Chapter 4 and 5

Asfand Yar
 d-block elements:
• Those elements in which valence electron enters in (n-1) d orbital are called d
block elements.
• They are also called outer transition elements.
• They are located between s and p block elements.
• Their valence shell electronic configuration is ns2,(n-1)d1-ns2,(n-1)d10.
• In periodic table four series of these elements are present.
• Each series contain ten (10) elements except 4th series which is incomplete.
 f-block elements:
• Those elements in which valence electron enters in (n-2) f orbital are called f
block elements.
• They are also called inner transition elements or rare earth metals.
• In periodic table two series of these elements are present:
• i) Lanthanides ii) Actinides
 GENERAL PROPERTIES OF THE TRASNTITION
ELEMENTS:
i. All are metals and are ductile
ii. They are britle hard and have high melting and boiling point
iii. Their heats of vapourization are greater than non-transition metals
iv. Their ions and compounds are often coloured due to unpaired electrons.
v. They form many complex ion.
vi. they show multiple oxidation states although exception are there
vii.many of them are paramagnetic
viii.many of the metals or their compounds are good catalysts
ix. they form alloys.
x. They are good conductor.
 General Characteristics:
• 1- Electronic configuration:
• The electronic configuration of first series of d block elements is given
below:
• * The difference is observed in 3d orbital of penultimate shell, while the
outer most shell (4s) remains same, except Cr and Cu.
• In Cr and Cu one electron jump from 4s orbital to 3d orbital to gain more
stability.
Element Symbol ‘Z’ Electronic configuration
Scandium Sc 21 1s2,2s2,2p6,3s2,3p6,4s2,3d1
Titanium Ti 22 1s2,2s2,2p6,3s2,3p6,4s2,3d2
Vanadium V 23 1s2,2s2,2p6,3s2,3p6,4s2,3d3
Chromium Cr 24 1s2,2s2,2p6,3s2,3p6,4s1,3d5
Manganese Mn 25 1s2,2s2,2p6,3s2,3p6,4s2,3d5
Iron Fe 26 1s2,2s2,2p6,3s2,3p6,4s2,3d6
Cobalt Co 27 1s2,2s2,2p6,3s2,3p6,4s2,3d7
Nickel Ni 28 1s2,2s2,2p6,3s2,3p6,4s2,3d8
Copper Cu 29 1s2,2s2,2p6,3s2,3p6,4s1,3d10
Zinc Zn 30 1s2,2s2,2p6,3s2,3p6,4s2,3d10
 2-ATOMIC SIZE:
• From Sc to Zn atomic size decreases due to the increase in nuclear attraction
without increase in number of shells.
• 3- Ionization Potential:
• The ionization potential values of d-block elements are higher than s-block
elements and lower than p-block elements. Due to this reason they may form
either ionic or covalent compounds. Generally their compounds are ionic in
their lower oxidation state and covalent in higher oxidation states.
 4- Melting and Boiling Points:
M.P & B.P point of transition elements are high, except Zn, it is due to the
following factors:
i. small atomic size which have strong inter atomic attraction.
ii. valance electrons available for interaction.
Melting point of Zinc is low due to the completely filled d orbital.
 5- Variable Oxidation States:
• The transition elements shows variable oxidation states in their compounds
except Zn which has a fix oxidation number, i.e. +2.
• This is due to the very small energy difference between 4s and 3d orbitals
due to which electrons of both orbitals take part in the bond formation. The
highest oxidation state is shown by Mn, i.e. +7.
 6-MAGNETIC PROPERTIES:

• Many transition elements and their compounds are paramagnetic, i.e, they are
attracted into a magnetic field. The paramagnetism is due the presence of
unpaired electronic spin in the ions and atoms of the element. For example Cr,
Mn, etc.
• Some transition elements are diamagnetic, i.e, they do not attracted into magnetic
field. The diamagnetism is due to the presence of paired electronic spin in the ions
and atoms of the element. For example: Zn.
• Elements such as Fe, Co and Ni are ferromagnetic, i.e, they can be magnetized.
The ferromagnetism is due to the presence of pair and unpaired electrons.
 7- Catalytic Properties:
• Transition elements and their compounds are commonly used as
catalyst in chemical industries. This is because they may form
unstable intermediate compounds which immediately converted
into product or provide a suitable surface area where gases are
absorbed.
• For example: Ni is used as catalyst for hydrogenation of
vegetable oils into ghee, Fe is used in Haber’s process and V2O5
in contact process.
 8-INTERSTITIAL COMPOUNDS:
• The transition elements form special type of compounds with indefinite
composition and structure known as interstitial or non-stoichiometric
compounds. This is because of variable oxidation state and defects in their
solid structures. Therefore small atoms such as H, C, B and N can reside
with in the holes present in the crystal lattice of these elements.
For example: TiH1.73
Alloys are also considered as non stoichiometric compounds. Examples are
brass (Cu-Zn), bronze (Cu-Zn-Sn) etc.
 9- Complex formation:
• The transition elements form co-ordination compounds which are also
known as complexes. This is due to small highly charge ions and vacant d-
orbitals of suitable energy. These vacant d-orbitals accept lone pairs of
electron from ligands.
• For example: [Fe (CN)6]4-
• 10- Transition metal complexes:
• A compound containing the complex ion or molecule in which the central
atom or ion is surrounded by a number of ligands is called Complex.
 11- Colour:
• Many transition metal complex ions are coloured. Crystal field theory
(CFT) fully explain the colour formation. According to this theory the
bonding between ligands and a metal ion is electrostatic. The ligands
surrounding the metal ion create an electrostatic field around its d-orbitals
this field splits five degenerated d-orbitals into two sets with different
energies.
i) A higher energy pair dx2y2 and dz2 designated as eg
ii) A lower energy trio, dxy, dyz and dzx, designated as t2g
• The energy difference between these energy sets is denoted by ∆◦.
• In many cases, the energy difference ▲0 between two sets of d-orbitals is
equivalent to a wave length in to visible region. Thus by absorbing visible
light, an electron may be able to move from lower energy set (t2g) to higher
energy set (eg) of d-orbitals. In doing so, some of the component wave
length of white light is removed, so the remaining component wave length
of the light transmitted shows the colour to the viewers. For example Cu2+
ion absorb red light, hence transmitted light gives blue colour.
 Ligands:
• An ion or molecule which donate electron pair to central atom in a
coordination sphere to form complex is called Ligand.
• They are also called Lewis bases.
• Ligands are either negative or neutral.
• For example: NH3, H2O, Cl-, OH- etc.
 Classification:
• Monodentate Ligands:
• Ligands which can donate only one electron pair to central atom in a
complex are called monodentate ligands.
• They are also called Unidentate Ligands.
• For example: NH3, H2O, Cl-, OH- etc.
• Polydentate Ligands:
• Ligands which can donate more than one electron pair to central atom in a complex
are called polydentate ligands.
• They are also called multidentate Ligands.
• Bidenate Ligands:
• Ligands which can donate two electron pairs to central atom in a complex are called
bidentate ligands.
• For example: C2O4-2 (oxalate), NH2-CH2-CH2-NH2 (Ethylenediamine) etc.
• Tridenate Ligands:
• Ligands which can donate three electron pairs to central atom in a complex are
called tridentate ligands.
• For example: NH2-CH2-CH2-NH-CH2-CH2-NH2 (diethylene triamine).
• Hexadenate Ligands:
• Ligands which can donate six electron pairs to central atom in a complex are called
hexadentate ligands.
• For example: EDTA(Ethylene diamine tetraacetate)
 IUPAC Naming of Coordination
Compounds(Complexes):
• Rules:
• 1- Name the cation before anion just like ionic compounds.
• 2- In the naming of complex ion name of ligand is written before the name of
metal.
• 3- If two or more identical ligands are present in a complex then prefix di, tri, tetra
etc. are used.
• 4- In case of polydentate ligands prefix bis, tris, tetrakis etc. are used.
• 5- If two different ligands are present in a complex then name of negative ligand is
written before the name of neutral ligand.
• 6- Oxidation number of metal is written in roman after the name of metal.
• 7- Name of negative ligand is ends with suffix –o-.
• 8- In case of anionic complex suffix ate is added with the Latin name of metal.
• Fe=Iron=Ferrum=ferrate
• Ag=Silver=Argentum=argentate
• Au=Gold=Aurum=aurate
• Cu=Copper=Cuperum=cuperate
Ligand Name in Complex Ligand Name in Complex
Cl- Chloro O-2 Oxo
Br- Bromo C2O4-2 Oxalato
OH- Hydroxo CO3-2 Carbonato
CN- Cyano SO4-2 Sulphato
NH2- Amido S2O3-2 Thiosulphato
SCN- Thiocyano NH3 Ammine
NCS- Isothiocyano H2O Aqua
NO2- Nitro CO Carbonyl
NO3- Nitrato NO Nitrosyl
CH3COO- Acetato NH2-CH2-CH2-NH2 (en) Ethylenediamine
 COMPLEXES:
•K4 [Fe(CN)6]
•Na3 [Co(NO2)6]
•[Cr (NH3)3 Cl3]
•[Co (H2O)6] SO4
•[Cu(NH3)4]SO4
•K[MnO4]
•[AuCl4]-
[Co(NH3)5Cl] (NO3)2
Pentamminechlorocobalt(III)nitrate
•[Co (NH3)6]–3
Hexamminecobaltate(III)ion
•NH4 [Cr (NCS)4 (NH3)2]
Ammoniumdiamminetetraisothiocyanochromate(III)
•Na2 [Zn (OH)4]
SodiumtetrahydroxoZincate(II)
•[Co (en)3 ]Cl3
Tris(ethylenediammine)cobalt(III)chloride
 IMPORTANT ORES OF COPPER
• Copper pyrite or chalcopyrite (CuFeS2).
• Chalocite (Cu2S) or copper glance.
• Malachite green [CuCO3.Cu(OH)2].
• Azurite blue [2CuCO3.Cu(OH)2].
• Bornite (3Cu2S.Fe2S3) or peacock ore.
• Melaconite (CuO)
 EXTRACTION OF COPPER FROM
SULPHIDE ORE
• Large amount of copper are obtained from copper pyrite (CuFeS2).
• It contain about 6% of Cu.
• CRUSHING AND CONCENTRATION:
• The ore obtained from mines are broken down into small piece by jaw crusher and then pulverized. The ore being sulphide ore is concentrated
by froth floatation process. Pulverized ore is kept in water containing pine oil and the mixture is agitated by passing compressed air. Ore forms
froth with pine oil and comes to the surface and is skimmed off while impurities are left in water.
• ROASTING:
• Ore is roasted in a furnace in the presence of a current of air and following changes are occur:
1. large amount of sulphur burns to SO2
2. Iron and other impurities oxidize to form volatile oxides with O2.
3. Cu changes to Cu2S.
2CuFeS2 + 4O2 ------> Cu2S + 2FeO + 3SO2
 SMELTING
• The roasted ore is mixed with coke and silica (sand) SiO2 to remove iron as ferrous
silicate.(FeSiO3).
• FeSiO3 form a slag(Slag is the by-product left over after a desired metal has been
separated from its raw ore.It is usually a mixture of metal oxides and silicon
dioxide.) which float over the surface of molten copper matte(Matte is a term used
in the field of metallurgy given to the molten metal sulfide phases typically formed
during smelting of copper, nickel, and other base metals). containing Cu2S with
some un reacted ferrous sulphide (FeS).
• * (Smelting=its main use is to produce a base metal from its ore by heating or by
using chemical)
 BESSEMERIZATION
• Copper metal is extracted from molten matte through bessemerization. The matte is introduced in to Bessemer
converter.
• The air is blown through the molten matte.
• FeS oxidize to FeO and SO2.
• FeO reacts with sand to form FeSiO3.
• blast of air partly convert Cu2S into Cu2O which reacts with remaining Cu2S to give metallic copper in its molten
state.
• 2FeS + 3O2 ---->2FeO + 2SO2
• FeO + SiO2 --------> FeSiO3
• 2Cu2S + 3O2 ------> 2Cu2O + 2SO2
• 2Cu2O + Cu2S ------> 6Cu + SO2.
• The copper so obtained is called "Blister copper" because, as it solidifies, SO2 hidden in it escapes out producing
blister on its surface.
 IMPURITIES IN BLISTER COPPER AND
THEIR EFFECTS
• Blister copper is 99% pure. It contains impurities mainly iron but little
amount of As, Zn, Pb, Ag and Au may also be present.
• These impurities adversely affect the electrical as well as mechanical
properties of copper. Therefore, they must be removed.
 REFINING OF COPPER
• Blister copper is refined by electrolysis.
• Blocks of blister copper are used as anodes and thin sheets of pure copper act as
cathodes.
• The cathode plates are coated with graphite in order to remove depositing copper.
• The electrolyte is copper sulphate (CuSO4) mixed with a little amount of H2SO4 to
increase the electrical conductivity.
• Optimum potential difference is 1.3 volt for this electrolytic process.
• During electrolysis, pure copper is deposited on the cathode plates and impurities
which are soluble and fall to the bottom of the cell.
ELECTROCHEMICAL CHANGES DURING ELECTROLYSIS

