ChE PE 3

Air Pollution Control

The Composition
and Structure of
the Atmosphere
 Atmosphere
• Comprised of a mixture of invisible permanent and
variable gases as well as suspended microscopic
particles (both liquid and solid) above the earth’s
surface
• Permanent Gases – Form a constant proportion of the
total atmospheric mass
• Variable Gases – Distribution and concentration varies
in space and time
• Aerosols – Suspended particles and liquid droplets
(excluding cloud droplets)
Thickness of the Atmosphere

• No defined top
• 99.99997% of atmosphere is below 100
km (60 mi)
• Weather occurs in lowest 11 km (7 mi)
• Atmospheric depth is very thin relative to
earth’s horizontal distances
• Radius of the Earth is over 6,371 km
• Atmosphere is a thin shell covering the
Earth.
 The Evolution of the Atmosphere
• Earth’s early atmosphere contained mostly hydrogen and helium
• Two hypotheses exist that explain the dispersion of this early
atmosphere
1) The gases escaped to space by overcoming gravity with large enough escape
velocities
2) Collisions between earth and other large bodies launched the early
atmosphere to space
• A modern atmosphere began to form through outgassing by volcanic
eruptions, and possibly through collisions of comets with earth (Both
supplying mostly carbon dioxide and water vapor)
 The Evolution of the Atmosphere
• Water vapor condensed and precipitated to form oceans
• Carbon dioxide lost to oceans
• Oxygen released first through primitive oceanic bacteria, later through plants
(protected by ozone layer)
• Plants further reduced carbon dioxide
• Nitrogen slowly increased over long periods of time through outgassing
 Composition of the Modern Atmosphere
• The atmosphere today contains:
• Permanent Gases
• Variable Gases
• Microscopic solid particles (Aerosols)
 What Determines Atmospheric
Composition?
• Composition of gases on a planet is determined
largely by how easily gases can escape to space
• Also depends on the existence of life or geologic
processes
• For a gas to escape to space, it must reach its “escape
velocity.”
• Escape velocity is the speed required to overcome the
gravitational pull of the planet
• Molecular velocity is determined by the gas temperature
(or average kinetic energy)
 Escape Velocity
• Gas is made up of free molecules in constant
motion.
• Speed of the gas molecules is determined by the
temperature
• Temperature determined largely by proximity to the
Sun
• Escape velocity depends on the gases’ molecular
weight and the planets size
• Lighter molecules require less speed to escape
• Larger planets have stronger gravitational pull
 Permanent Gases
• Permanent gases form a constant proportion of the
atmosphere, and have long residence times
(thousands to millions of years)
 Homosphere and Heterosphere

• Homosphere: Turbulent
mixing causes atmospheric
composition to be fairly
homogenous from surface to
~80-100 km (i.e., 78% N2,
21% O2)
• Heterosphere: Above ~80-
100km, much lower density,
molecular collisions much
less, heavier molecules (e.g.,
N2, O2) settle lower, lighter
molecules (e.g., H2, He) float
to top
The Chemical Profile
• Homosphere – The atmosphere below 80km (~50miles)
• Permanent gases are in constant concentration
• Generally “atmosphere” refers to the homosphere

• Heterosphere – Above the homosphere

• Lighter gases dominate (helium, hydrogen)
• No permanent gases
 Variable Gases

Variable gases vary in atmospheric concentration in both time and space

Typical percentage values (by volume):

Water vapor (H2O) 0 to 4%
Carbon Dioxide (CO2) 0.038%
Methane(CH4) 0.00017%
Ozone(O3) 0.000004%

(Note: Water vapor is the third most common

molecule in Earth’s atmosphere after nitrogen
and oxygen.)
 Water Vapor
• Water vapor (H2O) – Extremely important variable gas with short
residence time (~10 days)
• Water vapor is the gaseous phase of water
• Atmospheric concentration highest near ocean surface in tropics (~4%)
• Atmospheric concentration lowest in deserts and at high altitudes (nearly 0%)
 Water Vapor Satellite Imagery
• Satellite imagery reveals variable nature of water vapor concentration
• Water vapor satellite imagery also reveals moist and dry regions of the
atmosphere
Water vapor imagery Visible imagery
The Hydrologic Cycle
 Carbon Dioxide
• Carbon dioxide (CO2) – An important greenhouse gas with concentration
0.0386% (386 ppm) and residence time of 150 years

• Sources: 1) Plant and animal respiration

2) Volcanoes
3) Organic decay
4) Combustion

• Sinks : 1) Photosynthesis
2) Oceans
Atmospheric CO2 Cycle
Global climate models used to
examine greenhouse warming
must be able to account for
multiple, complex processes in
atmosphere, over land, and in
ocean.

