Lecture 02 Fall 2023 - With Solutions

AIR POLLUTION
CONTROL ENGINEERING
ENCH 643 / ENEN 697
FALL 2023
Dr. Mujtaba Shareef
mujtaba.shareef@ucalgary.ca
SCHULICH SCHOOL OF ENGINEERING
LECTURE 02 –
SEP 13, 2023
CONTENTS
• Secondary pollutants
• Formation of Ozone
• Controlling Ozone
• Ozone Depletion
• CFCs and Ozone Hole
Fall 2023 ENCH 643 / ENEN 697 Course use only. No further distribution allowed 2 Instructor: Dr. Mujtaba Shareef
URBAN SMOG
SECONDARY POLLUTANTS
• Pollutants formed in the
atmosphere due to
complex reactions
• Example, Ozone,
secondary particulate etc.
• Non-linear relationship
• Difficult to control
URBAN SMOG
• A noxious mixture of gases and particles
often appears as haze.
• Primarily two pollutants
• Ground-level ozone
• Particulate matter
• Generally, occurs in summer due to
energy from sunlight, but can occur in
winter due to wood heating and vehicle
usage
• Strategies to control demand thorough
understanding of process
Source: http://energyeducation.ca/encyclopedia/Air_pollution
HEALTH ISSUE RELATED TO SMOG
• Acute respiratory disease is responsible for some 4 million deaths a
year of children under five in developing countries.
• In Jakarta, Bangkok and Manila, the social costs from exposure to
airborne dust and lead accounted for nearly 10% of average urban
incomes in the early 1990s.
• In many Chinese cities a coal-based energy has resulted in poor air
quality and higher costs of pollution-related illness and death.
• Over one million of the 18 million Mexico City residents suffer
permanent breathing difficulties, headaches, coughs and eye
irritations
• http://www.theguardian.com/world/2014/feb/25/china-toxic-air-
pollution-nuclear-winter-scientists
SMOG TYPES
http://news.bbcimg.co.uk/media/images/64604000/jpg/_64604286_ http://media.treehugger.com/assets/images/2013/06/los-angeles-la-
71531338.jpg smog-1912.jpg.662x0_q100_crop-scale.jpg
SMOG TYPES
• London smog
• Smoke + Fog
• High concentrations of smoke from coal burning for residential
heating
• Fog droplets with sulfuric acid concentration (impurities in coal)
• Little or no sunlight
• Los Angeles Smog or Photochemical smog
• Gaseous pollutants from cars, industries etc.,
• Creation of secondary pollutants
• Not just smoke + fog but pollutants
EFFECTS OF URBAN SMOG
• Tropospheric O3
• O3 may be the most harmful air pollutant. It readily attacks organic
materials with C-C bonds, for example in the lungs.
• O3 produces harmful irritation in the respiratory system.
• It is believed that, because O3 damages lung tissue, it leads to a
decreased resistance to infectious disease.
• O3 attacks rubber (e.g., rubber tires). This effect is noticeable in the
cracking of the sidewalls of tires.
• VOCs
• VOCs (volatile organic compounds) combine with various other
compounds or radicals to create noxious organic molecules or O3.
• Examples are gasoline-related compounds such as MTBE, benzene,
toluene, ethylbenzene, and xylenes.
EFFECTS OF URBAN SMOG
• Particulate Matter
• Coarse particulates removed by the nose and throat before reaching
the lungs.
• Fine particulates (d<2.5 μm) can enter the lungs and can then cause
respiratory illnesses or aggravate existing conditions such as asthma.
• PAN (Peroxyacyl nitrates)
• One of the evolved products of urban smog is PAN (peroxacyl nitrate,
RC(O)OONO2) and numerous related peroxacyl compounds.
• It forms in catalytic reactions starting with CH4 and NO2
• These are strong oxidants; they are highly phytotoxic, i.e.,
• damaging to plants and potent lachrymators (they make your eyes water).
• It is easily converted back to the peroxyl radical, but is stable enough to survive
downwind transport to the suburbs.
FORMATION OF PAN
FORMATION OF PHOTOCHEMICAL SMOG
• Solar energy
• NO/NO2
• Hydrocarbon
• Cyclic
PHOTOCHEMICAL SMOG CYCLE
MODELING OF SMOG
• Valuable insights can be gained by describing mathematically
• Sophisticated computer models are available
• Modeling Approach
• Lagrangian
• One particle is chosen and is followed as it moves through space and time, the
line traced out by that one particle is called path line.
• Eulerian
• A Eulerian approach is used to obtain a clearer idea of the airflow at one
particular instant.
• comprising this flow field are called streamlines
• Thus, a path line refers to the trace of a single particle in time
and space whereas a streamline presents the line of motion of
many particles at a fixed time.
MODELING OF SMOG
MODELING OF SMOG
PHOTOCHEMICAL CYCLE
• O2 + O → O 3 (Reaction 1)
• NO2 + (Sunlight) → NO + O (Reaction 2)
• NO + O3 → NO2 + O2 (Reaction 3)
Reaction rates
• R3= k3[NO][O3]
• R2 = k2[NO2]
• R1 = k1[O2][O]
Photo stationary state relationship
𝑘2[𝑁𝑂2]
[O3] =
𝐾3[𝑁𝑂]
ROLE OF HYDROCARBONS
• Formation of hydroxyl radicals
O + H20 -----> OH• + OH•
• Formation of organic radical (methyl)
CH4 + OH• -----> CH3• + H2O
• Formation of methyl peroxy
CH3• + O2 + M -----> CH3O2• + M
• Reaction with NO and formation of methoxy
CH3O2• + NO -----> CH3O• + NO2
• Formation of formaldehyde and hydroperoxyl
CH3O• + O2 -----> HCHO + HO2•
• Overall result (conversion of NO to NO2)
CH4 + OH• + NO -----> HCHO + HO2• + NO2
• Generalized
RH + OH• + NO -----> RCHO + HO2• + NO2
PHOTOCHEMICAL SMOG AND METEOROLOGY
• High pressure systems promote high ozone concentration
• Air falling from higher altitudes of the atmosphere
• Creates temperature inversion
• Wind speeds associated with high pressure systems are typically low
• Clear sky, sunshine and warm conditions usually accompany high
pressure systems
CONTROLLING O3 FORMATION
• Effect of VOC Concentrations

