6 General Principles and of Processes of Isolation Elements

Thermodynamics illustrates why only a certain reducing element and a minimum specific temperature are suitable for reduction of a metal oxide to the metal in an extraction. A few elements like carbon, sulphur, gold and noble gases, occur in free state while others in combined forms in the earths crust. The extraction and isolation of an element from its combined form involves various principles of chemistry. A particular element may occur in a variety of compounds. The process of metallurgy and isolation should be such that it is chemically feasible and commercially viable. Still, some general principles are common to all the extraction processes of metals. For obtaining a particular metal, first we look for minerals which are naturally occurring chemical substances in the earths crust obtainable by mining. ut of many minerals in which a metal may be found, only a few are viable to be used as sources of that metal. Such minerals are known as ores. !arely, an ore contains only a desired substance."t is usually contaminated with earthly or undesired materials known as gangue. The extraction and isolation of metals from ores involve the following ma#or steps$ % &oncentration of the ore, % "solation of the metal from its concentrated ore, and % 'urification of the metal. The entire scientific and technological process used for isolation of the metal from its ores is known as metallurgy. "n the present (nit, first we shall describe various steps for effective concentration of ores. After that we shall discuss the principles of some of the common metallurgical processes. Those principles shall include the thermodynamic and electrochemical aspects involved in the effective reduction of the concentrated ore to the metal. 6.1 Occurence of Metals )lements vary in abundance. Among metals, aluminium is the most abundant. "t is the third most abundant element in earths crust *+.,- approx. by weight.. "t is a ma#or component of many igneous minerals including mica and clays. /any gemstones are impure forms of Al and the impurities range from &r *in 1ruby. to &o *in 1sapphire.. "ron is the second most abundant metal in the earths crust. "t forms a variety of compounds and their various uses make it a very important element. "t is one of the essential elements in biological systems as well. The principal ores of aluminium, iron, copper and 2inc have been given in Table 3.4.
0 ,

/)TA5

!)S

&

/'
x

S"T"
,:0x

7auxite8aolinite *a Aluminium form of clay. 9aematite /agnetite Siderite "ron pyrites &opper pyrites malachite cuprite copper glance Ainc blende or sphalerite calamine Aincite

Al * 9. ;where < =amp>amp>amp>amp>amp>amp>lt> x =amp>amp>amp>amp>amp>amp>lt> 4? Fe Fe Fe& FeS

0 , , @ ,

"ron

&opper

&uFeS &u& .&u* 9. &u &u S

0 , 0 0

Ainc

AnS An& An

Table Table 3.4$ 'rincipal res of Some "mportant /etals For the purpose of extraction, bauxite is chosen for aluminium. For iron, usually the oxide ores which are abundant and do not produce polluting gases *like S that is produced in case iron pyrites. are taken. For copper and 2inc, any of the listed ores *Table 3.4. may be used depending upon availability and other relevant factors. 7efore proceeding for concentration, ores are graded and crushed to reasonable si2e. 6.2 Concentration of Ore !emoval of the unwanted materials *e.g., sand, clays, etc.. from the ore is known as concentration, dressing or benefaction. "t involves several steps and selection of these steps depends upon the differences in physical properties of the compound of the metal present and that of the gangue. The type of the metal, the available facilities and the environmental factors are also taken into consideration. Some of the important procedures are described below.
0

6.2.1 Hydraulic Washin This is based on the differences in gravities of the ore and the gangue particles. "t is therefore a type of gravity separation. "n one such process, an upward strem of running water is used to wash the powedered ore. The lighter gangue particles are washed away and the heavier ores are left behind. 6.2.2 Ma netic !eperation This is based on differences in magnetic properties of the ore ot the gangue *one of these two. is capable of being attracted by a magnetic field, then such seperations are carried out *e.g. in case of

iron ores.. The ground ore is carried on a conveyer belt which passes over a magnetic roller *fig.3.4..

6.2." #roth #lotation Method This method has been in use for removing gangue from sulphide ores. in this process, a suspension of the powdered ore is made with water. To it, collectors and forth stabili2ers are added. &ollectors *e.g., pine oils, fatty acids, xanthates, etc.. enhance non B wettability of the mineral particles and froth stabilisers *e.g. , cresols, aniline. stabilise the forth. The mineral particles become wet by oils while the gangue particles by water. A ratating paddle agitates the mixture and draws air in it. As a result, forth is formed which carries the mineral particles . The forth is light and is skimmed off. "t is then dried for recovery of the ore particles. Sometimes, it is possible to seperate two sulphide ores by ad#usting proportion of oil to water or by using 1depressants. For example in case of an ore containing Ans and 'bS, the depressant used is 6a&6. it selectively prevents AnS from coming to the forth but allow 'bS to come with the forth.

$he Inno%ati%e Washer&oman ne can do wonders if he or she has a scientific temperament and is attentive to observations. A washerwoman had an innovative mind too. Chile washing a miners veralls, she noticed that sand and similar dirt fell to the bottom of the washtub. Chat was peculiar, the copper bearing compounds that had come to the clothes from the mines, were caught in the soapsuds and so tehy came to the top. ne of her clients was a chemist, /rs. &arrie )verson. The washerwoman told her experience to /rs. )verson. The latter thought that the idea could be used for seperating copper compounds from rocky and earth materials on alrge scale. This way an invention was born. At taht time only those ore were used for extraction of copper, which contained large amounts of the metal. "nvention of the Forth Flotation method made copper minning profitable even from the low B grade ores. Corld production of copper soared and the metal became cheaper. 6.2.' (eachin 5eaching is often used if the ore is soluble in some suitable solvent. The following examples illustrate the procedure$ *a. 5eaching of alumina from bauxite The principal ore of aluminium, bauxite, usually contains Si , iron oxides and titanium oxide *Ti . as impurities. &oncentration is carried out by digesting the powdered ore with a concentrated solution of 6a 9 at @D, B E0, 8 and ,E B ,3 bar pressure. This way, Al is leached out as sodium aluminate *and Si too as sodium silicate. leaving the impurities behind$ Al *s. F 06a 9*aG. F ,9 *l. H 06a;Al* 9. ?*aG.III..*3.4. The aluminate in solution is neutralised by passing & gas and hydrated Al is precipitated. At this stage, the solution is seeded with freshly prepared samples of hydrated Al . which induces the precipitation$ 06a;Al* 9. ?*aG. F & *g. H Al .x9 *s. F 06a9& *aG.III.*3.0. The sodium silicate remains in the solution and hydrated alumina is filtered, dried and heated to give back pure Al $
0 0 0 , 0 0 , 0 @ 0 0 , 0 , @ 0 0 , 0 , 0 ,

IIIII.*3.,. *b. ther examples "n the metallurgy of silver and that of gold, the respective metal is leached with a dilute solution of 6a&6 or 8&6 in the presence of air *for . from which the metal is obtained later by replacement$ @/*s. F +&6 *aG.F 09 *aG. F *g. H @;/*&6. ? *aG. F @ 9 *aG. */K Ag or Au.III *3.@. 0;/*&6. ?*aG. F An*s. H ;An*&6. ? IIII. *3.E. Inte)t *uestion 3.4 Chich of the ores mentioned in Table 3.4 can be concentrated by magnetic separation methodL 3.0 Chat is the significance of leaching in the extraction of aluminiumL
0 J 0 0 0 J J 0 @ 0J

