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C1 Iron, steel and aluminium
Iron is a high-density, magnetic transition metal and the most abundant element on Earth owing to its presence in the Earth’s core (it is usually regarded as the fourth most abundant element in the Earth’s crust). Iron is vital for life as part of haemoglobin in red blood cells, but its primary industrial uses are as a building material and for conversion to steel. Iron is a fairly reactive metal and is rarely found native (in an elemental from); it reacts with oxygen to form a mixture of oxides and can combine with other elements to form a number of ores. The main mineral sources of iron include: Haematite: Fe2O3 – iron(III) oxide Magnetite: Fe3O4 – a mixed ore of iron(II) oxide and iron(III) oxide Siderite: FeCO3 – iron(II) carbonate Goethite: FeO(OH) – hydrated iron(III) oxide Limonite: FeO(OH).nH2O – a mixture of hydrated iron(III) oxides The largest producers of mined iron ore are China, Australia and Brazil, producing between 250 and 500 million tonnes of iron ore annually.
Describe the manufacturing processes for iron, steel and aluminium Understand how the modi cation of iron, steel and aluminium a ects their properties and uses Describe the environmental impact of ore and metal production
The blast furnace
Usable iron ores can be chemically reduced from the oxide forms to yield metallic iron. Although iron is reasonably reactive, it is below carbon in the reactivity series. Iron can be reduced from its +2 or +3 oxidation states to the element by reacting it with carbon or carbon monoxide. A specialised brick-lined furnace, called the blast furnace (Figure C1), is used to reduce iron ores to metallic iron, as the process requires extremely high temperatures. In addition to iron ore, a number of other raw materials are needed in the reduction process. These include: • coke – as a source of carbon, produced from heating coal in the absence of oxygen • hot air – as a source of heat and oxygen • limestone (mostly CaCO3) – to react with impurities in the ore. The solid raw materials are added from the top of the furnace. Once the furnace has been charged with the raw materials, hot, oxygen-enriched air at between 900 and 1300 °C is blown in to the furnace from the bottom through pressurised inlet pipes called tuyères. The heat from the injected air causes a series of reactions to take place, which result in the reduction of the iron ore. The temperature inside the furnace may reach in excess of 2300 °C.
Wüstite, FeO and iron pyrite, FeS2, are two additional mineral sources of iron. These are, however, rarely used in the manufacture of the metal because of: (1) scarcity in the case of wüstite; and (2) being used in other processes, such as the production of sulfur dioxide and iron(II) sulfate from iron pyrite.
Examiner’s tip Other than mineral sources, an important source of iron is through the recycling of scrap iron and steel.
If the temperature in the furnace drops too much, fuels such as hydrocarbons are injected into the hot air blast to provide extra heat energy and carbon monoxide when they combust: 2CH4(g) + 3O2(g) → 2CO(g) + 4H2O(l)
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input of raw materials waste gas outflow
450 °C HOT
HOTTEST 1750 °C slag tap hole iron
Figure C1 The blast furnace for the reduction of iron ore to molten iron.
Reactions in the blast furnace
Inside the furnace, carbon monoxide (CO) acts as the primary reducing agent. Carbon monoxide may be produced in two ways in the blast furnace. The combustion of coke can produce carbon monoxide: 2C(s) + O2(g) →2CO(g) This reaction is exothermic, and the energy released helps to maintain the extremely high temperatures required in the blast furnace. Coke can also react with carbon dioxide (produced either when limestone decomposes or when some coke burns in oxygen): CO2(g) + C(s) → 2CO(g) The hot carbon monoxide rises up the furnace and reacts with the iron ore, reducing it to molten iron and becoming oxidised to CO2 in the process. The overall reaction is: Fe2O3(s) + 3CO(g) → 2Fe(l) + 3CO2(g) Iron is reduced, as its oxidation number decreases from +3 to 0. The molten iron formed falls to bottom of the furnace, where it pools, waiting to be tapped o .
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Carbon in the coke may also act as a reducing agent: Fe2O3(s) + 3C(s) → 2Fe(l) + 3CO(g)
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The iron ore added to the furnace is a mixture of iron oxides. In the blast furnace, a number of di erent reactions occur between the reducing gases and the ores, depending on the temperature and position in the furnace. These reactions serve to purify the iron by gradually reducing the oxygen content of the ore: 3Fe2O3(s) + CO(g) → 2Fe3O4(s) + CO2(g) 2Fe3O4(s) + 2CO(g) → 6FeO(s) + 2CO2(g) 6FeO(s) + 6CO(g) → 6Fe(l) + 6CO2(g) Combining the equations we get: 3Fe2O3(s) + 2Fe3O4(s) + 6FeO(s) + 9CO(g) → 2Fe3O4(s) + 6FeO(s) + 6Fe(l) + 9CO2(g) which simpli es to: Fe2O3(s) + 3CO(g) → 2Fe(l) + 3CO2(g) 450 °C 600 °C 700 °C Top of furnace
Hot, unreacted gases exit at the top of the furnace and are circulated back to the tuyères at the base of the furnace, providing a ‘jump start’ to the air-heating process. This recycling helps to reduce the energy requirements of the industrial process.
The iron ores are not pure and contain a signi cant amount of impurities, usually in the form of silicon and aluminium oxides, which have very high melting points. These contaminant compounds are removed by reaction with calcium oxide (CaO) produced by the thermal decomposition of the limestone: CaCO3(s) → CaO(s) + CO2(g) CaO(s) + SiO2(s) → CaSiO3(l) Alumina (Al2O3) dissolves in the molten calcium silicate (CaSiO3) to form a complex aluminosilicate slag. This slag is less dense than the molten iron and oats on top of the pool of iron. It can be tapped o separately. Molten slag is processed into pellets by spray cooling; these pellets are used as an aggregate in roadmaking or used to produce cement.
The molten iron formed in the blast furnace is still impure, despite the removal of the high-melting-point impurities. This iron contains small amounts of sulfur, phosphorus and silicon, as well as up to 5% carbon. Iron with a carbon content this high is called pig iron and is extremely brittle as a solid and therefore of limited usefulness. In order to remove the impurities and to reduce the carbon content of the iron, a process called basic oxygen conversion is employed (Figure C2). Molten iron is poured into a vessel lined with calcium oxide and magnesium oxide. Hot, 99% pure oxygen is injected at high pressure into the molten iron and causes many of the impurities to be oxidised. C + O2 → CO2 4P + 5O2 → P4O10 Si + O2 → SiO2
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hood input of CaO, Mg, Mn, etc
tap-hole when tilted
CaO/MgO refractory lining O2 O2
Figure C2 The basic oxygen converter, which removes impurities from the molten iron and converts it to steel.
During the basic oxygen conversion process, the carbon content of the iron is reduced to 0.1–2.0%, depending on the grade of steel desired.
The CO2 escapes as a gas; the phosphorus(V) oxide and silicon(IV) oxide react with added calcium oxide (lime) to form a layer of calcium phosphate (Ca3(PO4)2) and calcium silicate (CaSiO3) slag. Sulfur is removed by adding a large quantity of powdered magnesium, which reduces the sulfur to magnesium sul de in an extremely violent exothermic reaction. This reduction reaction and the basic oxidation reactions are all exothermic and produce the heat necessary to keep the iron molten and the reaction rate high. However, the temperature of the process must be carefully controlled in order to produce steel of the desired quality. To prevent the temperature from rising too high, scrap steel is added to the vessel, which melts when the reaction temperature is high enough, preventing it from increasing further.
Alloying metals changes the mechanical and chemical properties of the metal product: for example, resistance to corrosion, hardness and strength. The properties of steel can be modi ed by adding di erent transition metals to the molten steel towards the end of the steelmaking process. The conferred properties of the steel alloy will depend on the identity of the metal added. The alloying process allows the production of metal alloys for speci c purposes based on their properties (Table C1). An alloy is a homogeneous mixture of two or more metals, or a mixture of a metal and non-metal. Brass is an example of a twometal alloy, containing copper and zinc; mild steel is an alloy of iron and the non-metal carbon.
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Steel heat treatment Di erent heat treatments on simple carbon steel (i. Typically. water or salt solutions. machine and car parts nails. CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 C CHEMISTRY IN INDUSTRY AND TECHNOLOGY 5 . more ductile steel. malleable. steel with no added metals) can a ect the mechanical properties of the steel. the steel is heated to between approximately 200 and 250 °C (although the exact temperature depends on the type of steel) and then cooled slowly in a controlled manner. Annealing Annealing results in softer. The rapid cooling of steel heated to over 900 °C causes the metal to increase in hardness and strength. The steel is then control cooled and. Quenching can be carried out in cool gas.Metal added Amount added / % chromium vanadium nickel 10–15 0. hard. corrosion resistance ultra-high strength even at high temperature. it causes the rearrangement of the carbon atoms within the steel structure. railings. easily machined <0. depending on the carbon content of the steel – and held at that temperature for a long period. In the tempering process. properties such as hardness. Steel is heated to a much higher temperature than required for tempering – between 700 and 1000 °C. brittle 2–4% carbon. strength and impact resistance are enhanced. gates.01% carbon. that is.e. Properties and uses of steel and iron The properties and uses of some di erent types of iron and steel are shown in Tables C2 and Table C3. wear resistance. as with tempering.25–5 10 Properties corrosion resistance increased strength increased strength. easily welded Uses steelmaking piping. yielding highly ductile steel. aircraft and missile parts molybdenum 1–8 Table C1 Various modiﬁed steel alloys with their associated characteristics and uses. piping. ductile. This modi es the crystal structure within the alloy. Type of iron pig iron cast iron wrought iron Properties high carbon content (4–5%). easily welded Uses stainless steel in kitchenware and cutlery tools stainless steel applications tools. Tempering and quenching often go hand-in-hand to reduce the brittleness of hardened steel. resulting in a new form that is less brittle. brittle. Quenching Quenching is the process of rapid cooling. owing to the formation of a new internal crystal structure. oil. rarely produced now Table C2 The properties and uses of different forms of iron. chains. a structural rearrangement of the atoms in the alloy occurs. Tempering Tempering increases the toughness and malleability of the steel.
Amphoteric oxides and hydroxides are able to act as a base or an acid. bauxite. Electrolysis of alumina Owing to the high reactivity of aluminium. relies on the amphoteric nature of aluminium oxide and hydroxide and the basic nature of other metal oxides. CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 Smelting (extraction of the aluminium) is an expensive and energy-intensive process that uses huge amounts of electricity. Therefore.15–0. Many aluminium smelters are therefore located near to hydroelectric or other power stations to ensure a good (and preferably cheap) supply of electricity. In the Bayer process.g. high-strength wires. kitchenware. Heating the alumina to this temperature and then maintaining it for the electrolytic process would cost more in energy and electricity than the aluminium produced at the end would be worth. not ductile. reacting with sodium hydroxide. called the Bayer process. very strong and hard 15% chromium. punches. This requires melting the alumina (so that the strong electrostatic forces between the oppositely charged ions are broken). corrosion resistance. major appliances Table C3 The properties and uses of different forms of steel.5–2% carbon. strong. the ions must be free to move. In the rst step of aluminium production.3–0. 10% nickel.Type of steel mild steel medium carbon steel high and ultra-high carbon steel stainless steel Properties 0. axles cutlery.3% carbon. Aluminium Aluminium is a low density. Reﬁning bauxite The bauxite is crushed and then dissolved in hot sodium hydroxide at 175 °C. 6 C CHEMISTRY IN INDUSTRY AND TECHNOLOGY . It is the most abundant metal in the Earth’s crust. however. aluminium hydroxide is acting as an acid. e. surgical equipment. This causes the hydroxide to decompose into alumina and water: 2Al(OH)3(s) → Al2O3(s) + 3H2O(l) This process.5% carbon. balanced car parts (body and engine) strength and ductility 0. reactive metal not found native in nature. The resulting solution is cooled. The aluminium compounds dissolve to form sodium tetrahydroxoaluminate (NaAl(OH)4): Al(OH)3(s) + NaOH(aq) → NaAl(OH)4(aq) AlO(OH)(s) + NaOH(aq) + H2O(l) → NaAl(OH)4(aq) but the impurities are insoluble and can be ltered out. will corrode Uses structural steel used in construction 0. malleable. specialist uses. In order to conduct electricity. electrolysis must be employed in order to extract it from alumina. a clever method is employed to produce molten alumina at lower temperatures. wear resistance. is a mixture of aluminium hydroxide (Al(OH)3) and hydrated aluminium oxides (AlO(OH)) with iron oxide impurities. alumina (Al2O3) must be extracted from the bauxite and puri ed. Aluminium is more reactive than iron and carbon and cannot be extracted by heating with carbon or carbon monoxide. The principal ore of aluminium. cheap. and this causes solid aluminium hydroxide to precipitate from solution as u y. hard springs. Alumina is an ionic solid comprising Al3+ and O2− ions. alumina has a very high melting point (2072 °C) owing to the high charges on the individual ions. white crystals: NaAl(OH)4(aq) → Al(OH)3(s) + NaOH(aq) The aluminium hydroxide crystals are removed from the solution and heated to over 1000 °C in a process called calcination.
