KPS PU COLLEGE, ARSIKERE

Chapter 13
Kinetic theory of gases

The study of properties of gas assuming it to be made of molecules which are continuously in random
motion is the kinetic theory of gases
Avagadro’s hypothesis: Equal volumes of all gases under identical conditions of temperature and pressure
would contain equal number of molecules.
22.4L of any gas at STP (1 atm, 273K) contain 6.023 × 10 atoms/ molecules which is Avagadro number.
Avagadro number, 𝑁 = 6.023 × 10
Mole: One mole of any substance contains Avagadro number of atoms/ molecules.
Note: One gram atomic/ molecular mass of any substance contains Avagadro number of atoms/molecules.
∴ 1𝑔𝑟𝑎𝑚 𝑎𝑡𝑜𝑚𝑖𝑐/𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 = 1𝑚𝑜𝑙𝑒
Eg: Molecular mass of 𝑂 is 32. Then 32g of 𝑂 contains 6.023 × 10 molecules of 𝑂 .
Similarly atomic mass of He is 4. 4g of He contains 6.023 × 10 atoms of He
Relation between number of moles and mass of a substance:
𝑀
𝜇=
𝑀
𝜇 → 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑎 𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑐𝑒
𝑀 → 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑐𝑒
𝑀 → 𝑔𝑟𝑎𝑚 𝑎𝑡𝑜𝑚𝑖𝑐/𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑐𝑒
Relation between number of atoms/molecules and Avagadro number:
𝑁
𝜇=
𝑁
𝜇 → 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑎 𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑐𝑒
𝑁 → 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑒
𝑁 → 𝐴𝑣𝑎𝑔𝑎𝑑𝑟𝑜 𝑛𝑢𝑚𝑏𝑒𝑟

Gas laws:
Boyles law: At a constant temperature, the pressure of a given mass of gas is inversely proportional to its
volume.
1
𝑃∝ (𝑎𝑡 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑇)
𝑉
𝑃𝑉 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
Charles law: At a constant pressure, the volume of a given mass of gas is directly proportional to its
temperature.
𝑉∝𝑇 (𝑎𝑡 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑃)
𝑉
= 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑇

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Gay Lussac’s law: At a constant volume, the pressure of a given mass of gas is directly proportional to its
temperature.
𝑃∝𝑇 (𝑎𝑡 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑇)
𝑃
= 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑇
These laws are not obeyed by gases at all temperatures and pressure. They are obeyed by gases at high
temperature and low pressure.
Real gases: The gases we know like 𝐻 , 𝑂 , 𝑁 … do not obey the above laws at all temperature and
pressures. Hence they are called real gases
Ideal gas:
An ideal gas is a one which obeys the above laws at all temperatures and pressures.

Ideal gas equation:

An ideal gas is a one which obeys the above laws at all temperatures and pressures. Its equation of state is
𝑃𝑉 = 𝜇𝑅𝑇
𝑃 − 𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒
𝑉 − 𝑣𝑜𝑙𝑢𝑚𝑒
𝜇 − 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑔𝑎𝑠
𝑅 − 𝐺𝑎𝑠 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 = 8.314 𝐽𝐾 𝑚𝑜𝑙
𝑇 − 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒
Dalton’s law of partial pressures:
Statement: The total pressure of a mixture of ideal gases is the sum of partial pressures of each gas..
Explanation:
Consider a mixture 𝑛 non interacting ideal gases 1,2, … 𝑛 with number of moles µ , µ … µ in a container.
Then by equation the equation state

𝑃𝑉 = (µ + µ + ⋯ + µ )𝑅𝑇
µ 𝑅𝑇 µ 𝑅𝑇 µ 𝑅𝑇
𝑃= + +
𝑉 𝑉 𝑉
𝑃 = 𝑃 + 𝑃 + ⋯+ 𝑃
𝑤ℎ𝑒𝑟𝑒 𝑃 𝑖𝑠 𝑡𝑒 𝑝𝑎𝑟𝑡𝑖𝑎𝑙 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 𝑜𝑓 𝑔𝑎𝑠1, 𝑃 𝑖𝑠 𝑡𝑒 𝑝𝑎𝑟𝑡𝑖𝑎𝑙 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 𝑜𝑓 𝑔𝑎𝑠2 𝑎𝑛𝑑 𝑠𝑜 𝑜𝑛

