ATOC/CHEM 219: Problem Set 5

Due Mar. 14, will be handed back Mar. 18.

1. Calculate the number of Dobson Units assuming that the entire atmospheric O3 column is at a uniform
concentration of 3 × 1012 molecules cm−3 between 15 and 30 km and zero everywhere else.
2. Calculate the total mass of O3 present in the atmosphere if the average overhead amount is 350 Dobson
Units.

3. You have installed solar panels on your roof and notice that their outputted current varies throughout the
day. Reading online, you learn that the current is proportional to the intensity of the sun light that is
hitting the panels.

(a) On a clear day, you observe the maximum current to be 5 A. Later on the same clear day you
see that the current is at 3.4 A when the sun is at a solar zenith angle of 45◦ . What is the total
attenuation/optical depth for the atmosphere on this day?
(b) Later the current drops to 1.4 A. What is the solar zenith angle?
(c) On a cloudy day the maximum current is 3 A. What is the total attenuation/optical depth on this
day?

4. Derive an expression for the time-dependent concentration of IO in a system where IO radicals will only
react with themselves.
5. In the overall reaction that produces nitric oxide from N2 and O2 , the slow step in the mechanism is the
reaction between atomic oxygen and molecular nitrogen to produce nitric oxide and atomic nitrogen.

(a) Write out the chemical equation for the slow step and the rate equation for it.
(b) Given that its rate constant at 800 ◦ C is 9.7 × 1010 L mol−1 sec−1 , and that its activation energy is
315 kJ mol−1 , calculate the factor by which the rate constant increases if the temperature is raised
to 1100 ◦ C.

6. The reaction
k
O + O2 + M −
→ O3 + M
is made up of two elementary steps
k1f
∗
O + O2 −
)−
−*
− O3
k1b

k
O∗3 + M −→
2
O3 + M
Using the steady-state assumption, express the rate of formation of O3 as a function of O, O2 , and M.
7. The rate coefficients for O(1 D) + O3 −−→ 2O2 and O + O3 −−→ 2O2 are given below. In the middle
stratosphere, at about 30 km, T = 230 K, typical noontime concentrations of O(1 D) and O are 50 molecules
cm−3 and 7.5 × 107 molecules cm−3 , respectively. Evaluate the rates of both O3 loss processes at this
altitude. Which loss process dominates?

kO(1 D)+O3 = 1.2 × 10−10 cm3 molecule−1 s−1

kO+O3 = 8 × 10−12 exp(−2060/T ) cm3 molecule−1 s−1

 8. For the catalytic cycle
k1
Cl + O3 −→ ClO + O2 k1 = 2.9 × 10−11 exp(−260/T )
k
2
ClO + O −→ Cl + O2 k2 = 3.0 × 10−11 exp(70/T )
determine the ratio of [ClO]/[O3 ] at which the rate of ozone destruction from this cycle equals that from
the Chapman cycle at 20 km where T = 220 K. If the O3 mixing ratio is 4 ppm, what concentration of
ClO does this correspond to? You will need kO+O3 from Question 7 to solve this.

9. Consider the following 3-step mechanism for the production and destruction of excited oxygen atoms,
O(1 D), in the atmosphere:
jO 2 1
O2 + hν −−→ O + O( D)
1 2k
O( D) + M −→ O+M
1 3 k
O( D) + H2 O −→ 2OH
Using the steady-state approximation, develop an expression for the rate of formation of OH that does
1
not include O( D).
10. CH3 Br reacts with OH with a room temperature rate constant of 2.9 × 10−14 cm3 molecule−1 s−1 .

(a) What is the lifetime of methyl bromide with respect to reaction with OH at a global mean concen-
tration of 5 × 105 molecules cm−3 ?
(b) Colman et al. (1998) report an atmospheric lifetime of 0.8 ± 0.1 years for methyl bromide. Since
it is also taken up by soils and oceans, what must the lifetime with respect to uptake by soils and
oceans be? Assume that the total lifetime τ can be expressed as
1 1 1
= +
τ τ1 τ2

(see Seinfeld and Pandis page 25).

(c) If the global mean OH concentration is really 1 × 106 molecules cm−3 , what must the lifetime be
with respect to uptake by soils and oceans?