CHAPTER 8

AIR AND THE ATMOSPHERE

From Green Chemistry and the Ten Commandments of
Sustainability, Stanley E. Manahan, ChemChar Research,
Inc., 2006
manahans@missouri.edu
8.1. MORE THAN JUST AIR TO BREATHE
A Sea of Gas
We live and breathe in the atmosphere, a sea of gas consisting
primarily of elemental O
2
and N
2
.
Gas molecules are in constant, rapid motion, which explains
Pressure Temperature Diffusion
The Gas Laws
Gas laws
Pressure in atmospheres (atm) Temperature absolute (C + 273)
Avogadros law: At constant temperature and pressure the volume
of a gas is directly proportional to the number of moles.
Charles law: At constant pressure the volume of a fixed number of
moles of gas is directly proportional to the absolute temperature.
Boyles law: At constant temperature the volume of a fixed number
of moles of gas is inversely proportional to the pressure.
General gas law relating volume (V), pressure (P), number of moles
(n), absolute temperature (T), a constant (R)
PV = nRT (8.1.1)
Gas law calculations of volumes based upon
R =
P
1
V
1
=
P
2
V
2
n
1
T
1
n
2
T
2
V
2
= V
1

n
2
T
2
P
1
n
1
T
1
P
2
Rearanged:
Gas Law Calculations
Calculate the volume of a fixed number of moles of gas initially
occupying 12.0 liters when the temperature is changed from 10C to
90C at constant pressure.
T
1
= 10 + 273 = 283, and T
2
= 90 + 273 = 363
P and n are constant and cancel
Remember that an increase in temperature increases the volume and
an increase in pressure decreases the volume and vice versa
V
2
= V
1

T
2
= 12.0 L
363
= 15.4 L
T
1
283
Calculate V
2
at constant T when P on a volume of gas occupying
initially 11.4 L is changed from 1.16 atm to 0.858 atm
The Protective Atmosphere
Keeps Earths surface warm by delaying outgoing infrared radiation
Absorbs very short wavelength ultraviolet radiation from the sun
Nature of air
In the troposphere within a few kilometers of Earths surface, a
mixture of gases of generally uniform composition
On a dry basis, 78.1% (by volume) nitrogen, 21.0% oxygen, 0.9%
argon, and 0.04% carbon dioxide
Water vapor 1-3% of the atmosphere by volume
Trace gases below 0.002% including ammonia, carbon monoxide,
helium, hydrogen, krypton, methane, neon, nitrogen dioxide, nitrous
oxide, ozone, sulfur dioxide, and xenon.
The Protective Atmosphere (Cont.)
If Earth is represented as a globe, the relative thickness of the
atmosphere would be about that of the paint on the globe surface.
The atmosphere is so thin that in an aircraft that suddenly loses
pressure cruising at 35,000 feet (about 6.6 miles or 10.7 kilometers),
the pilot has only about 15 seconds to grab an oxygen mask before
losing consciousness.
Earths diameter is almost 13,000 km.
Aircraft cruise at the upper limit of the troposphere (next slide)
Average T of about 15 C at sea level
Average T of -56 C at 11 km
The Troposphere
10-16 km, -56C
Temperature
inversion
O
2
, N
2
, Ar, CO
2
, trace gases
NO
2
+ h NO + O
Photoche mical reactions
Stratosphere, upper atmosphere
Troposphere
We athe r
H
2
O
Vapor
Droplets
Particle s
Air pollutants
The Stratosphere
-2 C at 50 km altitude
Virtually no water vapor in the stratosphere
Contains ozone, O
3
, and O atoms as the result of ultraviolet radiation
acting upon stratospheric O
2
The ozone in the stratosphere absorbs damaging ultraviolet radiation
and is essential for protecting life on Earth
The Stratosphere (Cont.)
10-16 km, -56C
O
2
+ h O + O
O
2
+ O O
3
O
3
+ h O
2
+ O
(filtration of ultra-
violet radiation)
Stratosphe re
~ 50 km, -2C
Ultraviolet be tween 200-330
nanometers pe netrating to
around 50 km altitude
High-ene rgy ultraviolet, wave-
length less than 100 nanometers,
penetrating to around 200 km
altitude
Ultraviolet above 330 nano-
meters, visible light, infrared,
penetrating through the strat-
osphere and to Earths surface
8.2. ATMOSPHERIC CHEMISTRY AND PHOTOCHEMICAL
REACTIONS
Atmospheric chemistry refers to chemical processes that occur in
the atmosphere.
Atmospheric chemistry occurs in the gas phase where molecules are
relatively far apart.
A second major aspect of atmospheric chemistry is the occurrence of
photochemical reactions.
Initiated when a photon of ultraviolet radiation is absorbed by a
molecule
The energy of a photon, E, is given by E = h where h is Plancks
constant and is the frequency of the radiation.
Electromagnetic radiation of a sufficiently short wavelength can
cause chemical bonds to break in molecules
This can lead to the formation of reactive species that can
participate in reaction sequences called chain reactions.
Photochemical and Chain Reactions
Example of dichlorodifluoromethane, CCl
2
F
2
, which was used in
automobile air conditioners
CCl
2
F
2
+ h CCl
2
F
2
+ Cl


