UNIT-IX

KINETIC THEORY OF GASES

Concept Map

Kinetic Theory of gases

I3RT _ I3PV
1. vrms= Jf 3. Vrms=
>/ M
~~
M

2. E= |RT 4. V ctVf

Law of Equipartion of Energy

Mean free Path
\ mvx2=i mvy2 1
x = V2"nTTd2
= jmF2=2 =ikBT P=- PC2
3

50

r 1
 GIST
Boyle’s Law: At constant temperature volume of given mass of gas is inversely
proportional to its pressure.
1
Va —P or PV = constant
Charle’s Law: At constant pressure volume of a given mass of gas is directly
proportional to its absolute temperature.
V
V a T or —
T
= constant
*For 1° rise in temp.

v'=v°<1+ÿi?)
Gay Lussac’sLaw:At constant volume, pressure of a given mass of gas is directly
proportional to its absolute temp.

= constant.
For 1°C rise in temperature Pt= P0(l + 273 15)
Ideal Gas Equation: for n mole of gas

PV=nRT,

for 1 mole , PV=RT

Universal gas constant: R = 8.31 J mol'V"1

Boltzmann constant:!ÿ = —where
NA
ke = Boltzmann constant,ÿ = Avogadro’s

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no.

Ideal gas: A gas which obeys gas law strictly is an ideal or perfect gas. The
molecules of such a gas are of r*"*1 force of attraction between
them.

Assumptions of Kinetic Theory of Gases

1. All gases consist of molecules which are rigid, elastic spheres identical in all
respect for a given gas.

2. The size of a molecule is negligible as compared with the average distance

between two molecules.

3. During the random motion, the molecules collide with one another and
with the wall of the vessel. The collisions are almost instantaneous.

4. The molecular density remains uniform throughout the gas.

5. The collisions are perfectly elastic in nature and there are no forces of
attraction or repulsion between them.

Pressure exerted by gas:

1
P=-
3 V 3H 3

Where: n=no. of molecules per unit volume.

m=mass of each molecule.

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 V2 =mean of square speed.

V = Volume

M = mass of gas

Average Kinetic energy of a gas: If M is molecular mass and V is molecular volume

and m is mass of each molecule. Then

1. Mean K.E per mole of a gas,

E =
1 — = -PV = - RT = — KB NAT
—2 Mv2
3 3 3
2 2 2
2. Mean K.E per molecule of a gas,

E=±mv2 = ikBT
3. K.E of lgram of gas,

-mv2
2 = —
3 RT
M0 gram molecular weight

Avogadro Law: Equal volumeof all gases under similar condition of temp, and
pressure contain equal number of molecules.

Avogadro Number:

NA =6.0225 x 1023mor1
Graham's Law of diffusion:

n \P2
r2 Pi
r = rate of diffusion

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 P = density
Delton’s law of partial pressure: Total pressure exerted by a mixture of non¬
reacting gases occupying a given volume is equal to the sum of partial pressures
which gas would exert if it alone occupied the same volume atgiven temp.

P = P1+P2+P3+
Vi+V2+V3 + ...+Vn
Average Speed :-V — n

8 kbT 8RT
V=
nm 7TMO
Root mean square:

V
v rms
v?+vf+- + vg
11

3KbT 3RT 3PV

Vr ms m M M

Most probable speed:

12RT _
Relation between :v,vrms&vmp
— J 2KbT
m
/ 2PV
-y] M

v = 0.92v
vrms : v : V mp
s 1 vmp - 0.816v
= 1.73 : 1.6 : 1.41
s

Therefore:
Vrms > V > Vmp
Degree of freedom:

254
 f = 3N-k
where , f= no. of degree of freedom.
N = no. of of atoms in a molecule, k = no. of independent relation between the
atoms.
1. Monoatomic gas - 2 degree of freedom.

2. Diatomic gas - 5 degree of freedom.

Law of equipartion of energy: For any thermodynamical system in thermal

equilibrium, the energy of the system is equally divided amongst its various degree
of freedom and energy associated with each degree of freedom corresponding to

each molecule is T , where KBis the Boltzmann’s constant and T is

absolute temperature.

> The law of equipartition of energy holds good for all degrees of freedom
whether translational , rotational or vibrational.
> A monoatomic gas molecule has only translational kinetic energy
Et=1/2mVx2 + 1/2mVy2 + 1/2mVz2 = 3/2KBT
So a monoatomic gas molecule has only three (translational) degrees of
freedom.

> In addition to translational kinetic energy, a diatomic molecule has two

rotational
Kinetic energies

Et +Er = 1/2mVx2 + 1/2mVy2 + 1/2mVz2 + 1/2lYWy2 + 1/2IZWZ2

O-O
Here the line joining the two atoms has been taken as x-axis about which there is
no rotation. So, the degree of freedom of a diatomic molecule is 5, it does not
vibrate.

