Basic Principle of Extraction Basic Principle of Extraction NEEDS FOR EXRACTION OF METALS Section - 1 Well use metals in our day to day life sometimes directly and sometimes indirectly. For example, rons used making eectromagnets chains, etc. Stel used in making machinery parts, household utensils Silver and gold are used in making jewellery. We can find numerous examples where we use metals, Since metals do not occur in pure formin earth’s crust, we need to extract metals from their ores or minerals Occurrence of Metals : “Metals occur in various forms. Some in native form, some in carbonate form and some inoxide form. Those metals that are east reactive and have very tte affinity for oxygen, moisture and other chemicalreagents ‘ccure in free oF metallic or native state, > Natural substances in which metals or their compounds occur in earth are called minerals, > Those minerals form which metals can be extracted conveniently and proditably are known as ores ustration: certain metal M occurs in three compounds namely A, B,C. Aas 15% of M, B has 66% of Mand C has 71% of M. If we extract M from, itcosts Rs 35 per kg, if we extract it from B, it costs Rs 45 perkg and if we extract from, it costs Rs 1110 per kg. Now both A, B, Care minerals as they contain M, but all eannot be called ores. Extraction of M from mineral A would cost less but would result ina very less amount. Similarly extraction from C wouldresultin large amount but it wll also costa large sum. Hence, B is the appropriate mineral from which M should be extracted as it would give suficient amount and would not evencost much. In that case, B isthe ore of M. forexample: Bauxite (Alj03.2H 0) and Clay (Al03.2Si02.2H130) bothare minerals of Aluminium, But still Bauxite is appropriate ore bat not Clay since we can extract Aluminium more profitably anelquan- titatively rom Bausie Commercially Important Ores: 1. Native Ores ‘These ores contain metals in the free state. They exist in fee state because they are very unreactive. ‘Some of important metals are Sulphurised and Arsenical ores : ‘These ores consists of sulphides and arsenides in simple and complex forms of metals.bese ipo Eaton Metal Name of the ore Pb Galena PbS. Zn Zine blende Z0S He Cinnabar Hes. Ag ‘Argentite or Silver glance As Fe Iron pyrites Fes, Ca ‘Copper pyrites Cures, Chaleocite or Copper glance | Cu,S Oxidised Ores In these ores, metals are present as their oxides or oxy-salt as carbonates, nitrates, sulphates, phosphates, silicates, ete, Oxides : Hematite Fe,0, Magnetite Fe,0, Bauxite Al,0,.2H,0 ‘Conundum ALO, (Chomite FeO.Cr,0, Tinstone (Casstrite) ‘Sn0, Pyrolusite MnO, Carbonates: | Magnesite Mgco, [Lime stone Cac, | Dolomite ‘CaCO,MgCO, 1 Calamine ZnCO, Malachite ‘Cuco,,CuOHD, Aasite CuCOH), 2CuCo, Cenussite PbCO, Siderite FeCO, Nitrates : Chile satpetre NaNO, Salt petre KNO, 2 Se Study Course fr IEE with One SupportBasic Principle of Extraction Sulphates : | Epsom salt MgSO,7H,0 Gypsim CaS0,.2H,0 Glauber salt Na,SO,.10H,0 Phosphates and Sillicates Fluor-apatite 3Ca,(PO,),.CaF, Felspar KAISi,O, 4, Halide Ores : Metallic halides are very few in nature, Chlorides are most common ores. Commonsalt NaCl Hom siver Ag Camalite KCLMgCl,.6H,0_ Floorspar CaF, Cyplite Bee Note: You Don't need to cram all these compounds in one go. As you will read the chapter these com- pounds will slowly set in your mind. Self Study Course for ITTJEE with Online Support Po 3Basic Principle of Extraction METALLURGY “The complete process of obtaining a pure metal fromone ofits ores known metallurgy.The method to extract ametalis generally not universal, sit depends upon number of factors such asitschemial nature and reactivity, nature of ore, nature of impurities and local conditions, etc. But silin general. metallurgy is divided into folowing thre steps. 1. Concentration ofthe Ore ‘TL. Obtaining Crude Metal from Concentrated Ore TIL. Refining of Crude Metal Different methods are availabe for each ofthese tages. Choice of any method depends upon the nature of metal and type ofimpurit present inthe ore |. Concentration of the Ore : Concentrationof an deals with removal of unwanted impurities. Ores usually contain sol sand, stones and other useless silicates. These unwanted impurities are named gangue or matrix. For concentration, metal is ‘crushed and powdered and then it undergoes concentration, Concentration of ore involves physical as wellas chemical methods. Itisako known as Dressing or Benefcation ofthe oe. © Hydraut Principle Itis based on the difference in specific gravity of ore and gangue particle Working: Powdered ores agitated with running water which carries lighter particles ike sand, clay away with it Washing (Gravity Separation) Powdered ore Gangue Suspension ofthe ore Concentrated ore Self Study Course for IITIEE with Online Supportoun Self Study Course for INTJEE with Online Support Basic Principle of Extraction Type of Ore : ‘The oxides and carbonates type of ores are suitable for this method. For example Tin's oreCassiterite (Sn02), ron's ore Haematite (F303). (i) Magnetic Separation Principle Iisbased on the magnetic and non-magnetic properties of ore and gangue. Working: ‘A magnetic separator consists ofa belt which moves on two rollers, one of the roller being a strong ‘magnet. Now the powdered ore is dropped on the belt near the non-magnetic roller and as the ore reaches the magnetic roller the magnetic particles get attracted and fall nearer to the roller whilethe ‘non-magnetic particles fllaway from the rollers Moving belt Magnetic Type of Ore : Separating Wolframite (Tungsten) ore from Cassiterte (Tin) ore, separating