Environmental Science

Chemistry of the environment, systems and surroundings,

environmental composition and segments, ecosystem and
natural cycles of the environment, regions of atmosphere,
composition of the atmosphere and the influence of solar
radiations. Earth's radiation balance, Green House effect
and global warming.
22/02/2016

Environmental Chemistry
Origins, transport, reactions, effects and

fates of chemical species in the water, air,

terrestrial and living environments.
Physics

Organic
Chemistry

Analytical
Chemistry

Biochemistry

Physical
Chemistry

Geochemistry

Photochemistry

Life Sciences
Agricultural
Sciences
Medical Sciences
Public Health
Sanitary Engineering

Environmental Segments:
Atmosphere
Hydrosphere
Lithosphere
Biosphere

Atmosphere:
The atmosphere is the protective blanket of gases which

is surrounding the earth.

It protects the earth from the hostile environment of
outer space.
It absorbs IR radiations emitted by the sun and
reemitted from the earth and thus controls the
temperature of the earth.

 It allows transmission of significant amounts of

radiation only in the regions of 300 2500 nm (near

UV, Visible, and near IR) and 0.01 40 meters (radio
waves). i.e it filters tissue damaging UV radiation below
300 nm.
It acts as a source for CO2 for plant photosynthesis and
O2 for respiration
It acts as a source for nitrogen for nitrogen fixing
bacteria and ammonia producing plants.
The atmosphere transports water from ocean to land.

Hydrosphere:
Ground
water

Oceans

Reservoir

Seas

Streams

Rivers
Lakes

Distribution of earth's water supply

Fresh Water
1%

Ocean 97%

Polar Ice Caps

2%

Major use of fresh water

Sales
Thermal
power plants

Irrigation

13%

Industrial Use

Domestic Use

7%
50%

30%

Lithosphere

Upper mantle
Lower Mantle
Outer Core
and Inner Core

 The lithosphere consists of upper mantle and

the crust.
The crust is the earths outer skin that is
accessible to human.
The crust consists of rocks and soil
Soil is the important part of lithosphere

Biosphere
Domain of living organisms and their interactions with the

environment (VIZ: atmosphere, hydrosphere and lithosphere)

The biosphere is very large and complex and is divided into
smaller units called ecosystems.
Plants, animals and microorganisms which live in a
definite zone along with physical factors such as soil,
water and air constitute an ecosystem.
Within each ecosystems there are dynamic inter relationships
between living forms and their physical environment

 These inter relationships demonstrate as natural

cycles.

1. Hydrologic cycle
2. Oxygen cycle
3. Nitrogen cycle
4. Phosphorous cycle
5. Sulphur cycle

Hydrologic cycle

 The land surface and water surfaces on earth lose water by

evaporation by solar energy.

Normal evaporation of water from ocean exceeds precipitation

by rain into seas by 10% .

This 10% excess which precipitates on land balances the

hydrological cycle.
Some of the precipitated rain seeps into the soil as ground water.

 Ground water moves up by capillary action and there by

maintains a continuous supply of water to the surface layer

of soil.
The water from the surface layer of the soil is absorbed by
plants, which in turn is returned to atmosphere through
transpiration.
Surface water or runoff flows into streams, rivers, lakes and
catchment areas or reservoirs.
Animals also take water which is also returned to the
atmosphere through evaporation.
Thus there is always a balanced continuous cycling of
water between earths surfaces and atmosphere.

Oxygen cycle

23/02/2016

Importance of oxygen in atmospheric chemistry,

geo chemical transformation and life processes

Contributes largely to the processes on the earths

surface.
Energy producing reactions such as burning of fossil
fuels:
CH4 + 2O2
CO2 + 2H2O
Aerobic organism in the degradation of organic material:
[CH2O] + O2 Organism
CO2 + H2O
Some oxidative weathering processes of minerals:
4FeO + O2
2Fe2O

Oxygen Returns to Atmosphere

Photosynthesis by plants.
CO2 + H2O

h
Plants

CH2O + O2

Importance of photosynthesis in the oxygen balance of

atmosphere.
O3 occurring in the rarified region of the atmosphere
(stratosphere) absorbs harmful UV radiation and serves as
radiation shield.

