Extraction of Metals Introduction The large scale processes involved in the extraction of pure metals from their respective ore is called metallurgy. There is several numbers of metallurgical processes involved in the process of extraction of different metals and other various compounds in industry and laboratory. For the extraction of metals the following steps and processes include: Concentration of ore. The process of removal of gangue, the rocky impurities like SiO2 present in an ore is called concentration of ore or ore dressing and purified ore is called concentrate. It can be done with the following processes: Gravity Separation, Froth floatation, Electromagnetic separation, and so on. Then it will be followed by Extraction of metals from the concentrated ore. To this processes it involves the reduction process, reduction process, and refining of the metals. In order to refine the metals it should undergo distillation, liquation, and oxidation. Finally it will have to undergo Electro-refining to pure metal and compounds. This very assignment purely contains extraction of Aluminium, Copper, Zinc, and Iron. It too has their properties- chemical and physical and applications as well. Moreover, this assignment encompasses of commercial preparation of Ammonia and Nitric Acid. The industrial preparation of Cement and preparation of Glass can also be found here. By doing this assignment I assure that I will be able to convince and beware that any readers and learners of this very assignment would be very useful in their practical knowledge to continue and carry out their further studies hereafter. Page 1 Extraction of Metals Extraction of metal and its process The large scale processes involved in the extraction of pure metals from their respective ore is called metallurgy. Extraction of metals from is ore take place in the following ways; (i). Concentration of ore. The process of removal gangue, the rocky impurities like SiO2 present in an ore is called concentration of ore or ore dressing and purified ore is called concentrate. It involves the following ways: Gravity Separation: Where the difference in the densities of ore and gangue is the main. The ore is poured over a vibrating slopped table with grooves and jet of water is allowed to flow over it. The denser ore particles settle down in the grooves and lighter gangue washed down by water. Froth floatation: this process depends on preferential wettability of the ore and the gangue particles. The crushed ore is taken in a large tank containing oil and water and agitated with a current of air. The ore is wetted by the oil and separates from the gangue in the form of froth. Electromagnetic separation: this method is used to separate ores which are magnetic in nature. Crushed ore is placed over conveyer belt, which rotates around tow metal wheels, one of which is magnetic. The magnetic particles are attracted to the magnetic wheel and fall separately apart from the non magnetic particles. (ii) Extraction of metals from the concentrated ore. The metal is obtained from the concentrated ore by chemical reduction or electrolytic process. Reduction process In the reduction process it is the oxide ore that is reduced. If the ore is not an oxide ore it is just converted to the oxide by roasting or by calcinations. Roasting is the process of heating the Page 2 Extraction of Metals concentrated ore to the high temperature in excess of air. Roasting is usually done in sulphide ores like zinc blende (ZnS), and galena (PbS). A part of zinc sulphide is converted to zinc sulphate by heating to a temperature of 800- 9000C at which ZnSO4 decomposes back to zinc oxide. If the ore is carbonate or hydrated oxide it is heated in the absence of air at a temperature insufficient to melt the ore. This process is called calcinations. Reduction process The metallic oxide obtained is then reduced by carbon in the form of coke, carbon monoxide, or hydrogen. Oxides of potassium, calcium, sodium, magnesium, and aluminium cannot be reduced by carbon and carbon monoxides or hydrogen. These metals are placed on the top in the metal activity series, they are very reactive and have great affinity towards oxygen and so cannot be reduced by reducing agents. (iii) Refining of the metals. It is the separation of the above extracted metal from the residual impurity which is carried out using the following processes. Distillation Metals like mercury and zinc which is volatile distils over in