CHAPTER 21: ENVIRONMENTAL CHEMISTRY

CHAPTER 21
ENVIRONMENTAL CHEMISTRY
21.5

For ideal gases, mole fraction is the same as volume fraction. From Table 21.1 of the text, CO 2 is 0.033%
of the composition of dry air, by volume. The value 0.033% means 0.033 volumes (or moles, in this case)
out of 100 or
0.033
CO2
3.3 104
100
To change to parts per million (ppm), we multiply the mole fraction by one million.
(3.3 104)(1 106) 330 ppm

21.6

Using the information in Table 21.1 and Problem 21.5, 0.033 percent of the volume (and therefore the
pressure) of dry air is due to CO2. The partial pressure of CO2 is:
PCO 2 CO 2 PT (3.3 104 ) 754 mmHg

1 atm
3.3 104 atm
760 mmHg

21.7

In the stratosphere, the air temperature rises with altitude. This warming effect is the result of exothermic
reactions triggered by UV radiation from the sun. For further discussion, see Sections 21.2 and 21.3 of the
text.

21.8

The total mass of air is 5.25 1018 kg. Table 21.1 lists the composition of air by volume. Under the same
conditions of P and T, V n (Avogadros law).
Total moles of gases (5.25 1021 g)

1 mol
1.81 1020 mol
29.0 g

Mass of N2
(78.03%):
(0.7803)(1.81 1020 mol)

28.02 g
3.96 1021 g 3.96 1018 kg
1 mol

Mass of O2
(20.99%):
(0.2099)(1.81 1020 mol)

32.00 g
1.22 1021 g 1.22 1018 kg
1 mol

Mass of CO2
(0.033%):
(3.3 104 )(1.81 1020 mol)
21.11

44.01 g
2.63 1018 g 2.6 1015 kg
1 mol

Strategy: We are given the bond enthalpy of the OH radical and are asked to determine the minimum
wavelength of light required to break the bond. The bond enthalpy is given in kJ/mol, so we first must
determine the energy required to break a single bond. We then use Equation 6.2 to calculate the frequency,
and Equation 6.1 to convert from frequency to wavelength.

CHAPTER 21: ENVIRONMENTAL CHEMISTRY

Solution: Determine the energy required to break a single OH bond.
460 kJ 1000 J
1 mol

7.64 10 19 J
1 mol
1 kJ
6.022 10 23 photons
The frequency can now be calculated using Equation 6.2.
E h
v

E
7.64 10 19 J

1.15 1015 s1
h 6.63 10 34 J s

Finally, using Equation 6.1, we convert from frequency to wavelength.

21.12

3.00 108 m/s

1.15 1015 s 1

2.6 10 7 m = 260 nm

Equation 6.2 of the text relates the energy and frequency of an electromagnetic wave.
E h
First, we calculate the frequency from the wavelength, then we can calculate the energy difference between
the two levels.
Calculate the frequency from the wavelength.

c
3.00 108 m/s

5.38 1014 /s

558 109 m

Now, we can calculate the energy difference from the frequency.

E h (6.63 1034 Js)(5.38 1014 /s)
E 3.57 1019 J
21.21

Strategy: We are asked to calculate the number of O3 molecules in the stratosphere and their mass in kg.
We can simplify the calculation of volume by multiplying the thickness of the layer by the surface area of a
sphere the radius of Earth. Then we can use the molar volume of an ideal gas to determine the amount of
ozone.
Solution: The formula for the volume is 4r2h, where r 6.371 106 m and h 3.0 103 m (or 3.0 mm).
V 4(6.371 106 m) 2 (3.0 103 m) 1.5 1012 m3
Recall that at STP, one mole of gas occupies 22.41 L.
moles O3 (1.5 1015 L)

1 mol
6.7 1013 mol O3
22.41 L

1000 L
1 m3

1.5 1015 L

CHAPTER 21: ENVIRONMENTAL CHEMISTRY

21.22

molecules O 3 (6.7 1013 mol O3 )

6.022 1023 molecules

4.0 1037 molecules
1 mol

mass O 3 (kg) (6.7 1013 mol O3 )

