ESCI 341 – Atmospheric Thermodynamics

Lesson 4 –Ideal Gases

References: An Introduction to Atmospheric Thermodynamics, Tsonis

Introduction to Theoretical Meteorology, Hess
Physical Chemistry (4th edition), Levine
Thermodynamics and an Introduction to Thermostatistics, Callen

IDEAL GASES
An ideal gas is a gas with the following properties:
ο There are no intermolecular forces, except during collisions.
ο All collisions are elastic.
ο The individual gas molecules have no volume (they behave like point masses).
The equation of state for ideal gasses is known as the ideal gas law.
The ideal gas law was discovered empirically, but can also be derived
theoretically. This derivation is as follows:
ο Imagine a box of volume V containing N molecules. The sides of the box
have area A. The molecules move at random, with an average speed of v.
ο If the average x component of velocity is vx, then one-half of the molecules in
a sub-volume given by Avx∆t (shaded area in figure below) would be expected
to strike the right-hand side of the box in time ∆t.

The reason only one-half the molecules will strike, is because the other
half are moving the other way, on average.
ο The number of molecules in the sub-volume is the number density, N/V,
multiplied by the sub-volume. Dividing this by 2 gives the number of
collisions in time ∆t,
 NA
Collisions = v x ∆t . (1)
2V
ο The force on a molecule of a single collision between the molecule and the
wall is given by
dv x
F (t ) = m . (2)
dt
Averaging (2) over the time interval ∆t gives the average force on a molecule
during a collision against the wall. This average fore is
t + ∆t t + ∆t
1 1 dvx 1 2mvx
F= m dt = m [ v (t + ∆t) − v (t) ] = − .
∆t ∫
t
F (t)dt =
∆t ∫
t dt ∆t x x
∆t

ο The force on the wall is opposite the force on the molecule, so the force on the
wall due to a single collision is
2mv x
F= (3)
∆t
ο The pressure on the wall due to the collision of one molecule is the force
[Eqn. (3)] divided by the area of the wall,
2mv x
pone = (4)
A∆t
ο The pressure due to all the particles that collide in time interval ∆t is the
pressure of a single molecule [Eqn. (4)] multiplied by the total number of
collisions in time ∆t [Eqn. (1)],
2mv NAv ∆t mN v
2 (5)
p= x
× x
= x
A∆t 2V V
ο vx is related to v by
v 2 = v x2 + v 2y + v z2 = 3v 2x
(since there is no preferred direction of motion, all three average velocity
components are of the same magnitude). Therefore, the pressure is equal to
mN v2
p= . (6)
3V

ο The term m v2 represents the average translational kinetic energy of the

molecules, and is proportional to temperature. Thus, we can write

2
 mv 2 = CT (7)
where C is just a constant of proportionality.
Substituting (7) into (6) and rearranging gives
pV = (C 3)NT . (8)

Experiments show that C/3 has a value of about 1.38×10−23 J K−1. This is
defined to be the Boltzmann constant, k, so we can write (8) as
pV = kNT . (9)
ο Rather than deal with the total number of molecules, N, we would like to use
the number of moles, n. If we multiply and divide by Avogadro’s number
(NA), we get
N
pV = N A kT
NA
and defining NAk to be the universal gas constant, R, we finally arrive at the
form of the ideal gas law we are most familiar with,
pV = nRT . Ideal Gas Law (10)

R has a value of 8.3145 J-mol−1-K−1, and n is the number of moles (not

molecules).
A true ideal gas would be monatomic, meaning each molecule is comprised of a
single atom.
Real gasses in the atmosphere, such as O2 and N2, are diatomic, and some gasses
such as CO2 and O3 are triatomic.
Real atmospheric gasses have rotational and vibrational kinetic energy, in
addition to translational kinetic energy.
Even though the gasses that make up the atmosphere aren’t monatomic, they
still closely obey the ideal gas law at the pressures and temperatures encountered
in the atmosphere, so we can still use the ideal gas law.

