CFC's and Ozone Depletion

Ozone in the Atmosphere

Ozone in the Lower Atmosphere (troposphere)

About 10% of all ozone (O3) in the atmosphere is found in the troposhere (up to 16km above
the earth's surface).

Ozone in the troposhere has harmful effects on many living things because it is toxic.

In humans, ozone causes eye irritation, compromised lung functions, aggrevation of

respiratory conditions like asthma, and increases the susceptibility to infection.

Ozone pollution in the troposphere is often linked to photochemical smog.

Ozone in the lower atmosphere is formed during electrical discharge from high voltage
appliances as shown in the equations below:

O2(g) -----> 2O(g)

O2(g) + O(g) -----> O3(g)

Ozone in the Upper Atmosphere (stratosphere)

About 90% of all ozone (O3) in the atmosphere is found in the stratosphere (16 to 32 km
above the earth's surface).

In the stratosphere ozone acts as the primary UV radiation shield, short wavelength UV
radiation from the sun (<240nm) provides the energy to split oxygen molecules into oxygen
atoms:

UV radiation
O2(g) 2O(g)
------------>

Oxygen atoms then react with oxygen molecules to form ozone:

O(g) + O2(g) -------> O3(g)

Ozone can absorb harmful UV-B and UV-C radiation, preventing it from reaching the earth's
surface:

UV radiation
O3(g) O2(g) + O(g)
------------>

The constant formation and destruction of ozone maintains a balance over time.
Human acitivities, such as the release of chlorofluorocarbons in to the atmosphere, have
disturbed this balance.

Chlorofluorocarbons (CFCs) and Halons

 CFCs and halons belong to the haloalkanes.
 Chlorofluorocarbons (CFCs) are compounds containing only carbon, chlorine and
fluorine (no hydrogen).
Halons are compounds containing only carbon, bromine and other halogens (no
hydrogen).
 Chlorofluorocarbons (CFCs) are sold under the trade name of Freons.
 CFCs are used as working fluids in refrigerators and air conditioners because they are
gases at room temperature wich can be easily liquified by compression and because
they are stable and non-toxic
 CFCs are used as foaming agents in the production of polystyrene and polyurethane
foam plastics used for insulation and packing materials
 CFCs are used as a propellant in spray cans for paint, insect repellants, deodorants
 Halons are used in fire extinguishers because they are dense, non-flammable liquids.
Bromochlorodifluoromethane, CF2ClBr, is commonly used in halon fire extinguishers.

CFC Name Formula Code Uses

refigeration,
trichlorofluoromethane
CCl3F CFC-11 aerosols,
freon-11
foams

refigeration,
dichlorofluoromethane aerosols,
CCl2F2 CFC-12
freon-12 foams,
air conditioning

electronics,
1,1,2-trichloro-1,2,2-trifluoroethane
CCl2FCClF2 CFC-13 dry cleaning,
freon-13
fire extinguishers

1,2-dichloro-1,1,2,2-tetrafluoroethane
CClF2CClF2 CFC-14 aerosols
freon-14

degreasing and
1,2,2-trichloro-1,1,2-trifluoroethane
CClF2CCl2F CFC-113 cleaning printed
freon-113
circuit boards

Chemistry of Ozone Depletion by CFCs

 CFCs destroy the ozone in the stratosphere (15 - 20 km above the earth's surface)
(Ozone concentrations are measure in Dobsen units, 1 Dobsen unit represents 1
molecule of O3 for every 1 billion air molecules)
 Ozone loss is greatest over Antarctica where the ozone depletion has been recorded
and is commonly referred to as the "ozone hole".
 Ozone (O3), an allotrope of oxygen, is poisonous to humans if breathed in, but is
important to life in that it filters out or absorbs short wavelength ultraviolet radiation
(u.v) in the 280 - 320nm range which can cause serious sunburn, skin cancer and eye
disorders.
 The inertness and lack of water solubilty of CFCs mean they are not destroyed nor are
they dissolved in rain water so they stay in the atmosphere for a very long time and
diffuse up to the stratosphere
 In the stratosphere, CFCs come into contact with short wavelength ultraviolet
radiation which is able to split off chlorine atoms from the CFC molecules

u.v radiation
CCl3F(g) CCl2F(g) + Cl(g)
--------------->

 These chlorine atoms destroy the ozone layer

Cl(g) + O3(g) -------------> ClO(g) + O2(g)

 There are significant numbers of oxygen atoms in the stratosphere (since ozone
undergoes a natural photochemical decomposition producing oxygen atoms and
molecules) which leads to the regeneration of chlorine atoms in the stratosphere.
So, 1 CFC molecule can destroy many ozone molecules.

