Module 2 Study Guide – Environmental Chemistry
Excited state, *: The product of a photochemical
Subtopic 1: The
Atmosphere and
Atmospheric Chemistry
Composition of the Atmosphere
The atmosphere consists of the thin layer of mixed
gases covering the Earth’s surface. Exclusive of water,
atmospheric air is 78.1% (by volume) nitrogen, 21.0%
oxygen, 0.9% argon, and 0.04% carbon dioxide.
Air contains 1%–3% water vapor by volume. In
addition, air contains a large variety of trace-level
gases below 0.002%, including neon, helium,
methane, krypton, nitrous oxide, hydrogen, xenon,
sulfur dioxide, ozone, nitrogen dioxide, ammonia, and
carbon monoxide.
Dry air up to several kilometers altitude consists of
two major components:
• Nitrogen, 78.08% (by volume)
• Oxygen, 20.95%
two minor components:
• Argon, 0.934%
• Carbon dioxide, 0.040%
in addition to argon and four more noble gases:
• Neon, 1.818 . 10−3%
• Helium, 5.24 . 10−4%
• Krypton, 1.14 . 10−4%
• Xenon, 8.7 . 10−6%
Photochemical Reactions
The most significant feature of atmospheric chemistry
is the occurrence of photochemical reactions
resulting from the absorption by molecules of photons
of electromagnetic radiation from the sun, mostly in
the ultraviolet region of the spectrum.
Some Important Terms:
The energy, E, of a photon of visible or ultraviolet light
is given by the equation, E = hν, where h is Planck’s
constant and ν is the frequency of electromagnetic
inversely proportional to its wavelength, λ.
The involvement of a photon in a photochemical
reaction is shown by the following reaction with
ozone, O3:
O3 + hν (λ < 420 nm) → O* + O2
reaction may be electronically energized in an excited
state commonly denoted with an asterisk, *
Free radicals containing an unpaired electron
denoted with a dot, •. Reaction of an excited oxygen
atom with a molecule of water vapor
O* + H2O → HO• + HO•
Oxides of Nitrogen and Sulfur
The two most significant nitrogen oxide air pollutants
are nitric oxide, NO, and nitrogen dioxide, NO2.
These tend to enter the atmosphere as NO, and
photochemical processes in the atmosphere can
convert NO to NO2.. Further reactions can result in the
formation of corrosive nitrate salts or nitric acid,
HNO3.
Nitrogen dioxide is particularly significant in
atmospheric chemistry because of its photochemical
dissociation by light, to produce highly reactive O
atoms. This is the first step in the formation of
photochemical smog.
Sulfur dioxide, SO2, is a reaction product of the
combustion of sulfur containing fuels (especially
coal). Part of this sulfur dioxide is converted in the
atmosphere to sulfuric acid, H2SO4, normally the
predominant contributor to acid precipitation.
Atmospheric Methane,
Hydrocarbons, and Photochemical
Smog
Methane
 The most abundant hydrocarbon in the
atmosphere is methane, CH4. During the last
250 years, levels of atmospheric methane
have more than doubled.
 Per molecule, methane is a much more
effective greenhouse gas than is carbon
dioxide. Methane affects both tropospheric
and stratospheric chemistry, particularly by
influencing levels of hydroxyl radical, ozone,
and stratospheric water vapor.
Hydrocarbons and Photochemical Smog
 Hydrocarbons containing two or more
carbon atoms per molecule are released to
the atmosphere primarily from automobile
exhaust emissions.
 Many of these contain carbon–carbon
double bonds, which makes them very
reactive.
 Module 2 Study Guide – Environmental Chemistry
 In the presence of NO, these hydrocarbons In some cases, the electron thus promoted retains a
produce undesirable photochemical smog spin opposite to that of its former partner, giving rise
manifested by the presence of visibility- to an excited singlet state.
obscuring particulate matter, oxidants such In other cases, the spin of the promoted electron is
as ozone, and noxious organic species such reversed, such that it has the same spin as its former
as aldehydes. partner; this gives rise to an excited triplet state.

