CHAPTER 13:

Gas laws and kinetic theory

1
 Learning Outcome:
13.1 Ideal gas equations
At the end of this chapter, students should be able to:
a) Solve problems related to ideal gas equation,
pV = nRT
b) Discuss 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.

2
13.1 Ideal gas equations
13.1 Boyle’s law
 states : “The pressure of a fixed mass of gas at constant
temperature is inversely proportional to its volume.”
OR 1
p if T = constant
V
 The related equations to the Boyle’s law are

pV = constant OR p1V1 = p2V2

where p1 : initial pressure
p2 : final pressure
V1 : initial volume
V2 : final volume
3
 Graphs of the Boyle’s law.
a. p b. pV

T2
T1
T2
T1
0 V 0 p
c. p d. pV
T2

T1 T2
T1

1
0 V 0
4V
13.1b Charles’s law
 states : “The volume of a fixed mass of gas at constant
pressure is directly proportional to its absolute
temperature.”
V T If p = constant
OR

 The related equations to the Charles’s law are

V V1 V2
= constant OR =
T T1 T2
where T1 : initial absolute temperatu re
T2 : final absolute temperatu re
V1 : initial volume
V2 : final volume
5
  Graphs of the Charles’s law.

a. V b. V

−273.15 0 T(C) 0 T(K)

6
13.1c Gay-lussac’s (pressure) law
 states : “The pressure of a fixed mass of gas at constant
volume is directly proportional to its absolute
temperature.”
OR
p  T If V = constant
 The related equations to the Gay-lussac’s law are
p p1 p2
= constant OR =
T T1 T2
where T1 : initial absolute temperatu re
T2 : final absolute temperatu re
p1 : initial pressure
p2 : final pressure
7
  Graphs of the Gay-lussac’s (pressure) law.

a. p b. p

−273.15 0 T(C) 0 T(K)

8
13.1d Equation of state for an ideal gas
 An ideal gas is defined as a perfect gas which obeys the
three gas laws (Boyle’s, Charles’s and Gay-Lussac’s)
exactly.
 Consider an ideal gas in a container changes its pressure p,
volume V and temperature T as shown in Figure 1.

p1 p2 p2
2nd stage
V1 1st stage V' V2
T1 T1 T2
Figure 1
9
⚫ In 1st stage, temperature is kept at T1 ,
Using Boyle’s law :
p1V1
p2V ' = p1V1 V '= (1)
p2
⚫ In 2nd stage, pressure is kept constant at p2 ,
Using Charles’s law :
V ' V2 V2T1
= V '= (2)
T1 T2 T2
⚫ Equating eqs. (1) and (2), thus

p1V1 p2V2 pV
= OR = constant (3)
T1 T2 T

Initial Final
10
 Consider 1 mole of gas at standard temperature and pressure
(S.T.P.), T = 273.15 K, p = 101.3 kPa and Vm = 0.0224 m 3

( )
⚫ From equation (3),
pVm 101.3  10 3 (0.0224 )
R= =
T −1
273.15
−1
R = 8.31 J K mol
where R is called molar gas constant and its value is the
same for all gases.
⚫ Thus pVm
=R
T
pVm = RT where V
m : 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
11
 mgas where
n= mgas : mass of a gas
M M : molar mass of a gas
OR
N where
n= N : number of molecules
N A N : Avogadro' s constant
A
= 6.02  10 23 mol −1
⚫ If the Boltzmann constant, k is defined as
R
k= = 1.38  10 − 23 J K −1
NA
then the equation of state becomes

pV = NkT
12
Example 1 :
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 2.

A B
(300 K) (500 K)

Figure 2
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.

13
Solution : V
A = 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, finally i.e.
pA = pB = p
The system is in the steady state, thus
T0A = TA = 300 K;T0B = TB = 500 K
By applying the equation of state for an ideal gas,
mgas
pV = nRT and n =
 mgas  M
pV =   RT
Therefore,  M 
Vessel A :  mA 
pAVA =   RTA
M 
m
p (3VB ) =   R (300 )
M  14
Solution : V = 3VB ; mA = m; T0A = 300 K;T0B = 500 K
A
m
pVB = 100  R (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

15
Example 2 :
connecting tap

B  A

Figure 3
Refer to Figure 3. 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.

