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Purification of copper When copper is made from sulphide ores by the first method above, it is impure.

The blister copper is first treated to remove any remaining sulphur (trapped as bubbles of sulphur dioxide in the copper - hence "blister copper") and then cast into anodes for refining using electrolysis.

Electrolytic refining The purification uses an electrolyte of copper(II) sulphate solution, impure copper anodes, and strips of high purity copper for the cathodes. The diagram shows a very simplified view of a cell.

At the cathode, copper(II) ions are deposited as copper.

At the anode, copper goes into solution as copper(II) ions.

For every copper ion that is deposited at the cathode, in principle another one goes into solution at the anode. The concentration of the solution should stay the same. All that happens is that there is a transfer of copper from the anode to the cathode. The cathode gets bigger as more and more pure copper is deposited; the anode gradually disappears. In practice, it isn't quite as simple as that because of the impurities involved.

What happens to the impurities? Any metal in the impure anode which is below copper in the electrochemical series (reactivity series) doesn't go into solution as ions. It stays as a metal and falls to the bottom of the cell as an "anode sludge" together with any unreactive material left over from the ore. The anode sludge will contain valuable metals such as silver and gold. Metals above copper in the electrochemical series (like zinc) willform ions at the anode and go into solution. However, they won't get discharged at the cathode provided their concentration doesn't get too high. The concentration of ions like zinc will increase with time, and the concentration of the copper(II) ions in the solution will fall. For every zinc ion going into solution there will obviously be one fewer copper ion formed. (See the next note if you aren't sure about this.) The copper(II) sulphate solution has to be continuously purified to make up for this.

Electrolysis of Brine
Sodium chloride solution contains:

sodium ions, chloride ions, hydrogen ions (from the water), hydroxide ions (from the water).

The hydrogen and hydroxide ions come from the equilibrium:

The diaphragm cell

At any one time, the concentration of hydrogen ions or hydroxide ions will be very small - the position of equilibrium lies well to the left-hand side.

At the anode The negative ions, chloride and hydroxide, get attracted towards the positively charged anode. It is actually easier to liberate hydroxide ions (to give oxygen) than chloride ions (to give chlorine), but there are far, far more chloride ions arriving at the anode than hydroxide ions. The major reaction at the anode is therefore:

Two chloride ions each give up an electron to the anode, and the atoms produced combine to give chlorine gas. The chlorine is, however, contaminated with small amounts of oxygen because of a reaction involving hydroxide ions giving up electrons as well.

The chlorine has to be purified to remove this oxygen.

At the cathode Sodium ions and hydrogen ions (from the water) are attracted to the negative cathode. It is much easier for a hydrogen ion to pick up an electron than for a sodium ion. So this reaction happens:

As the hydrogen ions are converted into hydrogen gas, the water equilibrium tips to the right to replace them.

The net effect of this is that there is a build up of sodium ions and these newly-produced hydroxide ions around the cathode. In other words, sodium hydroxide solution is being formed around the cathode.

The need to keep all the products separate If chlorine comes into contact with hydrogen, it produces a mixture which will explode violently on exposure to sunlight or heat. Hydrogen chloride gas would be produced. Obviously, the two gases need to be kept apart. However, chlorine also reacts with sodium hydroxide solution to produce a mixture of sodium chloride and sodium chlorate(I) - also known as sodium hypochlorite. This mixture is commonly sold as bleach. Therefore, if you are trying to manufacture chlorine and sodium hydroxide rather than bleach, you have to keep the chlorine and sodium hydroxide apart as well.

The diaphragm and membrane cells are designed so that all the products are kept separate.

The diaphragm The diaphragm is made of a porous mixture of asbestos and polymers. The solution can seep through it from the anode compartment into the cathode side. Notice that there is a higher level of liquid on the anode side. That makes sure that the flow of liquid is always from left to right - preventing any of the sodium hydroxide solution formed finding its way back to where chlorine is being produced.

Production of the chlorine Chlorine is produced at the titanium anode according to the equation:

It is contaminated with some oxygen because of the reaction:

The chlorine is purified by liquifying it under pressure. The oxygen stays as a gas when it is compressed at ordinary temperatures.

Production of the hydrogen The hydrogen is produced at the steel cathode:

Production of the sodium hydroxide A dilute solution of sodium hydroxide solution is also produced at the cathode (see above for the explanation of what happens at the cathode). It is highly contaminated with unchanged sodium chloride solution. The sodium hydroxide solution leaving the cell is concentrated by evaporation. During this process, most of the sodium chloride crystallises out as solid salt. The salt can be separated, dissolved in water, and passed through the cell again. Even after concentration, the sodium hydroxide will still contain a small percentage of sodium chloride.

Extracting aluminium from bauxite Introduction Aluminium is too high in the electrochemical series (reactivity series) to extract it from its ore using carbon reduction. The temperatures needed are too high to be economic. Instead, it is extracted by electrolysis. The ore is first converted into pure aluminium oxide by the Bayer Process, and this is then electrolysed in solution in molten cryolite - another aluminium compound. The aluminium oxide has too high a melting point to electrolyse on its own.

