Ideal gas equation

Boyles law
states : The pressure
of a fixed mass of gas
at constant
temperature is
inversely proportional
to its volume.
OR

1
P
V

The related equations to the

Boyles law are

PV constant
OR

P1V1 P2V2
where

if T constant

P1 : initial pressure
P2 : final pressure
V1 : initial volume
V2 : final volume

Charless law
states : The volume
of a fixed mass of
gas
at
constant
pressure is directly
proportional to its
absolute
temperature.
OR

V T

If P constant

The related equations to the Charles law are

V
constant
T
OR

V1 V2

T1 T2
where

T1 : initial absolute temperature

T2 : final absolute temperature
V1 : initial volume
V2 : final volume

Gay-lussacs (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 Gaylussacs law are

P
constant
T
OR

P1 P2

T1 T2
where

T1 : initial absolute temperature

T2 : final absolute temperature
P1 : initial pressure
P2 : final pressure

Equation of state for an ideal gas

An ideal gas is defined as a perfect gas which obeys the
three gas laws (Boyles, Charless and Gay-Lussacs)
exactly.
Consider an ideal gas in a container changes its pressure P,
volume V and temperature T as shown in Figure.

P1
V1
T1

1st stage

P2
V'
T1

2nd

stage

P2
V2
T2

 In 1st stage, temperature is

kept at T1 ,
Using Boyles law :

P2V ' P1V1

P1V1
V '
P2

(1)

In 2nd stage, pressure is kept

constant at P2 ,
Using Charless law :

V ' V2

T1 T2

V2T1
V '
T2

(2)

Equating eqs. (1) and (2), thus

P1V1 P2V2

T1
T2
Initial

OR

Final

PV
constant
T

(3)

 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 m3
From equation (3),

PVm 101.3 103 0.0224

R

T
273.15
R 8.31 J K 1 mol1

where R is called molar gas constant and its value is the

same for all gases.
PVm
Thus

T
PVm RT

where

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

m
n
M
where

m : mass of a gas
M : molar mass of a gas

If the Boltzmann constant, k

is defined as

R
k
1.38 10 23 J K 1
NA

OR

N
n
NA
where

N : number of molecules
N A : Avogadro's constant
6.02 10 23 mol1

then the equation of state

becomes

PV NkT

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.

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.

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.

Wall B

Figure
14.5

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.
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.

Wa
ll B

Wall A
Wa
ll B

Wa
ll A

Wa
ll A

Therefore the change in the

linear momentum of the
molecule is given by

Px mvx mvx
Px 2mvx
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 Newtons
second law of motion gives

Px 2mvx
Fx1

t 2d

vx

m 2
Fx1 vx
d

For N molecules of the ideal gas,

m 2 m 2
m 2
Fx v x1 v x 2 ....... v xN
d
d
d

Fx

m 2
2
2
v x1 v x 2 ....... v xN
d

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

v x1 v x 2 ....... v xN
2
v x
N
2

2
x1

v x 2 ....... v xN
2

N vx
2

Thus, the x component for the

total force exerted on the wall of
the cubical container is

m
2
Fx N v x
d
The magnitude of the velocity
v is given by

v vx v y vz

then

v v x v y v z
2

 Since the velocities of the molecules in the ideal gas are

completely random, there is no preference to one direction
or another. Hence v 2 v 2 v 2
x

v 3 v x
2

2
v x
3
2

The total force exerted on the wall in all direction, F is given by

m
2
F N vx
d

m v2

F N
d 3
N
F
3

where

m v2

v 2 : mean square velocity of the molecule

Pressure of an ideal gas

From the definition of pressure,

F
P
A

where

A d2

and

N m v2

F
3
d

1 Nm v 2
3
and
d
V

P
3

3
d

1 Nm

2
P
v
3 V

1
2
PV Nm v
3
where

(1)

(2)

Nm : mass of an ideal gas in the container

 Since the density of the

gas, is given by

Root mean square velocity (

vrms
)is defined as
vrms v 2

Nm

V
hence the equation
(15.1) can be written as

1
P v2
3
where

From the equation of state in terms

of Boltzmann constant, k :
(4)
PV NkT

(3)