6." E)traction of Crude Metal #rom Concentrated Ore

The concentrated ore must be converted into a form which is suitable for reduction. (sually the sulphide ore is converted to oxide before reduction. xides are easier to reduce *for the reason see box.. Thus isolation of metals from concentrated ore involves two ma#or steps vi2., *a. conversion to oxide, and *b. reduction of the oxide to metal. *a. &onversion to oxide *i. &alcination$ &alcinaton involves heating when the volatile matter escapes leaving behind the metal oxide$

*ii. !oasting$ "n roasting, the ore is heated in a regular supply of air in a furnace at a temperature below the melting point of the metal. Some of the reactions involving sulphide ores are$ 0AnS F , H 0An F 0S IIII*3.M. 0'bS F , H 0'b F 0S IIII*3.4<. 0&u S F , H 0&u F 0S III..*3.44.
0 0 0 0 0 0 0 0

The sulphide ores of copper are heated in reverberatory furnace. "f the ore contains iron, it is mixed with silica before heating. "ron oxide 1slags of N as iron silicate and copper is produced in the form of copper matte which contains &u S and FeS. Fe F Si H FeSi IIII*3.40. *slag. The S produced is utilised for manufacturing 9 S .
0 0 , 0 0 @

*b. !eduction of oxide to the metal !eduction of the metal oxide usually involves heating it with some other substance acting as a reducing agent *& or & or even another metal.. The reducing agent *e.g., carbon. combines with the oxygen of the metal oxide. / F y& H x/ F y & IIII*3.4,. Some metal oxides get reduced easily while others are very difficult to be reduced *reduction means electron gain or electronation.. "n any case, heating is reGuired. To understand the variation in the temperature reGuirement for thermal reductions *pyrometallurgy. and to predict which element will suit as the reducing agent for a given metal oxide */ ., Oibbs energy interpretations are made. 6.' $hermodynamic Principles of Metallur y Some basic concepts of thermodynamics help us in understanding the theory of metallurgical transformations. Oibbs energy is the most significant term here.The change in Oibbs energy, PO for any process at any specified temperature, is described by the eGuation$ PO K P9 B TPSIIIII*3.4@. where, P9 is the enthalpy change and PS is the entropy change for the process. For any reaction, this change could also be explained through the eGuation$
x y x y

PO K B !Tln8IIIII.*3.4E. where, 8 is the eGuilibrium constant of the 1reactant B product system at the temperature,T. A negative PO implies a Fve 8 in eGuation 3.4E. And this can happen only when reaction proceeds towards products. From these facts we can make the following conclusions$
Q

4. Chen the value of PO is negative in eGuation 3.4@, only then the reaction will proceed. "f PS is positive, on increasing the temperature *T., the value of TPS would increase *P9 =amp>amp>amp>amp>amp>amp>lt> TPS. and then PO will become Bve. 0. "f reactants and products of two reactions are put together in a system and the net PO of the two possible reactions is Bve, the overall reaction will occur. So the process of interpretation involves coupling of the two reactions, getting the sum of their PO and looking for its magnitude and sign. Such coupling is easily understood through Oibbs energy *PO . vs T plots for formation of the oxides *Fig. 3.@.. Ellin ham +ia ram The graphical representation of Oibbs energy was first used by 9.R.T.)llingham. This provides a sound basis for considering the choice of reducing agent in the reduction of oxides. This is known as )llingham Siagram. Such diagrams help us in predicting the feasibility of thermal reduction of an ore. The criterion of feasibility is that at a given temperature, Oibbs energy of the reaction must be negative.
Q

*a. )llingham diagram normally consists of plots of P O vs T for formation of oxides of elements i.e., for the reaction, 0x/*s. F *g. H 0/ *s. "n this reaction, the gaseous amount *hence molecular randomness. is decreasing from left to right due to the consumption of gases leading to a Bve value of PS which changes the sign of the second term in eGuation *3.4@.. SubseGuently PO shifts towards higher side despite rising T *normally, PO decreases i.e., goes to lower side with increasing temperature.. The result is Fve slope in the curve for most of the reactions shown above for formation of / *s.. *b. )ach plot is a straight line except when some change in phase *sHliG or liGHg. takes place. The temperature at which such change occurs, is indicated by an increase in the slope on Fve side *e.g., in the An, An plot, the melting is indicated by an abrupt change in the curve..
f Q 0 x x

*c. There is a point in a curve below which PO is negative *So / is stable.. Above this point, /x will decompose on its own. *d. "n an )llingham diagram, the plots of PO for oxidation *and therefore reduction of the corresponding species. of common metals and some reducing agents are given. The values of P O , etc.*for formation of oxides. at different temperatures are depicted which make the interpretation easy. *e. Similar diagrams are also constructed for sulfides and halides and it becomes clear why reductions of /xS is difficult. There, the P O of / S is not compensated. (imitations of Ellin ham +ia ram 4. The graph simply indicates whether a reaction is possible or not i.e., the tendency of reduction with a reducing agent is indicated. This is so because it is based only on the thermodynamic concepts. "t does not say about the kinetics of the reduction process *&annot answer Guestions like how fast it could be L..
x Q f Q f Q x

0. The interpretation of POQ is based on 8 *PO K B !T ln8.. Thus it is presumed that the reactants and products are in eGuilibrium$ / F A l x/ F A This is not always true because the reactantTproduct may be solid. ;9owever it explains how the reactions are sluggish when every species is in solid state and smooth when the ore melts down."t is interestng to note here that P9 *enthalpy change. and the PS *entropy change. values for any chemical reaction remain nearly constant even on varying temperature. So the only dominant variable in eGuation*3.4@. becomes T. 9owever, PS depends much on the physical state of the compound. Since entropy depends on disorder or randomness in the system, it will increase if a compound melts *sHl. or vapourises *lHg. since molecular randomness increases on changing the phase from solid to liGuid or from liGuid to gas?.
Q x red ox

The reducing agent forms its oxide when the metal oxide is reduced. The role of reducing agent is to provide PO negative and large enough to make the sum of PO of the two reactions *oxidation of the reducing agent and reduction of the metal oxide. negative. As we know, during reduction, the oxide of a metal decomposes$ / *s. H x/ *solid or liG. F 4T0 IIII.*3.43. The reducing agent takes away the oxygen. )Guation 3.43 can be visualised as reverse of the oxidation of the metal. And then, the P O value is written in the usual way$ x/*s or l. F 4T0 *g. H /x *s. ;PO ?IIII.*3.4D. "f reduction is being carried out through eGuation 3.43, the oxidation of the reducing agent *e.g., & or & . will be there$
x 0 f Q 0 Q */,/x .

