Atmosphere

- a layer of gases (air) at the surface of the earth.

- a protective covering of earths life against solar
radiation and excessive heating
Composition of Dry Air
Gas
% by Volume
Nitrogen, N2
78.03
Oxygen, O2
20.99
Argon, Ar
0.94
Carbon dioxide, CO2
0.033
Neon, Ne
0.0015
Helium, He
0.000542
Krypton, Kr
0.00014
Xenon, Xe
0.000006
Source: Chang, R. Chemistry, 7th ed., McGraw-Hill, 2002

Nitrogen
-

nitrogen is the most abundant element in the

atmosphere but, its diatomic form, N2, is
relatively
inertassimilated by living organisms
it
is not easily

and does not easily react with other chemicals

to form new compounds
- it has to be transformed into its reduced forms
(such as
ammonia, ammonium, nitrates, nitrites, and
-nitrogen
the process of nitrogen fixation transforms
this
diatomic
oxides)
nitrogen to other compounds of nitrogen to
be used in the
formation of biological compounds (such as
nucleic acids,
amino acids,
andcan
proteins),
industrial
- nitrogen
fixation
be natural
or synthetic

amples of Nitrogen Fixation

1. Nitrogen fixation brought about by lightning
Steps: N2(g) + O2(g) electrical energy
2NO(g
)

2NO(g) + O2(g)

2NO 2(g)

2NO2(g) + H2O(l)

HNO2(aq) + HNO3(aq)

2. Biological Fixation of Nitrogen, BFN

- Organisms such as the Cyanobacter,
Azotobacter, and Azospirillum can produce the
enzyme nitrogenase which they use
catalytically for the conversion of atmospheric
N2 to NH3. Another group of organism, the
Rhizobium
N works
+symbiotically with legumes
2NH3 + H2
2 + 8H
and other plants to reduce N2.
)

3. Synthetic Fixation by Haber-Bosch Industrial Process

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

The Nitrogen Cycle

Nitrogen in its consumable form is made
possible by the process called the nitrogen
cycle, in which nitrogen is taken from the
atmosphere and converted to nitrates by
The nitrates
nitrogen
fixation. are absorbed by plants
converting them to proteins and nucleic acids
which are further eaten by animals
Eventually the nitrogen from the plants and
animals (together by industrial nitrogen) is
converted to N2 by another group of
microorganisms called the denitrifying

The Nitrogen Cycle

he Atmospheric Oxygen
- dry air contains approximately 20.99%
-2a
reactive element, it easily reacts
O
byvery
volume
with other
elements or substances and disappears
-from
the
its concentration
in the atmosphere is
atmosphere
almost
always
constant
Oxygen is removed mainly from the
atmosphere by
The main routerespiration
for the regeneration
of the diatomic
oxygen into the atmosphere is by the
process
of
This
continuous
cycling of oxygen
photosynthesis
through these
two processes for the
stable concentration of oxygen in the

Respiration is the process by which energy is

released from the cellular oxidation of glucose
in a process called glycolysis
Equation: C6H12O6 + 6O2 6CO2 +
6H2O + energy
Photosynthesis is the process by which plants
convert light energy to chemical energy (stored
in the chemical bonds of sugar) with the
simultaneous release of oxygen gas.
Equation: 6CO2 + 6H2O + energy
C6H12O6 + 6O2

yers of the Atmosphere

1. Troposhere
2. Stratosphere

3. Mesosphere
4.
Ionosphere

Troposphere
- thinnest layer, extends up to
10 - 11 km from the earths
surface
most
dense, contains 80% of
air mass
- where all weather
changes are observed, a
region of rising and falling
of
packets
of air
- air
pressure
at the
topmost part is 10% of
that at sea level. The
atmospheric pressure at
sea
level is 1 atm.
- temperature
is highest at the lowest portion and
decreases with
altitude
- tropopose isincreasing
the zone separating
the troposphere
from the

