COMPREHENSIVE

SELF – STUDY MATERIAL

FOR

NEET & AIIMS

CHEMISTRY - XII

Content Page

Module 3 .............................................................................................................................. 2

(1) p-Block Elements .................................................................................................. 3

(2) Transition Elements (d & f Block) ...................................................................... 89
(3) Coordination Compounds ................................................................................. 136
(4) Metallurgy ......................................................................................................... 191
COMPREHENSIVE
SELF - STUDY MATERIAL
FOR
NEET & AIIMS

CHEMISTRY

Module - 3

n P-Block Elements
o Transition Elements (d & f Block)
p Coordination Compounds
q Metallurgy

2
P-BLOCK ELEMENTS
CHAPTER
06
if all the elements are arranged in the order of atomic weights, a
periodic repitition is obtained. This is expressed by the law of
periodicity.

'' DMITRI MENDELEEV''

INTRODUCTION

T
he elements is which last electron enters into p-subshell are called as p-block ele-
ments. The number of p-orbitals are three and, therefore, the maximum number of
electrons that can be accommodated in a set of p-orbitals is six, hence p-block con-
tains six groups. The general electronic configuration of these elements is ns2np1– 6
(except for He).
p-block elements can be either metals, metalloids or non-metals. Maximum oxidation
state shown by p-block elements is equal to the sum of valence electrons (i.e., sum of
s-and p-electrons) or the group number minus 10 known as group oxidation state.
Absence of d-orbitals in the elements of second period and presence of d- and f-
orbitals in rest of elements have significant effects on the properties as a result lower
oxidation state will be more stable. This effect is known as inert pair effect.

3
CHEMISTRY FOR NEET & AIIMS
Important Concepts
(I) Back bonding
(II) Dimerisation
(III) Inert pair effect
(IV) Oxyacids
(V) Hydrolysis
(VI) Drying agent and bleaching agents

(I) Back bonding

It is formed between two covalently bonded adjacent atoms.
Conditions for back bonding :
(i) Both bonded atoms must belong to 2nd period or one bonded atom must belong to 2nd period and the other
must belong to 3rd perid.
(ii) One bonded atom must possess vacant orbital and the bonded atom must possess lone pair.
y As a result of back bonding, bond length decreases and bond energy increases.

Back bonding :
It is a partial sideways overlap in which there is a slight electron transference from electron rich atom to electron
deficient atom. As a result the electron deficiency of the deficient atom gets slightly compensated.

F F–donor
F–B B–acceptor
F

F F F F
F B F B F B F B (B–F) B.O = 4/3 = 1.33
F F F F

Types of back bonding :

Based on type of orbital : (2 type)
(1) pS-pS back bonding
(2) pS-dS back bonding

(1) pS-pS back bonding :

Order of strength : 2p – 2p > 2p – 3p > 2p – 4p ....
_______________________
Size n extent of B.B. p

It is used to explain following observations.

(a) Abnormal bond length and bond energy of B–F bond in BF3.

(b) Lewis acidic order of Boron and Beryllium halides.

BeF2 < BeCl2 < BeBr2 < BeI2

4
 P-BLOCK ELEMENTS
(c) Hybridisation : If a lone pair participates in back bonding then it is not considered in hybridisation.
Ex. : B3N3H6 (inorganic benzene or borazene or borazole)
y Hybridisation of B as well as N = sp2

y Inorganic benzene is more reactive than organic benzene as in it the bonds are polar, although over all molecule
is non polar.
(d) If back bonding is present then tendency to form dimer or polymer decreases.
Ex. : BF3, BeF2

(2) S-dS back bonding :

pS
p d
2nd period 3rd period
with lp empty

it is used to explain following observations :

(a) Hybridisation
Ex. Trimethyl amine Trisilyl amine
(CH3)3 N (SiH3)3 N

SiH3

N
CH3 N
CH3 CH3 SiH3 SiH3
(3d) (3d)

y sp3 hybrid (N) y sp2 hybrid (N)

y trigonal pyramidal y trigonal planar
y Lewis base (due to presence of lp) y Not Lewis base
y Bond angle increases
(b) Acidic strength
CH3 – O – H SiH3 – O – H
Methyl alcohol Silyl alcohol

• No back bonding • Back bonding present in conjugate base

• Less acidic • More acidic

(II) Dimerisation / Polymerisation

Types of Dimerisation

3C—2e 3C—4e
B2H6 (BeCl2)2
(BeH2)2 (BeCl2)n
(BeH2)n
(AlCl3)2
Al2(CH3)6
(ICl3)2
Ga2(CH3)6

5
CHEMISTRY FOR NEET & AIIMS
(A) By banana Bond or by 3C–2e bond or by e– deficient bond
(a) B2H6

Hybridisation state = sp3

Electron deficient molecule (act as Lewis acid)
y All four terminal hydrogen and two boron atoms are present in same plane both bridging H are present in
perpendicular plane.
y If substitution reaction takes place than only four terminal hydrogen atom will be substituted.

(b) (BeH2)2 (dimer of BeH2 in vapour state)

H
Hybridisation state = sp2
Ht Be Be Ht
Planar
H electron deficient molecule

(c) (BeH2)n (polymer of BeH2 in solid state)

H H Hybridisation state = sp3
Be Be Be Non-planar
electron deficient molecule
H H

(B) By-coordinate Bond / 3C-4e bond

(a) Al2Cl6 (dimer of AlCl3 in liquid or solid state)
BA = D < E
BL = x > y
Hybridisation state = sp3
Non-planar
octet complete
(b) (BeCl2)2 (dimer of BeCl2 in vapour state)
Cl Hybridisation state = sp2
Cl Be Be Cl Planar
Cl electron deficient molecule

(c) (BeCl2)n (polymer of BeCl2 in solid state)

Cl Cl Cl Hybridisation state = sp3d2
Be Be Be Non-planar
Cl Cl Cl octet complete

6
 P-BLOCK ELEMENTS
(d) I2Cl6 (dimer of ICl3)
Cl Cl x y Cl Hybridisation state = sp3d2
I I Planar
super octet complete (12 electrons)
Cl Cl Cl

Note :
(i) BCl3, BBr3 & BI3 do not form dimer due to smaller size of boron & large size of halogen (due to more steric
repulsion)
(ii) BF3 cannot form dimer due to its back bonding.
(iii) AlF3 cannot form dimer due to its ionic nature.

(III) Inert Pair Effect

Group-13 Group-14 Group-15
2 1 2 2 2 3
(group oxidation state) ns np ns np ns np
+3 +4 +5

y While moving down the group the stability of lowe oxidation state (2 less than group oxidation state) progressively
increases, for the last element of the group the stability of lowe oxidation state becomes even greater then
group oxidation state. This is called inert pair effect.
y For the last element group oxidation state is highly oxidising in nature.
Group- 13 Group-14 Group-15
B +3 C +4 N +5
Al +3 Si +4 P +5
-------------------------------------------------------------------
Ga +3 > +1 Ge +4 > +2 As +5 > +3
In +3 > +1 Sn +4 > +2 Sb +5 > +3
Tl +3 < +1 Pb +4 < +2 Bi +5 < +3

Reason : As we move down the group there is presence of d & f-orbitals in inner shells which have poor shielding
effect hence Zeff increases. As a result the ns2 electron pair becomes more and more tightly held to the nucleus and
becomes reluctant to participate in bonding.

Examples :
1. PbCl2 is more stable than PbCl4. 2. TiCl is more stable than TiCl3
2. GaCl3 is more stable than TiCl3 4. SnCl4 is more stable than PbCl4
5. TlI3 does not exist. 6. PbI4 does not exist.
Ex. Only BiF5 exists but BiCl5 does not exist?

Bi5  5F– 
Sol. (Oxidising o BiF5
) (Less reducing ) (Stable)

2e–
Bi+5 5Cl– Bi+3 + 3Cl– + Cl2
Oxidising Reducing

7
CHEMISTRY FOR NEET & AIIMS
(IV) OXYACID
General Formula of Oxy acdi : HxZyOz (Z = non metal)
y Compounds which contain Z-OH bond are known as oxyacids.

y Acidic oxide
or + H2O Oxyacids
Non metallic oxide
Anhydrides of oxyacids

CO2 + H2O
H2CO3

(So CO2 is anhydride of H2CO3)
SO3 + H2O
H2SO4
Cl2O7 + H2O
2HClO4
Mn2O7 + H2O
2HMnO4
Permanganic acid
Anhydrides of their CrO3 + H2O
H2CrO4
corresponding oxyacids Chromic acid

N2O5 + H2O
2HNO3

N2O4 + H2O
HNO2 + HNO3 (Special case)
(N2O4 is mixed anhydride of HNO2 & HNO3)
Cl2O6 + H2O
HClO3 + HClO4
(Cl2O6 is mixed anhydride of HClO3 and HClO4)

y Oxidation state of central atom does not change.

Pyro Meta Per Hypo

2 mole oxy acid 1 mole oxy acid oxy acid

-H2O -H2O
us acid ic acid
-O -O
pyro acid meta acid Z—O—O—H
Hypo us acid Hypo ic acid

Ex. H2S2O5 Ex. HPO3 Ex. H2SO5 Ex. HOX Ex. H4P2O6
H2S2O7 HBO2 H2S 2O8 H3PO2
H4P2O7 HNO4
CH3CO3H
C6H5CO3H

Oxy Acids of Sulphur

sulphurous acid sulphuric acid peroxodi sulphuric acid (Marshall’s) pyro sulphuric acid
O O O O O
S
S S S S S
HO O
O O O O O O O O
HO HO
HO HO HO HO HO

8
 P-BLOCK ELEMENTS

Peroxo monosulphuric acid

(Caro acid)
O
Thiosulphuric acid Pyrosulphurous acid
O O O
S
HO S OH HO S S OH
O S S
HO
O

HO

Oxy Acid of Phosphorus

Hypo phosphorous
Phosphoric acid Phosphorous acid Hypo phosphoric acid
acid
O O O O O
(i) HO P OH (ii) HO P OH (iii) HO P H (iv) HO P P OH
OH H H OH OH
Pyro phosphoric acid Pyro phosphorous acid
O O O O Meta phosphoric acid
O
(v) HO P O P OH (vi) HO P O P OH (vii)
O P OH
OH OH H H

Oxy Acids of Halogens

Hypohalous Halous Halic Per halic

O O
HO—X O=X—OH HO X HO X O
O O
+1 +3 +5 +7
HOCl HClO2 HClO3 HClO4
HOBr — HBrO3 HBrO4
HOI — HIO3 HIO4

Oxy acids Containing s-s Linkage

Polythionus Polythionic
H2SnO4 H2SnO6
o.s.= +3 o.s.= +5
O O O O
HO S (S)n S OH HO S (S)n S OH
O O
[Number of S-S linkage = number of sulphur atom-1]

9
CHEMISTRY FOR NEET & AIIMS

Important points : H2S2O3

H2S2O4 (S-S bond)
H2S2O5
H2S2O6
H2S2O7 [S-O-S]
H2S2O8 [S-O-O-S]

Trick for drawing structure of oxy compound

Oxy Group
compounds present
–q
X2O6 [X-X]
X2O7
–q
[X-O-X]
X2O8
–q [X-O-O-X]

Some important points :

(i) Oxy acid of phosphorus having +1 & +3 oxidation state (having P-H bond) can act as reducing agent or give
disporportionation reaction on heating.
3 5 3
H 3PO3 
'
o H 3 PO 4  PH 3
H3PO3 + Ag2O o H3PO4 + 2Agp

Order of reducing nature.

H3PO2 > H3PO3 > H3PO4

Two P – H OneP – H ZeroP – H
bonds bond bond
Note : Nitrogen compound having +1 & +3 oxidation state gives disporportion to reaction in acidic medium.
3  5 2
HNO 2 o
H
HNO3  NO

(ii) Heating effect of phosphoric acid

200°C 600°C
2H3PO4 -H2O
H 4 P 2O 7 -H2O
H 2 P 2O 6 P2O 5

(HPO 3)2

100°C
(iii) Heating effect of boric acid 2H3BO3 2HBO2 B2O3
-2H2O

(iv) SO3 exists as a cyclic trimer (S3O9)

O O
S sp3
O O 6 S=O bonds
3 S–O–S bonds
O O sp3 hybrid 'S', Non planar
S S
O O O

10
 P-BLOCK ELEMENTS
(v) Metaphosphoric acid exists as dimer, cyclic trimer or polymer

(HPO3)2 (HPO3)2 (HPO3)n

O O O O OH
O O O
P P P
HO O OH O O —O – P – O – P – O – P – O —

O P P O OH OH OH
O OH
HO Basic unit

(vi) Acidic nature of oxy acids.

General concept :
§ Acidic nature Oxidation number of ·
For same elements ¨ v ¸
© of oxyacids active element ¹
(Acidic nature of oxyacids v EN of active element) for different elements

Exception :
y for oxy acids of P
§ 1 ·
¨ Acidic nature v ¸
© Oxidation number ¹
Example : H3PO2 > H3PO3 > H3PO4 (acidic order)

(V) Hydrolysis
Chemical reaction of H2O with a covalent compount.
Condition :
One atom must posses vacant orbital and positive charge.
Mechanism : (SN2 mechanism)
–
2e
-HL
H2O + A L A – OH
Leaving Product
group
(weaker base)

y Weaker base goes out and a stronger base substitutes it.

Example :
H H
Cl Cl O OH OH
-2HCl
B +
+ H2O B OH2 -Cl–
B -H+
B B
Nucleophile +2H2O
Cl Cl Cl Cl Cl Cl Cl Cl HO HO

y For hybridisation of transtion state

Reactant o Transition state
Ex. : sp o sp2
sp2 o sp3
sp3 o sp3d

11
CHEMISTRY FOR NEET & AIIMS
Important examples of hydrolysis
1. Hydrolysis of some important covalent molecules.
(a) BeCl2 + 2H2O o Be(OH)2 + 2HCl
(b) MgCl2 + 2H2O o Mg(OH)2 + 2HCl
(c) BCl3 + 3H2O o B(OH)3  3HCl
or H3 BO3
(orthoboric acid )

(d) PCl3 + 3H 2O P(OH)3 + 3HCl

O–H O
P
P (P=O is more stable than P–O bond)
HO OH HO OH
OH
(Hydrolysis + Tautomerism) (H3PO3) (Phosphorous acid)
(Basicity = 2)

(e) AsCl3 + 3H2 O As(OH)3 + HCl

OH
No tautomerism & only hydrolysis
As (As=O is not formed due to large size of As)
HO OH

(f) AlCl3 + 3H 2O Al(OH)3 + 3HCl

(steam) (white gelatinous
ppt)

+3 –
AlCl3 + 3H2O [Al(H 2O)6] + 3Cl
(normal) Ionic compound
due to hydration

(g) PCl5 + H2O PCl3 (Cl2) + H2 O POCl3 + 2HCl

two axial
bonds

O O
P + 3H2O P + 3HCl
Cl Cl HO OH
Cl OH
H3PO4 = phosphoric acid

• Hydrolysis is not a redox reaction

Cl
(h) N–Cl + H2O NH 3 + 3HOCl
Cl 3d
(vacant)
(Hypochlorous
acid)

(i) NF3 + H 2O No reaction

• Partial hydrolysis

(j) SbCl3 + H2O SbOCl + 2HCl

(Antimonyl
due to ionic chloride)
character
(k) BiCl3 + H2O BiOCl + 2HCl
(Bismuthyl
chloride)
(white ppt also known
as white pearl)

12
 P-BLOCK ELEMENTS
2. Hydrolysis of interhalogen compounds
(a) Type xx’ : Cl – F + H 2O HF + HOCl
Halogen Oxy acid
acid (Hypochlorous
acid)

x = oxy acid (same oxidation number)

x' = Halogen acid
(b) Type xx'3 : ClF3 + H2O HF + HClO2
(Chlorous acid)

(c) Type xx'5 : ClF5 + H2O HF + HClO3

(Chloric acid)

(d) Type xx'7 : IF7 + H2O HF + HIO4

(Periodic acid)

(VI) Bleaching Agents and dehydrating Agents

(A) Bleaching Agents
y Bleaching can be done by oxidation or reduction.
[O]
y Coloured substance Oxidation
Colourless (Permanent bleach)

[H]
y Coloured substance Reduction
Colourless (Temporary bleach)
air
[O]

Examples :
By oxidation By Reduction
(1) O3 (Dry bleach) SO2 (with moisture)
(2) H2O2 (with moisture)
(3) Cl2 (with moisture)

y Bleaching powder : Used in textile inductries. Bleaches by oxidation.

CaCl2 . Ca(OCl)2 . Ca(OH)2 . 2H2O (average oxidation number of Cl = 0)
or
+1
O Cl
Ca (Oxidation number of Cl = +1 and –1)
Cl
–1

(B) Dehydrating Agents

Ex : [P4O10, (Conc.) H2SO4, CaO (Quick line), CaCl2 (Anhydrous)]
dehydrating
y Acid agent
H2O + Oxide
Ex :
conc.
y HCOOH H2SO4
H2O + CO (Lab preparation of CO)

COOH conc.
y H2SO4
CO + CO2 + H2O (Lab preparation of CO & CO2)
COOH

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CHEMISTRY FOR NEET & AIIMS

COOH
conc.
y CH2 H2SO4
2H2O + O = C=C=C=O (Carbon suboxide)
COOH
[Malonic acid]

2HClO4  o H2O + Cl2O7

PlO10
y

2HNO3  o H2O + N2O5

PlO10
y
y Charring of sugar (dehydration ) :
conc.
C12H22O11 H2SO4
11 H2O + C (Black mass)

Some extra points :

(i) NH3 can be dried by conc. H2SO4, P4O10 and CaCl2.
(ii) Alcohols, phenols can not be dried by metal hydrides.
(iii) MgCl2.6H2O and AlCl3.6H2O can not be dried heating alone.

BORON FAMILY
Physical properties of boron:
y Boron is non-metallic in nature.
y It is extremely hard and black coloured solid. It exists in many allotropic forms.
y Due to very strong crystalline lattice, boron has unusually high melting point.
y Rest of the member are soft metals with low melting point and high electrical conductivity. Gallium with low
melting point (303 K), could exist in liquid state during summer. Its high boiling point (2676 K) makes it a useful
material for measuring high temperatures.

Extraction of boron :
Amorphous boron of low purity (called moissan boron) is obtained by reducing B2O3 with Mg or Na at a high
temperature. It is 95–98% pure (being contaminated with metal borides), and is black in colour.
acid heat Mg or Na
Na2[B4O5(OH)4].8H2O H3BO3 B2O3 2B + 3 MgO
It is difficult to obtain pure crystalline boron, as it has a very high melting point (2180ºC) and the liquid is corrosive.
Small amounts of crystalline boron may be obtained :
(a) By reducing BCl3 with H2. This is done on the kilogram scale.
(b) Pyrolysis of Bl3 (Van Arkel method).
(c) Thermal decomposition of diborane or other boron hydrides.
red hot W or Ta filament
2BCl3 + 3H2 2B + 6HCl
red hot W or Ta filament
2BI3 2B + 3I2
Van Arkel

heat
B2H6 2B + 3H2

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 P-BLOCK ELEMENTS
Chemical Property of Boron :
(a) Burning in air
4B + 3O2 2B2O3
(b) Reaction with water
cold & hot
B + H2O No reaction
2B + 3H2O Red hot B2O3 + H2
(c) B + HCl No reaction
B + H2SO4 dil. No reaction
2B + 3H2SO4 conc. 2H3BO3 + 3SO2
B + 3HNO3 H3BO3 + 3NO2
(d) 2B + 2NaOH + 2H2O 2NaBO2 + 3H2
(e) 2B + N2 2NB
4B + C B4C
(f) 3Mg + 2B Mg3B2

COMPOUNDS OF BORON
(I) Boranes
Boranes are boron hydrogen compounds with general molecular formula BnHn+4 or Bn Hn+6.They are electron
deficient compounds. The lighter boranes (upto B5) spontaneously react with air whereas remaining compound are
air stable. The physical properties of boranes are given as under :

Melting point Boiling point

Formula Name
°C °C
B2 H6 Diborane – 165.6 – 92.5
B4 H10 Tetraborane – 120 18
B5 H9 Pentaborane -9 – 46.6 48
B5 H11 Pentaborane -11 – 123 63
B6 H10 Hexaborane -10 – 62.5 110
B6 H12 Hexaborane -12 – 82.3 80-90
B8 H12 Octaborane -12 – 20 —
B8 H14 Octaborane -14 – 20 —
B9 H15 Enneborane 2.6 —
B10 H14 Decaborane 99.7 213
B20 H16 Isosaborane-16 196.2 —

Preparation of Diborane :
(a) Mg3B2 + HCl B2H6 + B4H10 + B5H9 etc.
(10%)
'
(b) B4H10 100° C
B2H6 + H2 + higher borane

Electric
(c) 2 BCI3 (or B Br3) + 6 H2 B2H6 + 6HCl
discharge at low pressure

(d) 3Li AlH4 /LiBH4 + 4BF3 3LiF/3BF3 + 3 AlF3 + 2 B2H6

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CHEMISTRY FOR NEET & AIIMS
Chemical Properties :
(a) B2 H6 + O2 burns in B2O3 + H2O
air spontaneously
cold is enough
(b) B2H6 + H2O H3BO3 + 6H2
(c) B2H6 + 2KOH 2KOBH2 + 2H2
anh.
(d) B2H6 + HCl B2H5Cl + H2
AlCl 3
dry

Structure of diborane :

Structure of diborane (B2H6)

The structure of diborane is shown in fig. The four terminal hydrogen atoms and the two boron atoms lie in one
plane. Above and below this plane, there are two bridging hydrogen atoms. The four terminal B-H bonds are regular
two centre-two electron bonds while the two bridge (B-H-B) bonds are different and can be described in terms of
three centre - two e– bonds.
Bonding in diborane :– Each B atom uses sp3 hybrids for bonding. Out of the four sp3 hybrids on each B atom, one
is without an electron shown in broken lines. The terminal B-H bonds are normal 2c-2e bonds but the two bridge
bonds are 3c-2e bonds. The 3c-2e bridge bonds are also referred to as banana bonds or tau bonds.

(II) Boric acid

Structure of boric acid –

H
O

H B
O O
H H
O O
H B H H
O O
H O
B H
O H B
O O O
H H
Structure of boric acid, the dotted lines
represent hydrogen bonds

16
 P-BLOCK ELEMENTS
Preparation :
It is prepared by borax reacting with sulphuric acid.
Na2 B4O7 + H2SO4 + 5H2O o Na2SO4 + 4H3 BO3

Physical Properties :
(a) Its crystals are soft, white, needle like having a soapy touch.
(b) It is steam volatile.

Chemical Properties :
(a) Ortho boric acid does not donate proton, like most of the acids but rather it accepts OH–, therefore it is a lewis
acid and is represented by B(OH)3.
B(OH) + 2H O YZZ ZZZ XZ H O+ + [B(OH) ]– ( Pk = 9.25)
3 2 3 4 a

(b) B(OH)3 partially reacts with water to form H3 O+ and [B(OH)4–] and behaves as a weak acid. Thus B(OH)3 can
not be titrated satisfactorily with NaOH because a sharp end point is not obtained. If polyhydroxy compound
like glycerol, mannitol or sugar are added to titration mixture than it can be titrated with NaOH.
B(OH)3 + NaOH o Na[B(OH)4]
(c) Effect of temperature at 100°C H3BO3 losses water and convert into metaboric acid.
H3BO3 100°C HBO2 + H2O
metaboric acid form tetraboric acid on heating at 160° C.
4HBO2 160°C H2B4O7 + H2O
On strong heating B2O3 is produced
H2B4O7 o2B2O3 + H2O
(d) Boric acid react with ethyl alcohol to form ethyl borate which burns with green edged flame.
H3BO3 + 3C2H5OH o B(OC2H5)3 + 3H2O

Structure of orthoboric acid OH

At lower concentration, its structure is a plane triangle. B
OH OH
(III) Borax Plane triangle
PREPARATION :
(a) In making glass, enamel and glaze of pottery.
(b) As antiseptic in medicinal soaps preparation.

17
CHEMISTRY FOR NEET & AIIMS
(c) Orthoboric acid on neutralization with Na2CO3 gives borax.
Na2CO3 + 4H3BO3 oNa2B4O7 + 6H2O + CO2
(d) Colemanite is converted into borax by boiling it with concentrated solution of Na2CO3.
Ca2B6O11 + 2Na2CO3 o Na2B4O7 + 2CaCO3 + 2NaBO2.

Chemical Properties :
The solution of borax is alkaline in nature due to hydrolysis.
Na2B4O7 + 7H2O o 2NaOH + 4H3BO3

ALUMINIUM
Properties :
(a) Burning in air
4Al + 3O2 o2Al2O3
(b) Reaction with water

3
Al + 3H2O o Al (OH)3 + H
2 2
(c) 2Al + 6H2SO4 o Al2(SO4)3 + 3SO2 + 6H2O
Al + HNO3 o Al2O3 (passive layer) and does not react further.
(d) 2Al + 2NaOH + 2H2O o 2NaAlO2 + 3H2
(e) 2Al + N2 o 2AlN
4Al + 3C o Al4C3

COMPOUNDS OF ALUMINIUM
(I) Aluminium chloride (AlCl3)
(a) Hydrated AlCl3 oAlCl3.6H2O
(i) AlCl3 is prepared by dissolving aluminium oxide or its hydroxide in dilute HCl.
Al2O3 + 6HCl o2AlCl3 + 3H2O
Al(OH)3 + 3HCl oAlCl3 + 3H2O

(b) Anhydrous AlCl3

(i) Anhydrous aluminium chloride can be obtained by passing dry chlorine gas and dry HCl gas over heated
aluminium in vaccum.
2Al + 3Cl2(dry) o 2AlCl3
(ii) Macaffe's process - The anhydrous salt is prepared by heating alumina with coke and chlorine.
Al2O3 + 3C + 3Cl2 o 2AlCl3 + 3COn
(dry)
Properties :
(a) Aluminium chloride is a white crystalline substance which fumes in moist air. It fumes in moist air due to its
hydrolysis.
AlCl3 + 3H2O o Al(OH)3 + 3HCln
(b) On heating it sublimates at 1800C.
(c) At sublimation point its vapour density corresponds to formula Al2Cl6 i.e, it exists as a dimer. At higher
temperatures i.e, above 7500C it exists as a monomer AlCl3.
(d) It is largely covalent hence it does not conduct current in fused state.

18
 P-BLOCK ELEMENTS
USES of AlCl3
Anhydrous AlCl3 is employed as a catalyst in organic reactions i.e, Friedal crafts reaction.
(II) Alum
(a) Alums are double sulphates with their general formula R 2 SO 4 .M 2 (SO 4 ) 3 .24H 2 O where
R = monovalent radical like Na+ , K+, NH4+ and M = Trivalent radical like Al+3, Cr+3. Fe+3.

(b) The different alums are -

(i) Potash alum – K2SO4.Al2 (SO4)3.24H2O
(ii) Chrome alum – K2SO4 Cr2(SO4)3. 24 H2O
(iii) Iron alum – (NH4)2SO4. Fe2(SO4)3. 24H2O
(iv) Ammonium alum – (NH4)2SO4. Al2(SO4)3. 24H2O
(c) In alums each metal ion is surrounded by six water molecules.
(d) Lithium does not form alum because Li ion is too small to have a coordination number of six.

PROPERTIES :
(a) It is a white crystalline solid highly soluble in water.
(b) On heating it undergoes dehydration and swells up.
(c) It is highly acidic in aqueous solution due to the hydrolysis of aluminium sulphate to sulphuric acid
(d) It is a double salt and its aqueous solution gives reaction of all the constituents ions K+, Al+3, SO4–2.

USES :
(a) Alum is used to stop bleeding.
(b) It is used for purification of water.
(c) It is used as a mordant in dyeing industry.
(d) Alum is used for tanning of leather.

CARBON FAMILY
Physical Properties :
y All group 14 members are solids.
y Carbon and silicon are non-metals, germanium is metalloid whereas tin and lead are soft metals with low melting
points.
y Melting points and boiling points of group 14 elements are much higher than those of corresponding elements
of group 13 due to stronger metallic bonding.

Allotropes of Carbon

Crystalline Amorphous
Ex. Diamond Ex. Cake
Graphite Charcoal
Fullerin Coal

Allotropic form of carbon

(A) Crystalline
(a) Diamond
(i) Three dimensional polymeric structure.
(ii) In diamond each carbon is in sp3 hybridized state and is linked to four other neighbouring carbon atoms held
at the corners of a regular tetrahedron by covalent bonds.

19
CHEMISTRY FOR NEET & AIIMS
(iii) In this structure C-C distance is 1.54 Å with a bond angle of 109.5°.
(iv) Due to these strong covalent bonds, diamond is the hardest
1.54 Å
substance having abnormally high melting point (3600° C) and is
extremely inert, chemically.
(v) It has very high refractive index (2.5), i.e. light rays are slowed
down by the tightly bound electron.
(vi) Due to unavailability of mobile electrons it is non-conductor of
electricity.
Crystal structure of diamond
(b) Graphite
(i) Unlike diamond, it has a two dimensional laminar structure.
(ii) The adjacent layers of sheet are held together by weak vander Waal forces.
(iii) Here each carbon atom is in sp2 hybridised state and is thus attached to three other carbon atoms by three V
bonds forming a hexagonal planar structure.
(iv) The fourth electron present in an unhybridised p-orbital of each carbon atom of a hexagonal unit then overlap
with each other to form a pi bond.
(v) The C—C bond length in graphite is shorter (1.42 Å) than that of diamond (1.54Å).

1.42 Å

3.4 Å

Structure of graphite

(vi) Since S-electrons (S – e–) are free to move throughout the entire layers, graphite is a good conductor of
electricity. Its conductivity increases with temperature.
(vii) It is a soft greasy, dark greyish coloured crystalline solid having density 2.5 g mL–1
(viii) Since it leaves a black mark on paper it is called black lead or plumbago.
(ix) It is thermodynamically more stable than diamond and its free energy of formation is 1.9 kJ less than diamond.
1600°C
Graphite diamond
50,000 - 60,000 atm

(x) Aqueous solution of graphite is known as aquadag.

(xi) Graphite use as dry lubricants.

(c) Fullerenes
(i) Discovered by smily & robert curl (Noble prize - 1996)
(ii) Fullerene normally contain C60 with smaller quantity of C70

20
 P-BLOCK ELEMENTS
Structure of C60
(i) C60 is also called buckminster fullerene in honour of robert
buckminster fuller.
(ii) Shape of C60 is Soccer ball & C70 is Rugby ball.
(iii) C70 & C60 having hexagonal & pentagonal unit.
12 Pentagonal
(iv) There are 32 rings 32
20 hexagonal
(v) Each carbon atom bonded with 3 other carbon by sigma and
double bond (resonance)
(vi) sp2 hybridization and aromatic in nature.

Dangling Bond : In diamond or graphite some surface carbon atom have free valency. These carbon atoms form new
bonds with impurities. These new bonds are known as dangling bond.

(B) Amorphous
Coal
(a) Naturally form & artificially.
(b) It is found in different form.
Ex. Peat, Lignite, Bituminous, Anthracite
(c) Max percent of C = Anthracite Min percent of C = Peat
(d) Calorific value Max in = Anthracite

COMPOUNDS OF CARBON
(I) Carbides
Carbides are of three types according to the type of bonding
(a) Salt like carbides (ionic bonding)
(i) These are formed by strong electropositive elements of groups 1, 2 and 13
(ii) These are transparent crystalline substances and do not conduct electric current in the solid state.
(iii) These are easily hydrolysed by water or dilute acids to give aliphatic hydrocarbons,

Methanides (Methides) : Methanides are the carbides which give methane on hydrolysis. They contain C4– ions.
Be2C + 4H2O o 2Be (OH)2 + CH4
Al4C3 + 12H2O o 4Al (OH)3 + 3CH4
Acetylides : These are the carbides which yield acetylene on hydrolysis. They contain the ion C 22 
Ex. CaC2, BaC2 and MgC2
CaC2 + 2H2O o Ca(OH)2 + C2H2 or C 22  + 2H+ o C2H2
Note: Most of these carbides have ionic NaCl - type of structure.
Allylides : These carbides give methylacetylene or allylene (CH3 – C {CH). On hydrolysis they contain C 34  ions.
The only example of this class is Mg2C3
Mg2C3 + 4H2O o2Mg(OH)2 + CH3 — C { CH

(b) Covalent carbides (giant molecular structure)

(i) Covalent carbides are the compounds of carbon with elements having similar electronegativity.
(ii) These are covalent, polymeric, thermally stable, extremely hard, high melting and technically inert solid.
(iii) B4C and SiC are two main covalent carbides.

21
CHEMISTRY FOR NEET & AIIMS
(c) Alloy type or interstitial type carbide
Transition metals like Ti, Zr, Hf, V, Nb, Ta and Mo form these carbides. The metals retains their close packed
lattice and carbons are incorporated in their interstitial spaces.These carbides are extremly hard and have very
high melting points. The carbides of V and Ta are very hard hence they are used for manufacture of high speed
cutting tools.

(II) Carbon monoxide (CO)

PREPARATION :
(a) It is invaribely present in automobile exhaust gas.

1
C(s) + O (g) o CO(g)
2 2
(b) Pure CO
H2SO4
HCOOH CO + H2O
(c) Industrially it is obtained in the form of water gas and producer gas when air (moist) is passed over a bed of
white hot coke.
2 C + O2+4N2 o2CO + 4N2
C + H2O oCO + H2 (water gas)

PROPERTIES :
(a) It is highly poisonous as it combines with haemoglobin to form carboxy haemoglobin which is not capable to
absorb oxygen.
(b) It burns with blue flame to form CO2. This is an exothermic process
2 CO + O2 o2CO2 + Heat
(c) Chemical reactions

Fe2O3
2Fe+3O2
600°–900° C
CO COCl2 (Phosgene)
Cl2 Sun light
NI(CO)l4 (mond's process)
Ni 80°C

How to detect
Burns with blue flame CO is passed through PdCl2 solution giving rise to black ppt.
CO + PdCl2 + H2O o CO2 n+ Pd p + 2HCl
Black metallic deposition
How to estimate
I2O5 + 5CO o I2 + 5CO2

I2 + 2S2O 23  o 2I– + S4O 26 

What are its absorbers

Cu2Cl2 : CuCl + CO + 2H2O o [CuCl(CO) (H2O)2]

22
 P-BLOCK ELEMENTS
(III) Carbon Dioxide (CO2)
PREPARATION :
(i) Complete combustion of carbon containing compounds.
CH4 + O2 o CO2 + H2O
(ii) In the laboratory it can be conveniently made by the action of dilute hydrochloric acid on marble chips :
CO32–(aq) + 2H+(aq) o CO2(g) + H2O (A)
(iii) Industrially it is produced as a by-product during the manufacture of quicklime and in fermentation processes :
CaCO3(s) o CaO(s) + CO2(g) ; C6H12O6 (aq){glucose} o 2C2H5OH(aq) + 2CO2 (g)

PROPERTIES :
(i) It is a colourless, odourles and heavy gas.
(ii) Carbon dioxide is the acid anhydride of carbonic acid, which is weak dibasic acid and ionises in two steps as
follows :
H2CO3(aq) + H2O (A) U HCO3–(aq) + H3O+ (aq)
HCO3– (aq) H2O (A) U CO32– (aq) + H3O+ (aq)
H2CO3/HCO3– buffer system helps to maintain pH of blood between 7.26 to 7.42.
A solution of carbonic acid in water will slowly turn blue litmus red and when the solution is boiled, all the CO2
is evolved.
(iii) Carbon dioxide readily reacts with alkalies forming the carbonate and, if CO2 is in excess, the hydrogen
carbonate. This is the basis of the lime-water test for CO2 gas.
Ca(OH)2(aq) + CO2(g) o CaCO3(s) + H2O (liq) ; CaCO3(s) + H2O(liq) + CO2(g) o Ca(HCO3)2(aq)
The above reaction accounts for the formation of temporarily hard water.
(iv) Gaseous CO2 is extensively used to carbonate soft drinks. Being heavy and non-supporter of combustion it is
used as fire extinguisher. A substantial amount of CO2 is used to manufacture urea.

Silicon (Si)
Silicon is the second most abundant (27.2%) element after oxygen (45.5%) in the earth's crust. It does not occur free
in nature but in the combined state, it occurs widely in form of silica and silicates. All mineral rocks, clays and soils
are built of silicates of magnesium, aluminium, potassium or iron. Aluminium silicate is however the most common
constituent of rocks and clays.
Silica is found in the free state in sand, flint and quartz and in the combined state as silicates like
(a) Feldspar – K2O.Al2O3.6SiO2
(b) Kaolinite – Al2O3. 2 SiO2. 2H2O
(c) Asbestos – CaO. 3MgO.4SiO2

PREPARATION :
(a) From silica (sand) : Elemental silicon is obtained by the reduction of silica (SiO2) with high purity coke in an
electric furnace.
SiO2 (s) + 2C (s) o Si (s) + 2CO (g)

23
CHEMISTRY FOR NEET & AIIMS
(b) From silicon tetrachloride (SiCl4) or silicon chloroform (SiHCl3) : Is obtained by reduction of highly purified
silicon tetrachloride or silicon chloroform with dihydrogen.
SiCl4 (A) + 2H2 (g) o Si (s) + 4HCl (g)
SiHCl3 (s) + H2 (g) o Si (s) + 3HCl (g)

Physical Properties :
(a) Elemental silicon is very hard having diamond like Structure.
(b) It has shining luster with a melting point of 1793 K and boiling point of about 3550 K.
28 29 30 28
(c) Silicon exists in three isotopes, i.e. 14
Si, 14
Si and 14
Si but 14
Si is the most common isotope.

USES :
(a) Silicon is added to steel as such or more usually in form of ferrosilicon ( an alloy of Fe and Si) to make it acid-
resistant.
(b) High purity silicon is used as semiconductors in electronic devices such as transistors.
(c) It is used in the preparation of alloys such as silicon-bronze, magnesium silicon bronze and ferrosilicon.

COMPOUNDS OF SILICON
(I) Silicates
Silicates have basic unit of SiO44–, each silicon atom is bonded with four oxide ions tetrahedrally.

O–

Si Oxygen
O– O–
Silicon
Plane projection of silicate ion

O–

There are following types of silicates

(a) Orthosilicates : These silicates contain single discrete unit of SiO44— tetrahedral.
Ex. Willemite [Zn2SiO4]

(b) Pyrosilicates

O– O–

Si Si
O– O–
O
O– O–

These silicates contain two units of SiO44— joined along a corner containing oxygen atom. These are also
called as island silicate.
Ex. Hemimorphite Zn3(Si2O7)Zn(OH)2 · H2O, Pyrosilicates ion Si2 O76–

24
 P-BLOCK ELEMENTS
(c) Cyclic structure : Cyclic or ring silicate having general formula (SiO32–)n or (SiO3)n2n–
Structure and example of cyclic silicates containing Si3O96– and Si6O1812– ions are given below

Ex. Beryl Be3Al2Si6O18

(d) Chain silicates : Chain silicates are formed by sharing two oxygen atoms by each tetrahedral. Anions of chain
silicate have two general formula.
(i) (SiO3)n2n– (ii) (Si4O11)n6n–

Ex. Spodumene Li2Al(SiO3)2 , Tremolite Ca2Mg5(Si4O11)2(OH)2

(e) Two dimensional sheet silicates : In such silicates, three oxygen atoms of each tetrahedral are shared with
adjacent SiO44– tetrahedral, such sharing forms two dimensional sheet structure with general formula (Si2O5)n2n–
Ex. Talc Mg(Si2O5)2Mg(OH)2

(f) Three dimensional sheet silicates : These silicates involve all four oxygen atoms in sharing with adjacent
SiO44– tetrahedral.
Ex. Quartz, Zeolites and Ultramarines

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CHEMISTRY FOR NEET & AIIMS
(II) Silicones
These are organosilicon polymers containing R2SiO repeating units and empirical formula analogous to ketone (R2CO)
| |
—Si—O—Si—linkage
| |

Alkyl substituted : These are formed by hydrolysis of alkyl chlorosilanes and their polymerisation. The alkyl or aryl
substituted chlorosilanes are prepared by the reaction of Grignard reagent and silicon tetrachlorides.
Organic polymers containing silicon in them are called as silicones.
(a) Straight chain silicone
2RCl Si R2SiCl2
Cu

R Cl R

Si + 2HOH HO Si OH

R Cl R

Dialkyldichloro Silane

R R
| | R R
(b) HO — Si — OH + OH — Si — OH H2O HO Si O Si OH
| |
R R R R
The terminal 'OH' groups which are active, allow the polymerisation reaction to continue and the length of the
chain continues to increase
R R R R R R
O Si O Si O Si O Si O Si O Si
R R R R R R

(c) A complex cross-linked polymer is obtained on the hydrolysis of alkyl trichloro silane.

Cl OH
3H2O
R Si Cl R Si OH
–3HCl
Cl OH

R R R R R R
| | | | | |
HO — Si — O — Si — O — Si — OH —O—Si—O—Si—O—Si—O—
| | | –3H2O | | |
O O O O O O
| | | | | |
OH OH OH
HO HO HO —O—Si—O—Si—O—Si—O—
| | | | |
HO — Si — O — Si — O — Si — OH R R R
| | |
R R R

26
 P-BLOCK ELEMENTS
(d) Cyclic (ring) silicones are formed when water is eliminated from the terminal –OH groups of linear silicones.
R R
Si
O O
R R
Si Si
R R
O
R3SiCl on hydrolysis forms only a dimer
R3SiO H + OH SiR3 oR3Si — O — SiR3

USES :
(a) They are used as greases, varnishes and resins.
(b) As they are water repellants, they are used for water-proofing.
(c) They are good electric insulators.

(III) SILICA (SiO2)

Silica or silicon dioxide occurs in nature in the free state as sand, quartz and flint and in the combined state as
silicates like Feldspar K2O.Al2O3.6SiO2, Kaolinite Al2O3. 2SiO2. 2H2O etc.

PROPERTIES :
(a) Pure silica is colourless, but sand is usually coloured yellow or brown due to the presence of ferric oxide as an
impurity.
(b) Silicon dioxide is insoluble in water and all acids except hydrofluoric acid.
SiO2(s) + 4HF (A) o SiF4(A) + 2H2O(A)
(c) It also combines with metallic oxides at high temperature giving silicates.
'
SiO2(s) + CaO (s)  o CaSiO3(s)
(d) When silica is heated strongly with metallic salts, silicates are formed and the volatile oxides are driven off as
vapours.
SiO2(s) + Na2CO3(s) o Na2SiO3(s) + CO2(g)
SiO2(s) + Na2SO4(s) o Na2SiO3(s) + SO3(g)
3SiO2(s) + Ca3(PO4)2 (s) o 3 CaSiO3 (s) + P2O5(g)
The first two examples quoted here are important in glass making.

Structures of Silica :
Silica has a three-dimensional network structure. In silica, silicon is sp3-hybridized and is thus linked to four oxygen
atoms and each oxygen atom is linked to two silicon atoms forming a three-dimensional giant molecule as shown in
figure. This three-dimensional network structure Imparts stability to SiO2 crystal and hence a large amount of
energy is required to break the crystal resulting in high melting point.
| | |
—Si—O—Si—O—Si—
| | |
O O O
| | |
—Si—O—Si—O—Si—
| | |
O O O
| | |
—Si—O—Si—O—Si—
| | |

27
CHEMISTRY FOR NEET & AIIMS
USES :
(a) Sand is used in large quantities to make the cement.
(b) Being transparent to ultraviolet light, large crystal of quartz are used for making lenses for optical instruments
and for controlling the frequency of radio-transmitters.
(c) Powdered quartz is used for making silica bricks.
(d) Silica gel (SiO2.xH2O) is used as a desiccate (for absorbing moisture) and as an adsorbent in chromatography.

Allotropes of Tin
Sn

low temp in powder form

Glass :
(a) Glass is a hard, brittle transparent, amorphous solid or supercooled liquid made up of silicates of Na, Ca and
other metals like Pb, Zn etc.
(b) Being amorphous solid (not a true solid) it has not sharp melting and melts at high temperature.
(c) Glass has no definite chemical formula, however it may be represented as :
xM2O.yM'O.6SiO2
where M = monovalent metals (eg : Na, K)
M' = bivalent metals Ca, Pb, Zn etc. x and y are integers.
(d) CaO + Na2CO3 + 6SiO2 
1700K
o Na 2SiO3  CaSiO 3  4SiO 2  CO 2
Glass

Different Types of Glass

(i) Soda or Soft glass or Sodalime glass : It is common glass. Contain Na & Ca metal carbonate. Used for formation
of tube, window.

(ii) Potash or Hard glass : It is a mixture of potassium and calcium silicates. It fuses with difficulty. It is used for
making hard glass aparatus.

(iii) Flint glass : It is mixture of potassium and lead silicates. It has a very high refractive index and is used for
making electric bulbs and optical instruments.

(iv) Crooke’s glass : It is a optical glass containing CeO2 which prevents the entry of UV rays.

(v) Pyrex glass or borasil or borosilicate glass : It is used to make lab appliances as it is resistant to heat, shock
and common reagents. It is a mixture of zinc and barium boro silicates and alumina silicate.
Small part of SiO2 is replaced by boric oxide/borax.
Low coefficient and thermal expansion, can with stand sudden change in temperature so used for making lab
glass wares.

Some Gaseous Fuels

(a) Water gas or syn gas = CO + H2 (b) Producer gas = CO + N2
(c) Semi water gas = CO + N2 + H2 (d) Natural gas = CH4
(e) Coal gas = [CO2 + CO + H2 + CH4]

28
 P-BLOCK ELEMENTS

KEY POINTS
Reactivity towards halogen :
Element in pure state Type of bonding Meling Point
C Covalenet 4100°C
Si Covalent 1420°C
Ge Covalnet 945°C
Sn Metallic 232°C
Pb Metallic 327°C
On moving down the group from carbon to lead stability of +4 oxidation state decreases while stability of +2
oxidation state increases andd hence decreases oxidising power decreases down the group due to inert pair effect.
These elements form two types of hallides – MX2 and MX4. Most of the MX4 are covalent. SnF4 and PbF4 are
ionic in nature.
Thermal stability decreases with increasing atomic size of molecular mass of tetrahalide or due to decreasing
polarity.
CX4 > SiX4 > GeX4 > SnX4 > PbX4 and
CF4 > CCl4 > CBr4 > Cl4
In these compounds :
Hybridisation o sp 3
Geometry o Regular tetrahedral
Polarity o NON-POLAR
Bond angle o 109° 28c
PbI4 is not stable as is strong reducing agent which reduces Pb+4 to Pb+2 and also stability of +4 oxidation state
I–
of Pb is lesser than +2 state.

Hydrolysis of halides
The chlorides except CCl4 are hydrolysed readily by water

SiCl4 + H2O o Si(OH) 4  4HCl

Silicie acid

Hydrolysis of silicon tetrafluoride gives silica and fluorosilicic acid

3 SiF4 + 4H2O o Si(OH) 4  2H 2SiF6

(Silica acid ) ( Fluorosilicic acid)

Due to unavailability of vacant d-orbitals, carbon tetrahalides cannot increase its co-ordination number hecne
does not form complexes while those having vacant d-orbitals form.

Sodium Zeolite [Na2Al2Si2O8] / [Na2O.Al2O3.2SiO2]

(i) It is a 3-D silicate
(ii) It is used in
(a) For softening of hard water
(b) For cracking of hydrocarbon & isomerisation
Ex. ZSM-5 (Zeolite) is used to convert ethyl alcohol into petrol.

29
CHEMISTRY FOR NEET & AIIMS
NITROGEN FAMILY
Physical Properties :
y Dinitrogen is a diatomic gas while all others are solids.
y Except nitrogen, all the elements show allotropy.
y As we go down the group, there is a shift from non-metallic to metallic through metalloidic character. Nitrogen
and phosphorus are non-metal, arsenic and antimony are metalloid and bismuth is a typical metal.

Chemical Properties :
(1) Oxidation States and trends in a chemical reactivity :
y The common oxidation states of these elements are – 3, +3 and +5. The tendency to exhibit –3 oxidation state
decreases down the group, bismuth hardly forms any compound in –3 oxidation state.
y Nitrogen also exhibits + 1, +2, +4 oxidation states when it reacts with oxygen. Phosphorus also shows +1 and +4
oxidation states in some oxyacids.
y In the case of nitrogen, all oxidation states from +1 to +4 tend to disproportionate in acid solution.
For example, 3HNO2 o HNO3 + H2O + 2NO
y Similarly, in case of phosphorus nearly all intermediate oxidation states disproportionate into +5 and –3 both in
alkali and acid. However +3 oxidation state in case of arsenic, antimony and bismuth become increasingly stable
with respect to disproportionation.