Postulates or assumptions of kinetic theory of gases: (3 mark)

The kinetic theory of gases is based on the following postulates
i. The gas is a collection of large number of molecules which are perfectly elastic hard spheres
ii. The size of a molecule is negligible compared to the distance between the molecules.
iii. The molecules are always in random motion.
iv. During their motion, the molecules collide with each other and with the walls of the container
v. The collisions are elastic and hence the total kinetic energy and the total momentum of the
colliding molecules are same before and after collisions
vi. The kinetic energy of a molecule is proportional to the absolute temperature of the gas.
vii. There is no force of attraction or repulsion between molecules.

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Molecular speeds:
Molecules a gas are in random motion with different speeds. All molecules do not move with a same speed.
At a given temperature there is a distribution of molecular speeds. A graph plotted for number of molecules
and speed as shown below.

For statistical purposes we can define three types of molecular speeds.

Consider a gas having 𝑁 molecules. Let 𝑣 , 𝑣 , … 𝑣 their speeds at a given temperature T. Then
Most probable speed 𝒗𝒎𝒑 : The speed possessed by most of the molecules is called most probable speed.
Average speed 𝒗𝒂𝒗 : The average speed of all the molecules of a gas.
𝑣 + 𝑣 + ⋯+ 𝑣
𝑣 =
𝑁
Root mean square speed 𝒗𝒓𝒎𝒔 : Square root of mean of squares of the speeds of the molecules

𝑣 + 𝑣 + ⋯+ 𝑣
𝑣 =
𝑁

Derive the expression for pressure due to an ideal gas (5 mark)

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Consider an ideal gas enclosed in a cubical container with volume 𝑉 and area of face 𝐴 as shown.
Let mass each molecule be 𝑚, 𝑁 be the total number of molecules and 𝑛 be the number molecules per unit
volume.
If a molecule with velocity 𝑣 , 𝑣 , 𝑣 hits the planar wall parallel to 𝑦𝑧 plane it rebounds with velocity
−𝑣 , 𝑣 , 𝑣 . y and z components do not change but only the 𝑥 component reverses because the
collision is elastic.
The change in momentum of the molecule = −2𝑚𝑣
Then the momentum imparted to the wall = 2𝑚𝑣
where 𝑚 is the mass of each molecule.
Let 𝑛 be the number of molecules per unit volume of the group of molecules having 𝑥 component of
velocity 𝑣 .
To find number molecules from that group hitting the wall in a time ∆𝑡, consider the volume 𝑣 ∆𝑡𝐴
beside the wall.
Number of molecules in that volume having x component 𝑣 = 𝑛 𝑣 ∆𝑡𝐴
Then, the number of molecules hitting the wall in a time ∆𝑡 = 𝑛 𝑣 ∆𝑡𝐴
Only half of the molecules hit the wall because the other half of the molecules will be moving away from
the wall.
The total momentum transferred to the wall by these molecules is
1
𝑄 = 2𝑚𝑣 𝑛 𝑣 ∆𝑡𝐴
2
𝑄 = 𝑛 𝑚𝑣 𝐴∆𝑡
Force exerted by these molecules is
𝑄
𝐹 =
∆𝑡
𝑛 𝑚𝑣 𝐴∆𝑡
𝐹 =
∆𝑡
𝐹 = 𝑛 𝑚𝑣 𝐴
And Pressure exerted by these molecules is
𝐹
𝑃 =
𝐴
𝑛 𝑚𝑣 𝐴
𝑃 =
𝐴
𝑃 = 𝑛 𝑚𝑣
There are many such groups. Total pressure is obtained by adding the pressures due to all such groups.
Then the total pressure is
𝑃 = 𝑚𝑛(𝑣 )
(𝑣 ) → 𝑡ℎ𝑒 𝑎𝑣𝑒𝑟𝑎𝑔𝑒 𝑜𝑓 𝑣 𝑓𝑜𝑟 𝑎𝑙𝑙 𝑡ℎ𝑒 𝑔𝑟𝑜𝑢𝑝𝑠
𝑛 → 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠 𝑝𝑒𝑟 𝑢𝑛𝑖𝑡 𝑣𝑜𝑙𝑢𝑚𝑒
But mean square velocity is
𝑣 = (𝑣 ) + 𝑣 + (𝑣 )
𝑆𝑖𝑛𝑐𝑒 𝑡ℎ𝑒 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑚𝑜𝑡𝑖𝑜𝑛 𝑖𝑠 𝑟𝑎𝑛𝑑𝑜𝑚, (𝑣 ) = 𝑣 = (𝑣 )
∴𝑣 = (𝑣 ) + (𝑣 ) + (𝑣 )
∴𝑣 = 3(𝑣 )

