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Metallurgy
Concepts

(i) What is metallurgy (ii) Minerals and Ores (iv) Processes involved in extraction of metals

(iii) Occurrence of metals

Introduction Copper and iron were the first metals put to extensive use by early man. Copper mixed with tin called bronze was so widely used for many years that this period came to be known as the ‘Bronze Age’. The increasing use of metals in day to day life aroused the interest of man in their properties and the sources from which they could be recovered. This gave birth to a new branch in chemistry called metallurgy.

The science that deals with procedures used in extracting metals from their ores, purifying and alloying metals and creating useful objects from metals is called metallurgy.

Metallurgy is also the practice of removing valuable metals from an ore and refining the extracted raw metals into a purer form. Mineral and Ore Natural materials found inside the earth containing metals in their combined states ( as a single compound or as a mixture of compounds ) mixed with non – metallic impurities of Earth and rock ( called gangue ) are termed minerals. These metals do not occur in the native form and need to be extracted for use. All minerals are not suitable for extraction of metals. Minerals from which the metal can be extracted easily and economically are called ores. Ores contain metal compounds with a lower percentage of impurities. Thus all ores are minerals but all minerals are not ores. Occurrence of metals Metals occur in nature in the free as well as in the combined states. The most unreactive metals i.e. which are not affected by air and water, like silver, gold and platinum are generally found in the free state. In other words, elements which have low chemical reactivity generally occur native or free or in metallic state and those which are chemically reactive or affected by air and water generally occur in combined state e.g. halogens, chalcogens.

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Ores can be divided into four general groups as follows. (i) Native ores – These ores contain metals in the free state. e.g. Ag, Au, Pt, Hg, Cu etc. These are usually found associated with rock or alluvilial materials like clay, sand etc. Sometimes, lumps of pure metals are also found in them. These are termed nuggets. Iron is found in free state as meteorites which also have 20% to 30 % nickel. (ii) Sulphurised and arsenical ores - These ores consist of sulphides and arsenides in simple and complex forms of metals. Some examples of this group are PbS, ZnS, Ag2S, NiAs, CuFeS2, 3Ag2S. Sb2S3 etc. (iii) Oxide ores - In these ores, metals are present as their oxides or oxysalts such as carbonates, nitrates, sulphates, phosphates, silicates etc. The examples include Fe2O3, Al2O3, BeO.Al2O3, MnO2, CaCO3, FeO.TiO2 , NaNO3, BaSO4 , Zn2SiO4, Ca3(PO4)2 etc. (iv) Halide ores - Metallic halides are very few in nature. Chlorides are more common. The examples include common salt, NaCl, , Carnallite, KCl, MgCl2.6H2O , Fluospar, CaF2 , Horn silver, AgCl etc. An overview of the processes The various processes involved in the extraction of metals from their ores and their subsequent refining are known as metallurgy. An overview of various processes involved during metallurgy is given below.

e. Ore is an impure metal containing large amount of sand and rocky material.Hydraulic washing . These are mostly physical methods of concentration. earthing particles. mica etc. limestone. It is essential to separate the large bulk of these impurities from the ore to avoid bulk handling and in subsequent fuel costs. one or more of the following steps are taken to concentrate the ore. tin. The removal of these impurities from the ores is known as concentration. Fig. The denser ore settles in the grooves while the lighter gangue particles are washed away. Concentration or dressing of the ore : These ores are usually obtained from the ground and therefore contain large amount of unwanted impurities. So it becomes necessary to break those lumps into small pieces. These impurities must be removed from the ore before the extraction of metal. is called gangue or matrix.1 . rocky materials. iron etc. limestone etc.3 Enrichment of ore This is also called as concentration or dressing of the ore. Crushing and grinding of the ore : These ores occur in nature as huge lumps. They are broken to small pieces with the help of crushers or grinders. Depending upon the nature of the ore. The concentration is done by physical as well as chemical methods (1) Hydraulic washing ( Gravity separation ) : In this process. rocky matter. the ore particles are poured over a hydraulic classifier which is a vibrating inclined table with grooves and a jet of water is allowed to flow over it. The impurities like sand. This process is called pulverisation. These pieces are then reduced to fine powder with the help of a ball mill or stamp mill.g. sand. The hydraulic washing method is shown in the following figure. This method is used for concentration of heavy oxide ores of lead... Sometimes the ore appears in the form of big lumps.

detergent and powdered ore is first taken in a tank.4 (2) Froth floatation . Sulphide being more electronegative attracts the covalent oil molecules. The sulphide ore particles are wetted and coated by pine oil and rise up along with the froth (froth being lighter). A mixture of water. The gangue being less electronegative is attracted by the water. which moves over two rollers one of which is magnetic. The powdered ore is dropped on to leather or brass conveyer belt. Thus sulphide ore is separated from the gangue. . pine oil. Fig. The magnetic ore and gangue thus form two separate heaps. washed and dried. The froth floatation process is shown in the following figure. A blast of compressed air is blown through the pipe of a rotating agitator to produce froth. The froth containing the sulphide ore is transferred to another container. it sticks to the belt due to the force of attraction and falls nearer to magnetic roller. The gangue particles wetted by water sink to the bottom of the tank ( water being heavier ).2 – Froth floatation process (3) Magnetic separation – Magnetic ores like pyrolusite ( MnO2) and chromite ( FeO. Following figure shows the magnetic separation method.Cr2O3 )are enriched by this method by making use of the difference in the magnetic properties of the ore and gangue particles. The gangue falls in a normal way under the influence of gravity.This method is especially used for sulphide ores. The method employs a mixture of water and pine oil which is made to agitate with the ore. When the ore passes over the magnetic roller.

