Vdoc - Pub Environmental Chemistry 101 200

Additional Problems 67
lower stratosphere at mid-latitudes even when the 7. Explain what changes are observed in the
particle concentration becomes enhanced by UV-B intensity at ground level during ozone hole
volcanoes. Deduce two reasons why this episodes.
mechanism is not important under these
conditions. 8. What would be the advantages of using
hydrocarbons rather than HFCs or HCFCs as
6. When Mechanism II for ozone destruction aerosol propellant to replace CFCs? What is their
operates with X Cl and X Br, the radicals major disadvantage? What type of agent should be
ClO and BrO react together to reform atomic added to aerosol cans containing hydrocarbon
chlorine and bromine (see Problem 2-1). A propellants to overcome this disadvantage and
fraction of the latter process proceeds by the make them safer?
intermediate formation of BrCl, which
undergoes photolysis in daylight. At night, 9. Consider the following set of compounds:
however, all the bromine eventually ends up as CFCl3, CHFCl2, CF3Cl, and CHF3. Assuming
BrCl, which does not decompose and restart the that equal numbers of moles of each were
mechanism until dawn. Deduce why all the released into the air at ground level, rank these
bromine exists as BrCl at night, even though four compounds in terms of their potential to
only a fraction of the ClO with BrO collisions catalytically destroy ozone in the stratosphere.
yields this product. Explain your ranking.
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3
The Chemistry of
Ground-Level
Air Pollution
In this chapter, the following introductory chemistry this most excellent canopy, the
topics are used: air,
look you, this excellent
m Ideal gas law o’erhanging
m Equilibrium concept, including redox reactions and their firmament, this magestic roof
balancing fretted
with golden fire, why, it
m Acid–base theory, including pH and weak acid calculations appears
no other thing to me than a
Background from previous chapters used in this chapter: foul
m Excited states and pestilent congregation of
vapours
m Photon energies, UV types (A, B, C)
Wm. Shakespeare, Hamlet, Act II,
m Gas-phase catalysis
Scene 2
m Sink concept
m Temperature inversions
Introduction
As one travels from city to city in various parts of the world, the most obvi-
ous environmental difference among them is often the extent of their air
pollution. Some cities seem pristine, while others are blanketed by a haze
that restricts visibility and induces coughing and tearing. As we shall see in
this chapter and the next, the chemical nature of the air pollution, the origin
of its reactants and the processes they undergo, and its effect on human
health all vary considerably from place to place.
Although people often think industry must be the source of most air
pollution—and the generation of electric power by coal can produce signifi-
cant amounts of emissions—in modern times it is often exhaust from vehicles
that is the main culprit. The most manifest sign of vehicular air pollution is
the black smoke emanating from the tailpipes of diesel trucks and buses. This
69
baird_ch03.indd 69 2/2/12 11:35 AM

70 Chapter 3 The Chemistry of Ground-Level Air Pollution
sight is more common now in developing countries, since such pollution has
largely been controlled in developed nations. Indeed, over the past decades,
as urban populations and vehicle densities have grown rapidly in developing
countries, air pollution there has dramatically worsened. In general, serious
regulation of air pollution is not attempted until a country has achieved a
reasonably high degree of affluence.
One of the most important features of the Earth’s atmosphere is that
it is an oxidizing environment, a phenomenon due to the large concentration
of diatomic oxygen, O2, which it contains. Almost all the gases that are
released into the air, whether they are “natural” substances or “pollutants,” are
eventually completely oxidized in the atmosphere, and the end products subse-
quently deposited on the Earth’s surface. The oxidation reactions are vital to
the cleansing of the air.
In this chapter, the chemistry underlying the pollution of tropospheric
air is examined. As background, we begin the chapter by discussing the con-
centration units by which gases in the lower atmosphere are reported, and the
constitution and chemical reactivity of clean air. The effects of polluted air
upon the environment and upon human health are discussed in Chapter 4.
3.1 Concentration Units for Atmospheric Pollutants

Air contains tiny, invisible suspended particles as well as gases. The particles
found suspended in air are usually heterogeneous mixtures, and conse-
quently no molar mass can be associated with them. Concentration scales for
such solids do not report the number of atoms or molecules, but rather the
mass of such particles found in a particular volume of air. The usual concen-
tration unit for particles in air is micrograms (of particles) per cubic
meter (of air), ␮g m3. This absolute concentration scale can also be used
for gases.
There is no consensus regarding the appropriate units by which to
express concentrations of gases in air. In Chapter 1, ratios involving numbers
of molecules—the “parts per” system—were emphasized as a measure. Other
measures are often also encountered and will be used in this chapter:
Molecules of a gas per cubic centimeter of air, molecules cm3
Micrograms of a substance per cubic meter of air, ␮g m3
Moles of a gas per liter of air, moles L1
The absolute concentration scale moles per liter, familiar to all chemists from
its use for liquid solutions, is itself rarely used for gases because they are so
dilute.
Given the lack of a consensus on a single appropriate scale, it is impor-
tant to be able to convert gas concentrations from one scale to another. This
form of manipulation is discussed in Box 3-1. Note that gas pressures cited in
units of atmospheres are synonymous with concentrations on the “parts per”
baird_ch03.indd 70 2/2/12 11:35 AM

Introduction 71
BOX 3-1 The Interconversion of Gas Concentrations
Now PV nRT, so
T he number of moles of a substance is pro-
portional to the number of the molecules
of it (Avogadro’s number, 6.02 1023, is the
V nRT/P
proportionality constant), and the partial 1.66 1018 mol
pressure of a gas is proportional to the number
0.082 L atm mol1 K1
of moles of it. Thus a concentration, for
example, of 2 ppm for any pollutant gas pres- 298 K atm1
ent in 1 atm air means
4.06 1017 L
2 molecules of the pollutant in 1 million
Since 1 L 1000 cm3, then V 4.06
molecules of air
1014 cm3, so it follows that the concentration
2 moles of the pollutant in 1 million moles in the new units is 2.0 molecules/(4.06
of air 1014 cm3), or 4.9 1013 molecules cm3.
In general, the most straightforward strat-
2 106 atm partial pressure of pollutants per
egy to use to change the value of a concentra-
1 atm total air pressure
tion a/b from one scale to its value p/q on
2 L of pollutant in 1 million liters of air (when another is to independently convert the units
the partial pressures and temperatures of pollu- of the numerator a to the units of the numera-
tant and air have been adjusted to be equal) tor p (both of which involve only the pollut-
ant) and then convert the denominator b to
Let us convert a concentration of 2 ppm
its new value q (both of which involve the
to its value in molecules (of pollutant) per
total air sample).
cubic centimeter (cm3) of air for conditions of
To convert a value in molecules cm3 or
1 atm total air pressure and 25°C. Since the
ppm to mol L1, we must change the mole-
value of the numerator, 2 molecules, in the
cules of pollutant to the number of moles of
new concentration scale is the same as in the
pollutant; for a pollutant concentration, again
original, all we need to do is establish the vol-
of 2 ppm, we can write
ume, in cubic centimeters, that 1 million
molecules of air occupy. This volume is easy to moles of pollutant
evaluate using the ideal gas law (PV nRT),
(2 molecules 1 mol)/
since we know that
(6.02 1023 molecules)
P 1.0 atm
3.3 1024 mol
T 25 273 298 K
Thus the molarity is (3.3 1024 mol)/
n (106 molecules)/
(4.06 1017 L), or 8.2 108 M.
(6.02 1023 molecules mol1) An alternative way to approach these
conversions is to use the definition that 2 ppm
1.66 1018 mol
means 2 L of pollutant per 1 million liters of
and the gas constant R 0.082 L atm mol1 K1. air and to find the number of moles and
(continued on p. 72)
baird_ch03.indd 71 23/02/12 5:10 PM

molecules of pollutant contained in a volume Thus the SO2 concentrations is

of 2 L at the stated pressure and temperature.
A unit often used to express concentra- 3.01 1018 molecules of SO2
______ 123 ppb
tions in polluted air is micrograms per cubic 2.45 1016 billion molecules of air
meter, i.e., ␮g m3. If the pollutant is a pure
Note that the conversion of moles to mole-
substance, we can interconvert such values
cules was not strictly necessary, as Avogadro’s
into the molarity and the “parts per” scales,
number cancels from numerator and denomi-
provided that the pollutant’s molar mass is
nator. As stated previously, ppb refers to the
known.
ratio of the number of moles as well as to the
Consider as an example the conversion of
ratio of the number of molecules.
320 ␮g m3 to the ppb scale if the pollutant is
It is vital in all interconversions to distin-
SO2, the total air pressure is 1.0 atm, and the
guish between quantities associated with the
temperature is 27°C. Initially the concentra-
pollutant and those of air.
tion is
320
___ ␮g of SO2
1 m3 of air PROBLEM
PR
ROB
OBLE
L M1
LE
First we convert the numerator from grams of Convert a concentration of 32 ppb for any
SO2 to moles, since from there we can obtain pollutant to its value on
the number of molecules of SO2: (a) the ppm scale,
1 mol SO (b) the molecules cm3 scale, and
320 106 g SO2 __2
64.1 g SO2 (c) the molarity scale.
6.02 1023 molecules of SO Assume 25°C and a total pressure of 1.0 atm.
_____2
1 mol SO2
PROBLEM
PROB
PR OBLE
OB L M2
LE
3.01 1018 molecules of SO2
Convert a concentration of 6.0 1014 mole-
Then, using the ideal gas law, we can change cules cm3 to the ppm scale and to the moles
the volume of air to moles and then mole- per liter (molarity) scale. Assume 25°C and
cules, using 1 L 1 dm3 (0.1 m)3: 1.0 atm total air pressure.
n PV/RT 1.0 atm 1.0 m3

PROBLEM
PR
ROB
O LE
LEMM3
__1 L n0.082 L atm
(0.1 m)3 Convert a concentration of 40 ppb of ozone,
____ O3, into
mol K 300 K
(a) the number of molecules cm3, and
40.7 mol
(b) micrograms m3.
Now 40.7 mol 6.02 1023 molecules/mol
2.45 1025 molecules, or 2.45 1016 billion Assume the air mass temperature is 27°C and
molecules of air. its total pressure is 0.95 atm.
baird_ch03.indd 72 2/2/12 11:35 AM

Introduction 73
PROBLEM
PROB
PR OBLE
OB L M4
LE this concentration expressed on the ppm
scale? On the molecules cm3 scale? Assume
The average outdoor concentration of carbon that the outdoor temperature is 17°C and that
monoxide, CO, is about 1000 ␮g m3. What is the total air pressure is 1.04 atm.
scales after correction for the magnitude of the denominator (of 1.0 atm usu-
ally). So, for example, a partial pressure of 0.002 atm in air is equivalent to
2000 ppm, since 0.002 atm 106 2000.
3.2 The Chemical Fate of Trace Gases in Air

From various natural sources—including fires, lightning, anaerobic biological
decay, and emissions from volcanoes—our atmosphere regularly receives
inputs of many gases including the partially oxidized compounds carbon mon-
oxide, CO, nitric oxide, NO, and sulfur dioxide, SO2, and several simple
compounds of hydrogen combined with another element in a highly reduced
form, such as ammonia, NH3, hydrogen sulfide, H2S, and methane, CH4.
The concentrations of these gases do not build up in clean air because
there are not only sources for them but also sinks, which result in their
continual destruction. For the gases mentioned above, the destruction pro-
cesses are oxidation reactions that occur in air. However, none of the gases
reacts directly with diatomic oxygen molecules because the activation energy
for such processes is too high. Rather, their reactions begin when they are
attacked by the hydroxyl free radical, OH, even though the concentration
of this species in air is exceedingly small, a few million molecules per cubic Recall that a free radical has
one electron in the
centimeter on average (see Problem 3-1). Its concentration has remained con- outermost shell of one of its
stant in air over the last few decades at least. atoms that neither
The presence of an unpaired electron makes most free radicals, including participates in a bond to
OH, very reactive. The Lewis structure for the hydroxyl free radical is another atom nor is part of
a nonbonding electron pair.
O9H
In clean tropospheric air, as in the stratosphere, the hydroxyl radical is

produced when a small fraction of the excited oxygen atoms resulting from
the photochemical decomposition of trace amounts of atmospheric ozone,
O3, react with gaseous water to abstract one hydrogen atom from each
H2O molecule:
UV-B
O3 9: O2 O*
O* H2O 9: 2 OH
See Additional Problem 2 for
The average tropospheric lifetime of a hydroxyl radical is only about one the lifetime calculation.
second, since it reacts quickly with one or other of many atmospheric gases.
baird_ch03.indd 73 2/2/12 11:35 AM

Because the lifetime of hydroxyl radicals is short and sunlight is required to

form more of them, the OH concentration drops quickly at nightfall.
PROBLEM 3-1
In one study, the concentration of OH in air at the time was found to be

8.7 106 molecules per cubic centimeter. Calculate its molar concentration,
and its concentration in parts per trillion, assuming that the total air pressure
is 1.0 atm and the temperature is 15°C. ●
In its reaction with otherwise-stable gases whose molecules contain

multiple bonds, OH adds itself to them, thereby forming a larger free radi-
cal. For example, hydroxyl adds to carbon monoxide molecules, forming the
transient free radical HOCO:
C#O
OH CO 9: HOCO
H!O ! C "O
Most collisions of OH and CO molecules are ineffective in promoting a reac-
tion. Consequently, the average lifetime of a carbon monoxide molecule in
air is a month or two.
Molecular oxygen reacts quickly with transient free radicals such as
HOCO once they are formed, thereby involving itself in the oxidation
process. In the present case, O2 abstracts a hydrogen atom from the free radi-
cal, thereby forming the hydroperoxy free radical, HOO, and the fully oxi-
H!O !O dized product CO2, carbon dioxide:
O" C "O O2 HOCO 9: HOO CO2
The hydroperoxy radical produced in the atmospheric oxidation of car-
bon monoxide, and indeed of most molecules, is in turn converted back
to the hydroxyl radical by its oxidation of nitric oxide, NO, which is
present in adequate concentration for this purpose in all but the very clean-
N"O est air:
O!N "O HOO NO 9: OH NO2

The general cycle of OH/HOO formation and consumption in the atmo-
spheric oxidation of various molecules is summarized by the diagram below;
in the case of some organic molecules, sunlight is required for intermediate
steps in the mechanism:
stable gas, O2 (light)
OH HOO
NO
baird_ch03.indd 74 2/2/12 11:35 AM

Introduction 75
FIGURE 3-1 Absorption

spectrum for gaseous NO2.
Ultraviolet [Source: J. H. Seinfeld and
Absorption cross section (10–20cm2)

100 Visible
UV-B UV-A S. N. Pandis, “Atmospheric
Chemistry and Physics,” John
Wiley & Sons, New York, 1998.]
10
1
300 400 500 600
Wavelength (nm)
Although suspected for decades of playing a pivotal role in air chemistry,

the presence of OH in the troposphere was confirmed only relatively recently
since its concentration is so very small. The great importance of the hydroxyl
radical to tropospheric chemistry arises because it, not O2, initiates the oxi-
dation of almost all reduced gases. Without OH and its related reactive spe- Indeed, OH has been called
the “tropospheric vacuum
cies HOO, most naturally occurring gases, and pollutant gases such as the cleaner” or “detergent.”
unburned hydrocarbons emitted from vehicles would not be efficiently
removed from the troposphere.
The reactions that OH initiates correspond to a flameless, ambient-
temperature “burning” of the reduced gases of the lower atmosphere. If these
gases were to accumulate, the atmospheric composition would be quite dif-
ferent, as would the forms of life that would be viable on Earth. Interestingly,
hydroxyl is unreactive toward molecular oxygen—in contrast to the behavior
of O2 with many free radicals—and to molecular nitrogen, thus it survives long
enough to react with so many other species.
Within a few minutes, most of the nitrogen dioxide, NO2, produced in
the OH/HOO cycle during the daytime absorbs UV-A from sunlight (see
its spectrum in Figure 3-1) and photochemically decomposes to nitric oxide
Light with wavelength
and atomic oxygen (this also occurs in the stratosphere, as mentioned in
shorter than 394 nm has
Chapter 1): sufficient energy to
NO2 UV-A 9: NO O decompose NO2 by this
reaction.
From the viewpoint of the nitrogen oxides, the cycle of NO oxidation by HOO
and the reduction of NO2 by sunlight are summarized on the next page:
baird_ch03.indd 75 2/2/12 11:36 AM

Some NO is oxidized HOO

instead by organic peroxy
free radicals, ROO, as
discussed in Chapter 17. NO NO2
sunlight UV-A
O
NO2* itself may react with
water molecules to produce The oxygen atoms produced in this cycle quickly react with molecular oxy-
OH radicals directly, rather gen to form ozone. As is the case in the stratosphere, this reaction is the only
than exclusively by prior source of ozone in the troposphere:
ozone production.
O O2 !: O3
In summary, stable gases in the air that are not already fully oxidized
react directly with OH, rather than O2, even though it is present in tiny
concentration. The OH is originally produced from reaction of O* from
ozone photodecomposition, the ozone having been created from the oxy-
Review Questions 1–4 are
based on the material
gen atom produced by photochemical decomposition of NO2. After it is
above. used for reaction initiation, the OH is transformed into HOO, which is
recycled back to OH by reaction with NO.
Urban Ozone: The Photochemical Smog Process

3.3 The Origin and Occurrence of Smog
Many urban centers in the world undergo episodes of air pollution during
which relatively high levels of ground-level ozone—an undesirable constitu-
ent of air if present in appreciable concentrations at low altitudes in the air
that we breathe—are produced as a result of the light-induced chemical reac-
tion of pollutants. This phenomenon is called photochemical smog, and is
sometimes characterized as “an ozone layer in the wrong place,” to contrast
it with the beneficial stratospheric ozone discussed in Chapter 1. The word
smog is a combination of smoke and fog. The process of smog formation
involves hundreds of different reactions, involving dozens of chemicals,
occurring simultaneously. Indeed, urban atmospheres have been referred to
as giant chemical reactors. The most important reactions that occur in such
air masses will be discussed in greater detail in Chapter 17. In the following
material, we investigate the nature and origin of the pollutants—especially
nitrogen oxides—and see how they combine to produce photochemical
smog.
The chief original reactants in an episode of photochemical smog are
molecules of nitric oxide, NO, and of unburned hydrocarbons and par-
tially oxidized hydrocarbons that are emitted into the air as pollutants from
internal combustion engines; nitric oxide is also released from electric power
baird_ch03.indd 76 2/2/12 11:36 AM

Urban Ozone: The Photochemical Smog Process 77
United States Canada

Total: 16.7 million tons/year Total: 2.9 million tons/year
(15.2 million tonnes/year) (2.7 million tonnes/year)
Industrial Nonindustrial Other

8% 9% 16%
Other
18% Electric generation Industrial
<1% 35%
Solvents
16%
On-road vehicles
Solvents 23% Off-road
26% vehicles Nonindustrial
14% 7%
Off-road vehicles On-road vehicles Electric generating units
16% 12% <1%
FIGURE 3-2 VOC emission sources in North America in 2006. [Source: International Joint
Commission, Canada–United States Air Quality Agreement: 2008 Progress Report, Washington, D.C. and
Ottawa, Ontario, 2008.]
plants. The concentrations of these chemicals are orders of magnitude greater

than are found in clean air.
Collectively, the substances, including hydrocarbons and their deriva- Formally, VOCs are defined
tives, that readily vaporize into the air are called volatile organic compounds, as organic compounds
or VOCs, many of which react in photochemical smog. having boiling points that lie
The emissions, by sector, of VOCs in the United States and Canada are between 50°C and 260°C.
illustrated by the pie charts in Figure 3-2. Emissions from on-road transporta-
tion especially have fallen drastically over the last two decades.
Gaseous hydrocarbons and partially oxidized hydrocarbons are VOCs
that are present in urban air as a result of the evaporation of solvents, liquid
fuels, and other organic compounds. For example, vapor is released into the air
when a gasoline tank is filled unless the hose’s nozzle is specially designed to
minimize this loss. Evaporated, unburned gasoline is also emitted from the tail-
pipe of a vehicle before its catalytic converter has been warmed sufficiently to
operate. Two-cycle engines such as those in outboard motor boats are particu-
larly notorious for emitting significant proportions of their gasoline unburned
into the air. Personal watercraft manufactured in the 1990s, before pollution
controls came into effect, emitted more smog-producing emissions in a day’s
operation than an automobile of the same era driven for several years! In many
regions, new lawn mowers are required to be outfitted with a catalytic converter,
though this issue is controversial since some mower manufacturers claim that a
hot converter could pose a fire hazard to the engine. Some outboard motors and
domestic firepit fireplaces are also now equipped with catalytic converters.
baird_ch03.indd 77 2/2/12 11:37 AM

Another vital ingredient in producing photochemical smog is sunshine,

which serves indirectly to increase the concentration of free radicals that
participate in the chemical processes of smog formation. Substances that
are emitted directly into air are called primary pollutants; in the smog
reaction, these are NO and VOCs, most of which are relatively innocuous with
regard to human health. Substances into which the primary ones are trans-
formed are called secondary pollutants; in smog they include ozone, nitric
acid, HNO3, and partially oxidized (and in some cases nitrated) organic com-
pounds, which are much more toxic than the reactants. An approximate
overall chemical equation for the smog reaction is
Overall reaction:
VOCs NO O2 sunlight 9: 9: mixture of O3, HNO3, organics
Primary pollutants Secondary pollutants
Other than those that absorb sunlight and subsequently decompose,

most atmospheric molecules that are transformed in air begin by reacting
with the hydroxyl free radical. The most reactive VOCs in urban air are
alkene hydrocarbons, since they contain a carbon–carbon double bond,
C R C; and aldehydes, which contain a C R O bond. These compounds are
particularly reactive since their reactions with OH, in which the hydroxyl
radical adds to a carbon atom participating in the double bond, analogous
with the case of carbon monoxide discussed previously, are very fast.
Hydroxyl initiates the reaction in the atmosphere of a hydrogen-
containing molecule that does not contain a multiple bond by abstracting
a hydrogen atom from it, thereby forming a water molecule and leaving a
free radical fragment of the hydride. For example, the first reaction of meth-
ane molecules in air is their loss of hydrogen to hydroxyl:
CH4 OH 9: CH3 H2O
The fragment CH3 contains an odd number of electrons, and is the methyl
free radical. Such free radicals do react with diatomic oxygen in a sequence
of reactions that involves their oxidation to carbon monoxide (and ulti-
mately to carbon dioxide):
OH O2 O2
CH4 9: CH3 9: 9: other intermediates 9: CO
As a result of reactions in the sequence in which peroxy free radicals oxidize NO
to NO2, the hydroxyl free radical is eventually regenerated in the same manner
Recall that a catalyst is
defined as a substance that as it is in the CO oxidation. Thus OH acts as a catalyst in the atmospheric
speeds up a chemical oxidation of most species and is effective in air even in tiny concentration.
reaction, but is regenerated In smog episodes, aldehydes are among the intermediates, and their pho-
during the process. tochemical decomposition by UV-A produces additional free radicals. Since
on average more than 1.0 molecule of HOO is produced in each cycle as a
result, more than 1.0 OH molecule is created by their reaction with nitric
oxide. Over time, the total concentration of OH and HOO free radicals
baird_ch03.indd 78 2/2/12 11:37 AM

builds up during a smog reaction, thereby accelerating it. Notice that the
operation of the OH/HOO cycle and the smog it produces depends upon the
simultaneous presence of NO and of reactive VOCs; without one or the other
of these key reactants the cycle could not proceed nearly as quickly. The NO
and VOCs here are said to act in synergism; their overall effect is much
greater than would be the sum of either acting in isolation.
When the reaction sequence of oxidizing CH4 to CO is combined with
that of CO oxidation to CO2, the overall reaction is seen to be the complete
oxidation of methane to carbon dioxide and water, the same reaction as
occurs when natural gas is burned in air:
CH4 2 O2 9: CO2 2 H2O
Details of the complete sequences by which such free-radical reactions oxidize
the gases emitted into clean and polluted air are explained in Chapter 17.
3.4 Ground-Level Ozone in Smog

Photochemical smog is a widespread phenomenon in the modern world. In
order for a city to generate photochemical smog, several conditions must be
fulfilled.
• First, there must be substantial vehicular traffic in order to emit
sufficient NO, reactive hydrocarbons, and other VOCs into the air.
• Second, there must be warmth and ample sunlight in order for the
crucial reactions, some of them photochemical, to proceed at a rapid rate.
• Finally, there must be relatively little movement of the air mass so that
the reactants are not quickly diluted or swept away.
For reasons of geography (e.g., the presence of mountains) and dense popula-
tion, cities such as Los Angeles, Denver, Mexico City, Tokyo, Athens, Sao
Paulo, and Rome all fit the bill splendidly and consequently are subject to
frequent smog episodes. Indeed, the photochemical smog phenomenon was
first observed in Los Angeles in the 1940s and has generally been associated
with that city ever since, although pollution controls have partially allevi-
ated the city’s smog problem in recent decades.
3.5 An Episode of Photochemical Smog

It is instructive to follow a heavy episode of photochemical smog, as occurred
in Los Angeles in the 1960s, through a day in order to understand the
sequence of processes that are important at different stages. Refer to Fig-
ure 3-3, in which the concentrations of various chemicals are plotted against
time of day, while reading the following.
• As discussed above, it is predominantly NO rather than NO2 that is
released from vehicles and power plants into the air. One can see the
baird_ch03.indd 79 2/2/12 11:37 AM

FIGURE 3-3 Time-of-day

(diurnal) variation in the 0.6
concentration of gases Hydrocarbons
during days of marked eye 0.5 Aldehydes
Pollutant concentration (ppm)

irritation in Los Angeles in Ozone
the 1960s. [Source: Redrawn NO2
from D. J. Speeding, Air 0.4
Pollution (Oxford: Oxford
NO
University Press, 1974).]
0.3
0.2
0.1
0
4 6 8 10 12 2 4 6
a.m. noon p.m.
Diurnal time scale
concentration of NO rising from emissions from early-morning vehicle

traffic in Figure 3-3. Over a period of hours, the NO is gradually oxidized to
NO2 by the buildup of HOO, as discussed above. One might have expected
the ozone concentration to have increased quickly as NO2 underwent
photochemical decomposition, but in the morning the ozone is quickly
destroyed by its reaction with NO to form NO2 and oxygen:
O3 NO 9: O2 NO2
The reactive hydrocarbons in emissions are beginning their oxidation, as
evidenced from the rapid buildup in the concentration of one of their inter-
mediate oxidation products, the aldehydes (medium-green curve).
PROBLEM 3-2
By adding up the three reactions, show that the net result of the photochemi-
cal decomposition of NO2, the formation of ozone from atomic oxygen, and
the above reaction constitute no overall reaction, i.e., a null process. ●
• By mid-morning, lesser amounts of NO enter the air since rush-hour

traffic is over and most of what has been emitted has been converted to
NO2. At this point, the level of OH free radicals has increased sufficiently
that the concentration of hydrocarbons (dark green curve) begins to
decline. At the same time, the concentration of ozone begins to build
rapidly since it is no longer quickly destroyed by reaction with NO since
the latter is quickly re-oxidized by radicals to NO2 instead. At about noon,
the production of aldehydes is overtaken by the photochemical and free-
radical decomposition of existing stock, leading to its subsequent decline.
baird_ch03.indd 80 2/2/12 11:37 AM

