CITY UNIVERSITY OF HONG KONG

Course code & title : SEE3203 Air Pollution

Session : Semester A 2021/22

Time allowed : Two hours

This paper has FIVE pages (including this cover page).

1. This paper consists of 5 questions.

2. Answer ALL questions.

This is a closed-book examination.

Students are allowed to use the following materials/aids:
Approved calculator

Materials/aids other than those stated above are not permitted. Students will be subject to
disciplinary action if any unauthorized materials or aids are found on them.

Academic Honesty Pledge

By taking this examination, I AGREE
honesty policy. I pledge that the answers in this examination are my own and that I will not seek
or obtain an unfair advantage in producing these answers. Specifically,

i. I will not plagiarize (copy without citation) from any source;

ii. I will not communicate or attempt to communicate with any other person during the exam;
iii. I will not give or attempt to give assistance to another student taking the exam;
iv. I will use only approved devices (e.g., calculators) and/or approved device models; and
v. I understand that any act of academic dishonesty can lead to disciplinary action.

On the first page of your answer scripts, students are required to:
i. Write their name and student ID number; and
ii. Reaffirm the honesty

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Attempt ALL of the questions. Show all your workings for questions 2, 3, 4, and 5. You will
be given zero if you write down the correct answer without showing all your workings. Some
useful constants can be found on after question 5.

why you believed the statement is false. (2 points for each correct response, which needs to
. 0 points for no response.
-1 points for an incorrect response and/or an incorrect explanation as to why the statement is

False. Wet deposition rates will

Dry deposition does not involve water.
(b) Fine aerosols refer to particulate matter with aerodynamic diameters larger than 2.5
µm.
False. Fine aerosols refer to particulate matter with aerodynamic diameters smaller than
2.5 µm. Coarse aerosols refer to particulate matter with aerodynamic diameters larger
than 2.5 µm.
(c) Biomass burning is considered both a natural and anthropogenic source of air
pollution.
True
(d) The puff model is used to describe the composition of the atmosphere within fixed
domains in space through which the air flows.
False. The box model is used to describe the composition of the atmosphere within fixed
domains in space through which the air flows. The puff model describes the composition
of one or more fluid elements (i.e., t
(e) Secondary air pollutants are formed in the atmosphere.

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True.

low atmosphere.

False. It is the boundary between the troposphere and stratosphere. Both the troposphere

False. Temperature decreases with altitude in the troposphere and increases with altitude
in the stratosphere.

(h) Infrared radiation emitted from the sun is usually energetic enough to break
chemical bonds in molecules.

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False. Infrared radiation is usually energetic enough to only cause vibrational motions in
molecules.
(i) Fine aerosols are mainly formed from the condensation of less volatile gases onto
existing aerosols and from coagulation.
True
(j) Long-lived air pollutants are more likely to cause problems on a global scale.
True

2. The figure below shows the typical vertical profile of the number density of ozone (O 3). O3
is formed in the stratosphere by the photolysis of O 2, which is important for our protection
from harmful UV radiation. Tropospheric ozone is harmful for humans and vegetation.

(a) Calculate the mixing ratio of O3 at the maximum of the curve (z = 25 km), where
the pressure and temperature are 35 hPa and 220 K. Express your answer in ppb. (4 points)

mixing ratio of ,

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Mixing ratio of

(b) Calculate the mixing ratio of O3 in surface air (z = 0 km, P = 1000 hPa, T = 290 K).
Express your answer in ppb. (4 points)

Mixing ratio of

(c) Compare the ratios between the O3 concentrations at 0 and 25 km altitude expressed
in mixing ratios vs. the ratio between the O3 concentrations at 0 and 25 km altitude expressed
in number density. Explain why these ratios are so different. (1 points)
The ratio of the two concentrations is larger when using the mixing ratio because this
unit expresses relative concentration, and thus takes into account that stratospheric air
contains fewer air molecules per volume unit than surface air.
(d) The O3 column expresses the total number of O3 molecules per surface area and
determines the efficiency of the air in filtering UV radiation. Estimate the O 3 column by
approximating the O3 profile with the triangle shown in the figure (see dashed lines). (2 points)

3. You learnt in class that stratospheric O3 O3

A mechanism for
O3 creation and destruction in the stratosphere is:

Reaction 1:

Reaction 2:

Reaction 3:

Reaction 4:
Use the reactions provided above to answer the following questions.

(a) (5 points) Determine the rate expressions for and . (4 points)

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 (b) Assume that both O and O3 can be treated by the steady state approximation. Show
that (i) and (ii) . (4 points)

Steady state approximation, and

From , rearrange the terms to

get .