pure form and the non volatile impurity remains behind. Liquation Metals like lead and tin have low boiling points, so they are heated on the sloping hearth of a furnace. The molten or fused metals flows away leaving behind the impurities. Oxidation Metals like iron are purified by this method. The volatile oxides of phosphorous, sulphur and other impurities rise to the surface and are removed while the molten metal remains behind. Page 3 Extraction of Metals Electro-refining It is the widely used process. The impure slab of the metals is made the anode, while a pure thin sheet of metals is made the cathode. Electrolyte used is a salt solutions of a metal, which is to be refined. Pure metal deposits at the cathode and impurities settle down forming anode mud. ALUMINIUM Extracting aluminium from bauxite Introduction Aluminium is too high in the electrochemical series (reactivity series) to extract it from its ore using carbon reduction. Instead, it is extracted by electrolysis. The ore is first converted into pure aluminium oxide and this is then electrolyzed in solution in molten cryolite. The aluminium oxide has too high a melting point to electrolyze 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. Page 4 Extraction of Metals Purifying 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 140°C to 240°C; 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 100°C. 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. Precipitation of aluminium hydroxide The sodium tetrahydroxoaluminate solution is cooled, and "seeded" with some previously produced aluminium hydroxide. Page 5 Extraction of Metals Formation of pure aluminium oxide Aluminium oxide (sometimes known as alumina) is made by heating the aluminium hydroxide to a temperature of about 1100 - 1200°C. Conversion of the aluminium oxide into aluminium by electrolysis The aluminium oxide is electrolyzed in solution in molten cryolite, Na3AlF6. Cryolite is another aluminium ore, but is rare and expensive, and most is now made chemically. The electrolytic 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 1000°C. The electrode reactions 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. Page 6 Extraction of Metals It is malleable and ductileIt is good conductor of heat and electricity Its M.P= 6600C and B.P=18000C Chemical properties (i) Action of air Al is not affected by air but in the moist a thin film of oxide is formed over its surface. It burns in oxygen producing brilliant light. 4Al +3O2 2Al2O3 (ii) Action of water Pure Al is not affected by pure water. The pure Al is readily corroded by water containing salts. Al decomposes boiling water evolving hydrogen. (iii)Action of acids Al being strongly electropositive, very reactive and powerful reducing agent. It dissolves in HCL and dilute sulphuirc acid evolving hydrogen. 2Al +6HCl 2AlCl3 +3H2 2Al + 3H2SO4 Al2(SO4)3 + 3H2 In conc. H2SO4 2Al + 6H2SO4 Al2(SO4)3 +3SO2 +6H2O (iv) Action of alkalies Al is attacked by caustic alkalies with the evolution of hydrogen. 2Al + 2NaOH + 2H2O 2NaAlO2 + 3H2 Sodium meta aluminate Copper extraction Hydrometallurgical extraction Oxidized copper ore bodies are with hydrometallurgical processes treat oxide ores dominated by copper carbonate minerals such as azurite and malachite, and other soluble minerals. Such oxide ores are usually leached by sulphuric acid, usually using a heap leach or dump leach process to liberate the copper minerals into a solution of sulphuric acid laden with copper sulphate in solution. The copper sulphate solution is then stripped of copper via a solvent extraction, with the barred sulphuric acid recycled back on to the heaps. Commonly sulfuric acid Page 7 Extraction of Metals is used as a leachant for copper oxide. Froth flotation generally is not used to concentrate copper oxide ores. Roasting In the roaster, the copper concentrate is partially oxidized to produce calcine and sulphur dioxide gas. The reaction takes place as follows: 2CuFeS2(s) + 3O2(g) → 2FeO(s) + 2CuS(s) + 2SO2(g) Smelting The calcine is then mixed with silica and limestone and smelted at 1200 °C to form a liquid called copper matte. Reactions as follows ; For example iron oxides and sulphides are converted to slag which is floated off the matte. FeO(s) + SiO2 (s) → FeO.SiO2 In a parallel reaction the iron sulphide is converted to slag: 2FeS (l) + 3O2 + 2SiO2 (l) → 2FeO.SiO2 (l) + 2SO2(g) Conversion to blister The matte, which is produced in the smelter, contains