&*s. F 4T0 *g. H & *g. ;PO ?IIII.*3.4+. & *g. F 4T0 H & *g. ;PO .?IIIII.*3.4M. "f carbon is taken, there may also be complete oxidation of the element to & $ 4T0 &*s. F 4T0 *g. H 4T0 & *g. ;4T0 PO .?III.*3.0<. n subtracting eGuation 3.4D ;it means adding its negative or the reverse form as in eGuation 3.43? from one of the three eGuations, we get$ / *s. F &*s. H x/*s or l. F & *g.IIII..*3.04. / *s. F & *g. H x/*s or l. F & *g.IIIII.*3.00. / *s. F 4T0 &*s. H x/*s or l. F 4T0 & *g.IIIII..*3.0,. These reactions describe the actual reduction of the metal oxide, / that we want to accomplish. The PrO values for these reactions in general, can be obtained by similar subtraction of the corresponding P OU values. As we have seen, heating *i.e., increasing T. favours a negative value of P OU . Therefore, the temperature is chosen such that the sum of P OU in the two combined redox process is negative. "n P OU vs T plots, this is indicated by the point of intersection of the two curves *curve for / and that for the oxidation of the reducing substance.. After that point, the PrO value becomes more negative for the combined process including the reduction of / . The difference in the two P OU values after that point determines whether reductions of the oxide of the upper line is feasible by the element represented by the lower line. "f the difference is large, the reduction is easier. E)ample 6.1 Suggest a condition under which magnesium could reduce alumina. !olution The two eGuations are$ *a. @T, Al F H0T, Al *b. 0/g F H 0/g At the point of intersection of the Al0 , and /g curves *marked VAW in diagram 3.@., the POU becomes A)! for the reaction$
0 *&, & . 0 0 *& , & 0 0 0 0 *&, & 0 x x 0 x 0 x f r r r x x r 0 0 , 0

0T, Al F0/g H 0/g F @T,Al 7elow that point magnesium can reduce alumina. E)ample 6.2 Although thermodynamically feasible, in practice, magnesium metal is not used for the reduction of alumina in the metallurgy of aluminium. Chy L !olution Temperatures below the point of intersection of Al and /g curves, magnesium can reduce alumina. 7ut the process will be uneconomical. E)ample 6." Chy is the reduction of a metal oxide easier if the metal formed is in liGuid state at the temperature of reductionL !olution The entropy is higher if the metal is in liGuid state than when it is in solid state. The value of entropy change *PS. of the reduction process is more on Fve side when the metal formed is in liGuid state and the metal oxide being reduced is in solid state. Thus the value of POU becomes more on negative side and the reduction becomes easier. 6.'.1 ,pplications -a. E)traction of iron from its o)ides xide ores of iron, after concentration through calcinationTroasting *to remove water, to decompose carbonates and to oxidise sulphides. are mixed with limestone and coke and fed into a 7last furnace from its top. 9ere, the oxide is reduced to the metal. Thermodynamics helps us to understand how coke reduces the oxide and why this furnace is chosen. ne of the main reduction steps in this process is$ Fe *s. F &*s. H Fe*sTl. F & *g.IIIIIII.*3.0@.
0 , 0 ,

"t can be seen as a couple of two simpler reactions. "n one, the reduction of Fe is taking place and in the other, & is being oxidised to & $ Fe *s. H Fe*s. F 4T0 *g. ;PO ?IIIIIIII.*3.0E. &*s. F 4T0 *g. H & *g. ;PO ?IIIIIIIII*3.03. Chen both the reactions take place to yield the eGuation *3.0@., the net Oibbs energy change becomes$ PO F PO K P O IIIIII..3.0D. 6aturally, the resultant reaction will take place when the right hand side in eGuation 3.0D is negative. "n POU vs T plot representing reaction 3.0E, the plot goes upward and that representing the change &H& *&,& . goes downward. At temperatures above 4<D,8 *approx.., the &,& line comes below the Fe,Fe line ;PO PO ?. So in this range, coke will be reducing the Fe and will itself be oxidised to & . "n a similar way the reduction of Fe and Fe at relatively lower temperatures by & can be explained on the basis of lower lying points of intersection of their curves with the & ,
*Fe , Fe. *&, & . *&, & . *Fe , Fe. r *&, & . *Fe, Fe . , @ 0 ,

&

curve in Fig. 3.@.

"n the 7last furnace, reduction of iron oxides takes place in different temperature ranges. 9ot air is blown from the bottom of the furnace and coke is burnt to give temperature upto about 00<<8 in the lower portion itself. The burning of coke therefore supplies most of the heat reGuired in the process. The & and heat moves to upper part of the furnace. "n upper part, the temperature is lower and the iron oxides *Fe and Fe . coming from the top are reduced in steps to Fe . Thus, the reduction reactions taking place in the lower temperature range and in the higher temperature range, depend on the points of corresponding intersections in the PrOU vs T plots. These reactions can be summarised as follows$ At E<< B +<< 8 *lower temperature range in the blast furnace. B , Fe F & H 0 Fe F & IIII..*3.0+. Fe F @ & H ,Fe F @ & IIIIII..*3.0M. Fe F & H 0Fe F & IIIIIII..*3.,<. At M<< B 4E<< 8 *higher temperature range in the blast furnace.$ & F & H 0& IIII..*3.,4. Fe F & H Fe F & IIII..*3.,0. 5imestone is also decomposed to &a which removes silicate impurity of the ore as slag. The slag is
0 , , @ 0 , , @ 0 , @ 0 0 , 0 0 0

in molten state and separates out from iron. The iron obtained from 7last furnace contains about @carbon and many impurities in smaller amount *e.g., S, ', Si, /n.. This is known as pig iron and cast into variety of shapes. &ast iron is different from pig iron and is made by melting pig iron with scrap iron and coke using hot air blast. "t has slightly lower carbon content *about ,-. and is extremely hard and brittle.

Further !eductions Crought iron or malleable iron is the purest form of commercial iron and is prepared from cast iron by oxidising impurities in a reverberatory furnace lined with haematite. This haematite oxidises carbon to carbon monoxide$ Fe F ,& H 0Fe F ,& IIIII..*3.,,. 5imestone is added as a flux and sulphur, silicon and phosphorus are oxidised and passed into the slag. The metal is removed and freed from the slag by passing through rollers.
0 ,

*b. )xtraction of copper from cuprous oxide ;copper*". oxide? "n the graph of PrO< vs T for formation of oxides *Fig. 3.@., the &u line is almost at the top. So it is Guite easy to reduce oxide ores of copper directly to the metal by heating with coke *both the lines
0

of &, & and &, & are at much lower positions in the graph particularly after E<< B 3<<8.. 9owever most of the ores are sulphide and some may also contain iron. The sulphide ores are roastedTsmelted to give oxides$ 0&u S F , H 0&u F 0S IIIIII*3.,@. The oxide can then be easily reduced to metallic copper using coke$ &u F & H 0&u F & IIIII.*3.,E. "n actual process, the ore is heated in a reverberatory furnace after mixing with silica. "n the furnace, iron oxide 1slags of as iron silicate and copper is produced in the form of copper matte. This contains &u S and FeS. Fe F Si H FeSi IIIII..*3.,3. *Slag. &opper matte is then charged into silica lined convertor. Some silica is also added and hot air blast is blown to convert the remaining FeS, Fe and &u0ST&u0 to the metallic copper. Following reactions take place$ 0FeS F , H 0Fe F 0S IIII*3.,D. Fe F Si H FeSi IIII..*3.,+. 0&u S F , H 0&u F 0S IIIII*3.,M. 0&u F &u S H 3&u F S IIIII*3.@<. The solidified copper obtained has blistered appearance due to the evolution of S and so it is called blister copper. *c. )xtraction of 2inc from 2inc oxide
0 0 0 0 0 0 0 0 , 0 0 0 , 0 0 0 0 0 0 0 0

