5.

60 Spring 2005 Lecture Summary #33 page 1

Chemical Kinetics in the Earth’s Atmosphere

A particularly important application of the principles and methods of chemical

kinetics is to the atmosphere of the Earth, which is a chemically reacting system
driven by radiation from the Sun.

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).

Reactions controlling [O3]

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

� (�)  quantum efficiency of dissociation

� (�)  radiation intensity [photons/cm2secnm]
 (�)  cross-section for absorption [(cm2/molecule)]

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

We now perform a steady state treatment for [O] and [O3].

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
� 

Typical experimental values:

[O2] = 1017.5 molecule/cm3
[M] = [O2] + [N2] ~ 1018 molecule/cm 3
j1 = 10-11.6 molecule-1sec -1
j3 = 10-3.5 molecule-1sec-1
k2 = 10-32.7 cm6 molecule-2 sec-1
k4 = 10-14.9 cm3 molecule-1 sec-1
5.60 Spring 2005 Lecture Summary #33 page 3

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
NO Catalysis
O (1 D) + N2O � NO + NO
____________________
Photolysis of O3
OH + O3 � HO2 + O2
HO2 + O � OH + O2
__________________
O + O3 � 2O2
NO + O3 � NO2 + O2
NO2 + O � NO + O2
O + O3 � 2O2

Cl Catalysis -- Molina & Rowland (1974)

(CFC-12) CCl2F2 + h� (� < 220 nm) � CF2 Cl + Cl
CCl2F2 + O � CF2Cl + ClO

(CFC-11) CCl3F Cl + O3 � ClO + O2

ClO + O � Cl + O2
_____________________
O + O3 � 2O2
5.60 Spring 2005 Lecture Summary #33 page 4

In the Antarctica, additional processes that destroy "odd oxygen" are important -­
in particular,

Molina ClO + ClO + M � Cl2O 2 + M

& Molina h� + Cl2O 2 � Cl + ClO2 ~ 80%
1987 ClO2 + M � Cl + O2 + M
2[Cl + O3 � ClO + O2]
__________________________
Net reaction: 2O3 � 3O2

McElroy Br + O3 � BrO + O2
et al., Cl + O3 � ClO + O2 ~ 20%
1986 ClO + BrO � Cl + Br + O2
_____________________
Net reaction: 2O3 � 3O2