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Chemical Principles and Processes: Atmospheric chemistry
Properties of Gases
• Layer of gases surrounding the Earth
retained by gravity
Dr Deborah Crittenden
[email protected]
Atmospheric composition Atmospheric layering
Pressure
Exosphere (690 –
10,000 km)
• Nitrogen (78%)
• Oxygen (21%)
• Argon (0.95%) Thermosphere
• Rest – 0.00000075 /Ionosphere
including CO2 (0.05%) 0.001 (85 – 690 km)
0.125
1 atm Mesosphere (50 – 85 km)
Stratosphere (15 – 50 km)
Earth
Troposphere (0 – 15 km)
Atmospheric layering Atmospheric layering
Temperature
Exosphere (690 – Exosphere (690 –
10,000 km) 10,000 km)
Thermosphere Thermosphere
-100 °C /Ionosphere Ozone /Ionosphere
0 °C (85 – 690 km) layer (85 – 690 km)
-60 °C
25 °C Mesosphere (50 – 85 km) Mesosphere (50 – 85 km)
Stratosphere (15 – 50 km) Stratosphere (15 – 50 km)
Earth Earth
Troposphere (0 – 15 km) Troposphere (0 – 15 km)
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Ozone layer The ozone cycle
• Region of the atmosphere rich in ozone light
O–O ➝ O + O
• Responsible for absorbing 97 – 99% of UV
radiation from the sun formation slow
O + O ➝ O3
2
UV-absorbing light
oxygen shuttle O3 + O2 ➝ O2 + O3 fast
reaction
termination O3 + O ➝ 2O2 rare
Ozone layer Ozone depletion
• Region of the atmosphere rich in ozone
• Responsible for absorbing 97 – 99% of UV
radiation from the sun
• Ozone formed by photolysis of O2 to make
atomic oxygen which then reacts with O2
• UV radiation absorbed by the oxygen shuttle 30
25
reaction, converted to heat Ozone hole area 20
(million square
• Ozone normally destroyed only when it
15
kilometres)
10
encounters atomic oxygen 5
0
1979 1984 1989 1994 2000 2005 2010
Ozone depletion Atmospheric chemistry
Ozone-depleting substances speed up
termination reaction by radical catalysis
mechanism (X = radical species)
Uncatalysed: O3 + O ➝ 2O2
Radical catalysis:
Methane Methyl Bromide
O3 + X ➝ XO + O2
Ozone-neutral Ozone-depleting
O3 + XO ➝
X + 2O2
2
O ➝3 O
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Halocarbons Photolysis of C-X bonds
• Carbon-halide bond is quite weak
C – X bond C – X bond Photolysis
length (Å) energy wavelength
(kJ/mol) (nm)
CH3F 1.385 461 259 (far-UV)
CH3Cl 1.784 356 336 (UV)
light
CH3Br 1.929 297 403 (violet)
CH3Br ➝ CH3 + Br CH3I 2.139 239 501 (blue-
green)
• Br acts as catalyst for O2 formation from O3
Solar spectrum Summary
• Ozone-depleting substances have
photolysable C-X (X = halide larger than
fluorine) bonds
The Greenhouse Effect The Greenhouse Effect
Exosphere (690 –
10,000 km)
• Earth’s surface is warmer than expected
Thermosphere
/Ionosphere
(85 – 690 km)
Mt
Everest Mesosphere (50 – 85 km) Tpredicted = 5 °C
Greenhouse Stratosphere (15 – 50 km)
Effect Weather Troposphere (0 – 15 km)
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The Greenhouse Effect The Greenhouse Effect
• Earth’s surface is warmer than expected • Earth’s surface is warmer than expected
Tpredicted = -18 °C Tactual = 14 °C
The Greenhouse Effect Greenhouse gases
• Which gases are greenhouse gases?
• Nitrogen (78%)
and converted into heat
• Oxygen (21%)
• Argon (0.95%)
• Rest –
including CO2 (0.05%)
Greenhouse gases Greenhouse gases
• Which gases are greenhouse gases? • Absorb infrared radiation from the sun
• How can molecules convert light into heat?
