The Earth’s Atmosphere

–Basic Chemistry and

Physics
Dr Willard Pinnock

C 26Q Course 2010

Lectures 1 and 2

Introduction

Why study the atmosphere?

Sustains and protects life on Planet

Provides O2 we breathe.

Provides O2 to support combustion for generation of
energy.

Shields us from harmful (uv-) radiation from Sun.

Mediates between incoming and outgoing radiation to
maintain temperature of biosphere at life-sustaining level.

Protects us from space debris (as in comets) and other
materials coming from space.

Composition fairly constant over years man has
inhabited the Planet.

But that is changing, particularly in some minor
constituents and this is affecting the atmosphere’s
ability to sustain and protect life.

1
Chemical Composition of
Atmosphere

Chemical Composition (Main Constituents at Ground Level)

Component Gas Concentration by Volume

N2 0.7808 or 78.08%

O2 0.2095 or 20.95%

Ar 0.0093 or 0.93%

H2O 0.5 – 4% (variable)

CO2 365 ppm

Ne 18 ppm

He 5 ppm

CH4 1.7 ppm

Kr 1 ppm

H2 0.5 ppm

Particles/dust usually in µg m-3 (variable)

Constancy of Chemical
Composition

This constancy is deceptive because atmosphere is
really in a “steady state” - the result of massive
influx and loss of material – the rates being equal.

Consider O2

3x1014 kg consumed per annum by living things.

Constancy suggests this loss is made up by influx of O2
from some source. (What is the source?)

6CO2 + 6H2O C6H12O6 + 6O2 (photosynthesis)

Note reservoir of O2 in atmosphere is ≈ 1018 kg. The rates

of input and loss are massive but small compared to the
reservoir, so amount of O2 in atmosphere is not affected
by short term variation in use.

2
Change in Chemical
Composition

In some cases the changes caused by man’s activities are affecting
the ability of the atmosphere to perform its life-protecting functions.

Consider the balance between incoming energy from the Sun and
outgoing energy from the Earth, for example.

About 1025J are incident upon the Earth over a calendar year.

All this energy must be radiated back to space to keep the Earth’s mean
temperature at a level that is amenable to life. That temperature is
actually 288 K or 15°C.

The atmosphere performs that balancing act – in a way that is very
sensitive to atmospheric composition.

CO2 content of the atmosphere is important in this – and its mass in the
atmosphere has been fairly constant over the time of man’s existence on
Earth. (2.7 x 1015 kg )

Over the past 150 years this has been increasing at a rate of about 1013
kg per year - because of anthropogenic activity.

This relatively small change affects the rate of re-radiation of energy
back to space and appears to be causing warming of the atmosphere.

Global or Trans-boundary
Issues in Atmospheric Science

Warming is predicted to have adverse effect on climate and to
affect Earth’s ability to sustain life – so is a global concern.

We will look at the Science behind this expectation of “Global
Warming” in this course.

Other issues:

Loss of stratospheric ozone at certain locations and times –
Ozone Depletion.

Trans-boundary transport of acidic gases has led to acidification
of lakes and streams far from the site where gases are generated
– Acid Rain.

Effects of atmospheric pollution – resulting in “Smog” that leads
to health and damage to property.

When you have done this course it is expected that you will be
able to discuss these issues from a scientific point of view.

See Detailed Course Outline.

3
Structure of Atmosphere and
Basis for Understanding Structure

In the next couple of lectures we will look at the physical
structure of the atmosphere and its main characteristics both in
the vertical and horizontal.

The physical structure and motion of the atmosphere is, to a

large extent, determined by:

its interaction with radiation from the Sun

the effect of gravity

the effect of rotation of the Earth

the distribution of land and water on the Earth’s surface.

We will examine this first to set some kind of basis that will help
us to understand how small changes in the Chemistry can have
such profound effects as mentioned earlier.

Vertical Structure of the

Atmosphere

The atmosphere has a very characteristic
temperature structure in the vertical, that is
maintained mainly by the characteristics of
absorption of energy from the Sun’s radiation at
various heights.

