SEE 3203 practice questions

1. Assume that an air mass at the tropopause (P = 250 hPa, T = -40 °C) has the volume 1 m3.
If we were to move this air mass to ground level (P = 984 hPa, T = +18 °C), what volume
would the air mass have at ground level?
Ideal gas law:

where is a constant.

2. Calculate the number density of CO2 (365 ppm) in the atmosphere at ground level (P = 984
hPa, T = +18 °C).

number density of CO2:

3. Consider the following chemical mechanism for the production of hydrogen peroxide (H 2O2)
in the absence of nitrogen oxides (NOx) where all the rate constants are computed at a pressure
of 1 atmosphere and a temperature of 298 K:

Reaction 1: k1 = 4.5 x 10-5 s-1

Reaction 2: k2 = 2.9 x 10-11 cm3 molec.-1 s-1

Reaction 3: k3 = 2.2 x 10-10 cm3 molec.-1 s-1

Reaction 4: k4 = 6.7 x 10-14 cm3 molec.-1 s-1

Reaction 5: k5 = 2.0 x 10-15 cm3 molec.-1 s-1

Reaction 6: k6 = 2.7 x 10-12 cm3 molec.-1 s-1

(a) Write out the steady-state expressions (i.e., production rate = loss rate) for O 1D, OH and
HO2.

equation 1

equation 2
 equation 3
(b) Using the steady-state equations in (a), show that d[H2O2]/dt can be expressed as a function
of [O3], [M], and [H2O].

From equation 2 and equation 3 in (a):

From equation 1 in (a):

(c) Using the d[H2O2]/dt equation derived in (b), calculate the initial rate of H2O2 production
for the following conditions: [M] = 2.5 x 1019 molecules cm-3, [O3] = 40 ppb, and [H2O] = 1.1
x 107 ppb.

Note that you will get the same result if you convert and
then use

4. HNO3 is one of the most water-soluble acidic gas in the atmosphere. Because of its high
water solubility, HNO3 is an important component of acid rain. Dissolution of HNO3 into water
droplets in the atmosphere leads to:

Reaction 4: KH = 2.1 × 105 M atm-1 at 298 K

Reaction 5: Ka = 15.4 M at 298 K

where KH and Ka
is the partial pressure of HNO3. Answer the following questions.

(a) Write out the mathematical expressions for K H and Ka in terms of ,[ ],

[ ], and [ ].

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 : partial pressure of

(b) Use your answer in part (a) to write a mathematical expression for the concentration of
in terms of KH, Ka, , and [ ].

(c) Write out a mathematical expression for the concentration of the total dissolved HNO 3 in
H2O (i.e., ) in terms of KH, Ka, , and [ ].

(d) Typical values of pH in cloud and rain drops lie in the range of pH 3 to 6. Calculate the
ratios of at pH 3 and pH 6. In what form (i.e., HNO 3 (aq) or NO3- (aq)) is most of
the nitrogen found in water droplets at pH 3 and pH 6? Does HNO3 partially or completely
dissociate in water droplets at pH 3 and pH 6?

For pH = 3, .

For pH = 6, .

At both pH 3 and 6, most of the nitrogen found in water droplets is in the form of NO 3-
(aq). This means that HNO3 completely dissociate in water droplets at pH 3 and pH 6.

5. NOx (= NO + NO2) gases are common air pollutants found in urban areas. Consider the
following reactions that take place in an urban atmosphere:

Reaction 1:

Reaction 2:

Reaction 3:

Reaction 4:

o
Reaction 5:

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Reaction 6:

Reaction 7:

At 20 km: = 3.5 10-15 cm3 molec.-1 s-1, = 0.02 s-1, = 1.1 10-11 cm3 molec.-1 s-1,
= 4.6 10-12 cm3 molec.-1 s-1, = 1.7 10-18 cm3 molec.-1 s-1, = 1.2 10-12 cm3 molec.-1
s-1, = 0.3 s-1, [O3] = 5 1012 molecules cm-3, [O] = 5 105 molecules cm-3, [OH] = 2 106
molecules cm-3, [NO3] = 5 104 molecules cm-3, [NO2] = 1 ppb.
Use the reactions and the information provided above to answer the following questions.
(a) List all the reactions that constitute sinks of NO 2 in the system. Which reaction leads to the
most significant loss of NO2 from the system? Justify your answer. Hint: You will need to
calculate the loss rates of NO2 for each of the reactions that constitute sinks of NO2.

Sinks remove from the system

Reactions 2, 3, 4, 5, 6 are sinks of

Reaction 2:

Reaction 3:

Reaction 4:

Reaction 5:

Reaction 6:

Reaction 2 will lead to the most significant loss of from the system.