transition metal ores such ‘as Magnetite (Fe30,), Pyrolusite (MnO3) and Chromite (FeO, 1,05) fromunwanted gangue. (i) Froth Floatation Principle : Mineral particles are wetted by oils and the gangue particles are welled by water. Working : Collectors frothing agents and froth stabilisers are added to the ore which mixed water. Collectors enhance the non-wettabilty of mineral particles and froth stabilizers stabilize froth, Mineral particles, become wet by oils while gangue particles by water. Liquid mixture is agitated and air blown, Froth is formed which carries off with it mineral particles. Light froth floats at the surface whichis taken off And from ths froth minerals recovered. me 5Basic Principle of Extraction Cine Foam carrying ore particles ie &. Water ore + Water. ‘Pine ol + Sodium ethyl xanthate ” Gargue Concentrated Frothing agents : Pine Oil Collectors Fatty acids, Sodium Ethyl Xanthate Froth Stabilizers: Cresols and Aniline Depressants : ‘These are those chemicals that are used to prevent certain type of particles from forming the froth with the bubbles, For example : NaCN (sodium cyanide) acts asa depressant in preveting ZnS from forming the frothasit forms layer of NayZn(CN), on surface of Zn in concentration of zine blende (ZnS). Ths s also known as selective frothing. Type of Ore : Sulphide ores eg: Galena (Pbs), Zinc blenda (ZnS), Cinnabar (HS). (v)_ Chemical Separation (Leaching) Principle : Itis based on the differences in the chemical properties ofthe ore and the gangue, Working: (Ore is made soluble ina solvent and is then separated from the gangue. The solvent’s choice depends upon the ore and gangue’s chemical properties. Example: 1. InBayer's process, the impurities of iron and silicon are removed from the bauxite ore [NaOH is added to the ore and as Alis amphoteric it dissolves forming sodium aluminate. ‘Si being acidicoxide also dissolves as silicate ions. The insoluble ron impurities are re moved by filtering. Next, CO, is bubbled through the solution owering the pH. Thisenables the precipitation of Al(OH); silicate ions remaindissolved). The Al(OH) precipitate is calcined (heated strongly) to give concentrated Al,O5, ‘ Se Sty Cu oc TE with Ot SipBasic Principle of Extraction [Alg03+ SiO + NaOH —> Nal AKOH),] + Si0* Na[Al(OH),] + CO) —+Na CO; + AKOH);(1) AI(OH) i) —2-> A303 + H30(7) 2. Cyanide's Process Another example isthe eyanie’s process for extraction of Au (ftom native form) and Ag (from ‘AgyS ore). The ore containing impurities is curshed and then treated with 0.1 —0.2% soluton of NaCN or KCN and aerated forming a soluble complex from complex which the metas extracted by the addition of Zn power inthe solution. For Au: 4Au + 8NaCN + 2H;0 + 0, —>4NalAu(CN)3 + 4NaOH ‘2Na[Au(CN)2] + Zn—> Nap[Zn(CN)4] + 2AuCL) For Ag: ‘AgyS + 4NaCN =? 2NalAg(CN)9] + NaS 2NalAg(CN)2] + Zn —+ NaglZn(CN)g] + 2Ag) Il. Obtaining Crude Metal This step involves reduction of concentrated ore. The concentrated ore ie. Metaloxides, Metal sulphides, Metal carbonates ete. are converted to metal inthis step. M"* ——>M reduction occursin this step. ‘Metal cabonates and Metal sulphides are difficult to reduce than metal oxides therefore they ae fist converted. to their oxides and then metal oxides s reduced to metal. Conversion into Oxide Forms Metallic ores are converted to metallic oxides by the two processes. 1. Caleination : It involves heating ofthe ore below its fusion temperature in absence of ar. It can remove moisture from hydrated oxides or carbondioxide from carbonates. Its suitable for carbonate ores. CuCO3 .Cu(OH}, —* 4 2Cu0 + CO, + 1,0 ZaCO;—* 420 + CO> CClcination makes the ore porous. The stepis generally performed ina reverberatory furnace. Set ty Ce or TE wt nine opr :bese ipo Eaton 2. Roasting: tinvoles heating ofthe ore strongly inthe presence of excess o ar below it fasion temperature. It is suitable for sulphide ores. 2ZnS(s) + 309(g)—4-+2Zn0(8) + 2809(g) Sometimes, apart of sulphide may at as reducing agent asin case of extraction of lead PbO formed by roasting is reduced to lead by PbS. 2PbS + 30) —>2PbO+280, PbS + 2P{0——>3Pb + SO» Exception : ° 2CuFeS, 24 CuyS + Fe + 380, UPS Taggee CUS * Fea0a + 3802 TRE OSs eS ns Ho GE CSS Pa er eee tee Pace eo fom Reduction to Crude Metal ‘When the oxide form is obtained, then the metal has to be reduced. The choice of the reducing agent is ec e fcomofemrgetesan econ Three main categories of reduction processes are : (A) ChmialRetucion (8) Hyometbsy (©) BeetobieRedson ‘Now, we will discuss few important points of each category. (A) Chemical Reduction Process Cason, Alanon Hyérogenand ome thermal reuse seeing agents These met epe [ewekroponinenetasombvione (Reduction by carbon : Catboncanbesedto rede amber ofsiesand othe conpouns and fea ofhe bw cost snlavlaityofcke hh mahal wed Te deaaapesaethas gh emperate peel ch expen al ecstatic Aan ta combie with caron, forming carbides, some examples are 05 +0 es 290 +6 20, 29 seu ci casP0y), +88 5P go +c 2 yg PbO + C —> Pb 3 Se stuly Course fr IEE with Onne SupportDome mers Basic Principle of Extraction (Reduction by another metal : [the temperature needed for carbon to reduce an oxide is too high for economic or practical purposes, the reduction can be done by another highly electropositive metal such as Al, which liberates a large amount of energy on oxidation to ALO,, This isthe bases ofthe thermite process: - 3Mn30, + 8Al—>9Mn +4A1,0; ; B30; + 2Al—> 2B + ALO; €r,03 + 2A —> 2Cr + AOS ‘Magnesium being more electropositive metal as compared to Alis used to reduce halides. TiCly + 2Mg OPE, 75 + 2MeCly (i) Reduction of oxides with