(2) Reactivity towards halogens :

y These elements react to form two series of halides : EX3 and EX5.
y All the trihalides of these elements except those of nitrogen are stable. In case of nitrogen, only NF 3 is known to
be stable. Trihalides except BiF3 are predominantly covalent in nature.

(3) Reactivity towards Hydrogen :

y All Group 15 eleements form hydrides of the type EH3. (E = N, P, As, Sb or Bi.)
NH3, PH3, AsH3, SbH3, BiH3
Thermal Stability decreases
Bond dissociation enthalpy decreases
Basicity decreases
Reducing character increases
Bond angle decreases

Boiling Point : PH3 < AsH3 < NH3 < SbH3 < BiH3.

Table : Properties of Hydrides of Group 15 elements

Property NH3 PH3 AsH3 SbH3 BiH3

Melting point / K 195.2 139.5 156.7 185 –
Boiling point / K 238.5 185.5 210.6 254.6 290
(E–H) Distance / pm 101.7 141.9 151.9 170.7 –
HEH angle (°) 107.8 93.6 91.8 91.3 –
'f HT / kJ mol–1 –46.1 13.4 66.4 145.1 278
'diss HT(E–H) / kJ mol–1 389 322 297 255 –

30
 P-BLOCK ELEMENTS
(4) Reactivity towards Oxygen :
All Group 15 elements form oxides of type E2O3 and E2O5. The oxide in higher oxidation state is more acidic than
in lowe oxidation state. In a particular state the acidic character decreases down the group.
Oxides of E2O3 type of N and P – Purely acidic
As and Sb – Amphoteric
Bi – Basic
Tendency to form pentoxide decreases down the group due to inert pair effect.

Oxides :
Acidic Character Increases
N2O NO N2O3 NO2 N2O5

Acidic Character Decreases

P2O3 P2O5

As2O3 As2O5

Sb2O3 Sb2O5

Bi2O3 Bi2O5

* NO2 is mixed anhydride

(I) Nitrogen (N2)

PREPARATION :
'
(a) NH4NO2 N2 + 2H2O
'
(b) (NH4)2Cr2O7 N2 + 4H2O + Cr2O3
'
(c) Ba(N3)2 Ba + 3N 2 ½ Purest N2 obtained
' ¾
2NaN3 2Na + 3N2 ¿ by this method
'
(d) 2 NH3 + 3NaOCl N2 + 3NaCl + 3H2O

(e) 2NO + 2Cu 

o 2CuO+ N 2
red over heated Black
(f) Cl2 passed into liquor NH3
3Cl2 + 2NH3 o N2 + 6HCl
6NH3 + 6HCl o 6NH4Cl
-----------------------------------------------------
3Cl2 + 8NH3 o N2 + 6NH4Cl
In this method NH3 conc. should not be lowered down beyond an particular limit.
3Cl2 + NH3 o NCl3 + 3HCl
(Trimendously explosive)

PROPERTIES
(a) It is inert due to high bond energy.
(b) It is absorbed by hot metal like Ca, Mg, Al etc.
3Ca + N2 o Ca3N2
2Al + N2 o 2AIN
'
Al2O3 + 3C + N2 2AIN + 3CO

31
CHEMISTRY FOR NEET & AIIMS
Inorganic graphite (BN)x : White slippery solid having 2D-sheet structure.
(BN)x 3000°C (BN)x
3–D network structure similar to diamond (Borazon) which is harder than diamond and used for dimond cutting.
'
Na2B4O7 + 2NH4Cl 2NaCl + 2NH3 + 2B2O3 + H2O
'
B2O3 + 2NH3 2BN + 3H2O

(c) N2 can be absorbed by calcium carbide at the temp around 1000ºC

1000°C
CaC2 + N2 CaNCN (It is very good fertiliser)
nitrolim

Cyanamide ion
2
N – C

N

N = C =
N
(Ca(NCN)+ C) + 3H2O oCaCO3 + 2NH3 + C

Slowly decomposes
NH2—CO—NH2
(Intermediate formed)

(II) Ammonia (NH3)

PREPARATION :

– –
(a) Nitrate or nitrite reduction : NO 3 /NO 2 + Zn /Al + NaOH o NH3 + [Zn(OH)4]2–/ [Al(OH)4]–
(b) Metal nitride hydrolysis : N3– + 3H2O o NH3n+3OH–
450°C
(c) Haber's process : N2 + 3H2 2NH3
200 - 1000 atm
 catalyst Fe/Mo
Note: NH3 can't be dried by H2SO4, P2O5 and anhydrous CaCl2 because –
2NH3 + H2SO4 o(NH4)2SO4
H2O + NH3 + P2O5 o(NH4)3PO4
CaCl2 + 8NH3 o CaCl2.8 NH3 (forms adduct)
Quick lime is used for this purpose
CaO + H2O o Ca(OH)2 (base)

½
¾ Hence nointeraction
NH3 (base) ¿
PROPERTIES :
(a) It dissolves several electropositive metals like Li, Na, K, Rb, Cs, Sr, Ba etc.
Ex. K in liq NH3 Ÿ (i) Blue in colour
(ii) Conducts electricity
(iii) Having reducing property

32
 P-BLOCK ELEMENTS

K K+ + e–

K+(NH3)n e (NH3)x It is the cause

solvated e
– for above property

K in liq
K2[Ni(CN)4] K4[Ni(CN)4]
NH 3

Squareplanar Tetrahedral

(b) Ag(NO3) (aq) + BaCl2 (aq) o AgCl p + Ba(NO3)2

Filtrate Residue
Ba(NO3)2 AgCl
liq NH 3 Ba(NO3)2
crystal –
Cl– + [Ag(NH3)2 ]+ BaCl2 ¯+[Ag(NH3)2]++NO 3

(c) CH3COOH is strong acid in liquid NH3 while in water is weak acid.
–
ZZZ
X
AcOH YZZZ AcO + H+

ZZZ
X
NH3 + H+ YZZZ NH 4 and H2O + H+ o H3O+
Basisity order NH3 > H2O
(d) Hydrolysis and Ammonolysis occurs is a same way.

SiCl4 + 4H2O o 4HCl + Si(OH)4 ' Si3O2 + 2H2O

'
SiCl4 + 8NH3 o4NH4Cl + Si(NH2)4 Si3N2 + NH3n

Rate of hydrolysis and Ammonolysis will be affected by the presence of HCl vapour & NH4Cl vapour respectively.

(e) NH4+ Salts PREPARATION

NaNO3
Gypsum suspension saturated CaCO3 + (NH4)2SO4 NH4NO3
with NH3 and CO2 passed
NaCl
NaNO2 CaCO3
NH4(NO2) NH4Cl (NH4)2CO3

33
CHEMISTRY FOR NEET & AIIMS
(III) Oxides of Nitrogen
Preparation and Properties of Oxides of Nitrogen

Formula Name Preparation & Structure Properties

Dinitrogen NH4 NO3 o N2 O + 2H2 O Colourless gas, rather
N2 O (Nitrous oxide) N{N o O (sp, Linear polar molecule) unreactive, diamegnatic
Laughing gas neutral to litmus
Nitrogen monoxide (a) 3Cu + 8HNO3 o 3Cu(NO3 )2 + 2NO Colourless gas,
(Nitric oxide) paramagnetic, Neutral to
NO Pt litmus
(b) 4NH3 + 5O2 900°C
4NO + 6H2O

Nitrogen dioxide Pb(NO3 )2 o 2PbO + 4NO2 + O2 Brown gas, reactive,

Mixed anhydride N paramagnetic, angular and
NO2 polar
132º
O O
H2O
2NO2 HNO2 + HNO3
Dark blue in liquid (–30ºC)
Low T
N2 O3 Dinitrogen trioxide NO + NO2 N2 O3 N 2O 3 or solid state, unstable
Room T
in the gas phase
O = N – O – N = O or
H2O
O N2 O3 2HNO2
O=N–N
O
Colourless, exists in
Low T
N2 O4 Dinitrogen tetroxide 2NO2 N2 O4 equilibrium with NO2 both
O O O in the gaseous and liquid
2N N–N state, in solid state, N 2 O4 is
O O O unstable.
N2 O5 Dinitrogen pentoxide 2HNO3 + P2 O5 o H2 O + N2 O5 No existance in gas phase,
H2 O + P2 O5 o 2HPO3 in the solid state exists as
O O nitronium nitrate
N N [NO2 ] + [NO3 ]–
O
O O

(IV) Nitric acid (HNO3)

It was named aqua fortis (means strong water) by alchemists.
H
1p O
m
102° 12
96

O 140.6 pm N 130° Structure of HNO3

pm

PREPARATION :
(a) Laboratory Method
KNO3 + conc. H2SO4 o KHSO4 + HNO3 (vap)
vapours of nitric acid evolved are condensed in a glass receiver.

34
 P-BLOCK ELEMENTS
(b) Industrial Prepration
On a large scale it is prepared mainly by Ostwald’s process.
This method is based upon catalytic oxidation of NH3 by atmospheric oxygen.
Pt/(Rh gauge catalyst
4NH3(g) + 5O2 (g) 4 NO(g) + 6H2 O(g)
500 K, 9 bar
(from air)

Nitric oxide thus formed combines with oxygen giving NO2.

2NO(g) + O2(g) U 2NO2(g)
Nitrogen dioxide so formed, dissolves in water to give HNO3.
3 NO2(g) + H2O(g) o 2 HNO3(aq) + NO(g)
NO thus formed is recycled and the aqueous HNO3 can be concentrated by distillation upto ~ 68% by mass.
Further concentration to 98% can be achieved by dehydration with concentrated H 2SO4.

Physical Properties :
(i) It is a colourless liquid. Freezing point is 231.4 K and boiling point is 355.6 K. Laboratory grade nitric acid
contains ~ 68% of the HNO3 by mass and has a specific gravity of 1.504.
(ii) In the gaseous state, HNO3 exists as a planar molecule.
(iii) In aqueous solution, nitric acid behaves as a strong acid giving hydronium and nitrate ions.
HNO3(aq) + H2O(A) o 2H3O+ (aq) + NO3– (aq)
(iv) Concentrate nitric acid is a strong oxidising agent and attacks most metals except Au & Pt. The product of
oxidation depend upon the concentratio of the acid, temperature and nature of metal.
(v) Concentrate HNO3 also oxidises non-metals and their compounds.

Chemical Properties :
It is very strong acid and it exhibits usual properties of acids. It reacts with basic oxides, carbonates, bicarbonates
and hydroxides forming corresponding salts.
CaO + 2HNO3 o Ca(NO3)2 + H2O
Na2CO3 + 2HNO3 o 2NaNO3 + H2O + CO2
NaOH + HNO3 o NaNO3 + H2O

Oxidising nature : Nitric acid acts as a strong oxidising agent as it decomposes to give nascent oxygen easily.
2HNO3 o H2O + 2NO2 + O
or 2HNO3 o H2O + 2NO + 3O

(a) Oxidation of non-metals : The nascent oxygen oxidises various non-metals to their corresponding highest
oxyacids.
(i) Sulphur is oxides to sulphuric acid
S + 6HNO3 conc. and hot H2SO4 + 6NO2 + 2H2O
(ii) Carbon is oxidised to carbonic acid
C + 4HNO3 o H2CO3 + 4NO2 + 2H2O
(iii) Phosphorus is oxidised to orthophosphoric acid.
2P + 10HNO3 conc. and hot 2H3PO4 + 10NO2 + 2H2O
(iv) Iodine is oxidised to iodic acid
I2 + 10HNO3 conc. and hot  2HIO3 + 10NO2 + 4H2O

35
CHEMISTRY FOR NEET & AIIMS
(b) Oxidation of metalloids : Metalloids like non-metals also form highest oxyacids
(i) Arsenic is oxidised to arsenic acid
conc. and hot
As + 5HNO3 2H3AsO4 + 5NO2 + H2O
(ii) Antimony is oxidised to antimonic acid
conc. and hot
Sb + 5HNO3 2H3SbO4 + 5NO2 + H2O
(iii) Tin is oxidised to meta-stannic acid.
Sn + 2HNO3 o H2SnO3 + 4NO2 + H2O

(c) Oxidiation of compounds

(i) Sulphur dioxide is oxidised to sulphuric acid
SO2 + 2HNO3 o H2SO4 + 2NO2
(ii) Hydrogen sulphide is oxidised to sulphur
H2S + 2HNO3 o 2NO2 + 2H2O + S
(iii) Ferrous sulphate is oxidised to ferric sulphate in presence of H2SO4
6FeSO4 + 3H2SO4 + 2HNO3 o 3Fe2(SO4)3 + 2NO + 4H2O
(iv) Iodine is liberated from KI.
6KI + 8 HNO3 o 6KNO3 + 2NO + 3I2 + 4H2O
(v) HBr, HI are oxidised to Br2 and I2, respectively.
2HBr + 2HNO3 o Br2 + 2NO2 + 2H2OSimilarly
2HI + 2HNO3 o I2 + 2NO2 + 2H2O
(vi) Ferrous sulphide is oxidised to ferric sulphate
FeS + 8HNO3 oFe2(SO4)3 + 8NO2 + 4H2O
(vii) Stannous chloride is oxidised to stannic chloride in presence of HCl
2HNO3 + 14H oNH2OH + NH3 + 5H2O
Hydroxylamine
NH3 + HNO3 oNH4NO3
----------------------------------------------------------------------------------------------------------------------
7SnCl2 + 14 HCl + 3HNO3 o7SnCl4 + NH2 OH + NH4NO3 + 5H2O
(viii) Cane sugar is oxidised to oxalic acid
C12H22O11 + 36 HNO3 o6(COOH)2 + 36NO2 +23H2O

Action on Metals : Nitric acid reacts with most of the metals except noble metals like gold and platinum. Towards its
reaction with metals, HNO3 acts as an acid as well as an oxidising agent. Like Other acids, HNO3 liberate nascent H
from metals which further reduces the nitric acid into number of products like NO, NO2, N2O, N2, NH2OH or NH3
according to the following reactions :
Metal + HNO3 o Nitrate + H
2HNO3 + 2H o 2NO + 2H2O
2HNO3 + 6H o 2NO + 4H2O
2HNO3 + 10H o N2 + 6H2O
2HNO3 + 16H o 2NH3 + 6H2O

36
 P-BLOCK ELEMENTS
The progress of the reaction is controlled by a number of factors :
(a) The nature of the metal
(b) The concentration of the acid,
(c) The temperature of the reaction
(d) The presence of other impurities

Concentration of nitric acid Metal Main products

Mg, Mn (2%) H2 + Metal nitrate
Very dilute HNO3 (6%)
Fe, Zn, Sn NH4 NO3 + metal nitrate + H2 O
Pb, Cu, Ag, Hg NO + metal nitrate + H2 O
Dilute HNO3 (20%) Fe, Zn N2 O + metal nitrate + H2 O
Sn NH4 NO3 + Sn(NO3 ) 2
Zn, Fe, Pb, Cu, Ag, Hg NO2 + metal nitrate + H2 O
Conc. HNO3 (70%)
Sn NO2 + H2 SnO3

Some Exceptional Points :

y Mg and Mn from H2 gas on reaction with very dilute HNO3
y Be, Al, Fe, Cr do not react with conc. HNO3 due to fromation of protective oxide layer.
y Au and Pt (Noble metals) do not react with conce. HNO3
y Sn reacts with conc. HNO3 and forms H2SnO3 (metastannic acid)
y Au and Pt react only with aqua regia (3 part of conc. HCl and 1 part of conc. HNO3)
3HCl + HNO3 o HAuCl 4
tetrachloro auric acid

Pt + 4Cl– + PtCl4 

2HCl
o H PtCl
2 6
hexachloro platinic acid

conc. HNO3 + skin o yellow spot (protein o xanthoprotein)

y The major use of nitric acid is in the manufacture of ammonium nitrate for fertilizers and other nitrates for use in
explosives and pyrotechnics. It is also used for the preparation of nitroglycerin, trinitrotoluene and other organic nitro
compounds. Other major uses are in the pickling of stainless steel, etching of metals and as an oxidiser in rocket fuels.

PHOSPHORUS
Allotropic modifications of phosphorus
Phosphorus exists in a number of allotropic forms. These forms are :
(A) Yellow or white phosphorus (B) Red phosphorus (C) Black phosphorus
Order of stability or MP or density o white < red < balck

conc.
Red Phosphorous H2SO4

inert
573K
medium

473K
White Phosphorous high P

37
CHEMISTRY FOR NEET & AIIMS
(A) White or yelllow phosphorus
Preparation :

(i)

(ii) Ca3(PO4)2 + 3H2SO4 conc. 3CaSO4 + 2H3PO4

H3PO4   HPO3

meta phosphoric acid

12C + 4HPO3 2H2n + 12COn + P4

Coke white 'P'

Properties :
(i) It has characteristic garlic smell and is poisonous in nature. Persons working with phosphorus develop a
disease in which the jaw bones decay. This disease is knwon as phossy jaw.
(ii) In contact with air, it undergoes slow combustion and glows in dark. This property is called phosphorescence.
(iii) Its ignition temperature is low (about 30° C). It readily catches fire giving dense fumes of phosphorus
pentoxide. It is, therfore, kept in water.
P4 + 5O2 oP4O10 or 2P2O5

Structure :

<P— P—P
60°
Vander waal bonds

(B) Red phosphorus

Preparation :
Red phosphorus is formed by heating yellow phosphorus, between 240–250° C, in presence of an inert gas.
240-250ºC
White 'P' Red 'P'
in an inert atm. like
N2 or CO2
I2 : catalyst

heated to 550ºC
Red 'P' White 'P'
in an inert atm and then
rapid cooling to room temp.
Structure of red phosphorus :- It is regarded as a polymer consisting of chains of P4 tetrahedral linked together
by covalent bond.

Proposed Molecular Structure of Red Phosphorus

38
 P-BLOCK ELEMENTS
(c) Black Phosphorus
Preparation : This is most stable form of Phosphorus
470K
White(P) Black P
at high P

Black P contain zig-zag & double layered structure.

Comparison between White and Red Phosphorus

Property White phosphorus Red phosphorus
Physical state Soft waxy solid. Brittle powder.
Colour White when pure. Red.
Attains yellow colour
on standing.
Odour Garlic Odourless.
Solubility in water Insoluble. insoluble
Solubility in CS2 Soluble. Insoluble.
Physiological action Poisonous. Non-poisonous.
Chemical activity Very active. Less active.
Stability Unstable. Stable.
Phosphorescence Glows in dark Does not glow in dark.
Reaction with NaOH Evolves phosphine. No action.
Molecular formula P4 Complex polymer.

(I) Phosphine Gas (PH3)

Preparation :
'
(a) 4H3PO3 PH3 + 3H3PO4
(b) PH4I + KOH oKI + PH3 + H2O ½
(PH3 + HI)
°
¾ purest PH 3
(c) 2AIP + 3H2SO4 oAl2(SO4)3 + PH3n °¿

Physical properities :
(a) It is having 'rotten fish' smell.
(b) It is soluble in CS2 and insoluble in water.
+ —
PH3 + H2O PH4 + OH
in s-orbital, so donating capacity is less

Note : PH 4 is formed with acids.

(c) Like NH3, PH3 also can form addition product.
CaCl2 • 8NH3, Cu2Cl2 • 2PH3, AlCl3 • 2PH3, SnCl4 • 2PH3
PH3 can be absorbed by Ca(OCl)Cl.
PH3 + 3Ca(OCl)Cl + 3H2O o PCl3 + 3HCl + 3Ca(OH)2
2NH3 + 3Ca(OCl)Cl o N2 + 3CaCl2 + 3H2O

39
CHEMISTRY FOR NEET & AIIMS
Chemical Properties :
(a) PH3 + O3 150°C P2O5 + H2O
(b) PH3 + 3Cl2 o PCl3 + 3HCl
(c) PH3 + 4N2O electrical H3PO4 + 4N2
sparking

(d)

(e) PH3 + 6AgNO3 o [Ag3P – 3AgNO3p] + 3HNO3

Yellow ppt.
Ag3 P • 3AgNO3 + 3H2O o 6 Ag p + 3HNO3 + H3PO3
Black ppt.
(f) PH3 + 4HCHO + HCl o [ P(CH2OH)4]+Cl– (which is used for making fire-proof cotton fabrics)
(White / colourless solid)

(II) Phosphorous Halides

Phosphorous forms two types of halides, PX3 (X = F, Cl, Br, I) and PX5 (X = F, Cl, Br).
Phosphorous Trichloride (PCl3)
(a) Method of preparation :
(i) It is obtained by passing dry chlorien over heated white phosphorus.
P4 + 6Cl2 o 4PCl3
(ii) It is also obtained by the action of thionyl chloride with white phosphorus.
P4 + 8SOCl2 o 4PCl3 + 4SO2 + 2S2Cl2

(b) Properties :
(i) It is a colourless oily liquid and hydrolyses in the presence of moistuer.
PCl3 + 3H2O o H3PO3 + 3HCl
(ii) It reacts with organic compounds containing –OH group such as CH3COOH, C2H3OH.
3CH3COOH + PCl3 o 3CH3COCl + H3PO4
3C2H5OH + PCl3 o 3C2H5Cl + H3PO3

Phosphorus Pentachloride (PCl5)

(a) Method of preparation :
(i) Phosphorus pentachloride is prepared by the reaction of white phosphorus with excess of dry chlorine.
P4 + 10Cl2 o 4PCl5
(ii) It can also be prepared by the actio of SO2Cl2 on phosphorus.
P4 + 10SO2Cl2 o 4PCl5 + 10SO2

(b) Properties :
(i) PCl5 is yellowish white powder and in moist air, it hydrolyses to POCl3 and finally gets converted to
phosphoric acid.
PCl5 + H2O o POCl3 + 2HCl
POCl3 + 3H2O o H3PO4 + 3HCl
(ii) When heated, it sublimes but decomposes on stronger heating.
PCl5  hEAT
o PCl3 + Cl2
(iii) It reacts with organic compounds containing –OH group converting them to chloro derivatives.
C2H5OH + PCl5 o C2H5Cl + POCl3 + HCl

40
 P-BLOCK ELEMENTS
(iv) Finally divided metals on heating with PCl5 give corresponding chlorides.
2Ag + PCl5 o 2AgCl + PCl3
Sn + 2PCl5 o SnCl4 + 2PCl3
(v) It is used in the synthesis of some organic compounds, e.g., C2H5Cl, CH3COCl.

NH4 + X– N2 + H2
Haber
process
H2O
CaCN2
O2 +
N2 Normal
NH3 NH2 + NH4 (Self ionisation)
conditions

Ostwald

O2
NO NO2
O2
H2O

HNO3 + NO

Ex. Mention the conditions required to maximise the yield of ammonia.

Sol. In accordance with Le Chatelier’s principle, high pressure would favour the formation of ammonia. The optimum
conditions for the production fo ammonia are a pressure of 200 × 105 Pa (about 200 atm), a temperature of ~ 700 K and
the use of a catalyst such as iron oxide with small amounts of K2O and Al2O3 to increase the rate of attainment of
equilibrium.

Ex. How does ammonia react with a solution of Cu2+?

Sol. The presence of a lone pair of electrons on the nitrogen ato of the ammonia molcule makes it a Lewis base. It donates
the electron pair and forms linkage with metal ions and the formation of such complex compounds finds applications
in detection of Cu2+.
Cu 2 (aq)  4NH 3 (aq) U [Cu(NH3 ) 4 ]2 (aq)
(blue) (deep blue)

Ex. Illustrate how copper metal can give different products on reaction with HNO3.
Sol. 3Cu + 8 HNO3(dilute) o 3Cu(NO3)2 + 2NO + 4H2O
Cu + 4HNO3(conc.) o Cu(NO3)2 + 2NO2 + 2H2O

Ex. Why is nitrogen di-oxide paramagnetic in gaseous state but the solid obtained on cooling it is diamagnetic.
Sol. NO2 contains odd number of electrons in its valence shell. On cooling it forms dimer and converted to stable N2O4
which is a colourless solid and diamagnetic in nature.

Ex. Why NH3 gas cannot be dried by passing over P2O5, CaCl2 and H2SO4 ?
Sol. CaCl2 + 8NH3 o CaCl2.8NH3
P2O5 + 6NH3 + 3H2O o 2(NH4)3PO4
H2SO4 + 2NH3 o (NH4)2SO4
So it is dried by passing over quick lime (CaO).
CaO + H2O o Ca(OH)2

41
CHEMISTRY FOR NEET & AIIMS

OXYGEN FAMILY
Physical Properties :
y Oxygen and sulphur are non-metal, selenium and tellurium metalloids, whereas polonium is a metal. Polonium is
radioactive and is short lived (Half-life 13.8 days).
y The melting and boiling points increase with an increase in atomic number down the group. The larger difference
between the melting and boiling points of oxygen and sulphur may be explained on the basis of their atomicity;
oxygen exist as diatomic molecules (O2) whereas sulphur exists as polyatomic molecule (S8).

Chemical Properties :
Oxidation states and trends in chemical reactivity :
The elements of group 16 exhibit a number of oxidation states. The stability of -2 oxidation state decreases down the
group. Except oxygen other elements of the group exhibit + 2, + 4, + 6 oxidation states but + 4 and + 6 are more
common. Sulphur, selenium and tellurium usually show + 4 oxidation in their compounds with oxygen and + 6
oxidation state with fluorine. The stability of + 6 oxidation state decreases down the group and stability of +4
oxidation state increases (inert pair effect). Bonding in + 4 and + 6 oxidation states are primarily covalent.

(i) Reactivity with hydrogen :

Table : Properties of Hydrides of Group 16 Elements
Property H2O H2S H2Se H2Te
m.p / K 273 188 208 222
b.p / K 373 213 232 269
H–E distance / pm 96 134 146 169
HEH angle (°) 104 92 91 90
'fH/kJ mol–1 –286 –20 73 100
'diss H(H–E) / kJ mol–1 463 347 276 238
Dissociation constanta 1.8 × 10–6 1.3 × 10–7 1.3 × 10–4 2.3 × 10–3
a Aqueous solution, 298 K
All elements of Group 16 form hydride of type H2E (E = S, Se, Te, O)
H2O H2S H2Se H2Te
Acidic character increases
(As bond dissociation energy decreases)
Thermal stability decreases

Reducing character increases

Note : Water does not show reducing property
Boiling point : H2S < H2Se < H2Te < H2O
Melting point : H2S < H2Se < H2Te < H2O

(ii) Reactivity with oxygen : All these elements form oxides of the EO2 and EO3 types where E = S, Se, Te or Po. Ozone
(O3) and sulphur dioxide (SO2) are gases while selenium dioxide (SeO2) is solid. Reducing property of dioxide
decreases from SO2 to TeO2 ; SO2 is reducing while TeO2 is an oxidising agent. Besides EO2 type sulphur, selenium
and tellurium also form EO3 type oxides (SO3, SeO3, TeO3). Both types of oxides are acidic in nature.

(iii) Reactivity toward the halogens : Elements of group 16 form a larger number of halides of the type EX6, EX4 and EX2
where E is an element of the group – 16 and X is an halogen. The stabilities of the halides decrease in the order
F > Cl > Br > l. Amongst hexahalides, hexafluorides are the only stable halides. All hexafluorides are gaseous in
nature. They have octahedral structure. Sulphur hexafluoride SF6 is exceptionally stable for steric reasons.
Amongst tetrafluorides, SF4 is a gas, SeF4 liquid and TeF4 a solid
All elements except selenium form dichlorides and dibromides. The well known monohalides are dimeric in nature,
Examples are S2F2, S2Cl2, S2Br2, Se2Cl2 and Se2Br2. These dimeric halides undergo disproportionation as given
2Se2Cl2 o SeCl4 + 3Se.

42
 P-BLOCK ELEMENTS
(I) OXYGEN (O2)
PREPARATION :
(a) From oxides
(i) By thermal decomposition of the oxides
3MnO2 ' Mn3O4 + O2
3Pb3O4 ' 6PbO + O2
2BaO2 ' 2BaO + O2
450°C
2HgO 2Hg + O2
2Ag2O 350°C 4Ag + O2
(ii) By the action of water on sodium peroxide (Oxone)
2Na2O2 + 2H2O o 4NaOH + O2

(iii) By the action of conc. H2SO4 on MnO2

2MnO2 + 2H2SO4 o 2MnSO4 + 2H2O + O2

(b) From salts

(i) Alkali metal nitrates on heating give out oxygen
2NaNO3 o 2NaNO2 + O2
2KNO3 o 2KNO2 + O2

(ii) KClO3, K2Cr2O7 and KMnO4 decompose at high temperatures evolving oxygen.
2KClO3 400°C 2KCl + 3O2
4K2Cr2O7 400°C 4K2CrO4 + 2Cr2O3 + 3O2
2KMnO4 250°C K2MnO4 + MnO2 + O2
(iii) By heating KMnO4 or K2Cr2O7 with concentrated H2SO4.
4KMnO4 + 6H2SO4 o 2K2SO4 + 4MnSO4 + 6H2O + 5O2
2K2Cr2O7 + 8H2SO4 o 2K2SO4 + 2Cr2(SO4)3 + 8H2O + 3O2

(iv) By adding H2O2 to acidified KMnO4 solution.

2KMnO4 + 3H2SO4 + 5H2O2 o K2SO4 + 2MnSO4 + 8H2O + 5O2

(c) Laboratory method

In laboratory, oxygen is prepared by heating of a mixture of potassium chlorate and manganese dioxide in 4 :1
ratio. (MnO2 used as a catalyst)
MNO2
2KClO3 '
2KCl + 3O2
Potassiumchlorate

(d) Electrolysis of water : Electrolysis of either acidified water using platinum electrodes or alkaline water using
nickel electrodes is made in an electrolytic cell for obtaining oxygen and hydrogen.
ZZZ
X
H 2SO 4 YZZ + 2-
Z 2H + SO 4

1
At cathode : 2H+ + 2e o H2 At anode : 2OH– o H2O + O + 2e
2 2

43
CHEMISTRY FOR NEET & AIIMS

PROPERTIES :
It is non inflammable but a supporter of combustion.
Some typical reactions of dioxygen –

O2(g)

H2O(g)

(II) OZONE (O3)

PREPARATION :
(a) Unstable deep blue, diamagnetic gas, with fishy smell. Toxic enough (more toxic than KCN). It's intense blue
colour is due to the absorption of red light.
(b) Ozonised oxygen is separated by passing into spiral tube cooled by liquid air. Ozone condense at –
112.4ºC. [B.P. of O2 – 183ºC ; B.P. of liquid air is – 190ºC]
2F2 + 2H2 O 4HF + O2
F2 + 3H2O 6HF + O3

PROPERTIES :
(a) Oxidising property
It is one of best oxidising agent, in acid solution, its standard, reduction potential value is 2.07V.
O3 + 2H+ + 2e o O2 + H2O Eº = + 2.07 V
(i) Metal Sulphides to Sulphates.
MS + 4O3 o MSO4 + 4O2 [M = Pb, Cu, Zn, Cd]
(ii) 2HX + O3o X2 + H2O + O2 [X= Cl, Br, I]
(iii) NaNO2 + O3 o NaNO3 + O2
Na2SO3 + O3 o Na2SO4 + O2
Na3AsO3 + O3 o Na3AsO4 + O2
(iv) S + H2O + 3O3 o H2SO4 + 3O2
2P + 3H2O + 5O3 o 2H3PO4 + 5O2
2As + 3H2O + 5O3 o 2H3AsO4 + 5O2

44
 P-BLOCK ELEMENTS
(v) Moist I2 o HIO3 + 5O2
I2 + 5O3 + H2O o 2HIO3 + 5O2
Dry I2 o I4O9 (yellow)
2I2 + 9O3 o I4O9 + 9O2
(vi) 2K2MnO4 + O3 + H2O o 2KMnO4 + 2KOH +O2
2K4 [Fe(CN)6] + O3 + H2O o 2K3 [Fe(CN)6] + 2KOH + O2
2FeSO4 + O3 + H2SO4 o Fe2 (SO4)3 + O2 + H2O
(vii) 2KI (acidified) + O3 + 2HCl o I2 + 2KCI + H2O + O2

2KI(neutral) + O3 + 2HCl  o I 2 + 2KOH + O 2 ½

 
°
KI+KOI °
KI + KOI + 2HCl  o 2KCl + I 2 + H 2 O ¾ O3 estimated by this reaction.
°
I 2 + 2S2 O32– 
o S4 O 62– + 2I °¿

­° KI + 3O3  o KIO3 + 3O 2
alkaline ®
°̄ KI + 4O3 
o KIO 4 + 4O2

(viii) Hg loses its fluidity (tailing of Hg)

2Hg + O3 o Hg2O + O2 Similarly

2Ag + O3 o Ag 2 O + O2
Brown

(ix) BaO2 + O3 o BaO + 2O2

H2O2 + O3 o H2O + 2O2
Na2O2 + O3 + H2O o 2NaOH + 2O2
(x) 2KOH + 5O3 o 2KO3 + 5O2 + H2O

Note: In all above reaction O3 gives up O2 but some reactions are there which consumes all O-atom.
x 3SO2 + O3 o 3SO3
x 3SnCl2 + 6HCl + O3 o 3SnCl4 + 3H2O

Depletion of ozone layer : Experiments have shown that nitrogen oxides (particularly nitric oxide) combine very
rapidly with ozone and there is, thus, the possibility that nitrogen oxides emitted from the exhaust systems of
supersonic jet aeroplanes might be slowly depleting the concentration of the ozone layer in the upper atmosphere.
NO(g) + O3(g) o NO2(g) + O2(g)
Another threat to this ozone layer is probably posed by the use of freons which are used in aerosol sprays and as
refrigerants.

Absorbent
(a) Turpentine oil
(b) Oil of cinnamon

USES :
(a) Sterilizing water
(b) Detection of position of the double bond in the unsaturated compound.

45
CHEMISTRY FOR NEET & AIIMS
Simple oxides
Binary compound of oxygen with other elements. Oxides vary widely in nature and properties.
Simple oxides can be classified as :
(i) Acidic Oxide :
Non metal oxides are acidic but oxides of some metals in higher oxidation state also show acidic character. They
combine with water to give acid e.g.,

SO2, Cl2O7, CO2, N2O5, Mn 2 O7 , CrO3 , V2O 5

 

metal oxide

For example, SO2 combines with water to give sulphurous acid.

SO2 + H2O o H 2SO3

Sulphurous acid

(ii) Neutral oxides :

They are neither acidic nor basic e.g., CO, NO, H2O and N2O

(iii) Mixexd oxides :

Oxides containing more than one cations with different oxidation states are called mixed oxides.
e.g., Pb3O4, MgAl2O4, Fe3O4 etc.

SULPHUR
Allotropes of Sulphur

Crystalline Amorphous
Rhombic sulphur (
-S) Milk of sulphur
most stable form Plastic sulphur (
-S)

Monoclinic sulphur (
-S) Colloidal sulphur

>95.6°C

-S
-S H2 S + 2HNO3 Redox S + 2NO2 + 2H2O
<95°, 6°C RA
95.6°C = transition Temp.
both are soluble in CS2
but insoluble in water
(a) density of DS > ES
(b) Both are puckered crown shape having S8 units
(c) S2 is paramagnetic sulphur which exist in vapour form at high temperature.
(d) S6 is chair form of S

Effect of temperature :

S8(D) 
95.5q C
o S8(E) 
119q C
o S(liq) 
130  200q C
o Viscosity of liquid increase 
! 200q C
o viscosity decrease

46
 P-BLOCK ELEMENTS
(I) Hydrogen Sulphide (H2S)
PREPARATION :
By the action of dil. HCl or H2 SO 4on iron pyrites.
FeS + H2 SO4 o FeSO4 +H2S n
Note : The gas is then dried over fused CaCl2 or P2O5. Conc. H2SO4 cannot be used for drying purpose
because H2S oxidize to sulphur.

PROPERTIES :
It is a colourless gas having an offensive smell of rotten eggs.
(a) It burn in air with blue flame
2H2S + O2  o 2H2O + S
If the air supply is in excess
2H2S + 3O2 o 2H2O + 2SO3
(b) It is a mild acid.
H2S o H+ + SH–
SH– o H+ + S–2
(c) It act as a reducing agent. It reduces halogen into corresponding hydroacid.
H2S + X2 o 2HX + S

Tests of H2S :
(a) Unpleasant odour resembling that of rotten eggs.
(b) It turns lead acetate into paper black
(CH3 COO)2 Pb + H2 S oPbSp+ 2 CH3 COOH
Black
(c) It gives a violet colouration with a solution of sodium nitroprusside.

Structure of H2S :
Similar to structure of water molecule i.e. V– shaped structure with bond length (H–S) 1.35A° and bond
angle (H–S–H) is 92.5°
S
1.3
5Å

92.5°
5Å
1.3

H H

USES :
(a) It is mainly employed in salt analysis for the detection of cation.
(b) Reducing agent for H2SO4, KMnO4, K2Cr2O7, O3, H2O2, FeCl3

(II) Sulphur Dioxide (SO2)

PREPARATION :
Prepared by any of the following methods.
(a) Cu + 2H2 SO4 ', conc CuSO4 + SO2+ 2H2 O
(b) C + 2H2SO4 o CO2 + 2SO2 +2H2 O
(c) 4Fe S2 + 11O2 o 2Fe2 O3 + 8SO2

47
CHEMISTRY FOR NEET & AIIMS
PROPERTIES :
(a) It has a pungent and suffocating odour.
(b) It acts as lewis base due to presence of a lone pair of electrons.
(c) Acidic nature
It dissolves in H2 O to give sulphurous acid, hence known as sulphurous anhydride.
SO2 + H2 O o H2SO3
Due to acidic nature, it can react with bases to give salts.
2NaOH + SO2 oNa2 SO3 + H2 O
(d) Reducing nature
In the presence of moisture it can liberate nascent hydrogen or in presence of an oxidising agent it can easily
take an oxygen atom.
HNO3
H2SO4 + NO 2

FeCl3 + H2O
H2SO4 + HCl + FeCl2
SO2
KMnO 4 + H2SO4
K2SO4 + MnSO4 + H2SO4
K2Cr2O7 + H2SO4
K2SO4 + Cr2(SO4)3 + H2O
(e) Oxidising nature
SO2 +2H2S o2H2 O+ 3S p
SO2+2CO o2CO2 +Sp
(f) Bleaching nature
(i) Sulphur dioxide acts as bleaching agent in the presence of water, it is oxidised with the liberation of nascent
hydrogen which reduces the colouring matter to colourless.
SO2+2H2O oH2SO4+2 [H]
Colouring matter + 2[H] o Colourless compound.
(ii) Since the colourless (reduced) compound is reoxidised by air to coloured compound, bleaching by SO2 is
temporary.
Note : Chlorine has permanent bleaching action, so reaction is not reversible.

(III) Sulphuric acid H2SO4 (Oil of vitriol)

King of chemical (due to very great commericial importance)

PREPARATION :
H2 SO4 is prepared by two methods
(a) Lead chamber process
The mixture containing SO2 , air & nitric oxide when treated with steam, sulphuric acid is formed.
Stage I : 2NO (Catalyst) + O2 o2NO2
Stage II : 2SO2 + 2NO2 o 2SO3 +2NO
Stage III : SO3 + H2 O o H2 SO4

48
 P-BLOCK ELEMENTS
(b) Contact process
In this process SO2 is oxidised by air in the presence of catalyst (platinised asbestos).
'
Stage I : S + O2 SO2
V 2O 5
Stage II : 2SO2 + O2 2SO3
Stage III : SO3 + H2 SO4 o H2 S2 O7 (oleum)
Stage IV : Sulphuric acid of any desired concentration can be obtained from oleum by
dilution with water
H2 S2 O7 + H2 O o2H2 SO4

Chemical Properties :
(a) As an oxidising agent
(i) H2SO4 gives oxygen on strong heating, hot conc.H2SO4 acts as an oxidising agent.
'
H2SO4 H2O + SO2 + [O]
(ii) Non metals oxidised to their oxides.
C + 2H2 SO4 oCO2 + 2SO2 + 2H2 O
(iii) Dilute acid releases hydrogen with all metals except mercury, copper and noble metals.
H2SO4 + Zn o ZnSO4 + H2 n
Hot conc. H2SO4 releases SO2 on reaction with metals.
Zn + 2H2SO4 oZnSO4 + 2H2O + SO2
(iv) Oxidation of compounds
'
2HX + H2 SO4 X2 + SO2 + 2H2O ( where X = Br or I)

(b) As a dehydrating agent

(i) Conc. H2 SO4 is a powerful dehydrating agent. Its corrosive action on skin is due to dehydration of skin
which then burns and produces itching sensation.
(ii) It's dehydrating property is due to strong affinity for water.
C12 H22 O11 H2SO4 12C + 11H2O
This is called as charring of sugar.
conc. H2SO4
CH3 CH2 OH CH2 = CH2 +H2 O
160°C
H2SO4
HCOOH CO + H2O
COOH conc. H2SO4
 CO + CO2 + H2O
COOH
conc. H2SO4
Chloro benzene + Chloral D. D. T..
H2O

2 : 1

USES :
(a) In the manufacture of fertilisers like ammonium sulphate, calcium superphosphate etc.
(b) As a drying agent.

49
CHEMISTRY FOR NEET & AIIMS
HALOGENS FAMILY
(A) Physical properties :
(i) Fluorine and chlorine are gases, bromine is a liquid whereas iodine is a solid.
(ii) Their melting and boiling points steadily increase with atomic number.
(iii) All halogens are coloured. This is due to absorption of radiations in visible region which results in the
excitation of outer electrons to higher energy level. By absorbing different quanta of radiation, they display
different colours.
For example, F2, has yellow, Cl2, greenish yellow, Br2, red and I2, violet colour.
(iv) Fluorine and chlorine react with water. Bromine and iodine are only sparingly soluble in water. But are soluble
in organic solvents such as chloroform, carbon tetrachloride, carbon disulphide and hydrocarbons to give
coloured solutions.
(v) Except the smaller enthalpy of dissociation of F2 compared to that of Cl2. The X-X bond disassociation enthalpies
from chlorine onwards show the expected trend : Cl – Cl > Br – Br > F – F > I – I. The reason for the smaller
enthalpy of dissociation of F2 is the relatively larger electrons-electrons repulsion among the lone pairs in F2
molecule where they are much closer to each other than in case of Cl2.

(B) Chemical Properties :

(i) Oxidation states and trends in chemical reactivity
y All the halogens exhibit – 1 oxidation state. However, chlorine, bromine and iodine exhibit + 1, + 3, + 5 and + 7
oxidation states also. The higher oxidation states of chlorine, bromine and iodine are realised mainly when the
halogens are in combination with the small and highly electronegative fluorine and oxygen atoms e.g., in
interhalogens, oxides and oxoacids.
y The fluorine atom has no d orbitals in its valence shell and therefore cannot expands its octet. Being the most
electronegative, it exhibits only – 1 oxidation state.
y All the halogens are highly reactive. They react with metals and non-metals to form halides. The reactivity of
the halogens decreases down the group.

Standard Reduction Potential (SRP)

X2 + 2e– o 2X–
F2 + 2e– o 2F– E– = + 2.87 V ; Cl2 + 2e– o 2Cl– E– = + 1.36 V
Br2 + 2e o 2Br
– –
E– = + 1.09 V ; I2 + 2e– o 2I– E– = + 0.54 V
More the value of the SRP, more powerful is the oxidising agent.
Hence the order of oxidising power is F2 > Cl2 > Br2 > I2
Order of reducing behaviour is I– > Br– > Cl– > F–

(ii) Halogen oxides :

y Fluorine forms two oxides OF2 and O2F2. However, only OF2 is the thermally stable at 298 K. These oxide are
essentially oxygen fluorides because of the higher electronegativity of flurorine than oxygen.
Both are strong fluorinating agents.
y O2F2 oxidises plutonium to PuF6 and the reaction is used in removing plutonium as PuF6 from spent nuclear
fuel.
y Chlorine, bromine and iodine form oxides in which the oxidation states of these halogen vary from +1 to 7. A
combination of kinetic and thermodynamic factors lead to the generally decreasing order of stability of oxides
formed by halogens, I > Cl > Br. The higher oxides of halogens tend to be more stable than the lower ones. This
is called middle row anamoly.
y Chlorine oxides, Cl2O, ClO2, Cl2O6 and Cl2O7 are highly reactive oxidising agents and tend to explode. ClO2 is
used as a bleaching agent for paper pulp and textiles and in water treatment.
y The bromine oxides, Br2O, BrO2, BrO3 are the least stable halogen oxides and exist only at low temperature.
They are very powerful oxidising agents.

50
 P-BLOCK ELEMENTS
y The iodine oxides, I2O4, I2O5, I2O7 are insoluble solids and decompose on heating. I2O5 is very good oxidising
agent and is used in the estimation of carbon monoxide.

Compounds of Halogen
(I) Chlorine Gas (Cl2)
Preparation :
(i) By heating chloride with concentrated H2SO4 in presence of MnO2.
4H+ + MnO2 + 2X– o X2 + Mn+2 + 2H2O
Bromides and iodides also liberate Br2 and I2 respectively with concentrated H2SO4 and MnO2.
OCl
(ii) y Ca + 2HCl o CaCl2 + Cl2 + H2O
Cl
y 2KMnO4 + 16 HCl o 2 KCl + 2 MnCl2 + 5 Cl2 + 8 H2O
y PbO2 + 4 HCl o PbCl2’ + Cl2 + 2 H2O

(iii) Manufacture of chlorine :

y Deacon’s process : By oxidation of hydrogen chloride gas by atmospheric oxygen in the presence of CuCl2
(catalyst) at 723 K.
4 HCl + O2 CuCl2
o 2 Cl2 + 2 H2O
y Electrolytic process : Chlorine is obtained by the electrolysis of brine (concentrated NaCl solution). Chlorine
is liberated at anode. It is obtained as a by-product in many chemical industries e.g.; in manufacturing of
sodium hydroxide.
NaX (aq) o Na+ (aq) + X– (aq)
Anode : 2X– o X2 + 2e–

Properties :
(i) It is greenish-yellow gas with pungent and suffocating odour. It is about 2–5 times heavier than air. It can be
liquefied into greenish-yellow liquid which boils at 239 K. It is soluble in water.

(ii) Oxidising & bleaching properties : Chlorine dissolves in water giving HCl and HOCl. Hypochlorous acid
(HOCl) so formed, gives nascent oxygen which is responsible for oxidising and bleaching properties of chlorine.
It is a powerful bleaching agent ; bleaching action is due to oxidation.
Cl2 + H2O o 2 HCl + O
Coloured substance + O o Colourless substance
It bleaches vegetable or organic matter in the presence of moisture. Bleaching effect of chlorine is permanent.
Cl2
Fe2+ Fe3+
SO32– SO42–
SO2 H2SO4
I2 HIO3
Br–/I– Br2/I2
NH3(excess) NH4Cl+N2
NH3(limited) NCl3 +HCl

Cl–

51
CHEMISTRY FOR NEET & AIIMS
(II) Halogen Acids (HCl )
Preparation :
By heating a halide with concentrated acid :
NaCl + H2SO4 
150q C
o NaHSO4 + HCl
NaHSO4 + NaCl  550q C
o Na2SO4 + HCl
y Above method is called as salt cake method as it involves the formation of NaHSO4 (salt cake).
y HCl cannot be dried over P2O5 (P4O10) or quick lime since they react with gas chemically.
CaO + 2HCl o CaCl2 + H2O
P4O10 + 3HCl o POCl3 + 3HPO3
y HCl is, hence dried by passing through concentrated H2SO4.

Properties :
(i) This is colourless, pungent smelling gas with acidic taste.
(ii) This is neither combustible nor supporter of combustion.
(iii) When perfectly dry, HX have no action on litmus, but in presence of moisture, they turn blue litmus red,
showing acidic nature. Among HX, HI is the strongest and HF is the weakest acid.

(III) Pseudo halogens and pseudo halides : Some inorganic compounds consisting of two or more atoms of which at
least one is N have been found to behave like halogens & they are known as pseudo halogen solids,
Pseudo halogens Pseudo halides
(i) (CN), cyanogen (i) (CN–) cyanide ion
(ii) (SCN), thiocyanogen (ii) (SCN–) thiocyanate ion
(iii) (SeCN), selenocyanogen (iii) (SeCN)– selenocyanate ion
(iv) (SCSN), azidocarbondisulphide (iv) (OCN)– cyanate ion
(v) (NCN)2– cyanamide ion
(vi) (N3)– azide ion etc.