P : pressure by the gas

: density of the gas

v 2 : mean square velocity

of the gas molecules

By equating the eqs. (4) and (2),

thus

1
NkT Nm v 2
3

3kT
v
m
2

 Since

Therefore

vrms

3kT

OR

3RT
vrms
M
thus

where

vrms : root mean square velocity (speed)

m : mass of a molecule gas

M : molar mass of a gas

T : absolute temperature

1
P v2
3
v
2

3P

therefore the equation of root

mean square velocity of the
gas molecules also can be
written as

vrms

3P

Example :

Solution :
a. The mean speed of the
Eight gas molecules chosen
molecules is given by
at random are found to have
speeds of 1,1,2,2,2,3,4 and
N 8
5 m s1. Determine
N
a. the mean speed of the
molecules,
b. the mean square speed of
the molecules,
c. the root mean square
speed of the molecules.

v
v

v
i 1

1 1 2 2 2 3 4 5
8

v 2.5 m s 1

Solution :

N 8

b. The mean square speed of

the molecules is given by
N

v
2

vi

vrms v
2

i 1

2
2
2
2
2
2
2
2

1 1 2 2 2 3 4 5

v 8 m s
2

c. The root mean square speed

of the molecules is

vrms 8
vrms 2.83 m s 1

Example :
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 mol1 K1, k = 1.38

1023 J K1, molar mass of oxygen, M = 32
g mol1, NA = 6.02 1023 mol1)

Solution :

V 0.08 m 3 ; T 280 K;
P 90 103 Pa
a.

By using the equation of

state, thus

PV nRT

and

m
PV RT
M

m
n
M

Solution :
a.

V 0.08 m 3 ; T 280 K; P 90 103 Pa

m
90 10 0.08
8.31280
0.032
3

m 9.90 10 2 kg
b. The number of oxygen molecules in the cylinder is

m
N
M

m
N
n

M NA

NA

9.90 10 2
6.02 10 23
N
0.032
N 1.86 10 24 molecules

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

vrms

3RT

vrms

38.31280

467 m s 1
0.032

Molecular kinetic energy and internal energy

Translational kinetic energy of molecule
From equation (1), thus

1 Nm

2
P
v
3 V

2 N 1

P m v 2
3 V 2

This equation shows that

P increases () When

(5)

N
increases
V

1
2
mv
2

increases

Translational kinetic energy of molecule

This equation shows that

N
increases
V

P increases () When

2
m v increases
2

Rearrange equation (5), thus

2 1

2
PV N m v
3 2

and

PV NkT

2 1

2
NkT N m v
3 2

1
3
2
m v kT
2
2

3
3 R
K tr kT
2
2 NA

where

K tr : average translational
kinetic energy of a

and

1
2
m v K tr
2

molecule
T : absolute temperature
k : Boltzmann constant
R : molar gas constant
N A : Avogadro constant

E NK tr
For N molecules of
an ideal gas in the
cubical
container,
the total average
(mean) translational
kinetic energy, E is
given by

3
E N kT
2

3
E NkT
2
OR

3
E nRT
2

Principle of equipartition of energy

States : the mean (average) kinetic energy of every degrees
of freedom of a molecule is

Therefore

f
K kT
2

1
kT .
2

Mean (average) kinetic

energy per molecule

OR

f
K RT
2
where

Mean (average) kinetic

energy per mole

f : degrees of freedom
T : absolute temperature

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.

vy
He

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.

vz
Figure

vx

Diatomic gas (e.g. H2, O2, N2)

The number of degrees of freedom is
Translational kinetic energy
Rotational kinetic energy

3
2
5

vy
H
vz vx

x
Figure

Polyatomic gas (e.g. H2O, CO2, NH3)

The number of degrees of freedom is
Translational kinetic energy
3
Rotational kinetic energy

vy

3
6

vz

vx

x
Figure

 Table shows the degrees of freedom for various molecules.