hydrogen ‘This method is not widely used because many metals react with hydrogen at elevated temperatures, forming hydrides. C0304 + 4H, —> 3Co + 4H,0 ‘2NHy[MoO4] + 7Hy —> 2Mo + 8H,0 + 2NH3 (iv) _SelfReduction Process ‘The sulphide ore of es lectropositive meta ike lead, mercury, copper are heated inairas to convert part ofthe ore into oxide or sulphate which then reacts with the remaining sulphide ore to sive the metal and $O, gas. ‘No exteral reducing agent is used in this process. Lead: 2PbS +30; —+ 2Pb0 +280, (Extraction of ead from Galena, PbS) 2PbO + PbS —> 3Pb + SO, Copper: 2Cu,$ + 30) —> Cuz0 + 280, (Extraction of copper from copper glance, Cu,S) CugS + 2Cu;0 —+ 6Cu + $0, Mercury: 2HgS +30; —> 2Hg0 +280, (Extraction of mercury from cinnabat, Hy) 2HgO + HgS —> 3Hg + SO) Another name for self reduction process is auto reduction process or ait reduction process. ®) Hydrometallurgy ‘This process is based on the principle that more electropositive metals can displace less electropositive ‘metals from theirs solution, The oe treated with such chemical reagents Which convert ic ino soluble compound. By addition of more electropositive metals tothe filtrate, the metal present inthe ore can be precipitated, Self Study Course for INTJEE with Online Support me 9Basic Principle of Extraction Cine Mustration : Malachite ore is first calcined and the oxide obtained is dissolve scrap iron is added which precipitates copper. HO, To the solution of CuSO, ‘CuCO;.Cu(OH)y —> 2CuO + CO) + HO CuO + H380, —> CuSO, + H;0 (oluble) CuSO, + Fe —> FeSO, + Cu (oluble) Similarly, silver can be obtained by cyanide process. © Electrolytic Reduction Oxide of highly electropositive metals ike Na, K ete cannot be reduced with carbonat moderate temperature, So, for theirreduction, a very hightemperature i required, at which they may combine with earbonto form carbide. Thus, they are obtained by electrolysis of their oxides in fused or molten state ‘Mustration : Sodiumis obtained by the electrolysis of fused mixture of NaCl and CaCl, (Down's Process) or by the ‘electrolysis of fused NaOH (Castner’s process). NaCl (molten) —> Na’ +Cr Cathode: Nat +l —+ Na Anode: 2Cr —+ Cl, +2 Similarly aluminiumis obtained by the electrolysis of alumina mixed witheryolite. (U) Refining of Crude Metal ‘The crude metal obtained is impure. The impure metal is subjected to some purifying processes, ‘known as refining in order to remove the impurities. The processes used for refining depend upon the nature ofthe metal and the nature of impurities. () Distiltion (B) Liguation (©) Pyrometaliurgical Oxidation (@— Capetiation (ii) Bessemerisation ——(ii)_—-Poling, (D) EketrolyticRefining (FE) Special Methods, ()— Mond'sProcess (ii). VanAArkelMethod (it) Zone Refining @) Distillation “This process is used for those metals which are easily Volatile such as:Zn, Hg, Cd. The impure metal is heated ina furnace and its vapours are separately condensed in a receiver. The non-volatile impurities are Jeft behind inthe furnace. 0 SolfStudy Course for ITIEE with Onine Supportoun Basic Principle of Extraction (®)_Liquation (© Bessemeris ‘This process is based on the difference in fusibilty of metal and impurities. When the impurities are less fusible than the metal, this process is employed. The impure metal is placed on the sloping hearth of the furnace and gently heated. The metal mets and ows down leaving behind the impurities on the hearth. This ‘method is used to purify Bi, Sn, Pb and Hg. tion (Pyrometallurgical oxidation) ‘The impure metal is heated ina furnace and a blast of compressed airs blown through the molten mass. ‘Theimpurities get oxidized. For example, the molten pig ion taken ina Bessemer converter and compressed airis passed which oxidizes the impurities. 2Mn +0, —+ 2Mn0— Si+ 0, — SiO, 2C +0, —+ 2CO_; MnO + SiO, —+ Mnsi0, (stag) (0) Electrolytic Refining Itis different from electrolytic reduction. The impure metal is made anode and a thin set of puremetalis ‘made eathode. Aselectrolysis proceeds, pure metal rom anode is transfered to the cathode, whereas the impurities settle down as anodic mud or anodic sludge. For examples Cu, Ag, Au, Pb, Za, tc. are refined by this method. © _ Special methods for Refining Self Study Course for INTJEE with Online Support @— Mond’s Process I is used mainly for refining of nickel. Impure Niis treated with carbon monoxide at 330K —350K, ‘when volatile compounds Ni(CO), i formed. ‘The impurities are left behind and the volatile Ni(CO) is transferred into another container, where itis heated more strongly at 450 K to give pure Ni, The CO gas produced is used again, Ni +4co SK, Ni(Co), EE Ni + 4c0 Inpure Volatile and (Pa) highly oxi (i) Van Arkel Method Inthis method, zirconium (or titanium) is heated in iodine vapourat about 870K to form volatile Zs, ‘The vapoursof volatile 1, are then decomposed electrically over tungsten filament to get pure metal, and iodine is recovered. s70K. 20k. Zee 2, Ey my EES Zr + 2p (am pure) (Vapors) (ur) As Van Arkel method and Mond’s process are quite related they are known as Vapour Phase Refining. me 1"bese ipo Eaton Zone Refining ‘This method is used for extracting ultra-pure metals. Ths method is based upon the principle that ‘when molten solution of impure metals allowed to cool, the pure metal crystallizes out, while the impurities remain in the melt. Amovable beaters fitted at one end ofthe rod of impure metal. The heater is slowly moved across the tod. The metal melts atthe point of heating and! s the heater moves Con fromone end ofthe rod to the otherend, the pare metal crystallizes while the impurities pass into