, probability decreases, because
by increase in the value of c2 the value of exponential term (equation 3) decreases. Thus
fraction of molecules having very low velocities, is very low.
(iii) Curve is asymmetrical and have clear maxima. At every temperature most of the molecules,
have the velocity of the maxima. This value of velocity is known as most probable velocity
and is denoted by α.
(iv) Curve is asymmetrical near maxima hence most probable velocity does not coincide with
average velocity.
(v) Effect of temperature on distribution of Velocities –value of most probable velocity
increases with increase in temperature (figure). By increase in temperature, the curve shifts
toward right side. Height of the maxima decreases and width of the curve increases, which
show that at high temperatures, of molecules having most probable velocity decreases.
Which shows that at high temperature range, distribution of velocities also increases.

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It is evident from figure that the fraction of molecules, having velocity more than a
reference point is low at temperature T1. A line drawn C, intercepting the curve I, II and II.
It is seen that area CDX > CBX> CAX, corresponding to temperature.

T3> T2> T1 respectively, which show that by increases in temperature fraction of molecules
having velocity higher than definite vale C.
(vi) Distribution of velocity also depends on molecular weights. Eq. (3). At constant
temperature distribution of molecular velocities is higher in lighter gases than in heavier
gases.
For examples distribution of velocities in CO2 (mol. wt. 44), is lower than O2 (mol. wt. 32)
in above figure shows distribution of velocities at room temperature in different gases.
Average kinetic Energy
The average kinetic energy (𝐾𝐸̅̅̅̅ ) is defined as
1
̅̅̅̅ = m𝑢̅̅̅̅̅2
𝐾𝐸 ̅̅̅̅ = 𝑝𝑉
𝐾𝐸
3
2 2 𝑁
For 1 mole of an ideal gas
PV = RT and N = 𝑁𝐴
With these, the above equation becomes
3 RT 3
̅̅̅̅
𝐾𝐸 = 2 𝑁 = 2 KT
𝐴
𝑅
Where k = 𝑁− and is known a the Boltzmann constant. Its value is given by
𝐴
RT 8.314 𝐾𝐽−1 𝑚𝑜𝑙−1
K = 𝑁 = 6.023 × 1023 𝑚𝑜𝑙−1 = 1.38 × 10−23 𝐽𝐾 −1
𝐴
3 𝑅 3
 Average kinetic energy of a single molecule = 2 𝑇 T = 2 𝑘𝑇
K = Boltzman constant = 1.3806 × 10−16 erg 𝑑𝑒𝑔−1.
3
 Total kinetic energy for one mole of a gas = 2 RT.
3
Kinetic energy of n moles of a gas = n × 2 RT.

Maxwellian Distribution of molecular speeds

Distribution of molecular Speeds: One must consider the statistical average of the speed
of the whole collection of gas molecules. The fraction of total number of molecules having
speed between any definite range must be constant, even though the speed of individual
molecules may be changing as a result of molecular collisions.
Law of Distribution of Molecular speeds: The manner in which the molecules of a gas
are distributed over the possible speed range, from zero to very high values, was first
investigated by J.C. Maxwell using the theory of probability. H is results are expressed as
the law of distribution of molecular speeds, one form of which is