The reduction of 2inc oxide is done using coke. The temperature in this case is higher than that in case of copper. For the purpose of heating, the oxide is made into brickettes with coke and clay. The metal is distilled off and collected by rapid chilling. Inte)t *uestions 3., The reaction, &r F 0Al H Al F 0&r *POU K B @04 kR. is thermodynamically feasible as is apparent from the Oibbs energy value. Chy does it not take place at room temperatureL 3.@ "s it true that under certain conditions, /g can reduce Al and Al can reduce /g L Chat are those conditionsL 6./ Electrochemical principles of Metallur y Ce have seen how principles of thermodyamics are applied to pyrometallurgy. Similar principles are effective in the reductions of metal ions in solution or molten state. 9ere they are reduced by electrolysis or by adding some reducing element.
0 , 0 , 0 ,

"n the reduction of a molten metal salt, electrolysis is done. Such methods are based on electrochemical principles which could be understood through the eGuation, POU K B n)UFIIIII.*3.@0. here n is the number of electrons and )U is the electrode potential of the redox couple formed in the system. /ore reactive metals have large negative values of the electrode potential. So their reduction is difficult. "f the difference of two ) values corresponds to a positive )U and conseGuently negative POU in eGuation 3.@0, then the less reactive metal will come out of the solution and the more reactive metal will go to the solution, e.g., &u *aG. F Fe*s. H &u*s. F Fe *aG.IIIIII*3.@,. "n simple electrolysis, the / ions are discharged at negative electrodes *cathodes. and deposited there. 'recautions are taken considering the reactivity of the metal produced and suitable materials are used as electrodes. Sometimes a flux is added for making the molten mass more conducting.
0F 0F

,luminium "n the metallurgy of aluminium, purified Al is mixed with 6a AlF or &aF which lowers the melting point of the mix and brings conductivity. The fused matrix is electrolysed. Steel cathode and graphite anode are used. The overall reaction may be taken as$ 0Al F ,& H @Al F ,& IIIII*3.@@. This process of electrolysis is widely known as 9all:9eroult process. The electrolysis of the molten mass is carried out in an electrolytic cell using carbon electrodes. The oxygen liberated at anode reacts with the carbon of anode producing & and & . This way for each kg of aluminium produced, about <.E kg of carbon anode is burnt away. The electrolytic reactions are$ &athode$ Al *melt. F ,e H Al*l.IIIIII.*3.@E. Anode$&*s. F *melt. H & *g. F 0e IIIIII..*3.@3.
0 , , 3 0 0 , 0 0 ,F J J

&*s. F 0 *melt. H &

*g. F @e IIIIIII*3.@D.
J

Copper from (o& Grade Ores and !craps &opper is extracted by hydrometallurgy from low grade ores. "t is leached out using acid or bacteria. The solution containing &u is treated with scrap iron or 9 *eGuations 3.@0> 3.@+.. &u *aG. F 9 *g. H &u*s. F 09 *aG.IIIIII..*3.@+. E)ample 6.' At a site, low grade copper ores are available and 2inc and iron scraps are also available. Chich of the two scraps would be more suitable for reducing the leached copper ore and whyL !olution Ainc being above iron in the electrochemical series *more reactive metal is 2inc., the reduction will be faster in case 2inc scraps are used. 7ut 2inc is costlier metal than iron so using iron scraps will be advisable and advantageous. 6.6 O)idation 0eduction 7esides reductions, some extractions are based on oxidation particularly for non:metals. A very common example of extraction based on oxidation is the extraction of chlorine from brine *chlorine is abundant in sea water as common salt. . 0&l *aG. F 09 *l. H 0 9 *aG. F 9 *g. F &l *g.IIII..*3.@M. The POU for this reaction is F @00 kR. Chen it is converted to ) *using POU K B n)UF., we get )U K B 0.0 Q. 6aturally, it will reGuire an external e.m.f. that is greater than 0.0 Q. 7ut the electrolysis reGuires an excess potential to overcome some other hindering reactions. Thus, &l is obtained by electrolysis giving out 9 and aGueous 6a 9 as by:products. )lectrolysis of molten 6a&l is also carried out. 7ut in that case, 6a metal is produced and not 6a 9. As studied earlier, extraction of gold and silver involves leaching the metal with &6 . This is also an oxidation reaction *Ag H Ag or Au H Au .. The metal is later recovered by displacement method. @Au*s. F +&6 *aG. F 09 *aG. F *g. H @;Au*&6. ? *aG. F @ 9 *aG.IIII..*3.E<.
0F 0 0 F J 0 0 0 0 0 J F F J 0 0 0 J

0;Au*&6. ? *aG. F An*s. H 0Au*s. F ;An*&6. ? *aG.IIIIIII.*3.E4. "n this reaction 2inc acts as a reducing agent. 6.1 0efinin A metal extracted by any method is usually contaminated with some impurity. For obtaining metals of high purity, several techniGues are used depending upon the differences in properties of the metal and the impurity. Some of them are listed below. *a. Sistillation *b. 5iGuation *c. )lectrolysis *d. Aone refining *e. Qapour phase refining *f . &hromatographic methods
0 @ 0J

These are described in detail here. -a. +istillation This is very useful for low boiling metals like 2inc and mercury. The impure metal is evaporated to obtain the pure metal as distillate. -2. (i3uation "n this method a low melting metal like tin can be made to flow on a sloping surface. "n this way it is separated from higher melting impurities. -c. Electrolytic refinin "n this method, the impure metal is made to act as anode. A strip of the same metal in pure form is used as cathode. They are put in a suitable electrolytic bath containing soluble salt of the same metal. The more basic metal remains in the solution and the less basic ones go to the anode mud. This process is also explained using the concept of electrode potential, over potential, and Oibbs energy which you have seen in previous sections. The reactions are$ Anode$ / H / F ne &athode$ / F ne H /IIIII.*3.E0. &opper is refined using an electrolytic method. Anodes are of impure copper and pure copper strips are taken as cathode. The electrolyte is acidified solution of copper sulphate and the net result of electrolysis is the transfer of copper in pure form from the anode to the cathode$ ,node4 &u H &u F 0 e Cathode4 &u F 0e H &uIIIIIII.*3.E,.
nF J nF 0F J 0F J

"mpurities from the blister copper deposit as anode mud which contains antimony, selenium, tellurium, silver, gold and platinum> recovery of these elements may meet the cost of refining. Ainc may also be refined this way. -d. 5one refinin This method is based on the principle that the impurities are more soluble in the melt than in the solid state of the metal. A circular mobile heater is fixed at one end of a rod of the impure metal *Fig. 3.D.. The molten 2one moves along with the heater which is moved forward. As the heater moves forward, the pure metal crystallises out of the melt and the impurities pass on into the ad#acent molten 2one. The process is repeated several times and the heater is moved in the same direction. At one end, impurities get concentrated. This end is cut off. This method is very useful for producing semiconductor and other metals of very high purity, e.g., germanium, silicon, boron, gallium and indium.