the adjacent melted zone. This process is repeated numberof times unless metal of desired purity is ‘bjained, The process is carried out in an inert atmosphere to prevent the oxidation of metal. For «example, Germanium, Sicon and Galium for being used in semiconductors are purified by this method. Nobal gas atmosphere Metal rod’ AY Indvetion- coil Molten zone heaters moving as shown Important Terms 1. Flux Flux isa substance which is added to remove non-fusible impurities by forming slag and decrease the ‘melting point of the melt during reduction, Flux can be of three types: (a) Acidic flux- Itisused to remove basic impurities. Examples of acidic flux include SiO, (in smelting of Cu) and borax. (b) Basie Flux- Its added to remove acidic impurities. Examples include Fe,O,, CaCO, (in blast furnance) ete 2. Furnance A furnanee isa structure built to produce high temperature, Examples of some farnaces are reverberatory furnance, blast fumance and muflle furance. 3. Refractory materials ‘These are compounds mixtures which can withstand very high temperature without melting and are notaffected by slags. They are used inthe form of bricks for intemal lining of furnaces, Referectory materials may be of three types (a) Acid Refractories -SiO,, quartz, (b) Basic Refractories - CaO(lime), magnesite, dolomite. (in last furnance) (©) Neutral Refractories - Graphite (used in Hall Heroult Process), Chromite, bone ash 2 Self Study Course for ITJEE with Online SupportBasic Principle of Extraction IN - CHAPTER EXERCISE - A List five ores which are smelted and give equations to show what occurs during smelting ‘Name the process(es) used for concentration of tinstone. Explain the role of collectors and froth stabilisers in Froth floation process. Why is reduction by hydrogen not widely used. Name three ores which undergo autoreduction give balanced equations. Explain thermite process. EXTRACTION OF IMPORTANT METALS Section - 3 (Sy Group 1 uTHIUM Sources : Lithium occurs mainly a SODIUM Sources : Sodiumis the most abundant alkali metal. Iis found in sea water, as rock salt (NaCD, Saltpetre (NaNO,), Borax, Glauber’s salt (Na,SO, . 10H,0), cryolit. Extraction : ate minerals like spodumene (LiAISi,O, ), Lepidolite Sodium is obtained on large scale by two processes (A) Castner's process : In this process, electrolysis of fused NaOH is carried out at 330°C using iron as cathode and nickel anode, NaOH —+Na* + OH™ AtFe cathode: = Na* +e” —>Na AUN anode : 40H” —> 2H,0 + 05 + de ‘water formed at the anode gets partly evaporeted and is partly broken down to form H, at cathode. (®) Down's process : ‘Sodium metal is manufactured mainly by tis process. It involves the electrolysis of fused sodium. chloride (40%), cakiumchloride (60%) and potassium Muoride using ron as cathode and graphite as anode at about 600°C. Sof Study Course for ITJEE with Online Support 8Basic Principle of Extraction Cine Molten electrolyte Cathode —_ Metal gauze NaCl —> Na’ + Ct At Iron cathode Nat 4 e° —+ Na At carbon anode 2Cr —> Ch +207 ‘The electrolysis of pure NaCl presents the following difficulties: > Thefusion temperature of NaClishigh, Le., 803°C. At tis temperature both sodium and chlorine are > Sodium formsa metallic fog at this temperature ‘To remove above difficulties, the fusion temperature is reduced to 600°C by adding CaCl, and KF, POTASSIUM Sources : Potassium occurs mainly as deposits of KCl and carallite (KCI, MgCl . 6H,) Extraction : cell similar to down’s cell can be used to obtain potassium by electrolysing fused KCL. [ay Group 2 MAGNESIUM Sources: Magnesium salts occur in sea water. Entire mountain ranges eg Dolomites in Italy) consist of the mineral dolomite [MgCO, . CaCO. Italso occurs as magnesite (MgCO,) and camallt. Extraction : (A) Dow's sea water process : ‘Sea water contains MgCl, . Water is treated with Ca(OH), which precipitates MgCl, as Mg(OH), MgCl + Ca(OH); —> CaCl, + Mg(OH), 4 Gin sea wate 4 Self Study Course for IITIEE with Online SupportBasic Principle of Extraction ‘This is then converted back to MgCl, Mg(OH)) + 2HCI1 —+ MgCl; (= MgCl; . 6H,0)+2H,0 MgCl; . 6H>0 HC, Mgct, (anhydrous) ‘The obtained anhydrous MgCl is then electrolysed in fused state, (8) From magnesite MgCO; —*> MgO + CO, MgO +C+C—> MgC + CO (anny) MgCl,is thenelectrolysed. (©) Electrolysis of Fused Carnallite Magnesium is prepared by electrolysis of fused MgCl, Anhydrous magnesium chloride is first prepared as in (A), (B) above Carbon anode OE coal gas (ce ve | FL revese 2 sored Inorderto lower fusion temperature of anhydrous MgCl, and to increase the conductivity of electrolyte NaCl or KCI (30%) is added. The electrolysis of MgCl, is carried out at 700°C. Anaiir tight Iron vessel serves as cathode. A carbon rod serves as anode and is enclosed by a porcelain tube, This arrangement prevents the contact between magnesium and chlorine. Before starting the electrolysis, airabove theelectrolyte is replaced by coal gas. This precaution is necessary because at about 700°C magnesium reacts rapidly with O,,N, and CO, present in air Self Study Course for ITJEE with Online Support 5Basic Principle of Extraction Cine MsCl, —> Mg” +2CI AtFecathode = Mg’ + 2e° —> Mg AtCarion anode 2Cr — Cl, + 2° (©) Insilico-thermic process / Pidgeon process : Here calcined dolomite (CaO + MgO) is reduced by ferrosilicon at about 1200°C inan electric furnace working under reduced pressure (3mm) where pure magnesium distils over. CaO + 2MgO + Si 2S, 2Mg + Casiog ‘mm CALCIUM Sources : toceurs in many common minerals ike limestne, marble and chalk (CaCO,), dolomite, gypsum, Fluorspar and also as coral. Extraction by Electrolysis : Caleiumis obtained by electrolysis ofa fused mass consisting six parts calcium chloride and one part ‘calcium fuoride at about 700°C in an electrolytic cell made of graphite which acts as anode and a water ‘cooled cathode of iron which is suspended from the top in the fused mass. On passing current, caleium is discharged at cathode. It gets solidified as cathode is water cooled. CaCly —> Ca?