around 70% copper primarily as copper sulphide as well as iron sulphide. The sulphur is removed at high temperature as sulfur dioxide by blowing air through molten matte: 2Cu2S + 3O2 → 2Cu2O + 2SO2 Cu2S + 2Cu2O → 6Cu + SO2 In a parallel reaction the iron sulfide is converted to slag: 2FeS + 3O2 → 2FeO + 2SO2 2FeO + 2SiO2 → 2FeSiO3 The end product is (about) 98% pure copper known as blister because of the broken surface created by the escape of sulfur dioxide gas as the copper ingots are cast. By-products generated Page 8 Extraction of Metals in the process are sulfur dioxide and slag. Reduction The blistered copper is put into an anode furnace to get rid of most of the remaining oxygen. This is done by blowing natural gas through the molten copper oxide. When this flame burns green, indicating the copper oxidation spectrum, the oxygen has mostly been burned off. This creates copper at about 99% pure. Electrorefining Apparatus for electrolytic refining of copper The copper is refined by electrolysis. The anodes cast from processed blister copper are placed into an aqueous solution of 3-4% copper sulphate and 10-16% sulphuric acid. Cathodes are thin rolled sheets of highly pure copper. A potential of only 0.2-0.4 volts is required for the process to commence. At the anode, copper and less noble metals dissolve.. Copper (II) ions migrate through the electrolyte to the cathode. At the cathode, copper metal plates out but less noble constituents such as arsenic and zinc remain in solution. The reactions are: At the anode: Cu(s) → Cu2+(aq) + 2e– At the cathode: Cu2+(aq) + 2e– → Cu(s) Properties Physical properties It has red color. It is highly malleable and ductile. It has the density of 8.93 and melting point is Page 9 Extraction of Metals 1083 0C and boiling point is 2320 0C. It is a good conductor of heat and electricity. Chemical Properties Action of air: copper is not affected by dry air at ordinary temperature but moist air and in presence of carbon dioxide, slowly converted to green basic carbonate. 2Cu + H 2O + CO2 + O2 CuCO3.Cu (OH) 2 Action of non-metals: (a) Oxygen. On heating(up to 11000C) copper forms first red cuprous oxide (Cu 2O) and on further heating it gives black cupric oxide(CuO) 4Cu + O2 2Cu + O2 2Cu 2O 2CuO (b) Chlorine. A heated copper foil burn in chlorine Cu + Cl2 CuCl2 Bromine and iodine also combine with copper similarly. Action of acid: the action of acids on copper is important. Since copper is below hydrogen in electrochemical series, hydrogen do not evolved. (a) Sulphuric acids. Dilute sulphuric acid reacts in presence of air or oxygen. Page 10 Extraction of Metals 2Cu + 2H2SO4 + O2 CuSO4 + 2H2O When heated in concentrated sulphuric acids it produce sulphur dioxide 2Cu + H2SO4 CuSO4 + SO 2 + 2H 2O (b) Hydrochloric acid. Dilute hydrochloric acid reacts in presence of air. 2Cu + 4HCl + O2 2CuCl2 + 2H2O Action of ammonia: copper has no action on nitrogen. When however ammonia gas is passed over red hot copper, hydrogen gas is liberated while nitrogen of ammonia is absorbed by copper metal. Reducing properties: copper reduces oxides of nitrogen to elementary nitrogen and Fe 2(SO4)3 to FeSO4 2Cu + 2NO 2CuO + N2 Fe 2(SO4)3 + Cu 2FeSO4 + CuSO4 Fe+++ + Cu 2Fe++ + Cu++ Action of water: water at ordinary temperature has no action on copper, and at high temperature very slight reaction takes place, but sea water slowly corrodes copper immersed in it. Uses of Cu Boilers and heat exchangers: It is a good conductor of heat and doesn't react with water. Electrical wiring: It is a very good conductor of electricity and is easily drawn out into wires. Page 11 Extraction of Metals Domestic plumbing: It does not react with water, and is easily bent into shape Extraction of Zinc Extraction of zinc It is not found in nature and it occurs in combine state. Principle zinc ore is zinc blende (ZnS). Zinc is extracted in two forms: A. The carbon reduction process. It consists of following steps: (i) Concentration of the ore. The powdered ore is washed in a tank of water. The heavier particles settle down while the light sand and clay particles are washed away. If the ore is sulphide ore, it is concentrated by Froth Floatation Process. (ii) Roasting The above concentrated zinc ore (ZnS) is now roasted at 9000 C in excess of air. The sulphide is first converted into oxide and sulphate of zinc. The latter decomposes into the oxide at that temperature. The roasted ore is mainly zinc oxide. (iii) Reduction