PHY-309: Thermal Physics

Books: Thermal Physics by: Garg, Bansal & Ghosh (1st Half)

Blundell (2nd Half)

Topics:
Kinetic Theory of Gases: Ideal Gases

 M.B. Distribution
 Expt. Verification

Transport Phenomenon

 Viscosity
 Thermal Conductivity
 Brownian Motion
 Random Walk

Real Gases

Thermodynamics

 Laws
 Free Energies, Thermodynamic Relations
 Production of Low Temperature

Lecture-0

Kinetic Theory of Gases

Basic Postulates
 NA molecules: identical hard spheres with point mass
 All directions are equivalent
 Elastic Collisions b/w molecules
 Free-space interactions: Ballistic motion- molecules move in straight line, no ext. forces
 Const. Density of Gas
 Gravity is negligible
 Velocity ranges from 0 to infinity
 Lecture-1

Maxwell Speed Distribution

Let us consider a closed system of N gas molecules in a volume V which follows the postulates of KTG
and thus if we take a small volume element dV, it’ll contain dNV no. of molecules.

Now, let us look at the setup from the velocity space. Each vector represents a molecule with velocity 𝑣⃗
and the no. of vectors within the shell of radius 𝑣⃗ and 𝑣⃗ + 𝑑𝑣⃗ represents the no. of molecules with
velocities between 𝑣⃗ and 𝑣⃗ + 𝑑𝑣⃗

Probability of molecules having x-velocities between vx and vx+dvx = = 𝑓(𝑣 )𝑑𝑣 = 𝑝 (lets say)

This is because as dvx increases, the fraction of molecules within that shell will increase. Similarly, we’ll
have 𝑝 and 𝑝 the same way.

Now, since velocities in all directions are independent, the total probability of getting a molecule in that
velocity space shell element = 𝑓(𝑣 )𝑓 𝑣 𝑓(𝑣 )𝑑𝑣 𝑑𝑣 𝑑𝑣

Therefore, the total no. of molecules in that volume element turns out to be

𝑑 𝑁 = 𝑁𝑓(𝑣 )𝑓 𝑣 𝑓(𝑣 )𝑑𝑣 𝑑𝑣 𝑑𝑣

Since density does not depend on direction of velocity and the Number Density is invariant in both the
position and velocity-spaces, we can say that

𝑁𝑓(𝑣 )𝑓 𝑣 𝑓(𝑣 ) = 𝑐𝑜𝑛𝑠𝑡

Also, because of Free-space interactions, another constraint is that the velocity of each molecule
remains constant. Therefore,

𝑣 = 𝑣 + 𝑣 + 𝑣 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡

Thus, from differentiating our constraints, we get the following two equations:
 𝑓 (𝑣 ) 𝑓 𝑣 𝑓 (𝑣 )
𝑑𝑣 + 𝑑𝑣 + 𝑑𝑣 = 0
𝑓(𝑣 ) 𝑓 𝑣 𝑓(𝑣 )

and

𝑣 𝑑𝑣 + 𝑣 𝑑𝑣 + 𝑣 𝑑𝑣 = 0

Now, using Lagrange Multipliers, we can combine the above eqn.s and write it as:

𝑓 (𝑣 ) 𝑓 𝑣 𝑓 (𝑣 )
+ 2𝐵𝑣 𝑑𝑣 + + 2𝐵𝑣 𝑑𝑣 + + 2𝐵𝑣 𝑑𝑣 = 0
𝑓(𝑣 ) 𝑓 𝑣 𝑓(𝑣 )

Since 𝑑𝑣 , 𝑑𝑣 , 𝑑𝑣 can be non-zero quantities, the only possible way for the above equation to be zero
is if each of the terms in brackets turn out to be zero. Therefore, for 𝑖 = {𝑥, 𝑦, 𝑧}
𝑓 (𝑣 )
+ 2𝐵𝑣 = 0
𝑓(𝑣 )
This implies

