TYBScCHEMISTRYC303

UNITIV
THEPRINCIPLESOFMETALLURGYANDCHEMISTRYOFFe,Cu,Ni,U,Ag&Pb

Minerals: Metals occur in nature, sometimes free but mostly in combined

state.ThosefoundinfreeorinnativestateareCu,Hg,Ag,AuandPb.
The metals are found in the combined state with other elements and are
obtainedbyminingfromtheearthareknownasmineralsi.e.Cumineralsare
oxideoresCu2O,CuCO3.Cu(OH)2,SulphidemineralsareCu2S,CuFeS2etc.
Ore: when a mineral contains sufficient quantity of a metal combined with
other element from which it can be readily separated so as to render the
extractionof metal of goodqualityprobable. Itissaidtobeanore ofmetal.

Alloresaremineralsbutallmineralsarenotores.

i.e.FeFe2O3.3H2OHaematite

AlAl2O3.3H2OBauxite

UU3O8Pitchblende
GangueorMatrix:Theoresusuallycontainsalargenumberofimpuritieslike
earthmatters, rock stones,sand, lime stones,micaand othersilicates. These
impuritiesareknownasgangueormatrix.
Theoresaredividedintofourgroups.
NativeoresorFreeState:ThelessreactivemetalslikeCu,Ag,Au,Pt,Hgand
PboccurinFreeState.Thesemetalsareknownasnativeores.
Oxidesores:Theseoresareclassifiedas:
OxidesandHydroxides:ThemetalslikeCu,Zn,Pb,Al,Sn,Cr,Mn,V,Fe,Ti,Mg,
Be,Bi,etcoccurasoxideandhydroxides.
i.e.Fe2O3.3H2OHaematite
CuCO3.Cu(OH)2Malachite
Carbonate : The metals like Fe, Cu, Zn, Pb, Mn, Ca, Sr, Ba, Mg etc occur as
Carbonateore.

i.e.MgCO3Dolomite

CaCO3.MgCO3Ca
Sulphate:ThemetalslikeSr,Ca,Ba,etcoccursassulphateores.

i.e.CaGypsumCaSO4.2H2O.
Silicate:ThemetalslikeCu,Zn,Ni,Al,Beetcoccursassilicate

i.e.BeBeryl3BeO.Al2O3.6SiO3.
Phosphateores:ThemetalslikeCa,Sr,areactasphosphateores

i.e.CaRockphosphateCa(PO4)2.
SulphideandArsenideores:ThemetalslikeCu,Zn,Fe,Co,Ni,Pb,andAgetc
occurassulphideandarsenideores


I.e.CuCuFeS2Copperpyrites

Ni(Ni,Cu,Fe)SPitchblende.
Halideores:IncludingchloridesandoxychloridesmetalslikeNa,K,Mg,Agetc
areobtainedasChloridesandOxychlorides.

i.e.NaCommonsaltNaCl

KCarnalite,KCl.MgCl2.6H2O.
Nitrateores:ThemetalslikeNa,Ketcoccursinformofnitrateores
i.e.NaChilisaltpeter,NaNO3.
Metallurgy:Itisabranchofsciencedealingwiththemethodofextractionof
metalsfromtheiroresandpreparationofalloys.
Generallyfewmethodsareusedforisolationorextractionofmetals.
OredressingorConcentrationofore:
Theoresusuallycontainslargequantitiesofimpuritieslikeearthymatter,rock,
stones,mica,feldspar,etc.whichisknownasthegangueormatrix.Removalof
theseimpuritiesfromoreiscalledasoredressingorconcentrationofore.
Duringoredressingthe%ofmetalincreasessoitisknownasconcentration.
ThePurifiedoreisknownasconcentrate.
Theoperationscarriedoutduringoredressingareasfollows:
Hand picking: The ores can be separated by sufficient degree of purity by
simplypickingitbyhandandbreakingtherockstoneswithhammers.
Thespecificgravity:Theoresiscrushedinjawcrushersandpowderedinball
mills. If the ore and gangue have different specific gravity, and if the ore is
lighterandgangueisheavier,thenitisconcentratedbygravityseparation.In
this method the powdered ore falls on jerky sloppy table and the stream of
waterispassed.Sotheoreisflownawaywithsteamofwaterandimpurities
fallbelowtablefromwhereitisremoved.
Magneticseparation:Thismethodisusedwhenoreandganguehavingsame
specific gravity, but one is magnetic and the other is nonmagnetic i.e. ore is
magneticandgangueisnonmagnetic.
Athinlayerofpowderedoreisallowedtofallonarubberbelt,whichmoves
horizontallyandthenpassesoverapulleynamagneticfield.Gangueparticles
ortheparticlesofanonmagneticmineralfallofasthebeltbecomesvertical.
The magnetic particles are retained on the belt until they pass out of the
influenceofthemagnet.


Froth floatation process: This process depends on the fact that certain
minerals are wetted by oil, while gangue is wetted by water. Mainly this
processisusedfortheconcentrationofsulphideoreofCu,Pb,Zn,Hg,etc.The
groundedpowderedoreistakenintoabigtank.Tothisamixtureofwaterand
small quantities of terpentine oil or pine oil and suitable additive (Na2CO3) is
added. Then compressed air is passed, so the whole mixture is agitated
violentlyandfrothisproduced.Theoreparticlessticktotheoilparticlesand
comeoutonthesurfaceasfoamanditiscollected.Theimpuritieslikeearthy
matters, rock stones, limestone, mica etc are wetted by water becomes
heavierandsettlesdownatthebottomofthetank.Byusingthisprocessthe
sulphideoresofCu,ZnandPbareseparatedfromimpurities.

Calcination and Roasting : For chemical reduction the concentrated ore is

convertedintooxidebycalcinationandroasting.
Calcination : It is the process of heating the ore at low temperature in the
absence of any blast of air. The moisture, CO2, etc. are removed and the ore
becomesporousi.e.whenlimestoneisheated,CO2isgivenoffanditissaidto
be calcinated. When bauxite is calcinated at high temperature, water is
removedandanhydrousaluminumisleft.

CaCO3
CaO+CO2
Al2O3+2H2O
Al2O3.2H2O
Roasting : It is a process of heating the ore strongly in excess of air . The
roastingincludesthefollowingtypes.

Oxidizing roasting : The volatile impurities like S, LiS, Sb are removed as

volatile.ItisusedforCuFeS2,ZnS,etc.
Blastroasting:Theblastofhotairispassedthroughtheorefortheexpulsion
of sulphur and metal is converted into oxide. This method is used for galena
andcopperpyrites.
Chloridisingroasting:Itmeanstheconversionofametaloforeintoachloride
byheatingwithcommonsaltinpresenceofair.SilverisconvertedtoAgCland
thenamalgamatedforextractionofmetalAg.

Sulphating roasting: It is partial oxidizing roasting, in which a sulfate is not

converted to an oxide but soluble sulfate i.e. copper sulphide to copper
sulphate. These soluble salts are taken out with water and used for further
treatment.
Calcinationsandroastingarecarriedoutinreverboratoryfurnace,sometimes
kilnsarealsoused.
SMELTING: It is a general term used for various operations where by the
metalisseparatedbyfusionfromore.
Chemicalreductionbyusingpowerfulreducingagent:Fortheextractionof
rather less electropositive metal, powerful reducing agents such as H2, CO,
watergas(H2 +CO),Na,K,Be,Al,Ti,Mgmaybeused.CrandMnareobtained
by reduction of their oxides by Al powder. This method is known as Gold
SchmidtAluminothermicprocess:AmixtureofmetallicoxideandAlpowder
isknownasthermiteandhencethisprocessisalsocalledThermiteprocess.
Cr2O3+2Al2Cr+Al2O3
3Mn3O4+8Al9Mn+4Al2O3
CarbonReductionProcess:TheoxidesoflesselectropositivemetalslikePb,
Zn,Cu,Sn,etcarereducedbyheatingthemwithcoalorcoke.