This solution is separated and subjected to further treatment like precipitation. definite chemical changes take place to form oxide or chloride of the metal. 1) Calcination – It is a process in which the ore is heated strongly in absence of air. They are converted to their chlorides which are easy to reduce. In this process. The ore is heated at a temperature well below its melting point.3 – Magnetic separation process (4) Leaching – It means washing. 2) Roasting – It is a process wherein the ore is heated either alone or with some other material in excess of air below the fusion point of the ore. Ores of some metals like lead may get partially oxidized and converted to sulphate. when roasted in air. Therefore. carbon dioxide etc. Ores of metals like zinc. it easily undergoes further chemical reactions. The gaseous product of sulphide roasting. lead. It is then treated further to recover the metal. Ores of metals like silver and gold are mixed with common salt and are heated in air. The purpose of roasting is to convert the ore in a form suitable to reduce. the ore is washed with some suitable reagent ( solvent ) so that the main metal passes into its salt solution. is often used to produce sulphuric acid. sulphur dioxide. carbonate or any other form. it is called sulphating roasting or partial roasting. Since the ore becomes porous and compact . are converted to their oxides.5 Fig. copper and nickel. undergoes phase transformation and eliminates the volatile impurities like moisture. In such case. Conversion of concentrated ore to oxide It is easier to obtain a metal from its oxide form as compared to its sulphide. this method is used for sulphide ores. Usually. The ore gets thermally decomposed. This type of roasting is called chlorinating roasting. prior to reduction usually the metal is converted to its oxide form. This method is generally used for carbonate and hydrated ores. This is a chemical method of concentration. Following methods are used to convert the concentrated ore to its oxide form. . In roasting.

can not be obtained by the reduction of their oxides by ordinary reducing agents. lot of heat is evolved and hence the metal may melt in the container. aluminium which are placed in the top of the electrochemical series i. Cr2O3 + 2 Al → Al2O3 + 2 Cr + Heat . PbO + CO → Pb + CO2 (iv) Use of aluminium – Oxides of metals like ZnO. So their oxides can be reduced by carbon or carbon monoxide or reactive metals like aluminium or sodium. They are somewhat active. FeO can be reduced by carbon monoxide at high temperature to give the corresponding metals. chromium. CuO + C → Cu + CO Fe2O3 + 3 C → 2 Fe + 3CO (iii) Use of carbon monoxide – Oxides of metals like PbO. When the oxides of these metals are heated with coke. . calcium. But the metals like sodium.e. 2 Ag2O → 4Ag + O2 (ii) Carbon reduction . zinc. An electric current is passed through the molten oxide or chloride of the metal. which are very active. 3MnO2 + 4Al → 2 Al2O3 + 3 Mn + Heat (v) Electrolysis – The metals like iron. PbO + C → Pb + CO ZnO + C → Zn + CO . The metal gets deposited at the cathode from where it is separated. calcium .Some metals like lead. the oxides are reduced to a metal. copper. lead. . It is tapped from the bottom of the container. magnesium.6 Reduction of oxide to a metal One or more of the following methods can be used to obtain a metal from its oxide. CuO. 2 HgO → 2 Hg + O2 . zinc and iron can be obtained by reducing their oxides by carbon. CuO + CO → Cu + CO2 : FeO + CO → Fe + CO2 . Cr2O3 and MnO2 can not be reduced by carbon because these metals have a greater affinity for oxygen than carbon. The reduction of a metal oxide by heating with aluminium is called aluminothermy. In this process. So they are obtained by passing an electric current through the purified molten ore. manganese lie in the middle of the electrochemical series. (i) Heating – Less reactive metals like silver and mercury can be obtained by heating their oxides alone. An active metal like aluminium ( in the form of powder ) is required to reduce the oxides of these metals. Carbon has more affinity for oxygen than the metals have it for oxygen hence carbon extracts the oxygen leaving behind the free metal. These metals are placed at the bottom of the electrochemical series.

Metals like zinc and mercury which boil at low temperature are purified by this method. (iv) The metal cations being positive. . pure metal is obtained. Activity 1 – Collect 2 to 3 ores from your teacher. or an alloy by partial melting. (v) At anode.The liquation method Electro. Pb. The sloping floor of the reverberatory furnace is used to melt the crude metal. Distillation . (vii) Anode finally disintegrates while the cathode gains in weight due to the collection of pure metal.7 Refining of metals (i) Liquation – It is a technique for separating constituents of an ore. Fig. The impure metal is taken in iron retort and heated strongly above the boiling point of the metal. (ii) A thick block of impure metal is made as the anode. Metals like Bi. By condensation of the vapours.refining . This way pure metal is obtained. settle down at the bottom and are removed as anode mud while the more electropositive impurities pass into the solution. if necessary. Hg etc. 4 . when pure metal flows down and impurities are left behind. (vi) The less electropositive impurities in the anode. (iii) A thin rod or sheet of pure metal is made as the cathode. At the boiling point. Sn. vapours of the metal are produced which are led to a condenser. Process – The process of electro-refining of metals involves the following steps : (i) The electrolyte is usually an aqueous solution of the salt of the metal with some corresponding acid. Suggest the steps and draw a flow sheet type diagram to recover the metal from its ore. form cations and enter the solution.Electro-refining of metals is a process of obtaining pure metal from the impure one by the process of electrolysis. migrate towards the cathode and get discharged. the atoms of the metal lose electrons. a metal. are purified by this technique. The technique is used when the melting temperature of the metal is lower than that of the impurity and the impurities are not miscible with the metal.

