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Chapter

Coordination Compund
& Metallurgy
1. INTRODUCTION

(a) The concept of coordination compounds arises from the complex formation tendency of
transition elements.
(b) These compounds play a vital role in our lives, as chlorophyll of plants and haemoglobin
of animal blood are also coordination compounds of Mg and Fe respectively
(c) One of the earliest known coordination compound is prussian blue which was accidently
prepared by a Berlin color maker, Diebach in 1704.
(d) The field of such compound is expanding due to their utilization in metallurgy, analytical
chemistry and polymerisation.

2. MOLECULAR OR ADDITION COMPOUNDS


(a) When solutions containing two or more simple stable compounds in molecular proportions
are allowed to evaporate, crystals of new substances are obtained. These substances are
termed as molecular or addition compounds
(b) Some common examples are as follows:
CuSO4 + 4NH3  CuSO4 . 4NH3
AgCN + KCN  KCN . AgCN
Simple stable Addition or molecular
compound compounds
4 KCN + Fe(CN) 2  Fe(CN2). 4KCN
K2SO4 + Al2 (SO4)3 + 24H2O  K2SO4 . Al2(SO4)3 . 24 H2O
(c) The molecular or addition compounds are of two types double salts lattice compound and
coordination or complex compound

2.1 Double salts or lattice compounds


(a) The addition compounds which are stable in solid state only but are broken down into
individual constituents when dissolved in water are called soluble salts or lattice compounds.
(b) For example when carnallite (KCl.MgCl2.6H2O) is dissolved in water it exhibits the
properties of KCl and MgCl2

2.2 Coordination or complex compounds


(a) The addition compounds in which some of the constituents ions or molecules lose their
identity and when dissolved in water they do not break up completely into individual ions
are called coordination compounds.
(b) The properties of their solutions are different than those of their constituents.
(c) In such compounds there is complex ion which is a central metal ion with lewis bases
attached to it through coordinate covalent bonds.
(d) On the basis of stability of complex ion, complex ions are further divided as follows:
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(i) Perfect complexes : Those in which complex ion is fairly stable and is either not
dissociated or feebly dissociated in solution state, e.g.
K4[Fe(CN) 6]  4K+ + [Fe(CN) 6]4–

Fe2+ + 6CN¯ (Feebly dissociated)
The ferrocyanide ion [Fe(CN) 6]4– is so insignificantly dissociated that it can be considered as
practically undissociated and does not give the test of Fe2+ or CN¯ ions
(ii) Imperfect complexes: Those in which complex ion is less stable and is reversibly dissociated
to give enough simple ions and thus imparts their tests, e.g
K2[Cd(CN) 4]  2K+ + [Cd(CN) 4]2–

Cd2+ + 4CN¯  (Appreciably dissociated)
Note : An imperfect complex may be too unstable to exist and may be completely dissociated in
solution, it then becomes a souble salt
3. VARIOUS TERMS USED IN COORDINATION COMPOUNDS
To understand concepts related to coordination compounds and their nature it is essential to
discuss some important terms. These are as follows:
3.1 Central ion : (Centre of coordination)
(a) The cation to which one or more neutral molecules or anions are attached is called as
centre of coordination
(b) Since the central ion acts as a acceptor and thus has to accommodate electron pairs
donated by the donor atom of the ligands, it must have empty orbitals
(c) This explains why the transition metals having empty d-orbitals form coordination
compounds very readily.
(d) In the complexes [Ni(NH 3)6]2+ and [Fe(CN) 6]3– , Ni2+ and Fe3+ respectively are the
central ions

3.2 Ligands
(a) The neutral molecules, anions or cations which are directly linked with the central metal
atom or ion in a complex ion are called ligands.
(b) Ligand donate a pair of electrons to the central atom
(c) Ligands are attached to the central metal ion or atom through coordinate bonds or dative
linkage
(d) Ligands are normally polar molecules like NH3 ; H2O or anions such as Cl¯, OH¯, CN¯
etc. which contain at least one unshared pair of valency electrons.
(e) With few exceptions, free ligands have one pair of electrons that is not engaged in bonding
for example. :CN:¯, Cl ¯
3.2.1 Types of Ligands on the basis of number of donor atoms present in them :
(a) Mono- or unidentate ligands: They have one donor atom, i.e. they supply only one
examples : F¯, Cl¯, Br¯, H 2O , NH3, CN¯, NO2¯, NO¯ CO
(b) Bidentate ligands: Ligands which have two donor atoms and have the ability to link
with central metal ion at two positions are called bidentate ligands. Some examples are:
CH 2 N
(1) (2) oxalate(ox)
CH 2 N
(3) 1,10-phenanthroline (o-phen)
Ethylenediamine (en)
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(4) Glycinato (Gly) (5) 2,2'-Dipyridyl (Dipy) (6) Carbonato
(c) Tridentate ligands : The ligands having three donor atoms are called tridentate ligands.
Examples are:

N N
(1) (2) Diethylene triamine (dien)
N

2,2',2"-Terpyridine (terpy)
(d) Tetradentate ligands: These ligands possess four donor atoms. Example are:

CH2COO¯
CH2COO¯
(1) N (2) Triethylene tetramine (Trien)
CH2COO¯
(Nitriloacetato)
(e) Pentadentate ligands : They have five donor atoms. For example, ethylenediamine
triacetate ion.
Ethylenediamine triacetato ion
(f) Hexadentate ligands : They are six donor atoms. The most important example is
ethylenediamine tetraacetateion.
Ethylenediamine tetraacetato ion (EDTA)4–
(g) Chelating ligands .
(a) Polydentate ligands whose structures permit the attachment of two or more donor sites to
the same metal ion simultaneously, thus closing one or more rings are called chelating
ligands and the compounds formed are known as chelate compounds.
(b) A chelate may be defined as a ring structure formed by the combination of a polydentate
ligand having two or more donor atoms with a metal ion forming part of the ring.
(c) The process of formation of chelates is called chelation.
(d) Chelate complexes are more stable than ordinary complexes in which the ligands is a
monodentate
(e) This increased stability of the compound due to chelation is called the chelate effect
(f) In the complex ion given below, 5 membered rings are formed. So all these are called
chelate complexes
2+
CH2—H2N NH2—CH2
Cu
CH2—H2N NH2—CH2
(g) Generally the chelate complexes with 5 or 6 membered rings are more stable.
(h) Flexidentate ligands: Polydentate ligands have flexidentate character. It is not necessary
that all the donor atoms present in the polydentate donor atoms present in the polydentate
ligands should form coordinate bonds with central metal atom (on ion). For example:
EDTA which is hexadentate ligand can functions as pentadentate (on tetradentate ligand
with certain metal ions. Finaly sulphate ion can also act as monodentate ligand.
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(i) Out of these, 5 membered rings are very stable when they involve saturated ligands
(j) On the other hand 6-membered ring structures acquire maximum stability when they
involved unsaturated ligands containing conjugate double bond. This is due to the resonance
effects involving metal d-orbitals and ligand p–orbital electrons.
(k) Ambidentate ligands: There are certain ligands which have two or more donor atoms
but during formation of complexes only one donor atoms is attached to metal ion. Such
ligands are called ambidentate ligands such as CN¯, NC¯.

3.2.2 Classification of ligands on the basis of donor and acceptor properties of the ligands.
(A) Ligands having one (or more) lone pair (or pairs) of electrons
(a) Ligands which contains vacant -type orbitals that can receive back donated e¯ from
M-ion in low oxidation state.
e.g. CO, NO, CN, NC, R–N=C, R 3P, R3As
- dipyridyl, o-phenanthroline
(b) All these ligands also have filled donor orbital in addition to vacant -type acceptor orbitals.
(c) Thus in these complexes both metal and ligand function as donors and acceptors.
(d) Ligands which do not have vacant orbitals to receive back donated electron from metals
eq. H2O, NH3
(e) Ligands having no lone pairs of electrons but have p bonding electron eq. Ethylene, benzene,
cyclopentadienyl-ion
3.3 Coordination number :
(a) The number of atoms of the ligands that are directly bonded to the central metal atom or
ion by coordinate bonds is known as the coordination number of the metal atom or ion.
(b) It is actually the number of coordinate covalent bonds which the ligands form with the
central metal atom or ion
(c) some common coordination numbers exhibited by metal ions are 2,4,6. The light transition
metals exhibit 4 and 6 coordination numbers while heavy transition metals may exhibit
coordination number more than 6
(d) For example the coordination number of Ni in the complex [Ni(NH3)4]Cl2 is 4 and that of
Pt in the complex K2[PtCl6] is 6

3.4 Coordination sphere :


(a) The central metal atom and the ligands directly attached to it are collectively termed as the
coordination sphere.
(b) Coordination sphere is written inside square bracket, for example [Co(NH3)6]3+
(c) The central metal atom and the ligands inside the square bracket behave as a single entity
(d) The part outside the bracket is called ionisation sphere.
(e) The species present in the coordination sphere are nonionizable
(f) The species present in the ionization sphere are ionisable.
Coordination sphere
Central metal ion Ligand

Ni (NH3)4 Cl2 Ionization sphere


Coordination number

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3.5 Oxidation state
(a) It is a number which represents the electric charge on the central metal atom of a complex
ion
(b) For example , the O.N. of Fe, Co and Ni in [Fe(CN) 6]4– , [Co(NH3)6]3+ and Ni(CO) 4 is
+ 2 , + 3 and zero respectively.
(c) The charge of the complex is the sum of the charges of the constituents parts.

3.6 Effective atomic number (EAN)


(a) In order to explain the stability of the complex, Sidgwick proposed effective atomic number
(b) It can be defined as the resultant number of electrons with the metal atom or ion after
gaining electrons from the donor atoms of the ligands.
(c) The EAN generally coincides with the atomic number of next noble gas in some case.,
(d) EAN is calculated by the following relation EAN = atomic number of the metal-number of
electrons lost in ion formation + number of electrons gained from the donor atoms of the
ligands
(e) The EAN values of different metal in their respective complexes are tabulated as follows:

Complex Metal At. No. Coordination Effective atomic number


(Oxid. state) of metal number
K4[Fe(CN) 6] +2 26 6 (26 – 2) + (6 × 2) = 36[Kr]
[Cu(NH3)4]SO4 +2 29 4 (29 – 2) + (4 × 2) = 35
[Co(CH3)6]Cl3 +3 27 6 (27 – 3) + (6 × 2) = 36[Kr]
Ni(CO)4 0 28 4 (28 – 0) + (4 × 2) = 36
K2[Ni(CN)4] +2 28 4 (28 – 2) + (4 × 2) = 34
K2[PtCl6] +4 78 6 (78 – 4) + (6 × 2) = 86
K3[Cr(C2O4)3 ] +3 24 6 (24 – 3) + (6 × 2) = 33
K3[Fe(CN) 6] +3 26 6 (26 – 3) + (6 × 2) = 35
K2[HgI4] +2 80 4 (80 – 2) + (4 × 2) = 86[Rn]
[Ag(NH3)2]Cl +1 47 2 (47 – 1) + (2 × 2) = 50
K2[PdCl4] +2 46 4 (46 – 2) + (4 × 2) = 52

4. I.U.P.A.C NAMING OF COORDINATION COMPOUNDS


Due to wide variety of coordination compounds it is essential to use a unified system of nomenclature.
Though a lot of compounds are known by their trivial names only, but I.U.P.A.C. has introduced
rules for the naming of coordination compounds are follows:

4.1 The order of listing the ions


(a) In common salts cation is named first and then the anion.
(b) In the complex ion (cation or anion) ligands are named first followed by the name of
central atom
(c) The oxidation state of the central metal is indicated by Roman numeral brackets immediately
after its name ; (0) indicates zero o.s.
(d) In case the complex is non ionic, it is named as one word e.g. [Ni(CO) 4] is called
tetracarbonyl nickel (0)
(e) The suffix- ate is added to the name of central metal forming anionic complex ion. In
cationic complex ion, the name of metal (usual name) is followed by the oxidation number
in bracket. However in some metals Latin names are preferred in place of English names
e.g. ion as ferrate, lead as plumbate and silver as argentate.

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4.2 Name of the ligands :
(a) If there are two or more different kinds of ligands, they are named in alphabetical order
without separation by hyphen.
(b) When there are several ligands of same kind, they are listed alphabetically
(c) Anionic ligands ending with 'ide' are named by replacing 'ide' by suffix 'O'
e.g Symbol Name as ligand
3–
N Nitrido
Cl¯ Chloro
O 2 2– Peroxo
Br¯ Bromo
O2H¯ Perhydroxo
CN¯ Cyano
2–
S Sulphido
O 2– Oxo
2–
NH Amido
OH¯ Hydroxo
(d) Ligands whose names end in 'ite' or 'ate' become 'ito' or 'ato i.e. by replacing the
ending 'e' with 'o' as follows:
Symbol Name as ligand
2–
CO 3 Carbonato
C2 O 42– Oxalato
2–
SO 4 Sulphato
NO 3 ¯ Nitrato
SO 3 2– Sulphito
CH 3COO¯ Acetato
NO 2 – Nitrito
(e) Neutral ligands are given the same names at the neutral molecules. For example. Ethylene
diamine as a ligand is named ethylene diamine in the complex. However some exceptions
to this rule are
H 2O Aqua
NH 3 Ammine
CO Carbonyl
NO Nitrosyl
CS Thiocarbonyl
(f) Names of positive ligands ends in 'ium' e.g.
NH4 + Ammonium
+
NO Nitrosylium
+
NH 2NH 3 Hydrazinium
(g) If the number of a particular ligand is more than one in the complex ion, the number is
indicated by using Greek numbers such as di, tri, tetra, penta, hexa, etc.
However, when the name of the ligand includes a number, e.g. dipyridyl, ethylene diamine,
then bis, tris, tetrakis are used in place of di, tri, tetra, etc.
(h) In case of chelating ligands or ligands having di, tri, tetra, etc, in their name the prefixes
bis, tris, tetrakis, are used before ligands placed in parenthesis
NH2
(en)2Co CO(en)2 (SO4)2 is named as
OH
Bis (Ethylenediamine) cobalt (III)--amido--
hydroxobis-(ethylenediamine) cobalt (III) sulphate
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(i) In poly nuclear complexes the bridging group is indicated in the formula of the complex
by separating it from the rest of complex by hyphens and adding before its name or in
poly nuclear complex (a complex with two or more metal atoms) bridging ligands (which
links two metal atoms) is denoted by the prefix  before its name.

5. BONDING IN COORDINATION COMPOUNDS

5.1 Werner's coordination theory


Alfred Werner (Considered as the father of coordination chemistry) studied the structure of
coordination complexes such as CoCl3, 6NH3 and CuSO4.4NH3 in 1893. According to him
(a) Each metal in coordination compound possesses two types of valencies:
(i) primary valency or principal valencies or ionisable valencies.
(ii) Secondary valency or nonionisable valencies.
(b) Primary valencies are satisfied by anions only. The number of primary valencies depends
upon the oxidation state of the central metal. It may change from one compound to other.
These are represented by dotted lines between central metal atom and anion.
(c) Secondary valencies are satisfied only by electron pair donor, the ions or the neutral
species. These are represented by thick lines.
(d) Each metal has a fixed number of secondary valencies also referred as coordination
number. The coordination number depends mainly on the size and the charge on the central
atom. The maximum number of ions or molecules that the central atom can hold by
secondary valencies is known as coordination number.
(e) The ions attached to primary valencies possess ionising nature whereas the ions attached
to secondary valencies do not ionise when the complex is dissolved in a solvent.
(f) Every central ion tends to satisfy its primary as well as secondary valencies.
(g) The secondary valencies are directional and are directed in space about the central metal
ion. The primary valencies are non-directional. The presence of secondary valencies gives
rise to stereoisomerism in complexes.
(h) Initially, Werner has pointed out coordination number of a metal atom to be four or six.
(i) The six valencies were regarded to be directed to the corners of a regular octahedron
circumscribed about the metal ion. For metals having four coordination number, the four
valencies are either arranged in a planar or tetrahedral nature.

Cl NH3
H3N

H3N Co NH3
Cl
H3N NH3
Cl
(j) Thus on the basis of werner theory, the CoCl3.6NH3 is called hexamminecobalt (III)
chloride because there are six ammonia ligands and the cobalt is in the +3 oxidation state,
i.e. cobalt has three primary valencies and six secondary valencies. The complex can
therefore be represented as shown.
Note : Now , it has been proposed that coordination number of a metal may be any whole
number between 2 and 9

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5.2 Sidgwick Theory and EAN rule
Sidgwick suggested that the metal ion will continue accepting electron pairs till the total number of
electrons in the metal ion and those donated by ligands is equal to that of the next noble gas.
This total number of electrons is called EAN of the metal which we have already discussed.

5.3 Valence Bond theory


The salient features of the theory are summarised below.
(a) The central metal ion has a number of empty orbitals for accommodating electrons donated
by the ligands. The number of empty orbitals is equal to the coordination number of the
metal ion for the particular complex.
(b) The atomic orbitals (s, p or d ) or the metal ion hybridize to form hybrid orbitals with
definite directional properties. These hybrid orbitals now overlap with the ligand orbitals
to form strong chemical bonds.
(c) The d-orbitals involved in the hybridization may be either inner (n-1) d orbitals or outer n
d-orbitals. The complexes formed in these two ways are referred to as low spin and high
spin complexes, respectively.
(d) Each ligand contains a lone pair of electrons.
(e) A covalent bond is formed by the overlap of a vacant hybridized metal orbital and a filled
orbital of the ligand. The bond is also sometimes called as a coordinate bond.
(f) If the complex contains unpaired electrons, it is paramagnetic in nature, while if it does not
contain unpaired electrons, it is diamagnetic in nature.
(g) The number of unpaired electrons in the complex, point out the geometry of the complex
as well as hybridisation of central metal ion and vice-versa. In practice, the number of
unpaired electrons in a complex is found from magnetic moment measurements as illustrated
below.
m= n (n  2) where n = no. of unpaired electron
Magnetic moment 0 1.73 2.83 3.87 4.90 5.92
(Bohr magnetons)
Number of 0 1 2 3 4 5
unpaired electrons
Thus the knowledge of the magnetic moment can be of great help in ascertain.... the type
of complex
(h) Under the influence of a strong ligand, the electrons can be forced to pair up against the
Hund's rule of maximum multiplicity.
Draw back of V.B. Theory
(i) It describes bonding in coordination compounds only qualitatively
(ii) It does not offer any explanation for the optical absorption spectra of complex.
(iii) It does not describe the detailed magnetic properties of coordination compounds.
5.4 Crystal field theory
This is the more advanced theory and satisfactorily explains the optical absorption spectra and
magnetic properties of complexes which were not explained by V.B.T. But its details are beyond
the scope of this text.
6. HYBRIDIZATION AND GEOMETRY
6.1 Formation of an Octahedral Complex:
Let us consider the case of six ligands forming an octahedral complex. For convenience, we may
regard the ligands as being symmetrically positioned along the axes of a Cartesian co-ordinate
system with the metal ion at the origin. To simplify the situation, we can consider an octahedral
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complex as a cube, having the metal ion at the centre of the body and the 6 ligands at the face
centres.

and if we take the metal ion as the origin of a Cartesian co-ordinate, the ligands will be along the
axes. As in the case of a spherical field, all of the d-orbitals will be raised in energy relative to the
free ion because of negative charge repulsions. However it should be pictorially obvious that not
all of the orbitals will be affected to the same extent. The orbitals lying along the axes
d z2

and dx 2  y 2 will be more strongly repelled than the orbitals with lobes directed between the

axes (dxy, dxz, dyz). The d-orbitals are thus split into two sets with the d z 2 and d x2 – y 2 at a higher
energy than the other three.

d z2
,d
x2 y2

0

dxy, dyz, dxz

6.2 Factors affecting the magnitude of  0


(i) Oxidation state of the metal ion: The magnitude of  0 increases with increasing ionic charge on
the central metal ion. As the ionic charge on the metal ion increases greater is the attraction for the
ligands, greater the repulsion and hence greater the magnitude of 0.
(ii) Nature of the ligands: Based on experimental observation for a wide variety of complexes, it is
possible to list ligands in order of increasing field strength in a spectrochemical series. Although it
is not possible to form a complete series of all ligands with a single metal ion, it is possible to
construct one from overlapping sequences, each constituting a portion of the series:
I–  Br–  S2–  SCN–  Cl–  N3 – , F–  urea, OH–  ox, O2– , H2 O  NCS–  py ,
NH3  en  bpy, phen  NO2 –  C6 H5 –  CN–  CO.
The spectrochemical series and other trends described allow one to rationalise differences in
spectra and permit some predictability. If the splitting of the d-orbitals resulted simply from the
effect of point charges (ions (or) dipoles), one should expect that anionic ligands would exert the
greatest effect. To the contrary most anionic ligands lie at the low end of the spectrochemical
series. Further more, OH – lies below the neutral H 2O molecule and NH3 produces a greater
splitting than H2O. Despite its imperfections, the basic theory can be used to interpret a number of
effects in co-ordination chemistry.
7. SHAPE OF COMPLEXES
The shape of complexes depends upon hybridization state of central atom, it is described as
follows:

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7.1 On the basis of hybridized orbitals it can be of two types as d2sp3 (inner orbital ) or sp3d2 (outer
orbital) Hybridized.
Outer orbital and Inner orbital complexes
Consider the complexes [CoF6 ]3– and [Co(NH3) 6]3+
The electronic configuration of Co3+ ion is
3d 4s 4p 4d
?? ? ? ? ?

In a weak ligand field such as [CoF6]3–, the approach of the ligand causes only a small split in the
energy level.

Since the ligand is a weak field ligand, its repulsions with the electrons in dz 2 and dx 2  y 2 orbitals

are very less (or) in other words we can say that the electrons in dz 2 and dx 2  y 2 cannot move
away from the approaching ligands since they have insufficient energy to pair up with the electrons
in dxy, dyz and dxz orbitals.
Thus there are no vacant orbitals in the 3d shell and the ligands occupy the first six vacant orbitals
(one 4s, three 4p and two 4d). Since outer d orbitals are used, this is an outer orbit complex. The
orbitals are hybridised and are written sp3d2 to denote this. Since none of the electrons has been
forced to pair off, this is a high spin complex and will be strongly paramagnetic because it contains
4 unpaired 3d electrons.
Under the influence of a strong ligand field as in the complex [Co(NH3)6]3+, the approach of the
ligand causes a greater split in the energy level.

Since, the split is very high, we can say that the energy difference between the two sets of orbitals
is much greater and this energy difference is sufficient to allow the electrons in dz 2 and dx 2  y 2
orbitals to move into the half filled d xz, dxy and dyz orbitals, even though this pairing requires
energy. We can also view this like, the ligand repel the electrons in higher energy level to an extent
such that they get paired up against Hund’s rule . So,

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The dz 2 and dx 2  y 2 orbitals become vacant. The six ligands each donate a lone pair to the first six
vacant orbitals, which are: two 3d, one 4s and three 4p. Inner d-orbitals are used and so this is an
inner orbital complex. The orbital are hybridised and written d 2sp3 to denote the use of inner
orbitals.
Since, the orginal unpaired electrons have been forced to pair off, there is a low spin complex and
is in fact diamagnetic.
The inner and outer orbital complexes may be distinguished by magnetic measurements. Since the
outer orbital complexes use high energy levels, they tend to be more reactive. The inner orbitals
are sometimes called inert orbitals.
Distribution of d-electrons in t 2g and eg sets in strong(er) and weak (er) octahedral
ligand fields.

Strong(er) field (low-spin or spin-paired Weak(er) field (high-spin or spin


Ions complexes) ( 0  P) free complexes) ( 0  P)
t p2g eqg t p2g e qg
n s n S
Configuration configuration

d1 t12g eg0 t12g e g0


1 ½ 1 ½
d2 t 22g e0g 2 1 t 22g e 0g 2 1
d3 t 32g e0g 3 3/2 t 32g e g0 3 3/2

t 42g e0g t 32g e1g


d4 2 1 4 2
d5 t 52g e0g 1 ½ t 32g e g2 5 5/2
d6 t 62g e0g 0 0 t 42g e 2g 4 2
d7 1 1/2 3 3/2
t 62g e1g t 52g e g2
t 62g eg2 1 t 62g e 2g
d8 2 2 1
6 3 ½ 6 3
d9 t 2g e g 1 t 2g e g 1 ½
0
d10 t 62g eg4 0 t 62g e 4g 0 0

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7.1.1. Inner orbital complexes:
We have already discussed that in these type of complexes the d-orbitals used are of lower
quantum number i.e. (n – 1) various examples are as follow
(a) Complexes formed by the use of inner orbitals are diamagnetic or have reduced
paramagnesium
(b) These are called as low spin or spin paired complexes.
7.1.1.1 [Fe(CN6 ) 4–
(a) e¯ configuration of Fe26 = [Ar] 3d64s2
(b) e¯ configuration of Fe+2 = [Ar] 3d6

(c) e¯ configuration of Fe+2 after rearrangement

=
CN CN CN CN CN CN

d2sp3
(d) The above rearrangement is due to presence of cyanide ligand
(e) In this state Fe2+ undergoes d2sp3 hybridisation to form six d2sp3 hybrid orbitals, each of
which accepts electron pair donated by CN¯ ions.
(f) The resultant complex is inner octahedral as shown in figure and it should be diamagnetic
as it has no unpaired electron. Formation of [Co(NH3)6]3+ takes place in the same manner.
NH3
H3N NH3

Co+3
H3N NH3
NH3

Octahedral shape of [Co(NH3)6]3+


76.1.1.2 [Fe(CN) 6 ]3–
3d 4s 4p

(a) Fe 26

3d 4s 4p

(b) Fe 3+

(c) Fe 3+ (rearranged due to presence of CN¯)

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3d 4s 4p

CN CN CN CN CN CN

d2sp3 hybridization
(d) The resulting complex is octahedral due to d2sp3 hybridization
(e) due to presence of unpaired e¯ it is paramagnetic

7.1.1.3 [Cr(NH3 )6 ]3+


3d5 4s 4P

(a) Cr 24

(b) Cr3+

(c) Cr3+ in d2sp3 hybridized state

3d5 4s 4P

NH3 NH3 NH3 NH3 NH3 NH3

d2sp3 hybrided
(d) This d2sp3 hybridisation leads to octahedral geometry, the complex [Cr(NH3)6]3+ will
be octahedral in shape
(e) Since the complex ion has 3 unpaired electrons it must be paramagnetic which is founded
to be so
(f) Other complexes of chromium with similar inner structure are [Cr(CN)6]3– and
[Cr(H2O)6]3+
7.1.2 Outer orbital complexes.
(a) In these complexes s, p as well as d orbitals involved in hybridization, belong to the
highest quantum number (n)
(b) Complexes formed by the use of outer n, d orbitals will be paramagnetic.
(c) These complexes are called high-spin or spin free complexes
(d) The outer orbital complexes have greater number of unpaired electrons

7.1.2.1 [CoF6 ]3–


3d 4s 4p 4d
(a) Co 27
(b) Co 3+ ion

(c) Co 3+ ion in sp3d2 hybridised state

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F F F F F F

sp3d2
(d) Due to octahedral orientation of six sp 3d2 hybridised orbitals shape [CoF6]3– complex ion is
octahedral
(e) Due to presence of four unpaired electrons is 3d orbital [CoF6]3– ion has paramagnetic character
(f) Other examples are [FeF6]3– , [Fe(NH3)6]2+, [Ni(NH3)6]2+, [Cu(NH3)6]2+, [Cr(H2O)6]3+

Formation of Tetrahedral Complexes :


A regular tetrahedron is related to a cube with an atom at the centre and four of the eight corners
occupied by ligands.
z

x
y

The directions x,y and z point to the centre of the faces. The dZ 2 and dx 2  y 2 orbitals point along
x,y and z axis and dxy, dyz and dxz orbitals point in between x,y and z.
The directions of approach of the ligands does not coincide exactly with either the dz 2 and dx 2  y 2
orbitals (or) the dxy, dyz and dxz orbitals. The approach of ligands raises the energy of both sets of
orbitals, but since the dxy,dyz and dxz orbitals correspond more closely to the position of the ligands,
their energy increases most and the dZ 2 and dx 2  y 2 orbitals are filled first. This is opposite to
what happens in octahedral complexes.
Consider, the complex ion, [FeCl4 ]– . The electronic configuration of Fe3+ ion is
3d 4s 4p
? ? ? ? ?

Since Cl– ion is a weak field ligand it is unable to pair the unpaired electrons and hence, the Cl– ion
uses 4s and 4p orbitals to form a tetrahedral complex of sp3 hybridisation.

7.2 Tetrahedral complexes :


These are formed by sp3 hybridisation. Complexes of Sn2+ are invariable tetrahedral because they
involve sp3 hybrid orbitals

7.2.1 [Zn(NH3)4]2+
3d 4s 4p
(a) e¯ configuration of Zn

3d 4s 4p
2+
(b) e¯ configuration of Zn

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3d 4s 4p
(c) Zn2+ in sp3 hybridised state

sp3 hybridised

(d) Zn(NH3)4]2+
NH3 NH3 NH3 NH3
(e) Since the complex is formed by sp3 hybridisation, it is tetrahedral
(f) Since all electrons are paired it is diamagnetic

7.2.2. [Ni(CO) 4]

sp3hybridization

Ni(28)
   
 C  C C C
O O O O
Ni electronic configuration – [Ar] 4s23d8

O
C

Ni
C C
C
O O
O
(tetrahedral)

Formation of a Square Planar Complex :


If the central metal ion has eight d-electrons, these will be arranged as

?? ?? ?? ? ?

In a weak octahedral ligand field, a regular octahedral complex is thus formed by using outer d-
orbitals.
However, under the influence of a strong ligand field, the electrons in the dz 2 and dx 2  y 2 orbitals
may pair up, leaving one vacant d-orbital, which can accept a lone pair from a ligand.
For example consider [Ni(CN)4 ]2–
The electronic configuration of Ni2+ ion is
3d 4s 4p
?? ?? ? ?
??

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Consider, a Ni2+ ion with one electron in the dx 2  y 2 orbital and one in the dz 2 orbital. The approach
of ligands along x, y and z axes will result in increase in the energy of these orbitals. Because the
dx 2  y 2 orbital is attacked by four ligands and the d 2 by only two, the energy of d orbital will
z x 2  y2

increase most. If the ligands have enough strong field, the electrons will be forced out of the
dx 2  y 2 orbital into the d 2 . Thus four ligands can approach along x, –x, y and –y axes.
z

A ligand approaching in the z (or) – z direction attempting to donate a lone pair meets the very
strong repulsive forces from a completely filled dZ 2 orbital. Thus only four ligands succeed in
bonding to the metal.

