Lecture #4

Measures of atmospheric composition

Course: ASL385: Fundamentals of Air Pollution Science

Sajeev Philip
Centre for Atmospheric Sciences (CAS), IIT Delhi
philipsajeev@iitd.ac.in
https://web.iitd.ac.in/~philipsajeev

January 11, 2024

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 Lecture #4: Outline
Measures of atmospheric composition
Course: ASL385: Fundamentals of Air Pollution Science

1. Recap: Air pollutants - Measures of composition

2. Mixing ratio vs number density

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 Atmospheric concentration for [X]

➢ Measures of atmospheric concentration

1. Mixing ratio

2. Number density

Column density

Mass concentration

3. Partial pressure
 Question #1
The mixing ratio CX of a gas X is defined as the number of moles of X per mole of air.
Atmospheric chemists frequently use customary units of parts per million (ppm),
parts per billion (ppb), and parts per trillion (ppt). Sometimes volume gets added to
the notation (ppmv, ppbv, and pptv) to clarify that these are molar (or equivalently
volume) mixing ratios. So, the mixing ratio CX is the “volume mixing ratio”.

✓ Define “mass mixing ratio (WX)” of a gas X.

# 𝒎𝒐𝒍𝒆𝒔 𝒐𝒇 𝑿
✓ Relate Cx and Wx. 𝑪𝑿 =
𝒎𝒐𝒍𝒆 𝒐𝒇 𝒂𝒊𝒓

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 Question #1

✓ Definition: The mass mixing ratio (WX) is the mass of a gas X

per mass of air.

𝑴𝑿 Mx [g/mol] is the molecular weight of X

✓ Relate Cx and Wx. 𝑾𝑿 = 𝑪 𝑿
𝑴𝒂 Ma [g/mol] is the molecular weight of air

# 𝒎𝒐𝒍𝒆𝒔 𝒐𝒇 𝑿
𝑪𝑿 =
𝒎𝒐𝒍𝒆 𝒐𝒇 𝒂𝒊𝒓
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 Question #2

✓ Find the mass mixing ratio of ozone if its volume mixing

ratio in an urban air parcel is 0.10 ppmv.
Given: the molecular weight of dry air is 28.966 g per mol.

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 Measures of atmospheric composition
Mixing ratio or Gas Mixing ratio (Cx) in
dry air (mol mol-1)
Nitrogen (N2) 0.78
Mole fraction
The 4th
Oxygen (O2) 0.21
Unit: mol/mol abundant
v/v Argon (Ar) 0.0093 gas is H2O
ppm (mixing
ppmv Carbon dioxide (CO2) 410 × 10-6 ratio is
highly
Neon (Ne) 18 × 10-6
# 𝒎𝒐𝒍𝒆𝒔 𝒐𝒇 𝑿 variable)
𝑪𝑿 = Ozone (O3) (0.01 - 10) × 10-6
𝒎𝒐𝒍𝒆 𝒐𝒇 𝒂𝒊𝒓 Trace
Helium (He) 5.2 × 10-6 gases

N2, O2, and Ar have uniform mixing Methane (CH4) 1.8 × 10-6
ratios in the atmosphere because
their lifetimes are sufficiently long Krypton (Kr) 1.1 × 10-6
to allow them to mix thoroughly
 Dry air versus moist air mixing ratio
➢ The fourth most abundant gas is water vapor, but its mixing ratio is highly
variable

➢ Water vapor mixing ratio is highly variable because of the source from
evaporation and the sink from precipitation

➢ The mixing ratio of water vapor can be as high as 3×10-2 mol mol-1 in surface
air over the tropical oceans and as low as 3×10-6 mol mol-1 in the stratosphere

➢ The variability of the water vapor mixing ratio is the reason why standard
tables of atmospheric composition are given for dry air

➢ If given for moist air (that is, including water vapor), then the mixing ratios of
all gases would fluctuate simply due to changes in water vapor
Credit: Jacob, 1999
 Question #3

✓ If CO2 has a uniform dry air mixing ratio of 410 ppb,

what is its moist air mixing ratio over the tropical
ocean with CH2O = 0.03 mol mol-1?

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 Question #4

✓ Consider an air parcel at sea level with a water mixing ratio of 0.03 mol
mol-1. Assume a CO2 wet mixing ratio of 410 ppm in that sea-level air
parcel. As the air parcel rises through the air, its water vapor may be
removed by cloud formation and precipitation. Assuming 100%
removal of water vapor and no dissolution of CO2 in the condensed
water, what is the mixing ratio of CO2 in the dried-out air parcel?

