Lecture 6: Spectroscopy and

Photochemistry II

Required Reading: FP Chapter 3

Suggested Reading: SP Chapter 3

Atmospheric Chemistry
CHEM-5151 / ATOC-5151
Spring 2005
Prof. Jose-Luis Jimenez

Outline of Lecture
• The Sun as a radiation source
• Attenuation from the atmosphere
– Scattering by gases & aerosols
– Absorption by gases
• Beer-Lamber law
• Atmospheric photochemistry
– Calculation of photolysis rates
– Radiation fluxes
– Radiation models

1
 Reminder of EM Spectrum

Blackbody Radiation
Linear Scale Log Scale

From R.P. Turco, Earth Under Siege: From Air Pollution to Global Change, Oxford UP, 2002.

2
 Solar & Earth Radiation Spectra
• Sun is a radiation source with
an effective blackbody
temperature of about 5800 K
• Earth receives circa 1368
W/m2 of energy from solar
radiation
From Turco
From S. Nidkorodov

• Question: are relative

vertical scales ok in
right plot?

Solar Radiation Spectrum II

From F-P&P

•Solar spectrum is
strongly modulated by
atmospheric scattering
and absorption
From Turco

3
 Solar Radiation Spectrum III

UV
Photon Energy ↑
CBA

From Turco

Solar Radiation Spectrum IV

• Solar spectrum is strongly
O3 modulated by atmospheric
absorptions
O2 • Remember that UV photons
have most energy
– O2 absorbs extreme UV in
mesosphere; O3 absorbs most UV
in stratosphere
– Chemistry of those regions
partially driven by those
absorptions
– Only light with λ>290 nm
penetrates into the lower
troposphere
– Biomolecules have same bonds
(e.g. C-H), bonds can break with
UV absorption => damage to life
• Importance of protection
From F-P&P provided by O3 layer

4
 Solar Radiation Spectrum vs. altitude

From F-P&P

• Very high energy photons are depleted high up in the atmosphere

• Some photochemistry is possible in stratosphere but not in troposphere
• Only λ > 290 nm in trop.

Solar Zenith Angle

• Aside form the altitude, the path length through the
atmosphere critically depends on the time of day and
geographical location.
• Path length can be calculated using the flat atmosphere
approximation for zenith angles under 80º. Beyond that,
Earth curvature and atmospheric refraction start to matter.

1 0 15
S o la r F lu x

Actual pathlength L
" Air Mass" = m = ≈ = sec θ
Vertical pathlength h
Solar Flux [Photons cm s nm ]
-1
-2 -1

1 0 14
SZ A = 0º
SZ A = 86º

1 0 13 At large SZA very

little UV-B radiation
reaches the
troposphere

1 0 12
300 400 500 700 1000
W a v e le n g th [n m ]

5
 Direct Attenuation of Radiation
I = I 0 × e -t×m From F-P&P & S. Nidkorodov

t = t sg + t ag + t sp + t ap
I ≡ radiation intensity (e.g., F)
I0 ≡ radiation intensity above atmosphere
m ≡ air mass
t ≡ attenuation coefficient due to
– absorption by gases (ag)
– scattering by gases (sg)
– scattering by particles (sp)
– absorption by particles (ap)

Rayleigh scattering
tsp ∝ λ-n tsg ∝ λ-4
much
more Deep UV – O, N2, O2
complex Mid UV & visible – O3
Near IR – H2O
Infrared – CO2, H2O, others
tag ∝ σ

Scattering by Gases
• Purely physical
process, not
absorption
• Approximation:
t sg = 1.044 ⋅105 ⋅ (n0 λ − 1) 2 / λ4
• Strongly
increases as λ
decreases
• Reason why “sky
is blue” during
the day
From Turco

6
 Scattering & Absorption by Particles
From Jacob
• Particles can scatter
and absorb radiation
• Scattering efficiency is
very strong function of
particle size
– For a given wavelength
• Visible: λ ~ 0.5 µm
– Particles 0.5-2 µm are
most efficient scatterers!
• Will discuss in more
detail in aerosol
lectures