48.00 g O3
1 kg

3.2 1012 kg O 3
1 mol O3
1000 g

The quantity of ozone lost is:

(0.06)(3.2 1012 kg) 1.9 1011 kg of O3
Assuming no further deterioration, the kilograms of O3 that would have to be manufactured on a daily basis
are:
1.9 1011 kg O3
1 yr

5.2 106 kg/day

100 yr
365 days
The standard enthalpy of formation (from Appendix 2 of the text) for ozone:
3O
2 2

H fo 142.2 kJ/mol

O3

The total energy required is:

(1.9 1014 g of O3 )
21.23

1 mol O3
142.2 kJ

5.6 1014 kJ
48.00 g O3 1 mol O3

The formula for Freon-11 is CFCl3 and for Freon-12 is CF2Cl2. The equations are:
CCl4 HF HCl CFCl3 (Freon-11)
CFCl3 HF HCl CF2Cl2 (Freon-12)
A catalyst is necessary for both reactions.

21.24

The energy of the photons of UV radiation in the troposphere is insufficient (that is, the wavelength is too
long and the frequency is too small) to break the bonds in CFCs.

21.25

250 nm

3.00 108 m/s

250 10

1.20 1015 /s

E h (6.63 1034 Js)(1.20 1015 /s) 7.96 1019 J

Converting to units of kJ/mol:
7.96 1019 J 6.022 1023 photons
1 kJ

479 kJ/mol
1 photon
1 mol
1000 J
Solar radiation preferentially breaks the CCl bond. There is not enough energy to break the CF bond.
21.26

First, we need to calculate the energy needed to break one bond.

CHAPTER 21: ENVIRONMENTAL CHEMISTRY

276 103 J
1 mol

4.58 1019 J/molecule

23
1 mol
6.022 10 molecules
The longest wavelength required to break this bond is:

hc
(3.00 108 m/s)(6.63 1034 J s)

4.34 107 m 434 nm

E
4.58 1019 J

434 nm is in the visible region of the electromagnetic spectrum; therefore, CF3Br will be decomposed in
both the troposphere and stratosphere.
21.27

The Lewis structures for chlorine nitrate and chlorine monoxide are:

Cl

Cl

O
21.28

The Lewis structure of HCFC123 is:

Cl

Cl

The Lewis structure for CF3CFH2 is:

Lone pairs on the outer atoms have been omitted.

21.39

The equation is: 2ZnS 3O2 2ZnO 2SO2

(4.0 104 ton ZnS)

21.40

1 ton mol ZnS 1 ton mol SO 2 64.07 ton SO 2

2.6 104 tons SO 2

97.46 ton ZnS 1 ton mol ZnS 1 ton mol SO 2

Because the balanced equation is given in the problem, the mole ratio between CaO and CO2 is known: 1
mole CaO is stoichiometrically equivalent to 1 mole CO2. If we convert grams of CaO to moles of CaO,
we can use this mole ratio to convert to moles of CO2. Once moles of CO2 are known, we can convert to
grams CO2.
mass CO 2 (1.7 1013 g CaO)

1 mol CO 2
1 mol CaO
44.01 g

56.08 g CaO 1 mol CaO 1 mol CO 2

1.3 1013 g CO2 1.3 1010 kg CO2

21.41

Total amount of heat absorbed is:

CHAPTER 21: ENVIRONMENTAL CHEMISTRY

29.1 J
3 K 1.6 1022 J 1.6 1019 kJ
K mol

(1.8 1020 mol)

The heat of fusion of ice in units of J/kg is:

6.01 103 J
1 mol
1000 g

3.3 105 J/kg

1 mol
18.02 g
1 kg
The amount of ice melted by the temperature rise:
1 kg

(1.6 1022 J)

3.3 105 J

4.8 1016 kg ice

21.42

Ethane and propane are greenhouse gases. They would contribute to global warming.

