1

Measures of Atmospheric
Composition

The objective of atmospheric chemistry is to understand the factors that

control the concentrations of chemical species in the atmosphere. In
this book we will use three principal measures of atmospheric composi-
tion: mixing ratio, number density, and partial pressure. As we will see,
each measure has its own applications.

1.1 Mixing Ratio

The mixing ratio C X of a gas X Žequivalently called the mole fraction.
is defined as the number of moles of X per mole of air. It is given in
units of mol!mol Žabbreviation for moles per mole., or equivalently in
units of v!v Žvolume of gas per volume of air. since the volume
occupied by an ideal gas is proportional to the number of molecules.
Pressures in the atmosphere are sufficiently low that the ideal gas law is
always obeyed to within 1%.
The mixing ratio of a gas has the virtue of remaining constant when
the air density changes Žas happens when the temperature or the
pressure changes.. Consider a balloon filled with room air and allowed
to rise in the atmosphere. As the balloon rises it expands, so that the
number of molecules per unit volume inside the balloon decreases;
however, the mixing ratios of the different gases in the balloon remain
constant. The mixing ratio is therefore a robust measure of atmospheric
composition.
Table 1-1 lists the mixing ratios of some major atmospheric gases.
The most abundant is molecular nitrogen ŽN2 . with a mixing ratio
C N 2 " 0.78 mol!mol; N2 accounts for 78% of all molecules in the
atmosphere. Next in abundance are molecular oxygen ŽO 2 . with CO 2 "
0.21 mol!mol, and argon ŽAr. with CAr " 0.0093 mol!mol. The mixing
ratios in table 1-1 are for dry air, excluding water vapor. Water vapor
mixing ratios in the atmosphere are highly variable Ž10#6 !10#2
mol!mol.. This variability in water vapor is part of our everyday
4 – CHAPTER 1. ATMOSPHERIC COMPOSITION

Table 1-1 Mixing Ratios of Gases in Dry Air

Mixing ratio
Gas (mol!mol)

Nitrogen ŽN2 . 0.78

Oxygen ŽO 2 . 0.21
Argon ŽAr. 0.0093
Carbon dioxide ŽCO 2 . 365 ! 10#6
Neon ŽNe. 18 ! 10#6
Ozone ŽO 3 . Ž0.01!10. ! 10#6
Helium ŽHe. 5.2 ! 10#6
Methane ŽCH 4 . 1.7 ! 10#6
Krypton ŽKr. 1.1 ! 10#6
Hydrogen ŽH 2 . 500 ! 10#9
Nitrous oxide ŽN2 O. 310 ! 10#9

experience as it affects the ability of sweat to evaporate and the drying

rate of clothes on a line.
Gases other than N2 , O 2 , Ar, and H 2 O are present in the atmosphere
at extremely low concentrations and are called trace gases. Despite their
low concentrations, these trace gases can be of critical importance for
the greenhouse effect, the ozone layer, smog, and other environmental
issues. Mixing ratios of trace gases are commonly given in units of parts
per million $ olume Ž ppm$ or simply ppm., parts per billion $ olume Ž ppb$
or ppb., or parts per trillion $ olume Ž ppt$ or ppt .; 1 ppmv " 1 ! 10#6
mol!mol, 1 ppbv " 1 ! 10#9 mol!mol, and 1 pptv " 1 ! 10#1 2
mol!mol. For example, the present-day CO 2 concentration is 365 ppmv
Ž365 ! 10#6 mol!mol..

1.2 Number Density

The number density n X of a gas X is defined as the number of
molecules of X per unit volume of air. It is expressed commonly in
units of molecules cm#3 Žnumber of molecules of X per cm3 of air..
Number densities are critical for calculating gas-phase reaction rates.
Consider the bimolecular gas-phase reaction

X % Y ! P % Q. Ž R1.

The loss rate of X by this reaction is equal to the frequency of

collisions between molecules of X and Y multiplied by the probability
that a collision will result in chemical reaction. The collision frequency
is proportional to the product of number densities n X n Y . When we
 CHAPTER 1 – 5

Fig. 1-1 Absorption of radiation by an atmospheric

column of gas.

write the standard reaction rate expression

d
& X ' " #k & X '& Y ' Ž 1.1.
dt

where k is a rate constant, the concentrations in brackets must be

expressed as number densities. Concentrations of short-lived radicals
and other gases that are of interest primarily because of their reactivity
are usually expressed as number densities.
Another important application of number densities is to measure the
absorption or scattering of a light beam by an optically active gas. The
degree of absorption or scattering depends on the number of molecules
of gas along the path of the beam and therefore on the number density
of the gas. Consider in figure 1-1 the atmosphere as extending from the
Earth’s surface Ž z " 0. up to a certain top Ž z " zT . above which
number densities are assumed negligibly small Žthe meaning of zT will
become clearer in chapter 2.. Consider in this atmosphere an optically
active gas X. A slab of unit horizontal surface area and vertical
thickness dz contains n X dz molecules of X. The integral over the
depth of the atmosphere defines the atmospheric column of X as

zT
Column " H0 n X dz. Ž 1.2.