• Nitrogen (78%) ✗ • Remember:
• Oxygen (21%) ✗ – ↑ T means ↑ kinetic energy (particles move
faster, or rotate more, or vibrate more)
• Argon (0.95%) ✗
• Rest –
including CO2 (0.05%) ✓
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Absorption of light by molecules Absorption of light by molecules
• Light can be thought of as oscillating • If frequency of light = frequency of vibration,
electromagnetic radiation we get resonant energy transfer from light to
molecule
• Required frequencies of light in infrared range
(wavelength = 700 nm – 1 mm)
• (Most) vibrating molecules set up an • Side note: this also holds for rotations, but the
frequency is much lower (less energy required
oscillating electric field to cause rotations than vibrations)
• Required frequencies of light in microwave
δ- δ- range (1 mm < λ < 1 m) - this is of course how
your microwave works!
δ+
Summary Overall summary
• Molecules can absorb energy from light if their • Ozone-depleting substances have:
dipole moment changes as they vibrate • bonds that photolyse under UV radiation to
form halide radicals
δ+ • halide radicals go on to catalyse ozone
recombination reaction
• Greenhouse gas activity determined by:
δ- δ- • bond polarities and molecular vibrations
• require two atoms with different
• Any molecule with δ+ and δ- can and will absorb electronegativities to form polar bonds
infrared radiation and convert it to heat
Lecture block summary Lecture block summary
4: PROPERTIES OF GASES (4.ii) Kinetic molecular theory and the ideal gas equation
(5 lectures; Chemistry3 1st ed. Chaps. 1, 3 & 7, 2nd ed. Chaps. 1, 4 & (Chemistry3 1st ed. 7.4 & 7.5, 2nd ed. 8.4 & 8.5)
8)
At the end of this section you should be able to:
(4.i) Molecular interactions and the gas laws
(Chemistry3 1st ed. 1.7 & 1.8, 7.1 & 7.2, 2nd ed. 1.7 & 1.8, 8.1 & 8.2)
• estimate the average velocity of a collection of identical gas
At the end of this section you should be able to: molecules given temperature and mass information;
• provide a molecular level explanation for temperature and
• explain why a collection of atoms or molecules exists as a gas, pressure;
liquid or solid at room temperature and pressure, given • rationalize the ideal gas equation in terms of both empirical
information about their interactions; (covered in lecture 4) and theoretical arguments;
• state the gas laws of Boyle, Charles, and Avogadro; • use the ideal gas equation to calculate the pressure,
• know how the gas laws are combined in the ideal gas equation volume, temperature and amount of a gas.
• know when it is appropriate and how to apply Boyles’, Charles’
and Avogadro’s Law
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Lecture block summary Lecture block summary
(4.iii) Mixtures of gases (4.iv) Physical versus chemical properties of gases
(Chemistry3 1st ed. 7.3–7.5, 2nd ed. 8.3–8.5) (Chemistry3 1st ed. 1.8 & 3.2– 3.3, 2nd ed. 1.8 & 4.2–4.3)
At the end of this section you should be able to:
At the end of this section you should be able to:
• define Dalton's Law both mathematically and in words;
• use Dalton’s Law to calculate the partial pressure of a gas in a • explain the relative reactivities of different gases, based
mixture of gases;
• define Graham's law both mathematically and in words;
upon bond order arguments and stabilities of products;
• explain the role of Graham’s law in the separation of gases from • predict trends in boiling points based upon molecular
mixtures; properties and intermolecular interactions;
• differentiate between physical and chemical separation • explain why O2 and CO have different chemical and
techniques biological properties despite having very similar physical
• list and explain the principles behind different carbon capture
and storage technologies. properties.
Lecture block summary Tutorial questions
(4.v) Atmospheric chemistry and physics
(Chemistry3 1st ed. 1.1 & boxes 27.2 & 27.6, 2nd ed. 1.1 & boxes Will be going through answers to problem
27.2 & 27.6)
sheets for lectures 4,5 on Thursday/Friday.
At the end of this section you should be able to: Try questions in advance, come prepared to
• describe the greenhouse effect in terms of the physical ask about those you have struggled with.
properties of CO2 and H2O and other greenhouse gases;
• distinguish between greenhouse gases and non-greenhouse E-mail me with anything you’d like me to recap
gases from the lectures.
• state the role and chemistry of ozone in the stratosphere:
its production, photochemistry and removal;
• distinguish between ozone-depleting substances and non-
ozone depleting substances
Quiz time!