and several large graphite blocks suspended from a support are immersed in the molten uid. Aluminium ions are attracted to the cathode at the base of the cell. which acts as the cathode. The free oxide ions are attracted to the suspended graphite anodes and are oxidised to oxygen. The application of a current causes the free ions to move towards the oppositely charged electrode. well above that of the molten alumina. The electrolytic cell is made of steel. + electrolyte crust molten cryolite and alumina + steel casing refractory lining molten aluminium graphite cathode tap-hole Figure C3 The Hall–Héroult cell for the electrolysis of molten alumina/cryolite. Examiner’s tip The usefulness of state symbols on the ion in these half equations is dubious. and so remains pooled at the bottom of the cell until it is tapped o . Now that the aluminium and oxide ions are no longer held in a lattice and are free to move. Hundreds of cells are lined up in series. 2O2−(l) → O2(g) + 4e− CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 3+ − The internal resistance of the passage of electricity through the molten cryolite generates enough heat to keep the compounds molten without the need for an external heat source such as a furnace. CaF2 (a far more common mineral). and there is not nearly enough of it easily extractable from the crust to use in aluminium production.Alumina will dissolve in molten cryolite (sodium aluminium uoride. Graphite is used for a number of reasons: • it conducts electricity well • it is cheap and easily replaced • it is relatively inert • it has a high melting point. and a huge current of several hundred thousand amps is applied through the circuit. with a refractory ceramic lining to withstand the high temperatures. and soda ash (sodium carbonate). A solution of aluminium oxide in cryolite is formed and costs much less to keep molten. where they gain electrons and are reduced to liquid aluminium: Al (l) + 3e → Al(l) Elemental aluminium is denser than molten cryolite. Na3AlF6) which melts at only 1012 °C (a full 1060 °C lower than alumina itself). Electrolysis of dissolved alumina is called the Hall–Héroult process (Figure C3). graphite anode Extension Cryolite is an uncommon mineral. they can be separated in an electrolytic cell. these act as the anode. C CHEMISTRY IN INDUSTRY AND TECHNOLOGY 7 . The base of the cell is further lined with graphite. Most cryolite used in aluminium smelting nowadays is produced synthetically by reacting some of the sodium tetrahydroxoaluminate from the Bayer process with hydro uoric acid obtained from uorspar. but if one is required in the examination then ‘(l)’ is probably most appropriate. The molten mixture of alumina and cryolite sits on top of this graphite cathode.
Mining • • • • • • • Opencast mining causes irreversible damage to the landscape. malleability. Mining machinery and transportation of ore creates signi cant pollution. sheet metal in vehicle production Properties and uses of aluminium Some properties and uses of aluminium are shown in Table C4. CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 8 C CHEMISTRY IN INDUSTRY AND TECHNOLOGY . ductility high reﬂection Table C4 The properties and uses of aluminium. used in aircraft • Silumin (silicon): strong and highly corrosion resistant. Use aircraft. cookware overhead power cables mirrors.The overall reaction for the process is: 2Al2O3(l) → 4Al(l) + 3O2(g) The high temperatures in the cell cause the oxygen gas produced at the anode to react slowly with the graphite. SO2. motorcycle frames. Blast furnace The blast furnace produces signi cant amounts of greenhouse and toxic gases (CO2. Unused waste products such as slag are pollutants. Much of the oor space of aluminium smelters is taken up with anode recycling. corrosion resistance corrosion resistance. bicycle. packaging (foil. low density. Aluminium alloys Aluminium can be alloyed with numerous metals to alter its mechanical properties. The blast furnace is unsightly and noisy. reﬂectors (heat and light) Related properties low density. Despite being a reactive metal that oxidises readily. good heat conductance. less malleable and more durable than aluminium alone. copper disrupts the lattice structure and prevents the layers sliding past one another as easily. etc. but susceptible to corrosion. Examples of aluminium alloys include: • Duralumin (copper): strong. Waste from coke production is polluting. oxidising the carbon to carbon dioxide: C(s) + O2(g) → CO2(g) The anodes gradually erode away and have to be replaced periodically. Environmental impact of iron and aluminium production Production of aluminium and iron has a signi cant e ect on the environment. This protects the more reactive metal underneath. cans). This is because of the formation of a thin. malleability good electrical conductance. strength. This is done by recycling the unreacted graphite and re-pressing it into blocks with new graphite. Examiner’s tip For a discussion of the advantages of recycling metals see Option E on the CDROM. and wherever possible these metals should be recycled. aluminium is a corrosion-resistant and inert material in many of the forms in which it is used. Most aluminium alloys are harder. easily welded. CO. NOx). used in humid environments • Birmabright (magnesium): strong. The blast furnace requires lots of energy (ultimately from fossil fuels) to keep the reaction temperature high. This is because of the incorporation of metals of di erent sizes – for example. unreactive and impermeable layer of aluminium oxide on the surface of the metal.
5O2 → 8CO2 + 9H2O ∆H = −5470. • Diverts oil supplies away from use as a chemical feedstock. 2 Write an ionic equation. The aluminium smelter is unsightly and noisy. diesel and fuel oil. only nd and tap new pockets yet to be discovered. such as coal.red power stations. which may come from fossil-fuel. ‘Red mud’ waste from bauxite re ning is unsightly and polluting when disposed of. Hazardous uorine compounds are produced from cryolite. This may seem a lot. and in more modern times as a chemical feedstock for producing petroleum-based products such as plastics. • Easy to store and transport owing to the majority of fuel compounds being easily compressible gases or liquid at room temperature. • Relatively cheap compared with renewable fuels. CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 C CHEMISTRY IN INDUSTRY AND TECHNOLOGY 9 . but global daily usage is about 85 million barrels. With a burgeoning world population. with more in unproven or probable reserves. C2 The oil industry Oil as an energy source or chemical feedstock? Crude oil is one of humankind’s most useful and used resources.5O2 → 4CO2 + 5H2O C8H18 + 12.25 trillion barrels (170 billion tonnes). including state symbols. it is only a limited resource.Aluminium smelter • • • • • The aluminium smelter requires huge quantities of electricity.We cannot ‘make’ oil.2 kJ mol−1 • More e cient release of heat energy compared with other traditional sources of energy. heated remains of prehistoric sea life. Learning objectives • • describe the use of crude oil as a fuel and a chemical feedstock describe the main di erences between the various types of cracking of petroleum products Crude oil as an energy source Advantages • Good source of combustible hydrocarbons from re nery gases (propane. meaning these proven reserves will provide oil for a mere 40 years before they are depleted. Suggest why electrolysis is not used for the production of iron. produced millions of years ago from the compressed. through gasoline (mainly octane) to aviation fuel (kerosene). For centuries it has been used as a source of heat and energy. wood and peat.5 kJ mol−1 C4H10 + 6. • Complete combustion of these hydrocarbons liberates large quantities of energy: ∆H = −2876. to show the reaction that occurs when aluminium hydroxide dissolves in sodium hydroxide solution. However. as carbon chain increases in length). Current estimates put the world’s proven oil reserves at 1. CO2 and SO2 byproducts are polluting. Disadvantages • Production of greenhouse gas (CO2) and poisonous carbon monoxide (complete combustion is less likely. butane). oil usage is likely to increase over that time period. Test yourself 1 Both iron and aluminium can be extracted from their ores using electrolysis.
they vaporise and decompose to form a mixture of smaller hydrocarbons. given the number of alternatives such as coal. a signi cant proportion of the bulk of crude oil is less-useful. but the products octane. etc. thermal cracking and steam cracking. longer-chain alkanes that combust less e ciently and are. e. There are three di erent methods for cracking alkanes: catalytic cracking.Crude oil as a chemical feedstock Advantages • Excellent source of compounds for making plastics and synthetic bres. Ultimately. • Excellent source of precursors for production of petrochemicals including pharmaceuticals. less pro table for oil companies. Cracking – formation of alkenes The process by which long-chain alkanes are split into shorter alkanes and alkenes is called cracking. From a chemical point of view. • It diverts oil away from production of fuels. nding alternative fuels is an easier proposition than nding alternative sources of chemicals for polymerisation. nuclear power and renewable sources.: C10H22 → C8H18 + C2H4 Do not forget that the equation must balance! Crude oil is a good source of highly combustible short-chain alkanes. The global demand for plastics and petrochemicals is huge. • When incinerated. • Source of compounds for other uses. road building. e. which is 10 C CHEMISTRY IN INDUSTRY AND TECHNOLOGY CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 . the exact reaction is di erent every time. and the most chemically straightforward manufacturing process is from crude oil. however. ethene and propene are far more valuable. Examiner’s tip Although the following methods produce a number of products. The alkanes are passed over a hot powdered catalyst at over 700 °C. Many would argue that using crude oil as a fuel is less appropriate. natural gas. generally.g. including alkenes: C16H34 → C8H18 + C2H4 + 2C3H6 octane ethene propene The C16 compound could be used a fuel oil. CO and toxic halogenated gases. Disadvantages • Polymers and petrochemicals are di cult to dispose of (they are nonbiodegradable). propane. Possible catalysts that can be used include alumina (Al2O3) and silica (SiO2). use of crude oil as both a fuel and as a chemical feedstock needs to be reduced if global reserves are to remain during our lifetimes. often a simple equation showing the production of one alkane and one alkene will su ce. The original alkane may split into any number of alkanes and alkenes of varying length. Catalytic cracking This process is used industrially to break alkanes with lengths in excess of 14 carbon atoms and tends to produce gasoline-length products.g. these produce CO2. waxes and lubricants. although most modern facilities use a zeolite. • Alternative renewable and environmentally ‘friendly’ sources of polymers are becoming increasingly available. When the alkanes come into contact with the catalyst. which cannot be used as chemical feedstock to the same degree. These longer-chain alkanes can be used as a chemical feedstock to produce both shorter-chain alkanes (for gasoline) and alkenes for making polymers and plastics. A balance needs to be struck as to which is the most prudent use of this dwindling resource.
Test yourself 3 Write an equation to show the cracking of an alkane with 20 C atoms. This causes homolytic ssion of C–C bonds within the alkanes to form alkyl free radicals. propane and ethane. disposal problems with non-biodegradable plastics generated from the polymerisation of alkenes.: CH3CH2CH2CH3 → 2CH3CH2• Initiation These free radicals can then undergo internal rearrangement to yield alkenes or react further (propagation and termination) to produce a variety of di erent products. The alkanes are mixed with superheated steam (>1000 °C) in a furnace in the absence of oxygen. e. global warming due to the combustion of hydrocarbon fuels. Thermal cracking This method of cracking alkanes involves a free radical mechanism. Zeolites have a porous three-dimensional structure that permits maximum e ciency and some control over the sizes of the products. water pollution if a leak or spillage of crude oil occurs. The mechanism by which steam cracking works also relies on free radicals. The reaction occurs in a fraction of a second. e. Environmental impact The re ning of crude oil into more useful products has a signi cant impact on the environment. Primary areas of concern are: air pollution caused by volatile hydrocarbons at the re nery and the combustion of the nal products. octane and one other product. CH3CH2• + CH3CH2CH2CH3 → CH3CH2CH3 + CH3CH2CH2• Propane produced CH3CH2CH2• → CH3CHCH2 + H• CH3CH2• → CH2CH2 + H• CH3CH2• + H• → CH3CH3 Propene produced Ethene produced Ethane produced Steam cracking Steam cracking is primarily used to produce low molecular weight alkenes such as ethene and propene from small alkanes such as naphtha.g.g. Is the other product an alkane or alkene? CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 C CHEMISTRY IN INDUSTRY AND TECHNOLOGY 11 . the toxic nature of some products of cracking and re ning. as in thermal cracking. benzene and other aromatic hydrocarbons. The alkanes are heated to between 500 and 750 °C at a pressure of approximately 70 atmospheres (7000 kPa). 4 Write an equation to show the cracking of an alkane with 14 C atoms to form ethene.a specialised material comprising both aluminium and silicon in an aluminosilicate.
