The Atmosphere

Troposphere, Stratosphere,
Mesosphere, Thermosphere,
Exosphere
ATMOSPHERE
 Atmosphere extends about 2000 km above Earth’s
surface

 Atmosphere divided into four regions

 Troposphere
 Stratosphere (Ozone Layer)
 Mesosphere
 Thermosphere

 Atmosphere is less dense the high you go

ATMOSPHERE
ATMOSPHERE
 Temperature inversion is seen between the different
regions

 Dry atmosphere

 78.1% N2
 20.9%O2
 0.9% Ar
 0.03% CO2
TROPOSPHERE
 Important reactions in the troposphere are photosynthesis
& nitrogen fixation

 The concentration of carbon dioxide in the atmosphere

depends on photosynthesis, repsiration & the amount of
CO2 dissolved in surface waters (including oceans)

 Carbon cycle & nitrogen cycle (know these!)

Atmospheric Pollution
ATMOSPHERIC POLLUTION - INTRO
 Emissions of pollutants into the atmosphere are in two
forms

 Gases
 Particulate material

 Particulate material

 Dust & liquid droplets

 Size = 10–8m – 10–4m

 Can also absorb gases

POLLUTANTS – TYPES
 Pollutants are either primary pollutants or secondary
pollutants

 Primary pollutants
 Emitted directly into the atmosphere

 Secondary pollutants
 Formed indirectly by reactions in the atmosphere

*Residence time is the length of time a particular chemical is present

in a given reservoir
ATMOSPHERIC EMISSIONS – FATE
 Emissions either
 Accumulate in the atmosphere or
 Those that are unreactive in troposphere escape to the
stratosphere & participate in chemical reactions

 Main air pollutants

 Oxides of carbon (CO, CO2)
 Sulphur dioxide (SO2)
 Hydrogen sulphide (H2S)
 Oxides of nitrogen (NO, NO2)
 Ozone (O3)
SOURCES OF MAIN ATMOSPHERIC
POLLUTANTS
Pollutant Pollutions Natural Sources Residence Time*
Sources
Carbon dioxide Combustion Biological decay 4 yrs

Carbon Monoxide Transport Forest fires 1-4 months

Combustion
Hydrocarbons Transport Biological 16 yrs
Combustion processes
Halogenocarbons Aerosols - over 20 yrs
(CFCs) Refrigerants
Sulphur Dioxide Combustion of Volcanoes 3–7 days
fossil fuels
Nitrogen Oxides Combustion Biological 4 days
processes
Particulates Combustion Dust Varies
 Oxides of Carbon

Carbon Dioxide & Carbon Monoxide

CARBON MONOXIDE & CARBON
DIOXIDE
 Carbon Monoxide (CO) & Carbon Dioxide (CO2) are the
largest produced air pollutants

 Main sources
 Decomposition of organic material
 Oxidation of methane
 Combustion of fossil fuels


2C(s)  O2(g)  2CO(g) ; H  220kJ

2CO(g)  O2(g)  2CO2(g) ; H  566kJ
CARBON MONOXIDE – SOURCES
 Naturally
 Oxidation of methane in swamps
 Oxidation of organic material in tropics
 These sources account for most of CO in the atmosphere
(more than human activities)

 Human activities
 Combustion of fossil fuels
 56% is for petrol used in transport
 CO produced during idling or deceleration of vehicles
 Other 44% – heating, cooking, electricity etc
CARBON MONOXIDE SINKS
 Carbon monoxide can be removed by

1. Reactions in troposphere
 OH  CO  CO2  H 

 This removes up to 50% of carbon monoxide emitted in the

troposphere
CARBON MONOXIDE SINKS
 Carbon monoxide can be removed by

2. Soil Bacteria (e.g. Bacillus oligocarbophilus,

Methanosarcina backerii ) or Soil Fungi

2 CO(g)  O 2(g)  2 CO2(g)

by Bacillus oligiocarbophilus

4 CO(g)  H 2O(l)  CH 4 (g)  3 CO2(g)

by Methanosarcina backerii

 Uptake of CO by soil bacteria is rapid

CARBON MONOXIDE SINKS
 Carbon monoxide can also be removed

3.
CO(g)  O(g)  M  2 CO2(g)  M

 Or by plant leaves
hf
CO(g)  plant leaves  NH 2CH(R)COOH
amino acids

night
CO(g)  plant leaves  CO2(g)
EFFECTS OF CARBON MONOXIDE
 Carboxyhaemoglobin
 Carbon monoxide combines with haemoglobin
 CO not easily released
 Haemoglobin not able to transport oxygen around body