𝑓(𝑣 ) = 𝐴𝑒

No. of molecules having velocities between 𝑣 and 𝑣 + 𝑑𝑣 = 𝑁𝐴𝑒 𝑑𝑣

Total no. of molecules having velocity between 𝑣⃗ and 𝑣⃗ + 𝑑𝑣⃗ = 𝑁𝐴 𝑒 𝑑𝑣 𝑑𝑣 𝑑𝑣

Therefore, the no. density of molecules w.r.t velocity-volume element in the velocity space is

ρ = 𝑁𝐴 𝑒
Thus, the no. of molecules having speed between v and v+dv in a shell-volume element of the velocity-
space is

𝑑𝑁 = 4π𝑁𝐴 𝑣 𝑒 𝑑𝑣

Hence, the fraction of molecules having speed between v and v+dv can be defined as = 𝑓(𝑣)𝑑𝑣
where

𝑓(𝑣) = 4π𝐴 𝑣 𝑒
 Lecture-2

Now from the above speed distribution, we can say that

𝑑𝑁 = 𝑁 𝑓(𝑣)𝑑𝑣

Since we’ll consider the speed of the molecules range from 0 to infinity, ∫ 𝑑𝑁 over all possible
velocities will give us the total no. of molecules present in the closed system, i.e. 𝑁. Thus,

𝑁 = 4𝜋𝑁𝐴 𝑣 𝑒 𝑑𝑣

Solving the integral, we get the relation: 𝐴=

From our setup of the closed system in position-space, now if we

calculate the pressure on the shaded wall, i.e. the net pressure due to
the molecules colliding the wall while travelling in positive x-direction,
we can say
𝐹
𝑑𝑃 =
𝑑𝐴
is the pressure on a small area element on the wall.

Since all the collisions are considered elastic, therefore the change in momentum of the gas molecules
after collision with the wall in x-direction is

Δ𝑝 = 𝑚𝑣 − (−𝑚𝑣 ) = 2𝑚𝑣
Hence, the impulse imparted on the wall by the molecules is 𝐹 𝑑𝑡 . Or,

𝐹 𝑑𝑡 = 𝑛 𝑑𝑉Δ𝑝
Where 𝑛 is the number density of molecules having velocity between vx and vx+dvx and 𝑑𝑉 = (𝑑𝐴)𝑣 𝑑𝑡
is the volume associated with the cross-section of the small area element and the length travelled by it
just before collision, i.e. 𝑣 𝑑𝑡

From the above equation, substituting the variables, we get

𝑑𝑃 = 2𝑚𝑛 𝑣
and from our definition of 𝑛 , we can say that
𝑁𝑓(𝑣 )𝑑𝑣
𝑛 =
𝑉
where 𝑁𝑓(𝑣 )𝑑𝑣 is the total no. of molecules having velocity between v x and vx+dvx and 𝑉 is the total
volume of the closed system. Hence the net pressure on the shaded wall will be
2𝑚𝑁
𝑃 = 𝑓(𝑣 )𝑣 𝑑𝑣
𝑉

Or
2𝑚𝑁
𝑃 = 𝐴𝑒 𝑣 𝑑𝑣
𝑉

Calculating the integral and substituting the value of A from the above obtained relation, we get
𝑚𝑁
𝑃𝑉=
2𝐵
Since it’ll be the same result for 𝑃 and 𝑃 for their respective walls, we can take the pressure as P. So,
𝑚𝑁
𝑃𝑉 =
2𝐵
But from the ideal gas equation, we know that 𝑃𝑉 = 𝑁𝑘 𝑇 . Therefore,
𝑚
𝐵=
2𝑘 𝑇
Finally, the speed distribution function 𝑓(𝑣) turns out to be

𝑚
𝑓(𝑣) = 4π 𝑣 𝑒
2π𝑘 𝑇

AVERAGE, ROOT MEAN SQUARED AND

MAXIMUM SPEEDS

The average speed of the molecules can be calculated as

∫ v dN
⟨𝑣⟩ = = 𝑣𝑓(𝑣)𝑑𝑣
N

On calculating the integral by substituting the values, we

get

8𝑘 𝑇
⟨𝑣⟩ =
π𝑚

Similarly, the RMS velocity is

⟨v ⟩ = v f(v)dv
 3𝑘 𝑇
𝑣 =
𝑚

For the maximum speed/ most probable speed, from the graph, we observe that
𝑓 (𝑣 )=0

Or, from this above condition, we get

2𝑘 𝑇
𝑣 =
𝑚

Lecture-3

EXERCISE
Q. What is the most probable speed for N2 molecules at 300K?