Stratosphere
- situated between 10 50
miles from the earths surface
where the ozone layer is found
-vertical stratified in
temperature, with warmer layers
higher up and cooler layers
farther down. The topmost is
- the formation
of ozone from
0
about -3 C
atomic oxygen and diatomic
oxygen is exothermic. Ozone also
absorbs ultraviolet rays turning
them to heat energy. Thus,
temperature increases towards the
top
ofvertical
this layer
where the ozone temperature convection.
- The
stratification,reduces
molecules
concentrate.
Thus
no associated
turbulence is observed, making this layer
dynamically stable. For this reason, airplanes prefer to fly at
the lower portion of the stratosphere.
Balloons and other gliders can go as far as the lower portion of
-the
The
boundary between the stratosphere and the next layer is
stratosphere.
called the

Mesosphere
- the mesosphere starts at
50 km above Earth's
surface and goes up to 85
- km
temperature
decreases
high.
with altitude. The top of the
mesosphere is the coldest
part of Earth's atmosphere,
around
- 90 C.from space
Most meteors
burn up in this
atmosphere
Not so much is known about this layer because
research instruments cannot easily be sent and
maintained at this level.
Mesopause is the layer that divides the
mesosphere and the next atmosphere.

hermosphere (ionosphere)
- extends from 85 -90 km to
500 - 1,000 km above the
earths
surface.increases
- temperature
with altitude with
temperature (500C -2,000C).
the air density is very thin.
- temperatures can go very
high but one would not feel
warm in the thermosphere
because there is so few
contact with the atoms of
- sound
would also
the
thin transfer
air.
be very low because of very
infrequent molecular
collision

hermosphere (ionosphere)
- where the space shuttles orbit
the earth
- most of the ultraviolet rays
and light photons from the
sun are absorbed in this layer

- the UV rays ionize the

gases excited ions. and
O N
H =
2. 2 2N
941.4 kJ
N N + + eH =
- results
1400 kJof ionization
+ eH = 1176
1.OHigh
2. Radiowaves
2 temperature
kJphenomenon
N+ , violet to blue

3. Aurora

he Ozone Layer

ozone is a triatomic molecule = O3

a blue colored gas with a very strong burnt odor
- most ozone molecules are found in the
stratosphere at 2-8 ppm concentration
- the ozone layer absorbs much of the
ultraviolet rays from the sun, preventing these
rays from reaching the planets surface.
- ultraviolet rays has been found to cause skin
cancer, cataracts, and other genetic mutations
both in animals and plant

Ozone , O3
- Pale blue gas (O3) that is irritating, explosive, and toxic.
- It is formed by the photochemical action on the atmosphere
UV
O2 (in air)
O+O
O2 + O O 3
-May also be manufactured on the spot by passing an electric discharge through
oxygen or air
-it is used in water purification, deodorization, bleaching, and various chemical
reactions that require a strong oxidizing agent
compared to chlorine, bacterial and viral disinfection with ozone is up to
5000 times more rapid.

Good Ozone or the ozone layer

occurs in the stratosphere
-maximum ozone concentration is 5 1012 molecules/cm3
(more than 1000 times the the concentration of bad ozone at earth's surface)
-This layer (atmospheric ozone) absorbs 9799% of the suns high frequency
ultraviolet light (UV) which is damaging to life on Earth.[
overexposure to UV is believed to be contributing to the increase
in melanoma, the most fatal of all skin cancers.
UV can also damage sensitive crops, such as soybeans, and reduce
crop yield
- Depletion of this ozone layer may increase the incidence of skin cancers.
ozone-depleting substances (ODS), includes chlorofluorocarbons (CFCs),
hydrochlorofluorocarbons (HCFCs), halons, methyl bromide, carbon
tetrachloride, and methyl chloroform.

- Bad ozone
Located at the troposphere layer at a usual concentration of 0.02 -0.03 ppm
In polluted places such as cities where there are high densities of smog, O3
concentration could go higher than 0.1 ppm
At concentrations greater than 0.1 ppm, ozone is toxic and can be a
potent bronchial irritant, making breathing difficult.
it also damages crops, trees and other vegetation.
Ground-level or "bad" ozone is the product of the chemical reactions
between
oxides of nitrogen (NOx) and volatile organic compounds (VOC) in the
presence
of sunlight. Emissions from industrial facilities and electric utilities,
motor vehicle
Photochemical
smogvapors,
containsand
a high
concentration
of Oare
exhaust, gasoline
chemical
solvents
some of the
3
major
smog mixture of smoke and fog
sources of NOx and VOC

ow the ozone layer absorbs UV radiations

Step

1. Photodissociation of O2 by solar UV radiation (

< 240 nm).
O O+O
Step 2. An oxygen radical 2combines with another O2 to
form an ozone, O3, molecule.
O + O2 + M O3 + M
Step