Gas Absorption: Beer-Lambert Law I

I = I 0 exp(−σ ⋅ L ⋅ N )
• Allows the calculation of
the decay in intensity of a
light beam due to
absorption by the
molecules in a medium

Solve in class: Show that in the small
absorption limit the relative change in light
intensity is approximately equal to
absorbance.
From F-P&P & S. Nidkorodov
Definitions:
• A = ln(I0/I) = Absorbance = σ⋅L⋅N
(also “optical depth”)
• σ ≡ absorption cross section
[cm2/molec]
• L ≡ absorption path length [cm]
• n ≡ density of the absorber
[molec/cm3]

7
 Beer-Lambert Law II
Pitfalls:
• Other units are frequently used to express absorbance,
for example:
A = ln(I0/I) = ε×L×C A = ln(I0/I) = α×L×P
ε ≡ extinction coefficient [L mol-1 cm-1]
α ≡ absorption coefficient [atm-1 cm-1]
C ≡ density of the absorber [mol L-1]
P ≡ partial pressure [atm]
• Base 10 is used in most commercial spectrometers
instead of the natural base:
Abase 10 = log(I0/I) = Abase e/ln(10)

Physical interpretation of σ
• σ , absorption cross section (cm2 / molecule)
– Effective area of the molecule that photon needs to
traverse in order to be absorbed.
– The larger the absorption cross section, the easier it
is to photoexcite the molecule.
– E.g., pernitric acid HNO4

Collisions Light absorption

σ ≈ 10-15 cm2/molec σ ≈ 10-18 cm2/molec From S. Nidkorodov

8
 Measurement of Absorption Cross Sections
Measurement of absorption cross sections is, in principle, trivial. We need a
light source, such as a lamp (UV), a cell to contain the molecule of interest, a
spectral filter (such as a monochromator) and a detector that is sensitive and
responds linearly to the frequency of radiation of interest:

Gas cell
Filter I0 I Detector
n [#/cm3]
L
Measurements are repeated for a number of
concentrations at each wavelength of interest.
Although seemingly trivial, in practice such
measurements are difficult because of
impurities, especially when it comes to very
small cross sections (< 10-20 cm2/molec)

Solve in class: Sample contains 1 Torr of

molecules of interest with σ=3x10-21 cm2/molec
and 1 mTorr of impurity with σ=2x10-18 cm2/molec.
What is the total absorbance in a 50 cm cell?
From S. Nidkorodov

Example: UV Attenuation by O3 and O2

Attenuation coefficient is dominated by O3
absorption in the 200-300 nm window.
Therefore, direct attenuation can be easily
calculated from known absorption cross
sections of O3. Similar formulas apply to
attenuation by O2 in 120-180 nm window.

I (λ ) = I 0 (λ ) × e -σ ( λ )× A×m
where A ≡ column density
∞
A = ∫ [O 3 ( z )]dz
z
From S. Nidkorodov
Alternatively written :
Solve in class: Using barometric law estimate
I ( λ ) = I 0 ( λ ) × e -τ ( λ , z ) column density of O2 in the atmosphere. By how
where τ ≡ optical depth much does atmospheric O2 attenuate solar
radiation at around 170 nm (σ ≈ 10-17 cm2/molec)
∞
at noon (m = 1)? Assume that O2 fraction (21%) is
τ (λ , z ) = ∫ σ (λ ) × m × [O 3 ( z )]dz independent of altitude and T = 270 K.
z Ans: 4x1024; by exp(-107)

9
 Solar Radiation Intensity
To calculate solar From F-P&P
spectral distribution in
any given volume of
air at any given time
and location one must
know the following:
– Solar spectral
distribution outside the
atmosphere
– Path length through the
atmosphere
– Wavelength dependent
attenuation by
atmospheric molecules
– Amount of radiation
indirectly scattered by
the earth surface, clouds,
aerosols, and other
volumes of air

Surface Albedo
Reflected Radiation(λ )
Albedo(λ ) =
Incident Radiation(λ )
• Wavelength
dependent!
• Question: for the
same incident UV
solar flux, will you
tan faster over
snow or over a
desert?
From F-P&P

10
 Total vs. Downwelling Radiation
From Warneck
• If atmosphere was
completely transparent
and surface completely
absorbing (albedo = 0)
– FU = 0
– FD =FT= 1
• Due to gas + aerosol
scattering and surface
reflection
– FU can be large
– FT > solar flux!