• VOCs (mostly hydrocarbons)
serve as fuel for formation of
ozone.
• To study the impact – dynamic
mass balance equation
• Mathematical box model is
used to calculate ozone
concentrations for different
initial conditions keeping NOx
constant and vary VOC.
• Zero VOCs produces small

quantity of Ozone
• Reaches saturation point
(point B and A)
• Reducing VOC from point A
to B, does not reduce
significant Ozone.
• To reduce Ozone to 120 ppb
we must reduce the VOC by Predicted maximum ozone concentration as a
approximately 77%. function of VOC level for constant NOx
• Effect of NOX concentrations

• O3 concentration increases with
NOX concentrations
• Reaches a maximum, then start
decreasing
• After the peak point, decreasing
NOx actually increases O3
Predicted maximum ozone concentration as a function

of NOx level for constant VOC
O3 ISOPLETH DIAGRAM
• An isopleth is a line of
constant concentration
(contour map showing
the maximum ozone
concentrations)
• Empirical Kinetic
Modelling Approach
(EKMA) technique:
Initial concentrations of
VOC and NOx are varied,
while all other variables
are held constant.
Example of an ozone isopleth diagram for an urban area
[Source: Jeffries and Crousse, 1990]
PROBLEM 1
• Assume the ozone concentrations in an urban area are
described by the isopleth plot, and the current state of the
atmosphere is at point A – that is [VOC]o = 600ppbC, [NOx]o
100 ppb and [O3]o = 143 ppb. Estimate the effect on the
atmospheric ozone concentration of the following changes in
emissions:
a) A 20 % reduction of VOC emissions (no changes in NOx)
b) A 20 % reduction of NOx emissions (no changes in VOCs)
c) A 20 % increase of VOC emissions (no change in NOx)
d) A 20 % increase of NOx emissions (no change in VOCs)
SHOULD WE INCREASE NOX EMISSIONS?
• Your Grandmother talks to you:

• I was watching TV yesterday and I heard a strange looking guy – I
think that he was a spokesperson for something – saying that cleaning
up the emissions of cars may increase this ozone thing in the air and
make smog problem worse. It doesn’t make sense to me. I mean, if
what he said was true, then we could make our car emissions dirtier,
and the air would get cleaner! You are my smartest grandchild. You’re
going to this university where they charge your parents a fortune for
tuition. What do you think?
SHOULD WE INCREASE NOX EMISSIONS?
CONTROL STRATEGY REGIMES
• Control Strategy Regimes
of an Ozone isopleth
diagram
PROBLEM 2
• An urban area is characterized by a VOC concentration of
1,800 ppbC and an NOx concentration of 60 ppb. Discuss the
advantages and disadvantages of the following strategies to
achieve ozone levels at or below national standard of 120 ppb:
a) NOx emission control program
b) A VOC emission control program
c) A control program for both NOx and VOC emissions
PROBLEM 2 - SOLUTION
PROBLEM 3
• Repeat the previous analysis for an urban area where the
current atmospheric concentration of NOx is 160 ppb and VOC
is 800 ppb.
O3 FORMATION POTENTIAL OF HYDROCARBONS
• Carbon Mass Approach
• Reactive Organic Gas Approach (ROGs)
• Chemical Reactivity Approach
• Improved Reactivity Scale
• Focus only on carbon mass emitted and neglect subsequent chemistry
• Assumes large molecules are more reactive than smaller
• Simple and straight forward
• Example
• m-xylene (C8H10) Vs Ethanol (C2H5OH)
• Reducing m-xylene concentration by 1 ppb is considered equivalent to reducing
ethanol by 4 ppb
• A Chemical Reactivity Approach
• Develop reactivity scale that could be used as weighting factor for
individual species
• Based on rate constant KOH for reactions with the OH radical.
• Comparing ozone forming potential of m-xylene and ethanol (24/3.3 =
7.3 ppb)
• Disadvantage of this scale is that it considers only the reaction rate of
the first step of the oxidation process of VOCs.
• The Reactive Organic Gas Approach (ROGs)
• Two categories, reactive and unreactive species
• Reactive – ROGS, most responsible for Ozone formation
• Reactivity of ethane (C2H6) with OH radical as the dividing line
between reactive and nonreactive species
• In contrast, compounds like methane and carbon monoxide are
considered to be unreactive for the formation of Ozone
• An Improved Reactivity Scale
• Accounts to overall chemistry of ozone formation
• Incremental reactivity (IR)
∆ [𝑂3]
• 𝐼𝑅 = (𝑓𝑜𝑟 ∆ 𝑉𝑂𝐶 → 0)
∆ [𝑉𝑂𝐶]
• IR Value of a given compound depends on the chemical properties of
the atmosphere (depends on VOC/NOx ratio)
• Maximum incremental reactivity (MIR) scale of an organic compound
is the IR value under conditions where IR has its maximum.
• KOH and Maximum
Incremental Reactivity (MIR)
for selected VOCs at 298K
PROBLEM 4
• An air pollution source in an urban area emits the following
mass of pollutants per day: 1.30 kg CO, 2.0 kg ethene, and 1.5
kg acetaldehyde. A new technology is proposed to reduce the
contribution of this source to ozone formation. The expected