 Effects/Symptoms of CO poisoning
 Reddening of lips (cherry lips)
 Unconsciousness
 Death by asphyxiation
 Parkinson’s disease (rare cases)
CARBON DIOXIDE – SOURCES
 Biological decay

 Burning of petrol (fossil fuels)

 Accounts for 31% of CO2 emissions
CARBON DIOXIDE – CONCENTRATION
 Levels of CO2 in the atmosphere have shown steady
increase since 1870
CARBON DIOXIDE – SEASONAL
VARIATION
 There are seasonal variations in CO2 concentration
 Northern Hemisphere – Peaks in April & at lowest in Sep–
Oct
CARBON DIOXIDE – VARIATION
 Seasonal variations are mainly due to photosynthesis

 Destruction of rainforest can significantly raise the levels of

carbon dioxide in the atmosphere

 Temperature change of 2–3 oC would have pronounced

effect on global & local climate
GREENHOUSE EFFECT
 Average temperature of the Earth is maintained at 14 oC
 Achieved by re-emitted IR radiation trapped by water vapour
& CO2 (greenhouse gases)
GREENHOUSE EFFECT
 If it was not for the re-emitted IR radiation from water &
CO2

 Earth’s Global temperature at the surface would be

– 20 oC to – 40 oC

 This method by which the Earth’s surface is kept

relatively warm is called the “greenhouse effect”

 ~50% of energy from the sun reaches Earth’s surface

GLOBAL WARMING
 Concern
 Rising levels of CO2 in the atmosphere & other greenhouse
gases will lead to GLOBAL WARMING

 Disastrous climatic effects

 Greenhouse gases
 Water vapour
 Carbon dioxide (CO2)
 Methane
 Nitrous Oxide
 Ozone
 CFCs
Sulphur Dioxide
SULPHUR DIOXIDE – SO2
 Primary pollutant

 Residence Time = 3 – 7 days

 150 million tonnes/yr of SO2 discharged in atmosphere

 Burning of fossil fuels, HFO (generate electricity)

 Coal
 Smelting (Extration of Zn, Pb, Cu)
SULPHUR TRIOXIDE – SO3
 Secondary pollutant

 Sulphur dioxide (SO2) is oxidized to sulphur trioxide

(SO3) which then reacts with water to form sulphuric
acid (H2SO4)

SO2  SO3  H 2SO4

SULPHUR TRIOXIDE – SO3
 Sulphur dioxide in the atmosphere can be oxidized to
sulphur trioxide in three ways:

 Free-Radical Oxidation
 Catalysis
 Photochemical Oxidation
OXIDATION OF SULPHUR DIOXIDE –
CATALYSIS

2SO2(g)  2H 2O(l)  O 2(g)  2H 2SO4(aq)

 Overall reaction is oxidised in water droplets &

catalysed by metal ions & metal oxides

 Mn2+,Fe3+, Cu2+
 Oxides of Cr, Al, Pb, Ca

 Surfaces of buildings act as catalytic centres

OXIDATION OF SULPHUR DIOXIDE –
PHOTOCHEMICAL OXIDATION

SO2(g)  O3(g)  SO3(g)  O 2(g)

 Reaction occurs rapid in water droplets – Ozone is
destroyed

SO 2(g)  NO 2(g)  SO3(g)  NO (g)

 Nitrogen dioxide from motor vehicle emissions can

increase the rate of oxidation
ACID RAIN
 Acid rain is produced when SO2 is dissolved in water to
give sulphurous & sulphuric acid (H2SO3 & H2SO4)

 Pure Rain–water has a pH ~ 5.6

 Rain water + SO2 emissions pH ~ 2

 SO2 is the main cause of acid rain, Nitrogen oxide

emissions also contribute when dissolved in water
droplets (nitric acid)
ACID RAIN
 Nitrogen oxide emissions originate from power stations
& motor vehicles

 Acid rain
 Increase acidity of lakes
 Destroy aquatic life
 Leaches nutrients from soils
 Enables toxic metal ions to enter soil solution, food chain,
drinking water–supplies
 Corrosion of metals & buildings containing limestone
 Affect the growth of trees
ACID RAIN – CORROSION OF BUILDINGS
& METALS
 Sulphur dioxide & sulphuric acid has a corrosive effect
 Buildings, metals, paper & clothing fabrics

 CaCO3 in limestone is converted to the more water

soluble CaSO4 by sulphur dioxide & sulphuric acid

2CaCO3(s)  2SO2(g)  O2(g)  2CaSO4(s)  2CO2(g)

CaCO3(s)  H 2SO4(aq)  CaSO4(s)  H 2O(l)  CO2(g)