3. Now the O3 absorbs UV radiations ( = 200 to

300 nm) and dissociates
O3 O2 + O
Step 4. The cycle of steps 1 to and 3 is repeated all
over or simultaneously occuring.
This dynamic equilibrium process of generation and
destruction of O3 by UV radiation accounts to the
almost constant concentration of ozone molecules in
the stratosphere.

pletion of the Ozone Layer

- ozone depleting substances

ODS
group of chemicals containing chlorine (Cl) and bromine
- these are the chloroflourocarbons (CFC),
hydrochloroflourocarbons (HCFC)
carbon tetrachloride (CCl4)
bromoflourocarbons,
hydroflourocarbons, and
oxides of nitrogen (NOX)
they are commonly used as coolants, refrigerants, aero
propellants, foams, fire-fighting chemicals, soil
fumigants, and solvents

he choroflourocarbons (CFC)
- examples: CFCl3 (Freon 11)
CF2Cl2 (Freon 12)
C2F3Cl3 (Freon 113) and
CF4Cl2 (Freon 114)
- when these substances are discharged in the
atmosphere, they remain stable for long
periods of time.

- when they reach the ozone layer, they react with

the ozone molecules.

pletion of the ozone layer by CFCs

1.

CFCl3 is decomposed by UV: CFCl3 CFCl2

+ Cl
2. The radical Cl reacts with O3:
Cl + O3
ClO + O2
3. The radical ClO takes
another O radical from
the atmosphere:
ClO + O Cl
+ O2
4. The regenerated chlorine radical takes
another O3 and
theCl
cycle
is repeated
5. The
radical
catalyzes the decomposition of
O3 much
faster than the decomposition of O3 by UV.
6. One Cl radical can destroy up to 100,000
ozone
molecules before it is consumed by other

epletion of the Ozone Layer by NOX

- NOx, such as NO and NO2 are products of fuel
gas combustion
- Most of these NOx are released to the
atmosphere by
supersonic aircrafts

O3 O 2 + O
- Reactions:
NO + O3 NO2 +

O2
Nitrogen dioxide (NO
with
2)2 can
NO
+ Oreacts
NO +
O2 the
radical ClO forming chlorine nitrate, a very stable
chlorine reservoir in the atmosphere. NO 2 +
ClOnitrate(ClONO
ClONOOverall:
2O3 of
3OCl
2 2) is a source
lorine
2 in the formation

of the ozone holes in the arctic and antarctic skies

he Polar Ozone Holes

- the repeated abnormal depletion of the ozone

layer (to as much as 50%) over the arctic and
antarctic regions during spring time

One DU is 2.691016 ozone molecules

The Antarctic ozone hole is an area of the

Antarctic stratosphere in which the recent ozone
levels have dropped to as low as 50% of their
pre-1975 values.
During winter, polar stratospheric cloud
Containing HCl and chlorine nitrate (ClONO2) is a
Good source of Cl radical which reacts
with ozone

Types of energy manifested by atoms and molecules:

electronic energy absorbed at UV and VIS wavelength (ex: light radiation)
vibration energy absorbed at IR or far IR wavelength (ex: heat radiation)
rotational energy absorbed at the longer wavelengths like micro, radio, etc.)
How heat is generated
As the UV and VIS rays strike the surface of the earth, earth molecules
start to vibrate. This process produces another form of energy (heat energy).
The earth surface releases this heat energy above the surface of the earth.

Greenhouse gases are largely transparent to shortwavelengths like the

ultraviolet rays (UV) and the visible rays VIS) (ex: light energy).
Greenhouse gases absorb and reflect heat energy

"greenhouse effect"
- is the heating of the Earth due to the presence of greenhouse gases
- is the process by which absorption and emission of radiation by gases
(called greehouse gases) in the atmosphere warm a planets lower
atmosphere and surface.

Short wavelength (UV and VIS) solar

radiation from the sun passes through
earth's atmosphere
then is absorbed by the surface of
the Earth, causing it to warm. Heat
energy involves longer wavelength IR
Part of the absorbed energy is then
reradiated back to the atmosphere
as
long wave infrared radiation (heat).
The greenhouse gases absorb
these
waves and reemits the waves
in all directions including
downward, causing the lower
atmosphere to warm.