7.3 Square planar complex.


These are formed due to dsp2 hybridisation.
These complexes tend to be formed when the central ion has only one d orbital in the inner shell
7.3.1 [Ni(CN)4 ]2–
3d 4s 4p
(a) e¯ configuration of Ni

3d 4s 4p
(b) e¯ configuration of Ni2+
CN CN CN CN

(d) The rearrangement is due to presence of strong ligand CN¯. The four orbitals make
dsp2 hybridisation
(e) The shape of resulting complex is square planar
(f) due to paired electrons it is diamagnetic.
Co-ordination numbers, hybridised orbitals and geometry of some co-ordination compounds
Cordination Hybridized Geometrical shape Example of
Number orbital of the complex complex

180º
2 sp L M L [Ag(NH3)2]+
[Ag(CN)2]¯ Linear

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2 sp2 [HgI3]¯

L
4 sp3 [FeCl4]¯
109º28' [Ni(CO)4]0
M Zn(NH3)4+2
[CuCl4]–2, [CuX4]–2
L L where X = CN¯
Cl¯, Br¯, I¯, CNS
L
Tetrahedral

dsp2 L L
The d-orbital involved
4. is dx2–y2 orbital of 90º [Ni(CN)4]–2
the inner shell, i.e. it 90º 90º [Pt(NH3)4]+2
is (n–1) dx2–y2 orbital M
90º

L L
Square planar

L L

dsp3 90º
5. The d-orbital is L
M
120º [CuCl5]–3
(n – 1) dz2 orbital [MoCl5]0
L L
[Fe(CO)5]0
Trigonal bipyramidal

L
L L
sp3 d 90º
5. The d-orbtal is ndx2 –y2 90º [SbF5 ]–2 , IF5
orbital M
L L
Square pyramidal

L
L L
d2sp3 90º
When d-orbitals (are (n–1) [Cr(NH3)6+3]
d-orbitals (Inner orbital complexes) 90º M [Ti(H2O)6]+3
6. or sp3 d2 [Fe(CN)6 ]–2
when d-orbital are ndorbital L L [Co (NH3)6]+3
L
(outer orbital complexes) Octahedral [PtCl6]–2[CoF 6]–3

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In both cases p-orbitals
are dz2 and dx2–y2 orbitals

L = Ligands indicated by white circles (same or different) M=Central metal indicated by blacks
circles

8. ISOMERISM IN COORDINATION COMPOUNDS


The compounds having same molecular formula but different physical and chemical properties on
account of different structure are called isomers and the phenomenon as isomerism

8.1 Classification

Type of isomerism

Structural isomerism stereo isomerism

Ionization Polymerisation Linkage


Hydrate Coordination Coordination Geometrical Optical
position

8.1.1 Ionization isomerism :


(a) This is due to exchange of groups or ions between the coordinating sphere and the ionization
sphere
(b) This type of isomerism give different ions in solution because only the ion from ionisation
sphere is released in solution
(c) The example is red violet [Co(NH3)5]SO4 and red [CO(NH3)5SO4] Br which give SO4–
2
and Br¯ respectively.
8.1.2 Hydrate isomerism
(a) This type of isomerism is due to presence of different number of water molecules inside
and outside the coordination sphere
(b) Its example is as below
violet [Cr (H2)5]Cl3
green [Cr(H2O)5Cl[Cl2.H2O
dark green [Cr(H2O)4Cl2]Cl.2H2O
8.1.3 Polymerisation isomerism:
(a) This type of isomerism exists in compounds having same stoichiometric composition but
different molecular compositions
(b) The molecular compositions are simple multiples of the simplest stoichiometric arrangement
(c) For example : [Pt (NH3)2Cl2] ; [Pt(NH3)4] [PtCl4] ; [Pt(NH3)3Cl]2 [PtCl2]
8.1.4 Coordination isomerism:
(a) The type of isomerism occurs when both cation and anion are complex
(b) The isomerism is caused by the interchange of ligands between the two complex ions of
the same complex
(c) Examples : [Co(NH3)6] [Cr(CN)6] and [Cr(NH3)6] [Co(CN) 6]

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8.1.5 Linkage isomerism:


(a) This is also called as salt isomerism
(b) This type of isomerism arises due to presence of ambidentate ligands like NO 2¯, CN¯,
CO and SCN¯
(c) These ligands have two donor atoms but at a time only one atom is directly linked to the
central metal atom of the complex.
(d) Such type of isomers are distinguished by infra red (I.R.) spectroscopy
(e) Example : [Co(NH3)5NO2]Cl2 and [Co(NH3)5 ONO]Cl2
8.1.6 Coordination position isomerism
(a) This is exhibited by poly nuclear complexes by changing the position of ligands w.r.t.
different metal atoms present in the complex
(b) Example
2+
NH2
(NH3)4Co Co(NH3)2Cl2 and
O2
2+
NH2
(NH3)3ClCo Co(NH3)3Cl
O2
8.1.7 Geometrical isomerism:
(a) This isomerism is due to ligands occupying different positions around the central metal
atom or ion
(b) The ligands occupy position either adjacent or opposite to one another
(c) This type of isomerism is also known as cis-trans isomerism
(d) This is common in coordination number 4 and 6 complexes.
(e) Basically in di-substituted complexes, the similar groups may be adjacent or opposite to
each other. This gives rise to geometrical isomerism
(f) When similar groups are adjacent to each other it is called a cis isomer whereas when they
are opposite to each other, it is called as trans isomer.
(g) Example
CH2—NH2 NH2—CH2 CH2—NH2 O——CO
Pt Pt
CH2—NH2 NH2—CH2 CO——O NH2—CH2
Diglycinato platinum (iv) complexes
(h) C.N. - 4 square planar complexes-
(i) Complexes with general formula, Ma2b2 (where both a and b are monodentate) can have
cis-and trans-isomers.

a b a a H3N Cl H3N NH3

M M Pt Pt

b a b b Cl NH3 Cl Cl
Trans-isomer Cis-isomer Trans
Cis
[Ma2b2) [Pt(NH3)2Cl2]

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(ii) Complexes with general formula Ma2bc can have cis- and trans-isomers.
a a a c H3N NH3 H3N NO2

M M Pt Pt

b c b a Cl NO2 Cl NH3
Cis Trans Cis Trans

[Ma2bc) [Pt(NH3)2ClNO2]

(iii) Complexes with general formula, Mabcd, can have three isomers.
a b a d a b

M M M

d c c b c d
(i) (ii) (iii)
Note: Geometrical isomerism is not observed in complexes of coordination number 4 of tetrahedral
geometry

8.1.8 Optical isomerism


(a) A Coordination compound which can rotate the plane of polarised light is said to be
optically active.
(b) When the coordination compounds have same formula but differ in their ability to rotate
directions of the plane of polarised light are said to exhibit optical isomerism and the
molecules are optical isomers. The optical isomers are pair of molecules which are non-
super impossible mirror images of each other
(c) This is due to the absence of elements of symmetry in the complex.
(d) Optical isomerism is expected in tetrahedral complexes of the type Mabcd
(e) These isomers are not ionisable due to their labile nature
(f) Wxample : Bis-benzoylacetonato- beryllium (ii)

H3 C CH3 H3 C CH3
C—O C—O C—O O—C
H—C Be C—H H—C Be C
C—H
C==O C==O C==O O==C
H5C6 C6H5 H5C6 C6H5

(g) Optical isomerism is not in squareplanar complexes on account of the presence of axis of
symmetry.
(h) Optical isomerism is very common in octahedral complexes.
(a) [Ma2B2C2]n± [Pt(py)2(NH3)2Cl2]2+
(i) Eg.

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py py
2+ 2+
Cl Py py Cl

Pt Pt

Cl NH3 H3N Cl
NH3 NH3
Cis-d-isomer Mirror Cis-l-isomer

(b) [Mabcdef] [Pt(py)NH3NO2ClBrI]

py py
py NO2 O2 N py

Pt Pt

Cl NH3 H3 N Cl
I I
d-isomer Mirror l-isomer
(c) [M(AA)3]n± [Co(en)3]3+

3+ 3+
en en
en

Co Co

en
en en
d-form Mirror l-form

en Co en en

'Meso' or optically inactive form


(d) [M(AA)2a2]n± [Co(en)2Cl2]+

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3+
en en 3+
Cl Cl

Co Co

Cl Cl
en en
Cis-d-form Cis-l-form
Mirror

Trans form of [M(AA)2a2]n± does not show optical isomerism

(e) [M(AA)2a2]n± (Co(en)2NH3Cl]2+

en 2+ en 2+
Cl Cl

Co Co

H3N NH3
en en
Cis-d-form Cis-l-form
Mirror

(f) [M(AB)3] (Cr(gly)3]

gly gly

Cr gly Cr
gly

gly gly
Cis or trans-d-form Cis or trans-l-form
Mirror

Some more example are:


[Cr(ox)3]3– ; [Fe(dipy)3]2+ ; [Cr(ox)2(H2O)2]¯ ; [Pt(en) 3]4+
9. STABILITY OF COMPLEX
(a) A complex is formed in solution by the stepwise addition of ligands to a metal ion
(b) This can be expressed as follows [M] + [L] [ML]
(c) The stability constant K for this reaction is as shown
[ML]
K=
[M][L]
(d) This metal can again get a ligand
[ML] + [L] [ML2]
(e) The forthcoming stability constant K' is
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[ML 2 ]
K1 = its value is less than K
[ML][L]
(f) The higher the value of stability constant stabler is the complex
(g) The value of stability constant for some of the complexes are given below:
Complex Stability constant
[Cu(NH3)4]2+ 4.5 × 1011
[Ag(NH3)2]2+ 1.6 × 107
2+
[Co(NH3)6] 1.12 × 1011
[Co(NH3)6]2+ 5.0 × 1033
[AgCl2]– 1.11 × 105

[AgBr2] 1.28 × 107
[Ag(CN)2]– 1.0 × 1022
2–
[Cu(CN)4] 2.0 × 1027
[Fe(CN) 6]3– 7.69 × 1043

9. STABILITY OF COMPLEX
9.1 Factors influencing the stability of complex
9.1.1 Nature of central ion–
(a) The complex will be more stable for higher values of charge density Ch arg e
Radius

(b) The higher the electronegativity of the central ion, the greater is the stability its complexes
(c) The higher the oxidation state of the metal the more stable is the compound
9.1.2 Nature of ligand
(a) A basic ligand is likely to easily donate its electrons. Thus a more basic ligand will form
more stable complex
(b) Chelating ligands form more stable complexes as compared to monodentate ligands

10. CHARACTERISTICS OF COORDINATION COMPOUNDS


Coordination compounds posses many remarkable physical-chemical properties. Which are
described as follows
10.1 Change in solubility
The solubility of a weak electrolyte increases if one of its ion is involved in the complex formation
10.2 Change in conductivity
The complex formation result in the change in number of ions and thus conductivity of solution
changes abruptly during complex formation
10.3 Change in chemical properties
Due to formation of complex ion, normal chemical properties of metal ion changes
10.4 Change in colour
As the complexes are formed from transition metals, which are colored and exhibit absorption in
the visible region of the electromagnetic spectrum it also shows colour which indicates the nature
of the metal ion, its oxide
10.5 Change in pH:
If complex formation involves use of H+ ion, the change in pH indicates the formation of complex
ion
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10.6 Paramagnetic nature: Due to presence of unpaired electron in valence shell of central atom this
shows paramagnetism.
10.7 Change in freezing point: During complex formation total no. of particles in solution changes.
Consequently freezing point changes.

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EXERCISE -1
Q.1 Which one will give Fe3+ ions in solution ?
(a) [Fe(CN) 6]3– (b) [Fe(CN)] 62– (c) (NH4)2SO4.FeSO4.6H2O (d) Fe2(SO4)3
Q.2 What is the coordination number of Cr in K3[Cr(ox)3] ?
(a) 6 (b) 5 (c) 4 (d) 3
Q.3 The oxidation state of Ni in [Ni(CO)4] is
(a) 0 (b) 1 (c) 2 (d) 4
Q.4 The correct IUPAC name for the compound [Co(NH3)4ClONO]Cl is
(a) Tetraammine chloronitro cobalt (III) chloride
(b) Chloronitritotetraammine cobalt(II) chloride
(c) Dichloronitritotetraammine cobalt (III)
(d) Tetraammine chloronitrito cobalt (III) chloride
Q.5 Coordination number of Ni in [Ni(C2O4)3]4– is
(a) 3 (b) 6 (c) 4 (d) 5
Q.6 The number of unpaired electrons in the complex ion [CoF6]3– is
(a) 3 (b) 4 (c) 0 (d) 2
Q.7 The unpaired electrons in [Ni(CO)4]are:
(a) zero (b) 1 (c) 2 (d) 3
Q.8 The correct IUPAC name of Mn3(CO)12 is:
(a) Dodecacarbonylmanganate (b) Dodecacarbonylmagnac (II)
(c) Dodecacarbonyltrimanganese(O) (d) Manganic dodecacarbonyl(O)
Q.9 Consider the following statements:
According the Werner’s theory.
1. Ligands are connected to the metal ions by covalent bonds
2. Secondary valencies have directional properties
3. Secondary valencies are non-ionisable.
of these statements:
(a) 1, 2 and 3 are correct (b) 2 and 3 are correct
(c) 1 and 3 are correct (d) 1 and 2 are correct
Q.10 (i) Higher the value of K, more is the stability of complex ion.
(ii) Larger the value of charge density, greater is the complex stability.
(iii) Ions having same charge Ca2+, Ni+2, Co +2, Fe+2, Cu+2 is having maximum stability due to
smallest size.
(iv) More basic ligand will form most stable complex.
(a) TTTT (b) TFFT (c) TFTT (d) TTTF
Q.11 (A) The ions attached to primary valence possess ionising nature where as ions attached to
secondary valencies doesn’t ionise
(B) Secondary valencies are directional about the central metal ion and primary valences are
non-directional.
(C) The presence of 2º valencies gives rise to stereo isomerism in complex.
(D) The six valencies are directed towards the corners of regular octahedron about the metal
ion and the four valencies are arranged in a square planar (or) tetrahedral manner
(a) TTTT (b) FFTF (c) FTFT (d) FTTF

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Q.12 Which of the following option is correct for imperfect complexes


(i) Imperfect complexes are less stable
(ii) Tt is reversibly dissociated
(iii) It will give simple ions and imparts test for their individual ions.
(iv) For the complex K2[Cd(CN) 4]. It gives tests for K+, Cd+2, CN– ions.
(a) FTTF (b) TTFT (c) TFFT (d) TTTT
Q.13 (i) Chelating ligands form stable complexes than monodentate ligands.
(ii) Chelating ligands form stable rings with large group due to steric effect.
(iii) Chelating ligands are used in softening hard water and in the separation of lanthanides
and actinides.
(iv) Chelating ligands will not form strain free rings with the metal ion.
(a) FTTF (b) TTFT (c) TFFT (d) TTTT

CO
Q.14 The correct name of , (CO) 3Fe CO Fe(CO)3 is :
CO
(a) tri--carbonylbis(tricarbonyl)iron(0)
(b) Hexacarbonyliron(III)-tricarbonyl ferrate (0)
(c) Tricarbonylirion(0)-tricarbonyl iron(0) tricarbonyl
(d) nonacarbonyl iron
Q.15 The correct IUPAC name of K2[Zn(OH)4] is
(a) Potassium tetrahydroxyzinc(II) (b) potassium tetrahydroxozincate (II)
(c) Potassium tetrahydroxyzincate (IV) (d) potassium hydroxozinc(II)
Q.16 In which of the following pair the EAN of central metal atom is not same?
(a) [Fe(CN) 6]3– and [Fe(CN) 6]4– (b) [Cr(NH3)6]3+ and [Cr(CN) 6]3–
(c) [FeF6]3– and [Fe(CN) 6]4– (d) [Ni(CO) 4] and [Ni(CN) 4]2–
Q.17 (i) The species present in the coordination sphere are ionisable
(ii) The species present in the ionisation sphere are non ionisable.
(iii) The coordination of Ni in complex [Ni(NH3)4]Cl2 is 4 and that of Pt is K2[PtCl6] is 6.
(iv) Oxidation no. of Fe in K3[Fe(C2O4)3] is +4.
(a) TTTF (b) TFFT (c) FFTF (d) FTTF
Q.18 The EAN of cobalt in the complex ion [Co(en) 2Cl2]+ is –
(a) 27 (b) 36 (c) 33 (d) 35
Q.19 The formula of the complex tris (ethylene diamine) cobalt (III) sulphate is –
(a) [Co(en) 2SO4] (b) [Co(en) 3SO4]
(c) [Co(en) 3]2SO4 (d) [Co(en) 3]2(SO4)3
Q.20 The correct IUPAC name of the compound [Co(NH3)4ClONO]Cl is –
(a) Tetraammine chloronitro cobalt(III) chloride
(b) Chloronitritotetraammine cobalt (II) chloride
(c) Dichloronitritotetraammine cobalt (III)
(d) Tetraammine chloronitrito cobalt (III) chloride
Q.21 The IUPAC name of the Ni(CO) 4 is –
(a) tetreacarbonyl nickelate(0) (b) tetracarbonyl nickelate (II)
(c) tetracarbonyl nickel(0) (d) tetracarbonyl nickel (II)

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Q.22 IUPAC name of complex, K3[Al(C2O4)3] is –
(a) potassium alumino oxalate (b) potassium trioxalatoaluminate (III)
(c) potassium aluminium (III) oxalate (d) potassium trioxalatoaluminate (VI)
Q.23 Coordination number of Ni in [Ni(C2O4)3]4– is –
(a) 3 (b) 6 (c) 4 (d) 5
Q.24 The geometry of [NI(CN) 4]2– and [NiCl4]2– ions are –
(a) tetrahedral (b) square planar
(c) square planar, tetrahedral respectively (d) tetrahedral and square planar respectively
Q.25 The effective atomic number of cobalt in the complex [Co(NH3)4]3+ is –
(a) 36 (b) 33 (c) 32 (d) 30

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EXERCISE -2

Q.1 [Co(NH3)5NO2]Cl2 and [Co(NH3)5ONO]Cl2 are related to each other as :


(a) geometrical isomers (b) linkage isomers
(c) coordination isomers (d) ionisation isomers
Q.2 Which of the following has the highest molar conductivity in solution ?
(a) [Pt(NH3)6]Cl4 (b) [Pt(NH3)5Cl]Cl3
(c) [Pt(NH3)4Cl2]Cl2 (d) [Pt(NH3)3Cl2]Cl
Q.3 Which of the following is paramagnetic ?
(a) potassium ferrocyanide (b) potassium ferricyanide
(c) hexaammine cobalt (III) chloride (d) tetracarbonyl nickel (0)
Q.4 Which of the following compounds is not coloured ?
(a) Na2[CuCl4] (b) Na2[CdCl2] (c) K4[Fe(CN) 6] (d) K3[Fe(CN) 6]
Q.5 What is the shape of [Fe(CO) 5] molecule ?
(a) tetrahedral (b) octahedral
(c) trigonal bipyramidal (d) square pyramidal
Q.6 In [Cr(C2O4)3]3– , the isomerism shown is
(a) ligand (b) optical (c) geometrical (d) ionisation
Q.7 One mole of the complex compound Co(NH3)5Cl3, gives 3 moles of ions on dissolution in water.
One mole of the same complex reacts with two moles of AgNO3 solution to yield two moles of
AgCl(s). The structure of the complex is
(a) [Co(NH3)5Cl]Cl2 (b) [Co(NH3)3Cl3].2NH3
(c) [Co(NH3)4Cl2]Cl.NH3 (d) [Co(NH3)4Cl]Cl2.NH3
Q.8 The complex used as an anticancer agent is –
(a) mer-[Co(NH3)3Cl3] (b) Cis-[PtCl2(NH3)2]
(c) Cis-K2[PtCl2Br2] (d) Na2[CoCl4]
Q.9 [Co(NH3)5Br]SO4 and [Co(NH3)5SO4]Br are the examples of:
(a) Linkage isomerism (b) Geometrical isomerism
(c) Ionisation isomerism (d) Optical isomerism
Q.10 Which statement about co-ordination number of a cation is true:
(a) Most metal ions exhibit only a single characteristic co-ordination number
(b) The co-ordination number is equal to the number of ligands bonded to the metal atom
(c) The co-ordination number is determined solely by the tendency to surround the metal
atom with the same number of electrons are one of the rare gases
(d) For most cations, the co-ordination number depends on the size, structure and charge
of the ligands.
Q.11 Among [TiF6]2–, [CoF6]3–, Cu2Cl2 and [Ni(Cl4]2– , the colourless species are:
(a) [CoF6]3– and [NiCl4]2– (b) [TiF6]2– and [CoF6]3–
(c) [NiCl4]2– and Cu2Cl2 (d) [TiF6]2– and Cu2Cl2
Q.12 Which one is the most likely structure of CrCl3.6H2O if 1/3 of total chlorine of the compound is
precipitated by adding AgNO3 to its aqueous solutions:
(a) CrCl3.6H2O (b) [Cr(H2O)3Cl3].(H2O)3
(c) [CrCl2(H2O)4].Cl.2H2O (d) [CrCl(H2O)5]Cl2.H2O
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Q.13 The brown ring complex compound is formulated as [Fe(H2O)5NO]SO4. The oxidation state of
Fe is:
(a) +1 (b) +2 (c) +3 (d) 0
Q.14 Cis-trans-isomerism is found in square planar complexes of the molecular formula : (A and B are
monodentate ligands):
(a) MA4 (b) MA3B (c) MA2B2 (d) MAB3
Q.15 The correct IUPAC name of the complex :
OH
H3C—C==N
CoCl2 is:
H3C—C==N
OH
(a) Dichlorodimethylglyoximatocobalt (II) (b) Bis(dimethylglyoxime)dichlorocobalt (II)
(c) Dimethylglyoximecobalt(II) chloride (d) Dichlorodimethylglyoxime-N, N-cobalt (II)
Q.16 The complexes given below show:
Cl Cl Cl (C2H5)3P Cl Cl
Pt Pt and Pt Pt
(C2H5)3P Cl P(C2H5)3 Cl Cl P(C2H5)3
(a) Optical isomerism (b) Co-ordination isomerism
(c) Geometrical isomerism (d) Bridged isomerism
Q.17 The incorrect statement is:
(a) The stability constant of [Co(NH3)6]3+ is larger than [Co(NH3)6]2+
(b) The cyano complexes are far more stable than those formed by halide ions
(c) The stability of halide complexes follows the order I¯ < Br < Cl¯
(d) The stability constant of [Cu(NH3)4]2+ is lesser than [Cd(NH3)4]2+ ion
Q.18 Which ion has tetrahedral geometry:
(a) [Fe(CO) 5] (b) [Co(NH3)6]2+ (c) [NiCl4]2– (d) [Ni(CN) 4]2–
Q.19 Which one of the following can show optical isomerism?
(a) FeSO4.7H2O (b) K3[Cr(C2O4)3] (c) K3.[Fe(CN) 6] (d) Cr(NH3)6Cl3
Q.20 On adding excess of HCl to a light pink coloured aqueous solution of cobalt (II) chloride, a deep
blue coloured solution is formed. This is due to:
(a) Transformation of octahedral [Co(H2O)]62+ into octahedral [CoCl]42–
(b) Transformation of octahedral [Co(H2O)]62+ into tetrahedral [CoCl]42–
(c) formation of undissociated [CoCl]42–
(d) formation of a complex of Co(III) in the redox reaction
[Co(H2O6)]2+ + H+ +Cl¯  [Co(H2O)5Cl]2+ + H2O + ½H2
Q.21 A metal complex of co-ordination number six having three different types of ligands a, b and c of
composition Ma2b2c2 can exist in several geometrical isomeric forms; the total number of such
isomers is
(a) 3 (b) 5 (c) 7 (d) 9
Q.22 The mononuclear complex salt having the molecular composition [Co(en)2 (SCN) (NO2)]Br can
exist in a number of isomeric forms. The total number of possible isomer of all type is
(a) six (b) nine (c) twelve (d) twenty-four

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Q.23 Which one of the following pairs of isomers and types of isomerism are correctly matched?
1. [Co(NH3)5(NO2)]Cl2 and [Co(NH3)5 (ONO)]Cl2........ Linkage.
2. [Cu(NH3)4][PtCl4] and [Pt(NH3)4] [CuCl4] ...............co-ordination
3. [Pt(NH)3]4Cl2B4 and [Pt(NH3)4Br2)] Cl2....... Ionization
Select the correct answer using the codes given below:
(a) 2 and 3 (b) 1, 2 and 3 (c) 1 and 3 (d) 1 and 2
Q.24 Consider the following isomerisms:
1. Ionization 2. Hydrate 3. Co-ordination 4. Geometrical (5) Optical
Which of the above isomerisms are exhibited [Cr(NH3)2(OH)2Cl2]–1?
(a) 1 and 5 (b) 2 and 3 (c) 3 and 4 (d) 4 and 5
Q.25 The value of ‘spin only’ magnetic moment for one of the following configuration is 2.84 BM. The
correct one is
(a) d4 (in strong field ligand) (b) d2 (in weak field ligand)
(c) d3 (in weak as well as in strong field ligand) (d) d5 (in strong field ligand)
Q.26 The complex ion which has no ‘d’ electron in the central metal atom is:
(a) [MnO4]¯ (b) Co(NH3)6]3+ (c) [Fe(CN) 6]3– (d) [Cr(H2O)6]3+
Q.27 (i) Octahedral complexes of coordination no. of ‘6’ showing geometrical isomerism
(ii) Tetrahedral complex of coordination no. of ‘4’ show geometrical isomerism
(iii) Square planar complexes of coordination no. of ‘4’ shows geometrical isomerism
(iv) Geometrical isomerism is not noticed in complex coordination no. 2 and 3 .
(a) TFTT (b) FTFT (c) TFTF (d) FTTF
Q.28 The coordination no. & hybridization and geometrical of the complex [Ag(CN)2]–
(a) 2, sp, linear (b) 4, sp2, trigonal planar
2
(c) 2, sp , trigonal planar (d) 3, sp2, linear
Q.29 The coordination no. 5 and dsp3 hybridisation is observed in
(a) [CuCl5]3– (b) [MoCl5] (c) [Fe(CO5)] (d) [Mn(CO) 5]
Q.30 (i) Perfect complexes are those in which complex ion is fairly stable.
(ii) It is either not dissociated or feebly dissociated in solution state.
(iii) It can be considered as undissociated and doesn’t give the individual tests for cations
and anions.
(iv) For the complex K4[Fe(CN)6] it will give 4K+ and [Fe(CN)6]4– but will not give individual
test for Fe2+ & 6CN– .
(a) FTTF (b) TTTT (c) TFTF (d) FTTF
Q.31 (i) A polydentate ligands have flexidentate character.
(ii) All the lone pairs are not necessarily used in coordinate bonding.
(iii) EDTA has six lone pairs but it will be less than 6 lone pair s can be used in some
coordinate complexes.
(iv) Ambidentate ligands are those in which only one donor atom is attached to metal atom
(a) TTTF (b) FTTF (c) TFTF (d) TFFT
Q.32 A group of atoms can function as a ligand only when
(a) It is a small molecule
(b) It is capable of acting as donor of electron pair
(c) It is a negatively charged ion.
(d) It is a positively charged ion.

