Chapter 5

Chapter : 5 d-BLOCK ELEMENTS
METALLURGY
Metals are found in universe as combined form. These combined forms of metals are called minerals. The
process by which metals can be extracted from their ores is known as metallurgy.
OR
The process involved in the production of pure metals from their ores is known as “metallurgy”.
MINERALS
When metals are found in nature in combined state with other elements, then such substances are called
MINERALS”.
Naturally occurring substances which may obtain from earth crust are called minerals.
ORES
That mineral which is used to extract metals from its combined state (mineral) is called “ORE”.
OR
Ore is that mineral from which the metal can be extracted. Thus all ores are accordingly minerals but all the
minerals are not ores.
GANGUE
Ore generally contains large percentages of rocky and earthy materials which are called “gangue”.
FLUX
The substance which is added to reduce the melting point of other substance is called flux.
ALLOY
When two or more metals mix together in molten form as a result a solid mixture id obtained which is called
alloy.
LIGANDS
An atom or group of atoms can donate lone pair of electrons is called ligand. It is also known as Lewis Base.
Ligands are two different types:
i) Inorganic ligands ii) Organic ligands
i) INORGANIC LIGANDS
Those ligands which have been composed of inorganic materials are called inorganic ligands. They are mono
dentate in nature.
ii) ORGANIC LIGANDS

Those ligands which have been composed of organic materials are called organic ligands. They are bi, tri or
polydentate in nature.
a) MONO DENTATE LIGANDS

That ligand can donate one lone pair of electron is called mono dentate.
e.g. Cl-, Br-, I-, CN-, OH-, NO3-, CO3-2, SO4-2, etc. They are negative mono dentate.
NH3, CO, H2O, etc they are neutral mono dentate.
Address: 31/216, Darakhshan Society, Malir Kalaboard, Behind Nehal Hospital, Karachi. Contact: 03323385161
Page 1 of 9 FROM THE DESK OF Muhammad Adeel
b) BIDENTATE LIGANDS
That ligand can donate two lone pair of electrons is called bidentate.
e.g. OOC __ COO (Oxalate ion) a negative bidentate.
H2N __ CH2 __ CH2 __ NH2 (ethylene diamine or e.n.) a neutral bidentate.
c) TRIDENTATE LIGANDS
That ligand can donate three lone pair of electrons is called tridentate.
e.g. H2N __ CH2 __ CH2 __ NH __ CH2 __ CH2 __ NH2 (diethylene triamine or DETA) a neutral tridentate.
d) POLYDENTATE LIGANDS
That ligand can donate four or more than four lone pair of electrons is called poly dentate or multi dentate.
They are also called chelating agents (Crab’s law).
e.g. (ethylene diamine tetra acetate or EDTA) a neutral polydentate.
CORDINATION NUMBER
The number of attach ligands with the transition element in a complex is called coordination number.
OXIDATION NUMBER
The positive charge present on the transition element in a complex is called oxidation number.
VALENCY
The positive or negative charge present on the complex is called valency or valence number.
COMPLEX ION
The compound which contains d-block transition element with the ligands is called complex ion.
It is positive, negative or neutral in nature. e.g. [ Fe(CN)6 ] +3 , [ Cu (NH3)4 ] – 2 etc.
CHEMISTRY OF COPPER
ORES OF COPPER
In the combined state copper occurs as oxide, sulphide and carbonates.
1. Sulphide ores (a) CuFeS2 Chalcopyrite or copper pyrite

(b) Cu2S Chalcocite or copper glance
2. Carbonate ores (a) CuCO3.Cu(OH)2 Malachite

(b) 2CuCO3.Cu(OH)2 Azurite
3. Oxide ore Cu2O Cuprite
EXTRACTION OF COPPER
Copper is generally extracted from its sulphide ore (CuFeS2). Following are the steps which are involved in the
extraction of Copper.
1. Concentration 2. Roasting 3. Smelting
4. Bessemerization 5. Refining
1. CONCENTRATION
The pyrite ore of copper generally contains sand, clay, limestone etc. as gangue (impurities). The removal of
these impurities is called concentration or ore-dressing. This increases the percentage of metal in ore.
The concentration of sulphide ore of copper is done by froth floatation process in which the crushed ore
is mixed with water and pine oil. Hot air is blown to mix them and froth is formed. The ore particles sticks with
oil and come up to the surface with froth where as impurities remains with water and settle down.
2. ROASTING
The concentrated ore is now heated strongly below its melting point in the excess of air. This is called roasting.
Sulphur is oxidized to SO2 and impurities of arsenous and antimony are removed as volatile oxides
Following reactions take place during roasting.
2CuFeS2 + O2 Cu2S + 2FeS + SO2

