Chemistry 321 Environmental Chemistry

Atmospheric structure and composition

– The Ozone Layer

References:
• Chapter 1, CB/MC
• Daniel Jacob "Atmospheric Chemistry“
• Free on-line text
• http://www.as.harvard.edu:16080/ctm/publications/jacobbook/
Correction:
In class, I incorrectly assigned the oxidation state of S in H3C-S-CH3 as 0.
The correct oxidation state of S in H3C-S-CH3 is -2.
My apologies for this error.
1
Sept 21, 2010
Previous lecture

• abundance of elements in Earth's crust CPS-1

• Global biogeochemical element cycles
• examples: N, S, C
• GBECs can change: e.g., phytoplankton fertilization

Main message from previous lecture: Man and other processes can
change/alter theses GBECs
CPS-1: What are the most abundant elements by mass, in the Earth’s
crust? Answer: Aluminum, Silicon, Oxygen

2
Objectives

Following this unit, you are expected to be able to:

• Define the terms troposphere, tropopause, stratosphere, stratopause

• convert between number densities (concentrations) and mixing ratios
• calculate number density of air (using ideal gas law)
• sketch approximate profiles of temperature, pressure, water, and ozone in
the atmosphere

• apply the Beer-Lambert law to calculate absorption and scattering of light

• describe how absorption by oxygen and ozone attenuate sunlight within the
atmosphere
• describe the potential impact of missing stratospheric ozone

Please review 1st year material:

• ideal gas law (partial pressures)
• Kinetics: rate laws; reaction mechanisms, activation energy, catalysis
3
 Earth
Q1: Earth's diameter? Q4: Where is the stratosphere?
Q2: Height of the atmosphere? 15 – 50 km

Q3: Up to what height can humans live? Q5: Where is the troposphere?
< 15 km

km

< 100 km
7 56
12 Atmosphere is very thin

humans:
< 8 km

4
http://earth.jsc.nasa.gov/
Units for gases
Volume mixing ratios ≈ composition
% = per cent = 10-2 (e.g., N2≈78%, O2≈21%)
parts-per-thousand 10-3 (e.g., Ar ~9.34 ppthv, ppth)
parts-per-million 10-6 (e.g., CH4, ~1.7 ppmv, ppm) not dependent on P, T
parts-per-billion 10-9 (e.g., nitrogen oxides; NO, NO2) Q6: What's a radical?
parts-per-trillion 10-12 (e.g., free radicals) Q6a: What's a free radical?
Note that these are North American billions and trillions (Europe: 1 billion = 1012 ).

Note that these are volume ratios (not mass ratios) radical = highly reactive unpaired e-
Free radical = does not travel long
distances and has fast rates of
formation
"Number density" ≈ concentration (M)

number of molecules units: molecules cm-3 (gases)

volume of air
• used to calculate gas-phase reaction rates (as a measure of collision probability)
• analogous to molarity in liquids

5
Ideal gas law
Ideal gas law:
PV = nRT
=> number density = n = n/V = P/RT
=> number density is a function of pressure and temperature

Conversion between number densities and mixing ratios:

# of molecules cm-3 of gas X nx = Cx nair # of molecules cm-3 of air

mixing ratio of gas X

calculate nair using ideal gas law:

PV = nRT
=> n = n/V = P/RT
and Avogadro's number (6.023×1023 molecules mol-1 )
and R = 8.314 J mol-1 K-1 or R = 0.08205 L atm mol-1 K-1

nair = P/(RT) function of temperature and pressure!