Earth’s greenhouse gases

contribute to a ~30oC warmer
surface temperature than
would otherwise exist.
 Carbon Dioxide
• Seasonal oscillation in concentration
• Long term increase in concentration (due to anthropogenic
combustion and deforestation)

Mauna Loa Observatory (~11,000 ft. in Hawaii)

 Methane
• Methane (CH4) – A variable gas with residence time ~10 years that has high
potential for greenhouse warming
• Concentrations of about 1.7 ppm
• Extremely potent green house gas – 21 times more powerful by weight than
carbon dioxide
• Increase attributed to agriculture, bio-mass burning, fossil fuel extraction, some
industry and ruminant out-gassing (cow/sheep burps)

Sources: 1) Agricultural waste

2) Biomass burning
4) Fossil fuel extraction
5) Animal digestion

Sinks: 1) Atmospheric chemical reactions

Methane

• Has varied cyclically on a 23,000 year

cycle
• Pattern broken in past 5,000 years
with unexpected increase – more
abundant now than in last 400,000
years
 Ozone
• Ozone (O3) – A beneficial and
harmful variable gas
• O3 concentrations in the
stratosphere are relatively high (15
ppm), occuring from natural
chemical reactions
• Absorbs UV radiation!

• O3 concentration near earth’s

surface is usually near zero, but can
increase to 0.15 ppm through
chemical reactions in polluted air
• Irritant!
Stratospheric Ozone Creation and Destruction
• Natural ozone cycle
O2 + uv –> O + O
O2 + O –> O3
O3 + uv –> O + O2

• After introduction of CFCs

CFC + uv –> Cl + CFCbyproduct
Cl + O3 –> ClO + O2
O + ClO –> Cl + O2
 Aerosols
• Aerosols – Small solid particles (e.g. dust, smoke, sea spray, volcanic
ash)
• Typical diameter: 10 microns (0.00001 meter)
• Typical life span: days to weeks
• May be man-made (anthropogenic) or naturally occurring
• Primary sinks include dry and wet deposition
• Some aerosols are beneficial and act as cloud condensation nuclei
Aerosols

Lubbock Dust Storm

Aerosols

Haboob in Phoenix, AZ

Forest fire smoke in CA Eruption of Mount St. Helens

 Atmospheric State
Variables
~
Vertical Structure of
the Atmosphere
Atmospheric State Variables
• State variables include:
• Pressure
• Temperature
• Density
• State variables are related to one another by the
Ideal Gas Law (IDL)
• IDL often referred to as the “Equation of State”
State Variables
Pressure
• Air is mostly made up of free molecules in
constant motion (gases).
• Air molecules have mass.
• You can feel the mass of the air when the wind is
blowing hard.
• Weight (a vertical force) = Mass x Gravity
• Air has mass therefore weight; pressure (weight/area)
is measured by a barometer.
 Surface Pressure
• The pressure at the surface is caused by the weight
of all the air molecules in the column above the
surface.
• Add more air molecules to the column and the
pressure goes up. (High Pressure areas)
• Take away air molecules from the column and the
pressure goes down. (Low Pressure areas)
 Pressure as Measured by Barometer
Weight of mercury in column equals weight of atmosphere
• Average sea level pressure is:
•14.7 pounds per square inch,
•760 mm or 29.92” mercury or
•1013.25 mb
Atmospheric Pressure Profile
 State Variables
Density
• Air density is the mass of the air divided by the volume
of measurement.
kg
 3
m
• As one goes higher in the atmosphere the number of
molecules in a given volume decreases, so like
pressure, density also decreases monotonically with
height.
• Since don’t have as many molecules on top of you, the
air pressure also decreases with height.
Density and Pressure with Height

Because of compression,
the atmosphere is more
dense near the surface.
Density decreases with
altitude
State Variables
Temperature
• Air molecules are moving all around us, bouncing
off each other and us.
• When the air molecules have greater kinetic
energy (energy of motion), they are moving faster.
• The temperature of the air molecules is a measure
of the average speed of the molecules per
standard volume
 Temperature Scales

K = °C +273.16

F = 9/5°C + 32
C = 5/9(°F – 32)
Temperature Change w/Altitude

• As a parcel of air rises, it expands due to lower pressure.

