Lecture 1: Introduction to

Atmospheric Chemistry

Required Reading: FP Chapter 1 & 2

Additional Reading: SP Chapter 1 & 2

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

Outline of Lecture 1
• Importance of atmospheric chemistry
• Atmospheric composition: big picture, units
• Atmospheric structure
– Pressure profile
– Temperature profile
– Spatial and temporal scales
• Air Pollution:
– historical origin: AP deaths
– Overview of problems: smog, acid rain, stratospheric
O3, climate change, indoor pollution
• Continue in Lecture 2

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 Importance of Atmospheric Chemistry
• Atmosphere is very thin and fragile!
– Earth diameter = 12,740 km
– Earth mass ~ 6 * 1024 kg
– Atmospheric mass ~ 5.1 * 1018 kg
– 99% of atmospheric mass below ~ 50 km
– Solve in class: order of magnitude of mass of the
oceans? Mass of entire human population?
• Main driving forces to study Atm. Chem. are big
practical problems:
– Deaths from air pollution, smog, acid rain,
stratospheric ozone depletion, climate change

Structure of Course
• Introduction
• “Tools”
– Atmospheric transport (BT)
– Kinetics (ED) & Photochemistry
– Aerosols (QZ)
– Cloud and Fog chemistry
• “Problems”
– Smog chemistry
– Acid rain chemistry
– Aerosol effects
– Stratospheric Ozone
– Climate change

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 Interdisciplinarity of Atm. Chem.
• Very broad field of both fundamental and applied nature:
– Reaction modeling → chemical reaction dynamics and kinetics
– Photochemistry → atomic and molecular physics, quantum mechanics
– Aerosols → surface chemistry, material science, colloids
– Instrumentation → analytical chemistry, electronics, optics
– Air pollution → toxicology, organic chemistry, biochemistry
– Global modeling → meteorology, fluid dynamics, biogeochemistry
– Global observations → aeronautics, space research
– Air quality standards → environmental policies and regulations
• Comparatively new field:
– First dedicated text book written in 1961 by P.A. Leighton
(“Photochemistry of Air Pollution”)
– Ozone hole discovered in 1985 by British scientists, and later by NASA
– 1995 Nobel prize awarded to Paul Crutzen, Mario Molina, Sherwood
Rowland for predicting stratospheric ozone depletion
Adapted from S. Nidkorodov, UCI

Atm. Composition: Big Picture I

• Units of mixing ratio:
– Mol fraction
= Volume fraction
– ppm: 1 molec in 106
– ppb: 1 molec in 109
– ppt: 1 molec in 1012
– ppmv, ppbv, pptv
• Beware European billion
(1012), trillion (1018) etc.
• ≠ mass fraction
• Q: approximate mass
fraction of Kr in air?
From Jacob

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 Atm. Comp: Unit Conversions

From FP&P

• More complete tables on inside front cover of

FP&P

More on Units

• Units change the view very significantly

• Lack of / wrong units in your assignments or
exams will be considered a serious a mistake.
Adapted from S. Nidkorodov, UCI

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 Example on Units
• Solve in class: Dr. Evil decides to poison humankind by
spilling 100,000 55-gallon drums of tetrachloromethane
in Nevada (MW = 154 g mole-1; ρ = 1.59 g cm-3, 1
gallon = 3.785 liters).
• Assuming that all CCl4 evaporated and that it does not
react with anything, calculate its mixing ratio after it
gets uniformly distributed through the entire
atmosphere.
• Did he accomplish his objective given that the present
day CCl4 mixing ratio is roughly 100 ppt?
• How many drums could one fill with all the CCl4 in the
atmosphere?
Adapted from S. Nidkorodov, UCI

Atm. Composition: Big Picture II

From S&P

• Strongly oxidizing atmosphere

• Most atm. chemistry deals with “trace species”

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 Earth’s Atmosphere in Perspective
• All major planets (except How about other planets?
Pluto and Mercury) and
some large satellites (Titan)
have atmospheres.
• Properties of atmospheres
on neighboring Mars,
Venus, and Earth are
amazingly different!
• Earth is unique in:
– Very high O2 content (close
to spontaneous combustion
limit)
– High H2O content
– Existence of graduate
students and professors on
Slide from S. Nidkorodov, UCI
the surface Table From Brasseur, 1999

Lower Atmosphere is “Flat”!

