9/1/2019 Problem Set #1

Meteo 532 Atmospheric Chemistry

Problem Set #1. Solutions.

Problem 1.1. The current mixing ratio of methane (CH4) is ~1760 parts per billion by volume (ppbv) and is
increasing at a rate of about 8ppbvper year. Its main sinks are reaction with the hydroxyl radical (OH) in the
atmosphere (kOH= 3x10-9s-1), and removal by soils (ksoils=2x10-10s-1).
a. What are the lifetimes (in years) of methane due to the two different processes?
b. What is the total methane lifetime (in years)?
c. Which process – reaction with OH or soils – is the most important in determining methane’s lifetime?

a. tOH = (3x10-9)-1 = 3.3x108 s = 10.5 yrs; tsoils = (2x10-10)-1 = 5x109 s = 159 yrs.

b. The total lifetime is ttotal = (1/tOH + 1/tsoils)-1 = (3x10-9 + 2x10-10)-1 = 3.12x108 s = 9.95 yrs.

c. OH is more important that soils in determining methane’s lifetime.

Problem 1.2. On the same typical State College summer’s day, plumes from power plants in the Ohio River
Valley can contain as much as 10 ppbv of sulfur dioxide (SO2).
1. What is the number concentration of SO2?
2. What is the mass concentration of SO2?
3. If all of this SO2is converted over to sulfuric acid,H2SO4, what is the resulting mass per unit volume of the
sulfuric acid?

solution:
1. In State College in summertime, a typical daytime temperature is 303 K and pressure is 970 hPA. Thus, the
air number density is [M] = 2.69x1019 (970/1013)(273/303) = 2.3x1019 molecules cm-3. To get from ppbv to
SO2 concentration, we must do the following:
[SO2] = 10 x 10-9 x [M] = 10-8 x 2.3x1019 = 2.3x1011 molecules cm-3

2. To get the mass, we must multiply by the molecular mass.

mSO2 = (0.032 + 2 x 0.016)/6.02x1023 = 1.06x10-25 kg molecule-1
So the total mass is: MSO2 = 2.3x1011x1.06x10-25 = 2.4x10-14 kg cm-3 = 24 mg m-3.

3. If it is all converted over to H2SO4, then the total mass associated with each S atom is not 0.064 kg/mole, as
for SO2, but is (0.032 + 4x0.016 + 2x0.001) = 0.098 kg/mole. Thus, the total sulfuric acid mass is MH2SO4 =
(0.098/6.02x1023)x2.3x1011 = 3.7x10-14 kg cm-3 = 37 mg m-3.

Problem 1.3. The mean global stratospheric ozone column Is about 300 DU.
1. What is the column density in molecules m-2?
2. What is the total number of ozone molecules in Earth’s atmosphere?
3. What is the total mass of ozone in Earth’s atmosphere?
4. What percentage the ozone is lost each year in the Antarctic ozone hole?

1. 300 DU means 3 mm of pure ozone at STP = 2.69x1025 molecules m-3 x 0.003 m. The column density =
8.1x1022 molecules m-2.
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9/1/2019 Problem Set #1

2. Earth’s radius is about 6400 km. Thus the total surface area is about 4π (RE)2 = 4π(6400x1000)2 =
5.15x1014 m2. Multiplying this surface area by the column density gives the approximate number of molecules
in Earth’s atmosphere: NO3 = 5.15x1014 x 8.1x1022 = 4.2x1037 molecules = 6.9x1013 moles

3. Each mole of ozone has a mass of 0.048 kg. Multiplying by the total number of moles gives:
MO3 = 3.3x1012 kg.

4. The ozone hole’s size is roughly 20x106 km2, where we have defined the size as the area which has
experienced about 150 DU of loss since the 1970’s. Thus, the total amount of ozone lost is the molecular
column density equivalent to 150 DU times the surface area of the ozone hole. Note that 150 DU is ½ of the 300
DU in 1.
Lost ozone = 4.05x1022 molecules m-2 x 2x1013 m2 = 8.1x1035 molecules = 1.3x1012 moles.
Compared to the total in 2., fraction = 8.1x1035/4.2x1037 = 0.019, about 2%.

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