This atmospheric column determines the total efficiency with which the
gas absorbs or scatters light passing through the atmosphere. For
6 – CHAPTER 1. ATMOSPHERIC COMPOSITION

example, the efficiency with which the ozone layer prevents harmful
solar ultraviolet radiation from reaching the Earth’s surface is deter-
mined by the atmospheric column of ozone Žproblem 1.3..
The number density and the mixing ratio of a gas are related by the
number density of air n a Žmolecules of air per cm3 of air.:

n X " CX n a . Ž 1.3.

The number density of air is in turn related to the atmospheric pressure

P by the ideal gas law. Consider a volume V of atmosphere at pressure
P and temperature T containing N moles of air. The ideal gas law gives

PV " NRT , Ž 1.4.

where R " 8.31 J mol#1 K#1 is the gas constant. The number density
of air is related to N and V by
A$ N
na " Ž 1.5.
V
where A $ " 6.022 ! 10 23 molecules mol#1 is Avogadro’s number. Sub-
stituting equation Ž1.5. into Ž1.4. we obtain
A$ P
na " Ž 1.6.
RT
and hence
A$ P
nX " CX . Ž 1.7.
RT
We see from Ž1.7. that n X is not conserved when P or T changes.
A related measure of concentration is the mass concentration " X ,
representing the mass of X per unit volume of air Žwe will also use " X
to denote the mass density of a body, i.e., its mass per unit volume; the
proper definition should be clear from the context.. " X and n X are
related by the molecular weight M X Žkg mol#1 . of the gas:
n X MX
"X " . Ž 1.8.
A$

The mean molecular weight of air Ma is obtained by averaging the

contributions from all its constituents i:

Ma " Ý C i Mi Ž 1.9.
i
 CHAPTER 1 – 7

and can be approximated Žfor dry air. from the molecular weights of N2 ,
O 2 , and Ar:

Ma " C N 2 M N 2 % CO 2 MO 2 % CAr MAr

" Ž 0.78 # 28 ! 10#3 . % Ž 0.21 # 32 ! 10#3 . % Ž 0.01 # 40 ! 10#3 .

" 28.96 ! 10#3 kg mol#1 . Ž 1.10.

In addition to gases, the atmosphere also contains solid or liquid

particles suspended in the gaseous medium. These particles represent
the atmospheric aerosol; ‘‘aerosol’’ is a general term describing a
dispersed condensed phase suspended in a gas. Atmospheric aerosol
particles are typically between 0.01 and 10 $ m in diameter Žsmaller
particles grow rapidly by condensation while larger particles fall out
rapidly under their own weight.. General measures of aerosol abun-
dances are the number concentration Žnumber of particles per unit
volume of air. and the mass concentration Žmass of particles per unit
volume of air.. A full characterization of the atmospheric aerosol
requires additional information on the size distribution and composition
of the particles.

Exercise 1-1 Calculate the number densities of air and CO 2 at sea level for
P " 1013 hPa, T " 0%C.

Answer. Apply Ž1.6. to obtain the number density of air n a. Use International
System ŽSI. base units at all times in numerical calculations to ensure
consistency:

A$ P Ž 6.022 ! 10 23 . # Ž 1.013 ! 10 5 .
na " " " 2.69 ! 10 25 molecules m#3 .
RT 8.31 # 273

After you obtain the result for n a in SI base units, you can convert it to the
more commonly used unit of molecules cm#3 : n a " 2.69 ! 10 19 molecules
cm#3. The air density at sea level does not vary much around the world; the
sea-level pressure varies by at most 5%, and the temperature rarely departs
by more than 15% from 273 K, so that n a remains within 25% of the value
calculated here.
The number density of CO 2 is derived from the mixing ratio CCO 2 " 365
ppmv:

n CO 2 " CCO 2 n a " 365 ! 10#6 ! 2.69 ! 10 25 " 9.8 ! 10 21 molecules m#3 .
8 – CHAPTER 1. ATMOSPHERIC COMPOSITION

Exercise 1-2 In surface air over the tropical oceans the mixing ratio of water
vapor can be as high as 0.03 mol!mol. What is the molecular weight of this
moist air?