ClO(g) + O(g) -------------> O2(g) + Cl(g)

Substitutes for CFCs

 The only long term solution to solve the problem of depletion of the ozone layer is to
phase out the use of CFCs
(Montreal Protocol of 1987 and subsequent modifications)
 Some CFCs can be replaced by HCFCs (hydrochlorofluorocarbons), compounds
containing at least 1 H atom.
The C-H bond makes these compounds more reactive in the atmosphere so they are
destroyed more quickly and so are less able to diffuse into the stratosphere

Name Formula Code Uses

air conditioning,
chlorodifluoromethane CHClF2 HCFC-22 refrigeration,
foams

1-chloro-1,1-difluoroethane CClF2CH3 HCFC-142b aerosols

aerosols,
1,1-difluoroethane CHF2CH3 HCFC-152a
refrigeration
Ozone is a pale blue gas irritating to the nose and throat; it is explosive and toxic. It is
produced and destroyed naturally in the atmosphere and until recently, this resulted in
a nicely balanced equilibrium. It is formed when oxygen molecules absorb ultraviolet
radiation with wavelengths less than 240 nanometres and is destroyed when it
absorbs ultraviolet radiation with wavelengths greater than 290 nanometres.

Allotropes
Key Concepts
 Allotropes are forms of the same element which exhibit different physical properties.
 Elements such as carbon, oxygen, phosphorus, tin and sulfur, display allotropy.
 The different physical properties displayed by allotropes of an element are explained
by the fact that the atoms are arranged into molecules or crystals in different ways.
 Some allotropes of an element may be more chemically stable than others.

Allotropes of Oxygen
There are two main allotropes of oxygen, molecular oxygen (O2) and ozone (O3).

Both allotropes of oxygen are made up only of oxygen atoms, but they differ in the
arrangement of the oxygen atoms.
O2 is a linear molecule while O3 is a bent molecule.

O2 and O3 have different physical properties such as colour, odour, melting and boiling point,
density and solubility.

Some properties of the allotropes of oxygen are shown below:

Property Oxygen (O2) Ozone (O3)

 O=O
Structure
linear
bent

colourless gas pale blue gas

Colour pale blue liquid deep blue liquid
pale blue solid deep violet solid

Odour odourless sharp, pungent

Melting Point (oC) -219 -193

Boiling Point (oC) -183 -111

Density (20oC) 1.3 g/L 2.0 g/L

Solubility in Water slightly soluble more soluble that O2

Chemical Stability stable decomposes to O2 easily

Uses common oxidiser sterilising agent

it is poisonous to many living things

Allotropes of Carbon
The two most common, naturally occurring allotropes of carbon are graphite and diamond.

Both graphite and diamond are made up of carbon atoms, but the arrangement of atoms is
different in each allotrope which results in different physical properties.
In particular, the presence of delocalised electrons in the structure of graphite results in it
being soft and a good electrical conductor whereas diamond is very hard and an electrical
insulator.

Property Graphite Diamond

Structure

Each carbon atom is bonded to 4 other carbon

Each carbon atom is bonded to 3 other atoms in a 3-dimensional covalent network.
carbon atoms in layers with delocalised All valence electrons are used in bonding.
electrons between the layers.

Colour black colourless

Melting Point
sublimes at ~3500 sublimes at ~4000
(K)

Electrical good poor (an insulator)

delocalised electrons between the layers no delocalised electrons to allow for the flow
Conductivity allow an electric current to pass through of electrical current

Hardness 1-2 (soft) 10

delocalised electrons allow the sheets to
(Mohs Scale) move over each other
(hardest known natural mineral)

Chemical
stable decomposes slowly over time
Stability

Uses lubricant abrasive

because it is soft because it is so hard

Allotropes of Phosphorus
There are three allotropes of phosphorus; white, red and black.

Some properties of the allotropes of phosphorus are given below:

Property White Phosphorus Red Phosphorus Black Phosphorus

Structure P4 molecules packed into Chains of P4 Puckered layers of
 a crystal molecules phosphorus atoms
polymer polymer

Colour white red black

Chemical intermediate
least stable most stable
Stability stability

Allotropes of Sulfur
Sulfur has several allotropes.
-sulfur forms yellow, rhombic crystals out of 8-membered rings of sulfur atoms (S8).

-sulfur forms yellow, monoclinic, needle-like crystals out of 8-membered rings of sulfur
atoms (S8).

Plastic sulfur is yellow and made up of long chains of sulfur atoms. It reverts to S8 rings in
time.

Allotropes of Tin
There are three allotropes of tin:

 Grey tin ( tin): a diamond-type lattice structure

 White tin ( tin): body centred tetragonal structure

 brittle tin: rhombic structure