GENERAL CHEMISTRY – IV

d and f – Block Elements

Introduction :

Periodic table is the systematic arrangement of elements in the order of increasing

atomic numbers of the elements. On the basis of electronic configuration the periodic table has
been divided into four blocks known as s , p, d and f block

d – Block Elements
Defination : The elements in which last electrons enters the ‘ d ’ orbital of the
penultimate shell i.e. (n-1) d orbital are cleed as d-block elements.

The d –block elements are called transition elements and consist of elements lying
between s and p –blocks starting from fourth period onwards. These elements have properties
which are transitional between those of s and p block elements. All these elements are metal.

The transition elements may be defined as elements whose atoms or simple ions in their
common oxidation state contain partially filled d- subshell. The geneal electronic
1-10 1-2
configuration of these metals is (n-1)d ns
Classification of d –block elements : These are divided into three transition series.

i) The first transition series. (3d-series) involves the filling of 3d- orbitals and has 10
elements from scandium ( Z = 21 ) to zinc ( Z = 30 ) in the fourth period.
ii) The second transition series ( 4d-series) involves the filling of 4d orbitals and has 10
elements from ytterium ( Z= 39) to cadmium ( Z= 48 ) in the fifth period.
iii) The third transition series ( 5d-series) involves the filling of 5d-orbitals and has 10
elements. The first element of this series is lanthanium( Z= 57 ) . it is followed by
14 elements ( lanthanides or lanthanons involving filling of 4f- orbitals). The next
nine elements are from hafnium ( Z =72)to mercury ( Z = 80).
iv) The fourth transition series ( 6d-series) involves the filling of 6d- orbitals and is
incomplete starting from Actinium ( Z= 89 ) and extenedupto element with atomic
number 104

General Characteristics Of Transition Elements :

The members of given transition series do not differ so much from one another as those of
non-transition elements ( representative elements) of the same period. The reason is that the
electronic configuration of transition elements differ only in the number of electrons in ( n-1)
d- subshell i.e., the number of electrons in the outermost shell ( n) remains the same. The
2
outermost configuration is ns where n is the number of the period to which the given
transition elements belong some important properties of transition elements are as follows.
1. Metallic Character. : d- Block elements have low ionisation energy and hence easily
lose electrons to form cations. Further more these elements have only one or two
 electrons in their outermost energy shell i.e., they have a large number of vacant
orbitals in the outermost shell which make them from metallic bond. Because of this all
the transition elements are metal.

They are generally (i) malleable and ductile (ii) forms alloys with several other
metals. ( iii) they are good conductors of heat and electricity. However , they differfrom
non-transition metals in being hard and brittle in certain cases. ( Mercury has an
exceptional behaviour. It is a liquid at room temperature). It is due to the presence of
unpaired electrons in d-orbitals of their atoms which has a tendency for covalent bonding
involving d-d overlappings. In a particular series the hardness increases upto the middle
with increasing number of unpaired d- electrons. Thus, Cr, Mn and W having maximum
number of unpaired d- electrons are very hard metals, while Zn ,Cd and Hg are not hard
metals due to the absence of unpaired electrons.

2. Melting and Boiling Points: The melting and boiling points of the transition elements
are generally very high. This is due to the presence of covalent bonding by the unpaired
d- orbital electrons.
3. Atomic Radii: The Variation in atomic radii across each transition series is not as
simple as that observed in s and p- block elements. However, following overall trends
in the variation of atomic radii across the period, are observed.
i) The atomic radii of the d-block elements of a given series generally decrease
with increases in the atomic number. This is due to the fact that with an increase
in atomic number the nuclear charge increases which in turn increasingly tends
to attract the elcectron cloud inward resulting in decrease in size. However, the
decrease in the radii across a period is not uniform. The decrease in radii of
transition metals is small as compared to the decrease in the radii of s and p
block elements for the same periods. For ex. The radii of the elements from Cr.
To Cu are very close to one another. This may be explained on the basis of
screeingeffect In d- block elements electrons are added to an (n-1) d- subshell
which adds to the primary screeing effect . the additional electrons effectively
screen the outer ns- electrons from the inward pull of the nucleus. As a result,
the size of the atom does not change much from Cr to Cu.
ii) In a given series the atomic radius decreases from group 3 elements upto the
group 10 elements and then increases again towards the end of the series. This
anomalous increase in atomic radius towards the end of the series is because of
the increased force of repulsion among the added electrons .also the d- orbitals
get completly filled in group 11 and 12 elements which also causes a decrease in
force of attraction.
iii) Atomic radius increases on decending down the groups although the increase is
not as significant as in case of s and p block elements. The very close similarity
between the radii of the elements of second and third transition series , ( Ex. Zr
and Hf , Nb and Ta , Mo and W , Tc and Re etc.) is the consequence of the
filling of 4f subshell.
4. Atomic Volume and Densities:
i) The atomic volume of the transition elements are much lower than those of their
neighbouring s and p block elements. This is due to the fact that in d- block
elements, the inner orbitals i. e. (n-1) d- orbitals are filled this leads to more
nuclear pull resulting in decrease in volume.
ii) Due to the decrease in atomic volume, the density of these elements increases.
Therefore, the transition elements have quite have high density. Following
trends are ovserved among the densities of the transition elements.
a) In a given transition series, the density increases across the series and reaches
a maximum value at the middle of the series.
b) The density increases down the group because the atomic size of the
elements of second and third transition series is nearly the same , their atomic
masses increases nearly two fold and the densities of the elements of the third
series are generally twice those of the corresponding elements of the second
transition series
5. Ionisational potential:
i) Since atoms of transition elements are small in size, their ionisation energies are
fairly high
ii) The ionization potentials of the most of the d-block elements lie in between
those of s and p –block elements. These are higher than those of s- block
elements and are lower than those of p – block elements. This indicates that the
d- block elements are less electropositive than the s- block elements.( alkali and
alkaline earth metals).
iii) The ionisation potential of d- block elements increases as we move across the
series from left to right . However, the increase in the value is not as pronounced
as in case of s and p – block elements of the same period. This is because in the
transition elements , the effect of increasing nuclear charge is almost
compensated by the extra screening effect provided by the increasing number of
(n-1)d electrons
6. Variable oxidation state.:
All transition elements, except the first and the last members of each series
exhibit variable oxidation state. The cause of showing different oxidation states
is due to the fact that there is only a small difference between the energies of the
electrons in the ns orbitals and (n-1)d –orbitals with the result that both ns as
well as (n-1)d –electron may be used for compound formation. Therefore , the
variable oxidation state of transition elements are related to their electronic
configuration. This is clear from the following table of oxidation state of
elements of first transition series.
 Elements Outer electronic configuration Oxidation
1 2
Sc 3d 4s +2 ,+3
2 2
Ti 3d 4s +2,+3,+4
3 2
V 3d 4s +2,+3,+4,+5
4 2
Cr 3d 4s +2,+3,+4,+5,+6,
5 2
Mn 3d 4s +2,+3,+4,+5,+6,+7
6 2
Fe 3d 4s +2,+3,+4,+5,+6
7 2
Co 3d 4s +2,+3,+4
8 2
Ni 3d 4s +2,+3,+4
10 1
Cu 3d 4s +1,+2
10 2
Zn 3d 4s +2
It must be noted that in some transition elements all of the (n-1)d –electrons are
6 2
not involved during bond formation, e.g. iron (3d 4s ) should have +8 as its hightest
oxidation state, but actually it is only +6 which is also very rare( +2 and +3 are the
common oxidation state of iron). The +6 ( and not +8) as the highest oxidation state is
explained on the basis that during bong formation only the unpaired electrons of the 3d-
subshell take part in bond formation. In iron there are 4 unpaired and 2 paired 3d-
electrons and hence the effective electrons for bond formation in 3d-orbitals are only
four which may give +6 as the highest oxidation state.

7. Complex Formation : The cations of transition metals have a great tendency to form
complexes with several molecules or ions called ligands. The tendency of formation of
complexes is due to the following two factors.
i) The cations of these metals are very small in size and have a high effective
nuclear charge. Thus they have a very high positive charge density which
facilitates the acceptance of lone pairs of electrons from other molecules or ions.
ii) The transition metal cations have vacant inner d-orbitals which are of
appropriate energy to accept lone pair of electrons from the ligands. The bond
involved in the formation of complexes are coordinate hence the complexes are
termed as coordinate complexes.
8. Formation of Coloured Compound: the transition metal ions have unpaired d-
electrons, which on absorbing visible light can jump from one d-orbital to another i.e.,
intra d-d transition takes place. Thus , when light falls certain visible wavelength are
absorbed. The transmitted ( unabsorbed) or reflected light ( or colour) appears coloured
and gives the colour of compounds. The ions having no d-d transition are colourless.