-e. 6apour phase refinin "n this method, the metal is converted into its volatile compound and collected elsewhere. "t is then decomposed to give pure metal. So, the two reGuirements are$ *i. the metal should form a volatile compound with an available reagent, *ii. the volatile compound should be easily decomposable, so that the recovery is easy. Following examples will illustrate this techniGue. /ond 'rocess for !efining 6ickel$ "n this process, nickel is heated in a stream of carbon monoxide forming a volatile complex, nickel tetracarbonyl$

The carbonyl is sub#ected to higher temperature so that it is decomposed giving the pure metal$

van Arkel /ethod for !efining Airconium or Titanium$ This method is very useful for removing all the oxygen and nitrogen present in the form of impurity in certain metals like Ar and Ti. The crude metal is heated in an evacuated vessel with iodine. The

metal iodide being more covalent, volatilises$ Ar F 0" H Ar" IIIIIII..*3.E3. The metal iodide is decomposed on a tungsten filament, electrically heated to about 4+<<8. The pure metal is thus deposited on the filament. Ar" H Ar F 0" IIIIIIII.*3.ED. -f. Chromato raphic methods This method is based on the principle that different components of a mixture are differently adsorbed on an adsorbent. The mixture is put in a liGuid or gaseous medium which is moved through the adsorbent. Sifferent components are adsorbed at different levels on the column. 5ater the adsorbed components are removed *eluted. by using suitable solvents *eluant.. Sepending upon the physical state of the moving medium and the adsorbent material and also on the process of passage of the moving medium, the chromatographic methodN is given the name. "n one such method the column of Al is prepared in a glass tube and the moving medium containing a solution of the components is in liGuid form. This is an example of column chromatography. This is very useful for purification of the elements which are available in minute Guantities and the impurities are not very different in chemical properties from the element to be purified. There are several chromatographic techniGues such as paper chromatography, column chromatography, gas chromatography, etc. 'rocedures
0 @ @ 0 0 ,

followed in column chromatography have been depicted in Fig. 3.+.

6.7 8ses of ,luminium 9 copper9 5inc and Iron Aluminium foils are used as wrappers for chocolates. The fine dust of the metal is used in paints and lacGuers. Aluminium, being highly reactive, is also used in the extraction of chromium and manganese from their oxides. Cires of aluminium are used as electricity conductors. Alloys containing aluminium, being light, are very useful. &opper is used for making wires used in electrical industry and for water and steam pipes. "t is also used in several alloys that are rather tougher than the metal itself, e.g., brass *with 2inc., bron2e *with tin. and coinage alloy *with nickel.. Ainc is used for galvanising iron. "t is also used in large Guantities in batteries, as a constituent of many alloys, e.g., brass, *&u 3<-, An @<-. and german silver *&u 0E:,<-, An 0E:,<-, 6i @<B E<-.. Ainc dust is used as a reducing agent in the manufacture of dye:stuffs, paints, etc. &ast iron, which is the most important form of iron, is used for casting stoves, railway sleepers, gutter pipes , toys, etc. "t is used in the manufacture of wrought iron and steel. Crought iron is used in making anchors, wires, bolts, chains and agricultural implements. Steel finds a number of uses.

Alloy steel is obtained when other metals are added to it. 6ickel steel is used for making cables, automobiles and aeroplane parts, pendulum, measuring tapes, chrome steel for cutting tools and crushing machines, and stainless steel for cycles, automobiles, utensils, pens, etc. !ummary /etals are reGuired for a variety of purposes. For this, we need their extraction from the minerals in which they are present and from which their extraction is commercially feasible.These minerals are known as ores. res of the metal are associated with many impurities. !emoval of these impurities to certain extent is achieved in concentration steps. The concentrated ore is then treated chemically for obtaining the metal. (sually the metal compounds *e.g., oxides, sulphides. are reduced to the metal. The reducing agents used are carbon, & or even some metals. "n these reduction processes, the thermodynamic and electrochemical concepts are given due consideration. The metal oxide reacts with a reducing agent> the oxide is reduced to the metal and the reducing agent is oxidised. "n the two reactions, the net Oibbs energy change is negative, which becomes more negative on raising the temperature. &onversion of the physical states from solid to liGuid or to gas, and formation of gaseous states favours decrease in the Oibbs energy for the entire system. This concept is graphically displayed in plots of POU vs T *)llingham diagram. for such oxidationTreduction reactions at different temperatures. The concept of electrode potential is useful in the isolation of metals *e.g., Al, Ag, Au. where the sum of the two redox couples is Fve so that the Oibbs energy change is negative. The metals obtained by usual methods still contain minor impurities. Oetting pure metals reGuire refining. !efining process depends upon the differences in properties of the metal and the impurities. )xtraction of aluminium is usually carried out from its bauxite ore by leaching it with 6a 9. Sodium aluminate, thus formed, is separated and then neutralised to give back the hydrated oxide, which is then electrolysed using cryolite as a flux. )xtraction of iron is done by reduction of its oxide ore in blast furnace. &opper is extracted by smelting and heating in a reverberatory furnace. )xtraction of 2inc from 2inc oxides is done using coke. Several methods are employed in refining the metal. /etals, in general, are very widely used and have contributed significantly in the development of a variety of industries.
& // 6 /)T9 S

/)TA5

&&(!!)6&)

F )XT!A&T"

!)/A!8S

4. 7auxite, Al .x9 0. Aluminium &ryolite, 6a AlF

0 , 0 , 3

)lectrolysis of Al dissolved in molten 6a AlF

0 , , 3

For the extraction, a good source of electricity is reGuired.

"ron

4. 9aematite, Fe /agnetite, Fe
,

0.

!eduction of the oxide with & and coke in 7last Temperature approaching 04D< furnace 8 is reGuired.

&opper

"t is self reduction in a specially 4. &opper pyrites, designed converter. The &uFeS 0. copper glance, reduction takes place easily. &u S,. malachite, !oasting of sulphide Sulphuric acid leaching is also &u& .&u* 9. @. cuprite, partially and used in hydrometallurgy from &u reduction low grade ores.
0 0 , 0 0

Ainc

Ainc blende or sphalerite, !oasting followed AnS0. &alamine, An& ,. by reduction with Aincite, An coke
,

The metal may be purified by fractional distillation.