) . Metallurgy of aluminium Concepts (i) Occurrence of aluminium (ii) Purification of bauxite (iii) Electrolysis of alumina (iv) Refining of aluminium (v) Physical and chemical properties of aluminium (vi) Uses of aluminium (vii) Alloys of aluminium Occurrence Aluminium is the most abundant ( 8. it is not found in nature in the elemental state but only in combined forms such as oxide or silicate. is the principal aluminium ore.13 % ) metallic element in the earth’s crust and after oxygen and silicon. the electrochemical effect of an electric current brings about the reduction of metallic compounds and thereby the extraction of metals from their ores ( electro-winning ) or the purification of the metals ( electro-refining.8 Test your understanding : 1) What is the difference between a mineral and an ore ? 2) What are the methods used to concentrate an ore ? 3) What is the purpose of the following processes ? (i) Calcination (ii) Roasting (iii) Magnetic separation (iv) Liquation 4) Which reducing agents are used in metallurgy ? Aluminium and iron are two important metals which are used as construction materials. in the soil derived from them as clay and upon further weathering as bauxite and iron-rich laterite. the third most abundant of all elements in the crust. Extraction of aluminium The extraction of aluminium is called elctrometallurgy. Hence we will study the metallurgy of these two metals here. Because of its strong affinity to oxygen. It deals with the use of electricity for smelting or refining of metals. Bauxite. a mixture of hydrated aluminium oxides. In electrometallurgy. So also they find many applications in domestic life. and mica. feldspathoids. Aluminium occurs in igneous rocks chiefly as alumino silicate in feldspar.

Powdered bauxite is mixed with carbon and heated up to 18000C in a current of nitrogen . aluminium oxide dissolves in NaOH to form sodium meta aluminate . 2 Al(OH)3 → Al2O3 + 3 H2O ↑ b) Baeyer’s process – This process is used when bauxite ore contains appreciable amount of Fe2O3 ( 7 to 10 % ) and low amount of silica ( less than 1 % ). in principle . pressure at 1500C for 2 to 8 hours. The bauxite containing iron oxide as major impurity is called red bauxite and the bauxite containing silica as major impurity is called white bauxite. should be easy because the ore occurs in oxide form which can be reduced by a suitable reducing agent to give the metal. Fe2O3 as the major impurity.9 The principal aluminium ore is bauxite Al2O3 . it is purified by Baeyer’s process or Hall’s process. aluminium oxide can not be reduced that easily. If it contains silica . AlN + 3 H2O → Al(OH)3 ↓ + NH3 The precipitate of Al(OH)3 is washed. . Iron and silicon both make aluminium metal brittle and liable for corrosion hence they must be eliminated. dried and ignited at about 15000C to get pure alumina. At this stage. it is purified by Serpek’s process. SiO2 as the major impurity. Hence aluminium is obtained by the electrolysis of pure alumina. However. If bauxite contains iron oxide. The extraction of aluminium.n H2O + 3C + N2 → 2 AlN + 3 CO + n H2O SiO2 + 2C → Si ↑ + 2 CO ↑ Silicon volatilizes at this temperature. silicon dioxide and titanium dioxide. It is essentially an impure aluminium oxide. Purification of bauxite Bauxite contains iron oxide or silica as major impurity. The major impurities include iron oxide. 2H2O. This does not make the process economic. If at all reduced by carbon. It precipitates aluminium hydroxide. (i) Serpek’s process – This process is used when bauxite ore contains appreciable amount of silica (above 7 %) and low amount of Fe2O3 ( less than 1 %) . The ore is first calcined and then finely ground. Aluminium nitride is hydrolyzed with hot water. Aluminium from bauxite is converted to aluminium nitride while silica is reduced to silicon. Al2O3 . Aluminium has great affinity for oxygen hence it can not be reduced by usual reducing agents Aluminium is too high in the electrochemical series ( it is a highly reactive element ) so it can not be reduced by hydrogen or carbon. in practice. the temperature required for the reduction is very high. It is then digested with a hot and strong solution of caustic soda ( 45 % ) in an autoclave under 80 lb.

2 Al(OH)3 → Al2O3 + 3 H2O ↑ c) Hall’s process . slowly cooled and then mixed with a little freshly precipitated aluminium hydroxide which acts as a nucleus for precipitation of aluminium hydroxide. 2 Al(OH)3 → Al2O3 + 3 H2O ↑ Pure alumina Electrolysis of pure alumina Aluminium can be obtained by electrolysis of pure alumina but it offers two problems. dried and ignited to get pure alumina ( Al2O3 ) . bauxite ore is fused with sodium carbonate. Alumina dissolves in cryolite. Sodium meta aluminate. NaAlO2 + 2 H2O → NaOH + Al(OH)3 ↓ Aluminium hydroxide precipitate is then washed. Al2O3 + 2 NaOH → 2 NaAlO2 + H2O Sodium meta aluminate ( soluble ) Silica dissolves in the form of silicate. sodium meta aluminate solution is diluted with water.( Alternatively CO2 can be passed till the solution becomes acidic ) It is then digested. NaAlO2 hydrolyses to give precipitate of aluminium hydroxide. 2 NaAlO2 + CO2 + 3 H2O → 2 Al(OH)3 ↓ + Na2CO3 The precipitate is filtered. (ii) When fused alumina is electrolyzed at 20000C . Cryolite lowers the temperature of the mixture.10 ( NaAlO2) while ferric oxide and titanium dioxide remain undissolved. (i) Pure alumina is a poor conductor of electricity and melts at about 20000C. Na2CO3 to give water soluble sodium meta aluminate . Alumina is fused with cryolite Na3AlF6. After filtration. In this process.Heroult process.This process is used for low grade bauxite ores. when Al(OH)3 is precipitated.. Al2O3 + Na 2CO3 → 2 NaAlO2 + CO2 ↑ The fused mass of sodium meta silicate is extracted with water and filtered. They are then removed by filtration.The filtrate containing caustic soda is concentrated and used again. Aluminium is usually prepared by Hall.the metal formed vapourises as its boiling point is 18000C. Pure alumina melts at 20000 C while the mixture melts at about 9500C The . Small amount of CaF2 and AlF3 are also added to lower the temperature of the mixture. The impurities Fe2O3 and SiO2 remain on the filter paper. NaAlO2 leaving behind Fe2O3 and SiO2. washed and ignited to obtain pure alumina. The filtrate containing NaAlO2 is warmed and CO2 is passed through it.