ZnO+CZn+CO
PbO+CPb+CO
FluxandSlag:Inordertoremoveinfusibleimpuritiesasuitablesubstance
known as Flux is added during reduction process to convert infusible
impuritiestofusiblematerial,whichisknownasslag.Theslagislighterthan
moltenmetalhenceitfloatsovermetalandisremovedfromslaghole.
Ore+gangue+reducingagent+flux+heatmetal+slag+Gases
Thenatureofthefluxuseddependsonnatureofimpuritytoberemoved.
Anacidicfluxisusedtoremovebasicimpurity.
FeO+SiO2FeSiO3
Basicimpurity
AcidicFlux
Fusibleslag
ABasicFluxisusedtoremoveacidicimpurity
SiO2+CaOCaSiO3
AcidicimpurityBasicfluxFusibleslag
Someoresareselffluxingbecausetheycontainsomeganguewhichisitself
fusibleandnoforeignfluxisrequired.
Air Reduction : This process is applicable to the extraction of less
electropositive metals may be reduced without using any additional
reducingagent,Highertemperatureandanionpresentwithmetalbringthis
changei.e.cinnabar(HgS)isroastedinair(untilapartisconvertedtooxide,
HgO) on further heating in the absence of air the oxide reacts with
unchangedHgStogiveHg.

2HgS+3O22HgO+2SO2
2HgO+HgS3Hg+SO2
thisprocessiscalledAutoreduction.

Electrolyticreduction:Whentheoxidesofhighlyelectropositivemetallike
alkali metals, alkaline earth metals, Al etc. are heated with carbon at high
temperature, the metal combine with carbon and form carbide. These
metals are extracted by electrolysis of their oxides, hydroxides and
chlorides in fused state. Some other salt may be used to lower the melting
pointofthecompoundunderelectrolysis.
Theadditionofthesaltshelpsinelectrolysisinfollowingways:
Tolowerthevaporpressureofmetal.
Itreducesthecorrosiontroubles.
For example in manufacture of Na by electrolysis of fused mixture of NaCl
andCaCl2,thereactionsareasunder.

OnFusion NaClNa++Cl

OnElectrolysis 1)AtcathodeNa++eNa

2)AtAnodeClCl+e

Cl+ClCl2
Refiningorpurificationofmetals:Themetalsobtainedaftersmeltingcontain
greater or lesser amount of impurities. These impure metals are purified by
variousways.
(1)Distillation(2)Liquidation(3)Sublimation(4)Electrolysis
Furnaces:Theprincipaltypesoffurnacesusedinmetallurgyareasfollows:
Reverboratoryfurnace(2)Blastfurnace(3)Openhearthfurnace
(4)Mufflefurnace(5)Electricalfurnace(6)Kilns.
ReverboratoryFurnace:


In this furnace the fuel is burnt in a separate part of the furnace, which is
knownasfireplace.Thefireplaceisclosedatthebottombyironbarsonwhich
thefuelisplacedandburnt.Therestofthehorizontalpartisknownashearth
or bed. The roof of the furnace is concave and takes bent towards the end
away from the fireplace and communicates with the chimney. The charge is
placed on the hearth and fuel is burnt on the fireplace so the hot gases and
flamesaredeflectedtowardsthehearthbytheconcaveroof.Thusthecharge
isheatedanditwillnot comeindirect contact withfuel. Since the fuel does
notcomeindirectcontactwithcharge,thereverboratoryfurnacecanbeused
for reduction as well oxidation process. For reduction the material is mixed
withreducingagentlikecokeandcarbon,whileforoxidationitisheatedina
currentofair.Thecalcinationsandroastingarecarriedoutinthisfurnace.
BlastFurnace:

Ithascharacteristicshape,itisabout30meterinheightand6to9meterin
diameter.Itismadeupofsteelplates.Itislinedinsidewithfireclaybricks.The
hearth maybe lined with carbon blocks for durability. On the top of this
furnaceiscupconeandhoppersystemthroughwhichchargeisintroducedin
thefurnace.Airheatedat550850Cbycombinationofwastegasesisblown
underpressurethroughtuyersornozzles.Thedowncomingchargemeetsthe
upwardmovinghotairblast.Thetemperatureattuyersis1500Candattopis
200300C.Theproductleavesfromthreeplaces.
1.Themoltenironistappedfromthebaseoftheheartheverysixhoursorso.
2. The less dense molten fusible slag floating on the molten iron is tapped
morefrequentlythroughseparateoutlet.
3.Wastegasesescapethroughtheexitnearthetop.Thesegasesarepurified
beforecombustion.
Blastfurnaceismainlyusedformanufacturingofcastiron.
OpenHearthfurnace:

These furnace is used for the manufacturing of steel and works on the
regenerativeprincipalofheateconomy.ThisfurnaceisknownasSimenMartin
Furnace.Thefurnaceisheatedbyproducergasburninginthefurnaceoverthe
hearth.Thehotproducergaspassesoutfromtheothersideofthefurnace.In
actual practice the hot gases are made to pass through a brick chamber and
then the incoming cold gases are preheated by first passing through this
chamber. In the regenerative system the heat carried away by the fuel (hot)
gasesisnotallowedtobewasted.Thehotfluegasesarepassedthroughbricks
chamber which gets heated and the gases going out of this chamber are at
muchlowertemperature.Aftersometimefuelgasesarepassedthroughthis
hotchamberandthefluegasesaremadetoheatanotherbrickchamber.The
fuel gases preheated in the chamber burns and supplies more heat. After
sometimethecurrentsareagainreversed.
Refractory Material : These are the substances, which can bear very high
temperaturewithoutmeltingorbecomingsoft.Asuitablerefractorymaterial
bearsfollowingproperties:
Thesetypeofsubstancedonotmeltorsoftentoanappreciableextentupon
exposuretointenseheat.
Theyresistsuddenandgreatextremetemperatures.
Theysupportconsiderablepressureathightemperaturewithoutcrumbling.
Theyresistscorrosionofslag.
Refractorymaterialareusedintheformofbricksfortheinternalliningofthe
material,Fluesandhotterpartsofthechimney.Thecommonlyusedrefractory
materialsaccordingtotheiracidicandbasicnatureareasfollows:

1.
Silicainformofgainster,quartz,sandstonesetc.(Acidic)
2.
Fireclaysconsistingof5065%SiO2and2235%Alumina(Semineutral)
3.
Graphite,chromite,boneash(Neutral)
4.
Limedolomitemanganese(Basic)
SiO2andkaolinresiststemperatureupto1740Cbauxitebricksupto1800C
aluminaupto2000Candmagnesiaandchromitebricksupto2200CGraphite
isoneofthemostvaluablematerialformanufacturingofthefurnace.Zirconia,
ZrO2 is one of the most refractory substances yet known and would up to
2600Cunchanged.
URANIUMEXTRACTION
ThechieforesofUare(1)PitchblendeORUraninite[U3O8](2)Carnotite[K2O.
2UO3.V2O5.3H2O] (3) Antunite {Ca[UO2]2(PO4)2.8H2O} U is extracted by two
processes:1.Aciddigestionprocess,