S + O2  SO2
4As + 3O2 As2O3
4Sb + 3O2  2Sb2O3
Cuprous sulphide and ferrous sulphide are further oxidized into their oxides.
2Cu2S + 3O2  2Cu2O + 2SO2
2FeS + 3O2 2FeO + 2SO2
3. SMELTING:
The roasted ore is now heated above its melting point and little coke and SiO2 is added. The FeO is removed
with silica in the form of iron silicate as slag.
FeO + SiO2  FeSiO3
Cu2O + FeS  Cu2S + FeO
Now a mixture of Cu2S and FeS is left called matte.
4. BESE-MERIZATION
Copper metal is extracted from molten matte through bessemerization . The matte is introduced in
to Bessemer converter which uphold by tuyers. The air is blown through the molten matte. Blast of
air converts Cu2S partly into Cu2O which reacts with remaining Cu2S to give molten copper.
2Cu2S + 3O2  2Cu2O + 2SO2
2Cu2O + Cu2S 6Cu + SO2
After the reaction is over the molten copper is poured into sand “moulds”
where the solid copper product gets a blister (bubbles) like shape due to
elimination of dissolved SO2, this is called blister copper. It is 98% pure and
contain 2% impurities of iron, zinc, lead, gold etc. it is then refined.
5. REFINING OF COPPER
Crude copper, which is usually obtained by Bese-merization, is not suitable to serve in electrical
applications because impurities greatly reduce the metal's conductivity. Purification of copper is achieved by
electro refining. Large slabs of blister copper serve as the anodes in the cell, and thin sheets of 100% pure
copper serve as the cathodes.
The electrolyte consists of an acidic solution of CuSO4. Application of a suitable voltage to the electrodes causes
oxidation of copper metal at the anode and reduction of Cu2+ to form copper metal at the cathode. This strategy
can be used because copper is both oxidized and reduced more readily than water.
Anode reaction Cu(s)  Cu+2(aq) + 2e–
Cathode reaction Cu (aq) + 2e–  Cu(s)
+2
Impurities fall down at the bottom called Anode mud. The refined copper is 100% pure.
PHOTOGRAPHY
“Photography is a technique used to make pictures by the action of light on chemically active surfaces”.
Photography involves the following steps.

1. PREPARATION OF PHOTOGRAPHIC FILM
A typical photographic film contains tiny crystals of very slightly soluble silver halide salts such as silver
bromide (AgBr) commonly called "grains." The grains are suspended in a gelatin matrix and the resulting
gelatin dispersion is called an "emulsion". It is melted and applied as a thin coating on a cellulose acetate sheet.
2. EXPOSURE
When photographic plate is exposed to light for a short time in camera several free silver atoms are
formed such as Ag20, Ag30 and Ag40. The free silver produces a "latent image". This latent image is not yet visible
to the eye and is later amplified by the development process.
3. DEVELOPER
The exposed film is dipped in a developing bath containing reducing agents like “pyrogallol” or
“hydroquinone” etc. They are called developers. The developers penetrate the gelatin and reduce the sensitized
silver atoms completely. The deposit of free silver produces a dark area in that section of the film. The
developer under the same conditions does not affect the unexposed grains.
C6H4(OH)2 + 2AgBr  C6H4O2 + 2Ag + 2HBr

Since the brightest part of the object appears blackest in the developed image, it is called a negative.
4. FIXING
The negative is immersed in a solution of “Sodium thiosulphate” called “Hypo”. This solution is called
fixer and it removes the undeveloped silver halide from the film by making a soluble complex ion.
2AgBr + 2Na2S2O3  [Ag(S2O3)3] – 3(aq) + 4Na+ + Br-
After fixing, film is washed thoroughly.
5. POSITIVE PRINTING
The positive printing is repetition of negative preparation. The printing paper is coated with an
emulsion of silver bromide and silver iodide in gelatin. An artificial light is passed through the negative on to
the printing paper; an invisible image (latent image) is made on it. It is developed and fixed to get positive
image.
ALLOY
When two or more metals mix together in molten form as a result a solid mixture id obtained which is called
alloy.
STAINLESS STEEL
The term stainless steel is used to those iron – based alloys which show resistance to corrosion. They are
formed by the addition of chromium or chromium and nickel in steel.
There are three main types of stainless steel which have different percentages of base metals and are listed
below:
 Stainless steel containing 13% Cr and 0.1 to 0.4% C.