* + 2c At graphite anode: 2C” —+Cl, +267 AtFe cathode: — Ca2* + 267+ Ca ‘Since metallic calcium is soluble infused CaCl, at electrolysis temperature, cathode is raised and Cais removed as soonas itis deposited. Note: Naor K is obtained by electrolysis of fused NaOH or KOH respectively but calcium cannot be obtained in the same manner as Ca(OH), decomposes into CaO (quick ime) which is ifficut to fuse, ie GROUP 3-7 > Ti istefined by Van Arkel -de-Boer method : ‘Ti(impure) + 21, we, ‘ TiO, is very stable and can’t be reduced by C or CO asit forms carbides and hence is reduced by Na or Mg. 16 Se Stuy Course for EE wth Online SupportBasic Principle of Extraction > Zirconium (Za) isalso refined by Van Arkel- de-Boer methods > Molybdenum and Tungsten are chemically reduced by H, ‘MoO + Hy —> Mo +H;0 WO3 +H, —> W +H;0 [a Group 8 IRON Sources : Ironisthe second most abundant metal and fourth most abundant element inthe earth's rust. It isextracted from haematite (Fe,O,), magnetite (Fe"Fe,!"O.) and iron pyrites (FeS,) Famously called Fools Gold. Extraction 1. Crushing and Concentration ‘The ore is crushed and washed with water (i.., concentrated by levigating ina stream of water _sravity separation or hydraulic washing) and then concentrated by electromagnetic process. 2. Roasting : ‘The concentrated ore is roasted in shallow kilns in the presence of excess of air Inroasting, > Most ofthe moisture is removed. > Impurities (ike C, $, P, As and Sb) are removed in the form oftheir volatile oxides. S+0,—>S0, : 4As +30, >2A8,0, ; P+0, —>P,0, > Carbonates and sulphides are converted into oxides. FeCO,—> FeO + CO,: 4FeS, + 110, —> 2Fe,0, + 850, > Ferrous oxide is oxidised to ferric and thus avoids formation of slag with sand in further processing 4FeO + 0, —>2Fe,0, (Otherwise FeO + > Theentire mass becomes porous which makes reduction easy. iO, —> Fesio,) 3. Smelting or Reduction : ‘The roasted ore (8 parts) mixed with coke (C), a reducing agent (4 parts) and limestone, a ux CL part) is smelted (reduced) ina blast furnace lined with dolomite. Hot air blast is introduced nearthe bottom ofthe furnace. Since the blast furnace has different temperature a different zones, different reactions take place at different zones (@) Zone of Combustion : (1500°C -1600°C) ‘This zone isnear the bottomof furnace and itl above the tuyeres. 2C + 0, —> 2CO + 58 Keal C +0, — CO, + 97 Keal Both reactions are exothermic, a high temperature of about 1500°C -1600°C is attained. Set uty Cue or Ewa On apa ”Basic Principle of Extraction Cine FeO + CO —> Fe + CO; C0) +€ —> 20 FeO +C —> Fe + CO (©) Zone of Fusion : (1200°C -1500°C) Its ust above the zone of combustion, Here the iron produced in upper zones melts and trickles down in hearth while the slag being lighter floats over the molten iron and thus prevents oxidationof Fe by blast ofhot air. The molten metal and slag are removed from different outlets. (0 Zone of Heat Absorption : (or middle zone) (800°C -1200") In this middie part of furnace, rising CO, (produced in the zone of combustion) is reduced to carbon monoxide CO, + C+ 2CO_; AH=+39 kcal ‘The reaction being endothermic lowers the temperature ofthe zone. In addition to this, following reactions also take place here. (Limestone decomposes forming CaO which reaets with SiO, forming slag, caco, 4+ C20 + CO, CaO + SiO, —+ CaSiO, (slag) (i) Any e,O, which escapes reduction in the zone of reduction is reduced inthis zone. Fe,0, +CO —> 3Fe0 +C0,t ‘Some impurities are reduced and get mixed up with Iron. MnO +C —+ Mn+CO 80, +2€ —+ $+2CO Si0, +26 — Si+2Co P.O, +5C —> 2P+5CO Ca(PO,), —> 3Cx0 + P,0, (@ Zone of Reduction : (300°C -700°C) Itisnear the top of the furnace. Here the roasted ore is reduced by rising carbon monoxide CO. The {following reactions taking place in this zone are all reversible in nature. Src —400rc 3Fe,0, + CO 2Fe,0, (spongy iron) + CO, Fe0, + Co —S0C= 20, Fe0 + CO —+Fe + C0, 3FeO + CO, Fe304+4CO—>3Fe+4COp 8 SolfStudy Course for ITIEE with Onine SupportBasic Principle of Extraction (re, Limestone and BR ‘hep Ey ye SS, Hot gases (eox0) cowper stoves tone ot fe] 200° reduction Fy ~ 700°C tone ofa FP goorc absorption Bl yc Retactory 40 metre brick ining Zone of 1200 son 1so0re vo 2one of ‘ an 36o0"C Bustle pipe Molen sa ruyeres ‘Slag tapped off z re tapped oft ete ul Top hale Malt on > Tron obtained is impure. The product from blast furnace in called as Pig ron. The net productof blast furnace consists of Pig Iron, slag and fuel gases. > Theoverall process forthe extraction of Feis thus 3C + Fex0; —> 4Fe + 3CO, CaCOs + Siz —> CaSiO3 + COz Cast iron : ‘The cas ironis specially made by igniting Pig iron with scrap iron and coke ina specially designed furnace by bist of hot ar It contains 3% carbon in the form of graphite and carbide and isextremely hard and brittle, [yj Group - 11 COPPER Sources : ‘The most common ore is chaleopyrites CuFeS, . Other ores include Cu,S (Copper glance / chalocite), basic copper carbonate CuCO, . Cu(OH), (called malachite and is green) and cuprite Cu,O (isruby red) cre 19 Self Study Course for ITTJEE with Online Support Ebese ipo Eaton Extraction : Itisaselfreduction method, Itcan be achieved by two ways. 1. Pyrometallurgical TL, Hyderometallurgical @)_Pyrometallurgical Method: 1. Concentration of Ore: The ores finely divided and concentrated by froth floatation method, Here froth is made from pine oil and water by bubbling air into the mixture. Concentrated ore adheres to the surface of froth leaving behind impurities. 