2.Alkalidigestionprocess.
1.AcidDigestionProcess:Firstofallpitchblendeore,U3O8isconcentratedby
gravityseparationprocesstoremovesand,clayetcandthenconcentratedore
isroastedinexcessofair,whereS,As,Sb,areremovedastheirvolatileoxides.
If Ag is present in mineral, it is removed is insoluble AgCl by roasting the
mineral with NaCl at 800oC. The roasted ore is digested with dil. H2SO4 in
presence of MnO2 for 24 hours where Ba, Pb, Ra etc are precipitated as
insolublesulphatesandUgoesinsolutionasUO2SO4[Uranylsulphate].UO2SO4
presentinsolutionisconvertedinsodiumuranylcarbonate[Na4UO2(CO3)3]by
additionofNa2CO3.
(Soluble)

2U2O8+6H2SO4+O26UO2SO4+6H2O

UO2SO4+3Na2CO3Na4UO2(CO3)3+Na2SO4 (Soluble)
The solution containing Na4UO2(CO3)3 is now neutralized with HCl to form
UO2Cl [Uranyl Chloride] and then it is saturated with H2S, so that Pb, Cu etc.
canbeprecipitatedasinsolublesulphides

Na4UO2(CO3)3+6HClUO2Cl2+4NaCl+3H2O+3CO2
UO2Cl2 is now treated with NH4OH to obtain (NH4)2U2O7 [ammonium
diuranate]anduponstrongignitionitgivesU3O8
UponreductionofU3O8withCandheatinginanelectricalfurnacegivesU
9899%uraniumisobtainedbyreducingwithAl,MgorCa
BergerreducedU3O8byvapourofCainvacuum
2.AlkaliDigestionProcess:FirstofallpitchblendeoreU3O8isseparatedfrom
sand,clayetcandthenconcentratedoreisroastedinaccessofairwherebyS,
As and Sb are removed as volatile oxides. If Ag is present, it is removed as
insoluble AgCl by roasting the mineral with NaCl at 800 oC. Now the roasted
ore is digested with Na2CO3NaHCO3 mixture solution where by U3O8 is

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converted to Na 4UO 2 (CO3) 3 [sodium uranyl carbonate] . it is treated with

NaOHtogiveNa2U2O7precipitates(sodiumdiuranate).
U3O8+3Na2CO3+6NaHCO3+1/2O23Na2CO3+3H2O+3Na4UO2(CO3)3
2Na4UO2(CO3)3+6NaOHNa2U2O7+3Na2CO3+3H2O
(insolubleppts)
TheprecipitatesofNa2U2O7isdissolvedindil.H2SO4togiveH2U2O7(Diuranic
acid). Then it is treated with NH4OH to give (NH2) 2U2O7 which upon strong
heatinggivesU3O8.
Na2U2O7+H2SO4H2U2O7+Na2SO4
H2U2O7+2NH4OH(NH4)2U2O7+2H2O
3(NH4)2U2O72U3O8+6NH3+3H2O+O2
TheU3O8isreducedbyCtogiveU
U3O8+8C3U+8CO.
9899%pureUisobtainedbyreductionofU3O8withAl.
3U3O8+16Al9U+8Al2O3
Extraction of U from Carnotite ore: In addition to U, carnotite also
containsBa,U,Fe,Al,Ra,etc.Fromthisore,Uisobtainedasbyproduct.The
heating is done by the steam. Most of the ore dissolves in HNO3, and the
solutionthusobtainedisneutralizedbyNaOHandthentreatedwithBaCl2and
H2SO4wherebyBaandRaareprecipitatedastheirinsolublesulphates,andU
and V are converted in to UO2SO4 and VO2SO4 respectively. The filtrate also
containsFeandAl,istreatedwithexcessofboilingsolutionofNa2CO3
whichprecipitatesFeandAl(reject)whileUO2SO4andVO2SO4areconverted
intosolubleNa4UO2(CO3)3andNa3VO4(sodiumVanadate)respectively.
UO2SO4+3Na2CO3Na4UO2(CO3)3+Na2SO4
(Soluble)
2VOSO4+5Na2CO3+1/2022Na3VO4+2Na2SO4+5CO2
ThesolutioncontainingNa4UO2(CO3) 3andNa3VO4isneutralizedwithHNO3
andtreatedwithNaOH,whichgivespptsofNa2U2O7ofUwhileNa3VO4do
notprecipitate.
Na4UO2(CO3)3+6HNO3UO2(NO3)2+4NaNO3+3H2O+2CO2
2UO2(NO3)2+6NaOHNa2U2O7+4NaNO3+3H2O
precipitatesofNa2U2O7areconvertedinto(NH4)2U2O7asinalkalidigestion
process.
Na2U2O7+H2SO4H2U2O7+Na2SO4
H2U2O7+2NH4OH(NH4)2U2O7+2H2O
(NH4)2U2O7onstrongignitioninairgivesU3O8
(NH4)2U2O72U3O8+6NH3+3H2O+O2
U3O8+8C3U+8CO
9899%pureuraniumisobtainedbyreductionofU3O8withCa,MgandAl.

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3U3O8+16Al9U+8Al2O3.

PropertiesofU:

The metal U resembles nickel in appearance. The pure U is white,

malleable,takespolish,softerthansteel,butbecomeshardandbrittlewhen
alloyedwithcarbonandchilled.Umeltsat1850oC.Thepowderedmetalburns
in air when heated at 190 oC in chlorine at 160 oC, and in fluorine at room
temperature.Itdecomposeswaterslowlyatroomtemperatureandrapidly
onboiling.Itdecomposeswaterslowlyatroomtemp.andrapidlyonboiling.
ItreactswithNH3athighertemperaturetogiveN2 .Itdissolvesindiluteacids
givingouthydrogen.

In ceramics, uranium compounds are sometimes used to give colored

glasseslikeorangeoryellow.Itssaltshavealsobeenusedasmordentsfor
silk and wool. The metal and its carbide are one of the best catalysts in
HabersprocessforNH3,Metalisusedinnuclearreactions,uraniumsteels
arealsooftechnicalimportance.
UF6[UraniumHexaflouride]:
Preparation:ItisobtainedbydirectcombinationofUF4andF2
UF4+F2UF6
ByreducingUF4withdryoxygenatabout800oC
2UF4+O2UF6+UO2F2
Properties:Itisacolorlessvolatilesubstanceandmeltsat
64.1oC.Itattackmanymetalsandalargenumberoforganiccompounds.
ItisreadilyhydrolyzedbyH2Otouranylfluoride[UO2F2]anditisreduced
toUF4
UF6+2H2OUO2F2+4HF
UF4+F2
UF6
Uses:Itisusedinseparatingtheuraniumisotopesandthusproducing
U235nuclearfuel.Itisapowerfulfluorinatingagent.
SILVER
Theoresofsilverareasfollows.
Nativestateorfreestate. 2.Argentine[Ag2S]
4Silvercopperglance[(Ag2Cu)2S]
3.RubySilver[Ag2SSb2S3]
5.HornSilver[AgCl]
Extractionofsilver: Silvercanbeobtainedbyfollowingprocesses.
Cupellationprocess:Inthisprocesssilveroreissmeltedwithleadores
forming an alloy of lead and silver. Then the alloy is subjected to a
process known as cupellation, where Pb forms lead oxide and silver is
obtainedinmetallicform.

