Module Code: PHY 1242

Properties of Matter and Thermodynamics

Academic year: 2021/2022
Year 1 Trimester 2
Combinations MPE, PCE &PGE
Module team: Dr Celestin Ntivuguruzwa
&
Mr. Theophile Musengimana
Tel: 0788305262 email: [email protected]

College of Education October 2022

Unit 11: Third law of
Thermodynamics
Unit outlines

11.1. Statement of the third law of thermodynamics

11.2. Consequences and applications of third law of

thermodynamics
Statement of third law of thermodynamics
In 1906, Nernst concluded from there that when one approach the absolute zero,
the value of entropy of any condensed substance tends toward some constant
value S 0 :
lim S  S 0 --- Nernst’s theorem.
T  0K

Afterwards, Planck completed that proposition in asserting that: S 0 0

Or lim S 0
T  OK

That is the reason why the third law of thermodynamics can be stated as follows:
As the temperature approaches absolute zero , the entropy of any system in
equilibrium involved in isothermal processes ceases to depend on
thermodynamic parameters of state and takes, at the limit a constant value, the
same for all systems, which can be assumed to be zero.
This statement is general because: first, it concerns any system in equilibrium; second, for T
tending towards zero (0K), the entropy does not depend on any parameter of the system.
According to the third law of thermodynamics,

lim = S T , x   S T , x  0  S 
T  OK 2 1
Or lim   0
T  OK x
 T

where x represents any thermodynamic parameter (for ex: p, V etc.)

The fact that entropy S 0 is constant when T tends towards 0K means that an isothermal
process occurring at T=OK is at the same time an isentropic process and therefore an adiabatic
process which is impossible to achieve.

Thus, according to the third law of thermodynamics the zero isotherm coincides with the zero
isentrope and the zero adiabat. From the third law of thermodynamics, it immediately follows
that it is impossible to attain the temperature 0K.
Third law of Thermodynamics

Nernst heat theorem: In the neighborhood of absolute zero, all reactions in a liquid or solid
in internal equilibrium take place with no change in entropy.

lim( S1  S 2 ) 0
T0
(consider e.g. a chemical reaction ) C
AB 

1 2
Albert Einstein Max Planck
Robert Milikan

Walther Nernst
Max von Laue

lim( S1  S 2 ) 0 Motivated by considering reactions in the limit of decreasing temperature

T0
Planck made further hypothesis known as the third law

Entropy of every solid or liquid substance in internal equilibrium at

absolute zero is itself zero
lim S 0
T0

Some consequences of the third law

T T
dT  dT 
Since S (V , T ) CV , S ( P, T ) CP finite at a given T
0
T 0
T
(*) Requires quantum mechanics to
lim CV lim CP 0 derive it in terms of statistical mechanics
T0 T0

 S   S 
From Nernst theorem lim( S1  S 2 ) 0 lim   lim   0
T  0 P T  0 V
T0
 T  T

 S   V   S   V  1  V 
With Maxwell relation      lim 
T  0 P
 lim   0 V lim   0
 P  T  T  P   T T  0  T  T T0 V
 T P
It is impossible to reach the absolute zero temperature
With a finite sequence of isothermal and adiabatic changes of pressure or
other variables like the magnetic field, e.g., in the case of adiabatic
T
demagnetization.
S P=P-P’ +P
P
isothermal T+Tad
compression
-Q
P’
adiabatic T
expansion
-P

T-Tad

T +Q
According to 3 law:
rd
S(T,P)=S(T,P’) for T=0
T
T=0 not achievable in a finite # of
compression and expansion steps
Gas compression refrigeration
Unit 12: Kinetic theory of gases
Unit outlines

12.1 Basic principles of the kinetic theory of gases

12.2 Fundamental equation of kinetic theory of ideal gases

12.3 Maxwell’s law on the distribution of molecules in an

ideal gas according to the velocities and energies of
thermal
12.1 Basic principles of the kinetic theory of gases

The kinetic theory of gases is the study of the composition and the physical
properties of gases based on statistical methods of research. Thus, it is part of
classical statistical physics.