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𝑚 3/2 −𝑚𝑢2 𝑚 3/2 −𝑚𝑢

𝑑𝑁𝑢 = 4𝜋𝑁 (2𝜋𝑅𝑇) exp ( 2𝑅𝑇 ) 𝑢2 𝑑𝑢 = 4𝜋𝑁 (2𝜋𝐾𝑇) exp ( 2𝐾𝑇 ) 𝑢2 𝑑𝑢
Derivation of some Expression from the Maxwell Distribution
Average Speed: The average value of speed is given by the relation
𝑢 + 𝑢 +𝑢 +⋯+ 𝑢𝑁 1
𝑢̅ = 1 1 𝑁1 = 𝑁 ∑𝑖 𝑢𝑖
1 ∞ ∞ 𝑑𝑁
𝑢̅ = 𝑛 ∫0 𝑢𝑑𝑁𝑢 = ∫0 𝑢 𝑁𝑢
Where 𝑑𝑁𝑢 is the number of molecules having speed u. The summation of different speeds
is replaced by integration since all types of speed ranging from zero to infinity are involved.
𝑚 3/2 𝑅𝑇 2 8𝑅𝑇 8𝐾𝑇
𝑢̅ = 4𝜋𝑁 (2𝜋𝑅𝑇) {2 ( 𝑀 ) } = √ 𝜋𝑀 = √ 𝜋𝑚
Root Means square speed: The mean square sped is given by
2
̅̅̅ 𝑢2 +𝑢2 +⋯+𝑢𝑁 1 1 ∞
𝑢2 = 1 2 = ∑𝑖 𝑢2 = ∫ 𝑢𝑑𝑁𝑢 𝑖
𝑁 𝑁 𝑛 0
3𝑅𝑇 3𝐾𝑇
Thus, 𝑢𝑟𝑚𝑠 = √̅̅̅
𝑢2 = √ 𝑀
=√ 𝑚
Thus, rms speed is directly proportional to the square root of temperature and inversely
proportional to the square root of molar mass. Hence, at a given temperature lighter molecules
(say H2, He) move faster than the heavier molecules (say O2, N2). There is no effect of change of
pressure or volume on the rms speed since, at a given temperature, PV = constant.
Exercise: Arrange root mean square, most probable and average speed in the order of
increasing value. Discuss the effect of temperature and pressure on these speeds.
3𝑅𝑇 3𝐾𝑇 3𝐾𝑇
Solution: 𝑢𝑚𝑝 = √ ; 𝑢̅ √ ; √̅̅̅
𝑢2 = √ 𝑀
𝑀 𝑚

Hence, √̅̅̅
𝑢2; 𝑢̅: 𝑢𝑚𝑝 : 1.732: 1.596: 1.414
From this, it follows that all the three velocities are directly proportional to the
square root of absolute temperature and are independent of pressure of gas.
Exercise: Calculate the temperature at which the average velocity of oxygen equals that of
hydrogen at 20K.
3𝑅𝑇 𝑇
Solution 〈𝑉〉 = √ = 〈𝑉〉 ∝ √𝑀 [M = mol. mass of gas]
𝑀
〈𝑉〉 𝑜𝑥𝑦𝑔𝑒𝑛 𝑇𝑜 × 𝑀112 𝑇𝑜 .2 𝑀𝐻2 2
∴ 〈𝑉〉 ℎ𝑦𝑑𝑟𝑜𝑔𝑒𝑛 = √𝑀 2 2
= √32.20 Given [𝑇𝐻2 = 20K] & [ ]
𝑜2 × 𝑇112 𝑀𝑂2 32

𝑜 𝑇
𝑙 = √3202 ∵ 〈𝑉〉 𝑂2 = 〈𝑉〉 𝐻2
2
2 𝑇𝑜2 1/2 𝑇𝑜2
[𝑙] = [(320) ] →𝑙= → 𝑇𝑜2 = 320𝐾
320

Exercise - I
1. If all the energy levels are degenerate, then at very low temperatures (T→OK). What is
the value of partition function q?
(a) equal to 1
(b) equal to ∞
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(c) equal to the degeneracy of ground level

