Copper

Major ore Occurrence in Nepal

1.Copper pyrite- CuFeS2(major) 1. Chitwan
2.Copper glance- Cu2S 2. Udayapur
3. Cuprite- Cu2O 3. Makwanpur
4. Malachite- CuCO3.Cu(OH)2
  1
 Extraction of copper
Copper is extracted from its chief ore copper pyrite/ chalcopyrite- CuFeS2.
The various steps adopted for the extraction are:
1. Crushing and pulverization: Huge lumps of ore are crushed using
jaw crushers and are finely pulverized(powderd) using ball mills.
2. Concentration of ore by froth-floatation process: Powered ore is
dipped into a tank containing water and small quantity of pine oil. The
mixture is agitated by using blast of air. Gangue particles were wetted by
water and get collected at the bottom of the tank. The sulphide particles
being preferentially wetted by oil come on the surface in the form of froth.
The froth is skimmed off to collect the concentrated ore.
3. Roasting: The concentrated ore is heated in excess supply of air on the hearth
of reberberatory furnace below its melting point. As a result moisture and
volatile impurities are driven out.i.e, sulphur, phosphorous, arsenic etc. are
removed as their oxides.
S + O2                SO2
P4 + 5O2              2P2O5

4As + O2 2As2O3
During roasting process,
Copper pyrite dissociates into charge

individual sulphide Fig : Reverberatory furnace

2CuFeS2 + O2            Cu2S + 2FeS + SO2    

Small amount of metal sulphides are oxidized to oxides.

2FeS + 3O2          2FeO   + SO2            
2Cu2S + 3O2          2Cu2O  + 2SO2

Thus, the roasted ore mainly consist a mixture of Cu2S, FeS, Cu2O and FeO.
 4. Smelting: The roasted ore is mixed with sand(flux) and powdered coke. It is
strongly heated in water jacketed blast furnace which is internally lined with fire
proof bricks and externally covered with steel. A blast of hot air at about 800°C is
introduced at lower part of the furnace during which the coke burns and the
temperature rises to 1000°C . During the smelting process following reaction takes
place:
a. Ferrous sulphide is converted into ferrous oxide.
2FeS + O2 2FeO + SO2
b. Some iron oxide combine with silica to form fusible slag.
FeO + SiO2 FeSiO3
c. A part of cuprous sulphide is also oxidised to cuprous oxide
2Cu2S + 3O2 2Cu2O + SO2
d. Any cuprous oxide formed above combines with ferrous
sulphide to give black cuprous sulphide and ferrous
oxide. Ferrous oxide thus formed again combines with
silica to form slag( due to greater affinity of iron towards
oxygen than copper). Ferrous oxide thus formed again
combines with silica to form slag.finally, Some Cu2O also
gets reduced to metallic copper by Coke.
 Cu2O + FeS Cu2S + FeO
FeO + SiO2 FeSiO3
Cu2O + C 2Cu + CO
At the end of smelting, two separate layers are formed at the bottom of the furnace. The
upper layer(which is lighter) consist of slag and is removed as waste while the lower
layer consist of molten copper called copper matte ( contains about 50% copper).
Finally the copper matte is poured in cold water and is obtained in granular form.
5. Bessemerization:
The molten matte is mixed with little silica and charged into a Bessemer converter,
Lined internally by basic lining of CaO or MgO. Hot air is blown into the mixture
which converts remaining FeS to FeSiO3.
      2FeS + 3O2     →     2FeO + 2SO2
                        FeO + SiO2     →   FeSiO3 (slag)
The slag is removed and air is passed. The air oxidized Cu 2S partially to Cu2O which
then reduces remaining Cu2S to metallic copper. During this process no external
reducing agent is used so it is an example of self-reduction.
2CuS + 3O2   →    2Cu2O + 2SO2
                        2Cu2O + Cu2S    →   6Cu + SO2
The reaction is highly exothermic and copper obtained is in
molten state. During solidification, SO2 escapes forming
blisters on the surface of metal. This variety of copper
containing about 2% of impurity is blister copper.
6. Refining:
The refining of blister copper is done in following steps:
a. Thermal refining or poling process
In this process, blister copper is melted in the hearth of blast furnace and
stirred with green pole of wood in the presence of air. Any cuprous oxide
formed during the process is reduced back to copper by
hydrocarbon(methane) obtained from green pole of wood.
3Cu2O + CH4 6Cu + CO + 2H2O
copper thus obtained is about 99.5% pure.

