Thermal

Phenomena 2017.1
BCJ0205-15
Lesson 8 Kine<c Theory of Gases
Based on:
Serway 6th Ed. Ch. 21
Halliday 8th Ed. Ch. 19

 The Kine<c Theory of Gases
We have previously studied empirical laws that govern the
macroscopic behavior of a gas.

Is it possible to deduce these laws by applying the basic laws

of Newtonian Mechanics to the fundamental cons<tuents
(atoms, molecules) of a gas?

We must nd the connec<on between the macroscopic
behavior of a gas and its microscopic proper<es.

This will lead us to a kine<c interpreta<on of ideal gases.

 Model of an Ideal Gas
Basic assump<ons needed
to describe a gas microscopically:

1. The number of molecules in the gas is very large
(of the order of the Avogadro number).

2. The typical dimensions of the molecule are much smaller than the average
distance between two molecules of the gas (the volume occupied by the
molecules is negligible compared to the container)

3. The molecules move constantly and randomly in all direc<ons (any direc<on
in space has the same number of molecules moving in the posi<ve and
nega<ve direc<ons). This causes collisions of the molecules with each other
and with the walls of the container.
4. The interac<on forces between two molecules, or between a molecule
and the container wall, are short in distance and in dura<on.

5. The collisions suered by the gas molecules (between themselves or
against the container walls) are elas<c (the total kine<c energy of the
molecules is conserved).
 Pressure, temperature and mean square velocity
Consider a cubic box of volume V and side
length d, with N molecules as shown in the
gure;
The are kept at temperature T;
What is the rela<on between the pressure
p exerted by the gas on the container
walls and the speed of the molecules?

The gas molecules are moving in all direc<ons and with

various speeds, colliding with one another and bouncing o
the walls of the box.
 Lets focus on a single (i-th) molecule in
the gas, of mass m, moving in the box;
We call vxi the x component of the speed
of this i-th molecule;
Since were assuming that all collisions
are elas<c, the molecule collides with a
wall and the only speed component that
changes is x, which switches sign;
Thus, the change in momentum of the
molecule is
 The molecule collides several <mes with the
shaded wall in the gure.
The interval t between these colisions is given
by:

travels a distance 2L
(back and forth) with
speed vxi

Now lets recall Newtons 2nd law, which tells us that the
rate of change in the momentum with <me is the force.

So the force exerted by the wall on the molecule is



And from Newtons 3rd law, the force of the molecule on the wall is



 To determine the total force we must add the contribu<ons of
all molecules that collide with that wall (note that their speeds
may be dierent)

where N is the number of molecules inside the box.

We can dene the average square value for the speed vx as

Thus
 For the i-th molecule with velocity components vxi, vyi and vzi the
squared speed is

If we take the average on both sides of this equa<on (i.e. sum
over all molecules and divide by N) we obtain that the average
squared speed is

Since the molecules are moving in random direc<ons (no
preferred direc<on), the average values of the squared
components of the speed are all the same. Thus

and therefore
Combining both equa<ons



We obtain that the total force on the wall is

From this expression we can obtain the pressure as

The pressure of a gas (a macroscopic quan3ty) depends on

the average velocity (or average kine3c energy) of the
molecules that form the gas (a microscopic quan3ty)
Note that the pressure that was derived is inversely propor<onal
to the volume




as we already new! Boyles Law



We have already related the pressure to the average kine<c
energy of the molecules. Now lets relate the temperature with
a microscopic descrip<on of the gs. For such, we must use the
equa<on of state for an ideal gas

 Equa<ng the right sides of both expressions:

Thus, when the temperature of a gas increases, the molecules move on
average with higher kine<c energy

At a given temperature T, all molecules of an ideal gas, regardless of their

masses, have the same average transla3onal kine3c energy. When
measuring the temperature of a gas we are also measuring the average

transla3onal kine3c energy of its molecules

We can rewrite the expression above as Each degree of freedom
contributes with kBT

Using our results that :

 Degrees of freedom refers to the number of independent
ways by which a molecule can store energy

Generaliza<on: Energy Equipar<<on Theorem

Each
degree of freedom contributes kBT to the energy of the
system, where possible degrees of freedom are associated with

transla3on, rota3on and vibra3on of molecules

The total transla<onal kine<c energy of the N gas molecules is:


Note that the total transla<onal
Where we have used that: kine<c energy is propor<onal to
the absolute temperature of the
system
 For a monoatomic gas, only the transla<onal degrees of
freedom are possible. So the internal energy of a monoatomic
gas is

Monoatomic gas

The square root of is called the root-mean-square (rms)

velocity

Note that at a
given temperature,
lighter molecules
where M is the molecular mass in kg/mol. move more rapidly
Some RMS speeds at room
temperature


Note that these speeds are
quite high -
For hydrogen
(vrms = 6900 km/h) is larger
than the speed of a military
rie bullet!

The higher the temperature,
the larger the speed

3RT
vrms =
M
The mean square velocity
of the lighter molecules is
much larger than that of
the heavier molecules.

3RT
vrms =
M
Understanding the dierence between
the average value (vavg) and the root-mean-square value (vrms)
Example:
Given the ve numbers: 5, 11, 32, 67 and 89;
(a) What is the average value navg of these numbers?

(b) What is the root mean square value nrms of these numbers?

Note that the rms value is larger than the avg value, because the
larger values, when squared, have more weight in the nal sum.
Understanding the dierence between
the average value (vavg) and the root-mean-square value (vrms)
Example:
Given the ve numbers: 5, 11, 32, 67 and 89;
(a) What is the average value navg of these numbers?

(b) What is the root mean square value nrms of these numbers?

Note that the rms value is larger than the avg value, because the
larger values, when squared, have more weight in the nal sum.
Example:
A tank used for lling helium balloons has a volume of 0.300 m3
and contains 2.00 mol of helium gas at 20.0 C. Assume that the
helium behaves like an ideal gas.

(a) What is the total transla<onal kine<c energy of the gas molecules?

(b) What is the average kine<c energy per molecule?

Example:
A tank used for lling helium balloons has a volume of 0.300 m3
and contains 2.00 mol of helium gas at 20.0 C. Assume that the
helium behaves like an ideal gas.

(a) What is the total transla<onal kine<c energy of the gas molecules?

(b) What is the average kine<c energy per molecule?

Example:
A tank used for lling helium balloons has a volume of 0.300 m3
and contains 2.00 mol of helium gas at 20.0 C. Assume that the
helium behaves like an ideal gas.

(a) What is the total transla<onal kine<c energy of the gas molecules?

(b) What is the average kine<c energy per molecule?

What If? What if the temperature is raised from 20.0C to 40.0C?

Because 40.0 is twice as large as 20.0, is the total transla<onal energy of
the molecules of the gas twice as large at the higher temperature?
 Summary
The pressure of N molecules of an ideal gas in a conned
volume V is

The average transla<onal kine<c energy per molecule is

related to the temperature T of the gas through the
expression:

where kB is Boltzmann's constant. Each transla<onal

degree of freedom (x, y, and z) contributes 1/2 kBT to
the energy associated with the molecule