Chapter 13

Kinetic Theory
Q.1: Calculate the ratio of molecular volume to the actual volume of
oxygen gas at standard temperature and pressure. (Diameter of oxygen
molecule = 3Å)
Sol:
Diameter of an oxygen molecule, d = 3Å

N AT IS
Radius, r =d/2 = 1.5 Å = 1.5 × 10–8 cm

C N
PY
O C D
We know:
O IO
Actual volume occupied by 1 mole of oxygen at STP = 22400 cm3
D U AA

O
Molecular volume of oxygen, V = NA (4πr3/ 3)
Where, N is Avogadro’s number = 6.023 × 1023 molecules/mole
ED PR

Therefore, molecular volume of oxygen, V = 6.023 × 1023 × 3.14 (1.5 ×

T
10–8)2 × (4/3) = 8.51 cm3
©

Thus, ratio of the molecular volume to the actual volume of oxygen =

8.51/22400 = 3.8 × 10-4
Q.2: The volume occupied by one mole of any (ideal) gas at STP is
called molar volume (STP: 0 °C, 1 atmospheric pressure). Prove that
molar volume is 22.4 liters.
Ans.
We know that the ideal gas equation: PV = n RT
Where, R is the universal gas constant = 8.314 J mol-1 K-1
n = Number of moles = 1
T = Standard temperature = 273 K
P = Standard pressure = 1atm = 1.013 × 105 Nm-2
Thus, V = (n RT)/p
= (1 × 8.314 × 273)/ (1.013 × 105)
= 0.0224 m3
= 22.4 liters
Thus, it is proved that molar volume of a gas at standard temperature
and pressure is 22.4 liters.
Q.3. The figure below is a graph of PV/T versus P for 1 × 10-3 kg of

N AT IS
oxygen at two different temperatures.

C N
PY
(𝑖) What is the significance of the dotted plot?
O C D
O IO
(ii) T1 < T2 or T1 > T2, which one is true?
D U AA

O
(iii) Find the value of PV/T where the curves come together on the y
axis.
ED PR

(iv) In place of oxygen if we used 1 × 10-3 kg of hydrogen and we

plotted similar graphs, would the value of PV/T be the same at the point
T
where the curves come in contact with the y axis?
©

If the answer is no, find the mass of hydrogen that would give the same
value (for high temperature low pressure region of the graph).
[Molecular mass of H2 = 2.02 u, of O2 = 32.0 u, R = 8.31 J mol-1 K-1]
Sol:
(i) The dotted plot signifies the ideal gas behavior of oxygen as it is
parallel to P –axis and it says that the ratio PV/T remains constant even
when P is changed.
(ii) The dotted line in the plot stands for an ideal gas. At temperature T1
the curve of the gas is closer to the dotted plot than at temperature T2. A
real gas behaves more like an ideal gas when its temperature rises. Thus,
T1 > T2 is true for the given graph.

N AT IS
(iii) At the point where the curves meet PV/T = μ R

C N
PY
Where μ = no. of moles = 1/32
O C D
O IO
R = 8.314 J mol-1 K-1
D U AA

O
Thus, PV/T = (1/32) × 8.314 = 0.26 J K-1
(iv) Even if we obtain a similar curve for 1 × 10-3 kg of hydrogen, we
ED PR

will not get the same value for PV/T because the molar mass of H2 is
2.02 u and not 32u.
T
We have:
©

PV / T = 0.26
Given:
Molecular mass of hydrogen, M = 2.02 u
PV/T = μ R
where, μ = m/M
i.e. PV/T = R (m/M)
i.e. m = MVP/ TR
= 0.26 × (2.02/8.31) = 6.3 × 10-5 kg
Hence, 6.3 × 10-5 kg of H2 will give the value of PV/T = 0.26 J K-1
Q.4: A 30-liter oxygen cylinder has an initial temperature and gauge
pressure of 27 0C and 20atm respectively. When a certain amount of
oxygen escapes from the cylinder the temperature and gauge pressure
drops to 17 0C and 22atm, respectively. Find the mass of oxygen that
escaped the cylinder.
[R = 8.31 J mol-1 K-1, molecular mass of O2 = 32 u]
Sol:
Given:

N AT IS
Initial volume of oxygen, V1 = 30 liters = 30 × 10-3 m3

C N
PY
O C D
Gauge pressure, P1 = 30atm = 30 × 1.013 × 105 Pa
O IO
D U AA
Temperature, T1 = 27°C = 300 K

O
Universal gas constant, R = 8.314 J mole-1 K-1
ED PR

Let the initial number of moles of oxygen in the cylinder be n1.