(IV) Interhalogen Compounds : We know that halogen atoms have different electronegativity. Due to this difference in
electronegativity the halogen atoms combine with each other and give rise to the formation of binary covalent
compounds, which are called interhalogen compounds. These are of four types.
AB AB3 AB5 AB7*
CIF CIF3 CIF5 IF7
BrF BrF3 BrF5
ICl ICl3 IF5
IF IF3
* Where A - halogen of smaller size and A is more electro positive than B.
Properties :
(i) These compounds may be gases, liquids or solids.
Gases : ClF, BrF, ClF3, IF7; Liquids : BrF3, BrF5 ; Solids : ICl, IBr, IF3, ICl3.
(ii) Interhalogens containing fluorine are colourless but inter halogens consisting of heavier halogens are
coloured. The intensity of colour increases with increase in the molecular weight of the compounds.
(iii) All interhalogens are covalent molecules and are diamagnetic in nature since all the valence electrons
present as beonding or non-bonding electrons are paired.
(iv) Interhalogen compounds are more reactive than the parent halogens but less reactive than F2.
ICl + 2Na o NaI + NaCl
The order of reactivity of some interhalogens is as follows :
ClF3 > BrF3 > IF7 > BrF5 > BrF.
(v) These compounds can be used as non aqueous solvents. Interhalogen compounds are very useful
fluorination agents. ClF3 and BrF3 are used for the production of UF6 in the enrichment of 235U.

52
 P-BLOCK ELEMENTS
Test of halogens :
1. F– = Itching of glass
2. AgNO3 test (Cl–, Br–, I–)
Cl - Salt + AgNO3 o AgCl(White ppt)
Br salt + AgNO3 o AgBr (Pale yellow ppt)
I – salt + AgNO3 o AgI (Yellow ppt)

3. Test of I2
I2 + Starch o Navy blue
I2 + CCl4 + Violet

4. Layer test (Br–, I–)

Cl2 + 2Br– o 2Cl– + Br2 
CCl4
o Reddish brown (Halogen displacement reaction)
(Note : In case of I– violet colour is obtained).

5. Chromyl chloride test (Test of Cl–) : see d-block

Ex. Liquid I2 conducts electricity. Explain

Sol. Due to its self ionisation 3I2 I 3+ + I 3–

Note : Acidity order : HI > HBr > HCl >> HF. (due to hydrogen bonding & less effective overlap with H atom)
Boiling point order HX : HF > HI > HBr > HCl

p
Due to H-bonding

Ex. CaF2 used in HF prepn must be free from SiO2. Explain

Sol. CaF2 + H2SO4 CaSO4 + HF
If SiO2 present as impurity

4HF + SiO2 SiF4 + 2H2O Hence presence of one molecule SiO2

SiF4 + 2HF H2[SiF6] consumer 6 molecule of HF

Ex. HF can not be stored in glass vessel. Explain.(same reason.)

Ex. In the salt-cake method of prepn. of HCl, NH4Cl is being used instead of NaCl. Explain.
150°C
Sol. NaCl + H2SO4 NaHSO4 + HCl
Insoluble
NaCl + NaHSO4 550°C Na2SO4 + HCl
(Salt Cake)
2NH4Cl + H2SO4 2HCl + (NH4)2SO4
[NH4HSO4 intermediate is water soluble and easy to handle]

53
CHEMISTRY FOR NEET & AIIMS
y Another altermative process to avoid the formation of NaHSO4
1
NaCl + SO2 + H2O + 2 O2 Na2SO4 + 2HCl

gaseous mixture

Ex. In the similar type of preparation of HBr and HI from bromide and iodide, H2SO4 can not be used and H3PO4 is
used. Explain.
Sol. Since H2SO4 is an oxidising agent it oxidises HBr & HI to Br2 and I2 respectively.
2HBr + H2SO4 Br2 + SO2 + 2H2O
Hence, NaBr + H3PO4 NaH2PO4 + 3HBr
Another process ; PBr3 + 3H2O H3PO4 + 3HBr

Ex. HCl, H2SO4, HNO3 are bases in liquid HF where as HClO4 is acid. Comment.
Sol. HCl + HF H2Cl+ + F– ; H2SO4 + HF H3SO4+ + F–; HNO3 + HF H2NO3+ + P–
But HClO4 + HF H2F + ClO4
+ –

HF is weak acid but addition of BF3, AsF5, PF5, SbF5 makes it strongly acidic. Explain

NOBLE GASES
Physical Properties :
(i) All the noble gases are mono-atomic.
(ii) They are colourless, and tasteless. They are sparingly soluble in water.
(iii) They have very low melting and boiling points because the only type of interatomic interaction in these
elements is weak dispersion forces.
(iv) Helium has the lowet boiling point (4.2 K) of any known substance. It has a unusual property of diffusing
through most commonly used laboratory materials such as rubber, glass or plastics.

Chemical Properties :
In general, noble gases are least reactive. Their inertness to chemical reactivity is attributed to the following reasons:
(i) The noble gases except helium (1s2) have completely filled ns2 np6 electronic configuration in their valence
shell.
(ii) They have high ionisation enthalpy and more positive electron gain enthalpy.
Neil Bartlett, observed the reaction of a noble gas. First, he prepared a red compound which is formulated as
O2+[PtF6]–. He, then realised that the first ionisation enthalpy of molecular oxygen (1175 kJ mol–1) was almost
identical with that xenon (1170 kJ mol–1). He made efforts to prepare same type of compound with Xe+ [PtF6]– by
mixing Pt F6 and Xenon. After this discovery, a number of xenon compounds mainly with most electronegative
elements like fluorine and oxygen, have been synthesised.
The compounds of krypton are fewer. Only the difluoride (KrF2) has been studied in detail. Compounds radon
have not been isolated but only identified (e.g., RnF2) by radiotracer technique. No true compounds of Ar, Ne
or He are yet known.

Xenon Fluorides :–
400ºC, 1 atm
2:1 XeF2

600ºC, 7 atm
(1) Xe + F2 1:5 XeF4

1 : 20 XeF6
300ºC, 60-70 atm

54
 P-BLOCK ELEMENTS
(2) H2 reduces Xe – fluorides to Xe
XeF2 + H2 Xe + 2HF and so on

(3) Xe - fluorides oxidise Cl– to Cl2 and I– to I2

XeF2 + 2HCl 2HF + Xe + Cl2
XeF4 + 4KI 4KF + Xe + 2I2

(4) Hydrolysis
XeF2 reacts slowly with water
2XeF2 + 2H2O 2Xe + 4HF + O2
XeF4 and XeF6 react violently with water giving XeO3

3
3XeF4 + 6H2O 2Xe + XeO2 + 12HF + O2
2
XeF6 + 2H2O XeO3 + 6HF

p
(explosive, white hygroscopic solid)

(5) SiO2 also converts XeF6 into XeOF4

2XeF6 + SiO2 SiF4 + 2XeOF4
violet
Similary, XeO3 + XeOF4 2XeO2F2 , XeO3 + 2XeF6 3XeOF4

(6) Xe - fluorides are also hydrolysed in alkaline medium.

2XeF2 + 4OH– 2Xe + 4F– + 2H2O + O2
XeF6 + 7OH– HXeO4– + 3H2O + 6F–
Xenate ion

2HXeO4– + 2OH– XeO64–p+ Xe + 2H2O + O2

(7) They are used as fluorinating agent

2SF4 + XeF4 2SF6 + Xe
Pt + XeF4 PtF4 + Xe

(8) Act as a fluoride donor

XeF2 + MF5 [XeF]+ [MF6]– (M = As, Sb, P)
XeF6 + BF3 [XeF5] [BF4 ]
+ –

XeF6 + HF [XeF5]+ [HF2]–

(9) Act as Flouride acceptor also :

XeF6 + RbF /CsF Rb+ /Cs+ [XeF7]–

2Cs+[XeF7]– XeF6 + Cs2[XeF8]

50ºC
XeF4 + MF M+ + XeF5–
(alkali metals fluoride)

55
CHEMISTRY FOR NEET & AIIMS
Uses of Inert Gases :
(1) He is non-inflammable and light gas, so it is used in filling balloons for meteorological observations.
(2) He is used in gas cooled nuclear reactors.
(3) Liquid He is used as cryogenic agent.
(4) He is used to produce powerful superconducting magnets.
(5) Ne is used in discharge tubes.
(6) Ar is used as inert atmosphere in metallurgical process.
(7) Xenon and Krypton are used in light bulbs designed for special purposes.

Important Order :
(1) He < Ne < Ar < Kr < Xe Atomic radius
(2) He > Ne > Ar > Kr > Xe Ionisation energy
(3) He < Ne < Ar < Kr < Xe < Rn Density
(4) He < Ne < Ar < Kr < Xe < Rn mpt. bpt
[Atomic mass / size / polarisability / London force] n
(5) He < Ne < Ar < Xe < Rn [solubility in water because of dipole-induced dipole attraction]

Clatherate Compounds : Larger inert gas atmos are trapped into cavity or crystal structure of some organic
compounds and form clatherate compounds. For eg xenondiquinol.
y Force of attraction between noble gas and organic compound is dipole-induced dipole attraction.

O H O H

Xe

O H O H

He, Ne do not form clatherate compounds due to smaller size.

56
 P-BLOCK ELEMENTS

BORON FAMILY
(1) Amorphous boron of low purity (called moissan boron) is obtained by reducing B 2O3 with Mg or Na at a high
temperature. It is 95–98% pure (being contaminated with metal borides), and is black in colour.

acid heat Mg or Na
Na2[B4O5(OH)4].8H2O H3BO3 B2O3 2B + 3 MgO
(2) BORANES
Boranes are boron hydrogen compounds with general molecular formula BnHn+4 or Bn Hn+6.They are electron
deficient compounds.
(3) ALUM
Alums are double sulphates with their general formula R 2 SO 4 .M 2 (SO 4 ) 3 .24H 2 O where
R = monovalent radical like Na+ , K+, NH4+ and M = Trivalent radical like Al+3, Cr+3. Fe+3.

CARBON FAMILY
(1) Carbon is found in nature in various allotropic forms which are:
(i) Crystalline Form : Diamond, Graphite, Fullerenes
(ii) Amorphous Form : Coal

(2) SILICON (Si)

Silicon is the second most abundant (27.2%) element after oxygen (45.5%) in the earth's crust. It does not occur free
in nature but in the combined state, it occurs widely in form of silica and silicates. All mineral rocks, clays and soils
are built of silicates of magnesium, aluminium, potassium or iron. Aluminium silicate is however the most common
constituent of rocks and clays.
Silica is found in the free state in sand, flint and quartz and in the combined state as silicates like
(a) Feldspar – K2O.Al2O3.6SiO2
(b) Kaolinite – Al2O3. 2 SiO2. 2H2O
(c) Asbestos – CaO. 3MgO.4SiO2
Silicates are also important :

Silicates have basic unit of SiO44–, each silicon atom is bonded with four oxide ions tetrahedrally.

O–

Si Oxygen
O– O–
Silicon
Plane projection of silicate ion

O–

57
CHEMISTRY FOR NEET & AIIMS
NITROGEN FAMILY
NITRIC ACID (HNO3)
conc. HNO3
Zn Zn(NO3)2
Cu Cu(NO3)2
Ccharcoal CO2 + H2O
Cdiamond ×
B H3BO3
P4 H3PO4

ic acid
As H3AsO4
S8 H2SO4
Sn H2SnO3
I2 HIO3
H2S S
–2
SO2 SO4
Cgraphite C6(COOH)6
maletic acid
NO2
(Brown Gas)

Types of Metal conc. HNO3 dil. HNO3 very dil. HNO3

negative SRP metal Metal nitrate Metal nitrate Metal nitrate
+ NO2 + N2O + NH4NO3/(NH3)
positive SRP metal Metal nitrate Metal nitrate ×
& Pb + NO2 + NO
Metalloids, ic acid × ×
Non-metals & Sn + NO2

• Zn(NO3)2 + N2O m  Zn  o Zn(NO3)2 + NO2

dil.HNO3 conc.HNO3
Ex.
• Cu(NO3)2 + NO m  Cu  o Cu(NO3)2 + NO2
dil.HNO3 conc.HNO3

OXYGEN FAMILY
PROPERTIES of O2
It is non inflammable but a supporter of combustion.
Some typical reactions of dioxygen –

O2(g)

H2O(g)

58
 P-BLOCK ELEMENTS
O3 (OZONE) :
O3
ite ate
(NO 2–, SO 3–2 (NO3–, SO4–2)
NO NO2
SO2 SO3
HX X2 (except HF)
PbS PbSO4
Hg Hg2O
dry I2 I4O9
moist I2 HIO3
O2

Depletion of ozone layer : Experiments have shown that nitrogen oxides (particularly nitric oxide) combine very
rapidly with ozone and there is, thus, the possibility that nitrogen oxides emitted from the exhaust systems of
supersonic jet aeroplanes might be slowly depleting the concentration of the ozone layer in the upper atmosphere.
NO(g) + O3(g) o NO2(g) + O2(g)
Another threat to this ozone layer is probably posed by the use of freons which are used in aerosol sprays and as
refrigerants.

SO2 (SULPHUR DIOXIDE)

Reducing nature :

SO2
2– +3
(Orange) Cr2O 7 Cr (Green)
– +2
(Purple) MnO 4 Mn
+3 +2
(Yellow) Fe Fe (Green)
2–
SO4

Oxidising nature :

SO2
–
NO2 NO3–
(Cl–, Br–, I–)X– Mn+2
H2S S (Milky sulphur)

59
CHEMISTRY FOR NEET & AIIMS
HALOGEN FAMILY

Method of Prepration
F2 : By electrolysis of KHF2 (which is obtained from CaF2)
CaF2 + H2SO4 CaSO4 + 2HF

KF decrease the m.p. of

HF + KF KHF2 the mix. depending upon
the composition.

KHF2 Electrolysis H2(at cathode) + F2 (at anode)

Cl2 :
(i) By electrolysis of aq. NaCl
2NaCl + 2H2O 2NaOH + H 2 + Cl2
(anode)
at cathode
Electrolysis
(ii) 2NaCl 2Na + Cl2
(Molten) (cathode) (anode)

(iii) In laboratory : Oxidising HCl by KMnO4 or MnO2

2KMnO4 + 16HCl 2KCl + 2MnCl2 + 5Cl2 + 8H2O
MnO2 + 4HCl MnCl2 + Cl2 + 2H2O

Br2 : From Bromine water (contains 65 ppm of Br–)

Cl2 + 2Br– 2Cl– + Br2 (Br2 is volatite in nature
Hence it is collected by
(i) removal of Br2 vapour by stream of air.
(ii) absorbing it into Na2CO3 solution.
Br2 + 6OH– Br– + BrO3– + 3H2O
Then acidified to get pure Br2
5 Br– + BrO3– + 6H+ 3Br2 + 3H2O

I2 : Chille salt petre contains traces ofNaIO3 which is reduced to I– by NaHSO3, then oxidation of I– to I2 by
IO3– .
2IO3– + 6HSO3– 2I– + 6SO42– + 6H+
+

5I– + IO3– 6H 3I2 + 3H2O

60
 P-BLOCK ELEMENTS

SOLVED EXAMPLE

Ex. 1 By adding gypsum to cement Ex. 3 Quartz is extensively used as a piezoelectric material.
it contains......
(A) Setting time of cement becomes less
(A) Pb (B) Si
(B) Setting time of cement increases
(C) Ti (D) Sn
(C) Colour of cement becomes light Ans. (B) Quartz, cristobalite and tridymite are some of
(D) Shining surface is obtained the crystalline forms of silica and they are
intercovertable at suitable temperature. Quartz is
Ans. (B) Raw materials for cement-limestone, clay,
edxtensively used as a piezoelectric material.
gypsum, Cement is a dirty greyish heavy powder
containing calcium aluminates and silicated. Ex. 4 The most commonly used reducing agent is
Gypsum (CaSO4.5H2O) is added to the components (A) AlCl3 (B) PbCl2
to increases the setting time of cement to that it gets (C) SnCl4 (D) SnCl2
sufficiently hardened. Setting of cement is an Ans. (D) Reducing agents are those substance which
exothermic process and involves hydration of resduced other subastance and it self oxidises
calcium aluminated and silicates. In SnCl2, Sn exists in +2 oxidation state, thus, acts
as a strong reducing agent i.e.,
Ex. 2 Silcon has a strong tendency to form polymers like SnCl 2  2FeCl3 
o 2FeCl 2  SnCl4
silicones. The chain length of silicon polymer can SnCl 2  2CuCl 2 
o 2CuCl  SnCl 4
be controlled by adding
Ex. 5 Which of the following piars of ions are isolectonic
(A) MeSiCl3 (B) Me2SiCl2
and isostructural
(C) Me3SiCl (D) Me4Si
(A) CO 32  , NO 3 (B) ClO 3 , CO 32 
Ans. (C) Silicon has a strong tendency to form polymers
like silicones. The chain length of silicon polymer (C) SO 32  , NO 3 (D) ClO 3 ,SO 32 
can be controlled by adding Me3SiCl which block Ans. (A) Compounds having same value of total number
the ends as shown below of electrons are known as isolectronic.

For CO32  For NO3

CH3 CH3 Total number of electons Total number of electrons
n HO – Si – OH + HO – Si – CH3 =6+8×3+2 =7+8×3+1
CH3 CH3 = 6 + 24 + 2 = 7 + 25
= 32 = 32
–H2O Polymerisation
O O

C O N O

CH3 CH3 O O

– O – Si – O –n Si – CH3
Hence, CO 32  and NO3 are isolectronic. These two
CH3 CH3
Silicone
ions have similar structure so they are isostructural.
Both have triangular planar structure as in both the
species carbon and nitrogen are sp2 hybridised.

61
CHEMISTRY FOR NEET & AIIMS
Ex. 6 Strong reducing behaviour of H3PO2 is due to oxidation state. However, bismuth forms only one
(A) Low oxidation state of phosphorus well characterised compound in +5 oxidation state.
The compound is
(B) Presence of two –OH groups and one P – H
(A) Bi2O5 (B) BiF5
bond
(C) BiCl5 (D) Bi2S5
(C) Presence of one –OH group and two P – H bonds
(D) High electron gain enthalpy of phosphorus Ans. (B) Stability of +5 oxidation state decreases top to
bottom and +3 oxidation state increases top to
Ans. (C) Strong reduciung behavious of H3PO2 is due to
bottom +5 oxidation state of Bi is BiF5. It is due to
presence of two P – H bonds and one P – OH bond.
smaller size and high electronegativity of flurone.

O Ex. 9 Hot conc. H2SO4 acts as moderately strong oxidising

agent. It oxidises both metals and non-metals. Which
P of the following element is oxidised by conc. H2SO4
H
into two gaseous products
H OH (A) Cu (B) S
Hypophosphorous following
(Monobasic) (C) C (D) Zn
Ans. (C) H2SO4 is a moderately strong oxidising agent
which oxidises both metals and non-metals as shown
Ex. 7 Which of the following statements is wrong below
(A) Single N – N bond is stronger than the single Cu  2H 2 SO 4 (conc) 
o CuSO 4  SO 2  2H 2 O
P – P bond
S  2H 2 SO 4 (conc) 
o 3SO 2  2H 2 O
(B) PH 3 can act a ligand in the formation of
coordiantion compound with transition elements. While carbon on oxidation with H2SO4 produces
(C) NO2 is paramagnetic in nature two types of oxides CO2 and SO2

(D) Covalency of nitrogen in N2O5 is four. C  2H 2SO 4 (conc) 

o CO 2  2SO 2  2H 2 O
Ans. (A) True statement is that single N – N bond is
weaker than the single P – P bond. This is why Ex. 10 A black compound of manganese reacts with a
phosphorous show allotropy but nitrogen does not halogen acid to give greenish yellow gas,. when
excess of this gas reacts with NH3 an unstable
(i) PH 3 acts as a ligand in the formation of
trihalide is formed. In this process the oxidation state
coordination compound due to presence of lone
of nitrogen changes from .......
pair of electrons.
(A) –3 to +3 (B) –3 to 0
(ii) NO2 is paramagnetic in nature due to presence of
(C) –3 to +5 (D) 0 to –3
one unpaired electron. Structure of NO2 is
Ans. (A) Black coloured compound MnO2 reacts with HCl
N to produce greenish yellow coloured gas of Cl2
O O
MnO 2  4HCl 
o MnCl 2  2H 2 O  Cl 2
(Black) (greenish
(iii) Covalency of nitrogen in N2O5 is 4. yellow gas)

O Cl2 on further treatement with NH3 produces NCl3

O O
N N 3 3

O NH 3  3Cl 2 
o NCl3  3HCl
O
NH3(–3) changes to NCl3 (+3) in the above reaction.
Ex. 8 Elements of group- 15 form compounds in +5

62
 P-BLOCK ELEMENTS
Ex. 11 In solid state PCl5 is a ....... Ex. 14 If you have a mixture of CO and CO2, how would
you know about the relative proportions of the two
(A) Covalent solid gases in the given mixture ?
(B) Octahedral structure Sol. (i) Pass mixture through the Ca(OH)2 solution; CO2
is absorbed by Ca(OH)2. The residual volume will
(C) Ionic solid with [PCl6]+ octahedral and [PCl4]– be that of CO
tetrahedral Ca(OH)2 + CO2 o CaCO3 + H2O
(D) Ionic solid with [PCl4]+ tetrahedral and [PCl6]– (ii) Pass mixture through I2O5 ; CO reduces I2O5 to I2.
octahedral 5CO + I2O5 o I2 + 5CO2
I2 thus liberated is determined by titration with
Ans. (D) In solid state PCl5 exists as an ionic solid with
Na2S2O3.
[PCl4]+ tetrahedral and [PCl4]– octahedral.
2Na2S2O3 + I2 o 2NaI + Na2S4O6
+ This is the quantitative method of estimation of CO.
Cl Cl
Cl Cl
P P Ex. 15 True / False
Cl Cl Cl Cl (A) BCl3 in aqueous solution exists as B3+ and Cl–.
Cl Cl
– +
(B) Pure crystalline boron is very unreactive and it
[PCl6] [P Cl4] is attacked only at high temperatures by strong
octahedral tetrahedral
oxidising agents such as a mixture of hot
concentrated H2SO4 and HNO3.
Ex.12 What will happen if borontrifluoride is kept in moist
(C) AlX3 (X = Cl, Br) exists as dimer and retains
air ? dimer formula in non-polar solvents like ether,
(A) It will strongly fumes. benzene etc.
(D) Be2C is called acetylide because it reacts with
(B) It will partially hydrolysed. water yielding ethyne.
(C) It will completely hydrolysed. (E) Pb3O4 a double oxide, is obtained by heating
lead (II) oxide in air.
(D) None of these
Ans. (A) False (B) True
Ans. (A) (C) True (D) False
Sol. In moist air it strongly fumes :but it is partially (E) True
hydrolysed by excess of water. Sol. (A) Statement is incorrect. BCl3 hydrolyses in
aqueous solution to give boric acid. Because it has
large ionisation energies and to make the enthalpy
4BF3 + 6H2O o 3H3O+ + 3BF4– + B(OH)3 of solution of BCl 3 negative, the enthalpy of
hydration of B3+ should be very high (~ 600 g kJ)
BF3 is a colourless gas.
which is unlikely for the small B3+ cation.
(B) 2B + 6HNO3 (aq.) o 2H3BO3 (aq.) + 6NO2
Ex. 13 Al and Ga are trivalent in their compounds but (g)
monovalent compounds are the most stable down the (C) Statement is correct and its dimer structure is as
13th group. Why ? follows. It acquires this structure for attaining an
octet of electrons. Dimer formula retains in non-polar
Sol. Down the group (13th), the stability of +3 state solvent like ether, benzene
decreases and that of +1 state increases due to the Cl Cl Cl
prominent "inert pair" effect. Al Al
Al > Ga > ln > Tl
3+ 3+ 3+ 3+
Cl Cl Cl
Most stable  o lest stable (D) Statement is incorrect as it is methanide because
stability it gives methane on reaction with water.
Be2C + 4H2O o 2Be(OH)2 + CH4
Tl+ > ln+ > Ga+ > Al+
'
(E) 3PbO + O2 o Pb3O4

63
CHEMISTRY FOR NEET & AIIMS
Ex. 16 What happens when : (write only chemical reactions) Ex. 21 Which of the following statement(s) is/are correct ?
(A) iodine is treated with SnCl2.
(A) B2O3 and SiO2 are acidic in nature and are
(B) carbondioxide is passed through a concentrated
aqueous solution of sodium chloride saturated important constituents of glass.
with ammonia.
(B) Borides and silicide are hydrolysed by water
(C) red lead is treated with nitric acid.
forming boranes and silanes respectively.
(D) dilute nitric acid is slowly reacted with tin.
Sol. (D) Sn + 10HNO3 (dilute) o 4Sn(NO3)2 + (C) Diborane on reaction with chlorine (g) forms
NH4NO3 + 3H2O B2H5Cl.
(B) NaCl + NH4OH + CO2 o NaHCO3 + NH4Cl (D) SiO44– gets hydrolysed by acid or water and
(A) 2SnCl2 + I2 o 2SnCl2I2 o SnCl4 + SnI4 form Si2O76–.
(C) Pb3O4 + 4HNO3 o 2Pb(NO3)2 + PbO2 +
2H2O Ans. (A), (B) and (D)
Ex. 17 Write the chemical equations to represent the Sol. (A), (B) and (D) are correct statements but (C) is
following reactions. incorrect.
(A) The oxidation of HCl (aq) to Cl2 (g) by PbO2.
B2H6 + 6Cl2 o 2BCl3 + 6HCl
(B) The disproportionation of SnO to Sn and SnO2.
Sol. (A) PbO2 + 4HCl o PbCl2 + 2H2O + Cl2 Ex. 22 Match the following :
(B) 2SnO o Sn + SnO2 Column - I Column - II
Ex. 18 What will happen if we take Si(CH3)Cl3 as a starting (A) Boron (p) Forms acidic oxides.
material for the preparation of commercial silicon
polymer ? (B) Carbon (q) Pure crystalline form
Sol. With Si(CH3)Cl3 the chain will grow in three places is obtained by Van Arkel
and we will get cross-linked silicon polymer as method.
shown below :
(C) Tin (r) Exists in allotropic
CH3 CH3
| | forms.
— O — Si — O — Si — O —
| | (D) Aluminium (s) Hydroxide is
O O amphoteric in nature.
| |
— O — Si — O — Si — O — Ans.. (A - p,q,r); (B - p,r) ; (C - r,s) ; (D - s)
| |
CH3 CH3 Sol. (A) Exists in various allotropic forms and its oxide,
B2O3 is acidic in nature.
Ex. 19 Give three properties of diamond.
Sol. Diamond is very hard, high melting solid. It is an red hot W
2BI3 2B + 3I2
electrical insulator. Van Arkel method

Ex. 20 Statement - 1 : PbO2 is an oxidising agent and (B) Exists in various allotropic forms like diamond,
reduced to PbO. graphite etc. and its oxide CO2 is acidic in nature.
Statement - 2 : Stability of Pb (II) > Pb (IV) on (C) Exists in allotropic forms like grey tin (D-Sn)
account of inert pair effect.
and white tin (E-Sn). Hydroxide is amphoteric
(A) Statement-1 is True, Statement-2 is True;
Statement-2 is a correct explanation for Statement-1. in nature.
(B) Statement-1 is True, Statement-2 is True; Sn(OH)4 + 2OH– o [Sn(OH)6]2–
Statement-2 is NOT a correct explanation for
Statement-1 Sn(OH)4 + 4H+ o Sn4+ + 4H2O
(C) Statement-1 is True, Statement-2 is False (D) Hydroxide is amphoteric in nature.
(D) Statement-1 is False, Statement-2 is True
Al(OH)3 + OH– o [Al(OH)4]–
Ans. (A)
Sol. Both are correct statements and statement-2 is the Al(OH)3 + 3H+ o Al3+ + 3H2O
correct explanation of statement-1.

64
 P-BLOCK ELEMENTS
Ex. 23 The silicate anion in the mineral kionite is a chain of Ex. 26 What happens when CO2 (g) is passed through
three SiO4 tetrahedra that share corners with adjacent
tetrahedra. The mineral also contains Ca2+ ions, Cu2+ sodium meta borate solution ?
ions, and water molecules in a 1 : 1 : 1 ratio. Sol. 4NaBO2 + CO2 o Na2B4O7 + Na2CO3
(A) Give the formula and charge of the silicate anion.
(B) Given the complete formula for the mineral. Ex. 27 Why anhydrous HF liquid is not electrolysed
Sol. (A) The silicate anion has three SiO4 tetrahedra that
alone to get F2?
share corners with adjacent tetrahedra thus silicate
is Si3O10, hence it can be represented as with charge Sol. Anhydrous HF is only slightly ionized and is,
as = 3 × 4n + 10 × (–2) = –8
therefore a poor conductor of electricity Thus a
8– mixture of KF and HF is electrolysed to increase the
ª O O O º
« | | | » conductivity.
«O — Si — O — Si — O — Si — O»
« | | | » Ex. 28 Identify [A] [B] and [C] and gives the complete
«¬ O O O »¼ chemical reactions involved.
(B) Ca2+, Cu2+ and H2O are in the ratio of 1 : 1 : 1 and
to balance (–8) charge of silicate as ion, (+8) charge
is required thus there are two units each of Ca2+,
Cu2+ and H2O thus, kinoite has formula Ca2Cu2Si3O10
. 2H2O.
Ex. 24 Statement - 1 : The thermal stability of hydrides of
carbon family is in order :
Ans. [A] = Br– ; [B] = BrO3– ; [C] = concentrated H2SO4
CH4 > SiH4 > GeH4 > SnH4 > PbH4
Statement - 2 : E—H bond dissociation enthalpies Sol. 3Br2 + 6OH– o 5Br– + BrO3– + 3H2O
of the hydrides of carbon family decrease down
5Br– + BrO–3 + 6H+ o 3Br2 + 3H2O
the group with increasing atomic size.
(A) Statement-1 is True, Statement-2 is True;
Statement-2 is a correct explanation for Ex. 29 Comment on the following.
Statement-1. (A) Electrolysis of ICN in pyridine solution.
(B) Statement-1 is True, Statement-2 is True;
Statement-2 is NOT a correct explanation for (B) Iodine dissolves in oleum.
Statement-1
(C) Electrical conductivity of molten iodine.
(C) Statement-1 is True, Statement-2 is False
Sol. (A) Iodine is liberated at cathode indicating the
(D) Statement-1 is False, Statement-2 is True
Ans. (A) ionisation of ICN into I+ and CN–.
Sol. Both are correct statements and statement-2 is the (B) Bright blue solution is formed which has been
correct explanation of statement-1. Down the group shown to have I2+ and I3+.
the size of atom increases and thus bond length
increases.
2 I2+ 6H2SO4. SO3 o 2I2+ + 2HS3O10– + 5H2SO4
Ex. 25 Which one of the following element does not
+ SO2
dissolve in fused or aqueous alkalies ?
(A) Boron (B) Silicon
3 I2 + 6H2SO4. SO3 o 2I3+ + 2HS3O10– + 5H2SO4
(C) Aluminium (D) None of these
Ans. (D) + SO2.
Sol. Boron dissolved in fused alkalies according to the (C) It is due to the presence of (I3 and I3 ) species
following reaction.
fused
2B + 6NaOH 2Na3BO3 + 3H2 produced by self ionisation of iodine 3I2 I3 + I3
Silicon and aluminium dissolved in both fused and
aqueous alkalies.

65
CHEMISTRY FOR NEET & AIIMS

Exercise PART - 1 PREVIOUS YEAR (NEET/AIPMT)

1. The oxidation states of sulphur in the anious (A) Only oxidised

(B) Only reduced
SO 2 ,S O 2 and S O 2 follows the order
3 2 6 2 6 (C) Both oxidised and reduced
[CBSE AlPMT 2003] (D) Only proton accepted
2 2 2 6. Among K,Ca, Fe and Zn, the element which can
(A) S2 O 4  S2 O6  SO3 form more than one binary compound with chlorline
is [CBSE AlPMT 2004]
2 2 2
(B) S2 O6  S2 O 4  SO3 (A) Fe (B) Zn
(C) K (D) Ca
2 2 2
(C) S2 O 4  SO3  S2 O6
7. Which one of the following oxides is expected to
exhibit paramagnetic behaviour?
(D) SO32  S2 O 24  S2 O62
[CBSE AlPMT 2005]
(A) CO2 (B) SO2
2. Which one of the following compounds is not a
(C) ClO2 (D) SIO2
protonic acid [CBSE AlPMT 2003]
(A) HOCl is a stronger acid than HOBr 8. Which one of the following arrangements represents
(B) HF is a stronger acid than HCl the correct order of electron gain enthalpy (with
(C) Among hailde ions. iodide is the most powerful negative sign) of the given atomic species
reducing agent [CBSE AlPMT 2005]
(D) Fluorine is the only halogen that does not show (A) Cl <F <S < O (B)O < S < F < Cl
a variable oxidation state (C) S < O < Cl < F (D) F < Cl < O < S

3. Which one of the following compounds is not a 9. Which of the following is the electron deficient
protonic acid? [CBSE AlPMT 2003] molecule? [CBSE AlPMT 2005]
(A) SO(OH)2 (B) SO2(OH)2 (A) B2H6 (B) C2H6
(C) B(OH)3 (D) PO(OH)3 (C) PH3 (D) SiH4

4. Which one of the following statements about the 10. Which one of the following orders is not in
zeolites is false ? [CBSE AlPMT 2004] accordance with the property state against
(A) They are used as cation exchangers [CBSE AlPMT 2006]
(B) They have open structure which enables them (A) F2 > Cl2 > Br2 > l2 Oxidising power
to take up small molecules (B) HI > HBr > HCl > HF Oxidising power
(C) Zeolites are aluminosilcates having three (C) F2 > Cl2 > Br2 > l2 Electronegativity
dimensional network (D) F2 > Cl2 > Br2 > l2 Bond dissociation energy
(D) Some of the SiO44 units are replaced by AlO54 11. Al2O3 can be converted into anhydrous AlCl3 by
and AlO9 ions in zeolites heating [CBSE AlPMT 2006]
6
(A) Al2O3 with HCl gas
5. Which is the best description of behaviour of (B) Al2O3 with NaCl in solid state
bromine in the reaction given below?
(C) a mixture of Al2O3 and carbon in dry Cl2 gas
H2O + Br2 o HBr + HoBr [CBSE AlPMT 2004]
(D) Al2O3 with Cl2 gas

66
 P-BLOCK ELEMENTS
12. Which of the following is the most basic oxide ? 19. The stability of + 1 oxidation state increases in the
[CBSE AlPMT 2006] sequence [CBSE AlPMT 2009]
(A) Al2O3 (B) Sb2O3 (A) Al < Ga < In < TI (B) TI < In < Ga< Al
(C) Bi2O3 (D) SeO2 (C) In < Ti < Ga < Al (D) Ga < In < Al < TI

13. Which of the following oxidation states are the most 20. The tendency of BF3 , BCl3 and BBr3 behave as Lewis
characteristics for lead and tin respectively? acid decreases in the sequence
[CBSE AlPMT 2007] [CBSE AlPMT 2009]
(A) +4,+2 (B) +2,+4 (A) BCl3 > BF3 > BBr3 (B) BBr3 > BCl3 > BF3
(C) +4,+ 4 (D) +2,+2 (C) BBr3 >BF3 > BCl3 (D) BF3 > BCl3 > BBr3

14. Which one of the following anions is present in the 21. Which one of the following molecular hydrides acts
chain structure silicates? [CBSE AlPMT 2007] as a Lewis acid? [CBSE AlPMT 2010]
 (A) NH3 (B) H2O
(A) HS- (B) NH 2
(C) B2H6 (D) CH4
(C) F- (D) I-
22. Oxidation states of P in H4P2O5, H4P2O6 and H4P2O7.
15. Which one of the following anions is present in the
respectively are [CBSE AlPMT 2010]
chainstructure silicates? [CBSE AlPMT 2007]
(A) +3,+5 and +4 (B) +5,+ 3 and +4
(A) Si 2 O67   2
(B) Si 2 O5  n
(C) +5,+ 4and +3 (D) +3,+4 and +5
23. Name the type of the structue of silicate in which
 2
(C) Si 2 O3  n
(D) SiO 4
4
 one oxygen atom of [SiO4)4- is shared ?
[CBSE AlPMT 2000]
16. Which one of the following arrangements does not (A)Sheet silicate
give the correct picture of the trends indicated (B) Pyrosilicate
against it? [CBSE AlPMT 2008] (C) Three dimensional sillcate
(A) F2 > Cl2 > Br2 > l2 Oxidising power (D) Linear chain silicate
(B) F2 > Cl2 > Br2 > l2 Electrongain enthalphy
24. Sulphur trioxide can be obtained by which of the
(C) F2 > Cl2 > Br2 > l2Bond dissociation energy
following reaction [CBSE AlPMT 2012]
(D) F2 > Cl2 > Br2 > l2 Electronegativity
'
(A) CaSO 4  C o
17. Among the following which is the strongest
oxidising agent? [CBSE AlPMT 2009] 
(B) Fe2 SO4 o3
'

(A) F2 (B) Br2 (C) S  H 2 SO 4 'o

(C) l2 (D) Cl2 'o
(D) H 2SO 4  PCl5 
18. The straight chain polymer is formed by
25. Which of the following statements in not valid for
[CBSE AlPMT 2009]
oxoacids of phosphorus? [CBSE AlPMT 2012]
(A) hydrolysis of (CH 3 ) 3 SiCl followed b y
(A) Orthophosphoric acid is used in the
condensation polymerisation
manufacture of triple superphosphate
(B) hydrolysis of CH 3 SiCl 3 followedb by
(B) Hypophosphorous acid is a diprotic acid
condensation polymerisation
(C) All oxoacids contain tetrahedral four
(C) hydrolysis of (CH 3 ) 4 Si b y addition
coordinated phosphorus
polymerisation
(D) All oxoacids contain at least one P=O unit and
(D) hydrolysis of (CH 3 ) 2 SiCl 2 followed by
one P-OH group
condensation polymerisation

67
CHEMISTRY FOR NEET & AIIMS
26. When Cl2 gas reacts with hot and concentrated (C) The bond energy of HF molecules is greater
sodium hydroxide solution, the oxidation number of than in other hydrogen hallides
chlorine changes from [CBSE AlPMT 2012] (D) The effect of nuclear shieldingis much reduced
(A) zero to + 1 and zero ot -5 influorine which polarises the HF molecule
(B) zero to -1 and zero to +5
34. The formation of the oxide ionO2- (g),form oxygen
(C) zero to -1 and zero to +3
atom requires first an exothermic and then an
(D) zero ot +1 and zero to -3 endothemic stepas shown below.
27. Which of these is not a monomer for a high molecular [CBSE AlPMT 2015]
mass silicon polymer ? [NEET 2013] O(g)+e o O (g); 'f H =-141 kJmol-1
- - 0

(A) MeSiCl3 (B) Me2SiCl2 O-(g)+e- o O2 (g) ; 'f H0 =+780 kJmol-1

(C) Me3 SiCl (D) PhSiCl3 Thus, process of formation of O2- in gas phase in
unfavourable even though O2- is isoelectronic with
28. XeF2 is isostructural with [NEET 2013] neon. It is due to the fact that
(A) TeF2 (B) ICI 2 (A) electron repulsion outweighs the stability
gained by achievingnoblegas configuration
(C) SbCl3 (D) BaCl2
(B) O- ion has comparatively smaller size than
29. The basic structural unit of silicates is [NEET 2013] oxygen atom
(A) SiO– (B) SiO 44  (C) Oxygen is more electronegative
(C) SiO 32  (D) SiO 24  (D) addition of electron in oxygen result inlarge size
of the ion
30. Which of the following structure is similar to
graphite [NEET 2013] 35. Which of the statements given below is incorrect

(A) BN (B) B [CBSE AlPMT 2015]

(C) B4C (D) B2H6 (A) Cl2O7 is an anhydride of perchioric acid

(B) O3 molecule is bent
31. Acidity of diprotic acids in aqueous solutions (C) ONF is isoelectronic with NO2
increases in the order [CBSE AlPMT 2014]
(D) OF2 is an oxide of fluorine
(A) H2S < H2Se < H2Te (B) H2Se < H2S < H2Te
(C) H2Te < H2S < H2Se (D) H2Se < H2Te < H2S 36. The stability of +1 oxidation state among Al,Ga,In
and Ti increases in the sequence
32. Strong reducing behavious of H3PO2 is due to [CBSE AlPMT 2015]
[CBSE AlPMT 2015] (A) Ga < In < Al < TI (B) Al < Ga < In < TI
(A) presence of one - OH group and two P-H bonds (C) TI < In < Ga < Al (D) In < TI< Ga < Al
(B) high electron gainenthalpy of phosphorus
 
(C) high oxidation state of phosphorus 37. Decreasing order of stability of O2 , O2 , O2 and
(D) presence of two -OH groups and one P-H bond
O2 is [CBSE AlPMT 2015]
2
33. The variation of the boiling point of the hydrogen
halides is in the order HF >HI>HBr >HCI. What (A) O 
2
! O ! O  ! O 2
2 2 2
explains the higher boiling point of hydrogen
fluoride ? [CBSE AlPMT 2015] (B) O 22 ! O 2 ! O 2 ! O 2
(A) The electronegativity of fluorine is much higher (C) O2 ! O 2
! O 2 ! O 
2 2
than for other elements in the group
(B) There is strong hydrogen bonding between HF (D) O  2 
2 ! O2 ! O2 ! O2
molecules

68
 P-BLOCK ELEMENTS
38. In which of the following pairs, both the species are 44. AlF3 is soluble in HF only in presence of KF. It is
not isostructural? [CBSE AlPMT 2015] due to the formation of [NEET 2016, Phase II]
 (A) K3[AlF3H3] (B) K3[AlF6]
(A) SiCl4 PCI4 (B) Diamond, carbide
(C) AIH3 (D) K[AlF3H]
(C) NH3,PH3 (D) XeF4 ,XeO4
45. Boric acid is an acid because its molecule
39. Maximum bond angle at nitrogen is present in which [NEET 2016, Phase II]
of the following? [CBSE AlPMT 2015] (A) contains replaceable H ion
+

(A) NO2 (B) NO 2 (B) gives up a proton

(C) accepts OH- from water releasing proton
 
(C) NO (D) NO
2 3 (D) combines with protonfrom water moiecule

40. Nitrogen dioxide and sulphur dioxide have some 46. Which one of the following orders is correct for the
properties in common, which property is shown by bond dissociation enthalpy of halogen molecules?
one of these compounds , but not by the other? [NEET 2016, Phase II]
[CBSE AlPMT 2015] (A) Cl2 > Br2 > F2 > l2 (B) Br2 > I2 > F2 > Cl2
(A) Forms acid-rain (C) F2 > Cl2 > Br2 > l2 (D) l2 > Br2 > Cl2 > F2
(B) Is a reducing agent
47. Among the following, the correct order of acidity is
(C) Is soluble inwater
[NEET 2016, Phase I]
(D) Is used as a food-preservative
(A) HCIO < HCIO2 < HCIO3 < HCIO4
41. Among the following, which one is a wrong (B) HCIO2 < HCIO < HCIO3 < HCIO4
statement [NEET 2016, PhaseII] (C) HCIO4 < HCIO2 < HCIO < HCIO3
(A) PH5 and BiCl5 do not exist (D) HCIO 3< HCIO4 < HCIO2 < HCIO
(B) pSdSbonds are present in SO2
(C) SeF4 and CH4 have same shape 48. Which is the correct statement for the given acide
(D) I 3 has bent geometry [NEET 2016, Phase I]
(A) Phosphinic acid is a monprotic acid while
42. The correct geometry and hybridisation for XeF4 phosphonic acid is a diprotic acid
are [NEET 2016 Phase II] (B) Phosphinic acid is a diprotic acid while
(A) octahedra,sp3d2 phosphonic acid is a monoprotic acid
(B) trigonal bipyramidal, sp3d (C) Both are triprotic acids
(C) planar triangle, sp d3 3
(D) Both are diprotic acids
(D) square planar, sp3d2 49. Match the compounds given in column I with the
hybridisation and shape given in column II and mark
43. Hot concentrated sulphuric acid is a moderately
the correct option [NEET 2016, Phase I]
strong oxidising agent,Which of the following
reaction does not show oxidising behaviour? Columu I Column II
[NEET 2016, Phase II] A. XeF6 1. Distorted octahedral
(A) Cu + 2H2SO4 oCuSO4 +SO2 +2H2O B. XeO3 2. Square planar
(B) 3S + 2H2SO4 o3SO2+2H2O C. XeOF4 3. Pyramidal
(C) CaF2 + 2H2SO4 oCO2 +2SO2 +2H2O D. Xef4 4. Square pyramidal
(D) CaF2 + H2SO4 oCaSO4 +2HF Codes

69
CHEMISTRY FOR NEET & AIIMS
A B C D A B C D 54. The species, having bond angles of 1200 is
(A) 1 2 4 3 (B) 4 3 1 2 [NEET 2017]
(C) 4 1 2 3 (D) 1 3 4 2 (A) PH3 (B) CIF3
(C) NCl3 (D) BCl3
50. In which pair of ions both the species contain S-S
bond [NEET 2017]
55. Which one of the following elements is unable to
(A) S2 O 72  ,S2 O32  (B) S4 O 62  ,S2 O32 
form MF63 ion ? [NEET 2018]
2 2 2 2
(C) S2 O ,S2 O 7 8
(D) S4 O ,S2 O
6 7
(A) B (B)Al
51. It is because of inability of ns electrons of the
2 (C) Ga (D) In
valence shell to participate inbonding that
[NEET 2017] 56. Which of the following statements is not true for
(A) Sn reducing while Pb is oxidising
2+ 4+
halogens ? [NEET 2018]
(B) Sn2+ is oxidising while Pb4+ is reducing (A) All but fluorine show positive oxdation states.
(C) Sn2+ and Pb2+ are both oxidising and reducing (B) All are oxidizing agents.
(D) Sn4+ is reducing while Pb4+ is oxidising
(C) All form monobasic oxyacids
52. Which of the following pairs of compounds is (D) Chlorine has the highest electron - gain
isoelectronic and isostructural? [NEET 2017] enthalpy.
(A) BeCl2, XeF2 (B) Tel2,XeF2
(C) IB2 XeF2 (D) IF3, XeF2

53. Match the interhalogen compounds of Column I

with the geometry in Column II and assign the correct
code. [NEET 2017]
Column I Column II
A. XX` (i) T-Shape
B. XX`3 (ii) Pentagonal
bipyramidal
C. XX5` (iii) Linear
D. XX`7 (iv) Tetrahedral
(v) Tetrahedral
Code
A B C D A B C D
(A) iii iv i ii (B) iii i iv ii
(C) v iv iii ii (D) iv iii ii i

70
 P-BLOCK ELEMENTS

Exercise PART - 2 PREVIOUS YEAR (AIIMS)

1. The paramagnetic species is [2004]

(A) KO2 (B) SiO2 10. Among the following molecules
(C) TiO2 (D) BaO2 [2003]

