BITS Pilani

K K Birla Goa Campus

EE ZG511
Environmental Chemistry
Lecture - 4
Dr. Sharad M. Sontakke
Department of Chemical Engineering

Email: [email protected]
Summary of previous lecture

• Various nutrient cycles: C, N, O, and P

• The atmospheric chemical reactions mainly due to the
air pollutants: CO, NOx, SO2, VOCs
• Sources and effects of the above air pollutants
• Formation of secondary pollutants: industrial and
photochemial smog, PAN
• Ozone as a pollutant
• Temperature inversion

BITS Pilani, K K Birla Goa Campus

Contents

Module 2 (part 2): Chemistry of Troposphere, Stratosphere,

Global warming and climate change

• Dobson Unit
• Production of Ozone in the stratosphere
• Determining the steady state concentration of Ozone
• Catalytic destruction of Ozone
• Depletion of ozone layer in the stratosphere

Ref: Chapter 6, Girard, Principles of Env. Chem.

BITS Pilani, K K Birla Goa Campus

Dobson Unit (DU)

The Dobson unit (DU) is used to describe the amount of

ozone in the stratosphere.
It is named after Gordon M. B. Dobson, the Oxford
University researcher who built the first instrument to
measure the total ozone abundance from the ground.
One DU is 2.7 × 1016 ozone molecules per square
centimeter.
One DU refers to a layer of ozone that would be 0.001 cm
thick under conditions of standard temperature (0°C) and
pressure (the average pressure at the surface of the
Earth).

BITS Pilani, K K Birla Goa Campus

For example, 300 DUs of ozone brought to the surface of
the Earth at 0°C would occupy a layer only 0.3 cm thick
in a 1 cm2 column.
In the past, the average amount of ozone covering the
Earth was more than 270 DU.
The amount of ozone over the Antarctic, however, has
been much lower than that found in other parts of the
Earth.
The global average ozone concentration varies from month
to month, and from region to region.
Many natural factors play roles in the fluctuation of the
ozone concentration.

BITS Pilani, K K Birla Goa Campus

The ozone hole above the Antarctic is defined as the area in
which the ozone is less than 220 DU.

BITS Pilani, K K Birla Goa Campus

The Production of Ozone in
the Stratosphere
In the absence of pollution, ozone (O3) is not present to any
appreciable extent in the troposphere, but it occurs
naturally in the stratosphere.

Its concentration is greatest at an altitude of 20 to 30 km from

the Earth’s surface.

The ozone layer is formed when ordinary molecules of

oxygen gas (O2) in the stratosphere absorb UV radiation
from the sun with wavelengths of less than 240 nm, which
causes them to dissociate into single oxygen atoms (O).

BITS Pilani, K K Birla Goa Campus

The dissociation of molecular oxygen into monatomic
atoms requires an enthalpy change of 498 kJ/mol; this is
the amount of energy that must be supplied (at
stratospheric temperature and pressure) to make the
reaction go.
To determine the wavelength of sunlight that will have
sufficient energy to dissociate oxygen, we use Planck’s
equation.
The energy (E) of the light is related to its frequency v and
the wavelength λ by this formula:

BITS Pilani, K K Birla Goa Campus

Planck’s constant (h) is 6.63 × 10–34 J.s, and the speed of
light (c) is 3.0 × 108 m/s.

Rearranging

multiply by Avogadro’s number, N, and then convert the λ to

nanometers (nm):

BITS Pilani, K K Birla Goa Campus

This calculation shows that sunlight with a wavelength of 240
nm or less has sufficient energy to dissociate O2.
This region of the sun’s spectrum is known as the Far-UV.
Sunlight with a shorter wavelength is more energetic than
sunlight with a longer wavelength.