A Summary of the ccurrence and )xtraction of some /etals is 'resented in the following Table )xercises 3.4 &opper can be extracted by hydrometallurgy but not 2inc. )xplain. 3.0 Chat is the role of depressant in froth floatation processL 3., Chy is the extraction of copper from pyrites more difficult than that from its oxide ore through reductionL 3.@ )xplain$ *i. Aone refining *ii. &olumn chromatography. 3.E ut of & and & , which is a better reducing agent at 3D, 8 L 3.3 6ame the common elements present in the anode mud in electrolytic refining of copper. Chy are they so present L 3.D Crite down the reactions taking place in different 2ones in the blast furnace during the extraction of iron. 3.+ Crite chemical reactions taking place in the extraction of 2inc from 2inc blende. 3.M State the role of silica in the metallurgy of copper. 3.4< Chat is meant by the term VchromatographyWL 3.44 Chat criterion is followed for the selection of the stationary phase in chromatographyL 3.40 Sescribe a method for refining nickel. 3.4, 9ow can you separate alumina from silica in a bauxite ore associated with silicaL Oive eGuations, if any. 3.4@ Oiving examples, differentiate between 1roasting and 1calcination. 3.4E 9ow is 1cast iron different from 1pig ironWL 3.43 Sifferentiate between VmineralsW and VoresW. 3.4D Chy copper matte is put in silica lined converterL 3.4+ Chat is the role of cryolite in the metallurgy of aluminiumL 3.4M 9ow is leaching carried out in case of low grade copper oresL 3.0< Chy is 2inc not extracted from 2inc oxide through reduction using & L 3.04 The value of PfO< for formation of &r is B E@< kRmol and that of Al is B +0D kRmol . "s the reduction of &r possible with Al L 3.00 ut of & and & , which is a better reducing agent for An L 3.0, The choice of a reducing agent in a particular case depends on thermodynamic factor. 9ow far
0 , J4 0 , J4 0 ,

do you agree with this statementL Support your opinion with two examples. 3.0@ 6ame the processes from which chlorine is obtained as a by:product. Chat will happen if an aGueous solution of 6a&l is sub#ected to electrolysisL 3.0E Chat is the role of graphite rod in the electrometallurgy of aluminiumL 3.03 utline the principles of refining of metals by the following methods$ *i. Aone refining *ii. )lectrolytic refining *iii. Qapour phase refining 3.0D 'redict conditions under which Al might be expected to reduce /g . *9int$ See "ntext Guestion 3.@. Answers to Some "ntext Yuestions 3.4 res in which one of the components *either the impurity or the actual ore. is magnetic can be concentrated, e.g., ores containing iron *haematite, magnetite, siderite and iron pyrites.. 3.0 5eaching is significant as it helps in removing the impurities like Si , Fe , etc. from the bauxite ore. 3., &ertain amount of activation energy is essential even for such reactions which are thermodynamically feasible, therefore heating is reGuired. 3.@ Zes, below 4,E<U& /g can reduce Al and above 4,E<U&, Al can reduce /g . This can be inferred from PO Qs T plots *Fig. 3.@..
0 0 , 0 , Q

I. Multiple Choice *uestions -$ype:I. 4. "n the extraction of chlorine by electrolysis of brine [[[[[[[[[[[[. *i. oxidation of &l ion to chlorine gas occurs. *ii. reduction of &l ion to chlorine gas occurs. *iii. For overall reaction PO has negative value. *iv. a displacement reaction takes place. 0. Chen copper ore is mixed with silica, in a reverberatory furnace copper matte is produced. The copper matte contains [[[[[[[[[[[[.
B B \

*i. sulphides of copper *"". and iron *"". *ii. sulphides of copper *"". and iron *""". *iii. sulphides of copper *". and iron *"". *iv. sulphides of copper *". and iron *""". ,. Chich of the following reactions is an example of autoreductionL

*i. Fe F @& H ,Fe F @& *ii. &u F & H 0&u F & *iii. &u *aG. F Fe *s. H &u *s. F Fe *aG. *iv. &u F40&u S H ,&u F40S @. A number of elements are available in earths crust but most abundant elements are [[[[[[[[[[[[.
, @ 0 0 0F 0F 0 0 0

*i. Al and Fe *ii. Al and &u *iii. Fe and &u *iv. &u and Ag E. Aone refining is based on the principle that [[[[[[[[[[[. *i. impurities of low boiling metals can be separated by distillation. *ii. impurities are more soluble in molten metal than in solid metal. *iii. different components of a mixture are differently adsorbed on an adosrbent. *iv. vapours of volatile compound can be decomposed in pure metal. 3. "n the extraction of copper from its sulphide ore, the metal is formed by the reduction of &u with *i. FeS *ii. & *iii. &u S *iv. S D. 7rine is electrolysed by using inert electrodes. The reaction at anode is [[[[[[[[.
0F 0F 0F

*i. &l *aG.. H 40&l *g. F e > &ell ) K 4.,3Q *ii. 09 *l . H *g. F @9 F @e > &ell ) K 4.0,Q *iii. 6a *aG.. F e H 6a*s. > &ell ) K 0.D4Q *iv. 9 *aG.. F e H 409 *g. > &ell ) K <.<<Q +. "n the metallurgy of aluminium [[[[[[[[[[[[[[[[.
B 0F B \ 0 0 F B \ F B \ F B 0 \

*i. Al is oxidised to Al *s.. *ii. graphide anode is oxidised to carbon monoxide and carbon dioxide. *iii. oxidation state of oxygen changes in the reaction at anode. *iv. oxidation state of oxygen changes in the overall reaction involved in the process.
,F

M. )lectrolytic refining is used to purify which of the following metalsL *i. &u and An *ii. Oe and Si *iii. Ar and Ti *iv. An and 9g 4<. )xtraction of gold and silver involves leaching the metal with &6 ion. The metal is recovered by [[[[[[[[[[[[[[[[. *i. displacement of metal by some other metal from the complex ion. *ii. roasting of metal complex. *iii. calcination followed by roasting. *iv. thermal decomposition of metal complex. 6ote $ Answer the Guestions 44:4, on the basis of Fig. 3.4.
B

44. &hoose the correct option of temperature at which carbon reduces Fe to iron and produces & . *i. 7elow temperature at point A. *ii. Approximately at the temperature corresponding to point A. *iii. Above temperature at point A but below temperature at point S. *iv. Above temperature at point A. 40. 7elow point 1A Fe can [[[[[[[[[[[[[[. *i. be reduced by carbon monoxide only. *ii. be reduced by both carbon monoxide and carbon.