• Cu --->Cu2+ + 2e-(at the anode)

Cu2+ +2e- --->Cu (at the cathode)
• This electrically refined copper is 100% pure.
Electrolytic Cell
 SILVERING OF MIRROR:
• To deposit a coating of pure silver on a glass sheet or a glass plate is called silvering
of mirror.
• Silvering process converts a plane glass sheet into a mirror.
• This process was originated by Liebig in 1938.
• THEORY OF SILVERING PROCESS
• Ammonical silver nitrate is a mild oxidizing agent.
• Its ion, [Ag(NH3)2]+ can oxidize many compounds such as aldehydes and a layer of
pure 'Ag' is deposited on the glass surface. In the process Ag+ ions are reduced to
Ag metal.
 METHOD OF SILVERING OF MIRROR

• Clear the glass sheet to remove any stain or oily materials. Cleaning is done with
ammonia solution.
• Prepare aqueous solution of AgNO3.
• Dilute this solution with ammonium hydroxide solution slowly until brown ppt of
silver oxide is redissolved.
• AgNO3 + NH4OH ---> AgOH + NH4NO3
• AgOH + 2NH4OH ---> [Ag(NH3)2]OH + 2H2O
• 2[Ag(NH3)2]OH ---> Ag2O + H2O + 4NH3
To this solution add glucose(reducing agent) and immediately pour the
solution on the glass sheet to be silvered. It spreads over the surface glass
sheet. The reduction begins and 'Ag' is deposited on the glass sheet and a
brilliant mirror is formed.
 Stainless Steel
• Stainless steel is an alloy of iron with some other metals such as Ni, Cr and a
non-metal carbon.
• Percentage of carbon in steel is 0.1% to 2.0%.
• Stainless steel has high resistance against corrosion.
• Percentage of Ni, Cr and C varies depending upon the use of steel.
• They are oxidizable to a very slight degree that a very thin film is formed on
its surface which resists further corrosion.
 Types of Stainless Steel
• Stainless steel containing 13% Cr, 0.1% to 0.4% C.
• Stainless steel containing 17% Cr, 2% Ni.
• Stainless steel containing 18% Cr, 6% Ni.
• Uses of Stainless Steel
• Utensils, cutlery, decoration items, automobile parts, machine tools, surgical
instruments, boiler components and unlimited applications in heavy
mechanical and light mechanical industries.
PHOTOGRAPHY
PHOTOGRAPHY
 5. CORROSION AND ITS PREVENTION:

• The harmful and an undesirable reaction of metal material as a result of

exposure to atmosphere or any chemical agent is known as corrosion.
• Almost all the metals undergoes corrosion except noble metals. (Ag, Au, Pt
etc.)
• Rate of corrosion is different in different metals depends upon their
reactivity.
• Alkali metals rapidly corrodes, while transition metals corrode slowly.
 Examples:
 Iron acquires brown flaky surface called rust.
 Copper surfaces become covered with a layer of green coloured substances.
 Cells of zinc get white powder deposits on their surface.
Types of Corrosion:
 When corrosion in a metal is due to the action of atmosphere, it is known as
atmospheric corrosion.
 When corrosion is due to the reaction of a liquid (like water) on a metal, it is
known as corrosion in liquid.
 Methods of Prevention:
 Protective Metal Coating:
• Iron or steel can be protected from corrosion by coating with another metal as in galvanized iron
i.e., covering with zinc, tin plating.
 Electroplating:
• Noble and bare metals are used for electroplating on any desired metal.
 Alloying of Metals:
• A metal can be protected from corrosion by mixing it with another metal i.e., alloy formation.
For example, stainless steel is an alloy of Fe, Cr and Ni.
 Coating with Non-metallic Material:
• Metal can be protected from corrosion by using various kinds of non-metallic materials such as
paints, oils, grease, plastic emulsion, etc.
 CHEMISTRY OF COPPER SULPHATE
(BLUE VITRIOL)
• The chemical formula of copper sulphate is ‘CuSO4.5H2O’. It is also called
‘Blue vitriol’ or ‘Blue stone’.
• Preparation:
• On commercial scale, copper sulphate is prepared by reacting metallic copper
metal with dilute sulphuric acid in presence of air.
• 2Cu + 2H2SO4 + O2  2CuSO4 + 2H2O
• In laboratory, copper sulphate is prepared by dissolving copper oxide or
copper carbonate in dilute sulphuric acid.
• CuO + H2SO4  CuSO4 + H2
• CuCO3 + H2SO4  CuSO4 + H2O + CO2
 (i)