BITS Pilani, K K Birla Goa Campus

Single oxygen atoms are very reactive and immediately
combine with O2 to form O3:

In this reaction, M designates a third molecule that is present

in the atmosphere, usually N2, the most abundant
molecule in the atmosphere.
The M molecule is necessary to carry away the heat
generated in the collision between O and O2.
The heat that this reaction releases causes the temperature
of the stratosphere to be higher than the temperature of
the air below or above it.
BITS Pilani, K K Birla Goa Campus
At the same time that the ozone is being formed, it is
absorbing UV radiation very strongly with wavelengths of
220 to 330 nm, which causes it to be broken down to form
an oxygen molecule and an oxygen atom:

Also, when O3 encounters an O atom, the two can combine

to form two O2 molecules:

BITS Pilani, K K Birla Goa Campus

A dynamic equilibrium is established, maintaining a fairly
constant concentration of ozone in the stratosphere.
This concentration varies with season and latitude, but
averages 10 parts per million.
Although it is low, this concentration of ozone is sufficient to
screen 95% to 99% of the sun’s dangerous UV radiation.

BITS Pilani, K K Birla Goa Campus

Determining the Steady-State
Concentration of Ozone
The steady-state concentration of ozone is calculated from
the rates of the reactions discussed previously.
In 1930, English physicist Sidney Chapman suggested that
ozone in the stratosphere must be produced from UV
irradiation of molecular oxygen.
The following reactions constitute the Chapman cycle, a
series of reactions that simulate stratospheric ozone
chemistry.
The reaction rate for each individual reaction is found by
multiplying the reactant concentration by the rate
constants, Kx.
The rates for the four reactions discussed previously can be
written as follows:
BITS Pilani, K K Birla Goa Campus
BITS Pilani, K K Birla Goa Campus
Ozone is produced in only the second reaction and is
destroyed in reactions 3 and 4.
The ozone steady state can be expressed as follows:

(6.1)

To determine the steady state, we need to assess which of

the concentrations we know and which we need to
compute.
Laboratory experiments have determined the concentration
of oxygen [O2], air [M], and the rate constants for these
equations.
BITS Pilani, K K Birla Goa Campus
What is not known is the concentration of the oxygen radical
[O] and ozone [O3].
We assume that the concentration of the oxygen radical [O]
is also at steady state.
The rate of O formation is twice the rate of the reaction of
reaction 1 plus the rate of reaction 3; the rate of reduction
is the rate of reaction 2 plus the rate of reaction of reaction
4:

(6.2)

(6.3)

BITS Pilani, K K Birla Goa Campus

This equation can be simplified further.
The highest-energy region of solar radiation is absorbed by
oxygen atoms at the upper regions of the stratosphere.
The influx of solar radiation with λ of less than 240 nm is
greatly reduced as it proceeds from the upper to the
lower portion of the stratosphere.
This means that there are too few photons with sufficient
energy to induce reaction 1.
A lower-energy solar radiation (λ = 240 – 330 nm) is not
absorbed and is available to carry out reaction 3.
This allows us to assume that K1[O2] <<<< K3[O3]. Thus we
can simplify equation 6.3 to
BITS Pilani, K K Birla Goa Campus
(6.4)

(6.5)

(6.6)

(6.7)

BITS Pilani, K K Birla Goa Campus

The numerical value obtained for this ratio depends on the
altitude.
As the altitude increases, the concentration of air [M]
decreases, and the solar flux and temperature increase.
This causes K1 and K3 to increase and K2 and K4 to
decrease.
At an altitude of 40 km, the concentration of air is
approximately 1016 molecules/cm3 and K1 = 10–11, K2 =
10–32, K3 = 10–3, and K4 = 10–15. These values, when
substituted into equation 6.7, give an [O3]/[O2] = 10–4.
Thus even the ozone layer has many more oxygen
molecules than ozone molecules.

BITS Pilani, K K Birla Goa Campus

This theoretical ratio is approximately a factor of 10 higher
than what is experimentally measured (approximately 10
ppm).

This finding leads to the conclusion that some other

reactions must be causing ozone destruction that we have
not already considered.

BITS Pilani, K K Birla Goa Campus

Catalytic Destruction of Ozone

Ozone is a very reactive molecule and is termed a meta-

stable molecule, meaning that isolated molecules will
decompose slowly, but when an ozone molecule comes
into contact with a molecule of another gas, it will react
quickly.
The equilibrium concentration of ozone in the stratosphere is
low, but there are very few other molecules present in the
stratosphere with which it can react.
In the 1960s, chemists realized that additional pathways for
ozone destruction were found in the stratosphere that
they had not considered previously.