9 percent aluminium and it contains small amounts of iron..The electrolysis is carried out at temperature of 9500C and with a voltage of 5. . Some coke is thrown on the surface of charge to control the oxidation of the metal. So Hoope’s electrolytic refining process is used to refine the metal. AlF3 ( 5 % ) and Al2O3( 5 % ) .→ 4 Al Diagram – Fig.5 volts in a graphite lined steel tank which acts as a cathode. The cell uses three liquid layers of different densities. Na3AlF3 → 3 NaF + AlF3 . Hoope’s process – In this process. The simplified mechanism of electrode reactions is given below. alumina and barium fluoride acting as electrolyte. fused salt electrolyte is used. 4C + 3O2 → 2 CO2 + 2 CO At cathode → 4 Al3+ + 12 e. 4 AlF3 → 4Al 3+ + 12 F- At anode → 2 Al2O3 + 12 F. This aluminium layer is connected with graphite electrode to the mains. 5 . The electrode reactions are complicated and their exact nature is not known . (ii) The middle layer consists of cryolite . (i) The bottom anode layer consists of impure aluminium. (iii) The top cathode layer is of pure metal.→ 4 AlF3 + 3 O2 + 12 e. The Al2O3 is added from feeder at the top.11 charge consists of cryolite ( 85 % ). silicon from the bath and some alumina and carbon. The anodes are made of graphite.Electrolysis of alumina Refining of aluminium metal Metal produced by Hall – Herouit’s process is almost 99. CaF2 ( 5 % ).

In moist air. From time to time . Physical and Chemical Properties of Aluminium (i) Aluminium is a white metal with a slight bluish tinge.7 ) which melts at 6580 C and boils at 18000C. it becomes brittle and can be ground to powder. (v) It is tough and has a moderate tensile strength. aluminium from the middle layer passes into the top layer and equivalent amount of aluminium passes from the bottom layer to the middle layer.Hoope’s cell for refining aluminium The cell is made of iron box. 4 Al + 3 O2 → 2 Al2O3 + Heat (vii) Action of acids . 6 .Aluminium is above hydrogen in the activity series and it displaces hydrogen from non-oxidising acids like HCl and dilute H2SO4. On passing electric current. (iii) It is malleable and ductile especially between 1000C and 1500C. The refined aluminium has purity of 99. pure aluminium is removed from the top and aluminium of lower purity is added to the bottom layer. there is transfer of aluminium from the base to the top while impurities are left behind. 2 Al + 6 HCl → 2 AlCl3 + 3 H2 2Al + 3 H2SO4 → Al2(SO4)3 + 3 H2 . forming aluminium oxide ( with little nitride AlN also ) liberating much heat.. Gravity 2. (vi) Finely divided aluminium or thin aluminium foil burns readily in air or oxygen when heated. it becomes dull owing to the formation of superficial protective layer of its oxide. It is lined from inside with carbon. Near about its melting point.99 %. (ii) It is a light metal ( sp. Pure aluminium is tapped from the top. Thus.12 Fig. The cell is shown in Fig. 6 . (iv) It is an excellent conductor of heat and electricity.

. (iv) Since it resists corrosion.13 But hot concentrated H2SO4 gives SO2 2 Al + 6 H2SO4 → Al2(SO4)3 + 3 SO2 + 6 H2O Concentrated HNO3 makes aluminium passive and with dilute HNO3. 2 Al + 2 NaOH + 2 H2O → 2 NaAlO2 + 3 H2 (ix) Action of non-metals . manganese etc. (v) Aluminium foils are used in wrapping cigaretts. a) 2Al + 3 Cl2 → 2 AlCl3 c) 2 Al + N2 → 2 AlN b) 4 Al + 3 C → Al4C3 d) 2 Al + 3 S → Al2S3 (x) Reducing action .Aluminium is an amphoteric metal so it reacts with acids as well as alkalies.Heated aluminium directly combines with halogens. confectionary items etc. it produces ammonium nitrate but no gas is evolved. (ii) On account of its good electrical conductivity. it is used for making electrical transmission cables. it is used in making cooking utensils. ( The reaction with acids are given above ) . aluminium is used in making body of air-ships and motor cars. (vii) It is used in thermite welding and in the aluminothermic process. Fe2O3 + 2 Al → Al2O3 + 2 Fe + Heat Uses of aluminium (i) Since it is lighter and has high tensile strength. (viii) Salts of aluminium such as alum are used as mordants in dyeing industries. aluminium has a strong affinity for oxygen and hence it reduces oxides of iron. it is used in aluminium paints.At high temperature. carbon nitrogen and sulphur. (iii) On account of its good thermal conductivity. (vi) Aluminium is used as a deoxidizer and for removing blow holes in metallurgy. 8 Al + 30 HNO3 → 8 Al(NO3)3 + 3 NH4NO3 + 9 H2O (viii) Action of alkalies .

readily jewellery. For making 20% Ni.14 Alloys of aluminium Alloy Composition Properties Uses -----------------------------------------------------------------------------------------------------------1) Magnalium 98 % Al. coins -----------------------------------------------------------------------------------------------------------4) Nickeloy 95 % Al. strong articles . light worked on lathe instruments. 2 % Mg Hard. 0. Test your understanding 1) Name the ore and give its composition from which aluminium is extracted.5 % Mg corrosion. 20%Al. Resistance to For making airships. ductile. Metallurgy of Iron . 2) Name the processes used to purify aluminium ore. light -----------------------------------------------------------------------------------------------------------3) Aluminium 10 t0 12 % Al. For making balance Can be excellently beams. 4% Cu. 10% Cu permanent magnets ------------------------------------------------------------------------------------------------------------ Activity 2 .Suggest the names of three alloys of aluminium which you use in day to day life. 5) Give the names . Resistance to For making utensils. 3) What is the composition of electrolyte when molten alumina is subjected to electrolysis ? 4) Draw a diagram of Hoop’s cell for refining aluminium metal. 4 % Mn. highly aeroplanes etc. For making airships 1 % Ni great mechanical strength -----------------------------------------------------------------------------------------------------------5) Alnico 50% steel. tough. decorative fusible. Bronze 88 to 90 % Cu corrosion. articles -----------------------------------------------------------------------------------------------------------2) Duralium 95 % Al. light. composition and uses of any two alloys of aluminium. Extremely light.