16
 Solution : V
0A = V1A = 3 . 00 m 3
; T0A = T1A = 250 K;
p0A = 5.00  10 4 Pa; V0B = V1B = 7.20 m 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
=
T0 T1
p0AV0A p0BV0B  V1A V1B 
+ = p + 
T0A T0B  T1A T1B 
(5.00 104 )(3.00) + (2.00 104 )(7.20) = p 3.00 + 7.20 
250 400  250 400 
p = 3.20  10 4 Pa
17
Exercise 1 :
Given R = 8.31 J mol−1 K−1 and NA = 6.0  1023 mol−1
1. 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)
ANS. : 66.2 cm 3
2. 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.
ANS. : 2.41  1022 molecules
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)
ANS. : 1.39  1024 molecules; 4.62 g; 1.93 kg m −3 18
 Learning Outcome:
13.2 Kinetic theory of gases
At the end of this chapter, students should be able to:
a) State the assumptions of kinetic theory of gases.
b) Discuss root mean square (rms) speed of gas molecules.
c) Solve problems related to root mean square (rms) speed of
gas molecules.
d) Solve problems related to

1
equations,
pV = Nmvrms
2

3
and pressure, 1
p =  vrms
2

3
19
13.2 Kinetic theory of gases
 The macroscopic behaviour of an ideal gas can be describe by
using the equation of state but the microscopic behaviour only
can be describe by kinetic theory of gases.
13.2a Assumption of kinetic theory of gases
 All gases are made up of identical atoms or molecules.
 All atoms or molecules move randomly and haphazardly.
 The volume of the atoms or molecules is negligible when
compared with the volume occupied by the gas.
 The intermolecular forces are negligible except during
collisions.
 Inter-atomic or molecular collisions are elastic.
 The duration of a collision is negligible compared with the
time spent travelling between collisions.
 Atoms and molecules move with constant speed between
collisions. Gravity has no effect on molecular motion.

20
13.2b Force exerted by an ideal gas
 Consider an ideal gas of N molecules are contained in a cubical
container of side d as shown in Figure 4.

Wall B
Figure 4

Wall A

 Let each molecule of the gas have the mass m and velocity v.
 The velocity, v of each molecule can be resolved into their
components i.e. vx, vy and vz.
21
 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 5.

Wall A
Wall B

Figure 5
Wall A

Wall B

 Therefore the change in the linear momentum of the molecule is

given by p = − mv − mv
x x ( x )
p x = −2 mvx 22
 The molecule has to travel a distance 2d (from A to B and back
to A) before its next collision with wall A. The time taken for this
movement is 2d
t =
vx
 If Fx1 is the magnitude of the average force exerted by a
molecule on the wall in the time t, thus by applying Newton’s
second law of motion gives
p x 2mvx m 2
Fx1 = = Fx1 =  v x
t  2d  d
 
 vx 
 For N molecules of the ideal gas,
m 2 m 2 m 2
Fx =  v x1 +  v x 2 + ....... +  v xN
d d d
m 2
d
(
Fx = v x1 + v x 2 + ....... + v xN
2 2
) 23
 where vx1 is the x component of velocity of molecule 1, vx2 is the
x component of velocity of molecule 2 and so on.
 The mean (average ) value of the square of the velocity in the x
direction for N molecules is
2vx12 + vx 2 2 + ....... + vxN 2
vx =
N
( )
2
vx1 + vx 2 + ....... + vxN = N v x 
2 2 2

 Thus, the x component for the total force exerted on the wall of
the cubical container is m 2
Fx = N vx 
d
 The magnitude of the velocity v is given by
v = vx + v y + vz
2 2 2 2

2 2 2 2
v = vx + v y + vz
then

24
 Since the velocities of the molecules in the ideal gas are
completely random, there is no preference to one direction
or another. Hence 2 2 2
vx = v y = vz2
2 2 2 v
v = 3v x  v x =
3
 The total force exerted on the wall in all direction, F is given by
m 2 m  v 
2

F = N vx F = N 
d d  3
 

N mv 
2

F=  
3 d 
2
 
where v : mean square velocity of the molecule
2 2
vrms = v or v 2
rms =v 25
13.2c Pressure of an ideal gas
 From the definition of pressure,
F N  mvrms
2

p = where A = d 2 and F=  
A 3 d 
1  Nmvrms
2

p=  3  and d3 =V
3 d 
1  Nm 2 
p=  vrms  (4)
3 V 
1
pV = Nmvrms
3
( 2
) (5)

where Nm : mass of an ideal gas in the container

26
 Since the density of the gas,  is given by
Nm
=
V
hence the equation (15.1) can be written as

1 2
p =  vrms (6)
3
where p : pressure by the gas
 : density of the gas
2
vrms : root mean square velocity of the gas molecules