21.49

(3.1 1010 g)

V
21.50

1 mol SO 2
2.4
1 mol S

2.3 107 mol SO 2

100 32.07 g S
1 mol S

nRT
(2.3 107 mol)(0.0821 L atm/mol K)(273 K)

5.2 108 L SO2

P
1 atm

Recall that ppm means the number of parts of substance per 1,000,000 parts. We can calculate the partial
pressure of SO2 in the troposphere.
PSO2

0.16 molecules of SO 2
6

10 parts of air

1 atm 1.6 107 atm

Next, we need to set up the equilibrium constant expression to calculate the concentration of H in the
rainwater. From the concentration of H, we can calculate the pH.

Equilibrium:

SO2

7
1.6 10 atm
K

H2O

H HSO 3
x
x

[H ][HSO3 ]
1.3 102
PSO2

1.3 102

x2
1.6 107

x2 2.1 109
x 4.6 105 M [H]
pH log(4.6 105) 4.34
21.57

(a)

Since this is an elementary reaction, the rate law is:

rate k[NO]2[O2]

CHAPTER 21: ENVIRONMENTAL CHEMISTRY

(b)

Since [O2] is very large compared to [NO], then the reaction is a pseudo second-order reaction and the
rate law can be simplified to:
rate k'[NO]2
where k' k[O2]

(c)

Since for a second-order reaction

1
k[A]0

t1
2

then,
t
1
[(A 0 )2 ]
2 1

[(A0 )1 ]
t
1
2 2
6.4 103 min
10 ppm

2 ppm
t
1
2 2
Solving, the new half life is:
3
t
1 1.3 10 min
2 2

Think About It: You could also solve for k using the half-life and concentration (2 ppm). Then
substitute k and the new concentration (10 ppm) into the half-life equation to solve for the new halflife. Try it!
21.58

Because no changes in gas properties occur, we can use the ideal gas equation to calculate the moles of
PAN. 0.55 ppm by volume means:
VPAN
0.55 L

VT
1 106 L
Rearranging Equation 11.6 of the text, at STP, the number of moles of PAN in 1.0 L of air is:

1.0 L
1 10 L

PV

2.5 108 mol

RT
(0.0821 L atm/K mol)(273 K)
(1 atm)

0.55 L
6

Since the decomposition follows first-order kinetics, we can write:

rate k[PAN]
2.5 108 mol
1.2 1011 M/s

1.0
L

rate (4.9 104 /s)

CHAPTER 21: ENVIRONMENTAL CHEMISTRY

21.59

The volume a gas occupies is directly proportional to the number of moles of gas. Therefore, 0.42 ppm by
volume can also be expressed as a mole fraction.

O3

nO3

ntotal

0.42
1 106

4.2 107

The partial pressure of ozone can be calculated from the mole fraction and the total pressure.
PO3 O3 PT (4.2 107 )(748 mmHg) (3.14 104 mmHg)

1 atm
4.1 107 atm
760 mmHg

Substitute into the ideal gas equation to calculate moles of ozone.

nO3

PO3V
RT

(4.1 107 atm)(1 L)

1.7 108 mol
(0.0821 L atm/mol K)(293 K)

Number of O3 molecules per liter:

1.7 10

mol O3

6.022 10 23 molecules
1 1016 molecules/L
1 mol O 3

21.60

The Gobi desert lacks the primary pollutants (nitric oxide, carbon monoxide, hydrocarbons) to have
photochemical smog. The primary pollutants are present both in New York City and in Boston. However,
the sunlight that is required for the conversion of the primary pollutants to the secondary pollutants
associated with smog is more likely in a July afternoon than one in January. Therefore, answer (b) is
correct.

21.65

The room volume is:

17.6 m 8.80 m 2.64 m 4.09 102 m3
Since 1 m3 1 103 L, then the volume of the container is 4.09 105 L. The quantity, 8.00 102 ppm is:
8.00 102
1 106

8.00 104 mole fraction of CO

The pressure of the CO(atm) is:

PCO CO PT (8.00 104 )(756 mmHg)

1 atm
7.96 104 atm
760 mmHg

The moles of CO is:

n

PV
(7.96 104 atm)(4.09 105 L)

13.5 mol
RT
(0.0821 L atm/K mol)( 293 K)

The mass of CO in the room is:

mass 13.5 mol

28.01 g CO
378 g CO
1 mol CO

CHAPTER 21: ENVIRONMENTAL CHEMISTRY

21.66

First, we need to write a balanced equation.