of Zinc oxide It is brought about by coke. The oxide is mixed with excess of powdered coke and fed into the top of a vertical retort heated by producer gas to about 14000C. The metallic zinc is formed as a vapor which along with carbon monoxide passes through an outlet near the retort. Page 12 Extraction of Metals ZnO + C Zn + CO The molten zinc is cast into ingots. This commercial zinc is known as zinc spelter. It contains impurities like iron, antimony, cadmium, arsenic and carbon which are 97% pure. (iv) Purification of zinc It is purified by melting spelter in a furnace when two immiscible layers are formed. The upper layer is of zinc containing minute impurities and the lower layer is of lead because of its heaviness. The upper layer is separated and heated. Arsenic and other are volatilized away to obtain pure zinc. B. Electrolytic Process for Extraction of Zinc In this process roasted ore of zinc oxide is dissolved in sulphuric acid and the resulting zinc sulphide solution is electrolyzed in a cell in which lead acts as the anode and aluminium acts as cathode. When an electric current is passed through the cell, pure zinc is deposited over the cathode. Properties Chemical Properties Zinc is a bluish white metal brittle at the ordinary temperature but malleable and ductile between 1000C and 1500C. At 2000C it becomes brittle again. Its specific gravity is 6.9. M.P- 4200C and B.P. - 9300C. Chemical Properties 1. Action of air. Zn is not affected by in dry air but in the moist air a protective coating of basic carbonate is formed on the surface. When heated strongly heated in the air it burns Page 13 Extraction of Metals with the greenish blue flame forming clouds of ZnO. 2Zn + O2 2ZnO 2. Action of water. Pure Zn is not dissolved by the water. Boiling water is slowly decomposed by impure Zn. Zn + H2O ZnO + H2 3. Action of acids. Pure Zn is attaked slowly by the acids but the presence of impurities accelerates the rate of reaction die to the formation of electro-chemical couples. It dissolves readily in dilute and conc. HCl. Zn + 2HCl ZnCl2 + H2 Dilute Sulphuric acid produces hydrogen Zn + H2SO4 ZnSO4 + H2 Hot and dilute sulphuric acid produces SO2 Zn + 2H2SO4 ZnSO4 + SO2 + 2H2O 4. Action of Alkalies. Zn dissolved in the hot solution of caustic alkalies forming zincates and liberating H2. Zn + NaOH Na2ZnO2 + H2 5. Precipitation of other metals. It displaces less electropositive metals like Cu, Ag, Au and Pb from their salt solution. SuSO4 + Zn 2Na [Ag (CN)2] ZnSO4 + Zn + 2Ag Cu + Na2[Zn (CN)4] 6. Action of Ammonia. Zn decomposes ammonia at red heat. Page 14 Extraction of Metals 3Zn + 2NH3 Zn3N2 + 3H2 Uses Zn is most importantly used for the galvanization of iron. It is also used for desilverisation of lead and in the extraction of Au and Ag. Preparation and Extraction of Iron The production of iron or steel is a process unless the desired final product is cast iron. The first stage is to produce pig iron in a blast furnace. The second is to make wrought iron or steel from pig iron by a further process. Blast furnace Iron is produced starting from iron ores, principally hematite -Fe2O3and magnetite -Fe3O4 by a carbothermic reaction (reduction with carbon) in a blast furnace at temperatures of about 2000 °C. In a blast furnace, iron ore, carbon in the form of coke, and a flux such as limestone is used to remove impurities in the ore which would otherwise clog the furnace with solid material and are fed into the top of the furnace, while a blast of heated air is forced into the furnace at the bottom. In the furnace, the coke reacts with oxygen in the air blast to produce carbon monoxide: 2 C + O2 → 2 CO The carbon monoxide reduces the iron ore to molten iron, becoming carbon dioxide in the process: 3 CO + Fe2O3 → 2 Fe + 3 CO2 The flux is present to melt impurities in the ore, principally silicon dioxide sand and other silicates. Common fluxes include limestone and dolomite -calcium-magnesium carbonate. CaCO3 → CaO + CO2 Page 15 Extraction of Metals Then calcium oxide combines with silicon dioxide to form a slag. CaO + SiO2 → CaSiO3 The slag melts in the heat of the furnace. In the bottom of the furnace, the molten slag floats on top of the denser molten iron, and apertures in the side of the furnace are opened to run off the iron and the slag separately. The iron once cooled, is called pig iron, while the slag can be used as a material in road construction or to improve mineral-poor soils for agriculture. Further