SOLUTION

𝑣 = =

where R=8.314 J mol-1 K-1 is the gas constant

M is the molar mass of the molecule. M(N2) =28 g/mol = 0.028 kg/mol

Substituting the values, we get 𝑣 = 422𝑚/𝑠

Q. Find out the value of ⟨𝑣⟩ ×

SOLUTION

1 𝑚 2𝑚
= 4π 𝑣𝑒 𝑑𝑣 =
𝑣 2π𝑘 𝑇 π𝑘 𝑇

1 8𝑘 𝑇 2𝑚 4
⟨𝑣⟩ × = =
𝑣 π𝑚 π𝑘 𝑇 π

Q. Find the fraction of N2 molecules which exceed the speed of 1000 m/s at 300K.

SOLUTION Required Fraction = 4π ∫ 𝑣 𝑒 𝑑𝑣 (use Mathematica)

Q. Find the fraction of molecules that lie within 1% of the most probable speed.

SOLUTION Using the following formula

𝑑𝑁 𝑚
𝑅𝑒𝑞. 𝐹𝑟𝑎𝑐𝑡𝑖𝑜𝑛 = = 4π 𝑣 𝑒 𝑑𝑣
𝑁 2π𝑘 𝑇
we know that 𝑑𝑣 = 1.01𝑣 − 0.99𝑣 = 0.02𝑣

and 𝑣 = 𝑣 =

.
Substituting the values, we get the fraction as =0.0166
√

Lecture-4

EXPRESSION FOR PRESSURE

Let 𝑛 be the no. of molecules per unit volume. Therefore, the number of molecules having speed 𝑣 and
𝑣 + 𝑑𝑣 per unit volume can be written as 𝑛𝑓(𝑣)𝑑𝑣 if we consider the no. of molecules having speed 𝑣
and 𝑣 + 𝑑𝑣 as 𝑑𝑁 = 𝑓(𝑣)𝑑𝑣

Now since the molecules are travelling at different speeds randomly in all directions, we can consider
each of their velocity vectors making an angle θ with the axis perpendicular to the wall. Thus, in the
velocity-space, we can calculate the solid-angle for molecules travelling at θ and θ + 𝑑θ which turns out
to be

𝑑Ω = 2π𝑠𝑖𝑛(θ)𝑑θ
So, the fraction of molecules travelling at θ and θ + 𝑑θ is

= 𝑠𝑖𝑛(θ)𝑑θ

Therefore, the no. of molecules per unit volume travelling at

speed 𝑣 and 𝑣 + 𝑑𝑣 and at angles θ and θ + 𝑑θ is

𝑓(𝑣)𝑑𝑣 𝑠𝑖𝑛(θ)𝑑θ

Now, for calculating the no. of molecules hitting the wall, we

calculate the volume subtended by the molecules in 𝑑𝑡 time on
an area A on the wall which is 𝐴𝑣𝑑𝑡 𝑐𝑜𝑠(θ). Thus, the number of
molecules hitting the wall = 𝐴𝑣𝑑𝑡 𝑐𝑜𝑠(θ) 𝑓(𝑣)𝑑𝑣 𝑠𝑖𝑛(θ)𝑑θ
So, the number of molecules hitting the wall per unit area per unit time can be written as
𝑛
𝑣𝑐𝑜𝑠(θ) 𝑓(𝑣)𝑑𝑣 𝑠𝑖𝑛(θ)𝑑θ
2
Change in momentum for each molecule= 2𝑚𝑣𝑐𝑜𝑠(θ) 𝑣𝑑𝑡