CO2 Ca(OH)2 CaCO3 H2O
The mole ratio between CaCO3 and CO2 is: 1 mole CaCO3 is stoichiometrically equivalent to 1 mole CO2.
If we convert grams of CaCO3 to moles of CaCO3, we can use this mole ratio to convert to moles of CO2.
Once moles of CO2 are known, we can convert to grams CO2.
Moles of CO2 consumed:
0.026 g CaCO3

1 mol CaCO3
1 mol CO 2

2.6 104 mol CO 2

100.1 g CaCO3 1 mol CaCO3

The total number of moles of air can be calculated using the ideal gas equation.

747 mmHg

1 atm
(5.0 L)
760 mmHg

PV

RT
(0.0821 L atm/mol K)(291 K)

0.21 mol air

The percentage by volume of CO2 in air is:

VCO2
Vair

100%

nCO 2
nair

100%

2.6 104 mol

100% 0.12%
0.21 mol

21.67

O3: green house gas, toxic to humans, attacks rubber; SO2: toxic to humans, forms acid rain; NO2: forms
acid rain, destroys ozone; CO: toxic to humans; PAN: a powerful lachrymator, causes breathing
difficulties; Rn: causes lung cancer.

21.68

An increase in temperature has shifted the system to the right; the equilibrium constant has increased with
an increase in temperature. If we think of heat as a reactant (endothermic)
heat N2 O2 2 NO
based on Le Chtelier's principle, adding heat would indeed shift the system to the right. Therefore, the
reaction is endothermic.

21.69

(a)

From the balanced equation:

Kc

(b)

[O 2 ][HbCO]
[CO][HbO 2 ]

Using the information provided:

212

[O 2 ][HbCO]
[8.6 103 ][HbCO]

[CO][HbO 2 ]
[1.9 106 ][HbO 2 ]

Solving, the ratio of HbCO to HbO2 is:

[HbCO]
(212)(1.9 106 )

0.047 or 4.7 102

[HbO 2 ]
(8.6 103)

CHAPTER 21: ENVIRONMENTAL CHEMISTRY

21.70

The concentration of O2 could be monitored. Formation of CO2 must deplete O2.

21.71

(a)

N2O O 2NO
2NO 2O3 2NO2 2O2
Overall: N2O O 2O3 2NO2 2O2

(b)

N2O is a more effective greenhouse gas than CO2 because it has a permanent dipole.

(c)

The moles of adipic acid are:

(2.2 109 kg adipic acid)

1000 g
1 mol adipic acid

1.5 1010 mol adipic acid

1 kg
146.1 g adipic acid

The number of moles of adipic acid is given as being equivalent to the moles of N2O produced, and
from the overall balanced equation, one mole of N2O will react with two moles of O3. Thus,
1.5 1010 mol adipic acid 1.5 1010 mol N2O which reacts with 3.0 1010 mol O3.
21.72

In Problem 21.6, we determined the partial pressure of CO2 in dry air to be 3.3 104 atm. Using Henrys
law, we can calculate the concentration of CO2 in water.
c kP
[CO2] (0.032 mol/Latm )(3.3 104 atm) 1.06 105 mol/L
We assume that all of the dissolved CO2 is converted to H2CO3, thus giving us 1.06 105 mol/L of H2CO3.
H2CO3 is a weak acid. Setup the equilibrium of this acid in water and solve for [H].
The equilibrium expression is:

H2CO3
Initial (M):
Change (M):
Equilibrium (M):

5
1.06 10
x
5
(1.06 10 ) x

H HCO3
0
x

0
x

K (from table 16.8) = 4.2 107 =

[H ][HCO 3 ]
x2

[H 2CO 3 ]
1.06 10 5 x

Solving the quadratic equation:

6

x 1.9 10

M [H ]
6

pH log(1.9 10
21.73

) 5.72

First we calculate the number of 222Rn atoms.