Brown Haematite or Limonite – 2 Fe2O3 .5 %. Principally iron occurs as oxides. Mn and S are present upto about 1. P. It is midway between cast and wrought iron as far as impurities are concerned.5 % carbon. it is not found in nature in the elemental state but only in combined forms such as oxide.2 % carbon.5 % to 4. . It is generally found associated with other metals like copper. H2O. Because of its strong affinity to oxygen. It contains 0. Magnetite – Fe3O4 (ii) Siderite – or Spathic Iron ore . The chief sources of iron are – (i) Red Haematite – Fe2O3. silicon and phosphorus. Iron is the fourth most abundant ( about 5 % ) metallic element in the earth’s crust .1 to 1. (ii) Wrought or Malleable iron – It is the purest form of iron. The three varieties differ from each other mainly in their carbon content.15 Concepts (i) Occurrence of iron (ii) Commercial forms of iron (iii) Manufacture of cast iron (iv) Blast furnace (v) Physical and chemical properties of cast iron (vi) Manufacture of steel (vi) Alloys of iron Occurrence Next to aluminium. Other impurities like Si. iron is the most abundant metal in earth’s crust. The first step in the extraction of iron is the production of pig or cast iron which is subsequently used in making wrought iron or steel.FeCO3 (iii) Iron pyrites – FeS2 (iv) Chalcopyrites – CuFeS2 Commercial forms of iron There are three commercial forms of iron . (iii) Steel – It is an alloy of iron with carbon and other elements like manganese. It contains about 1.5 % carbon. cobalt and nickel. much less as sulphide and sometimes as the carbonate. Iron is easily attacked by humid atmosphere. It contains about 0. (i) Cast or Pig iron – It is the most impure form of iron.

FeCO3 → FeO + CO2 ↑ . The ore being magnetic in nature. Following reactions take place. It is subjected to magnetic separation. Following changes take place during roasting and calcinations. iron obtained is impure and is known as pig iron or cast iron. This helps to remove gangue. falls apart as a separate heap. It is then broken into small pieces of 1” to 2” size. 4 FeO + O2 → 2 Fe2O3 .16 Extraction of iron The extraction of iron is pyrometallurgy. It is the extractive metallurgy which consists of the thermal treatment given to minerals or ores to recover the metal. The ore ( red haematite or hydrated oxide or carbonate ) is calcined in shallow kilns to remove moisture. Manufacture of cast ion It is done in following steps. silicious impurities are removed. Iron is normally extracted from its oxide ore called haematite and rarely extracted from carbonate ore called siderite. 3 H2O → Fe2O3 + 3 H2O ↑ . (i) Moisture escapes as steam and organic matter present burns off to give CO2 and sulphur and arsenic are oxidized to form their volatile oxides SO2 and As2O3 respectively. Due to washing. Fe2O3. The extraction of iron involves following steps. The ore thereby becomes porous and is then more easily reduced in the blast furnace. screened and shifted. Iron pyrite is an important source of sulphur and therefore it is not used in the extraction of iron. (ii) Ferrous oxide is converted to ferric oxide which avoids formation of ferrous silicate in the slag during smelting and (iii) The mass becomes porous and thus makes it more suitable for reduction to metallic iron. This way the ore becomes rich in oxide of iron. carbon dioxide etc. The process of extraction of iron is fundamentally very simple as it consists essentially of the reduction of iron oxide by carbon. (ii) Preliminary roasting and calcinations The concentrated ore is roasted and calcined with a little coal in shallow kiln ( furnace ) in excess air. The process involves chemical reactions at elevated temperature. The ore is thus concentrated. But as molten iron dissolves carbon and other impurities. (i) Washing and concentration or dressing of the ore Haematite ore is washed with water.

17 (iii) Reduction or smelting in a Blast Furnace The roasted and calcined ore ( 8 parts ) is mixed with coke ( 4 parts ) which acts as a reducing agent and limestone ( 1 part ) which acts as a flux. c) In its lower part. 7 - Blast Furnace . Description of Blast Furnace a) It consists of an outer shell which is made of steel plates riveted ( fastened ) together.e. Diagram – Fig. From inside it sis lined with fire bricks. ( boshes. ( Refer Figure ) b) It is about 15’ to 120’ tall. the furnace gradually narrows down below the boshes. The lower part of the furnace is called hearth (floor ) or crucible where molten iron and slag is collected. ( The height varies from place to place. d) The mouth of the furnace i. The mixture is introduced in a tall Blast Furnace. ) It is 15’ to 24’ in diameter at the wider end near the bottom. The hot gases escape through the flue. lower cone ) It is kept in a vertical position with the help of iron columns. The blast furnace has two functions (i) to reduce the ore to metallic iron and (ii) to remove the impurities in the form of slag. limestone and coke is fed from time to time. the top is closed by a double cup and cone arrangement through which the mixture ( called charge ) of the calcined ore. ( Refer diagram ) e) The cone is made of iron and is kept tight against the top of the furnace being counterpoised by weights.

