CHAPTER 14:

KINETIC THEORY OF GASES

1
14.1 IDEAL GAS EQUATIONS
 Learning objectives:

 Sketch and interpret the following graphs of an ideal gas:

 p-V graph at constant temperature

 V-T graph at constant pressure

 p-T graph at constant volume

 Use the ideal gas equation, pV = nRT

2
BOYLE’S LAW
 For a fixed amount of gas at a constant temperature, gas
pressure is inversely proportional to gas volume.
1
P if T  constant
V
 The related equation for Boyle’s law are:

PV  constant OR P1V1  P2V2

3
4
GRAPH OF THE BOYLE’S LAW

P
P T2

T1

T2
T1 1
0 V 0 V

5
CHARLES’S LAW
 For a fixed amount of gas at a constant pressure, gas
volume is directly proportional to its absolute
temperature.

V T If P  constant
 The related equations to the Charles’s law are

V V1 V2
 constant OR 
T T1 T2
6
7
GRAPH OF THE CHARLES’S LAW

V V

273.15 0 T(C) 0 T(K)

8
GAY- LUSSAC’S LAW/ PRESSURE LAW
 For a fixed amount of gas at a constant volume, gas
pressure is directly proportional to its absolute
temperature.

P T If V  constant
 The related equations to the Gay-Lussac's law are

P P1 P2
 constant OR 
T T1 T2
9
10
GRAPH OF THE GAY- LUSSAC’S LAW

P P

273.15 0 T(C) 0 T(K)

11
IDEAL GAS EQUATION
 An ideal gas is defined as a perfect gas which obeys
the three gas laws (Boyle’s, Charles’s and Gay-
Lussac’s) exactly.

 These 3 laws can be combined into a single more general

relation between absolute pressure, volume and absolute
temperature of a fixed quantity of gas:
pV  T
 Write in mathematic form:

P1V1 P2V2 PV
 OR  constant 12
T1 T2 T
 1 mole of any gas at standard temperature & pressure (
S.T.P. ), T = 273.15 K, p=101.3 kPa occupies Vm = 22.4
liters = 22.4 dm3 = 0.0224 m3:
Using
pVm 101.3 10  0.02243

T 273.15
 8.31J K 1 mol1
Vm : volume of 1 mole gas
 8.31 J K-1 mol-1 is known as molar gas constant , R

 Value of R is found experimentally same for all gases. 13

 Thus, for 1 mole of gas:
PVm
R PVm  RT
T

Vm : volume of 1 mole gas

 For n mole of an ideal gas, the equation of state is

written as

PV  nRT
where n : the number of mole gas

14
 The number of moles of gas can also be expressed as :

m where
n m : mass of a gas (in kg)
M M : molar mass of a gas (in kg mol-1 )
OR

where
N
n N : number of molecules
NA N A : Avogadro's constant
 6.02 10 23 mol 1

 Hence, the ideal gas equation can also be written as :

m N
PV  ( ) R T OR PV  ( ) R T 15
M NA
 If the Boltzmann constant, k is defined as

R  23 1
k  1.38 10 J K
NA
then the equation of state becomes

PV  NkT

16
EXAMPLE 1
What is the approximate number of atoms in a cubic metre
of an ideal monoatomic gas at a temperature of 27 °C and a
pressure of 1 x105 Pa ?

Answer: 2.41×1025 atoms

17
EXAMPLE 1 – SOLUTION
Given : P = 1 ×105 Pa
T = ( 27 + 273.15 ) = 300.15 K
V = 1 m3 ( cubic metre )
NA = 6.02×1023 mol-1
R = 8.31 J K-1 mol-1
number of atoms , N = ?
N
pV  ( ) RT
NA
pV NA (1105 )(1)(6.02 1023 )
N 
RT (8.31)(300.15) 18

N  2.41 10 25
EXAMPLE 2
A small bubble rises from the bottom of a lake, where the
temperature and pressure are 8 °C and 6.4 atm to the
water’s surface where the temperature is 25 °C and the
pressure is 1.0 atm. Calculate the final volume (in m3) of
the bubble if its initial volume was 2.1 cm3.

Answer: 1.425×10-5 m3

19
EXAMPLE 2 – SOLUTION
initial
P1= 6.4 (1.013 × 105) = 6.48×105 Pa
V1= 2.1 cm 3 = 2.1×10 -6 m3
T1=(8 + 273.15)=281.15 K

final P2= 1.013×105 Pa

V2= ? m 3
T2=(25+273.15)=298.15 K

* n1 = n 2 20
 p1 V 1 p 2 V 2 p1 V 1 T 2
 V2  
T1 T2 T1 p2

6
(6.48 10 ) (2.110 )
5
298.15
V2  
281.15 1.013 105

5
V 2  1.425 10 m 3

21
EXAMPLE 3
The volume of vessel A is three times of the volume vessel
B. The vessels are filled with an ideal gas and are at a
steady state. The temperature of vessel A and vessel B are
at 300 K and 500 K respectively as shown in Figure below.

