Introduction to Kinetics:

The Phasing Out of CFCs

Modern Chemistry II
Department of Chemistry, Carnegie Mellon University
 1930: Chapmans theory of stratospheric ozone

Formation of ozone Ozone protects earth Destruction of ozone

O2 + hv O + O from UV rays O + O 3 O2 + O 2
O + O 2 O3 O3 + hv O2 + O
O + O 2 O3
Modern Chemistry II The phasing out of CFCs
 1940s and 1950s
1945: Most home refrigerators use CFC-12 as a safe
refrigerant (CFC-12 = dichlorodifluoromethane, CF2Cl2)
1950: CFCs are used increasingly in manufacture of
styrofoam.

Modern Chemistry II The phasing out of CFCs

 1972
F. Sherwood Rowland attends talk in Ft. Lauderdale,
Florida on discovery of new molecule in the atmosphere:
CFC-12, CF2Cl2
Most scientists conclude this is nothing to worry about

Modern Chemistry II The phasing out of CFCs

 1972

Molina Rowland
Mario J. Molina leaves Mexico to attend graduate school at
Berkeley, to study with Rowland
Rowland and Molina begin thinking about implications of
finding CFCs in upper atmosphere

Modern Chemistry II The phasing out of CFCs

 1973
Rowland and Molina: What will happen to CFCs in the
stratosphere?
CCl3F +UV light Cl +CCl2F (lasts 50 yrs)
CCl2F2 + UV light Cl + CClF2 (lasts 100 years)
Proposed mechanism for chlorine atoms destroying ozone
Cl + O3 ClO + O2
ClO + O Cl + O2
O3 + O O 2 + O2 (overall reaction)

Modern Chemistry II The phasing out of CFCs

 1974
Molina and Roland publish paper in Nature entitled The
stratospheric sink for chlorofluoromethanes: chlorine atom-
catalyzed destruction of ozone.
Receives little attention at first
Rowland: At the time, the figure we had was 6 billion spray
cans produced every year in the world, and in our home we
had 15 of them. So my wife went around and threw them all
out, and I thought 15 down, 6 billion to go.

Modern Chemistry II The phasing out of CFCs

 1975
Molina: We were talking about this invisible
gas rising in the atmosphere to affect an
invisible layer that was protecting us from
invisible rays.
Molina: The idea that a lot of people
pressing these little buttons inadvertently
were actually polluting the planet --- this
eventually caught the attention of the
press.
Value of CFCs produced: 2 billion dollars.
Value of industrial processes that used
them: 200 billion dollars.
Modern Chemistry II The phasing out of CFCs
 Molina: looking back at 1975
Isnt it a responsibility of scientists, if you believe that you
have found something that can affect the environment, isnt
it your responsibility to actually do something about it,
enough so that action actually takes place? There was
nobody else at that time that would actually fulfill that role.
So thats why Sherry and I, pretty consciously then,
decided to take that additional step to make sure the
government would actually pay attention.

Modern Chemistry II The phasing out of CFCs

 1976-1977
The use of CFCs in spray cans is banned first in the U.S.,
then in Canada, Norway, and Sweden.
No other countries follow suit.
CFCs continue to be used as refrigerants and solvents.

Modern Chemistry II The phasing out of CFCs

 Early 1980s
Gradual improvement in techniques used to measure
concentrations of chemical species in the stratosphere

Modern Chemistry II The phasing out of CFCs

 1985
In early 80s, the British
Antarctic Survey notices a drop
in ozone when the sun rises in
the spring (September).
At first, they thought this was a
problem with their instruments.
Publish their results in 1985.

Modern Chemistry II The phasing out of CFCs

 1985
NASA TOMS (Total Ozone Mapping Spectrometer) realizes
that the anomalously low values of ozone their software
had been throwing away were real.

Modern Chemistry II The phasing out of CFCs

 1986
Senator John Chafee of Rhode Island: There is a very real
possibility that man, through ignorance or indifference or
both, has irreversibly altered the ability of our atmosphere
to support life.
Representatives of fluorocarbon manufacturers emphasize
that ozone depletion may be a completely natural
phenomenon.
Secretary of Interior Hodel: perhaps it is possible to protect
ourselves with sunglasses (press responds by running
cartoons of elephants, lions and zebras wearing
sunglasses).

Modern Chemistry II The phasing out of CFCs

 1987
Plan flights over the Antarctic just before October sun rise
U2 spy plane to fly 3000 miles over the Antarctic and back
again. One engine, with no backup plan for engine failure.
Data collection is automatic, with no monitoring.

Goal: simultaneous measurement of O3 and ClO: The

smoking gun experiment

Modern Chemistry II The phasing out of CFCs

 1987
Ozone detector worked fine
ClO detector failed on first two flights (mid August)
sketches in January
unassembled hardware in May
a marginally operational flight system in July
software developmentby an undergraduate--under the wing of
the airplane in driving rain at stops in Panama and Chile
Third flight (August 23): ClO high, Ozone normal
Fourth flight (September 16): ClO high, 2/3 of ozone gone

Modern Chemistry II The phasing out of CFCs

 1988
March 15: Press conference of Ozone Trends Panel
concludes that ozone hole is caused by CFCs
Weve found more than the smoking gun. Weve found the
corpse.
March 25: DuPont Company, largest manufacturer of CFCs,
announced that they would no longer manufacture these
compounds.

Modern Chemistry II The phasing out of CFCs

 1992
In Copenhagen, international agreement for a complete
ban of production of CFCs by all industrialized countries by
the end of 1995.
Because of long recovery times, ozone hole over Antarctica
will not disappear until around 2050.

Modern Chemistry II The phasing out of CFCs

 Kinetics
How do we think about the rate of reactions, such as those
that destroy ozone?
What is a mechanism?
How do we support (prove) a mechanism?

Modern Chemistry II The phasing out of CFCs

 Sources
Molina and Rolands speech in honor of Senator Chafee
http://www.ncseonline.org/NCSEconference/2000conferenc
e/Chafee
Ozone Milestones http://remus.jpl.nasa.gov/milestones.htm
Center for Atmospheric Science, University of Cambridge
http://www.atm.ch.cam.ac.uk/tour/index.html

Modern Chemistry II The phasing out of CFCs