The amount of branching present in polyethene has signi cant e ects on its physical properties and uses. including branching and the position of side groups. in which thousands of individual alkene molecules (monomers) combine to form straight or branched-chain alkanes called polymers. with the methyl group pointing up or down in relation to the methyl group at the growing end of the polymer. The presence of a C=C double bond makes them far more reactive than alkanes. straight-chain alkane polymer. Branching Ethene monomers do not necessarily add to one another in a linear fashion to create a long. LDPE can be used to make rigid containers. HDPE can be used for di erent purposes from those of LDPE because of its di erent mechanical properties.Learning objectives C3 Addition polymers The alkenes produced in the cracking methods described above are extremely valuable commodities. CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 C CHEMISTRY IN INDUSTRY AND TECHNOLOGY . Low-density polyethene Low-density polyethene (LDPE) contains a high proportion of branching (Figure C4a). but is more commonly used to make plastic bags and wrapping lms because of its exibility. As the intermolecular forces between the chains are weaker. This makes the polymer more rigid and increases its melting point and tensile strength. The more e cient packing of the chains increases the strength of van der Waals’ interactions. b HDPE Figure C4 The proportion of branching in LDPE (a) is signiﬁcantly higher than in HDPE (b) and contributes to its different properties and uses. including the ability to be moulded into shape. Position of side groups ( 12 CH CH3 CH2 ( n Figure C5 The repeat unit of the polymer polypropene. When propene is polymerised to polypropene. They have many useful properties. water pipes and food containers such as milk cartons and margarine tubs. We call the majority of these polymers plastics. and this permits the polymer chains to pack together more tightly. HDPE is commonly used for making plastic bins. and so the chains are held together more tightly. increasing the density of the plastic. a LDPE Structure and properties There are several factors that a ect the structure and properties of polymers. High-density polyethene High-density polyethene (HDPE) has a very low incidence of branching (Figure C4b). strength and durability. the repeating unit contains a methyl group side chain (Figure C5). has a lower melting point and is more easily stretched. The frequency of branch formation can be reduced by changing the reaction conditions: lowering the temperature and pressure and including a Ziegler–Natta catalyst (see Higher Level Section C9 on pages 31–32). and they are therefore useful as precursors for making more complex molecules. • • • describe how structure a ects the properties of a polymer describe how the properties of polymers are modi ed understand the advantages and disadvantages of polymer use The exact properties of any given polymer are dependent on its chemical structure and the manner in which the polymer chains interact with one another. This results in weaker van der Waals’ forces. The orientation of the methyl groups in relation to each other can a ect the properties of the nal material. One particular reaction that makes alkenes valuable is addition polymerisation. and therefore contact points between chains are reduced. Highly branched polymer chains are less able to pack closely together. and the polymerisation process normally results in the formation of polymer chains with branches. the polymer is more exible. thermostability. Propene molecules can be added on to one another in a di erent orientation. corrosion and water resistance.
C CHEMISTRY IN INDUSTRY AND TECHNOLOGY 13 .lled packaging material. a Expansion Polystyrene is a rigid. This exibility. plastic kettles. Atactic polypropene contains methyl groups orientated in a random manner. makes plasticised PVC suitable for making garden hoses. It is used to make plastic models. This causes the beads to expand to CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 b plasticiser molecules force chains apart Figure C6 Non-plasticised PVC (a) and PVC containing a plasticiser (b).Isotactic polypropene is the polymer of polypropene in which all the methyl groups are pointing in the same direction. It is created by rst dissolving the volatile hydrocarbon pentane (C5H12) in the polymer during initial manufacture. Isotactic polypropene is used for a wide range of purposes. However. which include use as a roo ng material. The beads of polystyrene that are formed during the polymerisation process are then heated in steam. gas. Most commercially produced polypropene is isotactic. Atactic polypropene has a low melting point and is soft and rubbery rather than rigid. low-density. chairs and ropes. incorporation of phthalate plasticisers makes it exible (Figure C6). however. glassy plastic polymer in its unexpanded form. forcing them apart and so reducing the strength of the intermolecular forces. CD cases and disposable cutlery. the most common plasticisers are phthalates. The steam causes the pentane to vaporise and form gas bubbles within the polystyrene beads. Modiﬁcation of addition polymers Adding plasticisers Plasticisers are small molecules added to the polymer to increase its exibility and durability. The plasticiser molecules insert between the polymer chains. In plastic polymers. most people would invariably describe a white. It has a limited number of applications. Unmodi ed PVC is a very rigid material used for guttering and piping. The irregular positioning of the methyl groups in atactic polypropene means that the polymer chains do not align themselves very well. Isotactic polypropene is therefore crystalline. including ip-top lids. rigid and strong. high-melting-point (240 °C). crates. due to the carefully controlled choice of catalyst during the polymerisation. allowing the chains to move more freely. This well-known form of polystyrene is the expanded form of the polymer. Atactic polypropene is not manufactured commercially. and almost all atactic polypropene is produced as a byproduct of isotactic polypropene manufacture. when asked to describe polystyrene. isotactic H3C atactic H H H H H H3C H3C H3C H3C H3C CH3 H CH3 H H H3C H H3C H The regular arrangement of methyl groups in isotactic polypropene allows the chains to pack together more easily and therefore maximises the van der Waals’ force strength. ooring. with a higher melting point than atactic polypropene. and as a result the intermolecular forces between the chains are weaker. in atable structures and some clothing. coupled with its impressive durability. as a waterproof membrane and in paper lamination.
Density: plastics have variable densities. Advantages and disadvantage of addition polymers Advantages • • • Petroleum-derived polymers can be combined with additives that will increase the polymer’s susceptibility to hydrolysis or oxidative decomposition. Current methods for disposal include land ll. a number of species of bacteria have been found to decompose plastic polymers. They are non-biodegradable. This makes them excellent for storage of corrosive substances and resistant to oxidation in air and hydrolysis in water. and recycling can be expensive.about 60–70 times their original volume.03 g/cm3). Perspex™ has a density of 1. and incineration. In addition. plasticisers and foaming agents (pentane) all come from petroleum-based feedstock. 6 The basic structure of the polymer chains in plastics A and B are shown below. • • • Depletion of crude oil: addition polymers. Disposal: the lack of reactivity of plastic polymers makes disposal tricky. Insulation: polypropene. Test yourself 5 Draw three repeat units of the addition polymer formed from but-2-ene and suggest whether it is possible to produce di erent forms. making them excellent thermal insulators. especially polyethene and polypropene can be easily recycled by melting and reforming. Explain which will have the higher melting point. making it an ideal packaging material. These can be added to land ll sites to reduce the volume of waste. Lack of reactivity: addition polymers contain unreactive. Flexibility: LDPE and plasticised PVC are easily rolled into sheets or lms. which makes it a good lightweight substitute for glass (density ~2. Impact absorption: expanded polystyrene absorbs impact very well because of the gas pockets within the macrostructure.2 g/cm3. PVC and Perspex™ are particularly strong. meaning they will not rot.015–0. which contributes to the greenhouse e ect by producing CO2 and releases toxic gases from halogenated polymers such as PVC. saturated C–C bonds and generally inert side groups.5 g/cm3). rigid and hardwearing. but expanded polystyrene has an extremely low density (0. which takes up vast spaces. Expanded polystyrene beads can then be pressed together in moulds to form sheets or appropriate packaging shapes. Disadvantages Examiner’s tip See Option E on the CDROM for a more detailed discussion of the options for disposing of polymers and some of the problems of recycling them. • • • • Strength and durability: HDPE. Recycling: many polymers. Not all polymers can be easily recycled. plastic A plastic B 14 C CHEMISTRY IN INDUSTRY AND TECHNOLOGY CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 . polyethene and polystyrene have high speci c heat capacities and extremely low thermal conductivity.
Reactions in which H+ is the catalyst are called acidcatalysed reactions. The enthalpy level diagram for a catalysed process such as this is shown in Figure C7. S2O82−(aq) + 2I−(aq) → 2SO42−(aq) + I2(aq) activation energy = Ea1 With catalyst: S2O82−(aq) + 2Fe2+(aq) → 2SO42−(aq) + 2Fe3+(aq) First catalysed stage activation energy = Ea2 2Fe3+(aq) + 2I−(aq) → 2Fe2+(aq) + I2(aq) activation energy = Ea3 The Fe2+ ion is regenerated in the second reaction. a two-stage reaction occurs involving rst the transition metal in a low oxidation state and then a second reaction involving the high oxidation state ion. as in most enzyme-catalysed biological processes. or vice versa. The proton is regenerated in the nal stage of the esteri cation reaction mechanism. Many reactions involving a homogeneous catalyst involve the catalyst forming an intermediate with a reactant. An example of homogeneous catalysis is the iron(II)-catalysed reaction between persulfate and iodide ions.C4 Catalysts Many spontaneous chemical and biological reactions occur incredibly slowly at room and body temperatures. Catalysts provide an alternative reaction pathway that has a lower activation energy than the uncatalysed pathway. Catalysts can be broadly categorised as homogeneous or heterogeneous. The most common form of homogeneous catalysis involves catalyst and reactants in solution (aqueous or organic). Carboxylic acids react with alcohols to form esters in an acid-catalysed reaction. so its nal concentration remains una ected at completion. Besides transition metal ions. C CHEMISTRY IN INDUSTRY AND TECHNOLOGY 15 . In the catalytic cycle. This intermediate reacts more easily than the original reactant. Catalysts are of vital importance to manufacturing and life processes. are in the same phase (solution). Overall reaction Second catalysed stage Note: all the reactants. Acid-catalysed esteri cation involves protonation of the carbonyl group on the carboxylic acid. CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 The ability to act as a catalyst relies on a transition metal atom/ ion being able to exhibit varying oxidation states and to coordinate other molecules/ions. another common homogeneous catalyst is the proton (H+). depending on the state of matter (phase) in which they and the reactants exist. as they increase the rate of these reactions without the need for dramatic changes to the reaction conditions. Learning objectives • • • Understand the di erences between heterogeneous and homogeneous catalysis Discuss advantages and disadvantages of heterogeneous and homogeneous catalysis Discuss the factors that in uence whether heterogeneous or homogeneous catalysis is used Homogeneous catalysts Homogeneous catalysts are in the same phase as the reactants. including catalyst.
In enzyme-catalysed reactions. Many heterogeneous catalysts are added to reactions as powders. as a ne mesh or attached to high-surface-area structures. which forms with a lower activation energy. This forms an enzyme–substrate complex. This is because heterogeneous catalysis occurs only at the surface of the catalyst. This means that there is a reduced ratio of active sites to catalyst molecules compared with homogeneous catalysts. reducing the energy barrier for reaction.E Ea1 Ea2 S2O82–+2I– +2Fe2+ 2SO42–+2I– +2Fe3+ uncatalysed Ea3 catalysed by Fe2+(aq) 2SO42–+I2 +2Fe2+ Reaction progress Figure C7 The change to the reaction proﬁle associated with homogeneous catalysis of an exothermic reaction. e. Ni in the hydrogenation of unsaturated hydrocarbons.V2O5 in the Contact process. Fe in the Haber process. and so they are commonly used as heterogeneous catalysts in industry.g. catalytic converters. it brings the reactants together in the correct orientation for reaction. The active site of the enzyme only recognises a subset of molecules with an adequate three-dimensional shape for binding in the active site. Fe(s) 2NH3(g) Many heterogeneous catalysts rely on their ability to adsorb reactant molecules on to active sites on their surfaces (Figure C8). the reactants are gases but the catalyst is a solid: N2(g) + 3H2(g) Examiner’s tip Adsorption means that the reactants bind to the surface of the catalyst – it is not the same as absorption. Rh and Pd in vehicle catalytic converters. CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 16 C CHEMISTRY IN INDUSTRY AND TECHNOLOGY . Heterogeneous catalysts Heterogeneous catalysts are in a di erent phase from the reactants. Heterogeneous catalysts are usually solids. the reactant or reactants must dock into a speci cally shaped active site within the enzyme protein.g. In the iron-catalysed production of ammonia. Transition metals and their compounds are particularly good at adsorbing gases. and reactions occur on their surface. e. like a key tting into a lock. Adsorption (note ‘adsorption’ and not ‘absorption’) performs three tasks: it increases the localised concentration of the reactants on the surface of the catalyst and thereby increases collision rate. and Pt. and it weakens the covalent bonds in the reactants.