A B
(300 K) (500 K)

If the mass of the gas in the vessel A is m, obtain the mass

of the gas in the vessel B in terms of m.
𝒎
Answer: 𝟓 22
EXAMPLE 3 – SOLUTION
Given VA  3VB ; mA  m; T0A  300 K;T0B  500 K

Since the vessels A and B are connected by a narrow tube

thus the pressure for both vessels is same:

PA  PB  P
The system is in the steady state, thus

T0A  TA  300 K;T0B  TB  500 K

23
 By applying the equation of state for an ideal gas,
m
PV  nRT and n 
M
m
PV    RT
M 
 Therefore,
 mA 
Vessel A: PAVA    RTA
M 
m
P 3VB     R 300 
M 
m
PVB  100  R
24
(1)
M 
Vessel B:

 mB 
PVB  500 R (2)
M 
 By equating the eqs. (1) and (2) hence

m   mB 
100  R  500 R
M  M 
m
mB 
5
25
EXAMPLE 4
connecting tap

B  A

Refer to Figure above. Initially A contains 3.00 m3 of an

ideal gas at a temperature of 250 K and a pressure of 5.00 
104 Pa, while B contains 7.20 m3 of the same gas at 400 K
and 2.00  104 Pa. Calculate the pressure after the
connecting tap has been opened and the system reached
equilibrium, assuming that A is kept at 250 K and B is kept
at 400 K.
Answer: 3.2×104 Pa 26
EXAMPLE 4 – SOLUTION
Given V0A  V1A  3.00 m 3 ; T0A  T1A  250 K;
P0A  5.00  10 Pa;V0B  V1B  7.20 m ;
4 3

T0B  T1B  400 K; P0B  2.00  10 4 Pa

After the connecting tap has been opened and the system
reached equilibrium, thus

P1A  P1B  P
By using the equation of state for ideal gas,
P0V0 P1V1
 27

T0 T1
 P0AV0A P0BV0B  V1A V1B 
  P  
T0A T0B  T1A T1B 
5.00 10 3.00  2.00 10 7.20  P 3.00  7.20 
4 4

250 400  250 400 

P  3.20  10 4 Pa

28
EXERCISE 1
a. A gas cylinder is fitted with a safety valve which
releases gas when the pressure inside the cylinder
reaches 2.0x106 Pa. Given that the maximum mass of
this gas the cylinder can hold at 10 °C is 15 kg, what
would be the maximum mass at 30 °C ?

b. A cylinder contains 12 L of oxygen at 20 °C and 15

atm. The temperature is raised to 35 °C and the volume
is reduced to 8.5 L. What is the final pressure of the gas
in atmosphere ? Assume that the gas is ideal.

29
Answer: (a) 14 kg ; 22 atm
EXERCISE 2
a. A gas has a volume of 60.0 cm3 at 20 C and 900
mmHg. What would its volume be at STP?
(Given the atmospheric pressure = 101.3 kPa and the
density of mercury = 13600 kg m3)

b. Estimate the number of molecules in a flask of

volume 5.0  104 m3 which contains oxygen gas at
a pressure of 2.0  105 Pa and temperature of 300 K.

Answer: 66.2 cm3 ; 2.41  1022 molecules

30
EXERCISE 3
A cylinder contains a hydrogen gas of volume 2.40  103
m3 at 17 C and 2.32  106 Pa. Calculate

a. the number of molecules of hydrogen in the cylinder,

b. the mass of the hydrogen,
c. the density of hydrogen under these conditions.
(Given the molar mass of hydrogen = 2 g mol1)

Answer: 1.39  1024 molecules; 4.62 g; 1.93 kg m3

31
14.2 KINETIC THEORY OF GASES
 Learning objectives:

 State the assumption of kinetic theory of gases.

1
 Apply the equation of ideal gas, 𝑝𝑉 = 3 𝑁𝑚 𝑣 2 and
1
pressure, 𝑝 = 3 𝜌 𝑣 2 in related problems.

 Explain root mean square (rms) speed of gas molecules and

3𝑘𝑇
use the equation, 𝑣𝑟𝑚𝑠 = 𝑣2 =
𝑚

32
ASSUMPTIONS OF KINETIC THEORY OF GAS
1. All gases are made up of atoms or molecules.

2. All atoms or molecules of the gas are in continuous and

completely random motion.

