4

Temperature tells us the direction of the flow of energy. If energy flows from A to B when they
are in contact, we say that the temperature of A is higher than that of B:
Energy flow: A→B then TA > TB

The zeroth law of thermodynamics:

If A is in thermal equilibrium with B, and B is in thermal equilibrium with C, then C is also in
thermal equilibrium with A.

This can be demonstrated by experiment

This result is very familiar and appears trivial but there is no self-apparent reason why it should
be so. It is only through experimental observation that this fact can be established.
A law is simply a statement of the results of millions of people-years of experience- a statement
which tells us how some feature of the universe operates.
The zeroth law of thermodynamics is really the scientific basis for the concept of temperature.
The law also justifies the use of a thermometer, a device for measuring temperature.
Description of the thermometer:
• Take 3 thermodynamic systems 


• A is a constant temperature bath (e.g. a mixture of ice and water which we

arbitrarily decide has a temperature of 0 degrees Celsius. 


• B is a graduated capillary containing a liquid (e.g. mercury) 


• C a test system which we believe to have the same temperature as the ice-water
mixture. 


• We place system B in A and note the reading on the graduated scale 


• We then place B in thermal contact with C 


• If the volume of the mercury changes (reading on the scale) we know that C has a
different temperature from that of A 


• If the reading is the same, then C is at 0 Centigrade 


• To make a useful thermometer, we calibrate the divisions on the glass capillary so

that the length of the column of liquid is at a point 100 divisions away from the ice point when
the thermometer is placed in boiling water 

 5

1.2 Kinetic Molecular Theory (see Textbook Section 1B)


A microscopic description of how atoms and molecules move around in gases. Can serve as a
basis for the description of the behaviour of fluids (and solids).

Why do we care? Implications in studies of:
• Transport properties, e.g., diffusion (matter down a concentration gradient), thermal
conduction (energy down a temperature gradient), electric conduction (electric charge along an
electrical potential gradient), viscosity (linear momentum down a velocity gradient)
• Effect on the rate of chemical reactions
• Basis for computer simulation of molecular systems including materials, interfaces, biological
systems, polymers, etc…

• The 3 assumptions of the kinetic model:

1. The gas consists of molecules of mass, m, in random motion obeying the laws of
classical mechanics.
2. The size of the molecules is very small compared to the volume of the container and is
therefore negligible.
3. The molecules do not interact, except that they undergo elastic collisions. 


What is an elastic collision? A collision where the translational kinetic energy of the molecules
involved in the collisions is conserved. Note that the collisions ensure that the molecules change
their speed and direction.

1.2.1 Pressure and Molecular Speed (Section 1.B.1(a))

Pressure of a gas: A gas in a container exerts a steady pressure because the molecules make
many collisions with the walls. This results in a force and the definition of pressure is:
p = force/area

In order to understand pressure in terms of molecular motion, we first take a look at this force.
We consider one dimension, the x-axis We have a particle of mass m moving in the x direction
with velocity component vx.

After a collision with the wall, there is a change in the sign of the velocity, vx → −vx
In terms of momentum (mass × velocity) we have, mvx → −mvx
 6

The total change in momentum per molecule is ∆px = 2mvx.

How many collisions with the wall occur in a time ∆t?

1. A molecule with velocity vx will travel a length vx∆t along the x-axis in the time interval ∆t
2. Therefore, all molecules within a distance vx∆t will hit the wall (if they travel towards it) 


3. If the wall area is A, then all particles in a volume A × vx∆t will reach it (if they go towards the
wall)
4. The number density of molecules is nNA/V (where n the total number of moles in volume V 

and NA is Avogadro’s number). So in our volume A × vx∆t, the number of molecules is


n NA n NA Avx Δt
× A × vx Δt =
V V
5. Half the molecules will go toward the wall on average (most reasonable assumption all things
1 n NA Avx Δt
being equal) and the number of collisions is: 

2 V
Returning to the momentum change, we had that the momentum change per collision per
molecule was 2mvx. Now we compute the total momentum change in the time interval ∆t:
total momentum change = (number of collisions) × (momentum change per collision)
n NA Avx Δt n M Avx2Δt
total momentum change = × 2mvx =
2V V
where M = mNA is the molar mass.

Recall that we want the force to relate it to pressure. In terms of Newton’s second law of motion:
Δvx
F = m ax = m
Δt
Δpx
or using momentum, px = mvx, and ∆px = m∆vx such that, F = 

Δt
nMAvx2 Δt
V n M Avx2
The force is therefore the rate of change of momentum, or, F = =
Δt V
F n Mvx2
and the pressure is, p = =
A V