FIGURE 3-4 Nitrogen-

Emissions Internal cycling Smog products based components of
photochemical smog.
ht O3
lig
O3 or HOO Sun
O2
Vehicles
Power plants
NO NO2
+OH
Sunlight
HNO3
• The concentration of NO2 peaks in the morning but remains at a lower

level throughout the rest of the day due to continuing production from NO
emissions. There exists a sink for NO2 when the concentration of free
radicals is high: it combines with hydroxyl radical to produce nitric acid,
one of the end-products of smog:
NO2 OH 9: HNO3
Some NO2 also reacts with hydrocarbon chains to nitrate them. Overall, the
smog process from the viewpoint of the nitrogen emissions as NO2 chains is
represented in Figure 3-4, showing NO continuously flowing into the atmo-
spheric reactor and ozone and nitric acid being produced following a period
of cycling of the nitrogen oxides.
ACTIVITY
Search the web for information about ground-level ozone levels in whichever
large city you inhabit most frequently. If historical records dating back a few
years are available, create a file of days with the highest levels each year. Is the
number of high-ozone days about the same each year? Do several high-ozone
days occur in sequence or are they isolated incidents? Beside each high-ozone
day, find and list the maximum afternoon temperature from weather records.
Is there a correlation of maximum ozone and maximum temperature? Why
might you expect such a correlation to exist? If ozone and/or nitrogen dioxide
levels by the hour are available for your city, plot them against time for a typi-
cal high-ozone day. Do they follow the trends in Figure 3-3?
3.6 Nitrogen Oxide Production During Fuel Combustion

Given the roles of NO and NO2 in photochemical smog where their concen-
trations are many times those of background, it is important to understand
baird_ch03.indd 81 2/2/12 11:37 AM

their origins as atmospheric pollutants. Nitrogen oxide gases are produced by

two different reactions whenever a fuel is burned in air with a hot flame.
• Some nitric oxide is produced from the oxidation of nitrogen atoms
contained in molecules of the fuel itself; it is called fuel NO. About
30–60% of a fuel’s nitrogen is converted to NO during combustion.
However, most fuels do not contain much nitrogen, so this process
accounts for only a small fraction of NO emissions.
• Nitric oxide is produced by the oxidation at high combustion
temperatures of atmospheric nitrogen, and it is called thermal NO.
At high flame temperatures, some of the nitrogen and oxygen gases in
the air passing through the flame combine to form NO:
hot flame
N2 O2 9: 2 NO
The higher the flame temperature, the more NO is produced. Since this reac-
LeChatelier’s principle; see
also Additional Problem 4.
tion is very endothermic, its equilibrium constant is very small at normal
temperatures but increases rapidly as the temperature rises.
One might expect that the relatively high concentrations of NO that are
produced under combustion conditions would revert back to molecular nitro-
gen and oxygen as the exhaust gases cool, since the equilibrium constant for
the above reaction is much smaller at lower temperatures. However, the
activation energy for the reverse reaction is also quite high, so the process
cannot occur to an appreciable extent except at high temperatures. The flow
of gases through the combustion zone is so rapid that the NO does not have
sufficient time to react at the high temperatures its reaction requires. Thus
the relatively high concentrations of nitric oxide produced during combus-
tion are maintained in the cooled exhaust gases. Equilibrium cannot be
quickly re-established and the nitrogen is “frozen” as NO.
Because the reaction between N2 and O2 has a high activation energy, it
is negligibly slow except at the very high temperatures such as occur in the
modern combustion engines of vehicles—particularly when they are travel-
ing at high speeds—and in power plants. Very little NO is produced by the
burning of wood and other natural materials since the flame temperatures
involved in such combustion processes are relatively low.
Two distinct mechanisms are involved in the initiation of the reaction
of molecular nitrogen and oxygen to produce thermal nitric oxide; in one it
is atomic oxygen that attacks intact N2 molecules, whereas in the other it is
free radicals, such as CH, that are derived from the decomposition of the fuel.
The initial reaction steps of the first mechanism are
Recall from introductory
0!
chemistry that the rate of a O2 !1 2 O
reaction step is proportional
to the product of the O N2 9: NO N
concentrations of its
reactants.
The rate of the second, slower step is proportional to [O] [N2]. However,
since, from the equilibrium in the first step, [O] is proportional to the square
baird_ch03.indd 82 2/2/12 11:37 AM

root of [O2], it follows that the rate of NO formation will be proportional to

[N2] [O2]1/2. Consequently, this process is relatively slow under oxygen-poor
conditions.
The nitric oxide released into air is gradually oxidized to nitrogen diox-
ide over a period of minutes to hours, the rate depending upon the concen-
tration of the pollutant gases present. Collectively, NO and NO2 in air is
referred to as NOX, pronounced “nox.” The yellow-brown color in the
atmosphere of a smog-ridden city is due in part to the nitrogen dioxide pres-
ent, since this gas absorbs visible light, especially near 400 nm (see its spec-
trum in Figure 3-1), removing sunlight’s purple component while allowing
most yellow light to be transmitted. The small levels of NOX in clean air
result in part from the operation of the above reactions in the very energetic
environment of lightning flashes and in part from the release of NOX and of
ammonia, NH3, from biological sources. NOX is also emitted from coniferous
trees when sunlight shines on them and when the ambient concentrations of
these gases are low.
The sources of anthropogenic NOX emissions in North America are shown
by sector in Figure 3-5. The quantities from on-road transportation, and from
electric power generation in the United States, fell substantially over the last
dozen years.
Although our analysis above has identified ozone as the main product of
smog, the situation is actually more complicated, as a detailed study in Chapter
16 indicates. For example, nitrogen dioxide reacts with organic free radicals to
produce organic nitrates. Many of the products form particles or are incorpo-
rated into them, as discussed in Section 3.24.

Solvents Other
Solvents Other <1%
<1% 2% <1%
Off-road Industrial Off-road
16% Industrial
vehicles vehicles
33%
24% 32%
Nonindustrial
4%
Electric generation Nonindustrial

20% On-road 3%
On-road vehicles
vehicles 22%
34% Electric generating units
10%
FIGURE 3-5 Anthropogenic NOX sources in North America, by sector in 2006.

[Source: International Joint Commission, Canada–United States Air Quality Agreement: 2008 Progress Report,
Washington, D.C. and Ottawa, Ontario, 2008.]
baird_ch03.indd 83 2/2/12 11:37 AM

3.7 Governmental Goals for Reducing

Ozone Concentrations
The ozone level in clean air amounts to only about 30 ppb. Many countries
individually, as well as the World Health Organization, WHO, have estab-
lished goals for maximum allowable ozone concentrations in air averaged
over an 8-hr period. The United States adopted an 8-hr ozone standard of
80 ppb in 1997, but this was revised downward to 75 ppb in 2008, and may
be dropped to the 60–70-ppb level eventually. The standard in Canada is
65 ppb. The European Union standard of 120 ␮g m3, when converted to
ppb units, is close to the U.S. limit (Problem 3-3).
PROBLEM 3-3
Convert into ppb units the EU ozone standard of 120 ␮g m3 and the WHO
standard of 100 ␮g m3, assuming summertime air temperatures of 27°C. ●
PROBLEM 3-4
Calculate the air temperature at which the EU ozone level of 120 ␮g m3 is
equivalent to the current U.S. standard of 75 ppb. Assume a total air pressure
of 1.0 atm. ●
3.8 Photochemical Smog Around the World

Many major cities in North America, Europe, and Japan exceed ozone levels
of 120 ppb typically for 5 to 10 days each summer. The levels of ozone in Los
Angeles air used to reach 680 ppb. Figure 3-6 illustrates the decline in
300 15
Ozone
Population (millions)
200 10
O3 (ppbv)
Population
100 5
FIGURE 3-6 Maximum

atmospheric ozone
concentration (left axis) and
human population (right 0 0
axis) in Los Angeles over a 1960 1970 1980 1990 2000 2010
half-century. [Source: D. D. Year
Parish and T. Zhu, Science 326
(2009): 674–675.]
baird_ch03.indd 84 2/2/12 11:38 AM

maximum ozone levels (dark green curve) in Los Angeles over time—by
more than a factor of two over the last half-century—notwithstanding the
continual increase in population of the area over that time period (light
green curve). Presumably the Los Angeles pollution level would have
increased greatly over the half-century, given the increase in the number of
vehicles, if pollution controls had not been instituted.
The air in Mexico City is so polluted by ozone, particulate matter, and
other components of smog, and by airborne fecal matter, that it is responsible
for thousands of premature deaths annually; indeed, in the center of the city
residents can purchase pure oxygen from booths to help them breathe more
easily! In 1990 Mexico City exceeded the WHO air guidelines on 310 days,
although peak smog levels have steadily declined since the 1990s and never
reached the maximums attained in Los Angeles. In contrast to temperate
areas where photochemical smog attacks occur almost exclusively in the
summer—when the air is sufficiently warm to sustain the chemical reac-
tions—Mexico City suffers its worst pollution in the winter months, when
temperature inversions prevent pollutants from escaping. Some of the smog
Butenes contain a CRC
in Mexico City originates from butenes that are a minor component of the bond and consequently are
liquefied gas that is used for cooking and heating in homes, some of which very reactive.
apparently leaks into the air.
Athens and Rome, as well as Mexico City, attempt to limit vehicular traf-
fic during smog episodes. One strategy used by Athens and Rome is to allow
only half the vehicles to be driven on alternate days, the allocation being based
upon the license plate numbering (odd or even numbers). France plans to ban
access in cities including Paris to vehicles made before 1997, when strict emis-
sion standards were instituted in Europe. Low-emission zones of various types
are already in existence in parts of Sweden, Germany, Italy, and London,
England and have succeeded in reducing urban air pollution.
Owing to the rapid increase in the number of vehicles on their roads and
their generally warm climates, ground-level ozone levels and episodes of pho-
tochemical smog occur more and more frequently in developing countries.
Peak ozone levels have been increasing in Beijing since the 1990s, especially
from May to October. Other Chinese megacities such as Shanghai and Guang-
zhou also now suffer from high ozone episodes.
When hot summertime weather conditions produce large amounts of ozone
in urban areas but do not allow much vertical mixing of air masses as they travel
to rural sites, elevated ozone levels are often observed in eastern North America
and western Europe in zones that extend for 1000 km (600 miles) or more. Thus
ozone control is a regional rather than a local air-quality problem. Indeed, on
occasion, polluted air from North America moves across the Atlantic to Europe,
northern Africa, and the Middle East; that from Europe can move into Asia and
the Arctic; and especially in springtime, that from Asia can reach the west coast
of North America and contribute to increasing ozone levels there. Some analysts
believe that by 2100, even the background level of ozone throughout the North-
ern Hemisphere will exceed current ozone standards.
baird_ch03.indd 85 2/2/12 11:38 AM

Due to the long-range transport of primary and secondary pollutants in

air currents, many areas which themselves generate few emissions are subject
to regular episodes of high ground-level ozone and other smog oxidants.
Indeed, some rural areas, and even small cities, that lie in the path of such
polluted air masses experience higher levels of ozone than do nearby larger
urban areas! This occurs because in the larger cities some of the ozone
Imported O3 local NO !:
NO2 O2.
transported from elsewhere is eliminated by reaction with nitric oxide
released locally by cars into the air, as illustrated previously in the reaction
of NO with O3. Ozone concentrations of 90 ppb are common in polluted
rural areas. This phenomenon occurs in northern European countries such as
Denmark, where ozone transported from southern countries reacts with NO
emitted from vehicles in the Danish cities, but remains unreacted over rural
areas, which consequently are more polluted by ozone than are urban areas.
Considerable amounts of ozone are transported from its origin in the
U.S. Midwest to surrounding states and Canadian provinces, especially
around the Great Lakes, such as the farmland in southwest Ontario, which
receives ozone-laden air from industrial regions in the United States that lie
across Lake Erie.
Contour diagrams like that
A plot of ozone concentration contours for summer afternoon smog condi-
in Figure 3-7 are similar to tions in North America in about 1990 is shown in Figure 3-7. At each point
geographic maps in which along any solid line, the concentration of ozone has the same value; hence
adjacent locations of equal contours connect regions having equal levels of ozone.
altitude are connected by The highest levels (100 ppb) occurred in the Los Angeles and New
lines.
York–Boston areas, but note the 80-ppb contour over a wide area south of
the Great Lakes and into the Southeast, as well as one surrounding Houston.
60
60 60
80
FIGURE 3-7 Ninetieth
percentile contours of
summer afternoon ozone 100
concentrations (ppb)
measured in surface air over
80
the United States. Ninetieth
percentile means that 60
concentrations are higher 100
than this 10% of the time. 80
[Adapted from A. M. Fiore, D. J. 80
Jacob, J. A. Logan, and J. H. Yin, 60 60
“Long-Term Trends in Ground-
Level Ozone over the 60
Contiguous United States,
1980–1995,” J. Geo-phys. Res.
103 (1998): 1471–1480.]
baird_ch03.indd 86 2/2/12 11:38 AM

Improving Air Quality: Photochemical Smog 87
Ozone levels were particularly high over Houston—reaching 250 ppb on

occasion—because of emissions of highly reactive VOCs containing C R C
bonds from the region encompassing the petrochemical industry. By the late
2000s, the most ozone-polluted cities in the United States were
• Los Angeles, and seven other California cities ranging from Bakersfield
north of it to San Diego to its south
• Houston, Texas
• Charlotte, North Carolina
The photochemical production of ozone also occurs during dry seasons
in rural tropical areas where the burning of biomass for the clearing of forests
or brush is widespread. Although most of the carbon is transformed immedi-
ately to CO2, some methane and other hydrocarbons are released, as is some based on material in the
NOX. Ozone is produced when these hydrocarbons react with the nitrogen sections above.
oxides under the influence of sunlight.
Improving Air Quality: Photochemical Smog

The history of attempts to improve the quality of the air that we breathe
stretches back many centuries. In the developed world, episodes of the type
of smog (mainly soot and sulfur dioxide) produced by unregulated coal burn-
ing began to be reduced in the mid-twentieth century and have largely disap-
peared there, as discussed further in Chapter 4. As we shall see below, the
conquest of photochemical smog is proving to be a harder objective.
3.9 Limiting VOC and NO Emissions to Reduce

Ground-Level Ozone
In order to improve the air quality in urban environments that are subject
to photochemical smog, the quantity of reactants, principally NOX and
hydrocarbons containing CRC bonds, plus other reactive VOCs, emitted
into the air must be reduced. The control strategies that have been put in
place in the United States have resulted in some reduction in ozone levels in
the past few decades, notwithstanding the huge increase in total vehicle-miles
driven—up to 100% more in the last 25 years—that has occurred.
For economic and technical reasons, the most common control strategy
has been to reduce hydrocarbon emissions. However, except in downtown
Los Angeles, the percentage reduction in ozone and other oxidants that is
thereby achieved usually has been much less than the percentage reduction
in hydrocarbons. This happens because usually there is initially an over-
abundance of hydrocarbons relative to the amount of nitrogen oxides, and
cutting back hydrocarbon emissions simply reduces the excess without Nitrogen oxides are the
limiting reactants in these
slowing down the reactions significantly. In other words, it is usually the areas.
nitrogen oxides, rather than reactive hydrocarbons, that are the species that
baird_ch03.indd 87 2/2/12 11:39 AM

determine the overall rate of the reaction. This is especially true for rural
areas that lie downwind of polluted urban centers.
Due to the large number of reactions that occur in polluted air, the func-
tional dependence of smog production upon reactant concentration is com-
plicated, and the net consequence of making moderate decreases in primary
pollutants is difficult to deduce. Computer modeling indicates that NOX
reduction, rather than VOC reduction, would be much more effective in
reducing ozone in most of the eastern United States. However, Mexico City’s
ozone is limited by VOCs, even though there are numerous sources of them.
An example of the predictions that arise from the modeling studies is
shown in Figure 3-8. The relationships between the NOX and the VOC con-
centrations that produce contours for three different values for the concen-
tration of ozone are shown. Notice that the same concentration of ozone
results from many different combinations of VOC and NOX. Point A repre-
sents a typical set of conditions in which the ozone production is NOX limited.
For example, reducing the concentration of VOCs from 1.2 ppm to 0.8 ppm
has virtually no effect on the ozone concentration, which remains at about
160 ppb since the contour in this region is almost linear and runs parallel to
the horizontal axis. However, a reduction of the NOX level, from about
0.03 ppm at point A to a little less than half this amount, which corresponds
to dropping down to the curve directly below it in the figure, cuts the pre-
dicted ozone level in half, from 160 ppb to 80 ppb. Chemically, NOX-limited
conditions occur when, due to the high concentration of VOC reactants, an
abundance of peroxy free radicals HOO and ROO are produced, which
quickly oxidize NO emissions to NO2:
HOO NO 9: OH NO2
0.28
Ozone =
0.24 80 ppb
160 ppb
0.20 B 240 ppb
VOC-
limited
NOX (ppm)
0.16 region
FIGURE 3-8 The
relationship between NOX 0.12
and VOC concentrations in
air and the resulting levels
of ozone produced by their 0.08
reaction. Points A, B, and C C
denote conditions discussed 0.04 A NOX-limited region
in the text. [Source: Redrawn
from National Research Council,
0
Rethinking the Ozone Problem 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0
in Urban and Regional Air
VOC (ppm of carbon)
Pollution (Washington, DC:
National Academy Press, 1991).]
baird_ch03.indd 88 2/2/12 11:39 AM

The nitrogen dioxide then photochemically decomposes to produce the free

oxygen atoms that react with O2 to produce ozone, as previously discussed
(see Figure 3-4).
In the portion of the VOC-limited region that lies to the left of the diago-
nal dashed line of Figure 3-8, there is a large excess of NOX; under such
conditions, the OH radical tends to react with NO2, and so less of it is avail-
able to initiate the reaction of more VOCs:
OH NO2 9: HNO3
Consequently, lowering the NOX concentration actually produces more
ozone, not less, since more OH is thereby available to react with the VOCs,
although production of other smog reaction products such as nitric acid is
thereby reduced. Thus, for example, when the VOC concentration is about
0.5 ppm, lowering the NOX concentration from 0.21 ppm—corresponding
to point B on Figure 3-8—even by two-thirds of this amount is predicted to
increase slightly the ozone level beyond 160 ppb; further reductions do not
begin to decrease ozone until NOX reaches about 0.05 ppm. Indeed, ozone
concentrations on weekends, when there is much less truck traffic, are
higher in Los Angeles and many other cities, since the very high weekday
levels of NO2 are lower then and so less of it is available to combine with
and provide a sink for OH.
In situations where the NOX is less abundant but VOCs are relatively
plentiful, i.e., to the right side of the dashed line in Figure 3-8, reducing NOX
does reduce ozone. Thus, when the VOC level is 0.5 ppm, the ozone concen-
tration falls back to 160 ppb when the NOX is reduced to 0.04 ppm (point C),
and declines more with further decreases of NOX.
PROBLEM 3-5
Using Figure 3-8, and assuming a NOX concentration of 0.20 ppm, estimate
the effect on ozone levels of reducing the VOC concentration from 0.5 to
0.4 ppm. Do your results support the characterization of that zone of the
graph as VOC limited? ●
PROBLEM 3-6
Using Figure 3-8, again with an initial VOC concentration of 0.50 ppm,
estimate the effect on ozone levels of lowering the NOX concentration from
0.20 to 0.08 ppm. Explain your results in terms of the chemistry discussed
above. ●
Some urban areas such as Atlanta, Georgia, and others located in the
southern United States, incorporate or border upon heavily wooded areas
whose trees emit enough reactive hydrocarbons to sustain smog and ozone
production, even when the concentration of anthropogenic hydrocarbons,
baird_ch03.indd 89 2/2/12 11:39 AM

i.e., those that result from human activities, is low. Deciduous trees and
shrubs emit the gas isoprene, whereas conifers emit pinene and limonene; all
three hydrocarbons contain C RC bonds.
In urban atmospheres, the concentration of these natural reactive hydro-
carbons normally is much less than that of the anthropogenic hydrocarbons,
and it is not until the latter are reduced substantially that the influence of
these natural substances becomes noticeable. In areas affected by the pres-
ence of vegetation, then, only the reduction of emissions of nitrogen oxides
will reduce photochemical smog production substantially. As an air mass
moves from an urban area to a rural one downwind, it often changes from
being VOC-limited to being NOX limited, since there are few sources of nitro-
gen oxides, but often substantial ones of reactive VOCs, outside of cities, and
since the reactions that consume nitrogen oxides occur more quickly than do
those that consume VOCs.
Although hydrocarbons with C RC bonds and aldehydes are the most
reactive types in photochemical smog processes, other VOCs play a signifi-
cant role after the first few hours of a smog episode have passed and the
concentration of free radicals has risen. For this reason, control of emissions
of all VOCs is required in areas with serious photochemical smog problems.
Gasoline, which is a complex mixture of hydrocarbons, is now formulated in
order to reduce its evaporation, since gasoline vapor has been found to con-
tribute significantly to atmospheric concentrations of hydrocarbons.
The control of VOCs in air is discussed in more detail in Chapter 11.
Regulations in California (with Los Angeles especially in mind) limit
the use of hydrocarbon-containing products such as barbeque-grill starter
fluid, household aerosol sprays, and oil-based paints that consist partially of
a hydrocarbon solvent that evaporates into the air as the paint dries. The air
quality in this region has improved because of current emission controls, but
the increase in vehicle-miles driven and the hydrocarbon emissions from
non-transportation sources such as solvents have thus far prevented a more
complete solution. Research has also indicated that any substantial increase
in the emissions of methane to the atmosphere could prolong and intensify
the periods of high ozone in the United States, even though CH4 is usually
considered to be a rather unreactive VOC.
The blue hazes that are observed over forested areas such as the Great
Smoky Mountains in North Carolina and the Blue Mountains in Australia
result from the reaction of natural hydrocarbons in sunlight—in the absence of
Recall that carboxylic acids
much NOX and hence largely without its involvement—to produce carboxylic
have the general formula
RCOOH. acids that condense to form suspended particles of the size that scatter sunlight
and thereby produce a haze. Some of the ozone molecules present above the
forests react with the CRC bond in the natural hydrocarbons to first pro-
duce aldehydes, which then are further oxidized in air to the corresponding
carboxylic acids. Eventually, the acids in the aerosol are attacked by hydroxyl
radicals, which initiate their decomposition, if the haze is not rained out of
the air beforehand.
baird_ch03.indd 90 2/2/12 11:39 AM

3.10 Catalytic Converters for Gasoline Engines

Over the last decades, automobile manufacturers have employed several
strategies to decrease VOC and NOX emissions from their vehicles and
Recall that the reaction of N2
thereby meet governmental standards. One early technique for NOX control with O2 has a high activation
was to lower the temperature of the combustion flame and thereby decrease energy, so its rate is very
the rate of creation of thermal nitric oxide. The temperature lowering was dependent upon
achieved by recirculating a fraction of the engine emissions back through the temperature.
flame.
In recent decades, more complete control of NOX emissions from
gasoline-powered cars and trucks has been achieved using catalytic convert-
ers placed just ahead of the muffler in the vehicle’s exhaust system. The
original two-way converters controlled only carbon-containing gases,
including carbon monoxide, CO, by completing their combustion to carbon Several hundred dollars’
dioxide. However, by use of a surface impregnated with a platinum-rhodium worth of precious metals are
present in each catalytic
catalyst, the modern three-way converter changes nitrogen oxides back to converter.
elemental nitrogen and oxygen using unburned hydrocarbons and the com-
bustion intermediates CO and H2 as reducing agents:
2 NO 9: N2 O2 overall
via, for example,
Reduction
2 NO 2 H2 9: N2 2 H2O
PROBLEM 3-7
Write and balance reactions in which NO is converted to N2 (a) by CO, and

(b) by C6H14. [Hint: The other reaction product is CO2, plus H2O in the lat-
ter case.] ●
The carbon-containing gases in the exhaust are catalytically oxidized

almost completely to CO2 and water by the oxygen that is present:
2 CO O2 9: 2 CO2
CnHm (n m/4) O2 9: n CO2 m/2 H2O
Oxidation
CH2O O2 9: CO2 H2O
The catalyst is dispersed as very tiny crystallites, initially less than 10 nm
in size. Oxygen sensors in the vehicle’s exhaust system are monitored by a
computer chip that controls the intake air/fuel ratio of the engine to the stoi-
chiometric amount required by the fuel in order to ensure a high level of con-
version of the pollutants. The whole process is illustrated in Figure 3-9a. If the
air/fuel mix is not very close to the stoichiometric ratio, the warmed catalyst
will not be effective for reduction (if there is too much air), causing nitrogen
oxides will be emitted into the air, or for oxidation (if there is too little air),
causing CO and hydrocarbons to be emitted, as illustrated in Figure 3-9b.
baird_ch03.indd 91 2/2/12 11:39 AM

(a) (b)
100
Catalytic 90
converter Hydrocarbons
Exhaust from 80
Conversion (percent)
motor
70
Catalytic converter
60
Muffler 50
Tailpipe 40
Exhaust 30
Platinum to tailpipe CO NOX
20
Rhodium 10
Porous
ceramic
0
coating <1 Rich 1.0 Lean >1
(excess fuel) (excess air)
Air/fuel ratio
FIGURE 3-9 (a) Modern catalytic converter for automobiles, with its position in the exhaust
system indicated. [Source: L. A. Bloomfield, “Catalytic Converter,” Scientific American (February 2000): 108.]
(b) Efficiency in conversion of catalytic converter versus air/fuel ratio. [Source: B. Harrison,
“Emission Control,” Education in Chemistry 37 (2000): 127.]
reduction
N2 NO
catalytic
converter
processes
CO
oxidation
CnHm CO2 ⫹ H2O
CH2O
Some progress has been reported in the use of less-valuable metals, such as
copper and chromium, instead of the expensive platinum-group metals as cata-
lysts in catalytic converters. Although the metals are recycled from old con-
verters, a portion is inevitably lost in the process. Scientists have expressed
concern about the environmental problem of widely broadcasting the tiny
particles of platinum, palladium, and rhodium that are lost from the converters
themselves during their operation.
The catalyst that reduces nitric oxide to nitrogen also reduces sulfur
dioxide, SO2, to hydrogen sulfide, H2S. The emitted gases include H2S and
other reduced sulfur compounds, which collectively often give vehicle emis-
sions their characteristic odor of rotten eggs. In addition, the small amounts
of sulfur-containing molecules in gasoline—and diesel fuel—can partially
deactivate catalytic converters if sulfate particles produced from them
baird_ch03.indd 92 2/2/12 11:39 AM

during the gasoline’s combustion become attached to and thereby cover the
sites of the catalyst metal, deactivating them. The maximum annual average
sulfur levels in gasoline, amounting to several hundred parts per million in
the past, have been reduced to 30 ppm in both the United States and
Canada, and to 10 ppm in the European Union. By contrast, the maximum
sulfur in gasoline for India’s cities is 150 ppm, though there are plans to
lower it to 50 ppm in the future.
The sulfur is removed from gasoline during refining, usually by hydrode-
sulfurization, itself a catalytic process, which reacts organic sulfur-containing
molecules in the gasoline with hydrogen gas, H2, to produce hydrogen sul-
fide, which then is removed. Alternatively, the sulfur-containing molecules
may be removed from the fuel by absorbing them during the refining
process.
In the first few minutes after a vehicle’s engine has been started up, the
catalysts are cold, so the converters cannot operate effectively and there are
bursts of emissions from the tailpipe. Indeed, approximately 80% of all the
emissions from converter-equipped cars are produced in the first few minutes
after starting. Once an engine has warmed up and the catalysts have been
heated to about 300°C by engine exhaust, three-way catalysts convert
80–90% of the hydrocarbons, CO, and NOX to innocuous substances before
the exhaust gases are released into the atmosphere. However, fuel-rich mix-
tures are fed to the engine in the first minute or so after the vehicle engine
is started, and also when high acceleration occurs, so carbon monoxide and
unburned hydrocarbons are emitted directly into the air under these oxygen-
starved conditions.
Research and development is underway to develop catalytic converters
that would convert start-up emissions so that these are not released into the
air. Various approaches being investigated include
• devising a converter that will operate at lower temperatures or that can
be preheated so it begins to operate immediately,
• storing pollutants until the engine and converter are heated, and
• recirculating engine exhaust through the engine until the reactions are
more complete.
Older cars (with no converters or just two-way converters) still on the road
continue to pollute the atmosphere with nitrogen oxides even during their
normal operation.
The maximum amounts of emissions that can legally be released from
Methane is much slower
light-duty motor vehicles such as cars have gradually been decreased in
to react than are other
order to improve air quality. The U.S. EPA sets regulations for the maxi- hydrocarbons, so its
mum emissions per mile of CO, NOX, total and non-methane hydrocarbons emissions are often excluded
for gasoline-powered vehicles. Some governments have recently instituted from regulations.
mandatory inspections of exhaust systems to ensure that they continue to
operate properly.
baird_ch03.indd 93 2/2/12 11:40 AM