To understand the cause of colour in transition metal complexes, consider

3+
complex [Ti(H2O)6] , In this case, titanium is in +3 oxidation state.
+3 1
The electronic configuration of Ti : [Ar]3d
 +3
During the formation of complex, as the six water molecules approach Ti ion
from different side these develop a negative field around it, as they donate lone pair
present on oxygen to metal ion. There occurs repulsion between electrons of metal ion
and ligand and energy of degenerate orbitals of metal ions increase and ultimately they
+3
split into two set of orbitals. The electron present in Ti , prefers lower set of d-
orbitals. The energy gap between two set of d- orbitals is very less and the energy
available in the visible light is sufficient to cause excitation of electron from lower set
+3
of d- orbitals to higher set of d –orbitals, called a d-d transitions. Ti absorbs greenish
yellow component of white light during excitation of electrons, hence its aqueous
solution appears as purple. This is because purple is the complimentary colour of
greenish yellow in white light.

9. Magnetic Properties: Most of the transition elements show paramagnetism.

Paramagnetism arises from the presence of unpaired electrons in atoms, ions or
molecules. The magnetic character is comparable in terms of magnetic moment given
by the expression = √ ( + 2) Bohr Magneton, where n= the number of unpaired electrons. In general,
greater the number of unpaired electrons, greater is the magnetic character. The maximum paramagnetism
5
is noticed in d case which has maximum number of unpaired electrons.
10. Formation of alloys :due to their almost equal atomic sizes, they can
mutually substitute one another in the crystal lattice to form alloys.
11. Formation of non-stoichiometric compounds and interstitial compounds. :
transition metal can trap some of the small size atoms like hydrogen, boron, carbon,
nitrogen etc., in the vacant spaces between the crystal lattice forming inter-orbital
compounds. For example, FeC , Fe8N, TiH2. This property differentiates these metals
from non-transition elements. The products obtained are hard and rigid. Non –
stoichiometric compounds like i.e. Fe0.98O ,Fe0.86S , VH0.56 , TiH1.7 are offen classified
as interstitial compounds.
12. Catalytic properties:Many transition metals and their compounds show catalytic
properties ,the most common being Fe , Pt ,Ni, V2O5 etc. This property may be either
due to their variablevalency (incomplete d- orbitals) which enables them to form
unstable intermediate compounds or due to the fact that they can provide a suitable
reaction surface.
 13. Reactivity : The d- block elements are unreactive due to the following factors:
i) High ionisation energies : on account of small size of their
atoms, ionisation energies of d- block elements are fairly high
ii) High heats of sublimation: Due to presence of covalent bonding, these
have high heats of sublimation.

The tendency to remain unreacctive is more pronounced inplatinum and gold in

the third transition series.

14. Standard Electrode Potential : The standard reduction potential of all the transition
elements (except Cu and Hg in 3d-series etc.) is lower ( negative ) than that of
hydrogen(taken as Zero ) . thus all the transition elements, with negative reduction
potential, liberate hydrogen from dilute acids
+2 +⟶ 2+ + 2↑

However, some metals evolve hydrogen very slowly because they are protected from
the attack of acids by the formation of an impervious layer of an inert oxide. For example,
chromium is so unreactive that it cna be used as a protective non-oxidising metals.

15. Reducing Properties: Tansition metals with sufficiently negative standard reduction
potential should be good reducing agents i.e, they should be oxidised easily to their
ions.
2+ -
M →M + 2e
However they are not good reducing agents as compared to elements of Group 1 , 2 and
13 . this is because the transition metals have less tendency to form ions due to their
low reactivity.
6 2
IRON :Fe , At. No. 26, [Ar] 3d 4s

It is a reactive metal and do not occur in free state. In combined state it occurs in the
ores

Some important ores are :

i) Haematite Fe2O3 iv) Magnetite Fe3O4

ii) Limonite Fe2O3.3H2O v) Iron pyrites FeS2
iii) Copper pyrites CuFeS2

Extraction.
Cast iron is extracted from its oxides by reduction with carbon and carbon monoxide in
a blast furnance to give pig iron. The extraction of iron from the oxide ores involves the
following steps :
1. Ore dressing. The large lumps of the ore are broken into small pieces. Most of the ores
are rich enough and do not require further concentration. However, if clay is present, it is
removed by washing with water.
2. Roasting. The ores are usually roasted to remove most of the moisture, to burn the
organic matter and some of sulphur and arsenic; and to convert ferrous oxide to ferric oxide.
Fe2O3.3H2O → Fe2O3 + 3H2O 2FeCO3→ 2FeO + 2CO2

4FeO + O2→ 2Fe2O3

(i) The ore becomes sintered (porous) and this facilitates its reduction to metallic iron
later on.
(ii) Ferric oxide does not form a slag at so low a temperature as ferrous oxide.
Therefore, the early formation of a fusible slag (which would attack the lining of the
furnace) is checked.
3. Smelting. The reduction of the roasted ore of ferric oxide is carried out in a blast
furnace.
Reactions in blast furnace. Thetemperature of the internal portions vary between
0 0
200 C at the top to about 1600 C at the furnace bottom. The various reaction taking place at
various parts of the furnace are described below.
(i) The reduction of ferric oxide is done by carbon and carbon monoxide. The
combustion of coke to carbon monoxide occurs at the hottest part of the furnace
(between 1473K to 1873K).
2C +O2 2CO →

The carbon monoxide is the essential reducing agent.

(ii) Carbon monoxide reacts with ferric oxide in two ways as shown below
Fe2O3+ 3CO ⇌

2Fe + 3CO2
Fe2O3+ CO 2FeO + CO2
→

Reaction (a) begins at 673 K. It is exothermic and reversible. Hence according to

Le-chatelier’s principle more iron will be produced in the furnace at lower
temperatures.
Reaction (b) is not reversible.
(iii) Ferrous oxide formed is reduced by coke in the endothermic reaction occurring at
about 1073 K.
FeO + C Fe + CO→

(iv) The lime stone decomposes at about 1073 K and the calcium oxide reacts with
sandy (silica) impurities to form a slag of calcium silicate.
Lime stone : CaCO3 → CaO + CO2

Impurity : SiO2 + CaO → CaSiO3

slag
(v) The reduction of iron oxide is completed by coke at about 1473 K and cementite
Fe3C and graphite enter the iron. Other reactions also occur at high temperatures
e.g., silica is reduced to silicon and these enter iron as ferrosilicon.
SiO2 +2C → Si + 2CO
 A similar reaction occurs with any phosphate present and some Fe3P is retained by
the iron. Other impurities present in iron are FeS and Mn, which form an alloy.
(vi) The slag, CaSiO3 being lighter than the molten iron, floats on the top of it
(incidentally preventing it from being oxidized by the air blast) and is withdrawn at
intervals.
The slag may be used in road making, in making foamed slag blocks for
building, cement etc.
The gases leaving at the top of the furnace contain upto 28% CO, and are burnt
in Cowper’s stoves to pre-heat and air for blast.
The molten iron tapped off is run into boat shaped moulds, in which it solidifies
into blocks known as pigs (hence the name pig iron) or more generally conveyed
directly in the liquid form to steel making plants.

The three commercial varieties of iron differ in their carbon contents. These are:
1. Cast iron or Pig-iron: It is the most impure form of iron and contains highest
proportion of carbon (2.5 – 4%).
2. Wrought iron or Malleable-iron: It is the purest form of iron and contains minimum
amount of carbon (0.12 – 9.25%).
3. Steel:It is the most important form of iron and finds extensive applications. Its carbon
content (impurity) is mid-way between cast iron and wrought iron. It contains 0.2 – 1.5%
carbon. Steels containing 0.2 – 1.5% of carbon are known as mild steels, while those
containing 0.5 – 1.5% carbon are known as hard steels.
Steel is generally manufactured from cast iron by three processes, viz., (i) Bessemer process
which involves the use of a large pear-shaped furnace (vessel) called Bessemer converter, (ii)
L.D. process and (iii) open hearth process, Spiegeleisen (an alloy of Fe, Mn and C) is added
during manufacture of steel.
Heat treatment of steels.: Heat treatment of steel may be defined as the process of carefully
heating the steel to high temperature followed by cooling to the room temperature under
controlled condition.Heat treatment of steel is done for the following two purposes.
(a) To develop certain special properties like hardness, strength, ductility etc. without
changing the chemical composition.
(b) To remove some undesirable properties or gases like entrapped gases, internal stresses
and strains. The various methods of heat treatment are :
(i) Annealing: It is a process of heating steel to redness followed by slow cooling.
(ii) Quenching or hardening: It is a process of heating steel to redness followed by
sudden cooling by plunging the red hot steel into water or oil.
(iii) Tempering: It is a process of heating the hardened or quenched steel to a
temperature much below redness (473 – 623 K) followed by slow cooling.
(iv) Case-hardening: It is a process of giving a thin coating of hardened steel to
wrought iron or to a strong and flexible mild steel by heating it in contact with
charcoal followed by quenching in oil.
0
(v) Nitriding: It is a process of heating steels at about 700 C in an atmosphere of
ammonia. This process imparts a hard coating of iron nitride on the surface of steel.
Properties of Steel:
The properties of steel depend upon its carbon contents. With the increase in carbon
content, the hardness of steel increases while its ductility decreases.
(i) Low carbon or soft steels contain carbon upon 0.25 percent.
(ii) Medium carbon steels or mild steels contain 0.25 – 0.5 percent carbon.
(iii) High carbon or hard steels contains 0.5 – 1.5 percent carbon.
(iv) Alloy steels or special steels are alloys of steel with Ni, Cr, Co, W, Mn, V etc., For
example, stainless steel is an alloy of Fe, Cr and Ni and it is sued for making
automobile parts and utensils. Tool steel is an alloy of Fe, W, V etc.
Uses of steel:
In general, steels are used for making machinery parts, girders, tools, knives, razors,
household utensils, etc. The specific use of steel depend upon the nature of metal added to
iron.
Compounds of Iron:
1. Oxides of Iron. Iron forms three oxides FeO, Fe2O3, (haematite), Fe3O4 (magnetite also
called magnetic oxide or load stone).
(i) Ferrous oxide, FeO: It is a black powder, basic in nature and reacts with dilute acids to
give ferrous salts.
FeO + H2SO4→FeSO4 + H2O

It is used in glass industry to impart green colour to glass.

