Solutions: Environmental Chemistry - a global perspective 4 Edition

In ozone there are six electrons that are involved in two bonds giving an average of 3 electrons per bond or
a bond order of 1.5. In dioxygen there are four electrons in one bond giving a bond order of 2.
Chapter 3: Stratospheric chemistry – ozone

Bond length:

Oxygen would have CHEM

a shorter bond length than
given ozone. 202below
calculated

The single bond

from: 0.015 Introduction
length
mg of to
m-3Oof–OO3 is 132 pm Environmental
(Chemistry
to: 7.6 and
ppbvchemical Chemistry
of O3 reactivity, Kotz & Treichel 4th ed., p.
401), and the oxygen double bond (O = O) for the element O 2 is 120.8 pm (CRC Handbook 60th ed. p. F-
217). Since ozone
Solved Problems from Chapter 3
Convert to moles perconsists
litre: of a resonance between the single and double bond, the actual length likely is
close to the average between these two values, approximately 126 pm. A reported value of bond lengths in
molecule
0.015 mg m of-3ozone canLbemfound
÷ 1000 -3 in Chemistry
÷ 1000 mg g-1 =and
1.5chemical
x 10-8 g reactivity,
L-1 Kotz & Treichel 4th ed., p. 392 and is
127.8 pm.
Problem no. 3
Therefore there are 1.5 x 10-8 g of O3 per L of air.
3. It has been suggested that the loss of ozone in the stratosphere could lead to a negative feedback that
Divide by the
might molar
allow mass
more (M.M.)
ozone to beofproduced.
ozone, 47.9982 mol-1such
Explaing why , giving:
a feedback is possible. (This ‘self-healing’
does in fact, occur, but only to a very small extent.)
1.5 x 10-8 g ÷ 47.9982 g mol-1 = 3.13 x 10-10 mol of O3 per L of air.
Solution
The ratio of the number of moles of ozone to the total number of moles is the mixing ratio as a fraction, but
when multiplied through by 109 it can be correctly expressed as a mixing ratio with the units of ppbv.
The loss of O3 high in the stratosphere can be compensated for by increased penetration of highly energetic
solar radiation
Mixing ratio = deeper
3.13 xinto
10-10the stratosphere
mol ÷ 0.04089and as ax result,
mol 1 x 10cause
9 an ppbv
= 7.6 enhanced rate of ozone generation in
the lower stratosphere. Thus creating more ozone, which then absorbs the UV radiation and prevents it
from penetrating any further through the atmosphere. This type of compensation is called ‘self-healing’
Ratio of Jarkarta O concentration : Tokyo O3 concentration (both in ppbv)
because in this case3 the increased production of ozone is a result of the initial loss of ozone.
7.6 ppbv / 20 ppbv = 0.38
4. Average ozone concentrations -3
in Jakarta, Indonesia
-3
have been reported
-3
to be 0.015 mg m-3 and in
(Note:
Problem unit conversion to mg m yields: 0.015 mg m / 0.039 mg m = 0.38)
no. 5Japan are 20 ppbv. What is the approximate ratio of these two values when expressed in the
Tokyo,
same units?
5.Solution
Using data from Table 3.4, identify the rate-determining step in the catalytic cycle involving hydrogen
and hydroxyl radicals, and determine the overall rate of ozone destruction as a consequence of this
Usecycle.
PV=nRT(Noteand
thatassume conditions
the calculation of Pº,
applies 25ºC, and
to reactions 1.00 L atfor30the
occurring km comparison
only.) of values and the
conversion of units (P = 1.01325 x 105 Pa, T = 298 K, R = 8.315 J K-1 mol-1 and V = 1.00 L = 1.00 x 10-3
m3)
Solution (refer to Table 3.4)
n = 0.04089 mol (total number of mol of gas per L of air)
Catalytic cycle involving hydroxyl and hydrogen radicals for ozone destruction:
Unit conversions for ozone; convert the Jakarta concentration of 0.015 mg m-3 to the ppbv units reported for
Tokyo. 1 •H + O3 → •OH + O2
Reaction k = 1.9 x 10-11 molecule-1 cm3 s-1
16
Reaction 2 •OH + O → •H + O2 k = 2.3 x 10-11 molecule-1 cm3 s-1
-------------------------------------
Net reaction O 3 + O → 2 O2