0.1
0.075
Fraction of total CO
0.05
0.025
0.0
’71 ’72 ’73 ’74 ’75 ’76 ’77 ’78 ’79 ’80 ’81 ’82 ’83 ’84 ’85 ’86 ’87 ’88 ’89 ’90 ’91 ’92 ’93 ’94 ’95 ’96 ’97
Model year
FIGURE 3-10 Fleet-weighted CO contribution of vehicles by model year in mid-1990s

Denver, Colorado, traffic analysis. Light green represents vehicles rated “good” in terms of their
CO emission levels, gray represents vehicles rated “fair,” and dark green those rated “poor.”
[Source: G. A. Bishop et al., “Drive-By Motor Vehicle Emissions: Immediate Feedback in Reducing Air
Pollution,” Environ. Sci. Technol. 34 (2000): 1110.]
Vehicles whose catalytic converters have been damaged or tampered with

produce most of the emissions: typically, 50% of the hydrocarbons and carbon
monoxide are released from 10% of the cars on the road. For example, a study of
soot emissions from cars in The Netherlands established that 5% of vehicles
accounted for 43% of pollution. A mid-1990s survey of carbon monoxide emitted
by passing traffic in Denver, Colorado produced the results shown in Figure 3-10.
The great majority of Denver’s vehicles of ages up to about 12 years were rated
“good” (light green in the figure) in terms of their control of tailpipe emissions.
Most of the carbon monoxide came from cars 6–12 years old (Figure 3-10),
because they were so numerous and because of the presence in that fleet of cars
with “poor” or “fair” emission levels (dark green and gray in Figure 3-10, respec-
tively). In recent decades, the gradual deterioration of catalytic converters is less
pronounced, so the occurrence of such high emitters is now far less common.
3.11 Air Quality Standards

The legislated Air Quality Standards for the common, important air pollut-
ants are listed in Table 3-1. Different jurisdictions differ slightly in the maxi-
mum concentrations they permit; usually an area is considered to be in
compliance if these maxima are only rarely exceeded. Notice that for several
pollutants different values are listed depending upon the time period over
which the concentration occurs, the assumption being that human health
can tolerate a higher concentration of the pollutant for a short period.
baird_ch03.indd 94 2/2/12 11:40 AM

TABLE 3-1 Air Quality Standards, in ppm, for Gases

Gas WHO USA Canada EU Australia China India
Ozone, O3 8 hr 0.051 0.075 — 0.061 (0.08 over 4 hr) — 0.051
1 hr — — 0.082 — 0.10 0.061–0.10 0.092
Carbon monoxide, — 9 13 9 9 (3.5–5.3 5.3
CO 8 hr over 1 day)
1 hr 35 31 3.5
Nitrogen dioxide, 0.11 0.10 0.21 0.11 0.12 — —
NO2 1 hr
1 yr 0.021 0.053 0.053 0.021 0.03 0.021–0.042 0.021
Sulfur dioxide, (0.19 for 0.075 0.33 0.13 0.20 — —
SO2, 1 hr 10 minutes)
24 hr 0.008 0.14 0.115 0.05 0.08 0.019–0.096 0.031
1 yr — 0.03 0.023 — 0.02 0.008–0.039 0.019
Note: Since all listed species are gases, the ppm scale has the moles/moles basis, equivalent to
volume/volume.
The U.S. EPA has traced the history of air quality improvement in the
United States over the last three decades (www.epa.gov/airtrends). For
example, the concentration of carbon monoxide over many areas exceeded
the 9-ppm maximum in 1980, but by 1990 there were few exceedences, and
nowadays the national average is 2 ppm. The decrease in NO2 and SO2 con-
centrations have been also been continuous but in a less dramatic fashion,
although almost all sites were always in compliance. However, improvement
in average ozone levels has been much harder to achieve, with many of the
monitoring sites still not in compliance and the national average barely
meeting the quality standard even in the late 2000s.
The control over the past half-century of carbon monoxide levels in urban
areas of developed countries has been one of the real success stories in environ-
mental management. Most of the reduction has resulted from the use of cata-
lytic converters on vehicles, from the ever-tightening regulations on vehicular
emissions, and from the natural continuing increase in the fraction of vehicles
built after standards had been tightened. The introduction of oxygenated sub-
stances, which are hydrocarbons in which some of the atoms have been
replaced by oxygen, into American gasoline has also reduced CO emissions
from vehicles (as will be discussed further in Chapter 7).
Average new-vehicle emissions before any emission controls were intro-
duced in the United States were about 38 g CO km1, compared to the present
standard of 1.5 g km1. Generally speaking, carbon monoxide emissions from
cars are greatest from cold engines (and cold catalytic converters) and when
the vehicle has an increased load due to rapid acceleration or climbing a hill,
baird_ch03.indd 95 2/2/12 11:40 AM

since under these conditions, a rich fuel mix supplies insufficient oxygen to
completely oxidize the gasoline.
There are some cities in developed countries that still are vulnerable to
CO concentration exceedences in winter due to meteorological and topologi-
cal conditions. The temperature inversions in Fairbanks, Alaska, for example,
produce several days each winter with high carbon monoxide levels. People
such as traffic police who work outdoors in areas of high vehicular traffic can
be exposed to elevated CO levels for long periods.
In the past, emission standards were applied only to passenger vehicles.
However, starting in 2004, new U.S. regulations required for the first time that
gasoline-powered sport-utility vehicles (SUVs)—which now account for about
half of new-vehicle sales—and light trucks also meet emission standards.
Motorcycles, and the three-wheeled tuk-tuk taxis common in Asia, are
gasoline powered and their emissions, especially of CO and unburned hydro-
carbons, make substantial contributions to air pollution. In a recent study in
Switzerland, scooters and motorcycles (some fitted with catalytic converters)
were found to emit more CO and hydrocarbons in urban driving, and signifi-
cantly more NOX on the highway, per kilometer travelled, than cars.
In general, most areas of most developed countries now meet their current
air quality standards most of the time. This result represents a major achieve-
ment in an important environmental problem; without emission regulations
and devices put into place over the last few decades, air quality, especially in
urban areas of these countries, would have worsened considerably with the
increase in the number of vehicles and the use of electricity generated by
fossil-fuel combustion. In this respect at least, the continuing use of fossil
fuels has become sustainable by regulations and technology formulated as a
result of the systems analysis of the chemistry underlying air pollution discov-
ered by chemical research.
Unfortunately, air quality in the urban areas of many developing countries
has generally deteriorated in recent times; it will be a major challenge for
these areas to institute controls to clean up their air. India in 2009 updated
its national ambient Air Quality Standards, which in most cases are more
stringent than EU values. China uses a three-grade system for air quality
standards—hence the ranges quoted in Table 3-1. About half its cities met
its intermediate standards in 2005.
3.12 Catalytic Converters for Diesel Engines

Most trucks and buses are powered by diesel engines, and similarly for half
the cars in Europe and many regions elsewhere outside North America. The
catalytic converters used on vehicles with diesel engines in the past were
much less effective than those on gasoline-powered vehicles. They typi-
cally removed only about half the gaseous hydrocarbon emissions, compared
to 80–90% removal for gasoline engine emissions. This difference was due to
the less-active catalyst formulations that had to be used with diesels because
baird_ch03.indd 96 2/2/12 11:40 AM

of the high sulfur content of diesel fuel; more-active catalysts would have
oxidized the sulfur dioxide gas to sulfate particles, which would have covered
the catalyst surface and rendered it ineffective. Much more effective catalytic
converters are now being installed on diesel equipment for use with low-
sulfur fuel. In addition, the loss of engine exhaust gases and particles to the
air—including that inside the vehicle—through crankcase emissions is being
eliminated by rerouting the emissions back into the engine.
Catalytic converters used in the past for diesel engines did not convert
Fuel economy is maximized
NOX since diesel engines are operated “fuel lean,” i.e., with excess oxygen pres- by running the engine under
ent, and hence the required chemically reducing conditions for NOX control lean conditions.
did not exist. However, lowering the engine operating temperature by recircu-
lating some of the exhaust gases through the engine reduces the amount of
NOX produced, as was also done in the past with automobiles, as mentioned
above.
In one modern scheme for NOX removal from diesel exhaust, the gas is
first completely oxidized to NO2—as CO and hydrocarbons are oxidized with
the engine running under “lean” conditions, i.e., with excess air, most of the
time. The NO2 is subsequently passed over an absorber such as barium oxide,
BaO, on which it is temporarily stored as barium nitrate, Ba(NO3)2. Periodi-
cally, when the absorber becomes saturated, the vehicle’s computer system
temporarily switches conditions to fuel-rich, at which time unburned diesel
fuel passes over the stored NOX, creating reducing conditions and thereby
promoting the catalytic reduction of NOX to N2.
A completely different scheme has been introduced by Mercedes-Benz Urea is resupplied to the
and BMW for some of their diesel cars and trucks. Each vehicle carries a sup- vehicle’s storage when it is
serviced. The structural
ply of the reducing agent urea, CO(NH2)2. This substance (heated, if neces-
formula for urea is
sary, in cold weather) is injected slowly into a catalyst to react with NOX, ORC(NH2)2.
converting the mixture to nitrogen, water, and carbon dioxide.
PROBLEM 3-8
Deduce the balanced redox equation that converts urea and nitric oxide into
N2, CO2, and water. [Hint: Assume for simplicity that the carbon is 4 in
both reactant and product. Note that the techniques from introductory
chemistry for assigning oxidation numbers and for balancing redox equations
are summarized in the Appendix.] ●
New emission regulations in North America demand substantial reduc-

tions in NOX emissions from diesel-powered vehicles. The U.S. EPA has also
proposed that train locomotives and ships powered by diesel should also be
forced to reduce substantially their emission of nitrogen oxides.
In addition to CO, hydrocarbon, NOX, and SO2 gases, diesel-engine
exhaust also includes significant quantities of solid and liquid particles, the
maximum emissions of which per mile is regulated in the United States. The
liquid particles consist of unburned fuel and lubricating oil, plus some sulfuric
baird_ch03.indd 97 2/2/12 11:40 AM

acid produced from sulfur in the fuel. The catalytic converters formerly used on
diesel-engine vehicles were designed to oxidize the carbon-containing gases
and liquids without oxidizing the SO2 further to sulfuric acid and sulfates.
Diesel fuel intended for new on-road vehicles in the United States and
Canada had its maximum allowed sulfur level drop from 500 ppm to a maxi-
mum of 30 ppm sulfur for low-sulfur diesel fuel and in 2010 to 15 ppm S for
ultra-low-sulfur diesel fuel. The maximum has been lowered to 50 ppm in the
European Union, which is the target also for India, although its current limit
is set at 150 ppm. Lowering the sulfur level in diesel fuel will also reduce
particle emissions to some extent. Ironically, some of the soot carbon reacts
with nitrogen dioxide in the exhaust gas to oxidize it to gases:
C(s) NO2 9: CO NO
A filter—sometimes known as a particle trap—is required to achieve a
suitable reduction in diesel exhaust particles. The traps can physically
remove up to 90% of small-particle emissions, thus preventing them from
escaping into the air from the exhaust system of light-duty diesel vehicles. In
order to prevent a buildup of solids, which would restrict engine exhaust flow
or melt the trap, the system is designed so that the soot will ignite and burn
away once a temperature of at least 500°C is attained. Alternatively, tiny
amounts of a metal catalyst compound containing iron or copper are added
to lower the temperature at which ignition will occur and assure more con-
tinuous regeneration of the filter. Eventually the filter requires cleaning since
nonorganic components of the exhaust build up over time.
Scientists and engineers currently are developing a new type of internal
combustion engine that combines the best aspects of gasoline and diesel
technologies. In the homogeneous charge compression ignition (HCCI) engine,
the fuel and the air are well mixed before ignition, thereby preventing forma-
tion of soot particles, as occurs in diesel engines. High compression of the air/
fuel mix allows combustion to begin at many locations in the cylinder, and
produces a much greater efficiency than in gasoline engines, thereby reduc-
ing CO2 emissions. Since the engine is run with an even larger excess of air
than in a diesel, and no “hot spots” occur where combustion temperatures are
high, much smaller amounts of NOX than normal are produced.
Eventually, vehicles using internal combustion may well be replaced by
emission-free ones powered by fuel cells. Such a prospect is discussed in
Chapter 7 when we consider various alternative fuels.
3.13 Control of Nitric Oxide Emissions

from Power Plants
Vehicles emit most of the In the United States, large quantities of NOX are emitted currently from
NOX in Mexico City, with vehicles (on-road and off-road) and from electric power plants, and collec-
rather little coming from
power plants.
tively they constitute the majority of the anthropogenic sources of these
gases (see Figure 3-5). In this section, we investigate the processes that are
baird_ch03.indd 98 2/2/12 11:40 AM

in use to decrease the quantity of nitrogen oxides emitted into the air by
power plants.
• To reduce their NOX production, some power plants use special burners
designed to lower the temperature of the flame. Alternatively, the
recirculation of a small fraction of the exhaust gases through the combustion
zone has the same effect, as previously discussed for vehicles.
• Nitric oxide formation in power plants can also be greatly reduced by
having the combustion of the fuel occur in stages. In the first, high-
temperature stage, no excess oxygen is allowed to be present, thus limiting its
ability to react with N2. In the second stage, additional oxygen is supplied to
complete the fuel’s combustion but under lower-temperature conditions, so
that again little NO is produced. Up to half the NO that would be produced
in one-stage combustion is eliminated by this method.
• Other power plants, especially those in Japan and Europe, have been
fitted with large-scale versions of catalytic converters that change NOX
back to N2 before the release of stack gases into the air. The reduction of
NOX to N2 in these selective catalytic reduction systems is accomplished
to 80–95% completion by adding ammonia, NH3, to the cooled gas stream.
This highly reduced compound of nitrogen combines in a redox reaction
with the partially oxidized compound NO to produce N2 gas in the
presence of oxygen:
4 NH3 4 NO O2 9: 4 N2 6 H2O
However, tight control is needed to regulate the addition of ammonia in
order to prevent its inadvertent oxidation to NOX. The catalytic pro-
cess occurs at 250°C to 500°C, depending upon the catalyst used, and is
80% effective. A small amount of unreacted ammonia is emitted into the
air. Urea can also be used as the reducing agent, as in the catalytic convert-
ers on diesel cars (Section 3-12, and Problem 3-8). Indeed, reduction can
be accomplished without expensive catalysts, though with much less effi-
cient nitric oxide removal, by reacting urea with the uncooled gases at
about 900°C. A combination of staged combustion and selective noncata-
lytic reduction can be used to eliminate up to 90% of NOX emissions.
• The wet scrubbing of exhaust gases by an aqueous solution can also be
used to prevent NOX from being emitted into outside air. Since NO itself is
rather insoluble in water and in typical aqueous solutions, half or more of the
NOX must be in the form of the much more soluble NO2 for such techniques
to be effective. Solutions of sodium hydroxide, NaOH, react with equimolar
amounts of NO and NO2 to produce an aqueous solution of sodium nitrite,
NaNO2:
NO NO2 2 NaOH 9: 2 NaNO2 H2O
baird_ch03.indd 99 2/2/12 11:40 AM

PROBLEM 3-9
Deduce the balanced reaction in which ammonia reacts with nitrogen diox-
ide to produce molecular nitrogen and water. Using the balanced equation,
calculate the mass of ammonia that is required to react with 1000 L of air at
27°C and 1 atm pressure containing 10 ppm of NO2. [Hint: Recall from
introductory chemistry that PV nRT, and that a balanced equation indi-
cates the number of moles of the substances that react with each other.] ●
3.14 Future Reductions in Smog-Producing Emissions

Although direct emissions of five (CO, VOCs, SO2, particulate matter, and
lead) of the six major air pollutants in the United States fell significantly
between 1970 and 2000, emissions of NOX grew by 20%, with half that
increase occurring during the 1990s. Since energy consumption grew 45%
and vehicle distances traveled grew 143% in that period, restrictions on
nitrogen oxide emissions have achieved some success in controlling some of
the growth in this pollutant, but not enough to prevent an overall increase.
Emissions of NO from electric power plants, their other major source, have
recently been falling somewhat.
As a consequence of the increase in overall NO emissions, ground-level
ozone concentrations increased in the southern (especially around Houston)
and north-central regions of the United States in the 1990s. The latter effect
can be seen in Figure 3-7, where high ozone levels center around the New
York–Boston area and a few midwestern sites, and somewhat lesser levels cover
most of the East Coast and Midwest, extending into southern Ontario. High
ozone levels have been a problem in Southern California for many decades.
To help reduce the incidence of summertime smog in south-central
Canada and the northeastern United States, the two nations have signed an
Annex to their Air Quality Agreement. The United States was committed to
reduce NOX emissions originating in northern and northeastern states by
35% by 2007, and also to reduce VOC emissions during summer months
when most smog forms in this region. Canada agreed to reduce its NOX emis-
sions from power plants in southern Ontario by 50% by the same date. The
drastic lowering of the allowed sulfur levels in gasoline should assist in the
reduction of NOX from vehicles. Emission standards for SUVs, trucks, and
buses are also being tightened to make them more in line with those for regu-
lar automobiles.
The long blackout of electrical power that occurred in August, 2003 in
eastern North America yielded some interesting information concerning the
contribution of power plants to air pollution in that region. Measurements
over Pennsylvania taken 24 hours after the blackout began found that SO2
levels were down 90%, and ozone levels down about 50%, compared to a
similar hot, sunny day a year earlier, and that visibility increased by about
40 km because haze from particulates had decreased by 70%.
baird_ch03.indd 100 2/2/12 11:40 AM

Green Chemistry: Strategies to Reduce VOCs Emanating from Organic Solvents 101
The Gothenburg Protocol, which controls the release of many pollutants

in Europe, was expected to have reduced NOX emissions there by more than
40% by 2010, compared to 1990 levels. Great Britain—which saw its emis-
sions decline by the late 1990s by almost 40% compared to their peak in the
late 1980s—had to reduce their emissions by another third from 1998 levels based on material in the
by 2010 in order to meet these regulations. European VOC emissions were above sections.
due to drop by 40% according to the protocol.
Green Chemistry: Strategies to Reduce VOCs

Emanating from Organic Solvents
In addition to their role in paints, organic solvents are used in many different
products and processes, in both commercial and household applications.
More than 15 billion kilograms of organic solvents are used worldwide each
year in such areas as the electronics, cleaning, automotive, chemical, mining,
food, and paper industries. These liquids include not only hydrocarbon sol-
vents but also halogenated solvents. Both types of solvents contribute not
only to air pollution as VOCs but also to water pollution (Chapter 11). Some
halogenated solvents contribute to the depletion of the ozone layer, as seen
in Chapter 2.
The following three sections give examples of green chemistry illustrat-
ing different strategies for reducing VOCs and their emissions. The first
illustrates a method for reducing the amount of VOCs in paints, while the
second and third are examples of replacing organic solvents with solvents
that do not produce VOCs.
3.15 Green Chemistry: A Nonvolatile, Reactive

Coalescent for the Reduction of VOCs
in Latex Paints
Paints generally consist of three major components: pigment, binder, and
solvent. The pigment gives the paint color and may be natural or synthetic,
and may be organic or inorganic. The binder, also known as the vehicle
or resin, provides adhesion, binds the pigment, and provides such proper-
ties as toughness, durability, flexibility, and gloss. The primary function of
the solvent is to act as the carrier for the nonvolatile components.
The solvent may be water (in latex or water-based paints) or organic (in
oil-based or alkyd paints). During the course of drying, the solvent evapo-
rates into the surrounding air and is the major source of VOCs from oil-
based paints.
Although oil-based paints have been known for centuries, latex paints
became commercially available only in the 1950s. The introduction of latex
baird_ch03.indd 101 2/2/12 11:40 AM

(a) (b)
O
O HO
O
O OH
FIGURE 3-11 Structures of (a) 2,2,4-trimethyl-1, 3-pentanediol monoisobutyrate (TMB) and
(b) propylene glycol monoester of linoleic acid (Archer RCTM).
paints greatly reduced the amount of VOCs compared to oil-based paints.

Recent, more stringent environmental regulations at the federal and state
levels have led to significant efforts to reduce VOCs even from latex paints
in the United States.
One significant source of VOCs in latex paints is an additive that acts as
a coalescent. The resin in latex paints is composed of very small particles of
an organic polymer suspended in water. Coalescents are organic compounds
that are absorbed by the resin particles and soften or plasticize these particles.
When the paint is spread, the water evaporates and these particles flow
together to form a thin, uniform film that adheres to the surface of the mate-
rial being painted. The paint hardens as the coalescent is slowly emitted into
the atmosphere. Paint contains 2–3% coalescent by mass. Since more than 2
billion liters (600 million gallons) of latex paint are used in the United
States each year, more than 50 million kilograms (120 million pounds) of
coalescents are emitted into the atmosphere annually. Worldwide emissions
of these VOCs are estimated to be more than three times this value.
In 2005, the Archer Daniels Midland Company (ADM)
won a Presidential Green Chemistry Challenge Award for the
development of coalescents (Archer RCTM) that actually bind
through covalent bonds to each other and to the resin, and
O2 thereby become part of the paint film; they are therefore not
emitted as VOCs. Figure 3-11a shows the structure of TMB, a
OH common coalescent, while Figure 3-11b is the structure of the
O coalescent developed by ADM. Both of these ester com-
pounds have low polarities and are thus absorbed by the resin
particles. However, (b) is an ester of propylene glycol and
linoleic acid. Linoleic acid is a major component of linseed oil
and, like linseed oil, it can undergo auto-oxidative cross-
linking in the presence of oxygen due to the carbon–carbon
double bonds present, as illustrated by the prototype reaction
O shown in Figure 3-12.
The oxidized, cross-linked polymer chains have low vapor
pressure and furthermore are absorbed into and bonded to the
FIGURE 3-12 Auto-oxidation cross-linking resin, further decreasing their volatility and ability to be
of an unsaturated system. emitted.
baird_ch03.indd 102 2/2/12 11:40 AM

Traditional coalescents such as TMB are made from petroleum feed-

stocks. Another green feature of the coalescent developed by ADM is that
it can be produced from the renewable bio-feedstocks linoleic acid
and propylene glycol. Linoleic acid is readily available from corn and
sunflower oils, and although propylene glycol has traditionally been pro-
duced from petroleum, it can be formed from glycerin, a by-product of the
synthesis of biodiesel (as we will see in Chapter 7 in another example of
green chemistry).
3.16 Green Chemistry: The Replacement of

Organic Solvents with Supercritical and Liquid
Carbon Dioxide; Development of Surfactants
for This Compound
Discovering solvents with less environmental impact, and even designing
processes that use no solvents at all, are the subjects of many green chemistry
initiatives. Carbon dioxide, CO2, is one solvent that is receiving consider-
able attention as a replacement for traditional organic solvents. Although
carbon dioxide is a gas at room temperature and pressure, it can be liquefied
easily by the application of pressure. In addition to liquid carbon dioxide,
there is considerable interest in supercritical carbon dioxide (a discussion of
supercritical fluids can be found in Box 3-2) as a solvent in the electronics
industry. The decaffeination of coffee and tea with carbon dioxide is a well-
known application of this solvent.
Liquid carbon dioxide is attractive as a solvent due to its low viscosity
and polarity and its wetting ability. Because of its low polarity, carbon diox-
ide is able to dissolve many small organic molecules. However, larger mole-
cules including oils, polymers, waxes, greases, and proteins are generally
insoluble in it. To increase the solubility of compounds in water, surfactants
such as soaps and detergents have been developed which allow this very
polar solvent to dissolve less polar materials such as oils and grease. In an
analogous fashion, surfactants for carbon dioxide have been developed which
increase the range of materials that will dissolve in it.
Joseph DeSimone, of the University of North Carolina and North Caro-
lina State University, earned a Presidential Green Chemistry Challenge
Award in 1997 for his preparation and development of polymeric surfactants
for carbon dioxide. DeSimone is currently the director of the National Sci-
ence Foundation Science and Technology Center for Environmentally
Responsible Solvents and Processes. This center focuses on discovering ways
to replace conventional organic solvents and water with carbon dioxide in a
multitude of processes. An example of a surfactant developed by DeSimone
baird_ch03.indd 103 2/2/12 11:40 AM

BOX 3-2 Supercritical Carbon Dioxide
T he supercritical fluid state of matter is pro-

duced when gases or liquids are subjected
to very high pressures and, in some cases, to
31.3°C, as illustrated in the phase diagram in
Figure 1. Depending upon exactly how much
pressure is applied, the physical properties of
elevated temperatures. At pressures and tem- the supercritical fluid vary between those of a
peratures at or beyond the critical point, separate gas (relatively lower pressures) and those of a
gaseous and liquid phases of a substance no liquid (higher pressures); the variation of prop-
longer exist. Under these conditions, only the erties with P or T is particularly acute near the
supercritical state, with properties that lie critical point. Thus the density of supercritical
between those of a gas and those of a liquid, carbon dioxide varies over a considerable range,
exists. For carbon dioxide, the critical pressure is depending upon how much pressure (beyond
72.9 atm and the critical temperature is only 73 atm) is applied to it
10,000
1000 Solid
Supercritical
fluid
100 Liquid
Pressure (atm)
10
Critical point
1 31°C at 72.8 atm
0.1
0.01
Gas
0.001
–120 –80 –40 0 40 80
Temperature (°C) FIGURE 1 Phase diagram for carbon
dioxide.
is the block copolymer shown in Figure 3-13a. This molecule has nonpolar
regions, which are CO2-philic, and polar regions, which are CO2-phobic.
When dissolved in carbon dioxide, the CO2-philic regions orient themselves
to interact with the surrounding carbon dioxide solvent, while the CO2-
phobic regions aggregate with one another. The overall result is the forma-
tion of a structure know as a micelle (Figure 3-13b). Polar substances that
normally do not dissolve in carbon dioxide will dissolve in the center polar
region of the micelle.
baird_ch03.indd 104 2/2/12 11:40 AM

DeSimone was one of founders of a dry- (a)

cleaning chain that uses liquid carbon dioxide, 999 CH2 9 CH 999 CH2 9 CH 999
along with surfactants that he developed, to
clean clothes. The spent liquid carbon dioxide n C"O m
is drained from the clothes after the wash
O CH2(CF2)6CF3
cycle (in much the same as the wash water in
our washing machines at home is drained off
CO2 -phobic CO2 -philic
after the wash cycle) and the carbon dioxide is chain segment
chain segment
allowed to evaporate by simply reducing the
pressure. The carbon dioxide vapors are then (b)
captured, liquefied by increasing the pressure,
and reused for another wash. Carbon dioxide Carbon dioxide solvent
is plentiful and inexpensive, since it can be
recovered as a by-product from natural gas
wells or ammonia production. Capture of car-
bon dioxide from these processes puts to good
use this compound which would normally be CO2-phobic
released to the atmosphere and contribute to chain segments
global warming (see Chapter 6). By way of
contrast, most dry cleaners in North America
CO2-philic
presently use perchloroethylene, Cl2CRCCl2, chain segments
known as PERC, as the solvent. PERC is a
VOC, since it has a high vapor pressure and
readily escapes into the troposphere if not FIGURE 3-13 A copolymer surfactant for carbon dioxide.
(b) A micelle in liquid carbon dioxide. [Source: M. C. Cann and M. E.
carefully controlled. PERC is also is a ground- Connelly, Real-World Cases in Green Chemistry (Washington, DC: American
water contaminant (see Chapter 11) and is a Chemical Society, 2000).]
suspected human carcinogen.
3.17 Green Chemistry: Using Ionic Liquids to

