Chapter 2: • Polar Ozone Depletion – The “Ozone Hole”

Protecting the Ozone Layer

Summary of Ozone Hole Problem: Ozone disappears in the

Antarctic and Artic stratosphere during the spring/summer.
Levels are replenished by fall/winter but disappear again the
following spring/summer
Chemistry and Life Ch 2 Slide 2

Consequences What we’re doing about it

• CFCs = chlorofluorocarbons = molecules containing
• Ozone absorbs a significant fraction of UV radiation. carbon, fluorine, and chlorine.
• If that UV radiation gets through: – These are inert – when released into the troposphere
they don’t break down & slowly drift to the stratosphere
– Increased rates of skin cancer
– they react with light, which enables them to react with
– Damage to marine organisms ozone and destroy it.
• Other animals are protected by fur
• UV light goes through H2O
Regulating CFCs is a global problem
• The use of CFCs in the US has no immediate impact on
– Damage to ecosystems and crops the US – this is very different from air pollution in the
– Cooling of the atmosphere: absorption of solar troposphere.
radiation by ozone heats the atmosphere. – CFCs have been valuable chemicals
• Food for thought: could this partly explain why • Stable, non-toxic, non-flammable
it’s been difficult to detect global warming?? • Used as coolants and solvents
Chemistry and Life Ch 2 Slide 4
Chemistry and Life Ch 2 Slide 3
• Absorption Spectrum of Human DNA
Chemistry and Life
Outline for Chapter 2
• Look at the details of ozone molecular
structure
• Why/how does it absorb UV light
• Reactions involving ozone
– Why is the decline so seasonal and so specific to
the poles
– What can be done?
– How to replace CFCs?
Ch 2 Slide 5 Chemistry and Life Ch 2 Slide 6

Structure of atoms The key things to know about subatomic particles :

At the center of an atom is the nucleus • Their charge
• The nucleus is composed of:
• proton: +1 charge • The number of electrons in the outer shell
– – • neutron: 0 charge
– –
– • protons and neutrons have the • How to use the periodic table to figure out the number of
– +
same mass subatomic particles.
+
+ +
–

Outside of the nucleus, are electrons

– • electrons: –1 charge
• 1/1838 mass of a proton!  Most of the
mass in an atom is in the nucleus
Keep in mind--this is an over-
simplified model of an atom.
Diameter of an atom ~ 1 × 10–10 m
Diameter of a nucleus ~ 1 × 10–14 m
Most of an atom is empty space.

Chemistry and Life Ch 2 Slide 7 Chemistry and Life Ch 2 Slide 8

 Elemental properties

Chemistry and Life

Atomic Structure and Periodicity
• # of protons + # of neutrons = atomic mass
• What about the neutrons?
• # of protons = the atomic number
– Neutrons help to stabilize the nucleus
– Each element has its own unique atomic number!
• In any electrically neutral atom, – Practically ALL elements have neutrons
the # of electrons = the # of protons – Only exception is atomic hydrogen
This information is 6 Atomic number • Has one proton and one electron
displayed in the
periodic table:
C – 1H in every 6700 will have a neutron
12.011 Atomic mass
• This is Deuterium
• Mass Number

Ch 2
– The sum of the number of protons and the number of neutrons
• It has one proton, one electron and one neutron,
in the nucleus of an atom and thus a different mass
– Identifies different isotopes Isotopes: Are two or more forms of the same element (same
number of protons) whose atoms differ in number of
• Atomic Mass

Slide 9
neutrons, and hence in mass.
– The weighted average of all naturally occurring isotopes of an
element Chemistry and Life Ch 2 Slide 10

Electron distribution in Atoms

• Electrons are arranged in shells, each shell can only hold
a certain # of electrons

– – – –
– –
– –
–
• Innermost shell can hold 2 e–
14 +
6 • Carbon 14 ( 6C) –
++
– • Second shell can hold 8 e–
C – Used in dating old materials – –
• Third shell can hold 8 e–
12.011 –
– Atomic number: 6 – – –
–
– Atomic mass: 14
Isotopes are why – # of neutrons = Atomic mass-Atomic # • Each shell must be filled before any e– can go into the next
the avg mass is shell!
– 6 protons, 6 electrons, 8 neutrons
different than • # of outer shell e– determines most of the chemical and
*The average mass is very close to 12.000 physical properties of the elements!
12.000*
b/c 126C is by far the most abundant isotope.
Chemistry and Life Ch 2 Slide 11 Chemistry and Life Ch 2 Slide 12
About outer e– Arrangement of the periodic table
e–
• Why are outer so important?
– Because atoms can share their outer e– (form covalent bonds)
– The bonds form so that every atom is surrounded by 8 e– (The
octet rule)
• THE EXCEPTION: Hydrogen (H) is satisfied with only 2 e–
– When an atom is surrounded by 8 e–, its electron shells are full.
These bonds form so that the atom can achieve the that having
full electron shells brings.

