Physics I

Kinetic Theory of Gases

Fundamental assumptions of the Kinetic Theory of gases (Clausius theory in 1860.)

i. A gas consists of minute particles called molecules for everyone chemical spaces
these are identical.
ii. The molecules are like perfectly rigid spheres like a steel ball bearing obey Newton’s
law of motion.
iii. There is no attraction or repulsion between two molecules. So they obey Newton’s
law.
iv. They have no potential energy but have only Kinetic Energy.
v. The size of a molecule is infinitesimally small.
vi. The molecules are very small dimensions

.
Charles law→ P constant. V ∝T
1
Boyle’s law →T constant. V∝
P
R →gram molecular gas constant ¿ 8.31 ×107 erg/mole /k
M Molecular weight∈gm
Avogadro’s no¿ N= =
m weight of a molecule.

2
¿
3.32×10−24
23
¿ 6.02 ×10 per gm molecule.

Boltzmann’s constant,

R
k=
N

8.31 ×107 −23

¿> k= 23
=1.38× 10 J /k
6.02× 10

Degrees of freedom: The total no. of independent coordinates needed to describe

completely the position and state/configuration of a dynamical system.

C p molar specific hea at constant pressure

υ= =
C v molar specific heat at constant volume
Expression for pressure exerted by a gas:

Consider certain quantity of gas confined in a cube of each side l . No. of molecules be n of
mass m of each. The molecules are moving at random with average speed c.

Consider the components of the velocity of a molecule c are u,v,w along x,y and z directions.

The component u is parallel to AB with in the wall ACED. So, no effect to other walls. Since,
u hits with the same momentum −mu .

The change of momentum per collision

¿ Original momentum−final momentum

¿ mu−(−mu)

¿ 2 mu

u
The distance between two opposite walls is l . Total no. of collisions per second is
l

change of momentum per collision

∴ Total change of momentum for u¿
total no of collision
2
u 2 mu
¿>2 mu × =
l l
2 2
2m v 2 mw
Similarly, , for v and w components.
l l

∴ Total change of momentum per molecule/second is

2 2 2
2m u 2 m v 2m w
+ +
l l l

2m 2 2 2
¿ (u +v +w )
l

2m 2
¿ c
l

There is n molecule. So, total change in momentum for all molecules

2m c 2
×n
l

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 2
2mn c
¿
l

Now, total pressure on the 6 walls of the cube is

2
6l × P P is the force per unit area

l 2 area of each wall

According to 2nd law of motion the impressed force is numerically equal to the rate of change
of momentum.
2
2mn c 2
=6 l × P
l
2
mnc
¿> P= 2
3l
2
1 mn c
∴ P= which is the required pressure exerted by gas molecules on the walls of
3 V
a cube/vessel.

C=
√ 3P
ρ
Where, P=
1
3V
mn c
2

M
ρ= , density of gas.
V

C=¿ root mean square

Example 16.1: Calculate the root mean square (r.m.s) velocity of the molecule of hydrogen,
oxygen and air at 0 ο C and at atm pressure.

Solution: We know,

1. C=
√ 3P
ρ
At NTP the density of H 2

¿>C=
√ 3× 76 ×13.6 × 981
0.000089
is ρ=0.000089 gm /cc

5
∴ C=1.84 ×10 cm/s Atmospheric pressure,
2
P=76 × 13.6 ×981 dyne / cm

2. C=
√ 3 × 76× 13.6 ×981
16× 0.000089
For oxygen then density

4
¿ 4.6 × 10 cm/s at NTP ρ=16 ×0.000089

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3. C=
√ 3 × 76× 13.6 ×981
0.001293
For air the density at NTP

¿ 4.850 ×10 4 cm/ s is ρ=0.001293 gm /cc

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Example 16.2: A kg-mole of H 2 occupies a volume of 22.4 m3 at NTP. Calculate the r.m.s
velocity of the molecules at NTP.

Solution:

1 2
PV = mn c M¿molecular weight
3

Again , PV =RT of H 2 in kg.

1
So, M c 2=RT R¿kg molecular gas constant
3

¿> c=
√ 3 RT
M
5
PV =RT

1.013× 10 × 22.4 PV
∴ R= ¿> R=
273 T
3
¿ 8310 J /kg−mole−K P=.76 × 13.6 ×9.8 ×10

∴ c=
√ 3 × 8310× 273
2
¿ 1.013 ×10 N /m
5 2

¿ 1845 m/s T=273 K

3
V =22.4 m

Example 16.6: Calculate the Kinetic Energy of H 2 / gm−molecule at 0 ο C .

[ R=8.3× 107 ergs/ gm−mol ]
Solution: We know,
1 2 3
M c = RT
2 2
3 7
¿ ×8.3 × 10 × 273
2
10
¿ 3.4 ×10 ergs

Example 16.7: Calculate the molecular Kinetic Energy of 1 gm of H 2 gas at 50ο C.

[ M =2 , R=8.3 × 107 ergs/ gm−molecule ]

Solution: For 1 gm molecule
1 3
M c2= RT T =50ο C=(273+50)
2 2
1 2 3 RT
¿> × 1× c = × ¿ 323 K
2 2 M
5

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 7
3 8.3 ×10 ×323
¿ ×
2 2
10
¿ 2.01 ×10 ergs.
Mean free path: According to kinetic theory between two consecutive collisions the
molecules move with constant speed along a straight line. This distance between any two
consecutive collisions is known as mean free path. The average distance between two
collisions is called mean free path .If S is the total distance travelled during N collisions then
S
¿ .
N

Expression for Mean free path:

Let n be the no. of molecules per unit volume of the gas. The no. of molecules lying within a
volume in the cylinder¿ π d 2 c n. So the no. of collisions made by the molecule A in one
1
second is also π d 2 c n. So one collision take place by 2 second. Time interval between
πd cn
1
two successive collisions is 2 second.
πd cn
So, distance travelled between two successive collisions =
1 1 m m
speed × time=c × 2 = 2 = 2 = 2 where m is the mass of a single
π d c n π d n π d mn π d ρ
molecule & ρ=mn is the density or total mass per unit volume.
A quantitative calculation taking into account the actual speed distribution of the molecules
gives mean relative speed c rel =√ 2c.

Hence the mean free path reduces to

c 1
= =
π d n √ 2 c √ 2 π d2 n
2

Ex. 16.17 Calculate the mean free path and collision frequency for air molecules at
0 ° C and 1 atm pressure. Given that the effective diameter of air molecule = 2Anstrom.
The r.m.s of air molecule at NTP is about 1 ×105 cm/s and the air molecules per cc
¿ 3 ×10 .
19

Solution
Using Maxwell’s relation the mean free path

1
¿
√2 π d 2 n

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 1
= −8 2 = 1.9 ×10−5
√2 ×3.14 × ( 2 ×10 ) ×3 × 10 19

c 1 ×105
The collision frequency is = = 5.2 ×109 / sec
❑ 1.9× 10−5
Thus on the average each molecule make 5.2 billion collisions per second.

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