Crutzen Chemistry Impact Discussion Appendix
The Influence of Nitrogen Oxides on the
Atmospheric Ozone Content
P. J. Crutzen 1970
Thomas Kuster
Department of Environmental Sciences
ETH Zürich
Stratospheric Chemistry, 7.12.2006
Thomas Kuster
Influence of NOx on O3 Content
Crutzen Chemistry Impact Discussion Appendix
Outline
1
Prof. Paul Jozef Crutzen
Personal, Academic Studies
Noble Prize
2
Chemistry
Balance of O3
Change of Odd Oxygen
3
Impact
4
Discussion
5
Appendix
List of figures
Bibliography
Thomas Kuster
Influence of NOx on O3 Content
Crutzen Chemistry Impact Discussion Appendix
Personal, Academic Studies Noble Prize
Paul Jozef Crutzen
Personal
Born December, 3, 1933 in
Amsterdam Holland
Married, two childern
Academic Studies
Civil Engineering, 1951–1954,
Amsterdam, Holland.
Academic Studies and
Research Activities
1959–1973 at the University
of Stockholm, Sweden.
http://nobelprize.org. . .
Thomas Kuster
Crutzen Chemistry Impact Discussion Appendix
Influence of NOx on O3 Content
Personal, Academic Studies Noble Prize
The Nobel Prize in Chemistry 1995
"for their work in atmospheric chemistry, particularly concerning the formation and
decomposition of ozone"
Paul Jozef Crutzen
*1933
the Netherlands
Mario José Molina
*1943 (Mexico City)
USA
Thomas Kuster
F. S. Rowland
*1927
USA
Influence of NOx on O3 Content
Crutzen Chemistry Impact Discussion Appendix
Balance of O3
Change of Odd Oxygen
Balance of O3
Odd Oxygen
balance between atomic oxygen and ozone
reaction is to slow to balance the O3
Equation: (5), (7), (8)
OH and HO2
destruction of ozone by OH or HO2
this hypothesis does not explain the ozone observation
Equation: (14), HO2 + O3 not used (very speculative)
Odd Nitrogen (NO and NO2 )
direct controlling effect on the ozone ⇒ controlling the
ozone production rates
Equation: (1), (2), (3)
Thomas Kuster
Crutzen Chemistry Impact Discussion Appendix
Influence of NOx on O3 Content
Balance of O3
Change of Odd Oxygen
Odd Oxygen
Reactions
k
O + O2 + M →5 O3 + M
j7
O3 + hν → O + O2
(5)
308 nm < λ < 1140 nm
(7)
λ < 308 nm
(8)
j
8
O3 + hν →
O(1 D) + O2
Rate Constants
k5 = 8 · 10
−35 (445/T )
e
cm3
#s
j7 = ?
k5 : k0300 = 6.0 · 10−34 , n = 2.4
j7 = ?
j8∞ = 7.8 · 10−3
j8 = ?
1
s
left: [Crutzen, 1970], right: [Sander, 2006] & [Brasseur & Solomon]
Thomas Kuster
Influence of NOx on O3 Content
Crutzen Chemistry Impact Discussion Appendix
Balance of O3
Change of Odd Oxygen
OH and HO2
Reactions
k
14
OH + O3 →
HO2 + O2
(14)
k
31
HO2 + O3 →
OH + 2O2
(31)
Rate Constants
k14
k31
3
−13 cm
= 10
#s
: not used
cm3
= 1.7 · 10
exp (−940/T )
#s
cm3
−14
= 1.0 · 10
exp (−490/T )
#s
−12
k14
k31
left: [Crutzen, 1970], right: [Sander, 2006]
Influence of NOx on O3 Content
Thomas Kuster
Crutzen Chemistry Impact Discussion Appendix
Balance of O3
Change of Odd Oxygen
Odd Nitrogen (NO and NO2 )
Reactions
k
NO + O3 →1 NO2 + O2
(1)
j
2
NO2 + hν →
NO + O
(2)
k
NO2 + O →3 NO + O2
(3)
Rate Constants
k1 = 1.7 · 10
−12
j2 = 5 · 10−3
·e
−1310/T
cm3
#s
1
k1 = 3.0 · 10
−12
j2 = 1 · 10−2
s
k3 = 3.2 · 10−11 · e−530/T
3
cm
#s
·e
cm3
#s
1
s
k3 = 5.1 · 10−12 · e210/T
left: [Crutzen, 1970], right: [Sander, 2006] & [Brasseur & Solomon]
Thomas Kuster
−1500/T
Influence of NOx on O3 Content
cm3
#s
Crutzen Chemistry Impact Discussion Appendix
Balance of O3
Change of Odd Oxygen
Change of Odd Oxygen (O and O3 )
Time Rate
d
[Ox ] = + 2j4 [O2 ]
| {z }
dt
P
− 2k3 [O][NO2 ]
{z
}
|
D1
− {(k11 [O] + k14 [O3 ])[OH] + k13 [O][HO2 ]}
{z
}
|
D2
− 2k6 [O][O3 ]
| {z }
(22)
D3
Thomas Kuster
Influence of NOx on O3 Content
Crutzen Chemistry Impact Discussion Appendix
Impact
Record Count (total 600 times cited)
Diagramm
30
Record Count
25
20
15
10
5
0
1971
1974
1977
1980
1983
1986
1989
1992
1995
1998
Year
Thomas Kuster
Influence
of NOx on O3 Content
Seite 1
2001
2004
Crutzen Chemistry Impact Discussion Appendix
Discussion
Nitrogen oxides are of great importance in ozone
photochemistry
Observations of the nitrogen oxides in the stratosphere
Sources of N2 O
Photodissociation products of N2 O
Most of the NO and NO2 is produced at very high levels,
influence by solar cycle?
What products are formed in the photolysis of ozone below
234 nm?
O3 + hν → O(1 S) + O2 (3 Σ−
g)
Thomas Kuster
Crutzen Chemistry Impact Discussion Appendix
Influence of NOx on O3 Content
List of figures Bibliography
List of figures I
Portraits of P. J. Crutzen, M. J. Molina and F. S. Rowland
http://nobelprize.org/nobel_prizes/
chemistry/laureates/1995/
Thomas Kuster
Influence of NOx on O3 Content
Crutzen Chemistry Impact Discussion Appendix
List of figures Bibliography
Bibliography I
P. J. Crutzen
The Influence of Nitrogen Oxides on the Atmospheric
Ozone Content.
Quarterly Journal of the Royal Meteorological Society,
96:320–325, 1970.
S. P. Sander et. al.
Chemical Kinetics and Photochemical for Use in
Atmospheric Studies
Jet Propulsion Laboratory Publication 06-2, Evaluation
Number 15, July 10, 2006.
http://jpldataeval.jpl.nasa.gov/pdf/JPL_15_
AllInOne.pdf
Thomas Kuster
Crutzen Chemistry Impact Discussion Appendix
Influence of NOx on O3 Content
List of figures Bibliography
Bibliography II
G. P. Brasseur and S. Solomon
Aeronomy of the Middle Atmosphere
Springer, 2005.
P. J. Crutzen
Autobiography
http:
//nobelprize.org/nobel_prizes/chemistry/
laureates/1995/crutzen-autobio.html
P. J. Crutzen
Personal Homepage
http://www.mpch-mainz.mpg.de/~air/crutzen/
Thomas Kuster
Influence of NOx on O3 Content