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The process is known as cupellation process because the alloy is heated in a

cupelorovalshapedwroughtironframe,whichisfilledwithporoussubstance
likeboneash,baritesorcement.Therearetwocupellationprocesses:(1)
EnglishProcess(2)GermanProcess.
i.
EnglishProcess: InthisprocessthecupelismovableandPbis
addedinPbAgalloy.Theflamescomeuponthesurfaceofthealloy
massandoxidizedcompletelybyairblast.ItformsleadoxidefromPb,which
is removed. The fresh Pb is added from time to time to replace the
deficiencyduetoformationofleadoxide.

ii. GermanProcess:Theoperationiscompletedinonestep.Thecupelis
madeupoflimestone(65%),clay(30%),andMagnesium,Carbonateandiron
oxide(5%).ThealloyandrequiredquantityofPbisreplacedinthecupel
andheatedinafurnace.Theheatisregulated.WhenallPbisconverted
to lead oxide and is removed, brilliant silver remains beneath and is
collected.
[2]Amalgamationprocessorratioprocess:Pyritesoreismixedwithsalt
androasted.ThenitisgroundedandmixedthoroughlywithHg.Thesaltand
roastedpyritesformFeCl3,whichthenreactswithAg2S.
Ag2S+2FeCl32AgCl+2FeCl2+S
TheAgClthenreactswithHgliberatingsilver.

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AgCl+HgAg+HgCl
The Silver dissolves in excess of mercury to from Amalgam. Mercury is
recoveredfromamalgambydistillationwhilesilverisleftbehind.
[3]Desilverisationoflead:
1.
Parkesprocess:Thisprocessisbasedonthefactthat
1.MoltenZnandmoltenPbareimmiscible
2.TheAgisoresolubleinmoltenZnthaninmoltenPb.
Therefore when fused leadsilver alloy is treated with molten Zn, it dissolves
most of Ag forming ZnAg alloy. This solidifies and floats on the surface and
skimmedoffbyperforatedladders.Thealloywhendistilledgivesthevaporsof
Znleavingmetallicsilverbehind.
2.
Pattinsons process : Desilverisation of lead containing very small
amountofsilveriscarriedoutbyPatinsonsprocess.Thisisbasedonthefact
thatoncoolingamoltenleadsilveralloyleadseparatesuntilconcentrationof
silverrisesto2.4%inthealloyandtheentiremasssolidifiedinblock.
Argentiferrous lead is melted and cooled. Crystal of lead is much power in
silver hence separates and is removed with perforated ladles. The process of
meltingandcoolingisrepeatedinabovetilltheentiremasssolidifiesinblock.
Silverisrecoveredfromthealloybycupellation.
3.
BettselectrolyticProcess: In this process argentiferrous lead is
usedasanode,whilepureleadsheetisusedascathodeinelectrolytic
cell.Anaqueoussolutionofleadfluorosilicate[PbSiF6],Hydrofluosilicic[H2SiF6]
andgelatinareusedforelectrolysis.Uponelectrolysis,leaddissolvesfrom
theanodeandgetsdepositedonthecathode.Whilesilveralongwith
goldandother impuritiesseparates fromthe anode inform ofslimy
mass.Thisanodesludgeisthensubjectedtocupellationtoobtainrefined
Ag.
4.
Thecyanideprocess:Thisisthemodernprocessfortheextraction
ofsilverandiscarriedoutasunder.
1. Concentration : The sulphide ore, Ag2S concentrated by froth
floatationprocess.
2. Treatmentwithcyanides:Theconcentratedoreisgroundedtoa
veryfinepowderinballmills.Itisthentreatedwith 0.40.6%NaCN
solutionandthewholemassisagitatedbyair.Agoforeformsasoluble
complexionwithcyanide.
Ag2S+4NaCN2NaAg(CN)2+Na2S
Sodiumargentocyanide
Ag2S2Ag+S22
2Ag++4CN2[Ag(CN)2]

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Theabovereactionisreversible.ByblowingtheairNa2Sisremovedfrom
the equilibrium mixture so the reaction can proceed in the desired
direction.
4Na2S+5O2+2H2O2Na2SO4+4NaOH+2S
Thesolublesodiumargentocyanideisobtainedbytitration.
3. RecoveryofSilver:
Now Zn is added to the solution of sodium
argentocyanide,Agisprecipitatedasadarkamorphousmass.
2NaAg(CN)2+Zn2Ag+Na2Zn(CN)4
The precipitated silver is obtained by titration is dried and fused when
brightcompactmassisobtained.
4. Purification:
Ag obtained is refined by electrolysis from
solutiononAgNO3containingabout10%HNO3solution.TheimpureAg
blocksactsasanode,whilepureAgStripsactsascathode.
Separationofsilverfromgold:Theseparationofsilverandgoldisknown
asparting.Itcanbecarriedoutbyfollowingmethods.
IfAuislessthan20%thenthismethodis
1. PartingwithH2SO4:
used.ThealloyistreatedwithboilingH2SO4.Aggoesintothesolutionas
Ag2SO4andAuremainsunchangedasaspongymass.Byfiltration,gold
isobtainedandfromfiltrateupondilutionwithH2OandbyusingCuor
Fe,Agisobtained.

Ifgoldismorethan20%someAgisaddedfromoutsidetoreduce
the%ageofgoldandthenpartingprocessisapplied.

Forthisreason,theprocessisknownasquartution.
2. Parting with Moebius method : In this electrolytic process, AgAu
alloy blocks make the anode, while pure Ag acts as the cathode, the
electrolysisiscarriedoutinAgNO3solution,containing1%HNO3.During
electrolysis,Agdissolvesfromtheanodegetsdepositedonthecathode,
Auremainsundissolvedandisrecovered.
AgNO3:
Preparation:ItisobtainedbydissolvingAgmetalinwarmdiluteHNO3,
anduponcrystallizationgivescrystalsorsticks.ItiscalledLunarCaustic.
3Ag+4HNO33AgNO3+2H2O+NO
Properties:
ItismostimportantAgsalt.
Incontactwithorganicsubstanceitblackensandthusleavesblackstains
whencomesincontactwithhandsorclothes.
Itishighlysolubleinwater,M.P.212oC,uponheatingfurther,decomposes
toAgNO2.
2AgNO32AgNO2+O2
whenheatedtoredheat,itfurtherdecomposestometallicAg.