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 Question #5

✓ Identify a relative measure of atmospheric composition.

A. NO2 column density

B. PM2.5 mass concentration
C. N2 mixing ratio
D. O3 number density

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 Mixing ratio

# 𝒎𝒐𝒍𝒆𝒔 𝒐𝒇 𝑿
𝑪𝑿 =
𝒎𝒐𝒍𝒆 𝒐𝒇 𝒂𝒊𝒓

➢ The mixing ratio of a gas X is a relative measure of concentration

➢ It defines the abundance of X relative to other gases within an

atmospheric volume

➢ Mixing ratio says nothing about the actual number of molecules of X

present in that volume
 Number density
➢ Mixing ratio says nothing about the actual
number of molecules of X present in that volume # 𝒎𝒐𝒍𝒆𝒔 𝒐𝒇 𝑿
𝑪𝑿 =
➢ An absolute measure of concentration is the 𝒎𝒐𝒍𝒆 𝒐𝒇 𝒂𝒊𝒓
number density 𝒏𝑿 , defined as the number of
molecules of X per unit volume of air

# 𝒎𝒐𝒍𝒆𝒄𝒖𝒍𝒆𝒔 𝒐𝒇 𝑿
𝒏𝑿 =
𝒖𝒏𝒊𝒕 𝒗𝒐𝒍𝒖𝒎𝒆

Number density
Unit: molecules/cm3
Number of molecules of X per cm3 of air
 Number density versus mixing ratio

# 𝒎𝒐𝒍𝒆𝒄𝒖𝒍𝒆𝒔 𝒐𝒇 𝑿 # 𝒎𝒐𝒍𝒆𝒔 𝒐𝒇 𝑿
𝒏𝑿 = 𝑪𝑿 =
𝒖𝒏𝒊𝒕 𝒗𝒐𝒍𝒖𝒎𝒆 𝒎𝒐𝒍𝒆 𝒐𝒇 𝒂𝒊𝒓
Number density Mixing ratio
Unit: molecules/cm3 Unit: mol/mol
Number of molecules of X per cm3 of air v/v
ppm

➢ The number density and the mixing ratio of a gas are related by the
number density of air na (molecules of air per cm3 of air)

𝒏𝑿 = 𝑪𝑿 𝒏𝒂
 Number density of air
➢ The number density of air na is defined as the number of molecules of “air”
per unit volume of air

➢ The number density of air is related to the atmospheric pressure p by the

ideal gas law

➢ Consider a volume V of the atmosphere at pressure p and temperature T

containing N moles of air

➢ The common expression for the ideal gas law is

pV=NRT

Ideal gas constant : R = 8.31 J mol-1 K-1

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 Number density of air
➢ Consider a volume V of the atmosphere at pressure p and temperature T
containing N moles of air

➢ The common expression for the ideal gas law is

pV=NRT Ideal gas constant : R = 8.31 J mol-1 K-1

➢ The number density of air is related to N and V by

✓ The number density of air na is

𝑵 𝑨𝒗 defined as the number of
𝒏𝒂 = molecules of “air” per unit
𝑽 volume of air

➢ Avogadro’s number: Av = 6.023 x 1023 molecules mol-1

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 Number density of air
➢ Consider a volume V of the atmosphere at pressure p and temperature T
containing N moles of air

➢ The common expression for the ideal gas law is

pV=NRT Ideal gas constant : R = 8.31 J mol-1 K-1

➢ The number density of air is related to N and V by

𝑵 𝑨𝒗 𝒑 𝑨𝒗
𝒏𝒂 = =
𝑽 𝑹𝑻
➢ Avogadro’s number: Av = 6.023 x 1023 molecules mol-1
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 Question #6

✓ Calculate the number densities of air and CO2 at sea level

for P = 1013 hPa, T = 0oC

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 Question #7

✓ Oxygen has a fixed mixing ratio in the atmosphere. How

would you expect its number density measured in
surface air to vary between day and night?

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 Question #8

✓ Derive an equation relating the mixing ratio CX and

the number density nX of a gas X in the atmosphere
at pressure p and temperature T.

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 Question #9

✓ The mass mixing ratio of ozone in an urban air parcel is

0.17 ppmm. Assume p = 1013 hPa and T = 288 K. Find
the number concentration of ozone.

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 Question #10

✓ If CO2 has a moist air mixing ratio of 398 ppm over

the tropical ocean, with CH2O of 0.03 mol mol-1.
Calculate the dry air mixing ratio of CO2.

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