 Stainless steel containing 17% Cr and 2% Ni and
 Stainless steel containing 18% Cr and 6% Ni
All the types of stainless steel are corrosion resistant alloys and are oxidizable only to such a slight degree that
a very fine film of oxide is formed on the material surface which resists further corrosion. This fine coating of
oxide is so thin that the colour and appearance of the basic material look like unchanged.
Stainless steel is used in the production of house hold utensils, cutlery, articles for decoration and its
application in industry is unlimited.
CORROSION
“The harmful and an undesirable reaction of a metal material as a result of exposure to atmosphere or any
chemical agent are called corrosion.”
When metal is corroded by the action of atmosphere, it is called atmospheric corrosion and when corrosion is
due to the action of a liquid on a metal, it is termed as corrosion in liquid. Different metals corrode at different
rates. For example, sodium and potassium metals tarnish immediately on exposure to air, calcium corrodes
quickly, iron corrodes slowly and tin, lead and copper corrode very slowly.
CORROSION OF IRON
The most familiar example of corrosion is the rusting of iron, a complex chemical reaction in which the iron
combines with both oxygen and water to form hydrated iron oxide (Fe2O3.xH2O). This brown deposit (rust) is
porous and if it is not prevented the whole metal is destroyed.
PREVENTION FROM CORROSION

Following are some methods used for the prevention of corrosion on the metal surface.
(I) PROTECTIVE METALLIC COATING:

A metal can be protected by corrosion by coating it with a thin protective layer of some other metal.
Coating with a layer of zinc is called “galvanizing”. Galvanized iron is used in making car bodies. Coating with a
layer of tin is called “tin plating”. It is used in food & drink cans. Chromium plating is used in pipes and
ornamental work.
(ii) ELECTROPLATING:
Noble and bare metals are used for electroplating on any desired metal.
(iii) ALLOYING OF METALS:

One of the most important way of protection of a metal from corrosion is by mixing of it with another metal i.e.,
alloy formation e.g., stainless steel is an alloy of Fe, Cr and Ni.
(iv) COATING WITH NON – METALLIC MATERIAL:
Metals can be protected from corrosion by using various kinds of non–metallic materials such as paints, oils,
grease, plastic emulsion etc.
TIN PLATING
DEFINITION
“Applying a coating of tin to thin steel sheet either by dipping in molten metal or by electrolytic deposition
(electroplating) is called Tin plating”
PURPOSES:
Tin plated iron sheets are used for making all types of food containers such as oil container and drink cans. The
household utensils of copper and brass are protected from poisoning by tin plating.
METHODS OF TIN-PLALTING:
Following are the well known method of tin plating:
1 Mechanical method 2 Electrolytic method 3 Classical method
1. MECHANICAL METHOD:
In this method the iron sheet are cleaned thoroughly by dipping in warm diluted sulphuric acid to
remove oxide film. The sheets are then washed with water and after drying, dipped in the bath containing
molten tin. The superfluous tin is removed by rolling the sheets.
2. ELECTROLYTIC METHOD:
In this method the iron sheet are cleaned and suspended into a bath containing a mixture of stannous
chloride and hydrochloric acid. Pure tin is made anode and the iron sheets are made the cathode. Tin deposits
on the iron sheets through passing the current.
3. CLASSICAL METHOD:
In this method tin-plating is done by means of a rag (cloth). Before coating with tin, the utensils are
heated and rubbed with ammonium chloride to remove the oxide film from the utensils.
SILVERING OF MIRROR
DEFINITION:
“The coating of a glass plate with silver particles to make it a mirror is called silvering of mirror.”
PRINCIPLE:
Ammonical silver nitrate (Tollen’s reagent) reduces easily by a compound containing aldehydic group
(reducing group). Like glucose.
PREPARATION OF SOLUTION:
Prepare the solution of AgNO3 in distilled water and add Ammonium hydroxide drop wise. The silver nitrate
solution will turn a brown colour. Stir constantly, adding the ammonium hydroxide drop wise till the solution
becomes clear.
Prepare the solution of glucose.(reducing sugar)
PROCEDURE:
Wash the glass plate with detergent solution at room temperature. Rinse completely.
Swab the surface of glass with acetone and apply nitric acid on the surface and rinse with distilled water
thoroughly. Now the glass plate is chemically clean and grease free.
Pour the main solution onto the mirror surface. The solution will continue to change in appearance. It will
become dark brown.
After some time (8 to 10 min) Silver will deposit on the surface. Pour the solution out and rinse with plenty of
water.
The silver film is coated with copal varnish and finally painted with some paint.
SILVER NITRATE (AgNO3)