Replace Organic Solvents: Cellulose, a Naturally
Occurring Polymer Replacement for Petroleum-
Derived Polymers
Cellulose (Figure 3-14) is a polymer of glucose that makes up about 40% of all
organic matter on Earth. About 700 billion tonnes of cellulose exist on Earth,
with another 40 billion tonnes produced each year by plants as the major
component of biomass from atmospheric carbon dioxide and water via photo-
synthesis. This removal of carbon dioxide from the atmosphere helps to miti-
gate some of the global warming caused by anthropogenic emissions of the gas.
Many polymers produced from crude oil are ubiquitous in our everyday
lives, including polyethylene terephthalate (PET), which is found in bever-
age bottles and polyester clothing, polyethylene, which is employed in mak-
ing plastic bags and milk jugs, polyvinyl chloride, which is found as plastic
baird_ch03.indd 105 2/2/12 11:40 AM

FIGURE 3-14 Structure of HO

cellulose. OH
H O
H
OH H
H
H OH
HO
O
H O
H
OH H
H
HO H OH
O
H O
H
OH H
H
H OH
n
HO
O
H O
H
OH H
HO H
H OH
pipes and shower curtains, and polystyrene, which we discussed in the green
chemistry section in Chapter 2. Hundreds of millions of kilograms of these
petrochemical-based polymers are produced each year, requiring as raw mate-
rial approximately 700 million barrels of crude oil. As the price of conven-
tional crude oil increases and the supply declines, a major focus of green
chemistry is the production of organic chemicals, including polymers, from
biomass (see the green chemistry section in Chapter 7). An even more
intriguing opportunity is to use naturally occurring polymers such as cellulose
to replace crude oil in these syntheses.
The use of cellulose is severely limited by its insolubility in water and in
traditional organic solvents. The strong intra- and inter-chain hydrogen
bonding between the numerous hydroxyl groups on the cellulose polymer are
likely the reason for this insolubility, which results in very poor processability
for cellulose. Consequently, only about 0.1 billion tonnes of cellulose has
been used annually as a feedstock for further processing.
In the previous green chemistry section, the replacement of traditional
organic solvents with supercritical and liquid carbon dioxide was discussed.
A very interesting and relatively unknown group of compounds that is of
baird_ch03.indd 106 2/2/12 11:40 AM

growing interest as replacements for

N N Cl
traditional organic solvents are called
room temperature ionic liquids, or just
ionic liquids (ILs). Most ionic com-
pounds have characteristically high
melting points due to their strong net- N AlCl4
work of ionic bonding. For example,
sodium chloride (table salt) has a melt-
ing point of 801°C. In contrast, a few
ionic compounds have melting points O
below or moderately above (100°C) O
room temperature; such compounds are H3C(H2C)12 P
known as (room temperature) ionic liq-
uids. ILs are generally composed of P (CH2)5CH3
bulky ions that have dispersed rather
than localized charges and large nonpo- H3C(H2C)5 (CH2)5CH3
lar groups (Figure 3-15). As a conse-
quence, their oppositely charged ions
have only weak attractive interactions
with one another, which results in the
low melting points of these compounds. F3C
CF2
One very attractive characteristic of
ILs is their very low vapor pressure, in
F2C
contrast to most organic solvents, which N CF2
because of their significant vapor pres-
sures are VOCs and contribute to tropo- O S O
spheric pollution. Because they are
ionic, many ILs are nonvolatile and thus O
their potential to replace VOCs is of
significant interest. Ionic liquids may FIGURE 3-15 Ion pairs in
also be purified and recycled, thereby adding to the green characteristics of four typical ionic liquids.
these solvents. In addition, they are nonflammable, and many are stable up
to 300°C, making them attractive for reactions and processes which require
high temperatures.
Another strong interest of the green chemistry community is the use of
microwave ovens to facilitate chemical processes and reactions. Conven-
tional heat sources—such as heating mantles, Bunsen burners, and oil
baths—heat materials from the outside in, transferring energy (in turn) from
the heat source to the bottom of the reaction vessel, to the solvent inside the
beaker, and finally to the dissolved reactants. In each step, heat energy is lost
to the surroundings as it is transferred. A microwave-absorbing reactant or
solvent, however, can be targeted by microwaves and therefore can be
directly heated by irradiation in a microwave oven or reactor. Thus with
microwave heating the contents may be heated directly without heating the
vessel. Most people have experienced this phenomenon when heating a cup
baird_ch03.indd 107 2/2/12 11:40 AM

of water in a household microwave oven. The water heats quite quickly while
the cup remains relatively cool. Chemists have found that many reactions
and processes can be accelerated in a microwave oven, whose efficiency of
heating has the potential to reduce energy requirements.
In order to heat effectively via a microwave source, a substance must be
polar and/or ionic. ILs heat up very quickly in a microwave since by nature
they are ionic. They can reach temperatures as high as 300°C in 15 sec of
microwave heating.
Robin Rogers and his group at The University of Alabama won a Presi-
dential Green Chemistry Challenge Award in 2005 for their discovery that
certain ILs readily dissolve cellulose when heated with a microwave oven.
The process they developed involves the use of gentle, pulsed microwave
heating in a domestic microwave oven to expedite the dissolution of cellulose
in ILs. Their studies indicate that with the IL 1-butyl-3-methylimidazolium
chloride, they can produce solutions with up to 25% (by mass) cellulose.
H3C
N N
CH3 Cl
There is evidence that the chloride ion in this compound disrupts the
internal hydrogen bonding in the cellulose, thereby leading to dissolution.
The addition of small amounts of water solvates the chloride ions, allowing
the hydrogen bonding of the cellulose to resume. The cellulose then pre-
cipitates from the solution, and can then be deposited as films, membranes,
and fibers.
By dispersing additives in the IL either before or after the dissolution of
cellulose, composite or encapsulated cellulose-based materials can be formed
when the polymer is regenerated. For example, laccase, an enzyme found in
fungi that degrades polyphenolic compounds, has been encapsulated in a
cellulose support without loss of its activity. The enzyme, when supported on
a cellulose film, can be immersed in an aqueous reaction environment and
easily removed at the end of the reaction by removing the film, which can
then be reused.
The Rogers group has also successfully suspended many other materials
in cellulose. These include dyes that can be used to detect metals such as
mercury, and magnetite (Fe3O4), which produces a composite with uniform
magnetic properties. Using this method, cellulose can be combined with
other polymers to produce blends. When mixed with polypropylene, a com-
posite that has excellent tear properties is formed. The use of this material
for packaging offers significant promise. Encapsulation of medically active
compounds along with magnetic materials has the potential to produce
microcapsules that can be directed to specific parts of the body. In addition,
baird_ch03.indd 108 2/2/12 11:40 AM

Improving Air Quality: Sulfur-Based Emissions 109
titanium dioxide infusion into cellulose fibers can produce clothing and bed- Green Chemistry
ding with antibacterial properties. The development of cellulose-based mate- Questions 1–7 at the end
rials has the potential to produce new materials with novel characteristics of the chapter are based on
that require less use of petroleum than conventional polymers. the three cases above.
Improving Air Quality: Sulfur-Based Emissions

On a global scale, most SO2 is produced by volcanoes and by the oxidation
of various sulfur-containing gases produced by the decomposition of
plants. Because this natural sulfur dioxide is mainly emitted high into the
atmosphere or far from populated centers, the background concentration of the
gas in clean air is quite small, about 1 ppb. However, a sizable additional
amount of sulfur dioxide is emitted into ground-level air, particularly over land
masses in the Northern Hemisphere, due to industrial activities.
3.18 Sulfur Dioxide and Hydrogen Sulfide

Sources and Abatement
Globally, the main anthropogenic source of SO2 is the combustion of coal,
a solid which, depending upon the geographic area from which it is mined,
contains 1 to 6% sulfur. All the sulfur present in coal when it is combusted
is oxidized to sulfur dioxide and mixed with the carbon dioxide and other
emission gases. In most countries, including the United States, the major use
of coal is to generate electricity. Indeed, electric generation accounts for the
majority of SO2 emissions in the United States (Figure 3-16).

Off-road vehicles Solvents Off-road vehicles Solvents

3% <1% 5% <1%
Other
On-road 1% On-road vehicles
Other
vehicles 1%
Industrial <1%
1% Electric
20%
generating
Nonindustrial units
4% 23%
Electric Nonindustrial
generation 2% Industrial
71% 70%
FIGURE 3-16 Anthropogenic SO2 emissions by sources in North America in 2006.

[Source: International Joint Commission, Canada–United States Air Quality Agreement: 2008 Progress Report,
Washington, D.C. and Ottawa, Ontario, 2008.]
baird_ch03.indd 109 2/2/12 11:40 AM

Approximately half of the sulfur is trapped as inclusions in the incom-

bustible mineral content of the coal. If the coal is pulverized before combus-
tion, much of this type of sulfur can be mechanically removed, as discussed
in the next section. The remaining sulfur, which usually amounts to about
1% of the coal’s mass, is bonded in the complex organic structure of the solid
and cannot be removed without expensive processing that breaks covalent
bonds.
Large point sources—individual sites that emit large amounts of a
pollutant—of SO2 are also associated with the nonferrous smelting indus-
try, where ores are converted into free metals. Many valuable and useful met-
als, such as copper and nickel, occur in nature as ores containing the sulfide
ion, S2. In the first stage of their conversion to the free metals, they were usu-
ally “roasted” in air to remove the sulfur; this was converted to SO2 and tradi-
tionally was released into the air. For example,
2 NiS(s) 3 O2(g) 9: 2 NiO(s) 2 SO2(g)
Ores such as copper sulfide can be smelted in a process that uses pure
oxygen forced into the smelting chamber, and the very concentrated sulfur
dioxide that is obtained from the reaction can be readily extracted, liquefied,
and sold as a by-product rather than being released into the air. On the other
hand, the SO2 concentration in the waste gases from conventional roasting
processes (such as that used for nickel) is high. Consequently, it is feasible to
pass the gas over an oxidation catalyst that converts much of the SO2 to
sulfur trioxide, to which water can be added to produce commercial concen-
trated sulfuric acid, H2SO4:
2 SO2(g) O2(g) 9: 2 SO3(g)
SO3(g) H2O(aq) 9: H2SO4(aq)
The latter reaction (which represents only initial reactants and end-product)
is in fact accomplished in two steps (not shown) in order to ensure that none
of the substances escape into the environment: first the trioxide is combined
with sulfuric acid, and then water is added to the resulting solution.
The alternative to sulfur dioxide control—to simply allow the pollutant
gas from smelting to be emitted into the air—can cause devastation from SO2
to the plant life in the surrounding area unless extremely high smokestacks are
used. The tallest such stacks in the world are located at Sudbury, Ontario, and
reach 400 m high. However, using tall stacks simply solves a local SO2 prob-
lem at the expense of creating a problem downwind. For example, emissions
from mainland North America can sometimes be detected in Greenland.
Sulfur occurs to the extent of a few percent in crude oil (with higher
concentrations in tar sands and shale oil), but is reduced to the level of a few
tens or hundreds of ppm in gasoline and diesel fuel. Some sulfur dioxide is
emitted into air directly as SO2 or indirectly as H2S by the petroleum industry
when oil is refined and natural gas is cleaned before delivery. The huge
baird_ch03.indd 110 2/2/12 11:40 AM

increase in usage of gasoline and diesel fuel over the past few decades has not
produced the corresponding increase in SO2 into the air since a greater and
greater fraction of the sulfur has been removed by refineries; indeed, the
amount of sulfur dioxide equivalent removed by refineries now exceeds that
emitted into the air.
The predominant component in natural gas wells is sometimes H2S
rather than CH4! The substantial amounts of hydrogen sulfide obtained from
its removal from oil and natural gas are often converted to solid, elemental
sulfur, an environmentally benign substance, using the gas-phase process
called the Claus reaction:
2 H2S SO2 9: 3 S 2 H2O
One-third of the molar amount of hydrogen sulfide extracted from the fos-
sil fuel is first combusted to sulfur dioxide to provide the other reactant for
this process. Huge amounts of elemental sulfur are produced by sulfur
removal, especially from natural gas. Notice the analogy between the Claus
reaction and the selective catalytic reduction process for nitric oxide con-
trol (Section 3-13): they both involve the reaction together of the oxidized
and reduced forms of an element (N or S) to form the innocuous elemental
form.
It is very important to remove hydrogen sulfide from gases before
their dispersal in air because it is a highly poisonous substance, more so
than sulfur dioxide. The concentration of H2S sometimes becomes elevated in
the area surrounding natural gas wells during flaring—the burning off of gas that
cannot be immediately captured. Flaring burns only about 60% of the hydrogen
sulfide content of the gas, so the remainder becomes dispersed into the sur-
rounding air. Hydrogen sulfide is also a common pollutant in the air emissions
from pulp and paper mills.
In addition to H2S, several other smelly gases containing sulfur in a highly The word reduced is not
reduced state are emitted as air pollutants in petrochemical processes; these used here to denote a
include CH3SH, (CH3)2S, and CH3SSCH3. The term total reduced sulfur is decrease in sulfur emissions,
but rather to the oxidation
used to refer to the total concentration of sulfur from H2S and these three number of the sulfur.
compounds.
3.19 Clean Coal: Reducing Sulfur Dioxide Emissions

from Power Plants
When the sulfur dioxide present in exhaust gases is dilute, as in the case of
power-plant emissions, its extraction by oxidation is not feasible. Instead, the
SO2 gas is removed by an acid–base reaction between it and calcium carbon- Reaction of water with the
CaO produces the basic
ate (limestone), CaCO3, or calcium oxide (lime), CaO, in the form of wet, hydroxide Ca(OH)2.
crushed solid.
The emitted gases are either passed through a slurry of the wet solid, or
bombarded by jets of the slurry. In some applications called dry scrubbing, a
very fine spray of aqueous calcium oxide or calcium carbonate is used to trap
baird_ch03.indd 111 2/2/12 11:40 AM

the sulfur dioxide from the emission gases; its water component evaporates
upon contact with the hot emission gases.
Almost all the sulfur dioxide gas can be removed by such scrubber pro-
cesses, more formally known as flue-gas desulfurization. In some operations,
notably in Japan and Germany, the product is fully oxidized by reaction with
air, and the resulting calcium sulfate, CaSO4, is dewatered and sold as gyp-
sum. Usually, the product is a mixture of calcium sulfite, CaSO3, and cal-
cium sulfate as a slurry which is then partially dewatered or as a dry solid if
granular calcium oxide was used. It is then usually buried in a landfill. The
reactions with calcium carbonate are
CaCO3 SO2 9: CaSO3 CO2

2 CaSO3 O2 9: 2 CaSO4
Alternatively, the sulfur dioxide can be captured by the use of slurries of a

base such as sodium sulfite or magnesium oxide or amine salts, and these reac-
tant compounds and concentrated SO2 gas later regenerated by thermally
decomposing the product. Wet scrubbing removes more of the SO2 (90%)
than does dry scrubbing (70%), so the latter technique is useful mainly
with low-sulfur coals.
Recently, clean coal technologies have been developed to use coal in
ways that are cleaner and often more energy efficient than those employed
in the past. In the various technologies, the cleaning can occur precombus-
tion, during combustion, postcombustion, or by conversion of the coal to
another fuel.
• In precombustion cleaning, the coal has some of the sulfur
associated with its mineral content—which exists usually in the form
of pyritic sulfur, FeS2—removed so it cannot subsequently produce sulfur
dioxide. The coal first is ground to a very small particle size, effectively into
separate mineral particles and carbon particles. Since they have different
densities, the two types of particles can be separated by mixing the pulverized
solid in a liquid of intermediate density—namely water—and allowing the
fuel portion to rise to the top, where it can be skimmed off, dried, and then
combusted. Up to half the pyritic sulfur is removed from the coal in this way.
As an alternative to such physical cleaning, biological or chemical
methods can be employed. For example, bacteria cultured to eat the
organic sulfur in coal can be utilized. Chemically, the sulfur can be leached
from coal with a hot sodium or potassium caustic solution.
• In combustion cleaning, the combustion conditions can be modified
so as to reduce the formation of pollutants, and/or pollutant-absorbing
substances are injected into the fuel to capture pollutants as they form.
In fluidized-bed combustion, pulverized coal and limestone (CaCO3) are
mixed and then suspended on jets of air (“fluidized”) in the combustion
chamber. About half the sulfur dioxide is thereby captured in solid form as
baird_ch03.indd 112 2/2/12 11:40 AM

calcium sulfite and sulfate before the gas can escape. This procedure
allows for much-reduced combustion temperatures and therefore also
greatly reduces the amount of nitrogen oxides that are formed and
released. Fluidized-bed combustion finds limited use since its capture
efficiency is not high enough to meet emission standards from the
combustion of high-sulfur coal.
• Some of the advanced techniques used in postcombustion cleaning—such
as the use of granular calcium oxide or calcium carbonate or sodium sulfite
solutions—have already been described. In the SNOX process developed in
Europe, cooled flue gases are mixed with ammonia gas to remove the nitric
oxide by its catalytic reduction to molecular nitrogen (by the reaction
discussed in Section 3.13). The resulting gas is reheated and the sulfur
dioxide oxidized catalytically to sulfur trioxide, which subsequently is
hydrated by water to sulfuric acid, condensed, and removed.
In coal conversion, the fuel is first gasified by reaction with steam, as will
be described in Chapter 7. The gas mixture is cleaned of pollutants, and the
purified gas is then burned in a gas turbine that generates electricity. The
waste heat of the combustion gases is used to produce steam for a conven-
tional turbine and thus generate more electricity. Alternatively, the gasified
coal can be converted into liquid fuels suitable for vehicular use.
Sulfur dioxide emissions from power plants can also be minimized by
burning oil, natural gas, or low-sulfur coal for the fuel, though they usually
are more expensive than is high-sulfur coal.
PROBLEM 3-10
What mass of calcium carbonate is required to react with the sulfur dioxide
that is produced by burning one tonne (1000 kg) of coal that contains 5.0%
sulfur by mass? ●
PROBLEM 3-11
Write the balanced reaction whereby sodium hydroxide can be used to scrub
sulfur dioxide from exhaust gases by a reaction that produces water and
sodium sulfite, Na2SO3. What substance would you have to react with this
solution to produce calcium sulfite and regenerate the sodium hydroxide?
Write the balanced equation for the latter process, and deduce the net reac-
tion for the cycle. ●
3.20 Governmental Goals for Reducing

Sulfur Dioxide Emissions
The history, by region, of anthropogenic SO2 emissions into the air over the
past century and a half is shown in Figure 3-17. Europe—including the eastern
baird_ch03.indd 113 2/2/12 11:40 AM

FIGURE 3-17 Global

anthropogenic SO2 50,000
emissions by region. [Source: Europe
S. J. Smith et al., Atmospheric Former Soviet Union
Chemistry and Physics
40,000 East Asia (including China)
10 (2010): 16111–16151.]
Emissions (Gg SO2)

North America
Middle East
30,000
20,000
10,000
0
1850 1900 1950 2000
Year
countries—was the largest source of SO2 emissions through the second half of
the twentieth century, but their contribution—along with that from North
America, which had been the second-largest emitter—have greatly dimin-
ished. East Asia became the leading contributor of the emissions in the 1990s,
and continues to be so today.
The global total of SO2 emissions (not shown; equal to the sum of all the
curves in Figure 3-17 plus smaller contributions from other regions) reached
its maximum in the 1970s and had been steadily declining from then until
the turn of the millennium, but now is again increasing. This recent increase
has occurred due to the rise in emissions from coal burning, which has always
been the dominant source. Petroleum production and combustion, including
emissions from fueling international shipping, is still globally the second
largest contributor of SO2 emissions, with metal smelting the third largest.
The distribution of anthropogenic SO2 emissions by sector for the
United States and Canada is shown in the pie charts in Figure 3-16; emis-
sions for the United States are dominated by electricity generation (coal
burning) and those for Canada by smelting (classed as “Industrial” on the
graphs). Because of federal regulations, the amount of sulfur dioxide emitted
into the air in North America has fallen substantially from its peak level in
1973.
The 1991 Air Quality Accord between the United States and Canada
required both countries to reduce substantially their sulfur dioxide emissions
beyond those of previous laws and agreements. Such emissions in the United
States are restricted in accordance with the Clean Air Act and its amendments.
baird_ch03.indd 114 2/2/12 11:40 AM

The average concentration of sulfur dioxide in air over the United States fell
from 13.2 ppb to 7.5 ppb from 1975 to 1991, and further to 3.3 ppm by 2008.
Whereas Phase I (1995 deadline) of the Clean Air Act imposed controls on
only the largest coal-fired plants, those of Phase II, which began in 2000,
imposed more stringent requirements, and applies to almost all plants. There
is an SO2 tonnage limit for each power plant that emits this gas, based upon
the power it produces, and a cap on overall national emissions as well. By 2009,
the SO2 emissions in the United States had dropped by 67% compared to 1980
levels.
The reductions in sulfur dioxide emissions by power plants in the U.S.
Midwest has been achieved at lower-than-expected cost, due in part to the
availability of cheap, low-sulfur coal (1% S, versus more than 3% S in the
high-sulfur coal used previously) and inexpensive scrubbers, and in part to
the implementation of a system of tradable emission permits. This permit
system, in operation since the early 1980s, allows industries to buy emission
allowances if they need to exceed their allowed levels, or to sell excess allow-
ances on the open market (through the Chicago Board of Trade) if they do
not need their whole allowance. A similar program has been initiated for
nitrogen oxide emissions.
In Europe, the EU issued a directive in 1988 specifying reductions from
large power plants of 50–70% of their SO2 emissions from 1980 levels by
2003. This cutback was achieved mainly by switching from coal to natural
gas in power stations, and by the use of low-sulfur coal and the scrubbing of
emissions in facilities where coal was still burned. According to the 1999
Gothenburg Protocol, Europe’s sulfur dioxide emissions are to be cut beyond
1990 levels by another 63% by 2020.
Much of the increase in global SO2 emissions in the early 2000s was due
largely to those from China (included in East Asia in Figure 3-17), which
increased by 53% from 2000 to 2006.This was due in large part to the expan-
sion of coal burning, which supplies about two-thirds of China’s energy.
Emissions from this source began to decline around 2006 when SO2 began to
be removed by flue-gas desulfurization—more than half its power plants now
have scrubbers—and by closure of many small coal-fired power plants. The
decline was reflected in atmospheric SO2 concentrations above eastern
China, which began to decrease after 2007. Nevertheless, China is now the
world’s leading source of the gas.
Japan initiated tight controls on SO2 emissions in the 1970s, and by Ironically, volcanic releases
1980 their power plants had almost eliminated such emissions by the wide- of the gas from Japan
outrank its anthropogenic
spread installation of scrubbers. The rate of emissions from Japan and from sources.
South Korea both now continue in gradual decline.
By the turn of the millennium, the high rate of SO2 emissions from the
former Soviet Union had declined by half (Figure 3-17), presumably due more
to economic problems than to intentional controls, but have begun to increase
again.
baird_ch03.indd 115 2/2/12 11:40 AM

3.21 The Oxidation of Sulfur Dioxide

in Suspended Water Droplets
Although some sulfur dioxide in air is oxidized by gas-phase reactions,
most of it is converted to sulfuric acid after it has dissolved in tiny sus-
pended water droplets present in clouds, mists, etc. The uncatalyzed oxida-
tion of dissolved aqueous SO2 by dissolved O2 proceeds at very slow rate
unless a catalyst such as Fe3 or the ions of other transition metals are also
present in the droplets.
The most important oxidizing agents in the airborne droplets, though
present only in tiny concentrations, are not molecular oxygen but the dis-
solved atmospheric gases ozone and hydrogen peroxide, H2O2. The con-
centration of these two pollutants is much greater in air masses undergoing
photochemical smog than in clean air.
In general, the concentration of a dissolved gas in the liquid phase can
be determined by considering the equilibrium between its two forms. Thus
for hydrogen peroxide, we have
0!
H2O2 (g) !1 H2O2(aq)
The useful form of the equilibrium constant for such processes is the Henry’s
law constant, KH, which is equal to the concentration of the dissolved
species divided by the partial pressure of the gas. For the above reaction,
we have
[H2O2]
KH __
PH O
2 2
If the concentration is expressed as a molarity, and the unit of pressure is

atmospheres, then from experimental data
KH 7.4 104 M atm1
Using this information, we can determine the molarity of H2O2 in
a raindrop for typical clean-air conditions of 0.1 ppb, i.e., equivalent to
0.1 109 atm.
[H2O2] KH PH O 2 2
7.4 104 M atm1 0.1 109 atm

7.4 106 M
For unknown reasons,
hydrogen peroxide levels in
Although a concentration of 7.4 ␮M seems tiny by comparison with values
suspended aerosol droplets routinely encountered in laboratories, it is sufficient to oxidize dissolved SO2 at
in the air at several an appreciable rate. The hydrogen peroxide concentration in smoggy air is an
California locations are order of magnitude or more larger than in clean air, so its concentration in water
orders of magnitude larger droplets rises accordingly, as does the rate of oxidation of sulfur dioxide.
even than predicted by
Henry’s law.
The calculation of the solubility of SO2 in raindrops is more compli-
cated, since in the aqueous phase it exists as sulfurous acid, H2SO3:
baird_ch03.indd 116 2/2/12 11:40 AM

0!
SO2(g) H2O(aq) !1 H2SO3(aq)
The Henry’s law expression does not include the concentration of the
solvent, water:
[H2SO3]
KH __
PSO 2
Since KH 1.0 M atm for SO2, and since its concentration in a typical
1
sample of air is about 0.1 ppm, i.e., equivalent to 0.1 106 atm, the equi-
librium concentration of sulfurous acid is
[H2SO3] KH PSO 2
1.0 M atm1 0.1 106 atm.

