Chemistry in the Atmosphere

Chapter 17

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The Nitrogen Cycle

17.1
Atmospheric Nitrogen Fixation
electrical
N2 (g) + O2 (g) energy 2NO (g)

2NO (g) + O2 (g) 2NO2 (g)

2NO2 (g) + H2O (g) HNO2 (aq) + HNO3 (aq)

Industrial Nitrogen Fixation

catalyst
N2 (g) + 3H2 (g) 2NH3 (g)

NH3 + 2O2 HNO3 + H2O

NH3 + HNO3 NH4NO3

CH4 + 2H2O 4H2 + CO2

17.1
The Oxygen Cycle

17.1
 hn + N2 2N
hn + N N + e-
hn + O2 O2+ + e-

17.1
 Atmospheric
Chemistry
EARTH’S
ATMOSPHERE
Exosphere
o1600 km; Very high
Temp.,
oH2, HE, Outer Space
o 90-500 Thermosphere
km; - 92 to 1200 C
o

Temp.,
oO2, NO+
Mesosphere
o 50-90 km; -2 to -92 oC Temp,
o( Ionoshere: O+2, O+ , NO+ , e-)
Stratosphere
o 11-50 km; -56 to - 2 oC Temp,
oO3 ( Ozone Layer: 15 km)
Troposphere
o 0- 11 km; 15 to - 56 oC Temp,
oN2, O 2, CO2, H2O
 Troposphere
The troposphere is the lowest layer of our
atmosphere.
Starting at ground level, it extends upward
to about 10 km (6.2 miles or about
33,000 feet) above sea level.
We humans live in the troposphere, and
nearly all weather occurs in this lowest
layer.
Most clouds appear here, mainly because
99% of the water vapor in the atmosphere
is found in the troposphere.
Air pressure drops and temperatures get
colder, as you climb higher in the
troposphere.
 Stratosphere
The stratosphere extends from the top of the
troposphere to about 50 km (31 miles) above the
ground.
The infamous ozone layer is found within the
stratosphere.
Ozone molecules in this layer absorb high-energy
ultraviolet (UV) light from the Sun, converting the
UV energy into heat.
Unlike the troposphere, the stratosphere actually
gets warmer the higher you go!
That trend of rising temperatures with altitude
means that air in the stratosphere lacks the
turbulence and updrafts of the troposphere beneath.
Commercial passenger jets fly in the lower
stratosphere, partly because this less-turbulent layer
provides a smoother ride.
The jet stream flows near the border between the
troposphere and the stratosphere.
 Mesosphere
Above the stratosphere is the mesosphere.
It extends upward to a height of about 85
km (53 miles) above our planet.
Most meteors burn up in the mesosphere.
Unlike the stratosphere, temperatures once
again grow colder as you rise up through the
mesosphere.
The coldest temperatures in Earth's
atmosphere, about -90° C (-130° F), are
found near the top of this layer.
The air in the mesosphere is far too thin to
breathe; air pressure at the bottom of the
layer is well below 1% of the pressure at sea
level, and continues dropping as you go
higher.
 Thermosphere
The layer of very rare air above the mesosphere is
called the thermosphere.
High-energy X-rays and UV radiation from the
Sun are absorbed in the thermosphere, raising its
temperature to hundreds or at times thousands of
degrees.
The air in this layer is so thin that it would feel
freezing cold to us!
The thermosphere is more like outer space than a
part of the atmosphere. Many satellites actually
orbit Earth within the thermosphere!
The top of the thermosphere can be found
anywhere between 500 and 1,000 km (311 to 621
miles) above the ground. Temperatures in the
upper thermosphere can range from about 500 °C
(932 °F) to 2,000 °C (3,632 °F) or higher.
The aurora, the Northern Lights and Southern
Lights, occur in the thermosphere.
 Thermosphere
The layer of very rare air above the mesosphere is
called the thermosphere.
High-energy X-rays and UV radiation from the
Sun are absorbed in the thermosphere, raising its
temperature to hundreds or at times thousands of
degrees.
The air in this layer is so thin that it would feel
freezing cold to us!
The thermosphere is more like outer space than a
part of the atmosphere. Many satellites actually
orbit Earth within the thermosphere!
The top of the thermosphere can be found
anywhere between 500 and 1,000 km (311 to 621
miles) above the ground. Temperatures in the
upper thermosphere can range from about 500 °C
(932 °F) to 2,000 °C (3,632 °F) or higher.
The aurora, the Northern Lights and Southern
Lights, occur in the thermosphere.
 Ionosphere
The ionosphere is not a distinct layer like
the other mentioned above.
The ionosphere is a series of regions in
parts of the mesosphere and thermosphere
where high-energy radiation from the Sun
has knocked electrons loose from their
parent atoms and molecules.
The electrically charged atoms and
molecules that are formed in this way are
called ions, giving the ionosphere its name
and endowing this region with some
special properties.
 Auroras
• Auroras are called also northern and southern
(polar) lights or Aurora.
• Auroras are observed at night in the polar
• regions.
Auroras are called after the Greek goddess of dawn

02
Aurora.
• Auroras are most visible closer to the poles dueto
the longer periods of darkness and the magnetic
field.
• The aurora australis (Latin word for “of the south”)
the southern polar
lights are the counterpart of the northern
lights. They are visible only from high
November Aurora Borealis Riquette Mory 13
southern latitudes in Antarctica and South
 Auroras
• Auroras are the result of the emissions of
photons in the Earth's upper atmosphere:
• oxygen emissions
• Green or brownish-red, depending on the
amount of energy absorbed.
• Nitrogen emissions
• Blue or red. Blue if the atom regains an electron
after it has been ionized. Red if returning to
ground state from an excited state.