new emissions per day would be 10 kg of CO, 0.3 kg of acetone
and 11 kg methanol. Compare the emissions from the two
technologies using each of the four methods for evaluating
ozone forming potential:
a) The carbon mass approach
b) The ROG carbon mass approach
c) The KOH reactivity scale
d) The MIR reactivity scale
Emissions
Compound No. Carbons Carbon (x12) (g) Mol. Wt % Carbon Current (Overall) Current (Carbon) New (Overall) New (Carbon)
CO 1 12 28 42.9 1.3 0.5577 10 4.29
C3H6O 3 36 58 62.1 0.3 0.1863
CH4O 1 12 32 37.5 11 4.125
C2H4 2 24 28 85.7 2 1.714
C2H4O 2 24 44 54.5 1.5 0.8175
3.0892 8.6013
• ROGS
Only emissions from ethene and acetaldehyde are included
Old
(2.0 x 0.857) + (1.5 x 0.545) = 2.5 kg C per day
New
11 x 0.375 = 4.1 kg C per day
• KOH reaction rate constants
Old
(1.1 x 0.21) + (2.0 x 8.5) + (1.5 x 16) = 41.3
New
(10 x 0.21) + (0.3 x 0.22) + (11 x 0.94) = 12.5
• MIR
Old
1.2 x 0.065 + (2.0 x 8.3) + (1.5 x 6.3) = 26.1
New
(10 x 0.065) + (0.3 x 0.49) + (11 x 0.665) = 7.1
OZONE DEPLETION
OZONE DEPLETION
• The problem of ozone depletion
• Natural ozone layer
• The structure of atmosphere
• UV radiation from sun
• Formation and destruction
• Measurement
• Chloroflurocarbons (CFCs) and Halocarbons
• What are CFCs
• Naming convention
• CFC destruction of stratospheric ozone
• Mechanism at Midlatitudes
• Mechanism at Antartic
OZONE DEPLETION
• UV Radiation
Vulnerabilities
• Melanoma
• Solar Keratoses
• Sunburns
• Herpes
• Weekend immune system
OZONE DEPLETION
http://flatplanet.wikispaces.com/file/view/effects_of_ozone.jpg/30605011/effects_of_ozone.jpg
OZONE DEPLETION
http://en.wikipedia.org/wiki/Ozone_depletion
OZONE DEPLETION
http://en.wikipedia.org/wiki/Ozone_depletion
NATURAL OZONE LAYER
• Structure of
Atmosphere
NATURAL OZONE LAYER
• Tropopause (line between troposphere and stratosphere) and
stratopause (line between stratosphere and mesosphere)
• 16 km at tropics to 9 km at poles
• Temperature in troposphere 15 to -55
• Increases in stratosphere as ozone absorbs sunlight and
releases energy
• Warmer air in stratosphere does not mix with cooler air in
troposphere
• Particles are injected by aircrafts or large volcanos
NATURAL OZONE LAYER
• UV Radiation
http://healthycanadians.gc.ca/environment-environnement/sun-soleil/radiation-rayonnement-eng.php
UV RADIATION
• Shortest wavelengths contain the most
energy, and the longer much less energy.
• Three ranges of ultraviolet radiation of
interest are:
• UV-C (200 to 280 nm) is the most damaging.
However, this radiation is entirely absorbed
by oxygen and ozone molecules in the
stratosphere and therefore never reaches the
earth's surface.
• UV-B (280 to 320 nm) is a potentially very
harmful form of radiation that is mostly
absorbed by ozone molecules in the
stratosphere.
• UV-A (320 to 400 nm) is the least damaging
form of UV radiation.
http://www.loc.gov/rr/scitech/mysteries/colors.html
FORMATION AND DESTRUCTION OF OZONE
• Creation of oxygen atoms (λ < 240 nm) Photolysis --- Reaction 1
𝑂2 + ℎ𝜗 → 𝑂 + 𝑂
• Formation of Ozone --- Reaction 2