(i) XeO 
(ii) XeOF
3 4
2. The true statement for the acids of phosphorus,

(iii) XeOF
H3PO2, H3PO3 and H3PO4 is 6

(A) the order of their acidity is H3PO4 > H3PO3 > Those having same number of lone pairs on Xe are
H3PO2 (A) (i) and (ii) only (B) (i) and (iii) only
(B) all of them are reducing in nature (C) (ii) and (iii) only (D) (i), (ii) and (iii)
(C) all of them are tribasic acids [2005]
(D) the geometry of phosphorus is tetrahedral in all
11. the number of P – O – P bridges in the structure of
the three. [2003, 2016]
phosphorus pentoxide and phosphorus trioxide are
3. The mixture of concentrated HCl and HNO3 made in respectively
3 : 1 rato contains (A) 6, 6 (B) 5, 5
(A) ClO2 (B) NOCl (C) 5, 6 (D) 6, 5 [2005]
(C) NCl3 (D) N2O4 [2003]
12. F2 formed by reacting K2MnF6 with
4. On dissolving moderate amount of sodium metal in (A) SbF5 (B) MnF3
liquid NH3 at low temperature, which one of the (C) KSbF6 (D) MnF4 [2005]
following does not occur ?
13. Tincture of iodine is
(A) Blue coloured solution is obtained.
(A) aqueous solution of I2
(B) Na+ ions are formed in the solution.
(B) solution of I2 in aqueous KI
(C) Liquid NH3 becomes good conductor of
(C) alcoholic solution of I2
electricity.
(D) aqueous solution of KI. [2006, 2009]
(D) Liquid ammonia remains diamagnetic [2003]
14. The compound molecular is nature in gas phase but
5. The element which form oxides in all oxidation state
ionic in solid state is
+I to +V is
(A) PCl5 (B) CCl4
(A) N (B) P
(C) PCl3 (D) POCl3 [2006]
(C) As (D) Sb [2004]
15. Which two of the following salts are used for
6. The statement true for N3– is
preparing iodized salt ?
(A) it has a non-linear structure
(i) KIO3, (ii) KI,
(B) it is called pseudohalogen
(iii) I2, (iv) HI
(C) the formal oxidation state of nitrogen in this anion
(A) (i) and (ii) (B) (i) and (iii)
is – 1
(C) (ii) and (iv) (D) (iii) and (iv) [2006]
(D) it is isoelectronic with NO2. [2004]
16. The compound used in enrichment of uranium for
7. For electron affinity of halogens which of the
nuclear power plant is
following is correct ?
(A) U3O8 (B) UF6
(A) Br > F (B) F > Cl
(C) UO2(NO3)2 (D) UCI4 [2006]
(C) Br > Cl (D) F > l [2004]
8. Shape of O2F2 is similar to that of 17. Inert gases are mixed in iodine vapours. Then there
(A) C2F2 (B) H2O2 are ____ between them.
(C) H2F2 (D) C2H2 [2004] (A) H-bonding (B) van der Waals forces
(C) electrostatic forces (D) metallic bonds
9. Which of the following is arranged in the increasing
[2007]
order of enthalpy of vaporization ?
18. XeF6 on complete hydrolysis produces
(A) NH3, PH3, AsH3 (B) AsH3, PH3, NH3
(A) XeOF4 (B) XeO2F2
(C) NH3, AsH3, PH3 (D) PH3, AsH3, NH3
(C) XeO3 (D) XeO2 [2007, 2015]

71
CHEMISTRY FOR NEET & AIIMS
(C) XeO2F2 - Distorted trigonal bipyramidal-sp3d
19. The element which is the most abundant in the earth
(D) XeO3F2 - Octahedral - sp3d [2010]
crust is
(A) O (B) S 27. PCl3 on hydrolysis gives fumes of
(C) Al (D) H [2007] (A) H3PO3 + HCl (B) H3PO4 + HCl
(C) H3PO2 and H3PO3 (D) H3PO2 + HCl [2011]
20. What is the correct relationship between the pHs of
isomolar solutions of sodium oxide (pH1), sodium 28. First compound of Xe synthesized was
sulphide (pH2), sodium selenide (pH3) and sodium (A) [XeF]+ [XePtF5]– (B) [XeO2]
telluride (pH4) ? (C) Xe[PtF6] (D) O2[XeF6] [2011]
(A) pH1 > pH2 = pH3 = pH4
29. How many P O bond present in (HP3)3 ?
(B) pH1 < pH2 < pH3 < pH4
(A) 0 (B) 3
(C)pH1 < pH2 > pH3 < pH4
(C) 6 (D) 9 [2012]
(D)pH1 > pH2 > pH3 > pH4 [2008]

21. The number of S – S bonds in sulphur trioxide trimer 30. S2 O82 have
(S3O9) is (A) S–S bond
(A) three (B) two (B) S–O bridge
(C) one (D) zero [2008] (C) O–O bridge
(D) all S–O bond lengths are same [2012]
22. Which acid has P – P linkage ?
(A) Hypophosphoric acid 31. N–N bond length is minimum in
(B) Pyrophoshoric acid (A) N2O (B) N2O3
(C) Metaphosphoric acid (C) N2O4 (D) N2O5 [2012]
(D) orthophosphoric acid [2008]
32. Which of the following is the correct statement for
23. KF combines with HF to form KHF2. This compound PH3 ?
contains the species (A) It is less poisonous than NH3.
(A) K+, F– and H+ (B) K+, F– and HF (B) It is less basic than NH3.
(C) K and [HF2]
+ –
(D) [KHF]+ and F2 (C) Electronegativity of PH3 > NH3.
[2009]
(D) It does not show reducing properties [1999, 2012]
24. The M – O – M bond angles in M2O (where M is
halogen) is in the order 33. Which of the following statement is not true for
(A) Br2O > Cl2O > F2O hydrolysis of XeF6 ?
(B) F2O > Br2O > Cl2O (A) XeOF4 in formed. (B) XeO2F2 is formed.
(C) F2O > Cl2O > Br2O (C) It is a redox reaction. (D) XeO3 is formed.
(D) Cl2O > F2O > Br2O [2009]
[2013]
25. Bromine is added to cold dilute aqueous solution of 34. Rhombic sulphur dissolves best in
NaOH. Then the mixture is boiled. Which of the (A) CS2 (B) H2O
following statements is not true ? (C) ethanol (B) ether [2014]
(A) During the reaction bromine is present in four
different oxidation states. 35. Enrichment of U235 is done by
(B) The greatest difference between the various (A) IF7 (B) CIF3
oxidation states of bromie is 5. (C) IF5 (D) CIF5 [2014]
(C) On acidification of the final mixture bromine is 36. Which halogen forms only one oxoacid (HOX)?
formed. (A) F (B) Cl
(D) Disproportionation of bromine occurs during (C) Br (D) I [2014]
the reaction. [2010]
37. Which is correct regarding acidity ?
26. The shape and hybridisation of some xenon
(A) H2S < H2Se (B) H2S > H2Se
oxyfluorides are given. choose the wrong set.
(C) H2Se > H2Te (D) none of these [2014]
(A) XeOF2 - T - Shape - sp3d
(B) XeOF4 - Square pyramidal-sp3d2

72
 P-BLOCK ELEMENTS
38 For which of the following elements it is difficult to 47. Assertion : BaCO3 is more soluble in HNO3 than in
disproportionate in +3 oxidation state ? plain water.
(A) N (B) As Reason : Carbonate is a weak base and reacts with
(C) Sb (D) Bi [2016] the H+ from the strong acid, causing the barium salt
to dissociate. [2003]
39. Best reagent for the conversion of AgNO3 to Ag is
(A) HClO4 (B) H3PO2 48. Assertion : Sb (III) is not precipitated as sulphide
(C) HIO4 (D) I2 [2016] when in its alkaline solution H2S is passed.
Reason : The concentration of S2– ion in alkaline
40. Chlorine oxidises sodium thiosulphate to form
medium is inadequate for precipitation. [2004]
(A) Na2SO3 (B) Na2O
(C) Na2SO4 (D) Na2CO3 [2016] 49. Assertion : HClO4 is a stronger acid than HClO3.
Reason : Oxidation state of Cl in HClO4 is +8 and in
41. Large difference in boiling points in observed in
HClO3 is +5. [2004]
(A) N and P (B) P and As
50. Assertion : Ozone is a powerful oxidising agent in
(C) As and Sb (D) Sb and Bi [2016]
comparison to O2.
42. Which of the following can be oxidised by SO2 ? Reason : Ozone is diamagnetic but O 2 is
(A) K2Cr2O7 (B) Mg paramagnetic. [2005]
(C) H2O (D) All of these [2016]
51. Assertion : SeCl4 does not have a tetrahedral
43. Which of the following fluorides does not exist? structure.
(A) NF5 (B) PF5 Reason : Se in SeCl4 has two lone pairs. [2005]
(C) AsF5 (D) SbF5 [2017] 52. Assertion : Ozone is an allotrope of oxygen.
44. Which of the following are peroxoacids of sulphur? Reason : Oxygen is bluish colour liquid and in sin-
[2017] glet state it is more paramagnetic. [2007]
(A) H2SO5 and H2S2O8 (B) H2SO5 and H2S2O7 53. Assertion : Bleaching powder reacts with dilute
(C) H2S2O7 and H2S2O8 (D)H2S2O6 and H2S2O7 acids to evolve chlorine.
Reason : The chlorine liberated by the action of
45. Which of the following is true for N2O5 [2018] dilute acids on bleaching powder is called available
(A) Paramagnetic chlorine. [2008]
(B) Anhydride of HNO2
(C) Brown gas 54. Assertion : Liquid ammonia is used for refrigeration.
(D) Exist in solid state In form of [NO2+ ] [NO3– ] Reason : It vaporises quickly. [1997, 2008]

46. Which of the following is incorrect [2018]

55. Assertion : The S-S-S bond angle in S8 molecule is
(A) Red P is toxic
105 °.
(B) White 'P' is highly soluble in CS2
Reason : S8 ha a V-shape. [2009]
(C) Black 'P' is thermodynamic is most stable.
(D) White 'P' is soluble in NaOH evolves PH3 56. Assertion : PCl5 is covalent in gaseous and liquid
ASSERTION AND REASON states but ionic in solid state.
In each of the following questions, two statement Reason : PCl5 in solid state consists of tetrahedral
are given one is assertion and the other is reason. PCl4+ cation and octahedral PCl6– anion. [2010]
Examine the statement carefully and mark the correct 57. Assertion : H2S is less acidic than H2Te.
answer according to the instruction given below Reason : Te has larger radius than S. [2011]
(A) If both the assertion and reason are true and
58. Assertion : R3P O exists but R3N O does not
reason explains the assertion
exist.
(B) If both the assertion and reason are true but
Reason : P is more electronegative than N. [2011]
reason does not explain the assertion
(C) If assertion is true but reason is false 59. Assertion : AgCl is more soluble in NH3 than in
(D) If assertion is false but reason in true water.
(E) Both assertion and reason are false Reason : Ammonia is more polar than water. [2011]

73
CHEMISTRY FOR NEET & AIIMS

71. Assertion : H2S is stronger acid than PH3.

60. Assertion : Helium is used in diving apparatus.
Reason : S is more electronegative than P, conjugate
Reason : solubility of helium is less in blood. [2011]
base HS– is more stable than H2P–. [2016]

61. Assertion : Chlorine undergoes disproportionation 72. Assertion : HClO4 is a stronger acid than HClO3.
reaction in alkaline medium. Reason : Oxidation state of Cl in HClO4 is +VII and
Reason : Cl2 is an oxidising agent. [2011] in HClO3 +V [2017]
73. Assertion : HCOOH formic acid react with H2SO4
62. Assertion : H3PO2 has strong reducing property
form CO. [2018]
but H3PO4 does not.
Reason : H2SO4 is mild (moderate) oxidizing agent
Reason : P-OH bond present in H3PO4. [2012]

63. Assertion : H2Se is less acidic than H2S. 74. Assertion : H3PO4 and H3PO3 both are present in
Reason : S is less electronegative than se. [2012] fertilizers. [2018]
Reason : H3PO3 increases the solubility of fertilizers.
64. Assertion : Bond dissociation energy is F2 > Cl2.
Reason : Cl2 has more electronic repulsion than F2.
75. Assertion : O3 has higher boiling point than O2.
[2013]
Reason : O3 is allotrope of oxygen [2018]
65. Assertion : Bond length of P–Cl bonds in gaseous
PCl5 and solid PCl5 are not equal.
Reason : Because in solid state two PCl5 molecules
are associated. [2013]

66. Assertion : Phosphoric acid has no reducing

properties.
Reason : Phosphoric acid does not contain P–H
bonds. [2013]

67. Assertion : O2 has higher bond length than O3.

Reason : O3 is paramagnetic. [2014]

68. Assertion : H3PO3 is dibasic acid.

Reason : Two hydrogen atoms are directly attached
to the P. [2014]

69. Assertion : Sb2S3 is not soluble in yellow ammonium

sulphide.
Reason : the common ion effect due to S2– ions
reduces the solubility of Sb2S3. [2015]

70. Assertion : Charcoal is used in separation of noble

gases.
Reason : Charcoal has porous structure. [2016]

74
 P-BLOCK ELEMENTS

ANSWER KEY

EXERCISE : PART # I
1. C 2. B 3. C 4. D 5. C 6. A 7. C 8. B 9. A 10. D 11. C 12. C 13. B
14. C 15. C 16. C 17. C 18. D 19. A 20. B 21. C 22. D 23. B 24. B 25. B 26. B
27. C 28. B 29. B 30. A 31. A 32. A 33. B 34. A 35. D 36. A 37. A 38. D 39. C
40. A 41. C 42. A 43. D 44. B 45. C 46. A 47. A 48. A 49. D 50. B 51. D 52. C
53. B 54. D 55. A 56. A

PART # II
1. A 2. D 3. B 4. D 5. A 6. C 7. D 8. B 9. D 10. D 11. A 12. A 13. B
14. A 15. A 16. B 17. B 18. C 19. A 20. D 21. D 22. A 23. C 24. A 25. B 26. D
27. A 28. C 29. B 30. C 31. A 32. B 33. C 34. A 35. B 36. A 37. A 38. D 39. B
40. C 41. C 42. B 43. A 44. A 45. D 46. A 47. A 48. C 49. C 50. B 51. C 52. C
53. B 54. B 55. C 56. A 57. B 58. C 59. C 60. A 61. B 62. B 63. C 64. D 65. A
66. A 67. D 68. C 69. D 70. A 71. A 72. B 73. B 74. C 75. B

75
CHEMISTRY FOR NEET & AIIMS 40-65*0/4

EXERCISE 5. (C) In the reaction

P-1 (NEET/AIPMT) 0 1 1
H 2 O  Br2 o HO Br  H Br
1. (C) Oxidation state of S in SO 32 
The oxidation number of bromine increases from 0 to +1
x+(-2×3)= - 2, and decreases from 0 to -1, due to this reason bromine is
x =+6-2=+4 both oxidised as well as reduced in the above reaction.

Oxidation state of S in S2 O 24 
6. (A) A binary compound is that compound which is formed
2x + (-2×4) = - 2 by two different elements, metals or elements which
2x = +8-2 = + 6 shows variable oxidation states can form more than one
binary compound . In the given elements only Fe shows
6 +2 and +3 oxidation states. So it can form two binary
x 3
2 compounds with chlorine as FECl2 and FeCl3 .

Oxidation state of S in S2 O 62  7. (C) ClO2 shows paramagnetic character due to presence

of unpaired electron in its structure.
2 x + (-2 ×6) = -2
2x = +12-2=10 **
* Cl
×*
10
x 5
2 O O

Hence, increasing order of oxidation states of S is

8. (B) The correct order of election gain enthalpy or
S2 O 42   SO32   S2 O 62  O < S < F < Cl
(value of electron affinity ineV) 1.48 2.207 3.45 3.61
2. (B) Due to strong H-F bond, H+ ions are not easily
removed due to higher electronegativity (EN) of F. Hence 9. (A) B2H6 is election deficient molecule because boron
more bond dissociation energy required. atom has three half-filled orbitals inexcited state. The
structe of B2H6 is represented as follows :
1
Acidic nture v
Bond dissociation energy
H

So. HF is not a stronger acid than HCl. H

970
H
0
112

H H 1220
3. (C) B(OH3)3 is not a protonic acid because it does not
give proton onionisation directly. while it acts as Lewis H
1.19 A 970 0
1.33 A H
H
acid due to acceptance of OH- from water and forms a
hydrated species
B(OH)3 + H2O o [B (OH4)- + H+ 0
1.77 A

4. (D) Zeolites are aluminosillcates having three

dimensional open structure in which four or six
membered rings predominates. Thus, due to open chain In it two electrons of a B-H bond are invoiced in formation
structure, they have cavities and can take up water and of three centre bond, these bonds are represented as
other small molecules. dotted lines.
10. (D) Incorrect order of bond dissociation energy F2 > Cl2
> Br2 >I2 due to following order of size I>Br > Cl > F.

76
 P-BLOCK ELEMENTS
11. (C) Al2O3 my be converted into anhyd. AlCl3 by
heating a mixure of Al2O3 and carbon in dry chiorine

Al 2 O 3  3C  3Cl2 o Al2 Cl6 18. (D)

CH3
Hot and dry AnhyAlCl3
Hydrolysis
Cl Si Cl HO Si OH
-Hcl
Note : Anhydrous AlCl3 exists in the form of dimer as
CH3 CH3
Al2Cl6
Dimethyl
dichlorosilane
12. (C) InAl2O3 + 6HCl o 2BiCl3 +3H2O is most baic
oxide.As across the period basic nature of oxide
-H2O
decreases and on moving down the group it increases. nHO Si OH (Condensation
Polymerisation)
Bl2O3 +6HCl o2BiCl3 +3H2O CH3

13. (B) The tendency to form +2 ionic state increse on

moving down the gropu due to inert pair effect.
O Si O Si O
Most characteristc oxidation state for lead and tin are
CH3
+2,+4 respectively n-1
Straight chain polymer
(silicon)
14. (C) Fluorine is the most electronegative element in the
periodic table.So. it has the greatest proton affinity to
form stable compounds.
Straight chain silanes are silicon oils. These are more
15. (C) [SiO 32  ]n and [Si4 O11]6- have chain structure of stableat high temperature than mineraloils and have less
silicates. tendency to thicken at low temperature.

16. (C) Generally as the size of the atom increases, bond 19. (A) The given elements belong to third group. These
dissociation energy decreases, so in halogens I2 hav elements mainly exhibit+3 and +1 oxidation states. As
lowest bond dissociation energy. but the bond we know, the stability of lower oxidation state, increases
sissociation energy of chlorine is higher than that of on moving down a group due to inert pair effect. Thus,
fluorien because in fluorine there is a greater repulsion the sequence of stability of +1state is
betwween non-bonding electrons (2p). Hence, the order Al < Ga < In < TI
of bond dissociation energy is
Cl2 > F2 > Br2 > I2 20. (B) As the size of halogen atom increases, the acidic
strength of boron halides increases. Thus.BF3 is the
Bond dissociation 243 159 193 151
weakest Lewis acid. This is because of the pS-pSback
energy (kJ/mol)
bonding between the fully filled unutlised 2p-orbitals of
F and vacant 2-p-orbitals of boron which makes BF3 less
17. (A) Fluorine is the most electronegaive element because
electron deficient. Such back donation is not possible in
electronegativity decreases on moving down the group.
case of BCl3 or BBr3 due to larger energy difference
Hence. it gets reduced readily inot F- ion and is the
between their orbitals. Thus, these are more electron
strongest oxidising agent.
deficient, Since on moving down the group the energy
NOTE difference increases, the tendency to behave as Lewis
The electron gain enthalpy of fluorine is less negative acid follows the order.
than that of chlorine inspite of that of that flourine is the BBr3 > BCl3 > BF3 d
strongest oxidising agent. This is due to its low bond
dissociation energy and high heat of hydration as
compared to those of chlorine.

77
CHEMISTRY FOR NEET & AIIMS
21. (C) Key Idea Electron deficient molecules behave as
' o SO HCl
H SO  PCl 
Lewis acid 2 4 5 3
Chloro sulphonic acid
Among the given molecules, only diborane is electron (d)
 POCl3  HCI
deficient,i.e does not have complete octet, Thus. it acts
as a Lewis acid. Thus, SO3 is obtained by heating Fe2 (SO4)3 .
22. (D) Oxidation state of H is + 1 and that of O is- 2. Let the
oxidation state of P in the given compounds is X 25. (B) Hypophosphorous acid, H3PO2 , has the following
structure.
In H4P2O5
(+1) × 4 + 2 × x + (-2) × 5 = 0
O
4 + 2 X - 10 = 0
OH
2x = 6
H P
? x= + 3
In H4P2O6
H
(+1) × 4 + 2 × x + (-2) × 6= 0
4+2x-12 =0 As it contains only one replaceable H-atom (that is
2x = 8 attached with O, not with P directly) so it is a monoprotic
? x=+4 acid.

In H4P2O7 All other given statements are true.

(+1) × 4 + 2 × x + (-2) ×7 = 0 26. (B) When chlorine gas reacts with hot and concentrated
4 + 2x -14 = 0 NaOH solution, it disproportionates into chloride (Cl-)
2x = 10 and chlorate [CiO3 ] ions.
? x=+5
Thus the oxidation states of P in H4 P2O5, H4P2O6 and Oxidation
H4P2O7 are + 3, +4 and + 5 respectively
O -1 +5
23. (B) In pyroslicate, only one oxygen atom is shared. 3Cl2 + 6NaOH 5NaCl+ NaClO3 + 3H 2O
Hot and
Concentrated Reduction
O O

O =O In this process, oxidation number of chlorine changes

= Si from 0 to-1 and 0 to +5
Pyroilicate
-O
NOTE
O
In disproportionation reactions, the same element
undergoes oxidation as well as reduction.

' o CaO  SO  CO
CaSO  C  27. (C) Me3SiCl is not a monomer for a high molecular mass
24. (B) (b) (a) 4 2
silicon polymer because it generates Me3 SiOH when
 '

(b) Fe2 SO4 o Fe2 O3  3SO3
3
subjected to hydrolysis which contains only one
reacting site. Hence, the polymerisation reaction stops
jus after first step.
'
(c) S  2H 2SO4 o 3SO 2  2H 2 O

78
 P-BLOCK ELEMENTS
28. (B) Species having the same number of bond pairs and
31. (A) Acidic strength of hydrides increases as the size of
lone pairs are isostructural (have same structure)
central atom increases which weakens the M-H b ond.
SPecies lp+bp Structure
Since, the size increases from S to Te thus acidic strength
XeF2 4lp +2bp Linear follows the order
H2S < H2Se < H2Te

1
F Xe F Acidicnature v
Bond dissociation enthalpy

S to Te size increases, bond dissociation enthalpy

decreases and acidic nature increases.
TeF2 2lp+2bp Angular or V-shape
32. (A) The oxy acid of phosphorus which contain P-H bond
Te act as a reducing agent or reductant

F F
O

ICI 2 4lp + 2bp - P

Cl I Cl
H OH
H

BaCl2 0/p +2bp Cl -Ba-Cl (linear)

In H3PO2 one -OH group and two P-H bonds are present

29. (B) The basic building unit of all silicates is the tetrahedra 33. (B) Since, there is a strong hydrogen bonding between
HF molecules. Hence, boiling point is highest fo HF
SiO 42  It is represented as
HF > HI > HBr > HI

O- 34. (A) Since, electron repulsion predominate over the

stability gained by achieving noble gas configuration.
Si O-
O =O
- Heence, formation of O2- i gas phase is unfavourable.
O = Si
O- 35. (D) Cl2O7 is an anhydride of perchloric acid
Structure of SiO4- unit
4
' Cl2O7
2HCIO4
-H2O

30. (A) Boron nitride (BN)x resembles with graphite in (b) Shape of O3 molecule is bent.
structrue as shown below

B B C C
N N N C C C
O
B B B C C C
N N C C O O
B B C C
N N C (c) Number of electrons in ONF = 24
Boron nitride Graphite Number of electrons in NO2 =24

79
CHEMISTRY FOR NEET & AIIMS
? ONF and NO2 both are isoelectronic.
(d) OF2 is a fluoride of oxygen because electronegativity
of fluorine is more than that of oxygen.
OF2 = Oxygen difluoride
N
36. (B) Al < Ga < In < Ti H H
This is due to inert pari effect or tendency of ns2 electrons H
Pyramidal
do not participate in bond formation. This tendency
decreases on moving down the group.
Structure of PH3
37. (A) Order of stability v bond order
? Order of the stability of given species

O 2 ! O 2 ! O 2 ! O 22 

Bond order 2.5 2 1.5 1

P
38. (D) (i) Structure of SiCl4
H H
H
Pyramidal
CI

Both NH3 and PH3 have sp3 geometry

Si
(iv) XeF4 has sp3 d 2 hybridisation while XeO4 has sp3
CI CI hybridisation
Cl Structure of XeF4
3
Sp hybridisation
tetrahedral


Structure of PCl4 F F
Xe
F F
CI

Square planar
+
P

CI CI Structure of XeO4
Cl
3
Sp hybridisation
tetrahedral O

Xe
(ii) Diamond and silicon carbide (SiC), both are isostructural
because their central atom is sp3 hybridised and both H H
have tetrahedral arrangement. H
Tetrahedral
(iii) Structure of NH3
Hence, XeF4 and XeO4 are not isostructural.

80
 P-BLOCK ELEMENTS
39. (C) Species Hybridisation Bond angel
NO2 sp less than 1200

NO
2
sp 2 115.40

NO 2 sp(linear) 1800

NO3 sp 2 1200 Geometry-Bent

So, NO2 has maximum bond angel.

Thus, option (c) is incorrect statement

40. (A) Nitrogen dioxide and sulphur dioxide forms acid ran. 42. (A) Geometry is detemined by electron pair arrangement
‘Acid rain’ is the rain water containing sulphuric acid whereas shape is detemined by arrangement of atoms
and nitric acid. around the centre atom.
HNO2 + 2H2O + O2 o 4HNO3
2SO2 + 2H2O + O2 o 2H2SO4
(b) NO2 and SO2 act as a good reducing agent e.g. SO2 F F
reduces halogens to halogen acid
Cl2 + 2H2O + SO2 o 2HCl +H2SO4 Xe

(c) NO2 and SO2 both are soluble inwater. F

F
(d) SO2 is used in the manufacture of sodium bisulphite
(NaHSO3) which is used as a presevative for jams, jellies
and squashes.
Geometry-octahedral, Hybridisation- sp3d2 Thus, option
41. (C) PH5 does not exist due to very less electronegativity (a) is correct.
difference between P and H.Hydrogen is slightly more
electronegative than phosphorus, thus could not hold 43. (D) An oxidising agent is a species,which oxidises the
significantly the sharing electrons. other species and itself gets reduced.
On moving down the group,+5 oxidation state becomes 0 2
(i) Cu  2H 2SO 4 o CuSO 4  SO 2  2H 2 O
less stable while +3 oxidation state becomes more statbel
Is SO2 . pS-dSand pS-pSboth types of bonds are present 0 4
(ii) 3S 2H 2SO 4 o 3SO 2  2H 2 O

H 0 4
(iii) C H 2SO 4 o CO 2  2SO 2  2H 2 O
C
F Se F H H 2 1 2 1
H (iv) CaF2  H 2SO 4 o CaSO 4  2HF

F F 44. (B) key Idea Al3+ shows maximum coordination number

See-saw shape
6, thus it will form AIF63

Thus,SeF4 and CH4 do not have same shape AlF3 forms K3[AlF6] when dissolved inHF inthe presence
of KF as shown below

AIF3  3KF 
HF
o K 3 [AIF6 ]

81
CHEMISTRY FOR NEET & AIIMS
45. (C) Boric acid can be considered as an acid because its 49. (D) A-1, B-3, C-4, D-2
molecule accepts OH- from water, releasing protion The structure of the xenon compounds are represented
- below :
H BO H O B (OH )4 + H+
3 3 2
Acid Base Conjugate Conjugate
base acid
F
Remember In the given options to the question, (a),(b)
F
F
and (c) are correct as all of these sentences have more or Xe Xe
less similar meaning but here (c) option is the most F
F
appropriate one as it gives complete explanation of the F
fact that how boric acid can be combined with an acid.
Distorted Pyramidal XeO3
46. (A) As the size increases, bond dissociation enthalpy Octahedra XeF6
becomes lower. Also, as the size of atoms get smaller, ion F F
pairs on the two atoms get lose enough together to F
F
experience repulsion. In case of F2 this repulsion is bigger Xe
and bond becomes weaker. Xe
F F
Hence, the correct order is Cl2 > Br2 > F2 > I2 F F
47. (A) As the oxidation state of halogen i.e -Cl in this case Square planar
Square pyramidal XeOF4
increase, acidity of oxyacid increases. XeOF4
HCIO : Oxidation state o Cl = +1
HCIO2 : Oxidation state of Cl = +3
HCIO3 : Oxidation state of Cl = +5+ 50. (B) S4 O 32  and S2 O 32  have S-S bond

HCIO4 : Oxidation state of Cl = +7 2e

Se
Therefore, the correct order of acidity would be O
HCIO < HCIO2 < HCIO3 < HCIO3 < HCIO4 O- S
S S O O
O S S -
O O
48. (A) Phosphinic acid O
O O Thiousulphate ion

(S O )
4
2-
6
(S O )
2
2-
3

P (tetrathionate)
H OH
H 51. (D) The inability of nis2 electrons of the valence shell to
Phosphonic acid participate in bondingis called as inert pair effect. Due to
O this effect. the lower oxidation state becomes more stable
ondescending the group. Thus, Sn2+ is a a reducing
P agent while Pb4+ act as an oxidising agent.
HO H
52. (C) Isoelectronic species have equal number of valence
HO
electrons.
Due to the presence of one replaceable proton in
phosphinic acid, it is monoprtoc acod. An due to presence Both IBr2 and XeF2 are linear and number of valence
of two replaceable proton in phosphonic acid, it is
electrons present in both the species in same. i.e they
diprotic acid.
are also isoelectronic

82
 P-BLOCK ELEMENTS
S.No Compounds Number of Valence Geometry
electrons
P
1. BeCl2 2+14=16 Linear PH3 H 93.50
H
2. XeF2 8+14=22 Linear H
(Pyramidal)
3. Tel2 6+14=20 Bent or
V-shape F

4. IBr2 7+14+1=22 Linear CIF3 CI F 900

5. IF3 7+21=28 T-Shape F

(T-shaped)

53. (B) Two different halogens may react ot form

interhalogen compounds as ..
NCl3 N d 107.80
XX` (CIF,BrF, BrCl, IF, ICI) Linear
Cl Cl
XX`3 (CIF3, BrF3, IF3, ICI3) Bent T shaped
Cl
XX`5 (CIF5,BrCl5,IF5) Square- pyrmidal (Pyramidal)
XX`7 (IF7) Pentagonal
bipyramidal CI

BCL3 B 1200
54. (D) The species having bond angles of 1200 is BCl3 .it is
sp2 - hybridsed and central atom does not have any lone Cl Cl
pair of electrons. (Trigonal planar)
Chemical Species Bond angle
Formula
55. (A) Due to absence of vacant d-orbitals
56. (A)

83
CHEMISTRY FOR NEET & AIIMS

EXERCISE
8. (B) : O2F2 and H2O2, both have open book type structure.
P-2 (AIIMS)

1. (A) : KO2 is a superoxide of potassium containing

superoxide ion, O2– which has a three electron bond.
F 87.5°
Thus, this ion can be represented as [ .O. . . . O
. . ]. The

.5°
presence of one unpaired electron in three electron bond

109
makes this ion paramagnetic. O 94° O O
1.27° H 97°
2. (D) : H3PO2, H3PO3 and H3PO4 contain one, two and three O
ionisable hydrogen atoms respectively. F
H3PO2 U H+ + H2PO2–
H3PO3 U H+ + H2PO3– U 2H+ + HPO32–
Nonlinear and nonplanar
H3PO4 U H+ + H2PO4– U 2H+ + HPO42– O2F 2 molecule
structure of H2O2 molecule
U 3H+ + PO43–
But there is very little difference in acidity.
In O2F2, one O – O bond and two O – F bonds are lying
O O O in different planes, i.e. this molecule like H2O2 has non-
H P OH H P OH HO P OH linear and non-planar structure.

H OH OH 9. (D)
3 3 3
sp sp sp
H3PO2 H3PO3 H3PO4

As sp3 hybridised, therefore all are tetrahedral. ..

3. (B) : 3HCl + HNO3 NOCl + 2H2 O + 2Cl
nitrosyl
aqua regia chloride 10. (D) : XeO3 : Xe
O O
4. (D) : The alkali metals dissolve in liquid ammonia without
evolution of hydroge. The colour of the dilute solution
O
is blue and is paramagnetic in nature.
M o M+ (in liquid ammonia) = e– (ammoniated) O
M + (x + y)NH3 o [M(NH3)x]+ + e– (NH3)y solvated F F
electron
5. (A) : Stability of oxides of higher oxidation states XeOF4 : Xe
decreases with increasing atomic number.
Nitrogen exhibits a large number of oxidation states such F .. F
as +1, +2, +3, +4, +5 in N2O, NO, N2O3, N2O4 and N2O5.
6. (C) : Azide ion is a linear molecule, it is a pseudo halide
and formal oxidation state of N in azide ion is –1. F
Resonance structures of N3– ion are : F
..

.. .. . . . 2. .. ..
.N. N
+
N N N N
+
.. N N N
Xe
7. (D) : F Cl Br I XeF6 : F F
Electron affinity –3.6 –3.8 –3.5 –3.2
The low value of electron affinity of fluorine is probably F
due to small size of fluorine atoms, i.e. electron density is F
high which hinders the addition of an extra electron.

84
 P-BLOCK ELEMENTS
.. III Na2Se + H2O o 2NaOH + H2Se
P
.. IV Na2Te + H2O o 2NaOH + H2Te,
O O
I will have the highest pH. Among H2S, H2Se, H2Te
O acidity goes on increasing on going down the group as
P .. P
.O. bond length increases on increasing size of central atom.
11. (A) : So, pH4 < pH3 < pH2.
O
.. .O. Overall order is pH1 > pH2 > pH3 > pH4
.P.
(P4O6) 21. (D) : O O
O
P
S
..
O O O O
O
O Cyclic trimer
.. O S S
.O. P .. P O
.O. O O O

.O. .O. 22. (A) : Hypophosphoric acid is

P
O O
.O.
(P4O10) HO P P OH
HO OH
Pyrophosphoric acid
1
12. (A) : K 2 MnF6  2SbF5 o 2KSbF6  MnF3  F2
2 OH OH
In this reaction, the stronger Lewis acid SbF5 displaces O P O P O
the weaker one, MnF4 from its salt. MnF4 is unstabel and OH OH
readily decomposes to give MnF3 and fluorine. Metaphosphoric acid
13. (B) : Tincture of iodine is an aqueous solution of I2 in KI, HO O OH
and French iodine is a solution in clcohol. P P
14. (A) : PCl5 is molecular in the gas phase but exists as O O O
[PCl4]+ [PCl6]– in the crystalline solid. Orthophosphoric acid

15. (A) : When traces of iodide in the form of KIO3/KI is O

added to the salt, iodised salt is obtained. HO P OH
16. (B) OH

17. (B) : There are several types of van der Waals attraction 23. (C) : The fluoride ion, by a process of hydrogen bonding,
: dipole-dipole, dipole-induced-dipole and spontaneous- forms the anion, HF2– . The compounds in written as
dipole-induced-dipole. the spontaneous-dipole-induced- K+[HF2]–
dipole attractions are also known as London dispersion
forces. LDF are surprisingly strong but are only short .. .. .. .. .. ..
range forces e.g. surface of neutral molecules. In case of
halogens, LDF increases as F2 < Cl2 < Br2 < I2. 24. (A) : O O O
116° 111° 105°
18. (C) : XeF6(s) + 3H2O(l) o XeO3(s) + 6HF(aq)
Br Br Cl Cl F F
highly
explosive In OF2 repulsion between lone pairs is greater than that
19. (A) : Oxygen is the most abundant element in the earth’s between bond pair since electrons are away from O and
crust. (above 45.5 wt %) nearer to F. In Cl2O, bonding electrons are nearer to O
than to Cl, so the bond angle is greater than 109°28'. In
20. (D) : I Na2O + H2O o 2NaOH Br2O, the bonding electrons are more closer to oxygen
II Na2S + H2O o 2NaOH + H2S than in Cl2O, so the bond angle is largest (116°).

85
CHEMISTRY FOR NEET & AIIMS
25. (B) : 2NaOH(dilute) + Br2 31. (A) : N – N bond length is minimum in N2O.
Compound Structure

o NaBrO + NaBr + H2O
cold

N2O N 113 pm N 119 pm O

3NaBrO 
300K
o NaBrO3 Linear
Sodium hypobromide
O O
On acidification, the final mixture gives bromine.

12

pm
1
5NaBrO + NaBrO3 + 6HCl –o

pm

4
186 pm

11
6NaCl + 3Br2 + 3H2O N2O3
130° N N
117°
Thus, during the reaction, bromine is present in four
O
different oxidation states i.e., zero in Br2, +1 in NaBrO, –
1 in NaBr and +5 in NaBrO3. The greatest difference Planar
between various oxidation states of bromine is 6 and not O O

12

pm
5. On acidification of the final mixture, Br2 is formed and

1
pm

12
175 pm
disproportionation of Br2 occurs during the reaction 135° N N
N2O4
giving BrO–, Br– and BrO3– ions.
O O
F
O Planar
26. (D) : The structure of XeO3F2 - O Xe
F O
No. of lone pair of Xe = 0 and no. of bond pair = 5 N2O5
Hybridisation of Xe = sp3d
Hance, shape of XeO3F2 should be trigonal bipyramidal
and not octahedral. Planar
32. (B) : Nitrogen is more electronegative than the
27. (A) : Phosphorus trichloride reacts violently with water
phosphorus atom. In NH3, nitrogen attracts the bonded
forming phosphorous acid.
pair of electrons between N and H atoms
PCl3 + 3HOH o H3PO3 + 3HCl
28. (C) : XePtF6 was first real compound of any of the noble 33. (C) : Hydrolysis of XeF6 is not a redox reaction. XeF6
gases. reacts violently with water, but slow hydrolysis by
atmospheric moisture gives highly explosive solid, XeO3.
XeF6(s) + 3H2O(l) o XeO3(s) + 6HF(aq)
29. (B) : O
O OH Partial hydrolysis of XeF6 yields XeOF4 and XeO2F2.
P P XeF6 + H2O o XeOF4 + 2HF
O XeF6 + 2H2O o XeO2F2 + 4HF
HO
O O 34. (A) : Rhombic sulphur is insoluble in water but readily
P soluble in carbon disulphide, CS2. It dissolves to some
O OH extent in benzene, alcohol and ether also.
35. (B) : CIF3 and BrF3 are used for the production of UF6 in
30. (C) : The structure of peroxodisulfate anion is : the enrichment of U235.
U(s) + 3ClF3(l) ® UF6(g) + 3CIF(g)
2-
O O 36. (A) : Due to high electronegativity and small size, fluorine
S O O forms only one oxoacid, HOF known as fluoric(I) acid or
O O S hypofluorous acid.
O O
37. (A) : Due to decrease in bond (H–E, where E = O, S, Se,
It has a O–O bridge. Te) dissociation enthalpy down the group, acidic
character increases.
Hence, the order is :
H2O < H2S < H2Se < H2Te

86
 P-BLOCK ELEMENTS
38. (D) : In nitrogen family, due to inert pair effect as the release easier and thus increases the acidic strength.
tendency to show +3 oxidation state increases down the
50. (B) : Due to the ease with which it can liberate nascent
group from As to Bi, tendency to disproportionate
oxygen, O3 acts as a powerful oxidising agent.
decreases.
O3 o O 2 + O
39. (B) : H3PO2 is a good reducing agent as it contains two . . .
O. . .O O
P-H bonds and thus reduces AgNO3 to Ag.
4AgNO3 + H3PO2 + 2H2O o 4Agp + H3PO4 + 4HNO3 paramagnetic O O
(due to presence of
diamagnetic
two unpaired electrons)
40. (C) : Na2S2O3 + H2O + Cl2 o Na2SO4 + 2HCl + S
51. (C) : SeCl4 possess see-saw geometry, which can be
Element Boiling point (K) Dofferemce regarded as a distorted trigonal bipyramidal structure,
N 772 having one lone pair (lp) of electrons in the basal position
41. (C) : } 476.8
P 554 of the trigonal bipyramida. See-saw geometry of SeCl4
} 334
As 888 molecules arises due to the sp3d hybridisation of the
} 972
Sb 1860 central atom. The distortion in shape is due to the
} 23
Bi 1837 presence of one lone pair of electrons.
52. (C) : Oxygen is a colourless, odourless and tasteless
gas. It is paramagnetic in gaseous, liquid and solid states.
42. (B) : With K2Cr2O7, SO2 works as reducing agent.
It can be liquefied to a pale blue liquid by compressing
K2Cr2O7 + H2SO4 + 3SO2 o
the gas at a very low temperature. Its allotropic
K2SO4 + Cr2(SO4)3 + H2O
modification is ozone.
With water the reaction is not a redox reaction,
53. (B) : The reaction involved is
43. (A) : NF5 does not exist because N does not form
CaOCl2 + H2SO4 o CaSO4 + H2O + Cl2
pentahalides due to the absence of d-orbital in its valence
The available chlorine may be defined as the % of chlorine
shell. While P, As and Sb form pentahalides of the general
liberated when one mole of bleaching powder (127 g) is
formula MX5 (where, M = P, As and Sb) due to the
treated with excess of dilute H2SO4.
presence of vacant d-orbitals in their respective valence
shell.
54. (B) : Liquid ammonia is used in refrigeration on account
44. (A) : Both have peroxy linkage of its large heat of evaporation.
45. (D) : N2O5 in solid form exists as NO3– & NO2–
55. (C) : As atoms in S8 molecule undergo sp3 hybridisation
46. (A)
and contain two lone pairs of electrons on each and
47. (A) : BaCO3 + 2HNO3 o Ba(NO3) + H2O + CO2 exists as staggered 8 atoms-rings.

48. (C) : Sb(III) is a basic redical of IIB group for which 56. (A) : PCl5 is trigonal bipyramidal containing sp3d
group reagent is H2S in presence of dilute HCl. hybridized P atom in liquid and gaseous states whereas
It is necessary to maintain the proper hydrogen ion in solid state it consists of tetrahedral PCl4+ cation and
concentration for the precipitation of IInd group cations octahedral PCl6– anion.
and to check the precipitation of IV group cations. 57. (A) : As the size of the atom M in H2M increases, the
49. (C) : Greater the number of negative ions present in the strength of the H – M bond decreases.
oxy-acid, greater the acidic strength. 58. (C) : The electronegativity of N (3.0) is much higher than
In general, the strengths of acids that have general P (2.1).
formula, (HO)mZOn can be related to the value of n. As
59. (C) : Solubility of AgCl (at 25°C) in H2O
the value of n increases, acidic character also increases.
= 0.0020 g AgCl per litre of H2O
The negative ions draw electrons away from the Z-atom
Solubility of AgCl in NH3 (at 25°C)
and make it more positive. The Z-atom, therefore,
= 14.00 g AgCl dissolved per kg of NH3
becomes more effective in withdrawing electron density
Solubility of AgCl is more in NH3 due to formation of
away from the oxygen atom that bonded to hydrogen. In
soluble stable complex [Ag(NH3)2]+.
turn, the electrons of O–H bond are drawn more strongly
Ammonia is less polar than water, as oxygen is more
away from the H-atom. The net effect is it makes proton
electronegative than nitrogen.

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CHEMISTRY FOR NEET & AIIMS
67. (D) : The resonance forms do not show any unshared
60. (A) : A mixture of 20% O2 and 90% He is used in diving
electrons. Hence. O3 molecule does not show any
apparatus which gives the same partial pressure of O2 as
paramagnetic properties.
in normal air at 1 atm. Due to high paratial pressure and
greater solubility, N2 gets dissolved in blood and form

12
pm
O O

8
O O

pm
12
bubbles (bends or decompression sickness). Hence, N2 Str. O O O O
is replaced by helium which is much less soluble in 121 pm
biological fluids. B.O. 2.0 1.5
The bond length decreases as bond order increases.
61. (B) : Cl2 + 2NaOH (dil.)  
cold
o Hence, bond length of O3 is higher than O2.
NaCl + NaOCl + H2O
68. (C) : Structure of H3PO3 is
3Cl2 + 6NaOH (conc.)  
heat
o
5NaCl + NaClO3 + 3H2O O
Chlorine undergoes the simultaneous oxidation- P
reducation. Chlorine is simultaneously reduced to OH
H
OH
chloride ion (Cl–) and is oxidised to either ClO– or ClO3–
ion. Halogens (e.g. Cl) have a strong tendency to accept Due to the presence of two hydroxyl protons it is dibasic
electrons, so they act as strong oxidising agents. acid.
69. (D) : Sb2S3 is soluble in yellow ammonium sulphide.
O O Sb2S3 + 3(NH4)2S o 2(NH4)3sbS3

P P 70. (A) : Inert gases are adsorbed on the charcoal.

H OH
62. (B) : HO H HO OH  
71. (A) : H 2S(g)  aq o HS(aq)  H (aq)
(H3PO2) (H3PO4)
 
PH 3(g)  aq o H 2 P(aq)  H (aq)
Oxoacids of phosphorus which contain P – H bond act
As S is more electronegative than P, conjugate base HS–
as reducing agents and reduce metal salts to free metals.
is more stable than H2P–. Hence, H2S is stronger acid
Thus, H3PO2 act as reducing agent while H3PO4 does
than PH3.
not.
63. (C) : S is more electronegative than Se.
72. (B) : Both Assertion and Reason are true but reason is
64. (D) : Bond dissociation energy is F2 < Cl2 because of not the correct explanation of assertion. Greater the
relatively large electron-electron repulsion among the number of negative atoms present in the oxy-acid make
lone pairs in F2 molecule where they are much closer to the acid stronger. In general, the strengths of acids that
each other than in Cl2. have general formula (HO)m ZOn can be related to the
value of n. As the value of n increases, acidic character
65. (A) : As in solid state, PCl5 exists as an ionic solid
also increases. The negative atoms draw electrons away
[PCl4]+[PCl6]– in which the cation, [PCl4]+ is tetrahedral
from the Z-atom and make it more positive. The Z-atom,
and the anion, [PCl6]– is octahedral. PCl5 in gaseous state
therefore, becomes more effective in withdrawing
has trigonal bipyramidal structure in which three
electron density awayfrom the oxygen atom that bonded
equatorial bonds are equivalent, while the two axial bonds
to hydrogen. In turn, the electrons of H – O bond are
are longer than equatorial bonds duw to more bond pair
drawn more strongly away from the H-atom. The net
repulsion.
effect makes it easier from the proton release and
66. (A) : Phosphoric acid is a tribasic acid, i.e,. increases the acid a strength.
3 hydroxyl groups are present.
O 73. (B) : In HCOOH  H 2SO4
o H2O + CO
H2SO4 behaves like dehydrating agent.
HO P OH
74. (C)
OH 75. (B) : Both statements are true but are not related.

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TRANSITION ELEMENTS
CHAPTER
07
(D & F - BLOCK)
I've always believed there are moments in our lives which can be defined
as a transition between the before and after, between the cause and
the effect.

''BENJAMIN X. WRETLIND''

INTRODUCTION

T
he d-block of the periodic table contains the elements of the groups 3-12 in which
the d orbitals are progressively filled in each of the four long periods. The elements
constituting the f-block are those in which the 4 f and 5 f orbitals are progressively
filled in the latter two long periods; these elements are formal members of group 3
from which they have been taken out to form a separate f-block of the periodic table.
The names transition metals and inner transition metals are often used to refer to the
elements of d-and f-blocks respectively.
There are mainly three series of the transition metals, 3d series (Sc to Zn), 4d series
(Y to Cd) and 5d series (La to Hg, omitting Ce to Lu). The fourth 6d series which
begins with Ac is still incomplete. The two series of the inner transition metals, (4f
and 5f) are known as lanthanoids and actinoids respectively.
The presence of partially filled d or f orbitals in their atoms sets the study of the
transition elements and their compounds apart from that of the main group elements.
However, the usual theory of valence as applicable to the main group elements can
also be applied successfully to the transition elements.

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CHEMISTRY FOR NEET & AIIMS

(a) The element lying between s- and p-block element of the periodic table are collectively known as transition
or transitional elements. (T.E'.S.)
(b) Their properties are transitional between the highly electropositive s- block element to least electropositive
p- block element.
(c) In d- block elements, the last differentiating electron is accommodated to the penultimate shell.
(d) The general electronic configuration of transition element is (n-1)d1-10 ns0, 1 or 2
(e) These elements either in their atomic state or in any of their common oxidation state have partly filled
(n-1)d orbitals of (n-1)th main shell.
(f) The transition elements have an incompletely filled d-level. Since Zn, Cd, Hg elements have d10 configuration
and are not considered as transition elements but they are d-block elements.

Electronic Configuration
Ist Transition Series
Symbol Sc Ti V Cr Mn Fe Co Ni Cu Zn
Atomic No. 21 22 23 24 25 26 27 28 29 30
3d electrons 1 2 3 5 5 6 7 8 10 10
4s electrons 2 2 2 1 2 2 2 2 1 2

Irregular electronic configuration Cr, Cu

IInd Transition Series
Symbol Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
Atomic No. 39 40 41 42 43 44 45 46 47 48
4d electrons 1 2 4 5 5 7 8 10 10 10
5s electrons 2 2 1 1 2 1 1 0 1 2

Irregular electronic configuration Nb, Mo, Ru, Rh, Pd, Ag

IIIrd Transition Series
Symbol La Hf Ta W Re Os Ir Pt Au Hg
Atomic No. 57 72 73 74 75 76 77 78 79 80
5d electrons 1 2 3 4 5 6 7 9 10 10
6s electrons 2 2 2 2 2 2 2 1 1 2

KEY POINTS
Irregular electronic configuration W, Pt, Au
The irregularities in the observed configuration of Cr (3d5 4s1 instead of 3d4 4s2 ), Cu (3d10 4s1 ), Mo (4d5
5s1), Pd ([Kr] 4d10 5s0 ), Au ( [Xe] 4f14 5d10 6s1 ), Ag ([Kr] 4d10 5s1 ) are explained on the basis of the concept
that half-filled and completely filled d-orbitals are relatively more stable than other d-orbitals.