2. Roasting: The concentrated ore is heated strongly in presence of arin areverberatry furnace. Sulphur, arsenic and antimony are removed in the form oftheir volatile Oxides while the proper ore is converted into a mixture of cuprous and ferrous sulphides. These sulphides are partially oxidised to oxides Haeess Charge hooper charge Ale and Ot ‘Magnesite Furnace charge Silica ‘section of a modern reverberatory furnace S +0, —> 80, 2AsS, +0, —> 2As,0, + 680, 28b,S, + 0, —+2Sb0, + 650, 2CuFeS, + 0, —+ Cu, + 2FeS + SO, Minor Reaction: 2Cu,S + 30, __, 2Cu,0 + 250, 2FeS + 30, _, 2FeO + 250, ‘Smelting (Auto Reduction) : The roasted ore is mixed with sand (fhux) and coke (fuel) and then heated inwaterjacketed bas. furnace called smelter. The oxidation of ferrous sulphide which started during roasting now goes upa step further, ferrous oxide, formed reacts with sand to form ferrous silicates (slag). Here some FeS reacts with Cu,O to form Cu,S again, 20 Self Study Course for ITIEE with Onine SupportBasic Principle of Extraction FeO + SiO, (sand) —> FeSiO, (Ski) Cu,0 + Fes: —+ Cu,S + FeO Slag, forming upper layer and molten mass consisting of Cu, and litle FeS, forming lower layer called “COPPER MATTE’ are removed from separate holes. 4, Bessemerisation : Molten matte is heated in Bessemer converter and blast of air mixed with sand is, blown through the molten mass. Here Iron (FeS) is completely removed as slag. Apart of Cu,Sis oxidised to Cu,O and a part of Cu,S reduces Cu,0 to metalic copper. 2Cu,S + 30, —» 2Cu,0 + 280, 2Cu,0 + Cu,S —+ 6Cu + SO, ‘The molten copper is poured off into sand moulds. As it cools, it gives up dissolved SO, which forms biister on the metal surface. The copper thus obtained iscalled as BLISTER COPPER (98% Cu). Waste gases Trey 7 tt asi ining Ss Molten mate + Send Refining of Copper : (@ Furnace or thermal Refining: Blister copper is meited ina reverberatory furnace provided with silver lining and aris blown in where the impurities oxidise. Some of oxides escape and other form slag with silica ‘The slagis removed. (©) Poling: Molten seen wood. Cu,0 + CO —+ 2Cu + CO, Cu,0 + H, —> 2Cu + H,0 Self Study Course for ITJEE with Online Support a stirred with poles of green wood to reduce Cu,0 to Cu by CO and H, frombese ipo Eaton (© Blectrorefining The electrolyte bath contains an acidified solution of copper sulphate, impure copper (blister copper acts as anode while pure copper strip acts as cathode. The cathode grows in thickness, and pure Cus seraped of. ‘Anode : Impure Cu Electrolyte: 3.55% CuSO, +15%H,S0, : Cu —+ Cu + 26 Cathode : Pure Cu Temperature: 50°C: Cut + 2° —> Cu Pu) ‘Note: ‘The impurities (Av, Ag, Pb...) collet below the anode and is called anode mud, @®)_Hydrometalturgical Method : Low grade ori rushed and exposed to air and water when copper sulphide is oxidised to copper sulphate. Some iron sulphate and sulphuric aids also produced. This proces takes one year (a) CuFes, + 40, —+ CuSO, + FeSO, (0) 2Cu,8 +50, —+ 2CuS0, + 2Cu0 Cu glance Cus + 20, —+ CuSO, pale green guid InNON-SULPHIDE ores, the crushed ores lached wit dilute H,S0, (9 CuCO,CulOH), + 2H,S0, —+ 2CuSO, + CO, + 34,0 Malachite “Thepale green quor draining fromthe bottom to the heapsis collected in pan and treated with ion scraps hich precipitate out copper. CuSO, + Fe —+ FeSO, + Cv “The precipitated coppers dried, meted and refioed SILVER AND GOLD Sources : Silver is mainly found as suphide or Ag, (argentte) Gold occurs mainly as grains of metal disseminated in ‘quartz veins. Extraction : ‘Au, Agare both fis crushed and concentrated by roth Nloatation, Ser then directly undergoes kaching while gol is leached after roasting. 2 Self Study Course for ITJEE with Online Supportoun Basic Principle of Extraction Leaching is done by Cyanide process. 1, Agore is leached with NaCN (or KCN) solution in presence of air when silver and its sol are converted to soluble complex. AgyS +4CN" =2h> 2[Ag(CN)jF +S ‘Agent Cyanide ‘Golub (O Jair) is pumped to force the reaction in forward direction. 48° Zine dustis then added o precipitate Ag. +503 +280 —» 280} + 284 + 40H [Ag(CN)2P + Zn —> Ag 4+ (Zn(CN)gI ure) 2. The leaching process used for Au i called Mac Arthur Forest Cyanide Process: Concentrated ore istaken in large vats made of eement or iron. Itis then treated with dilute (0.5%) solution of KCN in presence of arto forma soluble complex, 4 Au + 8KCN + 2H30 +0) —> 4K[Au(CN)3] + 4KOH (ore) Potassium Auocyanide ‘Soluble) Note: Ifexcess conc. KCN is used then 4Au +16CN~ +0 + 2H{0 —> 4[ Au(CN),/* + 40H~ (excess) Zine dust isthen added : 2K [AU(CN) 3] + 21 —> Ko Zn(CN)g] + 2A pu ‘The obtained Gold (or Silver sill contains traces of impurities and thus electrolytic refining is performed. ‘The electrolyte used is AgNO, + 10% HINO for silver) and AuCl, + 10% HCI (for gold). Anode isthe impure metal while cathode is made of pure metal > Agisalso obtained fromargnetiferrous lead (PbS . Ag,S) by Parke's Process or Pattinson's Process > Ag, Aucanalso be extracted from anode mud formed during electrolytic refining of copper. > Another method of extraction is amalgamation, Powdered ore i first converted to its amalgam and ‘then distilled to remove Hg in the form of vapour leaving behind pure metal Self Study Course for ITJEE with Online Support 2Basic Principle of Extraction Cine GROUP - 12 ZINC Sources : Zine is found as Zine Blende (Zn$), Colomine (ZnCO,) and zincite (20) Extration : 1. Concentration ‘The ore is concentrated first by gravity method and then by froth floatation process. IfFe,0, is present as an impurity, it s removed by magnetic separation. Roasting ‘The concentrated ore is then roasted at 900°C 1000°C to convert ZnS and ZnSO, to Zn0. 