Concentration of species from the data in Table 3.4:

O3 = 2.0 x 1012 molecule cm-3

•H = 2.0 x 105 molecule cm-3
•OH = 1.0 x 106 molecule cm-3
OSolutions: 109 molecule cm-3
= 1.0 xEnvironmental Chemistry - a global perspective 4th Edition
Rate = k[•H][O3]
Chapter
1
3: Stratospheric chemistry – ozone
= 1.9 x 10-11 molecule-1 cm3 s-1 x 2.0 x 105 molecule cm-3 x 2.0 x 1012 molecule cm-3
6 -3 -1
= 7.6 x 10 molecule cm s
Rate2 = k[•OH][O] 17
= 2.3 x 10-11 molecule-1 cm3 s-1 x 1.0 x 106 molecule cm-3 x 1.0 x 109 molecule cm-3
= 2.3 x 104 molecule cm-3 s-1

The second step (reaction 2) is the rate-determining step because it has the slower rate. The overall rate of
ozone destruction would be equal to Rate2 = 2.3 x 104 molecule cm-3 s-1.

6. A catalyst may be defined as a substance that enhances the rate of a chemical reaction without being
consumed in the process. By this definition, a catalyst would have an infinite lifetime. The ozone
decomposition catalysts, however, have finite lifetimes. What are possible sinks for removal of the
stratospheric catalysts, NO and •Cl?
 Rate2 = k[•OH][O] th
Solutions:
= 2.3 x 10Environmental
-11
molecule-1 cm3 s-1 xChemistry - a cm
1.0 x 106 molecule global
-3
x 1.0perspective
x 109 molecule4cm-3Edition
= 2.3 x 104 molecule cm-3 s-1
Chapter 3: Stratospheric chemistry – ozone
The second step (reaction 2) is the rate-determining step because it has the slower rate. The overall rate of
ozone destruction would be equal to Rate2 = 2.3 x 104 molecule cm-3 s-1.
Problem no. 6

6. ΔHº
A catalyst f (reaction)
may = 2asxa 90.3
be defined – [82.1
substance that+enhances
249.2] the rate of a chemical reaction without being
consumed in the process. By this definition, a catalyst would have an infinite lifetime. The ozone
ΔHºf (reaction)
decomposition catalysts,= however, mol-1finite lifetimes. What are possible sinks for removal of the
– 150.7 kJhave
stratospheric catalysts, NO and •Cl?

b) ΔHºf (reaction) = 2 x ΔHº f (NO(g)) – [ ΔHºf (N2O(g)) + ΔHºf (O(g)) + Ee(O)]

Solution
Note: the extra energy for the excited oxygen Ee(O) is about 190 kJ mol-1
NO can be removed by reaction with the hydroxyl radical which is present in the stratosphere at a
ΔHºf (reaction) = 2 6x 90.3 – [82.1 + 249.2 + 190]
concentration of about 1.0 x 10 molecule cm-3 to produce nitrous acid.
ΔHºf (reaction) = – 340.7 kJ mol-1
•NO + •OH + M → HNO2 + M