ACID RAIN – CORROSION OF METALS
 Sulphur dioxide increase the rate of corrosion of metals

Fe(s)  SO 2(g)  O 2(g)  FeSO 4(s)

 Sulphuric acid dissolves the metal protective oxide
layers (eg. Al or Cu) forming sulphates that are water
soluble

Fe(s)  H 2SO4(aq)  FeSO 4(aq)  H 2(g)

EFFECT OF SULPHUR DIOXIDE –
HUMANS, PLANTS & ANIMALS
Subject Effect
Humans Aggravate respiratory diseases (eg.
asthma, emphysema & chronic
bronchitis),
Irritation of eyes & respiratory tract,
Affects heart ,
Reduce lung function,
Death

Plants Bleached spots on leaves,

Yellowing of leaves,
Suppressed growth,
Inhibits photorespiration,
Chlorosis (loss of chlorophyll)
Animals Affects central nervous system
CONTROLLING SULPHUR DIOXIDE
EMISSIONS
 Reducing the sulphur content of fuels results in a
decrease in the amount of SO2 released when fuels are
burnt

 Sulphur in crude oil is removed by CaO & then

oxidation in air

3S(l)  2CaO(s)  2CaS(s)  SO2(g)

2CaS(s)  3O 2(g)  2CaO(s)  2SO2(g)

CONTROLLING SULPHUR DIOXIDE
EMISSIONS
 The SO2 produced is used to make sulphuric acid by
Contact Process

 Gaseous SO2 emissions from power plants can be

prevented by removing the sulphur dioxide by scrubbing
(using lime)

 Limestone reacts with sulphur dioxide to form fine

particles of calcium sulphate
CaCO3(s)  CaO(s)  CO2(g)
2CaO(s)  2SO2(g)  O2(g)  2CaSO4(s)
CONTROLLING SULPHUR DIOXIDE
EMISSIONS
 The calcium sulphate produced can be used to make
sulphuric acid

 Other bases such as magnesium oxide & ammonia can

be used instead of CaO

 End–product can also be used to make sulphuric acid

 Fewer nitrogen oxides are formed thus both SO2 & NOx
atmospheric pollutants are reduced using scrubbing
Photochemical Smog
WHAT IS PHOTOCHEMICAL SMOG
 Photochemical smog

a whitish yellow haze which is a mixture of smoke & fog

 contains chemical species which irritate the respiratory tract
 causes long term effects on health
PHOTOCHEMICAL SMOG –
CONSTITUENTS
 Chemical pollutants in photochemical smog

 Nitrogen monoxide (NO)

 Nitrogen dioxide (NO2)
 Hydrocarbons
 Peroxyethanoyl nitrate (PAN)
 Ozone (O3)
 Aldehydes

 Primary pollutants in photochemical smog are nitrogen

monoxide (NO) & hydrocarbons
PHOTOCHEMICAL SMOG
 Conditions needed to produced Photochemical Smog
 A particular combination of atmospheric pollutants
 Sunlight
 Stabletemperature inversion
 Land enclosed by hills
PHOTOCHEMICAL SMOG
 Primary pollutants (NO & hydrocarbons) concentrations
increase during early–morning rush hour traffic

 Nitrogen oxide (NO) is then oxidised to Nitrogen dioxide

(NO2)

 Nitrogen dioxide concentrations fall later in the day due

to

 Photolysis (complex series of reactions)

 Leads to formation of Ozone, Aldehydes & peroxynitrates
COMPLEX REACTIONS
 Formation of Ozone
2NO   O2  2NO 2 
hf
NO 2   NO   O
O  O 2  M  O3  M

 Formation of Aldehydes
RCH 3   OH  RCH 2   H 2O

RCH 2   O 2  RCH 2O 2 
peroxyl radical

RCH 2O 2   NO  RCH 2O   NO2 

RCH 2O   O 2  RCHO HO 2 
aldehyde
COMPLEX REACTIONS
 Formation of Peroxynitrates

RCOO   NO 2   RCOONO 2

O O
peroxyethanoyl nitrate

 Peroxyethanoyl nitrate (peroxyacetyl nitrate or PAN)

PHOTOCHEMICAL SMOG
 Nitrous & nitric acids, (HNO2, HNO3) are formed by
reaction of nitrogen oxides (NOx) with water

 Nitrogen oxides & hydrocarbons produced in the

afternoon rush hour traffic are removed by reaction with
ozone
NO  O3  2NO2   O 2