Silver nitrate or Lunar caustic is prepared by dissolving silver metal in dilute nitric acid. On crystallization, the
long crystals or sticks are formed.
3Ag + 4HNO3   3AgNO3 + NO + 2H2O
Silver nitrate is readily soluble in water. It is also soluble in organic solvents such as, ethyl alcohol, pyridine etc.
It decomposes at 450oC, giving out nitrogen dioxide and oxygen leaving silver as metal.
450o C
2AgNO3  2Ag + 2NO2 + O2
With sodium hydroxide (NaOH), silver nitrate first forms unstable silver hydroxide (AgOH) which changes into
a dark brown silver oxide (Ag2O).
AgNO3 + NaOH 
 AgOH + NaNO3
2AgOH 
 Ag2O + H2O
With ammonia in water, silver nitrate fist forms precipitates of silver oxide which in excess dissolves forming
silver – ammonia complex (Diammine silver nitrate).
AgNO3 + 2NH3   [Ag(NH3)2]NO3
Diamine silver nitrate
Silver nitrate produces black spots when it comes in contact with organic substances such as skin and cellulose.
Silver nitrate is used in laboratory as a reagent for the detection of halides. It produces white precipitates of
AgCl with chloride ions(Cl-), light yellow precipitates of AgBr with bromide ions (Br-) and yellow precipitates of
AgI with iodide ions (I-).
It is also widely used in photography and medicines.
COPPER SULPHATE (CUSO4 5H2O)
Cupric sulphate or copper sulphate which is also called blue vitriol or blue stone, is prepared by reacting
metallic copper with dilute sulphuric acid in the presence of air.
2Cu + 2H2SO4 + O2 
 2CuSO4 + 2H2O
It is also prepared by dissolving copper oxide (CuO) or copper carbonate (CuCO3) in dilute sulphuric acid and
crystallizing.
CuO + H2SO4 
 CuSO4 + H2O
CuCO3 + H2SO4 
 CuSO4 + CO2 + H2O
Copper sulphate crystalline is blue in colour which on heating loses all its water of crystallization slowly
changing into colourless form (anhydrous).
230o C
CuSO4 . 5H2O  CuSO4 + 5H2O
Blue (hydrated) White(anhydrous)
Copper sulphate is very soluble in water but insoluble in alcohol and is precipitated in small crystals from its
aqueous solutions by the addition of ethyl alcohol.
It liberates iodine precipitating white cuprous iodide (Cu2I2) on addition to potassium iodide solution.
2CuSO4 + 4KI   Cu2I2 + 2K2SO4 + I2
With aqueous ammonia, copper sulphate forms a pale blue gelatinous precipitate of cupric hydroxide
[Cu(OH)2], the latter dissolves very readily in excess aqueous ammonia (NH4OH), forming the deep – blue
complex Cu(NH3)4.
CuSO4 + 2NH3 + 2H2O 

 Cu(OH)2 + (NH4)2SO4
small
CuSO4 + 4NH3  [Cu(NH3)4]SO4

excess
Copper sulphate is used in copper plating, in electric cells, in making green pigments, as a mordant in dyeing
and with milk of lime to kill fungus and molds.
POTASSIUM CHROMATE (K2CrO4)

Potassium chromate can be prepared by strongly heating a mixture of powdered chromite ore (FeO.Cr2O3) and
potassium carbonate in air.
4FeO.Cr2O3 + 8K2CO3 + 7O2   2Fe2O3 + 8K2CrO4 + 8CO2
It can also be prepared by boiling chromium oxide with potassium hydroxide and bromine water when a yellow
solution of potassium chromate is formed. It is then crystallized out on evaporation.
Cr2O3 + 10KOH + 3Br2 
 2K2CrO4 + 6KBr + 5H2O
Potassium chromate is a lemon – yellow crystalline solids substance. It is very soluble in water and gives a
yellow coloured solution. The yellow colour of the potassium chromate solution changes into red on addition of