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Q.33 Effective atomic number of Fe in the complex K4[Fe(CN)6] is
(a) 24 (b) 12 (c) 36 (d) 18
Q.34 Which one of the following will be able to show geometrical isomerism?
(a) MA3B (Square planar) (b) MA2B2 (Tetrahedral
(c) MABCD (Square planar) (d) MABCD (Tetrahedral)
Q.35 Fac. mer isomerism is associated with which of following general formula
(a) M(AA')2 (b) M(AA)3 (c) MABCD (d) MA3X3
Q.36 Hexafluorocobaltate (III) ion is found to be high spin complex, the probable hybrid state of cobalt
in it is:
(a) d2sp3 (b) sp3 (c) sp3d (d) sp3d2
Q.37 The complex ion [Cu(NH3)4]2+ has
(a) the tetrahedral configuration with one unpaired electron configuration
(b) square planar configuration with one unpaired electron
(c) tetrahedral configuration with all electrons paired.
(d) square planar configutration with all electrons paired.
Q.38 Ferrocene is
(a) Fe(5–C5H5)2 (b) Fe(2–C6H5)2 (c) Cr(5–C5H5)5 (d) Os(5–C5H5)2.
Q.39 The colour of [Ti(H2O)6]3+ is due to
(a) Transfer of an electron from one Ti to another (b) Presence of water molecule
(c) Excitation of electrons from dd (d) Intra molecular vibration
Q.40 Fe2(CO)9 is diamagnetic. Which of the following reasons is correct?
(a) presence of one CO as bridge group (b) Presence of monodentate ligand
(c) Metal-metal (Fe-Fe) bond in molecule (d) Resonance hybridization of CO
Q.41 Optical isomerism is not shown by the complex :
(a) [Cr(ox)3]3– (b) [Co(en)2Cl2]+ (cis-form)
(c) [Co(en)2Cl2]+ (trans-form) (d) [Cr(en) 3]3+
Q.42 Among the following ions which one has the highest paramagnetism :
(a) [Cr(H2O)6]3+ (b) [Fe(H2O)6]2+ (c) [Cu(H2O)6]2+ (d) [Zn(H2O)2]2+
Q.43 -bonding is not involved in –
(a) ferrocene (b) dibenzene chromium
(c) Zeise’s salt (d) Grignard reagent
Q.44 The geometry of Ni(CO) 4 and Ni(PPH3)2Cl2 are –
(a) both square planar (b) tetrahedral and squaral planar respectively
(c) both tetrahedral (d) square planar and tetrahedral respectively
Q.45 Which of the following organometallic compound is and bonded –
(a) [Fe5(C5H5)2] (b) [PtCl3] (2 – C2H4)
2+
(c) [Co(CO) 5NH3] (d) [Al(CH3)3]
Q.46 Which of the following can not show linkage isomerism ?
(a) NO2– (b) SCN– (c) CN– (d) NH3

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Q.47 Consider the following complex : [Co(NH3)5CO3]ClO4
The coordinations number, oxidation number, number of d-electrons and number of unpaired d-
electrons on the metal are respectively –
(a) 6, 3, 6, 0 (b) 7, 2, 7, 1 (c) 7, 1, 6, 4 (d) 6, 2, 7, 3
Q.48 In electroplating of copper, K[Ag(CN) 2] is used instead of AgNO3. The reason is –
(a) a thin layer of Ag is formed on Cu
(b) more voltage is required
(c) Ag+ ions are completely removed from solution
(d) less availability of Ag+ ions , as Cu cannot displace from [Ag(CN)2]– ionsd
Q.49 Among the following, which is not the -bonded organometallic compound :
(a) (CH3)4Sn (b) Cr(6 – C6H6)2
5
(c) Fe( – C5H5)2 (d) k[PtCl3(2–C2H4)]
Q.50 According to IUPAC nomenclature, sodium nitroprusside is named as –
(a) sodium nitro ferrocyanide (b) sodium pentacyanonitrolsyl ferrate (II)
(c) sodium nitroferricyanide (d) sodium pentacyanonitrolsyl ferrate (III)
Q.51 The number of unpaired electron in the complex ion [CoF6]3– is
(a) 3 (b) 4 (c) 0 (d) 2

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NCERT QUESTIONS XII

10.1 Define the terms: coordination entity, central metal, ligand, donor atom, coordination number and
oxidation number.
10.2 What is meant by the denticity of a ligand ? Give examples of a unidentate and a didentate ligand.
10.3 Which postulates did Werner use to explain the bonding in coordination compounds? What is the
main weakness of Werner’s theory?
10.4 What is understood by: (a) a chelating ligand, (b) an ambidentate ligand? Answer using specific
examples.
10.5 Complete the following statements for the coordination entity (complex ion) [CrCl2(OX)2]3–
(a) OX is abbreviation for ________
(b) The oxidation number of chromium is ________
(c) The coordination number of chromium is ________
(d) ________ is a didentate ligand.
10.6 Specify the oxidation numbers of the metals in the following coordination entities:
(a) [Co(CN)(H2O)en)2]2+ (b) [PtCl4]2– (c) [CrCl3(NH3)3]
+
(d) [CoBr2(en)2] (e) K3[Fe(CN) 6]
10.7 Using IUPAC norms write the formulae for the following:
(a) Tetrahydroxozincate (II) (b) Hexaamine cobalt (III) sulphate
(c) Potassium tetrachloropalladate(II) (d) Potassium tri[oxalato)chromate(III)
(e) Diamminedichloroplatinum(II) (f) Hexaammineplatinum (IV)
(g) Potassium tetracyanonickelate(II) (h) Tetrabromocuprate(II)
(i) Pentaamminenitrito-O-cobalt(III) (j) Penetaamminenitrito-N-cobalt(III).
10.8 Using IUPAC norms write the systematic name of the following:
(a) [Co(NH3)6]Cl3 (b) [CoCl[NO2)(NH3)4]Cl
(c) [Ni(NH3)6]Cl2 (d) [PtCl(NH2CH3)(NH3)2]Cl
(e) [Ti(H2O)6]3+ (f) [NiCl4]2– (g) [Ni(CO) 4]
10.9 Explain with examples geometric and optical isomerism.
10.10 Specify which out of the following complexes structures exhibit geometric isomerism:
(a) Linear (b) square-planar (c) tetrahedral (d) octahedral
10.11 How many geometric isomers are possible in the following coordination entities:
(a) [Cr(OX)3]3– (b) [CoCl3(NH3)3]
10.12 Draw the structure of optical isomers of:
(a) [Cr(OX)3]3– (b) [PtCl2(en)2]2+ (c) [CrCl2(en)(NH3)2]+
10.13 Draw all the isomers (geometric and optical) of:
(a) [CoCl2(en)2]+ (b) [CoCl(en) 2(NH3)]2+ (c) [CoCl2(en)(NH3)2]+
10.14 Draw the structure of
(a) Cis-dichlorotetracyano-chromate (III)
(b) Mer-triamminetri chlorocobalt (III)
(c) Fac-triaquatrinitro-N-cobalt(III)

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10.15 Illustrate with an example each of the following:
(a) Ionization isomerism (b) Linkage isomerism (c) coordination isomerism
10.16 Sketch the geometrical shapes of the following sets of hybrid orbitals:
(a) dsp2 (b) dsp3 (c) d2sp3 (d) sp3
10.17 Explain on the basis of valence bond theory, the experimental findings that [Ni(CN)4]2– ion with a
square-planar structure is diamagnetic and the [NiCl4]2– ion with tetrahedral geometry is
paramagnetic.
10.18 Write the correct formulae for the following coordination compounds;
(a) CrCl3.6H2O (violet, with 3 chloride ions/unit formula)
(b) CrCl3.6H2O (Light green colour, with 2 chloride ions/unit formula)
(c) CrCl3. 6H2O (dark green colour, with 1 chloride ion/unit formula)
[ Hint : some of these compounds may exist as hydrates ]
10.19 Aqueous copper sulphate solution (blue in colour] gives :
(a) a green precipitate with aqueous potassium fluoride, and
(b) a bright green solution with aqueous potassium chloride .
Explain these experimental results.
10.20 What is the coordination entity formed when excess of aqueous KCN is added to an aqueous
solution of copper sulphate? Why is it that no precipitate of copper sulphide is obtained when
H2S(g) is passed through this solution?
10.21 Discuss the nature of bonding in the following coordination entities on the basis of valence bond
theory:
(a) Fe(CN) 6]4– (b) [FeF6]3– (c) [Co(OX) 3]3– (d) [CoF6]3– .
10.22 Write the valence bond description of
(a) [Ni(CN) 4]2– (b) [NiCl4]2–.
10.23 What is understood by the generalization, ‘Magnetic criteria of the bond type’?
10.24 Draw figure to show splitting of degenerate d orbitals in an octahedral crystal field
10.25 State the essential requirements for regarding a compound as an organometallic.
(a) B(CH3)3 (b) B(OCH3)3 (c) SiCl3(CH3) (d) N(CH3)3
10.26 Write the formulae of the following:
(a) Methyllithium (b) trimethylarsane
(b) Tetramethysilane (d) Hexamethyldialuminium
(f) trimethylbismuth (f) trimethylboron.
10.27 Sketch the structure of the organometallic compounds given in 10.26.
10.28 Give IUPAC name and draw the structure of:
(a) Ni(CO) 4 (b) Fe(CO) 5 (c) [PtCl3(C2H2)]– (d) [Cr(CO) 6].
10.29 Assign oxidation number to the metal atom in the compounds given in 10.28.
10.30 Discuss the nature of bonding in [Ni(CO)4]
10.31 Discuss briefly the role of coordination compounds in :
(a) biological systems. (b) analytical chemistry,
(c) medicinal chemistry , and (d) extraction/metallurgy of metals

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ANSWER
10.1
(a) The species which is written with in the square brackets is coordination entity.
(b) Central (metal) atom is a atom/ion to which a fixed no. of (other atoms (or) groups) are attached
in a definite geometrical arrangement around it:
(c) They are e¯ pair donor groups which are bounded to the central atom/ion in the coordination
entity.
(d) Donor atom : The atom in the lewis base that form the bond to lewis acid (central atom/ion).It
donates the pair of e¯ s required for bond formation.
(e) Coordination no: It is defined by the no. of sigma bonds between the ligands and the central
atom/ion.
(f) Oxidation No.: It is defined as the charge it would carry if all the ligands are removed along with
the e¯ pairs that are shared with the central atom.

10.2 Denticity of a ligand : The number of ligating groups (which donate sigma e¯ pair to the metal ion/
atom) present in a ligand.
Unidentate ligand :- NH3, H2O, Cl¯
Bidentate ligand:- Ethylene diamine, oxalate ion

10.3 Werner postulated that central metal atom possesed two types of valencies are shown by a central
metal atom.
(i) Primary valencies (ii) Secondary valencies.
(i) Primary valency : This is also called ionic valency or principal valency. It is no this but
the oxidation state of metal ion in the complex. It is always satisfied by the negative
ions.
(ii) Secondary or auxiliary valency: It corresponds to coordination number of central metal
ion in the complex. It is non-ionic type i.e. coordinate covalent bond type. It may be
satisfied either by negative ions or by neutral molecules having at least one lone pair of
electrons. The geometry of the complex depends upon the arrangements of secondary
valencies in the space.
In K4[Fe(CN) 6], the primary valency of Fe is two because its oxidation state is two, while the
secondary valency is six because its coordination number is six
(1) Werner couldn’t explained why certain elements process the remarkable property of
forming coordination compounds
(2) The bonds in coordination compounds have directional properties.
(3) The coordination compounds have magnetic and optical properties.

10.4 Chelating ligands: When coordination of two or more sigma electron pairs donor group takes
place from the ligand to same central metal ion/atom, it is known as chelation and the ligand is
called chelating agent.
2+
Example : CH2—NH2 NH2—CH2
Cu
CH2—NH2 NH2—CH2
10.5 (a) Oxalate (b) Ox. No. of Cr is +3
(c) Coordination no. of Cr is 6 (d) Oxalate ion is a bidentate ligand

10.6 (a) Co +3 (b) Pt +2 (c) Cr+3 (d) Co +3 (e) Fe+3


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10.7 (a) [Zn(OH)4]–2 (c) [Co +3(NH3)6]2(SO4)3–2 (c) K2 [PdCl4]


(d) K3[Cr(OX) 3] (e) [Pt(NH3)2Cl2] (f) [Pt(NH3)6]+4
(g) K2[Ni(CN)4] (h) [Cu(Br4)]–2 (i) [Co(No2)(NH3)5]+2
(j) [Co(No 2)(NH3)5]+2

ANSWER KEY
EXERCISE -1
Que. 1 2 3 4 5 6 7 8 9 10
Ans d a a d b b a c b a
Que. 11 12 13 14 15 16 17 18 19 20
Ans a d d a b a c b d d
Que. 21 22 23 24 25
Ans c c b c c

EXERCISE -2
Q ue . 1 2 3 4 5 6 7 8 9 10
Ans b a b b c b a b c d
Q ue . 11 12 13 14 15 16 17 18 19 20
Ans d c a c a c d c b b
Q ue . 21 22 23 24 25 26 27 28 29 30
Ans b d b d b a a a a ,b , c b
Q ue . 31 32 33 34 35 36 37 38 39 40
Ans a b c c d d b a c c
Q ue . 41 42 43 44 45 46 47 48 49 50
Ans c d c b d a d a b
Q ue . 51
Ans b

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10.8 (a) Hexamine cobalt (III) chloride
(b) Tetraamine chloronitrite-p-cobalt(III) chloride
(c) Hexaamine Nickel (II) chloride
(d) Diamine chlromethylamine platinum (II) chloride
(e) Hexaaquamagnese(II)
(f) Tris ethylene diamine cobalt (III)
(g) Hexa aquatitatinum(III)
(h) tetra chloro nickelate (II)
(i) Tetra carbonyl Nickel (O)

10.9 Cis and trans isomerism i.e., geometrical isomerism arises due to the different arrangement of
ligands arond the central metal ion. In cis (in latic cis means same) isomer two identical
ligandmolecules are adjacent to each other i.e., on same side while in trans (In latin trans means
across) isomer two identical ligand molecules are diametrically opposite to each other.
These two isomers different in physical and chemical properties of each other and can be separated
by some chemical and physical methods. This type of isomerism is not found in tetrahedral
complexes but is common in square planar and octahedral complexes.
Example : [Pt(NH3)2Cl2], [Co(en)2Cl2]+

NH3 Cl NH3 Cl

Pt Pt

NH3 Cl Cl NH3
cis-isomer trans-isomer
Cis and tans isomers of diamminedichloroplatinum (II) complex.

+ Cl +
en
Cl

Co en Co en

Cl
en
Cl
cis-isomer trans-isomer
Optical isomerisms: This type of isomerism arises due to the asymmetry of the molecule. Optical
isomers are the nonsuperimposable mirror images of each other. They rotate the plane polarised
light equally butin opposite direction. The isomer whichrotates the plane polarised light towards
the right side is known as dextrorotatory while the isomer which rotates it towards left side is
known as laevorotatory. This type of isomerism is common in octahedral comples having bidentate
lignads. Examples : [Cr(C2O4)3]3– , [Co(en)3]3+, [Rh(en2)Cl2]+. Following are the d and l form of
cis-Dichlorobis-(ethylenediaminerhodium (III)ion.

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+ en +
en
Cl Cl

Rh Rh

Cl Cl
en en

Following are the d and l form of Trioxalatochromate (III) ion.

3– ox 3–
ox

Cr ox Cr
ox

ox ox

10.10 Square planar and octahedral complexes show geometrical isomerism


10.11 [Cr(OX)3]3– exhibits cis and trans geometrical isomers
[CoCl3(NH3)3] exhibits and geometrical isomers facial and meridonial
10.12 (a) [Cr(OX)3]–3

3– 3–
OX OX

Cr OX OX Cr

OX OX

(b) [PtCl2(en)2]2+

2+ en
en
Cl Cl

Pt Pt

Cl Cl
en en

(c) [CrCl2(en)(NH3)2]+1

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SARWAR CLASSES Coordination Compund & Metallurgy

NH3 +1 NH3 +1
NH3 NH3

Cr en Cr
en

Cl Cl
Cl Cl

10.13 (a) [CoCl2(en)2]+ geometrical isomers


Cl +
en
+
Cl
en Co Co
en

Cl
en
Cl
trans Cis

(b) Optical isomerism

en en
Cl Cl

Co Co

Cl Cl
en en

d and l form
(b) [CoCl(en)2(NH3)]+2
geometrical isomerism

Cl
en +2
NH3 +2

Co en Co en

Cl
en
NH3

cis trans
optical isomerism

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SARWAR CLASSES Coordination Compund & Metallurgy

en
en
NH3 +2
NH3

Co Co

Cl Cl
en en

d/l form
(c) [CoCl2en(NH)2]+

Cl NH3

NH3 NH3

en Co
Co en
NH3 Cl
Cl Cl

cis trans

Cl Cl

Cl Cl

en Co
Co en

NH3 NH3

NH3 NH3

(d) (l)
d/l form

Cl 3–

CN Cl

10.14 (a) Cr

CN CN
CN

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Cl H2O

Cl O2N H2O
NH3

(b) Co (c) Co

Cl O2N H2O
Cl
NH3 NO2

10.15 (a) [PtCl2(NH3)4]Br2 [PtBr2(NH3)4]Cl2


(b) Linkage [Co(NH3)4(Br)(NO2)]+ [Co(ONO)(NH3)4Br]+
(c) [Co(H2O)6] [Cr(CN) 6] [Cr(H2O)6] [Co(CN) 6]

10.16 dsp2 – Square planar


dsp3 – trigonal-bi-pyramidal/square pyramidal
d2sp3 – octahedral
sp 3 – tetrahedral

10.17 [Ni(CN)4]2–
Ni+2 configuration
3d 4s 4p

Ni

Ni2+

[Ni(CN)4]2–
CN¯CN¯ CN¯ CN¯
dsp2 hybrid used
[Ni(CN)4]2– is square planar and diamagnetic. [NiCl4]2– , on the other hand, is paramagnetic and
has tetrahedral geometry. In this case, the VB treatment assumes that (i) the d-orbital occupnacy
remains the same as in the free Ni2+ ion and (ii) the metal uses sp3 hybrids (involving 4s and 4p
orbitals) for bonding with the ligands as shown below:
[NiCl4]2– is paramagnetic as there are two unpaired electrons.
3d 4s 4p

Ni

Ni2+

[Ni(Cl)4]2–
Cl¯ Cl¯ Cl¯ Cl¯
3
sp hybrid used

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10.18 [Cr(H2O)6] Cl3 violet
[Cr(H2O)5Cl]Cl2.H2O green
[Cr(H2O)4Cl2]Cl.(H2O)2 darkgreen colour

10.19 CuSO4 + KF CuF2 + K2SO4



 green ppt
CuSO4 + KCl CuCl2 + K2SO4
green solution

10.20 CuSO4 + KCN Cu(CN)2 Cu(CN)2


KCN KCN K3[Cu(CN)4]
Because it produces K ions so with H2S it forms K2S but not Cu2S due to lack of Cu2+ ions.
+

10.21 (i) [Fe(CN) 6]4–


Fe–26

Fe+2  3d6

d2sp3
(due to strong field ligand)
(ii) [FeF6]3–
Fe+3 3d5

sp3d2

(iii) [Co(OX)3]3–
(iv) Co–27 3d74s2
Co +33d 5

sp3d2
(v) [CoF6]3–
same as sp3d2
Co +33d 5

sp3d2

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10.22 [Ni(CN)4]2–
Ni+2 configuration
3d 4s 4p

Ni

Ni2+

[Ni(CN)4]2–
CN¯ CN¯ CN¯ CN¯
dsp2 hybrid used

[Ni(CN)4]2– is square planar and diamagnetic. [NiCl4]2– , on the other hand, is paramagnetic and
has tetrahedral geometry. In this case, the VB treatment assumes that in (i) the d-orbital occupnacy
remains the same as in the free Ni2+ ion and (ii) the metal uses sp3 hybrids (involving 4s and 3p
orbitals) for bonding with the ligands as shown below:
[NiCl4]2– is paramagnetic as there are two unpaired electrons.
3d 4s 4p

Ni

Ni2+

[Ni(Cl)4]2–
Cl¯ Cl¯ Cl¯ Cl¯
sp3 hybrid used

Q.23 Magnetic criteria of bond


K4[Fe(CN) 6] Fe – 3d64s2

Fe+2 3d6

d2sp3
This is diamagnetic in nature

K3[Fe(CN) 6]

d2sp3
Fe+3  3d5
This is paramagnetic in nature

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10.24 Octahedral cyrstal field spliting

dx2–y2 ,dz2
[ [eg

Energy
[ [ a
[ t2g
[
dxy,dyz,dxz
[ [
d oritals Average energy of Splitting of d-orbitals
in free ion the d orbitals in a in an octahedral cyrstal
spherical crystal field
field

10.25 It should contain atleast one carbon–metal bond


a , c are organometallic
10.26 (a) CH 3Li (d) As(CH3)3
(b) Si(CH3)4 (e) Al2(CH3)6
(c) Bi(CH3)3 (f) B(CH3)3

CH3 Bi

10.27 (a) Li–CH3 (b) (c) H3C CH3


Si
CH3
CH3
CH3
CH3

As H3C CH3 CH3


(d) CH3 (e) Al Al
H3C
CH3 H3C CH3 CH3

(f) H3C CH3


CH3

10.28 (a) Ni(CO)4 — Tetra carbonyl nickel (O)


CO

Ni
CO
OC
CO
(b) Fe(CO)5 — Penta carbonyl iron (O)

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CO

CO Fe CO

OC CO
(c) [PtCl3 (C2H2)]¯ Trichloroethene platinate(II)

Cl CH 2

Pt CH2
Cl Cl
(d) [Cr(CO6)] Hexa carbonyl chromium (O)
CO
CO

CO Cr CO
CO
CO

10.29 OX. NO. of Ni is zero,


Iron is zero
Platinum is two
Chromium is zero

10.30 [Ni(CO)4]
Ni electronic configuration – [Ar] 4s23d8

O
sp3hybridization
C

Ni
C C    
C 
O O C  C C C
O
(tetrahedral) O O O O

10.31 Chlorophylls (the green pigments in plants. Central to photosynthesis); haemoglobin (the red pigment
of blood, which acts as oxygen carrier) alongwith myoglobin (Which stores oxygen and is a
regulator of respiration): Vit B12, cyanocobalammiine, the anti-pernicious anaemia factor. All of
these, respectively, are the coordination compounds of magnesium, iron and cobalt with the
macrocyclic porphyrin and corrin ligands. Among the other compounds of biological importance
with coordinated metal ions are the enzymes like, carboxypeptidase A and carbonic anhydrase
(catalysts of biological systems)
The colour reactions given by metal ions with a number of ligands (especially the chelating ligands),
as a result of formation of coordination entities, form the basis for their detection and estimation
by classical and instrumental methods of analysis.
Some important extraction processes of metals, like those of extraction of silver and gold, make
use of complex formation. Gold, for example, combines with cyanide in the presence of oxygen

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SARWAR CLASSES Coordination Compund & Metallurgy
and water to form the coordination entity [Au(CN)2]¯ in aqueous solution. Gold can be precipitated
from this solution by the addition of Zinc.
Purification of metals can be achieved through formation and subsequent decomposition of their
coordination compounds. For example, impure nickel is converted to [Ni(CO) 4], which is
decomposed to yield pure nickel.
The treatment of problems caused by the presence of metals in toxic proportions in plant/animal
systems. Thus, excess of copper and iron are removed by the chelating ligands D-penicillamine
and desferrioxime B via the formation of coordination compounds. EDTA is used in the treatment
of lead poisoning. Some coordination compounds of platinum effectively inhibit the growth of
tumorus. Examples are : cis-platin and related compounds.

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METALS AND METALLURGY

Metals occur in nature, sometimes in free or native state but mostly in combined state i.e., in the
form of their stable compounds associated with gangue or matrix. The earthy impurities such as
sand, clay, rocks etc. associated with ore are collectively known as gangue or matrix. Metals like
Cu, Ag, Au and Pt occur in the native form (metallic state). The natural material in which the
metallic compounds (in the combined state) occur in the earth’s crust is known as mineral. A
mineral may be a single compound or a complex mixture. Those minerals from which the metal
can be readily and economically extracted are called ores. Thus all ores are minerals but all
minerals are not ores. For eg. , bauxite (Al2 O3 . 2H2O) and clay (Al2O3 . 2 SiO2 . 2H2 O) are two
minerals of aluminium, but aluminium can be profitably extracted only from bauxite and not from
clay. Hence bauxite is an ore of aluminium, while clay is a mineral. The biggest source of metals in
the earth’s crust and the process of taking out the ores from the earth crust is known as mining.
Ores obtained from earth crust are always associated with gangue or matrix. The gangue material
in the ore is separated by flux. A flux is a chemical substance added to convert gangue into fusible
mass. This fusible mass is called slag.
[ i.e., Gangue or matrix + Flux  Slag ].
Fluxes are mainly of two types :
(a) Acidic flux :
When the ore is associated with basic impurities such as FeO, CaO, MgO etc. a suitable acidic
flux (P2 O5 , SiO2 ) is used . For example, in the extraction of copper, the basic impurity FeO is
removed by adding flux SiO2 i.e.
FeO + SiO2  Fe SiO3 (Ferrous silicate)
Gangue Flux Slag
Similarly , lime may be removed with silica.
CaO + SiO2  CaSiO3 (Calcium silicate)
Gangue Flux Slag
(b) Basic Flux :
If the ore is associated with acidic impurities such as SiO2, P2O5 etc. then the flux used must be
basic (CaO, MgO etc.), e.g.,
SiO2 + MgO  MgSiO3 (Magnesium silicate)
Gangue Flux Slag
Thomas slag is calcium phosphate, Ca3(PO4)2. The slag (fusible mass) is removed and used in the
manufacture of cement and fertilizers.

Ores may be divided into native ores or combined ores. In combined state ores are found in the
form of oxides, sulphides, sulphates, silicates, carbonates etc.

The process of extracting a metal in pure form from its ores is known as metallurgy. The extraction
of metals can not be carried out by any universal method because the procedure of extraction

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SARWAR CLASSES Coordination Compund & Metallurgy
depends upon the nature and properties of metal. In general, noble metals like Ag, Au etc. are
extracted by cyanide process or amalgamation. Active metals such as Na, K, Ca, Mg, Al etc.
usually obtained by electrolysis of their oxides, hydroxides or chlorides. Heavy metals such as
Cu, Zn, Pb, Fe, Sn, etc. are extracted by roasting and smelting methods.

Classification Of Ores :
Type of Ore Ore or Mineral Composition Metal Present
Oxide Ores Bauxite Al2O 3.2H2O Al
Cuprite Cu2O Cu
Haematite Fe2O 3 Fe
Magnetite Fe3O 4 Fe
Cassiterite SnO2 Sn
Pyrolusite MnO 2 Mn
Pitch Blende U 3O 8 U
Zincite ZnO Zn
Halide Ores Rock Salt NaCl Na
Carnallite Kcl.MgCl2.6H2O Mg
Horn Silver AgCl Ag
Cryolite 3NaF.AlF3 Al
Sylvine KCl K
Sulphide Ores Copper Pyrites CuFeS2 Cu
Copper Glance Cu2S Cu
Cinnabar HgS Hg
Galena PbS Pb
Zinc Blende ZnS Zn
Argentite Ag2S Ag
Sulphate Ores Epsom Salt MgSO 4.7H2O Mg
Gypsum CaSO 4.2H2O Ca
Anglesite PbSO 4 Pb
Barytes BaSO 4 Ba
Silicate ores Asbestos CaSiO 3.3MgSiO 3 Mg
Felspar K2O.Al2O 3.6SiO 2 Al
Mica K2O.3Al2O 3.6SiO 2.2H2O Al
Willimite Zn2SiO 4 Zn
Nitrate Ores Chile Salt petre NaNO 3 Na
Bengal Salt petre KNO 3 K
Carbonate Ores Magnesite MgCO 3 Mg
Dolomite CaCO 3.MgCO 3 Mg
Calamine ZnCO 3 Zn
Malachite CuCO 3. Cu(OH)2 Cu
Lime Stone CuCO 3 Ca
Azurite 2CuCO 3. Cu(OH)2 Cu
Cerussite PbCO 3 Pb
Siderite FeCO 3 Fe
(Spathic iron ore)
Phosphate Ores Phosphorite Ca3(PO 4)2 P

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(a) These materials can withstand very high temperatures without melting or becoming soft.
(b) These materials can resist sudden variations of temperature.
(c) They do not crumble at high temperature and pressure.
(d) They can withstand the corrosive action of slags.
(e) Refractory materials are generally metals, metal oxides etc. These are used in the form of
bricks for the internal lining of furnaces, fluxes and hotter parts of chimneys.

(a) Acidic refractories are those which react with bases. Examples are silica in the form of
ganister (a silicious rock) containing 72 % SiO 2 and 27 % Al2O3, silicious sand stones
etc.
(b) Basic refractories are those which react with acids, e.g., limestone (CaCO3), magnesite
(MgCO3) and dolomite (MgCO3. CaCO3).
(c) Neutral refractories are those which neither react with acids nor bases i.e., graphite,
chromite etc. Semi-neutral refractories include fire clay consisting of about 60 %, SiO2
and 35 % Al2O3. Silica resists temperatures upto 1750 ºC bauxite bricks upto 1800 °C ,
alumina upto 2000 °C , magnesia and chromite bricks upto 2200 ºC .

A furnace is used for heating the substances to required temperatures in metallurgical operations.
For example, blast furnace is used for the smelting of iron, lead and copper ores. Reverberatory
furnace is used for calcination, roasting and smelting. An open hearth furnace, based on regenerative
system, is used for the manufacture of steel. Muffle furnaces are used for annealing of gold and
silver assaying Electric furnaces (e.g. induction furnances resistance furnace, are furnaces) are
used for manufacturing fine steel. Commonly used electric furnace is Heroult’s electric furnace.
Kilns and Bessemer converters are also used.

Metallurgical operations used in the extraction of pure metals from their respective ores are as
follows.
(A) Ore Dressing : The process of removing gangue or matrix (non-metallic and rocky
materials, such as mica, quartz, felspar) from the metal ore is called ore dressing. It
includes following methods.
(a) Hand Picking : The gross lumps of the rocks may be removed from the ore by
hand picking. The stony impurities from the iron ore (haematite) are removed by
this method.
(b) Hydraulic Washing or Levigation : The method is based on the differences in
the density of the gangue and the mineral particles. The ore after grinding is washed
with a running stream of water. The lighter gangue particles are washed away
while heavier particles settle down. Gravity separation is usually carried out by
using hydraulic classifier.
(c) Froth Floatation : This process is especially suitable for the concentration of
sulphide ores. The process is based on the different wetting characteristics of the

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ore and gangue particles with water and oil, the former is wetted by oil and the
latter (gangue) by water. The fine crushed sulphide ore, mixed with water (slurry)
and a small amount of pine oil (a foaming agent or frother) together with a little
lime or Na2CO3 is added to the flotation tank. In certain cases collectors (these
compounds attach themselves by polar groups of grains of minerals and pass into
the froth) such as ethyl xanthate, or amyl xanthate is added. The contents of the
tank are agitated with a mechanical stirrer and air, under pressure, is blown in.
The ore particles selectively become attached to air bubbles produced in the
aqueous pulp of ore and float on the surface, from where they can be skimmed
off. The gangue particles sink to the bottom of the tank and are separately
withdrawn. The froath is removed and suitably treated to get the concentrated
ore. Activators or depressants activate (or depress) the floating property of one
of the components of the ore and help in the separation of different materials
present in the same ore. CuSO 4 is used as activator, while NaCN or KCN are
used as depressants. The use of collector, activator and represent can be illustrated
in the separation of galena (PbS) which is associated with sphalerite (ZnS) and
pyrites (FeS2).
(d) Magnetic (electromagnetic) Concentration : The method is used when either
the ore or the impurities are magnetic in nature e.g., chromite FeO, Cr 2O3 being
magnetic, can be separated from the siliceous gangue. Similarly, wolframite, FeWO4
(magnetic) and cassiterite, SnO2 (non-magnetic) as well as rutile TiO2 (Magnetic)
and chlorapatite, 3Ca3(PO4)2.CaCl2 (non-magnetic ) are separated by magnetic
separators.
(e) Electrostatic Concentration : This method is based upon the fact that the
particles which are good conductors of electricity become electrically charged
under the influence of an electrostatic field and are thus repelled by the electrode
carrying the like charge. For example, lead sulphide (good conductor) can be
separated from zinc sulphide (poor conductor).
(B) Extraction of Crude Metal :
(a) Calcination : (originated from the ore calcite). It is a process in which ore is
heated at high temperature in the absence of air. This process is applied in case
of carbonate and hydrated ores. As a result of calcinations volatile impurities are
removed, gases may be expelled, the mass becomes porous and thermal
decomposition of the ore takes place. e.g. ,
MgCO3 (Magnesite)  MgO + CO2  ,
CaCO3 (Limestone)  CaO + CO2  ,
MgCO3 . CaCO3 (Dolomite)  MgO + CaO + 2 CO2  ,
CuCO3 . Cu(OH)2 (Malachite)  2 CuO + H2 O + CO2  ,
Calcination is usually carried out in reverberatory furnace.
(b) Roasting : In this process, the ore (usually sulphide) alone or mixed with other
materials is heated in excess of air, at temperature below the melting point.
Roasting is usually carried out in blast or reverberatory furnace. During roasting
(i) impurities like S, As, Sb etc., get oxidized and escape as volatile gases SO 2,
As2O3 and Sb2O3. (ii) The sulphide ores decompose to their oxides evolving
SO2. (iii) Moisture is removed. (iv) Mass becomes porous and can easily be
reduced.

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Types of Roasting :
(i) Blast Roasting : Here oxidation is carried out in a blast of hot air. The process is
applied for copper pyrites and galena.
(ii) Oxidising Roasting : Here impurities are oxidized into their volatile oxides by the
combined action of heat and air. The process is used for copper pyrites, zinc blende and
lead ores etc.,
2 Zns + 3 O2  2 ZnO + 2 SO2 ; 2 PbS + 3 O2  2 PbO + 2 SO2;
(iii) Reducing Roasting : In this process, the oxidized metallic mineral is subjected to the
action of reducing agents (e.g., active hydrogen, carbon or metallic sulphides) at a
temperature below the fusion point. For example, in the extraction of Cu or Pb, FeS acts
as reductant.
2 CuFeS2 + O2  Cu2S + 2 FeS + SO2 ;
2 CuS + 3 O2  2 Cu2O + 2 SO2
2 FeS + 3 O2  2 FeO + 2 SO2
(iv) Sulphating Roasting : Here the sulphide ore is converted to soluble sulphate which is
then leached with water.
CuS + 2O2  CuSO4 ; ZnS + 2O2  ZnSO4 ;
PbS + 2O2  PbSO4
(v) Chlorodising Roasting : The ore is heated with NaCl in presence of air to convert
it into a chloride.
Ag2 S + 2NaCl  2AgCl + Na2S ;
AgCl + 2Hg  AgHg + HgCl
(c) Smelting : The process is used for various operations whereby the metal is separated
by fusion from the ore. The ore is melted with a flux and often with a reducing agent. The
process is carried out in a blast furnace at high temperature.