Properties:
• Blue vitriol when heated at 230◦C in a current of dry air, it loses molecules
of water of crystallization and changes into anhydrous and white crystals
of CuSO4.
• CuSO4.5H2O  CuSO4 + 5H2O
• On adding KI, if gives ppt of cuprous iodide.
• 2CuSO4 + 4KI  Cu2I2 + I2+ 2K2SO4.
• When it reacts with small amount of ammonia, gelatinous blue precipitates of
cupric hydroxide are formed.
• CuSO4 + NH3 + 2H2O  Cu(OH)2 + (NH4)2SO4
• When it reacts with excess aqueous ammonia it form soluble blue complex.
• CuSO4 + 4NH3  [Cu(NH3)4]SO4
• Uses:
 It is used in copper plating and electric cell.
 It is used as a fungicide and insecticide.
 It is used in making of green pigments.
 It is used as mordant in dyeing.
 Potassium Chromate:
• The formula of potassium chromate is K2CrO4 and it is an oxidizing agent.
• Preparation:
• It is prepared by heating a mixture of powdered chromite ore 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.
• Cr2O3 + 10KOH + 3Br2  2K2CrO4 + 6KBr + 5H2O
• It is soluble in water and gives a yellow colour solution. On addition of an acid it is
converted into red solution due to the formation of dichromate ion.
• 2CrO42- + 2H+  Cr2O7-2 + H2O.
 Important Definitions:
• CO-ORDINATION NUMBER:
• The number of ligands bonded or the number of lone pairs surrounding to the central
metal atom or ion is called co-ordination number of metal.
• CHELATES: (Greek word meaning Crab’s claw)
• The chelating agents on co-ordination with a central metal atom or ion forms a ring
structure called chelates.
• CHELATING AGENT:
• The polydentate ligands are called as Chelating Agents.
 Important Reasons:
 Hydrated copper sulphate (CuSO4. 5H2O) is blue, while anhydrous copper sulphate (CuSO4)
is white.
• Hydrated copper sulphate contains five molecules of crystallization and water act as ligand. The lone
pair of electron of water molecule influences the electrons in 3d orbitals of Cu causing a splitting in
3d orbitals into t2g and eg. Thus by absorbing visible light, an electron moves from t2g to eg. In doing
so, the red component wavelength of white light is removed, so the remaining component shows the
blue colour. On the other hand, anhydrous copper sulphate is white due to the absence of ligand
(H2O) and presence of degenerate d-orbitals hence, movement electron is not possible.
•
 H2O and NH3 are ligands but H3O+ and NH4+ cannot behave as ligands.
• Ligands are Lewis bases which can donate one or more electron pair. Since, H2O and NH3 contain
lone pairs and can donate their lone pair of electrons therefore they can act as ligands. On the other
hand oxygen and nitrogen of H3O+ and NH4+ already donated their lone pairs due to this reason
they cannot behave as ligands.
 P-block Elements:
• Elements in which valence electron enters in p orbital are called p block
elements.
• Elements from III-A to VIII-A are included in p block except Helium.
• Their valence shell configuration is ns2,np1-ns2,np6.
• Total 30 elements are included in p block.
• 20 are non metals and 10 are metals.
• 20 are solids, 9 gases and 1 liquid.
 Industrial Preparation of NITRIC ACID
• On industrial scale, nitric acid can be prepared by the following methods.
(a) CHILLI-SALT PETER's METHOD: By NaNO3
(b) BRIKLAND-EYDE's METHOD: By using air
(c) OSTWALD' s METHOD : By ammonia

54
 OSTWALD'S METHOD

Materials used:
Ammonia gas
Water
Oxygen gas
CATALYST
Platinum
55
 First step
PRIMARY OXIDATION (formation of nitric oxide)
Oxidation of ammonia is carried out in a catalyst chamber in which one part of ammonia and
eight parts of oxygen by volume are introduced. The temperature of chamber is about 600oC.
This chamber contain a platinum gauze which serves as catalyst.

CHEMISTRY OF PRIMARY OXIDATION

Oxidization of ammonia is reversible and exothermic process. Therefore according to Le-

chatelier's principle.,a decrease in temperature favour reaction in forward direction. In primary
oxidization 95% of ammonia is converted into nitric oxide (NO).
56
 Second step
SECONDARY OXIDATION (formation of nitrogen dioxide)
Nitric oxide gas obtain by the oxidation of ammonia is very hot. In order to
reduce its temperature , it is passed through a heat exchanger where the
temperature of nitric oxide is reduce to 150oC. Nitric oxide after cooling is
transferred to another oxidizing tower where at about 50oC it is oxidize to
NO2.

57
 Third step
ABSORPTION OF NO2 (formation of HNO3)
• Nitrogen dioxide from secondary oxidation chamber is introduced into a
special absorption tower.
• NO2 gas passed through the tower and water is showered over it. By the
absorption, nitric acid is obtained. 3 NO2 + H2O 2HNO3 + NO
• Nitric acid so obtain is very dilute. It is recycled in absorption tower so that
more and more NO2 get absorbed. HNO3 after recycle becomes about 68%
concentrated.
58
 Fourth step
• CONCENTRATION
In order to increase the concentration of HNO3, vapours of HNO3 are
passed over concentrated H2SO4. Being a dehydrating agent H2SO4,absorbs
water from HNO3 and concentrated HNO3 is obtained.

