12ChF322 Chemistry of the Air

Chemistry of the Air

Candidates should be able to: (a) explain that infrared radiation is absorbed by C=O, OH and CH bonds in H2O, CO2 and CH4, and that these absorptions contribute to global warming; (b) explain that the Greenhouse Effect of a given gas is dependent both on its atmospheric concentration and its ability to absorb infrared radiation; (c) outline the importance of controlling global warming resulting from atmospheric increases in greenhouse gases; (d) outline the role of chemists in minimizing climate change resulting from global warming by: (i) providing scientific evidence to governments to verify that global warming is taking place, (ii) investigating solutions to environmental problems, such as carbon capture and storage, CCS, ie the removal of waste carbon dioxide as a liquid injected deep in the oceans, storage in deep geological formations, by reaction with metal oxides to form stable carbonate minerals, (iii) monitoring progress against initiatives such as the Kyoto protocol; (e) explain that ozone is continuously being formed and broken down in the stratosphere by the action of ultraviolet radiation; (f) using the chemical equilibrium O2 + O O3: (i) describe and explain how the concentration of ozone is maintained in the ozone layer, including the role of ultraviolet radiation, (ii) outline the role of ozone in the absorption of harmful ultraviolet radiation and the essential benefit of this process for life on Earth; (g) understand that radicals, eg from CFCs, and NOx from thunderstorms or aircraft, may catalyse the breakdown of ozone by the following simple representation: R + O3 RO + O2 RO + O R + O2 where R represents Cl from a CFC or NO from nitrogen oxides; (h) for carbon monoxide, oxides of nitrogen and unburnt hydrocarbons: (i) explain their formation from the internal combustion engine, (ii) state environmental concerns from their toxicity and contribution to low-level ozone and photochemical smog; (i) outline how a catalytic converter decreases carbon monoxide and nitrogen monoxide emissions from internal combustion engines by: (i) adsorption of CO and NO to the catalyst surface, (ii) chemical reaction, (iii) desorption of CO2 and N2 from the catalyst surface; (j) outline the use of infrared spectroscopy in monitoring air pollution.

The composition of the (dry) atmosphere is 21% oxygen, 78% nitrogen, 1% "other gases" of which the main one is 0.93% Argon. It is the remaining trace gases which dominate the behaviour of our atmosphere of our planet. These gases include carbon dioxide which is present at about 0.04% - however only a couple of hundred years ago it was 0.03%. The amount has increased by a quarter as a result of industrialisation and the burning of fossil fuels for energy. We will study the atmosphere under three headings: Climate Change The Ozone Layer Pollution of the lower atmosphere

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12ChF322 Chemistry of the Air

Climate Change
This is a huge area of global focus and concern, at the interface of science and politics. It is easy to construct scary stories about impending global catastrophe which makes marketing "green" products and initiatives easy based on consumer guilt and worry. Is it all about carbon dioxide ? No global warming is a result of molecules in the atmosphere absorbing the infrared emitted by the earth after it has been heated by the sun, rather than allowing this infrared to escape. Bonds that absorb infrared radiation include C=O, O-H and C-H bonds, so CO2, H2O and CH4 are all greenhouse gases, but so are lots of other trace gases. The infrared absorbed causes the bonds in these molecules to vibrate. How significantly a greenhouse gas contributes to Global Warming depends on - how strongly the bonds in it absorb infrared (e.g. recall C=O absorbs strongly at about 1700cm-1) - how much of that gas is present in the atmosphere H2O from the evaporation of oceans and lakes is most abundant CO2 is the 2nd most abundant; from volcanic eruptions, respiration, burning and decay of organic matter (including fossil fuel) CH4 is 3rd most abundant, (but makes a greater contribution to global warming than the same amount of CO2 because of the strong absorption of its four C-H bonds). It arises from rotting organic waste (in forests, landfill etc., as a by-product of digestion released from e.g.cows, emitted during the processing of fossil fuels

Work of research chemists in trying to minimise climate change dues to greenhouse gases: - develop Carbon Capture and Storage (CCS) see next paragraph - providing evidence to governments or international conferences - educating society or writing in journals/documentaries/books etc. - monitoring atmospheric changes - developing alternative energy sources e.g. fuel cells/solar power/fuel that don't produce CO2 - develop more efficient engines/learn burn engines/hybrid engines - find uses of CO2 e.g. dry cleaning, decaffeinating coffee, fizzy drinks etc. Methods that could be developed for CCS - store CO2 as liquid injected deep into the oceans - store CO2 under sea-bed or in suitable deepgeological formations - reaction of CO2 with metal oxides to form carbonates

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12ChF322 Chemistry of the Air

The Ozone Layer

Complex life on earth would not be possible, or at least would have evolved very differently, if we were fully exposed to the ultraviolet content of the sun's radiation. Harmful skin cancers and sunburn are caused by overexposure to ultraviolet radiation. Ozone (O3), represented as O=OO, is not normally present in the atmosphere close to the earth's surface, but 25km up in the stratosphere there is a layer containing ozone which is about 15km thick. This ozone absorbs ultraviolet radiation, preventing it from reaching the earth's surface. The "hole" in the ozone layer was discovered where the layer had significantly thinned over the Antarctic, allowing harmful uv through. The main cause of the hole in the ozone layer was found to be chlorine radicals. The presence of chlorine radicals in the stratosphere (which weren't there a few decades before!) was mainly attributed to the use of refrigerant and fire-suppressant gases called chlorinated fluorocarbons (CFCs). To understand how all this works, we need to appreciate that ozone is present in equilibrium with oxygen, and that uv is able to cause homolytic fission of covalent bonds: (we saw this before in initiation of the free radical substitution mechanism) O3 O2 + O: 300nm uv radiation breaks the bond in ozone forming an oxygen molecule and an oxygen radical.

Note: the oxygen di-radical has two unpaired electrons - consider its electron arrangement 1s2 2s2 2p4 (2px2 2py1 2pz1) rather than three lone pairs. O2 O: + O: Higher energy 242nm uv radiation breaks the stronger O=O bond forming two oxygen radicals

The reverse reaction in the equilibrium takes place when O reacts with O2 in the atmosphere: O: + O2 O3 So overall we can say O3 O2 + O:

The presence of chlorine radicals in the ozone layer is most likely to be due to the action of uv light on C-Cl bonds, e.g. in CFCs such as CF2Cl2 and CFCl3
Cl F C Cl F Cl

C F

+ Cl

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12ChF322 Chemistry of the Air The chlorine free radical then acts as a catalyst for the decomposition of ozone, being regenerated each time. It has been estimated that one chlorine radical can destroy approximately 1000 ozone molecules before it is terminated in a reaction with some other radical such as CF2Cl or another Cl. Propagation steps: Cl + O3 ClO + O2 ClO + O Cl + O2 The use of CFCs was phased out in the Montreal Protocol of 1987, but some of the replacement substances, such as C2H2F4 are also greenhouse gases. There is still concern about ozone depletion despite Montreal protocol and CFCs being banned and replaced in products beacause: - CFCs may take a long time to reach ozone layer/long residence time - CFCs are still being used in some countries/some products - there are other ozone-depleting substances than CFCs Compounds which contains C-Cl are not the only ones which supply radicals that can destroy ozone. The role of nitrogen monoxide (NO) is also of concern. Thunderstorms are a major natural source of this gas, but they are also created in the upper atmosphere by the high-temperature combustion of nitrogen and oxygen from the air inside jet engines. N2(g) + O2(g) 2NO(g) The fate of NO in the atmosphere is complex. Some is oxidised and combines with moisture to form HNO3 (nitric acid) contributing to acid rain. What happens in the stratosphere are the following propagation steps (in this case no initiation step is needed): NO + O3 NO2 + O2 NO2 + O NO + O2 destroying the ozone regenerating the NO so it can keep on reacting

It is worth noting that these two reactions are the same as those occurring with the chlorine radical, so we can generalise the destruction of the ozone layer to: R + O3 RO + O2 RO + O R + O2

where R is NO or Cl

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12ChF322 Chemistry of the Air

Pollution of the lower atmosphere

The main gases we are concerned about in the air layer that we live in and breathe are carbon monoxide, oxides of nitrogen, and hydrocarbons. We monitor the concentration of gases such as these using infrared spectrometers. The pollutants can be identified by matching their infrared spectra up with reference spectra in databases. The concentration of key gases can be monitored by measuring the amount of absorption of infrared at wavelengths characteristic to the bonds in e.g. CO, NOx and the most common polluting hydrocarbons. A network of monitoring stations across the country, and in other countries, allows monitoring and modelling to predict future trends and impacts. Carbon monoxide Origin: incomplete combustion of hydrocarbons/fossil fuels with limited oxygen in internal combustion engines, heat and power generation e.g. C8H18 (main alkane in petrol) + 8 O2 8CO + 9H2O Problem: Toxic, odourless, colourless Hydrocarbons Origin: unburnt or partially-burnt fossil fuels. Longer-chain molecules in diesel engines don't always burn completely, but produce particulates (tiny particles of carbon coated with unburnt hydrocarbons) Problem: Unburnt benzene (C6H6) is particularly dangerous because it is carcinogenic. The smaller particulates get deep into the lungs causing respiratory problems and asthma. Particulates in the atmosphere reflect sunlight back causing global dimming (plants photosynthesise less effectively, surface gets less warmed). Low-level ozone and photochemical smog - see later Nitrogen Oxides (NOx): Source: At the high temperatures inside internal combustion engines, N2 in the air burns, reacting with O2 to form a variety of oxides of nitrogen, the main ones being NO and NO2. The NO oxidizes within 30 minutes or so to NO2. Problems: NOx can be oxidized and react with atmospheric moisture to produce acid rain. Low-level ozone and photochemical smog see later Catalytic converters Fitting cars with exhaust catalyst systems has been a legislative requirement for all newly built cars for many years. The catalytic converter contains a honeycomb structure of aluminium or ceramic (large surface area) coated with a thin layer of alloy of Pt, Pd and Rh (expensive) on the surface of which a number of important reactions are catalysed as the exhaust gas flows over them. The catalyst is heated by the hot gases from the engine, and

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12ChF322 Chemistry of the Air catalysts only work at high temperature, so that catalyst systems in cars are only effective on longer journeys after they have warmed up. Heterogeneous catalysis (solid catalyst, gaseous reactants) takes place on the catalyst surface: i) Unburnt hydrocarbons removed by fully burning them in the remaining oxygen in the gas stream C8H18(g) + 12 O2 8CO2 + 9H2O ii) NO, NO2 and CO are removed by using the NOx to oxidize the CO: NO, NO2 and CO are adsorbed on the catalyst surface, weakening the bonds in these molecules (i.e. lowering the activation energy for them to react) Reaction takes place: 2 NO+ 2 CO N2 + 2 CO2 2 NO2 + 4CO N2 + 4 CO2 N2 and CO2 are desorbed and leave the vehicle in the exhaust gas stream Low-level ozone and photochemical smog The cocktail of CO, NO, NO2, water vapour and unburnt hydrocarbons released into the lower-level atmosphere, forms a mixture in which radical reactions can take place: i) ii) ozone is generated, which is very toxic complex organic molecules are created in the upper atmosphere but can be carried down such as CH3COO2NO2 (PAN) which causes breathing difficulties. In bright sunlight and still air, with a high concentration of pollutants in the atmosphere (rush hour in a big city) a brown haze can be seen (caused by the high concentration of NO2 molecules) indicating a severe risk. This is photochemical smog.

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