(ii) Ferric Oxide, Fe2O3: It is a reddish brown powder, not affected by air or water;
amphoteric in nature and reacts both with acids and alkalis giving salts. It can be reduced to
iron by heating with C or CO.
→

Fe2O3 +3C 2Fe + 3CO

Fe2O3 + 3CO → 2Fe + 3CO2
It is used as red pigment to impart red colour to external walls and as a polishing powder by
jewellers.
(iii) Ferrosoferricoxide, Fe3O4 (FeO.Fe2O3): It is more stable than FeO and Fe2O3,
magnetic in nature and dissolves in acids giving a mixture of iron (II) and iron (III) salts.
Fe3O4 + 4H2SO4→ FeSO4 + Fe2(SO4)3 + 4H2O

2. Ferrous sulphide, FeS. It is prepared by heating iron filing with sulphur. With dilute
H2SO4, it gives H2S.
FeS + H2SO4 (dil) → FeSO 4 + H 2S ↑

3. Ferric chloride, FeCl3:It is prepared by treating Fe(OH)3 with HCl

Fe(OH)3 + 3HCl FeCl3 + 3H2O →

The solution on evaporation give yellow crystals of FeCl3.6H2O

Properties.:
 (i) Anhydrous FeCl3 forms reddish-black deliquescent crystals.
(ii) FeCl3 is hygroscopic and dissolves in H2O giving brown acidic solution due to
formation of HCl
FeCl3 + 3H2O → Fe(OH)3 + 3HCl
(Brown)

3+
(iii) Due to oxidizing nature of Fe ions FeCl2 is used in etching metals such as copper.
2+ 2+
2Fe +Cu →
3+
2Fe + Cu (aq)
(iv) In vapour state FeCl3 exists as a dimer, Fe2Cl6

4. Ferrous sulphate, FeSO4, 7H2O (Green vitriol): It is prepared as follow.

Fe + H2SO4 → FeSO4 + H2
(i) On exposure to moist air crystals become brownish due to oxidation by air.
4FeSO4 + 2H2O + O2 4Fe(OH)SO4 →

(ii) On heating, crystals become anhydrous and on strong heating it decomposes to

Fe2O3, SO2 and SO3.
ℎ

FeSO4.7H2O → FeSO4 + 7 H2O

ℎ

2FeSO4→ Fe2O3 + SO2 + SO3

(iii) It can reduce acidic solution of KMnO4 and K2Cr2O7
(iv) It is generally used in double salt with ammonium sulphate.
(NH4)2SO4 + FeSO4 + 6H2O → FeSO4.(NH4)2SO4.6H2O Mohr’s slat is resistant to atmospheric oxidation.

(v) It is used in the ring test for nitrate ions where it gives brown coloured ring of
compound FeSO4.NO.
FeSO4 + NO → FeSO4.NO
Mohr’s slat, FeSO4.(NH4)2SO4.6H2O. It is also known as ferrous ammonium
sulphate and is a light green coloured double salt.

COPPER:

Important ores of copper are :

(i) Copper pyrites (chalcopyrite) CuFeS2 : Cu2S.Fe2S
(ii) Cuprite (Ruby copper) : Cu2O
(iii) Copper glance : Cu2S
(iv) Malachite : Cu(OH)2.CuCO3
 (v) Azurite : Cu(OH)2.2CuCO3

Extraction of copper.
Most of copper (about 75%) is extracted from its sulphide ore, copper pyrites, which
contains varying amounts of copper and iron sulphides.
The extraction of copper from its sulphide ores involves the following steps:
1. Concentration of ore: The ore is concentrated by the froth floatation process.
2. Roasting: The concentrated ore is roasted by hot blast of air when volatile impurities
are removed.
→
→
Main reaction : 2CuFeS2 + O2 Cu2S + 2FeS + SO2
Side reaction : 2Cu2S + 3O2 2Cu2O + 2SO2
2FeS + 3O2 → 2FeO + 2SO2

3. Smelting: The roasted ore is mixed with silica and heated in the furnace. The ferrous
oxide formed is converted into slag.
FeO + SiO2 FeSiO3 (slag) →

Some oxide of copper which is formed in the charge is converted into sulphide by FeS. Cu2O + FeS→ FeO + Cu2S

The mixture of copper and iron sulphides melt together to form ‘matte’ and the slag floats on
its surface. Molten matte is collected after removing the slag.
4. Conversion of matte into Blister copper – (Bessemerisation): Molten matte is
introduced into a Bessemer converter. Silica is added to it and a hot blast of air is passed.
The volatile oxides are driven off and the iron oxides combine with silica to form slag.
FeO + SiO2 FeSiO3 →

Slag is removed. By this time most of iron sulphide is removed.

Some of the cuprous sulphide is oxidized to cuprous oxide and the blowing is continued until
cuprous sulphide and oxide are present in right proportions to bring about auto reduction.
Cu2S + 2Cu2O 6Cu + SO2 →

When the matte is completely converted into copper, the blast of air is stopped and copper
poured off in sand moulds. As the copper cools any sulphur dioxide dissolved by the metal is
expelled and blisters are produced on the surface. The copper thus obtained is called the blister
copper which contains about 98% pure copper and 2% impurities (Ag. Au, Ni, Zn etc.)
5. Electrolytic refining: This method is used for obtaining copper used in electrical
industry. The electrolytic bath contains an acidified solution of copper sulphate, impure copper
(blister copper) acts as anode while cathode is of pure copper strip. When electric current is
passed, there is transfer of pure copper from anode to cathode which gradually gows in size.
The impurities like Fe, Zn, Ni, Co etc., dissolve in the solution as sulphates and others like Au
and Ag settle down below the anode as anode mud. The process gives copper of about 99.99
percent purity.
Properties of Copper.
(i) It has reddish brown colour.
(ii) It is highly malleable and ductile.
(iii) It has high electrical conductivity and high thermal conductivity.
(iv) In presence of CO2 and moisture Cu is covered with a green layer of CuCO3. Cu(OH)2.
2 Cu +H2O + CO2 + O2 CuCO3.Cu(OH)2 →

(v) It undergoes displacement reactions with lesser reactive metals e.g., with Ag. It can
displace Ag from AgNO3. The family divided Ag so obtained is black in colour.

Compounds of Copper.

1. Cuprous oxide, Cu2O: It is a reddish brown powder insoluble in water but soluble in
ammonia solution, where it forms diammine copper (I) ion.
+
Cu + 2NH3→
+
[Cu(NH3)2]
It is used to impart red colour to glass in glass industry.
2. Cupric oxide, CuO: It is dark black, hygroscopic powder which is reduced to Cu by
hydrogen, CO etc. It is used to impart light blue colour to glass. It is prepared by
heating copper nitrate
∆

2Cu(NO3)2 → 2CuO + 4NO2 + O2

3. Copper sulphate:CuSO4.5H2O (Blue vitriol). It is prepared by action of dil H2SO4 on
copper scrap in presence of air.
CuSO4 + 2H2O
2Cu + 2H2SO4 + O2(air)→

(i) On heating this blue salt becomes white due to loss of water of crystallization.
CuSO4.5H2O CuSO4 →
+ 5H2O
Blue White
At about 1000 K, CuSO4 decomposes to give CuO and SO3.
CuSO4 → 6.
000 K
1 CuO + SO3
(ii) It gives a deep blue solution of tetrammine copper (II) sulphate with
NH4OH.
CuSO4+ 4NH4OH→

[Cu(NH3)4]SO4 + 4H2O
(Blue Colour)

(iii) With KCN it first gives yellow precipitate of CuCN which decomposes to give
Cu2(CN)2.
Cu2(CN)2 dissolves in excess of KCN to give K3[Cu(CN)4]
2CuSO4 + 4KCN Cu2(CN)2 + 2K2SO4 + (CN)2
→

(iv) With KI it gives white ppt. of Cu2I2

4KI + 2CuSO4 2K2SO4 + Cu2I2 + I2
→
(White ppt.)
 (v) With K4[Fe(CN)6], CuSO4 gives a reddish brown ppt. of Cu2[Fe(CN)6]
→

2CuSO4 + K4[Fe(CN)6] Cu2[Fe(CN)6] + 2K2SO4

(Reddish brown ppt.)

Uses:
(i) For electroplating and electrorefining of copper.
(ii) As a mordant in dyeing.
(iii) For making Borderaux mixture (ii parts lime as milk of lime + 16 parts copper
sulphate in 1,000 parts of water). It is an excellent fungicide.
(iv) For making green pigments containing copper carbonate and other compounds of
copper.
(v) As a fungicide in starch paste for book binding work.

4. Cupric sulphide, CuS: It is prepared as follows:

Cu(NO3)2 + H2S → CuS + 2HNO3
Black ppt
5. Cupric chloride ,CuCl2:It is a dark brown solid soluble in water and its aqueous
solution first changes to green and then to blue on dilution.
6. Cuprous chloride, Cu2Cl2:It is a white solid insoluble in water and dissolves in conc.
HCl due to formation of H[CuCl2] complex.
Cu2Cl2 + 2HCl → 2H[CuCl2]

SILVER :

Silver is found in the free (native) as well as combined state. Native silver usually occurs
associated with copper and gold.
Important ores are;
(i) Argentite (silver glance) : Ag2S
(ii) Horn silver : AgCl
(iii) Ruby silver (pyrargyrite) : 3Ag2S.Sb2S3
Led and copper ores are generally contaminated with silver. Argentiferous galena (lead
sulphide containing argentite as impurity) contains 0.01 to 0.1% silver.

Extraction of silver by cyanide process or Mac Arthus-Forrest cyanide process.

This method depends on the fact that silver, its sulphide or chloride, forms soluble
complex with alkali cyanides in the silver. This implies that silver compound will dissolve in
solution of alkali cyanides in the presence of blast of air.
4Ag + 8NaCN + 2H2O + O2(air) ⇌ 4Na[Ag(CN)2] + 4NaOH
- - -
Or 4Ag + 8CN + 2H2O + O2 ⇌ 4[Ag(CN)2] + 4OH
 ⇌
⇌

Ag2S + 4NaCN 2Na[Ag(CN)2] + Na2S

AgCl + 2NaCN Na[Ag(CN)2] + NaCl.

The reaction with the sulphide is reversible and accumulation of Na2S must be
prevented. A free excess of air is continuously passed through the solution which oxidizes
Na2S into sulphate and thiosulphate.
2Na2S + 2O2 + H2O → Na2S2O3 + 2NaOH
Na2S2O3 + 2NaOH + 2O2→ 2Na2SO4 + H2O

The equilibrium can also be shifted in the forward direction by adding some litharge or
lead acetate which precipitates excess sulphide as PbS and helps in the dissolution process.
Na2S + (CH3COO)2Pb → PbS↓ + 2CH3COONa

Silver is recovered from solution by precipitation with zinc or aluminium. During

precipitation the solution should be strongly alkaline and sometimes caustic soda is added if
necessary.
2Na[Ag(CN)2] + 4NaOH + Zn → Na2ZnO2 + 4NaCN + 2H2O + 2Ag ↓

Refining:
Silver is refined by electrolysis of silver nitrate solution containing 1% nitric acid
using pure thin plate of silver as cathode and impure silver slab as anode. On passing electric
current, silver is deposited at the cathode and silver from the anode dissolves. Copper, if
present as impurity dissolve in the electrolyte solution and gold, if present, is deposited as a
anode mud.

Compound of silver:
AgNO3, Ag2S, AgCl, AgBr, AgI and AgO are some of the important compounds of
silver.

GOLD:
Some important ores.
(i) Bismuthaurite : BiAu2 (ii) Syvanite : AgAuTe2 (iii) Calverite : AuTe2

Extraction:
(i) Extraction of gold by cyanide or Mac Arther Forest cyanide process. This is a very
good method for the extraction of gold, even from quartz containing very small
amount of gold. The gold bearing quartz is mined by blasting. The rock is crushed
to very fine powder in stamp mills and a pulp of powdered ore and water is made
alkaline with slaked lime. The slury is treated with a dilute solution of sodium
 cyanide (0.03 to 0.08 per cent) and the solution is agitated by passing air though it.
Gold dissolves in sodium cyanide solution forming sodium aurocyanide.
4Au + 8NaCN + 2H2O + O2 → 4[NaAu(CN)2] + 4NaOH.

The gold recovered from the solution by precipitation with zinc dust in deareated
cyanide solution.
2Na[Au(CN2)] + Zn → Na2[Zn(CN)4] + 2Au

The excess of zinc is removed by dilute acid, when the gold is left as a slime which is
collected into a compact mass by fusion. Gold obtained in this way contains some silver and
other impurities.
Refining:
The crude gold is made the anode and the cathode is pure gold. The electrolytic bath
contains a solutions of gold chloride in hydrochloric acid. On electrolysis, gold is deposited on
the cathode.

(ii) Plattner chlorine extraction process: The roasted ore of auriferous pyrite ore is
moistened with water and treated with chlorine. Gold chloride is leached with water
and the solution is treated with reducing agent like H2S.
→ FeCl3 + Fe2(SO4)3

AuCl3 + 3FeSO4 + Au
→ 6HCl + 3S + 2Au

AuCl2 + 3H2S

Quartations process:
Refining of gold is carried by this process. It involves the separation of gold and silver
by sulphuric acid.
Gold is soft and hence for making ornaments it is generally hardened by adding Ag or Cu. The
weight of gold is expressed in terms of Carats. Pure gold is taken as 24 carats.
20 carats means, it contain 20 parts by wt. of gold in 24 parts by wt. of given alloy.
Percentage of gold in 20 carat gold sample = 20

×100=
250

= 83.33%
24 3

Properties of Gold:
(i) Gold is not affected by conc. H2SO4, conc. HNO3, or by strong alkalis.
(ii) However it dissolves in aqua regia to form H[AuCl4]
2Au + 3HNO3 + 11HCl →2H[AuCl4] + 6H2O + 3NOCl

Compounds of Gold:
 1. AuCl3: It is a reddish solid soluble in water. It reacts with HCl to give H[Au(Cl)4]
which is used in toning process in photography.
HCl + AuCl3 → H[Au(Cl)4]
2. Au2S: It is a dark brown solid insoluble in water prepared as follows.
2K[Au(CN) ] + H S→
2 2 Au2S + 2KCN + 2HCN

MERCURY :
10 2
Hg[Ar] 5d 6s
Important ore: Cinnabar :Hgs

Extraction of mercury from cinnabar:

(i) Concentration: The powdered ore is concentrated by froth floatation process.
(ii) Roasting : The concentrated ore is roasted in the presence of excess of air at 770 to
780 K to form HgO. At this temperature, mercury oxide formed decomposes into
mercury vapours and oxygen. The mercury vapours are then condensed.
2HgS + 3SO2 → 2HgO + 2SO2
2HgO→ 2Hg + O2
(iii) Refining: It is refined by filtering impure mercury through thick canvass or chamois
leather. It is then dropped into 5% nitric acid when metallic impurities like Fe, Cu,
Zn etc., get converted to their respective nitrates and go into solution and mercury
free from impurtities is received in the receiver. It is further refined by distillation
under reduced pressure. More volatile mercury is distilled first.

Compounds of Mercury:
1. Mercuric chloride, HgCl2 (Corrosive sublimate).
(i) It is a colourless solid, sparingly soluble in water.

(ii) It forms red ppt. of HgI2 with KI:

HgCl + 2KI →
2 HgI2 + 2KCl

(iii). With NH4OH it gives white ppt. of Hg(NH2)Cl.

HgCl2 + 2NH4OH → Hg(NH2)Cl + NH4Cl + 2H2O
White ppt.
2. Mercurous chloride, Hg2Cl2 (Calomel).
 (i) It is a white solid insoluble in water.
(ii) With NH4OH it forms a black mixture composed of black metallic mercury and
white mercuric aminochloride, Hg(NH2)Cl.
Hg2Cl2 + 2NH4OH → Hg + Hg(NH2)Cl + NH4Cl + 2H2O

Black Mixture

(iii) It is used as purgative in medicine and it sublimes on heating.

3. Mercuric iodide, HgI2:

(i) It is a yellow solid below 400 K but changes to red solid above 400 K
400K
HgI2 HgI2
⇌

Red Yellow
(ii) It dissolves in excess of KI forming K2HgI4.
HgI2 + 2KI K2HgI4→

Alkaline solution of K2HgI4 is called Nessler’s reagent.

ZINC :
10 2
Zn[Ar]3d 4s
Important ores.
(i) Znincite (red zinc ore): ZnO
(ii) Franklinite :ZnOFe2O3
(iii) Zinc blende : ZnS
(iv) Calamine (zinc spar) : ZnCO3

Extraction of zinc from zinc blende:

(i) Concentration: The powdered ore is concentrated by froth floatation process.

(ii) Roasting: The concentrated ore is roasted at 1200 K in excess of air.
△

ZnS + 3O2 → 2ZnO + 2SO2

Some ZnSO4 is also formed but at high temperature the sulphate decomposes to
give ZnO.
△

ZnS + 2O2 → ZnSO4

△

2ZnSO4 → 2ZnO + 2SO2 + O2

(iii) Reduction of ZnO: The oxide ore is mixed with crushed coke and heated to about
1670 K in fire clay retorts (Belgian process) zinc being volatile distils over and is
received in an earthen ware pot where it condenses. The crude metal obtained is
called zinc spelter.
 (iv) Refining: It is refined by distillation and by electrolytic method. The electrolytic
used is acidified zinc sulphate. The anode is made of spelter and cathode of pure
zinc wire.