e. CO2 + C → 2 CO . It is called the zone of reduction. the temperature in this region falls and comes in the range 8000C – 10000C.18 f) A blast of hot and dry air. . The different heat zones of the blast furnace are shown in the figure. the ascending CO2 is reduced to carbon monoxide when it reacts with carbon ( coke ). obtained by hot gases. In this zone. It combines with silica to form a fusible ( meltable ) slag. Lime thus obtained acts as a flux. Fe3O4 + CO → CO2 + 3 FeO c) Conversion of ferrous oxide to metallic iron. Reactions in the blast furnace Following chemical reactions take place in different zones of the blast furnace. Simultaneously. escaping from the blast furnace itself and freed from dust in a scrubber . is blown into the furnace . one for the removal of slag ( called slag hole ) and the other for taking out molten metal ( called metal hole or tap hole ). (i) Zone of reduction – ( 3000C to 8000C . It is maximum at the hearth ( about 17000C ) and decreases slowly towards the throat of the furnace ( about 3000C ) The Process The charge ( roasted ore + coke + limestone in the proportion 8: 4:1 ) is introduced in the furnace from the top.39 kcal As the reaction is endothermic. bright red heat ) This is the middle part or zone of the blast furnace. FeO + CO → CO2 + Fe When the spongy iron falls in the middle region ( zone of heat absorption ). there are two outlets on opposite sides. g) Near the bottom of the furnace. the furnace is lit and a hot blast of air is passed through the tuyeres. just above the hearth by a number of water-cooled pipes. CaO + SiO2 → CASiO3 ( slag ) (ii) Zone of heat absorption – ( 8000C to 12000C – i. Here the iron oxide from the charge is reduced by carbon monoxide to spongy iron.e. limestone. dull red heat ) This is the uppermost zone of the blast furnace. h) The temperature of the furnace is not constant in all the parts.ferric oxide 3 Fe2O3 + .i. CO → CO2 + 2 Fe3O4 b) Conversion of ferroso – ferric oxide to ferrous oxide. CaCO3 → CaO + CO2 . a) Conversion of ferric oxide to ferroso . called tuyeres or twyers ( pipe rings). Fe2O3 + 3 CO → 2 Fe + 3 CO2 ↑ The reduction of Fe2O3 actually takes place in following three stages. CaCO3 decomposes to give CaO ( lime ) and CO2.

7 to 3% d) Phosphorus –0. It is useful for road making and cement manufacture. white heat ) This is the zone near the tuyeres . 30 % CaO and 15 % CO2 and 15 % Al2O3. Varieties of cast iron When pig iron in the blast furnace is suddenly cooled.5 to 1 % e) Manganese . The molten iron collects at the bottom of the furnace while the fusible slag floats on it and protects the iron from oxidation.0.2 to1 % f) Sulphur – 0. (iv) Zone of fusion – (15000C to 19000C ) In this zone. It is softer and more coarse grained than the white form.e. b) Carbon – 2. crystalline cast iron is obtained. the temperature falls slowly to about 13000C.It is mostly calcium silicate containing some amount of aluminium silicate. The layers of molten iron and slag are withdrawn through separate tapping holes from time to time. if molten iron is slowly cooled in sand moulds a graphite coloured iron is formed. . The waste gases containing about 25% CO.5 % c) Silicon – 0.3 % (ii) Slag . As the hot gases go up and meet the descending charge. On the other hand.19 (iii) Zone of combustion – ( 13000C to 15000C – i. 56% N2 and 4% H2 are let out through the outer pipe. It Contains 55 % SiO2 . the spongy iron melts and dissolves some carbon. Iron so obtained is known as Pig Iron. (i) Pig iron – Average composition of pig iron is : a) Iron – 92 to 95 % . It is known as grey cast iron. It is remelted in a vertical furnace ( known as cupola )and can be cast or poured into moulds.1 to 0. It is known as white cast iron. In this type. C + O2 → CO2 ↑ + 97 kcal The heat evolved raises the temperature to 15000C. It is very hard and white in colour. phosphorus and silica. 15% CO2. In this form. The blast furnace can work day and night for years together. Thus cast iron is obtained after remelting pig iron. Here the carbon burns to form CO2 producing tremendous amount of heat. carbon is present in the combined state as iron carbide. It is then called cast iron. These are burnt with air to produce heat which is used for preheating the air blast passed through the tuyeres.5 to 4. The process is economical as it is continuous one. Products of Blast Furnace The products of blast furnace are (i) Pig iron (ii) Slag (iii) Flue gases . a part of carbon separates out as graphite and gives grey colour to the metal.

The gases leaving the blast furnace through the flue are known as flue gases. 4 Fe + 10 HNO3 → 4 Fe(NO3 )3 + NH4NO3 + 3 H2O Highly concentrated and pure nitric acid of specific gravity 1. When heated in air. (iv) Due to sulphur. it has melting point ( about 12000C ) lower than that of pure iron ( about 15300 C). the gaseous mixture has a fuel value and hence it is used for heating the air blast in Cowper’s stoves. Iron also becomes passive by other oxidizing agents like dichromates. etc. it is oxidized and gets covered with thick bluish black scales of ferroso – ferric oxide Fe3O4. railings. weights and heavier parts of machinery. It is suggested that passivity of iron is due to the formation of a thin protective invisible oxide film on the surface of iron. Fe + 2 H2SO4 → FeSO4 + SO2 + 2 H2O 2 FeSO4 + 2 H2SO4 → Fe2(SO4 )3 + SO2 + 2 H2O Cold and dilute HNO3 forms a mixture of ferrous nitrate and NH4NO3.45 has apparently no action on iron. (vi) Action of air . The average composition of the gaseous mixture is a) CO – 25 % b) CO2 – 10 % c) N2 – 58 to 60 % d) H2 – 1 to 2 % Due to the appreciable proportion of carbon monoxide. it is brittle when cold ( cold short ). . (vii) Action of steam – When steam is passed over iron heated to 8000C to 10000C. Major part of cast iron is used to manufacture steel. (ii) On solidifying. Physical and Chemical Properties of Cast Iron (i) Since cast iron is impure. it is brittle when red hot ( red short ) and due to phosphorus. Iron is made passive in such acid. Passivity is lost when such a passive metal is rubbed or treated with reducing agents.20 (iii)Flue gases . iron is oxidized to Fe3O4. 3 Fe + 4 H2O → Fe3O4 + 4 H2 ↑ (viii) Action of acids .Non-oxidising acids react with iron and form ferrous salts evolving hydrogen. In presence of moist air and carbon dioxide. Hot and concentrated sulphuric acid oxidizes iron forming a mixture of ferrous and ferric sulphates with the evolution of SO2. Passive iron is not affected by dilute acids. it expands (iii) It is harder due to the presence of carbon and silicon.Pure iron is not affected by dry air. It is also used for casting metal objects such as pipes. (v) It can not be welded and can not be permanently magnetized. nitrates. it begins to rust readily forming reddish brown hydrated ferric oxide.

