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Chemistryof the
Environment
© 2009, Prentice-Hall, Inc.
Chapter 18Chemistry of the
Environment
Chemistry, The Central Science, 11th editionTheodore L. Brown; H. Eugene LeMay, Jr.;
and Bruce E. Bursten
John D. BookstaverSt. Charles Community College
Cottleville, MO
Chemistryof the
Environment
© 2009, Prentice-Hall, Inc.
Atmosphere
• Temperature varies greatly with altitude.
• However, there is not a linear relationship between altitude and temperature.
Chemistryof the
Environment
© 2009, Prentice-Hall, Inc.
Atmosphere
Although the relationship between altitude and pressure is not linear, pressure does decrease with an increase in altitude.
Chemistryof the
Environment
© 2009, Prentice-Hall, Inc.
Radiation
The atmosphere is the first line of defense against radiation from the Sun.
Chemistryof the
Environment
© 2009, Prentice-Hall, Inc.
Composition of the Atmosphere
• Because of the great variation in atmospheric conditions, the composition of gases in the atmosphere is not uniform.
• Lighter gases tend to rise to the top.
Chemistryof the
Environment
© 2009, Prentice-Hall, Inc.
Composition of the Atmosphere
• Near the Earth’s surface, about 99% of the atmosphere is composed of nitrogen and oxygen.
• Oxygen has a much lower bond enthalpy than nitrogen, and is therefore more reactive.
Chemistryof the
Environment
© 2009, Prentice-Hall, Inc.
Outer Atmosphere
• The Sun emits a wide range of wavelengths of radiation.
• Remember that light in the ultraviolet region has enough energy to break chemical bonds.
Chemistryof the
Environment
© 2009, Prentice-Hall, Inc.
Photodissociation
• When these bonds break, they do so homolytically.
• Oxygen in the upper atmosphere absorbs much of this radiation before it reaches the lower atmosphere:
O2 + h 2 O
Chemistryof the
Environment
© 2009, Prentice-Hall, Inc.
Photoionization
• Shorter wavelength radiation causes electrons to be knocked out of molecules in the upper atmosphere; very little of this radiation reaches the Earth’s surface.
• The presence of these ions makes long-range radio communication possible.
Chemistryof the
Environment
© 2009, Prentice-Hall, Inc.
Ozone• Ozone absorbs much of the radiation
between 240 and 310 nm.• It forms from reaction of molecular oxygen
with the oxygen atoms produced in the upper atmosphere by photodissociation.
O + O2 O3
Chemistryof the
Environment
© 2009, Prentice-Hall, Inc.
Ozone Depletion
In 1974 Rowland and Molina discovered that chlorine from chlorofluorocarbons (CFCs) may be depleting the supply of ozone in the upper atmosphere by reacting with it.
Chemistryof the
Environment
© 2009, Prentice-Hall, Inc.
Chlorofluorocarbons
• CFCs were used for years as aerosol propellants and refrigerants.
• They are not water soluble (so they do not get washed out of the atmosphere by rain) and are quite unreactive (so they are not degraded naturally).
Chemistryof the
Environment
© 2009, Prentice-Hall, Inc.
Chlorofluorocarbons
• The C—Cl bond is easily broken, though, when the molecule absorbs radiation with a wavelength between 190 and 225 nm.
• The chlorine atoms formed react with ozone:
Cl + O3 ClO + O2
Chemistryof the
Environment
© 2009, Prentice-Hall, Inc.
Chlorofluorocarbons
In spite of the fact that the use of CFCs in now banned in over 100 countries, ozone depletion will continue for some time because of the tremendously unreactive nature of CFCs.
Chemistryof the
Environment
© 2009, Prentice-Hall, Inc.
TroposphereAlthough the troposphere is made up almost entirely of nitrogen and oxygen, other gases present in relatively small amounts still have a profound effect on the troposphere.
Chemistryof the
Environment
© 2009, Prentice-Hall, Inc.
Sulfur
• Sulfur dioxide is a by-product of the burning of coal or oil.
• It reacts with moisture in the air to form sulfuric acid.
• It is primarily responsible for acid rain.
Chemistryof the
Environment
© 2009, Prentice-Hall, Inc.
Sulfur
• High acidity in rainfall causes corrosion in building materials.
• Marble and limestone (calcium carbonate) react with the acid; structures made from them erode.
Chemistryof the
Environment
© 2009, Prentice-Hall, Inc.
Sulfur
• SO2 can be removed by injecting powdered limestone which is converted to calcium oxide.