59
60
 Reactions of Nitric acid:
• Reactions of nitric acid are divided into following three groups:
• Acidic nature
• Nitrating agent
• Oxidizing agent
Acidic Nature
HNO3 + NaOH  NaNO3 + H2O
HNO3  H+ + NO3-
 Nitrating agent:
• C6H6 + HNO3  C6H5-NO2 + H2O
• CH4 + HNO3  CH3-NO2 + H2O
• OXIDIZING AGENT
• It is a strong oxidizing agent. The oxidizing ability of nitric acid is due to the high
oxidation state of Nitrogen in the molecule, i.e. +5 so it tends to gain electron(s)
and reduce itself and oxidizes other elements.
• It oxidize metals as well as non metals.
• The degree of oxidation of metals depends upon the concentration of acid and
nature of metal.
• When less reactive metals like Cu reacts with conc. Nitric acid it reduces to NO2
• Cu + 4HNO3  Cu(NO3)2 + 2NO2 + 2H2O
Dilute nitric acid is reduced to NO on reaction with same metals.
3Cu + 8HNO3  3Cu(NO3)2 + 2NO + 4H2O
Dilute nitric acid on reaction with reactive metals like Mg etc is reduced to
N2O(Laughing gas)
4Mg + 10HNO3  4Mg(NO3)2 + N2O + 5H2O
Very dilute nitric acid on reaction with more reactive metals reduced to
NH4NO3.
4Zn + 10HNO3  4Zn(NO3)2+ NH4NO3 + 3H2O
 Non metals
• Nitric acid also oxidizes non metals and it is reduced to NO2.
• S + 6HNO3  H2SO4 + 6NO2 + 2H2O
• P + 5HNO3  H3PO4 + 5NO2 + H2O
• Si + 4HNO3  SiO2 + 4NO2 + 2H2O
 AQUA REGIA:
• A mixture of concentrated HNO3 and concentrated HCl is called aqua regia which
is also known as
“Royal Water".
• COMPOSITION:
• Composition of aqua regia is as follows:
• 1 part of concentrated HNO3 by volume
3 part of concentrated HCl by volume.
•
 FUNCTION:
• Noble metals such as gold and platinum are insoluble in either of the acid alone.
But they can be dissolved in aqua regia. Reason for solubility is the liberation of
atomic chlorine which forms a soluble compound.
When HNO3 and HCl are mixed, following reaction takes place.
• HNO3 + 3HCl  2[Cl] + NOCl + 2H2O
• Atomic chlorine forms metallic chloride with gold.
• Au + 3[Cl]  AuCl3
• Metallic chloride then reacts with HCl to produce hydrometallic chloride.
• AuCl3 + HCl  H+[AuCl4]-
• Hydrometallic chloride is soluble in aqua regia.
 Sulphuric Acid
• It is also called the King of Chemicals and Oil of Vitriol.
• It is widely used in industries and it is the indicator of industrial development
of a country.
• Due to the presence of strong hydrogen bonding it is very viscous and
having high boiling point.
 SULPHURIC ACID (H2SO4)
• On industrial scale, sulphuric acid can be prepared by the following two methods.
• Contact process
• Lead Chamber process
• CONTACT PROCESS
• Now a days, sulphuric acid is prepared by contact process all over the world.
• Preparation of sulphuric acid by contact process is based upon the catalytic
oxidation of SO2 to SO3.

68
 DETAILS OF CONTACT PROCESS

• Following steps are involved in the preparation of H2SO4.

• PREPARATION OF SO2.
• PURIFICATION OF SO2.
• OXIDATION OF SO2.
• ABSORPTION OF SO3.
• DILUTION OF OLEUM.

69
 PREPARATION OF SO2
• SO2 is obtained by burning sulphur or by heating iron pyrite (FeS2) in
pyrite burner.
S + O2 SO2
•
4FeS2 + 11O2 2Fe2O3 + 8SO2

70
 PURIFICATION OF SO2
• SO2 contains a number of impurities such as dust particles, Arsenous oxide, vapours,
sulphur etc. These impurities must be removed otherwise catalyst loses its efficiency
(catalyst poisoning).
• DUST CHAMBER:
SO2 is first passed through the dust chamber where steam is spread over the gas to
remove dust particles, which settle down. Fe(OH)3 also sprayed over to remove oxides
of Arsenic.
• WASHING TOWER:
SO2 is then passed through a washing tower after cooling. Here it is sprayed by water
to remove any other soluble impurities.

71
•DRYING TOWER:
The gas is now dried by passing through drying tower where conc. H2SO4
(dehydrating agent) is sprayed. H2SO4 removes moisture from SO2.
• TYNDALL BOX (TEST BOX):
•Arsenic oxide is a poison for the catalyst. It is removed when the gas is passed over
ferric hydroxide.
As2O3 + 2Fe(OH)3 2FeAsO3 + 3H2O.
•In order to remove traces of As2O3, it is passed through a test box, where a strong
beam of light is thrown against the gas. If there is no scattering of light in the box, it
indicates that gas is free from As2O3.

72
73
74
 CONTACT TOWER
• Oxidation of SO2 is carried out in contact tower where V2O5 is filled in different pipes. SO2 here reacts with air (O2)
to produce SO3. Under above conditions 98% SO2 is converted into SO3.
2SO2 + O2 2SO3 + 45Kcal
• CONDITIONS NECESSARY FOR MAXIMUM YIELD OF SO3:
Oxidation of SO2 is a reversible and exothermic process in which volume of product is less than the volumes of
reactants. In order to obtain maximum amount of SO3, according to Le-Chatelier’s Principle following conditions are
necessary.
• CONCENTRATION:
Excess of O2.
• TEMPEATURE:
A decrease in temperature favors reaction in forward direction. Optimum temperature for this process is 450oC to
500oC.
• PRESSURE:
Since volumes of reactants are greater than the product (3:2), therefore, according to Le-Chatelier’s Principle a
high pressure is favorable. Optimum pressure is about 1.5 to 1.7 atmosphere.
• USE OF CATALYST:
At low temperature, rate of reaction decreases. To increase rate of reaction a catalyst vanadium pentaoxide
75

(V2O5) is used
 ABSORPTION OF SO3 IN H2SO4
• SO3 is not directly passed in water, because a dense fog of minute particles
of H2SO4 is produced. It is therefore, dissolved in conc.H2SO4 to form
pyrosulphuric acid (oleum).
SO3 + H2SO4 H2S2O7 (OLEUM)
• DILUTION OF OLEUM
• Oleum is now diluted with water to form H2SO4 of required concentration.
• H2S2O7 +H2O 2H2SO4