6
Box 3-1, pp 93-95, CBMC
Exercises
Q8: Calculate the number density of air at sea level (P=1024 mbar; T=25 ºC)

CPS-2
Calculate the number density of air on Mount Everest (P=300 mbar; T = -36 ºC)

A = 9.3×1018 molecules cm-3

CPS-3
The number density of air at sea level _______________________________
molecules cm-3 .
Calculate the number density of 40 ppbv of O3. A = 9.8×1011 molecules cm-3

CPS-4
Suppose the number density of air on Mount Everest is ____________________
molecules cm-3 .
Calculate the number density of 40 ppbv of O3. 7
A = 3.7×1011 molecules cm-3
 Work for Exercises
Q8:
 Work for Exercises
CPS-2: Calculate the number density of air on Mount Everest (P=300 mbar; T =
-36 ºC)
 Work for Exercises
CPS-3: The number density of air at sea level 2.5X10e14 molecules
cm-3. Calculate the number density of 40 ppbv of O3

CPS-4: Suppose the number density of air on Mount Everest is

9.3X10E18 molecules cm-3. Calculate the number density of 40
ppbv of O3.
Composition of the atmosphere

U.S. Standard atmosphere (1976). Source: CRC handbook

very dated

and trace gases...

Q9: Why is water not included in the standard atmosphere? B/c it varies
so much from place to place.
CPS-5: The mixing ratio of CO2 was 314 ppm in 1976.
What is it today (2010)? 390ppm
11
http://www.esrl.noaa.gov/gmd/ccgg/trends/
 Regions of the atmosphere

Mesophere

Stratopause

Stratosphere

Tropopause
Troposphere
Boundary (or surface) layer

Q10/CPS6: Why is it so
warm at the stratopause?
More absorption12
Locations of Tropo- and Stratopause are variable
Dan Jacob, chapter 2
Distribution of water in the atmosphere

Stratosphere

~ Tropopause

Troposphere

13
Important: Very little water in the stratosphere! Tropo = water
Distribution of ozone in the atmosphere

Stratospheric
"Ozone layer"

Q11: Why is stratospheric ozone important? Because it absorbs radiation

14
 Q12: What effect does each
Review: electromagnetic radiation type of radiation have on
molecules?

ionization (ejection of
core electrons)

bonds break
and
molecules
dissociate

molecules vibrate
= heat

15
microwave molecules rotate
Absorption of radiation by gases: Beer-Lambert law

light source optical path detector

−σ×n×L
I
I0
=e

I = intensity transmitted
I0 = intensity of incident light
σ = absorption cross-section (cm2 molecule-1 )
n = number density of absorbing molecules (molecules cm-3 )
L = optical path length (cm)
e = Euler's number (= 2.7182818...) 16
Scattering of radiation by gases: Beer-Lambert Law
this process is called Rayleigh scattering

light source optical path detector

−σ×n×L
I
I0
=e
At low wavelengths, light is
I = intensity transmitted scattered more efficiently than
I0 = intensity of incident light at high wavelengths
=> The sky is blue.
σ = scattering cross-section (cm2 molecule-1 )
n = number density of molecules (molecules cm-3 )
L = optical path length (cm)
e = Euler's number (= 2.7182818...) 17
C. Frohlich and G. E. Shaw, Appl. Optics 19, 1773 (1980).
A. Bucholtz, Appl. Optics 34, 2765 (May 20, 1995)
Example calculation of absorption and scattering (I)
Calculate the distance that light with wavelength 150 nm can travel
through an atmosphere consisting of pure O2 at STP
before it is reduced to 0.1% of its initial intensity.

Given: σ abs (150 nm, O2) = 1.0×10-17 cm2 molecule-

1

σ (150 nm, air) = 1.6×10-24 cm2 molecule-1

Rayleigh
since e-a × e-b = e-(a+b)
− ( σ ×n + σ )× L
Given: I/I0 = 0.001
Rayleigh ×nair
I
I0 = 0.001 = e abs abs

What's nair at STP? STP (IUPAC, 1990) ≡ 273.15 K, 1.00×105 Pa

use ideal gas law:PV = nRT n = number of molecules

n = n/V = P/RT n = number density of molecules
and A = Avogadro's number (6.023×1023 molecules mol-1 ) and R = 8.314 J mol-1 K-1
nair = (A/R) × (P/T)
= (6.023×1023 molecules mol-1 / 8.314 J mol-1 K-1 ) × (1.00×105 Pa/273.15 K) 1J=1N×m
1 Pa = 1 N × m-2
= 2.65×1019 molecules cm-3
ln(0.001) − 6.9
L= = = 0.026cm
− ( σabs × nabs + σ Rayleigh × nair ) − ( 2.65 × 10 cm + 4.2 × 10 cm ) Goes virtually no
2 −1 −5 −1
18
distance in atmos.
Example calculation of absorption and scattering (II)
Calculate the distance that light with wavelength 200 nm can travel
through an atmosphere consisting of pure O2 at STP
before it is reduced to 0.1% of its initial intensity.