Compounds of Zinc:

1. Zinc oxide, ZnO:

(i) Zincite (ZnO) is also called Philospher’s wool.
(ii) ZnO is white powder, become yellow on heating and again white on cooling.
(iii) ZnO is amphoteric in nature.
(iv) ZnO is used as a white pigment under the name Zinc white or Chinese white.

2. Zinc Sulphate (White vitriol), ZnSO4.7H2O:

(i) It is a colourless transparent crystal highly soluble in water.
(ii) On heating it looses its molecules of water as:
ZnSO4.7H2O→ 375KZnSO4.H2O → 725KZnSO4→ △ ZnO + SO2 + O2
(iii) It is used as an eye-lotion and for preparing double salts.

PREPARATION, PROPERTIES AND USES OF KMnO4 AND K2Cr2O7:

Potassium dichromate, K2Cr2O7:

Preparation: It is prepared from chromite ore or ferro chromes (FeCr2O4 or FeOCr2O3) by
following steps.
(a) Fusion of the ore with molten alkali in presence of air
4FeCr O + 16 NaOH + 7O →
2 4 2 8Na2CrO4 + 2Fe2O3 + 8H2O.
The fused mass is extracted with water and filtered.
(b) Conversion of sodium chromate into sodium dichromate by treating the filtrate with dil
H2SO4
2Na2CrO4 + H2SO4 → Na2Cr2O7 + Na2SO4 + H2O

Na2SO4 being less soluble is separated as Na2SO410H2O by fractional crystallization.

(c) Conversion of sodium dichromate into potassium dichromate by heating with KCl.
Na2Cr2O7 + 2KCl → K2Cr2O7 + 2NaCl

Potassium dichromate being less soluble is obtained by fractional crystallization.

Properties:
(i) Physical state : Potassium dichromate forms orange red crystals which melts at 669
K. It is moderately soluble in cold water but freely soluble in hot water.
(ii) Action of heat : When heated strongly to white heat, it decomposes with the
evolution of oxygen.
△

4K2Cr2O7→ 4K2CrO4+2Cr2O3+ 3O2

Pot. Dichromate Pot. Chromate chromic oxide
(iii) Action of alkalis: When an alkali is added to an orange red solution containing
dichromate ions, a yellow solution is obtained due to the formation of chromate
ions. For example,
→

K2Cr2O7+ 2KOH 2K2CrO4 + H2 O

Pot. Dichromate Pot. Chromate
On acidifying the above yellow solution containing chromate ions, it again change
to orange red due to the formation of dichromate ions.
2K2CrO4 + H2SO4 →K2Cr2O7+ K2SO4 + H2O

Pot. Chromate Pot. Dichromate

In fact, in any given solution, dichromate ions and chromate ions exist in
equilibrium and are interconvertible by altering the pH of the solution.
2-
2CrO4 +
+ 2H ⇌
- 2-
2HCrO4 ⇌ Cr2O7 + H2O

Chromate ions hydrogenchromate dichromate ions

(yellow) ions ( Orange)

(iv) Action of concentrated sulphuric acid : In cold, red crystals of chromic anhydride
(CrO3) are formed
K2Cr2O7 + 2H2SO4(conc) 2CrO3 + 2KHSO4 + H2O →

(v) Oxidisingproperties : Potassium dichromate is a powerful oxidizing agent. In

acidic solution, its oxidizing action can be represented as follows.
0
Ionic equation :CrO7
2- + -
+ 14H +6e → 2Cr
3+
+7 H2O [ E = +1.31V]
Molecular equation :K2Cr2O7 + 4H2SO4→ K2SO4 Cr2(SO4)3 + 4H2O + 3[O]
Thus, equivalent mass of K2Cr2O7 = . 2 2 7 = 294 = 49
6 6

(a) It oxidises iodides to iodine

2- + - 3+
Cr2O7 + 14H + 6I → 2Cr + 7H2O + 3I2 (Ionic Equation)
This reaction is used in the estimation of iodide ions in the volumetric analysis.
(b) It oxidises ferrous salts of ferric salts:
2- + 2+ 3+ 3+
Cr2O7 + 14H + 6Fe → 2Cr + 7H2O + 6Fe
This reaction is used in the estimation of ferrous ions in the volumetric analysis.
(c) In oxidises H2S to S :
2- + 3+
Cr2O7 + 8H + 3H S → 2Cr + 7H2O + 3S 2

(d) It oxidisessulphur
2- + 3+
dioxide to2- sulpuric acid :
Cr2O7 + 2H + 3SO2→ 2Cr + H2O + 3SO4
 (e) If oxidises ethyl alcohol to acetaldehyde and acetic acid :
K2Cr2O7 + 4H2SO4 → K2SO4 + Cr2(SO4)3 + 4H2O + 3[O]
C2H5OH + [O] → CH3CHO + H2O
CH3CHO + [O] → CH3COOH
(vi) With hydrogen peroxide : Acidified potassium dichromate forms a deep blue
colour with hydrogen peroxide due to the formation of CrO5.
K2Cr2O7 + H2SO4 + 4H2O2→ 2CrO5 + K2SO4 + 5H2O

3+
The blue colour fades away gradually due to decomposition of CrO5 into Cr ions
and oxygen.

Uses.
(i) In volumetric estimation of reducing agents e.g., ferrous salts, iodides and sulphites.
This is due to the fact that K2Cr2O7 is obtained in a much higher degree of purity
than Na2Cr2O7
(ii) In the preparation of chromium compounds e.g., chrome alum.
(iii) In photography for hardening of gelatin.
(iv) In dyeing for producing Cr(OH)3 as mordant.
(v) Chromic acid mixture (K2Cr2O7 + conc. H2SO4) is used for cleaning glasswares in
the laboratory.
(vi) As an oxidizing agent.

Potassium permanganate, KMnO4:

It is prepared by fusing pyrolusite ore (MnO2) with KOH in the presence of
atmospheric oxygen or an oxidizing agent like KNO3 or KClO3 to get potassium manganate,
K2MnO4 (green mass). The green mass is extracted with water and is oxidized to potassium
permanganate, either electrolytically or by passing chlorine or ozone into the solution. The
purple solution is concentrated by evaporation which on cooling deposits crystals of KMnO4.
ℎ

2MnO2 + 4KOH + O2 → 2K2MnO4 + 2H2O

+ 2-
K2MnO4 ⇌ 2K + MnO4
- -
MnO4 →
2- MnO4 + e
Green Purple
Properties:
(i) Potassium permanganate exists as dark purple black prismatic crystals having a
greenish metallic lustre. It melts at 523 K. It is moderately soluble in water at room
temperature giving a purple solution. However, its solubility in water increases with
temperature.
(ii) Effect of heat. 2KMnO4 →K2MnO4 + MnO2 + O2

(iii) Oxidising properties.

(a) In acidic medium :
2KMnO4 + 3H2SO4 →K2SO4 + 2MnSO
. 158
4 + 3H2O + 5[O]
[Equivalent weight of KMnO4 in acidic medium = = = 31.6]
5 5

(b) In neutral medium :

2KMnO4 + H2O→2KOH +. 2MnO
158
2 + 3[O]
[Equivalent weight of KMnO4 in neutral medium = = = 52.6]
3 3

(c) In basic medium :

2KMnO4 + 2KOH→ 2K2MnO4 +. H2O158+ [O]
[Equivalent weight of KMnO4 in basic medium = = = 158]
1 1

-
In basic medium, MnO4 (managanate ions) is further reduced to MnO2 in the presence
of reducing agent. As such equivalent weight of KMnO4 in basic medium is same as in neutral
medium.
In acidic medium potassium permanganate oxidises.
(i) Ferrous- to ferric salt 2+ + 2+ 3+
MnO4 + 5Fe + 8H → Mn + 5Fe + 4H2O
(ii) Oxalates
-
to2- carbon
+
dioxide
2+
2MnO4 + 5C2O4 + 16H → 2Mn + 10CO2 + 8H2O

(iii) Iodides
-
to
-
iodine
+ 2+
10I + 2MnO4 + 16H → 2Mn + 5I2 + 8H2O
 (iv) Sulphites to sulphates
2- - + 2+ 2-
5SO3 + 2MnO4 + 6H →2Mn + 5SO4 +3H2O

In alkaline solution
(i) Iodides to iodates
- -
- -
I + 2MnO4 + H2O→ IO3 + 2MnO2 + 2OH

Uses.
(i) As oxidizing agent in laboratory and industry.
(ii) In volumetric estimation of ferrous salts, oxalates and other reducing agents in
redox titration.
(iii) As disinfectant in water.
(iv) For qualitative detection of halides, oxalates, tartarates.

Use of KMnO4 in redox – titrations:

Potassium permanganate is a powerful and versatile oxidizing agent and is widely used
for titration against reducing agents like oxalic acid and Mohr’s salt. During the titration, the
reduction of potassium permanganate by a reducing agent e.g., oxalic acid or Mohr’s salt,
produces manganous ions which are nearly colourless.
2+
- -
MnO4 + 8H+ + 5e → Mn + 4H2O
As the titration proceeds and when the whole of the reducing agent is consumed up,
then the addition of an excess drop of potassium permanganate solution gives its own colour
(pink) to the solution. Therefore, at the end point the colour changes from colourless to pink.
Thus, potassium permanganate acts as a self indicator.

SOME OTHER COMPOUNDS OF TRANSITION METALS :

Halides of transition metals:
(i) Halides of transition metals in higher oxidation states exhibit a greater tendency to
hydrolysis
e.g. TiCl4 + 2H2O →TiO2 + 4HCl

(ii) Bonding in fluorides is essentially ionic. In the chlorides, bromides and iodides, the
ionic character decreases with increase in atomic mass of the halogens. For example
CuF2 is ionic while CuCl2 and CuBr2 are covalent compounds consisting of infinite
chains. The structure of copper (II) chloride is given below.
Sulphides of transition metals.
(i) Sulphides of transition metals can be obtained direct union of sulphur with the
transition metals
△

Fe + S → FeS
(ii) In sulphides, the oxidation state of the metal is generally low because sulphur is a
weak oxidizing agent.
(iii) The sulphides of transition metals are usually coloured or back. For example CuS,
NiS, CoS are black, MnS is light pink, CdS is yellow etc. They are insoluble in
water.

Silver Nitrate or Lunar Caustic, AgNO3:

Silver nitrate can be prepared by heating silver with dilute nitric acid.
ℎ

3 Ag(s) + 4HNO3(aq) → 3AgNO3(aq) + NO(g) + 2H2O(l)

(dilute)

Properties:
(i) It is a colourless, crystalline compound, soluble in water and alcohol. It melts at 484
K.
(ii) In contact with organic substances (skin, clothes, paper etc.) it blackens due to
decomposition into metallic silver and thus leaves black stains when comes in
contact with skin and clothes.
(iii) It decomposes on exposure to light and hence is stored in brown coloured bottles.
On heating strongly, at red hot it decomposes to metallic silver.
△

2AgNO3(s) → 2Ag(s) + 2NO2(g) + O2(g)

(iv) With potassium chromate it gives a red ppt. of silver chromate.
(v) Aqueous solutions of halides, phosphates, sulphides, chromates, thiocyanates, give a
precipitate of the corresponding silver salt with silver nitrate solution
e.g.,
AgNO3(aq) + NaCl(aq) → AgCl(s) + NaNO3 (aq)

(white)
AgNO3(aq) + NaBr(aq) → AgBr(s) + NaNO3(aq)

(pale Yellow)
(vi) It forms precipitate of silver oxide with NaOH(aq). Originally, the ppt., has a brown
colour but turns black when dried.
2AgNO3(aq) + 2NaOH(aq) → Ag2O(s) + 2NaNO3(aq) + H2O(l)

(vii) Solid AgNO3 absorbs ammonia gas with the formation of an addition compound,
AgNO3.2NH3.
(viii) With potassium chromate it gives a red ppt. of silver chromate.
2AgNO3 + K2CrO4→Ag2CrO4 + 2KNO3

Red PPT
(ix) It gives white precipitate with hypo (sodium thiosulphate) which however dissolves
in excess of hypo due to complex formation.
2AgNO3(aq) + Na2S2O3(aq) →

Ag2S2O3(s) + 2NaNO3(aq)
Ag2S2O3(s) + 3Na2S2O3(aq)→

2Na3[Ag(S2O3)2](aq)
Sodium argentothiosulphate
However if hypo is not excess, the white ppt. changes to black Ag2S, slowly.
Ag2S2O3 + H2O → Ag2S + H2SO4
Black ppt.
(x) It gives white precipitate of AgCN with KCN which dissolves in excess of KCN
due to complex formation.
AgNO3(aq) + KCN(aq) → AgCN(s) + KNO3(aq)

AgCN(s) + KCN(aq) → K[Ag(CN)2](aq)

(xi) Tollen’s reagent: It gives brown precipitate with NH4OH which however dissolves
in excess of NH4OH due to complex formation.
2AgNO3 + 2NH4OH → Ag2O + 2NH4NO3+ H2O
Brown ppt.
Ag2O + 2NH4NO3 + 2NH4OH → 2[Ag(NH3)2]NO3+ 3H2O
 Diamminesilver(I)nitrate

The ammonical solution of AgNO3 is known as Tollens reagent and gives following reactions.
→Ag2C2↓+ 2NH4NO3+ 2H2O

(a) 2[Ag(NH3)2]NO3 + C2H2

Silver Acetylide
(b) Ag2O + C6H12O6 → 2 Ag ↓ + C6H12O7

Siver mirror
→ 2Ag↓+ HCOOH

(c) Ag2O + HCHO

Siver mirror
Uses.
(i) It is used as a laboratory reagent for the identification of various acidic radicals
especially for halides. Tollen’s reagent is used in organic chemistry for testing
aldehydes, reducing sugars, etc.
(ii) It is used for making silver halides which are used in photography.
(iii) It is used in the preparation of inks and hair dyes.
(iv) A very dilute solution of silver nitrate is used in causterisation of eyes and as dental
antiseptic.
(v) Silivering of mirror or for the preparation of silvered mirrors.
(vi) AgNO3 is popularly used both the quantitative and qualitative analysis. Presence of
- - -
chloride (Cl ) bromide (Br ) and iodide (I ) ions can be detected with the help of
-
silver nitrate. However, Fluoride ion (F ) cannot be detected by this method as
silver fluoride so formed on treatment with AgNO3 solution is soluble in water.

INNER TRANSITION ELEMENTS :

The elements which in their atomic or ionic form, in addition to their incomplete d-
subshell of the penultimate shell have party filled f-subshell of the ante-penultimate (inner to
the penultimate shell i.e. n-2) shell are called as f-block elements. They are also known as
inner transition elements. These are so called because these form a series within the transition
1-14 2
series. The general electronic configuration of the f-block elements is (n-2)f (n-1)s (n-1)
6 10 2
p (n-1) d ns .

Classification off-block elements:

The f-block elements can be subdivided into two series depending upon the nature of the
f-orbital of the antepenultimate shell (4f or 5f) in which the differentiating electron enters.

(i) 4f-series (First inner transition series). In these the differentiating electron goes to
4forbitals. This series consists of lanthanum (Z = 57) and the next 14 elements (Z =
58 to 71). These are known as Lanthanides.
(ii) 5f-series (Second inner transition series). In these elements differentiating electron
goes to 5f-orbitals. This series includes fifteen elements from actinium (Z=89) to
Lawrencium (Z = 103). These are known as actinides. Inner transition elements are
 placed outside the body of the periodic table. The reason for this is the remarkable
similarities among the chemeical properties of lanthanides and also among the
various members of the actinides. The similarities in properties, in turn is due to the
similar electronic configuration of the outermost shell. These elements differ only in
the number of f electrons which do not take part in chemical bonding (difference
from d-block elements in which the differentiating d-electrons are involved in
chemical interaction).

LANTHANIDES OR LANTHANONS :
In these elements differentiating electron goes to 4f-subshell. This series consists of 14
elements which follow lanthanum (Z = 57). It should be noted that fifteen elements starting
from La57 to Lu71 are generally considered as lanthanides because they resemble one another
closely. The name lanthanide has been derived from lanthanum which is the prototype of
lanthanides. However, lanthanum is not an element of f-block of the periodic table.
Originally these elements were called rare earths because for many years pure
compounds of these elements were difficult to obtain. Now a days the term rare earth is
avoided because many of these elements are far from rare