BITS Pilani, K K Birla Goa Campus

A number of species (which are described in the following
sections) react efficiently with ozone by abstracting an
oxygen atom from the ozone molecule.
Generally, the letter X designates the reactive species.
The abstraction reaction is as follows:

If this reaction takes place in a region of the stratosphere in

which atomic oxygen is present, the XO molecule will
react with it:

BITS Pilani, K K Birla Goa Campus

These reactions represent additional pathways for ozone
destruction.
The steady-state concentration of ozone will be lowered by
these oxygen-abstraction reactions.
The sum of these two reactions is:

Notice that this overall reaction does not contain the X

species. Because X is not consumed in the reaction, it
acts as a catalyst for the destruction of ozone.
X lowers the energy of activation (Ea) for the reaction and
increases the efficiency of the decomposition reaction.
BITS Pilani, K K Birla Goa Campus
The reaction requires atomic oxygen to regenerate X through
reaction with the XO intermediate:

In the lower stratosphere (15 to 25 km), where most ozone is

found, little UVC radiation (100–290 nm wavelength) from
the sun penetrates the atmosphere. In turn, the
concentration of molecular oxygen is high in this region.
As a result, atomic oxygen is rapidly converted into ozone,
which keeps the concentration of atomic oxygen very low.
This regeneration reaction will occur very slowly in the lower
stratosphere because of the scarcity of atomic oxygen.
BITS Pilani, K K Birla Goa Campus
Instead, most ozone destruction by catalytic species (X)
occurs in the upper and middle stratosphere (25 to 50 km).

Four catalytic species (X) have been identified as important

factors in the global destruction of ozone: the hydroxyl
radical, nitric oxide (NO), chlorine, and bromine atoms.

BITS Pilani, K K Birla Goa Campus

Hydroxyl Radical Cycle
The hydroxyl radical (˙OH) can be produced by two
different photochemical processes.
The first is a hydrogen abstraction reaction with either
water or methane:

BITS Pilani, K K Birla Goa Campus

The hydroxyl radical is responsible for nearly half of the total
ozone destruction in the lower stratosphere.
The ozone destruction reaction is shown here.
The hydroxyl radical is able to accept oxygen from ozone:

The hydroxyl radical participates in the catalytic ozone

destruction cycle, which is important in the lower
stratosphere.
BITS Pilani, K K Birla Goa Campus
Nitric Oxide Cycle

Automobile and truck engines release large quantities of

nitric oxide (NO) into the troposphere.
Almost all of this NO is oxidized to NO2 and then converted
to nitric acid (HNO3).
Rainfall washes the nitric acid from the troposphere before it
can reach the stratosphere.
Nitrous oxide (N2O), however, is much less reactive than NO
and eventually reaches the stratosphere.
N2O is a tailpipe pollutant but is also released by soil during
denitrification by anaerobic bacteria.
BITS Pilani, K K Birla Goa Campus
At altitudes above 30 km, the N2O can absorb high-energy
photons to produce molecular nitrogen and an excited
oxygen atom (O*).
The excited oxygen atom has an electron that is in an excited
state.

Below 30 km, in the stratosphere, the excited-state oxygen

reacts with the N2O to produce NO.

BITS Pilani, K K Birla Goa Campus

NO can act as an X catalytic species:

This sequence of reactions is called the NOx catalytic

ozone destruction cycle.

BITS Pilani, K K Birla Goa Campus

Chlorine Cycle
Few natural sources of chlorine and bromine atoms exist in
the stratosphere.
Although the expansive oceans of Earth contain significant
quantities of chloride and bromide ions, sea spray is
cleared from the troposphere by natural mechanisms.
In addition, many organochlorine and organobromine
compounds are released from natural sources; hydroxyl
radicals clear most of them from the troposphere before
they can reach the stratosphere.
Only methyl bromide (CH3Br) and methyl chloride are stable
and long lived enough to reach the stratosphere and
contribute to halogen-induced ozone destruction.
BITS Pilani, K K Birla Goa Campus
The major sources of stratospheric chlorine and bromine
have traditionally been the anthropogenic
chlorofluorocarbons (CFCs) and bromine-containing
halons.
CFCs and halons are nontoxic and nonflammable, which
make them superior to other gases that were used for the
same application.
Commercially, the most important CFCs are the halogenated
methanes Freon 11 and Freon 12 (Freon is a DuPont
trade name). They contain only carbon, chlorine, and
fluorine.