σ abs (200 nm, O2) = 1.0×10-23 cm2 molecule-1

σ Rayleigh (200 nm, air) = 3.6×10-25 cm2 molecule-1

since e-a × e-b = e-(a+b)

I/I0 = 0.001 ( )
− σabs ×nabs + σ Rayleigh ×nair ×L
I
I0 = 0.001 = e

What's nair at STP? STP (IUPAC, 1990) ≡ 273.15 K, 1.00×105 Pa

use ideal gas law:PV = nRT n = number of molecules

n = n/V = P/RT n = number density of molecules
and A = Avogadro's number (6.023×1023 molecules mol-1 ) and R = 8.314 J mol-1 K-1
nair = (A/R) × (P/T)
= (6.023×1023 molecules mol-1 / 8.314 J mol-1 K-1 ) × (1.00×105 Pa/273.15 K)
= 2.65×1019 molecules cm-3 1J=1N×m
1 Pa = 1 N × m-2
ln(0.001) − 6.9
L= = = 250m
− ( σabs × nabs + σ Rayleigh × nair ) − ( 2.65 × 10 cm + 9.5 × 10 cm )
−4 −1 −6 −1
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 Solar radiation
The sun emits "black body" radiation at T=5770 K.
The Earth "sees" (more or less) collimated light.

Intensity of the radiation emitted by a black body Spectrum of the sun in the upper atmosphere
as a function of wavelength

Planck equation

D.A. McQuarrie and J.D. Simon Physical Chemistry: A molecular approach (1997), Fig. 1-2 and 1-3

Q13: What colour is the maximum emission intensity of a Planck black

body at 5770K?
20
A = yellow
Electromagnetic radiation: Dissociation of O2

• Energy of radiation E = hν = h c/λ

h = Planck's constant = 6.626×10-34 J s
ν = frequency (s-1 )
c = speed of light (m s-1 ) = 2.99×108 m s-1
λ = wavelength (nm)

• Energy required to dissociate oxygen:

O2 + hν → 2 O, ∆ Hrxn ° = 498.4 kJ mol-1

∆ Hrxn ° = 498.4 kJ mol-1 × (1 mol / 6.023×1023 molecules) = 8.3×10-19 J molecule-1

≈ minimum photon energy required to dissociate 1 molecule of O2

λ = hc/E = 6.626×10-34 J s × 2.99×108 m s-1 / (8.3×10-19 J molecule-1 )

min
= 240 nm
Q14/CPS7:
Where in the atmosphere would you expect radiation with λ ≤ 240 nm?
21
A = high up (upper stratosphere)
 Absorption of radiation by O2 and O3
absorption cross-section σ (cm2 molecule-1 )

Absorption spectrum of O2 Hartley band

O3
Schumann-
Runge
continuum O2
Ionization Schumann-Runge
continuum bands

O3
Herzberg
continuum

Schumann-Runge continuum/band and Herzberg continuum:

O2 + hν → 2 O

Source of atomic O in upper atmosphere!

O3 + hν → O2 + O
Sink of O3 in upper 22
CB/MC
atmosphere!
 Absorption of radiation by N2, O2 and O3 in the upper
atmosphere
vacuum UV

Little UV B or C
at surface

Finlayson-Pitts, B. J., and J. N. Pitts (2000), Chemistry of the upper and lower
atmosphere: theory, experiments, and applications, Academic Press, San Diego,
Calif.

Only light >300nm makes it to surface, good b/c ozone CB/MC

mostly absorbed
Q15: What if there was no O3 in the stratosphere? 23
Ans: molecules would break down (ie. DNA plants)
Impact of excess UV radiation
What if there was no O3 in the stratosphere?
• DNA mutations, skin cancer (melanoma), death
• cataracts
• crop failure

at the
surface

24
CB/MC