Chemical composition also varies somewhat with
height mainly because of the nature of the solar
radiation to which the atmosphere is exposed, at
various heights.

There is a very characteristic variation of pressure
with height as well.

The factors which determine these features of the
structure are very well understood.

4
Temperature Profile for Daytime
Atmosphere up to 100 km.(1)
Typical Temperature Profile of Atmosphere
•Starting from bottom one
can see the highest

120
temperature in the region of
interest is at the surface. T Thermosphere N2,O2, O+,
O2+, NO+,e-
on average is 288 K.

100
• Temperature decreases

Height above Ground/ km

80
with height up to about 12 to
N2,O2, O2+,
17 km, at which height the N2+
trend reverses and Mesosphere

60
temperature begins to
increase with height.
40

N2, O2,
Stratosphere
O3
• This height where the
temperature trend reverses
is called the tropopause,
20

and the layer below this is N2, O2, H2O,

Troposphere Ar, CO2
called the troposphere.
0

170 190 210 230 250 270 290 310

Temperature /K

Temperature Profile for Daytime

Atmosphere up to 100 km.(2)
•Above the tropopause is a
region in which temperature Typical Temperature Profile of Atmosphere
increases with height – it is
120

called the stratosphere.

Thermosphere
•The stratosphere is N2,O2, O+,
O2+, NO+,e-
characterized by temperature
100

increase with height. It stops

at a height of about 55 km –
the stratopause.
Height above Ground/ km
80

•Above about 55 km the N2,O2, O2+,

N2+
temperature falls with height
Mesosphere
again, reaching its lowest
60

value of about 180 K at 90

km. The layer between 55 and
90 km is known as the
40

N2, O2,
mesosphere. Stratosphere
O3

•Above 90 km, the

20

mesopause, the temperature

increases with height with no Troposphere
N2, O2, H2O,
Ar, CO2
further reversals in the region
of interest.
0

170 190 210 230 250 270 290 310

Temperature /K

5
Chemical Composition of Daytime
Atmosphere up to 100 km.
• The composition of the
troposphere is essentially the Typical Temperature Profile of Atmosphere
composition described in the

120
table given earlier, mainly N2,
O2, CO2, and water vapour. Thermosphere N2,O2, O+,
O2+, NO+,e-
•There is not much water

100
vapour or CO2 in the
stratosphere, but the bulk of
the atmosphere’s O3 is

Height above Ground/ km

80
contained in the stratosphere. N2,O2, O2+,
O3 exists in a layer which has N2+

its peak between about 25 and Mesosphere

60
30 km.
• The Ozone concentration in
this layer is usually expressed 40
N2, O2,
Stratosphere
as a partial pressure. A typical O3

value is 150 nanobars or 15

mPa. In concentration units –
20

5 x 1012 molecules cm-3. N2, O2, H2O,

Troposphere Ar, CO2
•Above 55 km some ions
0

exist, while above 90 many 170 190 210 230 250 270 290 310
ions and even free electrons Temperature /K
appear to exist.

Pressure at Various Heights in

Atmosphere (Mean)
1 bar = 100,000 Pa 1 mb = 100 Pa 1 atm = 101,325 Pa
35

30

25
Altitude/ km

20

15

50% of
10 mass below
this level.
5

0
0 200 400 600 800 1000 1200

Pressure/ mbar

6
 Derivation of the Hydrostatic
Equation
•Consider a cylindrical shaped volume element
of air of height dz, area A, mass dm, and a
pressure difference of dP between top and
bottom. P2

•Force on element is F = g dm where g is the dP, dz

acceleration due to gravity. P1
Height
•P = F/A so dP= g dm/A above
ground
•Density ρ = mass/V = dm/(A dz) so Area,
•dm = ρA dz and dP = - gρAdz/A or - gρdz A

•So dP = - gρdz
•Note the negative sign, suggesting that
pressure decreases with height.
•This dP = - gρ dz is known as the hydrostatic
equation

Integrating The Hydrostatic

Equation

dP = - gρ dz

Lets express ρ in terms of P so we can separate and collect the variables and
integrate the equation.