processes Steelmaking and Ironworks Pig iron is not pure iron, but has 4–5% carbon dissolved in it with small amounts of other impurities like sulphur, magnesium, phosphorus and manganese. As the carbon is the major impurity, the iron (pig iron) becomes brittle and hard. This form of iron is used to cast articles in foundries such as stoves, pipes, radiators, lamp-posts and rails. Alternatively pig iron may be made into steel or wrought iron -commercially pure iron. The hardness of the steel depends upon its carbon content, the higher the proportion of carbon, the greater the hardness and the lesser the ductility. The properties of the steel can also be changed by tempering it. To harden the steel, it is heated to red hot and then cooled by quenching it in the water. It becomes harder and more brittle. This steel is then heated to a required temperature and allowed to cool. The steel thus formed is less brittle. Properties Physical Properties Iron is grayish substances. It is malleable, ductile and good conductor of heat and electricity. It is the most magnetic of all metals and loses this property above 7660C. Its M.P. is 15250C and B.P. is 24500C. Its specific gravity is 7.86. Chemical Properties I. Action of air or oxygen. When Fe is strongly heated in air or Oxygen, ferroso-ferric oxide is formed. Page 16 Extraction of Metals 3Fe + 2O2 II. Fe3O4 Action of moisture- rusting. Iron, when exposed to moisture or water, allowed to remain damp, is covered by a reddish yellow film or compound. This is known as rust and phenomenon is known as Rusting. Action of Water. Iron decomposes stream. III. 3Fe + 4H2O IV. Fe3O4 + 4H2 Action of Acids. Iron dissolves in dilute acids forming hydrogen and ferrous salts. Fe + H2SO4 FeSO4 + H2 Fe + 2HCl FeCl + H2 Dilute nitric acid gives a mixture of ferrous nitrate and ammonium nitrate. [Fe + 2HNO3 Fe (NO3)2 + 2H] * 4 2HNO3 + 8H NH4NO3 + 3H2O Conc. H2SO4 gives a mixture of ferrous and ferric sulphates. Fe + 2H2SO4 FeSO4 + SO2 + 2H2O 2FeSO4 + 2H2SO4 4Fe (SO4)3 + 2H2O + SO2 Fairly strong nitric acid gives ferric nitrate and a mixture of the oxides of nitrogen. V. Action of alkalies, halogens, and sulphur. Alkalies have no action on iron. Halogens and sulphur combines with the heated metal forming halides and sulphides respectively. 2Fe + 3Cl2 Fe + S VI. 2FeCl3 FeS Displacement of less electronegative metals. For example it displaces Cu from a solution of copper sulphates. Fe + Cu2+ Fe2+ + Cu Page 17 Extraction of Metals Applications Iron oxides (FeO, Fe3O4, and Fe2O3) are ores used for iron production. They are also used as a catalyst in the Space Shuttle Solid Rocket Boosters, and in the production of magnetic storage media in computers. They are often mixed with other compounds, and retain their magnetic properties in solution. It is used as a mordant in the dyeing of cloth and leather, and as a wood preservative. It is used in blueprints. Iron (III) arsenate (FeAsO4) is used in insecticides. Nitric acid Nitric acid (HNO3), also known as aqua fortis and spirit of nitre, is a highly corrosive and toxic strong acid. Commercial Preparation Ostwald Process Commercial grade nitric acid solutions are usually between 52% and 68% nitric acid. Production of nitric acid is via the Ostwald process- German chemist Wilhelm Ostwald. In this process, anhydrous ammonia is oxidized to nitric oxide, which is then reacted with oxygen in air to form nitrogen dioxide. This is subsequently absorbed in water to form nitric acid and nitric oxide. The nitric oxide is cycled back for reoxidation. By using ammonia derived from the Haber process, the final product can be produced from nitrogen, hydrogen, and oxygen which are derived from air and natural gas as the sole feedstocks. Properties Physical properties Pure anhydrous nitric acid (100%) is a colorless liquid with a density of 1.522 g/cm³ which solidifies at -42 °C to form white crystals and boils at 83 °C. When boiling in light, even at room temperature, there is a partial decomposition with the formation of nitrogen dioxide following the reaction: Page 18 Extraction of Metals 4 HNO3 → 2 H2O + 4 NO2 + O2 (72°C) which means that anhydrous nitric acid should be stored below 0 °C to avoid decomposition. Chemical Properties Acidic properties Being a typical acid, nitric acid reacts with alkalis, basic oxides, and carbonates to form salts, such as ammonium nitrate. Dissociation and ionization Nitric acid has an acid dissociation constant (pKa) of −1.4: in aqueous solution, it almost completely (93% at 0.1 mol/L) ionizes into the nitrate ion NO−3 and a hydrated proton, known as a hydronium ion, H3O+. HNO3 + H2O ⇌ H3O+ + NO−3 Oxidizing properties Reactions with metals Being a powerful oxidizing agent, nitric acid reacts violently with many organic materials and the reactions may be explosive. Cu + 4 H+ + 2 NO3− → Cu2+ + 2 NO2 + 2 H2O The acidic properties tend to dominate with dilute acid, coupled with the formation of nitric oxide . However, when the reaction is carried out in the presence of atmospheric oxygen, the nitric oxide rapidly reacts to form brown nitrogen dioxide. 