77
 Reactions of Sulphuric acid
• Reactions of sulphuric acid are divided into four different groups:
• Acidic nature
• Sulphonating agent
• Dehydrating agent
• Oxidizing agent
 Acidic Nature
• Sulphuric acid is a strong diprotic acid.
• H2SO4  2H+ +SO4-2
• H2SO4 + 2NaOH  Na2SO4 + 2H2O
Sulphonating agent:
C6H6 + H2SO4  C6H5-SO3H + H2O
C6H14 + H2SO4  C6H13-SO3H + H2O
Dehydrating Agent:
C12H22O11 + H2SO4  12C + 11H2O + H2SO4
HCOOH+ H2SO4  CO + H2O + H2SO4
H2C2O4 + H2SO4  CO + CO2 + H2O + H2SO4
 Oxidizing agent
• The oxidizing property of sulphuric acid depends upon:
• Concentration of acid
• Nature of metal
• Temperature
Reactive metals like Zn, Al, Fe etc reacts with dilute sulphuric acid and produce metal
sulphates and hydrogen gas.
Zn + H2SO4  ZnSO4 + H2
(These metals stand high in E.C.S)
• Less reactive metals like Cu, Hg, Pb etc does not react with dilute sulphuric acid but conc.
Sulphuric acid oxidize these metals to form SO2 and metal sulphates.
• Cu + 2H2SO4  CuSO4 + SO2 + 2H2O
Reactive metals on reaction with conc. H2SO4 form different products.
4Zn + 5H2SO4  4ZnSO4 + H2S + 4H2O
Sulphuric acid also oxidizes non metals:
C + 2H2SO4  CO2 + 2SO2 + 2H2O
S + 2H2SO4  3SO2 + 2H2O
 Industrial Preparation Of Chlorine
• Industrial preparation of chlorine:
• Chlorine is prepared on a large scale by the electrolysis of an aqeous concentrated solution of sodium
chloride (brine solution). For this purpose a special type of cell called nelson cell is used.
• Construction Of Nelson Cell:
• It consists of a u-shaped perforated steel vessel which act as cathode. The cathode is coated inside with a
porous diaphragm of asbestos the carbon rod is suspended in the u-shaped vessel which act as anode. The
u-shaped vessel is supported in a steel tank having an outlet for chlorine gas.
• Working:
• Sodium chloride solution is poured into cell and electric current is passed through it. As a result reactions
takes place in the cell. Chlorine is liberated at anode and is collected at chlorine outlet. Hydrogen gas is
formed at the cathode and is collected at the hydrogen gas outlet. Sodium hydroxide being forced is
collected in the catch basin placed under the u-shaped vessel.

82
83
 Cell reaction
• In the cell the following reaction takes place
• 2NaCl ---> 2Na+ + 2Cl-
• Reaction at anode:
• 2Cl- ---> Cl2 + 2e
• Reaction at Cathode:
• 2H + + 2e  H2

84
 ALUMINIUM
• CHIEF ORES OF ALUMINUM:
• Aluminium does not occur in free state, but it is widely distributed in nature
in the form of compounds. The chief minerals of aluminum are either
silicates or oxides.
• SILICATES:
Kaolin Al2O3.2SiO2.2H2O
Potash felspar K2O. Al2O3.6SiO2
Potash mica K2O.3Al2O3.6SiO2.2H2O
85
• OXIDES:
Bauxite Al2O3.nH2O
Gibbisite Al2O3.3H2O
Diaspore Al2O3.H2O
Corundum Al2O3
• FLOURIDES:
Cryolite Na3AlF6
• SULPHATES:
Alunite K2SO4.Al2(SO)3.4Al(OH)3

86
 METALLURGY OF ALUMINUM
• Aluminum is extracted from its oxide ore "Bauxite". The extraction of
aluminum involves the following steps.
• Purification of Bauxite
• Electrolysis of Alumina
• Refining

87
PURIFICATION OF BAUXITE TO ALUMINA

• Bauxite contains two main impurities Fe2O3 and SiO2.

• These impurities must be removed in order to get good quality aluminum. These
impurities make the aluminum brittle and liable to corrosion.
• Depending upon the nature of impurity in bauxite any one of the following
methods can be used for the purification of bauxite.
• Hall’s method
• Baeyer’s method
• Serpek’s method
88
 HALL’S METHOD
• Hall’s method is used for the purification of bauxite if it contains both Fe2O3 and
SiO2 in excess.
• Details of Process
• When finely divided bauxite is fused with sodium carbonate it dissolved to form
sodium aluminate, while the impurities of Fe2O3 and SiO2 are left unaffected.
Al2O3.nH2O + Na2CO3  2NaAlO2 + CO2 + (n) H2O
• The fused mass is extracted with water leaving behind both impurities. Sodium
aluminate is then heated up to 50oC to 60oC in the presence of CO2. The
precipitates of aluminum hydroxide are formed.

89
• 2NaAlO2 + 3H2O + CO2  2Al(OH)3 + Na2CO3
• The precipitates of Al(OH)3 are washed to remove Na2CO3, dried and ignited at about
1500oC to get pure alumina.
2Al(OH)3  Al2O3 + 3H2O

90
 BAEYER’S METHOD
• Baeyer’s method is suitable for the purification of bauxite if it contains
excess of iron oxide Fe2O3.
• Details of Process
• When finely divided bauxite is treated with strong caustic soda, then bauxite
is converted into sodium aluminate.
• Al2O3.nH2O + 2NaOH  2NaAlO2 + 2(n)H2O

91
• The solution is filtered to remove Fe2O3.
• The fused mass is extracted with water leaving behind both impurities Sodium aluminate
is then heated up to 50oC to 60oC in the presence of CO2, the precipitates of aluminum
hydroxide are formed.
•
2NaAlO2 + 3H2O + CO2  2Al(OH)3 + Na2CO3
• The precipitates of Al(OH)3 are washed to remove Na2CO3, dried and ignited at about
1500oC to get pure alumina.
• 2Al(OH)3  Al2O3 + 3H2O
•

92
 SERPEK’S METHOD
• Serpek’s method is used for the purification of bauxite if it contains excess
amount of silica (SiO2).
• DETAILS OF THE PROCESS:
• The powdered bauxite is mixed with carbon and heated up to 1800oC and a
current of nitrogen is passed, aluminum nitride is obtained.
Al2O3.nH2O + 3C + N2  2AlN + 3CO + (n)H2O