3. The volume of the gas molecules is negligible when

compared with the volume occupied by the gas.

4. The gas molecules undergo perfectly elastic collisions

with each other & with the walls of the container.
33
ASSUMPTIONS OF KINETIC THEORY OF GAS
5. The intermolecular forces are negligible except during
collisions.

6. The time of collisions between molecules is negligible

compared to the time between successive collisions.

7. The mass of each molecule is so small that the effect of

gravity on it is negligible.

34
GAS PRESSURE
 According to the kinetic theory of gasses, gas pressure is
the result of the collisions of large number of molecules
on the wall of the container.

 Consider a cube of side d containing N molecules of gas

each of mass, m.

35
 Consider, initially a single molecule moving with a
velocity vx towards wall A and after colliding elastically ,
it moves in the opposite direction with a velocity vx as
shown in Figure below:

Therefore the change in the linear

Wall momentum of the molecule is
Wall A given by
B
Px  mvx  mvx 
Wall

Wall
A Px  2mvx
B
36
 Assume no collision between molecules, the molecule
travels a distance of 2d (from A to B and back to A)
before it collides with the same wall.

 Thus time taken by 1 molecule between collisions with

the same wall
distance 2d
t 
speed vx
 When one molecule strikes the wall, it exerts a force on
the wall. The magnitude of force exerted by a molecules
on the wall :
p x 2mvx mv 2

F  
x

t 2d d 37

vx
 If the cube box contains N molecules moving with
velocities of vx1, vx2, vx3, …, vxN then the force on the
wall due to N molecules colliding with it is :
mvx1 2 mvx 2 2 mvx 3 2 mvxn 2
F   
d d d d
m 2
d

F  v x1  v x 2  v x 3  ...  v xN
2 2 2

 But the mean (average) value of all the squares of the x–
components of velocity is: Substitute
v 2
 v 2
 v 2
   v 2 in above
 vx 2  
x 1 x 2 x 3 xN
equation
N
38

vx1  vx 2  vx 3    vxN  N  vN 
2 2 2 2 2
 Thus we get
Nm
F  vx 2   (1)
d

v  vx  v y  vz
2 2 2 2
 Refer to the figure,

 Therefore  v 2    vx 2    vy 2    vz 2 

 The number of molecules N is large & molecules move

randomly (no preference to move in a one specific
direction), hence it follows that :
 vx 2    vy 2    vz 2  39
 Thus  v 2   3  vx 2 
 v 2

 vx  
2

3
 Equation (1) can be modified to :

Nm
F  v2   (2)
3d

40
Pressure P exerted on wall of the container :

Nm  v 2 
F
p p 3d
2
A d

Nm  v 2 
p 3
(Volume, V  d 3
)
3d
d
volume 1
pV  Nm  v 
2
d
3 d

Total no of molecules Mass of 1 molecule 41

 Nm
 Since the density of the gas : 
V

1
pressure p  v 
2

3 Mean square speed

density

42
ROOT MEAN SQUARE VELOCITY ( VRMS)
 Root mean square speed of a gas molecule is the square
root of the mean squares speed of the individual
molecules. It is considered as the average speed of one
gas molecule.

vrms   v  2

 From
1
pV  Nm  v 2  and pV  NkT
3

NkT  Nm  v 2  
1 3kT
 v 
2 43

3 m
 Therefore

3k T 3 RT
vrms  OR vrms 
m M
Mass of 1 molecule Molar mass of gas

vrms of N molecules vrms of n mol

44
EXAMPLE 5
A cylinder of volume 0.08 m3 contains oxygen gas at a
temperature of 280 K and pressure of 90 kPa. Determine

a. the mass of oxygen in the cylinder,

b. the number of oxygen molecules in the cylinder,
c. the root mean square speed of the oxygen molecules in
the cylinder.
(Given R = 8.31 J mol1 K1, k = 1.38  1023 J K1, molar
mass of oxygen, M = 32 g mol1, NA = 6.02  1023 mol1)

