大氣化學

(Atmospheric Chemistry)
Instructor: 洪惠敏 (Hui-Ming Hung)
Tel: (02)3366-3919
E-mail: [email protected]
Office hour: email for appointment, B309.
Textbook: Introduction to Atmospheric Chemistry (by Daniel J.
Jacob) 黎明書局, or you can read the book from the website of
https://acmg.seas.harvard.edu/education/introduction-atmospheric-chemistry
Additional books:
Upper and lower atmosphere by B.J. Finlayson-Pitts and Pitts
Atmospheric physics and Chemistry by Seinfeld and Pandis
Grading: first exam : 40%, second exam : 40%, and projects: 20%;
Quiz Bonus: 0-8%.
 Projects: 20%
14%: Box model (3%)
O3 formation in the Stratosphere (3%)
Diurnal pattern (4%)
Vertical profile (4%)
Due date: TBA
6%: Select one paper from 12.1, 13.4 and 8.2
to illustrate the linkage between the
problem set and the paper, and provide
further thoughts. (Due on 12/6)
No late submission.
 Quiz: Bonus, 0-8%

Friday 10:20AM-10:25AM

預習及複習 material
 Your TAs

• 黃維傑([email protected]) - A204
• 黃品潔([email protected]) - A204
大學部助教:
蔡杰森 ([email protected])
陳峰 ([email protected])
 Course Outline
• Introduction & Overview the Main Problems (Ch. 1, 2)
– Measures of Atmospheric Composition
– Atmospheric Pressure
• Simple Models (Ch. 3)
• Stratospheric Chemistry (Ch. 9, 10)
– Chemical Kinetics
– Stratospheric Ozone -Chapman Mechanism
– Stratospheric Ozone –Polar Ozone Loss
• Tropospheric Chemistry (Ch. 11,12, 13, 8)
– Oxidizing Power of the Troposphere
– Oxidation of CO and CH4
– Production of Ozone
– Ozone Pollution
– Aerosols & Acid Rain
• The Greenhouse Effect (Ch. 7)
• Geochemical Cycles (Ch. 6)
 Schedule for Atmospheric Chemistry Fall 2022

1.Introduction & Overview the Main Problems (Ch. 1, 2)

9/6,9
1-a. Measures of Atmospheric Composition (9/9 holiday)
1-b. Atmospheric Pressure
9/13,16
2.Simple Models (Ch. 3)
3. Stratospheric Chemistry (Ch. 9, 10)
9/20,23
3-a. Chemical Kinetics

9/27,30 3-b. Stratospheric Ozone -Chapman Mechanism

10/4,7 3-c. Stratospheric Ozone –Catalytic Loss Cycles
10/11,14 3-d. Stratospheric Ozone –Polar Ozone Loss
10/18,21 Review&Exam-1
4.Tropospheric Chemistry (Ch. 11,12, 13, 8)
10/25,28 4-a. Oxidizing Power of the Troposphere
11/1,4 4-b. Oxidation of CO and CH4
11/8,11 4-c. Production of Ozone
11/15,18 4-d. Ozone Pollution (11/15 no lecture)
11/22,25 4-e. Aerosols & Acid Rain (Ch 8)
11/29,12/2 5. The Greenhouse Effect (Ch 7)
12/6,9 6. Geochemical Cycles (Ch 6)
12/13,16 Review&Exam-2
The atmospheric chemistry studies

the chemical composition of the natural atmosphere,

the way gases, liquids, and solids in the atmosphere interact

with each other and with the earth's surface and associated
biota,

and how human activities may be changing the chemical and

physical characteristics of the atmosphere.
Jan 6, 2015 Jan 7, 2015
by 黃任廷
Trajectory Arriving
Taipei at local time, LT
Jan 6, 14:00
Jan 6, 20:00
Jan 7, 2:00
Jan 7, 10:00
Jan 7, 16:00

http://ready.arl.noaa.gov/hypub-
bin/trajresults.pl?jobidno=14853
Schematic of Global Warming Potential
and Ozone Depletion Potential

http://www.ccsr.u-tokyo.ac.jp/~imasu/Japanese/English/4.htm
Intergovernmental Panel on Climate Change (IPCC, 2007)
Discussion
 Discussion

NASA https://phys.org/news/2020-03-nasa-images-fall-china-pollution.html
Discussion
Drone video shows ominous red skies across
San Francisco skyline -2020

https://www.youtube.com/watch?v=x
BolnN8aiX8
1. MEASURES OF ATMOSPHERIC COMPOSITION

Homework: All problem sets of chapter 1

 The atmosphere seen from space

WHAT IS THE ATMOSPHERE?