We know:
T
P1V1 = n1RT1
©

i.e. n1 = P1V1 / RT1

= (30.39 × 105 × 30 × 10-3) / (8.314 × 300)
= 36.552
But, n1= m1/ M
Where,
m1 = initial mass of oxygen
M = molecular mass of oxygen = 32 g
i.e. m1 = n1 × M = 36.552 × 32 = 1169.6 g
After some oxygen escapes:
Volume, V2 = 30 × 10-3 m3
Gauge pressure, P2 = 22atm = 22 × 1.013 × 105 Pa
Temperature, T2 = 17°C = 290 K
Let the number of moles of oxygen left in the cylinder be n2.
Now:
P2V2 = n2 RT2

N AT IS
i.e. n2 = P2V2 / RT2
= (22.286 × 105 × 30 × 10-3)/ (8.314 × 290) = 27.72

C N
PY
O C D
But, n2 = m2 / M
O IO
D U AA
Where, m2 = remaining mass of oxygen

O
i.e. m2 = n2 × M = 27.72 × 32 = 906.2g
ED PR

Therefore, the mass of oxygen that escaped the cylinder = m1 – m2 =

1169.6 – 906.2 = 263.4 g
T
Q.5: An air bubble occupies a volume of 2 cm3 at the bottom of 20m
©

deep lake. Assuming the bottom temperature of the lake is 12 0C, find
the volume of this air bubble when it rises up to the lake surface which is
at 35 0C?
Sol:
Given:
Volume of the air bubble, V = 2.0 cm3= 2.0 × 10-6 m3
Bubble ascends a height of, d = 20 m
Temperature at a depth of 40 m, T = 12°C = 285 K
Temperature at the surface of the lake, T’ = 35°C = 308 K
The pressure on the surface of the lake: P’ = 1atm = 1 ×1.013 × 105 Pa
And, The pressure at the bottom: P = 1atm + 𝑑ρg
Where, ρ is the density of water = 103 kg/m3
g is the acceleration due to gravity = 9.8 m / s2
i.e. P = 1.013 × 105 + 20 × 103 × 9.8 = 297300 Pa
We know:
PV/T = P’V’/T’
Where, V’ is the volume of the bubble at the surface.

N AT IS
V’ = PVT’/P’T

C N
PY
O C D
= (297300 × 2 × 10-6 × 308) / (1.013 × 105 × 285) = 6.34 × 10-6 m3 or
O IO
D U AA
6.34 cm3

O
Therefore, the volume of this bubble when it reaches the surface is 6.34
cm3.
ED PR

Q.6: In a 50 m3 room, at a pressure of 1atm and temperature 270C, what

is the number of air molecules (oxygen, nitrogen, water vapor and other
T
constituents) present?
©

Sol:
Given:
Volume of the room, V = 50.0 m3
Temperature of the room, T = 27°C = 300 K
Pressure in the room, P = 1atm = 1 × 1.013 × 105 Pa
According to gas equation:
PV = kB NT
Where, kB is Boltzmann constant = 1.38 × 10-23 m2 kg s-2 K-1
N is the number of air molecules in the room
Now, N = PV/ kB T
= (1.013 × 105 × 50) / (1.38 × 10-23 × 300) = 1.22 × 1027
Therefore, there is 1.22 × 1027 molecules in the room.
Q.7: Calculate the average thermal energy of a helium atom at
(i) room temperature (27 0C),
(ii) the core of the earth (6150 K),

N AT IS
(iii) at the core of the sun (10 million K)
Sol:

C N
PY
O C D
Given:
O IO
D U AA
(i) At room temperature, T = 27°C = 300 K

O
Thus, average thermal energy = k T × (3/2)
ED PR

Where k is Boltzmann constant = 1.38 × 10-23 m2 kg s-2 K-1

Thus,
T
K T × (3/2) = 1.38 × 10-23 × 300 × 1.5 = 6.21 × 10-21 J
©

(ii) In the core of the earth, T = 6150 K

Thus, average thermal energy = k T × (3/2)
i.e. k T × (3/2) = 1.38 × 10-19 × 6150 × 1.5 = 1.27 × 10-19 J
(iii) At core of the sun, T = 107
Thus, average thermal energy = k T × (3/2)
i.e. k T × (3/2) = 1.38 × 10-19 × 107 × 1.5 = 2.07 × 10-16 J
Q.8: Three containers A, B and C, having the same capacity, contains
neon (monatomic), chlorine (diatomic) and uranium hexafluoride
(polyatomic) respectively at the same pressure and temperature. Do all
the containers contain the same number of molecules? Also, do the
molecules in the respective containers have the same root mean square
value of speed? If not, molecules of which gas has the highest value of
𝑉 rms?
Sol:
According to Avogadro’s principle, gases of the same volume at the
same values of temperature and pressure will contain the same number
of molecules. Thus, in the above case all the containers will contain
equal number of molecules.

N AT IS
For a gas of mass (m) at temperature (T), its root mean square speed;

C N
PY
O C D
3𝐾𝑇
𝑉 rms = √
O IO 𝑚
D U AA

Where k is the Boltzmann constant.

O
As k and T are constants, we get:
ED PR

1
𝑉 rms = √
𝑚
T
Thus, 𝑉 rms is not the same for the molecules of the three gases.
©

As mass of neon is the least, it will have the highest 𝑉 rms.

Q.9: Calculate the temperature at which the root mean square speed of
an argon atom is the same as the root mean square speed of a helium gas
atom at – 20 0C.
[Atomic mass of A r = 39.9 u, of He = 4.0 u]
Sol:
Given:
Temperature of the helium atom, T’ = –20°C = 253 K
Atomic mass of argon, M = 39.9 u
Atomic mass of helium, M’ = 4.0 u
Let, (VRMS) 𝐴𝑟 be the 𝑟𝑚𝑠 speed of argon and (VRMS) He be the rms
speed of helium.
Now, we know:
3𝑅𝑇
(VRMS)𝐴𝑟 = √ …(1)
𝑀

Where, R is the universal gas constant and T is temperature of argon gas

3𝑅𝑇′
Now, (VRMS)He = √ … (2)

N AT IS
𝑀′

C N
According to the question:

PY
O C D
(VRMS)𝐴r = (VRMS)He
O IO
D U AA

O
3𝑅𝑇 3𝑅𝑇′
i.e. √ =√
𝑀 𝑀′
ED PR

i.e. T/M = T’ / M’
T = M × (T’/M’)
T
Therefore, the temperature of argon, T = 39.9 × 253/4 = 2.52 × 103 K
©

Q.10: A cylinder contains nitrogen at 2atm and 17 0C, find the collision
frequency and the mean free path of a nitrogen molecule inside it.
Considering the nitrogen molecule to have a radius of 1Å compare the
time between two consecutive collisions and the collision time.
[Molecular mass of N2 = 28]
Sol:
Given:
Pressure inside the cylinder containing nitrogen, P = 1.0atm = 1 × 1.013
× 105 Pa
Temperature inside the cylinder, T = 17°C = 290 K
Radius of a nitrogen molecule, r = 1.0 Å = 1 × 1010 m
Diameter, d = 2 × 1 × 1010 = 2 × 10-10 m
Molecular mass of nitrogen, M = 28.0 g = 28 × 10-3 kg
3𝑅𝑇
We know, the root mean square speed, VRMS = √
𝑀

3×8.314×290
VRMS = √ = 508.26 m/s
28×10−3

For the mean free path (l) we have:

N AT IS
𝐾𝑇
l=
√2×𝜋×𝑑2 ×𝑃

C N
PY
O C D
Where, k is 1.38 × 10-23 kg m2 s-2 K-1
O IO
D U AA
1.38×10−23 ×390
Therefore, l = = 2.22 × 10-7 m