3 Cu + 8 HNO3 → 3 Cu (NO3)2 + 2 NO + 4 H2O 2 NO + O2 → 2 NO2 Reactions with non-metals Reaction with non-metallic elements, with the exceptions of nitrogen, oxygen, noble gases, silicon and halogens, usually oxidizes them to their highest oxidation states as acids with the formation of nitrogen dioxide for concentrated acid and nitric oxide for dilute acid. C + 4 HNO3 → CO2 + 4 NO2 + 2 H2O Page 19 Extraction of Metals Or 3 C + 4 HNO3 → 3 CO2 + 4 NO + 2 H2O Uses Nitric acid in laboratory. The main use of nitric acid is for the production of fertilizers, other important uses include the production of explosives, etching and dissolution of metals especially as a component of aqua regia for the purification and extraction of gold, and in chemical synthesis. Woodworking In a low concentration (approximately 10%), nitric acid is often used to artificially age pine and maple. The color produced is a grey-gold very much like very old wax or oil finished wood (wood finishing). Other uses A solution of nitric acid and alcohol, Nital, is used for etching of metals to reveal the microstructure. Commercially available aqueous blends of 5-30% nitric acid and 15-40% phosphoric acid are commonly used for cleaning food and dairy equipment primarily to remove precipitated calcium and magnesium compounds Alone, it is useful in metallurgy and refining as it reacts with most metals, and in organic syntheses. Commercial preparation of ammonia Page 20 Extraction of Metals All modern commercial production of ammonia is based on the Haber-Bosch synthesis process. The process reaction is given by the equation: N2 + 3 H2 2 NH3 + Heat This reaction happens in a special high pressure reactor in the presence of a special catalyst, usually a porous iron oxide. The reaction is exothermic which means that energy is released. The equation shows that the nitrogen, hydrogen and the ammonia exist in equilibrium which is determined by the conditions existing in the reactor. Typically for ammonia synthesis these conditions are: Pressure - about 200 - 900 atmospheres Temperatures 450 - 500o C Catalyst iron Promoter Molybdenum Definition: Under equilibrium conditions the proportion of reactants and the product of a chemical reaction are balanced and determined by the existing physical conditions such as pressure, temperature and concentrations. Factors influencing the rate of ammonia production (rate of reaction rx): Temperature - because the reaction is exothermic, lowering the temperature in the reactor will increase the yield of ammonia. But this also slows down the reaction therefore for the reason of efficiency in commercial production the temperature is kept as high as possible. Pressure - increasing the pressure will increase the yield of ammonia but there is a limit in pressure for safety reasons. Page 21 Extraction of Metals Uses of ammonia Fertilizer: Approximately 83% (as of 2003) of ammonia is used as fertilizers either as its salts or as solutions. Cleaner: Household ammonia is a solution of NH3 in water (i.e., ammonium hydroxide) used as a general purpose cleaner for many surfaces. Because ammonia results in a relatively streak-free shine, one of its most common uses is to clean glass, porcelain and stainless steel. It is also frequently used for cleaning ovens and soaking items to loosen baked-on or caked-on grime. As a fuel: Ammonia was used during World War II to power buses in Belgium, and in engine and solar energy applications prior to 1900. Liquid ammonia was used as the fuel of the rocket airplane, the X-15. Textile: Liquid ammonia is used for treatment of cotton materials and also used for pre-washing of wool Lifting Gas: At standard temperature and pressure ammonia is lighter than air, and has approximately 60% of the lifting power of hydrogen or helium. Ammonia has sometimes been Page 22 