15

2AgNO22Ag+2NO2+O2
withNH3itformscomplex.
AgNO3+2NH3[Ag(NH3)2]NO3
Uses : As laboratory reagent. In volumetric analysis for estimation of
chlorides.Silverhalidespreparedfromitareusedinphotography.Itis
usesasmarkinginkinsilveringmirrors,insurgeryasLunarcaustic.
Photography:Photographyisanartofproducingpicturesofilluminated
objectonchemicallypreparedsurfaces,Thephotographcanbeobtained
fromfollowingstages.
Makingasensitiveplate:Sensitivephotographicplatesareoftwotypes
(1)Plates(2)films.DryPlatesconsistsofsheetsofclearglass,whilefilms
aremadeupofstripsofcelluloidandthesearecoatedwithemulsion.To
make emulsion AgNO3, NH4Br and gelatin are slowly heated together
untilreactiontakesplacebetweenthen.
NH4Br+AgNO3AgBr+NH4NO3
Themixtureiskeptinawarmroom,untilthegrainsofAgBrbeginto
develop. This makes the metalloid more sensitive and the process is
calledrepening.Nowthisjellylike massisshreddedinmachine.Itis
now soaked in distillation H2O, melted and then dissolves out NH4NO3
from gelatin. The emulsion is now melted and the glass plates or the
celluloidfilmsarecoatedwithitandsealedinlighttightboxes.
Panchromaticplates:Thisemulsionhasonegreatdefectofbeingssensitiveto
onlyblue,violetandUVrays,whilethegreenyellow,orangeandredraysare
unaffected.
Anumberofphotosensitizesweresuggestedbydifferentworkerstoovercome
thiseffected.
VogelDyedplatewithaniline(1873),withcyanin(Bluedye)(1834)
Tailforandclaytonliosinisochromaticplates
EderErythrosin(reddye)
KocnigpanchromeandarthrochromeTfinallypinacyanol(agreenishdye)
BabcockNeocyanin
Exposer: To take a picture, the dry plate or film is put in camera and the
exposed.Inexposer,
Silversubbromideisproduced,inwhichitreducestosilver
2AgBrAg2Br+Br
On the basis of photo electric effect the loss of electrons of halides makes
moresensitivetoreduction
Development:Theplateorthefilmisnowtakenoutfromcameraindarkand
immersedinadevelopingbath,whichconsistsofaveryweaksolutionofsome
reducingagent,soonlyexposedpartsareaffected.

16

Recently, metal quinol or hydroquinone and amidol are used as modern

developer, it is made as follows: Metal 1.0 gm, Na2SO3 (crystals) 85 gm,
Hydroquinone4.5gm,Na2CO3(Crystals)1.6gm,dissolvedinwarmwaterand
makethesolutiononeliter.
The portion of the plate most affected by light is easily reduced so becomes
black,whilethosenotaffectedbylightremainwhiteandcorrespondtoblack
intheobject.Thevalueoftheimageisthereforenegativetotoneoftheobject
andiscallednegative.Thereactionis,
C6H4O+2Ag+2HBr
C6H4(OH)2+2AgBr
Hydroquinone
Quinone
Factors affecting the development : Time and temperature are important
factorswhichaffectsthedevelopment.
Temperature: All solution should be at same temperature below 13oC
chemicalsareunaffectedabove24oCbuttherearechangesingelatin2025oC
istheidealtemperature.
Time:Lowerthetemperaturelongerthetimerequired,moretimegivesover
developmentorunderdevelopment.
Fixing: Plate cannot yet be exposed to light, because it contains sufficient
amount of emulsion at the white point. It is immersed in a solution of
Na2S2O3(hypo)todissolveoutthisbalanceoftheemulsion.
Alittle,Na2S2O3isaddedtothefixingbathaspreservativeandsomechrome
alum for hardening the negative After mixing hypo should be removed by
washings.
Printing: The process of printing is a repetition of making negative printing
paperoftwotypes.
P.O.P.paperscoatedwithmixofAgCl,gelatinandsilvercitrate,Thenegativeis
placedagainstprintingpaperinaprintingframeandexposedtosunlight.The
process is slower, so it can be watched and controlled. After the image has
comeonthepaper,itisfixedandtoned.
Bromide paper requires very short time. Artificial or gaslight is sufficient to
exposethis.
Toning: Other metals to get different shades, may replace the silver in the
print.
GenerallyAgisreplacedbyAuorPt,byimmersinginsolutionofgoldchloride
or sodium auri chloride and potassium chloroplatinate. Gold solution gives
golden tint ranging from brown to purple, white platinum produces shining
gray.
AuCl3+3AgAu+3AgCl
After treatment of negatives: An after treatment of a negative is necessary,
whenitsimagedensityistoolowortoohigh.Themethodusedforincreasing

17

theimagedensityisknownasintensification,whilethatemployedforlowering
itiscalledreduction.
SilveringofMirrors:Silveringofmirrorisaprocessbymeansofwhichathin
anduniformlayerofsilverisdepositedonacleanglasssurface.Itisemployed
formakinglookingglasses,concavemirrorsandreflectingsurfaces.
Theprocessisbasedonthereductionofsilveroxidebyanorganicsubstance
likeformaldehyde,tartrates,etc.
2AgNO3+2NH4OH Ag2O+2NH4NO3+H2O
Ag2O+HCHO HCOOH+2Ag
Twoseparatesolutionarepreparedforthesepurpose,oneisammonicalsilver
nitrate (20 gm AgNO3 in 150 ml H2O and then adding NH4OH till the
precipitatesfirstformedandredissolved.Itismade320ml.)[Tollensreagent]
Thesecondsolutionconsistsofreducingagent.
The plate to be silvered is thoroughly cleaned with alcoholic KOH and then
washedwithwateranddried.Itisfixedinanenameleddishwithparaffinwax
sothatonlyoneofitssideisexposed.Thetwosolutionarenowpouredover
the surface in proper proportions and the mixture is given a slow motion by
movingthedishtoandfro.
After the silver has been deposited, the mirror is gently washed with water,
driedandpolishedwithsoftcottonwool.Thebackisgivenacoatofamixture
ofredleadandterpentineinordertogetlookingglass.
LEADMETALLURGY
PbLead:ThechieforeofleadisGalena,orleadsulphide(PbS),otheroresare
anglesite[PbSO4],cerrusite[PbCO3]TheextractionofPbiscarriedoutbytwo
methods
[1]Airreductionprocess:Thisprocessisusedwhenorearerichinlead.The
stepsareasfollows:
Concentration:Theore,PbS[Galena]iscrushedandsievedandconcentrated
byusingfrothfloatationprocess.
Roasting:Theconcentratedoreisroastedonareverboratoryfurnace.Theore
is partially converted to PbO and PbSO4 by controlling the air simply through
thedoors.
2PbO+2SO2
2PbS+3O2
Pbs+2O2
PbSO4
Now the air supply is reduced and the temperature raised up with more
addition of PbS. The oxide and sulphate produced in 1st operation react with
excessofPbSandreducedtometalliclead.
2PbO+PbS 3Pb+SO2
PbSO4+PbS 2Pb+2SO2

18

Thus in air reduction process roasting and smelting are done in the same
reverboratory furnace at two different temperatures molten Pb is removed
fromthelowerpartofthefurnaceandpurified.
[2] Carbon reduction process: This process is used for ores poor in lead
content.Itiscarriedoutinthefollowingsteps.
Concentration: The ore is crushed and made fine powdered in ball mills and
sieved.Itistakeninbigtank.Tothis,themixtureofwaterandsmallquantity
ofpineoilisadded.Thentheairispassedviolentlyunderpressure.Thewhole
mixtureisagitated,soitproducesfroth.Theoreparticlessticktooilparticles
and produces froth. The froth is lighter than water, and comes on upper
surface from where it is collected in separate container. The impurities are
wettedbywaterandsettledownatthebottomandremoved.