RCH  CH 2  O3  RCHO   H 2COO 

aldehyde
or RCHOO   H 2CO 
methanal
 Produces an aldehyde or ketone
EFFECT OF PHOTOCHEMICAL SMOG –
HUMANS & PLANTS
Subject Pollutant Effect
Humans NO2 Odour,
Lethal
Ozone Irritation of throat,
Shortness of breath,
Irritation of eyes & nose,
Impaired lung function,
chest pains, coughing
Unconsciousness,
Death

PAN Reduced Lung function

HCHO Odour,
Severe distress
EFFECT OF PHOTOCHEMICAL SMOG –
HUMANS & PLANTS
Subject Pollutant Effect
Plants NO2 Leaf lesions,
Inhibits photosynthesis

Ozone Leaf lesions,

Inhibits photosynthesis

PAN Collapse of young cells

HCHO Leaf symptoms

 Ozone

Stratospheric Ozone vs Tropospheric Ozone

Good vs Evil
STRATOSPHERIC OZONE
STRATOSPHERIC OZONE
 Production of stratospheric ozone is by UV radiation 190
– 242 nm

 Ozone (O3) is a form of oxygen with three oxygen atoms

STRATOSPHERIC OZONE PRODUCTION
 Ozone is produced in stratosphere by photochemical
reactions
hf
 
O2(g)  O(g)  O (g) 
   Formation of Ozone
O (g)  O2(g)  M (g)  O3(g)  M (g)
ozone



 Overall Reaction???
STRATOSPHERIC OZONE DESTRUCTION
 Ozone (O3) produced absorbs UV radiation <340 nm in two
reactions to re-form diatomic oxygen (O2)

hf

O3(g)  O 2(g)  O(g) 
 Destruction of Ozone
O3(g)  O(g)  2O2(g) 
 Overall Reaction??? 

 Both sets of reactions (production & destruction) maintain the

concentration of Ozone in the stratosphere
OZONE DESTRUCTION
 Ozone can also be removed by other reactions

NO  (g) O3(g)  2NO2  (g) O2 (g)

NO 2  (g)  O(g)  NO  (g)  O2 (g)

hf
NO 2  (g)  NO  (g)  O(g)

 The oxides of nitrogen enter the atmosphere

 Biological activity
 Fossil Fuel combustion
STRATOSPHERIC VS TROPOSPHERIC
OZONE
 Stratospheric Ozone is essential in screening the Earth
from dangerous UV radiation

 Ozone Layer absorbs most UV radiation < 320 nm

 Animals & plants are protected from this radiation

 While Tropospheric Ozone????

STRATOSPHERIC VS TROPOSPHERIC
OZONE
 Tropospheric Ozone is a dangerous pollutant

 High tropospheric ozone concentrations results from

 Motorvehicle emissions
 Incomplete combustions of fossil fuels
TROPOSPHERIC OZONE
TROPOSPHERIC OZONE – REACTIONS
 All species are in the gaseous state
 Nitrogen oxides participate in both the formation &
destruction of ozone

2NO   O 2  2NO2  
hf

NO2   NO   O  Formation of Ozone
O  O2  M  O3  M 


NO  O3  2NO2  O2  Destruction of Ozone

TROPOSPHERIC OZONE
 Nitrogen monoxide (NO) produced from vehicle
exhausts in morning rush hour traffic leads to a rise in
Ozone (O3) levels
EFFECT OF TROPOSPHERIC OZONE –
HUMANS & PLANTS
Subject Effect
Humans Irritation of throat
Shortness of breath
Irritation of eyes & nose
Impaired lung function, chest pains,
coughing
Unconsciousness
Death
Plants Leaf lesions, inhibits photosynthesis
OTHER EFFECTS OF TROPOSPHERIC
OZONE
 Tropospheric Ozone can cause oxidative cleavage in the
C=C double bond in rubber (polymer)

 Rubberto crack
 Damage to car tyres

 Tropospheric Ozone contributes to “greenhouse effect”

 Absorbs IR radiation emitted at the Earth’s surface

CFCs
CFCS
 Chlorofluorocarbons were used

 Aerosol cans
 Refrigerators
 Plastics

 Properties of CFCs

 Lack of reactivity (very stable)

 Low flammability
 Low toxicity
CFCS – TROPOSPHERE VS
STRATOSPHERE
 Troposphere

 CFCs are unaffected by UV radiation

 Stratosphere

 CFCs are susceptible to attack & release chlorine atoms

BALANCE OF OZONE – STRATOSPHERE
 Naturally for millions of years
 Chlorine atoms in the stratosphere react with CH4 to form
hydrogen chloride or

Cl  CH 4  HCl  CH 3 
 Chlorine atoms react with ozone to produce chlorine
monoxide (ClO) which then reacts with nitrogen monoxide
(NO) to form chlorine nitrate (ClNO3)