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At very high temperature, vibration is also activated due to which two extra degree
of freedom emerge from vibrational energy. Hence at very high temperature degree
of freedom of diatomic molecule is seven.

*(Each translational and rotational degree of freedom corresponds to one mole of

absorption of energy and has energy 1/2kBT).

Internal Energies & specific heats of monoatomic, diatomic& polyatomic

gases:

1. If ‘f is degree of freedom then for a gas of polyatomic molecules energy

associated with 1 mole of gas,

f f
U =-
2
RT , Cv =-R
2

Cp= (1 + £) R, Y = Cv = 1+ T
f

2. For a monoatomic gas f=3,

3 3
U = 2RT ' Cv = —
2
R

5
CP ~
2 Y = 1.66
3. For a diatomic gas with no vibrational mode f=5, so
5 5
U = — R.T , Cv = -R
2

7
Cp -
2
R. y = 1.4
4. For a diatomic gas with vibrational mode f=7, so
7 7
U = 2
RT ’ GV = 2R

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 Cp= \ R ,y = 1.28
Meanfree path: It is the average distance covered by a molecule between two
successive collisions. It is given by,

1
A = ypZinnd2)
Where, n is no. density and ‘d’ is diameter of the molecule.

Brownian Equation :-The zig-zag motion of gas molecules is Brownian motion

which occurs due to random collision of molecules.

(1 Marks Question)

1. What type of motion is associated with the molecules of a gas?

Ans:- Brownian motion.

2. On which factors does the average kinetic energy of gas molecules depend?

Ans:- The average K.E. of a gas molecule depends only on the absolute temperature of
the gas and is directly proportional to it.

3. Why do the gases at low temperature and high pressure, show large deviations from
ideal behaviour?

Ans:- At low temperature and high pressure , the intermolecular attractions become
appreciable. So, the volume occupied by the gas molecules cannot be neglected in
comparison to the volume of the gas. Hence the real gases show large from ideal gas
behaviour.

4. Following fig. shows the variation of the product PV with respect to the pressure (P)
of given masses of three gases, A,B,C. The temperature is kept constant. State with
proper arguments which of these gases is ideal.

257
 B

t A
PV
C

Ans:- Gas ‘C’ is ideal because PV is constant for it. That is gas ‘C’ obeys Boyle’s law
at all pressures.
5. When a gas is heated, its temperature increases. Explain it on the basis of
kinetic theory of gases.

Ans:- When a gas is heated, the root mean square velocity of its molecules
increases. As VrmsaVT so temperature of the gas increases.

6. The ratio of vapour densities of two gases at the same temperature is 8:9.
Compare the rms. velocity of their molecules?

Ans
(Firms)1 |M2= fp2 _ f9 = 3 : 2A/2
(Vrms) 2 V Ml y/A V 8
7. Cooking gas containers are kept in a lorry moving with uniform speed. What will
be the effect on temperature of the gas molecules?

Ans:- As the lorry is moving with a uniform speed, there will be no change in the
translational motion or K.E. of the gas molecules. Hence the temperature of the gas
will remain same.

8. What is the mean translational kinetic energy of a perfect gas molecule at

temperature T?

Ans:- A perfect gas molecule has only translational K.E.

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 E = 3/2 kBT

9. Name two factors on which the degrees of freedom of a gas depend?

Ans:- (i) Atomicity of the gas molecule.

(ii) Shape of the molecule.

(iii) Temperature of gas.

10. Define absolute zero, according to kinetic interpretation of temperature?

Ans:- Absolute zero is the temperature at which all molecular motion ceases.

(2 Marks question)
1. Write the relation between the pressure and kinetic energy per unit volume of a
gas. Water solidifies into ice at 273 K. What happens to the K.E. of water
molecules?

Ans:- P = 2/3 E. The K.E. of water molecules gas partly converted into the binding
energy of the ice.

2. The absolute temperature of a gas is increased 4 times its original value. What
will be the change in r.m.s. velocity of its molecules?

Ans:-Vrms« VT
V rms CL V 4T

V rms/ Vrms =2
v’rms= 2Vrms

Change in rms velocity of molecules = Vms - Vrms

= V rms
3.What will be the ratio of the root mean square speeds of the molecules of an ideal
gas at 270K and 30K?

259
 '270 3:1
Ans :-Vrms/ Vrms = -ÿr 30
=

4.A mixture of Helium and Hydrogen gas is filled in a vessel at 30 degree Celsius.
Compare the root mean square velocities of the molecules of these gases at this
temperature.