(Stratosphere)

(8.2.1)
Species with unpaired electrons such as Cl are very reactive and are
called free radicals.
Reaction of Cl

with stratospheric ozone and the O atoms required for
ozone formation
Cl

+ O
3
O
2
+ ClO (8.2.2)
ClO

+ O O
2
+ Cl (8.2.3)
Net reaction: O
3
+ O O
2
+ O
2
One Cl atom can bring about the destruction of as many as 10,000
ozone molecules!
Atmospheric Particles
Very small particles of the size of a micrometer or less called
aerosols are important in atmospheric chemical processes.
Particle surfaces can act to catalyze (bring about) atmospheric
chemical reactions.
Solution chemical reactions can occur inside water droplets.
Condensation nuclei, such as small particles of NaCl formed from
sea spray, act to form water droplets from atmospheric moisture.
8.3. ENERGY AND MASS TRANSFER IN THE
ATMOSPHERE
The flux of energy reaching Earths atmosphere is 1,340 watts/m
2
.
This enormous amount of energy is redistributed around Earths
surface and eventually radiated back out to space as electromagnetic
radiation.
Energy received from the sun is distributed away from the Equator
largely by convection in moving masses of air.
Sensible heat from the kinetic energy of rapidly moving air
molecules
Latent heat in the form of water vapor
Heat of vaporization of water is very large 2,259 joules per gram
(J/g)
Redistribution of Energy in the Atmosphere
Some reflected from
atmosphere, clouds,
Earths surface
Some absorbed
by atmosphere
Infrared out
Infrared absorbed
Infrared re-emitted
Energy redistributed
away from equator
Solar radiation
reaching atmosphere
Meteorology
The movement of air masses, cloud formation, and precipitation in
the atmosphere are covered by the science of meteorology.
Meteorologic phenomena have a strong effect upon atmospheric
chemistry by processes such as
Movement of air pollutants from one place to another
Conditions under which stagnant pollutant air masses remain in
place so that secondary pollutants, such as photochemical smog,
can form
Precipitation, which can carry acidic compounds from the
atmosphere to Earths surface in the form of acid rain.
Weather
Weather refers to relatively short term variations in the state of the
atmosphere as expressed by temperature, cloud cover, precipitation,
relative humidity, atmospheric pressure, and wind.
Weather is driven by redistribution of energy and water vapor
around Earths surface.
Clouds consisting of droplets of liquid water
Wind and air currents may influence air pollution
Long term trends in weather are expressed by climate.
Temperature Inversions
Temperature inversion in which warmer air masses overlay cooler
ones influence air pollution phenomena.
8.4. ATMOSPHERIC OXYGEN AND NITROGEN
N
2
and O
2
are by far the most abundant gases in the atmosphere.
Crucial importance of the stratospheric layer of ozone, O
3
Oxygen reacts with atmospheric chemical species.
Through action of intermediate species, particularly hydroxyl
radical, HO