• Can the catalyst be easily replaced or repaired if poisoned? Heterogeneous catalysts become poisoned by the build-up of substances such as sulfur or carbon. they can be cleaned fairly CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 C CHEMISTRY IN INDUSTRY AND TECHNOLOGY 17 . soot in catalytic converters Heterogeneous • easily removed from unused reactants and products by ﬁltration • one metal may catalyse more than one reaction Table C5 The advantages and disadvantages of employing heterogeneous and homogeneous catalysis. high pressure and temperature. despite the apparent advantages of homogeneous catalysis. But what factors should an industrial chemist take into account when deciding whether to use a heterogeneous or homogeneous catalyst for a given reaction? • Homogeneous catalysis is far more speci c to a particular reaction. so if selectivity of the product is desired. This is almost entirely down to the ease of separating a heterogeneous catalyst from the reaction products. • Is e ciency essential or can unreacted material be recycled? • Homogeneous catalysis is more e cient. e. homogeneous catalysis is more useful. e. Some advantages and disadvantages of homogeneous and heterogeneous catalysts are shown in Table C5. however.g. not required Disadvantages • difﬁcult to separate the catalyst from unused reactants and products • prone to permanent deactivation. Advantages Homogeneous • all reactant molecules exposed to catalyst • extreme reaction conditions. • Does the reaction require severe conditions? Homogeneous catalysts tend not to work well in extreme conditions such as high temperature. owing to greater availability of active sites. whereas heterogeneous transition metal catalysts withstand high temperature and pressure well. in which catalyst becomes useless • reactant molecules exposed only to the surface of the catalyst • prone to poisoning (blockage of active sites) by contaminants. Choice of catalytic method Over 90% of industrial processes use heterogeneous catalysis.H C H C H H H H adsorption Ni Ni Ni C H H H C H Ni H H H H C H C H H H dissociation active site free Ni Ni Ni H H C H reaction C H H H Ni Figure C8 The adsorption of ethene and hydrogen gases onto the surface of a heterogeneous solid nickel catalyst during hydrogenation.g.
and now fuel cell technology permits the generation of a current from unlikely sources of electricity such as hydrogen and ethanol. The two electrodes are separated by a porous matrix saturated with an electrolyte. e– external circuit H2 H2 H2 anode + OH– KOH(aq) electrolyte cathode O2 O2 H2 H2O H 2O H 2O OH– OH– OH– O2 O2 unused O2 Figure C9 An alkali hydrogen–oxygen fuel cell with a potassium hydroxide electrolyte. In the hydrogen–oxygen fuel cell. oxygen. However. react in the presence of an electrolyte to produce electrical energy. typically a solution of potassium hydroxide (KOH) is used. In the case of an alkaline electrolyte.g. the humble battery really is a masterpiece of chemical engineering. At the anode. Electrodes are typically made of carbon and incorporate a metal catalyst such as platinum. hydrogen reacts with oxygen to produce water and electricity. A fuel cell is a specialised type of electrochemical cell in which a fuel and an oxidising agent. the disposal of toxic metals such as mercury or cadmium? Learning objectives C5 Fuel cells and rechargeable batteries Safe. In the process. NiCad and lithiumion rechargeable batteries Discuss the di erences and similarities between fuel cells and rechargeable batteries Fuel cells Examiner’s tip The following examples are electrochemical cells. it generally needs to be replaced completely. Figure C9 shows an alkali hydrogen–oxygen fuel cell with a potassium hydroxide electrolyte. the hydrogen is oxidised and releases electrons: H2 + 2OH− → 2H2O + 2e− Anode 18 C CHEMISTRY IN INDUSTRY AND TECHNOLOGY CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 . Once a homogeneous catalyst has been deactivated. In recent years. • • • Understand the functioning of a hydrogen–oxygen fuel cell Describe the workings of lead–acid. which may be either an alkaline or acidic solution. hydrogen reacts with free hydroxide ions (OH−) to form water. Are there any environmental considerations to the use and disposal of the catalyst: for example. technological advances and some inspired chemistry now mean that such devices are commonplace. battery technology has advanced to the extent that batteries can be easily recharged and produce impressive amounts of electricity.• easily and need fully replacing less often than homogeneous catalysts. reliable and portable sources of electrical energy were once a pipedream. e. in which the anode is the negative electrode and the cathode is the positive electrode – the opposite to electrolytic cells.
However. are a portable type of electrochemical cell that generate a current via electrically reversible reactions. or recharge. In a hydrogen–oxygen fuel cell in a vehicle. steam cracking of methane and hydrolysis of water must be considered when thinking about the overall environmental impact of fuel cell use. CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 C CHEMISTRY IN INDUSTRY AND TECHNOLOGY 19 . electrical input can be used to reset. gaining electrons from the electrode in a reduction reaction to form hydroxide ions. which are depleted during use and require constant replenishing. commonly phosphoric acid (Figure C10). Both types of fuel cell rely on external sources of fuel and oxidising agent. as the only products are water. electricity and a small amount of heat. the battery by causing the reactions to occur in the reverse direction. oxygen may come from puri ed air or an oxygen tank.At the cathode. the production of hydrogen from the cracking of ethane. the hydrogen is stored on board the vehicle in a pressurised liquid form. O2 + 2H2O + 4e− → 4OH− Overall redox reaction: 2H2 + O2 → 2H2O The separation of the oxidation and reduction reactions permits the ow of electrons and the generation of an electrical current. That is. hydrogen–oxygen fuel cells are currently very expensive to produce. or secondary cells. using a phosphoric acid electrolyte. The reactions occurring at anode and cathode in an acidic (proton-exchange) fuel cell are di erent: H2 → 2H+ + 2e− 4H+ + O2 + 4e− → 2H2O e– external circuit Cathode Anode: oxidation Cathode: reduction H2 H2 anode H+ H+ H3PO4(aq) electrolyte + O2 O2 H2O cathode O2 H2 H2 unused H+ H+ O2 H2O H2O H2 H2O Figure C10 A proton-exchange fuel cell. They are therefore very di erent from batteries that contain stored chemical energy within them. Owing to the use of platinum catalysts and the need for hydrogen storage and precision engineering. Hydrogen–oxygen fuel cells do not produce any pollution. The alkaline electrolyte can be substituted for an acidic solution. Rechargeable batteries Rechargeable batteries. once the forward reactions have taken place and yielded the desired electrical energy (electrical output). oxygen reacts with water.
lead within the battery is in the form of elemental lead at the anode and lead(IV) oxide. When the battery loses charge. They typically generate smaller voltages than the lead–acid battery. is capable of releasing electrical energy. which accumulates on the electrodes and within the battery. Typically. The electrolyte is a complex lithium salt like lithium hexa uorophosphate (LiPF6) dissolved in an organic solvent (Figure C11). lead at the anode is oxidised. The lead–acid battery works on the simultaneous oxidation and reduction of lead in a concentrated sulfuric acid electrolyte. remote controls and toys. the chemical reactions above are reversed. calculators. During the discharge. the following reactions occur at the electrodes: Cd(s) + 2OH−(aq) Cd(OH)2(s) + 2e− Anode: oxidation NiO(OH)(s) + H2O(l) + e− Ni(OH)2(s) + OH−(aq) Cathode: reduction Cd(OH)2(s) + Ni(OH)2(s) Overall reaction Cd(s) + 2NiO(OH)(s) + 2H2O(l) Lithium-ion battery Lithium-ion (Li-ion) batteries are commonly used rechargeable cells in mobile telephones.e. i. NiCad batteries use a nickel oxide hydroxide (NiO(OH)) cathode and a metallic cadmium anode separated by a potassium hydroxide electrolyte. while the lead(IV) at the cathode is reduced. They are able to generate higher voltages (around 3–4 V) than NiCad batteries. laptop computers and high-energy usage portable electronic devices. the anode is made of carbon with lithium atoms inserted in the lattice. of around 1. During discharge: Pb(s) + SO42−(aq) PbSO4(s) + 2e− Anode: oxidation PbSO4(s) + 2H2O(l) Cathode: reduction 2PbSO4(s) + 2H2O(l) Overall reaction PbO2(s) + 4H+(aq) + SO42−(aq) + 2e− Pb(s) + PbO2(s) + 4H+(aq) + 2SO42−(aq) When a car is in motion the battery is charged. A typical car battery comprises six electrical cells in series and can therefore generate a signi cant potential di erence of about 12 V. Nickel–cadmium battery Nickel–cadmium (NiCad) batteries are often seen as the classic small rechargeable batteries (sizes AAA to D) used for powering small electronic devices such as clocks.2 V. and the cathode is a metal oxide such as manganese(IV) oxide or cobalt(IV) oxide. When the battery is charged. into the lattice structure of which Li+ ions can be inserted. at the cathode. 20 C CHEMISTRY IN INDUSTRY AND TECHNOLOGY CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 . The product is solid lead(II) sulfate. When the battery discharges. releasing electrons. as it is linked to the alternator. the lead(II) sulfate can be converted back to lead and lead(IV) oxide by applying an external electrical source. PbO2.Lead–acid battery One of the oldest forms of rechargeable cell is the lead–acid battery. still used in the majority of car engines.
and lithium ions move in the reverse direction. Fuel cells are capable of generating a far greater quantity of electricity than rechargeable batteries. Rechargeable batteries are generally much smaller than fuel cells. Reduction Similarities and differences between fuel cells and rechargeable batteries Similarities • • • They both generate electrical energy from chemical energy.e– external circuit + graphite electrode containing Li atoms Li Li Li Li Li Li Li+ ions discharge LiPF6 electrolyte Li+ Li+ CoO2 electrode containing Li+ ions. Fuel cell reactants need replenishing by replacement. Rechargeable batteries are far cheaper than fuel cells. where they become inserted into the lattice of the transition metal oxide: CoO2 + xLi+ + xe− → LixCoO2 The overall redox reaction during discharge is: LixC6 + CoO2 → 6C + LixCoO2 The net e ect of these reactions is that lithium atoms are oxidised at the negative electrode and cobalt ions are reduced at the positive electrode. C CHEMISTRY IN INDUSTRY AND TECHNOLOGY 21 CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 . but rechargeable batteries carry their chemical energy source with them. but rechargeable battery reactants are replenished by reversing reactions. forms LixCoO2 Li+ LixC6 Figure C11 A lithium-ion battery. During discharge. They both generate a current based on the separation of reduction and oxidation reactions and the ow of electrons through an external circuit. Lithium ions are exchanged between complexed lithium and graphite electrodes. The reverse reactions occur during charging. For every lithium ion present in LixCoO2. Differences • • • • • Fuel cells require an external source of chemical energy (fuel). They both require anode. the oxidation number of a cobalt ion must be reduced by 1 from +4 to +3 (an Li+ and Co3+ ion together give a charge of 4+ to cancel out the charge on two O2− ions). cathode and electrolyte. lithium atoms are oxidised at the negative electrode and electrons are released to the external circuit: LixC6 → xLi+ + xe− + 6C Oxidation The Li+ ions move through the electrolyte to the cathode.
as in a solid crystal. giving it liquid crystal properties at room temperature. Learning objectives C6 Liquid crystals When asked to describe the rst thing that comes to mind when we hear the words ‘liquid crystal’. fuel cells have a much better longevity. in the liquid crystal phase. so are di cult to dispose of. there is no byproduct of rechargeable batteries. the molecular orientation is disrupted as the molecules gain kinetic energy. the majority of us would no doubt think of the ubiquitous liquid crystal displays (LCDs) present in numerous electronic devices. Pb). The biphenyl nitriles used in some liquid crystal displays are examples of thermotropic liquid crystals. optical. These displays contain specially developed chemical compounds with liquid crystal properties. Generally. rechargeable batteries may contain toxic metals (Cd. too low a temperature causes the substances to form a normal solid crystal with no uidic properties. but retain the ability to ow and move. the molecules are orientated uniformly. cellulose. 4-cyano-4'-pentylbiphenyl (Figure C12) is a liquid crystal between 18 and 36 °C. but many common and ‘ordinary’ compounds can also be classed as liquid crystal. DNA and the solution secreted by spiders to make their silk. • • • Describe the behaviour of thermotropic and lyotropic liquid crystals Explain the functioning of a liquid crystal in terms of the arrangement of the molecules Understand how a liquid crystal display works What is a liquid crystal? Liquid crystal is a phase of matter in which the properties of a compound may exhibit characteristics of both a liquid and a solid. Test yourself 7 Write ionic half equations for the following reactions: a the reaction that occurs at the electrode attached to the negative side of a power supply when a lead–acid battery is charged. Other 22 C CHEMISTRY IN INDUSTRY AND TECHNOLOGY CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 . as in a liquid. They are uids with electrical. If the temperature rises too far. and a liquid forms. 8 Write an overall equation for the reaction that occurs when a lithium-ion cell is charged. Rechargeable batteries have a nite life and must be replaced eventually.• • • Fuel cells can produce drinkable water as a byproduct. Fuel cells are non-polluting. elastic and some other physical properties that depend on the orientation of the molecules relative to some xed axis in the material. Thermotropic liquid crystals Materials that show thermotropic properties are pure substances that exist in the liquid crystal phase only over a certain temperature range between the true solid and liquid phases. b the reaction that occurs at the electrode attached to the positive side of a power supply when a NiCad battery is charged. These substances do not necessarily display liquid crystal properties in their standard states. Examples of substances that possess liquid crystal properties under certain conditions include graphite.