Primary and Secondary Pollutants
o Primary pollutants in the atmosphere are
those that are emitted directly. An example
of a primary pollutant is sulfur dioxide, SO2,
which directly harms vegetation and is a
lung irritant.
In order for a photochemical reaction to occur, light
must be absorbed by the reacting species. The
processes that occur following absorption of a photon
of light to produce an electronically excited species are
largely determined by the way in which the excited
species loses its excess energy.

o Secondary Pollutants are formed by
atmospheric chemical processes acting on
primary pollutants and even non pollutant
species in the atmosphere. Secondary
pollutant sulfuric acid, H2SO4, is generated
by the oxidation of primary pollutant SO2
and secondary pollutant NO2 is produced
when primary pollutant NO is oxidized.
Subtopic 2: Chemical,
Photochemical, & Acid-Base
Loss of energy to another molecule or atom (M) by
physical quenching, followed by dissipation of the
energy as heat, a process that does not result in a
chemical reaction:
Dissociation of the excited molecule (the process
responsible for the predominance of atomic oxygen
in the upper atmosphere), a process that normally
results in additional chemical reactions:

Reactions in the Atmosphere

The absorption by chemical species of light, can bring Direct reaction with another species:
about reactions, called photochemical reactions.
Photochemical reactions, which are induced by intense
solar radiation, play a very important role in
determining the nature and ultimate fate of a chemical
species in the atmosphere.
Luminescence consisting of loss of energy by the
The Photochemical Process emission of electromagnetic radiation
There are 3 kinds of relatively reactive and unstable
species that are encountered in the atmosphere and are
strongly involved with atmospheric chemical
processes: free radicals, ions, and electronically
excited molecules
Intermolecular energy transfer in which an excited
Electronically excited molecules are produced when species transfers energy to another species that then
stable molecules absorb energetic electromagnetic becomes excited:
radiation in the ultraviolet or (rarely) visible regions of
the spectrum.

The nature of the excited state may be understood by

considering the disposition of electrons in a molecule. Intramolecular transfer in which energy is
Electrons occupy orbitals, with a maximum of two transferred within a molecule
electrons with opposite spin occupying the same
orbital. The absorption of light may promote one of
these electrons to a vacant orbital of higher energy.
 Module 2 Study Guide – Environmental Chemistry
(Denotes another excited state in the molecule)

Photoionization through loss of an electron:

By photolysis of ozone

Ions and Free Radicals in the

Atmosphere
Significant levels of electrons and positive ions are
found at altitudes of approximately 50 km and up, a
region called the ionosphere. Ultraviolet light is the
primary producer of ions in the ionosphere.
Among the important atmospheric trace species that
react with hydroxyl radical are carbon monoxide,
sulfur dioxide, hydrogen sulfide, methane, and nitric
oxide.

Earth’s magnetic field has a strong influence on the Acid-Base Reactions in the
ions in the upper atmosphere.
Atmosphere
The magnetic field surrounding Earth is the planet’s The atmosphere is normally at least slightly acidic
magnetosphere. It interacts with the solar wind to because of the presence of a low level of carbon
produce a plasmasphere located just beyond the outer dioxide, which dissolves in atmospheric water
regions of the ionosphere Earth’s magnetic field and droplets and dissociates slightly:
the plasmasphere provide essential protection from
potentially catastrophic damage from solar radiation
events. electromagnetic radiation in the atmosphere
may produce atoms or groups of atoms with unpaired
electrons called free radicals

Free radicals are involved with most significant

atmospheric chemical phenomena. Because of their Atmospheric sulfur dioxide forms a somewhat
unpaired electrons and the strong pairing tendencies stronger acid than carbon dioxide when it dissolves in
of electrons under most circumstances, free radicals water:
are highly reactive.

Hydroxyl and Hydroperoxyl

Radicals in the Atmosphere
The hydroxyl radical, HO•, is the single most
important reactive intermediate species in atmospheric
chemical processes. It is formed by several
mechanisms:
By photolysis of water
In the presence of organic matter, hydroxyl radical is
produced in abundant quantities as an intermediate in
the formation of photochemical smog
Particulate calcium oxide, hydroxide, and carbonate
can get into the atmosphere from ash and ground
rock, and can react with acids such as in the
following reaction:
The most important basic species in the atmosphere is
gas-phase ammonia, NH3. The major source of
atmospheric ammonia is from biodegradation of
nitrogen-containing biological matter and from
bacterial reduction of nitrate:

By photodissociation of hydrogen peroxide Ammonia is particularly important as a base in the air

because it is the only water-soluble base present at
 Module 2 Study Guide – Environmental Chemistry
significant levels in the atmosphere. Dissolved in
atmospheric water droplets, it plays a strong role in
neutralizing atmospheric acids: