Environmental Chemistry

E Environmental chemistry
E1 Primary air pollution

Primary pollutants are substances released directly into the atmosphere by either natural processes or from synthetic sources. Secondary pollutants are formed from primary pollutants when they react in the atmosphere.
Learning objectives
Describe the sources of carbon monoxide, nitrogen oxides, sulfur oxides, particulates and hydrocarbons in the atmosphere
Carbon monoxide
Carbon monoxide (CO) is a toxic gas that can be produced by human activities and natural processes. CO is formed by the incomplete combustion (when the oxygen supply is insu cient) of organic material especially in forest res and the incomplete combustion of fossil fuels such as coal (mostly carbon). 2C(s) + O2(g) 2CO(g) Incomplete combustion can also occur in internal combustion (car) engines, such as the incomplete combustion of octane in petrol (gasoline): 2C8H18(l) + 17O2(g) 16CO(g) + 18H2O(g) This is the largest anthropogenic source of CO and so CO levels are usually higher in urban areas, where there are more cars. Carbon monoxide can be removed using catalytic converters tted to the exhaust system. The CO is removed by the following reactions: 2CO + O2 2CO2 2CO + 2NO 2CO2 + N2 Ninety per cent of CO comes from natural sources, in particular the atmospheric oxidation of methane produced from anaerobic (without oxygen) decomposition of organic matter. The exact reactions involved are complex but the overall reaction is: 2CH4(g) + 3O2(g) 2CO(g) + 4H2O(l)
Examiners tip Throughout this topic, it is important to be able to write chemical equations whenever possible.
Examiners tip Combustion of petrol in the internal combustion engine is an anthropogenic source of CO anthropogenic means that it has been produced by human activities.
Some cars have lean burn engines where lower CO emissions are obtained by using a higher oxygen to fuel ratio.
Nitrogen oxides
The main anthropogenic sources of nitrogen oxides are the internal combustion engine, coal, gas, and oil-fuelled power stations and heavyindustry power generation. The combustion temperature of the fuel is very high and oxidation of atmospheric nitrogen occurs forming NO (nitrogen monoxide, nitric oxide or nitrogen(II) oxide). N2(g) + O2(g) 2NO(g) Natural sources of nitrogen oxides include soil bacterial activity and lightning. Lightning causes the high-temperature oxidation of atmospheric nitrogen: N2(g) + O2(g) 2NO(g)
CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011 E ENVIRONMENTAL CHEMISTRY 1
There are several di erent nitrogen oxides (e.g. NO, NO2, N2O). The symbol NOx is usually used to represent NO and NO2 together.
There are problems with the operation of lean-burn engines in cars because the catalytic converter is not as e cient at reducing NO under lean-burn conditions. Additional systems, such as NOx traps, therefore have to be used to reduce the NOx emissions from the exhaust.
Nitrogen oxides can be removed from engine exhaust gases using catalytic converters (forming nitrogen gas): 2CO + 2NO 2CO2 + N2 Heavy-duty natural gas engines can be designed to produce lower NOx emissions by increasing the oxygen to fuel ratio (lean burn).
Nitrous oxide (nitrogen(I) oxide, dinitrogen oxide, nitrous oxide)

Denitrifying bacteria in the soil can convert nitrate (NO) into N2O 3 this is a natural source. Anthropogenic sources of N2O include the use of arti cial fertilisers in agriculture (increasing the level of nitrates in the soil) and the manufacture of nitric acid.
Sulfur oxides
The two main sulfur oxides are sulfur dioxide (sulfur(IV) oxide, SO2) and sulfur trioxide (sulfur(VI) oxide, SO3). Anthropogenic sources of SO2 include: burning sulfur-containing fossil fuels, especially coal and oil S + O2 SO2
Burning petrol (gasoline) and natural gas do not contribute SO2 because the sulfur is removed during re ning.
smelting of metal ores Many metal ores contain metal sul des and these are usually roasted in air during the reduction process prior to reducing the ore to release the metal. The following reactions occur in the extraction of copper: 2Cu2S + 3O2 2Cu2O + 2SO2 2Cu2O + Cu2S 6Cu + SO2
the manufacture of sulfuric acid. Natural sources of SO2 include volcanic activity and decay of organic matter. Hydrogen sul de (H2S) produced by volcanic activity or organic decay is oxidised in the air to form SO2. 2H2S + 3O2 2SO2 + 2H2O SO2 is oxidised in the air to SO3 and H2SO4 (sulfuric(VI) acid). The exact reactions involved are complex (see Higher Level section on page 7) but the overall equations are: 2SO2(g) + O2(g) 2SO3(g) SO3(g) + H2O(l) H2SO4(aq) SO2 is a major pollutant and, as most of the sulfur dioxide released into the atmosphere comes from anthropogenic sources, it is important to develop methods to reduce emissions. The sulfur can be removed from fuels before, during or after combustion. Here we will concentrate on the latter two methods. The methods rely on the fact that sulfur dioxide is an acidic gas and will react with alkalis/bases. In uidised bed combustion, coal is mixed with limestone (CaCO3) and air is blown through the mixture as it combusts. The limestone
2 E ENVIRONMENTAL CHEMISTRY CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011
decomposes at the high temperatures involved and the CaO produced (a basic oxide) reacts with the SO2. CaCO3(s) CaO(s) + CO2(g) 2CaO(s) + 2SO2(g) + O2(g) 2CaSO4(s) Alkaline scrubbing can also be used to remove the sulfur dioxide from the ue gases that are produced when the fuel is burnt. The alkali is usually sprayed into the ue gases.Various alkalis are used and result in reactions such as these: Ca(OH)2 + SO2 CaSO3 + H2O CaCO3 + SO2 CaSO3 + CO2
Particulates (particulate matter)

These are solid or liquid particles in the air (the term for solid or liquid particles suspended in a gas is an aerosol). Particulate matter is usually classi ed according to size, such that particles with a diameter between 10 m and 2.5 m are termed coarse particles and those with diameters less than 2.5 m are called ne particles. Anthropogenic sources of particulate matter include: soot from incomplete combustion of wood, coal, petrol, diesel y ash this arises when fossil fuels are burnt in furnaces and contains soot and metal oxides dust from mechanical activity, demolition, etc. (including asbestos a brous silicate mineral used in the past as a ame retardant and heat insulator) metal particles (including lead and mercury) from metalworking activities. Natural sources of particulate matter include: pollen, dust, soot from forest res and sea spray. There are many ways of removing particulates from the atmosphere including: ltration, sedimentation, scrubbing and electrostatic precipitation. In electrostatic precipitation, the particles pass through a series of wires that are negatively charged. The particles pick up a negative charge as they pass through. The particles are then attracted to a positively charged plate. The plates are shaken periodically to remove and collect the particles. Electrostatic precipitators can remove more than 99% of particulate matter (e.g. from ue gases from a coal- red power station).
Diesel engines are a major source of particulates resulting from transport.
Volatile organic compounds (VOC)

This covers a wide range of organic compounds that are released into the atmosphere. Natural sources include: bacterial decay of organic material forming methane CH4 (marsh gas) plants and trees many plants and trees (e.g. pine trees) produce unsaturated hydrocarbons called terpenes. Anthropogenic sources include: unburnt hydrocarbons from the internal combustion engine these can be removed by using a catalytic converter: 2C8H18(g) + 25O2(g) 16CO2(g) + 18H2O(l)
CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011
Levels of VOCs are often higher indoors than outdoors due to the use of products containing solvents.
E ENVIRONMENTAL CHEMISTRY
solvents used in paints, varnishes, cleaning products, glues, marker pens, etc. incomplete combustion of wood and coal produces aromatic hydrocarbons which can be carcinogenic. The sources, e ects on health and methods for removal of primary pollutants are summarised in Table E1. Other ways of reducing the problems associated with these pollutants are to combust less fossil fuels and to use alternative sources (e.g. wind, solar) for generating electricity. Pollutants from transport can be reduced by increasing the use of public transport and decreasing the use of private vehicles.
Pollutant CO Anthropogenic sources incomplete combustion of fossil fuels Natural sources anaerobic decomposition of organic matter Method of removal/reduction catalytic converter; lean-burn engines Health effects Very poisonous. CO joins onto haemoglobin in the blood this prevents it from transporting oxygen molecules in the normal way. Leads to shortage of breath, fatigue, coma and death. Toxic. Cause irritation of eyes and nose. Cause respiratory distress due to uid accumulation in the lungs which can lead to infections and death. Causes respiratory irritation and infection. Damages the mucous membranes of the nose, throat and lungs. This is particularly bad for those who suffer from asthma. Causes severe eye irritation. Particles get into lungs. Can cause coughing, bronchitis, shortness of breath.
NOx
reaction of N2 and O2 in the internal combustion engine burning coal/oil; smelting of metal ores; sulfuric acid production
lightning; action of soil bacteria volcanic activity; decay of organic matter
catalytic converter; lean-burn engines
SO2 (SO3)
uidised bed combustion; alkaline scrubbing
particulates soot from incomplete combustion of wood, coal, petrol, diesel; dust from mechanical activity, demolition, etc. VOC unburnt hydrocarbons from the internal combustion engine; solvents used in paints, varnishes, etc.
pollen, dust, soot from forest res and sea spray
electrostatic precipitation
bacterial decay of organic material; many plants and trees produce terpenes
catalytic converter
Irritation to eye, nose and throat, headaches, damage to liver, kidneys and central nervous system. Aromatic hydrocarbons (containing benzene rings) can cause cancer.
Table E1 Sources, health effects and methods for removal of primary pollutants.
Test yourself
1 Draw the Lewis structure of carbon monoxide. 2 Write a balanced equation for the incomplete combustion of butane forming carbon monoxide. 3 Write an equation for the formation of SO2 from S and explain why it can be described as a redox reaction.
E2 Acid deposition
Rain is naturally acidic because of dissolved CO2. H2O(l) + CO2(g) H2CO3(aq)
carbonic acid
Learning objectives
H2CO3 is a weak acid and dissociates partially according to the equation: H2CO3(aq) H (aq) + HCO3 (aq)
+
Due to this process the pH of rain water is about 5.6. As this is a natural phenomenon, rain with a pH between 5.6 and 7 is not considered to be acid rain. Acid rain is therefore considered to be rain with a pH of less than 5.6. The average pH of rain in some areas may be as low as 4. Acid deposition is a more general term than acid rain. It refers to any process in which acidic substances (particles, gases and precipitation) leave the atmosphere. It can be divided into wet deposition (acid rain, fog and snow) and dry deposition (acidic gases and particles). Acidic pollutants include oxides of sulfur and nitrogen. We will rst of all consider sulfur compounds. Sulfur dioxide can be formed by various natural and anthropogenic processes, e.g. burning of sulfur-containing fuels: S(s) + O2(g) SO2(g) The processes by which SO2 is converted into SO3 and H2SO4 in the atmosphere are complex and do not involve simple oxidation by O2 (rather interaction with hydroxyl radicals, ozone or hydrogen peroxide). The reactions, however, can be summarised as: 2SO2(g) + O2(g) 2SO3(g)
sulfur(VI) oxide
State what is meant by acid deposition Outline the origins of acid deposition Describe the free radical HL mechanism by which sulfuric and nitric acids are formed in the atmosphere Explain the role of ammonia in acid deposition
SO3(g) + H2O(l) H2SO4(aq)

sulfuric(VI) acid
SO2 can also dissolve in water to produce sulfuric(IV) acid (sulfurous acid): SO2(g) + H2O(l) H2SO3(aq)
sulfuric(IV) acid
NO can be oxidised in the atmosphere to NO2. Again, the exact nature of the process is complex (see Higher Level section on page 7), but the reaction may be summarised as: 2NO(g) + O2(g) 2NO2(g) The NO2 can then react with a hydroxyl radical (HO) to form nitric(V) acid: NO2(g) + HO(g) HNO3(g)
Again, other reactions can occur and the reactions for the formation of nitric acid may also be shown as: 4NO2(g) + O2(g) + 2H2O(l) 4HNO3(aq) or 2NO2(g) + H2O(l) HNO2(aq) + HNO3(aq)
nitric(III) acid nitric(V) acid
Problems associated with acid deposition
E ect on vegetation it is not necessarily the acid itself that causes problems. The acid (H+ ions) can displace metal ions from the soil which are consequently washed away (particularly calcium, magnesium and potassium). Mg2+ ions are needed to produce chlorophyll, so plants could be prevented from photosynthesising properly. The acid rain also causes aluminium ions to dissolve from rocks, which damages plant roots and limits water uptake. This can cause stunted growth, and thinning or yellowing of leaves on trees. Lakes and rivers aquatic life is sensitive to the pH falling below 6. Insect larvae, sh and invertebrates, among others, cannot survive below pH 5.2. Below pH 4.0 virtually no life will survive. Acid rain can dissolve hazardous minerals from rocks, which can accumulate in lakes and damage aquatic life Al3+ ions in particular damage sh gills. Buildings limestone and marble is eroded by acid rain and dissolves away exposing more fresh surface to react with more acid. A typical reaction would be: CaCO3(s) + H2SO4(aq) CaSO4(s) + H2O(l) + CO2(g)
Human health acid irritates mucous membranes and causes respiratory illnesses (e.g. asthma, bronchitis). Acidic water can dissolve heavy metals such as Cu2+ or Pb2+ which are poisonous, and Al3+ which may be linked to Alzheimers disease.
Methods of dealing with acid deposition

Methods for dealing with acid deposition include: improving the design of vehicle engines, using catalytic converters, removing sulfur before burning fuels using renewable power supplies greater use of public transport designing more e cient power stations liming of lakes calcium oxide or hydroxide neutralises acidity. CaO(s) + H2SO4(aq) CaSO4(aq) + H2O(l) Ca(OH)2(s) + H2SO4(aq) CaSO4(aq) + 2H2O(l)
Test yourself
4 Explain why rain is naturally acidic. 5 Give the formulas of two acids that arise from human activities and that are present in acid rain.
The free radical mechanism and sulfuric and nitric acid formation
Like much of the chemistry of the atmosphere, the formation of H2SO4, HNO3 and HNO2 (the major constituents of acid deposition) is dominated by free radical reactions. The formation of hydroxyl radicals (HO) can be shown as: O3 O + O2
UV light
HL
ozone
O + H2O 2HO This can also be shown in one step as: H2O + O3 2HO + O2 The hydroxyl radicals can react with the oxides of nitrogen to form nitric(V) acid (HNO3) and nitric(III) acid (HNO2): HO + NO2 HNO3 HO + NO HNO2 The hydroxyl radical is also involved in the oxidation of sulfur(IV) oxide to sulfuric(VI) acid (H2SO4). HO + SO2 HOSO2 HOSO2 + O2 HO2 + SO3 SO3 + H2O H2SO4 These are both termination reactions and do not result in the formation of a free radical.
The role of ammonia in acid deposition

Ammonia is produced by bacterial action (nitrogen xation) in the soil and in the root nodules of some plants such as peas and beans (legumes). Ammonia is a base and neutralises a signi cant proportion of the acids in the atmosphere, forming ammonium salts: 2NH3 + H2SO4 (NH4)2SO4 NH3 + HNO3 NH4NO3 When these particles sink to the ground or are washed out of the atmosphere or rain containing ammonium salts falls they can cause acidi cation of the soil. This can happen in two ways. First, the ammonium ion is weakly acidic and can ionise to form ammonia and H+ ions: NH4+ NH3 + H+ Ammonium salts may be present in the atmosphere in solution or as ne particles. How much, or how little, ammonium is converted to nitrate (NO3) depends on various soil factors including the amount of organic matter, water content, oxygen supply, temperature and pH. Warm, moist soils with a good oxygen supply provide favourable conditions for nitri cation. A major source of ammonia in the atmosphere is from agriculture, especially intensive animal husbandry (animal waste).
Ammonium salts such as ammonium sulfate and ammonium nitrate are salts of a weak base with a strong acid and are therefore acidic. Secondly, nitrifying bacteria in the soil can cause oxidation of the ammonium ion to the nitrate(V) ion and this process also produces H+ ions: NH4+ + 2O2 2H+ + NO3 + H2O
HL
Test yourself
6 Draw Lewis structures for the radicals HOSO2 and HOO. 7 Explain how ammonia can both neutralise acid in the atmosphere and make soil more acidic.
Learning objectives
E3 The greenhouse effect

The greenhouse e ect is an important mechanism for maintaining the Earths temperature at a reasonable level. Without some sort of greenhouse e ect the Earth would be too cold to maintain life as we know it. Of the short wavelength solar radiation that reaches the Earth, some is re ected back into space and the rest passes through the atmosphere to reach the Earths surface. The surface absorbs some of this radiation and heats up. The warmed surface radiates longer wavelength, infrared radiation. Some of this radiation is absorbed by greenhouse gases such as CO2 in the atmosphere. Of the radiation absorbed by the greenhouse gases, some is re-radiated back to Earth. The overall e ect is therefore that the heat is trapped by the gases in the atmosphere (Figure E1). The natural equilibrium between incoming and outgoing radiation maintains the Earths mean temperature at about 15 C. If the level of greenhouse gases in the atmosphere increases then more infrared radiation will be absorbed and re-radiated back to Earth and the global temperature should increase.
Describe the greenhouse e ect Describe the sources and relative e ects of the main greenhouse gases Explain the e ects of increasing levels of greenhouse gases
When CO2 absorbs infrared radiation it vibrates more energetically. As it moves back down to a lower vibrational energy level, the extra energy is given out again.
The sources and relative effects of the main greenhouse gases

The main greenhouse gases, their sources and relative heat trapping ability are shown in Table E2. The contribution of a particular greenhouse gas to global warming depends on several factors: its ability to absorb infrared radiation, its abundance in the atmosphere, its atmospheric lifetime and the wavelength range in which it absorbs infrared radiation.
Sun
solar radiation reflected
outgoing infrared radiation
atmosphere
incoming solar radiation (shorter wavelength)
infrared radiation absorbed by greenhouse gases infrared radiation emitted by Earths surface (longer wavelength) Earth
Figure E1 The greenhouse effect.
Gas H2O CO2 CH4 N2O O3
Source evaporation from oceans and lakes on the Earths surface combustion of carbon fuels and biomass anaerobic decay of organic material agriculture: rice elds, marshes, animals agricultural soil management (fertilisers), nitric acid production photochemical smog
Heat trapping Approximate relative amounts effectiveness emitted in US per year 0.1 1 26 216 2 000 13 00023 000 100 9.6 5.4
CFCs refrigerants, propellants, foaming agents, solvents
Table E2 The main greenhouse gases, their sources and relative heat trapping ability.
CO2 has a greater in uence on global warming than some of the other gases from anthropogenic sources because, although it does not absorb as much infrared radiation as the other gases, it is produced in greater amounts. The contribution of each of the anthropogenic gases to global warming between 1980 and 1990 is shown in Table E3.
Gas CO2 CH4 N2O CFCs
Contribution to global warming / % 55 15 6 24
When considering factors that contribute CO2 to the atmosphere we should also consider the e ects of removing the mechanisms that reduce the amount of CO2 in the atmosphere. For instance, if areas of forest are cleared this can increase CO2 levels in the atmosphere in two ways rst, CO2 is not being removed by the process of photosynthesis and second, if the wood is burnt then CO2 is produced.
Table E3 The contribution of anthropogenic gases to global warming between 1980 and 1990.
The potential for a particular gas to cause global warming can be described in terms of its global-warming potential. The potential for 1 kg of a particular gas to cause global warming over a particular time period (e.g. 20 years) is compared to that of 1 kg of CO2 (see Table E4). Methane has a much higher global-warming potential than carbon dioxide, if we compare the same mass, but is produced in much smaller amounts. Water vapour is another important greenhouse gas and, indeed most scientists would regard water vapour as the most important greenhouse gas. The amount of water vapour in the atmosphere is, however, only directly in uenced to a small extent by human activities. However, if the Earth gets hotter, through the release of other greenhouse gases, this will increase the evaporation of water and so further increase the amount of water vapour in the atmosphere.
Gas CO2 CH4 N2O CFC-11
Global-warming potential (20 years) 1 72 289 3800
Table E4 The global-warming potential of various gases over 20 years.
The inuence of increasing amounts of greenhouse gases on the atmosphere

In the 10 000-year period up to 1750, the CO2 concentration in the atmosphere remained fairly constant at around 280 ppm (parts per million). This had risen to 379 ppm by 2005. Similarly, CH4 and N2O abundances in the atmosphere have increased since the industrial revolution.
The e ect of global warming on global food production is di cult to estimate but, depending on the size of the temperature change, it could actually result in an overall increase in the potential for global food production.
In the 100 years up to 2005, global temperatures increased by about 0.74 C and in the past 30 years temperatures are estimated to have increased by about 0.2 C per decade. Most current scienti c thinking is that the Earths climate is warming as a result of the increase in the amount of greenhouse gases present in the atmosphere, although there are a few scientists who dispute the reasons for these changes and whether it is really an anthropogenic e ect. It is di cult to predict the e ect of climate change on our planet but some suggested consequences are given here. As the Earths temperature rises, oceanic water expands increased sea levels could submerge low-lying areas and many islands. Large populations live in some of these areas. Only estimates can be made based on complex models but these predict sea-level rises of up to about 0.5 m during the next 100 years. Polar ice caps could melt (the melting of any oating ice does not cause sea levels to rise). Antarctic ice, glaciers and snow/ice cover on land could melt (this does increase sea levels). The occurrence of extreme weather events such as oods, droughts and heat waves could increase. The amount and distribution of precipitation (rain and snow) could change. A warming climate may mean that commercial crops can no longer be produced where they grow now. This could be a massive problem in grain-producing areas that currently produce a large amount of food. The distribution of pests and disease-carrying insects could change (e.g. changes in the distribution of the mosquito population could alter the regions where malaria is a danger).
Learning objectives
E4 Ozone depletion
Formation and depletion of ozone in the stratosphere
Ozone, O3, is an allotrope of oxygen. It is a toxic blue gas with a characteristic odour. The ozone layer is a region in the stratosphere where there is a higher concentration of ozone. The maximum concentration occurs in the lower regions of the stratosphere between about 15 and 35 km above the Earths surface. About 90% of the ozone in the atmosphere occurs in this region. Even in the ozone layer the concentration of ozone is very low and there is roughly only one ozone molecule for every 100 000 air molecules. The atmosphere can be divided into di erent regions: the troposphere is the region closest to the Earth and the stratosphere is the region between about 12 and 50 km, on average, above the Earths surface. UV light in the upper atmosphere enables O2 to form molecules of O3 (ozone). Higher energy, shorter wavelength UV radiation is absorbed by oxygen molecules in the upper layers of the atmosphere, which causes the O=O to break producing oxygen free radicals:

HL
Describe the processes that result in the formation and depletion of ozone in the stratosphere List the ozone-depleting pollutants and their sources Discuss the alternatives to CFCs Explain how the wavelength of light a ects photolysis of O2 and O3 Explain how CFCs and NOx catalyse ozone depletion Explain why greater ozone depletion occurs in polar regions
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O2 2O
UV light
oxygen free radicals
The UV radiation required to do this is in the UV-C part of the spectrum and must have a wavelength of less than 242 nm to provide su cient energy to break the bond. The oxygen atoms (free radicals) formed can react with molecular dioxygen to form ozone: O + O2 O3
ozone
Ozone molecules are particularly e ective at absorbing lower energy (longer wavelength) UV-B radiation (and some UV-C). Ozone can be destroyed (depleted) in two natural processes: O3 O + O2 O3 + O ozone 2O2
UV light
Ultraviolet (UV) light from the Sun reaching the Earth can be divided into three regions: UV-C (highest energy, shortest wavelength), UV-B and UV-A (lowest energy, longest wavelength). The wavelength ranges are: < 280 nm UV-C UV-B 280320 nm 320400 nm UV-A
This rst process is just the reverse of the formation of ozone.
If the rate at which ozone is produced and destroyed balance, then a steady state is reached and the concentration of ozone remains constant. All of the UV-C and most of the UV-B reaching the Earth from the Sun is absorbed by O2 in the upper parts of the atmosphere and ozone in the stratosphere before it reaches the Earths surface. Most of the UV radiation reaching the Earths surface is the less harmful UV-A (Figure E2). Some molecules released by human activity react very e ectively with ozone, reducing its concentration. This has created what is known as the ozone hole or the hole in the ozone layer. The ozone hole refers to the fact that, at certain times of year and in certain regions (centred on the Antarctic) the concentration of ozone in the stratosphere decreases signi cantly so that it falls below a certain value. The size of the ozone hole and the time for which it exists has on average increased over the past 30 years. This results in more UV-B radiation reaching the surface of the Earth. The e ects of increased exposure to UV radiation on humans include an increased risk of skin cancer and cataracts. UV radiation can also damage plants and phytoplankton.
Other natural processes involving, e.g. hydroxyl (OH) radicals, can also lead to ozone depletion. Ozone absorbs longer wavelength radiation than O2 as the OO bond is weaker and less energy is required to break it. See Higher Level section on page 13.
UV-C
Pollutants that cause ozone depletion

The main pollutants responsible for depletion of ozone are chloro uorocarbons (CFCs) and nitrogen oxides (NOx). The main sources of nitrogen oxides have already been discussed on page 1. CFCs (chloro uorocarbons), also called Freons, were developed and used from the rst half of the 20th century as non-toxic, non- ammable substances useful as refrigerants, aerosol propellants and foaming agents for plastics and re extinguishers and also as solvents for cleaning. Examples are: CCl3F (CFC-11, trichloro uoromethane) and CCl2F2 (CFC-12, dichlorodi uoromethane). CFCs are so unreactive that they can pass through the troposphere and up into the stratosphere without reacting. In the stratosphere UV light causes the CCl bond to break (it is weaker than the CF bond) to produce chlorine free radicals, which catalyse the depletion of ozone (see below). One chlorine free radical can destroy thousands of ozone molecules.
O2
2O
UV-B O3 O + O2 UV-A Earths surface
Figure E2 UV-B and UV-C radiation from the Sun is absorbed by ozone and oxygen respectively. Only UV-A radiation gets through to the Earths surface.
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Since 1998 the production of CFCs has decreased. No CFCs have been produced in developed countries since 1995 and the use and supply of CFCs was banned in the EU from 2000.
Alternatives to CFCs
Since the 1987 Montreal Protocol the use of CFCs is being phased out no new CFCs have been produced since 1995 in industrialised countries such as the UK, America and Japan. Total usage of CFCs has also fallen dramatically, particularly in aerosols. The only aerosols using CFCs in these countries are asthma inhalers and these too are being phased out. Alternatives to CFCs were required if they were to be phased out. The desirable properties for a replacement are that it should be nontoxic, non- ammable, not damage the ozone layer and not contribute to global warming as well as be able to ful l the required role as a refrigerant etc. Groups of compounds that have been used to replace CFCs are hydrocarbons (HCs), uorocarbons, hydrochloro uorocarbons (HCFCs) and hydro uorocarbons (HFCs). HCFCs (hydrochloro uorocarbons) e.g. CHF2Cl (chlorodi uoromethane, HCFC-22), are more reactive than CFCs due to the presence of the CH bond (they can react with hydroxyl radicals in the troposphere). They are less likely to make it through to the stratosphere without reacting. They do, however, contain a CCl bond and the molecules that survive through to the stratosphere will cause ozone depletion. HCFC-123 (CF3CCl2H, 2,2-dichloro-1,1,1-tri uoroethane) is used instead of CFC-11 in air-conditioning units but, although it is less damaging to the ozone layer, it is more toxic than CFC-11. It can cause eye irritation and studies of its e ect on animals have suggested that it could cause liver damage. HCFCs are non- ammable. Hydrocarbons such as butane, propane and 2-methylpropane are used as propellants in aerosols but, unlike CFCs, these are ammable. Hydrocarbons such as butane are non-toxic but are sometimes used in solvent abuse. Hydrocarbons do not contain a CCl bond that can be broken to produce free radicals, so have zero potential for ozone depletion. Hydro uorocarbons (HFCs) such as HFC-134a (CF3CH2F, 1,1,1,2-tetra uoroethane) are used in air conditioning and refrigeration. HFC-134a is non-toxic, non- ammable under normal conditions, and does not cause signi cant depletion of ozone (the CF bond is much more di cult to break than the CCl bond). Fluorocarbons such as CF4 (tetra uoromethane) are non- ammable and non-toxic and will not deplete the ozone layer due to the strong CF bonds. C4F10 (1,1,1,2,2,3,3,4,4,4-deca uorobutane!) can be used as a re suppressant and refrigerant. The alternatives mentioned here all have one severe disadvantage; they are all greenhouse gases and will absorb infrared radiation and contribute to global warming. Many of them, however, have global-warming potentials lower than CFCs. The global-warming potential of these substances are compared in Table E5.
Compounds containing CH bonds are more reactive than CFCs and are likely to react before they reach the stratosphere, where thay can cause ozone depletion.
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Test yourself
8 Classify each of the following compounds as a CFC, an HCFC, an HFC or an HC. c CH2F2 a CHCl2CHF2 b CH3CH2CH2CH2CH3 d CCl3F 9 Use the IUPAC naming system to name each of the compounds in Question 8.
Chemical CFC-11 CFC-12 HFC-134a C4F10 HCFC-22 HCFC-123 butane
Global-warming potential (over 100 years) 4 600 10 600 1 300 8 600 1 700 120 3
How the wavelength of light affects photolysis of O2 and O3

The Lewis structures for O2 and O3 are shown in Figure E3.
a 0.121 nm b
HL
Table E5 Global-warming potential of various pollutants over 100 years relative to CO2.
0.128 nm
O O
0.128 nm
Figure E3 (a) the Lewis structure of O2; (b) two alternative Lewis structures of O3. The arrows represent delocalisation of electrons.
Figure E4 The OO bond in O3.
The OO bond lengths in ozone are actually equal and between that expected for an O=O double bond and an OO single bond. Ozone has a delocalised structure in which the two electrons in the component of the double bond are shared between all three O atoms. The OO bond in ozone is thus longer and weaker than that in O2 (Figure E4). This means that higher energy UV radiation is required to break the OO bond in O2 compared to O3. UV radiation of wavelength shorter than 242 nm is required to break the double bond in O2: O2 2O
< 242 nm
oxygen free radicals
Ozone has a bond order of 1.5 compared to a bond order of 2 for O2. This process is called photolysis or photodissociation.
This is in the UV-C part of the spectrum and is absorbed in the uppermost reaches of the atmosphere. As the bond in ozone is weaker, lower energy (longer wavelength) UV radiation is absorbed by ozone to break the bond. O3 O + O2
< 330 nm
ozone
Ozone thus absorbs UV-C and UV-B radiation.
Catalysis of O3 depletion by CFCs and NOx

Ozone molecules are easily destroyed by free radicals. These are present in the stratosphere as nitrogen oxides or produced when CFCs are broken down by UV light.
Examiners tip There is some disagreement about the wavelength of UV radiation required to break apart the ozone molecule. The value of 330 nm is given on the IB syllabus and should be used in examinations.
CFCs
CFC molecules such as CCl2F2, are very stable at ground level, but they are broken down by absorbing UV radiation in the upper atmosphere: CCl2F2 CClF2 + Cl
UV light
chlorine free radical
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All reactions occur in the gaseous state.
HL The CCl bond is weaker than the CF bond and more readily
undergoes homolytic ssion. The chlorine free radical released by this process can then take part in a chain reaction which uses up ozone and regenerates the Cl free radical. Cl + O3 ClO + O2 ClO + O O2 + Cl
chlorine free radical regenerated
O atoms are available from the dissociation of oxygen or ozone.
The chlorine free radical is a catalyst in these reactions as it is not used up. One Cl free radical can destroy many thousands of O3 molecules.
The net e ect of these reactions can be seen if the intermediate and the catalyst are cancelled out: Cl + O3 ClO + O2 ClO + O O2 + Cl O3 + O 2O2
Nitrogen oxides, NOx

NO can be formed at high altitudes by aircraft and from the reaction of N2O or NO2 with atomic oxygen: N2O(g) + O(g) 2NO(g) NO2(g) + O(g) NO(g) + O2(g) Similar types of reactions to those discussed above for CFCs occur with nitrogen oxides. NO and NO2 both have unpaired electrons (their total number of electrons is an odd number). All reactions occur in the gaseous state. NO + O3 NO2 + O2 NO2 + O O2 + NO O3 + O 2O2 The cycles of destruction of ozone described above can stop when the free radicals involved collide: ClO + NO2 ClONO2
Extension
The bond order in NO is 2.5. A simple approach to the bonding does not explain this NO has one electron in a * antibonding molecular orbital.
Ozone depletion in polar regions

During winter a large-scale system of rotating winds develops over the Antarctic and essentially isolates the stratosphere there from the rest of the stratosphere. This is called the polar vortex. Normally clouds do not form in the stratosphere but, at the poles, there is no sunlight for three months and temperatures may drop below 90 C. At these temperatures stratospheric clouds containing ice particles do form. Ice crystals formed in the polar vortex can act as heterogeneous catalysts which allow the conversion of the relatively inactive ClONO2 to the much more active Cl2 and HOCl. These reactions occur on the surface of the ice particles: HCl + ClONO2 Cl2 + HNO3 H2O + ClONO2 HOCl+ HNO3 HCl and ClONO2 are both relatively inactive chlorine-containing species but these reactions convert them into Cl2 and HOCl which undergo homolytic ssion much more easily. In the spring the sunlight returns
Heterogeneous catalysts are in a di erent phase to the reactants and provide a surface on which the reaction can occur. The nitric acid formed in these reactions remains in the ice particles so that it is not available for formation of nitrogen oxides that can reduce the concentrations of ClO.
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causing particularly marked ozone depletion in the atmosphere above the HL poles due to conversion of the Cl2 and HOCl into chlorine free radicals: Cl2 2Cl HOCl HO + Cl As the temperature warms throughout the year the polar vortex dissipates and the ice crystals melt allowing molecules to escape into other parts of the atmosphere and stopping this process of reactions. This allows time for ozone concentrations to recover before the next winter. The Arctic is warmer than the Antarctic and ozone destruction has not happened to the same extent. Some scientists believe, however, that the conditions over the Arctic are becoming colder so that an ozone hole could occur in this region as well. This could have serious consequences for large parts of North America, northern Europe and Asia.
UV light UV light
Test yourself
10 Explain what is meant by the terms free radical and homolytic ssion. 11 Write equations to show how ozone can be depleted by CFCs such as CCl3F. Explain why the reaction involved can be described as a chain reaction.
E5 Dissolved oxygen
The concentration of dissolved oxygen in water at 20 C is about 9 mg dm3 (9 ppm) but decreases with temperature. Dissolved oxygen is important for the maintenance of life in aquatic systems. Dissolved oxygen comes from photosynthesis and from the atmosphere. The amount of oxygen needed for sh to survive is dependent on the type of sh and the temperature. In summer, certain sh will not survive when the dissolved oxygen level drops below 6 mg dm3 and if it drops below about 3 mg dm3 few sh are able to survive. The oxygen concentration needed for sh to survive is substantially higher at higher temperatures. In the winter, certain sh may survive down to levels of 0.25 mg dm3. Biochemical oxygen demand, also called biological oxygen demand or BOD, is used as a measure of the quality of water. It is a measure of the amount of oxygen used by microorganisms to oxidise the organic matter in the water. Any organic pollutants in river water will be decomposed (oxidised) by microorganisms (aerobic bacteria) in the water and this process uses up dissolved oxygen. The higher the BOD, the more organic waste there is in the water. If, for instance, sewage is released into a river or lake, this will greatly increase the BOD the water is more polluted. If the water is fast owing, new oxygen can be dissolved fairly quickly, but this process is much slower in still water.
Learning objectives
Understand what is meant by biochemical oxygen demand Discuss anaerobic and aerobic decomposition of organic matter in water Understand what is meant by eutrophication Discuss thermal pollution of water
Organic matter in water might include leaves, animal manure, dead plants and animals. E uent from water treatment plants will also contain organic matter.
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BOD is de ned as the amount of oxygen used by the aerobic microorganisms in water to decompose the organic matter in the water over a xed period of time (usually ve days) at a xed temperature (usually 20 C). Good-quality river water will have a BOD of less than 1 ppm. Water is generally regarded as unpolluted if it has a BOD of less than 5 ppm. Untreated sewage could have a BOD of 500 ppm but treated sewage from water treatment plants should have a BOD of less than 20 ppm. The basic principle of measuring BOD is to compare the initial amount of dissolved oxygen in a sample of water with the amount present when the sample has been incubated for 5 days at 20 C. Thus, if water has a dissolved oxygen concentration of 9 ppm and after incubation for 5 days this has fallen to 4 ppm the BOD is 9 4, i.e. 5 ppm. A typical method for determining the amount of dissolved oxygen is to use the Winkler titration method. The basic chemistry behind the Winkler method is that manganese(II) sulfate is added to the water and is oxidised under alkaline conditions to manganese(IV) by the oxygen in the water: 2Mn(OH)2(s) + O2(aq) 2MnO(OH)2(s) The sample is acidi ed with sulfuric acid to produce manganese(IV) sulfate: MnO(OH)2(s) + 2H2SO4(aq) Mn(SO4)2(aq) + 3H2O(l) Iodide ions, which have also been added are oxidised to I2 by the manganese(IV): Mn4+(aq) + 2I(aq) Mn2+(aq) + I2(aq) The liberated iodine can then be titrated against a standard sodium thiosulfate solution: I2(aq) + 2S2O32(aq) S4O62(aq) + 2I (aq) The outcome of these equations is that the number of moles of dissolved oxygen is 1 the number of moles of sodium thiosulfate used in the 4 titration or the mass of oxygen is eight times the number of moles of sodium thiosulfate. There is some disagreement about the reactions involved and an alternative set of equations is: 2Mn2+(aq) + 4OH(aq) + O2(aq) 2MnO2(s) + 2H2O(l) MnO2(s) + 2I(aq) + 4H+(aq) Mn2+(aq) + I2(aq) + 2H2O(l) 2S2O32(aq) + I2(aq) S4O62(aq) + 2I(aq) The stoichiometry of these reactions is the same as above. It is not even certain that the Mn2+ is oxidised to manganese(IV) it could also be oxidised to manganese(III)
Water containing a high proportion of organic matter must be diluted before analysing for BOD.
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Aerobic and anaerobic decomposition of organic material in water

With plenty of oxygen the decay of organic material will take place aerobically forming oxides or oxyanions. If there is insu cient oxygen, anaerobic respiration forms di erent, often smelly, toxic products. See Table E6. Aerobic decomposition results in oxidation (increase in oxidation number) and elements in their highest oxidation states whereas anaerobic decomposition results in the element being in a low oxidation state.
Element in organic Aerobic decay material produces carbon nitrogen sulfur phosphorus CO2 nitrate, NO3 sulfate, SO4
2
Oxidation number of element +4 +5 +6 +5
Anaerobic decay produces methane, CH4 ammonia, NH3 H2S (rotten egg smell very poisonous gas) PH3 (phosphine gas)
Oxidation number of element 4 3 2 3
phosphate, PO43
Table E6 Aerobic and anaerobic decomposition of organic material in water.
Redox equations for the decomposition of organic matter

The exact equations involved when organic matter is decomposed by bacteria are complex but some examples of reactions could be: Carbon compounds under aerobic condition a carbohydrate could be oxidised to CO2 and H2O: (CH2O)n + nO2 nCO2 + nH2O Under anaerobic conditions methane is formed (oxidation number of carbon = 4): 2(CH2O)n nCH4 + nCO2
Organic nitrogen compounds are rst converted to the ammonium ion/ammonia. This will occur under aerobic or anaerobic conditions. An example of this type of reaction is: (NH2)2CO + H2O 2NH3 + CO2
urea
Under aerobic conditions the ammonium ion can be oxidised to the nitrate(V) ion, e.g. NH4+ + 2O2 NO3+ H2O + 2H+ or 2NH4+ + 3O2 2NO2 + 2H2O + 4H+
and 2NO2 + O2 2NO3
Organic sulfur compounds are rst broken down by bacteria to hydrogen sul de.
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Under aerobic conditions the H2S is oxidised to sulfates. The exact nature of the reaction depends on the type of bacteria involved but redox equations for the processes could be written as: 2H2S + O2 2S + 2H2O 2S + 3O2 + 2H2O 2SO42 + 4H+
Major sources of phosphorus are from arti cial fertilisers and from phosphorus-based detergents.
Eutrophication
Eutrophication refers to enrichment of a body of water, such as a lake, with nutrients. These nutrients are mainly nitrates and phosphates and come from sewage e uent or the run-o from agricultural land where arti cial fertilisers are being used. Increased levels of nitrates and phosphates in a body of water cause increased plant and algal growth (algal bloom) (Figure E5). When these plants and algae die they sink to the bottom of the lake and are decomposed by aerobic bacteria. This uses up the dissolved oxygen in the water. If the amount of organic matter to be decomposed is excessive then all the oxygen in the water will be used up and anaerobic bacteria will take over the decomposition of the organic matter. This produces toxic and foul smelling substances such as hydrogen sul de (H2S). These toxic products cause living species to die. This causes more organic decay and further increases the BOD everything dies. An excessive amount of algae on the surface of the water will prevent light reaching the plants underneath and will reduce the amount of photosynthesis taking place. This will also reduce the amount of oxygen in the water as photosynthesis produces oxygen.
Figure E5 Eutrophication.
Phosphates are usually regarded as the limiting factor for algal growth in fresh water and it is important to control their entry to the body of water. Therefore it is important to limit the use of phosphate-based detergents.
The two main e ects of eutrophication are therefore reduction of the dissolved oxygen in the water so that it cannot support life and the production of toxic substances in the water, again reducing its capacity to sustain life. Eutrophication can also occur in the sea.
Thermal pollution in water

Water is an important coolant in industry and power stations. Water (e.g. from a lake or river) is drawn into the power station and discharged back into the body of water at a higher temperature. Oxygen is less soluble in hot water (Figure E6) so, at higher temperatures, less is available for animal and plant life. The higher temperature also increases the metabolic rate of sh and other organisms so that they use up food sources and the oxygen in the water more rapidly. These e ects can cause sharp population declines in the aquatic environment. The species that are able to live in the water can also be a ected by its temperature.
The e ect of thermal pollution can be reduced by having cooling towers to reduce the temperature of the water before it is returned to the environment.
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16 14 Dissolved oxygen concentration/ppm 12 10 8 6 4 2 0 0 10 20 30 Temperature /C 40 50
Figure E6 The variation in dissolved oxygen in fresh water with temperature.
Test yourself
12 a The concentration of dissolved oxygen in a fresh sample of water at 20 C is 9.0 ppm. Convert this to a concentration in mol dm3. b The concentration of dissolved oxygen in the sample of water when it has been incubated at 20 C for 5 days is 1.8 104 mol dm3. Convert this to a concentration in ppm. c Calculate the BOD of this sample of water and suggest whether it would be regarded as polluted. 13 The Winkler method was employed to measure the concentration of dissolved oxygen in a sample of water. Manganese sulfate, sulfuric acid and potassium iodide were added to 100.0 cm3 of water. The iodine liberated was titrated against sodium thiosulfate solution of concentration 5.00 103 mol dm3; 16.00 cm3 of sodium thiosulfate was required for the titration. a Calculate the number of moles of sodium thiosulfate used. b Calculate the number of moles of iodine present in the solution. c Calculate the number of moles of manganese(IV) that produced this number of moles of I2. d Calculate the concentration of dissolved oxygen in mg dm3 and ppm.
E6 Water treatment
Primary pollutants found in waste water and their sources
Heavy metals
There are many heavy metals that are regarded as pollutants (e.g. lead, mercury, chromium, copper, nickel, cadmium). Rocks and minerals which contain these metals can lead to local pollution as can mining and mineral processing. Small amounts of heavy metals may get into the environment and therefore into waste water from various industrial sources. Table E7 summarises some anthropogenic sources that may release heavy metals into the environment. Heavy metals often accumulate in the body and can eventually lead to various serious health problems. For instance, higher levels of lead can impair the mental development of children; mercury can damage the brain, central nervous system and kidneys; cadmium can cause kidney damage, bone disease and lung and prostate cancer; chromium compounds can cause lung cancer.
Learning objectives
List the primary pollutants in waste water and their sources Outline primary, secondary and tertiary water treatment Evaluate multistage ash distillation and reverse osmosis as ways of obtaining fresh water from sea water Understand what is meant by HL the solubility product Solve problems relating to the removal of heavy metal ions from water by precipitation.
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The term heavy metal is a very vague and imprecise term and there is no clear de nition of what it means. It is usually used to refer to a group of metals and metalloids (such as arsenic) that have harmful environmental e ects. It also often used to describe the compounds of these metals. Some of these sources result in heavy metals or their compounds entering the atmosphere. Precipitation/dry deposition can then cause them to enter the water system.
Heavy metal lead
Anthropogenic source iron and steel production, lead water pipes Lead used to be used in paints and as a petrol additive but this is no longer permitted in most countries. There may be quite high levels of lead in soil in inner city areas where the soil has absorbed the lead emitted when leaded petrol was still in use. Some older homes may also contain lead-based paint. industrial organic chemical industries, cement production, electroplating waste incineration, gold mining, coal combustion, the chloralkali industry, inappropriate disposal of batteries, crematoria copper water pipes, marine paint (additives designed to control algal growth), metal-producing industries, waste incinerators burning of fossil fuels, incineration of municipal waste, smelting of zinc, lead and copper, corrosion of galvanised water pipes, electroplating, manufacture of batteries (NiCd)
chromium mercury copper
cadmium
Table E7 Heavy metals and their anthropogenic sources.
Pesticides
Pesticides are substances used to control or destroy pests. Pesticides include herbicides (kill plants), fungicides (kill fungi), insecticides (kill insects), algicides (kill algae) and rodenticides (kill rodents). Some pesticides are added directly to water and others enter the water as run-o from agricultural land. One of the most famous (infamous) insecticides is DDT (Figure E7). Although relatively non-toxic to humans, DDT has been banned in many countries due to its adverse e ects on the ecosystem birds have been particularly a ected.
CCI3 CI C H CI
Figure E7 DDT. O
Dioxins
O O Figure E8 Compounds from which dioxin is derived. CI CI Figure E9 Dioxin. a O O CI CI
The term dioxins is usually used to describe the polychlorinated derivatives of the compounds in Figure E8. Dioxins are produced as byproducts in the manufacture of some chlorinated organic compounds. They are also produced if the temperature is not high enough (below about 1200C) when waste materials containing organochlorine compounds are incinerated. The most toxic of these derivatives is called 2,3,7,8-TCDD (or just TCDD or 2,3,7,8-tetrachlorodibenzo-p-dioxin, or just dioxin). The structure of this is shown in Figure E9. This is very persistent in the environment (high chemical stability and poorly biodegradable) and very poisonous. Its e ects include liver damage, the skin disease chloracne and damage to the peripheral nervous system.
b CI CI
PCBs
PCBs are polychlorinated biphenyl compounds. There are 209 possible PCBs where between 1 and 10 H atoms in the basic biphenyl structure (Figure E10a) are replaced by Cl atoms. An example of a PCB is shown in Figure E10b. PCBs are chemically inert, non- ammable and stable at high temperatures. They were used in electrical transformers and capacitors
CI Figure E10 (a) The basic biphenyl structure; (b) a PCB.
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because of their high electrical resistance and so factories making these would have discharged PCBs into the environment. PCBs have not been manufactured in the USA since 1979 but because they are unreactive they persist in the environment for a long time. They also accumulate in fatty tissue and have been linked to low reproduction rates among some marine animals and are thought to be carcinogenic (cancer-causing) in humans. PCBs can be passed from mother to child in milk.
Other pollutants in water

The sources of nitrates, phosphates and organic matter in water have been discussed on page 18 and this information is summarised in Table E8.
Pollutant nitrates Source waste water efuent both from cities and industrial plants or the run-off from agricultural land where articial fertilisers are being used Effects eutrophication levels too high in drinking water cause methemoglobinemia (the oxygen-carrying capacity of the blood is reduced this particularly affects babies (blue baby syndrome)) and possible link with some cancers eutrophication
phosphate
waste water efuent or the run-off from agricultural land where articial fertilisers are being used; detergents used in the home leaves, animal manure, dead plants and animals in water; efuent from water treatment plants
organic matter
bacteria present in human and animal wastes affect health fecal coliform, E. coli and cryptosporidium can cause diarrhoea, nausea, etc.
Table E8 The sources and environmental effects of nitrates, phosphates and organic matter in water.
Waste water treatment

Water from towns and cities is usually treated before it is returned to rivers. Treatment involves three main stages.
Primary treatment
At a sewage works primary treatment usually involves three stages. 1 Filtration/screening: mechanical screens are used to remove large solid objects (e.g. sticks, paper, rags). The screens are raked from time to time and the solid material transported to a land ll site. 2 Settling/grit removal: this occurs in a grit chamber where smaller particles (e.g. sand, grit) settle due to gravity. 3 Sedimentation: the water is transferred to a primary sedimentation tank (primary clari er). Grease and oil oat to the surface and can be removed by skimming. Suspended colloidal particles aggregate together and sink to the bottom of the tank as sludge. The process of sedimentation can be improved by adding aluminium sulfate. Under alkaline conditions (if the water is not suitably alkaline, extra alkali must be added) this forms insoluble aluminium hydroxide: Al3+(aq) + 3OH(aq) Al(OH)3(s) As the aluminium hydroxide forms it allows smaller particles to join together to form larger ones which settle out. This process is called coagulation and occulation.
CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011 E ENVIRONMENTAL CHEMISTRY 21
Secondary treatment
Secondary treatment uses bacteria to remove organic waste. There are three main methods used: the trickling lter, rotating biological contactors and the activated sludge process. Only the activated sludge process will be described here.
Activated sludge process Water from the primary treatment ows into an aeration tank (Figure E11) where air or oxygen is pumped in to ensure su cient oxygen is present to maintain aerobic conditions for the decomposition of the organic matter. The water in the aeration tank is mixed with sludge from the secondary settling tank, which contains a high concentration of bacteria that can break down organic matter. After several hours the water passes into the secondary settling tank where the activated sludge settles out. Some of this sludge is returned to the aeration tank.
secondary settling tank
water in
water out
aeration tank
sludge settles out air air air air excess sludge removed
activated sludge recycled
Figure E11 The activated sludge process.
Tertiary treatment
Tertiary treatment is used in some water treatment plants to remove suspended solids, dissolved organic compound and dissolved inorganic substances (nitrates, phosphates and heavy metals). Filtration can be used to remove suspended solids (e.g. through a bed of sand). Dissolved organic compounds can be removed by passing the water through activated carbon (carbon with a very high surface area). The compounds are adsorbed onto the surface of the carbon.
Removing phosphates Phosphates can be removed by making them into insoluble precipitates (e.g. by adding aluminium sulfate).
Al3+(aq) + PO43(aq) AlPO4(s)

Removing nitrogen compounds and nitrates Waste water contains nitrogen in the form of organic nitrogen compounds or ammonia/ammonium. The ammonium ion can be rst converted to the nitrate(V) ion by nitrifying bacteria:
NH4+(aq) + 2O2(g) NO3(aq) + 2H+(aq) + H2O(l) or and

22 E ENVIRONMENTAL CHEMISTRY
2NH4+ + 3O2 2NO2 + 2H2O + 4H+ 2NO2 + O2 2NO3

Denitrifying bacteria can then reduce nitrate(V) to nitrogen under anaerobic conditions. Methanol must be added as a source of carbon. 6NO3(aq) + 5CH3OH(aq) + 6H+(aq) 3N2(g) + 5CO2(g) + 13H2O(l)
Removing heavy metal ions Adding calcium hydroxide (increases pH) removes some heavy metals as insoluble precipitates, e.g.
The nitrogen compounds are thus removed as harmless nitrogen gas.
Cr3+(aq) + 3OH(aq) Cr(OH)3(s) Cu2+(aq) + 2OH(aq) Cu(OH)2(s) Not all metals can be removed by increasing the pH. Mercury, cadmium and lead are removed by bubbling hydrogen sul de (H2S) gas through the water to precipitate the insoluble sul des. Cd2+(aq) + H2S CdS(s) + 2H+(aq) The precipitates must then be removed from the water by sedimentation and ltration. Metal ions can also be removed by other techniques such as ion exchange.
Disinfection
Before waste water is released into the environment it may also be disinfected. Disinfection involves killing microorganisms present in the waste water. This can be accomplished using chlorine, UV light or ozone.
Obtaining fresh water from sea water

The process of obtaining fresh water from sea water is called desalination. Desalination is an expensive process and is generally only used when su cient fresh water is not available from other sources (e.g. in the Middle East). Fresh water obtained by desalination can be used for human consumption, agriculture or in industry. The two most commonly used processes for desalination are multistage distillation and reverse osmosis. The energy requirement of multistage distillation is roughly ve times that of reverse osmosis per cubic metre of water produced.
Multistage distillation
Sea water is heated by passing through the condensers in the ash chamber (Figure E12). All the chambers are maintained at low pressure so that water has a lower boiling point (a liquid boils when its vapour pressure equals atmospheric pressure). When sea water enters the rst chamber it is hotter than its boiling point at that pressure and ashes to steam. The steam (fresh water) condenses (transferring its heat to the sea water inlet) and is collected. The remaining brine then passes to the next chamber (which is at a lower pressure). Although the brine entering this chamber is at a lower temperature because the pressure in the chamber is lower it once again ashes to steam. This process is repeated in up to 40 chambers.
Reverse osmosis
Osmosis is where a solvent passes through a membrane from a less concentrated solution to a more concentrated one.
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sea water in heater steam condenses
fresh water out decreasing pressure flash chamber
pressure
semipermeable membrane
brine out decreasing temperature
Figure E12 Multistage distillation.

large hydrated ions movement of water
salt water
fresh water
Figure E13 Reverse osmosis.
In reverse osmosis (Figure E13), applying high pressure (up to about 80 atm) to sea water forces water to pass through a semipermeable membrane leaving the salt behind, i.e. the water moves from the more concentrated salt solution. The membrane only allows small water molecules to pass and not relatively large hydrated ions, e.g. Na+(aq) and Cl(aq). Some of the advantages and disadvantages of multistage distillation and reverse osmosis are considered in Table E9.
Reverse osmosis water must be pre-treated to remove solids and prevent microbial growth on the membrane risk of bacterial contamination of membranes
Multistage distillation
water is higher purity land area needed for a plant is larger more expensive energy costs thermal pollution from discharging hot waste brine into the environment higher volume of sea water required per m3 of fresh water produced
no membrane is perfectly impermeable to salt capital costs of building a plant lower membrane needs to be replaced periodically generally less expensive per m3 but costs can depend on local factors waste brine discharged into the environment has much higher salt concentration
Table E9 Advantages and disadvantages of multstage distillation and reverse osmosis.
Test yourself
14 Draw the structure of two PCBs that contain 4 Cl atoms.
A saturated solution is one in which the maximum amount of the substance is dissolved at that temperature.
HL
Solubility product constant

Even substances that we regard as being insoluble in water are soluble to a certain extent. In a saturated solution of a salt, an equilibrium will exist between the dissolved and the undissolved salt, e.g. BaSO4(s) Ba2+(aq) + SO42(aq)
This is a heterogeneous equilibrium.
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An equilibrium constant, known as the solubility product constant, can HL be derived for this system as: Ksp = [Ba2+(aq)][SO42(aq)] The concentration of the solid does not appear in the equilibrium expression as it is essentially constant. In general, for a salt of formula, MXn dissolving: MXn(s) Mn+(aq) + nX(aq) Solubility product constants are only applicable to sparingly soluble salts.
Ksp = [Mn+(aq)][X(aq)]n The units of Ksp can be worked out from the equilibrium expression as (mol dm3)x where x is the total number of ions in the formula unit. Thus x = 2 for AgCl and 3 for Fe(OH)2 and the units of the solubility product constant for AgCl are mol2 dm6 and mol3 dm9 for Fe(OH)3. The units of the solubility product constant are often omitted. The solubility product constant can be worked out from the solubility.
Worked example
Given that the solubility of iron(II) sul de is 2.5 109 mol dm3 at 298 K, calculate the solubility product constant. The equilibrium that is established is: FeS(s) Fe2+(aq) + S2(aq)
The expression for Ksp is: Ksp = [Fe2+(aq)][S2(aq)] Since the solubility of the iron(II) sul de is 2.5 109 mol dm3 the concentration of each ion in solution will be 2.5 109 mol dm3 and the solubility product constant will be given by: Ksp = (2.5 109) (2.5 109) = 6.3 1018 mol2 dm6
If the product of the concentration of the ions (taking into account the number of each ion present) is less than the solubility product constant, the substance will be soluble at that temperature, but if the product is greater than the solubility product constant some solid must precipitate out of the solution to bring the value back down to equal the solubility product constant. The origin of the ions does not matter. Thus, using FeS as an example: if the product of the concentrations of Fe2+ and S2 in a solution at 298 K is less than 6.3 1018, all the FeS will remain in solution. If su cient Fe2+ or S2 ions are added to raise the product of the concentrations above 6.3 1018, some FeS must precipitate out of the solution.
For a salt AB, if [A2+(aq)][B2(aq)] > Ksp then AB must precipitate out of the solution. If [A2+(aq)][B2(aq)] < Ksp then all AB will remain in solution.
25
HL
The common ion effect

A substance AB will be less soluble in an aqueous solution of A2+ or B2 ions than in water. If we consider the equilibrium AB(s) A2+(aq) + B2(aq)
adding A or B ions will shift the position of equilibrium to the left (Le Chateliers principle).
Worked example
Given that the solubility product constant of Ni(OH)2 is 6.5 1018 mol3 dm9 at 298 K, calculate the solubility of nickel(II) hydroxide in water and in 0.10 mol dm3 sodium hydroxide solution. Solubility in water: Ni(OH)2(s) Ni2+(aq) + 2OH(aq)
If the number of moles of Ni(OH)2 that dissolves is represented by s, the concentration of Ni2+(aq) will be s and that of OH(aq) 2s Ksp = [Ni2+(aq)][OH(aq)]2 6.5 1018 = s (2s)2 i.e. 6.5 1018 = 4s3 Solving this equation we get s = 1.2 106 mol dm3 The solubility of nickel(II) hydroxide in water under these conditions is thus 1.2 106 mol dm3 This calculation has been simpli ed by ignoring the hydroxide ions that come from the dissociation of water. The solubility is, however, su ciently high that this is a reasonable approximation. Solubility in 0.10 mol dm3 NaOH(aq) Sodium hydroxide is fully ionised so the concentration of OH ions in solution will be 0.10 mol dm3. Since the concentration of hydroxide ions is signi cantly higher than the solubility of Ni(OH)2 in water we will assume the concentration of hydroxide ions remains constant at 0.10 mol dm3. We can substitute this value into the Ksp expression: Ksp = [Ni2+(aq)][OH(aq)]2 6.5 1018 = [Ni2+(aq)][0.10]2 i.e. [Ni2+(aq)] = 6.5 1016 mol dm3 The concentration of nickel(II) ions is the same as the solubility of nickel(II) hydroxide since each time one Ni(OH)2 unit dissolves, one Ni2+ ion is formed. Therefore the solubility of nickel(II) hydroxide in 0.10 mol dm3 sodium hydroxide is 6.5 1016 mol dm3. This is signi cantly lower than its solubility in pure water. The addition of a common ion has reduced the amount of Ni(OH)2 that can dissolve at a certain temperature.
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Removal of heavy metal ions and phosphates from water in water treatment
The common ion e ect is used to precipitate heavy metal ions and phosphates from solution. Since many heavy metal hydroxides have extremely small Ksp values, adding hydroxide makes even very low concentrations of these ions become insoluble, so they precipitate out of solution, e.g. Cu(OH)2(s) Cu2+(aq) + 2OH(aq)
HL
Adding hydroxide ions causes the position of equilibrium to shift to the left. Hydroxide ions must be added until the product [Cu2+(aq)] [OH(aq)]2 is greater than Ksp. Similarly, bubbling hydrogen sul de through the water increases the concentration of sul de ions and can cause heavy metal ions to precipitate out as sul des, e.g.: CdS(s) Cd2+(aq) + S2(aq)
The position of equilibrium shifts to the left. Phosphate ions PO43 ions can be removed from water by adding aluminium sulfate. This precipitates aluminium phosphate (AlPO4) which has a Ksp of 1.4 1021 mol2 dm6. AlPO4(s) Al3+(aq) + PO43(aq)
In a later stage of the water treatment process, a coagulant is added to facilitate the formation of a sludge containing the heavy metals and other insoluble substances. The sludge settles out, is separated, dried and disposed of in land ll sites. Since it is so insoluble it does not present signi cant toxic issues to the environment.
Worked example
a A body of water contains a cadmium concentration of 1.2 1015 mol dm3. Hydrogen sul de is bubbled into the water to raise the concentration of sul de ions to 5.6 1015 mol dm3. Given that the solubility product constant for CdS is 1.6 1028 mol2 dm6 at 298 K, determine whether any cadmium sulfate will precipitate out. Ksp = [Cd2+(aq)][S2(aq)] If we work out the product [Cd2+(aq)][S2(aq)] we get: (1.2 1015) (5.6 1015) = 6.7 1030 mol2 dm6 This value is less than the solubility product constant and so all the cadmium sul de will be soluble and none will precipitate. b More hydrogen sul de is bubbled into the water so that the concentration of sul de ions is increased to 1.0 109 mol dm3. Determine the mass of cadmium sul de that will be precipitated from 1.0 106 dm3 of water.
27
The concentration of sul de ions is signi cantly higher than the concentration of cadmium ions in the water so we will assume that any changes in the concentration of sul de ions due to CdS dissolving will be negligible so the concentration of sul de ions in the water will remain at 1.0 109 mol dm3. We can then substitute this value into the Ksp expression: Ksp = [Cd2+(aq)][S2(aq)] 1.6 1028 = [Cd2+(aq)] 1.0 109 [Cd2+(aq)] = 1.6 1019 mol dm3 The concentration of cadmium ions is thus reduced from 1.2 1015 mol dm3 to 1.6 1019 mol dm3. In order for this to happen cadmium sul de must precipitate out of the solution. The amount of cadmium sul de that must precipitate out is given by 1.2 1015 1.6 1019, i.e. 1.2 1015 mol dm3 to 2 signi cant gures. If the volume of water is 1.0 106 dm3 the number of moles of cadmium sul de that must precipitate out is given by 1.0 106 1.2 1015= 1.2 109 mol 144.46 is the Mr of CdS The mass of CdS is given by 1.2 109 144.46, i.e. 1.7 107 g
Test yourself
15 Calculate Ksp for each of the following.
Compound AgCl Fe(OH)2 Fe(OH)3 Solubility / mol dm3 1.3 105 5.8 106 9.3 1011
16 Given the solubility product constants in the table calculate the solubility of each substance in water at 298 K.
Compound PbSO4 Ag2S Ag3PO4 Bi2S3 Ksp 1.6 108 6.3 1051 1.8 1018 1.0 1097
18 Ksp of Co(OH)2 is 2.5 1016 mol dm3 at 25 C; 10.0 dm3 of water is known to contain Co2+ ions at a concentration of 1.2 107 mol dm3. Solid sodium hydroxide is added gradually to raise the pH in stages from 7 to 8 then from 8 to 9, from 9 to 10 and from 10 to 11. Determine at which stage Co(OH)2 will begin to precipitate out of the water. 19 The solubility product constant of aluminium phosphate is 9.8 1021 mol2 dm6 at 298 K. Given that the concentration of phosphate ions in 1.0 dm3 of water is 1.2 1011 mol dm3, calculate the mass of aluminium phosphate that precipitates when su cient solid aluminium sulfate is added to the water to increase the concentration of aluminium ions to 1.0 105 mol dm3.
17 Calculate the solubility of each of the following in 0.10 mol dm3 sodium hydroxide solution.
Compound Mn(OH)2 Cr(OH)3 Ksp 2.0 1013 1.0 1033
28
E7 Soil
Soil is the top layer of the Earths continental crust in which plants grow. It is therefore the part of the Earths crust that allows the production of most of the food required by living things. Soils are very varied and complex but they all contain: inorganic material rock fragments, clay particles, soluble nutrients, water, air organic material decaying material and living organisms. Soils are porous and contain air spaces. Soils are usually divided into layers called horizons, the uppermost of which is called the topsoil and contains most of the soil organic matter (SOM).
Learning objectives
Soil degradation
Soil degradation refers to the physical loss of topsoil (i.e. the soil is moved from one place to another by the action of wind or water) and to the reduction in quality of topsoil. Here we will look at some of the factors that a ect the quality of the topsoil.
Salinisation
This is the process that causes soils to contain high levels of water-soluble salts. Ions that are present in increased concentrations are Na+, K+, Mg2+, Ca2+ and SO42. One of the causes of soil salinisation is excessive irrigation. Water used for irrigation contains dissolved salts and, on evaporation of the water, these are left behind in the soil. If the soil is poorly drained and/or there is low rainfall in that area, these salts accumulate. Plants cannot grow well in salty soil because the excess salt reduces their ability to take up water. Soil salinisation can be treated by applying extra water, containing very low levels of dissolved salts, to the soil, although this must be used with caution as it can cause high levels of salts in groundwater. Another approach to the problem is to switch the land use to growing crops, such as barley or cotton, that have a higher tolerance to salt. Plants will die when the concentration of salts in the soil is higher than in the root cells as osmosis will cause the water to move from the plant to the soil.
Discuss causes of soil degradation Outline the functions of soil organic matter (SOM) Describe the importance of SOM in preventing soil degradation Describe the physical and biological functions of SOM List common organic soil pollutants and their sources Explain what is meant by HL cation-exchange capacity Understand the e ect of soil pH on cation-exchange capacity and the availability of nutrients Describe the chemical functions of SOM
Salinisation tends to be a large problem in arid and semiarid regions, where the rate of evaporation of water is high, the rainfall is low and irrigation must be used to provide su cient water.
The levels of dissolved salts present in soil can be measured by mixing the soil with water and measuring the electrical conductivity of the solution.
Nutrient depletion
When plants grow they remove nutrients and minerals from the soil. If the plants die where they grow these nutrients are returned to the soil. However, harvesting crops removes the nutrients and, if they are not replaced, the soil becomes less fertile and the crop yields decrease. One way of dealing with the problem is to add arti cial fertilisers to the soil to replace nutrients and minerals. Excessive use of arti cial fertilisers can, however, lead to other problems such as eutrophication, as discussed on page 18. Crop rotation may also be used to reduce the problem.
29
The soil food web is the complex system of interdependent organisms that live in the soil. These range from plants and bacteria to nematodes, arthropods and small animals.
Soil pollution
Soil pollution (soil contamination) can arise from many sources (e.g. overuse of fertiliser, pesticides, chemical dumping, chemical spillages, road run-o , leaching from land ll sites). Fertilisers and pesticides (these can kill bene cial organisms as well as harmful ones) can disrupt the soil food web reducing the number of species present in the soil (reduced biodiversity). The soil food web is essential for healthy, fertile soil and if this is disrupted the soil can ultimately be ruined. Excessive use of pesticides and fertilisers can also have other consequences as these chemicals can run o the soil into rivers and lakes and also move through the soil and pollute groundwater. There are many ways to treat contaminated soil. These include digging it all up and dumping in a land ll site, incineration, bioremediation (use of plants, trees, microbes).
Soil organic matter (SOM)

Soil organic matter (SOM) is the organic part of soil and is vital for a healthy, fertile soil. The SOM includes undecayed plant and animal tissues, their partial decomposition products and soil biomass (living organisms in the soil, including microorganisms). Humus constitutes about 3555% of the non-living part of SOM. The decomposition products from organic matter in soil can be classi ed as humic and non-humic substances. Non-humic substances are released directly from cells and include identi able, high-molecular-mass molecules such as proteins and polysaccharides (e.g. starch) and simpler substances such as amino acids and sugars. Humus or humic substances are formed when organic matter is broken down by a series of di erent soil organisms. The substances present in humus are listed in Table E10.
Component fulvic acids humic acids humin Solubility soluble in alkali and does not form a precipitate when a strong acid is added soluble in alkali but forms a precipitate when a strong acid is added insoluble Colour yellow, yellow-brown dark brown, black black
Table E10 Substances present in humus.
Fulvic and humic acids are not single substances but complex mixtures of large molecules. They act as weak acids and are important in maintaining soil pH.
The functions of SOM

The functions of SOM can be divided into physical, biological and chemical roles. Here we will discuss the biological and physical functions. The chemical functions will be discussed in the Higher Level section on page 35.
30
Physical
SOM improves soil water retention, alters soil thermal properties and improves the structural stability of the soil. The SOM allows the soil to retain more water. This protects the soil against erosion. Soil particles come together to form aggregates (peds) with pores between them and it is these that give rise to the structure of soil. SOM is essential for the formation of these aggregates. Soil structural stability is a measure of how soil is able to maintain its structure when exposed to various stresses such as cultivation and irrigation. SOM helps to maintain the stability of the aggregates that are responsible for the soil structure. Generally, the higher the level of SOM, the darker the colour of the soil will be. Darker coloured soil absorbs more energy from the Sun. This does not, however, always make the soil warmer as a soil with a higher SOM content will also generally contain more water and water has a high speci c heat capacity, therefore more energy is needed to heat it up. The thermal properties of the soil are thus in uenced by the presence of SOM but the exact nature of the e ect may be di cult to predict.
Biological
SOM provides a source of energy and nutrients and contributes to the resilience of the soil system. An important biological function of SOM is to provide a source of energy for the metabolic processes that occur in the soil. Plants use photosynthesis to convert carbon dioxide and water into complex organic molecules and when the plants die these substances are used by other soil organisms (e.g. microorganisms) as a source of energy. SOM is an important source of nutrients such as nitrogen, phosphorus and sulfur that are essential for plant growth. When organic matter is broken down in the soil by microorganisms some of the compounds are converted into forms that can be used by plants and released into the soil. Soil resilience is a measure of how well the soil system is able to return to its initial state after some disturbance (e.g. adding chemicals to the soil), i.e. how stable the soil is. Generally, soils which contain a more diverse system of microorganisms are more resilient and resistant to disturbance.
Organic soil pollutants

Some common organic substances that can cause pollution of soil are given in Table E11. Anthracene (Figure E14) is an example of a polyaromatic hydrocarbon (PAH).
Figure E14 Anthracene.
Cation-exchange capacity
Cation-exchange capacity (CEC) is a measure of the amount of exchangeable cations (positively charged ions) in soil. The larger the CEC the more positively charged cations that can be made available by the soil. These cations (e.g. K+, Mg2+, Ca2+) are essential for plant health and therefore CEC is a good measure of soil fertility. Both clay minerals in soil
31
Soil pollutant petroleum hydrocarbons
Source spilt fuel (including from routine transport uses), leakage from underground storage tanks, inappropriate disposal of petroleum products
agrichemicals (agrochemicals) chemical products pesticides, fungicides, herbicides used in agriculture polyaromatic hydrocarbons (PAHs) or polycyclic aromatic hydrocarbons* or polynuclear aromatic hydrocarbons* polychlorinated biphenyls (PCBs) organotin compounds volatile organic compounds (VOCs) semi-volatile organic compounds (SVOCs) organic compounds that are less volatile (boiling points 240400 C) than VOCs
* Alternative names.
forest res and volcanic eruptions, incomplete combustion of wood and fossil fuels, petrol and diesel engines, asphalt manufacture discharged from factories making electrical transformers and capacitors pesticides, anti-fouling paint, an additive to PVC unburnt hydrocarbons from the internal combustion engine, solvents used in paints, varnishes, etc. chemical plants manufacturing plastics, pharmaceuticals and pesticides may be formed by incomplete combustion (larger PAHs count as SVOCs) plasticisers, ame retardants, pesticides
Table E11 Common organic substances that can cause pollution of soil.
HL and soil organic matter are able to exchange cations. Soil organic matter
has a very high CEC and contributes strongly to soil fertility. Nutrient ions (potassium, calcium and magnesium) are taken up by plants by exchange of the cations on the clay particles with H+ ions. [Clay]2 M2+(s) + 2H+(aq) H+ [Clay]2 H+(s) + M2+(aq)
Clay minerals are an important part of most soils. Clay particles are very small (usually less than 2 m). Clay minerals consist mainly of silicon, oxygen and aluminium joined together into a complex hydrous aluminium silicate structure. Clays have a layer structure where layers are held together by hydrogen bonding. Some of the silicon atoms (oxidation number +4) in clay particles can be replaced by aluminium (oxidation number +3) and some aluminium ions (Al3+) may be replaced by ions such as Mg2+ and Fe2+ that have a lower charge. This means that the clay particles are negatively charged and can bind cations. These cations are reasonably weakly bound and can then be replaced by other cations cation exchange.
Cation-exchange capacity is expressed in terms of milliequivalents (meq) per 100 g of soil (dry weight). 1 milliequivalent is 1 millimole of unipositive cations, i.e. 1 103 mol M+. Thus, if a soil sample has a CEC of 20 meq per 100 g, 100 g can exchange 20 1 103, i.e. 0.02 mol of K+ ions or 0.01 mol Mg2+ ions. CEC can also be expressed in terms of centimoles of charge per kg (cmolc kg1) these units are equivalent to milliequivalents per 100 g.
The effect of soil pH on cation-exchange capacity

In acidic soils, with a high concentration of H+ ions, a high proportion of the cation exchange sites are occupied by H+ ions which limits the ability of the soil to take up other nutrient ions. [Clay]2 M2+(s) + 2H+(aq) H+ [Clay]2 H+(s) + M2+(aq)
At low pH the higher concentration of H+ ions means that the above equilibrium shifts to the right and fewer metal cations are available in the soil for take up by plants. The released metal ions can be washed out of the soil. The cation-exchange capacity of some clay minerals can also be reduced at low pH by protonation of exposed surface OH groups. This reduces the CEC as cations will be repelled. clayAlOH(s) + H+(aq) clayAlOH2+(s)
32
At high pH some of the OH groups on the surface of the clay minerals in the soil ionise, which increases the negative charge of the clay particles and the ability to bind cations. The CEC thus increases. clayAlOH(s) + OH(aq) clayAlO(s) + H2O(l) In general, the CEC of soil increases with increasing pH making more nutrients available and the soil more fertile.
HL
Al3+ and H+ ions do not count as part of the CEC.
The effect of soil pH on availability of nutrients

The nutrients that will be discussed here are calcium, magnesium, iron, phosphorus, sulfur, copper and zinc. Iron, zinc and copper are classi ed as micronutrients (only required by plants in small amounts), whereas nitrogen and phosphorus (and potassium) as well as calcium, magnesium and sulfur are macronutrients. Aluminium will also be discussed although it is harmful to plants. The e ect of soil pH on nutrient availability is complex. Here we will discuss some of the factors that a ect the availability of nutrients such as whether a particular ion will be available in solution or whether it will form part of an insoluble precipitate, which cannot be taken up by plants, or whether the ion is adsorbed onto various mineral surfaces. pH also a ects CEC (see page 32). The ideal pH for soil is between 6.0 and 6.5 as most plant nutrients are in their most available state in this range.
Calcium and magnesium

These form insoluble carbonates at higher pHs. Ca2+(aq) + 2OH(aq) + CO2(aq) CaCO3(s) + H2O(l) At low pH there is also less Ca2+ available as the CEC of the soil is reduced, so the clay minerals cannot bind the Ca2+ ions as e ectively and they get leached away. Leaching washing of nutrients out of the soil.
Potassium
Potassium is less available at lower pH due to the CEC being reduced. The potassium ions are leached away and are not as available for uptake by plants.
Aluminium
When present in soil in the soluble form as Al3+(aq) ion, aluminium is harmful to plants. Al3+(aq) is only present in soil below pH 6 and only becomes a major problem below about pH 5. Aluminium ions can cause direct damage to roots and also reduce the availability of other nutrients by the formation of insoluble precipitates (e.g. aluminium phosphate). Aluminium ions can also bind to clay mineral particles and so reduce the CEC for desirable calcium, magnesium and potassium ions. Aluminium ions bind more strongly to clay minerals than other ions as they have a higher charge. More aluminium ions are available at lower pH as some aluminium minerals (such as kaolinite) tend to dissolve in acidic solution, e.g. Al2Si2O5(OH)4(s) + 6H+(aq) 2Al3+(aq) + 2H4SiO4(aq) + H2O(l)
kaolinite
33
HL
The aluminium ion produced has a high charge density and so causes polarisation of water. This hydrolysis reaction helps to replace the H+ ions used up in the dissolution reaction and can cause further breakdown of minerals. [Al(H2O)6]3+(aq) [Al(H2O)5(OH)]2+(aq) + H+(aq)
As the pH is raised aluminium ions will precipitate out of solution as aluminium hydroxide and therefore aluminium is less available at higher pH. Al3+(aq) + 3OH(aq) Al(OH)3(s)
Iron
Iron may be present in soil as Fe2+ and Fe3+. Iron is essential for plant growth. Soluble iron is more available at low pH because at high pH precipitation of the hydroxides occurs: Fe3+(aq) + 3OH(aq) Fe(OH)3(s) Fe2+(aq) + 2OH(aq) Fe(OH)2(s)
Nitrogen
Inorganic forms of nitrogen that are present in soil are ammonium (NH4+) ions and nitrate(V) (NO3) ions. At high pHs ammonium ions are converted to ammonia, which can be lost from the soil in gaseous form: NH4+(aq) + OH(aq) NH3(aq) NH3(g) NH3(aq) + H2O(l)
Nitrogen can be taken up by plants in the form of ammonium ions or nitrate(V) ions. Soil pH can a ect the availability of the di erent forms of nitrogen by in uencing microorganism activity (nitrifying bacteria) that can convert ammonium ions to nitrate ions. At lower pHs the ability of nitrifying bacteria to convert ammonium ions to nitrate ions is reduced and the ratio of ammonium : nitrate will be higher. Di erent plants have di erent preferences for taking up ammonium or nitrate ions. The relative availability of ammonium or nitrate ions will thus a ect di erent plants in di erent ways. The availability of soil clay minerals to bind ammonium ions will be reduced at low pH and they may be leached from the soil.
Phosphorus
Depending on the pH the main inorganic forms of phosphorus that are present in soils and can be used by plants are H2PO4 and HPO42. These two species will be in equilibrium and the position of equilibrium will be shifted to the right as the soil becomes more acidic. HPO4(aq) + H+(aq) H2PO4(aq)
Phosphorus is most available to plants between about pH 6 and 7. Below this pH it precipitates as aluminium or iron(III) phosphates. A simpli ed version of the reaction that occurs is: Al3+(aq) + PO43(aq)
34 E ENVIRONMENTAL CHEMISTRY
AlPO4(s)
The actual reactions that occur are more complex and species such as Al(OH)2H2PO4 may be formed. As discussed above, at low pH, clay minerals can develop a positive charge on the surface and this can allow phosphate ions to bind. This can also a ect the availability of phosphate ions. At higher pH phospate is less available because it forms a precipitate with calcium ions. Simpli ed versions of the reaction that can occur are: 3Ca2+(aq) + 2PO43(aq) Ca3(PO4)2(s) Ca2+(aq) + HPO42(aq) CaHPO4(s) As above, the actual reactions are more complex.
HL
Sulfur
Sulfur is taken up by plants in the form of the sulfate(VI) ion, SO42. Sulfate is readily available in the soluble form above about pH 6. As the pH is lowered and the surface of clay mineral particles can become positively charged the sulfate ions can be adsorbed onto these clay minerals and are held better in the soil and are less susceptible to leaching.
Zinc and copper

Zinc and copper are less available above pH 7. This is due to precipitation (e.g. as the hydroxides): Cu2+(aq) + 2OH(aq) Cu(OH)2(s) There will be less copper and zinc available at lower pH due to the lower CEC. The e ect of soil pH on the availability of nutrients is summarised in Table E12.
Nutrient calcium aluminium iron potassium nitrogen
Low pH less available due to reduced CEC more available due to dissolution of minerals more available due to dissolution of minerals less available due to reduced CEC NH4 less available due to reduced CEC, decrease in the activity of nitrifying bacteria will change the ratio of ammonium : nitrate ions less available due to precipitation of insoluble phosphates (iron/ aluminium) and adsorption onto mineral surfaces less available due to adsorption onto mineral surfaces less available due to reduced CEC less available due to reduced CEC
+
Intermediate pH available available less available due to precipitation less available due to precipitation available available
High pH less available due to precipitation as carbonate less available due to precipitation as carbonate less available due to precipitation as hydroxide less available due to precipitation as hydroxide available less available as given off as gaseous ammonia
magnesium less available due to reduced CEC
phosphorus
available
less available due to precipitation of insoluble phosphates (calcium)
sulfur zinc copper
available available available
available less available due to precipitation as hydroxide less available due to precipitation as hydroxide
Table E12 The effect of soil pH on the availability of nutrients.
35
HL
Chemical functions of soil organic matter (SOM)

SOM increases the ability of the soil to act as an acidbase bu er keeping soil pH fairly stable. It helps to bind pesticides, heavy metals and other organic and inorganic compounds in soil, thus reducing the environmental e ects they might have. SOM contributes to the CEC of the soil.
A phenol group is an OH group attached directly to a benzene ring:

OH
SOM has a high cation-exchange capacity. Thus, although a soil may only contain a small percentage SOM, this contributes an appreciable percentage of the total CEC. The cation-exchange capacity arises from the presence of many acidic functional groups (carboxylic acids and phenols) in humus. These weakly acidic groups will be partially dissociated, e.g. RCOOH RCOO + H+ RCOOK+ The carboxylate groups can then bind cations: RCOO + K+ The CEC of the SOM is more sensitive to pH than that of clay minerals. This is because, at low pH the acid groups are mostly in the undissociated form and unable to bind cations. SOM is a very important component in bu ering soil against changes in pH. The bu ering action arises mostly from the presence of carboxylic acid and phenol groups in the SOM. The exact nature of the reactions is complex due to the number of carboxylic acid and phenol groups present. Both undissociated and dissociated groups will be present in the SOM and an equilibrium will exist, that can be represented simply as: RCOOH RCOO + H+
If acid is added the soil then this will react with the RCOO group: RCOO + H+ RCOOH If base is added to the soil, this will react with the RCOOH group: RCOOH + OH RCOO + H2O As long as the there a large number of dissociated and undissociated groups present in the system the pH will remain fairly constant. Certain functional groups (carboxylic acid and phenol groups) in the SOM can act as ligands to metal ions and form stable complexes with these cations. The stability of these complexes is higher with more highlycharged ions. These stable complexes mean that heavy metal ions and aluminium are less available to be taken up by plants and are also less likely to be leached out into ground water. SOM binds to organic molecules such as herbicides in the soil. The exact nature of the interactions depends on the molecules involved but will include van der Waals forces and hydrogen bonding. This binding of organic molecules is important as it holds these molecules in the soil and does not allow them to be washed through to ground water.
Test yourself
20 A sample of soil has a CEC of 50 meq per 100 g. Explain what this means.
36
E8 Waste
Waste is basically anything that is no longer required and should be disposed of. This could be packaging from a chocolate bar, expanded polystyrene packaging used to protect a TV in transit, unwanted byproducts from industrial processes or mining, spent fuel rods from a nuclear power station.
Learning objectives
Methods of waste disposal

Landll
Land ll sites are used for the disposal of waste by burying it in a large hole. One of the key challenges when designing a land ll site is to contain liquid waste (including water that has passed through the land ll due to rain) and prevent it from contaminating the environment (ground water, soil, rivers, etc.). This liquid waste is called the leachate. The land ll consists of a pit with a base layer of compacted clay (low permeability to liquids) covered with a synthetic impermeable membrane. There is also a drainage system so that the leachate can be collected and treated. When the pit is lled the waste is covered with another impermeable membrane and layers of soil. Some of the waste dumped in land ll sites is biodegradable (e.g. food waste, paper, etc.) and some is non-biodegradable (e.g. most plastics). Biodegradable waste can be broken down by anaerobic bacteria to produce methane gas and carbon dioxide (both greenhouse gases). This methane gas can be collected and used as a fuel. In the European Union there is a move to reduce the amount of biodegradable waste that is dumped in land ll sites so that land ll sites can be used for mostly nonbiodegradable waste.
Compare the various methods of waste disposal Describe recycling of metal, glass, plastic and paper Describe the di erent types of radioactive waste Compare methods for storage and disposal of radioactive waste
Incineration
Incineration, or burning the waste, is an alternative to the use of land ll sites.Various technologies are employed in incineration plants, including moving grates, rotating kilns and uidised bed combustion. All systems must achieve a minimum temperature of 850 C and conditions must be optimised to achieve, as far as possible, complete combustion. The ash left over after combustion (bottom ash) is buried in a land ll site (it does, however, have substantially lower volume than the original waste) or can be used as aggregate for making roads. Some incinerators have systems for the recovery of recyclable materials (such as metals) either before or after combustion. Some of the heat produced in the incinerator can be recovered by heat exchange between waste gases and water and this can either be used in community heating projects or to generate electricity (the water must be converted to steam). One disadvantage, however, of combined heating and power schemes is that people often do not want these plants in the middle of their communities. Combustion of waste can produce polluting substances such as nitrogen oxides (NOx), SO2, particulates ( y ash), PAHs, acid gases, heavy metals and dioxins, however, more modern incinerators and stricter government regulations have signi cantly reduced the output of these. The emission of toxic substances, however, still raises health concerns for people living
The waste gases in modern incinerators are treated to remove, as far as possible, pollutants, including toxic gases and y ash. Alkaline scrubbing may be used to remove acid gases such as HCl and SO2 and activated carbon may be used to remove dioxins. Fly ash can be removed using lters and electrostatic precipitation.
37
nearby. Combustion also produces CO2, which is a greenhouse gas. Fly ash is considered as hazardous waste and, when recovered, must be disposed of in special land ll sites. The discussion here focuses on modern incinerators; older plants may burn waste at lower temperatures, which can produce higher levels of toxic substances, and have less e cient systems for removing hazardous substances from ue gases. Certain European countries, such as Denmark and Switzerland, incinerate large proportions of their waste but other countries, such as Spain, Finland and Ireland, use predominantly land ll sites. Some of the advantages and disadvantages of land ll and incineration are shown in Table E13.
Method of disposal Landll Disadvantages Unsightly, smelly and noisy May attract vermin Takes up large areas of land Gives off methane and carbon dioxide (greenhouse gases) when biodegradable waste is decomposed anaerobically May contaminate land Expensive (high capital costs and running costs) Can create pollutants (especially dioxins) Bottom ash must still be disposed of in landll sites Fly ash must be disposed of as hazardous waste Advantages Efcient for large volumes of waste Cheap The only method of disposing of some waste (e.g. ash from incineration) Methane gas can be used as an energy source Landll sites may be redeveloped for use by wildlife or for leisure activities Requires little space Signicantly reduces the physical volume of waste Bottom ash may be used as construction aggregate Can produce energy and/or heating
Incineration
Table E13 Advantages and disadvantages of landll and incineration.
Recycling of metal, glass, plastic and paper

Many of the problems discussed in the section above can be avoided/ reduced by e ective recycling programs. Recycling: preserves natural resources and raw materials uses less energy releases less CO2 into the atmosphere (since less fossil fuels are required than in the production of new materials) reduces waste and the need for land ll sites. However, the recycling processes described below all use energy and produce emissions and one way to reduce these is to reuse articles as much as possible.
Metal recycling
Metals that are commonly recycled include iron/steel, aluminium and copper. The advantages of recycling metals must be considered not just in terms of the environmental impact and energy consumption of the process to extract the metal from its ore (smelting) but also in terms of the mining process.
Metal recycling basically involves separating the di erent metals (e.g. steel is magnetic but aluminium is not, non-ferrous metals may be separated using eddy currents) and then melting and re-casting them. Recycling steel can result in an energy saving of up to about 74%, whereas recycling aluminium only uses about 5% of the energy compared with extraction from bauxite (aluminium ore). Metals produced by recycling may not be as pure as those produced directly from the ores and, for example, recycled aluminium is not suitable for some applications in the aerospace industry.
Glass recycling
Glass is separated according to colour, broken into smaller pieces then separated from other materials such as metal, paper, plastic (which are often present on glass bottles and jars). The glass is crushed, mixed with sand, sodium carbonate and limestone and melted. It is then remoulded into bottles and jars. Glass can be recycled continually without any loss of quality. Recycling glass uses less energy, produces less CO2 and uses less raw materials (sand, sodium carbonate, limestone).
Every tonne of recycled steel saves: 1.5 tonnes of iron ore 0.5 tonnes of coal 40% of the water required in production 74% of the energy needed to make steel from the original iron ore 1.28 tonnes of solid waste air emissions may be reduced by 86% water pollution may be reduced by 76%.
Plastic recycling
Plastics are derived from crude oil, a nite and valuable resource. There are many di erent types of plastics and before recycling they must rst be separated from each other. Plastic packaging and containers have recycling symbols on them, e.g. type 1 is PET (Figure E15) and type 2 is highdensity polythene (HDPE), to aid separation. Infrared spectroscopy may also be used to identify di erent types of plastic. Each di erent type of plastic is processed separately. The plastic is shredded and washed then melted, extruded through holes and chopped into pellets. These pellets can then be re-melted to make them into new products Not all plastics are equally easy to recycle. The most commonly recycled plastics are PET and HDPE as these contain least additives. Some plastics (e.g. PVC) containing higher proportions of additives may require more energy to purify them than would be required to make them from crude oil. Thermosets have cross-linking between polymer chains which means they cannot be re-melted and reformed; they are often crushed and used as insulation. Pyrolysis or cracking may also be used to recycle plastics. Pyrolysis involves heating plastics in the absence of oxygen to split them up again into smaller molecules that can be used as a chemical feedstock to make new plastics or as a fuel. Thermosets can also be processed in this way. PET, the main plastic used in zzy-drink bottles, can either be remelted and formed into new bottles or can be hydrolysed to break it down into its monomers. Plastic recycling is expensive (more expensive than dumping it in land ll sites) but it can, however, reduce energy consumption, reduce emissions of CO2, reduce the need for more land ll sites and conserve crude oil, which is an extremely valuable natural resource.
1
Figure E15 PET packaging symbol.
PET
39
Paper recycling
The paper is sorted, and water and chemicals added to produce a pulp. The pulp is ltered then de-inked to remove inks that can a ect the colour of the nal product. The pulp can then be converted into new paper. The bres in the paper are damaged by recycling so the grade of paper gradually degrades with recycling; it cannot be in nitely recycled like glass. The factors involved in determining whether recycled paper is better for the environment than producing new (virgin) paper are complex and many things must be considered. Producing recycled paper does require quite a lot of energy including transport of waste paper and the extra cleaning involved but overall, when the energy impact of growing and transporting trees etc are included it probably uses less energy than making new paper. Recycling paper does, however, consume more fossil fuels than producing virgin paper. Overall, recycling paper releases less greenhouse gases to the environment than burying it in land ll sites and making new paper. Recycling paper may however be more expensive than producing new paper. Recycling paper does, however, have the advantage that fewer trees must be cut down and there will be less waste in land ll sites.
Radioactive waste
Radioactive waste can be produced in nuclear power stations, research laboratories, military establishments, industry and hospitals. Numerous radioisotopes are used or produced in various processes and these have half-lives that vary enormously. Some such as 131I, which is used as a tracer in medicine has a half-life of just 8 days, whereas 239Pu, which is produced in nuclear power stations has a half-life of thousands of years. Radioactive waste can be divided into di erent categories: low-level and high-level radioactive waste. The category intermediate-level radioactive waste is also sometimes used. The classi cation of radioactive waste is important to determine how it can be disposed of and the safety measures that must be used in its transport and handling. The criteria used for the classi cation of radioactive waste are quite complex and low-level waste is divided into sub-categories (A, B, C and greater than C) depending on the activity. Generally, low-level waste has lower activity and usually contains isotopes with shorter half-lives.
Low-level waste
This includes items that have been contaminated with radioactive material or have been exposed to radioactivity. Examples of items that may be classi ed as low-level radioactive waste are gloves, protective clothing, tools, soil, rubble, carcasses of animals that have been treated with radioactive materials etc. Low-level waste may be stored on site until it has decayed to such an extent that it can be disposed of as ordinary waste or shipped to a central site for disposal. Low-level waste is often just buried underground (near surface disposal) for example in individual concrete canisters or in concrete-lined vaults. Some may even just be put into land ll sites. Low-level waste must be contained underground for up to 500 years depending on its activity.
High-level waste
This includes spent fuel rods or other materials from the reprocessing of nuclear fuels. It contains ssion products and transuranic (beyond uranium) elements generated in the reactor core. These have a high concentration of radioactive isotopes some of which (such as plutonium-239) in spent fuel will remain hazardous to humans and other living beings for thousands of years. Spent fuels rods may either be considered as waste and disposed of directly or reprocessed to extract usable material from them to be used as more nuclear fuel. High-level waste is rst stored on site at nuclear power plants in storage pools (cooling ponds). Storage under water is usually for a minimum of nine months but sometimes the spent fuel rods are stored in this way for decades. After su cient cooling the fuel rods may be transported to a reprocessing plant, left in the pools or transferred to dry storage casks. These dry casks have very thick walls and are made of steel and concrete. The dry casks are then stored in concrete bunkers. Most spent fuel rods from nuclear power stations in the US are left in cooling ponds or transferred to dry storage awaiting a more permanent method of storage. Permanent storage of high-level radioactive waste is a major problem and various solutions have been suggested such as burying the waste deep underground in stable geological areas. Over thousands of years, however, it is di cult to predict what processes could occur to cause release of the radioactive material.
Reprocessing of nuclear fuel produces highly radioactive liquid waste which can be converted to glass (vitri ed) to make storage easier.
E9 Smog
Photochemical smog
Photochemical smog can be seen as a brown haze hanging over cities such as Los Angeles soon after the morning rush to work. Photochemical smog can have adverse health e ects (such as eye irritation and respiratory problems), can damage plants and damage materials such as rubber. The conditions needed for the formation of photochemical smog are the presence of volatile organic compounds, nitrogen oxides, sunlight and a fairly stationary body of air. Ideal conditions for the formation of this fairly stationary body of air are a city in a bowlshaped valley, lack of wind and a temperature inversion.
HL
Learning objectives
Explain the conditions necessary for the formation of photochemical smog State the source of primary pollutants needed for photochemical smog Describe the formation of secondary pollutants in photochemical smog
Normally the temperature of the troposphere (the layer of the atmosphere closest to the Earth) decreases with altitude. These are favourable conditions for dispersal of pollutants formed at lower levels as the warmer air near the surface of the Earth can rise and cooler air can sink to take its place. In this way air can circulate and mix and pollutants are dispersed. A temperature inversion is the phenomenon of having a warmer layer of air above a cooler layer of air (Figure E16). This traps the cooler layer of air close to the Earth and prevents dispersal of pollutants.
41
HL
layer of warmer air cooler air trapped pollutants trapped
Figure E16 Temperature inversion.
Primary and secondary pollutants needed for photochemical smog