Following methods are used for the manufacture of steel from pig or cast iron. The converter can hold a charge of 20 tons at a time. Bessemer converter is provided with a number of fine holes at the bottom through which a hot blast of air can be forced in fine jets. ductile and malleable. It melts at a higher temperature ( 15000C) than cast iron. stirring ) It is grey in colour. It is obtained by purifying cast iron by the process known as puddling ( i. then a lining of CaO and MgO is used and the process is known as Basic Bessemer process. heavier parts of machines etc. . This is made of steel plates.process 1) Bessemer process Bessemer process was invented in 1855 by an English steel maker Henry Bessemer. It is lined with silica ( SiO2 ) or a mixture of lime (CaO ) and magnesia ( MgO) depending upon the nature of impurities present in cast iron. The carbon content in it is very low (less than 0. Bessemer converter is 20 feet high and 10 feet in diameter. wires. Fe + S → FeS Wrought Iron It is the purest form of iron. D . bolts. The process is carried out in a special kind of egg-shaped or pear-shaped furnace. silicon. (i) Bessemer process (ii) Open Hearth process (iii) L. On the other hand. railings. 2) Cast iron is used for casting metal objects such as pipes. like MnO. It is manufactured from cast iron by burning out carbon. 3) Iron is used as material of construction. . Iron containing 0. It is used to prepare chains.5 % carbon is called steel.1 to 1. Uses of iron 1) Major part of cast iron is used to manufacture steel. The furnace is called Bessemer converter. It is soft. if the impurities are acidic like P2O5 or SO2.e.Iron is not affected by alkalies.. 2 Fe + 3 Cl2 → 2 FeCl3 Manufacture of steel Steel is manufactured from pig or cast iron.2 %).It has very small amount of impurities. The Bessemer converter is shown in the following figure. If the impurities are basic. couplings for railway carriages etc. It is supported on two horizontal arms ( trunnions ) so that it can be tilted in a vertical plane. When heated with (a) sulphur it forms ferrous sulphide and (b) dry chlorine it forms ferric chloride. weights. then a lining of silica bricks is used and the process is known as Acid Bessemer process. Then a calculated quantity of carbon is added to it to get a required quality of steel.21 (ix) Other reactions . phosphorus and sulphur.

22 Figure 8 .This process is only used to treat pig iron containing phosphorus. Then molten pig or cast iron containing little or no phosphorus is introduced into it. The molten steel is then poured out and cast into moulds. the converter is again tilted. Si + O2 → SiO2 . 2 Mn + O2 → 2 MnO . 2 C + O2 → 2 CO . The air is used to oxidize the impurities. Phosphorus pentoxide reacts with lime and forms a slag containing calcium phosphate. P4 + 5 O2 → P4O10 . To get steel. A portion of iron is also oxidized. Carbon monoxide burns at the mouth of the converter. The molten iron is poured out into a ladle ( deep spoon with long handle ) separated from the slag and then mixed with the charge of requisite amount of spiegeleisen for recarburisation and deoxidation to form steel. A charge of limestone and coke is first introduced into the converter. MnO + SiO2 → MnSiO3 Fe2O3 + 3 C → 2 Fe + 3 CO b) Basic Bessemer process ( Thomas Gilchrist process ) .First the converter is turned into a horizontal position. The molten cast iron containing phosphorus is then added and the blast continued. Then phosphorus and carbon are oxidized simultaneously. It is known as Thomas Slag and is used as a fertilizer. C and Mn ) is added. The hot blast of air is turned on. The iron oxide ( Fe2O3 ) formed oxidizes Mn and Si. the molten metal in the converter becomes wrought iron containing little Fe2O3. When the flame dies out. 4 Fe + 3 O2 → 2 Fe2O3 . The converter is then brought almost to a vertical position and a hot blast of air is introduced. The reactions taking place in the Bessemer converter are summarized below. The hot blast of air is turned on again for few minutes for thorough mixing. if any. Silicon and manganese are first oxidized and pass into slag. 6 CaO + P4O10 → 2 Ca3(PO4)2 ( Thomas Slag ) . Silicon and manganese are partly oxidized and their oxides pass into slag. The iron oxide now reacts with the carbon present evolving CO which burns at the mouth of the converter with a blue flame.Bessemer Converter a) Acid Bessemer Process . the blast of hot air is stopped and a calculated quantity of molten spiegeleisen ( an alloy of Fe. Sulphur burns off as SO2. The reactions taking place in the converter are summarized below.

When the hearth ( floor ). It melts due to hot producer gas. This is a modern method of manufacture of steel.23 Merits of Bessemer process (i) Time required for the production of steel is less (ii) Production cost is low. works alternatively Fig. CO2 and CH4 ) and air. The process. 2) Open hearth process ( Siemens . The furnace is heated by means of producer gas ( a mixture of CO + N2 with little amount of H2 . the first two generators get cooled and the producer gas and air are switched over to the second set of generators and the spent hot gases are led through the first two generators. The spent hot gases are made to leave the hearth through two other generators. When the hearth is lined with lime and magnesia. Demerits of Bessemer process (i) Steel produced is of poor quality (ii) Loss of iron in slag is more. Pig or cast iron. . thus. Meanwhile.Martine process ) Most of the high grade steel is made by this process.When pig iron contains no phosphorus. then this method is used. There are two generators – one for the hot air and one for the producer gas. rusted steel scrap and iron ore are introduced on to the hearth of the furnace. is lined with silica. the process is called Basic Open Hearth process. the process is called Acid Open Hearth process. The furnace used for this purpose is shown in following figure. The process is carried out in a large shallow hearth. 9 – Open hearth furnace a) Acid Open Hearth Process . Iron oxide ( Fe2O3 ) acts as an oxidizing agent.