OneUsing
8. of thebond
largest sinks for
energies the chlorine
(Appendix B.3),radical
explainisthe
HCl, which sequence
reaction can be formed in the stratosphere
of ozone-destroying in at least
capability in
two the
ways.
stratosphere of hydrocarbons containing the halogens: Br > Cl > F.
•Cl + •H → HCl
Solution
where •H has a concentration of about 1x105 molecule cm-3.
Bond enthalpies can be obtained in Appendix B.3:
or •Cl + CH4 → HCl + •CH3
kJ mol-1
Methane or other similar Corganic
– Br species
276 may leak into the stratosphere where the chlorine radical can
abstract a proton and formCHCl. – Cl 338
C–F 484
For both radicals (•NO and •Cl) the products HCl and HNO2 can slowly leak back into the troposphere
where
Of the they
threecould
bonds,bethe
dissolved
weakestinbond
waterisand
C –subsequently ‘rainedrequires
Br and it therefore out’ for the
removal from
smallest the atmosphere.
amount of energy to
break. Longer wavelength radiation penetrates deeper into the atmosphere and will cause the formation of
•Therefore, there are processes by which both •NO and •Cl are removed in the stratosphere. Nevertheless,
Br, which can react first with ozone where it is more concentrated (lower in the stratosphere). The
they can still
strongest bondbeCconsidered
– F requiresas shorter
catalysts for the destruction
wavelengths of ozone,which
(higher energy), becauseare they are not
available at consumed in the
higher altitude
specificozone
where processes
is notofasremoving odd oxygen
concentrated. So whenspecies.
the •F radical is produced it will not have as much ozone
available to react with. Any bromine-containing compounds that are present in the stratosphere are potent
ozone destroyers. Chlorine falls between these two and its radical •Cl is also formed where ozone
7. Calculate the
concentrations canenthalpy change (Appendix
be significantly affected. B.2) in the following reaction:
Problem no. 9
N 2O(g) O(g) 2NO(g)
9. HCFC-123
(a) when thehas been isproposed
oxygen as a photolysis
derived from substitute for CFC-11.dioxide;
of nitrogen How would you expect the following
environmental properties to compare?
(b) when it is derived from photolysed ozone.
(a) tropospheric lifetime;
Comment on the results in terms of the tropospheric and stratospheric lifetimes of nitrous oxide.
(b) combustibility;
Solution
(c) ozone depletion potential (ODP);
a) (d)ΔHº f (reaction)
greenhouse = properties
gas 2 x ΔHºf (NO(g)) – [answered
(this can be ΔHºf (N2O(g)) + ΔHºf (O(g))]
after reading Chapter 8).

Solutions:
Solution Environmental Chemistry - a global perspective 4th Edition 18
(a) Tropospheric
Chapter 3: lifetime: HCFC-123 is a more reactive gas than CFC-11 because
Stratospheric it contains
chemistry – aozone
H–C
bond. Increasing hydrogen content reduces inertness. It will therefore not be as long lived in the
troposphere as compared to CFC-11 which is a relatively less reactive gas and it eventually will leak into
19
the stratosphere to a greater extent.

(b) Combustibility: Because of the C – H bond, HCFC-123 will be somewhat combustible. CFC-11 is
non-combustible.

(c) Ozone Depletion Potential (ODP): HCFC-123 is expected to have a lower ODP since there are only
two chlorine atoms within its structure, compared with three for CFC-11. As well, since HCFC-123 is
more reactive in the troposphere, the likelihood of the same amount of HCFC-123 (as CFC-11) reaching the
stratosphere is not as great and therefore would also act to reduce the ODP.

