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1) Ozone Production
One set of reactions that is of special importance (and is now fairly well
understood) is the mechanism that produces (and destroys) ozone between 15 and 40
km altitude in the stratosphere (see the figure below).
j1
O2 + h ( < 242 n m ) > O +O
R ate = j1 = 1 I d
Constant
spectr um
where
5.60 Spring 2005 Lecture Summary #33 page 2
After the dissociation reaction above, then three body collisions lead to O3. via the
Chapman Reactions (1930):
k2
O + O2 + M ���
��O3 + M
j
O3 + h� (� < 320nm ) ��3 ��O2 + O
k4
O + O3 ��� �O2 + O2
d [O ]
= 2j 1[O2 ] + j 3[O3 ] � [O ](k 2[O2 ][ M ] + k 4[O3 ]) = 0
dt
d [O3
]
= k 2 [O][O2 ][ M ] � j 3 [O3 ] � k 4 [O][O3 ] = 0
dt
2j 1[O2 ] + j 3 [O3 ]
[O ]ss =
k 2 [O2 ][M ] + k 4 [O3 ]
k 2 [O ][O2 ][ M ]
[O3 ]ss = j 3 � k 4 [O ]
Solving for [O3]ss:
� j1 � ��
1/ 2
j 3k 2 �
[O3 ]ss = [O2 ]� 2j
�1 + 4 [M ]
�1
� 3 � j1k 4
�
which yields
j3 k 2
� M ~ 107.9 >> 1
j1 k 4
j1 k 2 1/2
O3 = O2 � M � 1012.8 m olecules at 30 km
j3 k 4 cm 3
2) Ozone Destruction -- There are at least three catalytic cycles which lead to the
destruction of. atomspheric O3 (odd oxygen).
OH Catalysis
O + H2O � OH + OH
O + CH4 � CH3 + OH OH + O3 � HO2 + O2
HO2 + O � OH + O2
__________________
O + O3 � 2O2
NO Catalysis
O (1 D) + N2O � NO + NO NO + O3 � NO2 + O2
NO2 + O � NO + O2
____________________
Photolysis of O3 O + O3 � 2O2
In the Antarctica, additional processes that destroy "odd oxygen" are important -
in particular,
McElroy Br + O3 � BrO + O2
et al., Cl + O3 � ClO + O2 ~ 20%
1986 ClO + BrO � Cl + Br + O2
_____________________
Net reaction: 2O3 � 3O2