(d) equal to the degeneracies of all energy levels
2. What is he value of symmetry number 𝜎 for a molecule like O3.
(a) 1 (b)2 (c)3 (d)4
3. What is the degeneracy of the first excited state of Cl- atom having term 2𝑃1/2 ?
(a) 1 (b)2 (c)3 (d)4
4. What is the nuclear partition function qN for HCN?
(a) 1 (b)3 (c)6 (d)10
5. For an ideal gas, it is considered that-
(a) All particles are indistinguishable
(b) All particles are distinguishable
(c) Particles can be indistinguishable or distinguishable
(d) We cannot comment
6. Out of these, select a number whose factorial can be approximated more close to the true
value. Using sterling approximation
(a) 6 (b)10346 (c)1.375 ×106 (d) 4.2 ×10-3
7. A system has doubly degenerate ground state with energy E0 and very large number of
spaced excited states. If T →0, then partition function will be
(a) 0 (b)2 (c)1 (d)∞
8. The correct expression for change in Helmholtz energy (∆A) in terms of canonical
partition function (Q) is
1 𝜕𝑄
(a) 𝑄 (𝜕𝛽 ) (b) Kt In Q
𝑣
𝐼𝑛 𝑄 1 𝜕𝑄 𝐼𝑛 𝑄
(c) Ktv ( 𝜕𝑣 ) (d) -𝑄 (𝜕𝛽 ) + kTV( 𝜕𝑣 )
𝑇 𝑣 𝑇
9. The electronic partition function of an atom whose atomic state is 2𝐷3/2 is
(a) 3/2 (b)3 (c) 4 (d) 2
10. The units of the molar partition function are
(a) cm-1 (b) s-1 (c) JK-1 mol-1 (d) Dimensionless
11. Which of the following is true?
(a) 𝑞𝑡𝑟 > 𝑞𝑣𝑖𝑏 >𝑞𝑒𝑙 > 𝑞𝑟𝑜𝑡 (b) 𝑞𝑡𝑟 > 𝑞𝑟𝑜𝑡 >𝑞𝑣𝑖𝑏 > 𝑞𝑒𝑙
(c) 𝑞𝑡𝑟 > 𝑞𝑟𝑜𝑡 >𝑞𝑣𝑖𝑏 > 𝑞𝑒𝑙 (d) 𝑞𝑒𝑙 > 𝑞𝑣𝑖𝑏 >𝑞𝑟𝑜𝑜𝑡 > 𝑞𝑡𝑟
12. In term of the molar partition function q, the internal of a molecule is given by
(a)U = nRT2 ( 𝜕In q/𝜕𝑉)𝑇 (b)U = nRT ( 𝜕In q/𝜕𝑉)𝑇
2
(c)U = nRT ( 𝜕In q/𝜕𝑉)𝑉 (d)U = nRT ( 𝜕In q/𝜕𝑉)𝑉
13. If the temperature of a gas is doubled, the rms speed of molecules.
(a)increases by a factor of √2 (b) decreases by a factor of 2
(c) increases by a factor of √2 (d) decreases by a factor of √2
1/2
14. The 𝑉𝑛𝑛𝑠 of a gas 300 K is 30𝑅 . The molar mass of the gas, in kg mol-1 is
(a) 1.0 (b) 1.0× 10−1 (c) 1.0× 10−2 (d) 1.0× 10−31
15. According to the kinetic theory of gases, the root mean square velocity is
(a) Proportional to the temperature
(b) Proportional to the square of the temperature

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(c) Proportional to the square root of the temperature