FORM OF IDEAL GAS LAW MOST USED BY METEOROLOGISTS

In meteorology we use a modified form of the ideal gas law. We first divide (10)
by volume to get

3
 n
p= RT .
V
we then multiply the RHS top and bottom by the molecular weight of the gas, M,
to get
Mn R
p= T.
V M
Mn/V is just the density of the gas. By defining R/M to be the specific gas
constant, R′, we get the following form of the ideal gas law
p = ρ R′T . (11)
The specific gas constant is different for each gas! It is found by dividing the
universal gas constant by the molecular weight of the gas.
Dry air has a molecular weight of 28.964 g/mol. The specific gas constant for
dry air is then 287.1 J kg−1 K−1, and is given the symbol Rd. The ideal gas law for
dry air is then
p = ρ Rd T (12)

or equivalently, in terms of specific volume,

pα = Rd T . (13)

USEFUL RELATIONS FOR COMPARING TWO STATES OF AN IDEAL GAS

One very useful consequence of the ideal gas law that it can be rewritten [from
Eq. (13) for an arbitrary gas] as
pα
= R′ . (14)
T
This allows us to compare variables for two different states of the same gas by
writing
p1α1 p2α 2
= . (15)
T1 T2
As an example, imagine if a gas expands to twice its original volume while
maintaining a constant pressure. From Eq. (15) we can immediately figure out
the ratio of its final and initial temperatures by writing

4
 T2 p2 α 2 α 2 2
= = =
T1 p1 α1 α1 1
which shows that the gas’s temperature would also double.
As another example, imagine if a gas’s pressure increases to four times its
original value while keeping a constant temperature. Manipulating Eq. (15)
shows that its volume would decrease to one-fourth its original size,
α 2 T2 p1 p1 1
= = = .
α1 T1 p2 p2 4
As a final example, imagine if a gas’s pressure increases to six times its original
value while the volume decreases to one-fourth its original size. Manipulating
Eq. (15) shows that the temperature increase by 150%,
T2 p2 α 2 6 1 3
= = ⋅ = .
T1 p1 α1 1 4 2

INTERNAL ENERGY OF AN IDEAL GAS

Since there are no intermolecular forces in an ideal gas, there is no internal
potential energy. The internal energy of a monatomic gas is therefore due solely
to the translational kinetic energy of the molecules.
If the molecules have more than one atom, then there is also kinetic energy due
to rotation and vibration.
ο Though technically not an ideal gas, at normal temperatures and pressures
the main atmospheric gasses closely follow the ideal gas law, so we can still
speak of air as an ideal gas.
The translational kinetic energy has a value of
1 2 1 m 2 3 kT 3 N A k 3
utrans = v = v = = T = R′T
2 2m 2 m 2 N Am 2

ο The rotational kinetic energy depends on whether the molecule is monatomic

or multi-atomic, and whether it is linear or bent. It is
u rot = 0; monatomic molecule
u rot = R′T ; linear molecule
3
u rot = R′T ; bent molecule
2

5
ο The vibrational kinetic energy is a complicated function of temperature. For
light diatomic molecules (such as N2 and O2) it can be considered a constant
except at extremely high temperatures.
Thus, the internal energies for most monatomic and diatomic molecules are

3
u = u trans = R ′T + const.; monatomic gas
2
Internal Energy
5
u = u trans + u rot + u vib = R ′T + const.; diatomic gas
2
ο Note that when temperature is 0K, there is still some kinetic energy. Motion
does not cease at absolute zero.
An important point to notice is that, for an ideal gas, the internal energy is a
function of temperature only.

6
EXERCISES
1. From the ideal gas law pV = nRT, calculate how many molecules are contained in
a cubic centimeter (cm3) of air at a pressure of 1013.25 mb and a temperature of
15 °C? (R = 8.3145 J-mol−1-K−1; NA = 6.022 ×1023 molecules/mol)

2. How many oxygen molecules are there in a cm3 of air at a pressure of 1013.25 mb
and a temperature of 15 °C?

3. The table below gives the molecular weights and volume percentages for the
standard atmosphere. Use them to show that the molecular weight of air is
28.964 g/mol.

Gas M (g/mol) % by volume

N2 28.0134 78.084
O2 31.9988 20.9476
Ar 39.948 0.934
CO2 44.00995 0.0314

4. Show that the specific gas constant for dry air (Rd) is equal to 287.1 J-kg−1-K−1.

5. Levels of CO2 in the atmosphere have been increasing since the industrial
revolution. Is the specific gas constant for dry air larger or smaller now than it
was in 1800?

6. Explain why moist air is lighter than dry air (at the same pressure and
temperature).