November Aurora Borealis Riquette Mory 14

 Southern Lights Auroras Northern Lights

A predominantly red aurora australis

Aurora australis 1994

from Bluff, New Zealand
03 Aurora
Borealis

Aurora australis (September 11, 2005)

as captured by NASA's IMAGE satellite

November Aurora Borealis 4

Riquette Mory
 A u r o rAuroras
a s are formed When
a "solar wind" of charged
particles from the Sun
enters Earth's magnetic

04
field, accelerating
electrically charged
particles trapped within.
The high-speed particles
then crash into Earth's
upper atmosphere over the
Polar Regions, causing the
atmosphere to emit a
ghostly, multicolored glow.

November Aurora Borealis Riquette Mory 16

Chemical Rxs in the Thermosphere
e- + O O* + e-

p+ + N 2 N2+* + p+ + e-

O* O + hn green and red

N2 + hn blue and violet
+
N+2*

O + NO NO2*

NO2* NO2 + hn

orange
Glowing tail section of space shuttle
17.2
 Depletion of Ozone in the Stratosphere
O3 production
UV
O2 O+O
< 240 nm
dynamic equilibrium
O + O2 + M O3 + M
O3 destruction constant concentration
UV
of O3 in stratosphere
O3 O + O2
O + O3 2O2 UV

Ozone Layer

17.3
 Depletion of Ozone in the Stratosphere
Anthropogenic O3 destruction
UV
CFCl3 CFCl2 + Cl
UV
CF2Cl2 CF2Cl + Cl

Cl + O3 ClO + O2
+ ClO + O Cl + O2

O3 + O 2O2

Cl catalyzes the reaction

17.3
Concentrations of Chlorine Monoxide and
Ozone Versus Latitude

17.3
 Polar stratospheric clouds
provide a surface for the rx:
HCl + ClONO2 Cl2 + HNO3

Spring sunlight Cl2 + hn 2Cl

Cl + O3 ClO + O2
+ ClO + O Cl + O2

O3 + O 2O2
17.3
Ozone Depletion (in purple) Over the South Pole

17.3
2H2S (g) + 3O2 (g) 2SO2 (g) + 2H2O (g)
SO2 (g) + OH (g) HOSO2 (g)
HOSO2 (g) + O2 (g) HO2 (g) + SO3 (g)
SO3 (g) + H2O (g) H2SO4 (g)

H2SO4 aerosols have a local cooling effect on the atmosphere.

17.4
The trapping of heat near Earth’s surface by gases in the
atmosphere is the greenhouse effect.
H2O + hn H2O*
CO2 + hn CO2*

17.5
 Why don’t N2 and O2 contribute to
the greenhouse effect ?

N2 and O2 cannot
absorb IR radiation.

3 vibration
modes of
H2O
2 of the vibration modes of CO2
17.5
The Carbon Cycle

17.5
The Yearly Variation in the CO2 Concentration
At Mauna Loa, Hawaii

17.5
The Temperature Rise on Earth’s
Surface from 1880 to 1996

17.5
 Acid Rain
SO2 (g) + OH (g) HOSO2 (g)
HOSO2 (g) + O2 (g) HO2 (g) + SO3 (g)
SO3 (g) + H2O (g) H2SO4 (g)

Mean
precipitation
pH in 1994

17.6
 CaCO3 (s) + H2SO4 (aq) CaSO4 (s) + H2O (l) + CO2 (g)
2CaCO3 (s) + 2SO2 (g) + O2 (g) 2CaSO4 (s) + CO2 (g)

The Effect of Acid Rain on the Marble Statue of George

Washington (New York, City). Photos Taken in 1944 and 1994
17.6
17.6
Photochemical smog is formed by the reactions of
automobile exhaust in the presence of sunlight.

Primary pollutants: NO, CO and unburned hydrocarbons

Secondary pollutants: NO2 and O3

N2 (g) + O2 (g) 2NO (g)

2NO (g) + O2 (g) 2NO2 (g)
NO2 (g) + hn NO (g) + O (g)
O (g) + O2 (g) + M O3 (g) + M

17.7
Typical Variations with Time in the Concentration of
Air Pollutants on a Smoggy Day

17.7
 9 5
238 4.51 x 10 yr 234 24.1 days 234 1.17 min 234 2.47 x 10 yr
92U 90Th 91Pa 92U

230 7.5 x 104 yr 226 1.6 x 103 yr 222 3.82 d

90Th 88Ra 86Rn

17.8
 Post-Test
1. Describe the regions of Earth’s atmosphere.

2. Briefly outline the main processes of the nitrogen and

oxygen cycles.

3. What process gives rise to aurora borealis and aurora

australis?

4. Why can astronauts not release oxygen atoms to test the

mechanism of shuttle glow?
5. Briefly describe the absorption of solar radiation in the
stratosphere by O2 and O3 molecules.

6. Explain the processes that have a warming effect on the

stratosphere.
7. List three detrimental effects of acid rain.

8. Briefly discuss two industrial processes that lead to acid rain.

9. Discuss ways to curb acid rain.

10. What is photochemical smog? List the factors that favor the
formation of photochemical smog.
11. What are primary and secondary pollutants?

12. Identify the gas that is responsible for the brown color of
photochemical smog.