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 1
(𝑣 ) = 𝑣
3
1
∴ 𝑃 = 𝑚𝑛𝑣
3
Different forms of the above equation:
𝑁
𝑊𝑒 𝑘𝑛𝑜𝑤 𝑛 =
𝑉
1 𝑚𝑁𝑣
∴𝑃=
3 𝑉
𝑁𝑚
𝑏𝑢𝑡 𝑑𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑔𝑎𝑠, 𝜌 =
𝑉
1
𝑃 = 𝜌𝑣
3

Kinetic interpretation of temperature:

Show that average kinetic energy of gas molecules is directly proportional to the absolute temperature
(3 mark)
1
𝑊𝑒 ℎ𝑎𝑣𝑒 𝑃 = 𝑚𝑛𝑣 → (1)
3
𝑛 − 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠 𝑝𝑒𝑟 𝑢𝑛𝑖𝑡 𝑣𝑜𝑙𝑢𝑚𝑒
The average kinetic energy of gas molecules is 𝐾𝐸 = 𝑚𝑣 → (2)
Altering (1)
2 1
𝑃 = 𝑛 𝑚𝑣
3 2
Substituting (2) in (1)
2
𝑃 = 𝑛𝐾𝐸
3
If 𝑉 is the volume of the container and 𝑁 is the total number of molecules in the container.
𝑁
𝑛=
𝑉
2𝑁
𝑃= 𝐾𝐸
3𝑉
2
𝑃𝑉 = 𝑁𝐾𝐸
3
3 𝑃𝑉
𝐾𝐸 =
2 𝑁
𝑏𝑢𝑡 𝑃𝑉 = 𝜇𝑅𝑇
3 𝜇𝑅𝑇
𝐾𝐸 =
2 𝑁
𝑁
𝑏𝑢𝑡 𝜇 =
𝑁
3 𝑁 𝑅𝑇
𝐾𝐸 =
2 𝑁 𝑁
3𝑅
𝐾𝐸 = 𝑇
2𝑁
𝑅
𝑏𝑢𝑡 𝐵𝑜𝑙𝑡𝑧𝑚𝑎𝑛𝑛 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡, 𝑘 = = 1.38 × 10 𝐽𝐾
𝑁
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 3
𝐾𝐸 = 𝑘 𝑇
2
𝐾𝐸 ∝ 𝑇
Mention the expression for average kinetic energy of a molecule of an ideal gas and explain the terms
3
𝐾𝐸 = 𝑘 𝑇
2
𝐾𝐸 − 𝑎𝑣𝑒𝑟𝑎𝑔𝑒 𝑘𝑖𝑛𝑒𝑡𝑖𝑐 𝑒𝑛𝑒𝑟𝑔𝑦
𝑘 − 𝐵𝑜𝑙𝑡𝑧𝑚𝑎𝑛𝑛 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑇 − 𝑎𝑏𝑠𝑜𝑙𝑢𝑡𝑒 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒
Different forms of ideal gas equation:
𝑃𝑉 = 𝜇𝑅𝑇 → (1)
𝑀
𝑏𝑢𝑡 𝜇 =
𝑀
𝑀
∴ 𝑃𝑉 = 𝑅𝑇 → (2)
𝑀
𝑁
𝐴𝑙𝑠𝑜 𝜇 =
𝑁
𝑁
𝑓𝑟𝑜𝑚 (1), 𝑃𝑉 = 𝑅𝑇
𝑁
𝑅
𝑏𝑢𝑡 =𝑘
𝑁
∴ 𝑃𝑉 = 𝑁𝑘 𝑇
1 𝑀
𝑓𝑟𝑜𝑚 (2)𝑃 = 𝑅𝑇
𝑀 𝑉
𝑀
𝑏𝑢𝑡𝜌 =
𝑉
𝜌𝑅𝑇
𝑃=
𝑀
𝑀 → 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑔𝑎𝑠
Other symbols have their usual meaning