Answer: 9.90×10-2 kg ; 1.86×1024 molecules; 467 m s-1 45

EXAMPLE 5 – SOLUTION
Given V  0.08 m ; T  280 K; P  90  10 Pa
3 3

a) By using the equation of state, thus

m
PV  nRT and n
M
m 
PV    RT
M 

   m 
90  10 0.08  
3
8.31280
 0.032  46

m  9.90 10 2 kg
b) The number of oxygen molecules in the cylinder is

m N m 
n  N  NA
M NA M 
 9.90 102 
N   6.02 1023
 0.032 
N  1.86 10 molecules
24

c) The root mean square speed of the oxygen molecules is

3RT 38.31280
vrms  vrms   467 m s 1 47

M 0.032
EXERCISE 4
a. In a period of 1.00 s, 5.00  1023 nitrogen molecules
strike a wall with an area of 8.00 cm2. If the molecules
move with a speed of 300 m s1 and strike the wall
head-on in the elastic collisions, determine the pressure
exerted on the wall.
(The mass of one N2 molecule is 4.68  1026 kg)

b. Given that the r.m.s. of a helium atom at a certain

temperature is 1350 m s1, determine the r.m.s. speed of
an oxygen (O2) molecule at this temperature.
(The molar mass of O2 is 32.0 g mol1 and the molar
mass of He is 4.00 g mol1)
48

Answer: (a) 17.6 kPa ; (b) 477 m s-1

14.3 MOLECULAR KINETIC ENERGY AND
INTERNAL ENERGY
 Learning objectives:

 Explain and use translational kinetic energy of a molecule.

 State the principle of equipartition of energy.
 Define degree of freedom.
 State the number of degree of freedom for monoatomic,
diatomic and polyatomic gas molecules.
 Explain internal energy of gas.
 Relate the internal energy to the number of degree of freedom
and use the equation,

1
U  fNkT 49
2
TRANSLATIONAL KINETIC ENERGY
 From equation of ideal gas:
1
pV  Nm  v 
2
(1)
3
where N – total number of molecules in volume V
m – mass of one gas molecule
 To relate with kinetic energy, rewrite eq. (1) :

2 1
pV  N ( m  v 2 ) (2)
3 2
50
 Known the Ideal Gas Equation for n moles of gas at
pressure p, volume V & absolute temperature, T is given
by :
pV  n RT (3)
 Equating equation (2) & (3) :
2 1
N ( m  v 2 )  n R T
3 2
1 3 nR
mv 
2
T
2 2 N
N
[ Since Avogadro constant, NA = ]
n 51
 Kinetic 1 3 R
mv 
2
T
energy,K 2 2 NA
 Translational Kinetic Energy of a gas molecule :

3 R 3
K T OR K  kT
2 NA 2
R
where k = = the Boltzmann constant
NA
k = 1.38×10–23 J K-1

52
 The translational kinetic energy of a molecule is directly
proportional to the absolute temperature.

 The higher the temperature, according to kinetic theory,

the greater the kinetic energy and faster the molecules
are moving.

 For N molecules of the gas, the Total Translational

Kinetic Energy :
3
K  NkT
2
 For n moles of the gas, the Total Translational Kinetic
Energy :
3 N
K  nRT NA
n 53

2
EXAMPLE 6
What is the temperature at which the RMS speed of
nitrogen molecules is twice as great as their RMS speed at
300 K ?

Answer: 1200 K

54
EXAMPLE 6 – SOLUTION
Let v`RMS = RMS speed at T` = 300 K
vRMS = RMS speed at T

vRMS  2v`RMS
3k T 3k T`
2
m m
Squaring both sides of the equation
3k T 3k T`
 4[ ]
m m
T  4 T `  4 (300)
55

T  1200 K
EXAMPLE 7
A vessel contains Helium gas of mass 0.1 kg at pressure
150 kPa. The RMS speed of the Helium atoms is 1.35 km
s-1. Determine

(a) the volume of the gas

(b) the temperature of the gas.
( given: R = 8.31 J mol-1 K-1 ,
Relative atomic mass of He = 4 )

Answer: 0.405 m3 ; 292 K

56
EXAMPLE 7 – SOLUTION
Given mHe = 0.1 kg ; MHe = 0.004
P = 150 ×103 Pa ; vRMS = 1.35×103 m s-1
1
from : P    v 2 
3
3P
Thus : vRMS   v  
2


3(150 103 )
1.35 103    0.247 kg m 3

m m 0 .1
from :   V    0.405 m 3
V  0.247 57
PRINCIPLE OF EQUIPARTITION OF ENERGY
 States that the mean (average) kinetic energy of
1
each degree of freedom of a molecule is k T
2
 Therefore
f
 K  kT Mean (average) kinetic
energy per molecule
2
OR

f
 K  RT
Mean (average) kinetic
energy per mole
2 58
DEGREE OF FREEDOM
 is defined as a number of independent ways in which
an atom or molecule can absorb or release or store
the energy.