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 TRANSITION ELEMENTS (d & f BLOCK)
Ex. On what ground you can say that scandium (Z = 21) is a transition element but zinc (Z = 30) is not?
Sol. On the basis of incompletely filled 3d orbitals of scandium, [Ar]18 3d1 4s2 , and completely filled 3d orbitals of Zn,
[Ar]18 3d10 4s2, they are considered transition and non-transition elements respectively.

Ex. The element with the electronic configuration [Xe]54 4f14 5d1 6s2 is a :
(A) representative element (B) d-block element
(C) lanthanod (D) actinoid
Sol. After achieving 4f 5d 6s configuration, the next electron goes to 5d and this is the case of Lu(Z = 71) which is
14 0 2

the last element of lanthanoid series.

Therefore, (C) option is correct.

Ex. The number of transition series is :

(A) two (B) three (C) four (D) five
Sol. There are four transition series ; 3d, 4d, 5d and 6d series.
Therefore, (C) option is correct.

General properties of d-Block Elements

(a) The properties of d-block elements of any given period are not so much different from one another as those of
the same period of non transition elements.
(b) It is due to the fact that, in transition series, there is no change in number of electrons of outermost shell and
only change occur in (n-1)d electron from member to member in a period.

Metallic Character
(a) All the d-block elements are metals as the numbers of electrons in the outer most shell are one or two.
(b) They are hard, malleable and ductile (except Hg). IB group elements Cu, Ag and Au are most ductile and soft.
(c) These are good conductor of heat and electricity (due to free e—) Elements of IB group are most conductive
in nature. Their order of conductivity is Ag > Cu > Au > Al
(d) Covalent and metallic bonding both exist in the atom of transition metals.
(e) The presence of partially filled d-subshell favour covalent bonding and metallic bonding. These bonding are
favourable also due to possession of one or two electron in outermost energy shell.

Reducing Power
(a) Reducing power of d-block elements depends on their electrode potential.
(b) Standard oxidation potential (SOP) of Cu is minimum in the 3d series so it is least reducing elements in 3d series.
(c) Au is the least reducing element in the d-block because of highest +ve value of Standard reduction potential.
(d) The poor reducing capacity of the transition metal is due to high heats of vaporization, high ionization
potential and low heat of hydration of their ions, because reduction potential depends upon all these three factors.

Density
(a) The atomic volume of the transition elements are low, compared with s-block, so their density is comparatively
high (D = M/V)
(b) Os (22.57 gm cm—3) and Ir (22.61 gm cm—3) have highest density.

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CHEMISTRY FOR NEET & AIIMS
(c) In all the groups (except IIIB) there is normal increase in density from 3d to 4d series, and from 4d to 5d, it
increases just double. Due to lanthanide contraction Ex. Ti < Zr << Hf
(d) In 3d series

Sc Ti V Cr Mn Fe Co Ni Cu Zn
Density increases Density decreases
(e) In 3d series highest density – Cu lowest density – Sc
(f) Some important orders of density
Fe < Ni < Cu Fe < Cu < Au Fe < Hg < Au

Melting and boiling points

(a) Melting and boiling point of d-block > s-block
Reason : Stronger metallic bond and presence of covalent bond formed by unpaired d-electrons.)
(b) In Zn, Cd, and Hg there is no unpaired electron present in d-orbital, hence due to absence of covalent bond
melting and boiling point are very low in series. (Volatile metals Zn, Cd, Hg)
(c) In 3d series Sc to Cr melting and boiling point increases then Mn to Zn melting and boiling point decreases
(d) As the number of d-electron increases, the number of covalent bond between the atoms are expected to
increase up to Cr-Mo-W family where each of the d-orbital has only unpaired electrons and the opportunity for
covalent sharing is greatest.
(e) Mn and Tc have comparatively low melting point, due to weak metallic bond because of stable Half filled (d 5)
configuration
(f) Lowest melting point Hg (– 38°C), Highest melting point W ( ~ 3400°C)

2000
1900
1672 V Cr 1530 Co 1455
Ti 1710 Fe
Melting Point t/°C

1500 Sc Mn 1495 Ni
1397 1083
1244
Cu
1000

420 Zn
500

0 B
IIIB IV
B
V
B
VI
B
VII
B
VIII I B
II
Graphic representation m.p. of 3d-series elements

Characteristic properties of transition elements :

(a) Variable oxidation state (b) Coloured ions (c) Paramagnetic properties
(d) Catalytic properties (e) Formation of alloys (f) Formation of interstitial compounds
(g) Formation of complexes.

Ex. Why do the transition elements have higher boiling & melting points ?
Sol. Because of having larger number of unpaired electrons in their atoms, they have stronger interatomic interaction
and hence stronger bonding between atoms. Hence strong metallic bonds between the atoms of these elements
attribute to their high melting and boiling points.

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 TRANSITION ELEMENTS (d & f BLOCK)
Ex. The atomic radii of transition elements in a period are
(A) smaller than those of s-block as well as p-block elements.
(B) larger than those of s-block as well as p-block elements.
(C) smaller than those of s-block but larger than those of p-block elements.
(D) larger than those of s-block but smaller than those of p-block elements.
Sol. Across the period the atomic radii generally decrease with increasing atomic number as effective nuclear charge
increase.
Therefore, (C) option is correct.

Variable Valency or Variable Oxidation States :

(a) They exhibit variable valency due to involvement of (ns) and (n-1)d electrons. Due to less energy difference
between these electrons.
(b) The oxidation states of all transition elements of '3d' series are as follows -
Element Conf. Outer electronic configuration Oxidation states

Sc 3d14s2 +3

3d 4s

Ti 3d24s2 +2 +3 +4

V 3d34s2 +2 +3 +4 +5

Cr 3d54s1 +1 +2 +3 +4 +5 +6

Mn 3d54s2 +2 +3 +4 +5 +6 +7

Fe 3d64s2 +2 +3 +4 +6

Co 3d74s2 +2 +3 +4

Ni 3d84s2 +2 +3 +4

Cu 3d 104s1 +1 +2

Zn 3d 104s2 +2

(c) Highest oxidation state of transition elements can be calculated by n + 2 where (n = number of
unpaired electrons) It is not applied for Cr and Cu.
(d) The transition metal ions having stable configuration like d0 d5 or d10 are more stable.
Ex. Sc+3, Ti+4, V+5, Fe+3 , Mn+2, Zn+2 etc.

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CHEMISTRY FOR NEET & AIIMS
(e) In aqueous medium Cr+3 is stable.
(f) Co+3 and Ni+2 are stable in complexes..
(g) In aqueous medium due to disproportionation Cu+1 is less stable than Cu+2 while its configuration is 3d10
(h) Most common oxidation state among the transition elements is +2.
(i) Highest oxidation state shown by transition elements of '4d' and '5d' series is +8 by Ru (44) and Os (76).
(j) The common oxidation state shown by elements of IIIB i.e., Sc, Y, La and Ac is +3 as their divalent compounds
are highly unstable.
(k) In lower oxidation state transition elements form ionic compounds and in higher oxidation state their compounds
are covalent.
(l) They also shows zero oxidation state in their carbonyl compounds like Ni(CO)4.
(m) Usually transition metal ions in their lower oxidation state act as reducing agents and in higher oxidation state
they are oxidising agents.
Ex. Sc+2, Ti+2, V+2, Fe+2, Co+2 etc are reducing agents
Cr+6, Mn+7, Mn+6, Mn+5, Mn+4 etc are oxidising agents.

Electrode Potentials
In addition to ionisation enthalpy, the other factors such as enthalpy of sublimation, hydration enthalpy, ionisation
enthalpy etc. determine the stability of a particular oxidation state in solution. This can be explained in terms of their
electrode potential values. The oxidation potential of a metal involves the following process :
M(s) o M+(aq) + e–
This process actually takes place in the following three steps as given in following flowchart :

The oxidation potential which gives the tendency of the overall change to occur, depends upon the net effect of
these three steps. The overall energy change is 'H ' sub H 4  IE  ' hyd H

If SOP is +ve o Means Oxidation easy

If SRP is +ve o Means reduction easy

Some important examples

1. E0 +2 Ÿ +ve only for Cu among 3d elements because HE of Cu+2 is not enough to compensate
M /M

for sublimation energy, IP1 and IP2 for Cu.

2. E 0
Ÿ
M +3 /M +2

(a) E 0  ve
Cr 3 /Cr 2

Reason : t2g3eg0 m d3 > d4

(b) E 0  ve(high)
Mn 3 /Mn 2

Reason : d4 < d5

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 TRANSITION ELEMENTS (d & f BLOCK)

(c) E 0 less ve(learn)

Fe 3 / Fe 2

Reason : d5 > d6

Note : The SRP of E 0 is less then expected because of extra stability of d5 configuration of Fe+3 ion.
Fe3 /Fe2

Trends in Stability of Higher Oxidation States

Standard electrode potential data provide valuable information about the stabilities of different oxidation states
shown by an element. The highest oxidation states are shown generally among halides and oxides.

1. In metal halides. The transition elements react with halogens at high temperatures to form transition metal halides.
These reactions have very high heat of reaction. But once the reaction starts, the heat of reaction is sufficient to
continue the reaction. The halogens react in the following decreasing order ; F2 > Cl2 > Br2 > I2

HALIDES OF FIRST TRANSITION SERIES

Oxidation
Sc Ti V Cr Mn Fe Co Ni Cu Zn
Number
+6 CrF6
+5 VF5 CrF5
a
+4 TiX
X4 VX
X4 CrF4 MnF4
a
+3 ScX3 TiX3 VX
X3 CrF3 MnF3 FeX3 CoF3
c b
+2 TiX
X2 VX
X2 CrF2 MnX
X2 FeX
X2 CoX2 NiX
X2 CuX2 ZnX2
+1 c
CuX
X
a b c
where X = F, Cl, Br, I, X = F, Cl, Br, X = F, Cl, X = Cl, Br, I
Within each of the transition groups 3 - 12, there is a difference in the stability of the various oxidation states. In
general, the second and third transition series elements exhibit higher coordination number and their higher oxidation
states are more stable than the corresponding first transition series elements. The following trends are observed
from table regarding transition metal halides :
(i) In general, the elements of first transition series tend to exist in low oxidation states. Chromium to zinc form stable
diflourides and the other chlorides are also known.
(ii) Since fluorine is the most electronegative element, the transition metals show highest oxidation states with fluorine.
The highest oxidation states are found in TiX4 (tetrahalides, X = F, Cl, Br and I), VF5 and CrF6.
(iii) The +7 oxidation state for Mn is not shown by simple halides. However, MnO3F is known in which the oxidation
state of Mn is +7.
(iv) After Mn, the tendency to show higher oxidation states with halogens are uncommon. Iron and cobalt form
trihalides FeX3 (X = F, Cl or Br) and CoF3.
(v) The tendency of fluorine to stabilise the highest oxidation state is due to either higher lattice enthalpy as in case of
CoF3 or higher bond enthalpy due to higher covalent bonds e.g., VF5 and CrF6.
(vi) V(V) is shown by VF5 only. However, the other halides undergo hydrolysis to form oxohalides, VOX3.
(vii) Fluorides are relatively unstable in their low oxidation states. For example, vanadium form only VX2 (X = Cl, Br or I)
and copper can form CuX (X = Cl, I). All copper (II) halides are known except the iodide. This is because, Cu2+
oxidises I– to I2.
2Cu2+ + 4I– o Cu2I2(s) + I2

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CHEMISTRY FOR NEET & AIIMS
It has been observed that many copper (I) compounds are unstable in aqueous solution and they undergo
disproportionation to Cu(II) and Cu(0) as :

2Cu+ o Cu2+ + Cu

Copper in +2 oxidation state is more stable than in +1 oxidation state. This can be explained on the basis of much
larger negative hydration enthalpy ('hydH4) of Cu2+ (aq) than Cu+, which is much more than compensates for the
large energy required to remove the second electron i.e., second ionisation enthalpy of copper.

2. In metal oxides and oxocations.

Oxidation
Sc Ti V Cr Mn Fe Co Ni Cu Zn
Number
+7 M n 2 O7

+6 CrO 3

+5 V2 O 5

+4 TiO2 V2 O 4 CrO 2 M nO 2

+3 Sc 2 O 3 Ti2 O 3 V2 O 3 Cr2 O 3 M n 2 O3 Fe 2 O 3

+2 TiO VO (CrO) M nO FeO CoO NiO CuO ZnO

+1 Cu 2 O

M ixed oxides M n 3 O4 Fe 3 O 4 Co 3 O 4

The ability of oxygen to stabilize the highest oxidation state is demonstrated in their oxides. The highest oxidation
states in their oxides coincides with the group number. For example, the highest oxidation state of scandium of
group 3 is +3 in its oxides, Sc2O3 whereas the highest oxidation state of manganese of group 7 is +7, in Mn2O7.
However beyond group 7, no higher oxides of iron above Fe2O3 are known. Although higher oxidation state such as
+6 is shown in ferrates such as FeO42– in alkaline medium, but they readily decompose to Fe2O3 and O2. Besides the
oxides, oxocation of the metals also stabilise higher oxidation states. For example, VV as VO2+, VIV as VO2+ and TiIV
as TiO2+. It may be noted that the ability of oxygen to stabilise these high oxidation states exceeds that of fluorine.
For example, manganese forms highest fluoride as MnF4 whereas the highest oxide is Mn2O7. This is due to the fact
that oxygen has great ability to form multiple bonds to metals. In the covalent oxide. Mn2O7, each Mn is tetrahedrally
surrounded by oxygen atoms and has Mn–O–Mn bridge. The tetrahedral [MO4]n– ions are also known for vanadium
(V), chromium (VI), manganese (VI) and manganese (VII).
The transition elements in the +2 and +3 oxidation states mostly form ionic bonds whereas with higher oxidation
states, the bonds are essentially covalent e.g., in MnO4– all bonds are covalent. As the oxidation number of a metal
increases, the ionic character of their oxides decrease. For example, in case of Mn, Mn2O7 is a covalent green oil. In
these higher oxides the acidic character is predominant. Thus CrO3 gives H2CrO4 and H2Cr2O7 and Mn2O7 gives
HMnO4. V2O5 is, however amphoteric though mainly acidic and with alkalies as well as acids gives VO 43– and VO2+
respectively.

Ex. For the first series of transition metals the E4 values are
E4 V Cr Mn Fe Co Ni Cu
(M2+/M+1) – 1.18 – 0.91 – 1.18 – 0.44 – 0.28 – 0.25 + 0.34
Explain the irregularity in the above values.
Sol. This is because of irregular variation of ionization energies (,E1 + ,E2) and also the sublimation energies which are
much less for manganese and vanadium.

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 TRANSITION ELEMENTS (d & f BLOCK)
Ex. Write the formulae of different oxides of manganese. What is the oxidation state of manganese in each of them ?
Arrange them in order of their decreasing acidic character.
Sol. Mn+2O, Mn23+ O3, Mn4+O2, Mn27+O7, Mn3O4 (mixed oxide of MnO and Mn2O3)
As the oxidation state of Mn increases, the electronegativity values of the central metal ions increase. As a result of
this the difference in the electronegativity values between metals and oxygen decrease. So the acidic character
increases as given below.
MnO < Mn2O3 < MnO2 < Mn2O7

Ex. Name the oxo metal anions of the first series of the transition metals in which the metal exhibits the oxidation state
equal to its group number.
Sol. In Cr2O72– and CrO42– the oxidation state of Cr is +6 (2x + 7(–2) = –2 and x + 4 (– 2) = –2) . The group number is equal
to the number of electrons in (n-1) d and ns sub-shells for d-block elements. So group no. = 5 + 1 = 6.
In MnO4– the oxidation state of Mn is +7 (2x + 7(–2) = –1). The group number is equal to the number of electrons in
(n-1) d and ns sub-shells for d-block elements. So group no. = 5 + 2 = 7

Ex. Zinc does not show variable valency because of :

(A) complete ‘d’ sub-shell (B) inert pair effect (C) 4s2 sub-shell (D) none.
Sol. Zn = [Ar]18 3d10 4s2. Zinc has completely filled d-sub-shell so removal of electron from completely filled 4d sub-
30
shell would be quite difficult. Thus it does not show variable valency.
Therefore, (A) option is correct.

The relative stability of various oxidation states

(a) The relative stabilities of various oxidation states of 3d-series element can be correlated with the extra stability
of 3d°,3d5 & 3 d10 configuration to some extent.
Ex. Stability of Ti4+ (3d0) > Ti3 + (3d1 ) Mn2+ (3d5) > Mn3+ (3d4)
(b) The higher oxidation state of 4d and 5d series element are generally more stable than the elements of 3d series.
Ex. (i) Mo vi O -2 vi -2 vi 2  vii 
4 (oxidation state of Mo is +6), Mo O 4 (4d series) & W O 4 , Re O 4 (5d series) are more
stable due to their maximum oxidation state.

(ii) Cr vi O 42 & Mn vii O 4 (3d-series) are strong oxidizing agents.

(c) Strongly reducing states probably do not form fluorides or oxides, but may well form the heavier halides
Conversely, strong oxidizing state form oxides & fluoride, but not Bromide and lodide. Ex.
(i) V (Vanadium) react with halogens to form VF5 VCl5 , VBr3,but doesn' t form VBr5 or VI5 because in + 5 oxidation
state Vanadium is strong oxidizing agent thus convert Br – & I– to Br2 & I2 respectively, So VBr3 &VI3 are formed
but not VBr5 & VI5.
(ii) On the other hand VF5 is formed because V5+ ion unable to oxidize highly electronegative & small anion F–
(iii) Similarly highly electronegative and small O2 – ion formed oxides Ex. VO4 3 –, CrO42– & MnO4– etc.

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CHEMISTRY FOR NEET & AIIMS
Different oxidation state of chloride & oxides compound

+2 +3 +4 +5 +6 +7

TiCl2 TiCl3 TiCl4

VCl2 VCl3 VCl4 VOCl3

(Ionic, basic) Less ionic
(Amphoteric) Covalent and Acidic
(Strong lewis acid)

TiO Ti2O3 TiO2

VO V2O3 V2O5

CrO Cr2O3 CrO3

MnO Mn2O3 MnO2 MnO3 Mn2O7

Ionic, basic Less Ionic (Amphoteric) Acidic, covalent

(d) Such compounds are expected to be unstable except in case where vacant d-orbitals are used for accepting
lone-pair from S-bonding ligand.
Ex. [Ni(CO)4], [Ag(CN)2]– ,[Ag)(NH3)2]+

Ex. Zn forms only Zn2+ and not Zn3+, why?

Sol. In the formation of Zn3+, an electron from the d10 configuration has to be removed which requires abnormally higher
amount of energy.

Colour Property
(a) Most of the transition metal ions exhibit colour property.
(b) This is due to d-d transition of unpaired electrons in their t2g and eg sets of 'd' orbitals.
(c) They require less amount of energy to undergo excitation of electrons. Hence they absorb visible region of
light exhibiting colour.
Ex. Sc+2 : [Ar]3d1, Ti+2 : [Ar]3d2, V+2 : [Ar]3d3
(d) Transition metal ions which do not have any unpaired electrons in their 'd' orbitals like 3d 0 and 3d10
configurations, do not exhibit any colour property.
Ex. Sc+3 : [Ar]3d0, Cu+1 : [Ar]3d10, Ti+4 : [Ar]3d0 etc are colourless ions.
(e) A transition metal ion absorbs a part of visible region of light and emits rest of the colours, the combination of which,
is the colour of emitted light. The colour of metal ion is the colour of the emitted light.
(f) In transition metal ion the 'd' orbitals split into lower energy set t2g orbitals and higher energy set eg orbitals.
The electrons from t2g set get excited to higher energy set i.e., eg set. This excitation of electrons is called as
d-d' transition. Due to this 'd -d' transition the transition metal ions exhibit colour property.

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 TRANSITION ELEMENTS (d & f BLOCK)

Lower energy set = t2g

Higher energy set = eg
d x2- y2 d z2
light
Presence of ligands (eg) d-d Trnsition
d-orbitals (degenerate)

d xy dyz dyz
(t 2g)

Factors affecting the colour of complex

The colour of a transition metal complex depends on-
(a) The magnitude of energy difference between the two d-levels ('0 ),
(b) An increase in the magnitude of '0 decreases the wave length (O ) of the light absorbed by the complexes.

1
'0 v
λ(Wavelength of light absorb)

(c) Thus with a decrease in the O the colour of complex changes from Red to Violet.
Ex.
Complex ions [Co(H2O)6]3+ [Co(NH3)6]3+ [Co(CN)6]3–
Ligand field strength H2 O < NH3 < CN–
Magnitude of '0 '0(H2O) < '0(NH3) < '0(CN–)
Magnitude of O O(H2O) < O(NH3) < O(CN–)
Colour of the transmitted orange Green-blue violet
Colour of absorbed light Green-blue Orange Yellow-green
Light (i.e. colour of the
complex
(d) KMnO4 (dark pink), K2Cr2O7 (orange) having d° configuration but they are coloured due to charge trans
fer spectrum and charge is transferred from anion to cation.

Example of Some coloured metal ions

+3 +3 +2 +2
Ti Purple Cr Green Mn Light pink Fe Green
+3 +3 +2 +2
Fe Yellow Co Pink Ni Green Cu Blue
3+ 4+ 3+ 4+
Sc Colourless Ti Colourless Ti Purple V Blue
3+ 2+ 2+ 3+
V Green V Violet Cr Blue Cr Green
3+ 2+ 2+ 3+
Mn Violet Mn Pink Fe Green(light) Fe Yellow
2+ 2+ 2+
Co Pink Ni Blue Zn Colourless

Ex. Explain the blue colour of CuSO4.5H2O.

Sol. Cu2+ ion (3d9) absorbs red light from the visible region, for the promotion of 3d electrons, the ions reflect blue light
and appear blue.

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CHEMISTRY FOR NEET & AIIMS
Magnetic Properties
(a) Generally transition elements exhibits the magnetic property. A paramagnetic substance is one which is attracted
into a magnetic field. Paramagnetism is mainly due to the presence of unpaired electrons in atoms or ions or
molecules. It varies inversely with temperatures.
(b) Diamagnetic substance is one which is slightly repelled by a magnetic field. It's independent of temperature.
(c) As is evident most of the transition metal ions have unpaired electrons in their 'd' orbitals. Hence most of the
transition metal ions are paramagnetic in nature. Ex. Ti+2 [Ar]3d2, Ti+3 [Ar]3d1. V+2[Ar]3d3, Cr+3[Ar]3d3
(d) Transition metal ions having 3d0 and 3d10 configuration exhibit diamagnetic nature.
(e) The total magnetic moment of a substance is the resultant of the magnetic moments of all the individual electrons.
(f) The magnetic moment (P) created due to spinning of unpaired electrons can be calculated by using

μ = n(n + 2) Where - 'n' is the number of unpaired electrons in the metal ion.
P = Magnetic moment in Bohr Magnetons (B.M.)
(g) The magnetic moment of diamagnetic substances will be zero.
(h) Transition metal ions having d5 configuration will have maximum number of unpaired electrons therefore they
will be maximum paramagnetic in nature.

Catalytic Property
(a) Transition elements and their compounds exhibit catalytic properties. This is due to their variable valency as
well as due to the free valencies on their surface.
(b) When transition elements and their compounds are in powdered state, their catalytic properties exhibited will
be to a greater extent. This is due to greater surface area available in the powdered state.
(c) Transition metals and their compounds exhibiting catalytic properties in various processes are -
Catalyst Used
TiCl3 Used as the Ziegler-Natta catalyst in the production of polythene.
MnO2 Used as a catalyst to decompose KClO3 to give O2
Fe Promoted iron is used in the Haber-Bosch process for making NH3
FeCl3 Used in the production of CCl4 from CS2 and Cl2
FeSO4 and H2 O2 Used as Fenton's reagent for oxidizing alcohols to aldehydes.
PdCl2 Wacker process for converting C2 H4 + H2 O + PdCl2 to
CH3 CHO + 2HCl + Pd.
Pd Used for hydrogenation (e.g. phenol to cyclohexanone).
Pt/PtO Adams catalyst, used for reductions.
Pt Formerly used for SO2 o SO3 in the contact process for making
H2 SO4
Pt/Rh Formerly used in the ostwald process for making HNO3 to oxidize
NH3 to NO
Cu Is used in the direct process for manufacture of (CH3 )2SiCl2 used
to make silicones.
Cu/V Oxidation of cyclohexanol/cyclohexanone mixture to adipic acid
which is used to make nylone-66
CuCl2 Decon process of making Cl2 from HCl
Ni Raney nickel, numerous reduction processes (e.g. manufacture of
hexamethylenediamine, production of H2 from NH3 , reducing
anthraquinone to anthraquinol in the production of H2 O2

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 TRANSITION ELEMENTS (d & f BLOCK)
Ex. How iron (III) catalyses the reaction between iodide & persulphate?
Sol. 2Fe3+ + 2,– o 2Fe2+ + ,2
2Fe2+ + S2O82– o 2Fe3+ + 2SO42–

2,– + S2O82– Fe(III) ,2 + 2 SO42–

Formation of Alloy
(a) Transition elements have maximum tendency to form alloys.
(b) The reactivity of transition elements is very less and their sizes are almost similar. Due to this a transition metal
atom in the lattice can be easily replaced by other transition metal atom and hence they have maximum tendency
to form alloys.
(c) In the alloys, ratio of component metals is fixed.
(d) These are extremely hard and have high melting point.

SOME IMPORTANTALLOY
(a) Bronze Cu (75 - 90 %) +Sn ( 10 - 25 %)
(b) Brass Cu ( 60 - 80 %) +Zn (20 - 40 %)
(c) Gun metal (Cu + Zn + Sn) (87 : 3 : 10)
(d) German Silver Cu + Zn + Ni ( 2 : 1 : 1)
(e) Bell metal Cu (80 %) + Sn (20 %)
(f) Nichrome (Ni + Cr + Fe)
(g) Alnico (Al, Ni, Co)
(h) Type Metal Pb + Sn + Sb
(i) Alloys of steel
zVanadium steel V (0.2 - 1 %)
z Chromium steel Cr (2 - 4 %)
z Nickel steel Ni (3 -5 %)
z Manganese steel Mn (10 - 18 %)
z Stainless steel Cr (12 - 14 %) & Ni (2 - 4 %)
z Tungsten steel W (10 - 20 %)
z Invar Ni (36 %)
(j) 14 Carat Gold 54 % Au + Ag (14 to 30 %) + Cu (12 - 28 %)
(k) 24 Carat Gold 100 % Au
(l) Solder Pb + Sn
(m) Magnellium Mg (10%) + Al (90%)
(n) Duralumin (Al + Mn + Cu)
(o) Artificial Gold Cu (90 %) + Al (10%)
(p) Constantan Cu(60%) + Ni (40%)

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CHEMISTRY FOR NEET & AIIMS
% of Carbon in Different Type of Iron
Name % of C
(a) Wrought Iron 0.1 to 0.25
(b) Steel 0.25 to 2.0
(c) Cast Iron 2.6 to 4.3
(d) Pig Iron 2.3 to 4.6

Ex. Which of the following form an alloy ?

(A) Ag + Pb (B) Fe + Hg (C) Pt + Hg (D) Fe + C
Sol. Argentiferrous lead is an alloy contains Ag & Pb.
'Fe' and 'C' form an alloy called cementite, Fe3C.
Therefore, (A) & (D) option are correct.

Formation of Interstitial Compounds

(a) Transition elements form interstitial compounds with smaller sized non metal elements like hydrogen, carbon,
boron, nitrogen etc.
(b) The smaller sized atoms get entrapped in between the interstitial spaces of the metal lattices.
These interstitial compounds are non-stoichiometric in nature and hence cannot be given any definite formula.
(c) The smaller sized elements are held in interstitial spaces of transition elements by weak Vander Waals forces of
attractions.
(d) The interstitial compounds have essentially the same chemical properties as the parent metals but they differ in
physical properties such as density and hardness.
The process of adsorption of excess of H atom by the transition metals like Pd, Pt etc is called occlusion.
(e) Reaction with H2O2:- Acidified solution of dichromate ions give deep blue colour solution with H2O2 due to
the formation of [CrO(O2)2] or CrO5. The blue colour fades away gradually due to the decomposition of CrO5
into Cr+3 ions and oxygen.
O
O O
Cr
O O

Cr2 O72– + 4H 2 O2 + 2H + 

o 2CrO5 + 5H 2O (Butterfly structure)

SOME IMPORTANT COMPOUNDS

Potassium permanganate (KMnO4)
Preparation :
(A) Potassium permanganate is prepared from mineral pyrolusite (MnO2). The preparation involves the following steps.
(a) Conversion of pyrolusite ore to potassium manganate
The pyrolusite MnO2 is fused with caustic potash (KOH) or potassium carbonate in the presence of air or
oxidising agents, such as KNO3 or KClO3 to give a green mass due to the formation of potassium manganate
(K2MnO4).
2MnO2 + 4KOH + O2 o2K2MnO4 + 2H2O
2MnO2 + 2K2CO3 + O2 o2K2MnO4 + 2CO2

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 TRANSITION ELEMENTS (d & f BLOCK)
(b) Oxidation of potassium manganate to potassium permanganate
The green mass is extracted with water resulting is green solution of potassium manganate. The solution is then
treated with a current of Cl2 or ozone or CO2 to oxidise K2MnO4 to KMnO4. The solution is concentrated and
dark purple crystals of KMnO4 separate out.
2K2MnO4 + Cl2 o2KCl + 2KMnO4
2K2MnO4 + O3 + H2O o2KMnO4 + 2KOH + O2
3K2MnO4 + 2CO2 o2K2CO3 + MnO2p+ 2KMnO4
Alternatively, alkaline potassium manganate is electrolytically oxidised.

(B) Electrolytic method :- The potassium manganate solution is taken in an electrolytic cell which contains iron
cathode and nickel anode. When current is passed the manganate ion in oxidised to permanganate ion at anode
and hydrogen is liberated at cathode.
K2MnO4 o 2K+ + MnO42–
At anode : MnO4–2 o MnO4– + e–
Green Purple
At cathode : 2H+ + 2e– o2H
2H oH2
Properties :
(a) Colour and M.P. :- Dark violet crystalline solid, M.P. 523 K
(b) Solubility :- Moderately soluble is room temperature, but fairly soluble in hot water giving purple solution.
(c) Heating :- When heated strongly it decomposes at 746 K to give K2MnO4 and O2.
2KMnO4 746K K2MnO4 + MnO2 + O2
Solid KMnO4 gives KOH, MnO and water vapours, when heated in current of hydrogen.
2KMnO4 + 5H2 ' 2KOH + 2MnO + 4H2O
(d) Action of alkali :- On heating with alkali, potassium permanganate changes into potassium manganate and
oxygen gas is evolved.
4KMnO4 + 4KOH o4K2MnO4 + 2H2O + O2
(e) Action of con. H2SO4 :- With cold H2SO4, it gives Mn2O7 which on heating decomposes into MnO2.
2KMnO4 + 2H2SO4 oMn2O7 + 2KHSO4 + H2O
2Mn2O7 o4MnO2 + 3O2
(f) Oxidising character :- KMnO4 acts as powerful oxidising agent in neutral, alkaline or acidic solution because
it liberates nascent oxygen as :-
Acidic solution :- Mn+2 ions are formed
2KMnO4 + 3H2SO4 oK2SO4 + 2MnSO4 + 3H2O + 5[O]

ª Mº
or MnO4– + 8H+ + 5e– o Mn+2 + 4H2O «equal wt. = »
¬ 5¼

Neutral solution :- MnO2 is formed

2KMnO4 + H2O o2KOH + 2MnO2 + 3[O]

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CHEMISTRY FOR NEET & AIIMS

or MnO4– + 2H2O + 3e– o MnO2 + 4OH– ª Mº

«equal wt. = 3 »
¬ ¼
During the reaction the alkali produced generates the alkaline medium even if we start from neutral medium.
Alkaline medium :- Manganate ions are formed.
2KMnO4 + 2KOH o2K2MnO4 + H2O + [O]

Reactions in Acidic Medium : In acidic medium KMnO4 oxidizes –

(a) Ferrous salts to ferric salts
MnO4– + 8H+ + 5e– o Mn+2 + 4H2O
Fe+2 o Fe+3 + e– ] × 5

MnO4– + 5Fe+2 + 8H+ o Mn2+ + 5Fe+3 + 4H2O

(b) Oxalates to CO2 :
MnO4– + 8H+ + 5e– o Mn+2 + 4H2O] × 2
C2O42– o 2CO2 + 2e–] × 5

2MnO4– + 5C2O42– + 16H+ o 2Mn+2 + 10CO2 + 8H2O

(c) Iodides to Iodine
MnO4– + 8H+ + 5e– oMn+2 + 4H2O] × 2
2I– oI2 + 2e– ] × 5

10I– + 2MnO4– + 16H+ o 2Mn+2 + 5I2 + 8H2O

(d) Sulphites to sulphates
MnO4– + 8H+ + 5e– oMn+2 + 4H2O] × 2
SO32– + H2O oSO42– + 2H+ + 2e– ] × 5

5SO32– + 2MnO4– + 6H+ o 2Mn+2 + 5SO42– + 3H2O

(e) It oxidizes H2S to S
MnO4– + 8H+ + 5e– oMn+2 + 4H2O] × 2
S2– oS + 2e– ] × 5

2MnO4– + 16H+ + 5S–2 o2Mn+2 + 5S + 8H2O

(f) It oxidizes SO2 to sulphuric acid
2KMnO4 + 3H2SO4 oK2SO4 + 2MnSO4 + 3H2O + 5[O]
SO2 + H2O + [O] oH2SO4] × 5

2KMnO4 + 5SO2 + 2H2O oK2SO4 + 2MnSO4 + 2H2SO4

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 TRANSITION ELEMENTS (d & f BLOCK)
(g) It oxidizes Nitrites to nitrates
2KMnO4 + 3H2SO4 oK2SO4 + 2MnSO4 + 3H2O + 5[O]
KNO2 + O oKNO3] × 5

2KMnO4 + 5KNO2 + 3H2SO4 oK2SO4 + 2MnSO4 + 5KNO3 + 3H2O

Reactions in Neutral Medium

(a) It oxidizes H2S to sulphur :
2KMnO4 + H2O o2KOH + 2MnO2 + 3 [O]
H2S + O oH2O + S] × 3

2KMnO4 + 3H2S o2KOH + 2MnO2 + 2H2O + 3S

(b) It oxidizes Manganese sulphate (MnSO4 to MnO2) manganese dioxide :
2KMnO4 + H2O o2KOH + 2MnO2 + 3 [O]
MnSO4 + H2O + O oMnO2 + H2SO4] × 3
2KOH + H2SO4 o K2SO4 + 2H2O

2KMnO4 + 3MnSO4 + 2H2O o5MnO2 + K2SO4 + 2H2SO4

(c) It oxidizes Sodium thiosulphate to sulphate and sulphur :
2KMnO4 + H2O o2KOH + 2MnO2 + 3 [O]
Na2S2O3 + O oNa2SO4 + S] × 3

2KMnO4 + 3Na2S2O3 + H2O o2MnO2 + 3Na2SO4 + 2KOH + 3S

Reactions in Alkaline Medium

(a) It oxidizes Iodides to Iodates in alkaline medium :
2KMnO4 + H2O o2KOH + 2MnO2 + 3 [O]
KI +3O oKIO3

2KMnO4 + KI + H2O o2MnO2 + 2KOH + KIO3

(b) Alkaline KMnO4 (Baeyer’s reagent) oxidizes ethylene to ethylene glycol.

CH2 CH2—OH
+ H2O + [O] o
CH2 CH2—OH

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CHEMISTRY FOR NEET & AIIMS
Structure :
MnO 4 –

Uses :
(a) Used in volumetric analysis for estimation of ferrous salts, oxalates, and other reducing agents. It is not used
as primary standard because it is difficult to obtain it in the pure state.
(b) It is used as strong oxidising agent in the laboratory as well as industry.
(c) As disinfectant and germicide.
(d) In dry cells.
(e) A very dilute solution of KMnO4 is used for washing wounds.

Ex. Potassium permanganate acts as an oxidant in neutral, alkaline as well as acidic media. The final products obtained
from it in three conditions are respectively :
(A) MnO42– , Mn3+ and Mn2+ (B) MnO2 , MnO2 and Mn2+
(C) MnO2 , MnO2+ and Mn3+ (D) MnO , MnO2+ and Mn2+

Sol. 3e– + 2H2O + MnO4– o MnO2 + 4OH– (neutral medium)

e– +MnO4– o MnO4–2 (dilute alkaline medium)

MnO4¯ + 8H+ + 5e– o Mn2+ + 4H2O (acidic medium)

Therefore, (B) option is correct.

POTASSIUM DICHROMATE (K2Cr2O7) :

Preparation :
The chromite ore is roasted with sodium carbonate in presence of air in a reverberatory furnace
Roasting
4FeO. Cr2O3 (chromite ore) + 8Na2CO3 + 7O2 8Na2CrO4 + 2Fe2O3 + 8CO2
in air

The roasted mass is extracted with water when Na 2 CrO 4 goes into the solution leaving behind
insoluble Fe2O3. The solution is then treated with calculated amount of H2SO4.
2Na2CrO4 + H2SO4 o Na2Cr2O7 + Na2SO4 + H2O
The solution is concentrated when less soluble Na2SO4 crystallises out. The solution is further concentrated when
crystals of Na2Cr2O7 are obtained. Hot saturated solution of Na2Cr2O7 is then treated with KCl when orange red
crystals of K2Cr2O7 are obtained on crystallisation.
Na2Cr2O7 + 2KCI o K2Cr2O7 + 2 NaCl
Note : K2Cr2O7 is preferred over Na2Cr2O7 as a primary standard in volumetric estimation because Na2Cr2O7 is hygroscopic
in nature but K2Cr2O7 is not.

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 TRANSITION ELEMENTS (d & f BLOCK)
Properties :
(a) Physical :
It is orange-red coloured crystalline compound. It is moderately soluble in cold water but freely soluble in hot water.
It melts at 398°C.
(b) Chemical :
(i) Effect of heating :
On heating strongly, it decomposes liberating oxygen.

3
2K2Cr2O7 o 2K2CrO4 + Cr2O3 + O
2 2

On heating with alkalies, it is converted to chromate, i.e., the colour changes from orange to yellow. On
acidifying, yellow colour again changes to orange.
K2Cr2O7 + 2KOH o 2K2CrO4 + H2O

Cr2O 2
7 + 2OH¯
o 2CrO 2
4 + H2O

Orange Yellow

2CrO 2
4 + 2H
+
o Cr2O 2
7 + H2O

Yellow Orange
Thus CrO4 and Cr2O72– exist in equilibrium and are interconvertible by altering the pH of solution.
2–

2CrO 2
4 + 2H
+
2HCrO4– Cr2O 2
7 + H2O

In alkaline solution, chromate ions are present while in acidic solution, dichromate ions are present.
(ii) K2Cr2O7 + 2H2SO4 (conc. & cold) o 2CrO3 p (bright orange/red) + 2KHSO4 + H2O

2K2Cr2O7 + 8H2SO4 (conc. & Hot) o 2K2SO4 + 8H2O + 2Cr2(SO4)3 + 3O2
(iii) Acidified K2Cr2O7 solution reacts with H2O2 to give a deep blue solution due to the formation of CrO5.
Cr2O72– + 2H+ + 4H2O2 o 2CrO5 + 5H2O
Blue colour in aqueous solution fades away slowly due to the decomposition of CrO5 to Cr3+ ions and oxygen.
In less acidic solution K2Cr2O7 and H2O2 give salt which is violet coloured and diamagnetic due to the formation
of [CrO(O2)(OH)]–. In alkaline medium with 30% H2O2, a red-brown K3CrO8 (diperoxo) is formed. It is tetra peroxo
species [Cr(O2)4]3– and thus the Cr is in +V oxidation state. In ammoniacal solution a dark red-brown compound,
(NH3)3CrO4 - diperoxo compound with Cr(IV) is formed.
(iv) Potassium dichromate reacts with hydrochloric acid and evolves chlorine gas.
K2Cr2O7 + 14HCl o 2KCl + 2CrCl3 + 7H2O + 3Cl2
(v) Oxidising properties
The dichromates act as powerful oxidising agent in acidic medium. In presence of dil H2SO4, K2Cr2O7 liberates
Nascent oxygen and therefore acts as an oxidising agent.
K2Cr2O7 + 4H2SO4 o K2SO4 + Cr2(SO4)3 + 4H2O + 3[O]

In terms of electronic concept the Cr2 O 72  ion takes up electrons in the acidic medium and hence acts as an
oxidising agent.

Cr2 O72– +14H + + 6e – 

o 2Cr 3+ + 7H 2O

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CHEMISTRY FOR NEET & AIIMS
(a) It oxidises iodides to iodine :-

Cr2 O 72  + 14H+ + 6e– o 2Cr+3 + 7H2O

[2I– o I2 + 2e– ] × 3

Cr2 O 72  + 14H+ + 6I– o 2Cr+3 + 3I2 + 7H2O

or K2Cr2O7 + 7H2SO4 + 6KI o4K2SO4 + Cr2 (SO4)3 + 7H2O + 3I2

(b) Acidified ferrous sulphate to ferric sulphate

Cr2 O 72  + 14H+ + 6e– o 2Cr+3 + 7H2O

Fe+2 o Fe3+ + e– ] × 6

Cr2 O 72  + 14H+ + 6Fe+2 o 2Cr+3 + 6Fe+3 + 7H2O

or K2Cr2O7 + 6FeSO4 + 7H2SO4 oCr2 (SO4)3 + 3Fe2(SO4)3 + 7H2O + K2SO4

(c) Oxidises H2S to sulphur

Cr2 O 72  + 14H+ + 6e– o 2Cr+3 + 7H2O

H2S o S + 2H+ + 2e– ] × 3

Cr2 O 72  + 3H2S + 8H+ o 2Cr+3 + 3S + 7H2O

or K2Cr2O7 + 3H2S + 4H2SO4 oCr2 (SO4)3 + 3S + 7H2O + K2SO4

(d) SO2 is oxidised to H2SO4 :

Cr2O72– + 3SO2 + 2H+ o 2Cr3+ + 3SO42– + H2O ;
Chrome alum is obtained when acidified K2Cr2O7 solution is saturated with SO2.

K2Cr2O7 + H2SO4 + 3SO2 + 23H2O T < 70°C

K2SO4 . Cr2(SO4)3 . 24H2O
(e) It oxidises ethylalcohol to acetaldehyde and acetaldehyde to acetic acid
[O] [O]
C2H5OH CH3CHO CH3COOH
ethyl alcohol acetaldehydeacetic acid
(f) It also oxidises nitrites to nitrates, arsenites to arsenates, HBr to Br2. HI to I2, etc.
(g) K2Cr2O7 + 2C (charcoal) ' Cr2O3 + K2CO3 + CO n
(vi) Chromyl chloride test :
4Cl– + Cr2O72– + 6H+ o 2CrO2Cl2 n (deep red) + 3H2O
CrO2Cl2 + 4OH– o CrO42– (yellow) + 2Cl– + 2H2O
CrO42– (yellow) + Pb2+ o PbCrO4 p (yellow)

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 TRANSITION ELEMENTS (d & f BLOCK)
(vii) Cr2O72– (concentrated solution) + 2Ag+ o Ag2Cr2O7 p (reddish brown)

Ag2Cr2O7 p + H2O boil Ag2CrO4 p + CrO42– + 2H+ .

(viii) Cr2O72– + Ba2+ + H2O 2BaCrO4 p + 2H+

As strong acid is produced, the precipitation is only partial. But if NaOH or CH3COONa is added, precipitate
becomes quantitative.

Structure
The chromate ion has tetrahedral structure in which four atoms around chromium atom are oriented in a tetrahedral
arrangement.


O O

Cr Cr
or

O O O O
O O
Chromate ion
The structure of dichromate ion consist of two tetrahedra sharing an oxygen atom at the common corner.
pm

O O O O O O
0
18

Cr 130° Cr 160 pm or Cr Cr
O O O O



O O O O
Dichromate ion

Uses
It is used :
(i) As a volumetric reagent in the estimation of reducing agents such as oxalic acid, ferrous ions, iodide ions, etc.
It is used as a primary standard.
(ii) For the preparation of several chromium compounds such as chrome alum, chrome yellow, chrome red, zinc yellow,
etc.
(iii) In dyeing, chrome tanning, calico printing, photography etc.
(iv) As a cleansing agent for glass ware in the form of chromic acid.

Ex. An inorganic compound (A) has garnet red prismatic crystals.(A) is moderately soluble in water and dissolves in
cold concentrated H2SO4 to yield red crystals (B). In presence of dilute H2SO4 it converts a pungent gas(C) into a
yellow turbidity (D) and converts a suffocating gas (E) into a green solution (F). The gas (C)and (E) also combine
to produce the yellow turbidity (D). With K, and starch in presence of dilute. H2SO4 (A) yields blue colour. (A) and
concentrated H2SO4 mixture is used as a cleansing agent for glassware in the laboratory. Identify (A)and explain the
reactions.
Sol. As compound (A) has garnet red prismatic crystals which with cold conc. H2SO4 gives red crystals and a suffocating
gas (SO2) turns its solution in water in to green coloured solution, therefore compound (A) may be K2Cr2O7 .

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CHEMISTRY FOR NEET & AIIMS

K2Cr2O7 + 4H2SO4 + 3H2S o KHSO4 + 2 CrO3 (red crystals) + H2O

(A) (B)

K2Cr2O7 + 4H2SO4 + 3H2S o K2SO4 + Cr2 (SO4)3 + 7H2O + 3Sp (Yellow)

(C) (D)

K2Cr2O7 + H2SO4 + 3SO2 o Cr2 (SO4)3 (Green solution) + K2SO4 + H2O
(E) (F)

K2Cr2O7 + 7H2SO4 + 6K, o 4K2SO4 + Cr2 (SO4)3 + 7H2O + 3,2

,2 + Starch o Blue colour

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 TRANSITION ELEMENTS (d & f BLOCK)

THE INNER TRANSITION ELEMENTS (f-BLOCK)

INTRODUCTION
The elements constituting the f-block are those in which the 4f and 5f oribitals are progressively filled. These
elements are the members of group 3.
The f-block elements comprises of the two series, (i) lanthanoids (the fourteen elements following lanthanum) and
(ii) actinoids (the fourteen elements following actinum). It is important to note that the lanthanoids resembles one
another more closely than that of the ordinary transition elements in any series. Lanthanoids have only one stable
oxidation state and their chemical properties provide the excellent opportunity to observe the effect of small
changes in size and nuclear charge along a series of similar elements. On the other hand the chemistry of actinoids
is much more complicated and this complication arises partly owing to the occurrence of a wide range of oxidation
states in these elements and partly because of their radioactive nature.
Lanthanoid series (Z = 58 – 71) (Ce – Lu)
Actinide series (Z = 90 – 103) (Th – Lw)
LANTHANOIDS (4f - SERIES) :
Electronic configuration : The atoms of these elements have electronic configuration with 6s2 common but with
variable occupancy of 4f level. However, the electronic configurations of all the tripositive ions which is the most
stable oxidation state of all the lanthanoids, are of the form 4fn ( n = 1 to 14 with increasing atomic number)
[Xe] 4f1–145s25p65d0–16s2.
Atomic Element Symbol Outer electronic configuration
No. Atomic +3 ion
58 Cerium Ce 4f 1 5d1 6s2 4f1
59 Praseodymium Pr 4f 3 6s2 4f 2
60. Neodymium Nd 4f 4 6s2 4f 3
61. Promethium Pm 4f 5 6s2 4f 4
62. Samarium Sm 4f 6 6s2 4f 5
63. Europium Eu 4f 7 6s2 4f 6
64. Gadolinium Gd 4f 7 5d1 6s2 4f 7
65. Terbium Tb 4f 9 6s2 4f 8
66. Dysprosium Dy 4f 10 6s2 4f 9
67. Holmium Ho 4f 11 6s2 4f 10
68. Erbium Er 4f 12 6s2 4f 11
69. Thulium Tm 4f 13 6s2 4f 12
70. Ytterbium Yb 4f 14 6s2 4f 13
71. Lutecium Lu 4f14 5d1 6s2 4f 14

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CHEMISTRY FOR NEET & AIIMS
Atomic sizes : There is decrease in atomic and ionic radii from lanthanum to lutetium due to lanthanoid contraction.
The decrease in atomic radii is not quit regular as it is regular in M3+ ion. This contraction is of course, similar to that
observed in an ordinary transition series and is attributed to the imperfect shielding of one electron by another in
the same subshell. However, the shielding of one 4f electron by another is less than a d-electron by another with the
increase in nuclear charge along the series. There is fairly regular decrease in the sizes with increasing atomic
number.
The cumulative effect of the contraction of the lanthanoids series, known as lanthanoids contraction, causes the
radii of the members of the third transition series to be very similar to those of the corresponding members of the
second series. The almost identical radii of Zr (160 pm) and Hf (159 pm) is a result of the lanthanoid contraction. This
accounts for their occurrence together in nature and for the difficulty in their separation.