Nitrogen cycle

Nitrogen fixation
Bacteria, Algae
3(CH2O) + 2N2 + 3H2O + 4H+

3CO2 + 4NH4 +

Biological nitrogen fixation is mediated by organisms like

Rhizobium that live a symbiotic relation with nodules on the

roots of particular species of plants.
These organisms are capable of catalysing the conversion of
atmospheric nitrogen into forms usable by plants.
Nitrification:
N (-III) to N (V) by Nitrosomonas and Nitrobacter.

,
rosomonas
t
Ni
Nitrobacter
+
NO3 + 2H+ + H2O
2O2 + NH4

 Nitrogen is absorbed by plants primarily as nitrate.

Even when nitrogen is applied in the form of ammonium salts

as fertilizers, the ammonia is microbially oxidized to nitrate

so that it can be assimilated by plants.
Nitrate Reduction:
Reduction of nitrogen in chemical compound by microbial
action to lower oxidation states in the absence of free
oxygen.
-

2NO3 + {CH2O}
-

2NO2 + 3{CH 2O} + 4H+

2NO2 + H2O + CO2

2NH4++ 3CO2 + H2O

Denitrification:
Reduction of nitrate to form nitrogen gas.
Involves several steps.
A number of heterotrophic bacteria including species of

Pseudomonas and Anchromobacter mediate these

processes.
In this process N2 gas is produced from chemically fixed
nitrogen.
-

4NO3 + 5{CH2O} + 4H+

2N2 + 5CO2 + 7H2O

By this natural microbial mediated process N2 gas is

returned to the atmosphere.

Phosphorous cycle:
Animal bones and teeth .
Organophosphates

- Essential for cell division involving

production of nuclear DNA and RNA.
Major inorganic phosphorous - soluble H2PO4- and HPO42- and
insoluble Ca5(OH)(PO4)3, Fe3(PO4)28H2O.
Plants absorb inorganic phosphate salts
Organic
phosphate.
Animals by eating plants.
Plants and animals after their death return the phosphate to the
soil.
The microorganisms present in the soil
into soluble
inorganic phosphate
mineralisation or biodegradation.

 Biodegradation can also occur to highly toxic organophosphate

compounds such as phosphate ester insecticides).

Solubility phosphorous in H2O:
availability of iron and aluminium under acid conditions
availability of calcium under alkaline conditions
Each of these metals form insoluble phosphates.
When the pH is slightly acidic, phosphorous has its maximum
solubility and under these conditions H2PO4 is the predominant
species.

Sulphur cycle:

Oxidation convert lower oxidation state species into sulphate.

Present in many inorganic and organic forms exhibiting

oxidations states from -2 to + 6.

Interconversion among a number of sulphur species.
The major microbially mediated process in this cycle are:
Sulphate reduction to sulphide
bacteria desulfovibrio
In an organic rich reducing aqueous environment, sulphate is
readily reduced to species in the -2 or less commonly, o
oxidation states
-

SO4 + 2{CH2O} + 2H+

2

H2S + 2CO2 + 2H2O

Sulfide oxidation
by bacteria thiobacillus
Sulphide is unstable under aerobic conditions
Easily oxidised.
The sulphide might have been formed during the decomposition
of organic matter or might have been present as sulphide
mineral in the sediment or soil.
2H2S + 4O2

4H + 2SO4

Degradation of organic sulphur compounds:

The degradation of sulphur-containing organic compounds by

bacterially mediated processes can result in the production of

strong-smelling noxious H2S and other volatile organic sulphur
compounds such as methyl thiol CH3SH and dimethyl sulphide
CH3SCH3. Thus the above reactions give a brief outline of the
major microbially mediated processes in the sulphur cycle.

Commonly Used Terms

Pollutant:
If the concentration of a substance already present in nature is

increased to unrequired ratio due to human activity, which

ultimately has a detrimental effect on the environment either by
reducing the quality of life or affecting the health then it is
known as a pollutant. Examples: sulphur dioxide, carbon
monoxide, lead, mercury, excess heat, sound etc. are all called as
pollutants.
Contaminant:
A contaminant is a substance that does not occur in nature, but is
introduced by human activity into the environment. A
contaminant is called a pollutant when it exerts detrimental
effect on human health.