b.  Blister copper consists of about 2% of impurities consisting of Sliver, Gold,

Zinc, Nickel etc. It is mostly purified by electrolytic method. A block of
impure copper is anode, a strip of pure copper is cathode while solution of
CuSO4 containing dil H2SO4 is taken as electrolyte. On passing current,
impure copper dissolves and equivalent amount of pure copper is
deposited at cathode. Impurities are collected below anode as anode mud.
 CuSO4 (aq)      →      Cu++ + SO4--
            At cathode: Cu++ + 2e   →     Cu
            At anode:        Cu         →      Cu++ + 2e-
 Chemical properties of copper
1. Action of air:
Dry air has no effect but moist air containing CO2 gas forms a green layer of basic
copper carbonate.
Cu + O2+ CO2 + H2O      CuCO3.Cu(OH)2
                                Moist air                     basic copper carbonate(Malachite)

 On heating in air 9000c, copper forms cupric oxide or black oxide of copper,
4Cu + O2         900               2CuO
Cupric oxide
On further heating above 11000c, copper gives cuprous oxide or red oxide of copper.
4Cu + O2         1100             2Cu2O
2. Action of Acids:
a) With HNO3
dil HNO3 does not react with copper while moderately conc. HNO3 (1:1) is reduced  to
Nitric oxide by copper.
3Cu + 8HNO3                        3Cu (NO3)2 + 2NO + 4H2O
moderately conc.
Hot & Conc. HNO3 is reduced to Nitric oxide by copper.
Cu + 4HNO3                           Cu (NO3)2 + 2NO2 + 2H2O
Hot & conc.
 b) With H2SO4 :
dil. H2SO4  alone does not react but hot dil. H2SO4  in presence of air gives
CuSO4
2Cu + 2H2SO4 + O2                           2CuSO 4+ 2H2O
dil.
 But With hot and conc. H2SO4, Copper gives So2 gas.
Cu + 2H2SO4                          CuSO4 +SO2+2H2O
Hot & conc.
c) With HCl:-
Copper reacts with hot and conc. HCl in presence of air forming cupric
chloride.
2Cu+4HCl+ O2                                   2CuCl2+2H2O
3. Displacement reaction:-
Copper can displace metals lying below the electrochemical series from
their salt solution.
Cu + 2AgNo3                            Cu (No3) 2+ 2Ag
3Cu + 2Aucl3                         3Cucl2 + 2Au
4. Alloy formation:
SN Alloy Composition( %) Uses
1. Brass Cu = 60 - 80 For making
Zn = 20 – 40 utensils,
condenser tube,
tap etc
2. Bronze Cu = 75 - 90 For making
Sn = 10 – 25 cooking utensils,
statues, coins
etc
3. Bell metal Cu = 80 For making bells,
Sn = 20 gongs etc
4. German silver Cu = 25 - 50 for making
Zn = 25 - 35 jewellery,
Ni = 10 – 35 resistance wire
etc.
Chemistry of Blue vitriol / CuSO4.5H2O
Copper sulphate pentahydrate is calleed blue Vitriol. In nepali, it is
commonly called nilo tutho ( नीलो तुथो )
Preparation
1.  It is obtained in lab by dissolving CuO, Cu(OH) 2 or CuCO3 in dil H2SO4. The
solution on heating to crystallization point gives blue triclinic crystals of
CuSO4 5H2O.
CuO + H2SO4                             CuSO4   + H2O
Cu(OH)2 + H2SO4                      CuSO4   +  H2O
CuCO3 + H2SO4                          CuSO4   + H2O + CO2
CuSO4  heating to crystallization point       CuSO4.5H2O
2. It can also be preapared by action of copper with hot and conc H 2SO4
Cu + H2SO4 CuSO4 + 2H2O + SO2