Kinetic theory of gases is based on the principles of classical statistical physics. As

a system of particles it assumes:
• conservation laws of: energy, linear momentum, electric charge, numbers of
particles, etc.
• all the particles are distinguishable.
• all physical processes in the system occur in space and time in a continuous way.
• each particle of the system can have any coordinates and any components of
the velocity independently on the values of these parameters for other particles.
12.2 Fundamental equation of kinetic theory of
ideal gases

An ideal gas can be considered as a system constituted by balls

(molecules) in chaotic motion. The proper volume of
molecules should be negligible and molecules do not interact
at distance. Molecules are continuously in collision with other
molecules of the gas and with the walls of the container
exerting on them some pressure.
Thus, pressure is the macroscopic manifestation of thermal
motion of the gas molecules.
Maxwell has shown that in the case of an ideal gas, intermolecular collisions
do not influence the pressure exerted by molecules on the walls of the
container. Furthermore, Maxwell has shown that the gas pressure on the
walls does not depend on the nature of the material the walls are made of.

Let us consider a monatomic ideal gas in a container

Let consider some elementary surfaceS on the walls of the container and
calculate the pressure exerted by the gas on the surface.

S
A molecule moving perpendicularly to the surface transfer to
that surface a momentum:
m0 v   m0 v  2m0 v
Where m0 and v are the mass and the velocity of the molecule.

During the time interval t , the surfaceS will be attained by molecules

n S v t
where n is the concentration of molecules.

In reality molecules are moving toward the base of the cylinder under
different angles (and not only perpendicularly) and with different velocities
and the velocity of each molecule can change (in magnitude and direction)
at any collision. To simplify calculations, let us replace the chaotic motion of
molecules by the motion along three perpendicular axes.
1 1
In that way 3 molecules move along one axe and 6 move in one
direction and the other half move in opposite direction.

Therefore, the number of collisions of molecules moving in a given

direction to the surfaceS is:
1
n S t v
6
when molecules enter in collision with the surface, they transfer to that
surface a net momentum:

Thus, the gas exerts on the walls a pressure

1
or p  nm0 v 2
3

If the volume of the gas is V and the gas contain N molecules with speeds
v1 , v 2 , v3 ,..., v N , then we have to consider not the speed v but the
root-mean-square speed vq

N
1 v rms
vq 
N
v
i 1
2
i Often denoted as

1
Thus, we get: p  nm0 v q2 fundamental equation of kinetic theory of
3 gases for pressure.
N 1N
As n  , we get: p m0 v q2
V 3V
2
or 1 2 m 0 v q
pV  Nm0 v q2  N
3 3 2

On the other hand, we know that the total kinetic energy of the translational
motion of all the molecules of a gas is given by: 1
E  Nm 0 v q2
2
we can write: 2
pV  E
3
Let the total mass of the gas be m and m  Nm0

1 1
pV  Nm0vq2  mvq2
3 3
For one mole of a gas, m  M where M is the molar mass and Vm is the molar volume

1
we get: pVm  Mv q2
3
From the equation of state of an ideal gas (Clapeyron-Mendeleev
equation) pVm  RT

1
and therefore, we get: RT  Mvq2
3
3RT
Hence, v q 
M

Since M m0 N Awhere m0 is the mass of one molecule and N Ais the Avogadro
number, we get;
3RT 3kT
vq  
m0 N A m0
R
where k  is the Boltzmann’s constant.
NA
The average kinetic energy of translational motion of a molecule of an ideal gas
is: 2
E m0 v q 3 3
  0    kT or   0  kT
N 2 2 2

Thus, the average kinetic energy of translational motion of a molecule of an

ideal gas is proportional to the thermodynamic temperature.
3
From equation   0  kT, it follows that when T 0,   0 0
2
Thus, when temperature T reaches the value 0K, the translational motion of
ideal gas molecules ceases, and therefore the pressure equals zero.

