Kinetic Theory of Gases

Six Postulates of the Kinetic

Theory of Gases

A scientific postulate is a statement

assumed to be true unless proven
otherwise
1. A gas consists of very small particles,
each of which has a mass.

2. The distances separating gas

particles are relatively large.

The volume of the gas particles is assumed to be

zero because it is negligible compared with the
total volume in which the gas is contained.
3. Gas particles are in constant, rapid,
random motion.

Gases immediately fill a container and

quickly diffuse from one area to another.
4. Collisions of gas particles with
each other or with the walls of the
container are perfectly elastic.

Unlike “bouncing balls,” no energy of

motion is lost.
5. All energies of a molecule are kinetic
energy. Kinetic energy of a molecule
depends on the temperature only.
6. Gas particles exert no force on one
another. Attractive forces between
gas particles is assumed to be zero.

Gas particles do not slow down and condense into a liquid

because they exert only very weak attractive forces upon
each other.

Gas molecules don’t interact with one another.

Depending on the gas, this can be good or bad

assumption. H2O vapor has much stronger intermolecular
interactions than He.
Pressure of a Gas

The pressure that a gas exerts is

caused by the collisions of its
molecules with the walls of the
container.

8
A gas particle is shown
colliding elastically with
the right wall of the
container and
rebounding from it.

9
Force along X-direction due to one molecule

(final momentum-initial momentum)

Fx1= ---------------------------------------------
time between two successive collisions

mv x1  (mvx1 )
 Fx1 
2 L / v x1
2
mv x1

L
Force along X-direction due to all n molecule

2 2 2 2
m(v x1  v x 2  v x 3  ..........  v xn )
 Fx 
L
2
nmv x

L

where
2 2 2 2 2
nv x  v x1  v x 2  v x 3  ............  v xn
Similarly, Force along Y-direction due
to all n molecule

2
nmvY
 FY 
L
And force along Z-direction due
to all n molecule
2
nmvZ
 FZ 
L
Average force

2
nmvrms
F 
3L
Where

2 2 2
vrms  vx  vY  vZ
Average pressure

F
P  2
L
2
nmvrms
 3
3L
 nm= M, mass of the gas and
L3= V, volume of the gas

2
Mvrms
P 
3V

**Speed of air molecules at NTP.

(density = 0.00129gm/cc)
 Kinetic Energy and Temperature

We have from the kinetic theory of gas

2
Mvrms
P
3V
Rewrite this equation

2
Mvrms
PV  .............(1)
3
We have equation of state

 PV  RT .............(2)
n=1 mol. gas

From equs. (1) and (2)

2
Mvrms
 RT ...........(3)
3
 1 2 3
Mvrms  RT
2 2
3
KE  RT ............(4)
2
In equation (4) average kinetic energy of
a gas is directly proportional to the
absolute temperature of the gas.
 Degrees of Freedom

In general, a degree of freedom refers to

an independent means (Coordinates)
by which a molecule can possess energy.
Equipartition of Energy: When Rotational modes
a system is in thermodynamic
equilibrium, the average energy
per molecule is ½ kT per
degree of freedom.

Translational modes
Vibrational modes
 Theorem of Equipartition of Energy

Each degree of freedom contributes

½kBT to the energy of a system, where
possible degrees of freedom are those
associated with translation, rotation
and vibration of molecules.
From kinetic theory of gas

1 2 3
Mvrms  RT
2 2
1 2 3
nmvrms  RT
2 2 n= 1 mol. Gas and no.
1 2 3 of molecules in 1 mol.
Nmvrms  RT
2 2 Is N
1 2 3R 3
mvrms  T k BT R/N = kB
2 2N 2
1 2 1 2 2 2 3
mvrms  m(v x  vY  vZ )  k BT
2 2 2
If vx, vY and vZ are all equivalent

1 2 1 2 1 2 3
m3v x  m3v y  m3vZ  k BT
2 2 2 2
So, That

1 2 1
mv x  k BT
2 2
1 2 1
mvY  k BT
2 2
1 2 1
mvZ  k BT
2 2
Ex. At what temperature will rms
velocity of hydrogen be double of its
value at NTP?

Ex. At what temperature the malecular

rms velocity of oxygen will become half
That of NTP?
Ex. Calculate total random kinetic energy
of one gm. Mol. of oxygen at 100C.

Ex. Calculate average kinetic energy of

one molecule of hydrogen at 27C.