Extraction of Metals used to fill weather balloons as a lifting gas. Manufacture of Glass Raw Materials Silica (in the form of sand) Compounds of alkali metals, like Na2CO3, Na2SO4, NaNO3, K2CO3 and KNO3. Compounds of alkaline earth metals, like CaCO3, CaO, BaCO3. (For glass with high refractive index) Oxides of heavy metals, like PbO, Pb3O4 Calcium phosphate, Ca3(PO4)2 (for opalescent glass that also contains arsenic and antimony oxides) Colouring materials - Metallic oxides like ferric oxide (yellow), chromic oxide (green), manganese oxide (purple) and cobalt oxide (blue) are added to fused silicates to get coloured glass. Manufacture of Soda (Ordinary) Glass (Na2O.CaO.6SiO2) Soda glass, also called window glass, is got by fusing sodium carbonate (Na2CO3), calcium carbonate (CaCO3) and sand or quartz (SiO2) in proper proportions. Small amount of scrap glass (pieces and bits of waste glass from previous process runs) is added as a flux. The mixture is then fused in a tank furnace heated by producer gas. Page 23 Extraction of Metals Manufacture of Glass Since CO2 is liberated in the initial stages, frothing is a common observation. All the CO2 is driven out on continued heating and a clear viscous fluid mass is got. It is then poured into moulds of various shapes or stamped with die (a device for stamping, cutting, or moulding material into a particular shape) to produce different kinds of glassware. Properties of Glass As we have seen, glass is a mixture of number of silicates. Therefore, when heated, it does not melt at a fixed temperature. But, it softens gradually and hence can be molded into any desired shape. It is this property that makes glass one of the widely used materials. Annealing Glass if cooled rapidly becomes brittle and fragile and if cooled very slowly becomes opaque because of devitrification. For this purpose, before making articles, glass is passed through a long tunnel like furnace that is very hot at one end and very cold at the other. When glass is passed through this furnace, it is progressively cooled. This process is known as annealing and takes several days to be completed. Page 24 Extraction of Metals Manufacture of cement Raw materials needed; The common raw materials from which the cement is manufactured are limestone and clay. These contain the four basic chemicals which make up cement. They are calcium carbonate (CaCO3) found in limestone, silicon dioxide (SiO2), aluminum oxide (Al2O3) and iron oxide (Fe2O3) which is found in clay. Manufacturing process The cement manufacturing process begins when limestone, the basic raw material used to make cement, is transported from the limestone quarry to the manufacturing industry. The limestone is combined with clay, ground in a crusher and fed into the additive silos. Sand, iron and bottom ash are then combined with the limestone and clay in a carefully controlled mixture which is ground into a fine powder. A mixture of clay and limestone is crushed into fine powder and mixed with water. This mixture is called slurry. This slurry is fed at the upper end of a long rotary kiln as shown in the figure. The rotary kiln is a long cylinder which slowly rotates around its axis. The rotation of the kiln mixes the raw materials evenly. Burning coal and hot air are injected from the other end of the kiln. As the mixture gradually descends down the kiln, the temperature rises. (Or in the kiln, the powder is heated to 1500 degrees Celsius. This creates a new product, called clinker, which resembles pellets about the size of marbles). The reactions that take place in the rotary kiln are as follows: 1. In the upper end of the kiln where the temperature is about 4000C, the water present in the mixture gets evaporated. 2. In the central part the temperature is about 10000C. At this temperature, the limestone decomposes to calcium oxide and carbon dioxide. Calcium carbonate → calcium oxide + carbon dioxide (Limestone) (Quick lime) Page 25 Extraction of Metals CaCO3 → CaO + CO2 (Solid) (solid) (gas) 3. In the lower part of the kiln, the clay combines with the calcium oxide to produce a mixture of calcium silicate and calcium aluminate. Calcium + silicon + aluminium dioxide → calcium silicate + calcium aluminate oxide dioxide (cement) 4CaO (s) + 2SiO2(s) + 2Al2O3(s) → 2CaSiO3(s) + 2CaAl2O(s) The clinker is combined with small amounts of gypsum and limestone and finely ground in a finishing mill. The mill is a large revolving cylinder containing 250 tones