• Periodic Table
– Puts elements in order of increasing atomic number
– ‘Groups’ elements with similar chemical and physical
properties
– Main Group Elements (1A – 8A)
• Elements in the same group have the same # of outer e–
• Group Label defines the number of VALENCE ELECTRONS • This is why elements in the same group have similar properties
Chemistry and Life Ch 2 Slide 13 Chemistry and Life Ch 2 Slide 14

Atomic Structure and Periodicity

• F in group 7A so has 7 valence electrons, as do Cl, Br, I

• C in group 4A so has 4 valence electrons, as do Si, Ge, Sn

Molecules and Models

• Lewis Structure
– A representation showing valence electrons. Hydrogen
– Dot structure needs only
two electrons
• Covalent bond for it’s shell to
– Electrons are shared by two elements be full

– Single bond – when only one pair of shared

electrons involved in a covalent bond

Chemistry and Life Ch 2 Slide 16

Chemistry and Life Ch 2 Slide 15
 Molecules and Models
S=N–A Lewis Dot Structures

Chemistry and Life

• S = # of shared e–’s (Remember it takes 2 e– to make a bond).
• N = # of e–’s to needed to fill the valence shell [Usually 8 (the • A predictor of molecular structure using
octet rule) except for hydrogen it’s 2] the octet rule.
• A = # of e–’s available in the valence shell (The group number) • Example: water, H2O
Example: hydrogen fluoride, HF H + O + H  H O H
– Needed (N): H needs 2e– and F needs 8e–. N = 2 + 8 = 10

Ch 2
1 outer e– 6 outer e– 1 outer e– Each H now has 2 outer e–
– Available (A): H has 1e– and F has 7e–. A = 1 + 7 = 8 The O now has 8 outer e–

– Shared (S) = N – A = 10 – 8 = 2 • Example: HCl

The H now has 2 outer e–
– So 2e– shared between H and F, a single covalent bond H + Cl  H Cl The Cl now has 8 outer e–

Slide 17
1 outer e– 7 outer e–
Represents 2 e–
H Cl
Chemistry and Life Ch 2 Slide 18

Example: oxygen gas, O2

Tricks for determining Lewis structures
1) Atoms in the same column of the periodic table
Each O only has 7 e–
have the same # of outer e–
2) Molecules with the same # of total outer e– often
But if they share 4 e–, each O now has 8 e– have the same structure.
*Double bonds are shorter and stronger than single bonds N2 – each N contributes 5 e–, there are a total of 10 e–
distributed over 2 atoms
• Double Bond
– A covalent bond consisting of 2 pairs of shared electrons. N N N N
– Shorter, stronger and harder to break than single bonds CO – The C contributes 4 e–, the O contributes 6 e– so
again there are a total of 10 e– distributed over 2 atoms
• Triple Bond
– A covalent bond consisting of 3 pairs of shared electrons. C O C O
– Shorter, stronger and harder to break than double bonds *Triple bonds are shorter and stronger than double bonds

Chemistry and Life Ch 2 Slide 19 Chemistry and Life Ch 2 Slide 20

 • Molecules and Models
Molecules and Models
S=N–A
• Example: ozone, O3, an allotrope of oxygen
– Needed: N = 3 x 8 = 24
– Available: A = 3 × 6 = 18
– Shared: S = N – A = 24 – 18 = 6
– So 6 e– shared between the three oxygen • Resonance Forms
atoms – Structures that are hypothetical extremes of electron
arrangements that do not exist exactly as represented by any one
– HOW? Lewis structure.
• Ozone’s structure is ‘in-between’ the two resonance
structures. (Each O–O bond is ~ a 1.5 bond
Strength between single bond & a double bond)
Chemistry and Life Ch 2 Slide 21 Chemistry and Life Ch 2 Slide 22

Molecules and Models “Free Radicals”

• Species with an odd number of electrons – or
“unpaired” electrons – are referred to as Free Radicals,
or Radicals
O2 and O3 are different allotropes of oxygen. • Radicals are extremely reactive, because that single
Allotropes are 2 or more forms of the same element that differ in unpaired electron will do just about anything to make a
their molecular or crystal structure, and therefore also differ in
pair
their properties
• O2 – odorless, essential for life • Often (but not always), we indicate that a species is a
• O3 – strong odor (can smell as low as 10 ppb!), toxic to life in
troposphere, more reactive.
radical by representing the unpaired electron with a
Other examples of allotropes are the allotropes of carbon single dot: •
Diamond – hardest known substance
Graphite – soft, used in pencil lead
NO•, NO2•, Cl•, Br•, OH• , ...
Chemistry and Life Ch 2 Slide 23 Chemistry and Life Ch 2 Slide 24
 • So now we know the structure of ozone. Wavelength
• We know that an important characteristic of ozone is Wavelength (λ)= peak to
its ability to protect us from ultraviolet light. peak or trough to trough
Each color has a its own
• How does this property work? characteristic λ
• First we need to understand some characteristics of • red has the longest l at 7 10–7 m = 700 10–9 m = 700 nm
light…. • violet has the shortest l at ~ 400 nm