*iii. be reduced by carbon only. *iv. not be reduced by both carbon and carbon monoxide. 4,. For the reduction of Fe at the temperature corresponding to point S, which of the following statements is correctL *i. PO value for the overall reduction reaction with carbon monoxide is2ero. *ii. PO value for the overall reduction reaction with a mixture of 4 mol carbon and 4 mol oxygen is positive. *iii. PO value for the overall reduction reaction with a mixture of 0 mol carbon and 4 mol oxygen will be positive. *iv. PO value for the overall reduction reaction with carbon monoxide is negative. II. Multiple Choice *uestions -$ype:II. 6ote $ "n the following Guestions two or more options may be correct. 4@. At the temperature corresponding to which of the points in Fig.3.4, Fe will be reduced to Fe by coupling the reaction 0Fe H 0Fe F 0 with all of the following reactionsL *a. & F H & *i. 'oint A *ii. 'oint 7 *iii. 'oint S *iv. 'oint )
0

*b. 0& F

H 0& and *c. 0& F

H 0&

4E. Chich of the following options are correctL *i. &ast iron is obtained by remelting pig iron with scrap iron and coke using hot air blast. *ii. "n extraction of silver, silver is extracted as cationic complex. *iii. 6ickel is purified by 2one refining. *iv. Ar and Ti are purified by van Arkel method. 43. "n the extraction of aluminium by 9all:9eroult process, purified Al *i. lower the melting point of Al . *ii. increase the conductivity of molten mixture. *iii. reduce Al into Al*s.. *iv. acts as catalyst.
0 , ,F

is mixed with &aF to

0

4D. Chich of the following statements is correct about the role of substances added in the froth floation processL *i. &ollectors enhance the non:wettability of the mineral particles. *ii. &ollectors enhance the wettability of gangue particles. *iii. 7y using depressants in the process two sulphide ores can be separated. *iv. Froth stabilisers decrease wettability of gangue. 4+. "n the Froth Floatation process, 2inc sulphide and lead sulphide can be separated by [[[[[[[[[[[[[[. *i. using collectors. *ii. ad#usting the proportion of oil to water. *iii. using depressant. *iv. using froth stabilisers. 4M. &ommon impurities present in bauxite are [[[[[[[[[[[[. *i. &u *ii. An *iii. Fe *iv. Si 0<. Chich of the following ores are concentrated by froth floationL
0 , 0

*i. 9aematite *ii. Oalena *iii. &opper pyrites *iv. /agnetite 04. Chich of the following reactions occur during calcinationL *i. &a& H &a F & *ii. 0FeS F 44T0 H Fe F @S *iii. Al .x 90 H Al F x 9 *iv. AnS F ,T0 H An F S 00. For the metallurgical process of which of the ores calcined ore can be reduced by carbonL
, 0 0 0 0 , 0 0 , 0 , 0 0 0

*i. haematite *ii. calamine *iii. iron pyrites *iv. sphalerite 0,. The main reactions occurring in blast furnace during extraction of iron from haematite are [[[[[[[[. *i. Fe F ,& H 0Fe F ,& *ii. Fe F Si H FeSi *iii. Fe F ,& H 0Fe F ,& *iv. &a F Si H &aSi 0@. "n which of the following method of purification, metal is converted to its volatile compound which is decomposed to give pure metalL
0 , 0 0 , 0 , 0 ,

*i. heating with stream of carbon monoxide. *ii. heating with iodine. *iii. liGuation. *iv. distillation. 0E. Chich of the following statements are correctL *i. A depressant prevents certain type of particle to come to the froth. *ii. &opper matte contains &u S and AnS. *iii. The solidified copper obtained from reverberatory furnace has blistered appearance due to evolution of S during the extraction. *iv. Ainc can be extracted by self:reduction. 03. "n the extraction of chlorine from brine [[[[[[[[[[[[[.
0 0

*i. PO for the overall reaction is negative. *ii. PO for the overall reaction is positive. *iii. ) for overall reaction has negative value. *iv. ) for overall reaction has positive value. III. !hort ,ns&er $ype 0D. Chy is an external emf of more than 0.0Q reGuired for the extraction of &l from brineL 0+. At temperatures above 4<D,8 coke can be used to reduce Fe to Fe. 9ow can you #ustify this reduction with )llingham diagramL
\ \ \ \ 0

0M. Crought iron is the purest form of iron. Crite a reaction used for the preparation of wrought iron from cast iron. 9ow can the impurities of sulphur, silicon and phosphorus be removed from cast ironL ,<. 9ow is copper extracted from low grade copper oresL ,4. Crite two basic reGuirements for refining of a metal by /ond process and by Qan Arkel /ethod. ,0. Although carbon and hydrogen are better reducing agents but they are not used to reduce metallic oxides at high temperatures. ChyL ,,. 9ow do we separate two sulphide ores by Froth Floatation /ethodL )xplain with an example. ,@. The purest form of iron is prepared by oxidising impurities from cast iron in a reverberatory furnace. Chich iron ore is used to line the furnaceL )xplain by giving reaction. ,E. The mixture of compounds A and 7 is passed through a column of Al by using alcohol as eluant. &ompound A is eluted in preference to compound 7. Chich of the compounds A or 7, is more readily adsorbed on the columnL ,3. Chy is sulphide ore of copper heated in a furnace after mixing with silicaL ,D. Chy are sulphide ores converted to oxide before reductionL ,+. Chich method is used for refining Ar and TiL )xplain with eGuation. ,M. Chat should be the considerations during the extraction of metals by electrochemical methodL @<. Chat is the role of flux in metallurgical processesL @4. 9ow are metals used as semiconductors refinedL Chat is the principle of the method usedL @0. Crite down the reactions taking place in 7last furnace related to the metallurgy of iron in the temperature range E<<:+<< 8. @,. Oive two reGuirements for vapour phase refining. @@. Crite the chemical reactions involved in the extraction of gold by cyanide process. Also give the role of 2inc in the extraction. I6. Matchin $ype 6ote $ /atch the items given in &olumn " and &olumn "" in the following Guestions.
0 ,

@E. /atch the items of &olumn " with items of &olumn "" and assign the correct code$ &olumn " *A. *7. *&. *S. 'endulum /alachite &alamine &ryolite *4. *0. *,. *@. *E. Code 4 &olumn "" &hrome steel 6ickel steel 6a AlF
, , 3

&u& .&u * 9. An&

,

*i. A*4. 7*0. &*,. S*@. *ii. A*0. 7*@. &*E. S*,. *iii. A*0. 7*,. &*@. S*E. *iv. A*@. 7*E. &*,. S*0. @3. /atch the items of &olumn " with the items of &olumn "" and assign the correct code $ &olumn " *A. *7. *&. *S. &oloured bands "mpure metal to volatile complex 'urification of Oe and Si 'urification of mercury *4. *0. *,. *@. *E. Code 4 *i. A*4. 7*0. &*@. S*E. *ii. A*@. 7*,. &*4. S*0. *iii. A*,. 7*@. &*0. S*4. *iv. A*E. 7*@. &*,. S*0. @D. /atch items of &olumn " with the items of &olumn "" and assign the correct code $ &olumn " *A. *7. *&. *S. &yanide process Froth Floatation 'rocess )lectrolytic reduction Aone refining *4. *0. *,. *@. *E. Code 4 *i. A*@. 7*0. &*,. S*4. *ii. A*0. 7*,. &*4. S*E. *iii. A*4. 7*0. &*,. S*@. *iv. A*,. 7*@. &*E. S*4. &olumn "" (ltrapure Oe Sressing of AnS )xtraction of Al )xtraction of Au 'urification of 6i &olumn "" Aone refining Fractional distillation /ond 'rocess &hromatography 5iGuation