PV = nRT or

P =(m/MV)RT = ρRT/M

So ρ = PM/RT

Substituting for ρ in the hydrostatic equation we have:

dP= -P(Mg/RT) dz

∫dP/P= -∫(Mg/RT) dz

[ln P] = - Mg/RTz or ln[Pz] – ln[P0] = -Mg/RTz

This becomes

Pz = P0 exp[-z/H] where H = RT/ Mg known as the scale height.

This really sums up the effect of gravity on the Earth’s atmosphere. It causes the
pressure to decrease exponentially with height. Pressure decreases by 1/e of its
value over a distance equal to the scale height.

7
Variation of Atmospheric Pressure
with Height
1 bar = 100,000 Pa 1 mb = 100 Pa 1 atm = 101,325 Pa
35

30

Pz = P0 exp[-z/H] where H = RT/ Mg

is known as the scale height
25
Altitude/ km

20

15

50% of
10 mass below
this level.
5

0
0 200 400 600 800 1000 1200

Pressure/ mbar

Temperature Profile for Daytime

Troposphere (1)
•Temperature profile can be
understood in terms of interaction Temperature Profile of Lower Atmosphere
of solar radiation with lower
atmosphere.
30
•On an average day about 51% of
radiant energy passes through the 25
atmosphere and heats the surface.
•Both Earth and water (Oceans, 20
Rivers and Lakes) increase in
H e i g h t/ k m

temperature due to this heating. 15

•Air in contact with the surface is

heated, expands, and rises, as it is 10
less dense than its surroundings.
5
•The expansion however is
adiabatic, so the air cools as it
0
rises.
150 170 190 210 230 250 270 290 310
•This process eventually stops at a Temperature/K
height where temperature of the
rising air is the same as that of the
surroundings.

8
Temperature Profile for Daytime
Troposphere 2

Most of radiation from Sun heats lower troposphere by being
absorbed at the surface first and then heating the air in contact
with the surface.

Typical temperature profile has temperature decreasing with
height from 288 to about 225 K over height of ≈10 km in the
tropics.

So typical “lapse rate” = 63/10 = 6.3 K km-1

Useful to examine the temperature profile that would have

resulted from adiabatic expansion, assuming the atmosphere is
a perfect gas.

An adiabatic process is one in which no heat enters or leaves the
system. (q = 0). In that case the transfer of heat between the
parcel of air and the surrounding cooler air is small – and that’s a
reasonable assumption.

Temperature Profile for Daytime

Troposphere 3

We can in fact make an estimate of the lapse rate by considering the
case of an ideal gas expanding adiabatically with the pressure
decreasing at a rate given by the integrated hydrostatic equation.

We will do that in the next lecture, but we can consider the implications
of the result. It gives us a lapse rate:

dT/dz = -M g/Cp

Given that

M = 28.966 x 10-3 kg mol-1

Cp = 29.05 J K-1 mol-1 and g = 9.8065 m s-2

Lapse rate = 9.78 K km-1 which is quite a bit more than the typical
observed value in the tropics.

The difference is due in part to direct solar heating of upper troposphere

through absorption of radiation by CO2, H2O, O3 and particulates.

But part is also due to the fact that air is not always dry, and there is
release of latent heat when water in moist air condenses

9
Temperature Profile for Daytime
Troposphere 4

The main reasons for the difference between estimated and actual lapse rate
are:

Some heating occurs in higher part of atmosphere as a result of absorption of incoming
and outgoing radiation (H2O and CO2)

Condensation of moisture (water) in rising air releases heat in upper troposphere.

These both serve to make the actual lapse rate smaller than that estimated from
using adiabatic expansion, ideal gas assumptions.

As moist air rises its degree of saturation increases (as temperature decreases).

It eventually reaches a temperature where it is 100% saturated with water vapour.
Condensation occurs at and above this level.

Notice though that the troposphere is generally unstable because the warmer
(less dense) air is at the bottom, so air is continually rising – while this
temperature profile is maintained.

Particularly stable and unstable conditions in the troposphere are associated
with the actual lapse rate being greater than or less than the adiabatic lapse
rate. (Note lapse rate is really 1/[Slope of Plot])

10