Lanthanides Actinides
Name Symbol At. No. Configuration Name Symbol At.No. Configuration
2 0 2 0 2 2
Cerium Ce 58 [Xe]4f 5d 6s Thorium Th 90 [Rn]5f 6d 7s
3 0 2 2 1 2
Praseodymium Pr 59 [Xe]4f 5d 6s Protactinium Pa 91 [Rn]5f 6d 7s
4 0 2 3 1 2
Neodymium Nd 60 [Xe]4f 5d 6s Uranium U 92 [Rn]5f 6d 7s
5 0 2 4 1 2
Promethium Pm 61 [Xe]4f 5d 6s Neptunium Np 93 [Rn]5f 6d 7s
6 0 2 6 0 2
Samarium Sm 62 [Xe]4f 5d 6s Plutonium Pu 94 [Rn]5f 6d 7s
7 0 2 7 0 2
Europium Eu 63 [Xe]4f 5d 6s Americium Am 95 [Rn]5f 6d 7s
7 1 2 7 1 2
Gadolinium Gd 64 [Xe]4f 5d 6s Curium Cm 96 [Rn]5f 6d 7s
9 0 2 8 1 2
Terbium Tb 65 [Xe]4f 5d 6s Berkelium Bk 97 [Rn]5f 6d 7s
10 0 2 10 0 2
Dysprosium Dy 66 [Xe]4f 5d 6s Californium Cf 98 [Rn]5f 6d 7s
11 0 2 11 0 2
Holminum Ho 67 [Xe]4f 5d 6s Einsteinium Es 99 [Rn]5f 6d 7s
12 0 2 12 0 2
Erbium Er 68 [Xe]4f 5d 6s Fermium Fm 100 [Rn]5f 6d 7s
13 0 2 13 0 2
Thulium Tm 69 [Xe]4f 5d 6s Mendelevium Md 101 [Rn]5f 6d 7s
14 0 2 14 0 2
Ytterbium Yb 70 [Xe]4f 5d 6s Nobelium No 102 [Rn]5f 6d 7s
14 1 2 14 1 2
Lutetium Lu 71 [Xe]4f 5d 6s Lawrencium Lr 103 [Rn]5f 6d 7s
GENERAL CHARACTERISTICS OF LANTHANIDES:
1. There are hard metals with high melting points.
2. Oxidation state. The lanthanides too display variable oxidation states. The
3+
characteristic and the most stable oxidation state of lanthanides is + 3 (Ln ). This
oxidation state is obtained by the loss of one 5d-electron and two 6s-electrons. Along
with + 3 oxidation state, certain metals show + 2 and + 4 oxidation states so as to attain
0 7 14
f , f and f configurations.
3. Ionic radii-Lanthanide contraction. There is a regular decrease in the size of
atoms/ions with increase in atomic number as we move across from La to Lu. Thus
among lanthanides, lanthanum has the largest and luterium has the smallest radii. This
slow decrease in size is known as lanthanide contraction.

Cause of lanthanide contraction:

The configurations of lanthanides show that the additional electron enters the 4f-
subshell. The shielding of one 4f-electron by another is very little (imperfect), being
even smaller than that encountered in case of d-electrons (d-transition series). The
imperfect shielding of f-electrons is due to the shape of f-orbitals which is very much
diffused. Thus as the atomic number increases, the nuclear charge increases by unity of
each stop, white no comparable increase in the mutual shielding effect of 4f-electrons
occurs. This causes a contraction in the size of the 4f-subshell. Consequently the atomic
and ionic size goes on decreasing systematically from La to Lu.
It must be noted that the decrease in atomic radii, although continuous, is not regular.
The decrease is much more in the case of first six elements than in the subsequent
elements. Hence the properties of lanthanide compounds show some divergence from
regularity. However, decrease in ionic radii is more regular.

Consequences of Lanthanide Contraction:

(i) Separation of Lanthanides: Separation of lanthanides is possible only due to
lanthanide contraction. All the lanthanides have quite similar properties and due
to this reason they are difficult to separate. However, because of lanthanide
contraction their properties (such as ability to form complexes) vary slightly.
This slight variation in properties is utilized in the separation of lanthanides by
ion exchange methods.
(ii) Variation in basic strength of hydroxides: The basic strength of oxides and
hydroxides decreases from La (OH)3 to Lu (OH)3. Due to lanthanide contraction
3+
size of M ions decreases and there is increase in the cavalent character in M-
OH bond.
(iii) Similarity of second and third transition series:The atomic radii of second
row of transition elements are almost similar to those of the third row of
transition elements. For example, among the elements of group 3, there is
normal increase in size from Sc to Y to La. But after lanthanide the atomic radii
from second to third transition series do not increase for group 4 and group 5.
 i.e., for Zr – Hf and Nb – Ta pairs which have element same atomic radii. After
group 5 the effect of lanthanide contraction is not so predominant.
4. Colour: The lanthanide metals are silvery white but the trivalent lanthanide ions are
coloured both in the solid state and in the aqueous solutions.
3+ 0 3+ 14
5. Magnetic properties: La (4f ) and Lu (4f ) having no unpaired electron do not
show paramagnetism while all other tripositve ions of lanthanides are paramagnetic.
6. They have low ionization energy and are highly electropositive. Their ionization values
are quite comparable with those of alkaline earth metals particularly calcium.
7. These metals do not have much tendency to form complexes.
8. The lanthanides are highly reactive. This is in agreement with the low value of their
ionization energies.
9. The solubility of compounds of lanthanides follow the same order as group 2 elements.
Their fluorides, oxides, hydroxides carbonates are insoluble in water. However halides
(except fluorides), nitrates, acetales are soluble in water.

GENERAL CHARACTERISTICS OF ACTINIDES :

Actinides:
The elements with atomic numbers 90 to 103 i.e. thorium to lutetium (which come
immediately after actinium, (Z = 89) are called actinides or acitinones. These elements involve
1-14 0-1 2
the filling of 5f orbitals. Their general electronic configuration is [Rn] 5f 6d 7s .
They include three naturally occurring elements thorium, protoactinium and uranium
and eleven transuranium elements or transuranics which are produced artificially by nuclear
reactions. They are synthetic or man made. All actinides are radioactive.

Physico-chemical characteristics of Actinides:

(i) Oxidation states:These elements usually exhibit oxidation state of +2. However,
they also show oxidation states of +4, +5 and +6.
(ii) Physical state: These are silvery white metals and get tarnished with alkalies.
(iii) Density: All the actinides except thorium and americium have high densities.
(iv) Colour: The actinide ions, in general are coloured. The colour depends upon the
0 7
number of 5felectrons. The ions of 5f and 5f configurations are colourless while
3 6
ions with 5f to 5f configturations are coloured.
3+ 3 3+ 4
Li (5f ) : Red, Np (5f ): Bluish
3+ 5 3+ 6
Pu (5f ) : Blue Am (5f ) : Pink

(v) Ionisation energies: These elements have low values of ionization energies.
(vi) Electropositive character: All the actinides are highly electropositive and as such
are strong reducing agents.
(vii) Complex formation: Actinides have a strong tendency towards complex formation
2+ 2+ +
and form cationslike , UO , PuO2 , UO etc.
(viii) Actnide contraction: Actinides show actinide contraction. The size of atom/cation
decreases regularly along the actinide series. The steady decrease in ionic radii with
increase in atomic number is referred to as a actinide contraction. This is due to
poor shielding of 5f electrons.

Uses of Actinides:
(i) Polutonium as fuel for atomic reactors and in atomic bombs.
(ii) Uranium as nuclear fuel, its salts in glass industry (to impart colour), textile industry
and in medicines.
(iii) Thorium in atomic reactors as fuel rods, in treatment of cancer, in gas mentals (as a
mixture of thorium and cerium nitrate 99:1)
 Alcohols, Phenols and Ethers
Alcohols and Phenols

Alcohols and phenols are formed when a hydrogen atom in hydrocarbon, aliphatic and
aromatic respectively, is replaced by hydroxyl group (-OR group).

Classification of Alcohols and Phenols

In alcohols, -OR group is attached to Sp3 hybridised carbon. These alcohols are usually
classified as primary, secondary and tertiary alcohols.

Alcohols may be

v) monohydric-containing one – OR group,

vi) dihydric-containing two – OR groups and

vii) polyhydric-containing three or more -OR groups.

2
In phenols, -OR group is attached to Sp hybridised carbon. These may also be monohydric,
dihydric, etc. The dihydric phenol further rosy be ortho, meta’ or para derivative.

3
In allylic alcohols, – OH group is attached to sp hybridised carbon but next to C=C bond.
e.g., CH2 = CH – CH2OH, Benzylic alcoho1(C6H5CH2OH)

Structure of Alcohols and Phenols

3
The oxygen atom of alcohols is Sp hybridised and they have tetrahedral position of
hybrid atomic orbitals .

The value of LROH bond angle depends upon the R group. For methyl alcohol, it is (∠C – O – H) 108.9° due to repulsion of lone pairs.

2
In phenols, the – OH group is attached to Sp hybridised carbon and thus, the C – O
bond acquires a partial double bond character.

Nomenclature of Alcohols and Phenol

In IUPAC, system, alcohol or alkanols are named by replacing the last word ‘e’ of the
corresponding alkane by ‘ol’. e.g.,

Preparation of Alcohols

2. From alkenes

(a) By acid catalysed hydration in accordance with Markownikoff’s rule.

Mechanism
+
Step I Protonation of alkene by attack of H3O

Step II Nucleophilic attack

Step III Deprotonation to form an alcohol

4. By hydroboration-oxidation
From carbonyl compounds

(a) By reduction of aldehydes and ketones

Aldehydes yield primary alcohols whereas ketones give secondary alcohols, when subjected to
reduction.

(b) By reduction of carboxylic acids and ester

Reduction of aldehyde, ketones and esters with No Alcohol is called Bouveault-blanc

reduction.
The reaction produces a primary alcohol with methanol, a secondary alcohol with aldehydes
(except methanal) and tertiary alcohol with ketones

8. Hydrolysis of alkyl halides

R – X + KOH(aq) → ROH + KX

To avoid dehydrohalogenation of RX, mild alkalies like moist

Ease of hydrolysis of alkyl halides RI > R – Br > RCI > and t > s > p alkyl halides.

9. Hydrolysis of ethers

10. From primary amines By treatment with nitrous acid.

Methylamine does not give methyl alcohol when treated with HNO2. It gives CH3OCH3
and CH3ONO.