• For most practical
purposes, lower
atmosphere can be
regarded as flat. Earth
curvature only needs
to be considered in
Drawn to scale very special cases.
• Earth does drag a veil
of gas with itself
(“exosphere”) with
the size of
approximately 10,000
km, however it is
extremely dilute. For
reference, space
shuttle @ 300-600
km above the Earth
surface
From S. Nidkorodov, UCI

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 Atmospheric Structure I
From FP&P

• Questions:
– Physical basis for P
variation?
– Physical basis for T
variation?

AS II: Pressure Variation

From Jacob

• Write differential mass balance for slab

• Solution: p(z)/P0 = e-z/H

• 99.9% of mass below stratopause See S&P p.9

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 AS III: Species Variation?
• H(z) = RT(z)/(MWair * g)
• Dalton’s law: each component behaves as if it
was alone in the atmosphere
• Hi(z) = RT(z)/(MWi * g)
– O2 at lower altitudes than N2?
– Some scientists: CFCs could not cause stratospheric
O3 depletion; too heavy to rise to stratosphere
• But gravitational separation due to molecular
diffusion, much slower than turbulent diffusion
– Only > 100 km enriched in lighter gases

AS IV: T Variation
From FP&P
Fig. 1.9

• First order approximation:

– Atmosphere is transparent, only surface is heated
– Loss by convection + re-radiation
– Shape of atmospheric temperature profile?

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 AS V: T Variation
• In the absence of local heating, T decreases with
height
• Exceptions: Stratosphere: Chapman Cycle (1930s)
O2 + hv → 2O
O + O 2 + M → O3 (+ heat)
O + O3 → 2O2
O3 + hv → O + O2 (+ heat)
– Q: what is heat at the molecular level?
• Mesosphere: absorption by N2, O2, atoms…

Temperature Inversions
From FP & P

• “Inversion layer”: temperature increases with

height
• Supresses mixing. Why?

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 Atmospheric (Vertical) Stability I
• Adiabatic Lapse Rate (Γ)
– vertical temperature profile when air ascends or descends
adiabatically, i.e. w/o giving or receiving heat
– For Earth, Γ = 9.8 K km-1
– Will deduce it from first principles later in the course
• Buoyancy force Fb = ρ’g – ρg

From Jacob

Atmospheric (Vertical) Stability II

adiabatic Actual “Inversion”

z z z

T T T

• Q: which of the following profiles are stable and

unstable
– Stable: a small perturbation is damped
– Unstable: a small perturbation is amplified

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 Spatial Scales of Atm. Chemistry
From S&P

• Enormous range of variation

– Typically separate research communities, don’t talk
much to each other

Spatial and Temporal Scales

From S&P
• Tight link
between
spatial &
temporal
scales

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 A flavor about the main problems
• London smog
– Primary pollutants
• Photochemical (“LA”) smog
• Global tropospheric pollution
• Particles
– Health
– Visibility
• Acid deposition
• Stratospheric ozone depletion
• Global climate change

Air Pollution & Excess Deaths

• Cold days, strong

inversions, foggy
• Smoke + Fog = “Smog”
• Governments, industry
& scientists start to
recognize importance of
From FP & P AP

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From FP & P
Primary Pollutants
• “Primary”: emitted directly, e.g.
Pb
– You reduce emission to reduce
concentrations
• “Secondary”: formed in the
atmosphere, e.g. O3
• Pb was “easy”
– Almost all from gasoline vehicles
– Added to gasoline as anti-knock
agent
– Did without it after regulation
required its removal
• Many countries still use leaded
gasoline (~1/4 of gasoline in
Spain, most in Africa)

Phothochemical (“LA”) Smog

• Sharp contrast to
London: sunny, hot
days
• Eye irritation, plant
damage
• 1950’s: Haagen-Smit:
Organics + NOx +
sunlight → O3 +
“other products”
• Now widespread
problem throughout
the world
From FP & P

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 What causes photochemical smog?
• Observation: NO emitted first, then forms NO2,
then O3 peaking in afternoon
• Can Chapman mechanism produce O3 in LA?
– Requires O2 + hv → 2O
– Needs hard UV that does not reach surface
– Need another route
• Blacet, 1952: photodissociation of NO2
– NO2 + hv (λ < 430 nm) → NO + O
– O + O 2 + M → O3
– Also NO + O3 → NO2 + O2 (rapid)

What causes smog II

• How does NO form NO2? (w/o O3)
• Thermal reaction 2NO + O2 → 2NO2 very slow
• Answer: organic oxidation
– RCH2R’ + OH → RC.HR’ + H2O
– RC.HR’ + O2→ RCHR’ (peroxy radical)
O-O.
– RCHR’ + NO → RCHR’ + NO2 (alkoxy radical)
O-O. O.
– Every step in organic oxidation creates NO2, then O3

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