Expressions of statistical molecular speeds on the basis of kinetic theory:

2𝑘 𝑇 2𝑅𝑇
𝑣 = =
𝑚 𝑀

8𝑘 𝑇 8𝑅𝑇
𝑣 = =
𝜋𝑚 𝜋𝑀

3𝑘 𝑇 3𝑅𝑇
𝑣 = =
𝑚 𝑀
𝑣 <𝑣 <𝑣

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Law of equipartition of energy:
Degrees of freedom 𝒇: The number of independent ways by which a molecule can possess energy of
translation, rotation and vibration.
Law of equipartition of energy: The total energy of a molecule is equally divided among the different
degrees of freedom.
Energy per degree of freedom:
1
𝑇ℎ𝑒 𝑎𝑣𝑒𝑟𝑎𝑔𝑒 𝑒𝑛𝑒𝑟𝑔𝑦 𝑝𝑒𝑟 𝑑𝑒𝑔𝑟𝑒𝑒 𝑜𝑓 𝑓𝑟𝑒𝑒𝑑𝑜𝑚 = 𝑘 𝑇
2
𝑘 − 𝐵𝑜𝑙𝑡𝑧𝑚𝑎𝑛𝑛 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
Expression for degrees of freedom 𝒇
𝑓 = 3𝑁 − 𝑘
𝑁 → 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓𝑎𝑡𝑜𝑚𝑠 𝑖𝑛 𝑡ℎ𝑒 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒
𝑘 → 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑐𝑜𝑛𝑠𝑡𝑟𝑎𝑖𝑛𝑡𝑠

Degrees of freedom and energy of a monoatomic gas molecule:

A monotomic molecule has 3 degrees of freedom. Eg He, Ne, Ar
By law of equipartition of energy its total energy is
1
𝐾𝐸 = 3 𝑘 𝑇
2
3
𝐾𝐸 = 𝑘 𝑇
2
Degrees of freedom and energy of a diatomic gas molecule:
Rigid diatomic molecule: Eg: H2 O2
A rigid diatomic gas molecule has 5 degrees of freedom.
By law of equipartition of energy its total energy is
1
𝐾𝐸 =5 𝑘 𝑇
2
5
𝐾𝐸 = 𝑘 𝑇
2
Non Rigid diatomic molecule: Eg: CO
A non rigid diatomic gas molecule has 7 degrees of freedom.
By law of equipartition of energy its total energy is
1
𝐾𝐸 = 7 𝑘 𝑇
2
7
𝐾𝐸 = 𝑘 𝑇
2
Triatomic molecules:
Linear triatomic molecule:
A linear triatomic molecule has 7 degrees of freedom.Eg CO2
By law of equipartition of energy its total energy is
1
𝐾𝐸 = 7 𝑘 𝑇
2
7
𝐾𝐸 = 𝑘 𝑇
2

