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BROWNIAN MOTION
Brownian motion is the random movement of small particles suspended in a fluid (e.g
smoke particles in air, pollen grains in water). It provides experimental evidence of the
continuous random motion of molecules in liquids and gases.
To demonstrate Brownian motion in air, smoke particles are placed in
a glass cell which is illuminated with a beam of light from the side.
The smoke particles scatter the light shining on them. When they are
observed under a microscope they appear as bright specks (tiny
microscop
points) of light moving in a continuous and random way called
e
Brownian motion. These erratic movements of smoke particles
suggest that they are being bombarded continuously and randomly
(unevenly) from all sides by invisible air molecules in the glass cell.
Brownian motion is observable with only small particles such as
smoke particles because the molecules around them do not hit them
glass
equally from all directions, so resultant force makes them move. If a
cell
large particle is used, Brownian motion is less haphazard as the ligh
randomness of collisions between the large particle and the air t
particles tends to average out to zero and the large mass of the particle
air particles
changes its velocity less.
Note: (i) Smoke (graphite) particles are much larger than the water
(or air) molecules. The particles can be seen by the light they scatter
smoke
particle
but the molecules themselves are too small to be seen.
(ii) The size of the suspended particles and Brownian motion are
path
inversely proportional to each other due to greater inertia and less
uneven bombardment.
(iii) Brownian motion increases with increasing temperature of fluid
due to increase in k.e of fluid particles.
(iv) Brownian motion and diffusion in fluids both provide evidence of particles in continous
random motion.
IDEAL GASES
Gas Laws: Macroscopic Description of an Ideal Gas
For a fixed mass of gas,
Boyle's Law:
Charles Law:
Pressure Law (Gay-Lussac's Law):

for constant T
for constant p
for constant V

The equation of state of an ideal gas

The ideal gas obeys exactly the above three gas laws, which can be combined into a single
relationship, called the ideal gas law or the equation of state for an ideal gas, given by:
For a fixed mass of gas,
, where p is the gas
pressure, V is the volume occupied by the gas, n is the number of moles and R is the universal
(or molar) gas constant (=8.31 J mol-1 K-1 for all gases at very low densities) and T is the
thermodynamic temperature.

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An ideal gas is a gas (theoretical model) which obeys the equation
at all
values of , and (a macroscopic description of ideal gas). No such gas exists but lowdensity gases obey closely the ideal gas equation. In general, as p
0 or T
or V
,
real gases behave ideally. For approximate calculations, the ideal gas equation can be used
with real gases.
, where m is the mass of one molecule, N is the number
of molecules and NA is the Avogadros number 6.02

1023 mol-1.

Deriving
: At s.t.p where T=273K and p=1.01
occupies 22.4 L or 22.4 10-3 m3 (molar volume Vm).

pVm 1.01 105 22.4 10 3

8.31 J mol-1K -1
T
273
n moles of a gas occupy a volume of
,
Ideal gas equation

105 Pa, one mole of any gas

molar gas constant (for ALL GASES)

or

can be expressed as:

, where m = mass of gas, M = molar mass,

constant per unit mass.
, where is the density of the gas.

molar gas

NOTE: (1) In an ideal gas, potential energy of gas particles is zero as there are no
intermolecular forces. The internal energy U of an ideal gas is due only to the kinetic energy
of the random motion of its particles. It is dependent only on temperature of the gas and
number of molecules in the gas.
(2) If the pressure
and in two gas containers of volumes and respectively are
known, and the temperatures are
and
in the containers, the final pressure when the
containers are connected is given by
, where is the final temperature
of each container, since total number of moles of the two gases remains constant, that is
.
SUMMARY NOTES
An ideal gas is a gas that obeys the equation
, for an ideal gas of n moles
, for an ideal gas of N molecules
, for an ideal gas of mass m
Molar gas constant R= 8.31 JK-1 mol-1
Boltzmann constant
, where

and

under all conditions of T and P

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Connected gas containers:
When the valve is opened,
the final pressure in the two containers = p
the total number of moles in the two gases

p1, V1,
n1, T1

valve

p2, V2,
n2, T2

remains constant at n
the final temperature in the two containers = T

KINETIC THEORY OF GASES: Microscopic Description of an Ideal Gas

A gas consists of large number of identical molecules moving at high speeds in all directions
in such a way they make continuous and random collision with the walls of the container.
During a collision, the wall exerts a force on the molecule to change its momentum. By
Newtons 3rd Law, the molecule exerts an equal and opposite force on the wall. The gas
pressure is the average force exerted by the gas molecules per unit area of the container wall.
Kinetic theory of gases relates the macroscopic (experimentally observed such as temperature,
volume and pressure) behaviour of an ideal gas with the microscopic properties (e.g. speed,
mass) of its molecules. The following assumptions (describing an ideal gas microscopically)
are used to develop it:
1. Molecules do not exert any force on each other, except during collisions (no
Intermolecular forces of attraction).
2. Volume of gas molecules is negligible compared to volume occupied by the gas.
3. Molecules make elastic collisions with each other and with the walls of the container.
4. Duration of a collision is negligible compared with the time between collisions.
5. Molecules have random speed distribution.
6. There are a large number of molecules, so that statistical approach can be used.
From kinetic theory of gases, it can be shown that pressure p of a gas is given by

where N = number of molecules in the gas,

m = mass of one molecule,
V = volume of the gas
c2 = square of the speed of the gas molecules
= mean square speed of the molecules
Note:
1.
is the mean square speed of the molecules in a given direction, i.e, along a given
axis or along which pressure p acts,
2. p is the same on all sides of the container as motion of gas molecules is random,
3.
,

