Chemistry 232

Kinetic Theory of Gases

Kinetic Molecular Theory of
Gases
Macroscopic (i.e., large quantity)
behaviour of gases pressure, volume,
and temperature.
The kinetic molecular theory of gases
attempts to explain the behaviour of
gases on a molecular level.
Assumptions of Kinetic Theory
Total energy of the system
V E + 9 =
Intermolecular attractive interactions
are negligible.
Postulates of Kinetic Theory of
Gases
Gases consist of molecules of mass m
and diameter d.
Gas molecules are in constant, rapid,
straight-line motion. Collisions are
elastic.
The gas molecules interact only when
they collide.
Kinetic Theory Postulates
(Contd)
Average kinetic energy (K.E.) of
molecules depends on absolute
temperature (T) only.
All collisions are elastic.
Kinetic Theory of Gases
Explanation of Pressure
Gas pressure - collisions of gas
molecules with the container walls.
The force of a collision depends on
the number of collisions per unit time
how hard gas molecules strike the container
wall!
The greater the momentum of gas
molecules, the greater the effect of the
impact on the walls.
Force/A = P
( )
( )
)
`

=
)
`

=
2
i
2
i
i
x
i
i
x
dt
x d
m
dt
v d
m F
The Momentum Change During a
Collision
Particle of mass m
i
collides with the wall
with only the x component of the
momentum changing.
+ m v
ix

- m v
ix

Not All Particles Reach the Wall!
How many particles actually reach the
wall during a specified time interval At?
+v
J,x
At
These molecules dont
reach the wall!
These molecules come
into contact with the wall!
The Total Momentum Change
The total momentum change is
calculated form the sum of the
momentum changes for the individual
particles.
( )
2
,
A
total momentum change
J J x
n M v t
V
A
=
The Definition of Pressure
The pressure exerted by the gas is
calculated as follows
( )
2
,
P
J J x
n M v t
F
A V
A
= =
Distribution of Molecular Speeds
This speed in the above equation should
be an average speed (some will always
be fast, some slow).
Replace with the ensemble average
2
,
P
J J x
n M v t
F
A V
A
= =
The Mean Square Speed
Kinetic Molecular Theory of Gases
allows us to relate macroscopic
measurements to molecular quantities
P, V are related to the molar mass and
mean square seed
nRT v M n
i i
= =
2

3
1
PV
The Root Mean Square Speed
1/3 M
J
<v
J
>
2
= RT
<v
J
>
2
= 3RT / M
J

(<v
J
>
2
)
1/2
= v
rms
= (3RT/M
J
)
1/2
v
rms
= the root mean square speed
The Maxwell Probability Distribution
In kinetic theory, we are interested in the
fraction of molecules having a particular
range of speeds.
The probability distribution of speeds
3
2
( )
2
B
k T
J
M
g v e
RT
c
t

| |
=
|
\ .
The Maxwell Distribution for Typical
Gases
Other Speed Equations
In addition to the root-mean-square
speed, we have the
Most probable speed


The mean speed
1
2
2
mp
J
RT
v
M
| |
=
|
\ .
1
2
8
J
RT
v
M t
| |
=
|
\ .
The Root Mean Square Speed
Collisions With Walls and
Surfaces
Rate at which molecules collide with a
wall of area A
( )
t
=
1
2
2
Avo
w
J
pN
Z
RTM
Effusion
Rate at which molecules pass through a
small hole of area A
o,
r
( )
1
2
2
Avo o
w o
J
pN A
r Z A
RTM t
= =
Effusion (Contd)
Effusion.
A gas under pressure goes (escapes) from
one compartment of a container to another by
passing through a small opening.
Effusion
The Effusion Equation
Grahams Law - estimate the ratio of the
effusion rates for two different gases.
Effusion rate of gas 1 r
1
.
( )
2
1
1
1 , 1
2
r
RTM
A pN
A Z
o Avo
o w
t
= =
Effusion Equation (Contd)
Effusion rate of gas 2 r
2
.

( )
2
1
2
2 , 2
2
r
RTM
A pN
A Z
o Avo
o w
t
= =
Effusion Ratio
Ratio of effusion rates.

( ) ( )
2
1
2
1
2
1
1
2
1
2
1
2
2 2
r
|
.
|

\
|
=
=
M
M
RTM
A pN
RTM
A pN
r
o Avo o Avo
t t
Intermolecular Collisions in Hard-
sphere Gases
Quantitative picture of the events that
take place in a collection of gaseous
molecules.
Frequency of collisions?
Distance between successive collisions?
Rate of collisions per unit volume?

