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Revised Friday, January 6, 2012 !

ppmv
David Randall

In discussions of the carbon dioxide content of the atmosphere, the relative abundance of CO2 is usually discussed in terms of ppmv, or parts per million by volume. I wrote these rather simple-minded notes in an effort to understand what ppmv really means, and how it relates to the mass mixing ratio. A mole is a quantity of substance corresponding to Avogadro's number of the atoms, molecules, electrons, or other discrete entities of which the substance is composed. Avogadros number is 6.0221415 1023. Consider a substance denoted by subscript i . The molar mass of the substance, M i , is the mass of one mole of the substance. The molar volume, Vi , is dened to be the volume occupied by one mole of the substance, at a standard temperature and pressure. It follows that the density is

i =
It is useful to rearrange this as

Mi . Vi
(1)

Vi =

Mi . i
(2)

The ideal gas law can be written as

pi vi = ni R*T ,
(3)

where pi is the partial pressure of the gas (in general not the standard pressure); vi is the volume occupied (in general not the molar volume); ni is number of moles present; R* 8.31 J K-1 mol-1 is the universal gas constant; and T is the temperature (in general not the standard temperature), which is assumed to be the same for all species present. For the special case of one mole at the standard temperature and pressure, we know that vi = Vi and ni = 1 . Then (3) reduces to
Quick Studies in Atmospheric Science Copyright David Randall, 2011

Revised Friday, January 6, 2012 !

pstandardVi = R*Tstandard .
(4)

It follows that the molar volume is the same for all ideal gases. With pstandard = 100 kPa and

Tstandard = 0C , the molar volume is Vi = 2.27 10 2 m3 mol-1.

With ni moles, still at the standard temperature and pressure, the total volume is simply multiplied by ni . It follows that, at the standard temperature and pressure, the mole ratio of a gas is the same as its volume ratio. This is the origin of the expression parts per million by volume, or ppmv. The true meaning is moles per million, by volume. Personally, I nd the term ppmv confusing and even misleading, because the gas under discussion is usually not at the standard temperature and pressure. Returning to the general case, the mass of the sample is the number of moles times the molar mass, i.e., ni M i , so the density satises

i =

ni M i . vi
(5)

Using (5), we can rewrite the ideal gas law, (3), as

pi =

i * RT . Mi
(6)

From (3), for two gases at the same temperature and occupying the same volume vi , the ratio of the number of moles is the same as the ratio of the partial pressures. More generally, for N gases occupying the same volume, and sharing the same temperature, we can write

pi
N j j =1

p n
j =1

ni
N j

(7)

This says that the ratio of the partial pressure of gas i to the total pressure is the same as the ratio of the number of moles of gas i to the total number of moles. Similarly, from (6) we find that

i pi M = N i . N p j Mj j j =1 j =1
(8)

Comparing (7) and (8), we obtain

Quick Studies in Atmospheric Science Copyright David Randall, 2011

Revised Friday, January 6, 2012 !

i ni M = N i . N n j Mj j j =1 j =1
(9)

This could also be obtained directly from (5). Let ptot and tot , respectively, be the total pressure and total density of a mixture of gases:

ptot p j , tot j .
j =1 j =1

(10)

We can write the ideal gas law for the mixture as

R* ptot = tot T , M eff

(11)

where M eff is the effective molecular weight of the mixture, defined by

N j tot . M eff j =1 M j

(12)

For air, M eff = 28.97 g

mol-1.

Using (12) in (9), we obtain

i ni Mi = N tot n j M eff j =1
=
which can be rearranged to

i M eff , tot M i

i M i ni = . N tot M eff nj
j =1

(13)

This says that the mass fraction is the mole fraction times the ratio of the molecular weights.
Quick Studies in Atmospheric Science Copyright David Randall, 2011

Revised Friday, January 6, 2012 !

As an example, consider the following: The total mass of the atmosphere is about 5 x 1021 g. The total mass of water vapor in the atmosphere is about 1.25 x 1019 g. The mass fraction of water vapor in the atmosphere is about 2500 ppm. From (13), the molar fraction of water vapor is about (29/18)*2500 4000 ppmv. Note that I have written ppmv, as is conventional, even though this is really the molar fraction. For comparison, the current molar fraction of CO2 in the atmosphere is about 400 ppmv, which is about one tenth the molar fraction of water vapor. From (13), the mass fraction of CO2 is about (44/29)*400 600 ppm. The mass fraction of CO2 is thus about the mass fraction of water vapor.

Quick Studies in Atmospheric Science Copyright David Randall, 2011