Answer. The molecular weight Ma of moist air is given by

Ma " Ž 1 # C H 2 O . Ma, dry % C H 2 O M H 2 O

where Ma, dry " 28.96 ! 10#3 kg mol#1 is the molecular weight of dry air
derived in Ž1.10., and M H 2 O " 18 ! 10#3 kg mol#1. For C H 2 O " 0.03
mol!mol we obtain Ma " 28.63 ! 10#3 kg mol#1. A mole of moist air is
lighter than a mole of dry air.

1.3 Partial Pressure

The partial pressure PX of a gas X in a mixture of gases of total
pressure P is defined as the pressure that would be exerted by the
molecules of X if all the other gases were removed from the mixture.
Dalton’s law states that PX is related to P by the mixing ratio C X :

PX " C X P. Ž 1.11.

For our applications, P is the total atmospheric pressure. Similarly to

Ž1.6., we use the ideal gas law to relate PX to n X :

nX
PX " RT . Ž 1.12.
A$

The partial pressure of a gas measures the frequency of collisions of gas

molecules with surfaces and therefore determines the exchange rate of
molecules between the gas phase and a coexistent condensed phase.
Concentrations of water vapor and other gases that are of most interest
because of their phase changes are often given as partial pressures.
Let us elaborate on the partial pressure of water PH 2 O , commonly
called the water $ apor pressure. To understand the physical meaning of
PH 2 O , consider a pan of liquid water exposed to the atmosphere Žfigure
1-2a.. The H 2 O molecules in the liquid are in constant motion. As a
result of this motion, H 2 O molecules at the surface of the pan evapo-
rate to the atmosphere. If we let this evaporation take place for a long
enough time, the pan will dry out. Let us place a lid on top of the pan to
prevent the H 2 O molecules from escaping Žfigure 1-2b.. The H 2 O
molecules escaping from the pan bounce on the lid and must now
eventually return to the pan; a steady state is achieved when the rate at
 CHAPTER 1 – 9

Fig. 1-2 Evaporation of water from a pan.

which molecules evaporate from the pan equals the rate at which water
vapor molecules return to the pan by collision with the liquid water
surface. The collision rate is determined by the water vapor pressure
PH 2 O in the head space. Equilibrium between the liquid phase and the
gas phase is achieved when a saturation $ apor pressure PH 2 O, SAT is
reached in the head space. If we increase the temperature of the water
in the pan, the energy of the molecules at the surface increases and
hence the rate of evaporation increases. A higher collision rate of water
vapor molecules with the surface is then needed to maintain equilib-
rium. Therefore, PH 2 O, SAT increases as the temperature increases.
Cloud formation in the atmosphere takes place when PH 2 O "
PH 2 O, SAT , and it is therefore important to understand how PH 2 O, SAT
depends on environmental variables. From the phase rule, the number
n of independent variables determining the equilibrium of c chemical
components between a number p of different phases is given by

n " c % 2 # p. Ž 1.13.

In the case of the equilibrium of liquid water with its vapor there is only
one component and two phases. Thus the equilibrium is determined by
one single independent variable; at a given temperature T, there is only
one saturation vapor pressure PH 2 O, SAT ŽT . for which liquid and gas are
in equilibrium. The dependence of PH 2 O, SAT on T is shown in figure
1-3. Also shown on the figure are the lines for the gas-ice and liquid-ice
equilibria, providing a complete phase diagram for water. There is a
significant kinetic barrier to ice formation in the atmosphere because of
the paucity of aerosol surfaces that may serve as templates for conden-
sation of ice crystals. As a result, cloud liquid water readily supercools
Žremains liquid. down to temperatures of about 250 K, and the corre-
sponding curve is included in figure 1-3.
10 – CHAPTER 1. ATMOSPHERIC COMPOSITION

Fig. 1-3 Phase diagram for water. The thin line is the
saturation vapor pressure above supercooled liquid water.

In weather reports, atmospheric water vapor concentrations are fre-

quently reported as the relative humidity ŽRH. or the dew point ŽTd ..
The relative humidity is defined as

PH 2 O
RHŽ % . " 100 # , Ž 1.14.
PH 2 O , SAT Ž T .

so that cloud formation takes place when RH " 100%. The dew point is
defined as the temperature at which the air parcel would be saturated
with respect to liquid water:

PH 2 O " PH 2 O , SAT Ž Td . . Ž 1.15.