• Gaesous envelope surrounding the Earth https://www.space.com/8596-earth-colorful-

atmospheric-layers-photographed-space.html

• Mixture of gases, also contains suspended solid and liquid particles

(aerosols)
Aerosol = dispersed condensed phase suspended in a gas
Aerosols are the “visible” components of the atmosphere

California fire plumes Pollution off U.S. east coast Dust off West Africa
 WHAT ABOUT CLOUDS?

Clouds are made up of water droplets or

ice crystals (1-100 mm), much larger than
typical aerosols (0.01-10 mm). They are
technically aerosols but have unique
properties and are in practice considered
separately.
 ATMOSPHERIC GASES ARE “VISIBLE” TOO…
IF YOU LOOK IN THE UV OR IR

Nitrogen dioxide (NO2 ) observed by satellite in the UV

 1.1 Mixing ratio or mole fraction CX [mol mol-1]
# moles of X remains constant when air density changes
CX 
mole of air e robust measure of atmospheric composition

SPECIES MIXING RATIO

(dry air) Air also contains variable H2O
[mol mol-1]
vapor (10-6-10-2 mol mol-1) and
aerosol particles
Nitrogen (N2) 0.78
Oxygen (O2) 0.21
Argon (Ar) 0.0093
Carbon dioxide (CO2) 380x10-6
Neon (Ne) 18x10-6
Trace Ozone (O3) (0.01-10)x10-6
gases Helium (He) 5.2x10-6
Methane (CH4) 1.7x10-6
Krypton (Kr) 1.1x10-6

Trace gas concentration units:

1 ppmv = 1 µmol mol-1 = 1x10-6 mol mol-1
1 ppbv = 1 nmol mol-1 = 1x10-9 mol mol-1
1 pptv = 1 pmol mol-1 = 1x10-12 mol mol-1
ATMOSPHERIC CO2 INCREASE OVER PAST 1000 YEARS
Intergovernmental Panel on Climate Change (IPCC), 2007

Concentration units: parts per million (ppm)

number of CO2 molecules per 106 molecules of air

CO2 CONCENTRATION IS MEASURED AS MIXING RATIO

ATMOSPHERIC CO2 TREND OVER PAST 25 YEARS
IPCC [2007]

mmol mol-1 is the proper SI unit; ppm, ppmv are customary units
Taiwan Ambient Air Quality Standards

http://taqm.epa.gov.tw/taqm/tw/b0206.asp
 TAIWAN EPA SURFACE OZONE AIR QUALITY STANDARD
“8-hour average of 0.06 ppmv”

http://taqm.epa.gov.tw/taqm/tw/ContourMap.aspx
EPA air quality standard for surface ozone is 0.12 ppm or 120 ppb, 1-hour average
 1.2 Number density nX [molecules cm-3]

Proper measure for

# molecules of X • reaction rates
nX 
unit volume of air • optical properties of atmosphere


Column concentration  X =  nX ( z )dz Proper measure for absorption or
0 scattering of radiation by atmosphere

nX and CX are related by the ideal gas law: na = air number density
Av = Avogadro’s number
Av P
n X  naC X  CX P = pressure
R = Gas constant
RT
T = temperature
Also define the mass concentration (g cm-3): MX= molecular mass of X

mass of X M n
X   X X
unit volume of air Av
 STRATOSPHERIC OZONE LAYER
http://ozoneaq.gsfc.nasa.gov/

Method: UV solar backscatter

l1 l2
Ozone layer

Scattering by
Earth surface
and atmosphere

Ozone
1 “Dobson Unit (DU)” = 0.01 mm ozone at STP absorption
= 2.69x1016 molecules cm-2 spectrum
THICKNESS OF OZONE LAYER IS MEASURED
AS A COLUMN CONCENTRATION
l1 l2
 THE PARTICULATE MATTER (PM2.5)

PM2.5 ≡ concentration of aerosol particles < 2.5 mm diameter)

Taiwan air quality standard:

PM2.5 = 15 mg m-3
(annual mean)

35 mg m-3
(24-hr mean)

http://taqm.epa.gov.tw/taqm/tw/ContourMap.aspx
SPECIFIC ISSUES FOR AEROSOL CONCENTRATIONS
• A given aerosol particle is characterized by its size, shape, phase, and
chemical composition – large number of variables!