2ZnS + 30, —+ 2Zn0 + 280, ZnS +20, —+ ZnSO, ZnSO, —> 2Zn0 + 280, + O, ‘Note: Ifcalamine is used as the source, only calcination is required at high temperature 7200, 4+ 200 + €0, 3. Reduction by coke ‘The oxide, ZnO is reduced with coke at about 1500°C to obtain metalic zinc whichis distilled of and rapidly cooled. Z00+C —> Zn + CO Z00 +CO —+ Zn + CO, 4, Electrolytic Refining Zn thus produced contains impurities like Pb, Cd, and Fe. These impurities are removed by liquation. The pure zinc is obtained by electrolysing the Zinc in presence of acidified ZnSO, (ZnSO, + dil H,SO,) as electrolyte. Impure zinc is made the anode and pure zinc, the cathode ‘Note: Zine can also be extracted by electrolytic method. ZnS is first roasted at 700°C to produce ZnO. Then, the | oxide Zn0 is leached with H,SO, to convert to sulphate (ZnSO). After removing impurities by treating with ilk of lime, ZnS, is acidified and electrolysed to give pure zinc on cathode. MERCURY ‘The most important ores cinnabar (HigS) which i bright red coloured. The ore sist crushed and concentrated by froth floatation method. Itthen undergoes Auto / self reduction HgS + 0, —> Hg0 +S, Hg0 + Hgs —+ Hz+S02 Refining is done by either liquation or distillation Fy Self Study Course for ITIEE with Online SupportDome mers Basic Principle of Extraction [y Group - 13 ALUMINIUM : Sources : ‘Aluminiumisthe most abundant metal andis commercalyimportant The most important ore of aluminium isbauxite. Ths sa generic named for several minerals with formulae varying between ALO, H,O and ALO, 3H,0 Extraction (Electrolytic method from Bauxite) : 1. Purification of Bauxite ‘Bauxite contains mainly Iron oxide (Fe,O.) and silica as impurity. Ifiron oxide is the main impurity it is called red bauxite and if SiO, isthe main impurity, it iscalled white bauxite. It is difficult to remove iron or silicon from aluminium, so the ore is purified before hand. It can be achieved by either ofthe following processes. (@ —_Bayer's Process (for ores containing iron oxide as major impurity) : Finely grounded ore isroasted ata low temperature to convert FeO to Fe,O, and digested ‘witha concentrated solution of NaOH inan autoclave. ALO, (Amphoterie) dissolves forming Nal, while Fe,O, (basic) remains undissolved, Fe,O, is removed by filtration AL0,2H,O + 2NaOH —> 2NaAI0, + 3H,0 ‘The irate containing sodium aluminate i diluted, treated witha seed crystalof pure AKOH), and then agitated, when pure Al(OH), is precipitated. NaAlO, + 2H,0 —> NaOH + AKOH), 4 ‘The precipitated AM(OH), istered, washed and ignited to give pure alumina, ALO,, 2AKOH), “> ALO,(pure) + 34,0 (b) _Serpek’s Process (For ores containing silica, SiO,) : ‘The powdered ore is mixed with carbon and heated to 1800°C in acurrent of nitrogen, ‘where aluminium nitride is formed, SiO, is reduced to silicon, which volatilses away. WO, + 3C +N, BE yaa + 3C0 SiO, + C—> Sif(wolates of) + 2cOt Aluminium nitrides hydrolysed by water to KOH), shichon ignition gives pure alumina AIN + 2H,0 —> AKOH), + NH, 2ayor, 5 ayo ypure + 34,0 Set uty Cue or Ewa One apa =bese ipo Eaton (© Halts Process [mainly for Red Bauxite] : (Crude bauxite reacts with Na,CO, at 1000°C to give sodium aluminate and impurities Fe,O, and SiO, form NaFeO, and Na,SiO, respectively. ALO, + Na,CO, —> 2NaAlO, + CO,t CO, ata temperature of around 60°C is passed into sodium aluminate solution producing AKOH), 2NaAlO, + CO, + 34,0 “© > 2aKOH), + + Na,CO, 2AIOH), aye? ALO, (Pure) + 3H,0 2. Electrolytic reduction of alumina (Hall - Heroult Process) Aluminium can’t be isolated by electrolysis of aqueous solution of ALO,, since aluminium is more ‘lectropositve than hydrogen, soit electrolysis gives H, at cathode. AIO, is infusible (M.P.=2050°C), soit can’t be electrolysed, So pure alumina, dissolved in molten Cryolite (Na, AIF, containing some CaF, or NaF selectrolysed at about 800°C-1000°C. Cryolite decreases melting point and increases conductivity while CaF, and NaF are added only to increase ‘conductivity. The electrolysis is carried out in an iron cell lined with graphite (cathode). The anode isa series of graphite rods carbon copper ectrolytic cell for extraction of aluminiuen AIF, — AB + 3 At cathode : Al’ + 3e —> Al ‘At the same time, ALO, dissociates into AP* and O°. Since ‘O’ is below Fin the electronegativity series, O?- ions are selectively discharged at the anode as oxygen. 2AL0, —> 4A + 60> Atanode: 60> —+ 30, + I2e % Se study Course fr ITIEE wth Ontne Supportoun Basic Principle of Extraction ‘The oxygen liberated at anode combines with carbon of anode to form CO and CO, so anode, which burn away have to be replaced periodically, Molten Al collects at the bottom of cell(99% pure) Electrolytic Refining “The cells layers contain thre fused layers. (a) The bottom anode layer of analloy of Al, Cu, Si () Themiddle layer of Cryolte and BaF, (©) Thetopeathode yer of pure aluminium, ‘When a current is passed, AP* ions from the fused midlle layer get discharged at the cathode, while an equivalent amount of aluminium moves into the middle layer. Impurities (Cu etc) remain at the bottom, GROUP - 14 TIN: Sources : It is mainly obtained from Cassiterite (SnO.) which contains Wolffomite (FeWO, . MnWO, as an impurity. Extration : 1. Concentration of ore : Oreis crushed to fine powder and concentrated by gravity process. Ore is washed with the stream. Of water to remove gangue and other silicon impurities. Tinstone and wollramite are let. Wolframite is then removed by magnetic seperation 2. Roasting : ‘The oreis roasted to remove volatile impurities. S +0, 80, 2As,8, + 90, —+ 2As,0, + 650, ‘The roasted ore is washed with water fo remove soluble impurities and dried. It contains 60-70% of tinas SnO, called Black Tin. Smelting : ‘The oreis mixed with 1/5 th ofits weight of powdered anthracite anda little limestone and heatedin reverberatory furnace. SnO, isreduced to metallic tate and silica is removed as slag. SnO, + 2C —> Sn + 2CO Refining : Itisrefined by any ofthe following processes. (@) _Liquation : The crude tins melted on the stoping hearth of a reverberatory furnace when tin alone melts and flows out. The process is called sweating and the impure tin left is called dross. Set uty Cue or Ewa On apa abese ipo Eaton (b) _ElectrolyticRefining : The electrolyte consists of hydrofluorosilicic acid (H,SiF,) containing stannic sulphate (SnSO, ) and H,SO,,. Ablock of impure tin is anode and a thin strip of pure tin the cathode. LEAD Sources : Galena (PbS) isthe principal ore. Extraction : (A) Self Reduction or Air reduction process : Thisisused for samples of galena rich in lead. In this process roasting and smelting are done in same furnace, but a different temperatures. @ Crushing and Concentration ‘The ore is crushed, finely powdered and concentrated by froth floating process, NaCN is used asa depressant to prevent ZnS (if present) from coming out as froth. The concentrated ore contains 50 — 60% of ead, (Roasting ‘The concentrated ore is roasted at a moderate temperature in a reverberatory furnace and in limited supply of at. apes + 30, —I* 5 2p + 280, PbS + 20, —> PDsO, Gi) Reduction (Smelting) Air supply is cutoff, fresh galena is added to roasted ore and the temperature is raised Galena reduces lad oxide and lead sulphate to metalic lead. 2PbO + PbS —> 3Pb + SO, PbSO, + PbS —> 2Pb + 280, ‘Molten lead is drawn from time to time and purified. (B) Carbon Reduction Process : ‘This process is suitable when the ore contains more impurity (silica) and has low amount of ead. Here roasting and smelting are done indifferent furnaces, (Crushing and Concentration This is done as in above process. 2s Se study Course fr ITIEE wth Ontne Supportiii) ww) Basic Principle of Extraction Roasting Concentrated ore is mixed wit ‘mainly o PbO. 2PbS + 30, —+ 2Pb0 + 250, Lime performs two important functions. (a) Being more basic than PbO, lime preferentially reacts with SO, (formed in the above ‘oxidation to formealcium sulphite and thus favours the oxidation of galena in the forward direction, (b) _Itdecomposes lead silicate (Formed by reaction of PbSO, with sitca present as impurity) to PDO which would otherwise have gone as slag. PbS + 20, —+ PbSO, 2PbSO, + 2Si0, —> 2PbSiO, + 20, + O, PbSIO, + CaO —+ CaSiO, + PbO Smettin Theroatednasssmited itheok nine (us) an smetdin blast mace. olling reactions occur. PhO + C —+ Pb + CO PbO + CO —+ Pb + CO, CaO + SiO, —+ CaSiO, (lag) PbSIO, + CAO —> CaSiO, + PDO Little hematite is added to reduce any unchanged PbS to Pb. 2PbS + Fe,0, + 3C —+ 2Pb + 2FeS + 3CO Refining Impurities are Cu, As, Sb, Fe, Zn, Bi, Ag and sulphur. These are refined by either of owing processes () Oxidation or softening where impure metal isheated in current of air where Cu, Fe, Snete are oxidised before lead. (b) Desilverisation by Parke's or Pattinson method to remove Ag. (©) Electrorefining : Electrolysis of 1-15% Lead silica fluoride (PbSiF,) and 5-10% (hycrofluorosilicic acid, H,SiF,) is carried out between pure lead sheets serving as cathode, and crude impure lead as anode, Set uty Cue or Ewa On apa =Basic Principle of Extraction neice IN - CHAPTER EXERCISE - B Cinnabar (HgS) and galena (PbS) on roasting often give their respective metals but zine blende (Zn) does not. Explain: 2, A metal isin combined sate as sulphide. Mlentify the steps (A), (B) and (C) Sulphide] Q Oxide B Impure metal Pure ‘metal 3. Why Zine and not copper is used for the recovery of metallic silver from the complex [ Ag(CN), | 4. Describe the extraction of magnesium from sea water. SOLUTIONS - IN - CHAPTER EXERCISE - A 1. FeO; +C —> Fe: ZnO +C—> Zn +CO} + CO(gases) haematite) incite) PO+C—+Pb } — MgO+C—+4Mg + — Ca3(PO4)2 +C —>P. 2. Tinstone is concentrated first by gravity seperation and then magnetic seperation is used to remove magnetic impurities ike wolframite, 3. Collectors enhance the non wettability of mineral particles and froth - stabilizers stabilize the froth, 4. Reduction by hydrogen is not widely used because many metals react at elevated temperartures, forming hydrides. There isalso a risk of explosion. 5. Galena (PES), Chaleocite (Cu,S) and cinnabar (HyS), 6. Inthe thermite process, Als used to reduce metal oxide to metal while it itself gets oxidised to AO, which produces alarge amount of heat (1675 kW/moD. This is utilised to join broken railway tracks. Sol INE Self Study Course for IITJEE with Online SupportBasic Principle of Extraction SOLUTIONS - IN - CHAPTER EXERCISE - B ‘This is because HgS and PbS can undergoe self reduction while ZnS doesnot. ‘A= roasting, B= reduction, C= refining ‘Sea water contains MgCl, which is precipitated as Mp(OH), (using Ca(OH),). This is then converted back to MgCl, (by HCI and dried. MgCl, is then electrolysed. Self Study Course for ITIEE with Ontine Support TT STI” 31My Chapter Notes ‘ssid Conetoriet wine ipo TyWines NU 5 cree wit oiiPeaNW, 52150 ceecrezwinonesipprt