 Receptor:
A receptor may be any thing which is affected by the pollutant. For

example, man is a receptor of contaminated water because cholera and

gastroenteritis are caused by it.
Sink:
It is the medium, which interacts and retains the long lived pollutant.
Ground water and subsoil water act as sinks for pesticides employed in
agriculture.
Dissolved Oxygen (DO):
Oxygen dissolved in water is vital for aquatic life. The optimum value
for dissolved oxygen in a good quality water is 4-8mg/L. It is consumed
by oxidation of organic matter/ reducing agent etc. present in
water.Water which has DO value less than 4 mg/L is termed as
polluted and is unfit for human or aquatic animal consumptions.

 Chemical Oxygen Demand (COD):

It is an index of the organic content of water, since the most common

substance oxidized by the dissolved oxygen in water is organic matter,

which has a biological origin, such as dead plants etc. The COD of a
water sample is determined by the chemical oxidation of the organic
matter by K2Cr2O7 in 50% H2SO4. This method includes other
reducible inorganic species that may be present in water such as NO2-,
S2O3-, S2- etc., and hence this method does not truly reflect the
organic content in water. However since this method is rapid, it is
widely used.

 Biological Oxygen Demand (BOD):

The capacity of the organic matter in the sample of natural water

to consume oxygen is called its BOD. It is determined

experimentally by determining the dissolved oxygen (DO) at the
beginning and at the end of a 5-day period in a sealed sample.
The BOD gives the measure of oxygen utilized or consumed in
the period as a result of oxidation of dissolved organic matter
present in the water sample.

 Threshold limit value (TLV):

This value indicates the permissible level of a toxic pollutant in

atmosphere to which a healthy industrial worker can be exposed

during an eight-hour day without any adverse effect. TLV of a
pollutant is found by experimentation on animals, medical
knowledge and experience and environmental studies.

Regions of Atmosphere
Gaseous envelope surrounding the earth
Two major components in Air: N2 and O2

Troposphere (0
to 15 km)

Stratosphere
(15 to 50 km)

Mesosphere
(50 to 85 km)

Thermosphere
(85 to 500 km)

Troposphere

Inner Layer

80 % of total mass of air and almost all water vapour

0-15 km
Domain of all living organism
Temperature decreases, -56 0C at max. height
Temperature inversion

Stratosphere:
15-50 km
Temperature rises with increasing altitude, -2 0C at max. height
N2, O2, O3, and O atoms
Ozonosphere

Mesosphere
50 to 85km
Temperature decresases
In addition to, N2 and O2,O2+, O+, NO2+
Thermosphere:
85 to 500 km
Temperature increases
Free electrons and O2+, O+, NO+
Mesosphere + Thermosphere = Ionosphere

Composition of Atmosphere

Present Composition
78% Nitrogen; 21% Oxygen; trace amounts of CO2, Argon, etc.
Atmosphere Unique Among Other Planets
Venus & Mars CO2 Gaseous planets H, He, CH4
Pressure in Venus 100 x Earth on Mars 1/100
Surface Temperature 450-500oC Venus; -130-25oC Mars
Atmospheric Gases Controlled by volcanoes and

interactions between gases and the solid Earth & Oceans

Ozone (O3): produced by photochemical Rx absorbs
harmful UV radiation

Oxygen in the Atmosphere

Earth only planet in solar system with oxygen thus only

planet able to sustain higher forms of life

Oxygen produced by
Photosynthesis- algae and plants

Photolysis-fragmentation of water molecules into Hydrogen and

Oxygen

Oxygen consumed by
Respiration
Decay
Weathering (chemical oxidation)

What is the physical structure of the

atmosphere?
- multi-layered, with little chemical interaction
- most of the mass is near the surface
What is the chemical structure of the
atmosphere?
- nitrogen by far the most common element
- oxygen is second most common
- greenhouse gasses are small in amount, but
important!