(d) Inversely proportional to the square root of the temperature
16. As per the kinetic theory of ideal gases, which of the following statements is NOT
correct?
(a) gas particles have mass but no volume
(b) particles are in a Brownian motion between collisions
(c) during the collision, the system does not lose energy
(d) particles exert same force per unit area on all sides of the container.
17. According to ideal gas law:
(a) Molecules have neither attraction between them nor have finite size, being treated as a
point mass.
(b) Molecules have attraction between them but do not have finite size, being treated as a
point mass.
(c) Molecules have no attraction between them but do not have finite size
(d) Molecules have both attraction between them and have finite size
18. Factors affecting the average kinetic energy of gas molecules are
(a) Pressure only (b) Temperature only
(c) Both temperature and pressure (d) Neither temperature nor pressure
19. The temperature of a sample of a gas is raised from 127oC TO 527 oC. The average
kinetic energy of the gas
(a) does not change (b) is doubled (c) is halved (d) cannot be calculate
20. The kinetic energy of N molecules of O2 is x Jolues at -123oC. another sample of O2 at
27oC has kinetic energy of 2x joules. The latter sample contains
(a) N molecules of O2 (b) 2N molecules of O2
𝑁
(c) 2 molecules of O2 (b) None of these
21. The kinetic energy of any gas molecules at 0oC is
(a) 5.66 × 10−21 J (b) 3408 J (c) 2 cal (d) 0
22. The 𝑉𝑚𝑛𝑠 speed of N2 molecules in a gas sample can be changed by
(a) An increases in volume of sample
(b) Mixing with Ar sample
(c) An increase in volume of sample
(d) an increase in temperature.
23. The ration of the translation partition function of D2 and D2 at the same temperature and
volume
(a) 2 (b) 1.414 (c) 2.83 (d) 4
24. The rotational partition function (q ) of AB molecule 27oC is 19.6. what would be its qr
2

327oC?
(a) 19.6 (b) 27.7 (c) 39.2 (d) 55.4
25. The translational partition function has the unit of
(a) V (b) I/V (c) P (d) a number

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Exercise - II

1. What is the rotational contribution to the internal energy of O2 molecule at 500K?

(a) 4.157 kJ mol-1 (b) 6.235 kJ mol-1
-1
(c) 3.259 kJ mol (d) 4.792 kJ mol-1
2. What can be the expression for pressure of a gas in terms of partition function q.
𝛿 𝐼𝑛 𝑞 𝛿 𝐼𝑛 𝑞
(a)NkT ( 𝛿𝑉 ) (b) NkT ( 𝛿𝑇 )
𝑇 𝑉
𝛿 𝐼𝑛 𝑞 𝛿 𝐼𝑛 𝑞
(c) NkT ( 𝛿𝑉 𝑇
) (d) NkT ( 𝛿𝑇 𝑉
) +1
3. For methane molecule, what is the correct formula for rotational partition function 𝑞𝑟 if
𝜃𝑟 is the characteristic rotational temperature.
𝜃𝑟 𝜃 𝜃 𝑇
(a) 12𝑇 (b) 12𝜃𝑟 (c) 6𝑇𝑟 (d) 6𝜃
𝑟 𝑟
4. The maximum value of total internal energy (counting the contributions from transitional,
rotational and vibrational motion) is attained at very high temperature. what is the value?
5 9 7
(a) 2 NkT (b) NkT (c) 2 NkT (d) 2 NkT
5. If 10 distinguishable particles are to be distributed among energy levels such that total
energy is always 5E, then what are the total possible macrostates?
(a) 12 (b) 10 (c)7 (d) 5
6. The vibrational partition function for a molecule with fundamental frequency v is given
by
ℎ𝑣 ℎ𝑣 −1
(a)exp (− 𝐾 𝑇) (b) [1 − 𝑒𝑥𝑝 (− 𝐾 𝑇)]
𝐵 𝐵
ℎ𝑣 ℎ𝑣 −1 ℎ𝑣 ℎ𝑣 −1
(c)𝑒𝑥𝑝 (− 𝐾 𝑇) [1 − 𝑒𝑥𝑝 (−
𝐾𝐵 𝑇
)] (d)exp (− 𝐾 𝑇) [1 − 𝑒𝑥𝑝 − (𝐾 𝑇)]
𝐵 𝐵 𝐵
𝑇𝑚
7. A certain system of nointeracing particle has the single- partition function f = A 𝑉
wherer A is some constant. The average energy per particle will be
(a) mkT (b) AkT (c)𝑘𝑇/𝑚 (d) 𝑘𝑇/𝐴
8. N non interacting molecules are distributed among three non-degenerate energy levels
𝜀0 = 0, 𝜀1 = 1.38 × 10−21 𝐽 𝑎𝑛𝑑 𝜀2 = 2.76 × 10−21 𝐽, at 100K. If the average total energy
of the system at this temperature is 1.38 × 10−18 𝐽 the number of molecules in the system
is
(a) 1000 (b) 1503 (c) 2354 (d)2987
9. The translational partition function of a hydrogen molecule confined in a 100mL flask at
298k (Mol. wt. of hydrogen = 2.016) is
(a) 2.8× 1020 (b) 2.8× 1025
(c) 2.8× 1026 (d) 2.8× 1027
10. The rms velocity of N2 molecules in a gas at a given temperature is 500m/sec. The rms
velocity of He at the temperature is (rounded to the nearest m/sec)
(a) 1750 m/sec. (b) 1322m/sec (c) 6125m/sec. (d) 661m/sec.
11. Given that the rms velocity of N2 molecule in a gas is 500m/sec at 27oC, the rms value at
320oC is
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(a) 1000 m/sec. (b) 2000m/sec (c)707 m/sec. (d) 1740 m/sec.
12. The ration of rms velocity to average velocity of gas molecule at a particular temperature
is
(a) 1.0806:1 (b) [Link].086 (c)[Link].086 (d) 1.086:2
13. A monoatomic gas, a diatomic gas & triatomic gas are mixed, taking one mole of each
Cr/Cv for the mixture is
(a) 1.40 (b) 1.428 (c)1.67 (d) 1.33
14. The ration between the 𝑉𝑟𝑚𝑠 velocity of H2 at 50k & that O2 at 800K is
(a) 4 (b) 1 (c)1 (d) ¼
15. The translational partition function (q) for the H2 molecule in a 100cm-1 vessel at 298 K
is 2.77 × 1026. The q for the D2 molecule under the same condition would be
(a) 5.54 × 1026 (b) 3.29 × 1026 (c) 21.25 × 1026 (d) 7.83 × 1026