Volume of basement (14 m 10 m 3.0 m) 4.2 102 m3 4.2 105 L

CHAPTER 21: ENVIRONMENTAL CHEMISTRY

nair

PV
(1.0 atm)(4.2 105 L)

1.9 104 mol air

RT
(0.0821 L atm/mol K)(273 K)

nRn

PRn
1.2 106 mmHg
(1.9 104 )
(1.9 10 4 mol) 3.0 105 mol Rn
Pair
760 mmHg

Number of 222Rn atoms at the beginning:

(3.0 105 mol Rn)

6.022 1023 Rn atoms

1.8 1019 Rn atoms
1 mol Rn

0.693
0.182 d 1
3.8 d

From Equation 14.3 of the text:

ln

ln

[A]t
kt
[A]0
x
19

1.8 10

(0.182 d 1 )(31 d)

x 6.4 1016 Rn atoms

21.74

From H f values given in Appendix 2 of the text, we can calculate H for the reaction
NO2 NO O
Then, we can calculate U from H. The U calculated will have units of kJ/mol. If we can convert
this energy to units of J/molecule, we can calculate the wavelength required to decompose NO2.
We use the H f values in Appendix 2 and Equation 5.18 of the text.

H rxn
nH f (products) mH f (reactants)

Consider reaction (1):

H H f (NO) H f (O) H f (NO 2 )
H (1)(90.4 kJ/mol) (1)(249.4 kJ/mol) (1)(33.85 kJ/mol)
H 306.0 kJ/mol
From Equation 5.10 of the text,

U H PV

Using the ideal gas equation to substitute for PV, we get

U H RTn

CHAPTER 21: ENVIRONMENTAL CHEMISTRY

3
U (306.0 10 J/mol) (8.314 J/molK)(298 K)(1)
3
U 304 10 J/mol
This is the energy needed to dissociate 1 mole of NO2. We need the energy required to dissociate one
molecule of NO2.
1 mol NO 2
304 103 J

5.05 1019 J/molecule

1 mol NO2 6.022 1023 molecules NO 2
The longest wavelength that can dissociate NO2 is:

21.75

hc
(6.63 1034 J s)(3.00 108 m/s)

3.94 107 m 394 nm

E
5.05 1019 J

(a)

Its small concentration is the result of the high reactivity of the OH radical.

(b)

OH has an unpaired electron; free radicals are always good oxidizing agents.

(c)

OH NO2 HNO3

(d)

OH SO2 HSO3
HSO3 O2 H2O H2SO4 HO2

21.76

This reaction has a high activation energy.

21.77

The blackened bucket has a large deposit of elemental carbon. When heated over the burner, it forms
poisonous carbon monoxide.
C CO2 2CO
A smaller amount of CO is also formed as follows:
2C O2 2CO

21.78

The size of tree rings can be related to CO2 content, where the number of rings indicates the age of the tree.
The amount of CO2 in ice can be directly measured from portions of polar ice in different layers obtained
by drilling. The age of CO2 can be determined by radiocarbon dating and other methods.

21.79

The use of the aerosol liberates CFCs that destroy the ozone layer.

21.80

Cl2 O2 2ClO
H BE(reactants) BE(products)
H (1)(242.7 kJ/mol) (1)(498.7 kJ/mol) (2)(206 kJ/mol)
H 329 kJ/mol
H = 2H f (ClO) 2H f (Cl2 ) 2H f (O 2 )

CHAPTER 21: ENVIRONMENTAL CHEMISTRY

329 kJ/mol 2H f (ClO) 0 0

H fo(ClO)
21.81

329 kJ/mol
165 kJ/mol
2

There is one CBr bond per CH3Br molecule. The energy needed to break one CBr bond is:
E

293 103 J
1 mol

4.865 1019 J
23
1 mol
6.022 10 molecules

Using Equations 6.1 and 6.2 of the text, we can now calculate the wavelength associated with this energy.
E

hc

hc
(6.63 1034 J s)(3.00 108 m/s)