Cl   O3  ClO   O 2
ClO   NO  Cl   NO 2 
ClO   NO 2   M  ClNO3  M
chlorine
nitrate
BALANCE OF OZONE – STRATOSPHERE
 Naturally for millions of years, a balance of ozone in the
stratosphere has been maintained

 HCl produced goes down into the troposphere where it dissolves

in water & is washed out in rain

 ClNO3 cannot react with ozone & is a temporary sink for

chlorine atoms
CFCS – PROBLEMS
 CFCs

 Large quantity of CFCs reaching the stratosphere

 Length of time they remain in the stratosphere (unrecativity)

CFCs produce additional Chlorine atoms (Cl.) in stratosphere



 More Ozone (O3) is being destroyed than is being created

CFCS – REACTIONS
 CFCs Reactions that lead to a depletion of Ozone

 Initiation
hf
CCl2 F2  CClF2  Cl 
hf
CCl3F  CCl 2 F  Cl 

 Wavelength of radition required (175 – 220 nm)

CFCS – REACTIONS
 Propogation
Cl   O3  ClO  O2 
Very important
ClO   O  Cl  O2 
ClO   NO  Cl   NO2 

Chlorine atoms (Cl.)is regenerated by reaction with oxygen
atoms & nitrogen monoxide


Chlorine atoms (Cl.) produced react with more Ozone leading
to a loss of Ozone with absorption of radiation
CFCS – REACTIONS
 Termination

Cl   CH 4  HCl  CH 3 
Cl   H 2  HCl  H 


ClO   NO2   M  ClNO3  M Very important
chlorine
nitrate 
SUMMARY OF REACTIONS
SUMMARY OF REACTIONS
EFFECT OF CFCS - STRATOSPHERE
 The above reactions leads to

 Thinning of the Ozone Layer

 Increased level of UV radiation reaching Earth’s surface

 Ozone depletion in stratosphere leads to

 Cooling of stratosphere
 Increase in temperature of troposphere
 Decrease in ozone levels in stratosphere
 Increase in ozone levels in troposphere
OZONE HOLES AT THE POLES
 Most Ozone is produced in the tropics & transported to
the poles
 Chlorine gas is released from Chlorine nitrate

HCl  ClNO3(g)  HNO3  Cl2(g)

 Chlorine gas & chlorine nitrate can produce chlorine atoms
that react with ozone
hf
Cl2  Cl   Cl 
ClNO3  Cl    NO3
 These reactions occur at the poles (Antartica)
CONTROLLING IMPACTS OF CFCS
1. Montreal Protocol (1987)
 50nations agree to restrict production & consumption of
CFCs

 Problem = (CFCs remain unreacted for 50–80 yrs)

 Problem = Models predict it may take 100 yrs for existing

CFCs to disperse
CONTROLLING IMPACTS OF CFCS
2. CFCs substitutes
 Hydrofluorocarbons (HFCs) & Hydrochlorofluorocarbons
(HCFCs)

 Problem = HFCs & HCFCs are greenhouse gases

EFFECTS OF OZONE DEPLETION
 Effects related to UV radiation

 More UV radiation (<320 nm) reaching Earth’s surface

 Increase in skin cancers in humans (light–skinned people more

susceptible)

 Prevent normal immune responses in skin & other parts of body

 Affect crop yields in plants (cell damage)

 Affect the larvae of fish, shrimp & crab

 Affect zooplankton & phytoplankton (may become extinct)

EFFECTS OF OZONE DEPLETION
 Importance of Plankton (zooplankton & phytoplankton)
 Beginning of the food chain for all animals living in the sea

 Phytoplankton
 Give out oxygen into the water & atmosphere
 Only need H2O, CO2, salts & sunlight

 Zooplankton
 Feed on phytoplankton
 Eaten by fish which are eaten by animals & humans
Summary of Atmospheric
Pollution
SUMMARY
 Pollution of the atmosphere is caused mainly by
industrial & motor-vehicle emissions

 Primary pollutants are the original gases or particulates

emitted

 Secondary pollutants are formed by reactions involving

primary pollutants
SUMMARY
 Main primary pollutants are carbon dioxide, carbon
monoxide, sulphur dioxide & nitrogen oxides

 Secondary pollutants, formed mainly by photochemical

processes, are ozone, peroxyethanoyl nitrate (PAN) &
methanal
SUMMARY
 Use of catalytic converters in the car engines vehichle
exhaust system will enable maximum fuel economy &
oxidation of CO & hydrocarbon emissions

 CFCs were used in fridges & aerosols because of their

inactivity. This same inactivity enables them to reach the
stratosphere, where they cause destruction of ozone