Degrees of Freedom ( f )
Molecule

Example
Translational Rotational

Monatomic
Diatomic
Polyatomic

Total

He

H2

H 2O

(At temperature of 300 K)

Average kinetic
energy per
molecule,<K>

3
kT
2
5
kT
2
6
kT 3kT
2

 Specific Heat :
Consider one Mole of a Gas
(contains N molecules) and each
molecule has f degrees of
freedom.
Total
. degree of freedom of the
system = Nf

If T is the temperature of the

system,
From law of Equipartition of
Energy:

1
kT
2

is the energy associated with

each degree of freedom

Total Energy of the System

1
f
U Nf kT RT
2
2
Here Nk = R (gas constant for one mole of a gas)

dU
d f

Cv

RT
dT
dT 2

f
Cv
R
2
This is the molar specific heat at
constant Volume.
For an Ideal Gas,

C p Cv R

f
RR
2

C p 1 R
2

This is the molar specific heat at

constant Pressure

The ratio of two specific heats of the

gas is given by

R
Cp
2

f
Cv
R
2
2
1
f
Monoatomic gas:
For monoatomic gas, f=3
3
3
R 1.98 2.97cal mole 1 K 1
2
2
3
5

C p 1 R 1.98 4.95cal mole 1 K 1

2
2

2
1 1.67
3
Cv

Diatomic gas:
For diatomic gas, f=5
5
5
R 1.98 4.95cal mole 1 K 1
2
2
5
7

C p 1 R 1.98 6.93cal mole 1 K 1

2
2

2
1 1.4
5
Cv

 Degrees of freedom depend on

the absolute temperature of
the gases.
For example : Diatomic gas
(H2)
Hydrogen gas have the
vibrational
kinetic energy
(as shown in Figure) 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.

H
vibration
Figure

when the temperature,

At 250 K
At 250 750 K
At >750 K

f 3
f 5
f 7

Example :
A vessel contains hydrogen gas of
7.50 1017 molecules per unit
volume and the root mean
square speed of the molecules is
2.50 km s1at a temperature of 30
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 mol1, NA= 6.02 1023
mol1and k = 1.38 1023 J K1)

Solution :
N
7.50 1017 ; vrms 2.50 103 m s 1 ;
V
T 303.15 K

a. The average translational

kinetic energy of a molecule
is

3
K tr kT
2
3
K tr 1.38 10 23 303.15
2
K tr 6.28 10

21

Solution :

N
7.50 1017 ; vrms 2.50 103 m s 1 ; T 303.15 K
V

b. The pressure of hydrogen gas is given by

M
1 N
2
2
2
and

v
P m v where m
rms
NA
3V
1 N M 2
vrms
P
3 V N A
1
0.002
17
3 2
P 7.50 10
2.50 10
23
3
6.02 10
P 5.19 10 3 Pa

Mean Free
Path
Because of their finite size, molecules in a gas
undergo frequent collisions. The average
distance a molecule travels between collisions
is called the mean free path.

m0

m1

m1

m2

Mean Free Path

d
d

2d

d
d

2d

vdt
dV d 2 vdt
Consider n number of particles are present per unit volume of the sample

d is the diameter of each molecule, a molecule moving with a velocity v

Collides with all particles whose centers lie with in a distance of d from its
path
ndv particles will be present in dv volume which will collide with the
moving particle.
number of collisions suffered by the molecule in time dt are

N d 2 v dt n

Now, mean free path of a gas molecule

dis tan ce cov ered by the molecule in time dt

number of collisions suffered in time dt
v dt
2
d nv dt
1
2
d n

This expression is obtained by considering all molecules except one molecule under
consideration are at rest.
On taking the motion of all molecules into consideration, the mean free path will be

1
2d 2 n

 relative movement of particles

magnitude of the relative velocity :

vrel vrel vrel (v1 v2 ) (v1 v2 ) = v1 v1 2v1 v2 v2 v2

vrel v1 v1 2v1 v2 v2 v2

Since v1 and v 2 are random and uncorrelated, v1 v 2 0

vrel v12 v2 2
v rel 2v