At temperatures below freezing, one may also report the frost point Tf
corresponding to saturation with respect to ice.

Exercise 1-3 How many independent variables determine the liquid-vapor

equilibrium of the H 2 O-NaCl system? What do you conclude regarding the
ability of sea salt aerosol particles in the atmosphere to take up water?
 CHAPTER 1 – 11

Answer. There are two components in this system: H 2 O and NaCl. Liquid-
vapor equilibrium involves two phases: the H 2 O-NaCl liquid solution and the
gas phase. Application of the phase rule gives the number of independent
variables defining the equilibrium of the system:

n " c % 2 # p " 2 % 2 # 2 " 2.

Because n " 2, temperature alone does not define the saturation water vapor
pressure above a H 2 O-NaCl solution. The composition of the solution Ži.e.,
the mole fraction of NaCl. is another independent variable. The presence of
NaCl molecules on the surface of the solution slows down the evaporation of
water because there are fewer H 2 O molecules in contact with the gas phase
ŽFigure 1-2.. Therefore, NaCl-H 2 O solutions exist at equilibrium in the
atmosphere at relative humidities less than 100%; the saturation water vapor
pressure over a NaCl-H 2 O solution decreases as the NaCl mole fraction
increases. In this manner, sea salt aerosol particles injected to the atmos-
phere by wave action start to take up water at relative humidities as low as
75% Žnot at lower relative humidities, because the solubility constant of NaCl
in H 2 O places an upper limit on the mole fraction of NaCl in a NaCl-H 2 O
solution.. The same lowering of water vapor pressure applies for other types
of aerosol particles soluble in water. The resulting swelling of particles by
uptake of water at high humidities reduces visibility, producing the phe-
nomenon known as haze.

Further Reading
Levine, I. N. Physical Chemistry. 4th ed. New York: McGraw-Hill, 1995. Phase
rule, phase diagrams.

PR O BLEM S
1.1 Fog Formation
A weather station reports T " 293 K, RH " 50% at sunset. Assuming that
PH 2 O remains constant, by how much must the temperature drop over the
course of the night in order for fog to form?
1.2 Phase Partitioning of Water in Cloud
What is the mass concentration of water vapor Žg H 2 O per m3 of air. in a
liquid-water cloud at temperature of 273 K? Considering that the liquid water
mass concentration in a cloud ranges typically from 0.1 to 1 g liquid water per
m3 of air, is most of the water in a cloud present as vapor or as liquid?
1.3 The Ozone Layer
Consider the typical vertical profile of ozone ŽO 3 . number density measured
over the United States shown in figure 1-4. Ozone is produced in the
12 – CHAPTER 1. ATMOSPHERIC COMPOSITION

Fig. 1-4 Vertical ozone profile.

stratosphere Ž10!50 km altitude. by photolysis of O 2 and subsequent combi-

nation of O atoms with O 2 Žchapter 10.. The stratospheric O 3 layer protects
life on Earth by absorbing solar UV radiation and preventing this radiation
from reaching the Earth’s surface. Fortunately, the O 3 layer is not in contact
with the Earth’s surface; inhalation of O 3 is toxic to humans and plants, and
the U.S. Environmental Protection Agency ŽEPA. has presently an air quality
standard of 80 ppbv O 3 that is not to be exceeded in surface air.

1. Calculate the mixing ratio of O 3 at the peak of the O 3 layer Ž z " 25 km;
P " 35 hPa; T " 220 K.. Would this mixing ratio be in violation of the
EPA air quality standard if it were found in surface air? ŽMoral of the
story: we like to have a lot of O 3 in the stratosphere, but not near the
surface..

2. Calculate the mixing ratio of O 3 in surface air Ž z " 0 km; P " 1000 hPa;
T " 300 K.. Is it in compliance with the EPA air quality standard? Notice
that the relative decrease in mixing ratio between 25 km and the surface is
considerably larger than the relative decrease in number density. Why is
this?
 CHAPTER 1 – 13

3. The total number of O 3 molecules per unit area of Earth surface is called
the O 3 column and determines the efficiency with which the O 3 layer
prevents solar UV radiation from reaching the Earth’s surface. Estimate
the O 3 column in the above profile by approximating the profile with the
piecewise linear function shown as the thin solid line.
4. To illustrate how thin this stratospheric O 3 layer actually is, imagine that
all of the O 3 in the atmospheric column were brought to sea level as a
layer of pure O 3 gas under standard conditions of temperature and
pressure Ž1.013 ! 10 5 Pa, 273 K.. Calculate the thickness of this layer.