O
√2×3.14(2×10−10 )2 ×1.013×105

And, Collision frequency = VRMS / l = 2.29 × 10 9 s-1

ED PR

Collision time T = d / VRMS

T
= 2 × 10-10 / 508.26 = 2.18 × 10-10 s = 3.93 × 10-13 s
©

Time between consecutive collisions:

T’ = l / VRMS
= 2.22 × 10-7 / 508.26 = 4.36 × 10-10 s
Thus, T’/ T = (4.36 × 10-10)/ (2.22 × 10-7) = 1109.41.
Therefore, the time between two consecutive collisions is 1109.41 times
the collision time.
Q11: A narrow bore a meter long held horizontally contains a mercury
thread of 70 cm, which traps air column of 20 cm. What will happen if
tube is vertically held with bottom end open?
Sol:
Length of mercury thread, l = 70 cm
Length of the narrow bore, L = 1m = 100 cm
The air column length in between the closed end & mercury, la = 20 cm
Since the bottom end is open and the bore is vertically held in air, the air
space occupied by the mercury length is: 100 – (70 + 20) = 10 cm
Hence, total air column length = 20 + 10 = 30 cm
Let, mercury out flow due to atmospheric pressure be ‘h’ cm
Therefore,

N AT IS
The air column length in the bore = (30 + h) cm

C N
PY
O C D
And, mercury column length = 80 – h cm
O IO
D U AA
Initial pressure, P1 = 80 cm of mercury

O
Initial volume, V1 = 20 cm3
Final pressure, P2 = 80 – (80 – h) = h cm of mercury
ED PR

Final volume is V2 = (30 + h) cm3

T
Throughout the process the temperature is constant.
©

P1V1 = P2V2
70 × 20 =h (30 + h)
h2 + 30h – 1400 =0
−30±√(30)2 +4×1×1400
Therefore, h = = −55.3cmor25.3cm
2×1

Height is always positive. Hence, mercury that flow out from bore is
25.3 cm and mercury that remains in it is 54.7 cm. The air column length
is 30 + 25.3 = 55.3 cm
Q12. Hydrogen gas’s diffusion rate from one certain apparatus has
average value 30 cm2/ s. Under same condition the average diffusion
rate of another gas is 8 cm2/s. What gas is it?
[Hint: Graham’s law of diffusion states that: (M2/ M1)1/2 = R1/ R2, where
diffusion rates of gas 1 and gas 2 are given by R1, R2 and M1 and M2 are
their molecular masses]
Sol:
Diffusion rate of hydrogen, R1 = 30 cm3/ s
Diffusion rate of the other gas, R2 = 8 cm3/ s
According to Graham’s Law of diffusion, we have:
𝑅1

N AT IS
=√
𝑀2

C N
𝑅1 𝑀1

PY
O C D
Where, Molecular mass of hydrogen M1 = 2.020 g
O IO
D U AA

Molecular mass of the unknown gas is M2

O
𝑅 2
Therefore, M2 = M1 ( 1 )
ED PR

𝑅2

30 2
=2.02 ( )
T
8

=28.40g
©

Nitrogen has the molecular mass 28. Hence the other gas is nitrogen.
Q.13: Throughout the volume of a gas in equilibrium the density and
pressure is uniform. It is true only if no external influences are used. Gas
column because of gravity doesn’t have uniform density or pressure.
Density of the gas decreases with height. The dependence precise is
given by law of atmosphere n2 = n1exp [ -mg (h2 – h1)/kB T] Where n1,
n2 are referred to density at h1 and h2 respectively. The sedimentation
equilibrium equation of liquid column can be derived by using this
relation: n2 = n1exp [−mg NA(ρ–ρ′) (h2–h1)/(𝜌RT)] Where ρ is the
density of the particle suspended, and ρ′ is surrounding medium’s
density. [NA = Avogadro’s number & R the universal gas constant.] [To
find the suspended particle’s apparent weight use Archimedes principle]
Sol:
From law of atmosphere, we have:
n2 = n1exp [-mg (h2 – h1)/kB T] … (𝑖)
Where, at height h1, number density is n1, and at height h2, number
density is n2
Weight of suspended particle in gas column is mg
Medium density = ρ′