From , rearrange the terms to get

(c) Use your answers from (b) and show that is:

Show all the steps and assumptions that you needed to make to obtain the expression for .
No points will be given if you do not. Hint: You will need to solve a quadratic equation in the
form of . (4 points)

We must have a positive value for

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{Quadratic formula: , }

4. Similar to practice question 4 In class, we learnt that sulfur dioxide (SO2) is an air pollutant
that is commonly monitored by environmental agencies worldwide. SO 2 contributes to acid
rain formation by dissolving in atmospheric aqueous droplets (e.g., cloudwater) according to
the reaction scheme below:

(1) K1 = 1.2 M atm-1

(2) K2 = 1.3 × 10-2 M

(3) K3 = 6.3 × 10-8 M

After dissolution, these sulfur-containing ions can be oxidized within the aqueous droplet either
by hydrogen peroxide (H2O2) via reactions (4) and (5), or by ozone (O3) via reactions (6) and
(7):

(4) K4 = 1.02 × 105 M atm-1

(5)
k5 = 6.9 × 107 M-2 s-1

(6) K6 = 1.14 × 10-2 M atm-1

(7) k7 = 1.5 × 109 M-1 s-1

Ki ki are reaction rate constants.

(a) Write the mathematical expressions for the equilibrium
constants: K1, K2, K3, K4, and K6. Use pSO2, pO3, and pH2O2 to denote the partial pressures (in
units of atm) of SO2, O3, and H2O2, respectively, in your answer. Hint: You should pay
attention to the units of the given equilibrium constants and rate
constants. (10 points)

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 (b) Write a mathematical expression for the formation rate of SO 42- (i.e., ) via
the oxidation by H2O2 in terms of Ki ki , and pi
oxidation reaction depends on the pH of the aqueous droplet. (3 points)

This oxidation rate is independent of pH.

(c) Write a mathematical expression for the formation rate of SO 42- (i.e., ) via
the oxidation by O3 in terms of Ki ki , and pi
oxidation reaction depends on the pH of the aqueous droplet. (3 points)

This oxidation rate is strongly dependent on pH since it is inversely proportional to

.

5. Similar to practice question 5 Carbon monoxide (CO) and methane (CH4) are common air
pollutants found in urban environments, especially in those with high levels of traffic. In the
atmosphere, the largest sinks for CO and CH4 are via chemical reactions with hydroxyl (OH)
radicals. Formaldehyde (HCHO) is a significant sink for OH. The reaction rate constants at
298 K are as follows:

(1) k1 = 1.5 × 10-13 cm3 molec.-1 s-1

(2) k2 = 6.3 × 10-15 cm3 molec.-1 s-1

(3) k3 = 9.4 × 10-12 cm3 molec.-1 s-1

In a polluted air mass in Mongkok, the following concentrations were measured on a sunny
late morning:
[CO] = 1.0 × 1013 molecules cm-3
[CH4] = 5.3 × 1013 molecules cm-3
[HCHO] = 1.4 × 1010 molecules cm-3
Assume that only chemical reactions occur in this air mass.

(a) Consider reactions (1), (2), and (3), and calculate the lifetime of the OH radical in
this air mass. (2 points)

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 (b) Which reaction is the dominant sink of OH? Justify your answer by calculating and
comparing the individual lifetimes of the OH radical against reactions (1), (2), and (3). (7
points)

The reaction with CO (reaction 1) is the dominant sink of OH (shortest lifetime amongst
the three reactions).
(c) Based on your answer in part (a), can we assume a steady state for [OH]? Justify
your answer. (2 points)
Yes. The lifetime is short (0.5 s) compared to the variability of other factors controlling
the production and loss of OH, for instance the temporal variability of UV-radiation and
mixing of air masses.
(d) The main source of OH radicals in this air mass is the reaction:

(4) k4 = 8.6 × 10-12 cm3 molec.-1 s-1

Assuming that [OH] is at steady state, use reactions (1), (2), (3), and (4) to derive a
mathematical expression for [OH]. Use this expression for [OH] to show how the lifetime of
the OH radical relates to [OH]. Hint: You should start by using reactions (1), (2), (3), and (4)
to write a mathematical expression for . Suppose [HO2] = 8.2 × 107 molecules cm-3 and
[NO] = 1.0 × 1010 molecules cm-3, use your derived expression to calculate [OH]. (5 points)
(i) At steady state, there is balance between production and loss rates of OH radicals.

(ii) Substitute values into the equation to get 3.9 × 106 molecules cm-3.