and (c) above the liquid crystal temperature range – random orientation and arrangement. The detergent molecules in soap show lyotropic properties. C CHEMISTRY IN INDUSTRY AND TECHNOLOGY 23 . In a dilute aqueous solution. This phase is called the nematic phase. PAA exists in the liquid crystal phase between 118 and 136 °C. when the concentration increases. pointing in the same direction (Figure C13). Lyotropic liquid crystals These are formed by materials depending on the concentration of the compound in solution. Figure C13 The orientation and distribution of molecules in a thermotropic liquid crystal: (a) solid – regular arrangement and orientation. CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 Micelles can position themselves in an ordered arrangement that shows liquid crystal properties. micelles join to form bilayers that can stack to form a lamellar (layered) phase liquid crystal. hydrophilic carboxylate group. molecules such as sodium stearate (C17H35COO−Na+) contain a long hydrophobic. The two molecules above could be roughly described as rod-shaped. i.C biphenyl group N nitrile group Figure C12 The liquid crystal molecule 4-cyano-4'-pentylbiphenyl. they are signi cantly longer in one direction than the other two. the molecules begin to line up in a speci c manner owing to the formation of intermolecular forces and the minimisation of the interaction between the hydrophobic chains and the water. can form micelles (spheres) or bilayers to maximise favourable intermolecular forces (Figure C14). compounds such as para-azoxyanisole (PAA) were instrumental in the development of LCDs. on average. (b) nematic liquid crystal phase – random arrangement but fairly regular orientation. Molecules that exhibit liquid properties are often rod-shaped and polar. However. such as the phospholipids found in cell membranes. there is no speci c positional order.e. however. In the liquid crystal phase. these rods show some degree of alignment. although they are liquid crystal over less useful temperature ranges. the distance between the molecules is great. the molecules are positioned randomly relative to each other. At higher concentrations. with the rod-shaped molecules. orientational order is alternatively referred to as directional order. non-polar hydrocarbon chain and a polar. and they show no semblance of ordered orientation. so they can ow past each other. a b c Examiner’s tip In IB examinations. a member of the biphenyl nitriles. Soap molecules and related compounds.
ction future with microscopic robots and super-fast computers. The truth is rather di erent. The main problems with liquid crystal displays are that they can be damaged fairly easily and they only operate over the temperature range in which the molecules exist in the liquid crystal phase. Liquid crystal displays The ability of the molecules in a liquid crystal to transmit light is dependent on their orientation. The ideal properties for a compound that can be used successfully in an LCD are: • chemically stable • existing in the liquid crystal phase over a suitable and wide range of temperatures • polar. so that they change orientation when an electrical eld is applied • rapid switching speed between orientations Test yourself 9 Explain which of the following molecules would be more likely to show liquid crystal properties and be useful for a liquid crystal display.micelle bilayer sheet Figure C14 Two structural forms that can be adopted by lyotropic liquid crystal molecules. In the LCD. their orientation can be controlled by applying a low voltage. By altering the orientation of the crystals using an electrical eld. Nanotechnology deals with the research and development of technology at the ultramicroscopic level between 1 and 100 nm (1 nm is one billionth of a metre). C N I II Learning objectives C7 Nanotechnology What is nanotechnology? When the term ‘nanotechnology’ is mentioned. a small electrical eld is applied to a thin lm of the liquid crystal material held between two layers. Nanotechnology creates and uses structures possessing novel CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 • • • Describe what nanotechnology is and how physical and chemical methods can be used Describe the structure and properties of carbon nanotubes Discuss the implications of nanotechnology 24 C CHEMISTRY IN INDUSTRY AND TECHNOLOGY . As the molecules are polar. Current applications for LCDs include pocket calculators. are controlled. digital watches and laptop computer screens. and thus appear light or dark in colour. most of our thoughts would wander to some sort of science. extreme hot and cold temperatures will temporarily disable an LCD. but nanotechnology is certainly out there and with us to stay. Liquid crystal displays are ideal for these purposes because of the requirement for only a tiny electrical current – making them more energy e cient than other types of display. the areas of the display that can and cannot transmit light.
Figure C15 A capped single-walled carbon nanotube. whereas some exhibit semiconducting properties. C CHEMISTRY IN INDUSTRY AND TECHNOLOGY 25 . Physical properties. pentagons must also be present in the structure. including electrical conductivity. In MWNTs. Some nanotubes are full conductors. much like in the layers of graphite (Figure C15). the use of nanotubes in electronic circuitry has been long proposed.properties because of their small size. which has multiple applications. as in C60 fullerene (see Chapter 3. As in graphite. including threedimensional visualisation of the surface of individual molecules. Some carbon nanotubes are closed at the end and some are open. there is a concentric arrangement of two or more nanotubes. up to 3 GPa). are dependent on the arrangements of the tubes. Atoms can be manipulated or moved into position by both chemical and physical techniques. Chemical techniques: atoms are positioned in molecules using chemical reactions. in which. MWNTs are signi cantly more resistant to chemicals than are SWNTs. they form a cylinder made only of hexagons of carbon atoms. Rather than having carbon atoms arranged in a spherical shape. This is because quantum-level e ects predominate at the nanoscale. Nanotechnology builds on the ability to control or manipulate at the atomic scale. electron-containing p-orbitals across the entire interconnected network of atoms. has been used to deposit individual atoms in speci c positions. This can be compared with graphite. In tests. a soft substance used as a dry lubricant is produced because of the weak van der Waals’ forces between the layers. as a result of changes in the behaviour of the delocalised electrons. A single nanotube is an extremely strong structure. the routes to success are quite di erent. page 135 of the Coursebook. although each individual layer (called graphene) has exceptional mechanical properties (it is very strong). when the layers come together to form graphite. SWNTs exhibit a tensile strength up to 50 gigapascals (compare with stainless steel. Chemical manipulation relies on the use of speci c chemical reactions or interactions to position the atoms in a molecule. Note the hexagons that make up the main body of the tube and the inclusion of pentagons at the capped ends. In order to allow the ends of the tubes to be sealed. Carbon nanotubes Carbon nanotubes are allotropes of carbon and members of the fullerene family. It may be possible to make bundles of these tubes that also show exceptional mechanical properties. because only covalent bonds are present between the atoms. Nanotubes are among the strongest and sti est materials ever created. Although the outcome may be similar. It is possible to create single-walled nanotubes (SWNTs) and multiwalled nanotubes (MWNTs). Physical manipulation positions atoms to speci c requirements. A powerful piece of technology called atomic force microscopy (AFM). DNA nanotechnology uses the intermolecular hydrogen bonding rules of base pairing to yield self-assembling branched DNA complexes with potentially useful applications in computing and nanorobotics. carbon nanotubes contain delocalised electrons HL as a result of the presence of only sp2 hybridised carbon atoms and overlapping. Physical techniques: atoms are manipulated and positioned to speci c requirements. For example. but the challenge is to produce su ciently long and well-aligned bres so that the strength of the bundle as a whole relies more on the strength of the covalent bonds between atoms in the individual nanotubes rather than the van der Waals’ forces between tubes. CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 A network of strong covalent bonds extends throughout the entire length of the tube. The degree to which a carbon nanotube conducts electricity is dependent on its length.
if and when nanotechnology enters the public domain. Determining the toxicity of nanotubes and nanoscale particles is di cult. The similarity between carbon nanotubes and asbestos threads has been noted and has led to worries that nanotubes might be able to cause respiratory and other health issues in the manner that asbestos does. stealth technology.Other interesting proposed applications of nanotechnology include: paper batteries. Nanotubes could be developed into specialist lters. There is no loss of small molecules when monomers join. the technology is so new that not enough is known about the potential implications for human health. in which the diameter of the tubes is set to permit the passage of particles up to a certain maximum size. solar cells. There are some serious concerns about nanotechnology in the health arena. Carbon nanotubes can also be used as highly e ective heterogeneous catalysts. a molecule of water. polyamides are formed when monomers with carboxylic acid and amine groups react together. many more. as they have a large surface area because both the outside and inside surfaces are available for binding to reactants. e. and the resulting polymer contains repeating units joined by carbon–carbon single bonds. for example in the desalination of water by allowing small water molecules through but excluding larger chloride ions. Government regulatory bodies and the industry itself will need to take responsibility for the safe introduction of nanotechnology into the world at-large. e.g. HL Learning objectives C8 Condensation polymers Addition polymerisation vs condensation polymerisation Addition polymerisation involves adding together many alkene monomers to form a long polymer chain. There is speculation that they could cross cell membranes and thereby induce harmful e ects. dihydric alcohols and amino acids. page 473 of the Coursebook. In the process. • • • • Describe the structure and formation of condensation polymers using speci c named examples Understand how structure a ects the properties and uses of a polymer Understand how modi cation of condensation polymers a ects their properties and uses Discuss the advantages and disadvantages of the use of condensation polymers See also Chapter 10. and many. as their properties depend on their size. New materials being created may have new and unforeseen health risks. Condensation polymerisation involves the joining of molecules that contain two reactive functional groups. visual displays. Currently. poly(ethene). synthesis of chemical nanowires. 26 C CHEMISTRY IN INDUSTRY AND TECHNOLOGY CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 . Thorough testing and regulation will be essential. or another small molecule. dicarboxylic acids. Public education would go some way to allaying fears and reducing risk factors. is eliminated at each junction (Figure C16). Implications of nanotechnology Other uses of carbon nanotubes include as a synthetic bre in conjunction with existing polymers to improve many of the desirable physical properties of these materials. Informed debate and public involvement in policymaking will be crucial. Concerns have surfaced that the human immune system would not be able to recognise particles on the nanoscale and would be defenceless against them. Polyesters are formed when monomers with carboxylic acid and alcohol groups react.g.
position creates cross-links between chains and creates a complex three-dimensional structure (Figure C19). eliminating a molecule of water in the process (Figure C18).position of a phenyl group (benzene ring) in another molecule. to yield a pink-coloured. including casings for electrical items such as radios and telephones. Multiple reactions at the 2.or 4. + H + H2O 4-position Figure C18 The polymerisation reaction in the formation of a phenol–methanal polymer. reaction at the 4. OH H C 2-position OH H OH OH H C OH In the presence of a base catalyst. tacky thermosetting plastic. Phenol–methanal plastics Phenol dissolved in methanal is able to undergo condensation polymerisation. as well as methylene (–CH2–) bridges. catalysed by either acid or base. The polymerisation occurs in two stages. 1 Phenol reacts with methanal to form a mixture of 2-(hydroxymethyl) phenol and 4-(hydroxymethyl)phenol with a small number of polyhydroxymethylated derivatives (Figure C17). CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 C CHEMISTRY IN INDUSTRY AND TECHNOLOGY 27 . One of the earliest created phenol– methanal plastics was Bakelite. forming a mixture of products that can undergo polymerisation. OH OH H OH CH2OH C H CH2OH OH CH2OH HOH2C OH CH2OH HOH2C OH CH2OH O The structure of phenol: OH + CH2OH CH2OH Figure C17 The reaction of methanal with phenol. 2 The hydroxymethyl group reacts with either the 2.O H O dicarboxylic acid O O H H C C dihydric alcohol O H H O dicarboxylic acid O O H H O O C C dihydric alcohol O O H condensation reaction ester group O chain can continue O C C O H H H O O O O C C O H HL O O H O H chain can continue H O H Figure C16 Formation of a polyester by a condensation polymerisation reaction. ether (C–O–C) bridges can also be formed between the monomers.positions build up long linear chains of repeating units. used for many purposes.