• The CaO reacts with SO2 to form a precipitate of calcium sulfite.
Chemistryof the
Environment
© 2009, Prentice-Hall, Inc.
Carbon Monoxide• Carbon monoxide
binds preferentially to the iron in red blood cells.
• Exposure to significant amount of CO can lower O2 levels to the point that loss of consciousness and death can result.
Chemistryof the
Environment
© 2009, Prentice-Hall, Inc.
Carbon Monoxide
• Products that can produce carbon monoxide must contain warning labels.
• Carbon monoxide is colorless and odorless, so detectors are a good idea.
Chemistryof the
Environment
© 2009, Prentice-Hall, Inc.
Nitrogen Oxides• What we recognize as
smog, that brownish gas that hangs above large cities like Los Angeles, is primarily nitrogen dioxide, NO2.
• It forms from the oxidation of nitric oxide, NO, a component of car exhaust.
Chemistryof the
Environment
© 2009, Prentice-Hall, Inc.
Photochemical Smog• These nitrogen oxides
are just some components of photochemical smog.
• Ozone, carbon monoxide, and hydrocarbons also contribute to air pollution that causes severe respiratory problems in many people.
Chemistryof the
Environment
© 2009, Prentice-Hall, Inc.
Photochemical Smog
As a result, government emission standards for automobile exhaust have become continually more stringent.
Chemistryof the
Environment
© 2009, Prentice-Hall, Inc.
Water Vapor and Carbon Dioxide• Gases in the atmosphere form an
insulating blanket that causes the Earth’s thermal consistency.
• Two of the most important such gases are carbon dioxide and water vapor.
Chemistryof the
Environment
© 2009, Prentice-Hall, Inc.
Water Vapor and Carbon Dioxide• This blanketing effect is
known as the “greenhouse effect.”
• Water vapor, with its high specific heat, is a major factor in this moderating effect.
• But increasing levels of CO2 in the atmosphere may be causing an unnatural increase in atmospheric temperatures.
Chemistryof the
Environment
© 2009, Prentice-Hall, Inc.
Oceans
• The vast ocean contains many important compounds and minerals.
• However, the ocean is only a commercial source of sodium chloride, bromine, and magnesium.
Chemistryof the
Environment
© 2009, Prentice-Hall, Inc.
Desalination
• “Water, water everywhere, and not a drop to drink.” Seawater has too high a concentration of NaCl for human consumption.
• It can be desalinated through reverse osmosis.
Chemistryof the
Environment
© 2009, Prentice-Hall, Inc.
Reverse Osmosis• Water naturally flows through a
semipermeable membrane from regions of higher water concentration to regions of lower water concentration.
• If pressure is applied, the water can be forced through a membrane in the opposite direction, concentrating the pure water.
Chemistryof the
Environment
© 2009, Prentice-Hall, Inc.
Water Purification
• Clean, safe fresh water supplies are of the utmost importance to society.
• There are many steps involved in purifying water for a municipal water supply.
Chemistryof the
Environment
© 2009, Prentice-Hall, Inc.
Water Purification
• Water goes through several filtration steps.
• CaO and Al2(SO4)3 are added to aid in the removal of very small particles.
Chemistryof the
Environment
© 2009, Prentice-Hall, Inc.
Water Purification• The water is aerated to
increase the amount of dissolved oxygen and promote oxidation of organic impurities.
• Ozone or chlorine is used to disinfect the water before it is sent out to consumers.
Chemistryof the
Environment
© 2009, Prentice-Hall, Inc.
Green Chemistry
• We have become increasingly aware over the past 30 to 40 years that modern processes are not always compatible with maintaining a sustainable environment.
• Promoting chemical processes that are environmentally friendly is part of the good stewardship chemists should exhibit.
Chemistryof the
Environment
© 2009, Prentice-Hall, Inc.
Green Chemistry Principles
1. Rather than worry about waste disposal, it is better to avoid creating waste in the first place.
2. In addition to generating as little waste as possible, try to make waste that is nontoxic.
3. Be energy conscious in designing syntheses.
Chemistryof the
Environment
© 2009, Prentice-Hall, Inc.
Green Chemistry Principles
4. Catalysts that allow the use of safe chemicals should be employed when possible.
5. Try to use renewable feedstocks as raw materials.
6. Try to reduce the amount of solvent used, and try to use environmentally friendly solvents.
Chemistryof the
Environment
© 2009, Prentice-Hall, Inc.
Solvents
Solvents such as supercritical CO2 are great “green” alternatives.