1.0 107 M
This value of about 107 M for the equilibrium concentration of H2SO3
is deceptive since it by no means represents all the sulfur dioxide that dis-
solves in a water droplet (see Figure 3-18). Sulfurous acid is a weak acid
whose ionization to the bisulfite ion, HSO3, must also be considered in
calculating the solubility of sulfur dioxide:
0!
H2SO3 !1 H HSO3
The acid dissociation (or ionization) constant Ka for H2SO3 is equal to 1.7
102, where Ka is related to concentrations by the expression
[H] [HSO3]
Ka ___
[H2SO3]
Water Droplet
The concentrations in such expressions
are equilibrium values. Since the equilib- O3
rium molarity of H2SO3 is determined in the
raindrop by its interchange with SO2 in air,
we can substitute that known value into the
Ka expression: HSO4–
[H] [HSO3] SO2 H2SO3 HSO3– + H+

Ka ___
1.0 107
Rearranging the equation to solve for the
ion concentrations, which from stoichiom-
etry are equal in value, we obtain
H2O2
[HSO3]2 1.7 102 M 1.0 107 M
and hence
FIGURE 3-18 Dissolution of atmospheric gases SO2, O3, and H2O2 into
[HSO3] 4 105 M a water droplet and their subsequent reactions.
baird_ch03.indd 117 2/2/12 11:40 AM

Most oxidation of dissolved

Thus, the equilibrium ratio of bisulfite ion to sulfurous acid in water is about
sulfur dioxide occurs via 400 : 1. Consequently, the total dissolved sulfur dioxide is about 4 105 M,
bisulfite ion, as indicated in rather than just the 1 107 M that represents the contribution from the
Figure 3-18. un-ionized acid.
Since the concentration of hydrogen ion produced by the reaction is also
4 105 M, the pH of such raindrops is 4.4. Rain does not become much
more acidic than this if no strong acids are dissolved in the droplets.
PROBLEM 3-12
Bisulfite ion can act as a weak acid and ionize further:

0!
HSO3 !1 H SO32
Given that Ka for HSO3 is 1.2 107, calculate the concentration of SO32
that is present in the raindrops of pH 4.4 discussed above. [Hint: The concen-
trations of bisulfite and hydrogen ion will be very close to their values estab-
lished previously.] ●
PROBLEM 3-13
Calculate the pH of rainwater in equilibrium with SO2 in a polluted air mass

for which the sulfur dioxide concentration is 1.0 ppm. [Hint: Recall the rela-
tionship between partial pressure and ppm concentration discussed earlier in
the chapter.] ●
PROBLEM 3-14
Calculate the concentration of SO2 that must be reached in polluted air if

the dissolved gas is to produce a pH of 4.0 in raindrops without any oxidation
of the sulfur. ●
PROBLEM 3-15
(a) Confirm by calculation that the pH of CO2-saturated water at 25°C is

5.6, given that the CO2 concentration in air is 390 ppm. For carbon dioxide,
the Henry’s law constant KH 3.4 102 M atm1 at 25°C. The Ka for
based on the material in the carbonic acid, H2CO3, is 4.5 107 at that temperature. (b) Recalculate
preceding sections. the pH for a carbon dioxide concentration of 560 ppm, i.e., double that of
the preindustrial age. ●
Particulates in Air Pollution

The black smoke released into the air by a diesel truck is often the most obvi-
ous form of pollution that we routinely encounter. The smoke is composed
largely of particulate matter. Particulates are tiny solid or liquid
baird_ch03.indd 118 2/2/12 11:40 AM

Particulates in Air Pollution 119
particles—other than those of pure water—that are temporarily suspended

in air and that are usually individually invisible to the naked eye. Collec-
tively, however, such particles often form a haze that restricts visibility.
Indeed, on many summer days the sky over North American and European
cities is milky white rather than blue. More importantly, breathing air that
contains particulates is known to be hazardous to human health. Ozone
and particulate matter have the greatest negative effects on human health of
all air pollutants in most parts of the world, as discussed in Chapter 4. In the
material that follows, we investigate the wide range of sizes of the suspended
particles and their origins.
3.22 Particulate Size

The particles that are suspended in a given mass of air are neither all of
the same size or shape nor do they all have the same chemical composi-
tion. The smallest suspended particles are about 0.002 ␮m (2 nm) in their
dimensions; by contrast, the length of typical gaseous molecules is 0.0001
to 0.001 ␮m (0.1 to 1 nm). The upper limit for suspended particles corre-
sponds to dimensions of about 100 ␮m (0.1 mm). When atmospheric water
droplets coalesce to particles bigger than this, they are raindrops and fall
out of the air so quickly they are not considered to be “suspended.” The
range of particle sizes for common types of suspended particulates is illus-
trated in Figure 3-19.
Although few of the particles suspended in air are exactly spherical in
shape, it is convenient and conventional to speak of all particles as if they
were so. Indeed, the diameter of particulates is their most important prop-
erty. Qualitatively, individual particles are classified as coarse or as fine
depending upon whether their diameters are greater or less than 2.5 ␮m,
respectively. (About 100 million particles of diameter 2.5 ␮m would be
required to cover the surface of a small coin.)
There are many common names for atmospheric particles: “dust” and
“soot” refer to solids, whereas “mist” and “fog” refer to liquids, the latter denot-
ing a high concentration of water droplets. An aerosol is a collection of
particulates, whether solid particles or liquid droplets, dispersed in air. A
true aerosol (as opposed, say, to the fairly large droplets from a hair-spray dis-
penser) consists of very small particles: their diameters are less than 100 ␮m.
Intuitively, one might think that all particles should settle out under the
influence of gravity and be deposited onto the Earth’s surface rapidly, but this
is not true for the smaller ones due to air turbulence. According to Stokes’
law, the rate, in distance per second, at which particles settle increases with
the square of their diameter. In other words, a particle half the diameter of
another falls four times more slowly. The small ones fall so slowly they are
suspended almost indefinitely in air (unless they stick to some object they
encounter). As we shall see later, the very small ones aggregate to form larger
ones, usually still in the fine-size category. Fine particulates usually remain
baird_ch03.indd 119 2/2/12 11:40 AM

FIGURE 3-19 Sizes of

common airborne fine and Coarse particles Fine particles
coarse particulates. [Source:
Adapted from J. G. Henry and
G. W. Heinke, Environmental
Science and Engineering (Upper
Saddle River, NJ: Prentice Hall, Rain Mist/Fog/Clouds Smog
1989).]
Coal dust Tobacco

smoke
Atmospheric dust
Foundry dust
Agriculture Oil
sprays smoke
Pollen
Bacteria Viruses
100,000 10,000 1,000 100 10 1 10–1 10–2 10–3 10–4

1,000,000 (1 mm) (1 nm)
(1 m)
Particle diameter in micrometers ( µ m)
airborne for days or weeks, whereas coarse particulates settle out fairly rap-
idly. In addition to this sedimentation process, particles also are commonly
removed naturally from tropospheric air by their incorporation into falling
raindrops, usually within a week or two.
3.23 Sources and Composition of Coarse Particles

The primary-versus-secondary distinction made between atmospheric gas-
eous pollutants (Section 3.3) is also applied to suspended particles. Most
coarse particles are primary, although they often begin their existence as
even coarser matter, since they originate chiefly from the disintegration of
larger pieces of matter. Minerals constitute one important type of the coarse
particulates in air. Because many of the large particles in atmospheric dust,
particularly in rural areas, originate as soil or rock, their elemental composi-
tion is similar to that of the Earth’s crust, namely high concentrations of Al,
Ca, Si, and O in the form of aluminum silicates, some of which also contain
the calcium ion (Chapter 16).
baird_ch03.indd 120 23/02/12 8:07 AM

• Wind storms in deserts sweep large amounts of fine sand into the air.
Dust storms in Asia, whose effects reach as far away as North America, are
increasing due to the continuing transformation of fertile land into desert
as a consequence of global warming, deforestation, and overgrazing.
• The wind generates coarse particles by the mechanical disintegration of
leaf litter.
• Pollen released from plants also consists of coarse, primary particles.
• Wildfires and volcanic eruptions generate both fine and coarse
particulate matter.
• Near and above oceans, the concentration of solid NaCl is very high,
since sea spray leaves sodium chloride particles airborne when the water
evaporates. Indeed, sea-salt aerosols are by far the largest mass of primary
particles in air, followed by soil dusts and debris from natural fires.
Although most coarse particulates originate with natural sources, human
activities such as stone crushing in quarries and land cultivation result in
particles of rock and topsoil being picked up by the wind. Coarse particles in
many areas are basic, reflecting the calcium carbonate and other such salts
in soils.
3.24 Sources and Composition of Fine Particles

Primary fine particles of anthropogenic origin include ones generated by the
wearing of tires and vehicles brakes, and the dust from metal smelting. The
incomplete combustion of carbon-based fuels such as coal, oil, gasoline, and
diesel fuel produces many fine soot particles, which are mainly crystallites
(miniature crystals) of carbon. Consequently, one of main sources of carbon-
based primary atmospheric particulates, both fine and coarse, is the exhaust
from vehicles, especially those having diesel engines. About half the organic
content from heavy-duty diesel vehicles is elemental carbon (EC); this soot
is commonly seen as the black smoke that emanates from such equipment.
Most carbon-containing emissions from gasoline-powered engines are com-
posed of organic compounds (OC) rather than elemental carbon.
Whereas coarse particles result mainly from the breakup of larger ones,
fine particles are formed mainly by chemical reactions between gases and
by the coagulation of even smaller species, including molecules in the
vapor state; they are mainly secondary particles in nature. Although most of
the mass of atmospheric fine particles arises from natural sources, that over
urban areas often has mainly an anthropogenic origin.
The average organic content of fine particles is generally greater than The main final products
that of coarse ones. In areas subject to photochemical smog, a substantial from photochemical smog
fraction of the organic compounds in the particulate phase are formed are gaseous ozone and fine
suspended particulates
from the reaction of VOCs and nitrogen oxides in the photochemical smog containing OC.
reaction, and correspond to partially oxidized hydrocarbons that have
baird_ch03.indd 121 2/2/12 11:40 AM

incorporated oxygen to form carboxylic acids, etc. and nitrogen to form nitro
groups, etc.
Aromatic hydrocarbons with at least seven carbon atoms (e.g., toluene)
that enter the air of cities as VOCs from the evaporation of gasoline also
form aerosols. Hydrocarbons having fewer than seven carbons give oxidation
products with substantial vapor pressures that remain in the gas phase.
Research performed following the 2010 Deepwater Horizon oil spill dis-
covered that, although VOC hydrocarbons in the surface oil formed organic
aerosols relatively quickly, longer-chain semivolatile and intermediate vola-
tility organic compounds reacted to form the bulk of the organic aerosol,
even though they were slower to vaporize.
The other important fine particles suspended in the atmosphere consist
predominantly of inorganic compounds of sulfur and of nitrogen. Much of
the natural sulfur in air originates as dimethyl sulfide, (CH3)2S, emitted from the
oceans. A by-product of its oxidation in air is carbonyl sulfide, COS, a long-
lived trace atmospheric component that also results from the atmospheric
oxidation of carbon disulfide, CS2, and from direct emissions from oceans and
biomass. Some of the COS makes its way into the stratosphere, where it is
oxidized and produces the natural sulfate aerosol found at those altitudes. Both
dimethyl sulfide and hydrogen sulfide are oxidized in air mainly to SO2.
Sulfur dioxide gas is also emitted directly in large quantities both by natu-
ral sources such as volcanoes and as pollution from power plants and smelters.
It becomes oxidized over a period of hours or days to sulfuric acid and sulfates
in the air. Sulfuric acid itself travels in air not as a gas but as an aerosol of fine
In Iceland itself, fluoride
droplets, since it has such a great affinity for water molecules. A huge volcanic
emitted from the volcano eruption in Iceland in 1783 produced enough sulfuric acid particles to blanket
was a worse problem, since Europe in a “great dry fog” for the entire summer, killing many people.
it proved fatal to crops, Another natural source of atmospheric particles has been discovered. Alkyl
livestock, and people. iodine compounds such as CH2I2 are emitted by seaweed into the air above
coastal regions. Absorption of the ultraviolet component of light is sufficient to
detach iodine atoms from such gaseous molecules. In subsequent reactions
analogous to those of chlorine in the stratosphere, the iodine atoms react with
ozone to form iodine monoxide, IO, which in turn dimerizes to form I2O2. The
dimer and other iodine-oxygen compounds condense to form fine particles.
PROBLEM 3-16
By analogy with the reactions of atomic chlorine discussed in Chapter 2,

write balanced equations for the reaction of atomic iodine with ozone and for
the dimerization of IO. ●
3.25 The Neutralization of Acids in Air

Fine particles in many areas are acidic, due to their content of sulfuric and
nitric acids. The nitric acid is the end-product of the oxidation of
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nitrogen-containing atmospheric gases such as NH3, NO, and NO2, and the
sulfuric acid comes from the oxidation of SO2. Because HNO3 has a much
higher vapor pressure than does H2SO4, there is less condensation of nitric
acid onto preexisting particles than occurs with H2SO4.
Both sulfuric and nitric acids in tropospheric air often eventually
encounter ammonia gas that is released as a result of biological decay pro-
cesses occurring at ground level. The atmospheric acids undergo an acid–
base reaction with the ammonia, which transforms them into the soluble salts
ammonium sulfate, (NH4)2SO4, and ammonium nitrate, NH4NO3. Since
sulfuric acid contains two hydrogen ions, the neutralization reaction occurs
in two-stages, the first producing ammonium bisulfate, NH4HSO4:
H2SO4(aq) NH3(g) 9: NH4HSO4(aq)
NH4HSO4(aq) NH3(g) 9: (NH4)2SO4(aq)
The ammonia that results from animal urine originates in the liquid as urea,
CO(NH2)2, which subsequently hydrolyzes:
CO(NH2)2 H2O 9: 2 NH3 CO2
The neutralization of acidity by ammonia gas released into the air from
livestock, from the use of fertilizers, and by carbonate ion suspended in air
from the dust raised by farming activities are the main reason that precipita-
tion over the central United States is not particularly acidic, and similarly for
that over regions of China. However, some acidification results from the
ionization of the ammonium ion, NH4, a weak acid that is produced by
ammonia neutralization:
0!
NH4 !1 NH3 H
Although the nitrate and sulfate salts initially are formed from acids in
aqueous particles, evaporation of the water can result in the production of
solid particles. The predominant ions in fine particles are the anions sulfate,
SO42, bisulfate, HSO4, and nitrate, NO3, and the cations ammonium,
NH4, and hydrogen ion, H. Aerosols dominated by oxidized sulfur com-
pounds are called sulfate aerosols.
(NH4)2SO4 NH3
NH4⫹ NH4HSO4
NH3 NH4NO3
NO3 ⫺
SO4 2⫺
HNO3 NH3
H⫹
HSO4⫺ H2SO4
sulfate
aerosol
particle
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On the west coast of North America, nitrate rather than sulfate is the
predominant anion since more pollution results initially from nitrogen
oxides than from sulfur dioxide, since coal mined in the western United
States tends be low in sulfur. In Great Britain, most of the fine particles in
the winter months originate as soot from car exhaust and pollution from
industry, whereas in the summer they arise from the oxidation of sulfur and
nitrogen oxides.
If there is substantial ammonia gas in the air, nitric acid will react with it
to form ammonium nitrate solid in the particulate phase. Recent simulations of
smog formation in Southern California indicate that, although reductions in
VOC concentrations without any change in NOX would reduce ozone forma-
tion, the production of nitrate-based particulates would actually increase
because more nitrogen dioxide would then react to produce nitric acid and
then nitrate ion. The simultaneous control of ozone and particulates presents
regulators with a formidable challenge!
In summary, coarse particles are usually either soot or inorganic (soil-
like) in nature, whereas fine ones are mainly either soot, sulfate, or nitrate
aerosols. Fine particles are usually acidic due to the presence of unneutral-
ized acids and are eventually neutralized by ammonia, whereas coarse ones
are usually basic also because of their soil content.
3.26 Smoke from Wood Stoves

The burning of wood in domestic fireplaces and wood stoves produces large
quantities of particulates, which are emitted from the chimneys into out-
door air. Indeed, in residential neighborhoods where wood is the predominant
fuel used for heating, wood stoves contribute up to 80% of the fine particles
in the air during the winter months. Some municipalities have controversially
limited the number of wood stoves permitted in a given geographical sub-
region in order to deal with the problem. Outdoor wood-fired boilers, used to
heat water for saunas and swimming pools, have grown so much in popularity
that the particulates they emit have become a significant problem.
Newer wood stoves and boilers have emission controls incorporated into
their design, which greatly reduce the quantity of particulates and gases they
release into the air. For example, U.S. EPA-certified wood stoves reduce the
amount of smoke from 15–30 (uncontrolled) down to 2–7 grams per hour of
operation. The control is accomplished in one of two ways:
• A catalytic converter, consisting of a coated ceramic honeycomb
structure is located near the top of the firebox. Smoke and gases from the
wood fire below are passed through it and more fully oxidized before
continuing upward to the chimney.
• More commonly, the firebox is designed so that near its top, secondary
combustion of the smoke occurs before it is emitted into the outside air. This is
accomplished by having some of the air entering the stove diverted through
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tubes under and around the fire, thereby

heating it (see Figure 3-20). The hot air is Chimney
released near the top of the firebox, where
the smoke combusts. A baffle is used above
this area to divert the air and maximize the
amount of time it spends in the secondary Outside air Baffle
combustion area before being released up
the chimney.
Preheated
Because these new stove designs com- Secondary combustion zone air
bust much more of the fuel value of the Smoke
wood, rather than emitting much of it as
smoke, they are about 50% more energy-
efficient than those of older design.
Outside air
3.27 Smoke over Large Areas
of Land
FIGURE 3-20 Noncatalytic wood stove (schematic) with preheated
Serious episodes of smoky haze pollution air and baffle for more complete combustion.
over large areas of land have occurred in
recent years in Southeast Asia, especially in Malaysia, Singapore, and
Indonesia. The smoke originates mainly from forest fires—many of them
in Indonesia—that are intentionally started in order to clear land that can
be subsequently used for agriculture and to grow trees for their rubber, palm
oil, or pulp content. A secondary source of the smoke is the smoldering
underground fires that slowly burn in underground coal and peat deposits.
Indeed, there are estimated to be a quarter million individual coal fires
currently burning in Indonesia, as well as many in China and India, and
there are also many peat fires in Malaysia. The fires are initiated when an
outcropping of coal or a peat deposit that has dried after draining is ignited,
typically during one of the fires set to clear the land. Fires can also be ignited
by lightning strikes in coal exposed to the air, and even by spontaneous com-
bustion when the surface pyrite is oxidized and the heat released by this
reaction sets the carbon ablaze. These underground fires can continue to
burn for decades after the original forest fires have stopped.
A so-called atmospheric brown cloud of particles and gases from forest fires,
vehicle exhausts, and domestic cookers—especially in rural areas—that burn
wood, dung, and agricultural waste overhangs most of East and Southeast Asia
annually from December to May, the main season for home heating. The
brown cloud over the Indian Ocean consists mainly of smoke from the burning
of dried manure in cooking fires. This haze lowers sunlight levels at the surface
by up to 15%, with a corresponding decline in the yield of crops such as rice
and an alteration to rainfall and monsoon patterns. In contrast to the pollution
aerosol over North America and Europe, to which it is comparable in magni-
tude, the “black carbon” content of the brown cloud is significant. The
baird_ch03.indd 125 2/2/12 11:40 AM

absorption of sunlight by this elemental carbon alters the local hydrological

cycle and hence the weather over the northern Indian Ocean. The lack of
nitric oxide produced in the low-temperature flames of burning biomass cur-
rently limits ozone production over the area, but that will likely be reversed in
the future with increased use of fossil fuels for vehicles.
Large forest fires in northern Canada produce huge quantities of carbon
monoxide and VOCs, which have been found to travel as far as the U.S.
Southeast and which may well increase ozone and particulate concentrations
in the air of this region.
Air Quality Indices and Size Characteristics

for Particulate Matter
As we shall see in Chapter 4, the effect of particles suspended in air upon
human health depends significantly upon the size of the particles involved.
In the material that follows, we investigate the pollution indexes used by
governmental agencies to characterize the level of particulate air pollution
present in an air sample as well as the effect of particle size on visibility
through air masses.
3.28 The PM Indices

When air quality is monitored, the most common measure of the concentra-
tion of suspended particles is the PM index, which is the amount of particu-
late matter that is present in a given volume. Since the matter involved
usually is not homogeneous, no molar mass for it can be quoted and thus con-
centrations are given in terms of the mass, rather than the number of moles, of
particles present. The usual units are micrograms of particulate matter per cubic
meter of air, i.e., ␮g m3. Because smaller particles have a greater detrimental
effect on human health than do larger ones, as we shall see later in this chapter,
usually only those having a specified diameter or less are collected and
reported; this cut-off diameter, in ␮m, is listed as the subscript to PM.
Government agencies in many countries, including the United States
and Canada, monitor PM10, which is the total concentration of all particles
having diameters less than 10 ␮m, which corresponds to all of the fine-
particle range plus the smallest members of the coarse range. These are called
inhalable particles since they can be breathed into the lungs. A typical value
for PM10 in an urban setting is 20–30 ␮g m3.
More commonly, regulators in developed countries now use the PM2.5
index, i.e., that which includes all and only fine particles, which are also
called respirable particles. The respirable range includes only particles that
can penetrate deep into the lungs, where there are no natural mechanisms such
as the cilia that line the walls of bronchial tubes to catch particles and move
them up and out. Urban PM2.5 values are usually in the 10–20 ␮g m3 range in
North America, although background concentrations are only 1–5 ␮g m3.
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Air Quality Indices and Size Characteristics for Particulate Matter 127
Some researchers have introduced the term PM10-2.5, which, although

termed “coarse” corresponds only to the smallest of the particles covered by
the conventional definition of coarse particles. The new term ultrafine is
applied to particles with very small diameters, usually taken to be less than
0.1 ␮m. Nanoparticles are still smaller, less than about 0.02 ␮m. (Figure 1
in Box 3-3 shows the distribution of particles in an air mass and visually sum-
marizes the size definitions.) Most ultrafine particles are anthropogenic in
origin. In the past, the total suspended particulates, abbreviated TSP, which
is the concentration of all particulates suspended in air, was often reported
instead of a PM index.
As the importance of suspended particulate matter to human health
(discussed in Chapter 4) became more and more apparent in the late twen-
tieth century, some governments set air quality standards for PM10. Now that
PM2.5 is recognized to be more relevant than PM10 and the instrumentation
for its measurement is widely available, standards for it have been imple-
mented in some countries such as the United States and have been proposed
for others, and in some cases have replaced PM10 regulation. The status of
PM regulations, as of 2010, is summarized in Table 3-2.
Governments generally do not attempt to regulate overall emissions of
particulate matter since so much of it is secondary in origin, not primary. An
exception is the emission of particulates from vehicles.
Particulate air pollution globally is a serious problem, especially in cities
in developing countries; as indicated in Figure 3-21, few of the world’s mega-
cities currently come close to meeting the World Health Organization
annual standard for PM10 (horizontal green line) of 20 ␮g m3. Several other
Chinese and Indian cities and Cairo are also among the most particulate-
polluted cities in the world. Given the continuing increase in vehicles, most
lacking emission controls, in developing countries, and the fact that many of
TABLE 3-2 Particulate Matter Air Standards, in units of ␮g m3

Country or PM2.5 PM2.5 PM10 PM10
Organization 24-hour Annual 24-hour Annual
WHO 25 10 50 20
USA 35 15 150
Canada (30)
EU — (25) 50 40
Australia (25) (8) 50
China — — 50–250 40–150
India 60 40 100 60
Note: Figures in round brackets are tentative standards.
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FIGURE 3-21 Particulate

air quality in major world 250
cities Note: Values are
annual PM10 means. The
green horizontal line is the 200
WHO air quality guideline
for this parameter. [Source:
PM10 (mg m–3)

D. D. Parish and T. Zhu, Science
150
326 (2009): 674–675.]
100
50
0
D i
Bu Cal hi
os ta
Be es
Ja g
Sh rta
M hai
ic ai
La y
Is s
M ul
o la
o
Lo To l
n o
ew s
rk
h
ou
go
N gele
n
ol
s A ky
en cut
ex b
Sa ni
ac
el
Ci
nb
ir
Yo
iji
ka
g
M um
Pa
Se
A
a
ar
an
ta
o
K
them are diesel-powered, it seems likely that PM levels will increase over
time. Most Chinese cities failed to meet the daily and annual WHO guide-
lines for PM2.5, Beijing and Shanghai by factors of ten and six, respectively,
in the early 2000s.
Ironically, although levels of primary particulate matter and that formed
from SO2 decreased over China in the late 2000s due to government controls
and an economic downturn, by 2009 particulate levels were again increasing
due to their formation as secondary pollutants from reaction of NOX emis-
sions from the increasing number of vehicles on the road. Almost all sites in
the United States meet its annual PM10 standard, although not the lower
limit more generally adopted, and there are still some areas that miss the
PM2.5 limit, notwithstanding gradual improvement over the last decade.
Many large cities in sub-Saharan Africa suffer from high levels of particu-
late air pollution from vehicle exhaust, although little regular monitoring is yet
in place there. In Nairobi, Kenya, for example, the air sampling during the mid-
2000s revealed very high levels of PM2.5, with enhanced black carbon. Most of
the vehicles in Nairobi at the time had been imported from Asia as used cars
and had no pollution control devices.
PROBLEM 3-17
What would be the correct PM symbol for an index that included only ultra-
fine particles? What would be the PM symbol for the TSP index? Numeri-
cally, would the value for the ultrafine component of a given air mass be
larger or smaller than its TSP? ●
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Air Quality Indices and Size Characteristics for Particulate Matter 129
As discussed in detail in Box 3-3, the distribution of particles suspended Review Questions 18–21 are
in air peaks in the micrometer region because smaller particles coagulate to based on material in the
form ones of this size and further growth is slow, and because much larger preceding sections.
ones rapidly settle out. The large increase in surface area that occurs when a
large particle is split into smaller ones is explored in Problem 3-18.
PROBLEM 3-18
Let k be a given measure of length; then suppose a cubic particle of dimen-

sion 3k 3k 3k is split up into 27 cubes of size k k k. Calculate the
relative increase in surface area when this occurs by comparing the surface
area (length times width) of the six faces of the larger cube to the sum of all
those of the smaller ones. From your answer, deduce whether the total
surface area of a given mass of atmospheric particle is larger or smaller when
it occurs as a large number of small particles rather than a small number of
large ones. ●
BOX 3-3 The Distribution of Particle Sizes in an Urban Air Sample
B ecause particles suspended in the atmo-

sphere are of different origins and compo-
sitions, and were often formed and interacted
particles into larger ones (which can occur in
minutes) and the deposition of gas molecules
onto them result in the broad distribution of
over a period of time in haphazard ways, there secondary particles. Particles of this size also are
is a wide distribution of particle sizes present created when water in aqueous droplets con-
in any air mass. taining dissolved solids evaporate. Growth
One way of looking at the distribution of beyond this size is slow because the larger the
sizes is to plot the number of particles having a particle, the slower it moves and thus the less
given diameter against the diameter; this is likely it is to encounter and coagulate with
done in the dark green curve of Figure 1 for a particles of comparable size. Growth by con-
typical urban air sample. densation of gases is also slow for larger particles
The peak in the distribution occurs at just since their surface-to-mass ratio is smaller than
under 0.01 ␮m. The oddly shaped net distribu- for small particles.
tion is presumably the sum of several symmetri- The particles associated with the right-
cal (“bell shaped”) distributions having peaks at side tail of the distribution are mainly soot or
different diameters. The particles of the distri- consist of material produced by mechanical
bution at the smallest diameter are primary in disintegration of soil particles, etc. Numeri-
nature, formed by the condensation of vapors of cally, there are few particles of mass larger
pollutants formed by chemical reactions, such than a few microns in diameter because each
as the sulfuric acid formed by the oxidation of has such a large mass and because the larger
gaseous sulfur dioxide and the soot particles ones quickly settle out of the air (Stokes’
formed by combustion. The coagulation of such law), although particles that then settle on
(continued on p. 130)
baird_ch03.indd 129 2/2/12 11:40 AM

roadways often become resuspended by the smaller ones; the whole distribution appears to
action of vehicular traffic. have shifted to higher diameters. Two sym-
The plots of particle numbers can be mis- metrical distribution curves, one centered in
leading for some purposes because tiny particles the fine region at about 0.4 ␮m and the other
of very small mass and surface area dominate in the coarse region at about 9 ␮m, appear to
the samples and thus the distributions. One be superimposed to produce the final bimodal
alternative way to represent the data in a more “double-humped” distribution. Notice that the
meaningful way is to plot the total mass of all total mass of the coarse-particle range (i.e., the
particles of a given size in an air sample against sum of the area under the dark green curve for
the diameter to see how mass is distributed d 2.5 ␮m) in Figure 1 is greater than that
among the different sizes. This type of plot is for the fine region; this ratio is even larger for
shown by the light green curve in Figure 1. clean, rural air masses.
The distribution function for mass is dis-
placed to larger diameters compared to that for
PROBLEM
PROB
PRO LE
OB LEM
M1
particle numbers for the following reason: the
mass (or volume) of a particle is proportional to The distribution of particle surface area
the cube of its diameter d (since for a sphere against size is proportional to the square of the
volume is proportional to the cube of the diameter times the number distribution, since
radius), so the height of the curve at any diam- the surface area of a sphere is proportional to
eter of the distribution in the light green curve the square of its radius or diameter. Given the
in Figure 1 corresponds to the value for the distribution for the particle volumes and
number distribution for this air mass times d3. masses (Figure 1), which is d3 times the num-
Very small particles, even though numerous, do ber distribution rather than d2 times it, quali-
not collectively have a large mass. Consequently, tatively predict the shape of the distribution
in the mass distributions, the peak heights for curve and approximate location of peak(s) for
larger particles are higher than are those for total particle surface area.
Number Mass
Condensates and other Secondary particles Mineral dust

FIGURE 1 The distribution primary particles
of particle numbers and of
particle masses versus particle
size for airborne particles. Soot Brake wear
Particles in the condensates,
soot, and brake-wear
0.001 0.01 0.1 1 10 100
categories originate mainly
from vehicular traffic. The Nanoparticles (µm)
mineral dust comes from Ultrafine particles
road abrasion and from
PM2,5 (fine particles)
agricultural and natural
sources. [Source: Modified from PM10
J. Fenger, Atmospheric
Environment 43 (2009): 13–22.]
baird_ch03.indd 130 2/2/12 11:40 AM