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4.

where

5. Average velocity of molecules in a gas is zero as random positive and negative velocities
cancel out. So the root mean square speed (
) of the molecules is used as a
measure of average speed. Since cr.m.s is a kind of average speed, some molecules move
much faster than cr.m.s and some much slower
6. Random distribution of speeds in an ideal gas:
500C
No. of
molecules

1000C
2000C

cmp crms

1800

2400

-1
3000 speed c/ms

As the temperature of the gas increases, the distribution of molecular speeds within it
changes. At higher temperatures the average speed of the molecules increases (as internal
energy of gas is greater), although the number of molecules with the most probable speed
(cmp) decreases. As temperature increases, the curve flattens & the maximum shifts to
higher speeds.
KINETIC THEORY OF TEMPERATURE
The kinetic theory of an ideal gas is given by:
The ideal gas equation is given by:

, where

Combining the above two equations gives

, where

is the universal molar

gas constant per molecule called the Boltzmanns constant. So, Kinetic theory enables us to
calculate the microscopic quantities such as
of a gas from the macroscopic
measurements such as T of the gas.
The equation
gives the average translational k.e of only a monatomic
molecule in an ideal gas. It can also be written as:

or

The equation
implies that temperature is a direct measure of average kinetic
energy of the random translational motion of its particles. So, absolute zero (T = 0 K) can be
defined as the temperature at which particles have zero k.e. It also suggests that an increase in
temperature of a gas is due to an increase of molecular speed of the gas molecules.
The total translational KE of the molecules in one mole of a gas is given by
,where M is the molar mass.

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The r.m.s speed of the molecules of one mole of an ideal gas is given by:

This expression shows that, at a given temperature, lighter molecules move faster on average
than heavier molecules.
For a given mass of gas,
For different gases at the same temperature T,

so that gas molecules of higher

mass have smaller r.m.s speeds.

For one mole of an ideal gas at temperature T, the total average translational k.e of the
molecules:
For n moles of an ideal gas at temperature T, the total average translational k.e of the
molecules:

The internal energy U of N atoms or

moles of a monatomic ideal gas is given in

terms of the Kelvin temperature as:

, i.e total translational kinetic energy

of the N atoms or n moles that constitute the gas.

The change in the internal energy U of n moles of an ideal gas due to a change in
temperature
Recall:

is given by:
and

, all ideal gas molecules at the same temperature have the

same average translational kinetic energy

the same as it depends on their mass.

, regardless of their mass, but their

is not

SUMMARY NOTES FOR KINETIC THEORY OF GASES

Basic assumptions:

Simplifying assumptions:

1. Gas consists of large number of molecules

1. Volume of molecules negligible

2. Motion of gas molecules is random

2. Intermolecular attraction negligible

3. Gas molecules has a distribution of speed

3. Elastic collisions

4. Gas pressure is due to collisions between 4. Time of collision negligible compared with
gas molecules and walls of container

time between collisions.

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EQUATIONS:
or

or

or

N = number of molecules in the gas,

m = mass of one molecule,
V = volume occupied by the gas

= mean square speed of the molecules

= root-mean-square speed of molecules
TEMPERATURE AND INTERNAL ENERGY OF AN IDEAL GAS
The internal energy of a system is the sum of the random distribution of kinetic and
potential energies of all its particles. The random k.e is due to random motion and potential
energy due to the attractive intermolecular forces.
Internal energy of an ideal gas is sum of only k.e of all particles in the gas (temperature
dependent)
Equate

and

gives

= average translational k.e of a monatomic molecule

= average translational k.e of N monatomic molecules

= average translational k.e of one mole of a monatomic ideal gas

= average translational k.e of n moles of a monatomic ideal gas
Internal energy U of an ideal gas of n moles:
For a given mass of gas,
For different gases at the same temperature T,

or

DERIVATION of
Consider a gas molecule of mass
speed cx along the x-direction.

in a cubic box of side L travelling at

cx

Change in momentum when a molecule collides with the right-hand wall

-cx
Time between a collision of a molecule with the right-hand wall and its
next collision with the same wall
L

Force applied by a molecule on the wall =

Area of right-hand wall = A = L2
Pressure exerted by a molecule on the wall =
Pressure exerted by N molecules on the wall is given by

, where
and
L3 = V, volume of cubic box.

,
c
Because the motion is random, the molecules are
equally likely to be moving in any of the 3 directions.
So
and
Hence

cz

cy
cx

NOTE:

force
on wall

average
force

wall
In oblique collisions with the wall, only
the component of momentum at 90 to the
wall changes.

time

t = time between collisons

The force exerted by a gas molecule is the
average of the forces due to each collision
Average force in a given time interval =
area under all spikes in that time inteval