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

E V

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

Fx i

d 2 xi
d v x i
mi
mi
2
dt
dt

The Momentum Change During a

Collision
Particle

of mass mi collides with the wall

with only the x component of the
momentum changing.
+ m vix
- m vix

Not All Particles Reach the Wall!

How

many particles actually reach the

wall during a specified time interval t?
+vJ,xt

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.

n A MJ v J ,x t
2

total momentum change

The Definition of Pressure

The

pressure exerted by the gas is

calculated as follows

F n M J v J ,x t
P
A
V
2

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

F n M J v J ,x
P
A
V

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

1
2
PV n Mi v i nRT
3

The Root Mean Square Speed

1/3 MJ<vJ>2 = RT
<vJ>2 = 3RT / MJ
(<vJ>2 )1/2 = vrms = (3RT/MJ)1/2
vrms = 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

MJ
g (v )
e

2 RT

kBT

The Maxwell Distribution for Typical

Gases

Other Speed Equations

In

addition to the root-mean-square

speed, we have the
1
Most probable speed
2RT 2
v mp

MJ

The mean speed

8RT
v

MJ

1
2

The Root Mean Square Speed

Collisions With Walls and

Surfaces
Rate

at which molecules collide with a

wall of area A

Zw

pN Avo

2 RTMJ

1
2

Effusion
Rate

at which molecules pass through a

small hole of area Ao, r

r Zw Ao

pN Avo Ao

2 RTMJ

1
2

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

r1 Zw ,1Ao

pNAvo Ao

2RTM1

1
2

Effusion Equation (Contd)

Effusion

rate of gas 2 r2.

r2 Zw ,2Ao

pNAvo Ao

2RTM2

1
2

Effusion Ratio
Ratio

of effusion rates.

r2
pNAvo Ao

1
r1 2RTM 2
2
M

M
2

pNAvo Ao

2RTM1
1
2

1
2

Intermolecular Collisions in Hardsphere 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.

The Collision Cylinder

2d

Stationary particles inside

the collision tube.

The Number Density

For

N-1 stationary particles, the number

of molecules per unit volume

N
N 1
Nd

V V

Collision Frequency
We

count the total number of molecules

with centres inside the collision tube.
# Inside tube = Nd<v>t

Collision Frequency (contd)

For

N-1 stationary particles

The collision frequency - z

z1 v Nd v d Nd
2

Examine the case where all the

molecules inside the collision tube are
moving.

Collision Frequency (Contd)

Relative

speed of the colliding particles.

v
z1 v

rel

2v
1
2

rel

16RT
2
Nd
d Nd
MJ

The Mean Collision Time

The

mean collision time is average time

elapsed between successive collisions.
Define

coll

= 1/z1

coll

1
2

MJ
1

2
d Nd
16RT

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 - - the collision cross section

= d2

The Mean Free Path

The

mean free path - the average

distance traveled between successive
collisions.

v coll

1
2
2 d Nd

The Mean Free Path

The Collision Density

We

define the collision density as the

total rate of collisions per unit volume.

Z11 1 z1Nd
2
4RT

MJ

1
2

d N
2

2
d

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.
d1

d2
Mean collision
diameter
d12 = (d1+d2)

The Collision Zone

For

a collision occurring along the x and

y axis.
x

Impact Zone

X1=tc<v1>
tc = time yet to
elapse before
the collision
occurs

y2=tc<v2>
y

Mean Relative Speed

The

mean relative speed.

rel

v1

v2

8RT 1

1

M1 M2

The Reduced Mass

The

reduced mass of two particles 1 and

2 is defined as follows

1
1
1

12 M1 M2

Mean Free Paths in Heteronuclear

Collisions
For

substance 1 colliding with substance

1 2

v1

v12 d12 Nd 2

M2

M1 M2

d12 Nd 2
2

Mean Free Paths (Contd)

For

substance 2 colliding with substance

2 1

v2

v12 d12 Nd 1

M1

M1 M2

d12 Nd 1
2

Heteronuclear Collision Frequencies

The

collision frequency of molecule 1

with molecule 2 is given by

8 RT
1
z1 2

1 2 12

1
2

d12 Nd 2
2

Heteronuclear Collision Frequencies

(contd)
The

collision frequency of molecule 2

with molecule 1 is given by
1
2

8RT
1
2
d12 Nd 1
z 2 1

2 1 12

Heteronuclear Collision Density

The

total rate of heteronuclear collisions

per unit volume

Z12 z1 2 Nd 1 z 2 1 Nd 2
8RT

12

1
2

d12 Nd 1 Nd 2
2