Kinetic theory of gases – all derivations

Pressure due to an ideal gas

Consider a cubical chamber of edge length  containing an ideal gas as shown. Let number
of molecules per unit volume be n. Consider a molecule with velocity v with velocity
components vx, vy and vz.
Momentum of this molecule before hitting wall ABCD = mvx
Since the collisions of an idea gas (according to KTG) are
perfectly elastic so the momentum of the molecule after hitting the wall
is mv x (negative sign because direction is opposite now)

Therefore, change in momentum = mv x  mv x = 2mv x

So, momentum imparted to the wall = 2mv x .

Therefore, average momentum of that each molecule imparts to the wall is 2mv x

where v x is the average of velocity components of molecules in x direction

No of molecules that can hit the wall in time t is nv x t 2 , but since half of these molecules
are moving away from the wall. Therefore, number of molecules that will actually hit the wall
1
in time t is nv x t2 .
2

1
So, total momentum imparted to wall in time t is nv x t 2  2mv x  mnv 2x t2
2

mnv 2x t 2
Therefore, force exerted on the wall =  mnv 2x  2
t

Force mnv 2x  2
Therefore, pressure exerted by x component, Px =  mnv 2x  2   mnv 2x . Since
Area 2
the velocity of gas in all directions should be same due to its random motion, therefore,
v 2x  v 2y  v 2z

1
Since v 2  v x2  v 2y  v z2 so we get v 2  3v 2x  v 2x  v 2
3

1
Therefore, we get P = mnv 2 . Since mn = ρ (density of gas), therefore
3

1 2
P v
3
Law of equipartition of energy
For a system in thermal equilibrium, the total energy is equally distributed in all possible
1
energy modes, with each mode having an average energy equal to k B T , where kB is
2
Boltzman’s constant and T is the absolute temperature of the system.
Derivation of Cp, Cv and gamma
1
Thus, average energy available per molecule per degree of freedom = kBT
2
n
If gas has n degrees of freedom, then average energy available per molecule, u  kBT
2
R n R
 kB  where R is universal gas constant, therefore u  T
NA 2 NA

n R n
So, average energy per mole U  T  NA  RT
2 NA 2

Since
dQ = dU + PdV

At constant volume, dV = 0 and dQ  Cv dT

 dU  Cv dT
dU n dT
 Cv   R
dT 2 dT
nR
 Cv 
2
 Cp  Cv  R
nR n 
 Cp   R  R   1
2 2 

n 
R   1
Cp 2 
So, γ   
Cv nR
2
2
 γ  1
n

2 5
If the gas is monoatomic, then, n = 3, then γ  1  
3 3
 2 7
If the gas is diatomic, n = 5, then γ  1  
5 5

2 9
For triatomic gas linear molecule, n = 7 γ  1  
7 7

2 4
For triatomic non-linear molecule n = 6, γ  1  
6 3

Mean free path

It is the average distance travelled by a gas molecule between two successive collisions.

Consider a gas having n molecules per unit volume. Let the diameter of each molecule be d
and it is moving with velocity v. Now, it will hit only those molecules in time t whose centres
are within a distance d from the centre of this molecule.

So, number of molecules that this molecule will hit in time t = nπd2 vt

nπd2 vt
Therefore, number of collisions per unit time =  nπd2 v
t
1
So, average time between two collisions =
nπd2 v
Therefore, average distance between two collisions,
1
λ v
nπd2 v
1
 λ
nπd2

In this derivation we have assumed that other molecules are rest, which is not possible in
reality. The actual result is

1
λ
2nπd2
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