SO
2
is converted to H
2
SO
4
CO is converted to CO
2
Atmospheric oxygen comes from photosynthesis
CO
2
+ H
2
O + h {CH
2
O} + O
2
(8.4.2)
where {CH
2
O} is a generic formula representing biomass
Nitrogen in the atmosphere
Atmospheric N
2
is very unreactive
Most important reaction of N-containing species in the atmosphere
NO
2
+ h NO + O (8.4.3)
Reactive O atom initiates many tropospheric photochemical reactions
Green Oxygen and Nitrogen from the Air
Elemental oxygen and nitrogen are obtained by distilling cold liquid
air, a process that can also produce noble gas neon, krypton, and
xenon, if desired.
Essentially pure oxygen is used in a number of applications, such as
for steel making, breathing, and many other applications.
Pure nitrogen provides inert atmospheres free of oxygen and is used
as the very cold liquid in cryogenics.
Oxygen and nitrogen can be separated from air at room temperature
based upon their different adsorption characteristics on solids or
variable permeability through membranes.
One common such process is called pressure swing adsorption
Emergency Oxygen
Chlorate candle on aircraft
2NaClO
3
2NaCl + 3O
2
(8.4.4)
Heat generated by
4Fe + 3O
2
2Fe
2
O
3
(8.4.4)
ValuJet crash over the Florida Everglades in 1997 from a fire of tires
fed by chlorate candles improperly shipped in the cargo compartment
8.5. ATMOSPHERIC POLLUTANT PARTICLES
Dispersion aerosols formed by grinding solids, dispersing dusts, or
atomizing liquids
Condensation aerosols produced when gases or vapors, often
formed as the result of atmospheric chemical processes, condense
Mists include raindrops, fog, cloud droplets, and droplets of sulfuric
acid produced when atmospheric SO
2
is oxidized.
Fly ash is the mineral residue from fuel combustion.
Health effects of atmospheric particles
Allergen pollen Acidic particles
Heavy metals, such as lead, mercury, beryllium
Radioactive radon including
222
Rn (half-life 3.8 days) and
220
Rn
(half-life 54.5 seconds), alpha emitters that decay to radioactive
218
Po
and
216
Po
Particles have both direct effects (reduction of visibility) and indirect
effects (reaction sites) in the atmosphere.