Oxidation state :
In the lanthaoids, La(III) and Ln(III) compounds are predominant species. However, occasionally +2 and +4 ions in
solution or in solid compounds are also obtained. This irregularity (as in ionisation enthalpies) arises mainly from
the extra stability of empty, half filled or filled f subshell. Thus the formation of CeIV is favoured by its noble gas
configuration, but it is a strong oxidant reverting to the common +3 state. The E° value for Ce4+ /Ce3+ is + 1.74 V
which suggests that it can oxidise water. However, the reaction rate is very slow and hence Ce(IV) is a good
analytical reagent; Pr Nd, Tb and and and Dy also exhibit +4 state but only in oxides, MO2. Eu2+ is formed by losing
the two s electrons and its f7 configuration accounts for the formation of this ion. However, Eu2+ is a strong reducing
agent changing to the +3 common oxidation state. Similarly Yb+2 which has f14 configuration is a reductant. TbIV has
half filled f-orbitals and is an oxidant. The behaviour of samarium is very much like europium , exhibiting both +2 and
+3 oxidation states.

Colour :
(i) The lanthanoid ions have unpaired electrons in their 4f orbitals. Thus these ions absorbs visible region of light
and undergo f–f transition and hence exhibit colour.
(ii) The colour exhibited depends on the number of unpaired electrons in the 4f orbitals.
(iii) The ions often with 4fn configuration have similar colour to those ions having 4f14–n orbitals.
(iv) Lanthanoid ions have 4f0, 4f14 are colouless.

Lanthanoid Contraction :
(i) In the lanthanoid series with increasing atomic number, there is a progressive decrease in the size from lanthanum
to lutecium or from La+3 to Lu+3 . This contraction in size is known as lanthanoid contraction.
(ii) The general electronic configuration of these elements is 4f 1–145s2p6d0–16s2. In these elements the added
electron enters the deep seated f-orbitals and therefore experiences considerable pull by the nucleus.
(iii) Due to very poor shielding effect of (n-2)f electrons, they exert very little screening effect on the outermost 6s2
electrons.
Hence with increasing atomic number, the enhanced nuclear charge leads to contraction in the size of atoms
and ions.
Ln
Nitrogen
Halogen

Sulphur

Oxygen
2773 K
Carbon

Burn
Water

Acids
'

'

LnX3 Ln(OH)3 LnC 2, Ln 2C3 LnN Ln2 S3 Ln2O3 H2

+ & Ln3C
H2

112
 TRANSITION ELEMENTS (d & f BLOCK)
USES OF LANTHANOIDS :
1. Used for the production of alloy steels for plates and pipes. e.g mischmetall which consists of lanthanoid
metal (~95%) and iron (~5%) and traces of S,C,Ca and Al. Mischmetall is used in Mg based alloy to
produce bullets, shell and lighter flint.
2. Mixed oxides of lanthanoids are employed as catalyst in petroleum cracking.
3. Some individual Ln oxides are used as phosphors in television screens and similar fluorescing surfaces.
4. Because of their paramagnetic and ferromagnetic character, their compounds are used in making magnetic
& electronic devices.
5. Ceric sulphate is a well knonw oxidizing agent in volumetric analysis.

ACTINOIDS (5f - SERIES) :

The actinoids include the fourteen elements from Th to Lr. The actinoids are radioactive elements and the earlier
members have relatively long half lives, the latter ones have half life values ranging from a day to 3 minutes for
lawrencium (Z =103).
Electronic Configuration : The general configuration of actinoids may be given as [Rn] 5f 1–14 6d0,1,2 , 7s2.
All the actinoids are believed to have the electronic configuration of 7s2 and variable occupancy of the 5f and 6d
subshell. The fourteen electrons are formally added to 5f, through not in thorium (Z = 90) but from Pa onwards the
5f orbitals are complete at element 103. The irregularities in the electronic configuration of the actinoid, like those in
the lanthanoids are related to the stabilities of the f°, f7 and f14 occupancies of the 5f orbitals. Thus the configurations
of Am and Cm are [Rn] 5f7 7s2 and [Rn] 5f76d17s2.
Ionic Sizes : The general trend in lanthanoids is observable in the actinoids as well. There is a gradual decrease in
the size of atoms or M3+ ions across the series. This may be referred to as the actinoids contraction (like lanthanoids
contraction). The contraction is, however, greater from elements to element in this series resulting from poor
shielding by 5f electrons.
Oxidation states : There is a greater range of oxidation states, which is in part attributed to the fact that the 5f , 6d
and 7s levels are of comparable energies.
The actinoids show in general +3 oxidation state. The elements, in the first half to the series frequently exhibit higher
oxidation state. e.g. The maximum oxidation state increases from +4 in Th to +5, +6 and +7 respectively in Pa, U and
Np but decreases in succeeding elements. The actinoids resemble the lanthanoids in having more compounds in +3
state than in the +4 state. However +3 and +4 ions tends to hydrolyse.
Note : The lanthanoids contraction is more important because the chemistry of elements succeeding the actinoids
are much less known at the present time.

USES OF ACTINOIDS :
1. Thorium is used in atomic reactors and in the treatment of cancer. Its salts are used in making incandescent gas
mantles.
2. Uranium is used as a nuclear fuel. Its salts are used in glass industry (for imparting green colour) , textile
industry, ceramic industry and in medicines.
3. Plutonium it is used as a fuel for atomic reactors as well as for making atomic bombs.

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CHEMISTRY FOR NEET & AIIMS
Ex. Name the members of the lanthanoids series which exibit +4 oxidation states and those which exhibit +2 oxidation
state. Try to correlate this type of behaviour with the electronic configurations of these elements.
Sol. + 4 = 58Ce, 59Pr, 60Nd 65Tb, 66Dy
+ 2 = 60Nd, 62Sm, 63Eu 65Tm, 66Yb
+2 oxidation state is exhibited when the lanthanoid has the configuration 5d 0 6s2 so that 2 electrons are easily lost;
+4 oxidation state is exhibited when the configuration left is close to 4f0 (e.g. 4f0, 4f1, 4f2) or close to 4f7 (e.g. 4f7 or 4f8).

Ex. The chemistry of the actinoid elements is not so smooth as that of the lanthanoid. Justify this statement by giving
some examples from the oxidation state of these elements.
Sol. Lanthanoids show limited number of oxidation state, viz, +2, +3 and +4 (out of which +3 is most common). This is
because of large energy gap between 4f, 5d and 6s subshells, the dominant oxidation state of actinoids is also + 3
but they show a number of other oxidation states also, e.g. uranium (Z = 92) and plutonium (Z = 94), show +3 +4 +5
and +6 neptunium (Z = 94) shows +3 +4 +5 and +7 etc. This is due to small energy difference between 5f, 6d and 7s
subshell of the actinoids

COMPARISON OF LANTHANIDES AND ACTINOIDS

POINTS OF RESEMBALANCE
(i) Both lanthanoids and actinoids show a dominant oxidatio state of +3.
(ii) Both are electropositive and act as strong reducing agents.
(iii) Cations with unpaired electrons in both of them are paramagnetic.
(iv) Most of the cations of lanthanoids and actinoids are coloured.
(v) Both of them show a steady decrease in their ionic radii along the series. Thus, lanthanoids show lanthanid
contraction and actinoids show actinide contraction.

POINTS OF DISTINCTION

Lanthanoids Actinoids
1. Besides the most common oxidation state of +3 Besides the most common oxidation state of +3,
lanthanoids show +2 and +4 oxidation states in actinoids show +4, +5 and +6 oxidation states
case of certain elements. in case of certain elements.
2. Lanthanoids have less tendency towards Actinoids have a stronger tendency towards
complex formation. complex formation.
3. Except promethium, they are non radioactive. All the actinoids are radioactive.
4. Oxides and hydroxide of lanthanoids are less basic Oxides and hydroxides of actinoids are
more basic

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 TRANSITION ELEMENTS (d & f BLOCK)

d-block
1. The f-blocks elements differ from those of d-blocks elements in that they have unstable electroconfiguration in the

outer shells in comparison to that of d-blocks element.

d-block elements electronic configuration

(n–1)d1–10 ns1–2

Most common oxidation state +2

2. The colour in d-block elements is due to d-excitation while in f-block element, it is due to f-f transitions.

3. They show variable oxidation state due to less energy difference between ns and (n-1) d sub shell.

4. Most of the d-block compounds act as catalyst due to their variable oxidation state or complex formation tendency

or adsorption on their surface. Example :

contact proecess = V2O5

Ostwald process = Pt/Rh

Haber process = Fe2O3 + Al2O3 + K2O

Zeigter Natta = TiCl4 + (C2H5)3 Al

Phenton reagent = FeSO4 + H2O2

Hydrogenation of Alkene = Ni/Pd

Decomposition of KClO3 = MnO2

Wilkinsion catalyst = RhCl + PPh3

5. Action of heat on copper sulphate

Exposure 373K 500K
CuSO4.5H2O CuSO4. 3H2O CuSO4.H2O CuSO4

Bluish green White

6. Chemical volcano. When crystals of red coloured ammonium dichromate are heated, a violent action takes place

accompained by flashes of light and nitrogen is liberated leaving behind a dark green residue of chromium sesquioxide

(Cr2O3)

(NH4)2Cr2O7 o N2 + 4H2O + Cr2O3

Ammonium dichromate Chromium sesquioxide

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CHEMISTRY FOR NEET & AIIMS

7. Reactions of Cr2O7–2 :

Cr2O7–(Orange)
–2
SO2 SO4
H2S S
SO3–2 SO4–2
– –
NO2 NO3
I– I2
–
Br Br2
S2O3–2 S + SO4–2
C2H5 OH CH3COOH
Sn+2 Sn+4
Fe+2 Fe+3

Cr+3(green)
Cr2O7–2 /H+(Orange)

H2O2 H2O

CrO5
(Blue)

8. Reaction of MnO4–

MnO4– (Purple)
C2 O4–2 CO2
–2
SO2 SO4
H2 S S
S2O3–2 S+SO4–2
NO2– NO3–
I– I2
Br– Br2
Cl– Cl2
C2H5 OH CH3–COOH
+2 +4
Sn Sn
Fe+2 Fe+3
+2
Mn (Purple colour is decolourise)

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 TRANSITION ELEMENTS (d & f BLOCK)

MnO4 –/OH–

– –
I IO3

CH2=CH2 CH2–CH2
OH– OH
MnO2
(Brown PPT)

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CHEMISTRY FOR NEET & AIIMS

SOLVED EXAMPLE
Ex. 1 Amongst [TiF6]2– , [CoF6]3– , Cu2 Cl2 and [NiCl4]2– is violet and
[Atomic number ; Ti = 22, Co = 27, Cu = 29, Ni = 28] paramagnetic.
the colourless species are :
(D)K2Cr2O7 + H2SO4 (s) One of the products
(A) [TiF6]2– and [Cu2Cl2] (B) Cu2Cl2 and [NiCl4]2–
(cold & conc.) exists as dimer.
(C) [TiF6]2– and [CoF6]3– (D) [CoF6]3– and [NiCl4]2–
Ans. (A) Ans. [A – r] ; [B – s ; [C – q] ; [D – p].
Sol. In [TiF6]2– the titanium is in +4 oxidation state having Zn
Sol. (A) TiCl4 TiCl3, violet (one unpaired
the electronic configuration [Ar]18 3d0 4s0. Similarly electron so d-d transition is
in Cu2Cl2 the copper is in +1 oxidation state having possible).
the electronic configuration [Ar]18 3d10 4s0. As they
do not have any unpaired electrons for d-d transition,
they are therefore colourless. (B) 2FeCl3 573K
In [NiCl4]2– the nickel is in +2 oxidation state and
electronic configuration is [Ar]18 3d8 4s0. As it has
gas dimer.
two unpaired electrons, so the complex is coloured.
750K
In [CoF6]3–, the cobalt is in +3 oxidation state having (C) 2KMnO4 K2MnO4 green (one
electron configuration [Ar] 3d6 4s0. As it has four unpaired electron so d-
unpaired electrons, so the complex is coloured. d transition is possible) + MnO2
Ex. 2 On the basis of trends in the properties of the 3d- + O2 .
series elements, suggests possible M2+ aqua ions
(D) K2Cr2O7 + 2H2SO4 o 2CrO3 bright orange
for use as reducing agents, and write a balanced
(diamagnetic) + 2KHSO4 + H2O.
chemical equation for the reaction of one of these
ions with O2 in acidic solution. Ex. 4 Among the following statements choose the true or
Sol. Because oxidation state +2 is most stable for the false statement(s).
later elements of 3d-series elements, strong reducing
(A) K2Cr2O7 on heating with charcoal gives metallic
agents include ions of the metals on the left of the
series: such ions include V2+ (aq) and Cr2+ (aq) The potassium and Cr2O3.
Fe2+ (aq) ion is only weakly reducing. The Co2+ (B) On heating in current of H2 the crystalline
(aq), Ni2+ (aq), and Cu2+ (aq) ions are not oxidized in KMnO4 is converted into KOH and Mn3O4.
water. (C) Hydrated ferric chloride on treatment with 2, 2–
+0.77 -0.44 dimethoxypropane gives anhydrous ferric
Fe3+
Fe 2+
Fe
The chemical equation for the oxidation is then chloride.
4 Fe2+ (aq) + O2(g) + 4H+ (aq) o 4Fe3+ (aq) + Ans. (A) False (B) False
2H2O (A). (C) True

Ex. 3 Match the reactions given in column-I with the Sol. (A) K2Cr2O7 + 2C (charcoal) Cr2O3 + K2CO3
characteristic(s) of the reaction products given in + CO n .
column-II.
(B) 2KMnO4 + 5H2 2 KOH + 2MnO + 4H2O.
Column-I Column-II
(A)TiCl4 Zn (p) One of the products OCH3
is bright orange |
coloured but (C) FeCl3 . 6H2O + 6CH3 — C — CH3 o FeCl3
|
diamagnetic. OCH3
(B)FeCl3 573K (q) One of the products
(anhydrous) + 12CH3OH + 6CH3COCH3 .
is green coloured and
paramagnetic. Ex. 5 A compound (A) is used in paints instead of salts of
750K lead. Compound (A) is obtained when a white
(C) KMnO4 (r) One of the products

118
 TRANSITION ELEMENTS (d & f Block)
compound (B) is strongly heated. Compound (B) is (A) Cr2+ is reducing in nature.
insoluble in water but dissolves in sodium hydroxide (B) Mn3+ is oxidising in nature.
forming a solution of compound (C). The compound (C) Both (A) and (B)
(A) on heating with coke gives a metal (D) and a gas (D) None of these
(E) which burns with blue flame. (B) also dissolves Sol. Cr2+ is reducing as its configuration changes from
in ammonium sulphate solution mixed with d4 to d3, the latter having a half-filled t32g energy
ammonium hydroxide. Solution of compound (A) in level of 3d orbitals in octahedral crystal field spliting.
dilute HCl gives a bluish white / white precipitate On the other hand, the change from Mn3+ to Mn2+
(F) with excess of K4[Fe(CN)6]. Identify (A) to (F) results in the half-filled (d5) configuration which has
and explain the reactions. extra stability.
Ans. (A) ZnO, (B) Zn(OH)2, (C) Na2 ZnO2 , (D) Zn, (E) Therefore, (C) option is correct.
CO, (F) K2Zn3 [Fe(CN)6]2
Ex. 8 Which of the following increasing order of oxidising
Sol. Zn(OH)2 (B) ZnO (A) + H2O. power is correct for the following species ?
VO2+ , MnO4– , Cr2O72–
Zn(OH)2 (B) p + 2OH o [Zn(OH)4]2– (C)
–
(A) VO2+ < Cr2O72– < MnO4–
(soluble complex). (B) VO2+ < MnO4– < Cr2O72–
ZnO (A) + C Zn (D) + CO (E). (C) Cr2O72– < VO2+ < MnO4–
(D) Cr2O72– < MnO4– < VO2+
Zn(OH)2 (B) + 4NH3 o [Zn(NH3)4]2+ (soluble Sol. This is attributed to the increasing stability of the
complex) + 2OH . – lower species to which they are reduced.
MnO4– is reduced to Mn2+ which has stable half
ZnO + 2HCl o ZnCl2 + H2O. filled valence shell electron configuration [3d5].
Cr2O72– is reduced to Cr3+ which has half filled t32g
3ZnCl2 + 2K4[Fe(CN)6] o K2Zn3[Fe(CN)6]2 p energy level of 3d orbitals in octahedral crystal field
(bluish white/white) (F) + 6KCl. spliting
VO 2+ is reduced to V 3+ which has electronic
Ex. 6 An unknown inorganic compound (X) gave the configuration [Ar]18 3d2 4s0.
following reactions:
So the order of increasing stability of the reduced
(i) The compound (X) on heating gave a residue, species is Mn2+ > Cr3+ > V3+ and, therefore, the
oxygen and oxide of nitrogen. increasing order of oxidising power is VO2+ < Cr2O72–
(ii) An aqueous solution of compound (X) on < MnO4– .
addition to tap water gave a turbidity which Therefore, (A) option is correct.
did not dissolve in HNO3.
(iii) The turbidity dissolves in NH4OH. Ex. 9. Which of the following statement(s) is/are correct
?
Identify the compound (X) and give equations for
the reactions (i), (ii) & (iii). (A) Tr ansiti on metals and many o f their
compounds show paramagnetic behaviour.
Ans. X = AgNO3
(B) The enthalpies of atomisation of the
Sol. 2AgNO3 (X) 2 Ag + 2NO2 + O2 . transition metals are high
(C) The t ransition meta ls generally fo rm
AgNO3 (aq.) + Cl— o AgCl p (white) + NO3— . coloured compounds
(D) Transition metals and their many compounds
AgCl + 2NH3 o [Ag(NH3)2]+ (soluble complex).
act as good catalyst.
Ex. 7 Which of the following is true for the species having Sol. (A) As metal ions generally contain one or more
unpaired electrons in them & hence their
3d4 configuration ?

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CHEMISTRY FOR NEET & AIIMS
complexes are generally paramagnetic Column I Column II
(B) Because of having larger number of unpaired (A) AgNO3(aq) + I2
electrons in their atoms, they have stronger inter
(excess) + H2O o (p) Disproportionation
atomic interaction and hence stronger bonding
(B) K2MnO4(aq)
between the atoms.
(C) According to CFT, in presence of ligands the + CO2(g) o (q) Comproportionation
colour of the compound is due to the d-d
(C) Na2Cr2O7 + C (r) Redox
transition of the electrons.
(D) CuCl2(aq)
(D) This activity is ascribed to their ability to
adopt multiple oxidation state and to form + Cu(s) o (s) One of the products
complexes. is insoluble in water
Therefore, (A,B,C,D) options are correct. Ans. (A o p, r, s) ; (B o p, r, s) ; (C o r, s) : (D o q, r, s)
0
Ex. 10 Statement-1 : The number of unpaired electrons in Sol. (A) 5AgNO3(aq) + 3 I 2 (excess) + 3H2O o
the following gaseous ions : V –1
Mn3+, Cr3+, V3+ and Ti3+ are 4, 3, 2 and 1 respectively. HIO3 + 5AgI + 5HNO3
Statement-2 : Cr3+ is most stable in aqueous solution So it is redox and disproportionation reaction. AgI
among these ions. insoluble in water.
(A) Statement-1 is True, Statement-2 is True; +VI +VII
Statement-2 is a correct explanation for Statement- (B) 3K 2 MnO 4 (aq) + 2CO2(g) o 2KMnO 4 +
1. +IV
(B) Statement-1 is True, Statement-2 is True; MnO 2 + 2K2CO3
Statement-2 is NOT a correct explanation for So it is redox and disproportionation reaction. MnO2
Statement-1 insoluble in water.
(C) Statement-1 is True, Statement-2 is False 0 +VI +III +IV

(D) Statement-1 is False, Statement-2 is True (C) 2C + Na 2 Cr2O 7 Cr2O3 + Na 2 CO3 +

Sol. (B) Mn3+ = [Ar]18 3d4 , Cr+3 = [Ar]18 3d3 , V3+ = [Ar]18 II
3d2 , Ti3+ = [Ar]18 3d1 CO n
Cr3+ is most stable in aqueous solution because it So it is redox reaction. Cr2O3 (green pigment) is
insoluble in water.
has half filled t32g energy level of 3d orbitals in
+II +I
octahedral crystal field spliting and according to 0
(D) CuCl2 (aq) + Cu (s) o Cu 2Cl 2 (s)
crystal field theory (CFT) it has highest value of
CFSE i.e. 1.2 'O. So it is redox and comproportionation reaction.
Cu2Cl2 is insoluble in water.
Ex. 11 S1 : Interstitial compounds have high melting points,
higher than those of pure metals. Ex. 13 When CO2 is passed into aqueous :
S2 : Permanganate titrations in presence of (A) Na2CrO4 solution, its yellow colour changes to
hydrochloric acid are unsatisfactory. orange.
S3 : KMnO4 does not act as an oxidising agent in (B) K 2MnO 4 solution, it disproportionates to
strong alkaline medium. KMnO4 and MnO2
S4 : KMnO4 on heating in a current of H2 gives (C) Na2Cr2O7 solution, its orange colour changes
to green
MnO.
(D) KMnO4 solution, its pink colour changes to
(A) T T F T (B) T F F T green.
(C) T F T T (D) F F T F
Sol. (A) Na2CrO4 H+ Na2Cr2O7 (orange colour)
Sol. S1 : Due to strong interatomic forces.
S2 : Some of the hydrochloric acid is oxidised to (B) MnO42– H+ MnO4– + MnO2 , in neutral or
chlorine and thus we get less volume of KMnO4 acidic medium
than the actual one. (C) False - In acidic medium no colour change takes
- place.
S3 : MnO4– + e– OH  MnO42– -
(D) MnO4– + e– OH MnO42– ; in strong alkaline
S4 : 2KMnO4 + 5H2 o 2KOH + 2MnO + H2O. medium pink colour of KMnO4 changes to green.
Therefore, (A) option is correct. Therefore, (A,B) options are correct.
Ex. 12 Match the reactions in Column I with nature of the Ex. 14 Which of the following statement(s) is (are) not
reactions/type of the products in Column II. correct with reference to ferrous and ferric ions

120
 TRANSITION ELEMENTS (d & f Block)
(A) Fe 3+ gives brown colour with potassium the compound from the following,.
ferricyanide (A) Mn2O7 (B) MnO2
(C) MnSO4 (D) Mn2O3
(B) Fe2+ gives blue precipitate with potassium Ans. (A) On addition of KMnO4 to concentrated H2SO4, a
ferricyanide green oily compound Mn2O7 is obtained which is
highly explosive in nature
(C) Fe 3+ gives red colour with potassium
2KMnO 4  2H 2 SO 4 (Conc.) o Mn 2 O 7
sulphocyanide
2KHSO 4  H 2 O.
(D) Fe2+ gives brown colour with potassium sulphocyanide
Sol. Fe3+ produces red colouration with KSCN but Fe2+ Ex. 19 When KMnO4 solution is added to oxalic acid
solution, the decolourisation is slow in the beginning
does not give brown colour with KSCN. but becomes instataneous after some time because
Therefore, (D) option is correct. (A) CO2 is formed as the product
(B) Reaction is exothermic
Ex. 15 Statement-1 : Ammonical silver nitrate converts (C) MnO 4 catalyses the reaction
glucose to gluconic acid and metallic silver is (D) Mn2+ acts as autocatalyst
precipitated. Ans. (D) When KMnO4 solution is added to oxalic acid
Statement-2 : Glucose acts as a weak reducing agent. solution, the decolourisation is slow in the beginning
but becomes instantaneous after some time because
(A) Statement-1 is True, Statement-2 is True; Mn2+ acts as autocatalyst
Statement-2 is a correct explanation for Statement- Reduction half
1. [MnO 4  8H   5e  
o Mn 2   4H 2 O] u 2
(B) Statement-1 is True, Statement-2 is True; Oxidation half
Statement-2 is NOT a correct explanation for [C 2 O 24  
o 2CO 2  2e  ] u 5
Statement-1 Overall equation
(C) Statement-1 is True, Statement-2 is False 2MnO 4  16H   5C 2 O 24  
o 2Mn 2
(D) Statement-1 is False, Statement-2 is True 10CO 2  8H 2 O
Sol. (A) Ag2O + C6H12O6 o 2Ag + C6H12O7. End point of this reaction Colourless to ligh pink.
Ex. 20 Which of the following is amphoteric oxide
Ex. 16 What is the composition of mischmetal alloy and
what are it's uses ? Mn 2 O7 , CrO3 , Cr2 O3 , CrO, V2 O 5 , V2 O 4
Ans. Mischmetal consists of lanthanoid metal (~95%) (A) V2 O5 , Cr2 O3 (B) Mn 2 O7 , CrO3
and iron (~5%) and traces of S,C,Ca and Al. (C) CrO, V2 O 5 (D) V2 O5 , V2 O4
Mischmetal is used in Mg based alloy to produce Ans. (A) V2O5 and Cr2O3 are amphoteric oxide because
bullets, shell and lighter flint. both react with alkalies as well as acids.
Ex. 21 Interstitial compounds are formed when small atoms
Ex. 17 The electronic configuration of Cu(II) is 3d9 where are trapped inside the crystal lattice of metals. Which
as that of Cu(l) is 3d10. Which of the following is of the following is not the characteristic property of
interstitial compounds
correct
(A) They have high melting points in comparison to
(A) Cu(II) is more stable pure metals
(B) Cu(II) is less stable (B) They are very hard
(C) They retain metallic conductivity
(C) Cu(I) and Cu(II) are equally stable (D) They are chemically very reactive
(D) Stability of Cu(I) and Cu(II) depends on nature Ans. (D) they are chemically very rective are trapped
of copper salts inside the crystal lattice of metals. Some of their
important characteristics are as follows
Ans. (A) Cu(II) is more stalbe than Cu(I). As it is known (i) They are very hard and rigid.
that, Cu(I) has 3d10 stable configuration while Cu(II) (ii) They have high melting point which are higher
has 3d9 configuration. But Cu(II) is more stable due than those of the pure metals
to greater effective nuclear charge of Cu(II) i.e., it (iii) They show conductivity like that of the pure
metal
hold 17 electrons insted of 18 in Cu(I). (iv) They acquire chemical inertness.
Ex. 18 On additionof small amount of KMnO 4 to
concentrated H2SO4, a green oily compound is
obtained which is highly explosive in nature. Identify

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 TRANSITION ELEMENTS (d & f Block)

Exercise PART - 1 PREVIOUS YEAR (NEET/AIPMT)

1. The basic character of the transition metal which one of them is expected to have the highest
monoxides follows the order third ionisation enthalpy? [CBSE AlPMT 2005]
(At. no. Ti=22, V=23, Cr= 24, Fe=26) (A) Vanadium (Z=23) (B) Chromium (Z=24)
[CBSE AlPMT 2003] (C) Iron (Z=26) (D) Managanese (Z=25)
(A) TiO > FeO > VO > CrO 7. The aqueous solution containing which one of the
following ins will be colourless?
(B) TiO > VO > CrO > FeO
[CBSE AlPMT 2005]
(C) VO > CrO> TiO> FeO
(D) CrO > VO > FeO > TiO (At. no Sc=21,Fe=26,Ti=22, Mn=25
(A) Sc3+ (B) Fe2+
2. The correct order of ionic redil of Y3+, La3+, Eu3+ and (C) Ti3+ (D)Mn2+
Lu3+ is [CBSE AlPMT 2003]
At.No.Y=39,La=57, Eu=63,Lu=71 8. More number of oxidation states are exhibited by
the actinides than by the lanthanides. The
(A) Lu < Eu <La < Y
3+ 3+ 3+ 3+
mainreasonfor this is [CBSE AlPMT 2006,2005]
(B) La3+ < Eu3+ <Lu3+ < Y3+
(A) more energy difference between 5ft and 6d-
(C) Y3+ < La3+ <Eu3+ < Lu3+ orbitals than that between 4f and 5d orbitals
(D) Y3+ < LU3+ <Eu3+ < Lu3+ (B) lesser energy difference between 5f and 6d-
orbitals than that betwee 4f and 5d orbitals
3. Which one of the following characteristics of the
transition metals is associated with their catalytic (C) greater metallic character of the lanthanides
activity? [CBSE AlPMT 2003] than that of the corresponding actinides
(A) Colour of hydrated ions (D) more active nature of the actinides
(B) Variable oxidation states 9. Copper sulphate dissolves in excess of KCN to give
(C) High enthalpy of atomisation [CBSE AlPMT 2006]
(D) Paramagnetic behaviour (A) CuCN (B) [Cu(CN)4]3+
(C) [Cu(CN)4]2- (D) Cu (CN)2
4. Lanthanides are [CBSE AlPMT 2004]
(A) 14 elements in the sixth period (At. no. = 90 to 10. In which of the following pairs are both the ions
103) that are filling 4f sub-level coloured inaqueous solution? [CBSE AlPMT 2006]
(B) 14 elements inthe seventh period (At. no. = 90 At. No. Sc=21, Ti=22, Ni=28, Cu=29, Co=27
to 103) that are filling 5f sub-level (A) Ni2+, Ti3+ (B) Sc3+, Ti3+
(C) 14 elements in the sixth period (At. no. = 58 to (C) Sc3+ Co2+ (D) Ni2+,Cu+
71) that are filling 4f sub-level
(D) 14 elements in the seventh period (At. no. = 58 11. Identify the incorrect statement among the following.
to 41) that are filling 4f sub-level [CBSE AlPMT 2007]
(A) There is a decrease in the radii of the atoms or
5. Among the following series of transition metal ions, ions as one proceeds from la or Lu
the one in which all metal ions have 3d2 electronic
(B) Lanthanide contraction is the accumulation of
configurations is [CBSE AlPMT 2004]
successive shrinkages
(At.No Ti=22, V=23,Cr=24, Mn=25
(C) As a result of lanthanide contraction . the
(A) Ti3+, V2+,Cr3+Mn4+ (B) Ti+, V4+, Cr6+, Mn7+ properties of 4d series of the transition elements
(C) Ti4+,V3+,Cr2+,Mn3+ (D) Ti2+,V3+ ,Cr4+,Mn5+ have no similarities with the 5d series of
elements
6. Four successive members of the first row transition
elements are listed below with their atomic numbers. (D) Shielding power of 4f electrons is quite weak

122
CHEMISTRY FOR NEET & AIIMS
12. Which one of the folloiwng ions is the most stable 19. Identify the alloy containing a non-metal as a
in aqueous soulutin ? [CBSE AlPMT 2007] constituent init. [CBSE AlPMT 2012]
[At. No. Ti=22, V=23, Cr=27, Mn=25 (A) Invar (B) Steel
(A) Cr3+ (B) V3+ (C) bell-metal (D) Broze
(C) Ti3+ (D) Mn3+
20. Which of the following statements about the
13. Which of the following pairs has the same size? interstitial compounds is incorrect? [NEET 2013]
[CBSE AlPMT 2010] (A) They retain metallic conductivity
(A) Fe , Ni
2+ 2+
(B) Zr , Ti
4+ 4+
(B) They are chemically reactive
(C) Zr4+,Hf4+ (D) Zn2+, Hf4+ (C) They are much harder than the pure metal
(D) They have higher melting points than the pure
14. Which one of the following ions has electronic
configuration [Ar]3d6? metals

[At.No Mn=25, Fe =26, Co=27, Ni=28] 21. Which of the following lanthanoid ions is
[CBSE AlPMT 2010] diamagnetic? [NEET 2013]
(A) Ni3+ (B) Mn3+ (At.no.Ce = 58, Sm=62, Eu=63, Yb=70)
(C) Fe3+ (D) CO3+ (A) Ce2+ (B) Sm2+
(C) Eu2+ (D) Yb2+
15. Which of the following ions will exhibit colour in
quueous solutions? [CBSE AlPMT 2010] 22. Which of the following does not give oxygen on
(A) La (Z=57)
3+
(B) Ti (Z=22)
3+
heating? [NEET 2013]
(C) Lu3+ (Z=71) (D) (Z=21) (A) KCIO3 (B) Zn(CIO3)2

16. Acidified K 2Cr 2O7 solution turns green when (C) K2Cr2O7 (D) (NH4)2 Cr2O7
Na2SO3 is added to it. This is due to the formation of
23. Reason of lanthanoid contractions is
[CBSE AlPMT 2010]
[CBSE AlPMT 2004]
(A) CrO 24  (B) Cr2(SO3)3 (A) negligible screening effect of f-orbitals
(C) CrSO4 (D) Cr2(SO4)3 (B) increasing nuclear charge
(C) decreasing nuclear charge
17. For the four successive transition elements
[Cr,Mn,Fe and Co), the stability of +2 oxidation state (D) decreasing screening effect
will be there in which of the following order
24. The reaction of aqueous KMnO4 with H2O2 in acidic
(At. no.Cr = 24, Mn=25, Fe=26, Co=27) conditions gives [CBSE AlPMT 2014]
[CBSE AlPMT 2011] (A) Mn4+ and O2 (B) Mn2+ and O2
(A)Fe > Mn > Co > Cr (B) Co > Mn >Fe > (C) Mn2+ and O3 (D) Mn4+ and MnO2
(C) Cr > Mn >Co > Fe (D) Mn >Fe >Cr > cp
25. In acidic medium, H2O2 changes Cr2 O 72  to CrO5
18. The d-electron configurations of Cr2+ ,Mn2+ Fe2+ and
Co2+ are d4,d5,d6 and d7 respectively. which one of which has two (-O-O-) bonds. Oxidation state of Cr
the following will exhibit minimum paramagnetic in CrO5 is [CBSE AlPMT 2014]
behaviour ? [CBSE AlPMT 2011] (A) +5 (B) +3
[At.no.Cr = 24, Mn=25, Fe=26, Co=27] (C) +6 (D) -10
(A) [Fe)H2O6)2+ (B) [Co(H2O6)2+ 26. The pair of compounds that can exist together is
(C) [Cr(H2O6]2+ (D)[Mn (H2O6]2+
[CBSE AlPMT 2004]
(A) FeCl3, SnCl2 (B) HgCl2 SnCl2
(C) FeCl2, SnCl2 (D) FeCl3, Kl

123
 TRANSITION ELEMENTS (d & f Block)
27. Magnetic moment 2.84 BM is given by (At. no Ni (A) [Xe]4f6 5d1 6s2 [Xe] 4f7 5d1 6s2 and [Xe[ 4f9 6s2
=28, Ti = 22, Cr=24, Co=27) [CBSE AlPMT 2015] (B) [Xe]4f6fd16s2,[4f7 5d1 6s2 and [Xe] 4f8 5d1 6s2
(A) Ni2+
(B) Ti 3+
(C) [Xe]4f7 6s2. [Xe] 4f75d16s2 and [Xe] 4f96s2
(C) Cr3+ (D) Co2+
(D) [Xe] 4f7 6s2 [Xe] 4f8 6s2 and [Xe] 4f8 5d1 6s2
28. Which of the following processes does not involve
34. Which one of the following statements is correct
oxidation of iron ? [CBSE AlPMT 2015]
when SO2 is passed through acidified K2Cr2O7
(A) Rusting of iron sheets solution? [NEET 2016, phase I]
(B) Decolourisation of blue CuSO4 solution by iron (A) The solution is decolourised
(C) Formation of Fe (CO)5 frp, Fe (B) SO2 is reduced
(D) Liberation of H2 from steam by iron a high (C) Green Cr2(SO4)3 is formed
temperature
(D) The solution turns blue
29. Because of lanthanoid contraction, which of the
35. Which one of the following statements is correct
following pairs of elements have nealy same atomic
when SO2 is passed through acidified K2Cr2O7
radii? (Numbers in the parenthesis are atomic
solution? [NEET 2016 Phase I]
numbes) [CBSE AlPMT 2015]
(A) Cu (No3)2 and NO
(A) Ti (22) and Zr (40) (B) Zr (40) and Nb (41)
(B) Cu (No3)2 No and NO2
(C) Zr (40) and Hf (72) (D) Zr (40) and Ta (73)
(C) Cu (No3)2 and N2O
30. Assuming complete ionisation, same moles of which (D) Cu (No3)2 and NO2
of the following compounds will require the least
amoun of acidified KMnO4 for complete oxidation 36. HgCl 2 and I 2 both when dissolved in water
[CBSE AlPMT 2015] containing I- ions the pair of species formed is
(A) FeSO4 (B) FeSO3 [NEET 2007]
(C) FeC2O4 (D) Fe (NO2)2 (A) Hgl2 , I3 (B) Hgl2, l-

31. Gadolinium belongs to 4f series. It’s atomic number (C) Hgl 24  , I  (D) Hg2l2, l-
is 64. Which of the following is the correct edectronic
configuration of gadolinium [CBSE AlPMT 2015] 37. Name the gas that can readily decolourise acidified
(A) [Xe]4f8 6d2 (B) [Xe]4f9 5S1 KMno4 solution. [NEET 2017]
(C) [Xe]4f7 5d1 6s2 (D) [Xe]4f6 5d2 6s2 (A) CO2 (B) SO2
(C) NO2 (D) P2O5
32. Which one of the following statements relted to
lanthanons is incorrect [NEET 2016, Phase II] 38. The reason for greate range of oxidation state in
(A) Europium shows +2 oxidation state actionids is attributed to [NEET 2017]
(B) The basicity decreases as the ionic radius (A) the redioactive nature of actinoids
decreases from Pr to Lu (B) actinoid contraction
(C) All the lanthanons are much more reactive than (C) 5f,6d and 7s levels having comparable energies
aluminium (D) 4f and 5d levels being close in energies
(D) Ce (+4) solutuion are widely used as oxidising
agent in volumetric analysis
39. Which one of the following ions exhibits d-d
33. The electronic configuration of Eu (Atomic no.63), transition and paramagnetism as well ?[NEET 2018]
Gd (Atomic no.64) and Tb (Atomic no.65) are (A) MnO 4 (B) Cr2 O 72 
[NEET 2016, Phase I]
(C) Cr2 O 42  (D) MnO 24 

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CHEMISTRY FOR NEET & AIIMS

Exercise PART - 2 PREVIOUS YEAR (AIIMS)

1. The colourless species is

9. Match list 1 with list II and select the correct answer
(A) VCl3 (B) VOSO4
using the codes given below the lists.
(C) Na3VO4 (D) [V(H2O)6] SO4.H2O
[2003]

2. Lanthanide for which +II and +III oxidation states

are common is
(A) La (B) Nd
(C) Ce (D) Eu [2003]

3. The liquefied metal expanding on solidification is Codes

(A) Ga (B) Al (A) A-1, B-3, C-5, D-4 (B) A-2, B-3, C-5, D-1
(C) Zn (D) Cu [2004] (C) A-4, B-3, C-5, D-1 (D) A-4, B-5, C-3, D-1
4. Among the following pair of ions, the lower oxidation [2010]
state in aqueous solution is more stabel than the
other, in
10. Which is not stable under ambient condition ?
(A) Tl+, Tl3+ (B) Cu+, Cu2+
(A) Fe3+ (B) Mn2+
(C) Cr , Cr
2+ 3+
(D) V , VO
2+ 2+
[2005]
(C) Ti4+ (D) Cu+ [2012]

5. The colour imparted by Co (II) compounds to glass 11. MnO3 in an acidic medium dissociates into
is
(A) MnO2 and MnO4– (B) MnO and MnO4–
(A) green (B) deep-blue
(C)MnO2 and MnO (D) MnO2 and MnO3
(C) yellow (D) red [2006]
[2012]

6. During estimation of nickel, we prepare nickel 12. Magnetic moment of Cr2+ is nearest to
dimethylgloyoxime, a scarlet red solid, This (A) Fe2+ (B) Mn2+
compound is ......
(C) Co2+ (D) Ni2+ [2012]
(A) ionic (B) covalent
13. Which of the following elements has lowest melting
(C) metallic (D) non-ionic complex point ?
[2007]
(A) Cr (B) Fe
(C) Ni (D) Cu [2013]
7. Mercurous chloride exists in the form of
(A) Hg+ (B) Hg22+ 14. Maximum number of unpaired electrons are present
(C) Hg2+ (D) Hg32+ [2009] in
(A) Gd3+ (B) Yb2+
8. What are constituents of ‘Mischmetal’ ?
(C) Tb2+ (D) Pm3+ [2013]
(A) La, Fe (B) La, Ce
(C) Fe, Ce (D) Ce, Cu [2010]

125
 TRANSITION ELEMENTS (d & f Block)
15. When calomel is treated with ammonium hydroxide, 23. Violet colour appear in glass when we add– [2018]
a black substance in formed. The black substance is
(A) Cr3+ (B) Mn4+
(A) Hg + Hgo
(C) I2 (D) K+
(B) HgO.HgCl2
24. In which 'd' electrons are zero? [2018]
(C) H2N – Hg – Cl + Hg
(A) Th (B) Es
(D) Hg(NH2)2 + HgO [2013]
(C) Lu (D) Am
25. Which is least stable in aqueous medium [2018]
16. Which of the following is most basic ?
(A) Fe+2 (B) Co+2
(A) Al(OH)3 (B) Cr(OH)3
(C) Ni+2 (D) Mn+2
(C) La(OH)3 (D) Fe(OH)3 [2013]
ASSERTION AND REASON
17. Which of the following ion does not exist ? In each of the following questions, two statement
(A) [Cul4] 2–
(B) VO 3– are given one is assertion and the other is reason.
4
Examine the statement carefully and mark the correct
(C) WO42– (D) CrO42– [2013]
answer according to the instruction given below
(A) If both the assertion and reason are true and
18. KMnO4 in alkaline medium changes to
reason explains the assertion
(A) Mn3+ (B) MnO2
(B) If both the assertion and reason are true but
(C) MnO4 2–
(D) Mn(OH)4– [2014] reason does not explain the assertion
(C) If assertion is true but reason is false
19. Choose the correctly paired gaseous cation and its
(D) If assertion is false but reason in true
magnetic (spin only) moment (in B.M.)
(A) Ti2+, 3.87 B.M. (B) Cr2+, 4.90 B.M. (E) Both assertion and reason are false

(C) Co3+, 3.87 B.M. (D) Mn2+, 4.90 B.M.

[2014] 26. Assertion : solution of Na2CrO4 in water is intensely
coloured.
20. In presence of acidic medium, KMnO4 converts H2S Reason : Oxidation state of Cr in Na2CrO4 is +VI.
into
[2003]
(A) Mn only (B) MnS only
(C) Mns + S (D) S only [2014] 27. Assertion : Potassium ferrocyanide is diamagnetic
whereas potassium ferricyanide is paramagnetic.
21. Copper sulphate is dissolved in water containing Reason : Crystal field splitting in ferrocyanide ion is
________ for making Bordeaux mixture. greater than that of ferricyanide ion. [2005]

(A) NaOH (B) KCN

(C) Ca(OH)2 (D) All of these [2015] 28. Assertion : K2Cr2O7 is used as primary standard in
volumetric analysis.
22. Colour imparted by Co(II) compounds to glass is Reason : It has a good solubility in water.
(A) green (D) brown [2006, 2015]

(C) violet (D) blue [2015]

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CHEMISTRY FOR NEET & AIIMS

29. Assertion : Change in colour of acidic solution of 37. Assertion : La(OH)3 is more basic than Lu(OH)3.
potassium dichromate by breath is used to test drunk
Reason : Size of Lu3+ increases and shows less
dirvers.
covalent character. [2012]
Reason : Change in colour is due to the
complexation of alcohol with potassium dichromate. 38. Assertion : Co (IV) is known but Ni(IV) is not.
[2006, 2015] Reason : Ni (IV) has d4 electronic configuration.
[2014]
30. Assertion : Copper sulphate solution is not stored
in zinc vassel.
39. Assertion : The correct order of oxidising power is
Reason : Zinc forms complex with CuSO4. [2007]
: VO 2  Cr2 O 72  MnO 4 .

31. Assertion : Magnetic moment of Dy is the highest Reason : The oxidation state of Mn is +7. [2014]
among the lanthanoids.
Reason : Orbital motion contributes magnetic 40. Assertion : Chemistry of actinoids is more
moment. [2007] complicated than lanthanoids.
Reason : Actinoid elements are radioactive. [2014]
32. Assertion : Copper metal gets readily corroded in
acidic aqueous solution.
41. Assertion : Magnetic moment values of actinides
Reason : Free energy change for this process in are lesser than the theoretically predicted values.
negative. [2008, 2004]
Reason : Actinide elements are strongly
33. Assertion : Transition metals are poor reducing paramagnetic. [2017]
agents.
Reason : Transition metals form numerous alloys
with other metals. [2010]

34. Assertion : The degree of complex formation in

actinides decreases in the order

M 4 ! MO 22 ! M 3 ! MO 2 .

Reason : Actinides form complexes with S-bonding

ligands such as alkyl phosphines and thioethers.
[2010]

35. Assertion : Reduction potential of Mn (+3 to +2) is

more positive than Fe (+3 to +2).
Reason : Ionisation potential of Mn is more than
that of Fe. [2011]

36. Assertion : Ce4+ is used as an oxidising agent in

volumetric analysis.
Reason : Ce4+ has the tendency of attaining +3
oxidation state. [2012]

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CHEMISTRY FOR NEET & AIIMS

ANSWER KEY

EXERCISE
: PART # I
1. B 2. D 3. B 4. C 5. D 6. D 7. A 8. B 9. B 10. A 11. C 12. D 13. C
14. D 15. B 16. D 17. D 18. B 19. B 20. B 21. D 22. D 23. A 24. B 25. C 26. C
27. A 28. C 29. C 30. A 31. C 32. C 33. C 34. C 35. D 36. C 37. B 38. C 39. D
PART # II
1. C 2. D 3. A 4. A 5. B 6. D 7. B 8. B 9. C 10. D 11. A 12. A 13. D
14. A 15. C 16. C 17. A 18. B 19. B 20. D 21. C 22. D 23. A 24. D 25. A 26. B
27. C 28. C 29. C 30. A 31. A 32. D 33. B 34. B 35. C 36. A 37. A 38. D 39. B
40. B 41. B

128
 TRANSITION ELEMENTS (d & f Block)
EXERCISE Fe = 1s2, 2s2 2p6, 3s2 3p6 3d6, 4s2
26

P-1 (NEET/AIPMT) Fe2+ = 1s2, 2s2p6, 3s2 3p6 3d6

d
1. (B) The order of basic character of the transition metal
monoxide is TiO > Vo > CrO> FeO because basic character
of oxides decreases with increase in atomic number. (It is coloured due to the presence of four unpaired
Hence, oxides of transitional metals in low oxidation electrons in d sub-shell)
state, i.e + 2and +3are generally basic except Cr2O3. 22
Ti = 1s2,2s2 2p6, 3s2 3p6 3d2, 4s2
Ti3+ = 1s2, 2s2 2p6, 3s2 3p6 3d1
2. (D) The correct order of ionic radii of Y3+, La3+,Eu3+ and d
Lu3+, is Y3+ < Lu3+ < Eu3+ <La3+ because Eu and Lu are
the members of lanthanide series (so they show
lanthanide contraction) and La is the representative (It is coloured due to the presence of an unpaired electron
element of all elements of such series and Y3+ ion has in d sub-shell)
lower radil as comparison to La 3+ because it lies 25
Mn = 1s2, 2s2 2p6, 3s2 3p6 3d5, 4s2
immediately above it in the periodic table Mn2+ = 1s2,2s2 2p6, 3s2 3p6 3d5
3. (B) The catalytic activity of transitional metals is due to d
their variable oxidation states.