 3 type of orientation mode in molecule :

 the number of degree of freedom of a molecule depends

59
on whether the molecule is monoatomic, diatomic or
polyatomic.
MONOATOMIC GASES
 such as Helium, Neon, Argon, Krypton, Xenon and
Radon.

 3 degrees of freedom which consists of translational

(linear) motion along x , y & z
y

vy
He
 x
 vx
vz 60

z
DIATOMIC GASES
 such as : H2 , O2 , Cl2 , N2 , CO

z


vy
H y
 H 
vz v x
x

 Rotational motion about y axis is negligible because 61

moment of inertia about y is negligible.
For rotational motion about y axis, distance of the diatom
from axis of rotation is very small compare to x & z. Thus
rotation about y is negligible. Rotation about x & z is much
larger because larger distance between the atoms &
rotational axis. 62
POLYATOMIC GASES
 such as : H2O , CO2 , O3 , NH3 , N2O4 , H2S
y


vy
O
 Number of degree of freedom for
 x
 various types of molecule discussed
H
vz H
vx applies for gases at normal
z  temperature.

At higher temperature, vibrational 63

motion increases the number of
degree of freedom.
 SUMMARY
Degrees of Freedom ( f ) Average kinetic
Molecule Example energy per
Translational Rotational Total molecule,<K>
3
Monatomic He 3 0 3 2
kT
5
Diatomic H2 3 2 5 2
kT
6
Polyatomic H2O 3 3 6 kT  3kT
2
(At temperature of 300 K)

64

Monoatomic Gas Diatomic Gas Polyatomic Gas

EXAMPLE 8
Calculate the mean kinetic energy of a molecule of Oxygen
& a molecule of Ozone at a temperature of 27 °C .

Answer: 1.035×10-20 J ; 1.242×10-20 J

65
EXAMPLE 8 – SOLUTION

O2 – diatomic : 5 degree of freedoms

f
KO 2  k T
2
5 23
 (1.38  10 ) (27  273.15)
2
20
KO 2  1.035 10 J
66
O3 – triatomic : 6 degree of freedoms
f
KO 3  k T
2
6 23
 (1.38  10 ) (27  273.15)
2
20
 1.242 10 J
67
EXERCISE 5
A vessel contains hydrogen gas of 2.20  1018 molecules
per unit volume and the mean square speed of the
molecules is 4.50 km s1 at a temperature of 50 C.
Determine

a. the average translational kinetic energy of a molecule for

hydrogen gas,
b. the pressure of hydrogen gas.
(Given the molar mass of hydrogen gas = 2 g mol1,
NA= 6.02  1023 mol1 and k = 1.38  1023 J K1)
68

Answer: 6.69×10-21 J ; 1.10×10-5 Pa

INTERNAL ENERGY
 Is defined as the sum of the total mean kinetic energy (K)
& total potential energy of the gas molecules .

 But for ideal gas the intermolecular forces are assumed

to be negligible.

 The potential energy of the molecules can be neglected.

Thus we have :

Internal energy, U = Mean Kinetic energy, K

69
The internal energy, U for an ideal gas :

f f
U  N kT OR U  n RT
2 2

where U – internal energy

f – number of degree of freedom
T – Absolute temperature ( Kelvin )
N – number of molecules
n – number of moles
k – Bolzmann constant
R – molar gas constant
70
EXAMPLE 9
A vessel contains monoatomic neon gas of mass 10g at
temperature 20 °C. Determine the internal energy of the
gas. Assume that the gas behaves like an ideal gas.
[ Boltzmann constant = 1.38 x 10 -23 J K-1
NA = 6.02 x 1023 mol-1
Relative atomic mass of neon = 40 ]

Answer: 916.3 J

71
EXAMPLE 9 – SOLUTION
Given Monoatomic gas – f = 3
mNe = 0.01
T = ( 20 + 273.15 )= 293.15 K

f
Internal energy , U  N k T
2
m N
Amount of gas in mole, n  
M NA

72
 mNA 0.01(6.02 1023 )
N 
M 0.04
N  1.511023 atoms
f 3
U  N k T  (1.51 10 23 ) (1.38 10 23 )(293.15)
2 2
U  916.3 J

73
EXERCISE 6
One mole of oxygen has a mass of 32 g. Assuming oxygen
behaves as an ideal gas, calculate

a. the volume occupied by one mole of oxygen gas

b. the density of oxygen gas
c. the r.m.s. speed of its molecules
d. the average translational kinetic energy of a molecule
e. the internal energy of oxygen gas

at 273 K and pressure of 1.01105 Pa.

Answer: 2.25102 m3; 1.42 kg m3; 461 m s1; 5.651021 J;
5.67103 J 74