The Greenhouse Effect

The Earths surface receives energy from two

sources: the sun & the atmosphere

As a result the Earths surface is ~33C warmer than it would be 0 0C

without an atmosphere

Greenhouse gases are transparent to shortwave

but absorb longwave radiation
Thus the atmosphere stores energy

Electromagnetic Spectrum
incoming

outgoing

1. Shorter, high
Energy wavelengths
Hit the earths
Surface

2. Incoming energy
Is converted to heat

3. Longer, infrared
Wavelengths hit
Greenhouse gas
Molecules in the
atmosphere

4. Greenhouse gas
Molecules in the
Atmosphere emit
Infrared radiation
Back towards earth

78% nitrogen
20.6% oxygen
< 1% argon
0.4% water
vapor
0.036% carbon
dioxide
traces gases:
Ne, He, Kr, H, O3
Methane, Nitrous
Oxide

Greenhouse gases

Contributes to the warming of the Earth's

atmosphere by reflecting radiation from
the Earth's surface.
Greatly affect the temperature of
the Earth; without them, Earth's surface
would be about 33 C (59 F) colder than at
present.
Can absorb and emit infrared radiation. In
order, the most abundant greenhouse
gases in Earth's atmosphere are:
Water vapor (H2O)
Carbon dioxide (CO2)

Selected Greenhouse Gases

Carbon Dioxide (CO2)

Source: Fossil fuel burning, deforestation

Anthropogenic increase: 30%
Average atmospheric residence time: 500 years

Methane (CH4)

Source: Rice cultivation, cattle & sheep ranching, decay

from landfills, mining
Anthropogenic increase: 145%
Average atmospheric residence time: 7-10 years

Nitrous oxide (N2O)

Source: Industry and agriculture (fertilizers)

Anthropogenic increase: 15%
Average atmospheric residence time: 140-190 years

What is artificial greenhouse

??

A greenhouse is a house made of glass. It has glass walls and a glass roof. People
grow tomatoes,flowers and other plants in them. A greenhouse stays warm inside,
even during winter. Sunlight shines in and warms the plants and air inside. But the
heat is trapped by the glass and can't escape. So during the daylight hours, it gets
warmer and warmer inside a greenhouse, and stays pretty warm at night too. Due to
artificial greenhouse people can grow plants in the off season too.

Summary
Greenhouse Effect, the capacity of certain gases in the
atmosphere to trap heat emitted from Earths surface, thereby
insulating and warming the planet.
Now scientists are growing increasingly concerned that
human activities may be modifying this natural process, with
potentially dangerous consequences.
Greenhouse gases absorb infrared radiation and prevent it
from escaping to space.
Carbon dioxide, methane, and nitrous oxide are very good at
capturing energy at wavelengths that other compounds miss.
Water vapor also cause green house effect.

Solutions to increasing
Greenhouse effect

Reduce the use of materials which produce greenhouse

gases.
Avoid the burning of fossil fuel and household residue.
Upgrade infrastructures.
Afforestation.
Using alternative sources of energy.
Using eco-friendly materials.
Pollution should be controlled

Greenhouse Effect & Global Warming

The greenhouse effect & global
warming are not the same thing.
Global warming refers to a rise in the temperature of the
surface of the earth

An increase in the concentration of

greenhouse gases leads to an
increase in the the magnitude of the
greenhouse effect. (Called enhanced
greenhouse effect)
This results in global warming

Measuring Ozone in Atmosphere

It is difficult to measure the amount of O3.
Instruments is taken in the field (insitu)
There are number of field stations which measure the

amount of O3 on an on-going basis (land based

monitoring sites or flight based systems operating
from aircraft and satellite)

 In all these instruments, measurement is based on

measuring the absorption of UV light (O3 absorbs UV

radiation 200 315 nm).
It is measured in Dobson Unit (DU).
Oxygen only Chemistry Formation and Turnover of

O3
Chapman Reaction Sequence:
Both decomposition and formation of O3 described

involving only oxygen containing species

 4 Fundamental rxnx
1.

O2 + h

2. O + O2+M

O+O
O3 + M

3. O3 + h

O2 + O

4. O + O3

O2 + O2

M = Neutral third body, N2 or O2

Catalytic decomposition of O3
Formation and decomposition of O3 a natural

process
Balance between two essential for steady state

situation for a well defined and stable ozone layer

Oxygen only chemistry does not explain present

situation
Other chemical enhanced destruction

 Some species Natural

Others Industrial and agricultural origin
Small amount chemicals

Troposphere

Stratosphere
take part in catalytic ozone consuming process
Many of such reactions General Mechanism
X +O3
XO + O2
XO + O
X + O2
Net Reaction: O + O3
O2 + O2