Frequency
The funky behavior of light • Waves can also be characterized
• Light behaves as a wave under many conditions, but by their frequency (ν) – the
sometimes it acts like a particle. number of cycles (wavelengths)
/second
– This is called the wave-particle duality of light.
• Instead of writing “waves/
• We need to understand both! second”, units are just 1/s or s–1.
– 1 hertz (Hz) = s–1
Chemistry and Life Ch 2 Slide 25 Chemistry and Life Ch 2 Slide 26

Relationship between l and n Particle nature of light

n = c = speed of light = meters light passes in a second • Electromagnetic radiation can also be thought of as particles of
l wavelength Distance between peaks in meters energy (photons)
* The speed of light, c, is always 3.00 × 108 m/s • In this view, the energy distribution is not continuous, but consists
Example 1: What is the frequency (n) of red light? of many individual steps—it is quantized.
• This view becomes important in understanding how light interacts
Red light has λ = 700 nm (109 nm = 1 m or 1 nm = 10–9 m) with molecules.
n = c = 3.00 × 108 m/s = 4.3 × 1014 1/s or s–1 or Hz
l 700 × 10–9 m • Molecules can absorb radiation – this absorption may make the
molecule rotate or vibrate more (heating) or it may break bonds.
Example 2: What is the frequency (n) of green light?
Energy of photons
Green light has λ = 550 nm • The energy of a photon is: h = Planck’s constant = 6.63 10–34 J s
λ = 550 nm = 550×10–9 m = 5.50×10–7 m E = hν = hc J = joule = a unit of energy
3.00×108
m l 1 J = the amount of energy required to
c s = 5.45×1014 / s = 5.45×1014 s-1
ν= = raise a 1 kg weight 10 cm
λ 5.5×10-7 m
Chemistry and Life Ch 2 Slide 27 Chemistry and Life Ch 2 Slide 28
 Electromagnetic Spectrum
Why is UV light more damaging than visible light?
• Visible light is only one type of radiant energy.
• Compare the energy difference between the two: • The entire range of radiant energy is called the
Visible red light: l =700 nm electromagnetic spectrum; visible light is just a tiny part of
UV light l = 300 nm the entire spectrum

Ered light = hc = (6.63×10–34 Js)(3.00×108m/s) = 2.84×10–19 J • All waves in the EM spectrum travel at 3.00 ×108 m/s, but
l 700 × 10–9 m they differ widely in n and l

EUV light = hc = (6.63×10–34 Js)(3.00×108m/s) 6.63×10–19 J Energy of EM Radiation

= l 300 × 10–9 m • Comparison of X-rays and radiowaves:
*Energy of a UV photon is > than energy of a visible photon!
Ex-rays = hc = (6.63×10–34 Js)(3.00×108m/s) = 1.99 × 10–15 J
l 1 × 10–10 m
• A UV photon has enough energy to break the bonds of
many molecules including DNA. Eradiowaves = hc = (6.63×10–34 Js)(3.00×108m/s) = 1.99 × 10–26 J
– This leads to mutations, which can lead to skin cancer l 1 × 101 m
*We try to limit our exposure to X-rays, but walk around with radiowaves
Chemistry and Life Ch 2 Slide 29 Chemistry and Life Ch 2 Slide 30

Waves of Light (Radiant energy from the sun) Waves of Light

• The sun emits infrared (IR), visible, and ultraviolet (UV)
radiation, but not all with equal intensity.

Chemistry and Life Ch 2 Slide 31 Chemistry and Life Ch 2 Slide 32

Waves of Light Waves of Light – Particles of Light?
• In the early 1900s, physical science was turned upside down by
the development of Quantum Mechanics (as opposed to Classical
Mechanics)
• Quantum Mechanics is required in order to apply physics to the
world on the scale of atoms and molecules
• One of the most shocking postulates of Quantum Mechanics was
that light simultaneously possesses properties of a wave and of a
particle
– “Wave/particle duality”
• A “particle” of light is called a photon, and while it definitely
possesses the frequency and wavelength of waves, it also carries
a specific amount of energy per photon
Chemistry and Life Ch 2 Slide 34

