Atmospheric Thermodynamics

The Empirical Gas Laws and the

Ideal Gas Law
 Empirical Gas Laws
The empirical gas laws form the basis for
the analysis and forecasting of
thermodynamics processes in the
atmosphere.

Empirical means that the laws were

developed through experimentation and
observation of gases.
 Empirical Gas Laws (Cont.)
According to Boyle’s law at a constant
temperature the pressure of a gas is
inversely proportional to its volume.

p  1/V
 Empirical Gas Laws (Cont.)
According to Gay-Lussac’s law at a
constant pressure the temperature of a
gas is directly proportional to its volume.

TV
 Ideal Gas
An ideal gas is any gas in which
thermodynamic processes can be
described exactly by Boyle’s Law and
Gay-Lussac’s Law.
 Ideal Gas Law
Boyle’s Law and Gay Lussac’s Law can be
combined into a single equation called the
ideal gas law (or the equation of state).

pV/T = constant

This form of the ideal gas law applies to a

gas composed a single type of molecule.
 Ideal Gas Law (Cont.)
We need to modify this form of the ideal gas
law to account for the different gases that
make up the composition of a mixture of
gases like we find in the Earth’s
atmosphere.
 Empirical Gas Laws (Cont.)
Avagadro’s Law states that at a specific
temperature and pressure one mole of a
gas will occupy the same volume as one
mole of any other gas.

A mole of a gas contains as many

elementary units (molecules, atoms, etc.)
as there are C atoms in exact 0.012 kg of
C12.
 Ideal Gas Law (Cont.)
Based on this observation the ideal gas law
is sometimes written as

pV = nR*T
where
n is the number of moles of a gas, and
R* is the universal gas constant
R* = 8.314 J mol-1 K-1
 Ideal Gas Law (Cont.)
Since

n = m/M
where
m is the mass of the gas, and
M is the molecular mass (weight) of the gas,
 Ideal Gas Law (Cont.)
we can rewrite the ideal gas law as

pV = mR*T/M

If we divide both sides by the volume, we

get
p = mR*T/(MV)
 Ideal Gas Law (Cont.)
p = mR*T/(MV)

Since density, ρ, is mass divided by volume,

ρ = m/V
we can write the ideal gas law as

p = ρR*T/M
 Ideal Gas Law (Cont.)
p = ρR*T/M

The specific gas constant, R, for any gas

is defined as
R = R*/M
Substitution produces
p = ρRT
 Ideal Gas Law (Cont.)
This form of the ideal gas law is valid for a
single gas, because it contains this
specific gas constant, R, for a single gas.

We need to modify R, if we want to create

an ideal gas law that we can use for the
mixture of gases in the Earth’s
atmosphere.
 Empirical Gas Laws (Cont.)
According to Dalton’s Law the total
pressure exerted by a mixture of gases is
equal to the sum of the partial pressures
exerted by the individual gases that
comprise the mixture.

p = ∑ pi = p 1 + p 2 + p 3 + … + p n
 Ideal Gas Law (Cont.)
p = ∑ pi

Using a form of the ideal gas law we had

earlier we can substitute for pi and write
Dalton’s Law as

p = ∑ ((miR*Ti)/(ViMi)
 Rule for Summations
Anything that is a constant can be pulled
outside the summation symbol and
multiplied after summing the remaining
terms.
 Assumptions About a Mixture of
Gases
If the mixture of gases is well mixed by the
winds, then all of the individual gases in
the mixture will occupy the same volume
(i.e. V1 = V2 = V3, etc.)
 Assumptions About a Mixture of
Gases (Cont.)
If the mixture of gases is well mixed by the
winds, then molecular collisions will
transfer internal energy and all of the
gases in the mixture will eventually have
the same temperature (i.e. T1=T2=T3, etc.)

By definition the universal gas constant, R*,

is a constant.
 Ideal Gas Law (Cont.)
p = ∑ ((miR*Ti)/(ViMi)

Thus, we can pull R*, T, and V out of the

summation and write

p = (R*T/V) ∑ (mi/Mi)
 Ideal Gas Law (Cont.)
p = (R*T/V) ∑ (mi/Mi)

Multiply the right hand side by

(∑mi/∑mi)
to get
p = (R*T)(∑mi/V)(∑(mi/Mi)/(∑mi)
 Ideal Gas Law (Cont.)
Since ∑mi = m, total mass of all of the gases
in the mixture, then

(∑mi/V) = ρ
 Ideal Gas Law (Cont.)
and
p = (R*T)(∑mi/V)(∑(mi/Mi)/(∑mi))
becomes
p = (R*Tρ)(∑mi/Mi)/(∑mi)
Mean Molecular Mass (Weight)
Meteorologists define a mean molecular
mass (weight), M, such that

1/M = (∑ (mi/Mi))/(∑mi)
 Dry Air
In thermodynamics the term dry air refers to
the normal mixture of gases observed in
the Earth’s atmosphere, except for the fact
that it contains no water vapor.
 Major Components of Dry Air
Gas M (kg/mol) Mass Fraction R (J kg-1 K-1)
Nitrogen (N2) 0.028 0.755 296.8
Oxygen (O2) 0.032 0.232 259.8
Argon (Ar) 0.040 0.013 208.1
Carbon
dioxide (CO2) 0.044 0.0005 188.9
Mean Molecular Mass of Dry Air
Meteorologists define the mean molecular
mass of dry air, Md based on the mass
fractions and molecular masses of the
individual gases in the table.

If we assume we have one kilogram of dry

air and plug the appropriate numbers into
the equation for 1/M, we get
Mean Molecular Mass (Weight)
Meteorologists define a mean molecular
mass (weight), M, such that

1/M = (∑ (mi/Mi))/(∑mi)
 Mean Molecular Mass for Dry Air
(Cont.)
0.755 kg + 0.232 kg + 0.013 kg + 0.0005 kg
1/Md = 0.028 kg mol-1 0.032 kg mol-1 0.040 kg mol-1 0.044 kg mol-1
0.755 kg + 0.232 kg + 0.013 kg + 0.0005 kg

Md = 0.029 kg mol-1
 Md = 0.029 kg mol -1

Gas M (kg/mol) Mass Fraction R (J kg-1 K-1)

Nitrogen (N2) 0.028 0.755 296.8
Oxygen (O2) 0.032 0.232 259.8
Argon (Ar) 0.040 0.013 208.1
Carbon
dioxide (CO2) 0.044 0.0005 188.9

Since approximately 75% of the mass of dry air is N2, it

should make sense that our Md is just a little larger than
M for N2.
 Ideal Gas Law for Dry Air
p = (R*Tρ)(∑mi/Mi)/(∑mi)
If we let
1/Md = (∑ (mi/Mi))/(∑mi)

then we can substitute to get

p = (R*Tρ)/Md
 Gas Constant for Dry Air
Meteorologists often define as gas constant
for dry air, Rd, as

Rd = R*/Md

Rd = 8.314 J mol-1 K-1 / 0.029 kg mol-1

Rd = 287 J kg-1 K-1

 Ideal Gas Law for Dry Air (Cont.)
p = (R*Tρ)/Md
and
Rd = R*/Md
so substitution produces
p = ρRdT
which is the most common form of the ideal
gas law for dry air.