27
13.2d Root mean square velocity ( vrms )
 is defined as
vrms =  v 2 
 From the equation of state in terms of Boltzmann constant, k :
pV = NkT (7)
 By equating the eqs. (14.4) and (14.2), thus
1
NkT = Nmvrms
3
2
( )
3kT
2
v
rms =
m
 Therefore 3RT
3kT
vrms = OR vrms =
m M
28
 where v rms
: root mean square velocity (speed)
m : mass of a molecule gas
M : molar mass of a gas
T : absolute temperatu re
1 2 3P
 Since p =  vrms thus v 2
=
3
rms

therefore the equation of root mean square velocity of the gas
molecules also can be written as

3p
vrms =


29
Example 3 :
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)
Solution : V = 0.08 m 3 ; T = 280 K; p = 90  10 3 Pa
a. By using the equation of state, thus
mgas
pV = nRT and n =
 mgas  M
pV =   RT
 M 
30
Solution : V = 0.08 m 3 ; T = 280 K; p = 90  10 3 Pa
 mgas 
( ) (8.31)280
a.
90  10 0.08 = 
3

 0.032 −2
mgas = 9.90  10 kg
b. The number of oxygen molecules in the cylinder is
mgas
N  mgas 
n= = N =   N A
M NA  M 
 9.90  10 −2 
N =  
 6.02  10 23

 0.03224 
N = 1.86  10 molecules
c. The root mean square speed of the oxygen molecules is
3RT 3(8.31)(280 ) −1
vrms = vrms = = 467 m s
M 0.032
31
Exercise 2 :
Given R = 8.31 J mol−1 K−1, Boltzmann constant, k = 1.3810−23 K−1
1. 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)
ANS. : 17.6 kPa
2. Initially, the r.m.s. speed of an atom of a monatomic ideal gas is
250 m s−1. The pressure and volume of the gas are each
doubled while the number of moles of the gas is kept constant.
Calculate the final translational r.m.s. speed of the atoms.
ANS. : 500 m s−1
3. 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)
ANS. : 477 m s−1 32
 Learning Outcome:
13.3 Molecular kinetic energy and internal energy
At the end of this chapter, students should be able to:
a) Discuss translational kinetic energy of a molecule,
3 R  3
K tr =  T = kT
2  NA  2
b) Discuss degree of freedom, f for monoatomic, diatomic
and polyatomic gas molecules.
c) State the principle of equipartition of energy.
d) Discuss internal energy of gas.
e) Solve problems related to internal energy,

1
U = fNkT
2
33
13.3 Molecular kinetic energy and internal energy
13.3 a Translational kinetic energy
 From equation (13.1), thus
1  Nm 2 
p=  vrms 
3 V 
2  N  1 2 
p =   mvrms  (8)
3  V  2 
This equation shows that N
  increases
V 
p increases () When
1 2 
 mvrms  increases
 Rearrange equation (14.5), thus 2 
2 1 2 
pV = N  mvrms  and pV = NkT
3 2  34
 2 1 2 
NkT = N  mvrms 
3 2 
1 2 3 1 2
mvrms = kT and mvrms = K tr
2 2 2
3 3 R 
K tr = kT =  T
2 2  NA 
where K : average translati onal kinetic energy
tr
of a molecule
T : absolute temperatu re
k : Boltzmann constant
R : molar gas constant
N A : Avogadro constant
35
 For N molecules of an ideal gas in the cubical container, the total
average (mean) translational kinetic energy, E is given by

E = NK tr
3 
E = N  kT 
2 
3
E = NkT
2
OR

3
E = nRT
2
36
13.3b Degree of freedom ( f )
 is defined as a number of independent ways in which an
atom or molecule can absorb or release or store the energy.
Monatomic gas (e.g. He, Ne, Ar)
 The number of degrees of freedom is 3 i.e. three direction of
translational motion where contribute translational kinetic
energy as shown in Figure 6.
y

vy
He
 x
 vx
vz
z
Figure 6
37
 Diatomic gas (e.g. H 2, O2, N2)
 The number of degrees of freedom is
y
 Translational kinetic energy 3
 Rotational kinetic energy 2
vy 5
H x
 H

Figure 7
vz v x
z y
Polyatomic gas (e.g. H 2O, CO2, NH3)
 The number of degrees of freedom is 
Translational kinetic energy 3 vy
Rotational kinetic energy 3
6
O

 x
H  vx
vz H
Figure 8 z  38
  Table 1 shows the degrees of freedom for various molecules.