The Interaction of Light with Molecules

O2 can do this for shorter l
• It turns out that the energy in one photon of
ultraviolet light has approximately the same
energy as a molecular bond!
• If a molecule is struck by a photon of the • Double bond of O2 is stronger than the bonds in O3.
right energy; that is, of the right frequency!,
• Expect that more energy is required (photons with a smaller
the molecular bonds will break.
wavelengths) to break the double bond of O2.
What’s so special about ozone? • Bond energy is 8 × 10–19 J, requires photons with l  242
• The O–O bond energy is ~ 6 ×1019 J (this is the energy required to nm
break the bond) • O2 + photon  2 O
• The energy of a UV photon (l = 300 nm) is ~ 7×1019 J
l  242 nm
7×1019 J > 6×1019 J
If this energy is transferred to an ozone molecule, the bond will • These two reactions occurring in the stratosphere effectively
break. O3 + photon  O2 + O l  320 nm filter the most dangerous wavelengths of UV radiation.
Chemistry and Life Ch 2 Slide 35
Chemistry and Life Ch 2 Slide 36
 The Interaction of UV Light with DNA
Ozone: What and Where Is It?

Ultraviolet Radiation From

The Sun Ozone absorbs UV radiation

http://earthobservatory.nasa.gov/Library/UVB

Chemistry and Life Ch 2 Slide 37 Chemistry and Life Ch 2 Slide 38

• Biological Effects of Ultraviolet Radiation Biological Effects of Ultraviolet Radiation

Melanin production
Sunburn
Premature skin aging
Skin cancer

As λ decreases, damage
to DNA increases.

Note the logarithmic

scale on the y-axis.
The geographical effect on radiation intensity and skin cancer
is greater than that caused by ozone depletion.
Chemistry and Life Ch 2 Slide 40
Chemistry and Life Ch 2 Slide 39
• Biological Effects of Ultraviolet Radiation • Polar Ozone Depletion – The “Ozone Hole”

Scientists have determined that a given % reduction in O3 concentration

will produce twice that % increase in skin cancer
Chemistry and Life Ch 2 Slide 42
Chemistry and Life Ch 2 Slide 41

• Polar Ozone Depletion – The “Ozone Hole” • P Sept. 2001

Chemistry and Life

Ch 2
Sept. 2003

Slide 44
Sept. 2002
Chemistry and Life Ch 2 Slide 43
Chemistry and Life Ch 2 Slide 44
TOMS (Total Ozone Mapping Spectrometer) The UV-Index
• A NASA Earth-observing instrument that measures long-term
changes in ozone concentrations to verify chemical models of the The UV Index, developed by the National Weather Service
stratosphere and so help predict future climatic trends. and EPA, indicates the strength of solar UV radiation on a
scale from 0 (minimal) to 15+ (very high).
• Versions of TOMS have flown aboard Nimbus-7 (1978), a Soviet
Meteor-3 (1991), TOMS-EP (1996), and ADEOS-1 (1996).
• TOMS-EP was placed into an orbit lower than originally planned
to obtain higher resolution measurements and data that was
complementary to that gathered by ADEOS.
• When TOMS-EP began to show signs of premature aging, NASA
ordered QuikTOMS as a gap-filler until ozone monitoring could be
taken over by the EOS (Earth Observing System) Aura satellite in
2004.
• However, the fifth flight of TOMS ended in failure on Sep. 21,
2001, when the Taurus rocket carrying the 162-kg QuikTOMS
(and also OrbView-4 ) broke up less than two minutes after liftoff Chemistry and Life Ch 2 Slide 46

Categories of UV Radiation

Chemistry and Life

Not screened by O3
or O2. Implicated in
premature wrinkling,
some skin cancer

Eye damage, skin

cancers, but most
is absorbed by O3.

Ch 2
O3 + photon  O2 + O
l  320 nm

O2 + photon  2 O

Slide 48
l  242 nm UVC UVB UVA
X rays 200-280 280-320 320-400 Visible
 X-ray UVC UVB UVA Visible Light
280-320
Skin & UV Rays
200-280 320-400 400-700

Solar UV radiation is
Stratosphere - Ozone Layer 95% UVA & 5% UVB.

UVA causes tanning,

aging & skin cancer.

UVB causes burning &

skin cancer.
EPIDERMIS
Tanning beds emit
DERMIS
2-3 times more UVA
than the sun.
SUBCUTIS
UVA does not produce
vitamin D.
Dead Sea Level Sea Level

Suntans & Sunburns Skin Cancer Formation

• A suntan tells you that your skin is trying to
protect itself from damaging UV rays.
• Suntans may give some protection from sunburn,
but the skin gets damage while getting the tan,
including aging from UVA rays and lifetime sun
exposure.
• Cumulative sun exposure (including tanning) can
lead to skin cancer.
• Sunburns increase risk for developing melanoma.
• UVA and UVB rays hit the epidermis.
• DNA in skin cells begins to break down.
• To fend off damage, skin produces melanin,
proof of DNA damage.
• The immune system kicks into gear and tries to
repair damaged cells.
• More sun exposure hampers the repair.
• Damaged cells can mutate into skin cancer
within 5 years.
Skin Cancer What is UPF?

