Kinetic Theory of Gases

Kinetic Theory of Gases

The macroscopic behaviour of an ideal gas can be described by using
the equation of state but the microscopic behaviour only can be
described 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 in constant motion. Gravity has no effect
on molecular motion.
Consider, initially a single molecule moving
with a velocity v
x
towards wall A and after
colliding elastically , it moves in the
opposite direction with a velocity v
x












Consider an ideal gas of N
molecules are contained in a
cubical container of side d












Wall A
Wall B
Force exerted by an ideal
gas
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. v
x
, v
y

and v
z
.
Wal
l A
Wal
l B
Wal
l A Wal
l B
Figure
14.5
Therefore the change in the
linear momentum of the
molecule is given by

( )
x x x
mv mv P = A
x x
mv P 2 = A
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
x
v
d
t
2
= A
If F
x1
is the magnitude of the
average force exerted by a
molecule on the wall in the time
At, thus by applying Newtons
second law of motion gives
|
|
.
|

\
|
=
A
A
=
x
x x
x
v
d
mv
t
P
F
2
2
1
2
1 x x
v
d
m
F
|
.
|

\
|
=
For N molecules of the ideal gas,
2 2
2
2
1
.......
xN x x x
v
d
m
v
d
m
v
d
m
F
|
.
|

\
|
+ +
|
.
|

\
|
+
|
.
|

\
|
=
( )
2 2
2
2
1
.......
xN x x x
v v v
d
m
F + + + =
where v
x1
is the x component
of velocity of molecule 1, v
x2
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










N
v v v
v
xN x x
x
2 2
2
2
1
2
....... + + +
>= <
( )
> < =
+ + +
2
2 2
2
2
1
.......
x
xN x x
v N
v v v
> < =
2
x x
v N
d
m
F
2 2 2
2
z y x
v v v v + + =
> < + > < + > >=< <
2 2 2
2
z y x
v v v v
Thus, the x component for the total
force exerted on the wall of the
cubical container is
The magnitude of the velocity v
is given by
then
Since the velocities of the molecules in the ideal gas are
completely random, there is no preference to one direction
or another. Hence




The total force exerted on the wall in all direction, F is given by
> < >= <
2
2
3
x
v v
> >=< >=< <
2 2 2
z y x
v v v
3
2
2
> <
>= <
v
v
x
|
|
.
|

\
|
> <
=
d
v m N
F
2
3
> < =
2
x
v N
d
m
F
|
|
.
|

\
|
> <
=
3
2
v
N
d
m
F
where molecule the of velocity square mean :
2
> < v
From the definition of pressure,
Pressure of an ideal gas
A
F
P =
2
d A =
where
|
|
.
|

\
|
> <
=
d
v m
3
N
F
2
and
|
|
.
|

\
|
> <
=
3
2
3
1
d
v Nm
P
|
.
|

\
|
> < =
2
v
V
Nm
3
1
P
V d =
3
and
( ) > < =
2
3
1
v Nm PV
where
container in the gas ideal an of mass : Nm
Since the density of the
gas, is given by



hence the equation can
be written as
V
Nm
=
where
gas by the pressure : P
gas the of density :
molecules gas the of
velocity square mean :
2
> < v
> < =
2
3
1
v P



is defined as

From the equation of state in terms of
Boltzmann constant, k :


By equating the eqs.


Root mean square
velocity ( v
rms
)
NkT PV =
( ) > < =
2
3
1
v Nm NkT
m
kT
v
3
2
>= <
> < =
2
rms
v v
Since





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









where
re temperatu absolute : T
gas molecule a of mass : m
(speed) velocity square mean root :
rms
v
gas a of mass molar : M
> < =
2
3
1
v P
thus

P 3
v
2
>= <

P
v
3
rms
=
Therefore
OR
m
kT
v
3
rms
=
M
RT
v
3
rms
=
Eight gas molecules chosen at
random are found to have
speeds of 1,1,2,2,2,3,4 and 5
m/s. Determine
a. the mean speed of the
molecules,
b. the mean square speed of
the molecules,
c. the root mean square
speed of the molecules.
Solution :
a. The mean speed of the
molecules is given by
8 = N
N
v
v
N
i
i
=
>= <
1
( ) ( ) ( ) ( ) ( ) ( ) ( ) ( )
8
5 4 3 2 2 2 1 1 + + + + + + +
>= < v
1
s m 5 . 2

>= < v
Sample problem #1
Solution :

b. The mean square speed of
the molecules is given by








8 = N
N
v
v
N
i
i
=
>= <
1
2
2
( ) ( ) ( ) ( ) ( ) ( ) ( ) ( )
8
5 4 3 2 2 2 1 1
2 2 2 2 2 2 2 2
2
+ + + + + + +
>= < v
2 2 2
s m 8

>= < v
c. The root mean square speed
of the molecules is
> < =
2
rms
v v
8
rms
= v
1
rms
s m 83 . 2

= v
Solution :



a. By using the equation of
state, thus
A cylinder of volume 0.08 m
3

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.

Pa 10 90
K; 280 ; m 08 . 0
3
3
=
= =
P
T V
nRT PV =
M
m
n =
RT
M
m
PV
|
.
|

\
|
=
and
(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
, N
A

= 6.02 10
23
mol
1
)
Sample Problem #2
Solution :
a.



b. The number of oxygen molecules in the cylinder is







c. The root mean square speed of the oxygen molecules is
( )( )
1
rms
s m 467
032 . 0
280 31 . 8 3

= = v
kg 10 90 . 9
2
= m
A
N
N
M
m
n = =
A
N
M
m
N
|
.
|

\
|
=
Pa 10 90 K; 280 ; m 08 . 0
3 3
= = = P T V
( ) ( )280 31 . 8
032 . 0
08 . 0 10 90
3
|
.
|

\
|
=
m
23
2
10 02 . 6
032 . 0
10 90 . 9

|
|
.
|

\
|

=

N
molecules 10 86 . 1
24
= N
M
RT
v
3
rms
=
Sample Problem #3
a.) What is the average translational kinetic
energy of a molecule of an ideal gas at a
temperature of 27 C?
b.) What is the total random translational kinetic
energy of the molecule in one mole of this
gas?
c.) What is the root-mean-square speed of
oxygen molecules at this temperature?