Pressure= 𝑃 = 𝑚𝑛 ∫ 𝑠𝑖𝑛(θ)𝑐𝑜𝑠 (θ)𝑑θ ∫ 𝑣 𝑓(𝑣)𝑑𝑣 = 𝑛𝑘 𝑇

Or 𝑃𝑉 = 𝑁𝑘 𝑇

Experiment for validating Maxwell Distribution

Zartman and Ko

In the experiment, the cylinder is rotated at a constant angular velocity and the Bismuth/Silver
molecules enter the cylinder via a slit and deposit on the plate. The deposit on the plate verifies
the Maxwell Distribution of molecular speeds. For more information regarding the Analysis of the
Experiment, you can refer to Appendix I of “Thermal Physics by Garg, Bansal and Ghosh”.
 Lecture-5

DEGREES OF FREEDOM FOR GAS MOLECULES

Classical Mechanics Defn: No. of independent co-ordinates.

Thermodynamic Defn: No. of quadratic terms in the energy expression.

Example: A free point mass in 3D has 3 degrees of freedom

1
𝐸 = 𝑚 𝑣 +𝑣 +𝑣
2
Equipartition Theorem: At a finite temperature T, energy per molecule per DOF = 𝑘 𝑇

From the following velocity distribution formula

𝑓(𝑣 )𝑑𝑣 = 𝐴𝑒 𝑑𝑣

Where 𝐴 = and 𝐵 =

Average Kinetic Energy along a specific direction = ϵ = ∫ 𝑣 𝑓(𝑣 )𝑑𝑣 = 𝑘 𝑇

Now we can say that the number of molecules having speeds 𝑣 and 𝑣 + 𝑑𝑣 will also be the number of
molecules having energy 𝐸 and 𝐸 + 𝑑𝐸 (let’s say NE) where 𝐸 = 𝑚𝑣

This implies that 𝑑𝐸 = 𝑚𝑣𝑑𝑣 or 𝑑𝑣 = (2𝑚𝐸) 𝑑𝐸

Thus 𝑑𝑁 = 𝑑𝑁 = 4πN 𝑣 𝑒 𝑑𝑣

Or 𝑑𝑁 = 2𝑁 𝑒 𝑑𝐸

Therefore, the average kinetic energy of a free point mass can be written as

∫ 𝐸𝑑𝑁 3
ϵ= = 𝑘 𝑇
∫ 𝑑𝑁 2
 DIATOMIC RIGID MOLECULES

As it can be seen in the diagram, the molecule can

perform translational motion in all 3 co-ordinates while
it can rotate about the x and y axes. The rotation about
the z-axis is negligible because the atoms can be thought
of as point masses. Therefore, the moment of inertia is
negligible and thus it can be assumed that it does not
contribute to the total energy expression. The total
energy of this system is
1 𝑚 𝑚 1
𝐸 =𝐸 +𝐸 = (𝑥̇ + 𝑦̇ + 𝑧̇ ) + 𝐼 ω + ω
2𝑚 + 𝑚 2

Therefore, from the thermodynamic definition of DOF, we can say ϵ = 𝑘 𝑇

The total energy of the spring-block system can be written as

1 1
𝐸 = 𝑚𝑥̇ + 𝑘𝑥
2 2
We will take the DOF according to the thermodynamic definition as it
considers the internal energy of the system which is technically the spring in this system. Thus, this
system has 2 DOFs. 𝜖̅ = 𝑘 𝑇

MIXING OF GASES

If an isolated container with two chambers has monoatomic gases such that one of them have n 1
molecules kept at T1 temperature while the other has n2 molecules kept at T2 temperature, the final
temperature T of the container after they are allowed to mix can be calculated using the conservation of
energy as following:
3 3 3
𝑛 𝑘 𝑇 + 𝑛 𝑘 𝑇 = (𝑛 + 𝑛 )𝑘 𝑇
2 2 2
Or
𝑛 𝑇 +𝑛 𝑇
𝑇=
𝑛 +𝑛
 Lecture-6

HEAT CAPACITY OF IDEAL GAS

For an ideal gas 𝑈 = 𝐾𝐸 = 𝑁 𝑘 𝑇 where 𝑓 is the DOF

Therefore, 𝐶 = = 𝑅

From the experimental data of

the CV vs T graph for the H2
molecule, we understand that
for the equipartition theorem to
be true, all the modes have to
be activated.