Basal Cell Squamous Cell • UPF = Ultraviolet Protection Factor

• Like SPF for fabric
• Fabrics are not tested on humans like sunscreen
• The higher the UPF the more UV that’s blocked

Melanoma
• Sun protective = UPF 15 to 50+
• White t-shirt = about UPF 5
• The finer the weave, the greater the protection
• Silk is best, Nylon stockings have an SPF ~ 2
• Panama hats give poor protection - holes let light
through, Cotton cricket hat is better

Sunscreen
3.3 Use Sunscreen
• Sunscreen (also known as sunblock or
• Choose SPF 15 or more. sun cream) is a lotion, spray, gel or
other topical product that absorbs or
• Use sunscreen that blocks UVA and UVB. reflects some of the sun's ultraviolet (UV)
radiation on the skin exposed to sunlight
• Apply 15-30 minutes prior to sun exposure.
and thus helps protect against sunburn.
• Apply over all exposed skin.
• Contain compounds that absorb UV-B to
• Slop it on! Don’t skimp. some extent.

• Don’t rub it in too hard – it reduces • Many sunscreens also contain

effectiveness by at least 25%. compounds that absorb UV-A.

• Reapply at least every two hours, or more • Sunscreen with a skin protection factor
often after swimming or sweating. (SPF) between 15-30 is recommended.

Chemistry and Life Ch 2 Slide 56

Sunscreen

Chemistry and Life

• Reflectant:reflect UVB and to a lesser extent UVA SPF (Sun Protection Factor):
• Absorbent:absorb principally UVB into specific chemicals
• SPF tells you how long a sunscreen will protect your
and re-emit as insignificant quantities of heat
skin from sunburn (Indication of the amount of time it is
– Contain compounds that absorb UV-B to some extent.
safe to spend in the sun without burning).
• SPF also tells you the strength of protection – how
much UV is absorbed or reflected.
• SPF is a measure of UVB protection, not a measure of
UVA protection.

Ch 2
Benzyl cinnamate— Avobenzone—
Absorbs UV up to 305 nm Absorbs UV up to 320 nm • However, most sunscreens block UVB and some UVA.
– Many sunscreens also contain compounds that absorb UV-A. Length of Protection
• Sunscreen with a skin protection factor (SPF) between 15-30 Your Time To Burn Without Protection
is recommended. × SPF of your sunscreen

Slide 57
– SPF of 15 means untreated skin will experience 15 times the = ____ MINUTES UNTIL SKIN BURNS
exposure to UV as skin treated with the sunscreen

The Ozone Cycle: Overview The Chapman Cycle

• Every day, 3 × 108 stratospheric ozone molecules form
and the same number of ozone molecules decompose.
– The rate of formation = the rate of destruction

• This is known as a steady-state condition – a dynamic

(reactions are continually occurring) system is in balance
Both of these
so that there is no net change in concentration of the
reactions give
major species involved.
off heat

• In the case of ozone, the steady state is the net result of

4 reactions that constitute the Chapman cycle.

Chemistry and Life Ch 2 Slide 60

Chemistry and Life Ch 2 Slide 59
The Chapman Cycle Factors influencing steady-state
concentration of O3
Step 1: Monatomic oxygen formation
(decomposition of O2)
O2 + UV photon 2O • Intensity of UV radiation
l ≤ 242 nm
– Expect O3 concentration will depend on season and
*O atoms are very reactive – only have 6e–
and they desperately want 8e–!
sun cycle
• Concentration of O2 and other reacting species
Step 2: Ozone formation (O2 and O
consumption) • Temperature
O2 + O  O3 Best to view as a cycle—all four
steps depend on each other • Reaction rates (some of the steps are faster than others)
• Many of these factors depend on altitude, so O3
Step 3: Ozone decomposition (O2 and O formation; opposite of step 2) concentrations also depend on altitude.
O3 + UV photon  O2 + O
l ≤ 320 nm
Step 4: Diatomic oxygen formation (O3 and O conversion)
O3 + O  2O2

Chemistry and Life Ch 2 Slide 61 Chemistry and Life Ch 2 Slide 62

O3 concentrations vs. altitude O3 concentrations over time

http://earthobservatory.nasa.gov/cgi-bin/texis/webinator/printall?/Library/Ozone/ozone_2.html

Chemistry and Life Ch 2 Slide 63 Chemistry and Life Ch 2 Slide 64

 • The Dobson unit (DU) is a
unit of measurement of ozone Stratospheric Ozone Destruction – A Polar Phenomenon
in the stratospheric layer.
• One DU refers to a layer of
ozone that would be 10 µm
thick under standard
temperature and pressure.