an acid such as sulphuric acid due to the formation of dichromate ion. Cr2 O72 . 
2  2
CrO 4  2H Cr2O 7  H 2O
Chromate in Dichromate ion
POTASSIUM DICHROMATE (K2Cr2O7)
Potassium dichromate is prepared from potassium chromate (K2CrO4) by adding a calculated amount of
sulphuric acid into its saturated solution. It is then crystallized out on evaporation.
2K2CrO4 + H2SO4 
 K2Cr2O7 + K2SO4 + H2O
It can also be prepared by treating the saturated solution of sodium dichromate with the calculated quantity of
potassium chloride. Potassium dichromate being less soluble separates out from the solution as orange – red
crystals.
Na2Cr2O7 + 2KCl 
 2NaCl + K2Cr2O7
Potassium dichromate is moderately soluble in water and gives an orange colour in solution. The colour
changes to yellow on the addition of an alkali due to the formation of potassium chromate.
K2Cr2O7 + 2KOH 
 2K2CrO4 + H2O
On addition of conc. H2SO4 to the cold solution of potassium dichromate, red crystals of chromic oxide (CrO3)
separate out.
K2Cr2O7 + 2H2SO4   2KHSO4 + 2CrO3 + H2O
USES:
Potassium dichromate is used as a powerful oxidizing agent in the volumetric determination of ferrous
iron, in preparation of chromium compounds such as chrome alum, chrome yellow, chrome red etc., which are
used as pigments and in the preparation of certain organic compounds such as acetaldehyde and ethyl alcohol.
POTASSIUM PERMANGANATE (KMnO4)
Potassium permanganate is prepared on large scale from manganese dioxide (MnO2). Manganese dioxide is
fused with potassium hydroxide in the presence of air to produce the green coloured potassium manganate
(K2MnO4).
2MnO2 + 4KOH + O2 
 2K2MnO4 + 2H2O
Potassium manganate is extracted with water and the solution is treated either with chlorine or ozone to get
the oxidized product potassium permanganate.
2K2MnO4 + Cl2 
 2KMnO4 + 2KCl
2K2MnO4 + H2O + O3 
 2KMnO4 + 2KOH + + O2
Potassium permanganate can also be prepared from potassium manganate by electrolytic oxidation.
2K2MnO4 + 2H2O   2KMnO4 + 2KOH + H2
Potassium permanganate is the most important chemical compound of manganese. It is a deep purple
crystalline solid and is readily soluble in water giving deep pink colour. On heating, it liberates oxygen and
forms potassium manganate and manganese dioxide.
2KMnO4   K2MnO4 + MnO2 + O2
In neutral or alkaline medium permanganate oxidizes potassium iodide to potassium iodate (KlO3) and
hydrogen peroxide to oxygen and itself reduces to manganese dioxide.
2KMnO4 + H2O + Kl  
 2KOH + 2MnO2 + KIO3
Alkaline
medium
2KMnO4 + 3H2O2  2MnO2 + 2KOH + 3O2 + 2H2O

Neutral
medium
USES:
Potassium permanganate is used as an oxidizing agent and as a disinfectant.

Chapter 5

Hochgeladen von

Dokumentinformationen

Originaltitel

Copyright

Verfügbare Formate

Dieses Dokument teilen

Dokument teilen oder einbetten

Freigabeoptionen

Stufen Sie dieses Dokument als nützlich ein?

Sind diese Inhalte unangemessen?

Copyright:

Verfügbare Formate

Chapter 5

Hochgeladen von

Copyright:

Verfügbare Formate

Chapter : 5 d-BLOCK ELEMENTS

ii) ORGANIC LIGANDS

a) MONO DENTATE LIGANDS

1. Sulphide ores (a) CuFeS2 Chalcopyrite or copper pyrite

2. Carbonate ores (a) CuCO3.Cu(OH)2 Malachite

3. Oxide ore Cu2O Cuprite

2CuFeS2 + O2 Cu2S + 2FeS + SO2

Photography involves the following steps.

C6H4(OH)2 + 2AgBr  C6H4O2 + 2Ag + 2HBr

 Stainless steel containing 13% Cr and 0.1 to 0.4% C.

PREVENTION FROM CORROSION

(I) PROTECTIVE METALLIC COATING:

(iii) ALLOYING OF METALS:

SILVER NITRATE (AgNO3)

It is also widely used in photography and medicines.

COPPER SULPHATE (CUSO4 5H2O)

CuSO4 + 2NH3 + 2H2O 

CuSO4 + 4NH3  [Cu(NH3)4]SO4

POTASSIUM CHROMATE (K2CrO4)

POTASSIUM DICHROMATE (K2Cr2O7)

POTASSIUM PERMANGANATE (KMnO4)

2KMnO4 + 3H2O2  2MnO2 + 2KOH + 3O2 + 2H2O

Das könnte Ihnen auch gefallen