4.09 107 m 409 nm

E
4.865 1019 J

CCl = 340 kJ/mol, so the photons that photolyze CCl bonds could easily photolyze the CBr bonds
as well. Light of wavelength 409 nm (visible) or shorter will break the CBr bond.
21.82

In one second, the energy absorbed by CO2 is 6.7 J. If we can calculate the energy of one photon of light with
a wavelength of 14993 nm, we can then calculate the number of photons absorbed per second.
The energy of one photon with a wavelength of 14993 nm is:
E

hc
(6.63 1034 J s)(3.00 108 m/s)

1.3266 1020 J
9

14993 10 m

The number of photons absorbed by CO2 per second is:

6.7 J
21.83

(a)

1 photon
1.3266 10

20

5.1 1020 photons

The reactions representing the formation of acid rain [H2SO4(aq)] and the damage that acid rain causes
to marble (CaCO3) statues are:
2SO2(g) + O2(g) 2SO3(g)
SO3(g) H2O(l) H2SO4(aq)
CaCO3(s) H2SO4(aq) CaSO4(s) H2O(l) CO2(g)
First, we convert the mass of SO2 to moles of SO2. Next, we convert to moles of H2SO4 that are produced
(20% of SO2 is converted to H2SO4). Then, we convert to the moles of CaCO3 damaged per statue (5% of
1000 lb statue is damaged). And finally, we can calculate the number of marble statues that are damaged.
(50 106 tons SO 2 )

1 mol SO 2
2000 lb 453.6 g

7.1 1011 mol SO 2

1 ton
1 lb
64.07 g SO 2

CHAPTER 21: ENVIRONMENTAL CHEMISTRY

(0.20) (7.1 1011 mol SO 2 )

1 mol H 2SO 4
1.4 1011 mol H 2SO 4
1 mol SO 2

The moles of CaCO3 damaged per stature are:

(0.05) (1000 lb CaCO3 )

1 mol CaCO3
453.6 g

226.6 mol CaCO3 /statue

1 lb
100.1 g CaCO3

The number of statues damaged by 1.4 1011 moles of H2SO4 is:

(1.4 1011 mol H 2SO 4 )

1 mol CaCO3
1 statue

6.2 108 statues

1 mol H 2SO 4 226.6 mol CaCO3

Of course we dont have 6.2 108 marble statues around. This figure just shows that any outdoor
objects/statues made of marble are susceptible to attack by acid rain.

21.84

(b)

The CO2 liberated from limestone contributes to global warming.

(a)

We use Equation 14.11 of the text.

ln

ln

E 1 1
k1
a

k2
R T2 T1
2.6 107 s 1
3.0 10

4 1

Ea
1
1

8.314 J/mol K 298 K 233 K

Ea 6.26 104 J/mol 62.6 kJ/mol

(b)

The unit for the rate constant indicates that the reaction is first-order. The half-life is:
t1
2

0.693
0.693

2.3 103 s 38 min

1
k
3.0 10 s

21.85

Most water molecules contain oxygen-16, but a small percentage of water molecules contain oxygen-18.
The ratio of the two isotopes in the ocean is essentially constant, but the ratio in the water vapor evaporated
from the oceans is temperature-dependent, with the vapor becoming slightly enriched with oxygen-18 as
temperature increases. The water locked up in ice cores provides a historical record of this oxygen-18
enrichment, and thus ice cores contain information about past global temperatures.

21.86

In order to end up with the desired equation, we keep the second equation as written, but we must reverse
the first equation and multiply by two.
2S(s) 3O2(g) 2SO3(g)

K2

2SO2(g) 2S(s) 2O2(g)

K1'

2SO2(g) O2(g) 2SO3(g)

K K2

1
( K1 )2
1
( K1 ) 2

CHAPTER 21: ENVIRONMENTAL CHEMISTRY

K K2

1
( K1 )

(9.8 10128 )

1
(4.2 1052 ) 2

K 5.6 1023
Thus, the reaction favors the formation of SO3. But, this reaction has a high activation energy and requires a
catalyst to promote it.