Greenhouse effect: Is it good or bad?

Good effect
- It controls the temperature of the atmosphere. Without it, the world with not be
livable
- It protects the earth from sub zero environment
Bad effect
-The overproduction of the so called greenhouse gases has made the geenhouse
shield too thick, thus increasing the temperature of the earth to almost undesirable
Temperature causing global warming and extreme weathers
Most common greenhouse gases
1. Carbon dioxide (CO2) and carbon monoxide (CO)
2. Methane (CH4)
3. Chloroflourocarbons (CFCs)
4. Nitrous oxide (NO2)

Major Greenhouse Gas

Formulas

Carbon dioxide

CO2

Methane
Ozone

CH4
O3

Lifetime
(years)

12

Other Gases of Anthropogenic Origins

Dinitrogen oxide
chloroflourocarbons

N2O

114

CFC-12
HCFC-22
tetraflouromethane
hexaflouroethane
Sulphur hexaflouride
Nitrogen triflouride

CCl2F2
CHClF2
CF4
C2H6
SF6
NF3

100
12
50,000
10,000
3,200
740

- naturally occurring greenhouse gases have a mean warming effect of about 33 C

- over the past century, greenhouse gases and other air pollutants
released into the
atmosphere
have been causing
big changes like global warming,
ozone
Ex:
Preindustrial
Increase since
Gas
Current level
holes, and acid
level
1750
rains
Carbon dioxide

280 ppm

388 ppm

108 ppm

Methane

700 ppb

1745 ppb

1045 ppb

Nitrous oxide

270 ppb

314 ppb

44 ppb

CFC-12

533 ppt

533 ppt

Carbon dioxide, CO2

- a colorless, odorless non-flammable gas

- carbon Dioxide is emitted into the air as humans exhale, burn fossil fuels
for energy, and deforest the planet.
Cellular respiration: C6H12O6 + 6O2 6CO2 + 6H20
Burning: Carbohydrate + O2 CO2 + H2O

Methane, CH4

- a colorless, odorless, flammable gas.

- It stays in the atmosphere for only 10 years, but traps 20 times more heat
than carbon dioxide.
- it is formed when plants decay and where there is very little air (swamp gas)
production is hastened by the presence of methanogens - are bacteria
that are commonly found in deteriorating plants in the absence of oxygen
and in the gut of animals
- Burning of methane produces CO2 and H2O which are also greenhouse gases
CH4 + 2O2 CO2 + 2H2O

Halocarbons - hydrocarbons with halogen substituents, CFCs and the HFC

Ex: dichlorodiflouromethane, CCl2F2
Chlorodiflouromethane, CHClF2
Tetraflouromethane, CF4
- they have no natural sources but are entirely synthesized as refrigerants, aerosol
propellants for fire retardants, and cleaning solvents
- their production started in 1928 and since then there was an observed rise
of CFCs in the atmosphere
- uses of CFCs are now being controlled under the terms of the Montreal Protocol
- they have long atmospheric lifetimes in the atmosphere.
Ex: CCl2F2 ~ 100 years in the atmosphere
CHClF2 ~ 12 years
CF4 ~ 50,000 years
- they also destroy the ozone layer

Nitrous oxide (N2O)

- colorless greenhouse gas, however, it has a sweet odor

- used as anaesthetic
- (laughing gas)
Sources:
- released naturally from oceans and by bacteria in soils.
- a by product of nitrogen based fertilizers
- by product of gasoline decomposition by automobiles

Other greenhouse gases

- SF6 (sulfurhexafluoride) and NF3 or N2F6 (nitrogen triflouride)
- They occur in very small amount but they are very potent greenhouse gases
- They are gases with high global warming potential (GWP)
GPW a measure of how much heat is trapped by the gas
Note: Major atmospheric constituents, N2, O2, and Ar are not greenhouses
- They do not absorb energy at IR wavelength
Note: Carbon monoxide is not a greenhouse gas
- can react with O2 to form CO2
2CO + O2 2CO2