Therefore, the thermodynamic temperature is the measure of the average

kinetic energy of translational motion of ideal gas molecules and equation
above gives the meaning of the temperature from the point of view of kinetic
theory.
12.3 Maxwell’s law on the distribution of
molecules in an ideal gas according to the
velocities and energies of thermal motion

The root-mean-square speed of a molecule in a ideal gas in

thermodynamic equilibrium state (at T=const) remains constant and is:

3kT 3RT
vq  or vq 
m0 M

This can be explained by the fact that in a gas in a thermodynamic

equilibrium state, some stationary distribution of molecules according to
the speeds and governed by a well defined statistical law takes place.
This law was theoretically established by Maxwell.

The law of Maxwell’s distribution is described by some function f v called

function of the distribution of molecules according to speeds.
If we divide the interval of molecule speeds into small intervals , then
to each small interval of speeds will correspond some number ofdv
molecules
dN v having a speed belonging to that interval.

The function f (v)determines the relative number of molecules dN (v) ,


whose speeds are in interval v, v  dv ,  N
i.e.
dN v  dN v 
 f v dv or f v  
N Ndv

Using the models of theory of probabilities,

Maxwell found that:

3
m0 v 2
 m0  2 2 
f v  4   v e 2 kT

 2 k T 
The distribution function f(v) depends on the mass m0 of molecules and
on a state parameter (the temperature T).


The function f(v) fulfils the normalization condition: f (v)dv 1

0

Maxwell’s distribution function f (v)

We call the most probable speed v p the speed corresponding to the
maximum of the distribution function of molecules.
df
This speed is obtained by solving the equation: 0
dv
which gives:

d  2  20kT 
2 2
mv mv
 m v 2
  0
 2v 1  0  e 2 kT 0
v e  
dv  
  2 kT 

The values v = 0 and v in equation correspond to the minimum values of

the distribution function f(v), whereas

2kT 2 RT
vp  
m0 M

is the most probable speed (i.e. the speed corresponding to the

maximum value of f (v) ).
When temperature increases, the maximum function of molecule
distribution according to speeds is displaced on the right (which means that
the most probable speed also increases) but the surface enclosed by the
curve and the speed axis remains constant (equal to 1).
This means that the maximum value of f (v) becomes more and more small
when temperature increases (see figure below)

f (v) for different temperatures

The arithmetic average speed v is defined as follows:
 
1
v  vdN (v)  vf v dv
N0 0

After integration, we get:

8kT 8 RT
v 
 m0 M

As we have seen above, 3RT

the root-mean-square speed is defined as: vq 
M
2kT 2 RT
and the most probable speed: vp  
m0 M

It is clear that: vq  v  v p
The distribution of molecules according to speeds can be written as:
3
m0 v 2
 m0  2 2 
dN v   Nf v dv  N .4   v e 2 kT
dv
 2kT 
We also write the distribution of molecules according to kinetic energy 
m0 v 2
Let us make a change of variables from v to 
2
2 1
we have: v and dv 2m0   d

m0 2

Then,
1 
2N 3 
dN    kT  
2 2
e kT
d  Nf  d

where dN  is the number of molecules having kinetic energy in

Interval  ,   d .
Therefore, the distribution function of molecules according to
energy of thermal motion is:
3 1 
2 
f    kT  
 2 2
e kT


The average kinetic energy   of one molecule of a monatomic ideal gas
is:
 3  3 
2  3
  f  d  kT  

2 2
e kT
d  kT
0  0
2

3
Thus,    kT
2

As it was expected, we have found the same result as the result

obtained above as the average energy of translational motion of the
molecule.
https://www.youtube.com/watch?v=SxfgHdfKjQA