A story about some

important science
Donald R. Blake
Department of Chemistry
University of CA, Irvine
June 18, 2014
Genealogy
Joseph Louis Gay-Lussac
Laws about combining gases
(1778-1850)
Willard Frank Libby
Nobel Prize 1960:
14
C Dating
(1908-1980)
F. Sherwood Rowland
Nobel Prize 1995:
Stratospheric ozone
Donald R. Blake
Not Much




Your face here!

Why were CFCs so attractive as
aerosol propellants?
CFC-11
F
Cl
Cl
Cl
F
Cl
Cl
F
Lifetime: 50 years 102 years
CFC-12
How are things removed from the atmosphere?
The Experiment
Published in Nature, 1974
CFC-12
Incident Light = L
i
Light Out = L
i
L
CFC12

Radiation absorbed by CFC-12, ! = 160-220nm ! UV
F
Cl
Cl
F
F
Cl
Cl
F

C
+ Cl
hv < 220nm
F
Cl
Cl
F
F
Cl
Cl
F
hv > 220nm
Stratospheric Chemistry
Chapman 1930

O
2
+ hv " O + O
O
2
+ O + M " O
3
+ M
*

O
3
+ hv " O
2
+ O
O
3
+ O " O
2
+ O
2

O
3
+ hv " O
2
+ O
hv < 320nm
Cicerone and Stolarski (catalytic cycle)

O
3
+ Cl " ClO + O
2

ClO + O " Cl + O
2

Rowland and Molina

CCl
3
F + hv " Cl + CCl
2
F
CCl
2
F
2
+ hv " Cl + CClF
2

What are the effects of reduced
stratospheric ozone?



What are the effects of reduced
stratospheric ozone?
Higher flux of uv to Earths surface
Higher energy uv to Earths surface
DNA absorption of uv is bad
DNA absorption of higher energy uv is worse
So increased skin cancer
Bad for plants and animals
Increased cataracts
???



The doldrums: 1978-1985
Blake rack Ridley rack
Total Ozone (Dobson Units)
110 220 330 440 550
Why is there an ozone hole in in the southern polar region
when almost all of the CFCs are emitted into the air in the
northern hemisphere?
Cl + CH
4
" HCl + CH
3
ClO + NO
2
" ClONO
2

Both HCl and ClONO
2
are
reservoirs for free chlorine






January 2005
Major chlorine gases in the stratosphere
Legislation
~200 countries have signed the Montreal Protocol
Imagine 200 countries agreeing on anything!
Two thirds of ALL stratospheric
ozone would be gone by 2065 if
there had been no regulations on
CFC emissions.
Nobel Prize Ceremony 1995
21 years after first ozone publication
Post Ceremony Dinner With 1320 Guests
2006
Acknowledgements
February 10, 2012