4. (C) lanthanides are the 14 elements of IIIB group and (It is coloured due to the presence of five unpaired
sixth period (at. n o = 57 to 71) that are filling 4f sub-shell electrons in d sub-shell)
of antipenultimate shell from 1 to 14. Actually. they are
placed below the periodic table in horizontal row as 8. (B) More number of oxidation states are exhibited by the
lanthanide series. actinides than by the corresponding lanthanides due ot
lesser energy difference between 5f and 6d orbitals than
5. (D) Ti2+ = 1s2, 2s2 2p6, 3s2 3p6 3d6 3d2, 4s0 that between 4f and 5d-orbitals.
V3+ = 1s2, 2s2 2p6, 3s2 3p6, 3d2,4s0
Cr4+ =1s2, 1s2 2p6,3s2 3p6 3d2, 4s0 9. (B) Copper sulphate when react with KCN first give
Mn5+ = 1s2, 2s2p6, 3s2 3p6, 3s2 3p6 3d2, 4s0 precipitate of cupric cyanide which reduce into Cu2CN2
and dissolve in excess of KCN to give solubel K3 [Cu
6. (D) In23 V = 1s2,2s2 2p6, 3s2 3p6 3d6, 4 s2 (CN4)] complex salt
Third electron which is removed to give third ionisation [CuSo 4  2KCN o Cu(CN) 2  K 2SO 4 ] u 2
potential, belngs to 3d3 subshell Cupric
cyanide
24
Cr = 1s2, 2s2 2p6, 3s2 3p6 3d5, 4s1
Third electron which is removed to give third inosisation 2Cu(CN) 2 o Cu 2 (CN) 2  NC  CN
potential, belongs to 3d5 subshell Cyanogen

Fe = 1s2, 2s2 2p6, 3s2 3p6 3d6, 4s2

26 Cu 2 (CN) 2  6KCN o 2K 3 [Cu  CN 4 ]
Third electron which is removed to give third ionisation So lub e complex salt

potential, belongs to 3d6 subshell. 2CuSO 4  10KCN o 2K3[Cu  CN 4 ]  2K 2SO 4   CN  2

25
Mn = 1s2, 2s2 2p6, 3s2 3p6 3d6 3d5, 4s2
Third electron which is removed to give third ionisation 10. (A) 28 Ni = 1s2, 2s2 2p6, 3s2 3p6 3d8, 4s2
potential, belongs to 3d5 subshell. Ni2+ = 1s2,2s2 sp6, 3s2 3p6 3d8
In all elements shell and subshells are same.
Required amount of energy (enthalpy) is based 3d8 (2 unpaired electrons)
upon the stability of d-subshell.
The 3d5 -subshell has highest stability in all because it is Ti = 1s2, 2s2 2p6, 3s2 3p6 3d2,4s2
22

half-filled subshell. so Mn shows highest third ionisation Ti3+ 1s2,2s2 2p6, 3s2 3p2 3p6 3d1
potential. (1 unpaired electron)
7. (A) SC =1s2,2s2 sp6, 3s23p6,3d1,4s2 21
Sc = 1s ,2s p , 3s2 3p6 3d18 4s2
2 2 6
21
So, Sc3+ = 1s2,2s2 2p6, 3s2, 3p6 Sc3+ = 1s2, 2s2 2p6, 3s2 3p6 d
(It is cp;pir;ess due to the absence of unpaired electrons (no unpaired electron)
in d sub-shell) 29
Cu = 1s2, 2s2 2p6, 3s2 3p6 3d10,4s1

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CHEMISTRY FOR NEET & AIIMS
Cu+ =1s2, 2s2 2p6 ,3s23p6 3d10 (no unpaired electron)
(no unpaired electron) Sc3+ (Z=21) = [Ar] 3d0 4s0
Hence, in the above ions Ni2+ and Ti3+ are coloured in (no unpaired electron)
aqueous solution due to the presence of unpaired
Hence, due to the presence of unpaired electron in Ti3+ ,
electrons in d subshell
it exhibit colour inaqueous solution
11. (C) The regular decrease in the radii of lanthanide ions
16. (D) K2Cr2O7 is oxidsing reagent.
from La3+ to Lu3+ is known as lanthanides contraction.
It is due to the greater effect of the increased nuclear K2Cr2O7 + 3Na2 +4H2SO4 o 3Na2 SO4 +K2SO4 +Cr2
charge than tht of screening effect (Shielding effect). (SO4)3 +4H2O
As a result of lanthanide contraction, the atomic radii of
17. (D) This can be understood on the basis of E0 values for
element of 4d and 5d come closer, so the properties of 4d
M2+|M.
and 5d come close, so the properties of 4d and5 d-
transitionelement shows the similarities. E0|V Cr Mn Fe Co
M2+/M - 0.90 -1.18 -0.44 -0.2 28
12. (D) Stability of transition metal ions is directly
E Value for Mn is more negative than expected form
0
proportional to the unpaired electrons. The exactly half-
filled and completely filled d-orbitals are extra stable. general trend due to extra stability of half-filled electronic
configuation of Mn2+ ion.
Cr3+ (21) = 3d3 , 4s0 (3 unpaired electrons)
Thus, the correct order should be
V3+(20) = 3d2 4s0 (2 unpaired electrons)
Mn > Cr > Fe > Co
Ti3+ (19) = 3d1 ,4s0 (1 unpaired electrons)
An Examination of E0 values for redox couple M3+/M2+
Mn3+ (22) 3d4 4s0 (4 unpaired electrons)
shows that Cr 2+ is strong reducing agent
So Mn3+ ion is most stable inaqueous solution.
13. (C) In general, the atomic and ionic radiiincreases on E 0
M3 / M 2 
0.41V and liberates H2 from dilute acids.
moving downa group but the elements of second 2 Cr2+ (aq) + 2H+ (aq) o 2 Cr3+ (aq) + H2 n (g)
transitionseries (Zr,Nb, Mo) have almost same radil as
the elements of third transition series (Hf.Ta.W, ect) This ? The correct order is Mn > Fe > Cr > > Co.
is because of lanthanoid contraction, i.e. imperfect
shielding of one 4f e- by another. 18. (B) Cr2+ : d4 (4 unpaired electrons)

14. (D) Ni3+ (28) = [Ar] 3d7 Mn2+ :d5 (5 unpaired electrons)
Mn (25) = [Ar] 3 d
3+ 4

Fe2+ : d6 (4 unpaired electrons)

Fe3+ (26) = [Ar] 3 d5
Co3+ (27) = [Ar] 3 d6 Co2+ : d7 ( 3 unpaired electrons)
Hence, Co3+ has 3d6 electronic configuration correct
answer is (D). ? [Co(H2O)6]2+ has miniumu number of unpaired
electrons and thus, shows minimum paramagnetic
15. (B) Key Idea Colour is obtained as a consequence of d- behaviour.
d (or-f-f) transition, and for d-d (or-f-f) transition, presence Higher the unpaired e-
of unpaired electrons is the necessary condition. Higher the magnetic moment
Electronic configuration of
P n  n  2
Electroni configuration of
La3+ (Z=57) = [Xe] 4f0 5 d0 6s0 n = Number of unpaired e-
(no unpaired electron) 19. (B) Alloy Constituents
Ti3+ (Z=22) = [Ar] 3 d1 4 s0 Invar Fe+Ni
(one unpaired electron) Steel Fe + C
Lu (Z=71) = [Xe] 4f14 5d0 s0
3+
Bell-metal Cu (80%)+Sn (20%) e

130
 TRANSITION ELEMENTS (d & f Block)
Bronze Cu (75.90%) + Sn (10.25) In the above reaction, KMnO4 oxidise H2O2 to O2 and
Among these alloys, only steel contains carbon which itself i.e [MnO 4 ] . Hence, aqueous solution of KMnO4
is a non-metal with with H2O2 yieds Mn2+ ion as MnSO4 . Hence,
aqueous solution of KMnO4 with H2O2 yields Mn2+ and
20. (B) Interstitial compounds are obtained when small
O2 inacidic conditions.
atoms like H,B,C,N, ect., fit inot the interstitial space of
lattice metals. These retain metallic conductivity. These 25. (C)
resemble the parent metal in chemical properties
(reactivity) but differ inphysical properties l ike hardness, 26. (C) When H2O2 is added toan acidified solution of a
melting point, ect dichromate [MnO4 ] , a a deep blue coloured complex,
chromic peroxide CrO5 [or CrO(O2)2] is formed.
21. (D) Lanthanoid ion with no unpaired electron is
diamagnetic innature. Cr2 O 72   2H  4H 2 O o 2CrO(O 2 ) 2
 

Ce58 =[Xe] 4f2 5d06s2 Chromic peroxide

Ce2+ =[Xe]4f2 (two unpaired electrons) (blue coloured complex)+ 5H2O

sm62 =[Xe] 4f6 5d06s2 This deep blue coloured complex has the following
Sm2+ = [Xe] 4f6 (six unpaired electrons) structure
Eu63 = [Xe] 4f7 5 d0 6s2
Eu2+ = [Xe] 4 f7 (seven unpaired electrons)
Yb70 = [Xe] 4f14 5d0 6s2
1150
Yb2+ = [Xe] 4f14
(no unpaired electrons)
Because of the absence of unpaired electrons , Yb2+ is Cr
diamagnetic

22. (D) Oxygen rich compounds like chlorate, perchlorate

Oxidation state of Cr in CrO5 is +6 due to the presence of
K2Cr2O7 ect. when heated gives oxygen but ammounium
two peroxide linkages which can be calculated as
dichromate gives nitrogen gas when heated.
' X   1 u 4  1u  2 
2KCIO3  o 2KCI  3O 2 n [For Cr ]
[For 0  0] For o

'
2Zn(CIO 3 ) 2  o ZnCl 2  3O 2 x-6=0
x=+6
'
4K 2 Cr2 O7  o 4K 2 CrO 4  2Cr2 O3  3O 2 n
Potassium Potassium Chromic
dichromate chromate oxide
27. (A) Magnetic moment P n  n  5  BM where,
 NH 4 2 Cr2 O7 
'
o N 2 n Cr2 O3  4H 2 O n=number of unpaired electrons
P JLYHQ
23. (A) Lanthanoid contraction is the regular decrease in
atomic and ionic radii of lanthanides. This is due to the ? 284 n  n  2 B.M
imperfect shielding [or poor screening effect] of f-orbitals (2.84)2 n (n+2)
due to their diffused shape which unable to 8 = n2 +2n
counterbalance the effect to the increased nulclear n2+2n-8=0
charge. Hence. the net result is a contraction in size of
n2 + 4n - 2n-8=0
lanthanoids.
n(n+4)(n+4) =4
n=2
24. (B) The reaction of aqueous KMnO4 wiht H 2O 2 in Ni2+ = [Ar]3d3 4s0 (two unpaired electrons)
acidic medium is Ti3+ = [Ar] 3d14s0 (one unpaired electrons)
3H2SO4+2KMnO4+5H2O2 o 5O 2 +2MnSO 4+8H 2 O Cr3+ = [Ar]3d3 .(three unpaired electrons)
+K2SO4 Co2+ = [Ar], 3d7 .(three unpaired electrons)
so, only Ni2+ has 2 unpaired electrons.

131
CHEMISTRY FOR NEET & AIIMS
The appearance of green colour is due to the reduction
0 III
Fe H 2 O 2 o Fe 2 O3 .xH 2 O of chromium metal.
28. (C) N
from air
35. (D) Nitric acid acts as an oxidising agent, while reacting
iii
0
(B) Fe  CuSO 4 o FeSO 4  Cu with copper. when dil. HNO3 reacts, reaction proceeds
as :
0 II
(C) Fe 5CO o Fe(CO)5 3Cu +8HNO3 (dill) o 3Cu (No3)2 +2No+4H2O
0 III
and when conc. HNo3 is used, reactionproceeds as
(D) Fe H 2 O o Fe 2 O3  H 2 Cu+4HNO3 (conc.) o Cu(No3)2 +2NO2+2H2O
Steam

? Formation of Fe(CO)5 from Fe does not involve 36. (C) HgCl2 and I2 both when dissolved in water containing
oxidation of because there is no change in oxidationstate.
I- ions, the pair of species formed is HGI 24  and I 3
29. (C) because of the lanthanoid contraction Zr (atomic In aqueous solution. I2 reacts with I- and maintains the
redii 160 pm) and Hf (atomic readill 158 pm) have nearly following equilibrium
same atomic radi.
I +I I
Lanthanoids include the elements from lanthanum la 2 3
(Z=57) to luteium Lu (Z=71) zirconium Zr (40) belong to Hg gives ppt.of Hgl2 on reaction with I-
2+

the second transition series (4d) and Hf (72) belongs to But Hgl2 is soluble in excess of I-
third transitionseries (5d). Lanthanoid contraction is
Hg 2 21 o Hgl p 2CI
associated with the intervention of the 4f orbitals which
are filled before the 5d- series of elements starts. The 2
Red ppt
filling of 4f oribitasl before 5d-orbitals results in regular
decrease in atomic radit which compensates the expected
HgI + I- [Hgl ]2-
increase in atomic size withincreasing atomic number . 2 4
As a result of this lanthanoid contraction, the elements
of secon and third transition series have almost similar 37. (B) SO2gas can readily oxidise acidified KMnO4 solution
atomic radil. because KMnO4 is an oxidising agent and SO2 act as
reducing agent.
30. (A) FeSO4 will require the least amount of acidified
2MnO 4  5SO 2  2H 2 O o 2Mn 2   5SO 24   4H 
KMnO4 for complete oxidation
While other options such as NO2 (strong oxidising
31. (C) 64 Gd +[Xe] 4f7 5d1 6s2 agent),CO2 (neither oxidising agent not reducing agent)
cannot decolourise acidified KnO4 Solution.
32. (C) Eu(63) = 4f7.5d0,6s2. Eu2+ = 4f7
In lanthanoids series, ionic radius decreases and covalent 38. (C) The reason for greater range of oxidation states in
character increases, thus basicity decreases. Lanthanons actinoid is attributed to the 5f,6d and 7 s levels having
are less rective than aluminium due to high ionisation comparable energies.
potential is lanthanoid contraction Ce 4+ is a good The 5f-orbitals extend into space beyond the 7s and 6p -
oxidising agent, it is easily converted to Ca3+ orbitals and participate in bonding . This is in direct
33. (C) Electronic configuration of contrast to the lanthanides where the 4f- orbitals ae buried
Eu = [He]54 4f7 6 s2 Electronic configuration of deep inside the atom, totally shielded by outer orbitals
63
and thus unable to take part in bonding.
64
Gd = [Xe]54 4f7 5d16s2 d
Electronic configuration of 65 Tb= [Xe]54 4f9 6s2
39. (D) MnO42– Mn 6+
34. (C) When SO2 is passed through through acidified 3d1
K2Cr2O7 solution, green chromium sulphate is formetd. In
this reaction, Oxidation state of Cr changes from +6 to 3.
K Cr O7  H SO  3SO o K SO  CI SO
2 2 2 4 2 2 4 2 4 3H O
2 
OS of Cr 6 OS of Cr 3
Green

132
 TRANSITION ELEMENTS (d & f Block)
EXERCISE
This planar complex is very poorly soluble and is used
P-2 (AIIMS) for the gravimetric determination of nickel e.g., ores.

1. (C) : Na3VO4 contains colourless ortho-vandate VO43– 7. (B)

ion.
8. (B) : The constituents of Mischmetal is approximately
2. (D) : La = + 3, ND = +2, +3, +4 50% cerium and 25% lanthanum with small amount of
neodymium and praseodymium.
Ce = +3, +4, Eu = +2, +3

3. (A) : Gallium is brittle at low temperature but is liquid 9. (C) : For Cr 3 3d 3 , P 3(3  2) 15 B.M.
above room temperature and can indeed melt in the hand.
Gallium metal expands by 3.1 percent when it solidifies, For Fe 2 3d 6 , P 4(4  2) 24 B.M.
and therefore should not be stored in either glass or
metal containers. Gallium also corrodes most other metals For Ni 2 3d8 , P 2(2  2) 8 B.M.
by diffusing into their metal lattice.
For Mn 2 3d5 , P 5(5  2) 35 B.M.
4. (A) : Tl+ ions are more stable than Tl3+ and thus, Tl3+
ions change to Tl+ ions thereby acting as oxidising 10. (D) : Copper (l) compounds are unstable in aqueous
agents. solution and undergo disproportionation.
Tl3+ compounds + 2e– o Tl+ compounds 2Cu+ o Cu2+ + Cu
(less stable, oxidising agent) (more stable, reducing The greater stability of Cu2+(aq) than Cu+(aq) is due to
agent) much more –ve 'hydH of Cu2+(aq) than Cu+(aq), which is
more than compensates for the second ionisation
5. (B) : Glass is an amorphuse and transparent of enthalypy of Cu.
translucent solid obtained by solidification of a mixture
of silicates of different metals, one of which is always an 11. (A) : In acidic solution, manganese (VI) becomes unstable
alkali metal. Addition of small amounts of transition metal and undergoes disproportionation to form manganese
salts to the glass mixture imparts colour to the glass. For (VII) and manganese (IV)
example, addition of small amounts of Fe3+, Fe2+, Co2+, VI IV VII
Cr3+ and Mn4+ salts imparts yellow-brown, light blue, 5MnO3 + 2H + 4e o 3MnO2 + 2MnO4– + H2O
+ –

deep blue, green or violet colour respectively.

12. (A) : Cr2+ = 3d4, No. of unpaired electrons (n) = 4

Magnetic moment n(n  2) B.M.

6. (D) : O H O
4(4  2) 24 4.89 B.M.
H3C C N: 2+
:N C CH3
+ Ni + Fe2+ = 3d6, No. of unpaired electrons (n) = 4
H 3C C N: :N C CH3
O H O Magnetic moment 4(4  2) B.M.
H
24 4.89 B.M.
O O
Mn2+ = 3d5. No. of unpaired electrons (n) = 5
H3C C N: 2+
N C CH3
Ni Magnetic moment 5(5  2) B.M.
H3C C N: N C CH3
O O 35 5.91B.M.
H Co2+ = 3d7, No. of unpaired electrons (n) = 3
Bis-(dimethylglyoximato) nickel (II) chelated comple
(red ppt) Magnetic moment 3(3  2) B.M.

133
CHEMISTRY FOR NEET & AIIMS
20. (D) : Acidified KMnO4 oxidises H2S S only.
15 3.87 B.M.
2KMNO4 + 3H2SO4 + 5H2S o K2SO4 + 2MnSO4
Ni2+ = 3d8, No. of unpaired electrons (n) = 2
+ 5S + 8H2O
Magnetic moment 2(2  2) B.M.
21. (C) : Bordeaux mixture consists of copper sulphate
8 2.82 B.M. (CuSO4) and lime [Ca(OH)2].

22. (D) :
13. (D) : Cu has lowest melting point because it has lowest
enthalpy of atomisation (i.e., heat required to break the 23. (A) : Cr3+ gives violet colour
metal lattice to get free atoms) among the elements.
24. (D)
Ni > Fe > Cr > Cu
25. (A) : Fe2+ quickly oxidizes to Fe3+ in aqueous medium.
Enthalpy of atomisation : 430 416 397 339
(in kJ mol–1) 26. (B) : Na2CrO4 solution in water is yellow in colour, when
acidified it changes to orange colour (due to the formation
of Cr2O72– ions).
14. (A) : No. of unpaired
2Na2CrO4 + H2SO4 o Na2Cr2O7 + Na2SO4 + H2O
electrons
3+
Gd : [Xe]4f
7
7 Let oxidation state of Cr in Na2CrO4 be x.
2+
Yb : [Xe]4f
14
0 Ÿ 2(+1) + x + 4(–2) = 0 Ÿ x = +6
Tb2+ : [Xe]4f 9 5 27. (C) : Ferrocyanide ion
3+ 4
Pm : [Xe]4f 4
3d 4s 4p
[Fe(CN)6]4- xx xx xx x x x x xx
NH2 Diamagnetic

15. (C) : Hg2Cl2 + 2NH4OH Hg + Hg + NH4Cl d2sp3 hybridisation

Calomel Cl + 2H2O [Fe(CN)6] 3-
xx xx xx x x x x xx
Paramagnetic
Black d2sp3 hybridisation

16. (C) In gerrocyanide ion, the oxidation state of Fe is +2

however in ferricyanide ion, the oxidation number of Fe
17. (A) : [Cul4]2– does not exist because I– being a stronger is +3.
reducing agent reduces Cu2+ to Cu+. Generally, the higher the oxidation state of the metal, the
2CuI2 o 2CuI + I2 greater the crystal field splitting. It means crystal field
splitting in ferrocyanide ion is lower than that of
18. (B) : In alkaline solution KMnO4 is first reduced to ferricyanide ion.
ganganate and then to insoluble manganese dioxide.
28. (C) : K2Cr2O7 is less soluble in water. K2Cr2O7 can be
2KMnO4 + H2O o 2MnO2 + 2KOH + 3[O]
alkaline
found in pure state and can be accurately weighed. It is
not hygroscopic in nature. So, K2Cr2O7 is used as aprimar
19. (B) : Using expression, P n(n  2) B.M. standard solution.
(where, n = No. of unpaired electrons)
Ion Outer n μ 29. (C) : Change in colour is due to the oxidation of alcohol
Ti2+ 3d2 2 2.84 with potassium dichromate.
22

Cr2+ 3d4 4 4.90 K2Cr2O7 in presence of dilute H2SO4 acts as an oxidising

24
agent. it is converted into chromic sulphate which is
Co3+ 3d6 4 4.90
27 green in colour.
Mn 2+ 3d5 5 5.92
25 K2Cr2O7 + 4H2SO4 o

134
 TRANSITION ELEMENTS (d & f Block)
(orange) has 3d6 electronic configuration.
K2SO4 + Cr2(SO4)3 + 4H2O + 3O Metals Outer electronic Oxi,states
(green) Configuration
Co 3d74s2 +2, +3, +4
30. (A) : Electropositive element like zinc precipitates copper
Ni 3d 4s8 2
+2, +3, +4
from a solution of copper sulphate and finally forms a
complex.
39. (B) : The oxidation states of the given compounds are
CuSO4 + Zn o Cu + ZnSO4(aq) o [Zn(H2O)4]SO4
VO2+ : x + 2(–2) = + 1
31. (A) Ÿ x=+5
Cr2O72– : 2x + 7(–2) = –2
32. (D) : Non-oxidising acids (HCl and dil. H2SO4) do not
Ÿ 2x = +12
have any effect on coper. However they dissolve the
metal in presence of air. As it is non-spontaneous process Ÿ x=+6
so, 'G cannot be –ve. MnO4– : x + 4(–2) = –1
x = –1 + 8 = + 7
33. (B) : In actual practice transition metals react with acid
The correct order of oxidising power is :
very slowly and act as poor reducing agents. This is due
to the protection of metal as a result of formation of thin VO2+ < Cr2O72– < MnO4–
oxide protective film. Further, their poor tendency as
reducing agent is due to high ionisation energy, high 40. (B) : Chemistry of actinoids is more complicated due to
heat of vapourisation and low heat of hydration. the possibility of large number of oxidation states.
34. (B) : Higher the charge on the metal ion, smaller is the
ionic size and more is the complex forming ability. Thus, 41. (B) The magnetic moments are lesser than the fact that 5f
the degree of complex formation decreases in the order electrons of actinides are less effectively shielded which
M4+ > MO22+ > M3+ > MO+2 results in quenching of orbital contribution.
The higher tendency of complex formation of MO22+ as
compared to M3+ is due to high concentration of charge
on metal atom M in MO22 + .

35. (C) : Mn2+ = [Ar] 3d5, Mn3+ = [Ar] 3d4

Fe2+ = [Ar] 3d6, Fe3+ = [Ar] 3d5
Thus, Mn2+ has more stable configuration than Mn3+
while Fe3+ has more stable configuration than Fe2+.
Hence, reduction potential for Mn3+/Mn2+ couple is more
positive than Fe3+/Fe2+.

36. (A) : The element which can reduce itself acts as an

oxidising agent.

37. (C) : Due to lanthanide contraction, the size of Lu3+ is

decreased, then, covalent character of hydroxides
increases and hence the basic strength decreases. Thus,
La(OH)3 is more ionic and thus more basic.

38. (D) : Both Co and Ni have (IV) oxidation state. Ni (IV)

135
COORDINATION
CHAPTER
08
COMPOUNDS
Coordination is critical to any large scale event. That's the lesson we
are learning.

''LYNETTE MILLER''

INTRODUCTION

C
ompounds formed due to combination of two or more simple stable salts, which
retain their identity is solid as well as in dissolved state, are called coordination
compounds. These are backbone of modern inorganic and bio-inorganic chemistry
and chemical industry. The concept of co-ordination compounds arises from the
complex formation tendency of transition elements. These compounds play a vital
role in our lives, as chlorophyll of plants, vitamin B12 and haemoglobin of animal
blood are the co-ordination compounds of Mg, Co and Fe respectively. The co-
ordination compounds play important role in analytical chemistry , polymerisation
reactions, metallurgy and refining of metals, photography, water purification etc. Co-
ordination compounds also find many applications in electroplating, textile dyeing
and medicinal chemistry.

136
CHEMISTRY FOR NEET & AIIMS

ADDITION COMPOUNDS
They are formed by the combination of two or more stable compounds in stoichiometric ratio.
Addition Compounds

Double salts Coordination compounds

(Complexes)

Molecular / Addition compounds are formed when stoichiometric amounts of two or more simple compounds join
together. Molecular / Addition compounds are of two types.
Double salts : Those which retain their identity in solutions are called double salts. For example.
KCl + MgCl2 + 6H2O KCl.MgCl2. 6H2O
carnallite
K2SO4 + Al2(SO4)3 + 24 H2O K2SO4.Al2(SO4)3.24H2O
potash alum

Complex compounds : Those which loose their identity in solution (complexes). For example.
CuSO4 + 4 NH3 CuSO4.4 NH3 or [ Cu(NH3)4]SO4
tetrammine copper (II) sulphate
Fe(CN2) + 4 KCN Fe (CN2). 4KCN or K4[Fe(CN)6]
potassium ferrocyanide

When crystals of carnallite are dissolved in water, the solution shows properties of K +, Mg2+ and Cl– ions. In a
similar way, a solution of potassium alum shows the properties of K+, Al3+ and SO42– ions. These are both examples
of double salts which exist only in the crystalline state. When the other two examples of coordination compounds
are dissolved they do not form simple ions, Cu2+ / Fe2+ and CN–, but instead their complex ions are formed.

Representation of Complex Ion :

Central metal ion Coordination sphere

[Cu(NH3)4]SO4 Ionization sphere

Ligand Coordination number

Outside region apart from coordination sphere is called ionisation sphere.

CENTRAL METAL ATOM / ION

Central ion acts as an acceptor (Lewis acid) and has to accommodate electron pairs donated by the donor atom of
the ligand, it must have empty orbitals. This explains why the transition metals having empty d-orbitals form co-
ordination compounds readily. Thus, in complexes [Ni(NH3)6]2+ and [Fe(CN)6]3–, Ni2+ and Fe3+ respectively are the
central metal ions.

137
 COORDINATION COMPOUNDS
LIGANDS
Species which are directly linked with the central metal atom/ ion in a complex ion are called ligands. The ligands are
attached to the central metal atom /ion through co-ordinate or dative bond free ligands have at least one lone pair.

H N H H O C N
H H
The ligands are thus Lewis bases and the central metal ions / atoms are Lewis acids.
Ligands can be of following types depending on the number of donor atoms present in them :
(i) Mono / Unidentate Ligands They have one donor atom, i.e., they can donate only one electron pair to the
central metal atom /ion eg., F–, Cl–, Br–, H2O, NH3, CN–,NO2–, OH–, CO etc.
(ii) Bidentate Ligands Ligands which have two donor atoms and have the ability to link with the central metal atom
/ion at two position are called bidentate ligands e.g.

H H N N
CH2 – N O– O–
C – C
CH2 – N O O
H H
ethylenediamine (en) oxalate (ox) 1,10-phenanthroline (phen)

H H
N N
CH2 – N –
O – C–O
–

C – O– O
O
glycinate (Gly) 2,2-dipyridine (dipy) carbonate

(iii) Tridentate Ligands Ligands having three donor atoms are called tridentate ligands. Examples are
H H
H–N N–H
N N
H2 C CH2
N
H2C N CH2
H

diethylene triamine (dien) 2,2'2"-terpyridine (terpy)

(iv) Tetradentate Ligands These ligands possess four donor atoms. Examples are
H H
– N (CH2)2 N
CH2COO
(H 2C) 2
CH2COO– (CH2)2

N N N
H H
CH2COO –
H H

Nitriloacetate Triethylene tetramine (trien)

138
CHEMISTRY FOR NEET & AIIMS
(v) Pentadentate Ligands They have five donor atoms. For example, ethylenediamine triacetate ion.

(vi) Hexadentate Ligands They have six donor atoms. The most important example is ethylenediamine tetraacetate
ion.
N CH2 CH2 N

CH2 CH2
H 2C
O= C– O
– –
O – C= O
CH2

C – O– O – C
–

O O
ethylenediamine tetraacetate (EDTA)
(vii) Ambidentate ligands : There are certain ligands which have two or more donor atoms but in forming complexes,
only one donor atom is attached to the metal / ion. Such ligands are called ambidentate ligands. Some examples
of such ligands are
M m NO2– M m ONO–
nitrite – N nitrite –O
M m CN– M m NC–
cyanide isocyanide
M m SCN– M m NCS–
thiocyanide isothiocyanide
(viii) Ligands having more than two donor atoms are called polydentate or multidentate ligands. Multidentate
ligands are known as a chelating ligands, it results in the formation of a stable cyclic ring thus, the complexes
formed are also called chelates. Chelating ligands are usually organic compounds.
(ix) Chelate ligand :
Chelate ligand is a di or polydentate ligand which uses its two or more donor atoms to bind a single metal ion
producing a ring. The complex formed is referred to as a chelate complex and the process of chelate formation is
called chelation. The number of such ligating groups is called the denticity of the ligand. Chelate rings may have
any number of atoms; the most common contain five or six atoms, including the metal ion. Smaller rings have smaller
angles and distances that lead to strain; larger rings frequently result in crowding both within the ring and between
adjoining ligands. Some ligands can form more than one ring; ethylene diamine tetraacetate (EDTA) can form five by
using the four carboxylate groups and the two amine nitrogens as given in the structures.
–
O H—O H2
H3C—C=N N=C—CH3 Cl N
2+
Ni CH2
Pt
H3C—C=N N=C—CH3 CH 2
Cl N
O—H O
– H2

The chelate complexes are more stable than similar complexes containing unidentate ligands. The greater stability of
the chelate complex in comparison to normal complex is called chelate effect. For example,
Ni2+ (aq) + 6 NH3 (aq) [Ni(NH3)6]2+ (aq) Kformation = 108
Ni2+ (aq) + 3 NH2CH2CH2NH2(aq) [Ni(en)3]2+ (aq) Kformation = 1018
The five and six membered rings are more stable.

139
 COORDINATION COMPOUNDS
DENTICITY AND CHELATION
COMMON MONODENTATE LIGANDS
Com m on Na m e IUPAC Na m e Form ula
m ethyl isocyanide methylisocy anide CH3 NC
triphenyl phosphine triphenyl phosphine/triphenyl phosphane PPh 3
pyridine pyridine C 5H 5 N (py)
ammonia ammine NH3
methyl amine methylamine MeNH 2
water aqua or aquo H 2O
carbonyl carbonyl CO
thiocarbonyl thiocarbonyl CS
nitrosyl nitros yl NO
fluoro fluoro or fluorido* F–
chloro chloro or chlorido* Cl –
brom o brom o or bromido* Br–
iodo iodo or iodido* I–
cyano cyanido or cyanido-C* (C-bonded) CN–
isocy ano is ocyanido or cyanido-N* (N-bonded) NC–
thioc yano thiocyanato-S(S-bonded) SCN –
isothiocyano thiocyanato-N(N-bonded) NCS –
cyanato (cyanate) c yanato-O (O-bonded) OCN –
isocy anato (isocyanate) c yanato-N (N-bonded) NCO –
hydroxo hydroxo or hydroxido* OH –
nitro nitrito–N (N–bonded) NO 2–
nitrito nitrito–O (O–bonded) ONO –
nitrate nitrato NO 3–
amido amido NH2 –
imido imido NH2–
nitride nitrido N 3–
azido azido N 3–
hydride hydrido H–
oxide oxido O 2–
peroxide perox ido O 2 2–
superoxide s uperoxido O 2–
acetate acetato CH3 COO –
sulphate sulphato SO 42–
thiosulphate thiosulphato S 2O 3 2–
sulphite sulphito SO 32–
hydrogen sulphite hydrogensulphito HSO 3–
sulphide sulphido or thio S 2–
hydrogen sulphide hydrogensulphido or merc apto HS –
thionitrito thionitrito (NOS)–
nitrosylium nitros ylium or nitrosonium NO +
nitronium nitronium NO 2+
* The 2004 IUPAC dra ft re com m e nds tha t a nionic liga nds w ill e nd w ith-ido.

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CHEMISTRY FOR NEET & AIIMS
COMMON CHELATINGAMINES

Chelating Common Name IUPAC Name Abbreviation Formula

Points
bidentate ethylenediamine 1,2-ethanediamine/ en NH2,CH2CH2NH2
ethane-1,2-diamine
bidentate propanediamine 1,2-propanediamine pn NH 2–CH–CH2–NH2

CH3

tridentate diethylenetriamine [N-(2-aminoethyl)-1 dien NH2CH2CH2NHCH2CH2NH2

2-ethanediamine
or diethylenetriamine

tetradenate triethylenetetraamine trien NH2CH2CH2NHCH2CH2NHCH2CH2NH2

tren NH2CH2CH2NCH2CH2NH2
triaminotriethylamine

CH2CH2NH2
pentadentate tetraethylenepentaamine 1,4,7,10 pentaazatridecane NH2CH2CH2NHCH 2CH2NHCH 2CH2NHCH 2CH2NH2
or tetraethylenepentaamine
–
OOCH2C CH2COO–
hexadentate ethylenediaminetetraacetate 1,2–ethanediyl (dinitrilo) EDTA
tetraacetate NCH2CH2N
or ethylenediaminetetraacetate –
OOCH2C CH2COO–

Common Multidentate (Chelating) Ligands

Com m on Na m e IUP AC Na m e Abbre via tion Form ula S tructure

2,4-pentanediono
ac ety lac etonato acac CH 3 CO CHCOCH 3 –
or acety lacetonato

2,2'-bipy ridine 2,2'-bipyridyl bipy C 10 H 8 N 2

1,10-phenanthroline/
1,10-diam inophenanthrene phen,o-phen C 12 H 8 N 2
phenanthroline

ox alato oxalato ox C 2 O 4 2–

dialk yldithioc arbam ato dialkylc arbam odithioato dtc S 2 CNR 2 –

1,2-ethanediy lbis
1,2-bis(dipheny lphophine)ethane dppe P h 2 PC 2 H 4 PP h 2
(dipheylphos phene)

o-pheny lenebis 1,2-pheny lenebis

diars C 6 H 4 (A s(CH 3 )2 )2
(dimethylarsine) (dim ethylarsene)

butanedienediox ime
dim ethy lglyox imato DM G HONC(CH 3 )C(CH 3 )NO –
or dim ethylgly oxim ato

O O
|| ||
1,2-ethanediy l —
O CH 2C C H 2CO —
ethylenediam inetetraacetato (dinitrilo)tetraac etato E DTA (– OOCCH 2 )2 NCH 2 CH 2 N(CH 2 COO – )2
:

or ethylenediam inetetraacetato —
O CH 2C
|| C H 2CO
||
—

O O

hydrotris-
py raz olylborato
(py raz o-1-y l)borato

141
 COORDINATION COMPOUNDS
(x) Flexidentate Ligand :
It is not necessary that all the donor items present in the polydentate ligands should form coordinate bonds with
the central metal atom or ion i.e. a polydentate ligand which is found to have different denticity in different
coordination compounds is called a flexidentate ligand. Note that in a particular complex denticity of a particular
ligand is fixed, it can not be flexible in the same compound.
EDTA can act as hexa, penta as well as tetra dentate ligand. For example ;
EDTA usually acts as hexadentate ligand but in [Cr(III)(OH)(EDTA)]2– and [Co(III)Br(EDTA)]2– as pentadentate and
in [Pd(II)H2(EDTA)]0 as a tetradentate ligand.
Sulphate ion, SO42– can also be mono or bi dentate ligand. For example ;

EFFECTIVE ATOMIC NUMBER -EAN (Sidgwick Theory and EAN Rule) : Total no. of electrons present on central
metal atom /ion. after accepting electron pairs from donar atom of ligands through coordinate bond is called E.A.N.
of central metal atom /ion.
E.A.N. = (No. of electron in the metal ion) + ( No. of e– gained from the ligand).
or

E.A.N = Z – O.S. + 2 × C.N.

Sidgwick also 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 nearest noble gas. This total number of electrons is
called effective atomic number (EAN) of the metal /ion. This will become clear by taking the example of
hexamminecobalt (III) ion [Co(NH3)6]3+
Atomic number of cobalt = 27
In the present complex, cobalt is present in the oxidation state of +3.
? E.A.N. of Co3+ = Z – O.S. + 2 × C.N.
= 27 – 3 + 2 × 6 = 36
In the above example since the number 36 corresponds to the atomic number of krypton, according to Sidgwick, the
complex will be stable. Though EAN rule (which states that those complexes are stable whose EAN is the same as
the atomic number of the next noble gas) is applicable in many metal carbonyl complexes, however there are several
examples in which EAN rule is not obeyed.
Example :
Complex Metal Atomic Coordination Effective atomic number
(Oxidation State) Number of Metal number (E.A.N.)
[Cu(NH3)4]SO4 +2 29 4 (29 – 2) + (4 × 2) = 35
[Co(NH3)6]Cl3 +3 27 6 (27 – 3) + (6 × 2) = 36 [Kr]
K2[HgI4] +2 80 4 (80 – 2) + (4 × 2) = 86 [Rn]
[Ag(NH3)2]Cl +1 47 2 (47 – 1) + (2 × 2) = 50

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CHEMISTRY FOR NEET & AIIMS
IUPAC NOMENCLATURE OF COMPLEXES
The rules for the systematic naming of co-ordination compounds are as follows.
z The positive part is named first followed by the negative part, whether it is simple or complex.
z In naming of a complex ion, the ligands are named first in alphabetical order, followed by naming of central metal
atom /ion.
z When there are several monodentate ligands of the same kind, then we normally use the prefixes di, tri tetra, penta
and hexa to show the number of ligands of that type. If ligand’s name already contain any of these prefix , then to
avoid confusion in such cases, bis, tris and tetrakis are used instead of di, tri and tetra and name of the ligand is
placed in parenthesis. For example, bis(ethylene diamine) for two en-ligands.
z Negative ligands have suffix-o, positive ligands have suffix -ium, where as neutral ligands have no specific suffix.
The names of negative ligands ending with -ide are changed to ‘o’. For example,
F– fluoro /fluorido H– hydrido HS– mercapto
Cl– chloro /chlorido OH– hydroxo/hydroxido S2– sulphido
– 2– –
Br bromo / bromido O oxo / oxido CN cyano / Cyanido
I– iodo / iodido O22– peroxo / Peroxido
Ligands ending with -ate/-ite are changed to -ato/-ito. For example, SO42– (sulphato), SO32– (sulphito) etc.
Positive groups end with -ium. For example, NH2 – NH3+ (hydrazinium) NO+ (nitrosonium)
z Neutral ligands have No special ending and usually common ligands are provided to neutral ligands except NH 3
(ammine) H2O (aqua) CO (carbonyl), NO(Nitrosyl).
z The oxidation state of the central metal ion is shown by Roman numeral in brackets immediately following its name.
z Complex positive ions and neutral molecules have no special ending but complex negative ions end with ate. suffix.

COMPLEX IONS

Example Negative complex Positive /neutral complex

Ni nickelate nickel
Pb plumbate lead
Sn stannate tin
Fe ferrate iron

z If the complex compound contains two or more metal atoms, then it is termed as polynuclear Complex compound.
The bridging ligand which link the two metal atoms together are indicated by the prefix P–. If there are two or more
bridging groups of the same kind, this is indicated by di– P–, tri – P– and so on. If a bridging group bridges more
than two metal atoms, it is shown as P3, P4, P5 or P6 to indicate how many atoms it is bonded.
z Ambidentate ligands may be attached through different atoms. Thus, M–NO2 is called nitro and M–ONO is called
nitrito. Similarly M–SCN (thiocyanato) or M–NCS (Isothiocyanato). These may be named systematically, thiocyanato–
S and thiocyanate –N respectively to indicate which atom is bonded to the metal. This convention may be extended
to other cases where the mode of linkage is ambiguous.
z If any lattice component such as water or solvent of crystallisation are present, these follow their name, and are
preceded by the number of these groups in Arabic numericals. These rules are illustrated by the following examples.

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 COORDINATION COMPOUNDS
(a) Complex cations IUPAC name
[Co(NH3)6]Cl3 Hexaamminecobalt(III) chloride
2+
[CoCl(NH3)5] Pentaamminechloridocobalt(III) ion
[CoSO4(NH3)4]NO3 Tetraamminesulphatocobalt(III) nitrate
[Co(NO2)3(NH3)3] Triamminetrinitrito-N-cobalt(III)
[CoCl.CN.NO2.(NH3)3] Triammine-chloro-cyano-nitro-N-cobalt(III)
2+
[Zn(NCS)4] Tetrathiocyannato-N-zinc(II) ion.
2+
[Cd(SCN)4] Tetrathiocyanato-S-cadmium(II) ion.

(b) Complex anions

Li[AlH4] Lithium tetrahydridoaluminate(III)
Na[ZnCl4] Sodium tetrachloridozincate(II)
K4[Fe(CN)6] Potassium hexacyanidoferrate(II)
Na2[Fe(CN)5NO] Sodium pentacyanidonitrosyliumferrate(II)
K2[OsCl5N] Potassium pentachloridonitridoosmate(VI)
Na3[Ag(S2O3)2] Sodium bis(thiosulphato)argentate(I)
K2[Cr(CN)2O2(O2)NH3] Potassium amminedicyanidodioxidoperoxidochromate(VI)

(c) Organic groups

[Pt(py)4] [PtCl4] tetrapyridineplatinum(II) tetrachloridoplatinate(II)
[Cr(en)3]Cl3 d or A Tris(ethylenediamine) chromium(III)chloride
[CuCl2(CH3NH2)2] Dichloridodimethylaminecopper(II)
Fe(C5H5)2 Bis(K5–cyclopentadienyl)iron(II)
[Cr(C6H6)2] Bis(K6-benzene)chromium(0)

(d) Bridging groups

[(NH3)5Co.NH2.Co(NH3)5](NO3)5 P-amidobis[pentaamminecobalt(III) nitrate
[(CO)3Fe(CO)3Fe(CO)3] Tri-P-carbonyl-bis [tricarbonyliron(0)]
[Be4O(CH3COO)6] Hexa-P- acetato(O,O')-P-oxidotetraberyllium(II)
(basic baryllium acetate)

(e) Hydrates
AlK(SO4)2. 12H2O Aluminium potassium sulphate 12-water

Writing the formula of a coordination compound

When writing the formula of complexes, the complex ion should be enclosed by square brackets. The metal is named
first, then the coordinated groups are listed in the order : negative ligands, neutral ligands, positive ligands (and
alphabetically according to the first symbol within each group).
[M negativeligands, Neutral ligands, positive ligands] nr

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CHEMISTRY FOR NEET & AIIMS

KEY POINTS
(1) Synergic Bonding :
Ligand which donate electron pair to central metal ion & form coordinate V bond but simulataneously they accept
electron pair from central metal ion through back bonding or synergic bonding.
CO, NO+, CN–, R3P, R3As etc.
The electronic configuration of CO molecule shows that it has lone pair of electrons on carbon and oxygen atom
each. Carbon atomn can donate its electron pair of a transition metal atom (M), forming OCoM coordinate bond.
Since the metal atom in metal carbonyl is in zero oxidation state, the formation of M o CO V bond accumulates a
negative charge on the metal atom. The accumulation of negative charge on the metal atom can be counter
balanced by transferring some negative charge from the metal atom to CO molecule (ligand). This transfer can be
done by making a M o CO S bond by the overlap between an appropriate filled orbital on the metal atom and
empty Sy* or S2* molecular orbital on CO molecule. This type of bonding between M and CO is called synergic
bonding.

Conclusion of synergic bonding : due to synergic bonding

(a) M–C bond strength increases; M–C bond length decreases; because double bond character increases
(b) C–O bond strength decreases; C–O bond length increases; because bond order of C–O decreases, electron
density in ABMO of CO increases.

(2) S-donor and S-acceptor ligands :

ligands w2hich donote S electron to central metal ion & also accept electron density from central metal ion through
synergic bonding.
(i) H2C=CH2 (K2 - ethylene) : it is a 2S electron donor

(ii) (K6 - benzene) : it is a 6S electron donor

(iii) / [C5H5]– (K5 - cyclopentadienyl) : it is a 6S electron donor

For Example

(a) [Cr(K6 –C6H6)2] Cr

sandwich compound
(b) [Fe(K5–C5H5)2] ferrocene (sandwich compound)
(c) K[PtCl3(K2–C2H4)] (Zeise salt)

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 COORDINATION COMPOUNDS
ISOMERISM IN COMPLEXES
Complex compounds that have the same molecular formula but have different structural /spacial arrangements of
ligands are called isomers. These are of two types, namely structural and stereo isomers.
Type of isomerism

Structural isomerism Space / stereo isomerism

–Ionisation isomerism –Geometrical isomerism
–Hydrate isomerism –Optical isomerism
–Linkage isomerism
–Coordination isomerism
–Coordination position isomerism

STRUCTURAL ISOMERISM
(i) Ionisation Isomerism : This type of isomerism is due to the exchange of groups between the complex ion and ions
outside it. [Co(NH3)5Br]SO4 is red -violet. An aqueous solution of it gives a white precipitate of BaSO4 with BaCl2
solution, thus confirming the presence of free SO42– ions. In contrast [Co(NH3)5SO4]Br is red. A solution of this
complex does not give a positive sulphate test with BaCl2. It does give a cream coloured precipitate of AgBr with
AgNO3, thus confirming the presence of free Br– ions. Other examples of ionisation isomerism are [Pt(NH3)4Cl2]Br2
and [Pt(NH3)4Br 2]Cl2 and [Co(en)2NO2.Cl]SCN, [Co(en)2NO2.SCN]Cl and [Co(en)2Cl.SCN]NO2.

(ii) Hydrate isomerism : These isomers arise by the exchange of groups in the complex ion with water. Three isomers
of CrCl3.6 H2O are known. From conductivity measurements and quantitative precipitation of the ionised Cl–, they
have been given the following
[Cr(H2O)6]Cl3 Violet
[Cr(H2O)5Cl]Cl2.H2O Green
[Cr(H2O)4Cl2]Cl.2H2O Dark Green

(iii) Linkage Isomerism : This type of isomerism arises when the ligand attached to the central metal ion of a complex
in different ways. Such ligands are called ambident ligands. Nitrite ion has electron pairs available for co-ordination
both on N and O atoms.
:

N
: :

:O: O

Ex.
(a) [Co(NH3)5 ONO]Cl2 and [Co(NH3)5 NO2] Cl2
pentaamminenitrito-o-cobalt(III) chloride pentaamminenitrito-N-cobalt-(III)-chloride
(red) (yellow)

(b) [Mn(CO5).SCN]+ and [Mn(CO5) (NCS]+

pentacarbonylthiocyanto pentacarbonylthiocyanato
–S-manganese (II) ion –N-manganese (II) ion

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CHEMISTRY FOR NEET & AIIMS
(iv) Co-ordination Isomerism : When both the cation and anion are complex ions, then isomerism may be caused by the
interchange of ligands between the anion and cation. For example [Pt(NH3)4] [PtCl4] and [PtCl(NH3)3] [PtCl3(NH3)].
These isomers are called co-ordination isomers.

(v) Position Isomerism : In polynuclear complexes, an interchange of ligands between the metal nuclei gives rise to co-
ordinaton position isomerism, for example.

NH2
(NH3)4.Co Co(NH3)4.Cl2 Cl2
O2

NH2
Cl(NH3)3Co Co(NH3)3Cl Cl2
O2

Co-ordination position isomers

Note : Polymerisation Isomerism
This is not true type of isomerism because it occurs among compounds having the same empirical formula, but
different molecular formula. Thus, [Pt(NH3)2Cl2],[Pt(NH3)4][PtCl4], [Pt(NH3)4][Pt(NH3)Cl3]2 and [Pt(NH3)3Cl]2[PtCl4]
all have the same empirical formula.