@+. /atch the items of &olumn " with the items of &olumn "" and assign the correct code $ &olumn " *A. *7. *&. *S. Sapphire Sphalerite Sepressant &orundum *4. *0. *,. *@. *E. Code 4 *i. A*,. 7*@. &*0. S*4. *ii. A*E. 7*@. &*,. S*0. *iii. A*0. 7*,. &*@. S*E. *iv. A*4. 7*0. &*,. S*@. @M. /atch the items of &olumn " with items of &olumn "" and assign the correct code $ &olumn " *A. *7. *&. *S. 7listerred &u 7last furnace !everberatory furnace 9all:9eroult process *4. *0. *,. *@. *E. Code 4 *i. A*0. 7*,. &*@. S*4. *ii. A*4. 7*0. &*,. S*E. *iii. A*E. 7*@. &*,. S*0. *iv. A*@. 7*E. &*,. S*0. 6. ,ssertion and 0eason $ype 6ote $ "n the following Guestions a statement of assertion followed by a statement of reason is given. &hoose the correct answer out of the following choices. &olumn "" Aluminium 0&u "ron Fe F Si 0&u S F ,
0 0 0

&olumn "" Al
0 ,

6a&6 &o AnS Fe

0 ,

F &u S H 3&u F S
0

H FeSi
0 0

H 0&u F 0S

*i. 7oth assertion and reason are true and reason is the correct explanation of assertion. *ii. 7oth assertion and reason are true but reason is not the correct explanation of assertion. *iii. Assertion is true but reason is false. *iv. Assertion is false but reason is true. *v. Assertion and reason both are wrong. E<. Assertion $ 6ickel can be purified by /ond process. !eason $ 6i *& .@ is a volatile compound which decomposes at @3<8 to give pure 6i. E4. Assertion $ Airconium can be purificed by Qan Arkel method. !eason $ Ar"@ is volatile and decomposes at 4+<<8. E0. Assertion $ Sulphide ores are concentrated by Froth Flotation method. !eason $ &resols stabilise the froth in Froth Flotation method. E,. Assertion $ Aone refining method is very useful for producing semiconductors. !eason $ Semiconductors are of high purity. E@. Assertion $ 9ydrometallurgy involves dissolving the ore in a suitable reagent followed by precipitation by a more electropositive metal. !eason $ &opper is extracted by hydrometallurgy. 6I. (on ,ns&er $ype EE. )xplain the following $ *a. & is a better reducing agent below D4<8 whereas & is a better reducing agent above D4<8. *b. Oenerally sulphide ores are converted into oxides before reduction. *c. Silica is added to the sulphide ore of copper in the reverberatory furnace. *d. &arbon and hydrogen are not used as reducing agents at high temperatures. *e. Qapour phase refining method is used for the purification of Ti. ,;!WE0! I. Multiple Choice *uestions -$ype:I. 4. *iii. 0. *iii. ,. *iv. @. *i. E. *ii. 3. *iii. D. *i. +. *ii. M. *i. 4<. *i. 44. *iv. 40. *i. 4,. *i.
0

II. Multiple Choice *uestions -$ype:II. 4@. *ii., *iv. 4E. *i., *iv. 43. *i., *ii. 4D. *i., *iii. 4+. *ii., *iii. 04. *i., *iii. 00. *i., *ii. 0,. *i., *iv. 0@. *i., *ii. 0E. *i., *iii.

4M. *iii., *iv. 03. *ii., *iii.

0<. *ii., *iii.

III. !hort ,ns&er $ype 0D. For the reaction 0&l *aG. F 09 *l. H 0 9 *aG.F 9 *g.F&l *g. Qalue of PO is F @00kR. (sing the eGuation PO K B nF) the value of ) comes out to be B0.0Q. Therefore extraction of &l from brine will reGuire an external emf of greater than 0.0Q. 0+. As per )llingham diagram at temperatures greater than 4<D, 8 PO*&, & . =amp>amp>amp>amp>amp>amp>lt> PO*Fe, Fe .. 9ence coke can reduce Fe to Fe. 0M. Fe F ,& H 0Fe F ,& 5imestone is added as flux and sulphur, silicon and phosphorus change to their oxides and pass into the slag. ,<. &opper is extracted by hydrometallurgy from low grade copper ores. "t is leached out using acid or bacteria. The solution containing &u is treated with scrap iron, An or 9 . &u *aG. F 9 *g. H &u*s.F 09 *aG. &u F Fe*s. HFe *aG.F &u*s. ,4. 7asic reGuirements for both processes are $ *i. The metal should form a volatile compound with an available reagent. *ii. The volatile compound should be easily decomposable, so that recovery of metal is easy.
B 0 B B B \ \ \ \ 0 0 , 0F 0 0F 0 F 0F 0F

,0. "t is because at high temperature carbon and hydrogen react with metals to form carbides and hydrides respectively. ,,. Two sulphide ores can be separated by ad#usting proportion of oil to water or by using depressants. For example, in the case of an ore containing AnS and 'bS, the depressant 6a&6 is used. "t forms complex with AnS and prevents it from coming with froth but 'bS remains with froth. ,@. 9aematite Fe F ,& H 0Fe F ,& ,E. Since compound 1A comes out before compound 17, the compound 17 is more readily adsorbed on column. ,3. "ron oxide present as impurity in sulphide ore of copper forms slag which is iron silicate and copper is produced in the form of copper matte. Fe F Si H FeSi ,D. Sulphides are not reduced easily but oxides are easily reduced. ,+. van Arkel method is used for refining Ar and Ti. "n this method crude metal is heated with iodine. Ar F 0" H Ar"
0 , 0 , 0 @

,M. Oenerally two things are considered so that proper precautions can be taken. *i. reactivity of metal produced. *ii. suitability of electrodes.

@<. Flux is used for making the molten mass more conducting. @4. Semiconducting metal is produced by 2one refining method which is based on the principle that the impurities are more soluble in melt than in the solid state of metals. @0. ,Fe F & H 0Fe F & Fe F @& H ,Fe F @& Fe F & H 0Fe F & @,. *i. The metal should form a volatile compound with available reagent. *ii. The volatile compound should be easily decomposable so that the recovery is easy.
0 , , @ 0 , @ 0 0 , 0

@@. @Au *s. F +&6 *aG. F 09 *aG. F *g. H @ ;Au *&6. *aG. F @ 9 *aG. 0;Au*&6. ? *aG. F An*s. H 0Au*s. F ;An*&6. ? *aG. "n this reaction 2inc acts as a reducing agent. I6. Matchin $ype @E. *ii. @3. *ii. @D. *i. @+. *i. @M. *i.
B 0 0 0 B B 0 B @ 0B

6. ,ssertion and 0eason $ype E<. *i. E4. *i. E0. *ii. E,. *ii. E@. *ii. 6I. (on ,ns&er $ype EE. *a. 9int $ (se )llingham diagram *b. 9int $ xides are easier to reduce. See )llingham diagram. *c. 9int $ Sulphide ore of copper contains iron as impurity which is removed as iron silicate *slag. Fe F Si H FeSi *Slag. *d. 9int $ &arbon and hydrogen react with metals at high temperature to form carbides and hydrides respectively. *e. 9int $ Ti reacts with iodine to form volatile Ti" which decomposes at high temperature to give extra pure titanium.
0 , @