(C) Extraction of free metal :


(a) Reduction by Carbon : The oxides of less electropositive metals Pb , Zn , Fe , Cu , Sn
etc., are reduced by strongly heating them with coal or coke. For example, in the extraction
of iron, haematite ore (Fe2O3) is smelted with coke and limestone (flux). As a result of
reduction iron is obtained in fused or molten state.
Fe2O3 + 3C  2Fe + 3CO ; Fe2O3 + 3C  2Fe + 3CO2;
CaCO3  CaO + CO2 ; CaO + SiO2  CaSiO3
Flux Gangue Slag
Similarly, in the extraction of copper from copper pyrites, the ore is smelted with coke
and heated in blast furnace . Insoluble impurity FeO is converted to FeSiO3 and is removed.
A mixture containing sulphides of copper and iron called matte is formed in the molten
state.
FeO + SiO2  FeSiO3
Other examples are :
ZnO + C  Zn + CO2 ; MnO2 + 2C  Mn + 2CO
PbO + C  Pb + CO2 ; SnO2 + 2C  Sn + 2CO
(b) Reduction by Hydrogen. The oxides of certain metals can be reduced by means of
hydrogen to the metal, e.g.,
WO2 + 2H2  2H2O + W ; NiO + H2  Ni + H2O
InO3 + 3H2  In + 3H2O ; Ca2O3 + 6H  2Ca + 3H2O
(c) Reduction by Magnesium . i.e. Rb2O3 + 3Mg  3MgO + 2Rb

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(d) Reduction by carbon monoxide : CO formed by incomplete combustion of carbon
reduce the metal oxide to metal e.g.
Fe2O3 + 3CO  2Fe + 3CO2 ; FeO + CO  Fe + CO2
PbO + CO  Pb + CO2 ; CuO + CO  Cu + CO2
(e) Reduction by Heating in air (auto-reduction) : The oxides and sulphides of less
active metals like Cu, Hg, Pb are unstable to heat and can be converted into metallic state
during roasting (heating in excess of air) . For example,
HgS (Cinnabar) + O2  Hg + SO2
2Cu2S + 3O2  2Cu2O + 2SO2 ; Cu2S + 2Cu2O  6Cu + SO2
2PbS + 3O2  2PbO + 2SO2 ; PbS + 2PbO  3Pb + SO2
(f) Reduction by Aluminium (Aluminothermic Reduction). Certain metal oxides like Cr2O3,
Mn2O3 etc., cannot be reduced effectively by carbon or carbon monoxide. In such cases,
aluminium is used as a reducing agent since Al is more electropositive than Cr and Mn.
the oxides of all refractory metals are commercially reduced by aluminium and the
process is known as Goldschmidt alumino thermic process. A mixture of metallic oxide
and aluminium powder (in 3 : 1ratio), known as thermite is taken in a graphite crucible
covered with a mixture of aluminium powder and barium peroxide. Magnesium is
embedded in the mixture. The charge is covered by a thick layer of carbon and a thin
layer of felspar to avoid loss of heat and to protect the mass from oxidation. The magnesium
ribbon which acts as a fuse is lighted. It starts burning and causes burning of the mixture.
Since the reaction is highly exothermic, the process is used for welding together the broken
pieces of rails, machinery and parts of ships etc.,
Cr2O3 + 2Al  Al2O3 + 2Cr + Heat ;
3Mn3O4 + 8Al  4Al2O3 + 9Mn + Heat
Fe2O3 + 2Al  Al2O3 + 2Fe + 185 Kcals (3000 ºC)
(g) Reduction by Na or Ca , Si , CaC 2 and water gas. Certain metal halides can be
reduced with Na or Ca in a closed vessel by heating.
TiCl4 + 4Na  Ti + 4NaCl ; TiCl4 + 4K  Ti + 4KCl
MnO . FeO + Si + FeO  MnSiO3 + 2Fe ;
MgCl2 + CaC2  Mg + 2C + CaCl2
NiO + CO  Ni + CO2 ; NiO + H2  Ni + H2O
(h) Reduction of complex salts (Hydrometallurgy) : More electropositive zinc metal can
be used to precipitate gold, silver etc., from their complex salt solutions
2KAu(CN)2 + Zn  K2Zn(CN) 4 + 2Au
2NaAg(CN) 2 + Zn  Na2Zn(CN) 4 + 2Ag
Alkali metals or aluminium can also reduce complex salts.
K2TiF6 + 4K  6KF + Ti ; K2ZnF6 + 2Al  2AlF3 + 2K + Zr
(i) Amalgamation method. This method is used for the extraction of noble metals like Ag,
Au from their native ores. The finely crushed ore is brought into contact with mercury
which takes up the meal forming its amalgam. The metal is then recovered by distilling its
amalgam.
2Tl3+ + 3Zn/Hg  3Zn2+ + 2Tl/Hg ;
2In3+ + 3Zn/Hg  3Zn2+ + 2In/Hg
(j) Electrolytic Reduction (Electrometallurgy) Highly electropositive (active) metals like
Na, K, Ca, Mg, Al etc., are extracted by the electrolysis of their oxides, hydroxides or
chlorides in fused state. For example, electrolysis of fused sodium chloride using iron
cathode and graphite anode gives sodium metal at cathode. NaCl  Na+ Cl-

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SARWAR CLASSES Coordination Compund & Metallurgy
At Cathode ; Na+ + e–  Na At Anode : 2Cl–  2e–  Cl2
Magnesium is prepared by electrolysis of fused carnallite.
MgCl2  Mg2+ + 2Cl–
At Cathode ; Mg2+ + 2e –  Mg At Anode : 2Cl– – 2e–  Cl2

(A) PHYSICAL METHODS :


(a) Fusion method. The method is employed when the crude metal is associated with absorbed
gases. The method is used to remove dissolved oxygen and SO 2 from silver and copper
metal respectively.
(b) Liquation Process. The method is used when the impurity is less fusible than the metal
itself. The impure metal is heated on the sloping hearth of a furnace. The metals and flows
down leaving behind the infusible material (dross) on the hearth. Hg, Sn, Pb, Bi, Zn, etc.,
are purified by liquation.
(c) Distillation. Volatile metals like Hg, Zn, Cd are refined by this method. Crude metal is
heated in a retort and its vapours are condensed in a receiver. the pure metal distills over
leaving behind the non-volatile impurities.
(d) Fractional Crystallisation. The method has been used for the separation of platinum
and iridium through ammonium hexachloroplatinate and iridate.
(e) Vacuum sublimation Method. The crude metal is compressed to an electrode which is
allowed to melt under vaccum in an electric furnace. the molten metal is chilled in an
externally cooled copper crucible when pure metal is obtained. Refractory metals (Te,
Zr, Mo) are purified by this method.
(f) Cage-Zone Melting Technique. The method is based on the principle that an impure
metal on solidification will deposit crystals of pure metal leaving behind the impurities in
the molten part of the metal. The process is capable of reducing the concentration of
impurities to less than one part per billion parts.

(B) CHEMICAL METHODS.


(a) Pyrometallurgical oxidation. Here impurities are oxidised by following methods.
(i) Poling or Furnace Refining. Impurities of reducible oxides from the metals are
removed by poling. For example, blister copper containing traces of cuprous
oxide as impurity is refined by melting the metal on the hearth of reverberatory
furnace. On striring the melt with green logs of woods, cuprous oxide is reduced
to copper and reducing gases are given off. Tin is also refined by poling.
(ii) Cupellation. The process is used to refine silver containing lead as impurity and
depends upon the selective oxidation of lead over silver. the crude silver is smelted
in a bone ash cupel in a blast of air in reverberatory furnace. Lead is oxidised to
litharge (PbO) and is blown away from the crucible by blast of air. The residue
melts and is absorbed by bone ash cupel.
(iii) Thermal Decomposition methods.
(a) Carbonyl method. It is used for the refining of Ni and Fe etc., The impure Ni
is heated with Co. Nickel Carbonyl thus formed is then decomposed to get pure
Ni and CO. The process is called Mond’s process.
Ni + 4CO  Ni(CO)4  Ni + 4CO 

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(b) Van Arkel method. The crude metal is converted into volatile compound, while
impurities remain unaffected during compound formation. The resulting compound
is then decomposed to get pure metal . The method is used for refining of Ti , Zr
, Be and Si.
Ti + 2I2 Heat
 TiI4  Ti + 2I2
(iv) Electrolytic Refining. Most of the metals like Ag, Au, Pb, Ni, Sn, Zn, etc., are
refined by this method. The impure metal, in the form of blocks, is made the
anode and thin plates of pure metal form the cathode. A solution of a salt of the
metal is used as the electrolyte. On passing the electric current, pure metal from
the anode dissolves and is deposited on the cathode. The soluble impurities pass
into the solution while the insoluble impurities settle down below the anode as
anode mud.

ALUMINIUM
OCCURRENCE
Aluminium is a third most abudant element forming 8.3 % of the earth’s crust. It is constituent of
clay, slate and many types of silicate rocks. It is found only in the combined state, the important
minerals ore:
(i) Oxides: corundum, ruby, sapphire, emerald, Al2O3.
(ii) Fluoride: Na3AlF6
(iii) Basic sulphate : K2SO4.Al2(SO4)3.4Al(OH)3
(iv) Silicates ; felspar , KAlSi3O8. kaolin , porcelain , mica china clay , slate etc.
Al2O3.2SiO2.2H2O

EXTRACTION
Aluminium is mainly isolated from bauxite ore which is generally contaminated with ferric oxide
and silica. The removal of ferric oxide and silica from bauxite ore is essential before it is subjected
to electrolysis because it is rather difficult to remove iron and silicon from aluminium metal. The
extraction of aluminium from bauxite ore involves the following three steps.
(i) Purification of bauxite ore i.e., removal of ferric oxide and silica.
(ii) Electrolytic reduction of Al2O3
(iii) Electrolytic purification of aluminium.

P URIFICATION OF BAUXITE ORE :


(a) Baeyer’s process
This process is mainly applied to bauxite ore containing ferric oxide as chief impurity. The colour
of such ore is usually red and hence called red bauxite.
Al2O3.2H2O + 2NaOH  2NaAlO2 + 3H2O
Sodium metaaluminate
(soluble)
NaAlO2 + 2H2O  NaOH + Al(OH) 3
Precipitate

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(b) Hall’s process
Bauxite is fused with sodium carbonate. Al2O3 combines with sodium carbonate forming sodium
metaaluminate . The fused mass is extracted with water where Fe2O3 and SiO2 remain as precipitate.
Al2O3 + Na2CO3  2NaAlO2 + CO2
2NaAlO2 + CO2 + 3H2O  2Al(OH)3 + Na2CO3
(c) Serpeck’s process
This process is used when silica is present in considerable amounts in bauxite ore. The ore is
mixed with coke and heated at 1800 ºC in presence of nitrogen, where AIN(aluminium nitride) is
formed.
Al2O3 + 3C + N2  2AIN + 3CO
SiO2 + 2C  Si + 2CO
Calcination of aluminium hydroxide : The aluminium hydroxide precipitate obtained from the
above process is calcined at 1500 ºC in a rotatory kiln to obtain pure alumina (Al2O3)
2Al(OH)3 1500 ºC
  Al2O3 + 3H2O

Electrolytic reduction of pure alumina


The Electrolysis of pure alumina faces two difficulties :
(i) Pure alumina is a bad conductor of electricity
(ii) The fusion temperature of pure alumina is about 2000ºC and at this temperature when the
electrolysis is carried of fused mass, the formed metal vapourise as the boiling point of
aluminium is 1800ºC
The above difficulties are overcome by using a mixture containing alumina, cryolite (Na3AlF6) and
fluorspar (CaF2) in the ratio of 20: 24 : 20. The fusion temperature of this mixture is 900 ºC
and it is a good conductor of electricity .

Frozen crust of alumina and


electrolyte

Copper Control
clamp lamp

Iron
pot
MOLTEN ELECTROLYTE Dynamo

Molten
aluminium
Carbon lining

(i) Heating of the electrolyte :


The temperature of the cell is automatically maintained at 900 – 50 ºC
(ii) Electrolysis : On passing current, aluminium is discharged at cathode. Aluminium being
heavier than electrolyte sinks to the bottom and is tapped out periodically from tapping
hole. Oxygen is liberated at anode. It attacks carbon rods forming CO and CO 2.
First Step :
AlF3 from cryolite ionises as
AlF3 Al3+ + 3F–
Al3+ ions are discharged at cathode and F¯ ions at anode.
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Al3+ + 3e  Al ( at cathode)
2F–  F2 + 2e (at anode)
The liberated fluorine reacts with alumina to form AlF3 and O2. The oxygen attacks the carbon
anodes to form CO and CO2.
Al2O3 + 3F2  2AlF3 + ½O2
2C + O2  2CO
C + O2  CO2

Refining of aluminium by Hoope’s electrolytic method :


Aluminium is further purified by Hoope’s process. The electrolytic cell consists of an iron box
lined inside with carbon. The cell consists of three layers which differ in specific gravities. The
upper layer is of pure aluminium which acts as cathode. The middle layer consists of a mixture
of the fluorides of Al , Ba and Na. The lowest layer consists of impure aluminium which acts as
anode. The middle layer works as electrolyte.

The graphite rods dipped in pure aluminium and Cu–Al alloy rod at the bottom in the impure
aluminium work as conductors. On electrolysis, aluminium is deposited at cathode from the middle
layer and an equivalent amount of aluminium is taken up by the middle layer from the bottom layer
(impure aluminium). Therefore, aluminium is transferred form bottom to the top layer through
middle layer, while the impurities are left behind. Aluminium thus obtained is 99.98% pure.
Name of alloy Approximate Uses
Composition
1. Magnalium 95 % Al , 5 % Mg In the construction of airships, balances
and pistons of motor enginers.
2. Duralumin 95 % Al , 4 % Cu , Aeroplanes and automobile parts as its
0.5 % Mg , 0.5 % Mn strength of toughness is comparable to
mild steels
3. Aluminium Bronze 90 % Cu , 9.5 % Al , For making utensils, cheap artificial
0.5 % Sn jewellery , Photo frames, coins,
golden paints
4. Nicke alloy 95 % Al , 4 % Cu ,1 % Ni Aircraft parts.
5. Y-alloy 93 % Al , 4 %Cu , For making pistons and machinery parts
2 % Ni , 1 % Mg

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FLOW SHEET FOR THE EXTRACTION OF ALUMINIUM


Aluminium ore , Al2O3. 2H2O (Bauxite)

REFINING OF BAUXITE

(a) Baeyer’s Process :


Bauxite ore Roasted
  as to convert FeO into Fe2O3
150ºC Hydrolysis
Roasted + NaOH NaAlO2 Al(OH)3 + NaOH
in presence
Solution 80 atm. ppt.
of little H2O

Al(OH)3
(b) Hall’s Process :

(c) Serpeck’s Process :


Bauxite ore + Coke 1800 ºC
  AIN H O
2 Al(OH)3 + NH3
+ nitrogen ppt. by product

Calcination
Al(OH)3 1500 ºC
  Al2O3
anhydrous alumina

ELECTROLYTIC REDUCTION
Electrolyte Al2O3 dissolved in Na3AlF6 and CaF2
Cathode – Carbon lining Anode– Graphite rods

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Electrolysis
Al2O3 950
ºC
 Al + O2

99.8 % pure

ELECTROLYTIC REFINING
(Hoope’s process)

Pure Al (99.98% pure)

COPPER
OCCURRENCE :
Copper constitutes ony 0.0001 per cent of the earth’s crust. Its deposits, however, are concentrated
. Copper is found in nature in the following forms .
1. Native state : Copper is found in the metallic condition in large quantities near lake superior in
U.S.A. in the Ural mountains (Russia) and Sweden.
2. Combined state : The principal ores of copper are sulphides, oxides and basic carbonates.
Sulphide ores :
(i) Chalcopyrites or copper pyrites, CuFeS 2
(ii) Chalcocite or copper glance, Cu2S
(iii) Bornite, Cu3FeS3

Oxide ore
Cuprite (red) ; Cu2O
Extraction
1. From sulphide ores :
(a) Dry process or Smelting proces : This is applied to those ores in which copper content
is more than 3 % .
(b) Wet process of Hydrometallurgical process : This is applied to poor ores containing
small percentage of copper.

2. From non-sulphide ores : Leaching process:


(a) Concentration of the ore : The concentration of the sulphide ores is done by forth
floatation process.
(b) Roasting : The concentrated ore is heated strongly in a current of air on the hearth of the
reverberatory furnace.. During roasting the following changes take place.
(i) Free sulphur is oxidised and removed as sulphur dioxide.
S + O2  SO2
(ii) The arsenic and antimony present in the ore are removed as volatile oxides.
4As + 3O2  2As2O3
4Sb + 3O2  2Sb2O3
(iii) The pyrite is converted into cuprous sulphide and ferrous sulphide with evaolution
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of sulphur dioxide
2CuFeS2 + O2  Cu2S + 2FeS + SO2
(iv) The sulphides of copper and iron are partially oxidised.
2FeS + 3O2  2FeO + 2SO2
2Cu2S +3O2  2Cu2O + 2SO2
(c) Smelting : The roasted ore is mixed with coke and silica and transferred to a small blast
furnace. The mixture is heated in the presence of excess of air. The modern blast furnace
is made of steel lined inside with refractory bricks and is about 15 to 20 feet in height. It
is water jacketed throughout and is provided near the top with a waste gas outlet. The air
blast enters the furnace through tyeres. The following changes occur in the blast furnace.
(i) The cuprous oxide reacts with ferrous sulphide.
FeS + Cu2O  FeO + Cu2S
(ii) Most of the iron sulphide is oxidised to ferrous oxide.
2FeS + 3O2  2FeO + 2SO2
(iii) Ferrous oxide combines with silica and forms ferrous silicate. By this reaction
most of the iron is removed as slag.
FeO + SiO2  FeSiO3
Ferrous silicate (Slag)
(d) Bessemerisation : The matter obtained from smelting is transferred to a Bessemer
converter. Some sand (silica) is added and a blast of air is blown through the molten mass.
(i) Remaining ferrous sulphide gets oxidised
2FeS + 3O2  2FeO + 2SO2
(ii) Ferrous oxide combines with silica to form slag which is drained out at intervals
by tilting the vessel. In about three hours time, all the iron is removed as ferrous
silicate.
FeO + SiO2  FeSiO3 (Slag)
(iii) The blast of air is continued for almost another two hours. Excess of silica is
absorbed by basic lining of the converter and part of cuprous sulphide is oxidised
which combines with remaining cuprous sulphide to form free copper metal.
2Cu2S + 3O2  2Cu2O + 2SO2
Cu2S + 2Cu2O  6Cu + SO2

Refining by poling :
The impure metal is melted in a reverberatory furnace lined with silica. A part of copper metal
is oxidised to cuprous oxide which dissolves in the melt and supplies oxygen to the more basic
elements contained in it as impurity.
CuSO4 Cu++ + SO4– –

Cathode Anode
Cu++ + 2e Cu Cu + SO4– – CuSO4 + 2e

Wet process or hydrometallurgical process :


The essential principle of this process consists in the conversion of copper present in the ore into
soluble copper compound and precipitation of copper by addition of iron or by electrolytic
process.
2Cu2S + 5O2  2CuSO4 + 2CuO
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CuSO4 + Fe  Cu + FeSO4
(ppt.)

Extraction of copper from non-sulphide ores :


The oxide and carbonate ores are crushed and concentrated by gravity process. The concentrated
ores are calcined in reverberatory furnace. The carbonate decomposes to form the oxide and the
impurities either volatilise or are oxidised.
CuCO3.Cu(OH) 2  2CuO + CO2 + H2O
The oxide so formed is either reduced with carbon in reverberatory furnace or leached with dilute
H2SO4 .
CuO + C  Cu + CO
Cu2O + C  2Cu + CO
or CuO + H2SO4  CuSO4 + H2O
Copper sulphate solution obtained is then electrolysed using copper sheet as cathode and lead
plate as anode. Copper can also be recovered by using scrap iron.
CuSO4 + Fe  Cu + FeSO4
FLOW SHEET FOR THE EXTRACTION OF COPPER
Copper pyrites (CuFeS2)

Crushed and sieved

Concentration by forth floatation


Powdered ore  water  pine oil  air 
 sulphide ore in the forth

Roasting in reverberatory furnace in presence of air


S  O2  SO 2
2As  3O 2  2As 2 O3
2CuFeS 2  O 2   Cu 2S  2FeS  SO 2

Silica + coke  Roasted ore


Smelting in blast furnace in presence of air
2FeS  3O 2   2FeO  2SO 2
FeO  SiO 2   FeSiO 3 (Slag )

Silica
 Matte (Cu2S, FeS)

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Bessemeris ation in bessemer converter in presence of air


2FeS  3O 2  2FeO  2SO 2
FeO  SiO 2  FeSiO 3 (Slag )
2Cu 2S  3O 2  2Cu 2O  2SO 2
Auto
2Cu 2O  Cu 2S   6Cu  SO 2
reduction

Blister copper (98 %Cu + 2 % impurities)

Electrolytic refining
Anode — Impure copper plates
Cathode — Pure copper plates
Electrolyte — CuSO 4 so ln .  H 2SO 4
Pure copper deposited at cathode

Pure copper (99.6–99.9%)

S I LV E R
OCCURRENCE
Silver is a rare element as it forms only 10–8 percent of the earth’s crust. However, it was known
in prehistoric times and used for its colour and beauty as a precious metal. Silver is found in nature
in two forms.
1. Native state : It occurs in the metallic condition usually associated with copper, gold and platinum
metals.
2. Combined state : The important ores of silver are:
(a) In the form of sulphide
(i) Argentite or silver glance, Ag2S
(ii) Pyrargyrite or Ruby silver, 3Ag2S.Sb2S3
(iii) Stromeyerite or silver copper lance, (Cu, Ag)2S
(b) In the form of halide : Chlorargyrite or Horn silver, AgCl

[A] Extraction of silver from argentite ore (Cyanide proces)


Cyanide process is the modern process for the extraction of silver. The process is also called as
Mac-Arthur and Forest process. It is based on two points.
(a) Silver compounds (or even free silver) dissolve in sodium cyanide solution forming a
complex salt, NaAg(CN) 2, in presence of air.
(b) Silver is precipitated from this complex salt by the addition of zinc.

(i) Concentration of the ore :


Concentration of the ore is done by forth floatation process.

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(ii) Cyanidation :
The concentrated ore is ground to a very fine powder in ball mill. The finely powdered
ore is treated with dilute solution (0.4 to 0.6 %) of sodium cyanide and a current of air is
blown through the whole mass.
A g2S + 4NaCN 2NaAg(CN) 2 + Na2S
4Na2S + 5O2 + 2H2O  2Na2SO4 + 4NaOH + 2S
4Ag + 8NaCN + 2H2O + O2 (air)  4NaAg (CN) 2 + 4NaOH
AgCl + 2NaCN  NaAg(CN) 2 + NaCl
(iii) Recovery of silver :
Silver is precipitated from the solution by addition of zinc powder in a finely divided
condition silver is precipitated as a dark morphous mass, while zinc goes into the complex.
2NaAg(CN) 2 + Zn  Na2Zn(CN) 4 + 2Ag
Sodium zinco cyanide
(iv) Refining :
The main impurities are of lead, copper and gold. These are removed by following methods
:
(a) Cupellation process : Cupel is a big oval dish with a shallow hearth and is made
of bone-ash or porous cement. The impure silver is fused on the hearth of the
cupellation furnace and a strong current of air is blown over it.
(b) Electrolytic process : The impure silver is made as anode and pure silver plate
as cathode. The electrolytic solution is of silver nitrate containing 10% nitric acid.
On passing electric current silver ions start depositing on cathode and equivalent
amount from anode comes into solution.
Ag2S + CuCl2  2AgCl + CuS
2AgCl + 2Hg  2Ag + Hg2Cl2
(c) Extraction of silver from argentiferous lead (desilverisation of lead) : This
poor amount of silver requires to be concentrated before de-desilverisation. The
recovery of silver from crude lead (argentiferous lead), thus involves two steps.
(i) Partial separation of lead :
(a) by pattinson’s process or (b) by Parke’s process.
(ii) Removal of lead as lead oxide by cupellation process.

(a) Pattinson’s Process : This process is based on the fact that silver-lead system has an
eutectic mixture with 2.6 % silver melting at 303 ºC whereas, pure lead melts at 372 ºC
. When the molten argentiferous lead is allowed to cool slowly, crystals of pure lead are
deposited until the silver content of the mixture has risen to 2.6 % . The crystals of pure
lead are removed with the help of perforated ladles. The alloy rich in silver content is then
subjected to cupellation to remove the remaining lead.
(b) Parke’ process : This is at present the most commonly used method. It depends on the
following points:
(i) Zinc and lead are not miscible
(ii) Silver is more describe with zinc than lead
(iii) Zinc-silver alloy is lighter than molten lead and have a higher melting point.

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FLOW SHEET FOR THE EXTRACTION OF SILVER
Silver ore
(Argentite)

CONCENTRAT ION BY FORTH FLOATATION PROCESS


Powdered ore  Water  Pine oil  air 
 Forth carrying sulphide particles

CYANIDATIO N
Concentrated ore NaCN solution (0.4 - 0.6%)  Air
Ag 2 S  4 NaCN 2NaAg(CN) 2  Na 2S
4 Na 2S  5O 2  2H 2 O 
 2 Na 2SO 4  4 NaOH  2S

PRECIPITATION OF SILVER WITH ZINC


2 NaAg (CN ) 2  Zn 
 2Ag  Na 2 Zn (CN ) 4
black ppt.
Fuse
Black ppt. of Ag  KNO 3  Compact mass
(Silver metal)

ELECTROLYTICREFINING
Anode : Impure Silver
Cathode : Pure silver plate
Electrolyte : AgNO 3solution  HNO 3
Pure silver deposited on the cathode

IRON
OCCURRENCE
Iron is the fourth most abundant element and the second most abundant metal in nature. It occurs
in combined state. The main ores of iron are:
1. Oxide ores :
(i) Magnetite, Fe3O4. It is usually black in colour. It is richest ore of iron and contains upto
70% of the metal.
(ii) Haematite, Fe2O3. It is usually red in colour.
(iii) Limonite or hydrated ferric oxide, Fe2O3.3H2O. It has yellow, brown or red colour

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2. Carbonate ore :
Siderite or sepathic iron, FeCO3. It is also called clay-iron stone due to the presence of excess
of clay in it.
3. Sulphide ores :
(i) Iron pyrites, FeS 2. It is mainly used for the manufacture of sulphur dioxide (sulphuric
acid). It is not used for extraction of iron.
(ii) Chalcopyrites, CuFeS2. It is used for the extraction of copper.

EXTRACTION OF IRON

Concentration of the ore


1. Dressing of the ores : The iron ores are first broken into small pieces 3-5 cm in size.
2. Roasting : During roasting S, As, P are oxidized to the respective oxides.
S + O2  SO2 
4As + 3O2 2As2O3 
FeCO3 decomposes as,
FeCO3 FeO + CO2 
Fe2O3.3H2O loses water
Fe2O3. 3H2O  Fe2O3 + 3H2O
Fe3O4 is decomposed to ferrous oxide and ferric oxides.
Fe3O4  FeO + Fe2O3
Ferrous oxide reacts with silica to forms ferrous silicate at high temperature.
FeO + SiO2 FeSiO3
But the conversion of FeO into Fe2O3 will prevent the formation of FeSiO3. Thus the mass of
the ore becomes porous casting the increase in the effective surface area.
3. Smelting in the Blast furnace : Blast furnace is a shaft furnace made of steel plate of 20-30 in
with 4 - 6 diameter.

Extraction of Cast Iron


Iron is usually extracted from the haematite. Concentrated ore after calcinations is reduced with
carbon i.e. smelted in the blast furnace. Reactions taking place in the blast furnace are
(i) Zone of combustion :
C + O2  CO2
(Coke)
CO2 + C  2CO ; H = +ve (Newmann’s inversion reaction)
(ii) Zone of reduction :
The following reduction reactions are called indirect reduction, which is done by CO, which is
unstable at higher temperature (See Ellingham diagram).
Fe2O3 + 3CO  2Fe + 3CO2
FeO + CO  Fe + CO2
(iii) Zone of slag formation :
CaCO3  CaO + CO2
(lime stone)
CaO + SiO2  CaSiO3 ;
Fusible slag
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(iv) Zone of fusion (lower part of furnace) :

Cup a nd c one
a rra nge ment Wa ste ga ses

200-250º C
400ºC Re fra ctory bricks
600ºC
700ºC
800-1000ºC
1300ºC Hot a ir
1600ºC
Tutere s

M olte n
sla g
M olte n metal

Molten iron is heavier from molten slag. The two liquid are periodically tapped off. The molten
iron tapped off from the furnace is solidified into blocks called ‘plags’.
Preparation of Wrought Iron : This is done by heating cast iron with haematite (Fe2O3) which
oxidizes C to CO , S to SO2 , Si to SiO2 , P to P4O10 and Mn to MnO .
Fe2O3 + 3C  2Fe + 3CO
Where CO and SO2 escape, manganous oxides (MnO) and Silica (SiO 2) combine to form slag.
MnO + SiO2  MnSiO3
Similarly phosphorus pentoxide combines with haematite to form ferric phosphate slag.
2Fe2O3 + P4O10  4FePO4
Bosh : The diameter of the furnace gradually increases from the top down wards. Widest part
of the furnace is called Bosh. At above 2m, tubes are there through which hot air blast is
blown into the furnace.
Hearth : Below the bosh this region exists.
(1) Slag notch is at higher height and
(2) tap hole for metal passage at lower position from the bottom. At the top of the furnace
the hopper is there which is cup and cone arrangement. Through this charge is introduced
till the charge bed in the furnace is 4/5th of the furnace. Hot air at 700ºC is forced into the
furnace through the tubes. The thermal gradient inside exists from 1800ºC (hearth) to
400ºC-900ºC in the upper region. Near the both the reactions temperature varies from
1200º-1300º.

Chemical reactions which have placed are :


1. At 1200ºC near the tuyeres,
C + O2  CO2 ; CO2 + C  2CO
2. Above bosh 600º - 900ºC, ferric oxide is partially reduced by CO as
Fe2O3 + 3CO  2Fe + 3CO2 
900ºC
3. CaCO3   CaO + CO2
1000 1300ºC
2CO   CO2 + C

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Fe2O3 + 3C  2Fe + 3CO
CaO + SiO2  CaSiO3 (slag)
4. The reaction at 1500ºC, MnO2 is reduced to
MnO2 + 2C  Mn + 2CO
Ca3(PO4)2  3CaO + P2O5
CaO + SiO2  CaSiO3
2P2O5 + 10C  P4 + 10CO
5. Collection of Cast Iron :
Metal is cast into ingots or in the ladle for further refining like steel making.
Wrought Iron : Minimum % of carbon is 0.1 to 0.25 % and other impurities like S, P, Mn, Si
less than 0.3 %.

Manufacturing Process :
Cast iron is taken in pudding furnace and melted by hot blast of air. The chemical reactions,
which occur are :
S + O2  SO2 ; 3S + 2Fe2O3  4Fe + 3SO2
3Si + 2Fe2O3  4Fe + 3SiO2
3Mn + Fe2 O3  2Fe + 3MnO
MnO + SiO2  MnSiO3
3C + Fe2O3  2Fe + 3CO
4P + 5O2  2P2O5 ; Fe2O3 + P2O5  2FePO4 (slag)
The impurities are removed from iron, the melting point of the metal rises and it becomes a semi
solid mass. Metal taken out from the furnace in the form of balls with the help of the rubbles. The
balls are then beaten under hammer to separate out of the slag. The product formed, is thus called
wrought iron.

FLOW SHEET FOR EXTRACTION OF IRON


IRON ORE
Concentration by gravity process
followed by electromagnetic separation

Calcination and Roasting


Ore + air Heat Moisture, CO2, SO2As2O3 removed
FeO is oxidised to ferric oxide

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Smelting in a blast furnace (ore  coke  limestone) . The following reactions occur.
400 700C
Fe 2 O 3     2Fe 3CO 2
Spongy iron
1000º C
CaCO 3    CaO  CO 2
CaO  SiO 2   CaSiO 3 (Slag )
Hot iron
2CO   CO 2  C
1200º C
SiO 2  2C    Si  2CO
MnO 2  2C   Mn  2CO
P4 O10  10C   4P  10CO
Spongy iron  C, Mn, Si, etc.   Impure iron
1600C
C  O 2    CO 2
1500 º C
CO 2  C    2CO

Pig iron
Remelted and cooled

Cast iron

It can be made as follows :


(i) By reducing the amount of carbon in cast iron.
(ii) By adding some carbon to wrought iron.
(iii) By mixing the required amounts of cast iron and wrought iron.
(iv) Directly from ore.
Generally steel is prepared from cast iron.
Production of steel from cast iron :
(i) Acidic Bessemer process :
[1] The Bessemer is lined with silica.
[2] In the acidic Bessemer, hot air oxidise Mn, Si and C impurities present in the cast iron.
2Mn + O2  2MnO
Si + O2  SiO2
2C + O2  2CO 
[3] MnO combines with SiO2 to give slag MnSiO3 which is separated. Carbon is oxidised to carbon
monoxide which burns with a blue flame at the mouth of converter.
[4] When the whole of the carbon is oxidised the blue flame suddenly stops.

The requisite amount of carbon is then added usually in the form of an alloy of Fe + Mn + C, Called spiegel.
The process is called spiegeleisen. The resulting product is manganese steel which is harder and possesses
much greater tensile strength.

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(ii) Basic Bessemer process :


[1] This process is used when cast iron contains comparatively the higher impurity of phosphorus.
[2] The Bessemer is lined with CaO or MgO.
[3] Cast iron and lime stone are taken in the Bessemer and hot air is passed through them. Mn, Si, C and,
P oxidise as
2Mn + O2  MnO
Si + O2  SiO2
MnO + SiO2  MnSiO3
Slag
4P + 5O2  2P2O5
2C + O2  2CO 
3CaO + P2O5  Ca3(PO4)2
Slag
Ca 3(PO4)2 is known as Thomas slag and is used as valuable fertilizer.
[4] Iron thus obtained undergoes spiegeleisen and steel is obtained.

(iii) Siemen’s Martin or open hearth process :


[1] Iron. ore hematites used for the oxidation of impurities.
[2] Scrap steel, wrought iron of low quality is added to reduce the quantity of carbon.
[3] Heat is reproduced for obtaining the high temperature.
[4] The hearth of the furnace is lined with silica or dolomite. (CaO. MgO) depending upon the nature of
the impurities.
C , S , P , Si , and Mn are oxidised by hematite as :
Fe2O3 + 3C  2Fe + 3CO 
2Fe2O3 + 3S  4Fe + 3SO2 
10Fe2O3 + 3P4  20Fe + 6P2O5
2Fe2O3 + 3Si  4Fe + 3SiO2
Fe2O3 + 3Mn  2Fe + 3MnO
CO and SO2 come out and other oxides form slag as follows which are separated.
MnO + SiO2  MnSiO3
slag
CaO + SiO2  CaSiO3
slag
3CaO + P2O5  Ca3(PO4)2
slag
(iv) The oxygen Top-Blowing process
In this process, liquid iron from the balst furnace is charged into a converter, scrap steel is added and a jet of
oxygen is blown through a retractable steel ‘lance’ into or over the surface of the liquid metal. Impurities
are oxidized and with the addition of lime form slag, which is usually removed by tilting the converter. When
steel of desired composition is obtained, The oxygen is turned off and the molten steel is poured into laddler
for casting into ingots.

Oxygen lance

liquid metal

The oxygen top-blowing process

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(v) The electric Arc process :
A charge of scrap steel and turnings is fed into the furnace and is melted by electric arc struck between
adjustable carbon electrodes. Again, acidic or basic linings are employed for scrap differing in phosphorus
content. This method is widely sed in the manufacture of alloys and other high quality steels such as
stainless steel and high-speed cutting steel.

Charge Carbon
electrodes

Rollers for
tilting furnace

Electric arc process

(vi) The high-frequency induction process :


A charge of alloy scrap of known composition, together with iron is fed into the furnace. Alternating current
at 500–2000 Hz per second passes through the insulted water-cooled copper coils. The resulting magnetic
field sets up steady current, which generates heat. The circulation of the metal caused by these currents
produces strong stirring effect. The induction furnace is capable of producing high quality alloy steels
containing tungsten. Vanadium, chromium, manganese, molybdenum, cobalt and nickel for making ball-bearing,
magnets dies and tool steel etc.

Casing of
crucible refractory
material

Liquid metal

H2 O

Water cooled
copper coils

High-frequency induction process

Alloys Composition
1. Chrome steel : 2 - 4 % Cr , 98 - 96 % Fe
2. Tungsten steel : 10 - 20 % W , 90 - 80 % Fe
3. Stainless steel : 12 - 14 % Cr , 88 - 86 % Fe or
2 - 4 % Ni + 86 - 82 % Fe
4. Manganese steel : 10 - 18 % Mn , 90 - 82 % Fe
5. Nickel steel : 3 - 5 % Ni , 97 - 95 % Fe
6. Vanadium steel : 0.2 - 1 % V
7. Invar : 36 % Ni , 64 % Fe

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The hardness and elasticity of steel can be controlled by proper heat treatment.
Annealing : If steel is heated to redness and then allowed to cool slowly. it becomes malleable, soft and
pliable. This operation is called annealing.
Hardening : If steel is heated to redness and is suddenly quenched by plunging into water or oil, it
becomes extremely hard and brittle. This process is called hardening.
Tempering : Hard steel is heated up to 270°C and then allowed to cool slowly . It becomes’ comparatively
less hard and less brittle.
GOLD
Occurrence of Gold :
Gold is mainly found in native state either as vein good, placer gold or alluvial good. It is also
present to a small extent in the combined state as sulphide, telluride and arsenosulphide. Some
important ores of gold are :
(i) Calaverite , AuTe2 (ii) Sylvanite , AuAgTe2 and (iii) Bismuth aurite , BiAu2

Extract of gold :
(i) Mac-Arthur-Forest Cyanide process : The powdered gold ore, after concentration by Forth-
floatation process, is roasted to remove easily oxidisable impurities of tellurium, arsenic and sulphur.
The roasted ore is then treated with a dilute solution of KCN in presence of atmospheric oxygen
when gold dissolves due to the formation of an aurocyanide complex.
4Au + 8KCN + 2H2O + O2  4K[Au(CN) 2] + 4KOH
Soluble
The metal is then extracted by adding zinc dust.
2 K [Au(CN) 2] + Zn  K2 [Zn(CN) 4] + 2Au
ppt.
(ii) Plattner’s chlorine process : The roasted ore is moistened with water and placed in wooden
vats with false perforated bottoms. It is saturated with current of chlorine, gold chloride thus
formed is leached with water and the solution is treated with a reducing agent such as FeSO4 or
H2S to precipitate gold.
AlCl3 + 3FeSO4  Au + FeCl3 + Fe2(SO4)3
2AuCl3 + 3H2S  6HCl + 3S + 2Au 
The impure gold thus obtained contains imparities of Ag an Cu. The removal of Ag and Cu forms
gold is called parting. This is done by heating impure gold with conc. H2SO4 (or HNO3) when
Ag and Cu dissolve leaving behind Au.
Cu + 2H2SO4  CuSO4 + SO2 + 2H2O
2Ag + 2H2SO4  Ag2SO4 + SO2 + 2H2O
Properties of gold :
Gold is a yellow, soft and heavy metal. Gold and Ag are called noble metals since they are not
attacked by atmospheric oxygen. However, Ag gets tarnished when exposed to air containing
traces of H2S. Gold is malleable, ductile and a good conductor of heat and electricity. Pure gold
is soft. It is alloyed with Ag or Cu for making jewellry. Purity of gold is expressed in terms of
carats. Pure gold is 24 carats. Gold ‘14 carats’ means that it is an alloy of gold which contains 14
parts by weight of pure gold and 10 parts of copper per 24 parts by weight of the alloy. Thus the
percentage of gold in “14 carats” of gold is = 10024 × 14 = 58.3%
Most of the jewellery is made from 22 carat gold (91.66% pure gold). Gold is quite inert. It does
not react with oxygen, water and acids nut dissolves in aqua regia (3 parts concentrated HCl + 1
part concentrated HNO3)
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3HCl + HNO3  2H2O + 2Cl] × 3
Au + 3Cl  Au Cl3] × 2
2Au + 9 HCl + 3HNO3  2AuCl3 + 6H2O + 3NOCl
Auric chloride nitrosyl chloride

Oxidation states of gold :


The principal oxidation states of gold are + 1 and + 3 though + 1 state is more stable than + 3

Compounds of gold :
(1) Auric chloride AuCl3 . It is prepared by passing dry Cl2 over finely divided gold powder at 573
K
2 Au + 3Cl2 573 K
 2AuCl3
It is a red coloured crystalline solid soluble in water and decomposes on heating to give gold(i)
chloride and Cl2.
AuCl3 Heat AuCl + Cl2
It dissolved in conc. HCl forming chloroauric acid
AuCl3 + HCl  H [AuCl4]
Chloroauric acid is used in photography for toning silver prints and as an antidote for snake
poisoning.
(2) Aurous sulphide , Au2S . It is prepared when H2S is passed through an acidified solution of potassium
aurocyanide, K[Au(CN)2]
2K [Au (CN) 2] + H2S  Au2S + 2KCN + 2HCN
It is dark brown solid, not attacked by dilute mineral acids and hence is probably the most stable
gold (l) compound
ZI N C
Occurrence of zinc :
Zinc does not occur in the native form since it is a reactive metal . The chief ores of zinc are (i)
Zinc blende (ZnS) (ii) Calamine or zinc spar (ZnCO3) and (iii) Zincite (ZnO).

Extraction of zinc :
Zinc blende, after concentration by Froth floatation process, is roasted in air to convert it into
ZnO. In case of calamine, ore is calcined to get ZnO. The oxide thus obtained is mixed with
crushed coke and heated at 1673 K in fire clay retorts (Belgian Process) when ZnO gets reduced
to metallic zinc. Being volatile at this temperature, that metal distils over and is condensed leaving
behind Cd, Pb and Fe as impurities. The crude metal is called spelter. The metal may be refined
either by electrolysis or by fractional distillation.

Properties of Zn :
Zinc is more reactive than mercury. It is good conductor of heat and electricity. Zinc readily
combines with oxygen to form ZnO. Pure zinc does not react with non-oxidising acids (HCl or
H2SO4) but the impure metal reacts forming Zn2+ ions and evolving H2 gas.
Zn + 2HCl  ZnCl2 + H2 
Hot and conc. H2SO4 attacks zinc liberating SO2 gas
Zn + 2H2SO4  ZnSO4 + SO2 + 2H2O
Zinc also reacts with both dilute (hot and cold) HNO3 and conc. HNO3 liberating nitrous oxide
(N2O), ammonium nitrate (NH4NO3) and nitrogen dioxide (NO2) respectively.
4 Zn + 10 HNO3 (warm, dilute)  4 Zn (NO3)2 + N2O + 5H2O

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4Zn + 10 HNO3 (cold, very dilute)  4 Zn (NO3)2 + NH4NO3 + 3H2O
Zn + 4NO3 (hot and conc.)  Zn (NO3 )2 + 2NO2 + 2H2O
zinc dissolves in hot concentrated NaOH forming the soluble sod. zincate
Zn + 2NaOH + 2H2O  Na2 [Zn (OH) 4] + H2
or Zn + 2NaOH  Na2ZnO2 + H2

Special varieties of zinc :


(i) Zinc dust : It is prepared by melting zinc and then atomising it with a blast of air.
(ii) Granulated zinc : It is prepared by pouring molten zinc. into cold water.
Both these varieties of zinc are used as reducing agents in laboratory

Compounds of zinc :
(1) Zinc oxide (Zinc white or Chinese white) ZnO . It is obtained by burning zinc in air or by
heating zinc carbonate or zinc nitrate.
2 Zn + O2 Heat
 2 ZnO ; ZnCO3 Heat
 ZnO + CO2
2 Zn(NO3)2 Heat  2 ZnO + 4NO2 + O2
It is a white powder but becomes yellow on heating and again white on cooling,.
It is insoluble in water and is very light and hence commonly known as philosopher’s wool.
It is amphoteric in nature.
ZnO + 2HCl  ZnCl2 + H2O
(basic)
ZnO + 2NaOH  Na2ZnO2 + H2O
(acidic) Sod. zincate
or ZnO + 2NaOH + H2O  Na2[Zn(OH) 4]
Sod. tetrahydroxozincate (II)
It is reduced both by carbon and H 2 and is used as a white paint
ZnO + C  Zn + CO ; ZnO + H2  Zn + H2O
(2) Zinc chloride , ZnCl2 : It is obtained when Zn metal ZnO or ZnCO3 is treated with dil HCl.
It crystallizes as ZnCl2. 2H2O and becomes anhydrous on heating . ZnCl2 is highly deliquescent
and is highly soluble in H2O and also readily dissolves in organic solvents like acetone, alcohol,
ether etc. It aqueous solution is acidic due to hydrolysis.
ZnCl2 + H2O  Zn (OH) Cl + HCl
Anhydrous ZnCl2 is used as a Lewis acid catalyst in organic reactions. mixed with moist zinc
oxide, it is used for filling teeth and its solution is used for preserving timber.
(3) Zinc sulphide , ZnS : It is a white solid. It is soluble in dil. HCl an thus does not get precipitated
by H2S in the acidic medium.
ZnS + 2HCl  ZnCl2 + H2S
It is a constituent of lithopone (ZnS + BaSO4).
(4) Zinc sulphate , ZnSO4 . 7H2 O : It is commonly known as white vitriol and is obtained by the
action of dil. H2SO4 on zinc. metal ZnO or ZnCO3. On heating , it first loses six molecules of
water of crystallization at 373 K. At 723 K, it becomes anhydrous and on further heating, it
decomposes.
ZnSO4.7H2O 373 K 373 K 1073 K
 ZnSO4.H2O  2 ZnSO4    2 ZnO + 2SO2 + O2
It is also used as an eye lotion.

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Alloys of Zinc :
(i) Brass (Cu = 80 % , Zn = 20 %) is used for making utensils, machinery parts and wires.
(ii) German Silver (Cu = 60 % , Zn = 20 % and Ni = 20 %) is used for making silver ware
and silver plating.

M E R C U RY

Occurrence and extraction of mercury :


Cinnabar (HgS) is the only important ore of Hg. It is concentrated by forth floatation method and
mercury is extracted from this ore by heating it in air at 773–873 K (auto reduction)
873K
HgS + O2 773    Hg + SO2
The mercury vapours thus obtained are condense to give liquid metal. Hg thus obtained contains
impurities of Zn, Sn and Pb. These are removed by treating the impure metal with dio. HNO 3.
Mercurous nitrate, Hg2(NO3) thus formed reacts with metals present as impurities forming their
nitrates which pass into solution leaving behind pure mercury. However, ti si best purified by
distillation under reduced pressure.
6Hg + 8HNO3 (dil.) warm  3Hg2 (NO3)2 + 4H2O + 2NO
Zn + Hg2(NO3)2  Zn(NO3)2 + 2Hg
Similar reaction is given by Pb and Sn.
Properties of mercury :
Mercury is less reactive than Zn. it is liquid at room temperature and has low thermal and electrical
connectivity. Mercury forms dimeric mercury (i) ion, Hg2+2 in which the two Hg atoms are bonded
by a covalent bond. It is lowly oxidised to HgO at about its boiling point. Hg does not react with
dil. HCl or dil. H2SO4 but reacts with hot concentrated H 2SO4 to form HgSO4. It, however,
reacts with both warm dil and conc. HNO3 evolving NO and NO2 respectively.
Hg + 2H2SO4 (hot, conc.)  HgSO4 + SO2 + 2H2O
Hg + 4HNO3(conc.)  Hg(NO3)2 + 2NO2 + 2H2O

TIN
Occurrence of tin :
Tin does not occur in nature in the native state. Its chief ore is cassiterite or tin stone (SnO2).

Extraction of tin from tin stone :


The ore is crushed, washed and concentrated magnetically to remove magnetic impurities of
tungstate of iron (wolframite, FeWO4) and manganese. The concentrated ore is roasted to remove
sulphur and arsenic as their oxides. The roasted ore is then subjected to smelting i.e. ore is mixed
with anthracite (coke) in the ratio 1 : 4 and little limestone (flux) and heated in a reverberatory
furnace.
1600 K
SnO2 + 2C 1500
   Sn + 2CO ; CaCO3  CaO + CO2
CaO + SiO2  CaSiO3
The molten metal is tapped out from the bottom of the furnace and cast into blocks. The tin thus
obtained is called block tin and contains impurities of Fe, Pb and Cu etc. The crude metal is finally
refined by either liquation, poling or electro-refining.

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In electro refining, impure metal is made the anode while a sheet of pure metal acts as the cathode.
The electrolyte consists of stannous sulphate SnSO4 containing little H2SO4 and hydrofluosilicic
acid (H2SiF6). On passing current, tin dissolves from the anode and passes into the electrolyte
while an equivalent amount of tin from the electrolyte gets deposited on the cathode.

Properties of tin :
It is a soft white metal, malleable and ductile and can be rolled into sheets and foils. When heated
in air, it forms SnO2, with S it forms SnS2 and with Cl2 it gives SnCl4. It dissolves in hot concentrated
alkalies evolving H2 gas
Sn + 2NaOH + H2O  Na2SNO3 + 2H2
and reacts with HNO3 to give metastannic acid (H2SnO3)
Sn + 4HNO3  H2SnO3 + 4NO2 + H2O
With dil. HCl or H2SO4 tin reacts liberating H2 gas
Sn + 2HCl  SnCl2 + H2 
With hot conc. H2SO4 tin reacts to give SO2 gas
Sn + 2H2SO4 (conc.)  SnSO4 + SO2 + 2H2O
Tin is widely used for plating iron and brass vessels to resist corrosion. Tin foils are also used for
wrapping cigarettes and making food containers.
LEAD

Occurrence of lead :
Lead does not occur in the free state. The important ores of lead are :
(i) Galena (PbS) (ii) Anglesite (PbSO4) and (iii) Cerussite (PbCO3).

Extraction of lead :
(i) Self reduction process :
Galena, after concentration by Froth-floatation process, is roasted in air to form PbO and PbSO4.
The unchanged galena then brings about the reduction of PbO and PbSO 4 to Pb metal (auto
reduction).
Heat
3PbS + 5O2  2PbO + PbSO4 + 2SO2
Roasting

Heat Heat
2PbO + PbS   3Pb + SO2 ; PbSO4 + PbS   
Auto reduction
 2Pb + 2SO2
Auto reduction

(ii) Carbon reduction process :


The roasted ore is reduced to metal by heating with coke.
Heat
PbO + C Coke
 Pb + CO.

The metal obtained by above methods contain Ag, Cu, Fe, Sn and Sb as impurities. It is refined
by either liquation, softening, desilverisation or electrolytic refining processes.
In electrolytic refining the electrolyte taken consists of a solution of lead fluorosilicate (PbSiF6)
and hydrofluosilicic acid (H2SiF6) with a little gelatin.

Properties of lead :
Lead is a bluish grey lustrous metal but when exposed to air, it acquires dull appearance due to
the forming of a thin layer of Pb(OH)2 and PbCO3 on its surface. It dissolves in hot concentrated
alkali evolving H2.
Pb + 2NaOH  H2 + Na2.PbO2 (Sod. plumbite)
Other reactions with acids, S, Cl2 are similar to those of Sn
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Lead forms two series of compounds i.e. Pb (II) and Pb(IV) compounds but Pb(II) compounds
are more stable than Pb (IV) compounds. Pb (II) compounds are essentially ionic while Pb (IV)
compounds are covalent in nature.
Lead used for making cable coverings, bullet shots, lead accumulators, tetraethyl lead (antiknocking
agent) and a number of pigments such as red lead (Pb3O4); white lead [2Pb(OH2.PbCO3], chrome
yellow (PbCrO4) and chrome red (PbO.PbCrO4).

SODIUM
1. Sodium Monoxide (Na2O)
Preparation :
It is obtained by burning sodium at 180 °C in a limited supply of air or oxygen and distilling off
the excess of Na in vaccum or by heating Na2O2 (sodium peroxide), sodium nitrate (NaNO 3)
with sodium.
2Na  12 O 2 
 Na 2 O ; Na 2 O 2  2Na 
 2Na 2O
2NaNO3  10Na 
 6Na 2O  N 2
Properties :
1. It is a white amorphous substance.
2. It reacts with water violently forming NaOH .
Na2O + H2O  2 NaOH
3. On heating above 400 °C , it disproportionates to give peroxide and metallic sodium.
400 C
2Na 2 O   Na 2O 2 2Na
4. It reacts with liquid ammonia forming sodamide and NaOH .
Na2O + NH3  NaOH + NaNH2

2. Sodium Peroxide (Na 2O2)


Preparation :
It is formed by heating the sodium metal in excess air or oxygen. The air should be moisture free
and the temperature required is 300 °C .
2 Na + O2  Na2O2

Properties :
1. It is a yellow substance but turns white on exposure to moist air due to the formation of
NaOH and Na2CO3.

2. Action of water : 2Na 2 O 2  2H 2O (warm) 


 4NaOH  O 2
cold
3. Action of acids : Na 2 O 2  H 2SO 4  Na 2SO 4  H 2O 2
hot
2Na 2 O 2  2H 2SO 4   2Na 2SO 4  2H 2O  O2
4. Oxidizing action : It is a powerful oxidizing agent and oxidizes chromic compounds to
chromates, manganous salts to manganates, SO 2 to SO3 or sulphates, and sulphides to
sulphates. For example,
[Na 2 O2  H 2 O 
 2NaOH  O]  5

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Cr2 (SO 4 )3  10NaOH  5O   3Na 2SO 4  2Na 2 CrO 4  O 2 5H 2 O


Cr2 (SO 4 )3  5Na 2 O 2 
 3Na 2SO 4  2Na 2 CrO 4  O 2
5. Reducing action : It reduces potassium permanganate, a stronger oxidising agent.
Na 2 O 2  H 2SO 4 
 H 2 O 2  Na 2SO 4
2KMnO 4  3H 2SO 4  5H 2 O 2 
 K 2SO 4  2MnSO 4  8H 2O  5O 2
6. It combines with CO to form Na CO
2 3
Na 2 O 2  CO 
 Na 2CO3
3. Sodium Hydroxide (Caustic Soda), NaOH
Preparation :
Sodium hydroxide is commonly called caustic soda because of its corrosive action on animal and
vegetable tissues. Large quantity of sodium hydroxide is now a days, prepared by electrolytic
process. There are two electrolytic methods commonly used for preparing sodium hydroxide.
(a) Castener Kellner cell :
NaCl(aq) Na   Cl –
At cathode (mercury) : 2 Na+ + 2 e–  2 Na

Na + Hg  NaHg (sodium amalgam)

At anode (graphite) : 2 Cl–  Cl2 + 2 e–

Sodium amalgam is removed from the cell. It is then decomposed in a separate cell by water
giving NaOH, hydrogen and mercury. Mercury is recirculated to the cell.
(b) Nelson cell (or Diaphragm cell)
NaCl (aq) Na   Cl –
H2O H   OH –
At cathode (perforated steel) : 2 H+ + 2 e–  H2

At anode (carbon rod) : 2 Cl–  Cl2 + 2 e–
Note : This cell is used for the industrial production of Cl2. As well as this cell can be used for
production of Na2CO3, for which CO2 is mixed with steam.

Properties :
1. NaOH is stable towards heat but is reduced to metal when heated with carbon
2NaOH + 2C  2Na +2CO + H2
2. FeCl3 + 3NaOH  Fe(OH) 3 + 3NaCl
NH4Cl + NaOH  NaCl + NH3 (pungent smell) + H2O
HgCl2 + 2NaOH  HgO (yellow powder) + 2NaCl + H2O
excess
Zn(OH) 2  + 2NaOH   Na2ZnO2 + 2H2O
excess
Al2O3  + 2NaOH   2NaAlO2 + H2O
SiO2 + 2NaOH  Na2SiO3 + H2O
P4 + 3 NaOH +3H2O  PH3 + 3NaH2PO2
2Al + 2 NaOH + 2H2O  3H2 + 2NaAlO2

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4. Sodium Carbonate : Na 2CO3 :
It exists in various forms, namely anhydrous sodium carbonate Na2CO3 (soda-ash); monohydrate,
Na2CO3.H2O (crystal carbonate); heptahydrate, Na 2CO3. 7H2O and decahydrate, Na 2CO3.
10H2O (washing soda or sal soda). It occurs in the form of reh and sajji matti in U.P. and Bihar.
Manufacture : (Solvay or ammonia soda process). In this process, brine (NaCl), ammonia and
carbon dioxide are the raw materials. The chemical reactions involved are as below :
NH3 + CO2 + H2O   NH4 HCO3
30 C
NH 4 HCO3  NaCl   NaHCO3   NH 4 Cl
Sod. bicarbonate

250 C
2NaHCO3   Na 2 CO3  H 2 O  CO 2
Sod. bicarbonate (used again)

2NH 4 Cl  Ca(OH)2 
 CaCl 2  2H 2O  2NH 3
Amm. chloride Slaked lime (used again )

Note : Solvay process cannot be used for the production of K2CO3, since KHCO3 has much
greater solubility than NaHCO3. So, KHCO3 cannot be precipitated.
Properties :
1. Sodium carbonate crystallizes from water as decahydrate. It is a white solid which
efflorescence on exposure to dry air forming the monohydrate.
dry
Na 2CO3 .10H 2O 
air
 Na 2CO3. H 2O  9H 2O
On heating, the monohydrate changes to anhydrous salt (m.p. 853°C) which does not
decompose on further heating even to redness.
2. It is soluble in water with considerable evolution of heat. The resulting solution is alkaline
due to hydrolysis.
Na CO  2H 2O
2 3 H 2CO3  2NaOH
Sod. carbonate (weak acid) (Strong alkali )

3. It is readily decomposed by acids with the evolution of CO2 gas.


4. It reacts with metal salts to form insoluble normal or basic carbonate.
CaCl2 Na 2 CO3 
 CaCO3   2NaCl
2MgCl2  2Na 2CO3  H 2 O   MgCO3 . Mg(OH) 2   4NaCl  CO 2
Carbonates of metals like Al , Fe , Sn, etc. when formed are immediately hydrolysed to
hydroxides.
3H 2 O
Fe 2 (SO4 )3  3Na 2 CO3 
 Fe 2 (CO3 )3   2Fe(OH) 3  3CO 2
5. When CO2 gas is passed through aqueous solution of sodium carbonate, sodium
bicarbonate is formed.
Na 2 CO3  H 2O  CO 2 
 2NaHCO3
Sod. bicarbonate

5. Sodium sulphate (Glauber’s salt): Na 2SO4. 10H2O


Preparation :
(a) The anhydrous sodium sulphate (salt cake) is obtained as a by-product in the manufacture
of hydrochloric acid.
(b) Salt cake is also produced during the manufacture of sodium carbonate when NaCl is
heated with H2SO4.

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2NaCl  H 2SO4   Na 2SO 4  2HCl


(c) Salt cake is now-a-days manufactured by heating NaCl with sod. bisulphate (nitre cake).
Nitre cake is obtained by the action of H2SO4 on sodium nitrate (Chile saltpeter).
NaNO  H 2SO 4 
3  NaHSO 4  HNO3
Chile saltpetre Nitre cake

NaCl  NaHSO 4 
 Na 2SO 4  HCl 
Nitre cake Salt cake

Properties :
1. The decahydrate sodium sulphate effloresces in dry air forming the anhydrous salt. It is
crystalline solid, soluble in water.
2. When treated with lead , barium or strontium salts, it forms the corresponding insoluble
sulphate, e.g.
Pb(NO3 ) 2  Na 2SO 4   PbSO 4   2NaNO3
3. When a solution having equivalent quantity of anhydrous Na 2SO4 and conc. H2SO4 is
cooled, prismatic crystals of sodium bisulphate (sodium hydrogen sulphate, NaHSO4) are
formed .
Na2SO4 + H2SO4  2 NaHSO4
4. When heated with carbon it is reduced to sodium sulphide
Na2SO4 + 4 C  Na2S + 4 CO

6. Sodium Chloride (NaCl)


Preparation :
It is also called common salt occurs abundantly in nature as rock salt or halite. The most abundant
source is sea-water where sodium chloride occurs to the extent of 2.6 – 2.9 percent. The sea
water is exposed to the sun and air in large shallow pits. The gradual evaporation of water lead to
the crystallization of the salt. The purification is done by dissolving the salt in minimum volume of
water and filtering, if necessary, to remove insoluble impurities. The solution is then saturated with
a current of dry hydrogen chloride whereby crystals of pure sodium chloride separate out.
Properties :
1. NaCl is a colourless crystalline salt, almost insoluble in alcohol and highly soluble in water.
2. It gives rise to HCl when heated with conc. H2SO4 and Cl2, with MnO2 plus H2SO4.
NaCl + H2SO4   NaHSO4 + HCl
NaHSO4 + NaCl  Na2SO4 + HCl
2NaCl + MnO2 + 2H2SO4  MnSO4 + Na2SO4+ 2H2O + Cl2 

Illustration 1 : Give reason for decreasing order of conductivity of following


Cs+  Rb+  K+  Na+  Li+
Solution : Ions are hydrated in solution. Since Li is very small it is heavily hydrated. This make the
radius of the hydrated ions large and hence it moves only slowly (although Li+ is very
small) and the radius of hydrated Cs+ ion is smaller than the radius of hydrated Li+.