Chemical Processes on and in Atmospheric Particles
Limiting Emissions of Atmospheric Particles
Devices for limiting particle emissions include
Sedimentation Inertial mechanisms Scrubbers
Fabric filters in baghouses Electrostatic precipitators
An electrostatic pre-
cipitator (right)
8.6. POLLUTANT GASEOUS OXIDES
Carbon Monoxide
Toxic to humans by binding to blood hemoglobin and preventing the
hemoglobin from transporting oxygen from the lungs to other tissues.
Catalytic destruction in auto exhausts:
2CO + O
2
2CO
2
(8.6.1)
Modern automobile engines use computerized control of engine
operating parameters along with exhaust catalysts to control carbon
monoxide emissions.
Pollutant Gaseous Oxides (Cont.)
Sulfur Dioxide
From several natural and pollutant sources
Direct effects
On people with respiratory problems On plants
Most important indirect effect is atmospheric sulfuric acid formation
2SO
2
+ O
2
+ 2H
2
O 2H
2
SO
4
(8.6.2)
Avoiding sulfur dioxide pollution by not using sulfur-containing fuels
(coal)
Fluidized bed combustion in a granular medium of CaO that
absorbs SO
2
CaO + SO
2
CaSO
3
(8.6.3)
Scrubbing with substances that absorb sulfur dioxide from stack gas
Ca(OH)
2
+ SO
2
CaSO
3
+ H
2
O (8.6.4)
Green Chemistry and Sulfur Dioxide
Sulfur is a valuable raw material required in the manufacture of
sulfuric acid, one of the largest volume chemicals made.
Hydrogen sulfide, H
2
S, can be used to make sulfur dioxide.
In the Kalundborg, Denmark, industrial ecosystem, sulfur dioxide
scrubbed from stack gas is oxidized
CaSO
3
+
1
/
2
O
2
+ 2H
2
O CaSO
4
.
2H
2
O (8.6.5)
and used to make gypsum for wallboard.
Nitrogen Oxides in the Atmosphere
Nitrous oxide (N
2
O), colorless, odorless, nitric oxide (NO), and
pungent-smelling, red-brown nitrogen dioxide (NO
2
) occur in the
atmosphere.
Nitrous oxide generated by bacteria
In the stratosphere: N
2
O + h N
2
+ O (8.6.6)
Both NO and NO
2
, collectively designated as NO
x
, are produced
from natural sources, such as lightning and biological processes, and
from pollutant sources.
Pollutant concentrations can become too high locally and regionally.
In the internal combustion engine,
N
2
+ O
2
2NO (8.6.7)
Combustion of fuels that contain organically bound nitrogen also
produces NO.
Atmospheric chemical reactions convert some of the NO emitted to
NO
2
.
NO
2
in the Atmosphere
Electromagnetic radiation below 398 nm causes
NO
2
+ h NO + O (8.6.8)
Produces highly reactive O atoms
O atoms can participate in a series of chain reactions through which
NO is converted back to NO
2
, which can undergo photodissociation
again to start the whole cycle over.
NO
2
more toxic than NO
Exposure to 100-500 ppm of NO
2
causes a lung condition called
bronchiolitis fibrosa obliterans
Exposed plants may suffer decreased photosynthesis, leaf spotting,
and breakdown of plant tissue.
Reducing release of NO from combustion sources
Limiting excess air so that there is not enough excess oxygen to
produce NO
Exhaust catalytic converters reduce NO
x
emissions from automobile
exhausts.
8.7. ACID RAIN
Acid rain from H
2
SO
4
, HNO
3
, HCl
Acid deposition, refers to the effects of atmospheric strong acids,
acidic gases (SO
2
), and acidic salts (NH
4
NO
3
and NH
4
HSO
4
)
Acidic precipitation is a regional air pollution problem
4.5
4.5
4.4
4.4
4.3
4.3
4.2
5.3
5.2
5.1
4.9
5.1
4.7
4.5
4.4
4.3
Line of pH in precipitation
Acid Precipitation (Cont.)
Adverse effects of acidic precipitation
Direct effects of reduced and distorted visibility from and particles
of acidic salts, such as NH
4
HSO
4
Direct phytotoxicity (toxicity to plants) and destruction of sensitive
forests
Indirect phytotoxicity from release of Al
3+
ion by the action of
acidic rainfall on soil
Direct respiratory effects on humans and other animals
Effects upon plants and fish in acidified lake water
Damage to materials, especially acid-soluble limestone and marble
8.8. MISCELLANEOUS GASES IN THE ATMOSPHERE
Ammonia, NH
3
, from industrial pollution, coke manufacture,
bacterial sources, decay of animal wastes, accidental releases from
liquid anhydrous ammonia used as an agricultural nitrogen fertilizer
Ammonia dissolved in water droplets
Acts as base to produce corrosive salts
NH
3
+ H
2
SO
4
NH
4
HSO
4
(8.8.1)
NH
3
+ HNO
3
NH
4
NO
3
(8.8.2)
Halogen Gases in the Atmosphere
Gaseous chlorine, fluorine, and volatile fluorides are uncommon air
pollutants, but very serious where they occur.
Elemental chlorine, Cl
2
, is widely produced and distributed as a
water disinfectant, bleach, and industrial chemical.
Accidental releases of Cl
2
have killed people
Hydrogen chloride, HCl, from accidental releases and by reaction of
reactive chlorine-containing chemicals, such as SiCl
4
,
SiCl
4
+ 2H
2
O SiO
2
+ 4HCl