Calculation of Photolysis Rates I

Generic reaction: A + hν → B + C
d [ A]
= − J A [ A]
dt
• A “first-order process”
• What does JA depend on?
• JA depends on
– Light intensity from all directions
• “Actinic flux”
– Absorption cross section (σ)
– Quantum yield for photodissociation (φ)
– All are functions of wavelength

11
 Calculation of Photolysis Rates II
Generic reaction: A + hν → B + C
d [ A]
= − J A [ A] = − ∫ σ A (λ )φ A (λ ) F (λ )dλ × [ A]
dt
JA – first order photolysis rate of A (s-1)
σA(λ) – wavelength dependent cross section of A (cm2/#)
φA(λ) – wavelength dependent quantum yield for photolysis
F(λ) – spectral actinic flux density (#/cm2/s)

So, what are the smallest cross sections that matter?

The solar actinic flux (photons cm-2 s-1 nm-1) is of order 1014. In many
cases, we need to know whether the photolytic lifetime of a molecule is 10
days (J=10-6 s-1), or 100 days (J=10-7 s-1). This means that cross sections
as small as 10-20 cm2 or even smaller are potentially interesting. Such small
cross sections are very challenging to measure with sufficient accuracy.

Radiation Fluxes Definitions

Quantity Description Units
Actinic flux density: energy crossing a unit area per unit time without
F J m-2 s-1
consideration of direction (we do not care where photons come from)
F(λ) Spectral actinic flux density: same as flux but per unit wavelength J m-2 s-1 nm-1
E Irradiance: same as flux but for a unit area with a fixed orientation J m-2 s-1
E(λ) Spectral irradiance: same as radiance but per unit wavelength range J m-2 s-1 nm-1

L(θ, ϕ) Radiance: radiant flux density per unit solid angle J m-2 s-1 sr-1
J m-2 s-1 nm-1 sr-1
L(θ, ϕ, λ) Spectral radiance: same as radiance but per unit wavelength range

2π π
E = ∫ L(θ , ϕ ) cos θdω = ∫ ∫ L(θ , ϕ ) cosθ sin θdθdϕ
ω 0 0
2π π
F = ∫ L(θ , ϕ )dω = ∫ ∫ L(θ , ϕ ) sin θdθdϕ
ω 0 0

Radiance as a function of direction gives a complete description

of the radiation field. When L is independent of direction, the
field is called isotropic, in which case E = π L and F = 2π L.
From F-P&P Solve in class: There are 109 photons flying into a 0.01 cm diameter opening every
& S. Nidkorodov second. What is F with respect to this opening in units of #/cm2/s?

12
 Radiation Mesurements
Flat Plate → Irradiance 2π → ½ of Actinic Flux

• Radiation does not just come directly from the sun

– scattered radiation is just as important
– Measure total or spectrally-resolved flux
– Use models From F-P&P

Radiation Models
• Predict radiation intensity
– As f(time, altitude, latitude, λ)
– Results of Madronich (1998) described in text
• Will use extensively in homeworks & exams
– Typical model results: From F-P&P

13
 Example model results

From F-P&P

Q: summer/winter solstices intensity at 445 nm: @ 8 am? @ noon?

Examples of Photolysis Rates

From F-P&P

14
 Example: Photolysis of CH3CHO
λi
CH3CHO + hν → CH3 + HCO (a)
→ CH4 + CO (b)
J = ∫ σ (λ )φ (λ ) F (λ )dλ ≈
λ
∑ σ (λ )φ (λ ) F (λ )∆λ
= 290 nm

From F-P&P

15