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POTASSIUM
1. Potassium Oxides :
Three oxides are known :
(i) potassium mono-oxide (potassium oxide), K2O;
(ii) dioxide (tetroxide or superoxide), KO 2 or K2O4; and (iii) sesquioxide, K2O3.
Preparation :
180 C
1. 4K(excess)  O 2 
reduced pressure
 2K 2 O
Pot. monoxide

heat
2KOH  2K  2K 2O  H 2
2 KNO3 + 10 K  6 K2O + N2
burning
2. K  O 2 (excess)   KO2
Pot. dioxide

2 KOH + O3  2 KO2 + H2O


3O 2
3. 4K (dissolved in liq. NH3)   2K 2 O3
Pot. sesquioxide

Properties :
Potassium monoxide is a white hygroscopic solid while dioxide is a chrome yellow powder. The
important chemical property of oxides is their hydrolysis to form KOH .
K2O + H2O  2 KOH
2 KO2 + 2 H2O  2 KOH + H2O2 + O2

2. Potassium hydroxide (Caustic Potash), KOH


Preparation :
It may be prepared like that of NaOH , i.e., by the electrolysis of KCl solution and by the action
of lime on potassium carbonate. It may also be obtained by the action of baryta, Ba(OH) 2 on
potassium sulphate .
K 2SO 4  Ba(OH)2 
 BaSO 4   2KOH

Properties :
Its properties are similar to those of sodium hydroxide. However, it is a stronger alkali and more
soluble in alcohol and is therefore, used in organic reactions instead of caustic soda. Moreover, it
is a better absorber of CO2 than NaOH because potassium carbonate is more soluble and does
not separate out. Its aqueous solution is known as potash lye.

3. Potassium carbonate (K2CO3) :


It is also known as pearl ash.
Preparation :
It is made by passing CO2 into a conc. solution of the chloride, containing hydrated magnesium
carbonate in suspension at 20C when an insoluble potassium hydrogen magnesium carbonate is
precipitated.
2KCl + 3(MgCO3.3H2O) + CO2  2(MgCO3.KHCO34H2O) + MgCl2
The precipitate is separated by filtration, and then decomposed either by heating with water
under pressure at 140C or by the action of magnesium oxide below 20C.
2(MgCO3 KHCO3 4H2O)  2MgCO3 + K2CO3 + 9H2O + CO2
2(MgCO3KHCO34H2O) + MgO  3(MgCO3.3H2O) + K2CO3
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Properties :
1. It is white , deliquescent solid
2. K2CO3 resembles Na2CO3 in properties, but is more alkaline and more soluble than
Na 2 CO 3 .

4. Potassium Bicarbonate (KHCO3)


Preparation :
It is prepared by passing CO2 through a cold saturated solution of potassium carbonate.
K2CO3 + H2O + CO2  2 KHCO3

Properties :
It resembles sodium bicarbonate in all respects except that it is more soluble in water. It is used
in medicine and in baking powders.
5. Potassium Sulphate (K2SO4)
Preparation :
(a) By treating KCl or KOH with H2SO4
2 KCl + H2SO4  K2SO4 + 2 HCl
2 KOH + H2SO4  K2SO4 + 2 H2O
(b) By treating naturally occurring mineral, schonite (K2SO4. MgSO4. 6H2O) with sylvine (KCl).
K 2SO 4 .MgSO 4 .6H 2 O  2KCl 
 2K 2SO 4  MgCl2  6H 2O
Properties :
1. It is a white crystalline (m.p. 1050 °C) solid, not very soluble in water.
2. Unlike sodium sulphate, its crystals do not contain water of crystallisation.
3. When heated with carbon, it is reduced to potassium sulphide.
4. It forms a series of double salts with the sulphates of trivalent metals, e.g. potash alum, K2SO4.
Al2 (SO4)3. 24H2O.
6. Potassium Chloride (KCl)
Preparation :
KCl is prepared from fused carnallite. Nearly pure KCl separates from the melt, leaving fused
MgCl2 behind.
KCl . MgCl 2 . 6H 2O 
 KCl  MgCl 2 . 6H 2O

Properties :
It is a colourless cubic crystal soluble in water. Its solubility increases almost linearly with
temperature.

Illustration 2 : Explain the stability of oxides of alkali metals.


Solution : Li forms only oxide, Na forms oxide and peroxides and remaining all alkali metal form
oxides, peroxides and super oxides.
Li + O2  2Li2O 4Na + O2  2Na 2O
( Oxide ) ( Oxide )

2Na + O2  Na 2O 2 K + O2  KO 2
(Peroxide ) (superoxides)

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Peroxide [– O – O –]2 has no unpaired electron therefore, it is diamagnetic. On the other hand
super oxide [O2]– has an unpaired electron therefore it is paramagnetic, super oxides are stronger
oxidizing agent than peroxides Stability of the peroxides and super oxides increases as the
metal ions become large peroxide and super oxide are larger. It is same, if both ions are similar in
size, then coordination number will be high and thus gives a high lattice energy. KO2 is used in
space capsules, breathing masks because it both produces dioxygen and remove carbon dioxide.
4KO2 + 2CO2  2K2CO3 + 3O2
4KO2 + 4CO2 + 2H2O  4KHCO3 + 3O2
MAGNESIUM

1. Magnesium Oxide (MgO)


Preparation :
It is prepared by burning Mg in air, by heating hydroxide, nitrate, sulphate or carbonate. Oxide
prepared by heating magnesite (MgCO 3) is called calcined magnesia.
2 Mg (NO3)2  2 MgO + 4 NO2 + O2
2 Mg SO4  2 MgO + 2 SO2 + O2
Properties :
1. Magnesium oxide is a light white powder, which is highly infusible (m.p. 2800°C), and
only slightly soluble in water.
2. It is a basic oxide and hence reacts with acids to form salts .
MgO + 2 HCl  MgCl2 + H2O
3. It is reduced by carbon at very high temperature to form magnesium carbide.
MgO + 3 C  MgC2 + CO
4. It dissolves in aqueous solution of magnesium chloride or bromide forming basic salts
such as MgCl2. 9Mg(OH) 2 . 5H2O.

2. Magnesium Hydroxide (Mg(OH) 2)


Preparation :
It is obtained by adding caustic soda solution to a solution of magnesium sulphate or chloride.
MgSO4 + 2NaOH  Na2SO4 + Mg(OH) 2
Properties :
1. It is converted into its oxide on heating.
Mg(OH) 2  MgO + H2O
2. It dissolves in NH4Cl solution easily.
Mg(OH) 2 + 2NH4Cl  MgCl2 + 2NH4OH

3. Magnesium Carbonate, (MgCO3) :


It occurs in nature as magnesite, MgCO3 and dolomite, MgCO3.CaCO3.

Preparation :
(a) By adding sodium bicarbonate solution to a hot solution of magnesium salt.
MgSO 4  2NaHCO3 
 MgCO3   Na 2SO 4  H 2O  CO 2

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In case Na2CO3 is used in place of NaHCO3, a basic carbonate is obtained.

2MgSO 4  2Na 2 CO3  H 2O   MgCO3 .Mg(OH) 2  2Na 2SO 4  CO 2


When CO2 gas is passed through the suspension of basic carbonate, magnesium bicarbonate is
formed which on heating forms MgCO3.
MgCO3 .Mg(OH) 2  3CO 2  H 2O 
 2Mg(HCO3 ) 2
heat
Mg(HCO3 ) 2  MgCO3  H 2 O  CO 2 
(b) Pure magnesium bicarbonate and hence carbonate can be prepared by passing CO 2 through
suspension of magnesium oxide in water.
MgO  H 2 O  2CO 2 
 Mg(HCO3 ) 2
Mg(HCO3 ) 2  MgO 
 2MgCO3  H 2O

Properties :
1. Magnesium carbonate is a white powder, insoluble in water .
2. It dissolves in acids forming salts .
MgCO3 + 2 HCl  MgCl2 + H2O + CO2 
3. Its aqueous solution also dissolves on passing a current of carbon dioxide because of
the formation of Mg(HCO3)2, a temporary hardness causing substance .
MgCO3 + H2O + CO2  Mg((HCO)3)2
A solution of magnesium bicarbonate containing 12 gm. of the salt per 100 ml is known
as fluid magnesia.
4. It decomposes on heating to form magnesium oxide.
heat
MgCO3  MgO  CO2

4. Magnesium Sulphate (MgSO4.7H2O) or Epsom salt :


It occurs in nature as kieserite, MgSO4.H2O; Epsom salt, MgSO4.7H2O; and kainite, KCl.MgSO4
. 3H2O. It is also found in some mineral springs.
Preparation :
(a) From magnesite or dolomite.
MgCO3  H 2SO 4 
 MgSO 4  H 2O  CO 2
Magnesite

MgCO3 . CaCO3  2H 2SO 4 


 MgSO 4  CaSO 4   2H 2O  2CO 2
Dolomite

(b) From kieserite (Commercial method). By boiling kieserite in water and cooling the resulting solution
when crystals or Epsom salt separate out.

Properties :
1. It is a colourless , efflorescent crystalline substance with bitter taste.
2. It forms a number of hydrates .
3. When heated to 150°C, it changes to monohydrate which on further heating changes to
anhydrous state at 200°C.
160 C 200 C
MgSO 4 .7H 2 O 
(–6H 2 O)
 MgSO 4 .H 2 O   MgSO 4  H 2 O

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On further heating, it decomposes to form MgO.
above 200 C
4MgSO 4  4MgO  2SO 2  2SO3  O 2
4. It is reduced by lamp black at 300°C
2MgSO 4  C 
 2MgO  2SO 2  CO 2
5. It forms double salts with alkali metal sulphates, e.g., K2SO4. MgSO4.6H2O.
5. Magnesium Chloride (MgCl 2.8H2O)
Preparation :
It is prepared in the laboratory by crystallizing a solution of the oxide, hydroxide or carbonate
in dilute hydrochloric acid.
MgO + 2HCl  MgCl2 + H2O

Properties :
It is colourless, crystalline salt, deliquescent in nature and exceedingly soluble in water.

CALCIUM

1. Calcium oxide (CaO) or Quick lime


Preparation :
By heating lime stones at 804 °C.
800 C
CaCO3 CaO  CO 2
(a) The reaction is reversible and thus in order to assure the complete decomposition of CaCO3
, CO2 formed must be swept away by a current of air .
(b) Temperature should not be too high because at high temperature clay will react with lime to form
fusible silicates.
Properties :
1. It is white amorphous powder, which emits intense white light (lime light), when heated
in the oxy-hydrogen flame.
2. It reacts with strongly heated silica,forming easily fusible calcium silicate.
CaO + SiO2  CaSiO3
3. CaO reacts with water evolving huge amount of heat and produce slaked lime.
CaO + H2O  Ca(OH) 2

2. Calcium Hydroxide (Slaked lime), [Ca(OH) 2]


Preparation :
(a) By treating lime (quick lime) with water .
CaO + H2O  Ca(OH) 2
(b) By the action of caustic alkalies on a soluble calcium salt.

Properties :
1. It is a white amorphous powder, only sparingly soluble in water. Its solubility decreases
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with the increase in temperature.
2. When dried and heated to redness, it loses a molecule of water and converted into calcium
oxide (lime).
3. Action of CO 2 : Lime water [Lime + H2O  Ca(OH) 2] is frequently used for the
detection of CO2 gas; CO2 gas turns lime water milky due to formation of CaCO3.
Ca(OH) 2 + CO2  CaCO3  + H2O
However , the precipitate disappears on prolonged treatment with CO2 because of the conversion
of CaCO3 (insoluble) to calcium bicarbonate (soluble).
CaCO3  H 2 O  CO 2 
 Ca(HCO3 )2
Insolub le Soluble

3. Calcium Carbonate, (CaCO3) :


Calcium carbonate is found in nature as limestone, marble, coral, ice land spar, calcite, chalk,
dolomite, etc.
Preparation :
It is prepared as a white powder, known as precipitated chalk by dissolving marble or limestone
in hydrochloric acid followed by precipitation with sod. or ammonium carbonate.
CaCO3 + 2 HCl  CaCl2 + H2O + CO2
CaCl2 + (NH4)2 CO3  CaCO3 + 2 NH4Cl
In the laboratory, it is prepared by passing CO2 through lime-water or by adding sod. or ammo.
carbonate solution to CaCl2.
Ca (OH)2 + CO2  CaCO3  + H2O
Properties :
1. It is a white powder and exists in two crystalline forms: calcite and aragonite.
2. It is insoluble in water but dissolves in the presence of CO2 due to the formation of calcium
bicarbonate .
CaCO3 + H2O + CO2  Ca (HCO3)2

4. Calcium Bicarbonate , (Ca(HCO3)2) :


It does not exist in solid state. However, its solution can be prepared by passing CO2 gas through
a suspension of calcium carbonate in water. On warming, it decomposes to calcium carbonate
along with the evolution of carbon dioxide gas.

5. Calcium Sulphate , (CaSO4) :


It occurs in nature as anhydride (CaSO 4) and gypsum (CaSO4. 2H2O).
Preparation :
It may be prepared by adding dilute sulphuric acid or soluble sulphate (e.g. Na 2SO4) to the
solution of a calcium salt .
CaCl2 + H2SO4  CaSO4 + 2 HCl

Properties :
1. It is a white crystalline solid. Like slaked lime, it is sparingly soluble in cold water and its
solubility decreases further with the increase in temperature.
2. It dissolves much more readily in dilute acids, even in acetic acid than in water. It dissolves

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also in ammonium sulphate solution forming CaSO4.(NH4)SO4.H2O.
3. Monoclinic crystals of gypsum when heated, first changes into orthorhombic form without
any loss of water. On further heating to 120°C, it loses three-fourth of its water of
crystallization and forms the hemihydrate, (2CaSO 4).H2O or CaSO 4 . 12 H 2 O which is
commonly known as Plaster of Paris.
120 C
CaSO 4 .2H 2 O   CaSO 4 . 12 H 2 O  1 12 H 2O
Plaster of Paris is a white powder which when mixed with water takes up the water of
crystallization again, thus converted back into the dehydrate and sets to a hard mass
with slight expansion. Setting takes about 10–15 minutes and may be catalysed by the
addition of common salt or delayed by the use of alum or borax.
H2O hardening
CaSO 4 . 12 H 2 O 
setting
 CaSO4 .2H 2 O   CaSO 4 .2H 2 O
Plaster of Paris Orthor hom bic Monoclinic (gypsum)

Plaster of paris or gypsum when heated to about 200°C is converted into anhydrous
calcium sulphate. The anhydrous form (anhydrite) is known as dead burnt because it does
not set like Plaster of Paris when moistened with water.

6. Calcium Chloride (CaCl 2)


Preparation :
It separates out as deliquescent crystals when a solution of lime or calcium carbonate in HCl is
evaporated . CaCO3 + 2HCl  CaCl2 + H2CO3
But it separates out from the reaction mixture as CaCl26H2O. The anhydrous salt is obtained
on heating above 200C .
Properties :
It is a colourless, deliquescent salt, highly soluble in water. The anhydrous salt is an excellent
drying agent.

Potassium dichromate , K2Cr2O7


Potassium dichlromate is a very important chemical used in leather industry and as an oxidation
for preparation of many azo compounds. dichromate are generally prepared from chromates,
which in turn are obtained by the fusion of chromite ore ((FeCr 2O4) with sodium or potassium
carbonate in free access of air. The reaction with sodium carbonate occurs as follows : 4
FeCr2O4 + 8 Na2CO3 + 7 O2  8 Na2CrO4 + 2 Fe2O3 + 8 CO2
the yellow solution of sodium chromate is filtered and acidified with sulphuric acid to give a
solution from which orange sodium dichromate, Na2Cr2O7.2H2O can be crystallisd.
2 Na2CrO4 + 2H+  Na2Cr2O7 + 2 Na+ + H2O
Sodium dichromate is more soluble than potassium dichromate. The latter is prepared by treating
the solution of sodium dichromate with potassium chloride.
Na2Cr2O7 + 2 KCl  K2Cr2O7 + 2NaCl
Orange cystals of potassium dichromate crystallise out. The chromates and dichromates are
interconvertable in aqueous solution depending upon pH of the solution. The oxidation state of
chromium in chromate and dichromate is the same
2CrO42– + 2 H+  Cr2O72– + H2O
Cr2O72– + 2 OH–  2CrO42– + H2O
The structure of chromate ion CrO42–, and the dichromate ion, Cr2O72– are shown here. Whereas
the chromate ion is tetrahedral, the dichromate ion consists of two tetrahedra sharing one corner
with Cr – O – Cr bond angel of 126º.

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2– 2–
O
O pm O O
179
Cr Cr Cr
O 126º O

16
O

3
O O

pm
O

Chromate ion. Dichromate ion


Sodium and potassium dichromates are strong oxidizing agents: the sodium salt has a greater
solubiloity in water and is extensively used as an oxidizing agent in organic chemistry. Potassium
dichromate is used as a primary standard in volumetric analysis. In acidic solution. Its oxidizing
action can be represented as follows:
Cr2O72– + 14 H+ + 6e–  2C3+ + 7H2O (E = 1.33 V)
Thus , acidified potassium dichromate will oxidise iodides to iodine, sulphide to sulphur, tin (II)
to tin (IV) and iron (II) salts to iron (III). The half-reactions are noted below :
6 I–  3 I2 + 6 e– ; 3 H2S  6 H+ + 3 S + 6 e–
2+ 4+ –
3 Sn  3 Sn + 6 e ; 6 Fe2+  6 Fe3+ + 6 e–
The full ionic equation may be obtained by adding the half-reaction for potassium dichromate
to the half-reaction for the reducing agent, e.g.
Cr2O72– + 14H+ + 6Fe2+  2Cr3+ + 6Fe3+ + 7H2O

Potassium permaganate , KMnO4


(i) Potassium permanganate is prepared by fusion of MnO2, with an alkali metal hydroxide and an
oxidising agent like KNO3. This produces the dark green K2MnO4 which disproportionates in a
neutral or acidic solution to give permanganate.
2 MnO2 + 4 KOH + O2  2 K2MnO4 + 2 H2O
3 MnO42– + 4 H+  2 MnO4– + MnO2 + 2 H2O
(ii) Commercially it is prepared by the alkaline oxidaative fusion of MnO2 followed by the electrolytic
oxidation of manganate (VI).
fuse with KOH, oxidise
with air or KNO3
MnO2       MNO42–
manganate
electrolyt ic oxidation in
alkaline solution
MNO4 2–       MnO4–
permanganate
Potassium permanganate is a strong oxidizing agent, both in alkaline an acidic medium. The relevant
half-reactions are:
Alkaline solution : MnO4– + 2 H2O + 3 e–  MnO2 + 4 OH– (E = 1.23 V)
Acidic solution : MnO4– + 8 H+ + 5 e–  Mn2+ + 4H2O (E = 1.551 V)
Alkaline permanganate oxidise iodide to iodate
I– + 3 H2O  IO3– + 6H+ + 6 e–
To provide the acidic medium, sulphuric acid is used instead of hydrochloric acid as the latter
is oxidized to chlorine. Acidifed permanganate oxidises oxalates to carbon dioxide, iron (II) salt
to iron (III), nitrites to nitrates, and liberates iodine from potassium iodide.

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5 COO¯  10 CO2 + 10 e–
COO¯
5 Fe2+  5 Fe3+ + 5 e–
5 NO2– + 5H2O  5NO3– + 10H+ + 10e–
10 I –  5 I2 + 10e–
The full ionic equation is obtained by adding the half-reaction for permanganate to the half-reaction
for the reducing agent, balancing where necessary.
Potassium permanganate is used as an oxidant both in the laboratory and in industry. It is an
important volumetric reagent . Its uses as a bleaching agent for wood, cotton, silk, and other
textiles and for the decolourisation of oils are dependent on its oxidizing power.
IMPORTANT POINTS
1. The process of extraction of metals from their ore is known as metallurgy
2. A mineral from which a metal can be profitably extracted is called an ore.
3. A metal compound occuring in earth crust is called mineral
4. All minerals are not suitable for the extraction of metals commercially. Thus all ores are minerals,
but all minerals are not ores.
5. Gangue is the unwanted substances mixed with the ores.
6. The process of removing gangue from the ore is called concentration.
7. A substance added to convert the gangue (or matrix) into fusible mass is called flux (Gangue
+ Flix  Slag).
8. Sulphide ores are concentrated by froth floatation method.
9. Oxide and carbonate ores are concentrated by gravitational method.
10. Liquation process is used for the concentration of ores which are having lesser melting point than
impurities
11. Calcination is the process in which concentrated ore is heated in the absence of air.
12. Roasting is the process in which concentrated ore is heated in the presence of air below the
melting point.
13. Calcination and roasting are carried out in reverberatory furnace.
14. Smelting is carried out in blast furnace.
15. matte is a mixture of Cu2S containing little FeS.
16. Spelter is 98 % pure Zinc.
17. The slow cooling of red hot steel is called annealing.
18. Heating of steel in contact with charcoal is called cast hardening.
19. Heating steel in presence of an atmosphere of ammonia is called nitriding.
20. Zone refining is used to obtain metals of very high purity.

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NAMES AND FORMULAE OF SOME COMPOUNDS
1. Washing Soda : Na 2CO3.1OH2O . 2. Baking soda : NaHCO3
3. Common salt : NaCl 4. Glauber’s salt : Na2SO4.10H2O
5. Hypo salt-Na 2S2O3.5H2O 6. Chili salt petre : NaNO3
7. Nitre or Indian salt petre : KNO3 8. Salt cake : Na 2SO4
9. Salammoniac (Nausadar) : NH4CI 10. Rock phosphate (Bone ash) : Ca 3(PO4)2
11. Mohr’s salt : FeSO4(NH4)2SO4.6H2O 12. Calomel : Hg2Cl2
13. Corrosive sublimate : HgCl 2 14. Philosopher’s wool : ZnO
15. Blue vitrol : CuSO4. 5 H2O 16. Green vitriol : FeSO4. 7H2O
17. Lunar caustic : AgNO3 18. White vitrol : ZnSO4.7 H2O
19. Litharge : PbO 20. White lead : Pb(OH)2.2PbCO3
21. Red lead : Pb3O4 22. Chrome red : PbO.PbCrO4
23. Chrome yellow : PbCrO4 24. Chrome alum : KCr(SO4)2.12H2O
1
25. Plaster of Paris : CaSO4. H2O 26. Lithopone : BaSO4 + ZnS
2
27. Microcosmic salt : Na(NH4)HPO4. 4H2O 28. Hydrolith : CaH2
29. Pink salt : (NH4)2SnCI6 30. Laughing gas : N2O
31. Spodumene : LiAI(SiO3)2 32. Nitrolium : CaCN2
33. Ferric alum : NH4Fe(SO4)2.12H2O

FAMOUS PROCESS AND RELATED METAL


Poling : Cu Perkes Process : Ag
Pattinson process : Ag Cupellation process : Ag
Baeyer’s Process : Al Serpek’s process: Al
Hall’s process : Al L.D. Process : Fe
Siemens Martin open halth furnace : Fe Temperine : Fe

CHIEF ORES OF ALUMINIUM


Bauxite : Al2O3. 2H2O
Diaspore : Al 2O3. H2O
Cryolite : AlF3. 3NaF or Na 3AlF6
China clay/Caolin : Al2O3. 2SiO2. 2H2O
Mica : K2O. 3Al2O3. 6SiO22H2O
Felspar : KAlSi3O8
Corundum /Ruby/Sapphire/emerald/Topaz : Al 2O3
Gibbsite : Al2O3. 3H2O
Aunite or Alum stone : K2SO4. Al2(SO4)3 .4Al(OH)3
Turquoise : AlPO4. Al(OH)3.H2O
Beryl : 3BeO.Al2O3. 6SiO2

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SOME IMPORTANT ALLOY
1.  - Iron : Fe (100 %)
2. Bronze : Cu(75 – 90 %) + Sn (10 – 25 %)
3. Brass : Cu (60 – 80 %) + Zn (20 – 40 %)
4. Aluminium Bronze : Cu(90 %) + Al (10 %)
5. Gun metal : (Cu + Zn + Sn) (87 : 3 : 10)
6. German Silver : Cu + Zn + Ni (2 : 1 : 1)
7. Bell metal : Cu (80 %) + Sn (20 %)
8. Monel Metal : Cu : Ni : (Fe + Mn) (30 : 67 : 3)
9. Nichrome : (Ni + Cr + Fe) (24 : 26 : 28)
10. Alnico : (Al, Ni, Co)
11. Britania Metal : (Sn + Pb)
12. Babbit metal : Sn + Pb + Cu
13. Munz metal : Cu + Zn (60 – 62 %) – (68 – 40 %)
14. Type metal : Pb + Sn + Sb
15. Alloys of steel
[1] Vanadium steel V (0.2 – 1 %)
[2] Chromium steel Cr (2 — 4 %)
[3] Nickel Steel Ni (3 – 5 %)
[4] Manganese steel Mn (10 – 18 %)
[5] Stainless steel Cr (12 – 14 %) & Ni (2 – 4 %)
[6] Tungston steel W (10–20 %)
[7] Invar Ni (36 %)
16. 14 Carat Gold : 54 % Au + Ag (14 to 30 %) + Cu (12–28 %)
17. 24 Carat Gold : 100 % Au
18. Genny Gold or coil
of Gold : Au + Cu (11 : 1)
19. Solder : Pb + Sn
20. Delta metal : Cu + Zn + Fe
21. Coin of Silver : Ag (92.5 %) + Cu (7.5 %)
22. Coin of aluminium : Mg + Al
23. Coin of Steel : 3.5 % Ni in steel
24. Magnellium : Mg (10 %) + Al(90 %)
25. Duralumin : (Al + Mn + Cu)
26. Y-alloy : Al(93 %) + Cu(4 %) + Ni(2 %) + Mg (1 %)
27. Dutch metal : Cu (80 %) + Zn (20 %)
28. Artificial Gold : Cu(90 %) + Al(10 %)
29. Constantan : Cu(60 %) + Ni(40 %)
30. Rinman Green : CoZnO2

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% OF CARBON IN DIFFERENT TYPE OF IRON
Name % of C
1. Wrought iron/Meleable 0.1 to 0.25
2. Steel 0.25 to 2.0
3. Pig Iron 2.3 to 4.6
4. Cast Iron 2.6 to 4.3

SOME IMPORTANT COMPOUNDS/MINERALS


MIXTURE & THERE FORMULA’S

1. Epsom salt - MgSO4.7H2O


2. Gypsom salt - CaSO4.2H2O
3. Glober’s salt - Na2SO4.10H2O
4. Lime water - Ca(OH)2(slaked lime)
5. Quick lime - CaO
6. Washing soda - Na2CO3.10H2O
7. Crystal carbonate - Na2CO3.10H2O
8. Soda ash - Na2CO3
9. Baking Soda - NaHCO3
10. Baking powder - NaHCO3 Tartaric acid
11. Plaster of pairs - 2CaSO4.H2O or CaSO4.1/2 H2O
12. Chile salt petre - NaNO3
13. Indian salt petre - KNO3
14. Brine or table salt or
rock salt - NaCI
15. Potash ash or pearl ash - K2CO3
16. Nitre or Indian salt petre
or chemical refrigerator - KNO3
17. Norwegian salt petre - Ca(NO3)2
18. Salt Cake - K2SO4
19. Carnalite - KCI, MgCI2.6H2O
20. Hypo - Na2S2O3, 5H2O

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TRANSITION ELEMENTS (d-block)

Electronic configuration of the transition elements :


Electronic configuration of these elements is (n – 1)d 1–10 n s1–2.

Properties of transition elements :


1. Physical properties :
Their melting and boiling point are high. The high melting points are attributed to strong interatomic
bonding, which involves the participation of both ns and (n–1) d electrons. In any row, the melting
points of these metals rise to a maximum at d6 except for anomalous values of Mn and Tc and fall
regularly as the atomic number increases.

2. Variation in atomic and Ionic size :


The filling of 4 f before 5 d orbitals results in a regular decrease in atomic radii called lanthanide
contraction Which essentially compensates for the expected increase in atomic size with increasing
atomic number. The net result of the lanthanide contraction is that the second and the third d
series exhibit similar radii (e.g. Zr 160 pm, Hf 159 pm) and have very similar physical and chemical
properties.

3. Ionization enthalpies :
With increasing nuclear charge, which accompanies the filling of the inner d orbitals, there is an
increase in ionization enthalpy along each series of the transition elements from left to right, but
many small variation occur.

4. Oxidation states :
The variability of oxidation states, a characteristic of transition elements, arises out of incomplete
filling of d orbitals in such a way that their oxidation states differ from each other by unity, e.g.,
VII, VIII, VIV, VV. This should be contrasted with the variability of oxidation states of non-
transition elements where oxidation states normally differ by units of two.

5. Chemical reactivity and E values :


Transition metals vary widely in their chemical reactivity.
The metals of the first series with the exception of copper are relatively more reactive and are
oxidised by 1M H+, though the actual rate at which these metals react with oxidizing agents like
hydrogen ion (H+) is sometimes slow. For example, titanium and vanadium, in practice, are passive
to dilute non-oxidising acids at room temperature. The E values for M2+/M indicate a decreasing
tendency to form divalent cations across the series.

6. Magnetic properties :
When a magnetic field is applied to substances, two types of magnetic behaviour is observed;
diamagnetism and paramagnetism. Diamagnetic substances are repelled by the applied field while
the paramagnetic substances are attracted. Substances which are attracted very strongly are said
to be ferromagnetic.
The magnetic moment is determined by the number of unpaired electrons and is calculated by
using the ‘spin-only’ formula, i.e.
m= n (n  2) B.M.

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7. Formation of complex compounds :
Complex compounds are those in which the metal ions bind a number of anions or neutral molecules
giving complex species with characteristic properties. A few examples are :
[Fe(CN) 6]3– , [Fe(CN)6]4– , [Cu(NH3)4]2+ and [PtCl4]2–.

8. Formation of interstitial compounds :


Interstitial compounds are those which are formed when small atoms like H, N or C are trapped
inside the crystal lattices of metals. They are usually non-stoichiometric and are neither typically
ionic non covalent. Many of the transition metals form interstitial compounds particularly with
small non-metal atoms such as hydrogen, boron, and nitrogen. These small atoms enter into the
voids sites between the packed atoms of the crystalline metal, e.g., TiC, Mn4N, Fe3H, TiH2, etc.

9. Alloy formation :
An alloy is a blend of metals prepared by mixing the components. Alloys may be homogeneous
solid solution in which the atoms of one metal are distributed randomly among the atoms of the
other. Such alloys are formed by atoms with metallic radii that are within about 15 percent of each
other. Because of similar radii and other characteristics of transition metals, alloys are readily
formed by these metals. The alloys formed are hard and have often high melting points. The best
known are ferrous alloys; chromium, vanadium, tungsten, molybdenum, and manganese are used
for the production of variety of steels and stainless steel.

10. Lanthanoid contraction :


The fillling of 4 f before 5 d orbital results in a regular decrease in atomic radii called lanthanoid
contraction which essentially compensates for the expected increase in atomic size with increasing
atomic number. The net result of the lanthanoid contraction is that the second and the third d
series exhibit similar radii (e.g., Zr, 160 pm, Hf 159 pm) and have very similar physical and
chemical properties.

11. Actinoid contraction :


The general trend observed in lanthanoids is observable in the actinoids as well. There is a gradual
decrease in the size of atoms or M3+ ions across the series. This may be referred to as the actinoid
contraction (like lanthanoid contraction). The contraction is, however, greater from element to
element in this series resulting from poor shielding by 5f electrons.