<100K: Monoatomic behavior

200-1000K: Diatomic behavior

It approaches 𝑅 when it reaches

its dissociation temperature.

MEAN FREE PATH

The mean free path λ of a molecule can be defined as the
total distance travelled by the molecule by the total number
of collisions in its path.
∑ λ
λ=
𝑁
where λ is the distance travelled between successive
collisions and N is the total number of collisions. Therefore,
if the molecule moves at 𝑣̅ between each of its collisions
∑𝑡
λ = 𝑣̅ = 𝑣̅ τ
𝑁
where τ is the mean time between successive collisions.

Now let’s say we have dNi number of molecules with mean free path between xi and xi+dxi

∑ 𝑥 𝑑𝑁 1
λ= = 𝑥𝑑𝑁
∑ 𝑑𝑁 𝑁

where No is the total number of molecules. Since λ ≪ 𝐿, we can rewrite the above equation as
1
λ= 𝑥𝑑𝑁
𝑁
To calculate the integral, we need to write N as a function of x. So, we can say that the number of
molecules that have not undergone any collision can be written as

𝑁 = 𝑁 𝑓(𝑥)
where f(x) is the probability that a molecule travels a distance x without collision.

Considering the linear probability density that the molecule suffers a collision within x and x+dx as p x

Thus, the probability that the molecule travels x+dx without any collision is

𝑓(𝑥 + 𝑑𝑥) = 𝑓(𝑥)(1 − 𝑝 𝑑𝑥)

Rearranging the above equation, we get

𝑓 (𝑥) = −𝑝 𝑓(𝑥)
Or

𝑓(𝑥) = 𝐴𝑒
In the above equation, we can put the boundary condition that if the molecule remains at rest, it does
not suffer collision, i.e. the probability that the molecule travels x=0 without collision is 1. Therefore, we
get 𝐴 = 1

So, we get the number of molecules that have not undergone any collision as

𝑁=𝑁 𝑒
Therefore,
1
λ= 𝑥𝑒 𝑑𝑥 =
𝑝

Similarly, if we consider 𝑝 𝑑𝑡 as the probability of collision within t and t+dt, we can perform similar
calculations to show that
1
τ=
𝑝
Therefore, we can write the survival equation as

𝑁(𝑥) = 𝑁 𝑒 𝑁(𝑡) = 𝑁 𝑒
 Lecture-7

COLLISION CROSS-SECTION
From the figure, we observe that collision between two molecules
occurs only when the center-to-center distance (d) between the two
molecules in their respective paths of motion is less than the sum of
their radii. Therefore, the maximum possible distance required for both
the molecules to collide in their respective paths is

𝑑 = 𝑑 +𝑑
The cross-sectional area of the circle with d as the radius is defined as
the Collision Cross-Section(σ)

σ = π𝑑

Expression for Mean Free Path

Zeroth Order Approximation: (One molecule in motion)
Here, the assumption is that we only have one molecule travelling among the sea of molecules which
are at rest and thus the relative velocity of that molecule with respect to all other molecules is v. Note
that it is a purely hypothetical situation.