Exercise –III

1. At room temperature, which molecule have the maximum rotational entropy?

(a) O2 (b) H2 (c) D2 (d) N2
2. The relative population in two states with energies E1 and E2 satisfying Boltzmann
distribution is given by n1/n2 = (3/2) exp. [-(E1 - E2) 𝐾𝐵 𝑇]. The relative degeneracy g2/g1
is
(a) 2 (b) 2/3 (c) 3/2 (d) 3
3. The rotational partition function of H2 is
(a) ∑𝐽=0,1,2…(2𝐽 + 1)𝑒 −𝛽ℎ𝑐𝐵𝐽(𝐽+1)
(b) ∑𝐽=1,3,5…(2𝐽 + 1)𝑒 −𝛽ℎ𝑐𝐵𝐽(𝐽+1)
(c) ∑𝐽=0,2,4…(2𝐽 + 1)𝑒 −𝛽ℎ𝑐𝐵𝐽(𝐽+1)
1
(d) 4 [∑𝐽=0,1,2…(2𝐽 + 1)𝑒 −𝛽ℎ𝑐𝐵𝐽(𝐽+1) + 3 ∑𝐽=1,3,5…(2𝐽 + 1)𝑒 −𝛽ℎ𝑐𝐵𝐽(𝐽+1) ]
4. Calculate the total number of microstates for 6 identical particle with their occupation
number {1, 2m 3} in three states is
(a) 6 (b) 12 (c) 60 (d) 720
5. The equilibrium population ratio (nj/ni) of a double-degeneratre energy level (Ej)lying at
energy 2 units higher than a lower nondegenerate energy level (Ei), assuming 𝐾𝐵 𝑇 = 1
unit, will be
(a) 2𝑒 −2 (b) 2𝑒 2 (c) 𝑒 2 (d) 𝑒 −2
6. A system has 100 degenerate energy levels and 100 bosons are Kept in it. Find the
entropy of the system at equilibrium-
(a) 10−2 𝐾𝐵 (b) 102 𝐾𝐵 (c) 460.6 𝐾𝐵 (d) 4.606 𝐾𝐵
7. The number a ways in which four molecules can be distributed in two different energy
levels is
(a) 6 (b) 3 (c) 16 (d) 8
8. The molecule with the smallest rotation partition function at any temperature among the
following is
(a) 𝐶𝐻3 − 𝐶 ≡ 𝐶 − 𝐻 (b) 𝐻 − 𝐶 ≡ 𝐶 − 𝐻