Catalytic Species
HOx ( H, OH and HOO )
NOx ( NO and NO2)
ClOx (Cl and ClO)

Varying ability to destroy (altitude, mixing ratio)

Eg., altitude - 50 km HOx causes 70 % of total

mechanism of O3 destruction
30 km 70 % - NOx

Catalysis by HOx Species

This set of catalytic reaction depend on availability of H2 to

combine with O2 (plentiful in stratosphere)

Source- H2O and CH4
Water content vary with time and locations quite large

Stratosphere
However, very little

(Tropopause

temp

apprx. -50 0C) form of ice crystals (do not readily cross)

 Other source for H2 is CH4

Less abundant, but it does not freeze out, some of its

drawn into Stratosphere

Through a series of photochemical reactions involving

oxygen species Hydrogen is extracted from methane

React with Oxygen and form water in stratosphere
This water (derived from CH4 by reacting with

Oxygen) produce HOx in two ways

 O + H2O

2 OH
H2O + h
H + OH
OH, then catalytically decompose O3
OH + O3
HOO + O2
HOO + O
OH + O2
Net Reaction: O + O3
O2 + O2
The Hydrogen radical can also participate in O3
removal
H + O3
OH + O2
OH + O
H + O2

Catalysis by Nitrogen containing

species
Two Nitrogen oxides (NO, NO2) are produced as a

result of combustion process in power plants, vehicles,

etc.
Very short atmospheric lifetime (4 days) (converted to
HNO3 and removed - Rainfall)
small fraction (NOx)
stratosphere
Other than small fraction drifted from troposphere,
NOx produced directly
Principal source another N compound N2O (Niros
oxide)

 At altitude below 30 km, N2O combine with E.S.

Oxygen
NO
N2O + O
2 NO
N2O not a radical, stable (120 Yrs )(does not absorb
visible light and undergo photolysis)
Migrates to Stratosphere, where undergo conversion to
NO
N2O originates from soil, water sources
Produced from natural process denitrification (for
this nitrate ion is necessary and is introduced in soil by
large qtys of fertilizer)

 NOx are produced above 30 km

At these altitude photochemical decomposition - N2

N2 + h
N (G.S) + N (E.S)
N (G.S.) high translational energy combine O2
N(G.S) + O2
NO + O
(Once NO is formed take part Cat. Decomp. Of O3)
NO + O3
NO2 + O2
NO2 + O
NO + O2
Net Rxn O +O3
O2 + O2
Advantage: F.R. may not give additive effect all time
Two F.R. (which individually decomp. O3) may give a
non F.R. which reduce decomp. O3

 NO + OH

HNO2
(Nitrous Acid does not decomp. O3)
ClOx and BrOx
Cl, ClO (H. reactive among all stratospheric species
which Destruct O3)
Derived (a) Natural (b) Anthropogenic
Most. Imp. Natural precursor of Cl F.R. is CH3Cl
Introduced to Troposphere - by biological reaction
throughout ocean & smaller amount from burning,
Volcanic emission
In stratosphere:
CH3Cl + h
CH3 + Cl

 All CH3Cl does not reach Stratosphere

Some are removed at lower altitude by rxn with OH
CH3Cl + OH

CH2Cl + H2O
Cl formed from CH3Cl undergo catalytic Decomp. Of
O3
Cl + O3
ClO + O2
ClO + O
Cl + O2
Net rxn: O + O3
2 O2
Other catalytic cycle involving :
ClO + HOO
HOCl + O2
HOCl + h
OH + Cl

 Cl +O3
ClO + O

Net Rxn: O3 + O
OH + O3
HOO + O
Net Rxn: O3 + O

ClO + O2
Cl + O2
2 O2
HOO + O2
OH + O2
2 O2

CFCs (Chlorofluorocarbon
compounds)
1930
Low , , bp, chem. Inertness, biol. Inertness
Non-flammable, non-toxic

preferred in applications
At RT, under pressure becomes liquid and when
pressure is released, revert back to gases by absorbtion
of large amount of heat
The advantage of this property is being used in its
application as Refrigerant, blowing agent for polymer
foam, etc.