• Measures of aerosol concentrations must be given in some integral

form, by summing over all particles present in a given air volume that
have a certain property

• The aerosol size distribution is a continuous function

URBAN
Typical U.S. aerosol
size distributions
by volume
RURAL
 1.3 Partial pressure Px [Pa]

Dalton’s law: PX  C X P Proper measure for phase change

(such as condensation of water vapor)

Evaporation of liquid water from a pan:

No lid: water molecules escape from pan to

atmosphere (evaporation)

Add a lid:
• escaping water molecules collide on lid and
return to surface; collision rate measures PH2O

• eventually, flux escaping = flux returning :

saturation (PH2O,SAT)

• cloud formation in atmoshere requires

PH2O > PH2O,SAT

•Tk e PH2O,SAT k
 CLAUSIUS-CLAPEYRON EQUATION: PH2O, SAT = f(T)
1 1 A = 6.11 hPa
PH 2O , SAT  A exp[ B (  )] B = - 5310 K
PH2O,SAT (hPa) T To To = 273 K

單組分系統在相平衡時氣壓隨溫度的變化率的關係 T (K)
 PHASE DIAGRAM FOR WATER

gas-liquid
metastable
equilibrium

Relative humidity (%) = 100(PH2O/PH2O,SAT)

Dew point: Temperature Td such that PH2O = PH2O,SAT(Td)

 RUNAWAY GREENHOUSE EFFECT ON VENUS
due to accumulation of water vapor from volcanic outgassing early in its history
…did not happen on Earth because farther from Sun; as water accumulated it
reached saturation and precipitated, forming the oceans

EARTH VENUS
 WHY CAN YOU SEE YOUR BREATH ON COLD MORNINGS?
Draw mixing lines (dashed) to describe dilution of your breath plume w/outside air

PH2O is plotted on linear

scale to draw the mixing
lines

LIQ
Your breath
37oC, ≈ 100%RH

ICE cloud!
no cloud

warm outside air

cold outside air GAS
 PHASE DIAGRAM FOR WATER

gas-liquid
metastable
equilibrium

Relative humidity (%) = 100(PH2O/PH2O,SAT)

Dew point: Temperature Td such that PH2O = PH2O,SAT(Td)

 AIR POLLUTION HAZE

Views of Acadia National Park

http://www.hazecam.net/

“clean” day “moderately polluted” day

Visibility is limited by high concentrations of aerosol particles that have swollen

to large sizes due to high (but <100%) relative humidity
 RAOULT’S LAW

Po
H 2 O , SAT PH 2O , SAT  xH 2O PHo 2O , SAT

solute
molecules
in green
water saturation vapor pressure water saturation vapor pressure
over pure liquid water surface over aqueous solution of water
mixing ratio xH2O

An atmosphere of relative humidity RH can contain at equilibrium

aqueous solution particles of water mixing ratio PH 2O , SAT RH
xH 2 O  
PHo 2O , SAT 100
Droplet Evaporation
 HOWEVER, AEROSOL PARTICLES MUST ALSO
SATISFY SOLUBILITY EQUILIBRIA

Consider an aqueous sea salt (NaCl) particle: it must satisfy

xNa  xCl   K s (solubility equilibrium) solubility product

溶度積常數
xNa   xCl  (electroneutrality)
xNa   xCl   xH 2O  1 (closure)

This requires:
1
RH  100(1  2 K s ) "deliquescence RH"
2

At lower RH, the particle is dry.

solubility of NaCl: 359g per liter of water

NaCl phase transition-ESEM Measurement

RH
increasing
UPTAKE OF WATER BY AEROSOLS: HAZE

NaCl/H2O

Deliquescence RH;
depends on particle
composition
UPTAKE OF WATER BY AEROSOLS: HAZE
Intergovernmental Panel on Climate Change (IPCC, 2007)
 Homework_1

All problem sets of chapter 1

+
 Phase Rule

n=c+2-p

n = number of independent variables

c = chemical components
p = different phases

The basis for the rule is that equilibrium between phases places a
constraint on the intensive variables. More rigorously, since the phases are
in thermodynamic equilibrium with each other, the chemical potentials of
the phases must be equal. The number of equality relationships
determines the number of degrees of freedom. For example, if the
chemical potentials of a liquid and of its vapour depend on temperature (T)
and pressure (P), the equality of chemical potentials will mean that each of
those variables will be dependent on the other. Mathematically, the
equation μliq(T, P) = μvap(T, P), where μ = chemical potential, defines
temperature as a function of pressure or vice versa.