Reactions can also be.HL polymer chain OH CH2 CH2 OH cross-link OH CH2 CH2 OH CH2 OH OH CH2 OH CH2 CH2 polymer chain CH2 OH CH2 Figure C19 Part of the structure of a phenol–methanal polymer. seals and carpet underlay.2-diol (Figure C21). So. CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 28 C CHEMISTRY IN INDUSTRY AND TECHNOLOGY . polyurethane production does not yield water (or any other small molecules) during formation. Polymers formed in chain reactions include the addition polymers that we have met. Polyethylene terephthalate (PET) is a polyester formed by the reaction of benzene-1. The formation of polyurethane is classi ed under condensation polymerisation on the IB syllabus. should polyurethane be classi ed as an addition polymer? The problem arises because the classi cation of polymerisation reactions as addition and condensation is not the only way of classifying reactions. perhaps more usefully. whereas polymers formed in stepwise reactions include the condensation polymerisation we have met and polyurethane. The isocyanate functional group is R–NCO. The resulting polymer contains monomers joined together by carbamate linkages (Figure C20). Polyethylene terephthalate See also Chapter 10. including foam seating and insulation. PET is highly resistant to a number of solvents and is easily moulded. Polyurethanes have a wide spectrum of uses. elastane bres. wrapping lms and similar products. however. Polyurethane Polyurethane polymers are created from the reaction between a diisocyanate and a dihydric alcohol in the presence of a catalyst. carbamate linkage diisocyanate O C N + HO N OH C O O C N H H N C O O O n Figure C20 The polymerisation of a diisocyanate and a dihydric alcohol to yield a polyurethane polymer. It is an ideal material for making drinks bottles.4-dioic acid (terephthalic acid) with ethane-1. classi ed according to the mechanism of polymerisation. page 480 of the Coursebook.
in phenol–methanal plastics there are covalent bonds. CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 C CHEMISTRY IN INDUSTRY AND TECHNOLOGY 29 . H N N H O C O C N H O C C O H N C O H N N H O C hydrogen bond Figure C22 The two monomer units for the production of Kevlar: (a) 1. Phenol–methanal plastics In Kevlar. few cross-links form.4-diaminobenzene and (b) teraphthaloyl chloride.4-dioic acid) (Figure C22). Figure C23 A short double-ﬁbre section of the condensation polymer Kevlar. The polymer chains align themselves in such a way that allows for the formation of comparatively strong intermolecular hydrogen bonds between amide groups (C=O to H–N) along the whole chain (Figure C23). the methanal : phenol ratio is varied. The same is true for many polymers formed by condensation reactions. As covalent bonds are much stronger than intermolecular forces. Additional intermolecular interactions arise in the form of extensive van der Waals’ forces.g. As we saw in Figure C19. Kevlar is used in protective clothing. However. thermostable and resistant to chemicals. is eliminated. synthetic ropes and sporting equipment. HCl.4-diaminobenzene and terephthaloyl chloride (the diacyl chloride of benzene-1. when the molar ratio rises to about 1. To create a polymer with di ering levels of cross-linking. including armour. between chains. If the molar ratio of methanal :phenol is less than one. O C CI NH2 Properties of condensation polymers As explored in Section C3 on page 12. rather than water. intermolecular forces hold the polymer chains together. the structure of a polymer has a signi cant impact on its physical properties – e. the incidence of cross-linking is much higher and the plastic produced is far more rigid. hence their use in making items such as pool balls. called cross-links. NH2 CI C O Kevlar Kevlar is a para-aramid polymer (‘aramid’ is short for ‘aromatic amide’) created by the reaction between 1.5. This means that in the formation of Kevlar.2-diol O C H O PET O C O H C H H C H O H + (2n–1) H2O n a b Figure C21 The formation of polyethylene terephthalate (PET). except that the OH group has been replaced with a Cl. An acyl chloride has a similar structure to a carboxylic acid. cross-linked phenol–methanal plastics are harder and more rigid than Kevlar.4-dicarboxylic acid heat ethane-1.O n H O C C O + O H n H O H C H H C H O H HL benzene-1. atactic vs isotactic polypropene. These hold the polymer chains together very tightly and contribute to Kevlar’s high tensile strength.
The process is similar to doping silicon semiconductors with group 3 or group 5 atoms (see Section C10). H alternating C C/C creates a conjugated system Figure C24 A section of the polymer. Examiner’s tip Air is stated as the blowing agent for the manufacture of polyurethane foams on the IB syllabus. Doping of polyethyne with a group 1 metal has a similar e ect by adding extra electrons. we looked at expanded polystyrene as a protective packing material due to its high shock-absorption capacity. However. comprising three repeat units. making it as good a conductor as the best conducting metals. In this unadulterated form. one of the π bonds in the − carbon=carbon triple bond is broken. polyester bres can often feel uncomfortable to wear and do not retain coloured dyes well (they are not dye-fast). polyethyne is a semiconductor. By blending polyester bres with other synthetic or natural bres such as cotton. polyethyne. 30 C CHEMISTRY IN INDUSTRY AND TECHNOLOGY CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 . This creates a space for other electrons to ll. which can move along the chain. Water is added to the mixture of diisocyanate and dihydric alcohol. silver and copper. A conjugated system is a series of alternating single and double bonds. producing carbon dioxide gas. and one or more electrons are lost from the system. The size and number of bubbles can be varied to yield foams of di ering strengths and densities. As the polyurethane forms. and the resulting polymer contains − alternating double and single bonds. doping the polymer with iodine leads to oxidation of the polymer. Doping polyethyne with iodine increases its conductivity by almost one billion times. Polyesters When woven alone. comfort is signi cantly increased and the ability of blended bre to retain dyes is increased. and so the π electrons can move freely from one end of the chain to the other. H C C H H C C H C C H C Polyethyne When ethyne (HC=CH) is polymerised. p orbitals can overlap side-on to produce a π delocalised system – see Option A on the CD-ROM for more details. Water reacts with the diisocyanate. giving o large quantities of gas.HL Modiﬁcation of polymers The properties of many polymers can be modi ed during manufacture to produce materials with more speci c applications. as there are no ‘gaps’ for them to move into. This forms an extensive conjugated system along the entire length of the polymer chain (Figure C24). The foams produced can be used in seating or for insulation. compared with non-expanded polystyrene used to make model kits and CD cases. depending on the intended application. Polyurethane foam Polyurethanes possess the desirable quality of being able to be converted into a foam using a blowing agent. the CO2 bubbles cause it to expand before it solidi es. On pages 13–14. Other blowing agents that are also used include highly volatile liquids that boil during the polymerisation process. the electrons are not truly free to move.
Name the functional groups in the monomers. Test yourself 10 Draw the repeat unit of the polymer formed when the two molecules shown below react. resistant to most chemicals except concentrated acids and alkalis polymers are not broken down by moisture and/or bacteria. the linkage formed between the groups and the type of polymer formed. Name the functional group that links the monomers together and the type of polymer formed. landﬁll requirements are large. phenol–methanal plastics are thermosets and cannot be re-melted to make new articles because of the presence of the cross-links insulation – incorporation of air pockets in polyurethane foam gives it excellent insulating properties chemical resistance – ester and amide linkages are highly biodegradability – owing to their chemical resistance.Advantages and disadvantages of polymer use Advantages strength – Kevlar and phenol–methanal plastics are extremely strong and durable density – strength : density ratio is greater than that of metals disposal – PET is extensively recycled HL Disadvantages use of natural resources – many aromatic compounds are derived from crude oil disposal – incineration creates signiﬁcant quantities of polluting gases such as CO and CO2. H O C N C H H C H N C O + H O H C H H C H H C H H C H O H 11 Write an equation for the formation of Kevlar using the monomers given in Figure C22. polymerisation of ethene to LDPE involves initiation. propagation and termination steps. As with other free radical mechanisms. Learning objectives • • Describe the free radical mechanism for the production of low-density polyethene Outline the use of Ziegler– Natta catalysts in the production of high-density polyethene Initiation The weak O–O bond in the organic peroxide initiator (R–O–O–R) undergoes homolytic ssion under high temperature to yield two freeradical species: R–O–O–R → 2RO• CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 C CHEMISTRY IN INDUSTRY AND TECHNOLOGY 31 . C9 Mechanisms in the organic chemicals industry Manufacture of low-density polyethene Low-density polyethene (LDPE) is manufactured via a free-radical mechanism initiated by the introduction of oxygen or an organic peroxide to ethene at a high temperature (>300 °C) and extreme pressure (~2000 atm). polluting and unsightly Table C6 Advantages and disadvantages of condensation polymers.
Termination Termination can occur in a number of ways when two free radicals combine. This happens when the chain twists back on itself and an intramolecular reaction occurs. This produces an unpaired electron at the C at the end of the chain: H RO + C H H C H RO H C H H C H The unpaired electron interacts with the π bond of another ethene molecule.HL Propagation The free radical formed then reacts with an ethene molecule. not at the end. in which the free radical centre is relocated to a position within the growing chain. For example: H RO C H H C H C H C + RO H RO H C H H C H C H C H OR H n H H n H or H RO C H H C H C H C + RO H H C H H C H C H C H RO H C H H C H C H C H H C H H C H H C H H C H m OR H n H H mH H n H Extension Branching in LDPE occurs via a mechanism called backbiting. transferring R O CH2 CH2 CH2 CH2 chain flexes a hydrogen atom from a methylene (CH2) group to the end of the chain. breaking the π bond. and in the process. creating a C-C single bond and an unpaired electron at the end of the chain: H RO C H H C H H + C H H C H RO H C H H C H H C H H C H This cycle of breaking the π bond and forming a C–C single bond to extend the chain continues until termination occurs. When the unpaired electron then reacts with an ethene molecule. it starts to create a side chain rather than extend the main chain: R O CH2 H2C CH2 CH2 CH H-atom transferred R O CH CH2 CH3 CH2 R O CH CH2 CH2 CH2 CH2 CH3 + H2C CH2 R O CH2 CH2 CH3 chain straightens 32 C CHEMISTRY IN INDUSTRY AND TECHNOLOGY CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 . a single covalent bond is created between the rst carbon and the radical’s oxygen atom.
they are used to control the tacticity of polymers such as polypropene. Manufacture of HDPE is by a mechanism completely di erent from the free radical polymerisaton that yields LDPE. The polymer chains are better able to align with each other and maximise contact points. CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 C CHEMISTRY IN INDUSTRY AND TECHNOLOGY 33 . The ligand is C2H5−. crystalline product. with an organoaluminium compound such as triethylaluminium (CH3CH2)3Al. increasing the yield of isotactic structures rather than the less useful atactic variety.Manufacture of high-density polyethene High-density polyethene (HDPE) contains very little branching and is therefore more crystalline with a higher density than LDPE and increased rigidity. lengthening the polymer chain: CH3 CH2 CH3 CH2 Ti Cl Cl H H Cl C C H H CH2 CH2 Ti Cl Cl Cl There is now a free space on the Ti for coordination of another ethene. Ethene coordinates to the Ti using the π electrons from the double bond: CH3 CH2 Ti Cl Cl H Cl + H C C H H CH3 CH2 Ti Cl Cl H H Cl C C H H HL Ziegler–Natta catalysts are generally a mixture of titanium(III) chloride (TiCl3) or titanium(IV) chloride (TiCl4). In this manner. the addition of monomers is highly controlled and the incidence of branching is reduced. increasing the strength of the van der Waals’ interactions. This type of polymerisation results in less chain branching and a more regular. no free radicals are involved. hence the ionic nature of the mechanism. as the ligands around the Ti prevent branching. which is already attached to the nascent chain. A proposed mechanism is as follows. Owing to the control that Ziegler–Natta catalysts impart to polymerisation of alk-1-enes. An ethyl group from Al(C2H5)3 coordinates to the Ti ion. HDPE is polymerised under low pressure (1–30 atm) and reduced temperature in the presence of a specialised catalyst called a Ziegler– Natta catalyst. The mechanism is complex and not fully understood. Test yourself 12 Draw the mechanism for the polymerisation of propene under high temperature and pressure using an organic peroxide initiator. but polymerisation occurs via ionic intermediates in which the incoming ethene monomers coordinate with the titanium in the catalyst. The C2H5− group then migrates to the ethane.
In a metal. silicon acts as a semiconductor. Doping of silicon The electrical conductivity of silicon can be increased by incorporating atoms of group 3 or 5 elements as impurities into the lattice. The electrical conductivity of silicon thus increases as the temperature increases. whereas the conduction band is empty. there is nowhere for the electrons to move. A hole is regarded as a positive charge carrier – if an electron has been removed. with the ability to conduct electricity to a degree that can be used in electrical circuits. The promotion of electrons from the valence band also creates ‘holes’ in this band that other electrons can move into. Because the valence band is full.and n-type semiconductors Describe how sunlight enhances electrical conductivity in a semiconductor empty conduction band orbitals conduction band closely spaced orbitals containing pairs of electrons valence band Si Si Si Si Si Si Si Si hole electron movement Si Si Si Si Si Si Si Si hole hole movement These bands consist of a very large number of orbitals that are closely spaced in energy. under certain conditions. the band gap in silicon is su ciently small that as the temperature is raised some electrons are promoted to the conduction band and become free to move. However. this also contributes to the electrical conductivity (Figure C25). and at normal temperatures electrons cannot jump to the higher level.Learning objectives HL C10 Silicon and photovoltaic cells Silicon is a semiconductor Silicon is a silvery. This process is called doping. However. and neither insulators nor semiconductors conduct electricity at absolute zero. the energy gap between valence and conduction bands is large. At absolute zero in insulators and semiconductors. page 133 of the Coursebook. non-metal with a giant covalent structure similar to that of diamond (see Chapter 3. this makes silicon a poor electrical conductor under standard conditions. The outer orbitals of the atoms making up a solid overlap to form valence and conduction bands of orbitals: conduction band conduction band band gap valence band valence band insulator semiconductor conductor conduction band valence band • • Describe how the doping of silicon is used to produce p. Electrons within the structure of silicon are xed in position within the covalent bonds. and the metal is a good conductor of electricity. as a large number of electrons are free to move. Figure C25 The movement of a negatively charged electron in one direction is equivalent to the movement of a positively charged hole in the opposite direction. In an insulator. aluminium or gallium into the silicon structure creates a p-type semiconductor (where ‘p’ stands for positive). These group 3 atoms 34 C CHEMISTRY IN INDUSTRY AND TECHNOLOGY CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 . the valence band containing the outer shell electrons of the solid is full. Inclusion of a small proportion of a group 3 element such as boron. what is left has a positive charge. The electrical conductivity of solids can be described in terms of band theory. the conduction and valence bands overlap.