93
• Silica is converted in to silicon (Si).
SiO2 + 2C  Si +2CO
• Aluminum nitride on hydrolysis with hot water produces
precipitates of Al(OH)3.
AlN + 3H2O  Al(OH)3 + NH3
• The precipitates of Al(OH)3 are washed to remove NH3, dried
and ignited at about 1500oC to get pure alumina.
2Al(OH)3  Al2O3 + 3H2O

94
 ELECTROLYSIS OF ALUMINA
• The electrolysis of alumina is carried out in a steel tank lined inside with graphite.
• The graphite lining serves as cathode. Anode is also made of graphite rods hanging
in the molten mass.
• The electrolyte consists of alumina dissolved in fused cryolite(Na3AlF6) and
fluospar(CaF2).
• Cryolite lowers the melting point of alumina to 9500C and fluospar increases the
fluidity of the mass so that the liberated aluminum metal may sink at the bottom of
the cell.
95
96
• When electric current is passed through this mixture, the aluminum is collected at the
cathode in molten state and sinks at the bottom and is tapped off.
• IONIZATION OF ALUMINA:
2Al2O3  6O-2 + 4Al+3

• AT THE CATHODE:
4Al+3 + 12e-  4Al
AT THE ANODE:
6O-2  3O2 + 12e-
C + O2 CO2

97
 REFINING OF ALUMINIUM
• Aluminum metal produced by the electrolysis of alumina is 99% pure but contains impurities of
Fe, Si and Al2O3. Aluminum is further refined by hoope’s method.
• HOOPE’S METHOD:
• This is an electrolytic process. Electrolytic cell is made of iron, which is lined with carbon at the
bottom. It contains three layers of fused mass. The lower layer consists of an alloy of
impure aluminum with copper. This layer serves as anode. The middle layer consists of a
solution of cryolite (Na3AlF6) and barium fluoride. The upper layer consists of pure aluminum
and serves as cathode. These three layers are separated from each other due to difference in
specific gravity.

98
• During electrolysis Al+3 ions from the middle layer
migrate to the upper layer where they are reduced to
aluminum by gaining 3 electrons. Equal numbers of
Al+3 ions are produced in the lower layer. These ions
migrate to the middle layer. Pure aluminum is tapped
off from time to time. Hoope’s method gives 99.99%
pure aluminum.

99
100
 ELECTRO-CHEMICAL CHANGES:
• Na3AlF6 3NaF + AlF3
AlF3  Al+3 + 3F-
• At the cathode:
• Al+3 + 3e-  Al
• At the anode:
• Al  Al+3 + 3e-
Overall reaction:
• Al+3 + Al  Al + Al+3
101
 ALUM

• DEFINITION:
• Alum is a series of double sulphate salts of monovalent cations and trivalent cations
containing 24 molecules of water of crystallization.
• GENERAL FORMULA:
• M2SO4.T2(SO4)3. 24H2O
• Where
M = monovalent cation (Na+, K+,NH4+)
T = trivalent cation (Al+3,Fe+3,Cr+3)

102
 NOMENCLATURE
OF ALUM
• If alum contains aluminium then it is named with monovalent cation.
For example:
K2SO4.Al2(SO4)3.24H2O (potash alum)
• If alum does not contain aluminium then it is named with trivalent cation.
For example:
K2SO4.Cr2(SO4)3.24H2O (chrome alum)

103
 EXAMPLES
• K2SO4.Al2(SO4)3.24H2O (potash alum)
(NH4)2SO4.Al2(SO4)3.24H2O (ammino alum)
(NH4)2SO4.Fe2(SO4)3.24H2O (ferric alum)
K2SO4.Cr2(SO4)3.24H2O (chrome alum)

104
 PREPARATION OF POTASH ALUM
• Potash alum is commonly known as "PHITKARI“
• Potash alum is prepared by mixing equi-molecular masses of potassium
sulphate and aluminum sulphate in water followed by evaporation.
• K2SO4 + Al2(SO4)3 + 24H2O  K2SO4.Al2(SO4)3.24H2O

105
 Reactions of Aluminium
• With Oxygen
• Does not react at room temperature, react at high temperature and
large amount of energy is released.
• 4Al + 3O2  2Al2O3
• With Halogens
• 2Al + 3X2  2AlX3
• With Nitrogen
• 2Al + N2  2AlN
• With Carbon
• 4Al + 3C  Al4C3
• With Acids
• Dissolved by HCl and dilute sulphuric acid and H2 is liberated
• 2Al + 6HCl  2AlCl3 + 3H2
• 2Al + 3H2SO4  Al2(SO4)3 + 3H2
• On reaction with concentrated sulphuric acid SO2 is produced.
• 2Al + 6H2SO4  Al2(SO4)3 + 3SO2 + 6H2O
• Does not react with HNO3.
• With Strong Alkali:
• Strong alkalis dissolved Al and H2 is liberated.
• 2Al + 2NaOH + 2H2O 2NaAlO2 + 3H2
• Thermite Process:
• A process in which metal oxides are reduce by using Al powder is called Thermite
process.
• 2Al + Fe2O3  Al2O3 + 2Fe + heat
• In this reaction Al behave as a reducing agent.
• Highly exothermic reaction and produces a flame having a temperature of 35000C and
used in welding.
 Alloys of Aluminium:
• Aluminium Bronze: 90% Cu and 10% Al.
• Used in making of Jewelry, making of coins.
• Dura-lumin: 95% Al, 4% Cu, 0.5%Mg and 0.5% Ni.
• Used in making of aeroplanes.
• Ammonal  it is a mixture of Aluminium powder and Aluminium nitrate.
 Allotropes of Sulphur
• SULPHUR AND ITS ALLOTROPIC FORMS
• The existence of an element in two or more different forms in the same physical state is
called allotropy, while different forms are known as allotropic modification or allotropes.
• Sulphur exists in several forms.
• Rhombic Sulphur
• Monoclinic Sulphur
• Plastic Sulphur
• i) RHOMBIC SULPHUR:
• It is stable crystalline form at ordinary temperature. It is prepared by slow evaporation
of solution of ordinary sulphur in carbondisulphide (CS2).
• PREPARATION
• Rhombic sulphur is prepared by slow evaporation solution of ordinary sulphur in
carbon disulphide or S2Cl2, which is filtered first to remove insoluble impurities filtrate
110

on evaporation. Produce octahedral crystal of rhombic sulphur.