𝑂2 + 𝑂 → 𝑂3
• Absorption of UV (240 nm < λ < 320 nm) --- Reaction 3
𝑂3 + ℎ𝜗 → 𝑂2 + 𝑂
• Destruction of ozone Recombination --- Reaction 4
𝑂 + 𝑂3 → 2𝑂2
VARIATION OF OZONE CONCENTRATIONS
• Concentration of ozone varies naturally with latitude, with season,
day to day
• Ozone is produced in largest quantity over equator due to sunlight
• However due to winds, thickest at poles and thinnest near equator.
• Concentrations are low in the troposphere, increase to a peak value
in the mid-stratosphere, and then decrease above this height.
• The variation in ozone with altitude is responsible for the
temperature profile in the stratosphere.
• UV radiation is continually being converted to heat as a result of
the destruction and reformation of ozone.
PROBLEM 5
• Confirm that there is no buildup of ozone, molecular oxygen,
or atomic oxygen in the sequence of chemical reactions just
described.
MEASUREMENTS
• Four common ways
• Fraction
• Parts per million (ppm)
• Microgram per cubic meter (µg/m3)
• Dobson units (DU)
• Fraction
• 𝐶𝑂 𝑒𝑥𝑝𝑟𝑒𝑠𝑠𝑒𝑑 𝑎𝑠 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛
𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠 𝑜𝑓 𝑜𝑧𝑜𝑛𝑒 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑜𝑧𝑜𝑛𝑒 𝑛𝑂3
= = =
𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠 𝑜𝑓 𝑎𝑖𝑟 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑎𝑖𝑟 𝑛
Where n is the number of molecules of air and is the sum of molecules of all the
constituents in the air such as nitrogen, oxygen and trace constituents.
MEASUREMENTS - FRACTION
• Fraction
• 𝐶𝑂 𝑒𝑥𝑝𝑟𝑒𝑠𝑠𝑒𝑑 𝑎𝑠 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛
𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠 𝑜𝑓 𝑜𝑧𝑜𝑛𝑒 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑜𝑧𝑜𝑛𝑒 𝑛𝑂3
= = =
𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠 𝑜𝑓 𝑎𝑖𝑟 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑎𝑖𝑟 𝑛
Where n is the number of molecules of air and is the sum of molecules of all the
constituents in the air such as nitrogen, oxygen and trace constituents.
MEASUREMENTS - PPM
• 𝐶𝑂 𝑒𝑥𝑝𝑟𝑒𝑠𝑠𝑒𝑑 𝑎𝑠 𝑝𝑝𝑚
𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠 𝑜𝑓 𝑜𝑧𝑜𝑛𝑒 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑜𝑧𝑜𝑛𝑒 𝑛 𝑂3
= = =
106 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠 𝑜𝑓 𝑎𝑖𝑟 106 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑎𝑖𝑟 𝑛
Note
10−6 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑜𝑧𝑜𝑛𝑒 1 𝑚𝑜𝑙𝑒 𝑜𝑓 𝑜𝑧𝑜𝑛𝑒
= = 1 𝑝𝑝𝑚
1 𝑚𝑜𝑙𝑒 𝑜𝑓 𝑎𝑖𝑟 106 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑎𝑖𝑟
Thus we multiply the fractional concentration by 106 to obtain