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EXERCISE -1
Q.1 NaOH is prepared by the electrolysis of :
(A) aqueous solution of sodium chloride with platinum electrode
(B) Molten sodium chloride with graphite anode and iron cathode
(C) Sodium carbonate with platinum electrodes
(D) Sodium carbonate with Nickel electrode
Q.2 The raw material in Solvay process are :
(A) NaOH, CaO and NH3 (B) Na2CO3, CaCO3 and NH3
(C) Na2SO4, CaCO3 and NH3 (D) NaCl, NH3, CaCO3
Q.3 Electrolysis of fused KCl, MgCl2, 6H2O gives :
(A) Potassium only (B) Magnesium only
(C) Magnesium and chlorine (D) Potassium magnesium and chlorine
Q.4 At high temperature nitrogen combines with CaC2 to give :
(A) Calcium cyanide (B) Calcium cyanamide
(C) Calcium carbonate (D) calcium nitride
Q.5 An important ore of Mg is :
(A) Dolomite (B) Amblygonite
(C) cinnabar (D) Galena
Q.6 Thermite a mixture used for welding is :
(A) Fe and Al (B) Ferric oxide and Aluminium powder
(C) Barium peroxide and Magnesium powder (D) Cu and Aluminium
Q.7 Aluminium is obtained by :
(A) Reducing Al2O3 with coke (B) Electrolysing Al2O3 dissolved in Na3AlF6
(C) Reducing Al2O3 with cryolite (D) Heating Al2O3 and cryolite
Q.8 Hoope's process is used in the refining of :
(A) Al (B) Zn
(C) Ag (D) Cu
Q.9 All alums contain :
(A) one monovalent and one trivalent metal (B) Both monovalent metal
(C) One divalent and monovalent metal (D) Both divalent metals
Q.10 Aluminium vessels should not be washed with material containing washing soda because :
(A) Washing soda is expensive
(B) Washing soda is easily decomposed
(C) Washing soda reacts with aluminium to form soluble aluminate
(D) Washing soda reacts with aluminium to form insoluble aluminium oxide
Q.11 Froth Floatation process is based on :
(A) Specific gravity of the ore particles (B) Magnetic properties of the ore particles
(C) Wetting properties of the ore particles (D) Electrical properties of the ore particle
Q.12 Electrolytic reduction process is used for the altercation of :
(A) Alkali metal (B) Alkaline earth metals
(C) Aluminium (D) All the above

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Q.13 In the Froth floatation process for the purification of ores the ore particle float because :
(A) They are light (B) Their surface is not easily weted by water
(C) They bear electrostatic charges (D) They are insoluble
Q.14 Of the following metals the one which can not be obtained by electrolysis of the aqueous solution
of its salt :
(A) Ag (B) Mg
(C) Cu (D) Al
Q.15 Cryolite is :
(A) Na3AlF6 and is used in the electrolyusis of alumina for decreasing electrical conductivity
(B) Na3AlF6 & is used in the electroysis of alumina for lowering the melting point of alumina
(C) Na3AlF6 and is used in the electrolytic purification of alumina
(D) Na3AlF6 and is used in the electrolysis of alumina
Q.16 Coinage metals are :
(A) normal elements (B) transition elements
(C) Active elements (D) Highly electropositive element
Q.17 In the extraction of the copper, metal is formed in the Bessemer converter due to reaction :
(A) Cu2S + 2Cu2O 6 Cu + SO3 (B) Cu2S 2 Cu + S
(C) Fe + Cu2O 2 Cu + FeO (D) 2 Cu2O 4 Cu + O2
Q.18 Silver nitrate is usually supplied in coloured bottles because it is :
(A) Oxideed in air (B) Decomposes in sunlight
(C) Explodes in sun light (D) Reacts with air in sun light
Q.19 Impurities of lead in silver are removed by :
(A) Parkes process (B) Solvay process
(C) Cyanide process (D) Amalgamation process
Q.20 Bessemer converter is used in the manufacture of :
(A) Pigiron (B) Steel
(C) Wrought iron (D) Cast iron
Q.21 Which of the following metal corrodes readily in moist air :
(A) Au (B) Ag
(C) Ni (D) Fe
Q.22 Platinum, palladium, iridium etc. are called nobel metals because :
(A) Alfred nobel discovered them
(B) They are inert towards many common reagents
(C) They are shining, lustrous and pleasing to look at
(D) They are found in native state
Q.23 Addition of high proportion of manganese make steel useful in making rails of rail roads because
manganese :
(A) Give strength steel (B) Helps the formation of oxide
(C) Can show highest oxidation state of + 7 (D) Impart special colour to steel
Q.24 Blister copper is :
(A) Pure copper (B) Copper containing 2% impurity
(C) Alloy of copper (D) None
Q.25 German silver is an alloy of :
(A) Copper zinc and nickel (B) Copper and silver
(C) Copper and tin (D) Copper, zinc and silver
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Q.26 After partial roasting the sulphide ore of copper is reduced is reduced by :
(A) Reduction by carbon (B) Electrolysis
(C) Self reduction (D) Cyanide process
Q.27 Photographic films or plates have .................. as an essential in gradient :
(A) Silver bromide (B) Silver oxide
(C) Silver thiosulphate (D) Silver nitrate
Q.28 Chemical name of corrosive sublimate is :
(A) Mercurous chloride (B) Zinc chloride
(C) Mercuric chloride (D) Aluminium chloride
Q.29 Iodide of millon's base is :

(A) K2[HgI4] (B)

(C) [Hg2O.NH2OH].H2O (D) Hg(NH2) I + Hg


Q.30 Zn and Cd do not show variable valency because :
(A) They have only two electrons in outer most subshell
(B) Their d - sub shells are complete
(C) Their d-subshells are in complete
(D) They are relatively soft metal
Q.31 Two prevent corrosion iron pipes carrying drinking water are coated with zinc. The process
involved is :
(A) Alloy formation (B) Electroplating
(C) Galvanising (D) Sodering
Q.32 Galvanising means :
(A) Deposition of Zn on Fe (B) Deposition of Al on Fe
(C) Deposition of Sn on Fe (D) Deposition of Cu on Fe
Q.33 Soft and pliable steel is obtained by :
(A) Tempering (B) Nitriding
(C) Annealing (D) none
Q.34 Red how steel rod on suddenly immersing in water becomes :
(A) Soft and malleable (B) Hard and brittle
(C) Tough and ductile (D) Fibrous
Q.35 Speiglesen is an alloy of :
(A) Fe and Mn (B) Fe, Mn, C
(C) Fe, Mn and Cr (D) Fe and Cr
Q.36 The furnace which gives the highest temperature is :
(A) Blast furnace (B) reverberatory furnace
(C) Electrical furnace (D) Muffle furnace
Q.37 The common method of extraction of metal from oxide ores :
(A) reduction with carbon (B) reduction with hydrogen
(C) reduction with Aluminium (D) Electrolytic method
Q.38 AgCl dissolves in ammonia solution giving :
(A) Ag+, NH4+ and Cl– (B) Ag(NH3)+ and Cl–
(C) Ag2(NH3+)2 and Cl– (D) Ag(NH3)2+ and Cl–
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Q.39 Copper metal of high purity is obtained by :


(A) Carbon reduction (B) Hydrogen reduction
(C) electrolytic method (D) Thermite process
Q.40 Copper reduces :
(A) Na (B) Al
(C) Mg (D) None
Q.41 Which metal is used to gold to make is hard ?
(A) Cu (B) Ag
(C)Ni (D) Zn
Q.42 Horn silver is :
(A) AgCl (B) Ag2S
(C) SnS (D) AgNO3
Q.43 Lithophone, a white pigment consist of :
(A) Al2O3 and CaCO3 (B) BaS and PbSO4
(C) ZnS and BaSO4 (D) PbS and MgO
Q.44 The colour of zinc sulphide is :
(A) Yellow (B) White
(C) Brown (D) Black
Q.45 Which of the following is used for sterilization of surgical instrument ?
(A) HgCl2 (B) ZnCl2
(C) Hg2Cl2 (D) ZnO
Q.46 The formula of haematite is :
(A) Fe3O4 (B) Fe2O3
(C) FeCO3 (D) FeS2
Q.47 The brown ring complex compound is formulated as [Fe(H2O)5(NO)]SO4. The oxidation state
of iron is :
(A) + 1 (B) + 2
(C) + 3 (D) + 4
Q.48 From a solution of CuSO4 the metal used to recover copper is :
(A) Na (B) Ag
(C) Hg (D) Fe
Q.49 When KMnO4 reacts with acidified :
(A) Only FeSO4 is oxidised (B) Only KMnO4 is oxidised
(C) FeSO4 is oxidised and KMnO4 is reduced (D) None of these
Q.50 Iron rust in the presence of :
(A) O2 and N2 (B) O2 and mositure

(C) moisture only (D) O2 only

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EXERCISE -2
Q.1 On heating sodium metal in current of dry ammonia gas the compound formed is :
(A) Sodium nitrate (B) Sodium hydride
(C) Sodium amide (D) Sodium azide
Q.2 Na2CO3 can be manufactured by Solvay process but K2CO3 can not be prepared because :
(A) K2CO3 is more soluble (B)K2CO3 is less soluble
(C) KHCO3 is more soluble than NaHCO3 (D) KHCO3 is less soluble than NaHCO3
Q.3 Calcium is extracted by the electrolysis of :
(A) Fused mixture of CaCl2 and CaF2 (B) CaCl2 solution
(C) Fused mixture of CaCl2 and NaF (D) Ca3(PO4)2 solution
Q.4 Magnesium wire burns in the atmosphere of CO2 because :
(A) Magnesium acts as an oxidising agent
(B) Magnesium has 2 electron in the outer most orbit
(C) Magnesium act as a reducing agent and remove oxygen from CO2
(D) None
Q.5 MgBr2 and MgI2 are soluble in acetone because of :
(A) Their ionic nature (B) Their o-ordinate nature
(C) Their metallic nature (D) Their covalent nature
Q.6 Aluminium becomes passive in nitric acid because it :
(A) Nobel metal (B) Forms a thin film oxide
(C) Positive reduction potential (D) None
Q.7 The purification method used for mineral Al2O3.2H2O is :
(A) Froth floatation (B) Leaching
(C) Liquation (D) Magnetic separation
Q.8 In the alumino thermic process aluminium act as :
(A) An oxidising agent (B) A flux
(C) A reducing agent (D) Solder
Q.9 In the electrolysis of Alumina, cryolite is added to :
(A) Lower the melting point of aluming (B) Increase the electrical conductivity
(C) Both A and B (D) Remove impurities from alumina
Q.10 Aluminium is more reactive than iron but aluminium is less easily corroded than iron because :
(A) Aluminium is a nobel metal (B) Oxygen form a protective oxide layer
(C) Iron undergoes reaction easily with water (D) Iron from both mono and divalent ions
Q.11 Heating of pyrites to remove sulphur is called as :
(A) roasting (B) Calcination
(C) Smelting (D) Fluxing
Q.12 From gold amalgam, gold may be recovered by :
(A) Addition of Zn metal (B) Electrolytic refining
(C) Distillation (D) Dissolving Hg in HNO3
Q.13 The main function of roasting is :
(A) To remove the volatile impurities (B) oxidation
(C) Reduction (D) to make slag

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Q.14 Zone refining is a method to obtained :


(A) Very high temperature (B) Ultrapure Al
(C) Ultrapure metals (D) Ultrapure oxide
Q.15 Van Arkel method of purification of metals involves converting the metal to a :
(A) Volatile stable compound (B) Volatile unstable compound
(C) non volatile stable compound (D) none of the above
Q.16 The electrolytic reduction technique is used in the extraction of :
(A) Highly electronegative element (B) transition metal
(C) Metalloids (D) Highly electropositive elements
Q.17 Which method of purification is represented by the following equation :
C C
Ni + 4CO 70   Ni (CO) 4 180
  Ni + 4CO
(A) Van Arkel (B) Zone refining
(C) Mond (D) Cupellation
Q.18 Match List–I with List–II and select the correct answer using codes given below in the list :
List – I List – II
I Cyanide process (a) Ultrapure Ge
II Floation process (b) Pine oil
III Electrolytic reduction (c) Extraction of Al
IV Zone refining (d) Extraction of Au
(A) I – c, II – a, III – d, IV – b (B) I – d, II – b, III – c, IV – a
(C) I – c, II – b, III – d, IV – a (D) I – d, II – a, III – c, IV – b
Q.19 When copper is placed in the atmosphere for sufficient time, a green crust is formed on its surface
the composition of green crust is :
(A) Cu(OH)2 (B) CuO
(C) CuCO3 (D) CuCO3.Cu(OH)2

Q.20 Roasting of copper pyrites is done :


(A) To remove moisture and volatile impurities (B) To oxide free sulphur
(C) To decompose pyrites in to Cu2S and FeS (D) All of the above
Q.21 When excess of SnCl2 is added to a solution of HgCl2, a white precipitate turning to grey, is
obtained. The grey colour is due to the formation of :
(A) Hg2Cl2 (B) SnCl4
(C) Sn (D) Hg
Q.22 In the metallurgy of iron when lime stone is added to the blast furnace, the calcium ion ends
up in :
(A) Slat (B) Gangue
(C) Metallic calcium (D) Calcium carbonate
Q.23 In comparison of ferrous salt, ferric salt are :
(A) More stable (B) Less stable
(C) Equally stable (D) None of these
Q.24 Which one of the following pairs of the substances on reaction will not evolve H2 gas :
(A) Iron and dilute H2SO4 (B) Iron and steam
(C) Copper and HCl(g) (D) Sodium and ethyl alcohol

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Q.25 The slag obtained during the smelting process in the extraction copper from copper pyrites is
composed mainly of :
(A) Cu2S (B) FeSiO3
(C) CuSiO3 (D) SiO2
Q.26 In solid CuSO4.5H2O copper is co-ordinated to :
(A) 4 water molecule (B) 5 water molecule
(C) 1 sulphate molecule (D) 1 water molecule
Q.27 The matte obtained in the extraction of copper contains :
(A) FeSiO2 (B) SiO2 + FeS
(C) FeS + Cu2S (D) CuS + SiO2 + FeO
Q.28 Which method is based on distribution law :
(A) Mond's process (B) Parkes process
(C) Cupellation process (D) Polling process
Q.29 Zinc white is a better white pigment than lead white because it :
(A) Has more covering power than lead white (B) Is not blackened by the action of H 2O
(C) Is soluble in water (D) Becomes yellow when heated
Q.30 Which statement about corrosive sublimate is incorrect :
(A) It is prepared by heating mercury & chlorine (B) It reduces stannic chloride
(C) It oxidises stannous chloride (D) It sublimes readily
Q.31 Acidic nature of Zn(OH)2 is shown from the formation of the following compounds with the formula:
(A) Na2ZnO2 (B) Na2CO3
(C) NaZnO2 (D) None
Q.32 When iron or zinc is added to CuSO4 solution, copper is precipitated. It is due to :
(A) Hydrolysis of CuSO4 (B) Oxidation of Cu+2
+2
(C) Reduction of Cu (D) Ionisation of CuSO4
Q.33 Rusting of iron is a chemical reaction. The reaction is :
(A) Analysis (B) Displacement
(C) Oxidation of Fe (D) Double decomposition
Q.34 Iron is obtained on large scale from Haematite Fe2O3 :
(A) By reduction (B) By oxidation
(C) By reduction followed by oxidation (D) By oxidation followed by reduction
Q.35 Iron, once dipped in concentration H 2SO4, does not displace copper from sulphate solution
because :
(A) It is less reactive than copper (B) A layer of sulphate is deposited on it
(C) A layer of oxide is deposited on it (D) None
Q.36 Stainless steel does not rust because :
(A) Nickel present in it does not rust
(B) Iron forms a hard chemical compound with chromium present in it
(C) Chromium and Nickel combine with iron
(D) Chromiurn forms an oxide layer that protects iron from rusting
Q.37 Pudding process us used in the manufacture of :
(A) Steel (B) Cast iron
(C) Wrough iron (D) Pig iron

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Q.38 To obtain chromium from chromicoxide (Cr2O3) the method used is :
(A) Carbon reduction (B) Carbon monooxide reduction
(C) Alumino thermic (D) electrolytic reduction
Q.39 Schweitzer's reagent used for dissolving cellulose in the manufacture of artificial silk is :
(A) CuSO4.5H2O (B) CuI
(C) Cu(NH3)4SO4 (D) Cu(CH3COO)2.Cu(OH)2
Q.40 Anhydrous CuCl2 and CuBr2 exist as :
(A) Monomer (B) Dimer
(C) Trimer (D) Polymer
Q.41 Spelter is :
(A) Impure Cu (B) Impure Zn
(C) ZnO (D) CuO
Q.42 Which cation from stronger complex salt :
(A) Zn+2 (B) Cd+2
(C) Hg+2 (D) All of same strength
Q.43 Zinc oxide is :
(A) A basic oxide (B) An acidic oxide
(C) A neutral oxide (D) A basic oxide
Q.44 On heating ZnCl2.H2O the compound obtained :
(A) ZnCl2 (B) Zn(OH) Cl
(C) Zn(OH)2 (D) ZnO
Q.45 Roasting is used during metallurgical operation using :
(A) Galena (B) Iron pyrites
(C) Copper glance (D) All
Q.46 Pig iron is converted in to steel by reducing the amount of carbon contained in it in a :
(A) Blast furnace (B) Pyrite burner
(C) Bessemer converter (D) None of these
Q.47 The extraction of Nickel involves :
(A) The formation of Ni(CO)4
(B) The decomposition of Ni(CO)4
(C) The formation and thermal dicomposition of Ni(CO)4
(D) The formation and catalytic decompostiion of Ni(CO)4
Q.48 Near the top of a blast furnace employed for the extraction of iron the metal oxide are reduced
to spongy iron by :
(A) Carbon (B) CO
(C) CO2 (D) Lime stone
Q.49 Which transition metal is used for the reduction of steam to hydrous :
(A) Mg (B) Fe
(C) Se (D) Pt
Q.50 The metal which acts as an Inert electrode :
(A) Ag (B) Cu
(C) Pt (D) Fe

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XII NCERT & CBSE
QUESTION & SOLUTION
1. What is the most common oxidation state of lanthanides ? [ CBSE ]
2. Why Sc3+ ion is colourless ? [ CBSE ]
OR
Which of the following is likely to form white salt ?
Fe3+, Cr3+, Ti3+, Sc3+
3. Give two uses of lanthanide compounds. [ CBSE ]
OR
Mention a use of pyrophoric alloys.
OR
Name an important alloy which contains some of the lanthanoid metals. Mention its uses.
4. Write the highest oxidation state of the element with atomic number 23. [ CBSE ]
5. How copper sulphate is prepared from metallic copper ? [ NCERT ]
6. Zinc salts are white while Cu2+ salts are coloured [ At nos. Zn = 30 , Cu = 29 ]
[ CBSE ]
7. In what way the electronic configuration of transition elements are different from those of
representative elements ? [ CBSE ]
8. Why are the ionization energies of 5d elements greater than those of 3d and 4d elements ?
9. What is the effect of pH on the colour of the solution of potassium dichloromate?
OR
What is the effect of increasing pH on a solution of potassium dichromate ?
10. Explain why transition metals are paramagnetic . [ CBSE ]
11. Giving reasons , indicate which one of the following would be colured .
Cu+ , VO2+ , Sc3+, Ni2+ [ Atomic number Cu = 29, V = 23, Sc = 21, Ni = 28 ]
[ CBSE ]
12.
(i) Of the ions Ag+, Co 2+ and Ti4+, which one will be coloured in aqueous solution .
[ Atomic nos : Ag = 47, Co = 27, Ti = 22 ]
(ii) If each one of the above ionic species is in turn placed in a magnetic field, how will it respond and
why ? [ CBSE ]
13. Write down the electronic configuration of :
(a) Cr3+ (b) Cu+ (c) Co 2+ (d) Mn2+ (e) Pm3+ (f) Ce4+
(g) Lu2+ (h) Th4+
14. Why are Mn2+ compounds more stable than Fe2+ towards oxidation to their + 3 state ?
15. Explain briefly how + 2 state becomes more and more stable in the first half of the first row
transition elements with increasing number ?
16. What may be the stable oxidation state of the transition element with the following d-electron
configuration in the ground state of their atoms :
3d3, 3d5, 3d8 and 3d4 ? [ NCERT ]
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17. What is meant by disproportion ? Give two examples of disproportion reaction in aqueous solution.
18. Name the members of lanthanoid series which exhibits + 4 oxidation states and those which
exhibit + 2 oxidation states. Try to correlate this type of behaviour with the electronic configuration
of these elements . [ NCERT ]
19. (a) The elements of the d-series exhibit a large number of oxidation state than the element
of f-series.
(b) The Cu+ salts are coloureless while Cu2+ salts are colourd . [ At. No. Cu = 29 ]
[ CBSE ]
20. Describe the preparation, properties and uses of potassium dichromate.
OR
Describe the preparation of potassium dichromate from chromite ore. Give balanced chemical
equations for what happens when acidified potassium dichromate solution reacts with : (i)
Ferrous sulphate solution (ii) hydrogen sulphide gas. [ CBSE ]
OR
Describe how potassium dichromate is made from chromite ore and the equation for the chemical
reaction involved . Write the balanced ionic equation for reacting ions to present the action of
acidified K2Cr2O7 solution on :
(i) potassium iodide solution (ii) acidified ferrous sulphate solution.
21. What is lanthanide contraction? Discuss its cause and consequences. [ NCERT ]
22.
(a) What are inner transition elements ?
(b) What is the difference between the electronic configuration of transition and inner transition element
?
(c) Complete the following equations .
(i) Na2Cr2O7 + KCl   (ii) 2MnO2 + 4KOH + O2 
– 2– +
(iii) MnO4 + C2O4 + H 
23. What are transition elements ? How do you account for the following :
(i) The ionic sizes of Zr4+ and Hf4+ are nearly same.
(ii) KMnO4 is a stronger oxidising agent in an acidic medium than in an alkaline medium.
(iii) Manganese (Z = 25) exhibits the largest number of oxidising states.
(iv) Only transition elements are known to form carbonyls.
24. Write the names of the important ores of silver. Describe the extraction of Ag by cyanide process.
OR
How does silver occur in nature ? Give an outliner of its extraction from its sulphide ore by the
cyanide process. How is silver containing traces of copper and gold purified electrochemically ?
OR
How is silver extracted from its ore ?
OR
Write the chemical reactions involved in the extraction of metallic silver from argentite.
25. Predict which of the following will be coloured in aqueous solution.
Ti3+, V3+, Cu+, Sc3+, Mn2+, Fe3+, Co 2+ and MnO4–
26. Calculate the number of unpaired electrons in following gaseous ions :
Mn3+, Cr3+, V3+ and Ti3+. Which one of these is the most stable in aqueous solution ?

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SOLUTION

Ans.1 +3
Ans.2 Sc3+, because there is no unpaired electron in d-sub-shell, hence d  d transition is not possible.
Ans.3
(i) Misch metal (an alloy) is pyrophoric and used in gas lighters, tracer bullets and shell.
(ii) Oxides of neodymium and praseodymium are used for making colour glasses.
Ans.4 The outer electronic configuration will be 3d3 4s2, therefore, the highest oxidation state will be five
(equals to the electrons).
Ans.5 By passing a current of air through copper scrap and dilute sulphuric acid, copper sulphate is
obtained 2Cu + 2H2SO4 + O2  2CuSO4 + 2H2O
Ans.6 Zn2+ salts have completely filled d-orbitals (3d10) Thus d  d transition is not possible, while
in Cu2+ salt d-orbitals are incomplete (3d9) and d  d transition is possible which makes its salt
coloured.
Ans.7 In representative elements last electron goes either s-sub-shell (for 1 and 2 group) or p-sub-
shell (for 13 to 17 groups) of last orbit, while in transition elements last electron goes to 3-dub-
shell of penultimate orbit, i.e., in transition elements last two orbits are incomplete. The outer
electronic configuration of representative element is either ns1–2 or ns2 np1–6, while in transition
element outer electronic configuration is (n –1) d1–10 ns1–2.
Ans.8 When we move downward in a particular group the atomic number is increased, consequently
nuclear charge is also increased. Due to this reason 5d-elements have higher nuclear charge than
3d and 4d elements, therefore, the outer electrons are attracted strongly by the nucleus in 5d
elements. On the other hand, the shielding effect of 4f electrons is very poor due to lanthanide
contraction in 5d elements, which further increases the attractive forces, hence more energy is
required to remove an electron from 5d elements than 3s and 4d elements, where no 4f electrons
and lanthanide contraction is present.
Ans.9 At lower, pH, the colour of the solution is orange due to the presence of dichromate ions (Cr2O72–
). But in alkaline pH (on increasing pH), the colour of the solution changes to yellow due to the
conversion of dichromate ions to chromate ions.
Alkali Alkali
Cr2O72– + H2O 2HCrO4– 2Cr O72– + 2H+
Acid Acid
dichromate Chromate
(orange) (yellow)
Ans.10
The ions of transition metals generally contain one or more unpaired electrons hence the compounds
of transition metal are paramagnetic i.e., they are weakly attracted by magnetic field. The
paramagnetic character is directly related to the value of magnetic moment, m which in turn depends
upon the number of unpaired electrons (n) i.e.,
m= n  (n  2) B.M.

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Ans.11
The ion which has one or more unpaired electron will show the colour, if the d-orbitals are vacant
or completely filled the ion will be white.
(i) Cu+  No unpaired d-electron,
therefore it will be colourless
3d 4d
(ii) VO  (oxidation state of V = +4) hence the outer configuration of V4+ will be:
2+

Due to one unpaired electron,


so it will be coloured
3d 4s
(iii) SC3+  No electron in d-orbitals so
it will be colourless.
3d 4s
Two unpaired electrons,
(iv) Ni2+ 
so it will be coloured.
3d 4s
Ans.12
(i) The electronic configuration of Ag+, Co2+ and Ti4+ are:
Ag + = [Kr], 4d10, 5s0 ; Co 2+ = [Ar], 3d7, 4s0
4+ 0 0
Ti = [Ar], 3d , 4s
Because only Co 2+ has unpaired electrons (three) in 3d-orbitals, it will be coloured in
aqueous solutions due to d  d transition.
(ii) When these ionic species are placed in magnetic field, only Co2+ gets attracted by it because
it contains unpaired electrons (paramagnetic) while Ag+ and Ti4+ would feel repulsion in
magnetic field because of the absence of unpaired electrons (diamagnetic).
Ans.13
(a) Cr3+ – 1s2, 2s2 2p6, 3s2 3p6 3d3
(b) Cu+ – 1s2, 2s2 2p6, 3s2 3p6 3d10
(c) Co 2+ – 1s2, 2s2 2p6, 3s2 3p6 3d10 3d7
(d) Mn2+ – 1s2, 2s2 2p6, 3s2 3p6 3d5
(e) Pm3+ – 1s2, 2s2 2p6, 3s2 3p6 3d10, 4s2 4p6 4d10 4f14, 5s2 5p6 5p10, 5f 2, 6s2 6p6
(f) Ce 4+ – 1s2, 2s2 2p6, 3s2 3p6 3d10, 4s2 4p6 4d10 4f 0, 5s2 5p6
(g) Lu2+ – 1s2, 2s2 2p6, 3s2 3p6 3d10, 4s2 4p6 4d10 4f 14, 5s2 5p6 5d1
(h) Th4+ – 1s2, 2s2 2p6, 3s2 3p6 3d10, 4s2 4p6 4d10 4f 14, 5s2 5p6 5d104f 0, 6s2 6p2
Ans.14
Mn2+ and Fe2+ have following configurations
Mn2+ – 1s2, 2s2 2p6, 3s2 3p6 3d5 4s0
Fe2+ – 1s2, 2s2 2p6, 3s2 3p6 3d6 4s0
Mn2+ ion is extra stable due to half filled d-orbitals while in Fe2+ extra stability will come after the
removal of one electron from it (Fe3+). Therefore, Mn2+ does not have tendency to lose an electron
easily while Fe2+ has a tendency to lose an electron. Due to this reason Mn2+ compounds are
more stable than Fe2+ towards oxidation to their +3 state.

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Ans.15Sc 3d1 4s2 + 3 oxidation state
Ti 3d2 4s2 + 2, + 3 and + 4
3 2
V 3d 4s + 2, + 3, + 4, + 5
Cr 3d5 4s1 + 2, + 3 (+ 4, + 5) + 6
5 2
Mn 3d 4s + 2, + 3, + 4, + 6, + 7
In Sc + 3 oxidation state is more common because 3d1 electron is also removed with 4s2 electrons.
In titanium also Ti(IV) is more stable than Ti (III) and Ti (II), because both 4s2 and 3d2 electrons
are used. But in vanadium electrons in 3d orbital exceed than the electrons in 4s-orbitals, therefore
4s-electrons can be lost without disturbing 3d electrons.. Thus +2 oxidation state is slightly stable.
In chromium also + 2 oxidation state exists (but less stable than +3) which is formed by losing one
electron each from 4s and 3d orbitals. But in Mn d-orbitals have extra stability due to d 5-
configuration (half filled) and only 4s2 electrons are lost and +2 oxidation state becomes very
stable.
Ans.16
All the transition elements with the above d-electron configuration contains 4s2 electrons too.
Thus the stable oxidation state of these configuration will be as follows:
Configuration stable oxidation states
3
3d + 3, + 5
3d 5 + 2, + 7
8
3d +2
3d 4 + 3, + 6
Ans.17
Disproportion reactions are those in which one oxidation state decomposes, forming some ions
in higher oxidation state and some in lower oxidation state. Disproportion occurs when a given
oxidation state is stronger oxidation agent than the next highest oxidation state.
Examples :
(i) 3CrO42– + 8H+  2CrO42– + 3Cr 3+ + 4H2O
(oxi. state = 5) (oxi. state = 6) (oxi state = 3)
(ii) 3MnO4 + 4H  2MnO4– + MnO2 + 2H2O
2– +

(oxi. state = 6) (oxi. state = 7) (oxi. state = 4)


Ans.18
Cerium (Ce) and Terbium (Tb) show + 4 oxidation state. Their electronic configuration are given
below :
Ce = [Xn] 4f1 5d1 6s2 ; Tb = [Xn] 4f9 6s2
It is clear from the configuration of Ce that Ce+4 is favoured by its noble gas configuration i.e.,
[Xn] 4f0 5d0 5s0, but can be easily converted into Ce3+ ([Xn] 4f1 5d0 6s0). Due to this reason Ce+4
is an oxidising agent. Tb4+ ion is stabilized due to half filled f-sub-shell i.e., [Xn] 4f7. It is also acts
as an oxidant.
Europium (63) and ytterbium (70) show + 2 oxidation state, thus act as reducing agents because
they can be converted into common oxidation state + 3. The electronic configuration of Eu and
Y are as follows :
Eu = [Xn] 4f7 6s2 ; Y = [Xn] 4f14 6s2
Formation of Eu ion leaves 4f configuration and Y2+ ion leaves 4f14 configuration. These
2+ 7

configuration are stable due to half filled and full field f-sub-shell. Samarium, Sm(62), 4f6 6s2 also
shows both +2 and +3 oxidation states like europium.