STRUCTURE
Rhombic Sulphur consists of Sulphur atoms in S8 molecules giving eight membered rings. Each S8 molecule
has the form of puckered rings. The S-S bond length is 2.12 A0 and S-S bond angle is 1050.These puckered rings
are unite with one another by Vander waal forces to form the crystal of Rhombic Sulphur.

ii) MONOCLINIC SULPHUR:

It is another crystalline form of sulphur which is stable above 95.5 oC to 119 oC and hence it changes slowly to
rhombic sulphur at ordinary temperature. The transformation of monoclinic sulphur to rhombic sulphur is
reversible and can be describe as:
RHOMBIC SULPHUR MONOCLINIC SULPHUR
Below 95.5 0C, the rhombic sulphur is stable and above 95.5 0C, monoclinic sulphur is stable. Thus the
temperature at which both forms coexist in equilibrium is called transition temperature. The transition
temperature of sulphur is 95.5 0C.

111
PREPARATION
Monoclinic sulphur is obtained by slow cooling molten sulphur until a crust is formed on
the surface of the molten sulphur. Pierce two holes through the crust and pout off the
remaining molten sulphur from inside the long needle shaped crystals of monoclinic
sulphur are formed on the sides of the dish.

STRUCTURE
Monoclinic sulphur consists of sulphur atoms in S8 molecules giving eight membered
puckered rings just like rhombic sulphur, the only difference in the difference in the shapes
of their crystals. The crystal of monoclinic sulphur is needle like.

112
iii) PLASTIC SULPHUR
When molten sulphur is heated up to boiling and then poured into cold water, it turns into elastic
rubber like material which is called plastic sulphur.

PROPERTIES
It is soft, sticky rubber like material.
It is soluble in CS2.

STRUCTURE
The plastic sulphur is composed of long chains of sulphur atoms coiled up, when it is stretched
these layers uncoiled and therefore it is elastic in nature.

113
 Hydrogen Sulphide
• Hydrogen sulphide is a colorless gas with characteristic rotten egg smell.
• It is widely used in qualitative analysis.
• PREPARATION:
• From Sulphur:
• H2S can be prepared by direct heating sulphur with hydrogen at 600oC to 650oC.
• H2 + S  H2S
 From Metal Sulphides
• H2S can be prepared by the action of mineral acids on different sulphide.
• ZnS + 2HCl  H2S + ZnCl2
Kipp’s Apparatus
• FeS + 2HCl  H2S + FeCl2
• FeS + H2SO4  H2S + FeSO4
• ZnS + H2SO4  H2S + ZnSO4
Stibinite
• Sb2S3 + 6HCl 3H2S + 2SbCl3
 Properties
• COMBUSTION :
• H2S gas burns in air with blue flame forming sulphur dioxide gas.
• H2S + 3O2 2SO2 + 2H2O
ACIDIC PROPERTY:
• Aqueous solution of H2S gas is acidic in nature.
• H2S + H2O  H3O+ + HS-
• HS- + H2O  H3O+ + S-2
REDUCING AGENT:
• In hydrogen sulphide, sulphur exists as S-2, therefore, it easily lose electron pair and behaves as a
reducing agent.
• H2S + Br2  2HBr + S
• FeCl3 + H2S  2FeCl2 + S + 2HCl
• 2HNO3 + H2S  2NO2 + S + 2H2O
• H2SO4 + H2S  SO2 + S+ 2H2O
 Lead Pigments
• Pigments are inorganic substances which are used to produce colour. Lead
forms various pigments which are used in paints. Some of them are:
• White lead pigment
• Red lead pigment
• Chrome yellow pigment
• Chrome red pigment
• Turner’s yellow pigment
 1- White lead pigment
• Chemical Composition:
• Basic lead carbonate is known as white lead pigment. Its chemical formula is
2PbCO3.Pb(OH)2 OR Pb3(OH)2 (CO3)2.
• Preparation:
• When aqueous solution of lead oxide is treated with CO2 and lead acetate, white
lead is formed.
• 2PbO2 + 2CO2 + 2H2O + Pb(CH3COO)2  2PbCO3.Pb(OH)2 + 2CH3COOH + O2
 2- Red Lead Pigment:
• Chemical Composition:
• Triplumbic tetraoxide is known as red lead pigment. It is also known as lead-
sesqui oxide or sandhur. Its chemical formula is Pb3O4 or 2PbO.PbO2
• Preparation:
• It is prepared by lead monoxide (litharge) in a revolving furnace with excess
of air at about 4500C.
• 6PbO + O2 4500C 2Pb3O4
 3- Chrome Yellow Pigment:
• Chemical Composition:
• Lead chromate is known as chrome yellow pigment. Its chemical formula is
PbCrO4.
• Preparation:
• Chrome yellow pigment is form by the reaction of K2CrO4 with Pb(NO3)2 or
Pb(CH3COO)2
• Pb(NO3)2 + K2CrO4  PbCrO4 + 2KNO3
• Pb(CH3COO)2 + K2CrO4  PbCrO4 + 2CH3COOK
 4- Chrome Red Pigment:
• Chemical Composition:
• Basic lead chromate is known as chrome red pigment. Its chemical formula is
PbCrO4.PbO or Pb2CrO5.
• Preparation:
• When lead chromate is heated with NaOH, chrome red pigment is formed.
• 2PbCrO4 + 2NaOH  Na2CrO4 + Pb2CrO5 + H2O
 5- Turner’s Yellow Pigment:
• Chemical Composition:
• The chemical formula of Turnere’s yellow pigment is PbCl2.4PbO.
• Preparation:
• When aqueous solution of sodium chloride is treated with litharge, Turner’s
yellow pigment is formed.
• 5PbO + H2O + 2NaCl  2NaOH + PbCl2.4PbO