There is thus a build up of charge at the p–n junction that prevents n-type semiconductor e– e– e– e– n-type semiconductor junction voltage prevents movement of electrons from n p and of holes from p n any further movement of charge across the junction (Figure C27). Test yourself 13 When silicon is doped with the following atoms.supply only three electrons to the valence band instead of four (as supplied HL Si Si Si Si Si Si Si Si by Si). movement movement Incorporation of a group 5 element (e. a p-type semiconductor and an n-type semiconductor are joined together. Photons of light with wavelength shorter than about 1100 nm have su cient energy to cause electrons to be promoted from the valence band to the conduction band and thus increase the electrical conductivity of silicon. electrons are promoted to the conduction band. phosphorus. Extension In photovoltaic cells. because the voltage at the junction prevents this. and therefore there is a hole in the valence band. When these two types of semiconductor (both neutral) are joined. These electrons are not able to ow from the n-type to the p-type directly. would n. it is termed an n-type semiconductor. leaving behind negative charge. As the current is carried by negatively charged electrons. Visible light has wavelengths between 400 and 750 nm. arsenic or Figure C26 The movement of holes in antimony) into the silicon lattice also increases the electrical conductivity of p-type semiconductors. electrons move from the n-type to the p-type semiconductor. electron hole this is now called a p-type semiconductor (Figure C26).or p-type semiconductors be produced? a Al b In c As d Sb CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 C CHEMISTRY IN INDUSTRY AND TECHNOLOGY 35 . Figure C28 How a photovoltaic cell can produce a current. of which four are used in forming covalent bonds and go into the valence band. When light hits the n-type semiconductor. such as the solar cells found in calculators and other small electronic devices. The introduction Si B Si Si Si B Si Si of extra gaps in the valence band increases the electrical conductivity of hole hole the silicon. and this can be used to power an electrical device (Figure C28). they leave behind positively charged ions. They must therefore travel from the n-type to the p-type through the external circuit. where they combine with some holes. The interaction of sunlight with silicon We have seen above that electrons can be promoted from the valence band to the conduction band of a semiconductor by thermal energy. the semiconductor. Because the main charge carriers are positively charged holes. These atoms have ve valence electrons. This e ect is used in photovoltaic cells (solar cells).g. Holes move from the p-type to the n-type semiconductor and combine with the additional electrons. but the fth is promoted easily to the conduction band. light n-type semiconductor e– depletion layer + – p-type semiconductor + – depletion layer hole p-type semiconductor + – p-type semiconductor + – external circuit e– Figure C27 The build up of charge at a p–n junction produces a layer that prevents any more movement of charge across the junction.
have a nitrile group at one end which makes the molecules polar. a b O N H H HO Figure C30 Molecules that display liquid crystal properties: (a) cholesterol. The two phenyl groups provide signi cant rigidity (Figure C29b) and make the molecule rod-shaped. The biphenyl nitriles can be used to illustrate this. (b) N-(4methoxybenzylidene)-4-butylaniline (MBBA).Learning objectives HL C11 Liquid crystals Identifying liquid crystals Molecules that display liquid crystal properties generally possess a number of structural features in common. and this helps maintain the liquid crystal phase (rather than forming the solid). Examples of other molecules that possess similar features and display liquid crystal behaviour are shown in Figure C30. (b) overlap of p orbitals between the benzene rings means that the rings are less likely to rotate relative to each other. but not too strong that they only form solid crystals. This provides a strong enough intermolecular force to align the molecules in the same direction. Molecules such as 4-cyano-4'-pentylbiphenyl (Figure C29a). a • • • Identify molecules with liquid crystal properties Describe how a twisted nematic liquid crystal works and is used in liquid crystal displays Understand why Kevlar exhibits liquid crystal properties in acid alkyl chain C biphenyl group δ+ N δ– b C C C C C C C C C C C C Figure C29 (a) 4-cyano-4’-pentylbiphenyl. each layered with a polariser on the external surface and a transparent electrode (a coating of indium tin oxide) on the inner surface. H Twisted nematic liquid crystal The twisted nematic liquid crystal cell is the basic unit behind the functioning of a simple liquid crystal display (Figure C31). the long alkyl chain ensures that the molecules cannot pack too closely together. The cell comprises a thin lm of the liquid crystal sandwiched between two glass plates. The inner surfaces of the glass plates are covered in thousands of tiny 36 C CHEMISTRY IN INDUSTRY AND TECHNOLOGY CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 .
voltage applied across the liquid crystal Figure C31 A twisted nematic liquid crystal cell commonly found in simple LCD devices. This technology is used in the classical digital displays in pocket calculators and wristwatches. the oxygen and nitrogen atoms in the amide linkage become protonated and the hydrogen bonding is lost. Indeed.parallel scratches.no voltage switch closed . the Kevlar strands will align in the same direction but not form a solid crystal because the intermolecular bonding is not strong enough. and the image formed appears dark. the plane-polarised light is rotated by exactly 90°. Kevlar The structure of Kevlar has already been discussed on page 29. This separates the Kevlar strands. This causes the liquid crystal molecules to adopt a twisted arrangment as they try to align with both sets of scratches.polarises the light light in switch open .display appears black liquid crystal liquid crystal molecules aligned with electric field glass plate with scratches polariser . CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 When Kevlar is dissolved in concentrated sulfuric acid. the liquid crystal molecules align with the eld rather than the scratches. in which the concentration of Kevlar determines the extent of liquid crystal behaviour. This means that when the light hits the top glass plate and polariser it has been rotated the precise amount to pass through the polariser. C CHEMISTRY IN INDUSTRY AND TECHNOLOGY 37 . The image formed appears transparent as the light passes through the cell uninterrupted. all prerequisites for liquid crystal molecules. the top glass plate is rotated exactly 90° relative to the bottom plate. In the twisted nematic cell. When no electrical eld is applied and the molecules are in a twisted arrangment. However. Kevlar contains numerous polar groups. At a speci c concentration. Kevlar acts as a lyotropic liquid crystal. The liquid crystal molecules positioned close to the plates line up with these scratches. is rigid due to the aromatic rings and is rod-shaped. when an external electrical eld is applied. The second polariser angled at 90° to the rst completely blocks out the light. It consists of long polymer chains held together by strong intermolecular hydrogen bonding formed between N–H and C=O groups in the amide linkages. light passes through – display appears clear display polariser at 90° glass plate with scratches at 90° to bottom one HL display light cannot pass through second polariser . when planepolarised light passes through the liquid crystal it is no longer rotated. this completely obliterates the twisted arrangement. Under normal conditions. in concentrated sulfuric acid. Now. Light entering the cell is rst polarised and then passes through the liquid crystal layer. Kevlar shows no liquid crystal properties.
Mercury cell In the mercury cell. sodium hydroxide and hydrogen gas using the mercury. The metals can be easily tapped o from the bottom of the vessel. this industry is directly worth several billion dollars every year. and sodium hydroxide solution. as high temperatures are not required to permit free movement of the ions. Electrolysis of molten sodium chloride is principally used to produce sodium metal. which escapes and is collected: 2Cl−(aq) → Cl2(g) + 2e− Anode At the cathode. and so it is di cult to oxidise chloride ions to chlorine gas chemically. Application of a current through the solution causes negatively charged chloride ions to migrate to the anodes. 15 Explain why the molecule shown below would be less suitable than the biphenyl nitrile shown in Figure C29 for use in a liquid crystal display. the mercury and amalgam remain at the bottom of the cell. from where they ow into a second vessel part. electrical energy is used to remove electrons from the ions to form the element. a thin layer of owing mercury is used as the cathode and graphite or titanium as the anodes (Figure C32). Electrolysis of brine produces three important chemicals: chlorine gas.HL Test yourself 14 Look at the molecules in Figure C30. rather than hydrogen ions being reduced. which escapes from the top of the vessel. In the USA. the sodium metal reacts to form hydrogen gas. sodium ions are reduced to sodium metal. Electrolysis of both molten sodium chloride and brine yields chlorine gas. Explain why they should form a liquid crystal phase. which cannot be obtained from electrolysis of an aqueous solution. which oats on the surface 38 C CHEMISTRY IN INDUSTRY AND TECHNOLOGY CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 . where they are oxidised to gaseous chlorine. approximately 12 million tonnes each of chlorine and sodium hydroxide are manufactured by the chlor-alkali industry annually. Both chemicals can be manufactured from brine. diaphragm and membrane cells Understand the environmental impact of these electrolytic cells Outline the major uses of the products of the electrolysis of brine Brine is a concentrated aqueous solution of sodium chloride. Chlorine is a powerful oxidising agent. A number of di erent electrolytic methods have been used to separate the chlorine from the sodium. H3C CH3 Learning objectives C12 The chlor-alkali industry Both chlorine and sodium hydroxide are extremely important and lucrative chemicals. In the USA.lled with water. which then forms an amalgam with the mercury cathode: Na+(aq) + e−(+ Hg(l)) → Na(l) (+ Hg(l)) Cathode Owing to di erences in density. Rather than using chemicals to oxidise chloride ions. hydrogen gas and sodium hydroxide. with the brine oating on top. as would be expected given the relative reactivity of hydrogen and sodium. It is cheaper to electrolyse brine to obtain chlorine. • • • Describe the production of chlorine gas. but end-use sales coming from chlorine chemistry are worth hundreds of billions of dollars. As the amalgam mixes with the water.
Brine is introduced into the anode-containing section of the cell. Despite best e orts to recycle the mercury. forming hydrogen gas and hydroxide ions: 2H2O(l) + 2e− → H2(g) + 2OH−(aq) Cathode Water is easier to reduce than sodium ions (see Chapter 9. Mercury is highly toxic and can cause neurological disorders in humans and animals. Cl2 + 2OH− → OCl−+ Cl− + H2O C CHEMISTRY IN INDUSTRY AND TECHNOLOGY 39 . to avoid reaction between the two and contamination of the solution with hypochlorite (chlorate(I)). water is reduced. Diaphragm cell In the diaphragm cell (Figure C33). several hundred kilos will be lost by each plant every year and end up in the water system. There are two other types of electrolytic cell employed in the chloralkali industry. at the cathode. it has met with erce opposition from environmentalists because of the use of toxic mercury. as the net ow of liquid is from the anode to the cathode compartment. which do not require a mercury cathode: the diaphragm cell and the membrane cell. the vessel is separated into two sections by a permeable asbestos diaphragm. Here. page 407 of the Coursebook. the mercury can be recycled into the electrolytic cell. With the sodium now removed. The chlorine escapes as a gas and is collected and puri ed. of the remaining mercury and can be siphoned o .CI2 graphite/Ti anode HL brine out + + + + H2 brine in water in Hg mercury cathode Hg H2 NaOH/ H2O Hg NaOH out Figure C32 The mercury cell. The level of brine in the anode compartment is higher than that in the cathode compartment – brine ows through the diaphragm – which helps to keep the hydroxide ions away from the chlorine gas. 2Na(l) (+ Hg(l)) + 2H2O → 2NaOH(aq) + H2(g) (+ Hg(l)) Although this is an e ective method for the manufacture of chlorine and sodium hydroxide. The remaining brine ows through the diaphragm and into the cathode-containing section of the cell. Once chlorine and hydrogen gases have been removed. the remaining solution is a mixture of about 12% sodium hydroxide and a slightly higher percentage of unused brine. as well as pollute farmland and waterways. The sodium hydroxide and sodium chloride CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 The use of a diaphragm means the chlorine and alkali are kept separate. where oxidation of chloride ions to chlorine gas occurs. The hydrogen gas escapes and the asbestos diaphragm prevents the hydroxide ions from returning back to the anode-containing side of the vessel.