 CFC ability to mix well with other gases

As they are inert, do not react with other species,

circulate throughout troposphere un till escaped in

to Stratosphere
At higher altitude, they undergo photolytic decomp.
(intense flux of more energetic UV radiation)
CFCl3 + h
CFCl2 + Cl
Cl +O3
ClO + O2
ClO + O
Cl + O2
Net Rxn: O3 + O
2 O2

Antarctic and Arctic ozone hole

formation
O3 importance
O3 amount has been monitored since 1950 (agency:

British Antarctic Survey at Halley Bay Station)

Early 1980 decline was found spring season
1984 understood recurring process increasing
each year
Average ozone column thickness - 314 DU 1956-66
150 DU - 2000 to 03

 In the Antarctic and Arctic conditions (complex

combination of climatic factors, accumulation of

reservoir species, react vigorously on the first day light
of polar spring ) exist where seasonal depletion of O3
occur.
During long dark winter in Antarctic, due to intense
cold and earth rotation, a stream of air is drawn
towards south pole creating a giant vortex (Whirlwind)
The area within the vortex acts like a chemical reactor
in which important and unique chemical processes
occur.
Some reactions takes place are:

Cl + CH4
HCl + CH3
HCl + ClONO2
Cl2 + HNO3
(on polar stratospheric clouds - PSC)
H2O + ClONO2
HOCl + HNO3
Cl2 + h
2 Cl
HOCl + h
Cl + OH
2 Cl + 2 O3
2 ClO + 2 O2
ClO + ClO
ClOOCl
ClOOCl + h
ClOO + Cl
ClOO
Cl + O2

Tropospheric Chemistry - Smog

Troposphere Space we live
Chemical reactions and gases immediately and

directly affect human life & total environment around

us
Smog = Smoke + Fog
Form of air pollution in which atmospheric visibility is
reduced by haze consisting of solid minute particles
Classical smog (London Smog) & Photochemical (Los
Angeles) smog

Classical smog
Arised from use of traditional fuel coal
Characterized by high concentration of C soot &

elevated levels of atmospheric SO2

Over all chemical properties are reducing and acidic
(SO2 a mild reducing agent and a precursor of acid)
- encountered in heavily populated industrial centres
where high sulfur content coal used for power
generation 19th century phenomenon
Pollution control measures have considerably reduced
the problem

Photochemical smog
-based on emission from petroleum combustion

(principally from motor vehicle)

-elevated levels of oxidants and C containing reaction
products
20th & 21st Century phenonmenon (as it require
unburned the unburned gaseous hydrocarbons and
nitrogen oxides which are emitted by internal
combustion engine)
Photochemical smog producing reactions some
favored by warm temperature and some require
sunlight

 Normal atmospheric conditions: Warm air rises and

cooler air descends to the surface

At this time any gas present also moves to upper side
Atmospheric inversion (temp inversion) less
common situation
Cooler Surface air remains on below and become more
dense than the air above
behaves as a stable atmosphere the released gas remains
in the same location where they are able to react

Chemistry of Photochemical Smog

Chemical
Composition:
NO, NO2,
Hydrocarbon,
Oxidants ,
Aldehyde.
Partially oxidized
hydrocarbon &
O3 , in addition
to haze, it causes
for irritation to
skin and eyes

Hydroxyl radical production

Has an important role in chemical reaction that lead

to formation of smog
Formation starts with production of NO
N2 +O2

2 NO

NO Endothermic, favored in high temperature, likein

internal combustion engine
When exhausted to atmosphere
NO to NO2 by O2 or other oxidants

(1) 2 NO + O2
(2)

NO + O3

O2 + O + M
(3) ROO + NO

(slow)
.
NO2 + O2 (imp )
2 NO2

O3 + M
NO2 + RO

Formation of O3 Similar to stratospheric region reaction

OOR radicals introduced from vehicle evaporation of tank, or unburned fuel
in emission
NO2 decompose to NO + O
O2 Combine with O form O3
O3 decompose O2 + O (absorption of UV light 315 nm)