Now, the mean time taken between two successive collisions is τ if the molecule is moving at average
velocity 𝑣̅
∑𝑡
τ=
𝑁
where N is the total number of collisions in the path of the molecule. Therefore, the collision frequency
𝑃 of each molecule can be defined as the total number of collisions by total time taken. Or,
1
𝑃 =
τ
Thus, we can say that the number of
collisions by one molecule per unit time is
equal to the number of molecules present in
the volume travelled by that molecule in
unit time with the collision cross-section. Or,

𝑃 = 𝑛σ𝑣

Therefore,
 τ= λ=

Since as the zeroth approximation, we consider the molecule to be moving at the average velocity, or
𝒗 = 𝒗 , therefore,
1
λ=
𝑛σ
The quantity 𝑛σ is called the macroscopic collision cross-section. Now, using the ideal gas equation

𝑃 = 𝑛𝑘 𝑇
The mean free path can be written as:
𝑘 𝑇
λ=
σ𝑃
First Order Approximation: (All molecules in motion)
For a system with all molecules in motion, we can
simplify the problem approximating that all molecules
travel at same speed (the average speed) but in
different directions. Thus, this can be reduced to the
Zeroth approximation by taking a two-molecule system,
stating that we can choose the reference frame of one of the molecules where it is at rest and say that it
is equivalent to the system where the other molecule is the only one moving at the relative velocity. The
average number of collisions per unit time for that molecule now depends on the average relative
velocity of it with respect to all other molecules with velocities in all directions. Or,

𝑃 = 𝑛σ𝑣

Now, 𝑣 = 𝑣 + 𝑣 − 2𝑣 𝑣 𝑐𝑜𝑠(θ) where θ is the angle between the velocity vectors

Since 𝑣 = 𝑣 = 𝑣̅ , the above equation can be written as

θ
𝑣 = 2𝑣̅ 𝑠𝑖𝑛
2
Since the relative velocity vectors are of same
magnitude but are aligned in different
directions, the average relative velocity can
be calculated with respect to the solid angle
of a sphere as follows:
1
𝑣 = 𝑣 dω
4π

𝑣 = ∫ 𝑠𝑖𝑛(θ)𝑠𝑖𝑛 𝑑θ ∫ 𝑑ϕ

Or 𝑣 = 𝑣̅
Therefore, in the equation of the mean free path above, substituting the value of 𝑣 , we get

λ= or λ=

Approximation using the Maxwell Distribution:

In practice, we generally use Maxwell Distribution to find the average relative velocity. However, we’ll
be skipping the proof here as it’s quite lengthy and tedious. For the present purpose, it’ll be sufficient to
quote the result. For those interested in the proof, please refer to Appendix II of “Thermal Physics by
Garg, Bansal and Ghosh”

λ= λ=
√ √

EXPERIMENTAL DETERMINATION OF 𝛌 (Born)

Pump Quarter Plates

P gauge

P4

P3 P4 P3

P2

P1

Heated Silver P2 P1

If at extreme vacuum, d10 is the density of deposit on P1 and similarly if d20 is the density of deposit on P2
then after the change of pressure at a certain temperature, using the survival equation, we can write the
density of deposit on each plate as

𝑑 =𝑑 𝑒

𝑑 =𝑑 𝑒
Where x1 and x2 are the distances from the heated silver to the plates P 1 and P2 respectively. Or,
𝑥 −𝑥
λ=
𝑑 𝑑
𝑙𝑛 −
𝑑 𝑑
Where 𝑥 − 𝑥 is the distance between the two plates and from the experiment, we observe that the
value of 𝑃λ is nearly constant at a certain temperature for the same molecule.
 Lecture-8

TRANSPORT PHENOMENA
PROPERTIES TRANSPORTED PROCESS
MATTER DIFFUSION
ENERGY THERMAL CONDUCTIVITY
LINEAR MOMENTUM VISCOSITY

The amount of a quantity passing per unit area per unit time through a certain cross-section is defined
as the flux and here, we’ll mainly focus on the transport phenomena of quantities caused due the spatial
gradient of their respective properties. Therefore,
𝑑
𝐹𝑙𝑢𝑥 = −α (𝑃𝑟𝑜𝑝𝑒𝑟𝑡𝑦)
𝑑𝑥

VISCOSITY (TRANSPORT OF LINEAR MOMENTUM)