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Non linear triatomic molecule:
Non linear triatomic molecule has 6 degrees of freedom. Eg O3
By law of equipartition of energy its total energy is
1
𝐾𝐸 = 6 𝑘 𝑇
2
𝐾𝐸 = 3𝑘 𝑇
Degrees of freedom and energy of a polyatomic gas molecule:
A polyatomic gas molecule has three degrees of freedom of translation, three degrees of freedom of rotation
and say 𝑓 modes of vibration. Each mode of vibration contributes two degrees of freedom (kinetic energy
and potential energy of vibration). So in total it has(𝟔 + 𝟐𝒇 ) degrees of freedom.
By law of equipartition of energy its total energy is
1
𝐸 = (6 + 2𝑓 ) 𝑘 𝑇
2
𝐸 = 3𝑘 𝑇 + 𝑓𝑘 𝑇
𝐸 = (3 + 𝑓)𝑘 𝑇

Specific heat capacity of gases:

Monoatomic gas:
Obtain the expression for total energy of one mole of monoatomic gas.
3
𝑇ℎ𝑒 𝐾𝐸 𝑜𝑓 𝑎 𝑠𝑖𝑛𝑔𝑙𝑒 𝑚𝑜𝑛𝑜𝑎𝑡𝑜𝑚𝑖𝑐 𝑔𝑎𝑠 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒 = 𝑘 𝑇
2
3
𝑇ℎ𝑒 𝑖𝑛𝑡𝑒𝑟𝑛𝑎𝑙 𝑒𝑛𝑒𝑟𝑔𝑦 𝑜𝑓 𝑜𝑛𝑒 𝑚𝑜𝑙𝑒 𝑜𝑓 𝑚𝑜𝑛𝑜𝑎𝑡𝑜𝑚𝑖𝑐 𝑔𝑎𝑠 ′𝑈′ = 𝑘 𝑇 × 𝑁
2
3
𝑈 = 𝑁𝑘 𝑇
2
𝑏𝑢𝑡, 𝑁 𝑘 = 𝑅
3
𝑈 = 𝑅𝑇
2
Obtain the expression for 𝜸 for ratio specific heats for a monoatomic gas.
The molar specific heat at a constant volume of a gas is
𝑑𝑈
𝐶 =
𝑑𝑇
3
𝑑 𝑅𝑇
𝐶 = 2
𝑑𝑇
3 𝑑𝑇
𝐶 = 𝑅
2 𝑑𝑇
3
𝐶 = 𝑅
2
𝑏𝑢𝑡 𝐶 − 𝐶 = 𝑅
3
𝐶 − 𝑅=𝑅
2
5
𝐶 = 𝑅
2
𝐶
𝛾=
𝐶

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 5
𝑅
𝛾=2
3
𝑅
2
5
𝛾=
3
Diatomic gas:
Rigid diatomic gas:
Obtain the expression for total energy of one mole of rigid diatomic gas.
5
𝑇ℎ𝑒 𝑒𝑛𝑒𝑟𝑔𝑦 𝑜𝑓 𝑎 𝑠𝑖𝑛𝑔𝑙𝑒 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒 = 𝑘 𝑇
2
5
𝑇ℎ𝑒 𝑒𝑛𝑒𝑟𝑔𝑦 𝑜𝑓 𝑜𝑛𝑒 𝑚𝑜𝑙𝑒 𝑜𝑓 𝑑𝑖𝑎𝑡𝑜𝑚𝑖𝑐 (𝑟𝑖𝑔𝑖𝑑) 𝑔𝑎𝑠 ′𝑈′ = 𝑘 𝑇×𝑁
2
5
𝑈 = 𝑁𝑘 𝑇
2
𝑏𝑢𝑡, 𝑁 𝑘 = 𝑅
5
𝑈 = 𝑅𝑇
2
Obtain the expression for 𝜸 for ratio specific heats for a rigid diatomic gas.
The molar specific heat at a constant volume of a gas is
𝑑𝑈
𝐶 =
𝑑𝑇
5
𝑑 2 𝑅𝑇
𝐶 =
𝑑𝑇
5 𝑑𝑇
𝐶 = 𝑅
2 𝑑𝑇
5
𝐶 = 𝑅
2
𝑏𝑢𝑡 𝐶 − 𝐶 = 𝑅
5
𝐶 − 𝑅=𝑅
2
7
𝐶 = 𝑅
2
𝐶
𝛾=
𝐶
7
𝑅
𝛾=2
5
2𝑅
7
𝛾=
5