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(c) 𝐻 − 𝐶 ≡ 𝐶 − 𝐷 (d) 𝐷 − 𝐶 ≡ 𝐶 − 𝐷
9. The number of configurations in the most probable state, according to Boltzmann
formula is
(a) 𝑒 𝑆/𝐾𝐵 (b) 𝑒 −𝑆/𝐾𝐵 (c) 𝑒 −𝐸/𝐾𝐵 𝑇 (d) 𝑒 −∆𝐺/𝐾𝐵 𝑇
10. Using Boltzmann distribution, the probability of an oscillator occupying the first three
levels (n = 0, 1 and 2) is found to be 𝑝0 = 0.633, 𝑝1 = 0.233 and 𝑝2 = 0.086.
(a) 0.032 (b) 0.048 (c) 0.952 (d) 1.000
11. When T →∞, value of the single – particle partition function will be (given: degeneracy
of level j =gj).
1
(a) 1 (b) 𝑔0 (c)∑𝑖 𝑔𝑖 (d) ∑ 𝑔
𝑖 𝑖
12. The low and high temperature limits of vibrational partition function are
(a)𝑒 −𝜃/𝑇 𝑎𝑛𝑑 𝑇/𝜃 −𝜃/𝑇 (b) 𝑒 −𝜃/2𝑇 𝑎𝑛𝑑 𝑇/𝜃 −𝜃/2𝑇
(a)𝑒 −2𝜃/𝑇 𝑎𝑛𝑑 𝑇/𝜃 −𝜃/𝑇 (d) 𝑒 −𝜃/2𝑇 𝑎𝑛𝑑 𝜃/𝑇 −𝜃/2𝑇
13. The indistinguishability correction in the Boltzmann formation is incorporated in the
following way: ( N = Total number of particles; f = single partition function)
(a) Replaced f by f/N! (b) Replaced fN by fN/N!
(c) Replaced f by f/ l (N!) (d) Replaced fN by fN/ l (N!)
14. The single- particle partition function (f) for a certain system has the form f = AVeBT.
The average energy per particle will then be (K is the Boltzmann constant)
(a) BkT (b) BkT 2 (c)kT/B (d) kT/B2
15. Though a constant shift of energy levels of a system changes the partition function, the
properties that do not change are
(a) Average energy, entropy and heat capacity
(b)Average energy and entropy capacity
(c) Average energy and heat capacity
(d) entropy capacity and heat capacity
16. The vibrational frequency of a homonuclear diatomic molecule is v. The temperature at
which the population of the first excreted state will be half that of the ground state is
given by
(a) hv. In 2/𝑘𝐵 (b) hv / (In 2 𝑘𝐵 ) (c) In 2/hv. 𝑘𝐵 (d) hv . log 2 /𝑘𝐵 )

Answer Key

Exercise- I

1- C 2- B 3D 4 -C 5. A

6C 7B 8B 9C 10-D

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11-C 12-C 13 C 14 D 15 C

16 B 17 A 18 B 19 B 20 A

21-A 22- D 23 C 24 -C 25. D

Exercise- II

1- * 2- A 3B 4 -D 5. C

6B 7A 8C 9C 10-B

11-C 12-A 13 B 14 C 15 D
Exercise- III

1- B 2- B 3D 4 -C 5. A

6B 7C 8B 9A 10-B

11-C 12-B 13 B 14 B 15 D

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