(atomic weight of Hydrogen is 4)

Ans (Vrms)He/(Vrms)H2 = {(MH2)/(MHe)} U2-& 1 : 2V2

5.The velocities of three molecules are 3V,4V and 5V.Determine the root mean
square velocity.

50
Ans:-Vrms = —V = 4.08V
3

6.Write the equation of state for 16g of 02.

Ans No. of moles in 32g of 02 = 1

No. of moles in 16g of 02 = 1/9 x 16 = %

As pv = nRT and n=1/2

So, PV=ÿ RT
7.Should the specific heat of monoatomic gas be less than, equal to or greater than
that of a diatomic gas at room temperature? Justify your answer.

Ans Specific heat of a gas at constant volume is equal to f/2R.

For monoatomic gases f = 3 so Cv= 3/2 R.

For diatomic gases f = 5 so Cv = 5/2 R.
Hence the specific heat for monoatomic gas is less than that for a diatomic gas.

8. A gas in a closed vessel is at the pressure P0. If the masses of all the molecules
be made half and their speeds be made double, then find the resultant pressure?

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Ans:-P0= - — V2
1 mN 779- 1 mN
= HF(2F) 7 =2P°
9. A box contains equal number of molecules of hydrogen and oxygen. If there is a
fine hole in the box, which gas will leak rapidly? Why?
1
Ans :-V rms0ÿ

Hence hydrogen gas will leak more rapidly because of its smaller molecular mass.

10. When a gas filled in a closed vessel is heated through 1°C, its pressure
increases by 0.4 %. What is the initial temperature of the gas?

Ans:- P' = P = 0.4/100. P, T =T+1

By Gay Lussac’s law PIT = (P + 0.4/1 00. P)/T + 1,

(P +.004 P)_P (1.004)

T+l T+l
T+1=(1.004)T

1= 004T

T=250K

(3 Marks Questions)

1. Show that rms velocity of 02 is V2 times that of S02. Atomic wt. of Sulphur is 32
and that of oxygen is 16.

Ans. Voc 4
vo2
VM
vso2
Or v02= A/2 S02.

2. Calculate the temperature at which rms velocity of S02 is the same as that of
Oxygen at27°C.

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 I3R x 300
Ans. For 02, Vrms= = 32

For S02, Vrms = 13 Rt _ 3R X f

M0 64

[3 Rt '3 R X300
As V0 =V 64 32

f = 600t = 600 - 273 = 327°C.

3. Calculate the total no. of degrees of freedom possessed by the molecules in
1cm3 of H2 gas at NTP
Ans. No. of H2 Molecules in 22.4 liters or 22400 cm3 at NTP =6.02 x 1023.
x 1023
••• No. of H2 Molecules in 1 cm3 at NTP =ÿ22400 = 2.6875 x 1019.
No. of degrees of freedom associated with each H2 (a diatomic) molecule =5
••• Total no. of degree of freedom associated with 1cm3 gas
= 2.6875 x 1 019 x 5 = 1 .3475 x 1 02°.
4. Derive Boyle’s law on the basis of Kinetic Theory of Gases.
5. Derive Charles’s law on the basis of Kinetic Theory of Gases.
6. State Dalton’s law of partial pressures. Deduce it from Kinetic Theory of Gases.
7. Using the expression for pressure exerted by a gas, deduce Avogadro’s law and
Graham’s law of diffusion.
8. State the number of degree of freedom possessed by a monoatomic molecule in
space. Also give the expression for total energy possessed by it at a given
temperature. Hence give the total energy of the atom at 300 K.
9. At what temperature is the root mean square speed of an atom in an argon gas
cylinder equal to the rms speed of helium gas atom at- 20°C? Atomic mass of
argon = 39.9 u and that of helium = 4.0 u.
Ans. Root mean square speed for argon at temperature T

V~
l3RT _ I3RT
yj M ~
39.9

Root mean square speed for helium at temp. 20°Cis

l3R X 253
V

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 '3RT 3R X 253
As V = V so we have
39.9 4

— —— T
39.9
253
4
orT =
253 X39.9
4

T = 2523.7 K

10. From a certain apparatus the diffusion rate of Hydrogen has an average
value of 28.7 cm3 s'1; the diffusion of another gas under the same conditions is
measured to have an average rate of 7.2cm3s"1. Identify the gas.

Ans. From Graham’s law of diffusion,

ri_ IMT
r2 -\J M2
M2 = £i)2m, = (ÿ)2 x 2
= 31.78 * 32
Thus the unknown gas is Oxygen.
(Long Questions)

11. Prove that the pressure exerted by a gas is P = where p is the

density and c is the root mean square velocity.

12. What are the basic assumptions of Kinetic Theory of Gases? On their
basis derive an expression for the pressure exerted by an ideal gas.

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