Non Rigid Diatomic gas:

Obtain the expression for total energy of one mole of non rigid diatomic gas.
7
𝑇ℎ𝑒 𝑒𝑛𝑒𝑟𝑔𝑦 𝑜𝑓 𝑎 𝑠𝑖𝑛𝑔𝑙𝑒 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒 = 𝑘 𝑇
2
Page | 9
 7
𝑇ℎ𝑒 𝑒𝑛𝑒𝑟𝑔𝑦 𝑜𝑓 𝑜𝑛𝑒 𝑚𝑜𝑙𝑒 𝑜𝑓 𝑑𝑖𝑎𝑡𝑜𝑚𝑖𝑐 (𝑛𝑜𝑛 𝑟𝑖𝑔𝑖𝑑) 𝑔𝑎𝑠 ′𝑈′ = 𝑘 𝑇 × 𝑁
2
7
𝑈 = 𝑁𝑘 𝑇
2
𝑏𝑢𝑡, 𝑁 𝑘 = 𝑅
7
𝑈 = 𝑅𝑇
2
Obtain the expression for 𝜸 or ratio specific heats for a non rigid diatomic gas.
The molar specific heat at a constant volume of a gas is
𝑑𝑈
𝐶 =
𝑑𝑇
7
𝑑 2 𝑅𝑇
𝐶 =
𝑑𝑇
7 𝑑𝑇
𝐶 = 𝑅
2 𝑑𝑇
7
𝐶 = 𝑅
2
𝑏𝑢𝑡 𝐶 − 𝐶 = 𝑅
7
𝐶 − 𝑅=𝑅
2
9
𝐶 = 𝑅
2
𝐶
𝛾=
𝐶
9
𝑅
𝛾=2
5
𝑅
2
9
𝛾=
7
Linear triatomic gas:
Obtain the expression for total energy of one mole of a linear triatomic gas.
7
𝑇ℎ𝑒 𝐾𝐸 𝑜𝑓 𝑎 𝑠𝑖𝑛𝑔𝑙𝑒 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒 = 𝑘 𝑇
2
7
𝑇ℎ𝑒 𝑖𝑛𝑡𝑒𝑟𝑛𝑎𝑙 𝑒𝑛𝑒𝑟𝑔𝑦 𝑜𝑓 𝑜𝑛𝑒 𝑚𝑜𝑙𝑒 𝑜𝑓 𝑡𝑟𝑖𝑎𝑡𝑜𝑚𝑖𝑐 (𝑙𝑖𝑛𝑒𝑎𝑟) 𝑔𝑎𝑠 ′𝑈′ = 𝑘 𝑇 × 𝑁
2
7
𝑈 = 𝑁𝑘 𝑇
2
𝑏𝑢𝑡, 𝑁 𝑘 = 𝑅
7
𝑈 = 𝑅𝑇
2

Obtain the expression for 𝜸 or ratio specific heats for a linear triatomic gas.
The molar specific heat at a constant volume of a gas is
𝑑𝑈
𝐶 =
𝑑𝑇
Page | 10
 7
𝑑 𝑅𝑇
𝐶 = 2
𝑑𝑇
7 𝑑𝑇
𝐶 = 𝑅
2 𝑑𝑇
7
𝐶 = 𝑅
2
𝑏𝑢𝑡 𝐶 − 𝐶 = 𝑅
7
𝐶 − 𝑅=𝑅
2
9
𝐶 = 𝑅
2
𝐶
𝛾=
𝐶
9
𝑅
𝛾=2
5
𝑅
2
9
𝛾=
7
Polyatomic gas:
Obtain the expression for total energy of one mole of rigid diatomic gas.
𝑇ℎ𝑒 𝑒𝑛𝑒𝑟𝑔𝑦 𝑜𝑓 𝑎 𝑠𝑖𝑛𝑔𝑙𝑒 𝑝𝑜𝑙𝑦𝑎𝑡𝑜𝑚𝑖𝑐 𝑔𝑎𝑠 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒 = (3 + 𝑓)𝑘 𝑇
𝑇ℎ𝑒 𝑒𝑛𝑒𝑟𝑔𝑦 𝑜𝑓 𝑜𝑛𝑒 𝑚𝑜𝑙𝑒 𝑜𝑓 𝑝𝑜𝑙𝑦 𝑔𝑎𝑠 ′𝑈′ = (3 + 𝑓)𝑘 𝑇 × 𝑁
𝑈 = (3 + 𝑓)𝑁 𝑘 𝑇
𝑏𝑢𝑡 𝑁 𝑘 = 𝑅
𝑈 = (3 + 𝑓)𝑅𝑇