Note that converting ppb s-1 to molecule cm-3 s-1 is unnecessary since the question did
not specify the units you need to use when justifying your answer. But you can convert
if you want to.
(b) Assuming steady state between NO and NO 2 during the day, calculate the mixing ratio of
NO. You can neglect reactions that contribute less than 1% to the reactivity of a molecule.

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Assume steady state between and , .

This means that production rate of = loss rate of .

For production rate of , we just need to consider reaction 2 since we can neglect
reactions that contribute less than 1% to the reactivity.

For loss rate of , we just need to consider reaction 1.

(c) Assume that the number density of air is 2 1018 molecules cm-3. Calculate the lifetimes
of NO3 (the nitrate radical) in the daytime and nighttime. Explain why they are different.

Lifetime of radical,

Daytime:

No photolysis at night.

Nighttime:

6. A chemical compound is removed from the atmosphere by deposition (0.2 % per day) and
residence time
in the atmosphere with respect to (a) deposition, (b) transformation, and (c) the total residence
time.
(a) : lifetime in the atmosphere with respect to deposition

: mass of the chemical compound ( ) : deposition rate

(

We need to convert the deposition rate to

(b) : lifetime in the atmosphere with respect to transformation

: mass of the chemical compound ( ) : transformation rate

(

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We need to convert the transformation rate to

(c) : total lifetime

7. The 1987 Montreal protocol was the first international agreement to control emissions of
CFCs harmful to the ozone layer. It was subsequently amended (London 1990, Copenhagen
1992) to respond to the increased urgency created by the discovery of the Antarctic ozone hole.
In this question, we compare the effectiveness of the original and amended protocols. We focus
on CFC-12, which has an atmospheric lifetime of 100 years against loss by photolysis in the
stratosphere. We start our analysis in 1989 when the Montreal protocol entered into force. In
1989, the mass of CFC-12 in the atmosphere was m = 1.0 × 1010 kg and the emission rate was
E = 4 × 108 kg yr-1.
Mass balance equations for a one-box model:

(a) The initial Montreal protocol called for a 50 % reduction of CFC emissions by 1999 and a
stabilization of emissions henceforth. Consider a scenario where CFC-12 emissions are held
constant at 50 % of the 1989 values. Viewing the entire atmosphere as a well-mixed box, use
the Mass Balance Equation to show that the mass of CFC-12 in the atmosphere would
eventually approach a steady state value m = 2 × 1010 kg, higher than the 1989 value. Explain
why the CFC-12 abundance would increase even though its emission has decreased.

CFC-12 abundance would increase even though its emission has decreased if the steady
state mass has not been reached yet.
(b) Subsequent amendments to the Montreal protocol banned CFC production completely as
of 1996. Consider another scenario where CFC-12 emissions are held constant from 1989 to
1996 and then drop to zero as of 1996. Viewing the entire atmosphere as a well-mixed box,
use the Mass Balance Equation to calculate the masses of CFC-12 in the atmosphere in years

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2050 and 2100. Compare the masses of CFC-12 in the atmosphere in years 2050 and 2100 with
the mass of CFC-12 in the atmosphere in year 1989.
1989 to 1996: 7 years

1997 to 2050: 53 years

m(2050) is 70.6 % of m(1989)

1997 to 2100: 103 years

m(2100) is 42.8 % of m(1989)

(c) Because of the Montreal protocol, CFCs have been phased out in favour of HCFCs.
Whereas the sink of CFCs was photolysis by UV radiation ( ~ 100 years), HCFCs can be
attacked by OH radicals leading to more rapid loss by oxidation ( ~ 5 years). Consider another
scenario where in 1989 the CFCs emissions of 4 × 108 kg yr-1 were replaced entirely by
emissions of HCFCs of the same magnitude. Prior to 1989, there had been no emissions of
HCFCs, and in 1989 the atmospheric burden of CFCs was 1 × 10 10 kg. Viewing the entire
atmosphere as a well-mixed box, use the Mass Balance Equation to calculate the masses of
CFCs and HCFCs that we would expect to see in the atmosphere in 2019.

For CFCs: k = 1/100 years = 0.01 yr-1

m(2019) = (1 x 1010 kg) x exp(-0.01 yr-1 x 30 years) = 7.4 x 109 kg
Note that S = 0, so there is no 2nd term
For HCFCs: k = 1/5 years = 0.2 yr-1
m(2019) = (4 x 108 kg yr-1 / 0.2 yr-1) x (1 - exp(-0.2 yr-1 x 30 years)) = 2 x 109 kg

Note that m(0) = 0, so there is no 1st term