Green Chemistry Questions 131
Review Questions
1. In the “micrograms per cubic meter” 11. Describe the manner in which emissions
concentration scale, to what substances do from diesel-powered vehicles can be controlled,
micrograms and cubic meters refer? including the use of catalytic converters.
2. What chemical substance initiates the air 12. Describe the reaction used in the selective catalytic
oxidation of stable molecules? How is it initially reduction of nitrogen oxides. What other techniques
formed, and how is it reformed? are used for NOX emission control from power plants?
3. In general terms, what is meant by 13. What are the main anthropogenic sources of
photochemical smog? What are the initial reactants sulfur dioxide? Describe the strategies by which these
in the process? Why is sunlight required? emissions can be reduced. What is the Claus reaction?
4. What is meant by a primary pollutant and by a 14. What species are included in the air pollution
secondary pollutant? Give examples. index called total reduced sulfur?
5. How does OH react with a stable molecule 15. Describe the three strategies used in clean coal.
containing a C RC bond? With an alkane?
16. What two species, other than O2, are active
6. What is meant by the term synergism? Give an oxidizing agents of sulfur dioxide in atmospheric
example. water droplets?
7. What is the chemical reaction by which 17. State Henry’s law.
thermal NO is produced? From which two sources
does most urban NO arise? What is meant by the 18. Define the term aerosol, and differentiate
term NOX? What is meant by fuel NO? between coarse and fine particulates. What are the
usual origins of these two types of atmospheric
8. Describe the strategies by which reduction of particles?
urban ozone levels has been attempted. What
difficulties have been encountered in these efforts? 19. What are the usual chemical components of a
Is photochemical smog strictly a localized urban sulfate aerosol?
problem? 20. Write a balanced equation illustrating the
9. What is meant by geographic regions that are reactions that occur between one molecule of
VOC-limited? NOX-limited? ammonia and (a) one molecule of nitric acid and
(b) one molecule of sulfuric acid.
10. Describe the operation of the three-way catalyst in
transforming emissions released by an automobile 21. What are the usual concentration units for
engine. Does the catalyst operate when the engine is suspended particulates? What would the
cold? Why is it important for converters that the designation PM40 mean? What do the terms
level of sulfur in gasoline be minimized? respirable and ultrafine mean?
Green Chemistry Questions

1. The development of a low-VOC coalescent for (a) Into which of the three focus areas (see
paints by ADM won a Presidential Green page xxviii) for these awards does this award
Chemistry Challenge Award. best fit?
baird_ch03.indd 131 2/2/12 11:40 AM

(b) List two of the twelve principles of green addressed by the green chemistry developed by
chemistry that are addressed by this discovery. DeSimone.
Justify each of your answers.
6. The ions in ionic liquids (ILs) have weak
2. What are the environmental advantages of the ionic attractions for one another. This weak
coalescent developed by ADM? interaction is due to one or more factors including
3. Consider the structure (Figure 3-11b) of the • the presence of bulky nonpolar groups which
coalescent developed by ADM. Using your prevent the close interaction of the charged
knowledge of organic chemistry, explain why this regions of the ions, and
molecule undergoes reaction with oxygen so • delocalized and/or dispersed charges resulting
readily. Would you expect linoleic acid to react in in low charge density.
a similar manner? Stearic acid? Inspect the (ILs) in Figure 3-15 and discuss the
4. PERC replaced gasoline and kerosene in the structural features of these compounds that result
dry-cleaning process. in weak interactions between the oppositely
charged ions.
(a) Describe any environmental problems or
worker hazards that would be associated with these 7. The discovery of the dissolution of cellulose
solvents. with ionic liquids and the formation of various
(b) Would these same environmental problems cellulose composites by Robin Rogers won
or workers hazards be eliminated by the use of a Presidential Green Chemistry Challenge
PERC? Award.
(c) By the use of carbon dioxide? (a) Which of the three focus areas (see page xxviii)
for these awards does this award best fit into?
5. The development of surfactants for carbon (b) The use of an abundant, naturally occurring
dioxide by Joseph DeSimone won a Presidential polymer, a microwave heat source, and ionic
Green Chemistry Challenge Award. liquids are three important green chemistry
(a) Which of the three focus areas (see page xxviii) aspects of this study. For each of these aspects
for these awards does this award best fit into? list at least two of the twelve principles of green
(b) List two of the twelve principles of green chemistry (see pages xxiii–xxiv) that are
chemistry (see pages xxiii–xxiv) that are addressed in this study.
Additional Problems
1. The rate constant for the oxidation of nitric for nitric oxide, deduce the rates of these two
oxide by ozone is 2 ⫻ 10⫺14 molecule⫺1 cm3 sec⫺1, reactions and decide which one is the dominant
whereas that for the competing reaction in which process. [Hint: The concentrations of the reactants
it is oxidized by oxygen, i.e., must be expressed in units appropriate to the rate
constant.]
2 NO ⫹ O2 9: 2 NO2
2. In a particular air mass, the concentration
is 2 ⫻ 10⫺38 molecule⫺2 cm6 sec⫺1. For typical of OH was found to be 8.7 ⫻ 106 molecules
concentrations encountered in morning smog cm⫺3, and that of carbon monoxide was
episodes, namely 40 ppb for ozone and 80 ppb 20 ppm.
baird_ch03.indd 132 2/2/12 2:25 PM

Additional Problems 133
(a) Calculate the rate of the reaction of OH with (a) Deduce the balanced reaction for the overall
atmospheric CO at 30°C, given that the rate process.
constant for the process is 5 1013 e300/T (b) Determine the ozone concentration, in ppb,
molecule1 cm3 sec1. in a 10.0-L sample of outdoor air if it required
(b) Estimate the half-life of an OH molecule in 17.0 ␮g of KI to react with it.
air, assuming that its lifetime is determined by its
6. The percentage of sulfur in coal can be
reaction with CO. [Hint: Re-express the rate law
determined by burning a sample of the solid and
as a pseudo-first-order process with the level of
passing the resulting sulfur dioxide gas into a
CO fixed at 20 ppm. Consult your introductory
solution of hydrogen peroxide, which oxidizes it
chemistry textbook to find the relationship
to sulfuric acid, and then titrating the acid.
between the half-life of a substance and the rate
Calculate the mass percent of sulfur in a sample
constant for its first-order decay.]
if the gas from an 8.05-g sample required 44.1 mL
3. In the overall reaction that produces nitric of 0.114 M NaOH in the titration of the diprotic
oxide from N2 and O2, the slow step in the acid.
mechanism is the reaction between atomic oxygen
7. Calculate the volume, at 20°C and 1.00 atm,
and molecular nitrogen to produce nitric oxide
of SO2 produced by the conventional roasting of
and atomic nitrogen.
1.00 tonnes (1,000 kg) of nickel sulfide ore, NiS.
(a) Write out the chemical equation for the slow What mass of pure sulfuric acid could be produced
step and the rate law equation for it. from this amount of SO2?
(b) Given that its rate constant at 800°C is
8. Ironically, SO2 could be extracted from gas
9.7 1010 L mol1 sec1, and that its activation
emissions by passing it through a solution of sulfite
energy is 315 kJ mol1, calculate the amount by
ion, SO32.
which the rate constant increases if the
temperature is raised to 1100°C. (a) Assuming sulfite ion acts as a base and the
sulfur dioxide is present in water initially as
4. At combustion temperatures, the equilibrium sulfurous acid, write an acid–base reaction
constant for the reaction of N2 with O2 is about between the species.
1014. Calculate the concentration of nitric oxide
(b) Devise a scheme by which dilute sulfur dioxide
that is in equilibrium with atmospheric levels of
in an emission gas could be captured by an
nitrogen and oxygen. Repeat the calculation for
aqueous solution of sulfite ion, and later released
normal atmospheric temperatures, at which the
as a concentrated stream of SO2.
equilibrium constant is about 1030. Given that
the concentration of NO that exits from the 9. Assuming its concentration in air is 2.0 ppb,
combustion zone in a vehicle is much higher than calculate the molar solubility of SO2 in raindrops
this latter equilibrium value, what does that imply whose pH is fixed (by the presence of strong acids)
about equilibrium in the reaction mixture? [Hint: to be 4.0, 5.0, and 6.0. The data required for the
Use the stoichiometry of the reaction to reduce calculations is present in Section 3.21 of the text.
the number of unknowns in the expression for K.]
10. The sulfur species that undergoes oxidation
5. The concentration of ozone in ground-level air in water droplets is the bisulfite ion, HSO3, so
can be determined by allowing the gas to react the rate of oxidation is proportional to its
with an aqueous solution of potassium iodide, concentration multiplied by that of the oxidizing
KI, in a redox reaction that produces molecular agent. Predict how changes in pH in the droplet
iodine, molecular oxygen, and potassium will affect the rate of oxidation (a) if O3 reacts
hydroxide. with bisulfite ion, and (b) if hydrogen peroxide in
baird_ch03.indd 133 2/2/12 11:40 AM

the protonated form H3O2, formed in the diameters (Stokes’ law), provided that their
equilibrium densities are equal. If emitted particulates with
0! a specific diameter are found to settle out after
H2O2 H !1 H3O2
two days, how long would it take particulates of
is the species that reacts with bisulfite.
the same material with half the diameter to settle
11. The settling rate of particulates in air is out if they are emitted from the same tall
directly proportional to the square of their chimney?
baird_ch03.indd 134 2/2/12 11:40 AM

4
The Environmental and
Health Consequences of
Polluted Air—Outdoors
and Indoors
In this chapter, the following introductory chemistry topics are
used:
m pH and acid–base concepts
m Balancing of redox equations
Background from previous chapters used in this chapter:

m Photochemical smog
m Coarse and fine particulates, aerosols; PMx indexes
m Thermal NO
m Temperature inversions; UV types
m ppm, ppb, and ␮g m⫺3 concentration scales for gases
Introduction
Smog, whether sulfur-based or photochemical, often has unpleasant odors due
to some of its gaseous components. More seriously, the initial pollutants, inter-
mediates, and final products of the reactions in smog affect human health and
can cause damage to plants, animals, and some materials. In this chapter, the
detrimental effects on humans and other animals, plants, and materials of the
gases and particles in polluted air—including the air we encounter indoors—
and methods by which air pollution can be combatted, are described. Included
in the discussions are the environmental effects of acid rain, a phenomenon
that results from polluted air.
135
baird_ch04.indd 135 23/02/12 8:02 AM

136 Chapter 4 The Environmental and Health Consequences of Polluted Air
4.1 Haze
The most obvious manifestation of photochemical smog is a yellowish-
brownish-gray haze that is due to the presence in air of small water droplets
containing products of chemical reactions that occur among pollutants in
air. This haze, familiar to most of us who live in urban areas, now extends
periodically to once-pristine areas such as the Grand Canyon in Arizona.
Particles whose diameter is about that of the wavelength of visible
light, i.e., 0.4–0.8 ␮m, can scatter light—reflect it in random directions—
and consequently interfere with its transmission, thereby reducing visual
clarity, long-distance visibility, and the amount of sunlight reaching the
ground. A high concentration in air of particles of diameters between
0.1 ␮m and 1 ␮m produces a haze. Indeed, one conventional technique of
measuring the extent of particulate pollution in an air mass is to determine
its haziness. The existence of smog in the air can often be determined by
simply looking at buildings or hills in the distance, and seeing if their appear-
ance is partially masked by haze.
The widespread haze in the Arctic atmosphere in winter is due to sulfate
aerosols that originate from the burning of coal, especially in Russia and
Europe. The enhanced haziness in summertime over much of North America
is due mainly to sulfate aerosols arising from industrialized areas in the
United States and Canada. Haze over China, produced by air pollution, so
reduces sunlight intensity that it may be cutting food production by as much
as 30% across a third of the country.
Fine particles are largely responsible for
the haze in Los Angeles and other locations
Nitrate, 4%
subject to episodes of photochemical smog.
Ammonium, 11%
The smog aerosols contain nitric and sulfuric
acids that have been neutralized to salts. Also
present in these aerosols are organic carbon
products that are formed in the photochemical
smog reactions; however, intermediates formed
from fuel molecules having short carbon chains
Sulfate, 37% usually have high enough vapor pressures that
Organic they exist as gases rather than condense onto
carbon, 24% particles. The typical composition of the fine
component of an aerosol suspended over conti-
nental areas is illustrated in Figure 4-1.
Since most fine particles in urban air are
Other, 19% secondary, their number can be controlled
only by reducing emissions of the primary pol-
Elemental lutant gases from which they are created.
carbon, 5% Thus governments have successively required
FIGURE 4-1 Typical composition of fine continental aerosol. more and more stringent emission controls on
[Adapted from J. Heintzenberg, Tellus 41B (1989): 149–160.] vehicles, power plants, etc., as discussed in
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Acid Rain 137
Chapter 3. The switch to low-sulfur gasoline and diesel fuels have made
catalytic converters on vehicles more efficient in reducing emissions.
Acid Rain
One of the most serious environmental problems facing many regions of
the world is acid rain. This generic term covers a variety of phenomena,
including acid fog and acid snow, all of which correspond to atmospheric pre-
cipitation of substantial acidity. In this section, the nature of the acids pres-
ent in precipitation is discussed.
4.2 Natural and Anthropogenic Acid Rain

The phenomenon of acid rain was discovered by Angus Smith in Great
Britain in the mid-1800s, but then it was essentially forgotten until the
1950s. It refers to precipitation that is significantly more acidic than “natu-
ral” (i.e., unpolluted) rain, which itself is often mildly acidic due to the
presence in it of dissolved atmospheric carbon dioxide, which forms carbonic
acid, H2CO3.
CO2(g) ⫹ H2O(aq) H2CO3(aq)
The weak acid H2CO3 then partially ionizes to release a hydrogen ion, H⫹,
with a resultant reduction in the pH of the system:
H2CO3(aq) H⫹ ⫹ HCO3⫺
Because of this source of acidity, the pH of unpolluted, “natural” rain is about
5.6 (see Problem 3-15a). Only rain that is appreciably more acidic than this—
i.e., with a pH of less than 5—is considered to be truly “acid” rain since,
because of natural trace amounts of strong acids, the acidity level of rain in
clean air can be a little greater than that owing to carbon dioxide alone.
Strong acids such as hydrochloric acid, HCl, produced by emissions of
hydrogen chloride gas by volcanic eruptions can produce “natural” acid rain
temporarily in regions such as Alaska and New Zealand. On the other hand,
the pH of unpolluted rain can be somewhat greater than 5.6 due to the pres-
ence of weakly basic substances such as carbonates originating with airborne
soil particles that have partially dissolved in the droplets.
The two predominant acids in acid rain are sulfuric acid, H2SO4, and
nitric acid, HNO3, both of which are strong acids. Generally speaking, acid
rain is precipitated far downwind from the source of the corresponding pri-
mary pollutants, namely sulfur dioxide, SO2, and nitric oxide, NO. The
strong acids are created during the transport of the air mass that contains
the primary pollutants.
O2
H O H2SO4
SO2 9: 2
Overall reactions
O2
NOX 9:
H2O HNO3
baird_ch04.indd 137 2/2/12 11:57 AM

The late economist- Consequently, acid rain is a pollution problem that does not respect state or
philosopher John Kenneth national boundaries because of the long-range transport that the atmospheric
Galbraith once noted, “Acid pollutants often undergo. For example, most acid rain that falls in Norway,
rain falls on the just and the Sweden, and the Netherlands originates as sulfur and nitrogen oxides emit-
unjust and also equally on
ted in other countries in Europe. Indeed, the modern recognition of acid rain
the rich and poor.”
Economists recognize this as a problem stems from observations made in Sweden in the 1950s and
effect as an externality or an 1960s, which were due to emissions from outside its borders.
external cost. The
economic, environmental,
and social costs of acid rain 4.3 The Acids and Acidity of Acid Rain
are not reflected in the
Acid rain has a variety of ecologically damaging consequences, and the pres-
price of fossil fuels, but this
cost is borne by all who ence of acid particles in air may also have direct effects on human health.
reside in “the commons.” However, the effects of acid rain on soil vary dramatically from region to
region. In this section, we investigate the chemical processes underlying the
ecological effects of acid rain.
Nitric oxide is not especially soluble in water, and the acid (sulfurous) that
sulfur dioxide produces upon dissolving in water is a weak one. Consequently,
the primary pollutants NO and SO2 themselves do not make rainwater par-
ticularly acidic. However, some of the mass of these primary pollutants is
converted over a period of hours or days into the secondary pollutants nitric
acid and sulfuric acid, both of which are very soluble in water and are strong
acids. Indeed, virtually all the acidity in acid rain is due to the presence of these
two acids. In eastern North America, sulfuric acid greatly predominates
because some electrical power is generated from power plants that use high-
sulfur coal. In western North America, nitric acid attributable to vehicle emis-
sions is predominant, since the coal mined and burned there is low in sulfur.
Figure 4-2 shows a contour map of the average pH in precipitation in
different regions of the world. The lowest pH ever recorded, 2.4, occurred for
a rainfall in April 1974 in Scotland. Indeed, central-west Europe, including
the United Kingdom, has a serious acid rain problem, as can be seen from the
pH ⫽ 4.0 and 4.5 contours surrounding the area in Figure 4-2. In North
America, the greatest acidity occurs in the eastern United States and in
southern Ontario, since both regions lie in the path of air originally polluted
by emissions from power plants in the Ohio valley. On the other hand, much
of the acidity that falls in upper New York State stems from emissions in
southern Ontario.
In addition to the acids delivered to ground level during precipitation, a
comparable amount is deposited on the Earth’s surface by means of dry
deposition, the process by which nonaqueous chemicals are deposited
onto solid and liquid surfaces at ground level when air containing them
passes over the surfaces. Much of the original SO2 gas is not oxidized in the
air but rather is removed by dry deposition from air before reaction can occur:
oxidation and conversion to sulfuric acid occurs after deposition. Wet deposi-
tion processes encompass the transfer of pollutants to the Earth’s surface by
rain, snow, or fog—i.e., by aqueous solutions.
baird_ch04.indd 138 2/2/12 11:57 AM

Acid Rain 139
5.0 4.5
5.0 5.5
4.5 4.0
6.0 6.0
4.0
5.0 5.0 6.0
5.0
5.5
5.5
Estimated distribution of pH
FIGURE 4-2 Global pattern of acidity of precipitation. [Source: Redrawn from J. H. Seinfeld and
S. N. Pandis, Atmospheric Chemistry and Physics (Chichester: John Wiley, 1998).]
In recent years, a new source of sulfuric acid in lakes has appeared—the

oxidation of sulfur in shallow wetlands dried up by global warming and
thereby exposed to the air.
As Problem 4-1 shows, the oxidation of ammonium ion, NH4⫹, to
nitrate ion produces hydrogen ions. Indeed, the large emissions of ammonia
into the air from manure in areas of livestock and poultry farming result in
the atmospheric deposition of ammonium ion, which then is oxidized by soil
microbes. The resulting H⫹ contributes to the acidification of soil. Large-
scale agriculture in China produces extensive emissions of ammonia, so acid-
ity from ammonium ion presents a problem there.
PROBLEM 4-1
Note that the techniques
Deduce the balanced redox half-reaction of conversion of ammonium ion, for balancing redox
equations are reviewed in
NH4⫹, to nitrate ion, NO3⫺, and thereby show that H⫹ is also produced in the Appendix.
this process. ●
4.4 Neutralization of Acid Rain by Soil

The extent to which acid precipitation affects biological life in a given area
depends strongly upon the composition of the soil and bedrock in that
baird_ch04.indd 139 2/2/12 11:57 AM

area. If the bedrock is limestone or chalk, the acid can be efficiently neutral-
ized (“buffered”), since these rocks are composed of calcium carbonate,
CaCO3, which acts as a base and reacts with acid, producing bicarbonate
ion, HCO3⫺, as an intermediate:
CaCO3(s) ⫹ H⫹(aq) 9: Ca2⫹(aq) ⫹ HCO3⫺(aq)
HCO3⫺(aq) ⫹ H⫹(aq) 9: H2CO3(aq) 9: CO2(g) ⫹ H2O(aq)
The reactions here proceed almost to completion, owing to the excess of H⫹
that is present. Thus the rock dissolves, producing carbon dioxide and replac-
ing the hydrogen ion by calcium ions. Neutralization by calcium carbonate
and similar compounds that are commonly present as suspended particles in
atmospheric dust is the mechanism by which carbonic acid in normal rain-
The milky-white color of fall, and acid rain over some areas, has a greater than expected pH. These
India’s famed Taj Mahal is same reactions are responsible for the deterioration of limestone and marble
losing its luster and turning
pale due to acid rain.
statues; fine detail, such as ears, noses, and other facial features, are gradually
lost as a result of reaction with acid and with sulfur dioxide itself.
In contrast, areas strongly affected by acid rain are those having gran-
ite or quartz bedrock, since the soil there has little capacity to neutralize the
acid. Figure 4-3 shows areas of North America having low soil alkalinity, i.e.,
low amounts of basic compounds with which acids can react. Large areas
susceptible to acidity are the Precambrian Shield regions of Canada and
Scandinavia. Acid rain resulting from the
massive development of the tar sands to
produce synthetic crude oil in northern
Alberta, and the SO2 and NOX emissions
that result, are now affecting areas in
Manitoba and northern Saskatchewan
that lie upwind from them, since the soils
in these two areas have very little neutral-
izing capacity (Figure 4-3).
Acidity from precipitation leads to
the deterioration of soil. When the pH of
soil is lowered, plant nutrients such as the
cations of potassium, calcium, and mag-
nesium are exchanged with H⫹ and there-
upon leached from it. Lakes rely on
calcium ion produced by weathering of
land-based soil and rocks that later is
washed into them. The initial effect of
acid rain therefore is to increase the cal-
cium ion concentration in nearby lakes,
FIGURE 4-3 Regions of North America with low soil alkalinity for
but eventually the Ca2⫹ level declines
neutralizing acid rain. [Source: D. J. Jacob, Introduction to Atmospheric once the acid has leached most calcium
Chemistry (Princeton, NJ: Princeton University Press, 1999), p. 233.] from the soil. Waterborne life that
baird_ch04.indd 140 2/2/12 11:57 AM

Acid Rain 141
depends on calcium can be threatened by the subsequent low levels of the

element.
China now has serious acid rain problems due to its high emissions of SO2
from power plants. Acidification is more serious in southern and southwestern The neutralizing dust does
areas than in northern China, where airborne alkaline dust swept in from desert not reach southern China.
areas neutralizes the acidity. Some of the acid rain that originates in China is
carried by the wind to Japan and on occasion all the way to North America.
4.5 Neutralization of Acid Rain by Anthropogenic Actions

Although as a consequence of governmental regulations sulfur dioxide emis-
sion levels fell significantly in recent decades in both Europe and North
America, there has not been as large a corresponding change in the pH of the
precipitation, especially in northeastern North America. Ironically, the lack
of corresponding reduction in acidity is attributed to a decline over the
same period of fly ash emissions from smokestacks and of other solid par-
ticles, all of which are alkaline and in the past neutralized a fraction of the
sulfur dioxide and sulfuric acid in the same way that calcium carbonate
operates in soil. The reduction in sulfate deposition in the northeastern
United States and south-central Canada from the early 1980s to the late
1990s is shown in Figures 4-4a and 4-4b, respectively. Overall, sulfate deposi-
tion rates had fallen by 43% across the eastern United States by 2009.
1980–1983 1995–2000
kg/ha/yr kg/ha/yr
35 35
30 30
25 25
20 20
15 15
FIGURE 4-4 Wet sulfate deposition in eastern North America as a four-year mean (kilograms
per hectare per year). [Source: Canadian National Atmospheric Chemistry Database, Meteorological
Service of Canada, Environment Canada.]
baird_ch04.indd 141 2/2/12 11:57 AM

Because of acid rainwater falling and draining into them, tens of thousands
of lakes in the Precambrian Shield regions of both Canada and Sweden have
become strongly acidified, as have lesser numbers in the United States, Great
Britain, and Finland. Lakes in Ontario are particularly hard hit, since they lie
directly in the path of polluted air and since the soil there contains little lime-
stone. In a few cases, attempts have been made to neutralize the acidity by
adding limestone or calcium hydroxide, Ca(OH)2, to the lakes; however, this
process must be repeated every few years to sustain an acceptable pH. Adding
phosphate ion, PO43⫺, to lakes can also control acidity, since it stimulates
plant growth during the natural denitrification process by which nitrate ion,
NO3⫺, is converted to reduced nitrogen with the consumption of large quanti-
ties of hydrogen ions, as shown in the reduction half-reaction
⫹
Nitrate neutralizes H ;
ammonium ion produces it.
2 NO3⫺ ⫹ 12 H⫹ ⫹ 10 e⫺ 9: N2 ⫹ 6 H2O
In Australia, soil acidity has a completely different origin. Acidification
is associated there with the removal, by harvest of plant and animal crops
and by soil leaching, of nitrate ion. Presumably, the loss of nitrate prevents
its natural buffering of acidity by the reaction shown above. As in Canadian
lakes, the effects of the acidification have been partially reversed in Australia
by the addition of lime to the soil.
The regulatory scheme used in the United States of requiring reductions in
sulfur dioxide emissions in certain designated geographical regions has been
extended by European scientists and regulators into the concept of critical
load, which recognizes that different levels of risk from acid rain are faced
in different regions. Geographical areas having buffering capacity can with-
stand a much greater input of acid rain before damage occurs than those with-
out the capacity. Thus, higher sulfur dioxide emissions from a particular region
can be allowed if the area in which the resulting sulfuric acid is usually depos-
ited has a high critical load. To determine the critical loads for different
regions, scientists use computer models that incorporate soil chemistry, rainfall,
topography, etc. The use of the concept has had great success in Sweden, for
example.
In using critical loads, pollution control becomes effects-based rather
than source-based. Although the critical loads concept has been imple-
mented in regulations in Europe and Canada, and is favored by many scien-
tists and politicians in the United States, it has not been implemented there.
Although significant progress has been made in reducing SO2 emissions, and
more reductions are scheduled both for it and for NOX, scientists predict that
these efforts will be insufficient to allow a full recovery to lakes and forests in
northeastern United States and south-central Canada.
Acid rain is still a serious environmental problem in many areas of the
world, especially where unregulated coal-fueled power plants are numerous
and there is no source of alkalinity to neutralize it. Although acid rain is less
of a problem now in developed countries than it was in the late twentieth
century, it is becoming a serious concern in many developing countries.
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Acid Rain 143
4.6 Environmental Effects of Acid Rain

Acid rain in the United States was considered initially to be a problem for
its northeastern region. Indeed, one of the hardest-hit regions is the Catskill
Mountains in New York State, whose surface rocks consist of calcium-poor
sandstone and from which most of the nutrients have now been leached. At
the Hubbard Brook Experimental Forest in New Hampshire, half the calcium
and magnesium in soil was leached by 1996 and, as a result, vegetative
growth almost stopped. However, as a consequence of the reduction in SO2
emissions, by 2003 over half the lakes in the Adirondack Mountains of New
York State showed some significant recovery from acid rain. Unfortunately,
full recovery for these lakes is predicted to take another 25 to 100 years to
achieve.
Acid rain now is also a concern in the southeastern United States. Here
soils are generally thicker and were able to neutralize more acid. However,
much of that leaching ability now has been exhausted and acid levels in
many waterways have increased substantially. It has been discovered that the
recovery of such soils, and of those in Germany, is slowed once acid precipi-
tation has declined, because previously stored sulfate ion is then released,
causing more cation leaching and penetration of acidity deeper into the
ground.
Acidification reduces the ability of some plants to grow, including those in
fresh-water systems. Because of the decrease in this productivity in lakes and
streams that feed them, the amount of dissolved organic carbon (DOC) in the
surface water has declined. The DOC contains molecules that absorb some of
the ultraviolet from sunlight; thus, a decline in DOC levels has allowed more
penetration of UV light into the lower layers of the lake. In addition, global
warming has resulted in the drying up of some streams that supplied DOC to
lakes. Furthermore, stratospheric ozone depletion has also allowed more UV to
reach the Earth’s surface, including lakes, in the first place. Thus fresh-water
lakes have suffered a “triple whammy” from global environmental problems.
ACTIVITY
Using the internet and/or library resources, discover the region geographi-
cally closest to you that has or has had a problem with acid rain. What is or
were the main sources of emissions that caused the acidity? What steps have
been taken to reduce the emissions, and to remediate the soil and water of
excess acidity?
4.7 Release of Aluminum into Water Bodies by Acid Rain