315 nm
O3
O* + H2O

*O + O*
2
2 OH

Sum of previous
reaction
NO2 helps to form 2
OH radicals
NO2 + H2O

2 OH + NO

Quantitatively this is
the most important
- formation 2 OH
radicals

Both excited state large fraction is

deactivated by collision with G.S. O2
or N2. But, the one which retains the
energy reacts with H2O - 2 OH

2nd mechanism Formation of OH radical

below 400 nm
2 HONO

NO + NO2 + H2O

2 OH + 2 NO

Actual (normal) atmospheric concentration of OH radical (molecules

per c.c.): 2.5 x 105
Polluted area (molecules per c.c.): 10 7
In the urban atmosphere, accelerated synthesis of OH radical is a
consequence of

large production of NO2 (internal combustion

engine). Other factors which enhance OH radical synthesis are: high T

and intense sunlight

Oxidation of Hydrocarbons
OH + RCH3

Internal Combustion

RCH2 + H2O
alkyl

RCH2 + H2O + M

RCH2OO + M
peroxyalkyl

RCH2OO + NO

RCH2O
alkoxyl

RCH2O
alkoxyl
HOO

+ O2

+ NO

+ NO2

RCHO + HOO
hydrperoxyl
NO2 + OH

engines source of
NO
Besides,
emit
unburned
volatile
hydrocarbons which
are oxidized through
reactions initiated by
highly reactive OH
radical.

In discussing oxidation of organic compound and

generation Photochemical Smog
Hydrocarbon CH4 (Aliphatic Saturated HC)
Many other VOC
(a) Anthropogenic (b) Natural Process
Vehicular emission:
compounds are many depending on fuel, type
of engine, operating condition
Imp. Emission in most of the cases: hydrocarbons
(Ethene, Ethyne, benzene, toluene, xylene,
higher alipahtic hydrocarbons)
- Each of these compound can be released to
atmosphere and undergo oxidation.

 -Vehicular

emission where no. vehicles are

more
Toluene, (o, m, p)-Xylene, Benzene,
Ethylbenzene, 1,3,5-Trimethylbenzene, 1Ethyl-4-methylbenzene, Heptane, Hexane, 1Ethyl-2-methylbenzene
Benzene:
beisdescausing
annoying
physiological properties such as dizziness,
membrane irritation, it is Carcinogen
In these hydrocarbons, hydroxyl radical
initiate oxidation

OH + RCH3

RCH2 + H2O
alkyl

RCH2 + H2O + M

RCH2OO + M
peroxyalkyl

RCH2OO + NO

RCH2O
alkoxyl

RCH2O
alkoxyl
HOO

+ O2

+ NO

+ NO2

RCHO + HOO
hydrperoxyl
NO2 + OH

Hydroxyl radical abstracts a H from hydrocarbon to form water and

an organic radical. The abstraction rxn takes place whenever there
is h atom on hydrocarbon. But. rate depends on strength of C-H
bond

 Here,

hydoxyl radical adds to olefine

Electrophile hydroxyl adds to double or triple
bonds
OH

R"

R"

+ OH
R'"

R'

R'"

R'

Following this, one mechanism continues with the addition of

dioxygen to hydroxylated species
OH
R

R"

OH

R"

+O2
R'

R'"

R'

.
O

R'"

-hydroxy peroxyl compounds then

transfer an O atom to NO and the resultant
-hydroxy
alkoxyl
compound
usually
undergoes decomposition to form hydroxy
alkyl radical and ketone

The

OH

R"

OH

R"

+ NO
R'

+ NO2
R'

R'"

R'"

O
O
R

OH

R"

OH

+
R'

.
O

R'"

R'

R"

R'"

 Hydroxy

form
radical

alkyl radical reacts with oxygen to

another ketone and hydroperoxyl
O

OH

+ O2
R'

+ HOO
R

R'

Depending on R, ketone or aldehydesare obtained (if R= H)

 Oxidation

rxns are initiated by hydroxyl

radical. If aromatic compounds are
substituted by alkyl groups, abstraction of
proton takes place from this alkyl groups and
final products would be aldehydes.
If there is no alkyl group, an alternative
reaction pathway may be followed:
HO

+ OH

 Hydroxyl

benzene radical is resonance

stabilized among other C atoms. However,
reacts with dioxygen to form phenol and
hydroperoxyl radical

HO

OH

+ O2

+ HOO