Aluminium ore The usual aluminium ore is bauxite. Bauxite is essentially an impure aluminium oxide. The major impurities include iron oxides, silicon dioxide and titanium dioxide. Purifiying the aluminium oxide - the Bayer Process Reaction with sodium hydroxide solution

Crushed bauxite is treated with moderately concentrated sodium hydroxide solution. The concentration, temperature and pressure used depend on the source of the bauxite and exactly what form of aluminium oxide it contains. Temperatures are typically from 140C to 240C; pressures can be up to about 35 atmospheres. High pressures are necessary to keep the water in the sodium hydroxide solution liquid at temperatures above 100C. The higher the temperature, the higher the pressure needed. With hot concentrated sodium hydroxide solution, aluminium oxide reacts to give a solution of sodium tetrahydroxoaluminate.

The impurities in the bauxite remain as solids. For example, the other metal oxides present tend not to react with the sodium hydroxide solution and so remain unchanged. Some of the silicon dioxide reacts, but goes on to form a sodium aluminosilicate which precipitates out. All of these solids are separated from the sodium tetrahydroxoaluminate solution by filtration. They form a "red mud" which is just stored in huge lagoons.

Precipitation of aluminium hydroxide The sodium tetrahydroxoaluminate solution is cooled, and "seeded" with some previously produced aluminium hydroxide. This provides something for the new aluminium hydroxide to precipitate around.

Formation of pure aluminium oxide Aluminium oxide (sometimes known as alumina) is made by heating the aluminium hydroxide to a temperature of about 1100 - 1200C.

Conversion of the aluminium oxide into aluminium by electrolysis The aluminium oxide is electrolysed in solution in molten cryolite, Na3AlF6. Cryolite is another aluminium ore, but is rare and expensive, and most is now made chemically.

The electrolysis cell The diagram shows a very simplified version of an electrolysis cell.

Although the carbon lining of the cell is labelled as the cathode, the effective cathode is mainly the molten aluminium that forms on the bottom of the cell. Molten aluminium is syphoned out of the cell from time to time, and new aluminium oxide added at the top. The cell operates at a low voltage of about 5 - 6 volts, but at huge currents of 100,000 amps or more. The heating effect of these large currents keeps the cell at a temperature of about 1000C.

The electrode reactions These are very complicated - in fact one source I've looked at says that they aren't fully understood. For chemistry purposes at this level, they are always simplified (to the point of being wrong! - see comment below).

This is the simplification: Aluminium is released at the cathode. Aluminium ions are reduced by gaining 3 electrons.

Oxygen is produced initially at the anode.

However, at the temperature of the cell, the carbon anodes burn in this oxygen to give carbon dioxide and carbon monoxide. Continual replacement of the anodes is a major expense.

Economic considerations Think about:

The high cost of the process because of the huge amounts of electricity it uses. This is so high because to produce 1 mole of aluminium which only weighs 27 g you need 3 moles of electrons. You are having to add a lot of electrons (because of the high charge on the ion) to produce a small mass of aluminium (because of its low relative atomic mass). Energy and material costs in constantly replacing the anodes. Energy and material costs in producing the cryolite, some of which gets lost during the electrolysis.

Environmental problems in mining and transporting the bauxite Think about:

Loss of landscape due to mining, processing and transporting the bauxite. Noise and air pollution (greenhouse effect, acid rain) involved in these operations.

Extracting aluminium from the bauxite Think about:

Loss of landscape due to the size of the chemical plant needed, and in the production and transport of the electricity. Noise. Atmospheric pollution from the various stages of extraction. For example: carbon dioxide from the burning of the anodes (greenhouse effect); carbon monoxide (poisonous); fluorine (and fluorine compounds) lost from the cryolite during the electrolysis process (poisonous). Pollution caused by power generation (varying depending on how the electricity is generated.) Disposal of red mud into unsightly lagoons. Transport of the finished aluminium.

Recycling Think about:

Saving of raw materials and particularly electrical energy by not having to extract the aluminium from the bauxite. Recycling aluminium uses only about 5% of the energy used to extract it from bauxite. Avoiding the environmental problems in the extraction of aluminium from the bauxite. Not having to find space to dump the unwanted aluminium if it wasn't recycled. (Offsetting these to a minor extent) Energy and pollution costs in collecting and transporting the recycled aluminium.

Uses of aluminium Aluminium is usually alloyed with other elements such as silicon, copper or magnesium. Pure aluminium isn't very strong, and alloying it adds to it strength. Aluminium is especially useful because it

has a low density;

is strong when alloyed; is a good conductor of electricity; has a good appearance; resists corrosion because of the strong thin layer of aluminium oxide on its surface. This layer can be strengthened further by anodising the aluminium. Anodising essentially involves etching the aluminium with sodium hydroxide solution to remove the existing oxide layer, and then making the aluminium article the anode in an electrolysis of dilute sulphuric acid. The oxygen given of at the anode reacts with the aluminium surface, to build up a film of oxide up to about 0.02 mm thick. As well as increasing the corrosion resistance of the aluminium, this film is porous at this stage and will also take up dyes. (It is further treated to make it completely non-porous afterwards.) That means that you can make aluminium articles with the colour built into the surface.

Some uses include:

aluminium is used for aircraft other transport such as ships' superstructures, container vehicle bodies, tube trains (metro trains) overhead power cables (with a steel core to strengthen them) saucepans because light, strong, resists corrosion light, strong, resists corrosion light, resists corrosion, good conductor of electricity light, resists corrosion, good appearance, good conductor of heat

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