Acidified lakes characteristically have elevated concentrations of dissolved
aluminum ion, Al3⫹, and it is now known that many of the biological Aluminum is called
aluminium in many parts of
effects of acid rain are due to increased levels of aluminum ion dissolved the world.
in water rather than to the hydrogen ion itself.
baird_ch04.indd 143 2/2/12 11:57 AM

Aluminum ions are leached from rocks in contact with acidified water
by reaction with the hydrogen ions; under normal, near-neutral pH condi-
tions, the aluminum is immobilized in the rocks by their insolubility.
H⫹
Al compounds(s) 9: Al3⫹
Plots of dissolved aluminum concentration versus water acidity for lakes in
the Adirondack Mountains of New York State and for lakes in Sweden are
illustrated in Figure 4-5 and confirm this origin. (The chemistry underlying
these processes is further discussed in Chapter 10, as are the reasons why
natural waters have pH values of 7 or 8, rather than the 5.3 of rain, and why
aluminum mobilization leads to dieback of trees.)
Scientists believe that both the acidity itself and the high concentra-
tions of aluminum together are responsible for the devastating decreases in
fish populations that have been observed in many acidified water systems.
Different types of fish and aquatic plants vary in their tolerances for alumi-
num and acid, so the biological composition of a lake varies as it gradually
becomes increasingly acidic. Generally speaking, fish reproduction is severely
diminished even at low levels of acidity that can, however, be tolerated by
adult fish. Very young fish, hatched in early spring, are also subject to the
shock of very acidic water that occurs when the acidic winter snow all melts
in a short time and enters the water systems.
Healthy lakes have a pH of about 7 or a little higher; few fish species
survive and reproduce when the pH drops much below 5. As a result, many
lakes and rivers in affected areas are now devoid of their valuable fish; e.g.,
30% of the salmon rivers in Nova Scotia are too acidic for Atlantic salmon
to survive. The water in many acidified lakes is crystal clear due to the death
of most of the flora and fauna.
However, aluminum levels in drainage from soils at medium-to-high eleva-
tions in the United States declined significantly over the period from 1984 to
1998, and if the trend continues, will not be a threat to fish by about 2012.
Adirondacks, U.S.A. West coast, Sweden
(a) (b)
1.0 1.0
Aluminum concentration
FIGURE 4-5 Aluminum

(mg/L)
concentrations versus pH of
the water in different fresh-
water lakes in (a) the 0.1 0.1
Adirondacks and (b)
western Sweden. Notice the
logarithmic vertical axis.
[Source: M. Havas and
0.01 0.01
J. F. Jaworski, Aluminum in the
4 5 6 7 8 4 5 6 7 8
Canadian Environment (Ottawa:
National Research Council of
pH pH
Canada Report 24759, 1986).]
baird_ch04.indd 144 2/2/12 11:57 AM

The Human Health Effects of Outdoor Air Pollutants 145
4.8 Effects of Air Pollution on Trees and Crops

Air pollution can have a severe effect on trees. The phenomenon of forest
decline was first observed on a large scale in western Germany and occurs
mainly at high altitudes. However, the cause-and-effect relationship behind this
forest decline has been very difficult for scientists to untangle. As discussed
above, acidification of the soil can leach nutrients from it and, as occurs in
lakes, solubilize aluminum. This element may interfere with the uptake of nutri-
ents by trees and other plants. Apparently, both the acidity of the rain falling
on affected forests and the tropospheric ozone and other oxidants in the air
to which they are exposed pose significant stresses to the trees. These two
stresses alone will not kill them, but when combined with drought, temperature
extremes, disease, or insect attack, the trees become much more vulnerable.
Forests at high altitudes are most affected by acid precipitation, possibly
because they are exposed to the base of low-level clouds, where the acidity is most
concentrated. Fogs and mists are more acidic even than precipitation, since there
is much less total water to dilute the acid. For example, white birch trees along
the shores of Lake Superior experience dieback in regions where acid fog occurs,
as it frequently does there. Deciduous trees (i.e., those that lose their leaves annu-
ally) affected by acid rain gradually die from their tops downward; the outermost
leaves dry and fall prematurely and are not replenished the following spring. The
trees become weakened as a result of these changes, and become more susceptible
to other stressors. In some regions of Europe and North America, forest soils are
limed in order to combat the effects of acidity on trees.
Ground-level ozone itself has an effect on some agricultural crops due to
its ability to attack plants. Apparently the ozone reacts with the gas (ethene)
that the plants emit, generating free radicals that then damage plant tissue.
The rate of photosynthesis is slowed, and hence the total amount of plant
material is reduced, by the action of ozone. As in the case of trees, air pollu-
tion acts as a stressor to plants.
The collective damage from air pollution to North American crops, e.g.,
alfalfa in the United States and white beans in Canada, is estimated to be
$3 billion a year—another example of external costs arising from environmental
problems. Other crops whose yields are adversely affected by current levels of
ozone include wheat, corn, barley, soybeans, cotton, and tomatoes. Ozone has
also caused crop losses in many regions of China. The fraction of the world’s Review Questions 1–6 are
based on the material
cereal crops that are grown in regions of high ozone, and therefore subject to covered above.
damage, is predicted to more than triple by 2025.
The Human Health Effects of Outdoor Air Pollutants

Breathing polluted air can have a dramatic, negative influence on human
health. In this section, the most important of these effects of outdoor air pol-
lutants are described, and the variation in concentration of the dominant air
pollutants between different countries is discussed.
baird_ch04.indd 145 2/2/12 11:57 AM

The effect that pollutants have on human health cannot be deduced

from general principles of biology or physiology, but must be established by
experimentation. One can imagine experiments involving animals or
human volunteers in which the health effects of exposure to brief periods
of artificially produced high-level pollution are studied. However, the
extrapolation of information gained from short-term studies of high-level
pollution to long-term exposures at low levels is difficult. In particular, for
some pollutants, there may exist a threshold pollutant concentration, or
exposure below which a particular health effect does not occur. In these
cases predictions obtained by assuming simple direct proportionality
between exposure and effect would be unwarranted. In addition, there
could be deleterious effects of chronic exposure that do not come into play
when exposure, even intense exposure, to pollutants occurs only for brief
periods of time.
For these reasons, the best information regarding the effects of pollutants
on health comes from the large scale “experiment” in which we are all
enrolled as “test animals”—namely, living in a society in which we are rou-
tinely exposed to these pollutants for our whole lives. Because the level of
exposure to any given pollutant varies considerably from place to place, sci-
entists can collect information on health and on pollution levels in different
locations, and correlate them using statistics to establish the effect of one
upon the other.
For example, several North American studies have statistically linked
the rate of hospitalization for congestive heart failure among elderly people
to the daily carbon monoxide concentration in outside air. Mexico City cur-
rently has the highest levels of carbon monoxide among the world’s most
polluted cities. However, both CO and NO2 are usually more of a problem in
indoor air, and will be discussed in detail in a later section.
It is a historical characteristic that once an undeveloped country starts
industrial development, its outdoor air quality worsens significantly. The
situation continues to deteriorate until a significant degree of affluence is
attained, at which point emission controls are enacted and enforced, and
the air begins to clear. Thus, although the quality of air is now improving
with time in most developed countries, it is worsening in the larger cities of
developing countries.
Mexico City and several urban areas in China, especially Beijing, are
generally considered to have the worst urban air pollution in the world at
present. In 2002, thirteen of the twenty world cities having the highest aver-
ages for airborne particulate matter were located in China, five in India, plus
Cairo, Egypt, and Jakarta, Indonesia. Half the respiratory disease in China is
caused by air pollution. A report by the United Nations Environmental
Program (UNEP) estimates that deaths worldwide from all forms of air
pollution amounted to 2.7–3.0 million in 2001, a figure that may rise to
8 million by 2020.
baird_ch04.indd 146 2/2/12 11:57 AM

As would be expected, the major effects on human health from air pol-
lution occur in and through the lungs. For example, asthmatics suffer worse
episodes of their disease when the sulfur dioxide or the ozone or the particulate
concentration rises in the air that they breathe. A study in California found
that asthma can be caused by air pollution, specifically by ozone, and espe-
cially among highly active children, who naturally inhale more air into their
lungs. A study in British Columbia found that exposure to air pollution—
especially NOX and CO—from traffic during gestation and the first year of life
increases the risk of developing asthma in childhood.
4.9 The Health Effects of Soot-and-Sulfur-Dioxide Smog

In the middle decades of the twentieth century, several Western industrial-
ized cities experienced wintertime episodes of smog from soot-and-sulfur
pollution that were so serious that the death rate increased noticeably. For
example, in London, England in December 1952 about 4,000 people died
within a few days—plus 8,000 more in the next few months—as a result of
the high concentrations of these pollutants that had built up in a stagnant,
foggy air mass trapped by a temperature inversion close to the ground. Those
at most risk were elderly persons already suffering from bronchial problems,
and young children. A ban of household coal burning, from which most of
the pollutants originated, has now largely eliminated such problems. Scien-
tists are still unsure whether the main sulfur-containing agent that caused
such serious problems in London was the SO2, the sulfuric acid droplets, or
the sulfate particulates.
Today, due to pollution controls, soot-and-sulfur smogs are no longer a
major problem in Western countries. For example, deaths from bronchitis
have fallen by more than half in the United Kingdom, the result of changes
in air quality (and smoking habits). However, the quality of winter air in
some areas of what was the Eastern bloc of countries, such as southern
Poland, the Czech Republic, and eastern Germany, until recently was very
Brown coal can contain up
poor on account of the burning of large amounts of high-sulfur “brown coal” to 15% sulfur.
for both industrial and home-heating purposes.
For example, although the acceptable limit for the concentration of SO2
in air is 80 ␮g m⫺3 in many countries, the level of this gas in Prague surpassed
3,000 ␮g m⫺3 on occasion in the late twentieth century. Indeed, four out of
five children admitted to the hospital in some areas of Czechoslovakia in the
early 1990s were there for treatment of respiratory problems. However, the
average SO2 level in Prague decreased by about 50% from the early 1980s to
the early 1990s, and overall in the Czech Republic SO2 emissions are now
only a few percent of 1990 levels. The tremendous improvement of air qual-
ity in eastern Germany since 1990, where mean SO2 levels have dropped
from 113 to 6 ␮g m⫺3, has seen a decrease in childhood respiratory infections
and an increase in lung function.
baird_ch04.indd 147 2/2/12 11:57 AM

The effects of sulfur dioxide are also evident in cities such as Athens,
where the death rate increases by 12% when the concentrations of the gas
exceeds 100 ␮g m⫺3. Carved detail on the ancient statues and monuments of
Athens is also being seriously eroded by sulfur dioxide and its secondary pol-
lutants. And the air in London is not so improved that it does not affect
human health. A recent study concluded that one in every 50 heart attacks
was triggered by outdoor air pollution, from a combination of smoke, CO,
SO2, and NO2.
European cities are not the only ones affected by air pollution. Both
sulfur dioxide and particulate matter levels regularly exceed World Health
Organization guidelines (see Tables 3-1 and 3-2) in Beijing, Seoul, and
Mexico City. In many large cities in the developing world, coal is still the
predominant fuel and in many of them diesel-powered vehicles substantially
worsen the problem. In Beijing, high SO2 emissions from coal-burning fur-
naces in buildings, plus smoke from smelters on the edges of the city, plus
windblown dust and sand from the Gobi Desert, combine to produce poor air
quality. Indeed, there are a number of cities in China in which the air quality
is among the poorest in the world. According to recent projections, if no
attempts are made to reduce SO2 emissions as industrialization increases,
then by 2020 the concentration of the gas in Mumbai and the Chinese cities
of Shanghai and Chongqing will be about four times the WHO maximum
safe limit.
Although acute smog episodes from soot and sulfur-based chemicals
have been eliminated in the West, many residents in these countries still are
chronically exposed to measurable levels of suspended particles containing
sulfuric acid and sulfates due to the long-range transport of these substances
from industrialized regions that still emit SO2 into the air. For example,
research has shown a positive correlation between atmospheric concentra-
tions of oxidized sulfur and ozone and hospital admissions for respiratory
problems in southern Ontario. There is some evidence that the acidity of the
pollution is the main active agent in causing lung dysfunction, including
wheezing and bronchitis in children. Asthmatic individuals are adversely
affected by acidic sulfate aerosols, even at very low concentrations.
It has been speculated that pollution due to SO2
and sulfates causes a decrease in resistance to colon and
breast cancer in people living in northern latitudes.
The suggested mechanism of this action is a reduction
in the amount of available UV-B that is necessary to
form vitamin D, which is a protective agent for both
AP Photo/Mikhail Metzel
types of cancers. Since sulfur dioxide absorbs UV-B and

sulfate particles scatter it, significant concentrations of
either substance in air will reduce the amount of UV-B
reaching ground level. Thus too little UV-B can have
detrimental health effects, just as too much of it does—
as was outlined in Chapter 1.
baird_ch04.indd 148 2/2/12 11:57 AM

4.10 The Health Effects of Photochemical Smog

Photochemical smog, which arises from nitrogen oxides, is now more
important than is soot-and-sulfur smog in most cities, particularly those
with high population and vehicle density. As discussed in Chapter 3, it
consists of gases such as ozone, and an aqueous phase containing water-
soluble organic and inorganic compounds in the form of suspended particles.
In contrast to “London smogs,” which chemically were reducing in nature
due to the presence of sulfur dioxide, photochemical smogs are oxidizing.
PROBLEM 4-2
Deduce the balanced half-reaction in which SO2 acts as a reducing agent

in an acidic environment, given that it is oxidized to sulfate ion, SO42⫺, in
the process. ●
Ozone itself is a harmful air pollutant. In contrast to sulfur-based chemi-

cals, its effect on the robust and healthy is as serious as on those with pre-
existing respiratory problems. Experiments with human volunteers have shown
that ozone produces transient irritation in the respiratory system, giving rise
to coughing, nose and throat irritation, shortness of breath, and chest pains
upon deep breathing. People with respiratory problems can often tell from their
symptoms—such as the tightening of the chest or the beginning of a cough—
when the air quality is poor. Even healthy young people often experience such
symptoms while exercising outdoors by cycling or jogging during smog episodes.
Indeed, there is evidence that the daily race times of cross-country runners
increase with increasing ozone concentration in the air that they inhale.
A few percent of the day-to-day fluctuations in mortality rate in Los
Angeles is explained by variations in the concentrations of air pollutants. An
analysis of 95 urban centers in the United States discovered that a period of
high ozone concentrations increased daily cardiovascular and respiratory
mortality by about 0.5% per 10-ppb increase following a few days of continu-
ous exposure. It is not yet clear what, if any, long-term lung dysfunction
results from exposure to ozone. Exposure to ozone produces a number of
indirect health effects as well—including a decrease in sperm count.
One anticipated effect of ozone is a decreased resistance to disease from
infection because of the destruction of lung tissue; chronic exposure to high
levels of urban ozone leads to the premature aging of lung tissue. At the molec-
ular level, ozone readily attacks substances containing components with
CRC bonds, such as occur in biological tissues of the lung. As discussed later,
the fine particulates produced in the photochemical smog process can have a
deleterious health effect on humans.
Ozone is not the only gas in photochemical smog that can affect health.
A recent study of patients of a respiratory disease clinic in Toronto discovered
that the subsequent rate of mortality from circulatory disease suffered by the
patients increased the higher their exposure to traffic-related air pollution, as
baird_ch04.indd 149 2/2/12 11:58 AM

measured by the concentration of NO2 in the air near their homes. This study
reinforced similar results found from studies in Holland, Norway, and Califor-
nia regarding the toxicity and health effects of vehicle emissions.
Finally, we note that there are some positive effects of photochemical air
pollution upon human health! For example, the rate of skin cancers in areas
heavily polluted by ozone is probably reduced because of the ability of the gas
to filter UV-B from sunlight.
4.11 Particulates as Health Risks

Particulate matter in the form of smoke from coal burning has been an air
pollution problem for hundreds of years, especially in the United Kingdom.
John Evelyn wrote in his January, 1684 diary that “London by reason of the
excessive coldness of the air, hindering the ascent of the smoke, was so filled
Perhaps Shakespeare was with the fuliginous [sooty] steam of sea-coal, that hardly could one see across
referring to this type of air the street, and this filling the lungs with its gross particles exceedingly
pollution in the quotation obstructed the breast, so as one would scarce breathe.” Indeed, unsuccessful
from Hamlet that opened
Chapter 3.
attempts to control coal burning and punish offenders had begun in the thir-
teenth century in Britain.
One important reason that inhaled particles cause so much damage to
human health is their ability to carry organic molecules and metal ions on
their surfaces into the lungs and to release them there. Substances that dis-
solve into the body of a particle are said to be absorbed by it; those that
simply stick loosely to the surface of the particle are said to be adsorbed
(see Figure 4-6). An important example of the latter is represented by the
adsorption of large organic molecules onto the surfaces of carbon (“soot”)
particles, as discussed later in Chapter 15. Many insoluble airborne particles
are surrounded by a film of water, which can itself dissolve other substances.
Large particles—coarse ones, according to the defini-
Adsorbed tion in Chapter 3—are of less concern to human health
molecule than are small (“fine”) ones for several general reasons:
• Since coarse particles settle out quickly, human
exposure to them via inhalation is reduced.
Particle
• When inhaled, coarse particles are efficiently filtered by
the nose (including its hairs) and throat and generally do
not travel as far as the lungs. In contrast, inhaled fine
particles usually travel through to the lungs (which is why
Absorbed
they are called respirable), can be adsorbed on cell surfaces
molecule there, and can consequently affect our health.
• The ratio of surface area to mass of large particles is
FIGURE 4-6 Contrast smaller than that of small ones, and thus, gram for gram, their ability to
between adsorption and
absorption of molecules on
transport adsorbed gas molecules to any parts of the respiratory system and
and in an airborne particle there to catalyze chemical and biochemical reactions is correspondingly
(schematic). smaller.
baird_ch04.indd 150 2/2/12 11:58 AM

• Devices such as electrostatic precipitators, spray towers, and cyclone

collectors that are used to remove particulates from air are efficient only for
coarse particles. Thus, although a device may remove 95% of the total
particulate mass, the reduction of surface area and of respirable particles is a
much lower fraction; see Problem 4-3. Baghouse filters, which are finely
woven fiberglass fabric bags through which air is forced (as in a vacuum
cleaner), are highly efficient in removing fine particles in the 1-␮m size
range, and all the larger ones as well.
PROBLEM 4-3
An air-filtering device is tested and is found to remove all particles larger

than 1 ␮m in diameter, but almost none of the smaller ones. Calculate the
percentage of surface area removed by the device for a sample of particulates,
95% of the mass of which is particles of diameter 10 ␮m and 5% of which is
particles of diameter 0.1 ␮m. Assume all particles are spherical and of equal
density. [Hint: Recall that the surface area of a sphere is 4␲r2. Calculate the
surface areas of particles of each size from this formula.] ●
The air pollution parameter that correlates most strongly with

increases in the rate of disease or mortality in most regions is the concen-
tration of respirable (fine) particulates, PM2.5. Epidemiological studies have
shown consistent and significant strong associations between mortality from
both acute and long-term exposure to airborne particulate concentrations in
Acute means short-term
the air, especially to the fine component (PM2.5), whether produced by exposure at a high level.
vehicle exhaust or power-plant emissions. Indeed, particulate-based air pol-
lution is found to have a greater influence on degrading human health
than that produced directly by any gaseous pollutant, even ozone.
The strongest links between human health and exposure to airborne Case
particulate matter are based on studies involving cities in the United States, Studies
and are the subject of the Case Study The Effect of Urban Air Particulates on
Human Mortality at the website associated with this chapter.
An even more recent study of teachers in California found a correlation
between the level of long-term exposure to PM2.5 and the likelihood of death
from cardiopulmonary diseases; the most dangerous fine particulates were
discovered to be sulfates and organic carbon. A new study of data from across
the United States confirms that, although PM2.5 particulates play the stron-
gest role among air pollutants in increasing acute mortality from stroke, heart
attacks, cardiovascular disease, and respiratory problems, the smallest of the
coarse ones (i.e., those included in PM10⫺2.5) also cause some increase in the
death rate, although there are regional variations in the toxicity of these
larger particles.
A number of studies have correlated day-to-day urban morbidity (sickness)
rates, as measured by hospital admission rates, for respiratory problems, against
the pollution levels during the same short time period. For example, there have
baird_ch04.indd 151 2/2/12 11:58 AM

been several reports concerning the imme-

diate effects on the population of southern
Ontario of the pollutants—ozone gas and
sulfate particulates—to which they are most
exposed. In one study, the average number
of hospital admissions for respiratory prob-
lems correlated best with the ozone level of
the previous day, and to a slightly lesser
Erik Simonsen/Getty Images
degree with the sulfate level from the previ-

ous day, for the summers of 1983–1988. Air
pollution was found to account for about
6% of summertime hospital respiratory
admissions, a magnitude close to that found
in previous investigations in Ontario and
The California wildfires of 2008. New York State. Respiratory admissions
correlated significantly with both PM10 and ozone concentrations in Spokane,
Washington—an area where atmospheric sulfur dioxide is essentially nonexis-
tent and therefore can be ruled as the true culprit in causing the illnesses.
Airborne particulates in both the PM2.5 and PM10–2.5 ranges collected
from the air during wildfires in California and Alaska have been found to be
much more toxic than comparable quantities from ambient air in studies
performed on mice. The toxicity apparently results from carbon-centered
free radicals, which may have been produced from reactive metals on the
particles.
Although most of the studies relating human health to air pollution have
not dealt with cancer, it is nevertheless of some concern. The exhaust from
diesel engines has been classified as “likely to be carcinogenic to humans” by
Review Questions 7–9 are the U.S. EPA. Studies in California and in Seattle conclude that 70% or more
based on the material in the
preceding section.
of the risk to human health arises from hazardous organic pollutants in the
diesel exhaust.
Indoor Air Pollution

The levels of some common air pollutants often are greater indoors than
outdoors, although pollutant concentrations do vary significantly from one
building to another. Since most people spend more time indoors than out-
doors, exposure to indoor air pollutants is an important environmental
concern, and may cause more problems to human health than does poor
outdoor air.
In the material that follows, we investigate the various indoor air pollut-
ants that are thought to have the most serious effects on human health. In
order that the necessary background material will have been covered, a dis-
cussion of several other indoor air pollutants of interest to human health is
deferred until later chapters: radon is discussed in Chapter 9, pesticides in
Chapter 13, and PAHs in Chapter 15. Chloroform in indoor air is considered
baird_ch04.indd 152 2/2/12 11:58 AM

Indoor Air Pollution 153
when water purification is discussed, along with indoor air contamination by

chlorinated organic solvents, in Chapter 11.
4.12 Formaldehyde
The most controversial indoor organic air pollutant gas is formaldehyde,
H2CRO. It is a widespread trace constituent of the atmosphere since it
occurs as a stable intermediate in the oxidation of methane and of other
VOCs. While its concentration in clean outdoor air is too small to be impor-
tant—about 10 ppb in urban areas, except during episodes of photochemical
smog—the level of formaldehyde gas indoors is often orders of magnitude
greater, in certain cases exceeding 1,000 ppb (1 ppm). The indoor formalde-
hyde concentration is usually in the 5–20-ppb range in American homes.
The chief sources of indoor exposure to this gas are emissions from ciga-
rette smoke and from synthetic materials that contain formaldehyde resins (a
type of plastic) used in urea formaldehyde foam insulation and in the adhesive
employed in manufacturing plywood and particleboard (chipboard). Many useful
resins (which are rigid polymeric materials) are prepared by combining formal-
dehyde with another organic substance. Formaldehyde itself is used in the dyeing
and gluing of carpets, carpet pads, and fabrics. In the first few months and years
after their manufacture, such materials release small amounts of free formal-
dehyde gas into the surrounding air. Consequently, new prefabricated struc-
tures such as mobile homes that contain chipboard generally have much higher
levels of formaldehyde in their air than do older, conventional homes. Many
manufacturers of pressed-wood products have now modified their production
processes in order to reduce the rate at which formaldehyde is released.
The rate of formaldehyde emission from synthetic materials increases
with temperature and relative humidity, and declines as the materials age.
Initially, formaldehyde temporarily trapped as a gas or simply adsorbed onto
the materials is released into the surrounding air. There is also release of
formaldehyde due to the rearrangement and dissociation of amide end-groups
on resin polymers, from R!NH!CH2OH to R!NH2 ⫹ H2CO. Later, slow
but continuous reactions of water vapor in humid air with the methylene
bridges joining amide groups within the polymer backbone provide a con-
stant emission of formaldehyde:
R!NH!CH2!NH!R ⫹ H2O 9: 2 R!NH2 ⫹ H2CO
Formaldehyde has a pungent odor, with a detection threshold in humans Formaldehyde’s odor is
of about 100 parts per billion, i.e., 0.1 ppm. At somewhat higher levels, many often noticeable in stores
people report problems of irritation to their eyes, especially if they wear con- that sell carpets and
tact lenses, and to their noses, throats, and skin. The formaldehyde in ciga- synthetic fabrics.
rette smoke can cause eye irritation. Common symptoms of acute formaldehyde
exposure include coughing, wheezing, bronchitis, and chest pains. Chronic
exposure to low levels of formaldehyde produces similar effects and respira-
tory symptoms.
baird_ch04.indd 153 2/2/12 11:58 AM

Formaldehyde in air may cause children to develop asthma, and to have

more respiratory infections and allergies and asthma, although evidence for
these effects is controversial. Dampness in homes, allowing the proliferation
of dust mites, fungi, and bacteria, also plays a large role in increasing lower
respiratory tract illnesses, especially in children.
Formaldehyde is thought to be the most important VOC in producing
what is known as sick building syndrome. This term is used to describe
situations in which the occupants of a building experience acute health and
comfort effects that seemed to be linked to the time they spend in a particu-
lar building, though no specific illness or cause is apparent. Complaints com-
monly include
• headaches;
• irritation of eyes, nose, or throat; dry cough;
• dizziness and nausea; fatigue;
• difficulty in concentrating; and
• dry or itchy skin.
Indoor air can also be

In addition to VOCs emitted from indoor sources, other factors that contrib-
contaminated with some ute to the syndrome include inadequate ventilation, pollutants entering from
of the newer organic outside the building, and biological contamination of the air from bacteria,
compounds in fire molds, pollen, and viruses that have bred in stagnant water that has accumu-
retardants, etc., as will be lated in air vents, etc.
discussed in Chapter 15.
Compounds chemically related to formaldehyde, namely the ketones
acetone, (CH3)2CRO, and 2-butanone (also called methyl ethyl ketone,
MEK) are also commonly found in indoor air in U.S. homes, owing to their
use as solvents in nail polish, paint removers, etc.
Formaldehyde is established as a carcinogen (a cancer-causing agent) in
test animals and may also be carcinogenic to humans; it was classified as a prob-
able human carcinogen by the U.S. EPA in 1987. In 2010, the EPA released a
draft report concerning the health effects, including cancer, of formaldehyde.
The expected cancer sites are in the respiratory system, including the nose, and
cancers at these sites have been found in some people who are exposed to the
gas in occupational settings.
However, studies of human populations exposed to formaldehyde have
led to no clear-cut conclusions concerning an increase in cancer frequency
arising from nonoccupational exposure to it. From animal studies, an upper
limit to the possible effect in humans can be estimated: it corresponds to an
increase in the cancer rate of one or two cases per 10,000 people after
10 years of living in a high-formaldehyde house or trailer. However, the
lower limit to the effect could well be a zero increase in cancer rate. In sum-
mary, no scientific consensus has yet been reached on the dangers to
human health of low-level exposure to formaldehyde.
baird_ch04.indd 154 14/02/12 12:20 PM