10. By alcoholic fermentation

Preparation of Phenols

13. From haloarenes

14. From benzene sulphonic acid

15. From diazonium salts

N From cumene
Physical Properties of Alcohols

iv) Lower alcohols are colourless liquids, members from C5 – C11 are oily liquids and
higher members are waxy solids.
v) The hydroxyl groups in alcohols can form H-bonds with water, so alcohols are miscible
with water. The solubility decreases with increase in molecular mass.

vi) Boiling points of alkanes are higher than expected because of the presence of
intermolecular hydrogen bonding in the polar molecules.

[The boiling point decreases in the order 1° > 2° > 3° as the van der Waals’ forces of
attraction decreases]

Physical Properties of Phenols

2. These are colourless liquids or crystalline solids but become coloured due to slow
oxidation with air.
3. Phenol is also called carbolic acid.
4. Because of the presence of polar -OH bond, phenols form intermolecular H-bonding
with other phenol molecules and with water.

Chemical Reactions of Alcohols and Phenols

3. Reactions involving cleavage of O – H Bond

(a) Acidity of alcohols and phenols

Alcohols are weaker acids than water due to +1 group present in alcohols, which decreases the
polarity of -O-H bond.
Acid strength of alcohols

Electron releasing group increases electron density on oxygen to decrease the polarity of – OH
bond.

Order of acidity is

RCOOH > H2CO3 > C6H5OH > H2O > R – OH.

Phenol is more acidic than alcohols due to stabilisation of phenoxide ion through resonance.
Presence of electron withdrawing group increases the acidity of phenol by ,
stabilising phenoxide ion while presence of electron releasing group decreases the acidity of
phenol by destabilising phenoxide ion.

Thus. increasing acidic strength is

o-cresol < p-cresol < m-cresol < phenol < o-nitrophenol < 2, 4. 6.trinitrophenol (picric acid)

Higher Ka and lower pKa value corresponds to the stronger acid.

2 Esterification
The reaction with R’COOH and (R’ CO)2O is reversible, so cone, H2SO4 is used to
remove water.

The reaction with R’ COCI is carried out in the presence of pyridine so as to neutralise HCI
which is formed during the reaction.

The introduction of acetyl (CH3CO-) group in phenols is known as acetylation.

Acetylation of salicylic acid produces aspirin.

4. Reaction involving cleavage of C-O bond in alcohols In these reactions, the reactivity
order of different alcohols :

Alkyl group due to +1 effect increases the electron density on the carbon and oxygen atom of
C-OH bond. As a result, the bond cleavage becomes easy. Greater the number of alkyl groups
present, more will be the reactivity of alcohol. Thus, the relative order of reactivity of the
alcohols is justified.
Reaction with halogen acids Alcohols can be converted into haloalkanes by the action of
halogen acids.

R – OH + HX (HCI, HBr, HI) → R-X +H2O

For a given alcohol order of reactivity of HX is

H-1 > H-Br > H-Cl

For a given halogen acid order of reactivity of alcohols

Tertiary > Secondary > Primary

Lucas test

(iii) Reaction with phosphorus halides

(iv) Reaction with thionyl chloride

(v) Dehydration of alcohols It requires acid catalyst and the reaction proceeds via
intermediate carbonium ion. Acidic catalyst converts hydroxyl group into a good leaving
group.

Since, the rate determining step is the formation of carbocation, the ease of dehydration is
Mechanism

Step I Formation of protonated alcohol

Step II Formation of carbocation

Step III Formation of ethene by elimination of a proton

In dehydration reaction, highly substituted alkene is the major product and if the major
product is capable of showing cis-trans isomerism, trans-product is the major product.
(Saytzeff’s rule).

(vi) Oxidation reactions Oxidising reagents used for the oxidation of alcohols are
neutral, acidic or alkaline KMnO4 and acidified K2Cr2O7.

\
A common reagent that selectively oxidises a primary alcohol to an aldehyde (and no
further) is pyridinium chlorochromate (pCC).

(vii) Dehydrogenation

Distinction among 1°,2° and 3° Alcohols

1°, 2° and 3° alcohols are distinguished by Lucas test, oxidation and reduced copper.

Victor Meyer’s test is also used to distinguish them.

In this test, primary (1°) alcohols give red colour, secondary (2°) alcohols give blue colour
and tertiary (3°) alcohols give no colouration.
Reactions of Phenols

4. Electrophilic substitution reactions The -OH group attached to the benzene ring activates
it towards electrophilic substitution at ortho and para positions .

(vi) Halogenation

With calculated amount of Br2 in CS2 or CHCI3 it gives ortho and para product.
(v) SuLphonation

2. Nitration

The ortho and para isomers can be separated by steam distillation. This is because o-
nitrophenol is steam volatile due to intramolecular hydrogen bonding while p nitrophenol
is less volatile due to intermolecular hydrogen bonding which causes the association of
molecules.
(ii) Reimer-Tiemann reaction

This reaction is an electrophilic substitution reaction and electrophile is dichlorocarbene.

Similarly with carbon tetrachloride and alkali, c- and p-hydroxybenzoic acid are obtained

(iii) Kolbe’s reaction

(iv) Reaction with zinc dust

Terms Related to Alcohols

3. Rectified spirit It contains 95% ethyl alcohol and 45% water. It is an azeotrope (constant
boiling mixture) and boils at 74°(.
4. Absolute alcohol Alcohol containing no water, i.e; 100% C2H5OH is known as
absolute alcohol. It is prepared as follows.

4. Quick lime process

5. Azeotropic method

(iii) Methylated spirit The rectified spirit rendered poisonous by addition of 4-5%
methyl alcohol, traces of pyridine and some copper sulphate and is known as methylated
spirit or denatured alcohol.

(iv) Power alcohol Alcohol mixed with petrol or fuel and used In internal combustion
engines Is known as power alcohol.

(v) Wood spirit Methyl alcohol (CH3OH) is also called wood spirit. It is obtained by
destructive distillation of wood. Pyroligneous add, the product of destructive distillation
of wood, contains acetic acid (10%), methyl alcohol (25%) and acetone (05%). Drinking
of methanol causes blindness.

(vi) Grain alcohol Ethyl alcohol C2H5OH is also called grain alcohol. It is used
In the preparation of various beverages containing different percentages.

Dihydric Alcohols
These are generally called glycols because of their sweet taste. Ethylene glycol (CH 2OH
– CH2OH) is the first and most important member of dihydric alcohol series.

Methods of Preparation
Physical Properties

(iv) It is a colourless, syrupy liquid with sweet taste.

(v) Because of its tendency of formation of H-bonds, it is miscible with H2O and
ethanol but not with ether.

Chemical Properties

It gives all the general reactions of -OH group.

The per-iodic acid cleavage of 1,2-g1ycols is sometimes called Malaprade reaction.

Trihydric Alcohols

Glycerol or glycerine, CH2OH – CH(OH)- CH2OH is the first member of this

group. Its IUPAC name is propane-l,2,3-triol.

Method of Preparation
Cone HNO3 gives II; dil HNO3 gives II and III; Bi(NO3)3 or NaNO3 gives VI; Fenton’s
reagent or NaOBr or Br2 water in Na2CO3 gives a mixture of I and IV.

Solid KMnO4 oxidises glycerol to VII and CO2 and H2O.

With HIO4 (periodic acid). glycerol gives HCOOH and HCHO.

Ethers

Ethers are the organic compounds in which two alkyl or aryl groups are attached to a
divalent oxygen. known as ethereal oxygen. These are represented by the general formula R–
O-R” where R may be alkyl or aryl groups. e.g.,

These are the functional isomers of alcohols. These also exhibit chain isomerism and
metamerism.

Nomenclature of Ethers

In the IUPAC system, ethers are regarded as ‘alkoxy alkanes’ in which the ethereal oxygen is
taken along with smaller alkyl group while the bigger alkyl group is regarded as a part of the
alkane.

Preparation of Ethers
5. Williamson’s synthesis Only primary alkyl halides when react with sodium alkoxide give
ether while tertiary alkyl halides give alkene due to steric hindrance.

Physical Properties of Ethers

Ethers are polar but insoluble inH20 and have low boiling point than alcohols of
comparable molecular masses because ethers do not form hydrogen bonds with water.
Structure of Ether
3
The hybridisation of 0 atom in ethers is sp (tetrahedral) and its shape is V-shape.

Chemical Reactions of Ether

(ii)Reaction with HX

Ethers with two different alkyl groups are also cleaved in the same manner and results in the
2
formation of a primary halide (or smaller and less complex alkyl halide) by SN mechanism.

R-O-R’ + HX → RX + R’OR

The order of reactivity of hydrogen halides is as follows

HI > HBr > HCl

In ethers if one of the alkyl groups is a tertiary group, the halide formed is a tertiary halide by
1
SN mechanism.

(iii) Halogenation
v) Electrophilic 8ublititutioD reactions In ethers,-OR is ortho, para directing group and
activate. the aromatic ring towards electrophilic substitution reaction
 Ethyl phenyl ester C6H5OC2H5 is also, known as phenetole.

Uses of Ethers

(v) Dimethyl ether is used as refrigerant and as a solvent at low temperature.

(vi) Diethyl Ether is used as an anaesthesia in surgery .