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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.
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. :CN:¯, 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
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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.
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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.
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.
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
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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.
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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
=
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
(a) Fe 26
3d 4s 4p
(b) Fe 3+
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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
(a) Cr 24
(b) Cr3+
3d5 4s 4P
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
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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+
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.
7.2.1 [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)
?? ?? ?? ? ?
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.
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
8.1 Classification
Type of isomerism
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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
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
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
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3+
en en 3+
Cl Cl
Co Co
Cl Cl
en en
Cis-d-form Cis-l-form
Mirror
en 2+ en 2+
Cl Cl
Co Co
H3N NH3
en en
Cis-d-form Cis-l-form
Mirror
gly gly
Cr gly Cr
gly
gly gly
Cis or trans-d-form Cis or trans-l-form
Mirror
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
10.6 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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SARWAR CLASSES Coordination Compund & Metallurgy
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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SARWAR CLASSES Coordination Compund & Metallurgy
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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SARWAR CLASSES Coordination Compund & Metallurgy
EXERCISE -2
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SARWAR CLASSES Coordination Compund & Metallurgy
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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SARWAR CLASSES Coordination Compund & Metallurgy
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 dd (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) [Fe5(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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SARWAR CLASSES Coordination Compund & Metallurgy
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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SARWAR CLASSES Coordination Compund & Metallurgy
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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SARWAR CLASSES Coordination Compund & Metallurgy
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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SARWAR CLASSES Coordination Compund & Metallurgy
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
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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SARWAR CLASSES Coordination Compund & Metallurgy
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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SARWAR CLASSES Coordination Compund & Metallurgy
+ en +
en
Cl Cl
Rh Rh
Cl Cl
en en
3– ox 3–
ox
Cr ox Cr
ox
ox ox
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
Cl
en
Cl
trans Cis
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
10.17 [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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SARWAR CLASSES Coordination Compund & Metallurgy
10.18 [Cr(H2O)6] Cl3 violet
[Cr(H2O)5Cl]Cl2.H2O green
[Cr(H2O)4Cl2]Cl.(H2O)2 darkgreen colour
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 +33d 5
sp3d2
(v) [CoF6]3–
same as sp3d2
Co +33d 5
sp3d2
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SARWAR CLASSES Coordination Compund & Metallurgy
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
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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SARWAR CLASSES Coordination Compund & Metallurgy
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
CH3 Bi
Ni
CO
OC
CO
(b) Fe(CO)5 — Penta carbonyl iron (O)
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SARWAR CLASSES Coordination Compund & Metallurgy
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
10.30 [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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SARWAR CLASSES Coordination Compund & 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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SARWAR CLASSES Coordination Compund & Metallurgy
(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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SARWAR CLASSES Coordination Compund & Metallurgy
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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SARWAR CLASSES Coordination Compund & Metallurgy
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.
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SARWAR CLASSES Coordination Compund & Metallurgy
(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
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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.
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SARWAR CLASSES Coordination Compund & Metallurgy
(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
Copper Control
clamp lamp
Iron
pot
MOLTEN ELECTROLYTE Dynamo
Molten
aluminium
Carbon lining
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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SARWAR CLASSES Coordination Compund & Metallurgy
REFINING OF BAUXITE
Al(OH)3
(b) Hall’s Process :
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
ºC
Al + O2
99.8 % pure
ELECTROLYTIC REFINING
(Hoope’s process)
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.
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
Silica
Matte (Cu2S, FeS)
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Electrolytic refining
Anode — Impure copper plates
Cathode — Pure copper plates
Electrolyte — CuSO 4 so ln . H 2SO 4
Pure copper deposited at cathode
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
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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)
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
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
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.
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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 3CaO + 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.
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Smelting in a blast furnace (ore coke limestone) . The following reactions occur.
400 700C
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
1600C
C O 2 CO 2
1500 º C
CO 2 C 2CO
Pig iron
Remelted and cooled
Cast iron
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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Oxygen lance
liquid metal
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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
Casing of
crucible refractory
material
Liquid metal
H2 O
Water cooled
copper coils
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
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
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
TIN
Occurrence of tin :
Tin does not occur in nature in the native state. Its chief ore is cassiterite or tin stone (SnO2).
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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
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
Properties :
1. It is a yellow substance but turns white on exposure to moist air due to the formation of
NaOH and Na2CO3.
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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 )
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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
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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
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
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.
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 .
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.
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
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.
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
(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
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
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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SARWAR CLASSES Coordination Compund & Metallurgy
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.
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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
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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
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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
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TRANSITION ELEMENTS (d-block)
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.
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–.
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.
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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 :
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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.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+
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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– +
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.
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
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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)
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
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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
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 ]
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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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SARWAR CLASSES Coordination Compund & Metallurgy
ANSWER SHEET OF IITJEE PROBLEMS
A.
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)
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
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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