BITS Pilani, K K Birla Goa Campus

Because CFCs are so unreactive, they do not break down
when released and can persist in the troposphere for
more than 100 years. Over time, air currents carry them
into the stratosphere.

As early as 1974, two chemists at the University of

California at Irvine, F. Sherwood Rowland and Mario
Molina, predicted that when exposed to UV radiation in
the stratosphere, CFCs would break down to form
chlorine radicals (Cl˙):

BITS Pilani, K K Birla Goa Campus

Each chlorine radical would then destroy a molecule of
ozone with the formation of a chlorine monoxide radical
(ClO˙) and a molecule of oxygen (Step 2).
The chlorine monoxide radical in turn would react with an
oxygen atom to yield another molecule of oxygen and
another chlorine radical, which could then start the chain
reaction over again (Step 3).
The net result would be the destruction of a molecule of
ozone.

BITS Pilani, K K Birla Goa Campus

It has been estimated that each chlorine radical involved in
a chain reaction has the potential to destroy 100,000
molecules of ozone before winds carry it back to the
troposphere.
Although more industrial chlorine-containing compounds
are in use than those that contain bromine, bromine-
containing compounds are more efficient at destroying
ozone.

BITS Pilani, K K Birla Goa Campus

Null Cycles
Other processes occur in the stratosphere that compete
with the catalytic cycles.
These reactions further complicate our ability to predict the
extent of ozone depletion under certain stratospheric
conditions.
Null cycles (also known as holding cycles) are processes
that prevent certain species from taking part in the
catalytic cycles.

BITS Pilani, K K Birla Goa Campus

One example of a null cycle begins with the reaction of NO2
with O3, which results in the production of NO3:

Some of the NO3 can then react to produce N2O5:

As has been seen before, the M in this equation is a third

molecule that participates in the reaction but is not
incorporated into the product.
BITS Pilani, K K Birla Goa Campus
M can be any molecule that happens to be present.
In the atmosphere, it is most likely to be a molecule of
nitrogen.
N2O5 is a relatively unreactive molecule that is not a catalyst
for ozone destruction; it can be considered an unreactive
reservoir of NOx.
At any given time, it accounts for as much as 10% of the total
stratospheric NOx.
The formation of N2O5 can be considered a holding cycle for
NOx because it temporarily limits this molecule’s ability to
participate in the catalytic cycles.

BITS Pilani, K K Birla Goa Campus

Nitric and hydrochloric acid are formed in the stratosphere
and are important reservoirs for ozone-depleting NOx
and chlorine species.

Almost 70% of the stratospheric chlorine is present as

hydrochloric acid, and 50% of NOx is stored as nitric
acid.
The reservoirs that the null cycles produced are important
in the chemistry of Antarctic ozone depletion.

BITS Pilani, K K Birla Goa Campus

Depletion of the Ozone Layer

Since 1985, satellite images have revealed a “hole” in the

ozone layer each spring over the South Pole.
The largest ozone hole ever recorded (29.5 million square
kilometers) was observed in September 2006.
Convincing evidence indicates that CFCs, a class of
synthetic organic compounds, are responsible for this
destruction of the ozone layer.
An ozone hole occurs as a result of the harsh winter weather
conditions in the lower stratosphere

BITS Pilani, K K Birla Goa Campus

During the long, dark winter (June to September) in the
Antarctic in the intense cold (–80°C), a stream of air is
drawn toward the South Pole because of the rotation of
the Earth.
A giant vortex with speeds exceeding 300 km/hr is created,
and the area within the vortex acts like a chemical
reaction chamber.
The outside air cannot penetrate the vortex, and at the
South Pole, the vortex persists throughout the winter and
into the spring (October).