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Ans.19
(a) The large number of oxidation states in d-series are found because of incomplete filling of
d-orbitals in such a way that their oxidation states differ from each other by unity, e.g.,
V2+, V3+, V4+ and V5+. On other hand, in f-block elements, f-orbitals are present in second
last shell. Thus there is larger difference in energy between ns and (n – 2) f orbitals in f-
series than the difference between ns and (n – 1) d orbitals in d-series. Due to this reason
f-block elements show less number of oxidation states.
(b) In Cu+ salt (3d10) no d  d transition is possible due to completely filled d-orbitals while
in Cu2+ salts (3d9) d  d transition is possible. Thus the Cu2+ salts are coloured and Cu+
salts are white.

LONG ANSWER TYPE QUESTIONS

Ans.20
Preparation : It involves following steps :
(a) Conversion of chromite ore into sodium chromate : The powdered ore is heated
with sodium carbonate and quick lime in presence of air in reverberatory furnace to get
the yellow coloured sodium chromate, which is extracted with water.
4FeO.CFr 2O3 + 8Na2CO3 + 7O2  8Na2CrO4 + 3Fe2O3 + 8 CO2
chromite sodium chromate

(b) Conversion of sodium chromate into sodium dichromate : When sodium chromate
solution is treated with conc. H2SO4, sodium dichromate is formed.
2Na2CrO4 + H2SO4  Na2Cr2O7 + Na2SO4 + H2O
sodium dichromate
Sodium sulphate, being less soluble crystallizes out as hydrated sodium sulphate
(c) Conversion of sodium dichromate into potassium dichromate : When a calculated
amount of potassium chloride is added to the solution of hot and concentrated solution of
sodium dichromate, the crystals of potassium dichromate are obtained on cooling.
Na2Cr2O7 + 2KCl  K2Cr2O7 + 2NaCl
Potassium dichromate
Properties : It is an orange coloured crystalline substance, which melts at 669 K.
(i) Action of heat : On heating it decomposes and evolves oxygen
4K2Cr2O7  4K2CrO4 + 2Cr 2O3 + 3O2
Potassium Potassium chromide
dichromate chromate oxide
(ii) Action of conc H 2 SO4 : It gives chromium trioxide in cold.
K2Cr2O7 + 2H2SO4  2CrO3 + KHSO4 + H2O
Chromium trioxide
But on heating oxygen is evolved .
2K2Cr2O7 + 8H2SO4  2K2SO4 + 2Cr 2(SO4)3 + 8H2O + 3O2
(iii) Oxidising properties : In acidic medium it acts as a powerful oxidising agent.
Cr2O72– + 6e– + 14 H+  2Cr3+ + 7H2O
(a) It converts ferrous into ferric in acidic medium
Cr2O72– + 6e– + 14 H+  2Cr3+ + 7H2O
[Fe2+  Fe3+ + e– ] × 6

Cr2O72– + 6Fe2+ + 14 H+  2Cr3+ + 6Fe3+ + 7H2O


(b) It converts iodide to iodine
Cr2O72– + 6e– + 14 H+  2Cr3+ + 7H2O
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[2I–  I2 + 2e– ] × 3

Cr2O72– + 6I– + 14 H+  2Cr3+ + 3I2  + 7H2O


(c) It converts sulphide (hydrogen sulphide) into sulphur.
Cr2O72– + 6e– + 14 H+  2Cr3+ + 7H2O
[S2–  S  + 2e– ] × 3

Cr2O72– + 14 H+ + 3S2–  2Cr3+ + 3S  + 7H2O


Uses : (a) Used in dyeing, photography and chrome tanning.
(b) As volumetric reagent for the estimation of ferrous salt and iodides.
Ans.21
The steady decrease in atomic and ionic radii of lanthanum ions as we move from La to Lu, is
known as lanthanide contraction,.
Cause : In lanthanides, last electron enters the 4f sub-shell i.e., second last shell. The shape
of f-orbitals is very much diffused, because of this reason the mutual shielding of 4f-electrons is
very little. The nuclear charge increases at each step due to the increase in atomic number, while
the mutual shielding effect of 4f-electrons is comparatively negligible. This causes a decreases in
size of the 4f sub-shell with the increase in atomic number.
Consequences : Following are the main consequence of lanthanide contraction.
(a) Basic strength of oxides and hydroxides of lanthanides : The basic strength of oxides
and hydroxides of lanthanides decrease with the increase in atomic number, With the
increase in atomic number the size of lanthanum into (Ln3+) decreases, due to lanthanide
contraction. The decrease in size of Ln3+, increases the covalent character i.e. decreases
the ionic character between Ln3+ and OH¯ ions, consequently the basic strength of oxide
and hydroxide will decrease.
(b) Similar size of second and third transition series elements : Normally the atomic
radii increases with the increase in atomic number in the same subgroup, but after lanthanides
the atomic radii of the elements of second and third transition series are almost similar.
3 4 5
21
Sc–144 pm 22
Ti–132 pm 23
V–122 pm
39
Y–162 pm 40
Zr–145 pm 41
Nb–134 pm
57
La–169 pm Lanthanides 73
Hf–144 pm 73
Ta–134 pm
58
Ce–71Lu
The expected increase in size from second to third transition series is cancelled by the
decrease in size due to lanthanide contraction. Due to the similar atomic radii of second
and third transition series elements, they resemble each other very closely.
(c) Separation of lanthanides : The properties of lanthanides are very similar, therefore,
it is difficult to separate them. However, due to lanthanide contraction, decrease in size of
lanthanides make the separation possible by ion exchange methods.
Ans.22
(a) The elements in which the last electron (also called differentiating electron) enters in (n
– 2) f-orbitals, are called f-block elements or inner transitions elements [since
(n – 2) f-orbitals lie comparatively deep within the kernel (being inner to penultimate
shell., hence inner transitional word is used.
(b) In transitional elements last electron goes to (n – 1) d-orbitals and in inner transitional
elements last electrons goes to (n – 2) f-orbitals. The general electronic configuration of
transition element is (n – 1) d1–10 ns1–2 and general electronic configuration of inner transition

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elements is: (n – 2) f1–14 (n – 1) d0–1ns2.
(c)
(i) Na2Cr2O7 + 4KCl + 6H2SO4 2NaHSO4 + 4KHSO4 + 2CrO2Cl2 + 3H2O
Chromyl
chloride
heat
(ii) 2MnO2 + 4KOH + O2 
 2K2MnO4 + 2H2O
Pyrolusite Potassium
manganate (green mass)

(iii) 2MnO4– + 5C2O42– + 16H+ 2Mn2+ + 10CO2 + 8H2O


permanganate oxalate
ion ion

Ans.23
Transition elements are those elements whose atoms or simple ions contain partially filled d-
orbitals i.e., the electronic configuration of transition elements is (n – 1)d1–10 ns1–2.
(i) The ionic sizes of Zr4+ and Hf4+ are nearly same due to lanthanide contraction The expected
increase in size from second to third transition series i.e., Zr 4+ to Hf4+ is cancelled by the
decrease in size due to lanthanide contraction in third transition series after La.
(ii) KMnO4 is a strong oxidisng agent in an acidic medium than in an alkaline medium because
it gives five nascent oxygen in acidic medium and three nascent oxygen in basic medium
or the standard electrode potential (E) for the reducing half of MnO 4– ion is higher in
acidic medium (1.51 V) than in basic medium (1.23 V).
In acidic Medium
2KMnO4 + 3H2SO4  K2SO4 + MnSO4 + 3H2O + 4[O]
or MnO4– + 8H+ + 5e¯  Mn2+ + 4H2O [E 0 = 1.51 V]
In basic Medium
2KMnO4 + H2O  2KOH + 2MnO2 + 3[O]
or MnO4– + 2H2O + 3e¯  MnO2 + 4OH– [E 0 = 1.23 V]
(iii) In manganese the electronic configuration is 3d5 4s2. Its all electrons present in d-orbitals(5
electrons) and s-orbitals (2 electron can take part in bonding, thus it shows maximum
oxidation state i.e., 7 in first transition series. After Mn, the elements present (Fe, CO, Ni,
Cu) do not allow the d-electrons to take part in bond formation, thus their oxidation states
are lower than that of 7.
(iv) Only transition elements have partially filled d-orbitals thus, they can form metal-carbon
-bond due to the donation of one pair of electrons present on the carbon of carbonyl
group into the vacant d-orbitals of the transition metal atoms. Simultaneously they can
form metal-carbon p-bon due to the donation of a pair of electrons from a filled d-orbital
of transition metal into a vacant antibonding *2p molecular orbital of carbon monoxide
(CO). Due to this typical bonding only transition elements can form the metal carbonyls.
Ans.24
Silver occurs in nature in free form as well as in combined form. The important ores of silver
are :
(i) Argentite or silver glance , Ag2S (ii) Horn silver, AgCl
(iii) Ruby silver , 3Ag2S Sb2S3
(iv) Stromeyerite or silver copper glance, Cu2S.Ag2S
In India it is found mainly as sulphide ore, Ag2S alongwith lead and zinc ores in Zewer mines of
Rajasthan and in small amounts with gold ores at Kolar fields in Karnataka and Anantpur mines at
Tamil Nadu.
Extraction of silver from argentite ore. Silver is extracted from the argentite ore (Ag 2S) by
using cyanide process. It consists of the following steps :
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(i) Crushing and concentration : The ore is crushed and converted into powdered form
and concentrated by forth-floatation process. The finely powdered ore is mixed with water
and some pine oil which acts as frothing agent. The contents are kept agitated by the blast
of air, due to which forth is produced. The ore particles are preferentially wetted by oil
and thus come to the surface in the form of froth, from where it is skimmed off. The
impurities, which are preferentially wetted by water, sink to the bottom of the tank .

Air Froth

Ore
+ Ore
Pine oil

Fig. Forth floatation process


(ii) Treatment of the concentrated ore with sodium cyanide : Dilute solution of sodium
cyanide (0.5%) is added to the concentrated ore and the mixture is continuously agitated
by the current of air for several hours. Silver sulphide forms a soluble complex and goes
into the solution.
AgS + 4NaCN 2Na[Ag(CN) 2] + Na2S
sodium argentocyanide
Sodium sulphide formed in the above reaction gets oxidised by the oxygen or air, to
sodium sulphate. Thus the equilibrium in the above reaction is shifted towards forward
direction.
4 Na2S + 5O2 + 2H2O 2Na2SO4 + 4NaOH + 2S
(iii) Precipitation of silver: To remove the insoluble impurities, the solution is filtered. Filtrate,
containing the soluble complex of silver, is treated with zinc. dust. The zinc being more
electropositive displaces less electropositive silver metal, thus the silver gets precipitated
from sodium argentocyanide complex. The silver obtained in this step is called spongy
silver.
2Na [Ag(CN2)] + Zn  Na2 [Zn(CN) 4] + 2Ag¯
The precipitate silver is fused with borax or KNO3 to obtained a compact mass of shining
silver
(iv) Purification by electrolytic refining : The silver thus obtained contains some impurities
like gold, copper and zinc. To remove these impurities electrolytic process is used. for
this purpose anode is made up of impure silver and cathode is made up of pure silver
metal. The electrolytic solution of silver nitrate and 1% HNO3 is taken in electrolytic tank.
When the electricity is passed, pure silver get deposited at cathode, while the equivalent
amount of silver metal comes from anode to solution.
At anode : Ag  Ag+ + e–
At cathode : Ag+ + e–  Ag
The impurities like zinc and copper pass into solution as a soluble solution and the gold
impurity settle down under the anode as anode mud.

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Ans.25
Any ion which has none ore more unpaired electros in d-orbital will be coloured while any ions
having no electron or 10 electrons (fully filled) in d-orbitals will be colourless.
Ion Number of electrons in d-orbitals Colour/colourless
3+ 1
Ti 3d Purple
3+ 2
V 3d green
Cu+ 3d 10 colourless
3+ 0
Sc 3d colourless
Mn2+ 3d 5 pink
3+ 5
Fe 3d yellow
2+ 7
Co 3d pink
In MnO4– the oxidation state of Mn is +7. Due to the sharing of all d-electrons with oxygen atoms,
Mn has d0 configuration, therefore, no d  d transition is possible in MnO4– ion. The colour of
MnO4– arises from charge transfer nd not from d - d spectra. In MnO4– an electron is transferred
momentarily from oxygen to Mn because of which O2– is changed momentarily to O– and Mn (+ 7)
to Mn(+ 6). The energy levels of these two different atoms (in which charge transfer) are fairly
close. Due to this charge transfer an intense colour is produced.
Ans.26 The atomic number of Mn is 25. Thus the electronic configuration of
Mn3+ =
3d 4s
Thus Mn3+ has four unpaired electrons.
The atomic number of Cr is 24. Thus the electronic configuration of
Cr3+ =
3d 4s
3+
Thu Cr has three unpaired electrons.
The atomic number of V is 23. Thus the electronic configuration of
V3+ =
3d 4s
3+
Thus V has two unpaired electrons.
The atomic number of Ti is 22. Thus the electronic configuration of
Ti3+ =
3d 4s
Thus Ti3+ has one unpaired electron.
The Mn3+ is not stable due to disproportion. V3+ is also reducing thus it is also not very stable. Ti3+
also changes to Ti4+ thus not very stable. How ever, Cr3+ is stable in aqueous solution.

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IIT-JEE QUESTIONS

A. Fill in the blanks


1. The absorption of hydrogen by palladium is commonly known as ________ . [ 1983 ]
2. Sodium dissolved in liquid ammonia conducts electricity because ________ . [ 1985 ]
3. In extractive metallurgy of zinc partial fusion of ZnO with coke is called ________ and reduction
of the ore to the molten metal is called ________ .
[ smelting, calcining, roasting, sintering ] [ 1988 ]
4. The electrolysis of molten sodium hydride liberates ________ gas at the ________ .
[ 1989 ]
5. Ca2+ has a smaller ionic radius than K+ because it has ________ . [ 1993 ]
6. A solution of sodium in liquid ammonia at – 33 ºC conducts electricity. On cooling, the conductivity
of this solution ________ . [ 1997 ]

B. True/False
1. MgCl2.6H2O on heating give anhydrous MgCl2. [ 1982 ]
2. The softness of group I-A metals increases down the group with increasing atomic number.
[ 1986 ]
3. Sodium when burnt in excess oxygen gives sodium oxide. [ 1987 ]

C. Multiple choice questions with ONE correct


1. A solution of sodium metal in liquid ammonia is strongly reducing due to the presence of
(A) sodium atoms (B) sodium hydride (C) sodium amide (D) solvated electrons
[ 1981 ]
2. Heavy water is :
(A) H218O (B) water obtained by repeated distillation
(C) D2O (D) water at 4ºC [ 1983 ]
3. In the aluminothermite process, aluminium acts as :
(A) an oxidizing agent (B) a flux (C) a reducing agent (D) a solder
[ 1984 ]
4. The hydration energy of Mg++ is larger than that of :
(A) Al+3 (B) Na+ (C) Be++ (D) Mg+2 [ 1984 ]
5. The oxide that gives hydrogen peroxide on treatment with a dilute acids is :
(A) PbO2 (B) Na2O2 (C) MnO2 (D) TiO2 [ 1985 ]
6. Molecular formula of Glauber’s salt is :
(A) MgSO4.7H2O (B) CuSO4.5H2O (C) FeSO4.7H2O (D) Na2SO4.10H2O
[ 1985 ]
7. Hydrogen gas will not reduce :
(A) heated cupric oxide (B) heated ferric oxide
(C) heated stannic oxide (D) heated aluminium oxide [ 1985 ]
8. The pair of compounds which cannot exist together in solution is :
(A) NaHCO3 and NaOH (B) Na2CO3 and NaHCO3
(C) Na2CO3 and NaOH (C) NaHCO3 and NaCl [ 1986 ]
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9. The metallic lustre exhibited by sodium is explained by :
(A) diffusion of sodium ions (B) oscillations of loose electrons
(C) excitation of free proton (D) existence of body centered cubic lattice
[ 1987 ]
10. The volume strength of 1.5 N H2O2 solution is :
(A) 4.8 (B) 8.4 (C) 3.0 (D) 8.0 [ 1991 ]
11. Read the following statement and explanation and answer as per the options given below :
Statement : The alkali metals can form ionic hydrides which contain the hydride ion H¯.
Explanation : The alkali metals have low electronegativity; their hydrides conduct electricity
when fused and liberate hydrogen at the anode.
(A) Both S and E are true and E is the correct explanation of S.
(B) Both S and E are true but E is not the correct explanation of S.
(C) S is true but E is false
(D) S is false but E is true [ 1994 ]
12. The following compounds have been arranged in order of their increasing thermal stabilities. Identify
the correct order :
(I) K2CO3 (II) MgCO3 (III) CaCO3 (IV) BeCO3
(A) I < II < III < IV (B) IV < II < III < I
(C) IV < II < I < III (D) II < IV < III < I [ 1996 ]
13. Property of all the alkaline earth metals that increases with their atomic number is :
(A) ionisation energy (B) solubility of their hydroxides
(C) solubility of their sulphate (D) electronegativity [ 1997 ]
14. Among the following statement, the incorrect one is :
(A) calamine and siderite are carbonates (B) argentite and cuprite are oxides
(C) zinc blende and pyrites are sulphides (D) malachite and azurite are ores of copper
[ 1997 ]
15. The chemical composition of ‘slag’ formed during the smelting process in the extraction of copper
is :
(A) Cu2O + FeS (B) FeSiO3 (C) CuFeS 2 (D) Cu2S + FeO [ 2001 ]
16. The set representing the correct order of first ionization potential is :
(A) K > Na > Li (B) Be > Mg > Ca (C) B > C > N (D) Ge >Si > C
[ 2001 ]
17. Which of the following process is used in the extractive metallurgy of magnesium ?
(A) fused salt electrolysis (B) self reduction
(C) aqueous solution electrolysis (D) thermite reduction [ 2002 ]
18. A sodium salt on treatment with MgCl2 gives white precipitate only on heating . The anion of the
sodium salt is :
(A) HCO3– (B) CO32 (C) NO 3 (D) SO 32
[ 2004 ]
19. Which ore contains both iron and copper ?
(A) Cuprite (B) Chalcocite (C) Chalcopyrite (D) malachite
[ 2005 ]

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D. Multiple choice questions with One or more than one correct answer
1. When zeolite, which is hydrated sodium aluminium silicate, is treated with hard water, the sodium
ions are exchanged with :
(A) H+ ions (B) Ca++ ion (C) SO4– – ions (D) Mg++ ions
2. Off the following, the metals that cannot be obtained by electrolysis of the aqueous solution of
their salts are :
(A) Ag (B) Mg (C) Cu (D) Al
3. The species that do not contains peroxide ion are :
(A) PbO2 (B) H2O2 (C) SrO2 (D) BaO2
4. Highly pure dilute solution of sodium in liquid ammonia :
(A) shows blue colour (B) exhibits electrical conductivity
(C) produces sodium amide (D) produces hydrogen gas
5. The species present in solution when CO2 is dissolved in water are :
(A) CO2, H2CO3, HCO3– , CO32– (B) H2CO3, CO32–
2– –
(C) CO3 , HCO3 (d) CO2, H2CO3
6. MgSO4 on reaction with NH4OH and Na2HPO4 forms a white crystalline precipitate. What is
its formula ?
(A) Mg(NH4)PO4 (B) Mg3(PO4)2 (C) MgCl2.MgSO4 (D) MgSO4

E. Subjetive problems :
1. Give reasons for the following:
(i) Sodium carbonate is made by Solvay process but the same process is not extended to
the manufacture of potassium carbonate.
(ii) an alkaline solution of potassium ferricyanide is reacted with hydrogen peroxide.
(iii) Metals can be recovered from their ores by chemical methods.
(iv) High purity metals can be obtained by zone refining method.
(v) Hydrogen peroxide is a better oxidising agent than water.
(vi) Magnesium oxide is used for the lining of steel making furnace.
(vii) Why is sodium chloride added during electrolysis of fused anhydrous magnesium chloride
?
(viii) Why is chalconite roasted and not calcinated during recovery of copper ?
(ix) Hydrogen peroxide acts as an oxidising as well as reducing agent.
(x) The crystalline salts of alkaline earth metals contain more water of crystallisation than the
corresponding alkali metal salts. Why ?
(xi) BeCl2 can be easily hydrolysed.
2. How will you prepare bleaching powder fro slaked lime
3. Write down the balanced equations for the reaction when :
(i) calcum phosphated is heated with a mixture of sand and carbon;
(ii) carbon dioxide is passed through a concentrated aqueous solution of sodium chloride
saturated with ammonia.
(iii) Potassium ferricyanide reacts with hydrogen peroxide in basic solution.

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(iv) carbon dioxide is passed through a suspension of lime stone in water.
4. Give the equations for the recovery of lead from Galena by air reduction.
5. Give briefly the isolation of magnesium from sea water by the Dow process. Give equations for
the steps involved.
6. Complete and balance the following reactions :
Ca5(PO4)3F + H2SO4 + H2O Heat
 ........... + 5CaSO4.2H2O +..........
7. A 5.0 cm3 solution of H2O2 liberates 0.508 g of iodine from an acidified KI solution. calculate the
strength of H2O2 solution in terms of volume strength at STP.
8. Explain the difference in the nature of bonding in LiF and LiI.
9. Write the reaction involved in manufacture of triple super phosphate from fluorapatite.
10. To a 25 ml H2O2 solution, excess of acidified solution of potassium iodide was added. The iodine
liberated required 20ml of 0.3 N sodium thiosulphate solution. Calculate the volume strength of
H2O2 solution.
11. Give reactions for the oxidation of hydrogen peroxide with potassium permanganate in acidic
medium.
12. Element A burns in nitrogen to give an ionic compound B. compound B reacts with water to give
C and D. A solution of C becomes ‘milky’ on bubbling carbon dioxide. Identify A, B, C and D.
13. Arrange the following sulphates of alkaline earth metals in order of decreasing thermal stability;
BeSO4, MgSO4, CaSO4, SrSO4
14. Work out the following using chemical equations :
Chlorination of calcium hydroxide produces bleaching powder.
15. Hydrogen peroxide acts both as an oxidising and as a reducing agent in alkaline solution towards
certain first row transition metal ions. Illustrate both these properties of H 2O2 using chemical
equations.

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ANSWER KEY

EXERCISE -1

Que. 1 2 3 4 5 6 7 8 9 10
Ans B D D D A B B A A C
Que. 11 12 13 14 15 16 17 18 19 20
Ans C D D B B B A B A B
Que. 21 22 23 24 25 26 27 28 29 30
Ans D B A B A C A C B B
Que. 31 32 33 34 35 36 37 38 39 40
Ans C A C B B C A D C D
Que. 41 42 43 44 45 46 47 48 49 50
Ans A A C B A B A D C B

EXERCISE -2

Que. 1 2 3 4 5 6 7 8 9 10
Ans D C A C D B B C C B
Que. 11 12 13 14 15 16 17 18 19 20
Ans A C D C A D C B D D
Que. 21 22 23 24 25 26 27 28 29 30
Ans D A A C B A C B B B
Que. 31 32 33 34 35 36 37 38 39 40
Ans A C C D C D C C C D
Que. 41 42 43 44 45 46 47 48 49 50
Ans B C D B D C C B B C

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ANSWER SHEET OF IITJEE PROBLEMS

A.

1. occlusion 2. of solvated electrons 3. sintering , smelting


4. Hydrogen, anode 5. higher effective nuclear charge 6. decreases

B.

1. F 2. F 3. F

C.

1. D 2. C 3. C 4. B 5. B 6. D 7. D
8. A 9. B 10. B 11. A 12. B 13. B 14. B
15. B 16. B 17. A 18. A 19. C
D.

1. BD 2. BD 3. AC 4. AB 5. A 6. A

E.

1. (i) Potassium carbonate cannot be manufactured by solvay process, since unlike sodium
hydrogen carbonate, potassium hydrogen carbonate is rather too soluble in water to be
precipitated like NaHCO3.
(ii) Ferricyanide is oxidised to ferrocyanide on treatment with alkali.
2 K3Fe (CN)6 + H2O2 + 2 KOH  2 K4 Fe (CN)6 + 2 H2O + O2.
(iii) Because they occus as oxides, carbonates, sulphides which have to be calcined or roasted.
(iv) Zone refining is based on the difference in solubility of impurities in molten and solid state
of the metal. This method is used for obtaining metals of very high purity. Ge, Si and Ga
used as semi-conductors are refined in this manner.
(v) H2O2 is a better osidising agent than H2O because oxidation number of oxygen in H2O2 is
– 1 and that in water it is – 2. So H2O2 easily reduces to – 2 oxidation number.
(vi) MgO is used for the lining of steel making furnace because it acts as basic flux and facilitates
the removal of acidic impurities of Si , P and S from steel through slag formation.
(vii) The anhydrous magnesium chloride is fused with NaCl to provide conductivity to the
electrolyte and to lower the fusion temperature of anhydrous MgCl2.
(viii) Air (used during roasting) is necessary for converting chalcocite (a sulphide ore) to oxide.
Calcination does not use oxygen.
(ix) The oxidation state of oxygen in H2O2 (i.e. – 1) can be changed to 0 or – 2 i.e. oxygen in
H2O2 exists in an intermediate oxidation state with respect to O 2 and O2– . Hence it acts
both as an oxidising and reducing agent.
(x) Lower the size of cation, higher will be hydration tendency because hydration energy of

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SARWAR CLASSES Coordination Compund & Metallurgy
cation is inversely proportional to size of cation. The size of alkaline earth metal ions are
lower than the size of alkali metal ions. So in crystalline form the salts of alkaline earth
metals have more water molecules than those of alkali metals.
(xi) BeCl2 is hydrolysed due to high polarising power and presence of vacant p - orbitals in Be
atom. (Be = 1 s2 . 2 s2 2 px1 2 py0 2 pz0)

2. 3 Ca(OH) 2 + 2 Cl2 below


  Ca (OCl)2 . CaCl2 . Ca(OH) 2 . H2O + H2O
35 º C

Slaked lime Bleaching powder

electric
3. (i) 2 Ca3 (PO4)2 + 6 SiO2 + 10 C furnace
  6 CaSiO3 + 10 CO + P4

This is the electrothermal process to extract phosphorus from phosphorite or bone ash
[Ca3 (PO4)2].
(ii) NaCl + NH4OH + CO2  NH4Cl + NaHCO3
(iii) 2 K3 Fe (CN)6 + H2O2 + 2 KOH  2 K4 Fe(CN)6 + 2 H2O + O2
(iv) CaCO3 + CO2 + H2O  Ca (HCO3)2
Calcium bicarbonate
4. Recovery of Pb from galena :
2 PbS + 3 O2  2 PbO + 2 SO2 
PbS + 2 PbO  3 Pb + SO2
5. In sea water Mg exists as MgCl2
On treating sea water with slaked lime Mg(OH)2 is obtained.
MgCl2 + Ca(OH)2  Mg (OH)2  + CaCl2
in sea water slaked lime
On reacting Mg(OH) 2 with HCl , MgCl2 is obtained
Mg (OH)2 + 2 HCl  MgCl2 + H2O
From MgCl2 , Mg as obtained by reduction of MgCl2 with CaC2 .
MgCl2 + CaC2  Mg + CaCl2 + 2 C

6. 
Ca5 (PO4)3 F + 5 H2SO4 + 10 H2O  3 H3PO4 + 5 CaSO4 . 2 H2O + HF
7. H2O2 + H2SO4 + 2 KI  K2SO4 + I2 + 2 H2O
Acidified KI sol
34 gm 254 gm
3
5 cm or ml 0.508 gm
i.e. 254 gm of I2 is released by 34 gm H2O2
34
 0.508 gm of I2 will be released by  0.508 = 0.068 gm
254
5 ml of H2O2 sol contains 0.068 gm of H2O2
0.068
 1 ml of H2O2 sol contains gm H2O2
5
The strength of H2O2 is generally calculated in terms of volume strength. According to which
10 volume of H2O2 means that 1 ml of H2O2 sol gives 10 ml of O2 at STP.
2 H2O2  2 H2O + O2
2  34 gm 32 gm or 22400 ml at STP
i.e. 68 gm of H2O2 gives 22400 ml of O2 at STP
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SARWAR CLASSES Coordination Compund & Metallurgy
or 1 ml of H2O2 sol

or 0.068 22400 0.068


5 gm of H2O2 gives 68  5 = 4.48 ml
or 1 ml of H2O2 sol gives 4.48 ml of O2 i.e. strength of H2O2 sol is 4.48 volumes.
8. LiF has more ionic character while LiI has more covalent character. The latter is due to the
greater polarizability of larger iodide ion than the lithium ion.
9. [ Ca3 (PO4)2 . CaF2 ] + 6 H3PO4  4 Ca (H2PO4)2 + 2 HF
(triple super phosphate)
10. Meq of H2O2 = Meq of Na2S2O3
w
 1000 = 20  0.3  w = 0.102 g
17

H2O2  H2O + 12 O2

11200  0.102
 Volume of O2 = = 33.6 ml
34
33.6
 Volume strength = = 1.344
25
11. 2 KMnO4 + 3 H2SO4  K2SO4 + 2 MnSO4 + 3 H2O + 5 [O]
[H2O2 + [O]  H2O + O2]  5
------------------------------------------------------------------------
2 KMnO4 + 5 H2O2 + 3 H2SO4  K2SO4 + 2 MnSO4 + 8 H2O + 5 O2
12. 3 M + N2  M3N2
A B
M3N2 + 6 H2O  3M (OH)2 + 2 NH3
B C D
M (OH)2 + CO2  MCO3 + H2O
C D
M may be either Ca or Ba. It is not magnesium because Mg (OH)2 has very low solubility in
water. So , A is Ba , B is Ba3N2 , C is Ba (OH)2 , D is BaCO3 .
13. SrSO4 > CaSO4 > MgSO4 > BeSO4 (based upon size of cation or ionic character)
14. 3 Ca (OH)2 + 2 Cl2  Ca (OCl2) . Ca (OH)2 . CaCl2 . 2 H2O
Bleaching power (a mixture of Ca (OCl)2 and basic chloride)

15. When H2O2 acts as oxidising agent, therefore, following reactions takes place :
H2O2 + 2 e  2 OH–
While regarding its action as reducing agent, the following reactions takes place :
H2O2 + 2 OH–  O2 + 2 H2O + 2 e
Examples of oxidising character of H2O2 in alkaline medium
2 Cr (OH)3 + 4 NaOH + 3 H2O2  2 Na2CrO4 + 8 H2O
Here Fe3+ (Fe is a first row transition metal) is reduced to Fe2+.
Example of reducing character of H2O2 in alkaline medium
2 K3 Fe (CN)6 + 2 KOH + H2O2  2 K4 [Fe (CN)6] + 2 H2O + O2
Here Cr3+ (Cr is a first row transition metal) is oxidised to Cr6+.

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