19

Roasting:Theconcentratedoreisroastedinasinterer,whichismountedon
trunniousforcharginganddischarging.Thereisahoodatthetopandgrating
nearthebottom.Theslowblastofairispassedandiscirculatedthroughthe
chargebysuctionfromthetopofhood.
The charge made up of ore [PbS] and lime is placed on the coal fire at the
gratingPbSchangestoPbO.
2PbO+2SO2
2PbS+3O2
Thelimeisusedfortwopurpose:
ItismorebasicthanPbO,sopreventstheformationofPbSO4.
ItpreventstheformationofPbSiO3,whichwouldotherwisegointoslag.Ifitis
formeditdecomposes.
PbSiO3+CaO PbO+CaSiO3
Smelting:Thesinteredoreisbrokenintosmallpiecesandplacedintheblast
furnaceofthetypeasshowninfigure3.
Asthechargemovesdownthefollowingreactionsoccur.
PbO+C Pb+CO
PbO+COPb+CO2
CaO+SiO2
CaSiO3(slag)
PbSiO3+CaO PbO+CaSiO3
(LeadSilicate)
TheslagislighterthanmoltenPbandthusfloatsoveritandremovedfromthe
upperslagholewhilethemoltenPbisremovedfromthelowertappinghole:

20

Purification: The lead obtained by any of the methods contain large no of

impuritieslikeBi,Cu,Sb,andAg.TheBi,Cu,Sb,etc.areremovedbysoftening
processwhileAgbyvariousdesilverizationprocess.
Softening Process: The impure metal is melted in reverboratory furnace and
airispassed,soimpuritiesoxidizedandtheoxidesareremoved.
Desilverization Process: The lead is desilverised by following processes:
1.Parkes process : This process is based on the fact that (I) Molten Zn and
moltenPbareimmiscible.(II)TheAgismoresolubleinmoltenZnthanmolten
Pb. Therefore when the silver containing Pb is mixed with molten Zn the Ag
almostdissolvesinmoltenZnformingZnAgalloy.Thisissolidifiedandfloats
on the surface is slimmed off by perforated ladles. The alloy when distilled
givesthevapourofZn.Leavingmetallicsilverbehindandiscollected.Leadis
considerablyreducedbyrepeatingthisprocess.
Usesorindustrialapplications:
Itisusedformaking:
Waterpipesandcablecovering
Leadaccumulators
LeadShot
LeadChambersformanufacturingofH2SO4
LeadpigmentslikeRedlead,whitelead,Chromeyellow,chromered
Compoundsoflead.
Formanufacturingofalloys
White lead 2PbCO3Pb(OH) 2: At present white lead is the most important
pigment.ItispreparedbyDUTCHPROCESS.
Dutch Process: This process is based on the action of CH3COOH on metallic
lead in presence of moist air and CO2. The process is essentially one of
corrosionandtakesplaceintheearthenpotsglazedinsideandprovidedwith
shouldersfromwhichthepureleadstripsaresuspended.Thepotsare8inches
highand4incheswideandcontainsasolutionof3%CH3COOHatthebottom.
SoPbdoesnotcomeindirectcontactwithCH3.COOH.Alternatelayersoftan
bark,potsandwoodenplanksarebuildup.

21

Theheatdevelopedbythefermentationoftanbark[somethinglikeleather]
volatilizes the fluid, which in contact with atmospheric O2 corrodes the Pb
formingBasicacetate.
2Pb+2CH3COOH+O2 (CH3COO)2Pb.Pb(OH)2
Basic lead acetate is finally decomposed by the CO2 liberated in the
fermentationprocess.
3[(CH3COO)2Pb(OH)2]+4CO2+O2 2[PbCO3.Pb(OH)2]+6CH3COOH
The CH3OOH again react with more lead in presence of moisture and air
corrosionproducesmorewhiteleadviabasicacetate.Thecycleiscontinued.
Afterreaction issubsidingthe white leadiswashed, grounded,collectedand
dried.
Uses:Whiteleadisusedaspigmentinpaints.

22

COPPERMETALLURGY
Occurrence : Copper is widely distributed all over the world. The Ores are
classifiedasfollows.
Nativeoreor.FreestateMetalliccopper5%ofthetotal
production.
Malachite),
OxideoresCU2O[Rubycopper),CuCO3Cu(OH)2[(green
2CuCO3.Cu(OH)2(blue)Azurite)
SuphideoresCuFeS2[Copperpyrites],Cu2S[Copper.glancebornite)
ThechieforeisCuFeS2(orCu2SFe2S3)copperpyrites.
Mostoftheworld'scoppersupplyisfromsulfideores.
ExtractionofCu:therearetwomethodsforextractionofCu.
Dryprocess: This process is used when Cu content in the ore is large. It is
knownaspyrometallurgy.
WetProcess:ItisusedwhenCucontentintheoreisless.Itis
knownashydrometallurgy.
CuFeS 2Contains FeS as impurity. So due to presence of FeS, Cumetallurgy
becomesmoredifficult.Thereasonsareasfollows.
Cu has greater affinity for S than for oxygen. As temperature increases this
affinityincreases.
Fe has more affinity for Oxygen than for sulphur. This affinity increases as
temperatureincreases.
SandOhaveaffinityforeachotherthanforCuandFe.

23

DryProcess:Dryprocessdividedintofollowingsteps.
[1]Concentration:Theorecontainingsulfideisfirstlyconcentratedbyfroth
floatation process. The finely powered red ore is taken into big tank. To this
mixtureofmixtureofwaterandasmallquantityofpineoilterpentineoiland
some active whole mixture is agitated. It produces froth. The ore particles
sticktooilparticlesandfrothisproduced.Theoreparticlessticktooilparticles
and froth is produced. It is lighter than water. Coming on the upper surface
fromwhereitiscollectedinseparatecontainer.Theimpurities,earthymatter,
sand,rockystones,mica,etcarewettedbywater,becomesheavierandsettle
downatthebottomofthetank.Inthiswayoreisconcentrated.

[2] Calcination&roasting:Theconcentratedore is roastedinacurrentof

airatlowtemperatureareverboratoryfurnace.Alargeportionoffreesulpher
present as impurity is oxidized to SO2 and removed as such. As and Sb are
removedasvolatileoxides,As2O3andSb2O3respectively.
S+O2SO2
2As+3/2O2AS2O3
2Sb+3/2O2Sb2O3
CuFeS2isconvertedasCu2SandFeS.TheseCu2SandFeSarefurtherpartially
oxidizedasCu2OandFeO.
2CuFeS2+O2Cu2S+2FeS+S02.
2Cu2S+3/2022CU02+2S02(Smallchange)
2FeS+3/2022FeO+2S02(Partialchange).
ThusS02obtainedasbyproduct.

24

[3]Smelting:Theroastedoreismixedwithcokeandsandandsmeltedinto
blastfurnace.DuringsmeltinggetsoxidizedtoFeO.FeOthenreactswithSiO2
formingFeSi03Ferroussilicate(Slag)
2FeS+3O22FeO+SO2
FeO+SiO2FeSiO3(slag)
FeSiO3slagislighterthanmoltensulphidesofCuandFe,henceitisremoved.
Cu20isalsoformedduringroasting,reactswithFeStogiveFeO.ThisFeOalso
reactswithSiO2formingSlag.
Cu20+FeSCu2S+FeO
FeO+SiO2FeSi03(slag)
Itisalsoremoved
ThemoltenmixturethusobtainedduringsmeltingcontainsmainlyCU2Sand
FeSMoltenCu2SwithFeS(little)calledmatteandisremovedthroughtheslag
holematteisalsoremovedthroughanoutlet.
[4]Bessemerisation:Ironleftinmatteisremovedbybessemerisation.Itis
carriedoutinBessemerconverter.MoltenmatteispouredinBessemer
converter and calculated quantity of sand is added. After adding sand
Bessemerconverteriskeptuprightandhotairisblownthroughitat
high pressure. FeS oxidized to FeO. This FeO reacts with SiO2 forming
FeSiO3,slag.
2FeS+302+SiO22FeSiO3+2S02
After, all FeS oxidized to FeO, Cu2S start to convert Cu2O : This Cu2O reacts
withCu2StoproduceCuinmoltenform.
2Cu2S+3022Cu2O+2S02
2Cu2O+Cu2S6Cu+SO2
ThismoltenCuistakenOutfromBessemerconverter,whenoregetscooled.
SO2gascomesoutfromitandproducesblisterontheCumetalsurface.The
cuproducedinthiswayisknownasblisterCu.Itis95%purecontaining
Fe,Mn,Zn,Pb,Bi,Sn,Ni,Ag,Au,PtandCu2Oasimpurities.Itisusedfor
utensils.