(8.8.3)
HCl gas from combustion of polyvinylchloride (PVC) plastic
Exists as droplets of hydrochloric acid
Elemental fluorine (F
2
) and hydrogen fluoride, both highly toxic, are
rarely released to the atmosphere.
Gaseous silicon tetrafluoride, SiF
4
, can be released when fluorspar
(CaF
2
) reacts with sand (SiO
2
):
2CaF
2
+ 3SiO
2
2CaSiO
3
+ SiF
4
(8.8.4)
Sulfur hexafluoride, SF
6
, is astoundingly unreactive and a powerful
greenhouse warming gas
Hydrogen Sulfide, H
2
S
Hydrogen sulfide, H
2
S is as toxic as hydrogen cyanide.
From geothermal sources, the microbial decay of organic sulfur
compounds, and the microbial conversion of sulfate, SO
4
2-
, to H
2
S
when sulfate acts as an oxidizing agent in the absence of O
2
Wood pulping processes can release hydrogen sulfide.
H
2
S is a common contaminant of petroleum and natural gas.
Poza Rica, Mexico, incident in 1950 killed 22 people
H
2
S is phytotoxic (harms or kills plants)
H
2
S forms a black coating of copper sulfide, CuS, on copper roofing
which weathers to CuSO
4
3Cu(OH)
2
.
H
2
S

oxidizes to

SO
2
.
COS and CS
2
, occur in the atmosphere
8.9. CO
2
: THE ULTIMATE AIR POLLUTANT?
Carbon dioxide, CO
2
, is a normal essential constituent of the
atmosphere.
Levels now about 380 parts per million by volume and increasing by
at least 1 ppm/year
Potential greenhouse effect
Evidence of warming during 1980s, 1990s, early 2000s
Other gases such as N
2
O and CH
4
can cause greenhouse warming
Increase in Atmospheric Carbon Dioxide Levels
Global Temperature Trends
Adverse Effects of Greenhouse Warming
Adverse effects of greenhouse warming
Predictions of average global temperature increase of 1.55 C, as
much again as since the last ice age
Would greatly affect climate and rainfall
Melting of the polar and Greenland ice caps along with expansion
of warmer ocean water would raise sea levels by 0.51.5 meters
Decreased rainfall and increased water evaporation would
contribute to severe drought and water shortages
Can Green Chemistry Help Deal With Global Warming?
Provide means to prevent global warming from taking place
Coping with global warming, if it occurs.
Avoid release of carbon dioxide by using biomass as fuel or raw
material for the manufacture of various products
Carbon sequestration in which carbon dioxide is produced, but is
bound in a form such that it is not released to the atmosphere
Convert carbon in coal to concentrated carbon dioxide that is
pumped underground or into oceans
2C + O
2
+ 2H
2
O 2CO
2
+ 2H
2
(8.9.1)
Alternative methods of energy production
More efficient photovoltaic cells
Devices for direct photochemical dissociation of water to produce
elemental hydrogen and oxygen, which could be used in fuel cells
Plants with much higher efficiencies for photosynthesis
Dealing with Global Warming
Prevent release of greenhouse gases other than carbon
Replacement of very persistent chlorofluorocarbons (Freons) with
compounds readily destroyed in the troposphere
Limit emissions of methane, CH
4
.
Green chemistry, biochemistry, and biology can be used to deal with
global warming when it occurs.
Crops, fertilizers, and pesticides can be developed that enable plants
to grow under the drought conditions that would follow global
warming
Development of salt-tolerant crops that can be grown on soil
irrigated with saline water, where fresh water supplies are limited.
8.10. PHOTOCHEMICAL SMOG
Photochemical smog occurs in dry, stagnant air masses, usually
stabilized by a temperature inversion, that are subjected to intense
sunlight.
A smoggy atmosphere contains ozone, O
3
, organic oxidants, N
oxides, aldehydes, and other noxious species, as well as a haze of
fine particles.
The chemical ingredients of smog are nitrogen oxides and organic
compounds, both released from the automobile, as well as from other
sources.
The driving energy force behind smog formation is electromagnetic
radiation with a wavelength at around 400 nm or less, in the
ultraviolet region, just shorter than the limit for visible light.
Formation of active species starting photochemical reactions.
Reactions Leading to Photochemical Smog
Absorption of a photon of electromagnetic radiation with a
wavelength less than 398 nm by a molecule of nitrogen dioxide,
NO
2
+ h NO + O (8.10.2)
CH
4
+ O H
3
C + HO (8.10.3)
Methyl radical, H
3
C, and a hydroxyl radical, HO, where the dot
shows a single unpaired electron
A chemical species with such a single electron is a free radical.
The hydroxyl radical is especially important in the formation of smog
and in a wide variety of other kinds of photochemical reactions.
The methyl radical can react with an oxygen molecule,
H
3
C + O
2
H
3
COO (8.10.4)
to produce a methylperoxyl radical, H
3
COO, a strongly oxidizing,
reactive species
Reactions Leading to Photochemical Smog
Important reaction is oxidation of NO back to photochemically active
NO
2
NO + H
3
COO NO
2
+ H
3
CO (8.10.5)
Literally hundreds of other reactions can occur, leading eventually to
oxidized organic matter that produces the small particulate matter
characteristic of smog.
Numerous noxious intermediates are generated.
Aldehydes, which are irritants to
eyes and the respiratory tract
Ozone, O
3
, is the single species most characteristic of smog, toxic
to plants and animals.
Oxygen-rich organic compounds containing nitrogen that are potent
oxidizers, of which peroxyacetyl nitrate, PAN, is the most common
example.
Peroxyacetyl nitrate (PAN)
NO
2
O C
H
H
H
O
C O
Formaldehyde
H C H
C
Harmful Effects of Smog
Adverse effects upon human health and comfort, plants, materials,
and atmospheric quality
Ozone is generally regarded as being most harmful to humans,
plants, and materials
People exposed to 0.15 parts per million of ozone in air experience
irritation to the respiratory mucous tissues accompanied by
coughing, wheezing, and bronchial constriction.
Especially pronounced for people exercising
Plants are harmed by exposure to nitrogen oxides, ozone, and
peroxyacetyl nitrate (PAN, see above)
PAN is the most harmful of these constituents, damaging younger
plant leaves, especially.
Ozone exposure causes formation of yellow spots on leaves, a
condition called chlorotic stippling (below):