BITS Pilani, K K Birla Goa Campus

Condensation of gases into liquid droplets (clouds) or solid
crystals does not usually occur in the stratosphere over
Antarctica because the concentration of water vapor in the
air is so low.
Inside the vortex, however, stratospheric clouds form as a
result of the exceptionally low temperatures and the
absence of sunlight.
The crystals produced inside the vortex form PSCs (Polar
stratospheric clouds). In comparison to tropospheric
clouds, PSCs have fewer particles per unit volume of air
and are optically thin.
Once the PSC particles form in the vortex, chemical reactions
begin to take place on their surfaces.
BITS Pilani, K K Birla Goa Campus
BITS Pilani, K K Birla Goa Campus
The figure shows how the vortex acts as a reaction chamber
for these reactions, which are heterogeneous and occur
only after the reacting gas has adsorbed on the surface of
a particle.
Adsorption is a process that proceeds through a collision
between the gas and the surface in which the gas bonds
to the surface.

Gas-phase HCl attaches itself

to the surface of the ice crystals
of PSCs, as shown in the Fig

BITS Pilani, K K Birla Goa Campus

When pollutants collide with the adsorbed HCl, the
heterogeneous reaction takes place, producing chlorine
gas, Cl2.

In the polar winter, chlorine-containing molecules

accumulate; in the spring, when sunlight returns to the
area, relatively inactive forms of chlorine in the
stratosphere, such as ClONO2 and HCl, are converted to
photochemically active forms, such as Cl2.
These reactions are known as chlorine activation.
BITS Pilani, K K Birla Goa Campus
The Cl2 produced can go on to attack ozone.

BITS Pilani, K K Birla Goa Campus

Each November, the Antarctic warms enough that the polar
vortex breaks down and the PSC solids melt.
Ozone from regions adjacent to the Antarctic diffuses over
the area where the vortex was and reestablishes the
ozone layer.
The ozone hole is an annual, regional event that is
controlled by the temperature of the polar stratosphere
and the presence of chlorine and bromine.
Convincing field evidence for the involvement of CFCs in
ozone depletion came in 1987.
A number of related bromine-containing compounds called
halons have also been implicated in ozone destruction.

BITS Pilani, K K Birla Goa Campus

Effects of Ozone Depletion on Human Health and the
Environment

Depletion of the ozone layer leaves the Earth vulnerable to

the damaging effects of UV radiation.
UVB radiation (wavelength of 280 to 320 nm), because it
transmits more energy, is more damaging to living
organisms than longer-wavelength UVA radiation (320 to
400 nm).
In humans, exposure to UVB radiation causes cataracts,
tanning and sunburn, and suppression of the immune
system.

BITS Pilani, K K Birla Goa Campus

By damaging DNA, UVB radiation can cause several types of
skin cancer, including deadly melanoma.
It also harms crops and kills phytoplankton, the microscopic
photosynthetic organisms that are at the lowest level of
ocean food chains.
It has been calculated that for every 1% decrease in
stratospheric ozone, the amount of UVB radiation reaching
the Earth’s surface increases by 2%.

BITS Pilani, K K Birla Goa Campus

Summary

In this lecture, we have studied:

• Dobson unit for quantification of Ozone
• The factors and reactions involved in the production of
Ozone in the stratosphere
• The measurement of steady state concentration of
Ozone
• Different factors for the catalytic destruction of ozone
• The factors involved in the depletion of ozone layer in
the stratosphere
• Effects of Ozone Depletion on Human Health and the
Environment

BITS Pilani, K K Birla Goa Campus

Questions

1. What is the unit for measuring the amount of ozone?

2. Which are the key factors in the production of ozone?
3. What assumptions are made during the measurement
of steady state concentration of ozone?
4. Name any two cycles through which catalytic
destruction of ozone occurs.
5. What are the key factors responsible for the depletion of
ozone layer?
6. Mention any two health effect of depletion of ozone
layer.

BITS Pilani, K K Birla Goa Campus

Topics for the next lecture

Module 2 (part 3): Chemistry of Troposphere, Stratosphere,

Global warming and climate change

• Infrared Adsorption and Molecular Vibrations

• Residence Time of Atmospheric Gases
• Radiative Forcing
• Evidence for Global Warming
• Effect of Global Warming

Ref: Chapter 4, Girard, Principles of Env. Chem.

BITS Pilani, K K Birla Goa Campus