4.13 Benzene and Other Gasoline-Related Hydrocarbons

Like formaldehyde, benzene is classified as a hazardous air pollutant, HAP,
a group of compounds also called air toxics. Benzene, C6H6, is a stable, vola-
tile liquid hydrocarbon that through the modern age has found a variety Benzene
of uses.
It is a minor constituent of gasoline, and was commonly used as a solvent
for many organic products, including paints and inks. The public is exposed
to benzene vapor indoors from the use of solvents and gasoline, through
smoking (mainly for the smoker but to a lesser extent for those inhaling
second-hand smoke), and from the importing of benzene from outdoor air
into the house. The levels of benzene generally are smaller outdoors and in
large buildings than in individual homes, especially those with smokers liv-
ing in them. A significant fraction of benzene vapor exposure occurs while
riding in motor vehicles and refueling them at gas stations.
Benzene is classified by the U.S. EPA as a known human carcinogen.
Chronic exposure at high occupational levels increases the rate of leukemia
to individuals. Indeed, there were many deaths among workers in the first
half of the twentieth century from exposure to benzene from petroleum-
based solvents, such as those used in the rubber and glue industries; in the
making of paints, adhesives, and coatings; and in dry cleaning. It also causes
aplastic anemia, a condition in which an individual is chronically tired and is
especially susceptible to infections, because the bone marrow produces insuf-
ficient red blood cells. There continues to be some uncertainty, however,
about whether occupational or domestic exposure to low levels of benzene
vapor does indeed increase the risk for leukemia and multiple myeloma. It
has been estimated that benzene accounted for one-quarter of cancer deaths
caused by air toxics in the United States.
Because of the serious health problems it causes, the use of benzene CH3
as a solvent has largely been phased out. In addition, its maximum allow-
able level in gasoline has been reduced. Benzene can be replaced in many
applications by toluene, C6H5CH3, which consists of molecules of benzene
with one hydrogen atom replaced by a methyl group. The !CH3 group in
toluene provides liver enzymes with a site that is much easier to attack and Toluene
thereby initiate metabolism than any of the very strong bonds in benzene
itself. Toluene, the corresponding dimethylated benzenes called xylenes, the
1,2,4-trimethylated benzene, and ethylbenzene are all present in modern
unleaded gasoline, and are very commonly detected in indoor air, as are the
nonaromatic hydrocarbons cyclohexane and decane. The concentration of
toluene usually greatly exceeds that of benzene itself. However, there is
evidence that methylated benzenes are demethylated in automotive catalytic
converters, and that as a consequence, additional benzene is emitted into the
air under some operating conditions.
Another gaseous indoor and outdoor pollutant of concern is 1,3-
butadiene, which has the structure CH2RCH!CHRCH2. This hydrocarbon 1,3-Butadiene
baird_ch04.indd 155 2/2/12 11:58 AM

is classified as an air toxic since there is evidence that it causes cancer—

leukemia and non-Hodgkin’s lymphoma especially—and may also negatively
affect human reproduction. It is produced as a by-product of the incomplete
combustion of fuels, in forest fires and wildfires, and is a component of cigarette
smoke.
4.14 Nitrogen Dioxide

Indoor concentrations of NO2 often exceed outdoor levels in homes that
contain stoves, space heaters, and water heaters that are fueled by gas. The
N2 ⫹ O2 9: NO 9: NO2 flame temperature in these appliances is sufficiently high that some nitrogen
and oxygen in the air combine to form (thermal) NO, which eventually is
oxidized to nitrogen dioxide. In one study it was established that NO2 levels
in homes that use gas for cooking or that have a kerosene stove average
24 ppb, compared to 9 ppb of NO2 for homes that have neither. Peak con-
centrations near gas cooking stoves can exceed 300 ppb.
Some nitric oxide is also released from the burning of wood and other
biomass fuels since these natural materials contain nitrogen. However, the
flame temperature in burning such fuels is much lower than in burning gas,
so relatively little thermal NO is produced from nitrogen in the air.
Nitrogen dioxide is soluble in biological tissue and is an oxidant, so its
effects on health, if any, are expected to occur in the respiratory system.
There have been many studies of the effects on respiratory illness in children
owing to exposure to low levels of NO2 emitted by gas appliances, but the
results of different studies are not mutually consistent and are inadequate for
establishing a cause-and-effect relationship. One study found that a 15-ppb
increase in the mean NO2 concentration in a home leads to about a 40%
increase in lower respiratory system symptoms among children aged 7 to
11 years. Nitrogen dioxide is the only oxide of nitrogen that is detrimental
to health at concentrations likely to be encountered in residences.
Nitrogen dioxide is presumably responsible for the finding that indoor
concentrations of nitrous acid, HNO2, exceed those found outdoors, since
the gas reacts with water to form nitrous and nitric acids:
2 NO2 ⫹ H2O 9: HNO2 ⫹ HNO3
Indoor nitrous acid concentrations were found to correlate inversely with
HNO2 ⫹ O3 9: HNO3 ⫹ O2
ozone gas concentrations, presumably because the acid is oxidized to nitric
acid by the gas.
4.15 Carbon Monoxide

Carbon monoxide, CO, is a colorless, odorless gas whose concentration
indoors can be greatly increased by the incomplete combustion of carbon-
containing fuels such as wood, gasoline, kerosene, or gas. High indoor
concentrations usually are the result of a malfunctioning combustion
baird_ch04.indd 156 2/2/12 11:58 AM

appliance, such as a kerosene heater. Even properly functioning kerosene

or gas heaters in poorly ventilated rooms can result in CO levels in the
50–90-ppm range. Average indoor and outdoor CO concentrations usually
amount to a few parts per million, though elevated values in the 10–20-ppm
range are common in parking garages due to the carbon monoxide emitted
by motor vehicles. Exhaust fumes containing high levels of CO and other
pollutants can enter homes having attached garages. In developing countries,
carbon monoxide poisoning is a serious hazard when biomass fuels are used
to heat poorly ventilated rooms in which people sleep.
The major danger from carbon monoxide arises from its ability, when
inhaled, to complex strongly with the hemoglobin in blood and thus to
impair its ability to transport oxygen to cells. Hemoglobin’s affinity for CO
is 234 times that for oxygen, and once one CO is bound to a given hemoglo-
bin molecule, the rate of release of its remaining oxygen molecules to cells is
reduced. Recent research established that mental functioning is reduced dur-
ing short-term exposure to high levels of CO, and perhaps also as a result of
long-term exposure to low concentrations, because the brain, like the heart,
is a body organ with a high requirement for oxygen.
One important feature of the reduction in vehicular pollutant emissions
over the last few decades has been the substantial decline in accidental death
from acute carbon monoxide poisoning. In the United States alone, it has
been estimated that tens of thousands of deaths have been avoided as a
result.
Smoking tobacco is a significant source of carbon monoxide indoors.
Although nonsmokers usually have less than 1% of their hemoglobin tied up
as the complex with CO, the figure for smokers is many times this value
because of the carbon monoxide that they inhale during smoking. Studies
have shown that increased mortality from heart disease can result even if
only several percent of hemoglobin is chronically tied up as the CO complex.
Exposure to very high concentrations of CO results in headache, fatigue,
unconsciousness, and eventually death (if such exposure is sustained for long
periods).
Low-priced, easily installed carbon monoxide detectors suitable for
warning residents in homes and offices when high CO levels occur are now
widely available. However, scientists have begun to worry about the poorly
known health effects of chronic exposure to low levels of CO and the fact
that such exposure may be quite common.
4.16 Smoke from Cooking Stoves

The use of highly polluting indoor stoves—used for cooking and in some
regions also for heating and lighting—is widespread in rural areas of many
developing countries, involving an estimated three billion people. The lack
of a chimney over the stove, or even of a hole in the ceiling for smoke to
escape, means that the occupants—especially the women and small children,
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who spend more time indoors—are exposed to carbon monoxide and to high
levels of particulate pollution for extended periods every day.
Smoke production is especially pronounced as a result of inadequate
ventilation when the fuels used for the stove or for an open fire pit are wood,
coal, animal dung, crop residues, and other forms of unprocessed biomass,
presumably because such fuels are fairly high in moisture content and conse-
quently their combustion is rather incomplete. In some countries, the women
use blowpipes to give the fire more oxygen, but they inhale smoke in the
process.
As a result of being exposed to and inhaling the smoke, the young children
are particularly susceptible to eye problems and both acute and chronic respira-
tory infections such as pneumonia. Indeed, the smoke is a major killer of chil-
dren under 5 years of age. Children whose families use fire pits often suffer
severe burns when they accidently fall into them. The women also suffer from
respiratory ailments such as lung cancer, emphysema and chronic obstructive
China has set an indoor air pulmonary disease (COPD), and chronic bronchitis. Cooking smoke from bio-
quality PM10 standard of mass fuels increases asthma rates among elderly men and women. Overall,
150 ␮g m⫺3, still three times more than 1.5 million people die prematurely each year from indoor air
that recommended by the
WHO.
pollution from cooking stoves, including almost half a million in China
alone.
The World Health Organization has designated the indoor cooking
stove problem to be one of the four most critical global environmental
problems. In response, a number of public and private organizations are spon-
soring an initiative called The Global Alliance for Clean Cookstoves, whose aim
is have 100 million homes in the developing world adopt clean, fuel-efficient
stoves and fuels by 2020. The particulate emissions from traditional cook-
stoves can be reduced by 90% by switching from wood to charcoal, although
this is not an efficient use of the wood supply where it is scarce.
4.17 Environmental Tobacco Smoke

It is well established that smoking tobacco is the leading cause of lung can-
cer and is one of the main contributors to heart disease. Nonsmokers are
often exposed to cigarette smoke, although in lower concentrations than
smokers since it is diluted by air. This environmental tobacco smoke, ETS
(“second-hand smoke”), has been the subject of many investigations in order
to determine whether or not it is harmful to people who are exposed to it.
ETS consists of both gases and particles. The concentration of some
toxic products of partial combustion is actually higher in sidestream smoke
than in mainstream, since combustion occurs at a lower temperature—and
so is less complete—in the smoldering cigarette compared to one through
which air is being inhaled. Since the sidestream smoke is usually diluted by
air before being inhaled, however, the concentrations of pollutants reaching
the lungs of nonsmokers are much lower than those reaching the lungs of
smokers themselves.
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The chemical constitution of tobacco smoke is complex: it contains

thousands of components, several dozen of which are carcinogens. The gases
present in cigarette smoke include
• carbon monoxide, carbon dioxide;
• formaldehyde and several other aldehydes, ketones, and carboxylic
acids;
• nitrogen oxides, hydrogen cyanide, ammonia, and a number of organic
nitrogen compounds;
• methyl chloride;
• 1,3-butadiene;
• toluene, benzene, and several hundred different polycyclic aromatic
hydrocarbons (PAHs), to be discussed in Chapters 7 and 15; and
• cadmium and radioactive elements such as polonium (see
Chapter 9).
Included in the nitrogen compounds are several nitrosamines, organic nitro-
gen compounds of formula R2N!NRO, which together with the PAHs, are
probably the most important respiratory carcinogens in the smoke.
The particulate phase of cigarette smoke is called the tar, and much of
it is respirable in size. The zone in a cigarette that actively burns, as occurs
when a smoker inhales a puff, is quite hot (700–950°C) and produces CO
and H2 as well as the expected CO2 and water vapor. Immediately down-
stream of this area is a cooler zone (200–600°C) where smoke constituents
such as nicotine distill out of the tobacco. When this vapor cools further
along the cigarette path toward the smoker, much of it condenses to aerosol
particles that constitute the particulate phase of the smoke.
Many people experience irritation of their eyes and airways from expo-
sure to ETS. The gaseous components of ETS, especially formaldehyde,
hydrogen cyanide, acetone, toluene, and ammonia, cause most of the odor
and irritation. Exposure to ETS aggravates the symptoms of many people
who suffer from asthma or from angina pectoris, chest pains brought on by
exertion. ETS, particularly when it originates with maternal smoking, is
known to induce new cases of asthma in children, especially those of pre-
school age. Indeed, the rate of children being diagnosed with asthma has
declined over the last decade, due at least in part to a decline in the number
of homes in which adults smoke.
Some studies have established correlations between the rate of acute respi-
ratory illness and the level of indoor PM2.5 (which would include the total
amount of respirable particulates from all sources, including tobacco smoke).
Passive smoking—which involves inhalation of sidestream as well as already
exhaled smoke—is believed by scientists to cause bronchitis, pneumonia, and
other infections such as those of the ear in up to 300,000 infants, and several
baird_ch04.indd 159 2/2/12 11:58 AM

thousand instances of sudden infant death, in the United States each year.
Second-hand smoke may even reduce the cognitive abilities of children,
whether they are exposed prenatally or when young. Being exposed to second-
hand smoke, whether on the job or by living with a smoker, approximately
doubles a nonsmoker’s chance of developing asthma.
In 1993, the U.S. EPA classified ETS as a known human carcinogen, and
estimated that it causes about 3,000 lung cancer deaths annually. ETS is also
considered to be responsible for killing as many as 60,000 Americans annu-
ally from heart disease. In a study of American nurses, it was found that
nonsmoking women regularly exposed to ETS had a 91% greater rate of heart
attacks than women who had no exposure. Apparently, the smoke leads to
hardening of the arteries, a main cause of heart attacks.
An analysis of all recent studies on passive smoking led to the conclusion
that the risks of developing lung cancer and heart disease are each increased
by about one-quarter for nonsmoking spouses of smokers. Longtime workers
in bars and restaurants in which smoking is permitted also have an increased
rate of lung cancer, even if they themselves do not smoke. A British study
estimated that ETS kills 140,000 Europeans annually through cancer and
heart disease. In 2010, the World Health Organization estimated that ETS
globally kills 600,000 people each year.
4.18 Asbestos
The term asbestos refers to a family of six naturally occurring silicate
minerals that are fibrous. Structurally, they are composed of long double-
stranded networks of silicon atoms connected through intervening oxygen
atoms. The net negative charge of this silicate structure is neutralized by the
presence of cations such as magnesium.
The most commonly used form of asbestos, chrysotile, has the formula
Mg3Si2O5(OH)4. It is a white solid whose individual fibers are curly.
Chrysotile, mined mainly in Russia, China, Brazil, Canada (Quebec), and
Kazakhstan, is the principal type of asbestos used in the world. It has been
employed in huge quantities because of its resistance to heat, its strength,
and its relatively low cost. Common applications of asbestos include its use
as insulation and spray-on fireproofing material in public buildings, in auto-
mobile brake-pad lining, as an additive to strengthen cement used for roofing
and pipes, and as a woven fiber in fireproof cloth.
The use of asbestos has been sharply reduced since the 1970s in
developed countries because it is now recognized from studies on the
health of asbestos miners and other asbestos workers to be a human car-
cinogen. It causes mesothelioma, a normally rare, incurable cancer of the lin-
ing of the chest or abdomen. In addition, airborne asbestos fibers and
cigarette smoke act synergistically: their combined effect is greater than the
sum of their individual effects (in this case equal to the product of the two)
in causing lung cancer.
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Review Questions 161
There is much controversy concerning whether chrysotile should be One scientist has stated:
banned outright from further use and whether or not existing asbestos insula- “Removing asbestos is like
tion in buildings should be removed. Many experts feel that existing asbestos waking up a pit bull terrier
should be left in place unless it becomes damaged enough that there is a by poking a stick in its ear.
chance that its fibers will become airborne. Indeed, its removal can increase We should let sleeping dogs
lie.”
dramatically the levels of airborne asbestos in a building unless extraordinary
precautions are taken.
Some environmentalists, however, feel that existing asbestos is a ticking
time bomb—that it should be removed as soon as possible, as one can never
predict when building insulation will be damaged.
Most of the initial concern about asbestos was related to crocidolite, blue
asbestos, and amosite, brown asbestos. Evidence implicating crocidolite in
causing cancer in humans was already well established several decades ago. It
is a material with thin, straight, and relatively short fibers that more readily
penetrate lung passages, and it is a more potent carcinogen than the white
form. Crocidolite and amosite are mined in South Africa and Australia and
were not used much in North America, but were used in many areas of
Europe, including the United Kingdom.
More than 50 countries, including the European Union and Australia,
have now banned all forms of asbestos. Some environmentalists and physicians
worry that, although workers in developed countries wear masks and overalls
and handle white asbestos properly to greatly minimize their exposure to it,
these practices are not common yet in developing countries, in some of which
it is still used in construction. Canada, among other countries, has resisted
efforts by agencies of the United Nations to place chrysotile on the list of most Review Questions 10–15 are
based on the material in the
hazardous substances, even though there is strong evidence that it causes preceding section.
cancer.
Review Questions
1. Discuss the relationship between atmospheric 6. Describe the effects of acid precipitation upon
particulates and haze. (a) dissolved levels of aluminum, (b) fish
2. What is acid rain? What two acids predominate populations, and (c) trees.
in it? Explain why the predominant acid in acid 7. Explain the difference between soot-and-
rain differs in eastern and western North America. sulfur-dioxide smog and photochemical smog in
3. What is the difference between dry and wet terms of the chemicals involved and the health
deposition? effects they cause.
4. Using chemical equations, explain how acid 8. What is the difference in meaning between
rain is neutralized by limestone that is present in absorbed and adsorbed when they refer to
soil. Describe ways in which humans have tried to particulates?
neutralize acidified lakes. 9. List four important reasons why coarse
5. Explain what is meant by the expression critical particles usually are of less danger to human
load. health than are fine particles.
baird_ch04.indd 161 2/2/12 11:58 AM

10. What are the main sources of formaldehyde 13. Why is smoke from cooking stoves an
in indoor air? What are its effects? What are the important health problem in many developing
characteristics of sick building syndrome? countries?
11. What is meant by the phrase air toxic? What 14. What are some of the constituents of
are the main exposure routes to, and effects on tobacco smoke? What is meant by tar in the
health of, benzene? What chemicals can be used smoke?
to replace benzene?
15. What are the three forms of asbestos
12. What are the main sources of nitrogen called? Why is asbestos of environmental
dioxide and of carbon monoxide in indoor air? concern?
Additional Problems
1. A sample of acidic precipitation is found to principle (which states that the position of
have a pH of 4.2. Upon analysis, it is found to equilibrium shifts so as to minimize the effect of
have a total sulfur concentration of 0.000010 M. any stress)? [Hint: Write the expression for the
Calculate the concentration of nitric acid in the acid dissociation constant for the weak acid in
sample, and from the ratio of nitric to total acid, terms of the concentrations of the reactants and
decide whether the air sample probably originated products, and use the stoichiometry of the
in eastern or in western North America. balanced equation to reduce the number of
unknowns to one.]
2. If the pH of rainfall in upstate New York is
found to be 4.0, and if the acidity is half due to 5. Calculate the mass of fine particles inhaled by
nitric acid and half to the two hydrogen ions an adult each year, assuming that he/she inhales
released by sulfuric acid, calculate the masses of about 350 L of air per hour and that the average
the primary pollutants nitric oxide and sulfur PM2.5 index of this air is 10 ␮g m⫺3. Assuming that
dioxide that are required to acidify 1 liter of such each particle has a diameter of about 1 ␮m, and
rain. that the density of the particles is about 0.5 g mL⫺1,
calculate the total surface area of this annual load
3. The pH in a lake of size 3.0 km ⫻ 8.0 km and
of particles. [Hint: The surface area of a spherical
an average depth of 100 m is found to be 4.5.
particle is equal to 4␲r2, where r is its radius.]
Calculate the mass of calcium carbonate that must
be added to the lake water in order to raise its pH 6. The detection threshold of formaldehyde by
to 6.0. humans is about 100 ppb. Would a typical human
be able to detect formaldehyde at a concentration
4. The pH of a sample of rain is found to be 4.0.
of 250 ␮g m⫺3 if the air temperature was 23°C and
Calculate the percentage of HSO4⫺ that is ionized
the pressure 1.00 atm?
in this sample, given that the acid dissociation
constant for the second stage of ionization of 7. What mass of formaldehyde gas must be
H2SO4 is 1.2 ⫻ 10⫺2 mol L⫺1. Repeat the released from building materials, carpets, etc.
calculation for a pH of 3.0. Is the trend shown by in order to produce a concentration of 0.50 ppm
these calculations consistent with qualitative of the gas in a room having dimensions of
predictions made according to Le Châtelier’s 4 m ⫻ 5 m ⫻ 2 m?
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PART II
ENERGY AND
CLIMATE CHANGE
Contents of Part II
Chapter 5 The Greenhouse Effect
Chapter 6 Energy Use, Fossil Fuels, CO2 Emissions,
and Global Climate Change
Chapter 7 Biofuels and Other Alternative Fuels
Chapter 8 Renewable Energy Technologies: Hydroelectric,
Wind, Solar, Geothermal, and Marine Energy
and Their Storage
Chapter 9 Radioactivity, Radon, and Nuclear Energy
Introduction
By general consensus, the most serious environmen- atmospheric particles in either reinforcing or miti-
tal problem facing humanity today is global climate gating global warming. The role of fossil fuels in
change—the continuous increases in average global energy production in modern societies, and with it
air temperatures and changing weather patterns, the cumulative increase that has occurred in atmo-
resulting in drought for some areas and flooding for spheric CO2 levels, is then analyzed. We then
others. Most atmospheric scientists are now con- concentrate our attention on the search for sustain-
vinced that this climate change results mainly from able solutions to the carbon dioxide problem—
the anthropogenic enhancement of the greenhouse such as burying the gas emissions underground or in
effect caused by ever-increasing levels of carbon the sea or avoiding their generation by using energy
dioxide and other “greenhouse gases.” sources such as biofuels or hydrogen, wind, photo-
In this part of the book, we investigate the voltaics, solar power towers, or even nuclear energy.
mechanism of the greenhouse effect, the atmo- As we shall see, chemistry and chemists play an
spheric gases that cause it, and the role of suspended important role in all these topics. ●
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5
The Greenhouse Effect
In this chapter, the following introductory chemistry topics are
used:
m Combustion
Background from previous chapters used in this chapter:

m Sunlight wavelength regions (UV, visible, IR)
m Absorption spectra
m ppm, ppb, ppt concentration scale for gases
m CFCs and their replacements
m Tropospheric ozone
m Aerosols
Introduction
Everyone has heard the prediction that the greenhouse effect will signifi-
cantly affect climates around the world in the future. The terms greenhouse
warming and global warming in ordinary usage simply mean that average
global air temperatures are expected to increase by several degrees as a result
of the buildup of carbon dioxide and other greenhouse gases in the atmo-
sphere. Indeed, most atmospheric scientists believe that such global warming
has been under way already for some time and is largely responsible for the
air temperature increase of about two-thirds of a Celsius degree that has
occurred since 1860.
The phenomenon of rapid global warming—with its demands for
large-scale adjustments—is generally considered to be our most crucial
worldwide environmental problem, although both positive and negative
effects would be associated with any significant increase in the average
global temperature. Unlike stratospheric ozone depletion, which has mani-
fested itself in spectacular fashion in the form of the ozone hole, the phenom-
enon of global warming due to the greenhouse effect has yet to be observed
in a fashion that convinces everyone of its existence. No one currently is sure
of the extent or timing of future temperature increases, nor is it likely that
reliable predictions for individual regions will ever be available much in
advance of the events in question. If current models of the atmosphere are
correct, however, significant warming will occur in coming decades. It is
165
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166 Chapter 5 The Greenhouse Effect
important that we understand the factors that are driving this increase so
that we can, if we wish, take steps to avoid potential catastrophes caused by
rapid climate change in the future.
In this chapter, the mechanism by which global warming could arise is
explained, and the nature and sources of the chemicals that are responsible
for the effect are analyzed. The extent of the atmospheric warming to date,
and other indications that change is underway, are also discussed. The pre-
dictions concerning global warming in the future, and an analysis of steps
that could be taken to minimize it, will be presented here and in Chapter 6.
The Mechanism of the Greenhouse Effect

5.1 The Earth’s Energy Source
The Earth’s surface and atmosphere are kept warm almost exclusively by
energy from the Sun, which radiates energy as light of many types. In its
radiating characteristics, the Sun behaves much like a blackbody, i.e., an
object that is 100% efficient in emitting and in absorbing light. The wave-
length, ␭peak, in micrometers, at which the maximum emission of energy
occurs by a radiating blackbody decreases inversely with increasing Kelvin
temperature T according to the relationship
␭peak 2,897/T
Since for the surface of the Sun, from which the star emits light, the tem-
perature T~5800 K, from the equation it follows that ␭peak is about 0.50 ␮m,
a wavelength that lies in the visible region of the spectrum (and corresponds
to green light). Indeed, the maximum observed solar output (see the dashed
portion of the curve in Figure 5-1) occurs in the range of visible light, i.e.,
that of wavelengths between 0.40 and 0.75 ␮m.
Energy
Incoming
FIGURE 5-1 Wavelength Outgoing
solar light
distributions (using different light from Earth
(UV, visible, IR)
scales) for light emitted by (thermal IR)
the Sun (dashed curve) and
by the Earth’s surface and
troposphere (solid curve).
[Source: Redrawn from 0.1 0.2 0.3 0.5 1.0 1.5 2 3 5 10 15 20 30 50
J. Gribbin, “Inside Science: UV Visible light Infrared light
The Greenhouse Effect,”
Wavelength ( µm)
New Scientist, supplement
(22 October 1988).]
baird_ch05.indd 166 14/02/12 1:13 PM

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Additional Problems 67

baird_ch02.indd 67 2/2/12 11:18 AM

baird_fm.indd ii 22/02/12 9:45 AM

baird_ch03.indd 69 2/2/12 11:35 AM

3.1 Concentration Units for Atmospheric Pollutants

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BOX 3-1 The Interconversion of Gas Concentrations

baird_ch03.indd 71 23/02/12 5:10 PM

molecules of pollutant contained in a volume Thus the SO2 concentrations is

n PV/RT 1.0 atm 1.0 m3

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3.2 The Chemical Fate of Trace Gases in Air

In clean tropospheric air, as in the stratosphere, the hydroxyl radical is

baird_ch03.indd 73 2/2/12 11:35 AM

Because the lifetime of hydroxyl radicals is short and sunlight is required to

In one study, the concentration of OH in air at the time was found to be

In its reaction with otherwise-stable gases whose molecules contain

O!N "O HOO  NO 9: OH  NO2

baird_ch03.indd 74 2/2/12 11:35 AM

FIGURE 3-1 Absorption

Absorption cross section (10–20cm2)

Although suspected for decades of playing a pivotal role in air chemistry,

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Some NO is oxidized HOO

Urban Ozone: The Photochemical Smog Process

baird_ch03.indd 76 2/2/12 11:36 AM

United States Canada

Industrial Nonindustrial Other

plants. The concentrations of these chemicals are orders of magnitude greater

baird_ch03.indd 77 2/2/12 11:37 AM

Another vital ingredient in producing photochemical smog is sunshine,

Other than those that absorb sunlight and subsequently decompose,

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3.4 Ground-Level Ozone in Smog

3.5 An Episode of Photochemical Smog

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FIGURE 3-3 Time-of-day

Pollutant concentration (ppm)

concentration of NO rising from emissions from early-morning vehicle

• By mid-morning, lesser amounts of NO enter the air since rush-hour

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FIGURE 3-4 Nitrogen-

• The concentration of NO2 peaks in the morning but remains at a lower

3.6 Nitrogen Oxide Production During Fuel Combustion

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their origins as atmospheric pollutants. Nitrogen oxide gases are produced by

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root of [O2], it follows that the rate of NO formation will be proportional to

United States Canada

Electric generation Nonindustrial

FIGURE 3-5 Anthropogenic NOX sources in North America, by sector in 2006.

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3.7 Governmental Goals for Reducing

3.8 Photochemical Smog Around the World

FIGURE 3-6 Maximum

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Due to the long-range transport of primary and secondary pollutants in

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O!N "O HOO NO 9: OH NO2

NO NO2 2 NaOH 9: 2 NaNO2 H2O

CaCO3 SO2 9: CaSO3 CO2