concentration expresses as ppm
MEASUREMENTS – G/M3
• 𝐶𝑂 𝑒𝑥𝑝𝑟𝑒𝑠𝑠𝑒𝑑 𝑎𝑠 𝑔/𝑚3
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑜𝑧𝑜𝑛𝑒 𝑝𝑀𝑂3
= = 𝐶𝑜 (𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛)
𝑉𝑎𝑖𝑟 𝑅𝑜 𝑇
PROBLEM 6
• The fractional concentration of ozone in clean tropospheric air
is about 1 x 10-8 at 1 atmosphere pressure and T= 0OC.
Calculate this concentration in ppm and also in g/m3.
GAS CONSTANT
atm.cm3/(mol.K) : 82.0575 atm.ft3/(lbmol.K) : 1.31443
atm.ft3/(lbmol.oR) : 0.73024 atm.l/(mol.K) : 0.08206
bar.cm3/(mol.K) : 83.14472 bar.l/(mol.K) : 0.08314472
Btu/(lbmol.oR) : 1.9859 cal/(mol.K) : 1.9859
erg/(mol.K) : 83144720 hp.h/(lbmol.oR) : 0.0007805
inHg.ft3/(lbmol.oR) : 21.85 J/(mol.K) : 8.314472
kJ/(kmol.K) : 8.314472 J/(kmol.K) : 8314.472
(kgf/cm2).l/(mol.K) : 0.084784 kPa.cm3/(mol.K) : 8314.472
kWh/(lbmol.oR) : 0.000582 lbf.ft/(lbmol.oR) : 1545.349
mmHg.ft3/(lbmol.K) : 999 mmHg.ft3/(lbmol.oR) : 555
mmHg.l/(mol.K) : 62.364 Pa.m3/(mol.K) : 8.314472
psf.ft3/(lbmol.oR) : 1545.349 psi.ft3/(lbmol.oR) : 10.73
Torr.cm3/(mol.K) : 62364
MEASUREMENTS – DOBSON UNITS
• Concentrations as fractions, ppm, and g/m3 are most useful close to the
ground where air density, pressure, and temperature are roughly con-
tant.
• At high altitudes, however, properties of the air may vary greatly, and it
is more convenient to express the ozone concentration using Dobson
Units.
• 1 DU is defined as 0.01 mm thickness of pure ozone at 0 oC and 1
atmosphere.
• This method is named after the scientist who designed an instrument to
measure ozone. The instrument reports the total number of ozone
molecules occupying a vertical column of air stretching from the earth's
surface to the top of the stratosphere.
• Named after the UK geophysicist Dr. G. M. B. Dobson (1889-1976) who in
1928 invented the photoelectric spectrophotometer (also called Dobson
meter) used in measuring the total ozone over an area from the ground
level.
MEASUREMENTS – DOBSON UNITS
SPECTROPHOTOMETERS
• Based on the principle of
differential absorption of solar light
by ozone in the UV (between 280
and 330 nm). From the knowledge
of the absorption spectrum of ozone
, the ozone content of the
atmosphere is derived.
• There are two main types of these
instruments: the Dobson and the Dobson Spectrophotometer
Brewer spectrophotometers.
• During the 1970's, the Brewer
instrument was developed. It is
based on the same measurement
principle as the Dobson instrument,
but uses more state-of-the-art
technology. With completely
automated .
Brewer Spectrophotometer
SPECTROPHOTOMETERS
• Canada has been concerned about
stratospheric ozone depletion since
the issue was first raised by scientists
in the 1960s and 1970s.
• The Brewer ozone spectrophotometer
was developed in Canada and is
presently the principal instrument
(most accurate and popular) for
ground-based ozone measurements.
• Furthermore, our collection of
monitoring stations is among the
largest and most proficient in the
world.
• Canada also remains the archival
spot for storing ozone measurements
from all around the world in the
World Ozone and Ultraviolet
Radiation Data Centre.
PROBLEM 7
• Calculate the number of molecules of ozone per cm2 of the
earth’s surface for 1 DU, based on the definition of DU given
in the ideal gas law.
PROBLEM 8
• Concentrations of ozone at ground level on a smoggy day can
reach 0.2 ppm. If this concentration of ozone is mixed up to a
height of 1,000 m, express the ozone concentration in DU.
Assume air is an ideal gas with uniform values of T = 0°C and
p = 1 atmosphere over this height. Compare your answer
with the typical value of 300 DU for the entire atmospheric
column, including the stratosphere.
• 1 DU = 2.69 x 1016 molecules of ozone per cm2 of earth’s surface
• We need to calculate ozone per cm2 in the air up to 1,000 m height and
divide by 2.69 x 1016 to get number of DU.
• Number of air molecules in a volume of 1cm x 1cm x 1,000 m
(Volume =0.1 m3)
𝑝𝑉𝑎𝑖𝑟𝑁𝑎 1 𝑎𝑡𝑚 𝑥 0.1 𝑚3 𝑥 6.023 𝑥 1023 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠/𝑚𝑜𝑙𝑒
• 𝑛𝑁𝑎 = =
𝑅𝑜𝑇 8.21 𝑥 10−5 𝑥 273 𝐾
• =2.69 x 1024 molecules of air