Water, H2O

- water vapor is a potent greenhouse gas owing to the presence of the

hydroxyl
bond
which
strongly
absorbs energy
infrared
region
- the
latent
heat
of vaporization,
whichin
is the
released
to the
atmosphere
whenever
condensation occurs contributes to further environmental heating
- positive feedback loop - a higher concentration of water vapor would be able to
absorb more thermal IR energy radiated from the Earth,
thus further warming the atmosphere.
greenhouse water vapor reflects heat to the earth
Earth atmosphere becomes hotter
Higher temperature allows higher water evaporation from seas/oceans/rivers
higher concentration of water vapor is then able to absorb more
thermal IR energy, thus further warming the atmosphere.
The warmer atmosphere can then hold more water vapor and so
on and so on.

Causes of global warming or increase in greenhouse production

1. Increasing population growth
- garbage to decompose: decomposition leads to more CO2 production
2. Increase in energy consumption increase in the release of CO2
increase in the release of NO2
3. Increase in the use of refrigerants using CFC gases.
- after use, these gases stay in the atmosphere for a long time
4. Increase in methane gas production.
- Farts from cattle contain high percentage of methane gas
- Methane gases from marshes, swamps, and rice paddy fields
- Methane resulting from termite bites

Predictable effects of global warming if the amount of CO2 now present is doubled
1. Melting of the arctic and antarctic ice edges increasing the sea levels
- Coastal areas or islands would be swamped and inundated
- Areas already below sea levels would be flooded
2. Faster evaporation of water would lead to dry lands getting drier
- Rainfall pattern would be disrupted
- There would be drastic changes in the existing climate
3. Change in life patterns
- Some plants and animals may cease to exist
- Food supply would drastically be lessened
- Inevitable population migration (great migration)
What can you do to arrest global warming?

dic solution one which contains an excess of the

hydrogen ion concentration

H
2O

H+ + OH-

- pH
negative logarithm of the H+ concentration (-log H
- a measure of the hydrogen ion
concentration of a
solution
pH > 7, basic
pH < 7, acidic
pH = 7, neutral

Distilled water pH = 7
normal rain slightly acidic
- has a pH of below 7 but not

CO2 + H2O - +
lower than 5.7

Acid Rain
- any form of wet (rain, snow, sleet, fog,
cloudwater, dew) and dry (other particulates
and gases) deposition from the atmosphere
containing higher than normal amounts of
nitric
and
sulfuric
acids.
+
- high H

- low pH, could go as low as 2.0

average pH = 4.2
l
Main Cause of Acid Rain
- the large emission of sulfur dioxide (SO2)
and nitrogen oxides (NOx) to the
atmosphere

Emission of SO2
- from volcanoes
y-product in power plant generation where coal is u
combustion of fuels for motor vehicles
- industries (like the pulp and paper
industries) that
produce as byproduct the volatile
-flammable
product of liquid
phytoplankton metabolism
dimethyl sulfide
Emission of NOX

- from lightning: N2(g) + O2(g) 2NO(g

- by-product in power plant generation where

coal is used
combustion of fuels for motor vehicles

How acid rain is produced from SO2

Step 1: SO2 + OH HOSO2
Step 2: HOSO2 + O2 HO2 + SO3
Step 3: SO3 + H2O H2SO4 2H+ +

How acid rain is produced from

NOX
With NO
Step 1: NO + OH HNO2
Step 2: HNO2 H+ +

With NO2
Step 1: NO2 + OH HNO3
Step 2: HNO3 H+ +

Effects of Acid Rain

cidification of lakes and bodies of water
pH of below 5 does not allow fish eggs to
some
fishes may not be able to tolerate low pH
hatch
corals which are mainly made up of limestone may
weakened
- acceleration of corrosion of metals

4Fe
+ 3O
2Fe2O3
2
,

oil biology and chemistry is changed

acids can make the metallic ions such as
aluminum, calcium, and magnesium more
soluble, removing them as food source of
plants
microbial organisms may not be able to
tolerate the high acidity

orests and plants may be damaged

- dry precipitation (SO2 and NOX gases)
contribute to lung
diseases
asthma
bronchitis
coronary obstructive disease
skin allergies
- erosion of stone statues made mainly of
limestone and marble. CaCO3 (s) + H2SO4 (aq)
CaSO4 (s) + CO2 (g) + H2O (l)