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)
Table 1

39
 Degrees of freedom depend on the absolute temperature of
the gases.
⚫ For example : Diatomic gas (H2)

H H

vibration
Figure 9
⚫ Hydrogen gas have the vibrational kinetic energy (as shown
in Figure 9) where contribute 2 degrees of freedom which
correspond to the kinetic energy and the potential energy
associated with vibrations along the bond between the
atoms.
when the temperature,
At 250 K f =3
At 250 – 750 K f =5
At >750 K f =7
40
 13.3c Principle of equipartition of energy
 States : “the mean (average) kinetic energy of every degrees
of freedom of a molecule is
1
kT .
Therefore 2

f
K = kT Mean (average) kinetic
energy per molecule
2
OR

f
K = RT Mean (average) kinetic
energy per mole
2
where f : degrees of freedom
T : absolute temperatu re
41
Example 4 :
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)
N
Solution : = 2.20 1018 ; v 2 = 4.50 103 m s −1 ; T = 323.15 K
rms
V
a. The average translational kinetic energy of a molecule is
3
K tr = kT
3
2
( )
K tr = 1.38  10 − 23 (323.15)
2
K tr = 6.69  10 −21 J
42
 N
Solution : = 2.20 1018 ; vrms
2
= 4.50 103 m s −1 ; T = 323.15 K
V
b. The pressure of hydrogen gas is given by
1 N  2 M
p =   mvrms where m =
3 V  NA
1  N  M  2
p =    vrms
3  V   NA 
1
(
= 2.20  10  18 
)0.002 
23 
4 . 50 (
 10 3
)
3  6.02  10 
−5
p = 1.10  10 Pa

43
Example 5:
A vessel contains an ideal polyatomic gas at temperature of 30 C.
The total translational kinetic energy of the gas molecules is
6.00  10−6 J. The mass of the gas is then doubled and the total
translational kinetic energy of the molecules becomes 13.00 
10−6 J. Determine the new temperature of the gas.
Solution :T = 303.15 K ; E = 6.00  10 −6 J; E = 13.00  10 −6 J
1 1 2
m2 = 2m1
By applying the equation of the total translational kinetic energy,
thus 3 m R
E = NkT where N =   N A and k =
2 M  NA
3 m  R 
E=  N A  T
2M  N A 
3 m 
E=   RT
2M  44
 Solution :T1 = 303.15 K ; E1 = 6.00  10 −6 J; E 2 = 13.00  10 −6 J
m2 = 2m1 3  m1 
For temperature T1 : E =   RT (1)
1 1
2M 
For temperature T2 : E =
3  m2 
2   RT2
2 M 
3  2m1 
E2 =   RT2 (2)
E2 2T2 2 M 
(2) (1) : =
E1 T1
−6
13.00  10 2T2
−6
=
6.00  10 303.15
T2 = 328 K
45
13.3d Internal energy, U
 is defined as the sum of total kinetic energy and total
potential energy of the gas molecules.
 But in ideal gas, the intermolecular forces are assumed to be
negligible thus the potential energy of the molecules can be
neglected. Thus for N molecules,
U = NK
f R
U = NkT and k=
2 NA
OR
f where
U = nRT U : internal energy of the gas
2

46
  Table 2 shows the properties for 1 mole of an ideal gas.

Monatomic Diatomic Polyatomic

Degrees of freedom, f 3 5 6
Average kinetic energy per 3 5 6
kT kT kT = 3kT
molecule, K 2 2 2
3 5 6
Internal energy, U per mole RT RT RT = 3RT
2 2 2
Table 2

47
Example 6 :
Two moles of an ideal monatomic gas in a closed container at
constant volume is heated until its pressure is doubled. If the final
temperature of the gas is 750 K, Calculate
a. the initial temperature of the gas.
b. the change of the internal energy of the gas.
(Given R = 8.31 J K−1 mol−1)
Solution : n = 2; p2 = 2 p1 ; T2 = 750 K
a. Apply Gay-Lussac’s law,
p1 p2
=
T1 T2
p1 2 p1
=
T1 750
T1 = 375 K
48
Solution : n = 2; p2 = 2 p1 ; T2 = 750 K
b. The change of the internal energy is given by
U = U 2 − U 1
 f   f 
=  nRT2  −  nRT1 
2  2 
f
= nR (T2 − T1 )
2
3
= ( 2 )( 8.31)( 750 − 375 )
2
 U = 9.35  10 J
3

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Exercise 3 :
Given R = 8.31 J mol−1 K−1, Boltzmann constant, k = 1.3810−23 K−1
1. 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.
ANS. : 2.2510−2 m 3; 1.42 kg m −3; 461 m s−1; 5.6510−21 J;
5.67103 J;

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THE END.

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