25


[5] RefiningofCu:
1. BypollingMethod:DuringbessemerizationasmallquantityofCu2O
produced by air blasts remain unreduced. So it is removed by polling
method.

MoltenimpureCuistakenintoreverboratoryfurnace.Uppersurfaceis
covered with coke layer and it is stirred with green wood pole. So
hydrocarbongasesproducedfromwoodpolereducesCu2OtoCuandifCu2O
produced on upper surface also reduced by coke and in this way Cu2O is
removed.Cuobtainedis97%pure.
2. ElectrolyticRefining: The impure Cu is refined by electrolytic
process.InthisprocessimpureCucastsintolargeplates,whichareused
asanodeandpureCuactsascathode.CuSO4anddil.H2SO4solutionare
usedaselectrolyte.

During electrolysis impure Cu dissolves and forms Cu+2 ion, which

reducesatcathodeandgetsdepositedonit.TheimpuritiesAg,AuandPtdo
notoxidizeandfalltothebottomofelectrolyticcellasanodicmudalong
withCu2O)andslagfromwheretheyrecovered.OtherimpuritiesZn,Pb,
Fe, Sn, etc oxidized as their ions and remains in the solution, The Cu
obtainedis99.9%pure.

Atanode:Cu(s)Cu2++2e

Impure
99%
+2
AtCathode:
Cu +2eCu(s)

Impure

26

IRONMETALLURGY
Iron readily occurs in free state, since it is highly reactive. Its important ores
are(1)redhematite[Fe2O3](2)Brownhematiteorlimonite[Fe2O23H2O](3)
magnetite [ Fe3O4] (4) Siderite [ Fe CO3]. Huge deposits of haematite are
availableinIndiainmayurbhanj(Orrisa),Singbhum(Bihar)andMysore.

Iron ore is worked for three variety of iron, which differs from each
othermainlyintheircarboncontent.
Cast iron or pig iron : It is the most impure form of iron and contains the
highest%ofcarbon(23%)andotherimpuritieslikeSi,P,Mn&S(1.5%).
Wroughtiron:Itisthemostpurestformofironandcontainsthelowest%of
carbon(0.120.25%)
Steel:The%ofCinthisformisinbetweencastironandwroughtiron(0.25
2%)
Q.Describethemanufactureofcastiron
Castironisusuallyobtainedfromhaematiteore.Thestepsareasfollows:
[1] Concentration : The impurities are removed as far as possible by hand
picking and the ore is broken into pieces. It is now washed with water to
remove the lighter impurities like sand, clay, etc. The washed ore is than
concentratedbyusingmagneticseparationprocess.
[2]Roasting:Theconcentratedoreisroastedwithlittlecoalinreverboratory
furnace.Duringroasting,moisture,CO2,etcareremovedasvolatileoxides.The
S content is lowered. Fe0 is converted into Fe2O3. Fe0 also forms slag with
SiO2,whileFe2O3doesnot.Themassbecomesporous.
Fe2O3,3H2OFe2O3+3H2O
FeCO3FeO+CO2
4FeO+O22Fe2O3

27

[3]Smelting:Theroastedoreismixedwithlimestoneanddesulpherised
cokeintheratioof8:1:4andsmeltedinblastfurnace.Duringsmeltingthe
followingreactionstakeplaceindifferentzonesofreactions.
Upper zone: This zone is near the mouth of furnace and is called the upper
zoneofthereduction.Thetemperaturerangesfrom400to700C.Inthiszone
cokeburnsinpresenceoxygenandhotairtofromCO2whichreducestoCO.
C+O2CO2:
CO2+C2CO
InthiszoneCOreduceFe2O3tospongyiron.

3Fe2O32Fe3O4+CO2

Fe3O4+CO3FeO+CO2

FeO+COFe+CO2

Spongyfrom
Atatemperatureabout600CapartofCaCO3getsdecomposedtoCaO.

CaCO3CaO+CO2

CaCO3+CCaO+2CO
Central zone: The temperature ranges from 900 to 1200C. It is called lower
zone of reduction. The spongy iron, which comes down, meets CO, and
decomposes to C party [2C CO2+C].The spongy iron absorb C at about
1000C,CaCO3almostcompletelydecomposestoCaOandfromslagwithSiO2.
CaCO3CaO+CO2,
CaO+SiO2CaSiO3.
Theslagislighterthanmoltenmetal,floatsovermoltenmetalandisremoved
fromtheupperslaghole.Thesilicatesphosphates,managanatesreducetoSi,
PandMn.Theyarepartyabsorbedbyslagandpartybyiron.
Lowerzone:Itisthehottestpartofthefurnaceandcalledthezoneof
fusion.Thetemperaturerangesfrom12001500C.Inthiszonecokeburnsby
blastofhotairtoproduceCO2andheat.
C+C2CO2+9700cal.
The spongy iron melts at 1300C and is collected at the bottom of hearth of
the blast furnace. FeO reduce of Fe in this zone. If any silica or alumina is
present it forms slag and as it is lighter than molten metal it floats on the
surface and is removed from the slag hole. Slag prevents molten metal from
oxidation. The molten metal is removed from lower tapping hole and is
solidified.Thisispigiron.Thispigironisremeltedinafurnaceheatedbycoke
andcastorpouredintomoulds.Thisisknownascastiron.
Wrought Iron : Wrought iron is obtained from pig iron by removing the
impurities by puddling process, in which the cast iron along with some scrap
ironisplacedontheheathofthereverboratoryfurnacelinedwithhaematite.
Fe2O3 oxidizes C, S, Si, Mn and P to their respective oxides i.e. CO, SO2, SiO2,

28

MnOandP2O5,MnOandSiO2combinetogiveMnSiO3(slag):P2O5withFe2O3
togiveFePO4(slag).
MnO+SiO2MnSiO3;
P2O5+Fe2O32FePO4
As the impurities are removed the melting point of the metal rises and iron
becomes pasty mass, which is stirred and forms balls and blooms. They are
spongy in nature due to large amount ofslag present inthem. Theballsare
takenoutfromthefurnaceandslagisremovedbyhammering.Finallyironis
rolledintosheetsandbars.
Uses: it is used to make anchors, wires, bolts, chains and agricultural
equipments.
Steel:

Bessemer process : Themoltenpigiron is poured into a Bessemer converter

whichismade upofsteelplates. Itislinedwith silica ormixtureorlimeand
magnesia(CaCO3,MgCO3)whenimpuritiesofMn,Si,etc.arepresent.WhenP
is present dolomite is used. The Bessemer converter is kept upright and the
hotairispassedSiandMnareconvertedintoSiO2andMnOandformsslag,
whichisremoved.
2Mn+O22MnO
Si+O2SiO2
MnO+SiO2MnSiO3

Pisremovedasphosphate.
As,Si,MnandPareremoved,thencarbonisconvertedtoCO.COburnswith
blueflameatthemouthoftheBessemerconverter.