Volatile organic compounds (e.g. unburnt hydrocarbons) and nitrogen oxides (NOx) are the primary pollutants that give rise to photochemical smog. These come from internal combustion engines and are given out through vehicle exhausts. Nitrogen(II) oxide is formed when nitrogen reacts with oxygen at high temperatures in an internal combustion engine: N2(g) + O2(g) 2NO(g) NO can be oxidised to NO2 (nitrogen(IV) oxide, nitrogen dioxide) in the atmosphere: 2NO(g) + O2(g) 2NO2(g) NO2 is thus a secondary pollutant. In strong sunlight, the NO2 can break down to release an oxygen free radical which can then react with atmospheric oxygen to form ozone. Ozone is a secondary pollutant. While we consider ozone bene cial to the Earth in the upper atmosphere, at ground level it causes headaches, fatigue and can aggravate respiratory problems. It can also cause damage to plants. NO2 O + NO O2 + O O3 Ozone can also react with NO to form more NO2. O3 + NO NO2 + O2 Hydroxyl radicals are formed in photochemical smog: O + H2O 2HO These can react with NO2 to form nitric acid: HO + NO2 HNO3
UV light
Formation of peroxyacetylnitrates (PANs)

Hydroxyl radicals can also react with hydrocarbons: RCH3 + HO RCH2 + H2O The alkyl radical formed can react with oxygen to form a peroxy radical: RCH2 + O2 RCH2OO
42
This peroxy radical can react in a two-step reaction to form an aldehyde: RCH2OO + NO RCH2O + NO2
alkoxy radical
HL
O RCH2O + O2 RC + HOO H
aldehyde
Aldehydes are secondary pollutants and can cause eye irritation and respiratory problems.
The aldehyde can react further with hydroxyl radicals: O H O O O O RC + O2 RC O RC + HO RC + H2O
The series of reactions above all involve the using up and production of free radical and so may be regarded as propagation steps in a free radical chain reaction. Two free radicals can come together in a termination step: O RC O O O + NO2 RC O O NO2
a PAN (peroxy acyl nitrate)
If R = CH3 the compound is called peroxyacetylnitrate (PAN). PANs cause eye irritation and respiratory problems; they also damage plants. The primary and secondary pollutants present in photochemical smog are summarised in Table E14.
Substance NO VOCs NO2 O3 PANs aldehydes Type of pollutant primary primary secondary secondary secondary secondary
Photochemical smog develops during the day. The early morning rush of tra c produces the primary pollutants required. Then as the Sun becomes more intense towards midday the photochemical reactions to produce the secondary pollutants occur and the smog reaches its maximum. As the Sun goes down the photochemical reactions stop.
Table E14 Primary and secondary pollutants in photochemical smog.
43
Exam-style questions
1 a Identify three primary pollutants produced in car engines and explain how each one is produced. b Write an equation to show how two of the primary pollutants in car exhaust react together when passing through a catalytic converter. 2 Primary air pollutants include nitrogen oxide(s), sulfur dioxide and hydrocarbons. a Explain the di erence between a primary pollutant and a secondary one. b Give an example of a secondary pollutant formed from NO. 3 Suggest one natural source for each of the following primary pollutants. a nitrogen oxide, NO b sulfur dioxide, SO2 c volatile organic compounds,VOCs 4 a Rainfall is naturally slightly acidic. Suggest the range of pH which would be considered to be appropriate to describe the pH of rain as acid rain. b Identify two polluting substances that dissolve in rain water to make it acidic and write an equation for each one reacting with water. c Suggest two ways in which the emissions of the polluting substances identi ed in part b could be decreased. d Explain brie y how acidic soil can damage plants and trees. e Write an equation for the reaction of acid rain on marble statues or limestone. f Write an equation to explain how the addition of calcium oxide to lakes neutralises the e ects of acid rain. 5 a The greenhouse e ect is a natural phenomenon. It occurs as a result of the way the Earths atmosphere interacts with the radiation from and to space. i The radiation absorbed from space heats the Earths surface. What type of radiation is absorbed from space? ii The warmed Earth now radiates energy back into space. In what way is this radiation di erent from that in part i? iii Greenhouse gases reduce the e ect in part ii. Explain how they can do this. iv Why may human activity be increasing the e ect of the natural greenhouse e ect? b Explain how each of the following statements can both be true? I Carbon dioxide is the most important greenhouse gas. II Methane is a much more important greenhouse gas than carbon dioxide. c Many people think that global warming is at least in part caused by the increasing concentrations of carbon dioxide in the atmosphere. Name some possible e ects of global warming. [1] [1] [1] [2] [1] [3] [2]
[1] [3] [2] [2] [1] [1]
[1] [1] [2] [2] [2]
[2]
44
6 a The presence of ozone in the upper atmosphere is important for life on Earth. i Which type of radiation does ozone absorb in the upper atmosphere? ii Suggest two e ects that ozone depletion could have on life on Earth. b Chloro uorocarbons (CFCs) are one type of pollutant responsible for ozone depletion. Suggest three properties required for hydro uorocarbons (HFCs) to be considered as alternatives to the use of CFCs. 7 a The biological oxygen demand (BOD) is a term applied to water. Explain what this term means and explain the di erence between the BOD of pure water and water containing organic waste. b The concentration of dissolved oxygen in river water can depend on local activities like farming and industry. Describe and explain what happens to the concentration of dissolved oxygen in river water: i when farmers use large quantities of fertilisers on the elds nearby. ii when a local factory, which uses water for cooling an industrial process, releases warm water into the river. c The concentration of dissolved oxygen in water can be measured by the Winkler method which involves redox reactions. 100 cm3 of water taken from a river was analysed using this method. The reactions taking place are summarized below. Step 1 Step 2 Step 3 2Mn2+(aq) + 4OH(aq) + O2(aq) 2MnO2(s) + 2H2O(l) MnO2(s) + 2I(aq) + 4H+(aq) Mn2+(aq) + I2(aq) + 2H2O(l) 2S2O32(aq) + I2(aq) S4O62(aq) + 2I(aq)
[1] [2] [2]
[3]
[2] [2]
i Is the O2 oxidised or reduced in step 1? Explain your answer. ii State the change in oxidation number for manganese in step 2. iii If 0.0002 moles of S2O32 were used in the titration in step 3, calculate the amount, in moles, of oxygen, O2, dissolved in the original 100 cm3 of water. 8 a State two di erent methods by which sea water can be converted into fresh water. Explain the essential features of each of the methods. b The majority of the water on Earth is sea water but there is much demand for fresh water. Suggest three main uses for fresh water. 9 a Discarded electrical equipment can pollute groundwater with substances known as PCBs which can cause harmful medical conditions in humans including cancer and damage to the immune and reproductive systems. What do the letters PCB stand for? b State two possible sources of mercury compounds in water. 10 Water treatment involves three stages: primary, secondary and tertiary. a What gets removed from the water during the primary stage? b In the secondary stage oxygen and bacteria are used. What is removed at this stage? c Heavy metal ions are removed in the tertiary stage. How is this done and what substances are used in this stage?
[2] [1] [2]
[3] [2]
[1] [2]
[1] [1] [2]
45
11 a The amount of soil organic matter (SOM) is important to the structure and function of a productive soil. It is a dark-coloured complex mixture often referred to as humus. i What is the source of the SOM in soil? [2] ii List two functions of SOM in soil. [2] b Two problems that a ect the composition of the soil and that lead to soil degradation are salinisation and nutrient depletion. i Explain what causes salinisation and what are its main e ects. ii Explain what causes nutrient depletion and how it can be overcome. 12 a List two advantages and two disadvantages of land ll as a means of disposal of waste materials. b There are two types of nuclear waste: high level and low level. Explain this di erence and suggest how the problem of disposing of each type is dealt with. c Paper, glass and steel are all recycled successfully for re-use but they are all made from readily available raw materials. i Why is it better to recycle these materials rather than make them from new raw materials? ii Explain the main steps in recycling paper. iii Why is it so much more di cult to successfully recycle plastics?
HL 13 a Identify two primary pollutants in photochemical smog.
[2] [2] [4] [6]
[2] [2] [2] [1] [3] [3]
b Ozone is a secondary pollutant in photochemical smog. Explain with the aid of equations the role of NO2 in ozone formation. c Explain how photochemical smog develops in some cities during the day. 14 Lead ions, Pb2+, can be precipitated from polluted water by treating the water with hydrogen sul de, H2S. The solubility product constant (Ksp) of lead(II) sul de at 298 K is 1.25 1028. a De ne the term solubility product constant by referring to lead(II) sul de. b Calculate the concentration of sul de ions in a saturated solution of lead(II) sul de. c State what is meant by the common ion e ect and explain how it can be used to lower the concentration of lead ions in a saturated solution of lead(II) sul de. 15 An important feature of any soil is its cation-exchange capacity (CEC). a Explain how clay minerals contribute to the CEC of soil. b Explain how the CEC is a ected by the pH of the soil.
[1] [2] [3]
[2] [4]
46

Environmental Chemistry

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E Environmental chemistry

E1 Primary air pollution

Nitrous oxide (nitrogen(I) oxide, dinitrogen oxide, nitrous oxide)

Particulates (particulate matter)

Diesel engines are a major source of particulates resulting from transport.

Volatile organic compounds (VOC)

lightning; action of soil bacteria volcanic activity; decay of organic matter

catalytic converter; lean-burn engines

uidised bed combustion; alkaline scrubbing

pollen, dust, soot from forest res and sea spray

CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

SO3(g) + H2O(l) H2SO4(aq)

CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

Problems associated with acid deposition

Methods of dealing with acid deposition

CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

The role of ammonia in acid deposition

E3 The greenhouse effect

The sources and relative effects of the main greenhouse gases

solar radiation reflected

outgoing infrared radiation

incoming solar radiation (shorter wavelength)

Figure E1 The greenhouse effect.

CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

Gas H2O CO2 CH4 N2O O3

CFCs refrigerants, propellants, foaming agents, solvents

Gas CO2 CH4 N2O CFCs

Contribution to global warming / % 55 15 6 24

Gas CO2 CH4 N2O CFC-11

Global-warming potential (20 years) 1 72 289 3800

Table E4 The global-warming potential of various gases over 20 years.

The inuence of increasing amounts of greenhouse gases on the atmosphere

CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

oxygen free radicals

This rst process is just the reverse of the formation of ozone.

Pollutants that cause ozone depletion

UV-B O3 O + O2 UV-A Earths surface

CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

Chemical CFC-11 CFC-12 HFC-134a C4F10 HCFC-22 HCFC-123 butane

How the wavelength of light affects photolysis of O2 and O3

Figure E4 The OO bond in O3.

Ozone thus absorbs UV-C and UV-B radiation.

Catalysis of O3 depletion by CFCs and NOx

chlorine free radical

CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

All reactions occur in the gaseous state.

O atoms are available from the dissociation of oxygen or ozone.

Nitrogen oxides, NOx

Ozone depletion in polar regions

CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

Aerobic and anaerobic decomposition of organic material in water

Oxidation number of element +4 +5 +6 +5

Oxidation number of element 4 3 2 3

Table E6 Aerobic and anaerobic decomposition of organic material in water.

Redox equations for the decomposition of organic matter

and 2NO2 + O2 2NO3

CHEMISTRY FOR THE IB DIPLOMA CAMBRIDGE UNIVERSITY PRESS 2011

Thermal pollution in water

16 14 Dissolved oxygen concentration/ppm 12 10 8 6 4 2 0 0 10 20 30 Temperature /C 40 50

Figure E6 The variation in dissolved oxygen in fresh water with temperature.

Heavy metal lead

chromium mercury copper

Table E7 Heavy metals and their anthropogenic sources.