The Definition of a Collision
A pair of molecules will collide whenever
the centres of the two molecules come
within a distance d (the collision
diameter) of one another.
No collision. Collision occurs.
d
The Collision Cylinder
2d
d
Stationary particles inside the
collision tube.
The Number Density
For N-1 stationary particles, the number
of molecules per unit volume

V
N
V
1 N
N
d
~
|
.
|

\
|

Collision Frequency
We count the total number of molecules
with centres inside the collision tube.
# Inside tube = N
d
o<v>At
Collision Frequency (contd)
For N-1 stationary particles
The collision frequency - z
1

d
2
d 1
N d v N v z t o = =
Examine the case where all the
molecules inside the collision tube are
moving.
Collision Frequency (Contd)
Relative speed of the colliding particles.
1
2
2
1
2
16
rel
d d
rel
J
v v
RT
z v N d N
M
o t
t
=
| |
= =
|
\ .
The Mean Collision Time
The mean collision time is average time
elapsed between successive collisions.
Define
t
coll
= 1/z
1

1
2
2
1
16
J
coll
d
M
RT d N
t
t
t
| |
=
|
\ .
The Mean Free Path
Gas molecules encounter collisions with
other gas molecules and with the walls
of the container
Define the mean free path as the
average distance between successive
molecular collisions
Note - o - the collision cross section
o = td
2

The Mean Free Path
The mean free path - the average
distance traveled between successive
collisions.
2
1 1
2
coll
d
v
d N
t
t
= =
The Mean Free Path
The Collision Density
We define the collision density as the
total rate of collisions per unit volume.
11 1
1
2
2 2
1

2
4

d
d
J
Z z N
RT
d N
M
t
t
=
| |
=
|
\ .
Collisions in Heteronuclear Systems
Modify the above discussion to include
collisions between unlike molecules.
The mean collision diameter.
The reduced mass of the colliding molecules.
The collision zone.
The Mean Collision Diameter
Define in terms of the collision diameters
of the colliding species.
d
1

d
2

Mean collision
diameter
d
12
= (d
1
+d
2
)
The Collision Zone
For a collision occurring along the x and
y axis.
Impact Zone
X
1
=t
c
<v
1
>
x
y
y
2
=t
c
<v
2
>
t
c
= time yet to
elapse before the
collision occurs

Mean Relative Speed
The mean relative speed.
( )
2
1
2 1
2
1
2
2
2
1
1 1
|
|
.
|

\
|
)
`

+
t
=
+ =
M M
8RT

v v v
rel
The Reduced Mass
The reduced mass of two particles 1 and
2 is defined as follows
2 1
1 1 1
M M
12
+ =

Mean Free Paths in Heteronuclear

Collisions
For substance 1 colliding with substance
2
( )
( ) ( )
( ) ( ) 2
1
2
1
2
2
12
2
1
2 1
2
2
12
12
1
1
d
d
N d
M M
M
N d
v
v
t
|
|
.
|

\
|
+
=
t
=
Mean Free Paths (Contd)
For substance 2 colliding with substance
1
( )
( ) ( )
( ) ( ) 1
1
1
1
1
2
12
2
1
2 1
1
2
12
12
2
2
d
d
N d
M M
M
N d
v
v
t
|
|
.
|

\
|
+
=
t
=
Heteronuclear Collision Frequencies
The collision frequency of molecule 1
with molecule 2 is given by
( )
( )
( ) ( ) 2 N d
RT 8
2
1
2 z
d
2
12
2
1
12 1
1
t
t t
|
|
.
|

\
|
= =
Heteronuclear Collision Frequencies
(contd)
The collision frequency of molecule 2
with molecule 1 is given by

( )
( )
( ) ( ) 1
8
1
1
1
2
12
2
1
12 2
2 d
N d
RT
z t
t t
|
|
.
|

\
|
= =
Heteronuclear Collision Density
The total rate of heteronuclear collisions
per unit volume
( ) ( ) ( ) ( )
( ) ( ) ( ) 2 1
8

2 1 1 2
2
12
2
1
12
2 1 12
d d
d d
N N d
RT
N z N z Z
t
t
|
|
.
|

\
|
=
= =