N AT IS
Suspended particle density = ρ

C N
PY
O C D
Suspended particle mass = m’
O IO
Displaced medium’s mass = m
D U AA

O
Suspended particle’s volume = V
Archimedes’ principle states that the weight of the suspended particle in
ED PR

the liquid column is given by

T
Now, displaced medium weight – suspended particle weight
=mg – 𝑚′𝑔
©

𝑚
=mg–V 𝜌’𝑔 = mg – ( ) 𝜌‘𝑔
𝜌
𝜌′
=mg (1 − ) … (ii)
𝜌

Gas constant, R=KBN

𝑅
KB = … (iii)
𝑁

Substitution equation (ii) in place of mg in equation (i) and the using

equation (iii), we; get:
n2 = n1exp [−mg (h2–h1)/kB T]
 ′ 𝑁
=n1exp [−mg (1 − (ℎ2 − ℎ1 ) )]
𝜌 𝑅𝑇𝜌

Q14: Density of some of the solids and liquids are given below. Provide
rough estimates of their atom sizes:
Substance Atomic mass Density (103 kg m-1)
Carbon (diamond) 12.01 2.22
Gold 197.00 19.32
Nitrogen 14.01 1.00

N AT IS
Lithium 6.94 0.53
Fluorine (liquid) 19.00 1.14

C N
PY
O C D
O IO
[Assume in solid and liquid phase the atoms are tightly packed, and use
D U AA
Avogadro’s number. Do not take actual numbers obtain for different

O
atomic sizes? Because of tight packing approximation of the crudeness,
the range of atomic size in between few Å]
ED PR

Sol:
T
Substance Radius (A)
Carbon (diamond) 1.29
©

Gold 1.59
Nitrogen (liquid) 1.77
Lithium 1.73
Fluorine 1.88

Substance’s atomic mass = M

Substance’s density = ρ Avogadro′s number = N = 6.023 × 1023
4 4
Each atom′s volume = πr3 N number of molecules′ volume = πr3N …
3 3
(𝑖)
𝑀
One mole′s volume = … (iii)
𝜌
4 𝑀
πr3 N =
3 𝜌

3 3𝑀
Therefore, r = √
4𝜋𝜌𝑁

For carbon:
M = 12.01 × 10−3 kg,
ρ = 2.22 × 103 kgm−3

N AT IS
1
3×12.01×10−3 3
Therefore, r = ( ) =1.29
4𝜋×2.22×103 ×6.023×1023

C N
PY
O C D
Hence, radius of carbon atom = 1.29 Å
O IO
D U AA
For gold:

O
M = 197.01 × 10−3 kg,
ED PR

ρ = 19.32 × 103 kgm−3

1
3×197×10−3
T
3
Therefore, r = ( ) =1.59
4𝜋×19.32×103 ×6.023×1023
©

Hence, radius of gold atom = 1.59 Å

For nitrogen (liquid):
M = 14.01 × 10−3 kg,
ρ = 1.00 × 103kgm−3
1
3×14.01×10−3 3
Therefore, r = ( ) =1.77
4𝜋×1.00×103 ×6.23×1023

Hence, radius of nitrogen (liquid) atom = 1.77 Å

For lithium:
M = 6.94 × 10−3 kg,
ρ = 0.53×103 kgm−3
 1
3×6.94×10−3 3
Therefore, r = ( ) =1.73
4𝜋×0.53×103 ×6.23×1023

Hence, radius of lithium atom = 1.73 Å

For fluorine (liquid):
M = 19.00 × 10−3 kg,
ρ = 1.14 × 103 kgm−3
1
3×19×10−3

N AT IS
3
Therefore, r = ( ) =1.88
4𝜋×1.14×103 ×6.023×1023

C N
PY
Hence, radius of fluorine (liquid) atom = 1.88 Å
O C D
O IO
D U AA

O
ED PR

T
©