(d) Greenhouse gas properties: It is expected that HCFC-123 would contribute less to the warming of the
 atmosphere
troposphere because it hastoa shorter
as compared CFC-11tropospheric lifetime. less reactive gas and it eventually will leak into
which is a relatively
the stratosphere to a greater extent.
10. CFC-114b has aBecause
(b) Combustibility: tropospheric
of thelifetime
C – H of 189 HCFC-123
bond, years. Would willyou
be expect CFC-115
somewhat to have CFC-11
combustible. a longer isor
shorter lifetime?
non-combustible. Why?
Solution
(c) Ozone Depletion Potential (ODP): HCFC-123 is expected to have a lower ODP since there are only
CFC-114
two chlorinemolecular formula
atoms within CF2ClCFcompared
its structure, 2Cl with three for CFC-11. As well, since HCFC-123 is
contains:
more reactive2 carbons, 0 hydrogens,
in the troposphere, the4likelihood
fluorines, of
andthe2 same
chlorines.
amount of HCFC-123 (as CFC-11) reaching the
stratosphere is not as great and therefore would also act to reduce the ODP.
CFC-115 molecular formula CF2ClCF3
contains: 2 carbons,
(d) Greenhouse 0 hydrogens,It5isfluorines,
gas properties: expectedandthat1HCFC-123
chlorine. would contribute less to the warming of the
atmosphere because it has a shorter tropospheric lifetime.
It would be expected that CFC-115 would have a longer tropospheric lifetime then 189 years since the C –
F bond is stronger than the C – Cl bond and it would be more resistant to breaking down. (See Table 3.1).
10. CFC-114b
Increasing has a tropospheric
the proportion of fluorinelifetime of 189 years.
at the expense Would
of chlorine youtoexpect
tends CFC-115
produce to havecompounds.
highly stable a longer or
Problem no. 11
shorter lifetime? Why?
Solution
11. HCFC-22 is one of the compounds recommended as a replacement for CFCs. Use the following
information
CFC-114 to determine
molecular formula itsCFreaction
2ClCF2Cl
rate and tropospheric residence time. Compare the residence time
with that
contains: of CFC–12
2 carbons, which is about
0 hydrogens, 102 y. and 2 chlorines.
4 fluorines,
[•OH] = 6.6 x 105 molec cm-3 (remains constant)
CFC-115 molecular formula CF2ClCF3
contains: [HCFC-22]
2 carbons, 0=hydrogens,
0.10 ppbv 5 fluorines, and 1 chlorine.
k = 4.0 x 10-15 cm3 molec-1 s-1
It would be expected that CFC-115 would have a longer tropospheric lifetime then 189 years since the C –
Solution
F bond is stronger than the C – Cl bond and it would be more resistant to breaking down. (See Table 3.1).
Convert thethe
Increasing units of ppbv of
proportion to fluorine
molec cmat-3the
forexpense
the [HCFC-22]
of chlorine tends to produce highly stable compounds.
x / 4.09 x10-5 mol x 1x109 = 0.1 ppbv (where 4.09 x 10-5 mol is the number of moles of gas in 1 cm3)
x11. HCFC-22 is= one
= [HCFC-22] 4.09ofx 10
the-15compounds
mol cm-3 recommended
(x 6.022 x 1023as
) a replacement for CFCs. Useththe following
Solutions: Environmental
information to determine
9
Chemistry
its reaction rate - a residence
and tropospheric global time.
perspective 4 residence
Compare the Editiontime
with that of=CFC–12
2.46 x 10
whichmolec cm-3 102 y.
is about
Chapter
reaction [•OH]3:
rate = kx[•OH]
= 6.6 cm-3 (remains constant) Stratospheric chemistry – ozone
[HCFC-22]
105 molec
th-3
Solutions:
reaction rate -15
=Environmental
[HCFC-22]4.0 x 10ppbv
= 0.10 cm3 molec-1Chemistry - a global
s-1 x 6.6 x 105 molec perspective
cm-3 x 2.46 x 109 molec 4
cm Edition
-15 3 -3 -1
Solutionk = 4.0 x =106.49cm molec moleccm-1 ss-1
Chapter
Solution
Tropospheric 3:
residence time = steady state concentration Stratospheric
/ reaction rate chemistry – ozone
The January
Convert 15 column
the units of ppbvshows
to molec the cm
expected
-3 trend
for the of typical-3values being higher-3in-1the Southern and Northern
[HCFC-22]
Hemispheres and lower near the Equator. x 109 molec
= 2.46October 15th’scm trend /shows
6.49 molec cm sinfluence of the spring-time
the possible
-5 9 -5 3
/ 4.09 x10
x‘ozone mol x 1x10 = 0.1
hole’ over Antarctica, causing=the ppbv (where
DUxvalue 4.09 x 10 mol is the number of moles
7 of while
gas inthe
1 cm ) two
20
3.79 108 s for (convert
Tierra deltoFuego years,to3.1536
be much lower,
x10 s/y) other
locations have DU values
x = [HCFC-22] = 4.09 x 10 mol cmthat
-15 are still -3
reasonable the same
(x 6.022 x 10 ) 23as earlier.
= 12 years
9 -3
Theresidence
trends going = 2.46 x 10 molecfor cmeach location,
The timeacross the rows
of HCFC-22 is about 1/8th the timeindicate
comparedthat it tois only in the Southern Hemisphere where
CFC-12.
ozone loss
reaction rate is significant and only
= k [•OH] [HCFC-22] at specific times of the year. Both the Equatorial and Northern Hemisphere
show reasonably consistent DU values throughout the year.
reaction rate = 4.0 x 10-15 cm3 molec-1 s-1 x 6.6 x 105 molec cm-3 x1 2.46 x 109 molec cm-3
12. The following
Problem no. 14 proposal to repair the ozone layer has been made. The suggestion is to inject ‘negative
charges’ into =the 6.49 molec
lower cm-3 s-1
stratosphere, and these would react with CFCs to produce harmless products.
From your knowledge
Tropospheric residence time of basic chemistry,
= steady state indicate if this process
concentration / reactionwould
rate be theoretically possible, and
According
14.discuss to the original
the practical Montreal
requirements Protocol, Australia’s ozone cap on CFCs and related compounds
of it. 9 -3
was set at 548 tonnes (t) after 1996 = 2.46 (this
x 10value wascm
molec later /modified
6.49 molec cm-3 s-1 in the text). In 1998, use
as described
of CFCs had been completely phased out and amounts of HCFCs were reported to be: 20
Solution
HCFC-22 2820 t
A possible chemical reaction sequence (using CFC-113
HCFC-134a as an example)
1700 t is:

Cl F HCFC-141b Cl F442 t
Cl – C – C – Cl +HCFC-123
hν → Cl – C – C•35 +t Cl•
F F F F
Do these quantities meet the original terms of the agreement?
Cl• + e- → Cl-
Solution
It seems possible that the reaction sequence shown above could work, theoretically, and this is what the
authors of the
Yes, the newidea intended. when
compounds, The practical requirements
calculated with CFC-11however seem quite
equivalents meetproblematic.
the original Given
terms the very
of the
low concentration (mixing ratios) of CFCs (Table 3.1) in the stratosphere, it would be difficult to produce
agreement.
and distribute the quantity of
ODPcharge necessary to effect change on a global scale. The rate of mixing in the
stable stratosphere
HCFC-22is very small.
2820 t x 0.05 = 141 t
HCFC-134a 1700 t x 0.0 = 0t
 HCFC-134a 1700 t
HCFC-141b 442 t
HCFC-123 35 t
Do these quantities meet the original terms of the agreement?

Solution

Yes, the new compounds, when calculated with CFC-11 equivalents meet the original terms of the
agreement.
ODP
HCFC-22 2820 t x 0.05 = 141 t
HCFC-134a 1700 t x 0.0 = 0t
HCFC-141b 442 t x 0.12 = 53 t
HCFC-123 35 t x 0.01 = 0.4 t
--------
total = 194.4 t

15. The synthesis and decomposition of ozone can be described using ‘oxygen-only chemistry’ as shown
in the sequence of reactions 3.2–3.5. Explain the nature and significance of the change from O 2 and O
species in Reaction 3.3 to O2* and O* in Reaction 3.4.

Solution

The significant difference between O2 and O in Reaction 3.3 and O2* and O* in Reaction 3.4 is the energy
state that these species are in. Ozone is only capable of producing either both ground state species or both
excited state species. The energy required to produce ground state species is low, only 106.5 kJ mol -1. The
corresponding wavelength of 1123 nm is not able to be absorbed by ozone (see ozone absorption cross-
section in Figure 3.3) and this process of producing the ground state oxygen species does not occur.
However, the reverse Reaction (3.3) occurs readily. In Reaction 3.4 higher energy photons are able to

22