• Work done by molecules to expand causes temperature to decrease (cools)
• As air sinks, the parcel experiences compression due to higher pressure
• Air molecules have work done on them, temperature increases (warms)
Temperature Change w/Altitude

Rising  Expansion  Cooling

Sinking  Compression  Warming

Layering the Atmosphere Based on
Temperature
• 4 layers identified by similar temperature rates of
change with height
Relating State Variables:
“Equation of State” or “Ideal Gas Law”
• Temperature, pressure and density related
• Pressure = density*gas constant*temperature
P = ρRT
• If the pressure decreases, the density will decrease for
constant Temp.
• If the pressure decreases, the temperature will
decrease for constant density, etc.
• It is possible for all three state variables to change at
the same time!
 Vertical Structure of the Atmosphere

• Vertical Structure of the Atmosphere commonly broken into layers

• Layers are most often defined by the vertical change of temperature
within the layer since this is related to the presence of vertical
motions (or lack of) in the layer
Layers of the Earth’s Atmosphere
From top to Bottom
• Exosphere
• Thermosphere
• Ionosphere
• Mesopause

• Mesosphere
• Stratopause

• Stratosphere
• Tropopause

• Troposphere
 Troposphere

• Lower part of the atmosphere

• Energy source is heating of the
earth’s surface by the sun.
• Temperature generally
decreases with height.
• Air circulations (weather) take
place mainly here.
• Troposphere goes from surface
to about 30,000 ft. (10 km).
 Stratosphere
• Sun’s ultraviolet light is
absorbed by ozone, heating the
air.
• Heating causes increase of
temperature with height.
• Boundary between troposphere
and stratosphere is the
tropopause.
• Stratosphere goes from about
10 to 50 km above the surface.
 Mesosphere
• Above 50 km, very little
ozone, so no solar heating
• Air continues to cool with
height in mesosphere
• Mesosphere extends from
about 50 km to 90 km
above the surface

http://www.bath.ac.uk/pr/releases/images/antarctic/noctilucent-clouds.jpg
 Thermosphere

• Above 90 km, residual

atmospheric molecules absorb
solar wind of nuclear particles,
x-rays and gamma rays.
• Absorbed energy causes
increase of temperature with
height.
• Air molecules are moving fast,
but the pressure is very low at
these heights.
Ionosphere
• The ionosphere is an atmospheric layer located from the upper
mesosphere into the thermosphere
• The ionosphere contains electrically charged particles called ions due to UV radiation
• The ionosphere affects AM radio waves, absorbing them in the day and reflecting them
at night
• The ionosphere creates the northern lights (aurora borealis) and the southern lights
(aurora australis) through interactions between the sun’s rays and earth’s magnetic field
The Ionosphere
The Ionosphere

Photo from climate.gi.alaska.edu/Curtis

The Northern Lights
Exosphere
• the interface
between Earth and
space
• atoms and molecules
can escape to space
 Importance of Stratosphere,
Mesosphere and Thermosphere
• Solar nuclear particles, x-rays, gamma rays, and ultraviolet light can
damage living cells.
• Thermosphere, mesosphere and stratosphere shield life on Earth
from these damaging rays.
Summary
• Atmospheric pressure caused by weight of column
of air above you.
• Pressure changes because of adding or taking
away air from the column.
• Temperature is a measure of the average speed of
the molecules per standard volume.
• Density is the mass per volume
• Pressure, Temperature, and Density all related by
the Ideal Gas Law (a.k.a. the Equation of State)
 Summary (cont.)
• Temperature decreases with height unless energy is
added.
• Troposphere temperature decreases with height.
• Stratosphere temperature increases with height
because of ozone absorption of dangerous UV radiation
• Mesosphere temperature decreases with height
• Thermosphere temperature increases with height
because of absorption of solar particles, x-rays and
gamma rays.
• Atmospheric composition remains fairly homogeneous
up to ~80-100 km