• e.g., 300 DU of ozone brought down to the surface of the Earth at

0 C would occupy a layer only 3 mm thick.
• One DU is 2.69 1016 ozone molecules/cm2. This is 0.447 millimoles
of ozone per square metre.
• 220 DU is chosen as the starting point for an ozone hole.
• 320 Du is average ozone level over the northern hemisphere
• 250 DU is typical at the equator
• The Dobson unit is named after Gordon Dobson, who built the
Dobson ozone spectrophotometer. Chemistry and Life Ch 2 Slide 66
Chemistry and Life Ch 2 Slide 65

Natural causes of O3 destruction Natural causes of O3 destruction

2) Reactions with water vapor (5ppm in Stratosphere) and its
1) Reactions with stratospheric nitrogen monoxide breakdown products: Free radicals very
reactive b/c they have
H2O + UV photon  H• + •OH unpaired e– Octet
• Formation of natural NO: N2O + O  2NO Rule is NOT satisfied
OH is the hydroxyl radical, also common in troposphere
– N2O produced by microorganisms
energy These free radical products can
• Formation of man-made NO: N2 + O2  NO
participate in reactions that convert O3 to O2:
– Energy is from lightning or high-temp engines of
O3 + H•  O2 + •OH
supersonic transport airplanes (like the Concorde)
that are designed to fly at altitudes of 15-20 km (the O3 + •OH  2O2 + H•
region of the ozone layer)
Example of a chain reaction.
• Lewis dot structure of NO?
Free radicals are very destructive
• Turns out that NO is also a free radical… • However, these natural “sinks” of ozone do not explain the
amount of ozone destruction seen in recent years…
Chemistry and Life Ch 2 Slide 67 Chemistry and Life Ch 2 Slide 68
 Stratospheric Ozone Destruction Chlorofluorocarbons: Properties, Uses and
Also A Global Phenomenon Interactions with Ozone
• CFCs
– Made up of carbon, fluorine, and chlorine
– Halogens – group 7A
• Diatomics in their standard state

F2 (g) and Cl2 (g) Br2 (l) I2 (s)

Chemistry and Life Ch 2 Slide 69 Chemistry and Life Ch 2 Slide 70

Chlorofluorocarbons: Properties, Uses and CFCs seem to be the culprit

Interactions with Ozone Naming scheme

Chemistry and Life Ch 2 Slide 71

Chemistry and Life Ch 2 Slide 72
 Chlorofluorocarbons: Properties, Uses and Chlorofluorocarbons: Properties, Uses and
Interactions with Ozone Interactions with Ozone
• Completely synthetic: invented in the 1930s by DuPont (“Freon”) • CFCs very stable (Freon-12 has lifetime of 120 years)
• Stable, nontoxic, nonflammable, cheap, widely available • CFCs do not react in the troposphere, but drift up into the
• Have low boiling point (makes them good to replaced NH3 and stratosphere where they are exposed to the same UV light that
SO2 as refrigerants and in air conditioning. breaks bonds in oxygen and ozone
• Used to create bubbles in plastic foams (Styrofoam)
• Used as propellants in aerosol spray cans
• Used as residue cleaners in electronic fabrication (computer
chips)
• Revolutionized Western civilization! atomic
chlorine:
• Fire extinguishers So… what’s the problem? a radical

Chemistry and Life Ch 2 Slide 73 Chemistry and Life Ch 2 Slide 74

Before we knew about the ozone hole… Reactions with •Cl

• Two scientists, Roland & Molina, set out to study fate of
atmospheric CFC molecules
• The reactions they hypothesized would occur suggested
that CFCs could destroy significant amounts of O3
– The destruction of O3 by CFCs later shown by scientific
experiments.
•Cl +O3  O2 + •OCl
•OCl + O  •Cl + O2
O3 + O  2O2
• You can see that once •Cl is created that it begins a chain
reaction—it can destroy many (~ 100,000!) O3 molecules.
• •Cl is acting as a catalyst—it is not used up in the reaction

• ~ 5 years after release in troposphere, CFCs make their
way into the stratosphere.
• A high-energy photon corresponding to wavelengths  220
nm has enough energy to break the chlorine-carbon bond:
CCl2F2 + photon  •CClF2 + •Cl
l  220 nm
• The presence of •Cl will affect the Chapman cycle balance!!!
Removal of •Cl:
• Carried to lower atmosphere by winds; once in lower atmosphere,
there are many other compounds for •Cl to react with.
• If it encounters another •Cl : •Cl + •Cl  Cl2
• May react with other species to form stable compounds such as
HCl and ClONO2
Reaction of atomic chlorine in stratosphere Proof of relationship b/w ozone depletion
and stratospheric Cl

