5a.

The Extraction of Lead The principal ore of lead is galena, chemical formula PbS lead sulphide (lead(II) sulfide) o There is also the less common lead ore cerussite, chemical formula PbCO3, lead carbonate (lead(II) carbonate) The crushed ores are concentrated by a technique known as froth flotation. The ores are roasted to drive off unwanted water and convert them to a more suitable chemical form e.g. lead oxide, for reduction to lead metal. o Roasting galena in air converts the lead sulphide into lead(II) oxide ... o 2PbS(s) + 3O2(g) ==> 2PbO(s) + 2SO2(g) ... but harmful and polluting sulfur dioxide is made in the process, which must be dealt with! Roasting cerussite coverts the lead carbonate into lead oxide ... o o o o PbCO3(s) ==> PbCO3(s) + CO2(g) ... an example of a thermal decomposition

The more concentrated lead oxide can then be reduced in a coke fired blast furnace ... 2PbO(s) + C(s) ==> 2Pb(l) + CO2(g) ... the lead oxide is reduced (oxygen loss) and the carbon/coke reducing agent is oxidised (oxygen gain) in the smelting process. ... as in the blast furnace from iron, the liquid lead can be drained off from the lead smelter. The above balanced equations, are a simplification of what can be quite complicated chemistry, BUT they do adequately describe and illustrate the chemical processes for obtaining lead from its ores.

The overall process from lead ore to very pure lead is quite complicated and lead ores contain other

valuable metals like silver, so there more stages in the process than are described here.

55. The Extraction and Purification of Zinc Zinc is extracted from either zinc blende/sphalerite ore (zinc sulphide) or sometimes calamine/Smithsonite ore (zinc carbonate). (1) The zinc sulphide ore is roasted in air to give impure zinc oxide. o o 2ZnS(s) + 3O2(g) ==> 2ZnO(s) + 2SO2(g) Note: calamine ore can be used directly in a zinc smelter because on heating it also forms zinc oxide. ZnCO3(s) ==> ZnO(s) + CO2(g) (endothermic thermal decomposition)

(2) The impure zinc oxide can be treated in two ways to extract the zinc: o (a) It is roasted in a smelting furnace with carbon (coke, reducing agent) and limestone (to remove the acidic impurities). The chemistry is similar to iron from a blast furnace. C(s) + O2(g) ==> CO2(g) (very exothermic oxidation, raises temperature considerably) C(s) + CO2(g) ==> 2CO(g) (C oxidised, CO2 reduced) ZnO(s) + CO(g) ==> Zn(l) + CO2(g) (zinc oxide reduced by CO, Zn undergoes O loss) or direct reduction by carbon: ZnO(s) + C(s) ==> Zn(l) + CO(g) (ZnO reduced, C oxidised) REDOX definition reminders - reduction is a process of oxygen loss (or electron gain) and oxidation is a process of oxygen gain (or electron loss). The carbon monoxide acts as the reducing agent i.e. it removes the oxygen from the oxide. The impure zinc is then fractionally distilled from the mixture of slag and other metals like lead and cadmium out of the top of the furnace in an atmosphere rich in carbon monoxide

which stops any zinc from being oxidised back to zinc oxide. o The slag and lead (with other metals like cadmium) form two layers which can be tapped off at the base of the furnace. The zinc can be further purified by a 2nd fractional distillation or more likely by dissolving it in dilute sulphuric acid and purified electrolytically as described below. (b)Two stages (i) It is dissolved and neutralised with dilute sulphuric acid to form impure zinc sulphate solution. ZnO(s) + H2SO4(aq) ==> ZnSO4(aq) + H2O(l) or using calamine ore/zinc carbonate directly: ZnCO3(s) + H2SO4(aq) ==> ZnSO4(aq) + H2O(l)+ CO2(g)

(ii) Quite pure zinc is produced from the solution by electrolysis. It can be deposited on a pure zinc negative electrode (cathode) in the same waycopper can be purified. The other electrode, must be inert e.g. for laboratory experiments, carbon (graphite) can be used and oxygen is formed. Zn
2+ (aq) -

+ 2e ==> Zn(s) A reduction process, electron gain, as zinc metal is deposited on the (-) electrode.

You can't use solid zinc oxide directly because its insoluble and the ions must free to carry the current and migrate to the electrodes in some sort of solution. For more details of the type of electrolysis system used, see purification of copper (just swap Zn for Cu in the method/diagram). PLEASE note: In the industrial production of zinc by electrolysis (called electro-winning) the negative (-) cathode is made of

aluminium (Al, where zinc deposits) and the positive (+) electrode is made of a lead-silver alloy (Pb-Ag, where oxygen gas is formed). Why these particular electrode metals are used in this 'electrowinning' process I'm not quite sure, but aluminium is so unreactive that it is effectively inert, and lead and silver are also of low chemical reactivity.

5c. The Extraction of Chromium and Titanium by Displacement Titanium is too reactive to be obtained by simple reduction of its oxide and has to be extracted by a costly multiple stage process involving chlorine and a more reactive metal like sodium or magnesium and all these three are themselves made from the costly process of electrolysis! So the process ain't cheap! and titanium is a very valuable metal! Titanium ore is mainly the oxide TiO2, which is converted into titanium tetrachloride TiCl4 by heating with carbon and chlorine. o o titanium dioxide + carbon + chlorine ==> titanium(IV) chloride + carbon dioxide TiO2 + C + 2Cl2 ==> TiCl4 + CO2

The chloride is then reacted with sodium or magnesium to form titanium metal and sodium chloride or magnesium Chloride. This reaction is carried out in an atmosphere of inert argon gas so non of the metals involved becomes

oxidised by atmospheric oxygen. o o o o o o titanium(IV) chloride + magnesium ==> titanium + magnesium chloride TiCl4 + 2Mg ==> Ti + 2MgCl2 or titanium(IV) chloride + sodium ==> titanium + sodium chloride TiCl4 + 4Na ==> Ti + 4NaCl These are displacement reactions in which a more reactive metal (Mg or Na) displaces a less reactive metal (Ti). Overall the titanium oxide ore is reduced to titanium metal (overall O loss, oxide => metal) and the magnesium or sodium acts as a reducing agent. Chromium ore is processed and purified into chromium(III) oxide. This is reacted, very exothermically, in a thermit style reaction, with aluminium (see reactions of aluminium) to free the chromium metal. o o o Cr2O3(s) + 2Al(s) ==> Al2O3(s) + 2Cr(s) REDOX definition reminders - reduction is a process of oxygen loss (or electron gain) and oxidation is a process of oxygen gain (or electron loss). The chromium(III) oxide is reduced to chromium by O loss, the aluminium is oxidised to aluminium oxide by O gain, and the aluminium is the reducing agent i.e. the O remover. These are examples of metal displacement reactions e.g. the less reactive chromium or titanium are displaced by the more reactive sodium, magnesium or aluminium.