29

When flame is stopped than air blowing is stopped. Then required quality of
carbon is added and it is distributed uniformly by passing air for some time.
Some quantity of alumina and ferrosilicone are added to remove dissolve N2
andO2.Steelisobtained.
Openhearthfurnace:Thechargewhichcontainscastironmixedwithabout
2540 % of its weight of scrap iron low grade wrought iron & haematite
(Fe2O3)and taken in furnace. The furnace is lined with silica or dolomite. The
openhearthfurnaceisheated.
CandSareoxidizedbyhaematite,Fe2O3toCOandSO2whileMn,SiandPare
removedastheirslag.

Fe2O3+3C2Fe+3CO(Cremoved)

2FeO3+3S4Fe+3SO2(Sremoved)

Fe2O3+Mn3MnO+2Fe

2FeO3+3Si4Fe+3SiO2

MnO+SiO2MnSiO3(Slag)

5Fe2O3+6P10Fe+3P2O5

P2O5+3CaOCa3(PO4)2(slag)
Some quantity of charge is taken out from time to time and analyzed for
carboncontent.Socarboncontentisadjusted.Aluminaandferrosiliconeare
addedtoremovedissolvedN2andO2.hencesteelismanufactured.

Q. HowopenhearthfurnaceprocessdiffersfromBessemerconverter.
1.
Impuritiespresentincastironareoxidizedbyhaematiteandnotbyair
asinBessemerconverter.

30

2.
% of carbon and Si in charge is lowered by adding low grade wrought
ironandscrapiron.
Q. Meritsdemeritsofopenhearthfurnacemerits

1.
Theprocessisslowereasytowork.

2.
TemperaturecanbecontrolledasheatingIdoneexternally.
Samplescanbeexaminedfromtimetotime.Socompositionand
qualitycanbecontrolled.
InBessemerprocessairispassedtooxidizesomeFeasslagthereisnolossof
ironinopenhearthfurnace.
Demerits:
The only disadvantage of open process is that the operation of this process
completesin5to10hoursinBessemerprocessittakesonly20minutes.

NICKELMETALLURGY
The chief ores of nickel are (1) smeltite [(Fe, Co Ni) As2] (2) Kupfer nickel or
nicolite,[NiAs](3)pentlandle[(Ni,Cu,Fe)S.

nickelismainlyextractedfromsulphideores,i.e.pentiandite.

Theprocessiscarriedoutinthefollowingsteps.
[1] Crushing and Concentration : the pentlandite ore is crushed in big jaw
crushers and then finely powered in ball mills. The sulphide ore is then
concentratedbyusingfrothfloatationprocess.Theconcentratedorecontains
NiS,FesandCuSasimpurities.

31

Theorecontainingsulphideisfirstlyconcentratedbyfrothfloatationprocess.
Thefinelypowered oreistakenintobigtank.Tothismixtureofwateranda
smallquantityofpineoilorterpentineoilandsomeadditivesaltsareadded.
Thenairisblownviolentlyandwholemixtureisagitated.Itproducesfroth.The
oreparticlessticktooilparticles.Itislighterthanwatercomingontheupper
surfacefromwhereitiscollectedinseparatecontainer.Theimpuritiesearthy
sandrockystone,micaetcarewettedbywater,becomesheavierandsettled
downatthebottomofthetank.Inthiswayoreisconcentrated.
[2] Production of NiS: From concentrated ore FeS is removed by following
steps.
1.
Roasting:Theoreisroastedinreverboratoryfurnacewherebyexcessof
SisoxidizedasSO2andFeSispartyoxidizedtoFeO.
S+O2SO2:
2FeS+3O22FeO+2SO2

2. Smelting: The roasted mass is mixed with SiO2, coke and some
limestone and smelted in blast furnace. FeS is oxidized to FeO. FeO
formedduringroastingandsmeltingcombineswithsilicaandformslag.
FeSiO3
FeO+SiO2
Atthesametime,CaOcombinedwithSiO2andformCaSiO3(slag)
CaCO3CaO+CO2
CaO+SiO2CaSiO3(Slag)
BothFeSiO3andCaSiO3areslagandfloatsoverthemoltensulphidesof
Ni,CuandFe.
3. Bessemerization:The molten mass of sulphides of Ni, Cu, and Fe
withasufficientquantityofSiOisintroducedintoaBessemerconverter.A
blastofhotairispassedunderpressure.ItoxidizesalmostallStoSO2
and FeS to FeO, which forms slag, FeSiO3. The slag is removed and a
sulphide of Ni, Cu and small quantity of Fe remains. The is known as
matte.
[3] Recovery of Nickel : from matte nickel is obtained by following
processes.
[I] OrfordsProcess:
Inthisprocess,aseparationofCuandNiis
carriedoutbytakingtheadvantageof
1. DifferenceinsolubilitiesofCuandNisulphidesinNa2Sinwhich
CuSissolubleinNa2S.
2. DifferenceinspecificgravitybetweenCusandNiScontainingdissolved
CuS,thelaterishigher.
The matte is melted with NaHSO4 and coke in a blast furnace. The coke
reduces NaHSO4 to Na2S, which dissolves CuS in presence of NiS and Na

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sulphides.ThemoltenproductisformedcontainingsulphidesofNi,Cuand
Na.therearetwolayersofproduct.
TheupperlayerisofCuandNasulphidesandlowerlayerisofNi,and
Nasulphides.TheupperlayerofCuNasulphideislighterthanNiNa
Suphides,itissenttocuconverterwherecuisextractedandlowerlayer
forNi.
ThelowerlayerisgroundedandNa2Sisleachedwithhotwater.TheCuis
presentinlowerlayer.Sosulphideiscalcinatedwith15%NaCl,itform
CuCl2,whichextractedwithwater.ThisNiSisconvertedtoNiO.
2NiS+CNiO+CO
[II] MondsProcess: Theprocessmakestheuseoftheformationand
decomposition of Ni (CO)4, nickel tetrahedral carbonyl liquid (B.P.. 48.20C)
whichdecomposesat180oCtoNiandCO.
NiS,CuSandFeSareroastedtoNiO,CuOandFeO.Theimpureoxidesare
treatedwithwatergas(H2+CO),at250350oC.Atthistemperaturethe
hydrogenofwatergasreduces,NiOandCuOtoNiandCu,butFeOisnot
reduced. Now CO is passed over the product at 60oC, Ni forms volatile
Ni(CO)4,Liquid.
Ni(CO)4Ni+4CO
TheNiballsareremeltedandcastintoingotsNithusobtainedis99.9%
pure.
[4] Refining:Niisfurtherrefinedbyelectrolysisbyasolutionofnickel
ammonium sulphate (NiSO4(NH4) 2.SO4 6H2O saturated] at 25 oC. A cast
nickel black is used as anode and pure nickel as cathode. On passing
electriccurrent,impurenickelblackdissolvesandformsNi+2theseionsmoves
towardscathode,reducesanddepositedoncathodeasNi,Ag,AuandPt
are deposited below anode and anodic mud and obtained from this
anodicmud.
INDUSTRIALUSES
Usedinmanufacturingofalloy.
Usedinmanufacturingofchemicals.
UsedinNiPlatimary
UsedinmanufacturingofNisteel.

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