of steel balls that is driven by a 4000 hp motor. The finished cement is ground so fine that it can pass through a sieve that will hold water. Cement is the mixture of the calcium silicate and calcium aluminate. This mixture is then cooled, crushed and mixed with gypsum powder (calcium sulphate). Gypsum is added to slow down the rapid setting of the cement water paste. The cement thus obtained is called Portland cement. When small stone and gravel is added to the cement and mixed with water and sand, it is known as concrete. When cement sets, it binds the sand and gravel to give a strong building material. For proper setting and hardening of cement, water is added every morning and evening for about a month. When water is added to cement, reaction occurs between cement and water. This reaction is called hydration reaction which means water is added. In our country, we have some well established Portland cement manufacturing industries like Penden cement authority ltd (PCAL) and Khaki cement factory in Gomtu and Dung Sum Cement project in Nganglam. Bhutan exports the cement to India. The most common use for Portland cement is in the production of concrete. Concrete is a composite material consisting of aggregate (gravel and sand), cement, and water. As a construction material, concrete can be cast in almost any shape desired, and once hardened, can become a structural (load bearing) element. These may be supplied with concrete mixed on site, or may be provided with "ready-mixed" concrete made at permanent mixing sites. Portland cement is also used in mortars (with sand and water only) for plasters and screeds, and in grouts (cement and water mixes squeezed into gaps to consolidate foundations, road-beds, etc). Page 26 Extraction of Metals Conclusion An assignment on extraction and its processes encompasses of many impacts on our approach towards the research and finding of information and sources for the very assignment. In fact, have many points and its implication. I felt that doing such assignment is not easy, so it needs a lot of hands and heads to be implemented in the formation of an assignment and finding information from various fields and sources. As aforementioned, I now have the better understanding on the extraction and the processes involved in it. This assignment works have catered with ample experiences, practically applying and knowing what the metallurgy and metallurgical processes are and even correct sequences that is required for writing assignment. It also gave us the correct path to be followed as and when we need in writing assignment. As we are the future teacher I felt that we have the greater responsibilities knowing the real and practical application of ones cognition on metallurgy for students’ welfare for their examination and for better tomorrow. On the evidence that I did the intimate and investigative research in finding sources and coverage for the implementation, and learning and teaching process in the field. Ultimately I would like to urge our future nation molders and educators to go through the components of extraction of metals and the processes involved in it. Therefore, what I actually felt is that by doing this very assignment it helped me and made me resourceful especially in the extraction of metals like: Aluminium, Copper, Zinc and Iron and in particular their processes involved for the extraction. I too became aware on preparation of compounds like Nitric acid and Ammonia and industrial preparation of Cement and also the processes involved. Page 27 Extraction of Metals References Madan, R.D. (2003). ISC Chemistry- Book I for Class XI. Ram Nagar, New Delhi- 110 055: S. Chand & Company Ltd. Madan, R.D. (2007). ISC Chemistry- Book I for Class XII. Ram Nagar, New Delhi- 110 055: S. Chand & Company Ltd. Snigh, S.P. (1999). New Concise Chemistry ICSE- Part I Class IX. New Delhi- 110002: Selina Publishers. Snigh, S.P. (2003). New Concise Chemistry ICSE- Part I Class X. New Delhi- 110002: Selina Publishers. Cement (n.d) retrieved 17/10/09, from http://en.wikipedia.org/wiki/Cement Retrieved 17th October 2009 from http://en.wikipedia.org/wiki/Copper_extraction_techniques Glass (n.d) retrieved 11/10/09, from http://en.wikipedia.org/wiki/Glass. Nitric acid (n.d) retrieved 09/10/09, from http://en.wikipedia.org/wiki/Nitric_acid Iron (n.d) retrieved 15/10/09, from http://en.wikipedia.org/wiki/Iron Zinc (n.d) retrieved 06/10/09, from http://en.wikipedia.org/wiki/Zinc Page 28