Obtain the expression for 𝜸 for ratio specific heats for a rigid diatomic gas.
The molar specific heat at a constant volume of a gas is
𝑑𝑈
𝐶 =
𝑑𝑇
𝑑(3 + 𝑓)𝑅𝑇
𝐶 =
𝑑𝑇
𝑑𝑇
𝐶 = (3 + 𝑓)𝑅
𝑑𝑇
𝐶 = (3 + 𝑓)𝑅
𝑏𝑢𝑡 𝐶 − 𝐶 = 𝑅
𝐶 − (3 + 𝑓)𝑅 = 𝑅
𝐶 = (4 + 𝑓)𝑅
𝐶
𝛾=
𝐶
(4 + 𝑓)𝑅
𝛾=
(3 + 𝑓)𝑅
(4 + 𝑓)
𝛾=
(3 + 𝑓)
Page | 11
Mean free path 𝝀:
In gases the molecules are always in random motion and they collide with each other and the walls of the
container.
The average distance travelled by a molecule between any two successive collisions is called mean free
path. It is given by
1
𝜆=
√2𝑛𝜋𝑑
𝑛 → 𝑛𝑢𝑚𝑏𝑒𝑟 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠 𝑝𝑒𝑟 𝑢𝑛𝑖𝑡 𝑣𝑜𝑙𝑢𝑚𝑒
𝑑 → 𝑑𝑖𝑎𝑚𝑒𝑡𝑒𝑟 𝑜𝑓 𝑡ℎ𝑒 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒
Miscellaneous:
Properties of thermal radiation:
i. A body at any temperature emits radiation of all possible wavelengths ranging from short to long.
ii. For a given temperature there is a particular wavelength which the body emits with maximum
energy in a given time.
iii. With increase in temperature, the wavelength corresponding to maximum energy shifts towards
lower wavelengths.
Deduce Meyer’s relation 𝑪𝑷 − 𝑪𝑽 = 𝑹
Consider one mole of ideal gas. Applying I law of thermodynamics
∆𝑄 = ∆𝑈 + 𝑃∆𝑉
If ∆𝑄 heat is absorbed by the gas at a constant volume then, ∆𝑉 = 0 & ∆𝑄 = ∆𝑈
∆𝑄
𝐶 =
∆𝑇
∆𝑈
𝐶 = → (1)
∆𝑇
Subscript v is dropped because internal energy is a function of temperature only.
If ∆𝑄 heat is absorbed by the gas at a constant pressure
∆𝑄
𝐶 =
∆𝑇
∆𝑈 + 𝑃∆𝑉
𝐶 =
∆𝑇
∆𝑈 ∆𝑉
𝐶 = +𝑃
∆𝑇 ∆𝑇
∆𝑈 ∆𝑉
𝐶 = +𝑃 → (2)
∆𝑇 ∆𝑇
𝑤𝑒 ℎ𝑎𝑣𝑒 𝑃𝑉 = 𝑅𝑇
Differentiating with respect to temperature at a constant pressure
∆𝑉
𝑃 = 𝑅 → (3)
∆𝑇
𝑆𝑢𝑏𝑠𝑡𝑖𝑡𝑢𝑡𝑖𝑛𝑔 𝑓𝑟𝑜𝑚 (3) & (1)𝑖𝑛 (2)
𝐶 =𝐶 +𝑅
𝐶 −𝐶 =𝑅

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