Chemistry and Life Ch 2 Slide 77

Chlorofluorocarbons: Properties, Uses and

Major sources of stratospheric Cl Interactions with Ozone
• Atomic chlorine acts as a catalyst
• 75-85% is from human activity
– A chemical substance that participates in a chemical reaction
– CFCs and influences its speed without undergoing permanent change
– Rocket fuel from space shuttles (<1%) • A single chlorine atom can catalyze the destruction of as many as
100,000 O3 molecules.
• 15-20% is from methyl chloride
– Most from natural sources and burning of biomass Other ozone-depleting compounds
• ~2% - Large, explosive volcanoes • “CFC”s which don’t actually contain Cl (i.e., CF4) produce similar
effects with F radicals
– Increase amount of HCl which can be converted to •Cl
• As do brominated species (CH3Br, one of the world’s most widely
– Only a few volcanoes have enough explosive power to used pesticides)
project material into the stratosphere. • “Halons” –C, B, and F– are widely used as firefighting foams

Info from http://www.nas.nasa.gov/About/Education/Ozone/depletion.html

Chemistry and Life Ch 2 Slide 80
Regulation of CFCs Regulation of CFCs – The Montreal Protocol
• The U.S. banned CFCs in spray aerosols in 1978, but international - Bound nations to reduce their CFC output to one half of 1986
regulation was required levels by 1998
• 1985 saw the Vienna Convention on the Protection of the Ozone - Required future meetings to revise standards
Layer, which led to scientific discussion, but the science wasn’t
well understood - In 1990, 100+ nations agreed to halt CFC production altogether by
2000, and this phaseout was accelerated further at later meetings
• The Montreal Protocol was signed in 1987, and made sweeping
changes - The Beijing Amendment of 1999 added bromine-containing
“halons” …
• Kofi Annan: “[It is perhaps the single most successful international
agreement to date...]" - … AND required the regulation of the short-term replacement
HCFCs.
- Important provisions were made for developing nations whose
economies couldn’t sustain the mandated changes.
Chemistry and Life Ch 2 Slide 81 Chemistry and Life Ch 2 Slide 82

The Global Response

• CFCs in spray cans banned in North America in 1978, and
use as foaming agents for plastics discontinued in 1990. Global Production of
CFCs 1950-2000
• 1987 Montreal Protocol—established a schedule to reduce
production & consumption of CFCs.
• The US and 140 other countries agreed to a complete ban
on CFC production after Dec. 31, 1995.
• Other ozone depleting compounds to be eliminated b/w
2002-2010:
• CFBr compounds (fire-fighting)
Stratospheric
• CCl4 (an industrial solvent) concentrations of
chlorine
• CH3Br (agricultural fumigant)

Chemistry and Life Ch 2 Slide 84

Black-market CFCs Looking to the Future
• While the protocols set dates for the halt of production, sale
of existing stockpiles will remain legal. • Find replacement molecules – make CFCs obsolete
– Hydrochlorofluorocarbons (HCFCs)
– US govt. is promoting conversion to less harmful substitute
refrigerants by imposing a tax of $5.35/lb on CFCs – Hydrofluorocarbons (HFCs)
• Price of CFCs has risen $1/lb in 1989 to $15/lb (as of 2003)
• Creates a black-market for CFCs, which are 2nd only to illegal
drugs as the most lucrative illegal import.
• “Freon busts” in 1997 led to the confiscation of 12 million lbs of
illegal CFCs
Ban on CFCs is making a difference: slowly
• Stratospheric concentration of chlorine peaked at 4.1 ppb in
the mid-90s and is now declining.
• However, the stratospheric chlorine is not expected to reach
2 ppb* until 2050 or 2075.
• *Antarctic ozone hole first appeared when chlorine levels Chemistry and Life Ch 2 Slide 86
reached 2 ppb.

• This requires a balancing act:

Looking to the Future
• Using H makes the molecule more reactive, more
• Why are they “better”? flammable and lighter
•OH + HCFCl2 → H2O + •CFCl2
• Using Cl makes the molecule heavier, but more toxic
• Since hydroxyl radical is prevalent in the troposphere, this
reaction may take place before the species has the opportunity to • Eventually, we’d like to eliminate Cl entirely; this is
reach the stratosphere where HFCs come in
• The radical fragment that’s left behind will react with something
to ensure that it is destroyed
• DON’T want to go back to previous technologies (NH3, SO2 as Hydrochlorofluorocarbons (HCFCs)
refrigerants)! • Replacing one or more of the halogen atoms with hydrogen
• Need to balance 3 undesirable properties and come up with the makes the compound more reactive
best compromise
– Toxicity -Flammability - Extreme Stability Compounds decompose long before reaching
stratosphere
Chemistry and Life Ch 2 Slide 87
Fluorocarbons (FCs)
• Made of only carbon and fluorine
– Non-toxic
– Nonflammable
– Don’t decompose in the stratosphere
• Why? The C–F bond is stronger—the energy
requirement to break this bond is higher than that
of a UV photon.
• The negative: No destruction pathways: the molecules
will accumulate in the atmosphere and contribute to the
greenhouse effect by absorbing IR radiation.
US Emissions
http://www.eia.doe.gov/oiaf/1605/vr98rpt/chapter6.html
Suitable HCFCs
• HCFC-22 is the most widely-used HCFC HCFC-22
– Used in air-conditioners and in the production
of foamed fast food containers
– 5% ozone depleting potential of CFC-12
• HCFC-141b used to form foam insulation CFC-12
– 250 million lbs produced worldwide in 1996 for this.
• Montreal Protocol calls for a production ban of HCFCs by
2030.
Hydroflurocarbons (HFCs)
• Example: HFC-134a H
• Has no Cl atoms to interact with ozone C C H
• The 2 H atoms facilitate decomposition
in the lower atmosphere, without making
it flammable under normal conditions.
Pyrocool FEF being applied to subterranean fires at Ground Zero,
North Tower at West Street, September 30, 2001.
Pyrocol FEF is environmentally benign and yet more effective
than the halons (molecules containing carbon, fluorine, and
bromine) traditionally used to fight fires.
Chemistry and Life Ch 2 Slide 92
Looking to the Future –CFC Regulation and Use
World Wide
• Your text asks you to investigate the planned 2005 phase-out of
methyl bromide
• In 2005 and 2006, the US successfully obtained a “critical use
exemption”, fearing that US agriculture would be unable to
compete with developing nations who are not required to
eliminate CH3Br until 2015.
• Some developing nations – particularly China and India – initially
refused to sign the Montreal Protocol due to economic concerns
• They and other reluctant countries were convinced to sign
because of the Multilateral Fund, which disburses money to help
modernize industry in poorer nations.
Chemistry and Life Ch 2
Looking to the Future – CFC Regulation and Use
World Wide
“Our development strategies cannot be sacrificed for the
destruction of the environment caused by the West”
– Ashis Kithari, a member of an Indian environmental
group
• CFC consumption by the developing world has
increased from 1986 – 2002
• Perhaps most pressing… we have since learned that
HFCs and HCFCs are “greenhouse gases”, and contribute
to global warming… Which is the subject of Chapter 3.
Slide 93 Chemistry and Life Ch 2 Slide 94

Why is the hole over Antarctica? Summer conditions replenish hole

• A special mechanism appears to be in effect here, related to the • In summer, sunlight warms the
fact that the lower stratosphere over the South Pole is the atmosphere
coldest spot on Earth.
– Ice crystals evaporate summer
– During the Antarctic winter (June to September), a strong • No ice crystals means
circumpolar wind develops in the middle to lower atmosphere the conversion of
• keeps warmer new air (w/ new O3) from entering ClONO2 & HCl to more
reactive species halts.
– Temps can get as low as –90 oC!
– HOCl UV light •Cl + •OH
– At temps < 80 oC, clouds of ice crystals containing sulfates Cl2 2 •Cl
and nitric acid can develop in the stratosphere.
– Air from lower latitudes spring
• In spring, when the sun comes out, chemical reactions occurring flows into the polar regions,
on the surface of these cloud particles convert otherwise safe replenishing depleted
(non-ozone depleting) molecules to more reactive species. ozone levels.
– ClONO2 & HCl converted to HOCl & Cl2 – Thus, “Ozone Hole” is largely replenished by end of summer.
http://earthobservatory.nasa.gov/Study/Tango/ • Same process is developing in the Arctic
 The Antarctic Ozone Hole: A Closer Look
The Antarctic Ozone Hole: A Closer Look
• Vortex winds blow around the South Pole
• Temperatures as low as –90°C
• Polar Stratospheric Clouds (PSCs) form
• Perpetual darkness during winter
• Reservoir molecules adsorb (“stick”) to clouds
– React to form active molecules (HOCl & Cl2)
• Spring comes
– Warmer weather
– Sunshine

Chemistry and Life Ch 2 Slide 97 Chemistry and Life Ch 2 Slide 98

Timeline
• 1928 – CFCs invented
• 1950s-1970s – Consumption and use of CFCs rises rapidly
• 1971 – CFCs measured in the atmosphere
• 1974 – Rowland & Molina link CFCs with ozone depletion
• 1985 – First scientific assessment of stratospheric ozone levels
• 1987 – “Smoking gun” evidence linking decreasing ozone levels
with increasing stratospheric chlorine levels
– Montreal Protocol established a schedule to reduce
production & consumption of CFCs.
• 1991 – Multinational fund established to provide financial and
technical assistance to developing countries to enable
them to comply with control measures.
- B/w 1991 & 2004 $1.6 billion given to more than 100 countries
• 1995 – Production ban of CFCs in US and 140 other countries
goes into effect
– Rowland & Molina win Nobel Prize for their work
• 2030 – Production ban of HCFCs goes into effect

Chemistry and Life Ch 2 Slide 99