• This is exactly 108 times greater than the number of zone molecules for 1
DU calculated before.
• Number of zone molecules in the 1,000 m column of air is calculated as
𝑛𝑂3 𝑁𝑎 = 𝐶𝑜3 𝑛 𝑁𝑎 = 0.2 𝑥 10−6 2.69 𝑥 1024 = 5.38 𝑥1017 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠 𝑜𝑓 𝑜𝑧𝑜𝑛𝑒
𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠 𝑜𝑓 𝑜𝑧𝑜𝑛𝑒 1 𝐷𝑈
5.38 𝑥 1017 𝑥
𝑐𝑚2 𝑜𝑓 𝑡ℎ𝑒 𝑒𝑎𝑟𝑡ℎ′ 𝑠 𝑠𝑢𝑟𝑓𝑎𝑐𝑒 𝑚𝑜𝑙. 𝑜𝑓 𝑜𝑧𝑜𝑛𝑒
2.69 𝑥 1016
𝑐𝑚2 𝑜𝑓 𝑡ℎ𝑒 𝑒𝑎𝑟𝑡ℎ′ 𝑠 𝑠𝑢𝑟𝑓𝑎𝑐𝑒
= 20 DU
• This is much smaller than the typical value of 300 DU for ozone in a column that extends upward to the
top of the stratosphere.
• This the amount of ozone close to the ground, even on a smoggy day is much smaller than the amount
of ozone in the entire atmospheric column, most of which is in stratosphere.
PROBLEM 9
• Determine the concentration of ozone in ppm averaged over
the column from the ground to the top of the stratosphere for
a typical value of 300 DU. Assume that there are a total of 1.1
X 1044 molecules of air in the troposphere and stratosphere
together, and that the average radius of the earth is 6,370 km.
DOBSON UNITS
• 1 Dobson Unit (DU) is the number of molecules of ozone that
would be required to create a layer of pure ozone 0.01 mm thick at
a temperature of 0o C and 1 atm.
• Expressed another way, a column of air with an ozone
concentration of 1 Dobson Unit would contain about 2.69x1016
ozone molecules for every square centimeter of area at the base of
the column.
• Ozone concentrations can vary naturally from more than 500 DU in
polar regions in the spring to less than 250 DU at the equator.
• The typical column of ozone is approximately 300 DU.
• What scientists call the Antarctic Ozone “Hole” is an area where the
ozone concentration drops to an average of about 100 Dobson Units
PROBLEM 10
• If the overall global average ozone concentration is 300 DU,
calculate the approximate number of ozone molecules in the
atmosphere at any given time.
PROBLEM 10 SOLUTION
• Radius of Earth = 6370 km
• 1 DU = 2.69 x 1016 molecules of ozone per cm2 of earth’s
surface
• 1DU = 2.69 x 1016 x 4π R2 = 2.69x1016 x 4 * 3.14 x (6370)2
• 300 DU = 4.11 x 1037 molecules of O3
PROBLEM 11
• The atmospheric column contains 280 DU of ozone on a
certain day. A ground level ozone monitor shows a
concentration of 0.05 ppm, which is assumed to be uniform up
to a temperature inversion height of 700 m. Assume p=1 atm
and T= 300K for the region below 700 m. What fraction of the
ozone molecules in the total atmospheric column are below
the inversion height?
HALOCARBONS
• Chlorine (Cl) belongs to a class of chemicals called halogens
including fluorine (F), bromine (Br) and iodine (I).
• When one of these elements combine with carbon, the
resulting compounds are called halocarbons.
• CFCs are the most well-known type of halocarbons.
CFCS
• Class of chemicals known as
chlorofluorocarbons were
responsible for the chlorine atoms
in the atmosphere.
• These compounds were thought to
be an ideal solution to the growing
demand for refrigerant chemicals.
• CFCs are odorless, colorless, non-
inflammable, non-corrosive and
non-toxic.
• Extremely stable, once produced
they could be used for years.
CFCS
Industrial
Refrigerants solvents for
23% cleaning
semiconductors
23%
Blowing agents
Propellants for for foam and
aerosol spray insulation
cans manufacturing
28% 26%
CFCS
CFCS
• Leaks, spills and disposal
• Stability – allowed them to remain
in atmosphere for long time
• Make their way up to the
stratosphere
MECHANISM OF DESTRUCTION
• When CFCs are emitted at the earth's surface they slowly
disperse. and some of them eventually reach the lower strato-
sphere in 3 to 5 years.
• The molecule can then diffuse upward to reach the upper
portions of the stratosphere (over 25 km height), where global
levels of ozone depletion are seen.
• A CFC molecule can take from 40 to 100 years to reach this
height after being emitted at the earth's surface.
• These molecules can be dissociated only by solar radiation with
wave lengths shorter than 230 nm (UV-C).
• Radiation with such short wavelengths cannot penetrate the
stratosphere to reach the troposphere because oxygen and ozone
at high altitudes absorb all radiation with wavelengths shorter
than 293 nm.
• At high elevations in the stratosphere short-wave radiation is
abundant, and CFCs can undergo photolysis to release a chlorine
atom.
• CFC-11 experiences the following reaction
𝐶𝐶𝑙3 𝐹 + ℎ𝑣 → 𝐶𝑙 + 𝐶𝐶𝑙2 𝐹 -- Reaction 5*
𝐶𝑙 + 𝑂3 → 𝐶𝑙𝑂 + 𝑂2 -- Reaction 6
𝐶𝑙𝑂 + 𝑂 → 𝐶𝑙 + 𝑂2 - Reaction 7
𝐶𝑙 + 𝐶𝐻4 → 𝐻𝐶𝑙 + 𝐶𝐻3 - Reaction 8**
* λ < 230 nm (25-40 km)

** Over about a month, Cl atom will destroy approximately 100,000 ozone
molecules before it eventually reaction with small amount of natural
atmospheric methane
OZONE DEPLETING GASES
QUANTIFIYING OZONE DESTRUCTION BY
CFCS
• THE MASS BALANCE MODEL
THANK YOU

Lecture 02 Fall 2023 - With Solutions

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Lecture 02 Fall 2023 - With Solutions

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AIR POLLUTION

• Effect of VOC Concentrations

• Zero VOCs produces small

approximately 77%. function of VOC level for constant NOx

• Effect of NOX concentrations

Predicted maximum ozone concentration as a function

• Your Grandmother talks to you:

• Formation of Ozone --- Reaction 2

Thus we multiply the fractional concentration by 106 to obtain

• =2.69 x 1024 molecules of air

* λ < 230 nm (25-40 km)

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