SiO2 + CaO → CaSiO3 ( Slag ) .e. (iv) Since there is no regenerative system of heat. (vi) The steel is of uniform and superior quality. The reactions are as follows. MnO ) and Si ( i. .24 Fe2O3 + 3 C → 2 Fe + 3 CO ↑ . (iv) Since there is regenerative system of heat. b) Basic Open Hearth Process . P4O10 + 6 CaO → 3 Ca3 ( PO4)2 ( Slag ) SiO2 + MnO → MnSiO3 ( Slag ) A small quantity of charge is taken out after certain interval of time and analysed for carbon content. sulphur and silicon get oxidized to their respective oxides. A comparison of both these processes is given in the following table. (vi)The steel is not of good quality. Open Hearth Process (i) The oxidation of impurities is carried out by Fe2O3. the temperature can not be controlled very well. The amount of carbon is adjusted to get desired quality of steel. Phosphorus is oxidized to form P2O5 which combines with CaO ( lime ) to form slag. (ii) It is adapted to pig iron of any composition. fuel can not be saved. (vii)It is quick and takes only ten minutes for its completion. A little aluminium or ferrosilicon is added to the molten steel which is drawn out from the furnace. (iii) On account of internal heating. When a chemical test indicates that metal contains the minimum required amount of carbon. 2 Fe2O3 + 3 S → 4 Fe + 3 SO2↑ The oxides of Mn (i. (v) The process is continuous and the charging is easier. the temperature can be controlled very well. Carbon. fuel can be saved . Comparison of Bessemer and Open Hearth process Open hearth process has many advantages over Bessemer process.When pig iron contains phosphorus. Bessemer Process (i) The oxidation of impurities is carried out by hot blast of air. (ii) It is restricted to pig iron of a particular composition. (vii) It is slow and takes twenty hours for its completion. 10 Fe2O3 + 12 P → 20 Fe + 3 P4O10 . then this method is used. (v) The process is not continuous and the charging is difficult. (iii) On account of external heating. SiO2 ) react with each other to form slag (MnSiO3 ). then calculated quantity of spiegeleisen is added.e. This removes any dissolved O2 and N2 in the molten steel.

process (i) Due to liberation of large amount of heat. The process requires about 30 to 40 minutes. it sinks to the bottom. process is shown in the following figure. Alloy Steels N 1 Metal added Alloy Steel Manganese Manganese steel Composition Properties 12 to 15 % Very hard and Mn resistant to wear Uses For rock crushing machinery.L. scrap iron can be used as starting material. . The process is much useful for getting low carbon steel. (iv) Process is very cheap and quick. armour plates. (viii)The loss of iron is not more than 4 % 3) L. Process Advantages of L.5 % pure oxygen is blown at supersonic speed on to the molten bath of pig or cast iron when all the impurities including phosphorus and sulphur are burnt away at high temperature. highly pure oxygen is blown from the top of the converter.D. (v) Nitrogen content in the finished steel is very low.10 . The converter for l. D.25 (viii)Approximately 15 % of iron is lost in slag. rail road tracks . leaving low carbon content and high quality steel. Fig. (ii) Carbon and phosphorus are removed at the same time.D. (iii) Superior quality of steel is obtained. The density of the metal is higher than impure metal. ( Linz and Donawitze ) Process In this process. A jet of 99.D. Therefore.

tutorvista. 2) What are the commercial forms of iron ? In which respect do they differ ? 3) Draw and describe the blast furnace and the reactions taking place in various zones in it during the manufacture of cast iron. axles and frames For drills and high speed tools For cutting tools and axles Activity 3 – (i) Find out the places in India where (a) you get iron ore. (ii) Mention names of three alloys of iron which you use in day to day life.com/topic/iron-sulphide-separate 2) Fig. 1 .Hydraulic washing http://www.26 etc. For making armour plates.3 to 3 % Mo Increased elasticity and hardness Resists corrosion Coefficient of expansion equals that of glass Extremely hard 6 7 8 Vanadium and chromium Tungsten Chromium – vanadium steel Tungsten steel Molybdenum Molybdenu m steel Good tensile strength Extremely hard and strong Retains hardness even at high temperature For cutting tools and crushing machinery.5 to 2 % Cr 0.15 %V + 1% Cr 14 to 20% W 0. cycle and automobile parts For clock pendulums and measuring tapes 2 Nickel steel Chromium Nickel Nickel steel 3. 4) Name the processes used to manufacture steel.2 % Ni 3 4 Chromium steel Invar 11. 5) Give the names. 2 – – Froth floatation process http://cbseportal. cables. shafts. armour piercing bullets For springs.5 % Cr 36 % Ni 5 Chromium Chromium steel 1. composition and uses of any two alloy steels .com/exam/Important-Topics/Chemistry-Froth-Floatation-Process . References / Figures / Diagrams : 1) Fig. (b) manufacture of cast iron or pig iron is done. Test your understanding 1) How does iron occur in nature ? Give any three source of iron. automobile parts For utensils.

steel. 10 – L. 9 – Open hearth furnace http://www.php 7) Fig.php 8) Fig.tutorvista. 5 – Electrolysis of alumina http://www. 7 – Blast Furnace http://www. 6 – Hoope’s cell for refining aluminium http://www.php 5) Fig. 4 – The liquation method http://www.php 10) Fig.27 3) Fig. 8 – Bessemer Converter http://qwickstep.D.com/search/the-bessemer-converter.jpg .tutorvista.com/content/chemistry/chemistry-iv/p-blockelements/aluminium.php 6) Fig.com/content/chemistry/chemistry-ii/chemicalcompounds/hearth-process.html 9) Fig.tutorvista.com/content/science/science-ii/metals-non-metals/enrichmentores.org/AM/images/learning/howmade/images/BOFvesseldwg. Process http://www.tutorvista.com/content/chemistry/chemistry-ii/metals/iron. 3 – Magnetic separation process http://www.tutorvista.tutorvista.com/content/chemistry/chemistry-iii/metals/metals-refining.com/content/chemistry/chemistry-iv/p-blockelements/aluminium.php 4) Fig.

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