(Chlorotic stippling is manifested
by yellow spots on a green leaf)
Harmful Effects of Smog (Cont.)
Materials are attacked by oxidants
Natural rubber is attacked by ozone; the hardening and cracking of
natural rubber has been used as a test for the presence of ozone in
the atmosphere.
Visibility-reducing aerosol particles
In general, quality of life and esthetics are harmed by photochemical
smog.
Smog and Green Chemistry: Can it Help?
A basic premise of green chemistry is to avoid the generation and
release of chemical species with the potential to harm the
environment.
The best way to avoid formation of smog is to avoid the release of
nitrogen oxides and organic vapors that enable smog to form.
At an even more fundamental level, measures can be taken to avoid
the use of technologies likely to release such substances, for
example, by using alternatives to polluting automobiles for
transportation.
Solutions to the Smog Problem
The evolution of automotive pollution control devices to reduce
smog provide an example of how green chemistry can be used to
reduce pollution.
Initially command-and-control and end-of-pipe measures which
often led to
Poor performance Very bad fuel economy
Now the automobile engine is a highly sophisticated computer-
controlled machine that generally performs well, emits few air
pollutants, and is highly efficient.
Has required an integrated approach involving reformulation of
gasoline
Elimination of tetraethyllead
Reduction in smog-forming hydrocarbons
Sustainable Measures with the Automobile
Electric automobiles that do not burn gasoline
Limited range
Hybrid automobiles using a small gasoline or diesel engine that
provides electricity to drive electric motors propelling the automobile
and to recharge relatively smaller batteries.
Fuel cells that can produce electricity directly from the catalytic
combination of elemental hydrogen and oxygen yielding water
exhaust
Best for fleet vehicles that can be refueled frequently
Other Measures to Reduce Smog-Forming Emissions
Green chemistry applied to devices and processes other than
automobiles to reduce smog-forming emissions
Organic solvents used for parts cleaning and other industrial
operations, vapors of which are often released to the atmosphere
contribute to photochemical smog.
Substitution of water with proper additives or use of supercritical
carbon dioxide fluid can eliminate such emissions.