It thus allows sodium (Na+) ions to pass through but not chloride (Cl−) ions or hydroxide (OH−) ions. are separated by evaporating away the water. Membrane cells work on a similar principle to the diaphragm cell but use a specialised ion exchange membrane to separate oxidation and reduction reactions (Figure C34). Membrane cell Membrane cell technology has now superseded both mercury and diaphragm cells. 40 C CHEMISTRY IN INDUSTRY AND TECHNOLOGY CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 . and because it is far less environmentally damaging.HL chlorine gas hydrogen gas + titanium anode steel cathode brine flow of brine brine + sodium hydroxide asbestos diaphragm Figure C33 The diaphragm cell. there are environmental and health considerations that need to be taken into account with use of the diaphragm cell. the use of asbestos diaphragms has been banned by law. chlorine gas hydrogen gas + titanium anode CI– OH– steel cathode brine Na+ ions sodium hydroxide solution ion permeable membrane Figure C34 The membrane cell. as a result of its impressive e ciency. Asbestos is the common material used in construction of the diaphragm. Again. and so as the water is removed. which can prove fatal. and this mineral is associated with some serious respiratory diseases. In many countries. chlorine and hydroxide ions are thus kept separate from each other. NaCl crystallises out of solution and can be removed. As hydroxide ions are produced only in the cathode compartment. The solubility of NaCl in water is three times lower than that of NaOH (~360 g dm−3 for NaCl and 1110 g dm−3 for NaOH). including asbestosis and mesothelioma. The membrane is made of uorinated compounds and allows positive ions to pass through but not negative ions.
in the latter. Mercury cell Construction costs most expensive to build Diaphragm cell relatively cheap Membrane cell more expensive than diaphragm cell but cheaper than mercury cell some issues but much less than the other two most energy efﬁcient high purity and required lowest purity and lowest concentration concentration (50%) high purity but lower than required concentration Environmental issues toxic mercury in efﬂuent Energy consumption Purity of NaOH(aq) asbestos diaphragms must be replaced regularly – problem with disposal of asbestos Table C7 A comparison of the three cell types. Sodium ions pass across the membrane into the cathode-containing side of the cell. The concentration of NaOH formed in the cell is almost three times greater in the membrane cell compared with the diaphragm cell (32–34% compared with 12%). Uses of chlorine. The ability to recycle unused brine more easily. The cells are compared in Table C7. in swimming pools and main water supplies The use of chlorine. makes the membrane cell a more e cient and economical technology. It is also the most energy-e cient process. and generate a more concentrated NaOH solution. The main di erence between the diaphragm and membrane cells is that. including those used in dry cleaning • plastics industry.g. is deeply opposed owing to the damaging e ect these toxic and volatile compounds have on the depletion of the ozone layer.g.g. especially in the production of organic solvents. where Cl− ions are oxidised to Cl2. insecticides • organic solvents. which catalyse the destruction of ozone. the brine is injected into the anodeHL containing side of the cell. C CHEMISTRY IN INDUSTRY AND TECHNOLOGY 41 . the unused brine and sodium hydroxide remain separate and so there is no requirement for separating NaCl and NaOH. Much of this is generated from the pharmaceutical industry. here they combine with hydroxide ions formed by the reduction of water (the same equation as for the diaphragm cell) to yield sodium hydroxide. Any unoxidised chloride ions remain on the anode side of the cell.As in the diaphragm cell. e. PVC manufacture • water puri cation. Other important industrial areas in which chlorine is important include: • manufacture of bleaches • manufacture of acids. Once in the upper atmosphere. ultraviolet light from the Sun is able bring about homolytic ﬁssion of the C–Cl bond. This generates Cl• free radicals. e. as they cannot move through the membrane. Comparison of cells The best available technology is the membrane cell – this produces high purity (although also less than the required concentration) sodium hydroxide without the environmental problems of the other two cells. sodium hydroxide and hydrogen Chlorine chemistry is worth hundreds of billions of dollars each year in the USA alone. CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 See Option E on the CD-ROM. HCl • agrochemical industry. e.
HL Sodium hydroxide is arguably the most important strong base used in the chemicals industry. a b i State two uses of crude oil. Exam-style questions 1 Iron is a common. 2 Crude oil is a non-renewable resource worth trillions of dollars annually. i Name three methods for obtaining alkene molecules from the products of fractional distillation. Alumina is produced by re ning bauxite. rather than an inert metal. ii Identify the reducing agent in your equation. including: • re ning of alumina in aluminium production • cleaning products and bleaches • soap manufacture • making paper. ii State and explain which of these methods could be used safely in a classroom environment. produced by electrolysis of alumina. It is used in a wide range of applications. production of methanol and as a fuel in fuel cells. Name a treatment suitable for realising this outcome and explain how it is carried out. but highly important. hydrogenation reactions in syntheses or production of margarine. d Expert swordmakers treat steel to make it harder and stronger and less likely to bend under stress. using balanced equations. among other things. b The reduction of iron ore takes place in the blast furnace. e Another metal made in large quantities is aluminium. aluminium hydroxide. The metal is obtained by reduction from one of its ores. i What property of aluminium hydroxide is crucial in allowing it to be converted to pure alumina? ii Give one advantage and one disadvantage of using graphite anodes in the production of aluminium. which contains. Hydrogen gas is used in the manufacture of ammonia (for fertiliser production). c Steel is made by blowing oxygen through molten iron at high pressure in a process called basic oxygen conversion. The products of crude oil re ning nd uses in almost every aspect of everyday life. including state symbols. a Name and give the chemical formula of one ore of iron. for the production of molten iron from iron(III) oxide in the blast furnace. ii Give one advantage and one disadvantage for each use given. i Write an overall equation. how phosphorus and silicon impurities are removed during this process. metal used in construction and the manufacture of numerous household items.             42 C CHEMISTRY IN INDUSTRY AND TECHNOLOGY CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 . i What is the primary purpose of the basic oxygen converter? ii Explain.
This is generally achieved by the ow of electrons from a reactive metal electrode to a less reactive metal electrode. ii For one of the methods in part i. whereas PVC exists in a number of di erent structural forms. Colour liquid crystal displays are now commonplace. indicate the species. c Explain why liquid crystal displays fail to work properly in overly cold and hot environments. a i What is the major structural di erence between LDPE and HDPE? ii How does ‘backbiting’ contribute to the formation of LDPE?      b Explain why Te on (polytetra uoroethene) exists in only one structural form. c i Name two methods used in the modi cation of addition polymers. Their versatility and wide spectrum of usages derives from di erent chemical structures and modi cation processes. Rechargeable batteries work on a slightly di erent principle. Describe the e ects on the positional and directional order of molecules of sodium stearate during evaporation of water from a dilute aqueous solution until a solid is formed. including state symbols. why is it important for a car to be driven regularly rather than left stationary for a long period of time? iii State the changes in the oxidation states of cadmium and nickel that occur during discharge in a NiCad battery according to the equation: Cd(s) + 2NiO(OH)(s) + 2H2O(l) Cd(OH)2(s) + 2Ni(OH)2(s)    b Electrical energy can also be produced via the conversion of chemical energy from non-metallic reactants in a fuel cell. 6 Liquid crystals were discovered towards the end of the 19th century. NiCad and Li-ion rechargeable batteries. The catalysed reaction rst involves the reduction of the persulfate ions to sulfate ions followed by oxidation of the iodide ions to molecular iodine. a i Explain how the shape and physical properties of biphenyl nitriles allow them to be used in LCDs. relying on reactions that can be easily reversed by applying a voltage.   CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 C CHEMISTRY IN INDUSTRY AND TECHNOLOGY 43 .3 Addition polymers and plastics are highly versatile products used to make items from garden hoses to prosthetic limbs. b Why is heterogeneous catalysis favoured in industrial processes over the more speci c and e cient homogeneous catalysis? c i Carbon nanotubes have a potential use as which type of catalyst? ii Suggest two reasons for this. ii Describe the e ect of increasing temperature on the relative orientation of biphenyl nitrile molecules.     5 Electricity can be generated by an electrochemical cell by converting chemical energy to electrical energy. 4 The reaction between aqueous persulfate ions (S2O82−(aq)) and aqueous iodide ions is catalysed by iron(II) ions in an example of homogeneous catalysis. and also activation energy where needed (assume the reaction to be exothermic). a i Other than their ability to covert chemical energy to electrical energy. a Draw an enthalpy level diagram showing the progress of the catalysed reaction.    b The stearate ion is an example of a lyotropic liquid crystal with behaviour that depends on its concentration in solution. Suggest one reason why liquid hydrogen and ethanol can be used as the fuel in a fuel cell. describe how it is performed and state how the properties of the product di er from the starting material. present at each stage. ii In the context of the lead–acid battery. but a solid fuel source cannot. advances in liquid crystal technology have been enormous. suggest three similarities between the lead–acid. Since then.
in the presence of sunlight?   b Although silicon possesses semiconducting properties in the presence of sunlight. a i Explain. but rather insulators. contains a carbon=carbon triple bond and can be polymerised to − form a polymer chain comprising alternating C=C double and C–C single bonds. how sunlight interacts with pure silicon to enhance its electrical conductivity. with a similarly large range of properties and applications. It is therefore important to be able to manufacture them individually. tubes and pipes. a How and why does the length of a carbon nanotube a ect its electrical conductivity? b Explain in terms of structure and bonding why carbon nanotubes have one of the highest tensile strengths of all known materials. ii Why do many other pure non-metals. i Name two elements present in di erent groups of the periodic table that can be added to silicon to increase its electrical conductivity. such as sulfur. C2H2. a i State three ways (not including mechanistic detail) in which the polymerisation processes that produce LDPE and HDPE are di erent. to name but a few.   44 C CHEMISTRY IN INDUSTRY AND TECHNOLOGY CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 . with the aid of a diagram. depending on the extent of branching. polyester and Bakelite. i Name an element that can be added to polyethyne to increase its electrical conductivity.7 Nanotechnology has the potential to become a world-changing scienti c discipline. Two of these. ii Explain how the incorporation of this element brings about the desired e ect. of which Bakelite is the most famous. Condensation polymers come in a large variety of structures. ii Why must protective clothing made from Kevlar must be replaced if it is ever exposed to acids?      b Phenol–methanal plastics. it is possible to increase its conductivity by doping it with small quantities of other elements. not act as semiconductors. c Suggest two bene ts and two possible problems associated with the use of nanotechnology. Most nanotechnology revolves around carbon atoms that can be constructed into various shapes. explain why Kevlar is useful in protective armour. ii State how the polymerisation of ethene to form LDPE and HDPE di ers mechanistically. have speci c uses dependent on their properties. 10 Semiconduction is an extremely useful and important property of a small number of elements and compounds. Kevlar.  c The alkyne molecule ethyne. but graphite is soft. 9 The addition polymer polyethene can exist in a number of di erent structural forms of varying density. with potential applications ranging from the fairly ordinary to those that would seem more at home in a science. It has been pivotal in the development of silicon chips. ii Identify and explain which of these elements is used to form a p-type semiconductor and which forms an n-type semiconductor.      b Describe the movement of electrons during the polymerisation of ethene to form LDPE. each containing three aromatic rings. computer microprocessors and miniaturised circuitry. including balls. Semiconductors are able to conduct an electrical current under certain conditions. 8 Condensation polymers include well-known compounds such as nylon. The polyaramid molecule. a i With reference to structure and bonding. is made by reacting a diamine with a diacyl chloride in a condensation reaction. rigidity and strength.ction novel. can adopt complex three-dimensional structures due to cross-link formation between polymer chains. low-density polyethene (LDPE) and high-density polyethene (HDPE). Draw the structure of a phenol–methanal plastic comprising two cross-linked chains. with a low tensile strength.
However. a Compare the environmental impact of the mercury. Chlorine and sodium hydroxide are produced from brine (concentrated sodium chloride solution) irrespective of the particular electrolytic cell used.    CHEMISTRY FOR THE IB DIPLOMA © CAMBRIDGE UNIVERSITY PRESS 2011 C CHEMISTRY IN INDUSTRY AND TECHNOLOGY 45 . c Suggest reasons why the chlor-alkali industry is so important to the world economy. With reference to the twisted nematic cell present in LCDs. Although most of these naturally occurring liquid crystals do not nd much use in modern liquid-crystal devices. a Describe the structural features that allow cholesterol to behave as a liquid crystal within a certain range of temperatures.11 Many common molecules surprisingly possess the ability to act as liquid crystals due to their chemical structure. there are still limitations on the conditions under which these devices will operate.   b State one way in which the diaphragm and membrane cells di er and one way in which they are similar. 12 The chlor-alkali industry is a lucrative and important chemical industry responsible for the production of a number of chemicals used directly or indirectly in a wide spectrum of applications. diaphragm and membrane cells. this property is sometimes crucial for their role. b Synthetic liquid crystal molecules have been designed for modern applications such as liquid crystal displays (LCDs). Cholesterol is found in animal cell membranes and is important in maintaining the membrane’s integrity across a range of temperatures. explain why the screen of a pocket calculator will not function correctly if it is too cold.
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