3) Env Chem3 - Stratospheric Chemistry

CHEM 433
Water and environmental chemistry
Chemistry Department
Taibah University
1
Chapter 1 : Stratospheric
chemistry -The Ozone Layer
2
Introduction
1) The chemistry of the stratosphere is
simple.
2) It initiated by short wavelength (more

energetic) light.
3) ~90% of O3 are found in the

stratosphere  it is called Ozone Layer.
3
Introduction
stratosphere is characterised by increasing
temperatures with increasing height.
Presence of O3 and O2 that:
absorb the UV light and
emit infrared radiation
 heats this region.
4
Introduction
What is ozone?
1) Ozone (O3 ) is a high-energy form of oxygen.

O3 → O2 + energy
O2 + energy → O3
2) The energy comes from UV photons that hits O2 in

atmosphere.
5
Functions of Ozone in the
atmosphere
Startosphere:
Useful function in this region
(protect from the sun’s
harmful UV radiations).
Troposphere:
Harmful function in this region
(can damage lung tissues and
plants).
6
The function of Ozone in
Stratospheric layer:
Protect biological systems from harmful UV

radiations.
a) UV can induce photochemical damage to

biological molecules.
b) O3 Layer acts as a filter for solar

radiation.
c) Because it screens out the UV radiation.

7
Protection against UV by Ozone
 O3 layer
absorbs
wavelengths
200-300 nm
 This UV light
in the
Solar irradiation
is harmful to life.
8
The Physics and Chemistry of the Ozone
Layer*
Chemical properties of Ozone :
1) O3 is unstable, but decomposes very slowly.
2) O3 is highly reactive and has a strong

pungent (electric) odour.
3) O3 can be destroyed by catalysts (e.g. NO, Cl

in Chlorofluorocarbons (CFCs).
9
Atmospheric Reactions
Ozone formation in the stratosphere
(Chapman Theory):
a) O2+ hv<242nm  2O*

(highly energic)
b) O*+O2+ M  O3 + M
Where M is a random air molecule (e.g N2 or O2)

10
Ozone formation in the
stratosphere (Chapman Theory)
11
Ozone destruction in the
stratosphere (Chapman Theory)
12
Atmospheric Reactions
Ozone destruction: in the stratosphere
(Chapman Theory):
a)O3 + hν  O2 + O
wavelengths < 325 nm
b) O + O3  2 O2 (explain in details )
Chapman Theory was not able to explain
why ozone concentration is lower than
expected  Catalytic Ozone Destruction
13
Ozone destruction in the stratosphere
(Catalytic Ozone Destruction)
3 important catalytic cycles or ways to lose ozone:

1. Hydroxyl radicals (OH.) OH/OOH
2. Chlorine (Cl) Cl/OCl
3. Nitric Oxide (NO) NO/NO2
14
(Catalytic Ozone Destruction/HOx cycle)
1. Hydroxyl radical (OH):

OH. + O3  . OOH + O2
.
OOH + O  OH. + O2
____________________________
Net: O + O 3  2 O2
15
Hydroxyl radical (·OH):
OH . (hydroxyl radical) and
OOH. (hydroperoxyl radical)
Sources (ways to form OH. in the atmosphere)
O3 + hv (<325 nm)  O2 + O(1D) (2%)

 O2 + O(3P) (98%)
(or simply like this reaction: O3 + hv  O2 + O)
16
Hydroxyl radical (·OH):
1) Hydroxyl radical from water with excited
atomic oxygen:
O(1D) + H2O  2 OH . (major)
2) Hydroxyl radical from methane with excited

atomic oxygen:
O(1D) + CH4  OH . +CH3. (minor)
methane comes from natural sources such as soils
and from cow flatus.
17
(Catalytic Ozone Destruction/NO/NO2 pathway)
3. Nitric Oxide (NO)

NO + O3  NO2 + O2
NO2 + O  NO + O2
____________________________________
Net: O + O3  2 O2
18
Sources of NO:
1) Natural source: NO in the stratosphere
produced from N2O (nitrous oxide or laughing
gas) , reaction of with excited oxygen atoms O
which is much less reactive than NO.
a)N2O + hv  N2 + O (90%)
Or b)N2O + O  2 NO (~10%)
can come from several tropospheric photolytic
reactions involving OH. or OOH..
19
Sources of NO:
2) Thermal reaction between N2 and O2:
N2 + O2  2 NO
occurs mostly in combustion systems such as
automobile and jet engines.
It is produced abundantly in the troposphere,

but all of it is converted into NO2  HNO3
(removed through precipitation).
20
Nitric oxide
Removal processes:
NO2 + OH.  HNO3

ClO. + NO2  ClONO2
The above reactions show
inhibition to the HOx and ClOx
cycles  inhibition to Ozone
destruction 21
The two-sided effect of NOx
Nitric oxide*
1) NOx provides a catalytic chain
mechanism for O3 destruction.
2) NOx inhibit the HOx and ClOx cycles

for O3 destruction by removing radical
species in the two cycles.
22
Nitric oxide
The two-sided effect of NOx
The relative magnitude of the two effects
are altitude dependent:
1) <25 km the net effect is O3 destruction (NOx
accounts for >50% of total O3 destruction in the
middle and upper troposphere).
2)In the lower stratosphere, the net effect is to

protect O3 from destruction.
23
(Catalytic Ozone Destruction/ClOx cycle)
2.Chlorine (Cl):
Cl could be produced from the photo degradation
of chlorofluorocarbons(CFCs) (will be discussed
later):
Cl + O3  ClO + O2
ClO + O  Cl + O2
_______________________
Net: O + O3  2 O2
24
End of Chapter 1
25

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CHEM 433

Water and environmental chemistry

2) It initiated by short wavelength (more

3) ~90% of O3 are found in the

1) Ozone (O3 ) is a high-energy form of oxygen.

2) The energy comes from UV photons that hits O2 in

Protect biological systems from harmful UV

a) UV can induce photochemical damage to

b) O3 Layer acts as a filter for solar

c) Because it screens out the UV radiation.

1) O3 is unstable, but decomposes very slowly.

2) O3 is highly reactive and has a strong

3) O3 can be destroyed by catalysts (e.g. NO, Cl

a) O2+ hv<242nm  2O*

Where M is a random air molecule (e.g N2 or O2)

3 important catalytic cycles or ways to lose ozone:

1. Hydroxyl radical (OH):

Sources (ways to form OH. in the atmosphere)

O3 + hv (<325 nm)  O2 + O(1D) (2%)

2) Hydroxyl radical from methane with excited

3. Nitric Oxide (NO)

It is produced abundantly in the troposphere,

NO2 + OH.  HNO3

2) NOx inhibit the HOx and ClOx cycles

2)In the lower stratosphere, the net effect is to

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