3. In large scale, CuSO4 is obtained by reacting scrap copper with dilute H 2SO4 in
presence of air.
2Cu + 2H2SO4 + O2                         2CuSO4   + H2O
dil.
physical properties
1. Hydrated copper sulphate is blue crystalline solid while anhydrous CuSO 4 is white
amorphous solid
2. It is soluble in water but insoluble in ethyl alcohol
3. Action of heat: following changes occurs when blue vitriol is heated
CuSO4.5H2O air CuSO4.3H2O 100°C CuSO4.H2O 300°C CuSO4(white)
Chemical properties
750°C

1. Action with potassium iodide: CuO +SO2 + O2

When solution of potassium iodide is added to copper sulphate solution, a dark brown
precipitate is formed. This color is due to formation of iodine.
CuSO4 + 4KI Cu2I2 + 2K2SO4 + I2
Dark brown ppt (violet)
2. Complex formation( Action with Ammonia):
when NH3 is added to CuSO4 solution, a bluish white ppt of Cu(OH)2 is formed which
dissolves in excess ammonia forming tetra amine copper (II) sulphate which is known
as Schweizer’s reagent and is used during manufacture of artificial silk.
CuSO4  + 2NH4OH                               Cu(OH)2 + (NH4)2SO4
Bluish white ppt
Cu(OH)2 + 2NH4OH + (NH4)2SO4                                [Cu(NH3)4]SO4 + 4H2O
3. Action with potassium ferrocyanide:
Cupric ions give reddish brown precipitate (chocolate ppt) with potassium
ferrocyanide
2CuSO4 + K4[Fe( CN )6 ] Cu2[Fe(CN)6] + 2K2SO4
4. Action with alkali: (chocolate ppt)

With NaOH solution it gives blueish white ppt of cupric hydroxide is obtained
CuSO4 + 2NaOH Cu(OH) 2 + Na2SO4
blueish white ppt

5. Formation of Double salt

When equimolar solution of potassium sulphate and copper sulphate is mixed with one
another double salt is formed.
CuSO4 + K2SO4 + 6H2O CuSO4.K2SO4.6H2O
Double salt(potassium copper sulphate)
Uses:
1. It is used as electrolyte in purification of copper & electroplating of Copper.
2. It is used in making schweizer’s reagent used for manufacturing of paper.
3. It is used as pesticide in controlling aphids and fungal growth.
4. Anhydrous CuSO4 is used for detection of presence of water traces in organic
compounds.
 Short Questions
1. What is copper matte?
Ans: The mixture of copper sulphide(Cu2S) containing little amount of ferrous
sulphide(FeS) where 50% copper is present and is formed in the hearth of
the blast furnace is called copper matte.
2. What is blister copper?
Ans: When molten copper containing huge amount of sulphur dioxide is
solidified, blister on the surface of metallic copper are formed due to
escaping of SO2 from the molten mass. This mass of copper is called
blister copper and is about 98-99% pure.
3. Give the balance chemical reaction for preparation of black oxide of
copper from blue vitriol.How is black oxide converted into red oxide?
Ans: the balance chemical reaction for preparation of black oxide of copper
from blue vitriol is given below:
 CuSO4.5H2O + 2NaOH Cu(OH)2 + Na2SO4 + 5H2O

CuO + H2O
Also, black oxide of copper can be converted into red oxide of copper by
heating it at 1100°C to 1200 °C.
4CuO 1100°C to 1200 °C.
2Cu2O + O2
4. What happens when NH3 is passed over red hot CuO?
Ans: when ammonia is passed over red hot CuO, the cupric oxide is reduced
to copper.
3CuO + NH3 3Cu + 3H2O + N2