STEREOISOMERISM
The isomers in which atoms are bonded to each other in the same order but that differ in the arrangement of these
atoms in the space are called as stereoisomers and the phenomenon as stereoisomerism.
(i) Geometrical Isomerism :
This type of isomerism arises in heteroleptic complexes due to different possible geometric arrangements of the
ligands. Geometrical isomerism is common among coordination compounds with coordination numbers 4 and 6.
(a) For Coordination Number Four :
Tetrahedral Complex :
The tetrahedral compounds can not show geometrical isomerism as we all know that all four positions are
equivalent in tetrahedral geometry.
Square Planar Complex :
In a square planar complex of formula [Ma2b2] [a and b are unidentate], the two ligands ‘a’ may be arranged
adjacent to each other in a cis isomer, or opposite to each other in a trans isomer as depicted.
Cl NH3 Cl NH3
Pt Pt
Cl NH3 NH3 Cl
cis– trans–
Geometrical isomers (cis and trans) of Pt(NH3)2Cl2 .
Square planar complex of the type Ma2bc (where a,b,c are unidentates) shows two geometrical isomers.
a b a c

M M

a c b a
cis– trans–

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 COORDINATION COMPOUNDS
Square planar complex of the type Mabcd (where a,b,c,d are unidentates) shows three geometrical isomers.

a b a d a b

M M M

d c c b c d
aTc aTb aTd

Example is [Pt(NH3)BrCl(py)]. Three isomers of the complex [Pt(NH3)(NH2OH)(py)(NO2)]+ have been isolated and
identified.
Square planar complex of the type M(AB)2 (where AB are unsymmetrical bidentates) shows two geometrical
isomers. Example is [Pt(gly)2] in which gly is unsymmetrical ligand.

A A A B

M M

B B B A
cis– trans–

Similarly, M(AB)(CD) also shows two geometrical isomers.

Note : M(AA)2, (where AA are symmetrical bidentates) does not show geometrical isomerism. e.g., [Cu(en)2]2+ [Pt(ox)2]2–,
etc.

(b) Coordination Number Six :

Geometrical isomerism is also possible in octahedral complexes.

+ +
Cl Cl
NH3 | Cl NH3 | NH3
Co Co
NH3 | NH3 NH3 | NH3
NH3 Cl
cis– trans–

Geometrical isomers (cis and trans) of [Co(NH3)4Cl2]+

Number of possible isomers and the spatial arrangements of the ligands around the central metal ion for the specific
complexes are given below.

Complexes containing only unidentate ligands :

(1) Ma2b4 – 2 (aa)(bb)(bb)
(ab)(ab)(bb)

(2) Ma4bc – 2 (aa)(aa)(bc)

(aa)(ab)(ac)
(3) Ma3b3
Complexes of the formula Ma3b3, where a and b are monodentate ligands, may show two isomeric forms called fac–
and mer–. Facial isomers have three identical ligands on one triangular face where as meridional isomers have three
identical ligands in a plane bisecting the molecule. Similar isomers are possible with some chelating ligands.

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CHEMISTRY FOR NEET & AIIMS

NH3 NH3
O2N NH3 H3N | NO2
Co Co
O2N NH3 O2N | NO2
NO2 NH3
fac– mer–

The facial(fac) and meridional(mer) isomers of [Co(NH3)3(NO2)3].

Unsymmetrical bidentate ligands also show fac-mer isomerism.
(4) Ma3b2c – 3 (aa)(ab)(bc)
(aa)(bb)(ac)
(ab)(ab)(ac)

(5) Ma3bcd – 4 (aa)(ab)(cd)

(aa)(ac)(bd)
(aa)(ad)(bc)
(ab)(ac)(ad)

(6) Ma2b2c2 – 5 (aa)(bb)(cc)

(aa)(bc)(bc)
(bb)(ac)(ac)
(cc)(ab)(ab)
(ab)(ac)(bc)
(7) Ma2b2cd – 6

(8) Ma2bcde – 9

(9) Mabcdef, [Pt(py)(NH3)(NO2)(Cl)(Br)(I)] – 15

Note : Ma6 and Ma5b have only one form.

Compounds containing bidentate ligand and unidentate ligands.

(1) M(AA)a3b – Two geometrical isomers are possible.

b a
A a A a

M M

A a A b
a a

bTa aTa

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 COORDINATION COMPOUNDS
(2) M(AA)a2b2 – Three geometrical isomers are possible.

a a
A b A a

M M

A b A b

a b

aTa aTb bTb

Note : With [M(AA)b4], only one form is possible. M(AA)abcd have six geometrical isomers.

(3) M(AA)2a2 – Two geometrical isomers are possible.

Geometrical isomers (cis and trans) of [CoCl2(en)2]

(ii) Optical Isomerism :

A coordination compound which can rotate the plane of polarised light is said to be optically active. When
the coordination compounds have same formula but differ in their ability to rotate directions of the plane of
polarised light are said to exhibit optical isomerism and the molecules are optical isomers. Optical isomers are
mirror images that cannot be superimposed on one another. These are called as enantiomers. The molecules
or ions that cannot be superimposed are called chiral. This is due to the absence of elements of symmetry in
the complex. The two forms are called dextro(d) and laevo(l) depending upon the direction they rotate the
plane of polarised light in a polarimeter (d rotates to the right, A to the left).

Octahedral complex :
Optical isomerism is common in octahedral complexes involving didentate ligands. For example, [Co(en)3]3+
has d and A forms as given below.

en en
3+ 3+
en Co Co en

en en
dextro mirror laevo

d and A of [Co(en)3]3+

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CHEMISTRY FOR NEET & AIIMS
Cis-isomer of [PtCl2(en) 2]2+ show optical isomerism as shown below because of the absence of plane of
symmetry as well as centre of symmetry.

2+ 2+
Cl Cl Cl
Cl
en Pt Pt en

en en
dextro
mirror laevo

d and A of cis-[PtCl2(en)2]2+
But trans isomer of [PtCl2(en) 2]2+ does not show optical isomerism.

2+
Cl

en Pt en
plane of symmetry

Cl

cis-[Co(NH3)2Cl2(en)] + can show optical isomerism due to the absence of plane of symmetry as well as centre
of symmetry.

+ +
Cl Cl Cl
Cl
en Co3+ Co3+ en

NH3 NH3 NH3 NH

3

dextro mirror laevo

Tetrahedral complex :
Optical isomerism is expected in tetrahedral complexes of the type [Mabcd] analogous to tetrahedral carbon
atom.

a a

M M

d b b d

c c
Mirror plane

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 COORDINATION COMPOUNDS
(i) For example [As(III)(CH3)(C2H5)(S)(C6H4COO)]2+, shows optical isomerism as given below.

2+ 2+
S S

As As

H3C C2H5 H5C2 CH3

C6H4COO– C6H4COO–
Mirror plane

Here it may be noted that 4 different groups round the central metal ion are not the only requirement to make the
complex to show mirror-image isomerism. All that is required is that the molecule should be asymmetric
(i.e., unsymmetrical), i.e., it should have no plane of symmetry so that it can exist in two mirror-image forms.
(ii) Tetrahedral complexes of Be, B, Cu(II) and Zn(II) with unsymmetrical bidentate ligands have been resolved into
optical isomers. In order for the complex to be chiral, the chelating ligand must be unsymmetrical (not necessarily
asymmetric or chiral, itself). An example is bis(benzoylacetonato) Be(II) complex, [(C6H5COCHCOCH3)2Be]0 whose
mirror-image isomers are shown in figure.

CH3 CH3 CH3 CH3

C O O C C O O C

II II
HC Be CH CH Be CH

C O O C C O O C

C6H5 C6H5 C6H5 C6H5

Here it may be noted from the figure that the complex has no centre or plane of symmetry and the two forms are not
superimposable on each other. This explains the resolution of the complex into d-and A-forms.

Square planar complex :

Square planar complexes are rarely found to show the optical isomerism. The plane formed by the four
ligating atoms and the metal ion is considered to be a mirror plane and thus prevents the possibility of
chirality. Although, square planar complexes seldom show optical isomerism, yet a four -coordinated complex
of Pt(II), [Pt(II)(NH2.CH(C6H5).CH(C6H5NH2).(NH2.CH2.C(CH3)2.NH2)]2+ which has square-planar shape has
been resolved into two forms by Mills and Quibell in 1935.

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CHEMISTRY FOR NEET & AIIMS
BONDING IN COMPLEXES
Werner’s Co-ordination Theory :
Alfred Werner put forward his concept of secondary valency for advancing a correct explanation for the characteristics
of the coordination compounds. The fundamental postulates of Werner’s theory are as follows.
(i) Metal possess two types of valencies, namely, primary (principal or ionisable) valency and secondary (auxillary or
non-ionisable) valency.
In modern terminology, the primary valency corresponds to oxidation number and secondary valency to coordination
number. According to werner primary valencies are shown by dotted lines and secondary valencies by thick lines.

(ii) Every metal cation in complex compound has a fixed number of secondary valencies for example Pt4+ cation has its
six secondary valency.

(iii) Primary valency is satisfied by negative ions, whereas secondary valency is satisfied either by negative ions or by
neutral molecules.

(iv) Primary valency has non-directional character, where as secondary valency has directional character, there fore a
complex ion has its definite geometry eg. [Co(NH3)6]3+ – octahedron.

(v) It is the directional nature of secondary valency due to which co-ordination compound exhibits the phenomenon of
isomerism.

Werner’s Representation of Complexes

Consider the case of CoCl3.xNH3 where primary valency = +3 and secondary valency = 6.
Various structures are summarised in Table.

Werner complexes Modern formula Ionisation Secondary valency Primary valency

satisfied by staisfied by
(A) CoCl3.6NH3 [Co(NH3 )6]Cl3 [Co(NH3)6]3+ + 3Cl– six (NH3 ) three (Cl–)

(B) CoCl3.5NH3 [Co(NH3 )5 Cl]Cl2 [Co(NH3)5Cl]2++2Cl– five (NH3) three (Cl–)

–
and one (Cl ) including one (Cl– )
with dual nature
(C) CoCl3.4NH3 [Co(NH3 )4Cl2 ]Cl [Co(NH3)4Cl2]++Cl– four (NH3) three (Cl–)
–
and two (Cl ) including two (Cl–)
with dual nature
(D) CoCl3.3NH5 [Co(NH3 )3 Cl3 ] [Co(NH3)3]Cl3 three (NH3)
and three (Cl– )
z From Table , It is clear that conduction of the complexes will be in the order D < C < B < A.
z They are represented as

NH3 Cl Cl Cl
NH3 Cl
H3N H3N H3N
NH3 NH3 NH3 NH3
Cl Co Cl Co Cl Co Co
NH3 NH3 NH3 NH3
H3N H3N H3N Cl
NH3 Cl NH3 Cl Cl Cl

(A) (B) (C) (D)

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 COORDINATION COMPOUNDS
VALENCE BOND THEORY
It was developed by Pauling. The salient features of the theory are summarised below :
(i) Under the influence of a strong field ligands, the electrons of central metal ion can be forced to pair up against the
Hund’s rule of maximum multiplicity.
(ii) Under the influence of weak field ligands, electronic configuration of central metal atom / ion remains same.
(iii) If the complex contains unpaired electrons, it is paramagnetic in nature, whereas if it does not contain unpaired
electrons, then it is diamagnetic in nature and magnetic moment is calculated by spin only formula.

Magnetic moment  μ  = n(n + 2) BM

where n is the number of unpaired electrons in the metal ion.

Relation between unpaired electrons and magnetic moment

Magnetic moment (Bohr magnetons) 0 1.73 2.83 3.87 4.90 5.92

Number of unpaired electrons 0 1 2 3 4 5

Thus, the knowledge of the magnetic moment can be of great help in ascertaining the type of complex.
(iv) When ligands are arranged in increasing order of their splitting power then an experimentally determined series is
obtained named as spectrochemical series.

I < Br < S < SCN < Cl < NO3 < F < OH < EtOH < CH3COO C2O4 < H2O
– – 2– – – – – – – 2–

Weak field ligands

< EDTA < NH3 py < en < dipy < phen < NO2– CN– < CO

Strong field ligands

(v) The central metal ion has a number of empty orbitals for accommodating electrons donated by the ligands.
The number of empty orbitals is equal to the co-ordination number of the metal ion for a particular complex.
(vi) The atomic orbital (s, p or d) of the metal ion hybridise to form hybrid orbitals with definite directional properties.
These hybrid orbitals now accept e– pairs from ligands to form coordination bonds.
(vii) The d-orbitals involved in the hybridisation may be either inner (n – 1) d orbitals or outer n d-orbitals. The complexes
formed in these two ways are referred to as inner orbital complexes and outer orbital complexes, respectively.
Following table provides the types of hybridisation with different coordination number.

Coordination number of metal Type of hybridisation Shape of complex

3
4 sp Tetrahedral
2
4 dsp Square planer
3
5 sp d Trigonal bipyramidal
3 2
6 sp d Octahedral
2 3
6 d sp Octahedral
It is to be noted that the type of hybridisation of metal and shape of complex involved can be predicted conveniently,
if some characteristic of the complex like magnetic nature, geometry or whether exhibits isomerism or not, etc., be
known.

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CHEMISTRY FOR NEET & AIIMS
Coordination Number Six :
In the diamagnetic octahedral complex, [Co(NH3)6]3+, the cobalt ion is in +3 oxidation state and has the electronic
configuration represented as shown below.

Co3+,[Ar]3d6

[Co(NH3)6]3+

(inner orbital or d2sp3 hybrid orbital

low spin complex) Six pairs of electrons from six NH3 molecules.

Thus, the complex has octahedral geometry and is diamagnetic because of the absence of unpaired electron. Since
in the formation of complex the inner d-orbital (3d) is used in hybridisation, the complex is called an inner orbital or
low spin or spin paired complex.
The complex [FeF6]4– is paramagnetic and uses outer orbital (4d) in hybridisation (sp3d2) ; it is thus called as outer
orbital or high spin or spin free complex. So,

Fe2+, [Ar]3d6

[FeF6]4–

sp3d2 hybrid orbitals

Six pairs of electrons from six F– ions.
Coordination Number Four :
In the paramagnetic and tetrahedral complex [NiCl4]2–, the nickel is in +2 oxidation state and the ion has the
electronic configuration 3d8. The hybridisation scheme is as shown in figure.

Ni2+, [Ar]3d8

[NiCl4]2–

sp3 hybrid orbitals

Four pairs of electrons from four Cl– ions.
The compound is paramagnetic since it contains two unpaired electrons.
Similarly complex [Ni(CO)4] has tetrahedral geometry and is diamagnetic as it contains no unpaired electrons. The
hybridisation scheme is as shown in figure.

Ni0, [Ar] 3d8 4s2

[Ni(CO)4]

sp3 hybrid orbitals

Four pairs of electrons from four CO molecules.

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 COORDINATION COMPOUNDS
Complexes of Pd(II) and Pt (II) are usually four-coordinate, square planar, and diamagnetic and this arrangement is
often found for Ni(II) complexes as well, e.g., in [Ni(CN)4]2– (here nickel is in +2 oxidation state and has electronic
configuration 3d8). In as much as the free ion is in the ground state each case is paramagnetic, the bonding picture
has to include pairing of electrons as well as ligand-metal-ligand bond angles of 90º and this occurs via hybridisation
of one (n–1) d, one ns and two np orbitals to form four equivalent dsp2 hybrid orbitals directed toward the corners
of a square. These orbitals then participate in covalent coordinate V bonds with the ligands, the bonding electron
pairs being furnished by the ligands. The hybridisation scheme for [PtCl4]2– is as shown in figure.

Pt2+, [Xe]4f14 5d8

[PtCl4]2–

dsp2 hybrid orbitals

Four pairs of electrons from four Cl– ions.
Similarly the hybridisation scheme for [Ni(CN)4]2– is as shown in figure.

Ni2+, [Ar]3d8

[Ni(CN)4]2–

dsp2 hybrid orbitals

Four pairs of electrons from four CN– ions.
It is found that [Cu(NH3)4]2+ is square planar and paramagnetic with one unpaired electron in 4p-orbital. The
hybridisation scheme is as follow.

Cu2+, [Ar]3d9

[Cu(NH3)4]2+

dsp2 hybrid orbitals

Four pairs of electrons from four NH3 molecules.
3–
Note. [Ni(CN)5] is found to be diamagnetic with 2 types of Ni – C bond lengths, out of which four bond lengths are
found to be equal and the fifth one is different. The hybridisation scheme for [Ni(CN) 5]3– is as shown in figure.

Ni2+, [Ar]3d8

[Ni(CN)5]3–

dsp3 hybrid orbitals

Five lone pairs of electrons from five CN– ions.

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CHEMISTRY FOR NEET & AIIMS

square pyramidal.

While the valence bond theory, to a large extent, explains the formation, structures and magnetic behaviour of
coordination compounds, it suffers from the following shortcomings :

1. A number of assumptions are involved.

2. There is no quantitative interpretation of magnetic data.
3. It has nothing to say about the spectral (colour) properties of coordination compounds.
4. It does not give a quantitative interpretation of the thermodynamic or kinetic stabilities of coordination compounds.
5. It does not make exact predictions regarding the tetrahedral and square-planar structures of 4-coordinate complexes.
6. It does not distinguish between strong and weak ligands.

CRYSTAL FIELD THEORY (CFT)

Crystal field theory is now much more widely accepted than the valence bond theory. It is assumed that the
attraction between the central metal and ligands in a complex is purely electrostatic. The transition metal which
forms the central atom cation in the complex is regarded as a positive ion of charge equal to the oxidation state. It is
surrounded by negative ligands or neutral molecules which have a lone pair of electrons If the ligand is a neutral
molecule such as NH3, the negative end of the dipole in the molecule is directed toward the metal cation. The
electrons on the central metal are under repulsive forces from those on the ligands. Thus, the electrons occupy the
d orbital remain away from the direction of approach of ligands.
In the crystal field theory, the following assumptions are made.
(i) Ligands are treated as point charges.
(ii) There is no interaction between metal orbitals and ligands orbitals.
(iii) All the d orbitals on the metal have the same energy (that, is degenerate) in the free atom. However, when a complex,
is formed, the ligands destroy the degeneracy of these orbitals, that is , the orbitals now have different energies. In
an isolated gaseous metal ion, all five d orbitals have the same energy and are termed degenerate. If a spherically
symmetrical field of ligands surrounds the metal ion, the d orbitals remain degenerate. However, the energy of the
orbitals is raised because of repulsion between the field of ligands and electrons on the metal. In most transition
metal complexes, either six or four ligands surround the metal, giving octahedral or tetrahedral structures. In both
these cases, the field produced by the ligands is not spherically symmetrical. Thus, the d orbitals are not all affected
equally by the ligand field.
Octahedral complex, the metal is at the centre of the octahedron and the ligands are at the six corners.
The direction x, y and z point to three adjacent corners of the octahedron as shown fig.
The lobes of the eg orbitals (dx2–y2 and dz2) point along the axes x,y and z. The lobes of the t2g orbitals (dxy, dxz and
dyz) point in between the axes. If follows that the approach of six ligands along the x,y,z, –x, –y, and –z directions will
increase the energy of the dx2 – y2 and dz2 orbitals (which point along the axes) than it increases the energy of the dxy,
dxz and dyz orbitals (which points between the axes). Thus, under the influence of an octahedral ligand field the d
orbitals split into two groups of different energies.
Rather than referring to the energy level of a isolated metal atom. The difference in energy between the two d levels
is given by the symbols '0 or 10 Dq.

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 COORDINATION COMPOUNDS

eg

t2g

Free metal ion

Fig. The directions in an
(five degenerate d orbitals) metal ion in
octahedral complex
Fig Crystal field spliting of energy octahedral field
levels in an octahedral field

It follows that the eg orbitals are +0.6 '0 above the average level, and the t2g orbitals –0.4 '0 below the average level.

eg

+0.6

Energy average energy level (Bari centre)

Average energy
of metal ion
in spherical field t2g
Metal ion in octahedral field

Fig : Diagram of the energy levels of d -orbitals in a octahedralfield

Tetrahedral Complexes A regular tetrahedron is related to a cube. One atom is at the centre of the cube, and four of
the eight corners of the cube are occupied by ligands as shown in Fig. The direction x,y and z point to the centres
of the faces of the cube. The eg orbitals point along x,y and z (that is , to centres of the faces.)

Fig : Relation of tetrahedron to a cube

The approach of the ligands raised the energy of both sets of orbitals. The energy of the t2g orbital raised most
because they are closest to the ligands. This crystals field splitting is opposite to that in octahedral complexes. The
t2g orbitals are 0.4 't above the average energy of the two groups (the Bari centre) and the eg orbitals are 0.6 't below
the average level.

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CHEMISTRY FOR NEET & AIIMS

t2g
d orbitals are
split into two
groups
energy
eg

Metal ion in a tetrahedral field

Free metal ion

(five degenerate d orbitals)
Fig : Crystal field splitting of energy levels in a tetrahedral field

STABILITY OF COMPLEXES
A co-ordination compound is formed in solution by the stepwise addition of ligands to a metal ion. Thus, the
formation of the complex, MLn (M = central metal cation, L = monodentate ligand and n=co-ordination number of
metal ion) supposed to take place by the following n consecutive steps.

[ML]
M+L ML; K1 =
[M][L]

[ML2]
M+L ML 2; K 2 =
[ML][L]

[ML3]
ML2 + L ML 3; K 3 =
[ML 2][L]

MLn–1 + L MLn; Kn =

K1, K2, K3........Kn are called stepwise stability constants. With a few exceptions, the values of successive stability
constants decrease regularly from K1 to Kn. The overall stability constant K is given as
M + nL MLn;

K = K1K2K3....Kn =

The higher the overall stability constant value of the complex, the more stable it is. Alternatively, 1/K values called
instability constant explain the dissociation of the complex into metal ion and ligands in the solution. The value of
the stability constant for some of the complexes are given in Table.

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 COORDINATION COMPOUNDS
STABILITY CONSTANTS OF COMPLEXES

Complex Stability constant

[Cu(NH3)4]
2+

[Ag(NH3)2]+
[Co(NH3)6] 2+
[Co(NH3)6] +
[AgCl2]–
[AgBr2]–
[Ag(CN)2]–
[Cu(CN)4] 2–
[Fe(CN)6]3–

COLOUR IN COORDINATION COMPOUNDS

Coordination compounds of transition metals have fascinating colours. According to the crystal field theory the
colour is due to the d-d transition of electron under the influence of ligands. We know that the colour of a substance
is due to the absorption of light at a specific wavelength in the visible part of the electromagnetic spectrum (400 to
700 nm) and transmission or reflection of the rest of the wavelengths. An object that absorbs all visible light appears
black. The mechanism of light absorption in coordination compounds is that photons of appropriate energy can
excite the coordination entity from its ground state to an excited state. Consider the Ti(III) ion in solution, that is
[Ti(H2O)6]3+. This is a violet colour octahedral complex, where in the ground state of the complex a single electron
is present in t2g level. The next higher state available for the transition is the empty eg level. If the light corresponding
to the energy of yellow-green is absorbed by the complex, it would excite the electron from t2g level to eg level.
Consequently the complex appears violet in colour. In case of copper (II) ions in solution, for example, it can be
imagined that one of the d-electrons from the t2g set (dxy, dyz, dxz orbitals) gets excited to the eg set ( d x 2  y 2 ,d z 2 orbitals).

In this case since high energy light is transmitted it means that low energy light (red region) is absorbed. For copper
(II) ions in aqueous solution, the energy gap 't is relatively small. Table below gives the relationship of the
wavelength of light absorbed and the colour observed.

Relationship between the wavelength of light absorbed and the colour observed In some coordination entitles

Wavelength of light Colour of light Colour of coordination

Coordination entity entity
absorbed (nm) absorbed
2+ Yellow Violet
[CoCl(NH3 )5 ] 535
[Co(NH3 )5 (H2 O)]
3+
500 Blue Green Red
3+ Blue Yellow Orange
[Co(NH3 )6 ] 475
[Co(CN)6 ]
3-
310 Ultraviolet Pale Yellow
[Cu(H2 O)4 ]
2+
600 Red Blue
[Ti(H2 O)6 ]
3+
498 Blue Green Purple

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CHEMISTRY FOR NEET & AIIMS
Note :
(a) In absence of ligand, crystal field splitting does not occur and as a consequence the substance appears
colourless. For example ; (i) removal of water from violet coloured complex [Ti(H2O)6]Cl3 on heating makes it
colourless, (ii) similarly anhydrous copper sulphate (CuSO4) is white, but hydrated copper sulphate (CuSO4.5H2O)
is blue coloured.
(b) The nature of the ligand and the molar ratio of metal : ligands also influence the colour of the complex. For
example ; in the pale green complex of [Ni(H2O)6], the colour change is observed when ethylenediamine is
progressively added to it.

Molar ratio of en : Ni Coloured obs erved

1 :1 Pale blue
2 :1 Blue/Purple
3 :1 Violet

Note : Ruby is Al2O3 in which 0.5–1% Cr3+ ions (d3 electron system) are randomly distributed in the positions
normally occupied by Al3+. We may consider Cr(III) species as octahedral Cr(III) complexes incorporated into the
alumina lattice ; d-d transition of electron at these centres/points give rise to the colour (red).
Emerland is the mineral beryl (Be3Al2Si6O18) in which Cr3+ ions occupy octahedral sites, but in this case low energy
corresponding to yellow red and blue is absorbed and light corresponding to green region is transmitted.

FACTORS AFFECTING STABILITY OF COMPLEX COMPOUNDS

(i) The values of stability constant differ widely depending on the nature of the metal ion and the ligand In general
higher the charge density on the central ion. The greater the stability of its complexes.
(ii) the more basic a ligands, the greater is the ease with which it can donate its lone pairs of electrons and therefore,
greater is the stability of the complexes formed by it.

Ex. The cyano and ammine complexes are far more stable than those formed by halide ions. This is due to the fact that
NH3 and CN– are strong Lewis bases.

(iii) The higher the oxidation state of the metal, the more stable is the complex. The charge density of Co 3+ ion is more
than Co2+ ion and thus, [Co(NH3)6]3+ is more stable than [Co(NH3)6]2+ . Similarly, [Fe(CN)6]3– is more stable than
[Fe(CN)6]4–.
(iv) Chelating ligands form more stable complexes as compared to mondentate ligands.

APPLICATION OF COMPLEXES
The complexes are of immense importance on account of their applications in various fields. During complex
formation there are drastic changes in the properties of metal atom/ion these changes in properties are made use of
in the application of metal complexes.

(i) The detection and estimation of Ni2+ is based on the formation of a scarlet red complex with dimethyl glyoxime.
OH O–

CH3 – C = NOH CH3 – C = N N = C – CH3

NH4OH
NiCl2 + 2 Ni + 2NH4Cl + 2H2O
CH3 – C = NOH CH3 – C = N N = C – CH3

O OH

H-bonding

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 COORDINATION COMPOUNDS
(a) Fe3+ is detected by formation of a blood red coloured complex with KSCN.

Fe3+ + 3 KSCN o Fe ( SCN )3 + 3 K+

blood red colour
or
[ Fe ( H2 O) 5 ( SCN )]2+
(b) Many ligands (organic reagents) are used for the gravimetric estimation of number of metal ions.

(c) EDTA is used as a compelexing agent in volumeter analysis of metal ions like Ca2+, Mg2+ and Zn2+.

(d) The co-ordination compounds of the transition metals exhibit a variety of colours. This property is utilised
in colorimetric analysis for the estimation of many metals.
(ii)
(a) Metallurgical process : Silver and gold are extracted by the use of complex formation. Silver ore is treated with
sodium cyanide solution with continuous passing of air through the solution. Silver dissolves as a cyanide
complex and silver is precipitated by the addition of scrap zinc.
Air
Ag2S + 4NaCN 2N[Ag(CN)2] + NaS O2(Air) Na2SO4 + S
argentine sodium argentocyanide

2Na[Ag(CN)2] + Zn Air Na2[Zn(CN)4]+ 2Ag

sodium tetracyanozincate(II)
(b) Native Gold and Silver also dissolve in NaCN solution in presence of the oxygen (air).
4 Ag + 8 NaCN + O2 + 2H2O 3Na[Ag(CN)2] + 3NaOH
Silver and Gold are precipitated by addition of scrap zinc. Nickel is extracted by converting it into a volatile
complex, nickel carbonyl, by use of carbon monoxide (Mond's process). The complex decomposes on heating
again into pure nickel and carbon monoxide.
Ni + 4CO Ni(CO)4 heating Ni + 4 CO

(iii) Photography In photography, the image on the negative is fixed by dissolving all the remaining silver bromide with
hypo solution in the form of a soluble complex.
AgBr + 2Na2S2O3 Na3[Ag(S2O3)2] + NaBr
(soluble) (soluble)
(iv) Electroplating Metal complexes release metal slowly and give a uniform coating of the metal on the desired object
Cyano complexes of silver, gold copper and other metals are used for the electrodeposition of these metals,

(v) Biological processes Metal complexes are of immense importance in biological processes. Haemoglobin, the red
blood pigment, which acts as oxygen carrier to different parts of the body is a complex of iron (II). Vitamin B 12 is a
complex of cobalt metal. The green colouring matter of plants, called chlorophyll, is a complex of magnesium. It acts
as a catalyst in photosynthesis.

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CHEMISTRY FOR NEET & AIIMS
ORGANOMETALLIC COMPOUNDS
Organometallic compounds are defined as those compounds in which the carbon atoms of organic (usually alkyl or
aryl) groups are directly bonded to metal atoms. The compounds of elements such as boron, phosphorus, silicon,
germanium and antimony with organic groups are also included in organometallics. Many organometallic compounds
are important reagents which are used for the synthesis of organic compounds.

Classification of Organometallic Compounds

Organometallic compounds are classified in three classes.
(i) Sigma bonded organometallic compounds: In these complexes, the metal atom and carbon atom of the
ligand are joined together with a sigma bond, For Examples:
(a) Grignard reagents, R – Mg – X where R is an alkyl or aryl group and X is a halogen.
(b) Zinc compounds of the formula R2Zn such as (C2H5)2Zn. (isolated by Frankland).
Other similar compound are (CH3)4Sn, (C2H5)4Pb, Al2(CH3)6, Al2(C2H5)6, Pb(CH3)4 etc.

H3C CH3 CH3

Al Al
H3C CH3 CH3

Al2(CH3)6 is a dimeric compound and has a structure similar to diborane, (B2H6). It is an electron deficient
compound and two methyl groups act as bridges between two aluminium atoms.

(ii) Pi-bonded organometallic compounds : These are the compounds of metals with alkenes, alkynes, benzene and
other ring compounds. In these complexes, the metal and ligand form a bond that involves the S-electrons of the
ligand. Three common examples are Zeise's salt, ferrocene and dibenzene chromium.
These are shown below.

H H
C
C
Cl H H

Pt + Fe Cr
K
Cl Cl
Zeise's Salt

Cr

The number of carbon atoms bonded to the metal in these compounds is indicated by the Greek letter K(eta) with a
number. The prefixes K2, K5 and K6 indicate that 2, 5 and 6 carbon atoms are the metal in the compound.

(iii) Sigma and Pi bonded organometallic compounds : Metal carbonyl compounds formed between metal and carbon
monoxide, belong to this class. These compounds possess both V-and S-bonding. Generally oxidation state of metal
atoms in these compounds is zero. Carbonyls may be mononuclear, bridged or polynuclear.

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 COORDINATION COMPOUNDS
O
O C O
C C

Fe
CO OC CO CO
Co OC O=C O=C C O
Fe CO
Ni Cr
OC CO Fe
CO CO OC CO
CO CO C
C C
O O
O
Tetracarbonyl nickel(0) Pentacarbonyl iron(0) Hexacarbonyl chromium(0) Fe2(CO)9
Ni(CO)4 Fe(CO)5 Cr(CO)6
In a metal carbonyl, the metal-carbon bond possesses both the V-and S-character. A V-bond between metal and
carbon atom is formed when a vacant hybrid orbital of the metal atom overlap with an orbital on C atom of carbon
monoxide containing a lone pair of electrons.

– M + + + C – M C O
Formation of p-bond is caused when a filled orbital of the metal atom overlaps with a vacant antibonding S* orbital
of C atom of carbon monoxide. This overlap is also called back donation of electrons by metal atom to carbon.

+
_ + + _ _ _

M + C O M C O
+ _ _ + + +
_

The S-overlap is perpendicular to the nodal plane of V-bond.

In olefinic complexes, the bonding S-orbital electrons are donated to the empty orbital of the metal atom and at the
same time to the back bonding p-orbital of the olefin.

APPLICATIONS OF CO-ORDINATION & ORGANOMETALLIC COMPOUNDS

(a) If excess of KCN & KI is added in CuSO4 insoluble CuCN & Cul is formed which later turn into soluble complex.

+2
Cu OA
–
CN RA 1
2KCN + CuSO4 Cu(CN)2 Cu+CN– + (CN)2
salt salt
–K2SO4
do not exist
redox 2
3KCN

K3 [Cu(CN)4]
soluble complex

(b) AgCl or AgBr ppt (Not Agl) are soluble in ammonia & NH4OH

AgCl 
2NH3
o[Ag(NH3 ) 2 ]  Cl 
ppt soluble complex

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CHEMISTRY FOR NEET & AIIMS
(c) In photography : undecomposed AgBr is removed from photography film by using hyposolution [Na2S2O3.5H2O]

1
AgBr 
hQ
o Ag  Br2
2

AgBr  2Na 2S2O3 

o Na 3 [Ag(S2 O3 ) 2 ]3  NaBr
so lub le complex

(d) Light blue colour of aqueous solution of CuSO4 turn into dark blue in presence of ammonia

[Cu(H 2O) 4 ]SO 4 

4 NH3
o > Cu(NH 3 ) 4 @SO 4
light blue dark blue

But in the presence of acid in above there is no colour change

(e) Rusting spots of iron [Fe2O3.XH2O] can be removed by using oxalic acid.
(f) cyano complex are used for electroplating of Ag or Au due to high stability.
e.g. [Ag(CN)2]–
(g) Wilkinson catalyst [RhCl(PPh3)3 is used for hydrogenation of alkene. (Homogeneous catalysis)
(h) [EDTA]4– is used for estimation of hardness of water.
(i) [Ca(EDTA)]2– is used to remove Pb poison.
[Ca(EDTA)]2– + Pb+2 o [Pb(EDTA)]2– + Ca+2
(g) Biological importance
Chlorophyll (Mg) haemoglobin (Fe+2) Myoglobin (Fe+3)
Vit B12(Co) Corboxypeptide (Zn) Insulin (Zn)

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 COORDINATION COMPOUNDS

1. CH3B(OCH3) is an organometallic compound but B(OCH3) is not.

2. The closed ring complexes formed by polydenatate ligands are called Chelates. Chelation leads to stability.

3. Estimation of nickel (II) is done by complexing with dimethyl glyoxime (DMG) whereas that of Ca+2 and Mg2+ ions
is done by titrating against EDTA.

4. Complex in which ligands can be substituted by other ligands are called labile complexes. For example [Cu(NH 3)4]2+
is a labile complex because NH3 ligands can be substituted by CN– ligands.
[Cu(NH3)4]2+ + 4 CN– o [Cu(CN)4]2 + 4NH3
(less stable) (more stable)

5. Another type of geometrical isomerism is also shown by octahedral complexes of the type Ma3b3.

if each trio of donor atoms occupy adjacent positions at the corner of an octahedral face, then it is called facial (fac)
isomer and when the position are around the meridian of the octahedron, then it is called meridional (mer) isomer.
a b
b a
b a
M M
b a a
a
b b
fac-form Mer-form

6. Haemoglobin is a complex of Fe, chlorophyll is a complex of Mg, vitamin B 12 is a complex of Co.

7. V-bond organometallic compounds generally contains a non-transition metal linked to carbon atom of alkyl group
by V bond. For example eg. R-MgX.

8. p-bonded organometallics are formed by donation of p-electrons of double bond to the metal atom. For example
Zeise's salt K[PtCl3K2 C2H4] and Ferrocene Fe(K5-C5H5)2

9. Grignard's reagent is one of the most useful organometallic compounds. Due to the high polarity of (CG–MgG+) bond,
it can be used to synthesise many organic compounds.

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CHEMISTRY FOR NEET & AIIMS

SOLVED EXAMPLE
Ex. 1 A solution containing 0.319 gm of complex CrCl3 . Ex. 3 Consider the following complexes :
6H2O was passed through cation exchanger and (i) K2PtCl6 (ii) PtCl4 . 2NH3
the solution given out was neutralised by 28.5 ml of (iii) PtCl4 . 3NH3 (iv) PtCl4 . 5NH3
0.125 M NaOH. The correct formula of the complex their electrical conductance in aqueous solutions
will be: [molecular weight of complex = 266.5] are :
(A) 256, 0, 97, 404 (B) 404, 0, 97, 256
(A) [CrCl(H2O)5]Cl2 . H2O
(C) 256, 97, 0, 404 (D) 404, 97, 256, 0
(B) [Cr(H2O)6]Cl3
Ans. (A)
(C) [CrCl2(H2O)4]Cl. 2H2O
Sol. The electrical conductance of the complexes depend
(D) All are correct upon the number of ions given by them in the
Ans. (B) aqueous solutions.
Sol. Cl– = HCl = NaOH aq
(i) K2[PtCl6] 2K+ (aq) + [PtCl6]2– (aq)
aq
nCl– + nH+ o nHCl (ii) [Pt(NH3)2Cl4] [Pt(NH3)2Cl4] (aq)
Thus 1 mol of complex will form n mol of HCl aq
(iii) [Pt(NH3)3Cl3]Cl [Pt(NH3)3Cl3]+ (aq) + Cl–
1 mole of complex = n mol of HCl = n mole of NaOH aq
(aq)(iv) [Pt(NH3)5Cl]Cl3 [Pt(NH3)5Cl]3+ + 3Cl–
0.319 Complex Number of ions Expected
mole of complex = = 0.0012; mole of NaOH
266.5 electrical
conductance
28.5× 0.125
used = = 0.0036 (i) K2[PtCl6] 3 256
1000
(ii) [Pt(NH3)2Cl4] 0 0
So 0.0012 mole of complex = 0.0036 mole of NaOH = (iii) [Pt(NH3)3Cl3]Cl 2 97
0.0036 mole of HCl (iv) [Pt(NH3)5Cl]Cl3 4 404
So, the correct option is (A).
0.0036
1 mole of complex = = 3 mole of HCl
0.0012 Ex. 4 Give the order of chelating effect of following ligands.
? n=3 (i) C2O42– (ii) EDTA
(iii) dien
So complex is [Cr(H2O)6]Cl3.
(A) iii > ii > i (B) i > ii > iii
Ex. 2 Calculate the effective atomic number of the metal (C) ii > iii > i (D) i > iii > ii
atoms in the following complexes / complex ions. Ans. (C)
(A) [Cr(CO)6] (B) [Fe(CN)6]3– Sol. As number of donor atoms increases the number of
bonds increase. So the chelating effect of ligands
(C) [Co(CN)6]4– (D) [Ni(NH3)6]2+
increase as oxalato, dien and EDTA has two, three
[Cr = 24 ; Fe = 26; Co = 27 and Ni = 28 as atomic and six donor atoms respectively.
numbers]
Ans. (A) 36 (B) 35 Ex. 5 Write the structural formula corresponding to each
of the following IUPAC names :
(C) 37 (D) 38
(A) potassium tetracyanidozincate (II)
Sol. EAN = Number of electrons in metal atom or ion +
(B) tetracarbonyl nickel (0)
Number of electrons donated by ligands to metal.
(C) potassium tetracyanonickelate (0)
(A) [Cr0(CO)6] ; EAN = 24 + 12 = 36 ; (D) potassium tris(oxalato)aluminate (III)
(B) [FeIII(CN)6]3–; EAN = 23 + 12 = 35 Ans. (A) K2[ZnII(CN)4] (B) [Ni0(CO)4]
(C) [CoII(CN)6]4–; EAN = 25 + 12 = 37 ; 0
(C) K4[Ni (CN)4] (D) K3[AllII(C2O4)3]
(D) [NiII(NH3)6]2+; EAN = 26 + 12 = 38 Sol. Refer IUPAC rule.

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 COORDINATION COMPOUNDS
Ex. 6 Write IUPAC names of the following : 3d 4s 4p
(A) [Cr(acac)3] (B) [V(H2O)6]Cl3 Co2+, [Ar] 3d7
(C) (NH4)3[Co(C2O4)3] (D) K2 [CrO4]
Ans. (A) tris (acetylacetonato) chromium(III) [Co(SCN)4]2–
(B) hexaaqua vanadium (III) chloride
(C) ammonium tris(oxalato)cobaltate(III) or sp3 hybrid orbitals
ammonium trioxalatocobaltate(III) Four pairs of electrons
(D) potassium tetraoxidochromate(VI) from four SCN– ions.
Sol. Refer IUPAC nomenclature rule. In Hg [Co(NCS)4] (Y), the cobalt is in +2 oxidation
state. Further ‘spin only’ magnetic moment of
Ex. 7 Explain the following :
c o m p l e x ,
(i) All the octahedral complexes of Ni2+ must be outer Hg[Co(NCS)4] is 1.73 B.M. So,
orbital complexes.
(ii) [CoF6]3– is paramagnetic but [Co(CN)6]3– is P = n(n + 2) ; So, 1.73 B.M = n(n + 2) or n = 1.
diamagnetic.
Sol. (i) Ni2+ configuration 4p
3d 4s
Co2+, [Ar] 3d7

During rearrangement only one 3d-orbital may be [Co(NCS)4]2–

made available for pairing of the electrons.
Thus, d2 sp3 hybridization is not possible. So only dsp2 hybrid orbitals
sp3d2 (outer) hybridization can occur. Four pairs of electrons
(ii) ln [CoF6]3– , Co3+ undergoes sp3d2 hybridization. from four NCS– ions.
Four d-orbitals are singly occupied. Hence, it is So, X is tetrahedral and Y is square planar.
paramagnetic.
Ex. 9 All the following complexes show a decreases in their
3d 4s 4p 4d
[CoF6] 3– weights when placed in a magnetic balance. Then
Rearrangement
3 2
sp d hybridization which of the these has square planar geometry ?
In [Co(CN)6] , Co undergoes d2sp3 hybridization.
3– 3+ (A) Ni(CO)4 (B) K[AgF4]
All electrons are paired and thus it is diamagnetic. (C) Na2[Zn(CN)4] (D) None of these
4p
Ans. (B)
3d 4s
Sol. In K [AgF4], Ag(,,,) has 4d8 configuration. This has
[Co(CN)6]3– higher CFSE which favours pairing of electrons
Rearrangement d2sp3 hybridization
and thus complex is diamagnetic and square planar.
Ex. 8 You are given the following two complexes X and Y Ex. 10 Which of the following statements is not correct?
which are isomers of each other ; X is Hg [Co(SCN)4].
(A) [Ni(H2O)6]2+ and [Ni(NH3)6]2+ have same value
It is further given that ‘spin only’ magnetic moment
of CFSE
of X is found to be 3.78 B.M. and that of Y is 1.73
B.M. Then which of the following is correct ? (B) [Ni(H2O)6]2+ and [Ni(NH3)6]2+ have same value
of magnetic moment
(A) Anion of X will be tetrahedral and that of Y will
be square planar. (A) Only a (B) Only b
(B) Anion of X will be square planar but that of Y (C) Both a and b (D) None of these
will be tetrahedral Ans. (A)
(C) Both the anions will be tetrahedral Sol. (A) Ammonia is a stronger field ligand than water.
(D) Both the anions will be square planar So [Ni(NH 3) 6] 2+ will have higher CFSE than
Ans. (A) [Ni(H2O)6]2+.
Sol. In Hg [Co(SCN)4] (X) , the cobalt is in +2 oxidation (B) Both complexes [Ni(H2O)6]2+ and [Ni(NH3)6]2+
state. have sp 3d 2 hybridisation with two unpaired
electrons. So, they possess same magnetic moment
P = n(n  2) ; So, 3.78 B.M = n(n  2) or n = 3. So, (‘spin only’)

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CHEMISTRY FOR NEET & AIIMS
Ex. 11 Statement-1 : [CoII(NH3)6]2+ is not readily oxidized Ex. 13 It is an experimental fact that Cs2[CuCl4] is orange
to [CoIII(NH3)6]3+ when air is bubbled through it. coloured but (NH4)2 [CuCl4] is yellow. It is further
Statement-2 : Crystal field stabilization energy of known that total paramagnetic moment of a unpaired
Co(+III) with a d6 configuration is higher than for electron is due to spin as well as due to nature of
Co(+II) with a d7 arrangement. orbital ; ‘d’ orbital contributing more than ‘s’ or ‘p’.
(A) Statement-1 is True, Statement-2 is True; Thus the total paramagnetic moment of orange
Statement-2 is a correct explanation for Statement- compound is found to be more than that of yellow
1. compound. Then which of the following is correct ?
(B) Statement-1 is True, Statement-2 is True; (A) Anion of orange compound is tetrahedral and
Statement-2 is NOT a correct explanation for that of yellow is square planar
Statement-1 (B) Anion of orange compound is square planar
(C) Statement-1 is True, Statement-2 is False and that of yellow is tetrahedral
(D) Statement-1 is False, Statement-2 is True (C) Both the anions are tetrahedral
Ans. (D) (D) Both the anions are square planar
Sol. Statement 1 is false statement. [CoII (NH3)6]2+ is Ans. (A)
readily oxidised in [CoIII(NH3)6]3+ in presence of air Sol. Cs2 [CuCl4] (orange) is tetrahedral because in Cu(,,)
due to the higher CFSE value (– 2.4'o) of d 6 the unpaired electron is in 3d. But (NH4)2 [CuCl4]
configuration than d7 configuration (– 0.8 'o). (yellow) is square planar because the unpaired
electron is not in 3d rather in some promoted state
Ex. 12 Which of the following is true about the complex ‘s’ or ‘p’.
[PtCl2(NH3)(OH2)] ? [Atomic number of Pt = 78]
Ex. 14 It is an experimental fact that :
(i) It will have two geometrical isomeric forms, cis
and trans. DMG + Ni(,,)salt + NH4OH o Red precipitate
(ii) The hybridisation state of Pt(,,) is sp3. Which of the following is wrong about this red
(iii) It is a square planar complex. precipitate?
(iv) It is a diamagnetic complex. (A) It is a non–ionic complex.
(v) It can show hydrate isomerism. (B) It involves intra molecular H–bonding.
(vi) It is a tetrahedral complex. (C) Ni(,,) is sp3 hybridised.
(A) (i), (iii),(iv) (B) (ii),(iv),(v) (D) It is a diamagnetic complex.
(C) (ii),(v),(vi) (D) (i),(v),(vi) Ans. (C)
Ans. (A) Sol. In complex [Ni(DMG)2], the nickel is in +2 oxidation
state ; the ion has the electronic configuration 3d8
Sol. Pt2+, [Xe]4f14 5d8 and dimethylglyoxime is a chelating ligand. So, the
hybridisation scheme is as shown in figure.
[PtCl2(NH3)(OH2)] 3d 4s 4p
Ni2+, [Ar]3d8
diamagnetic
dsp2 hybrid orbitals
[Ni(DMG)2]
Four pairs of electrons
from four Cl– ions. diamagnetic.
Ma2bc have cis- and trans isomers. dsp2 hybrid orbitals
NH3 Cl NH3 Cl
O¯ H O
2+ 2+ CH3 – C = N N = C – CH3
Pt Pt Ni2+
CH3 – C = N N = C – CH3
H2O Cl Cl H2O O H O
cis trans ¯
square planar

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 COORDINATION COMPOUNDS
Ex. 15 The correct order for the CFSE (numerical value) for Ex. 19 For the reaction Ni2+ + 4NH3 [Ni(NH3)4]2+ ;
the following complexes is :
at equilibrium, if the solution contains 1.6 × 10–4% of
Complex Formula nickel in the free state, and the concentration of
P [CoF6]3– NH3 at equilibrium is 0.5 M. Then the instability
Q [Co(CN)6]3– constant of the complex will be approximately equal
R [Co(NH3)6]3+[Co(NH3)6]3+ to :
S [Co(H2O)6]3+ (A) 1.0 × 10–5 (B) 1.5 × 10–16
(A) P > Q > R > S (B) Q > R > S > P (C) 1.0 × 10 –7
(D) 1.5 × 10–17
(C) S > R > P > Q (D) R > Q > P > S Ans. (C)
Ans. (B) Sol. Ni2+ + 4 NH3 [Ni(NH3)4]2+
Sol. CFSE depends on the relative magnitude of crystal
[Ni (NH3 ) 4 ]2+
field splitting, 'o and pairing energy, p and in turns ? k=
'o depends upon the field produced by ligand and [Ni 2+ ][NH 3 ]4
charge on the metal ion. So,the order of increasing [Ni 2+ ]
crystal field strength is But = 1.6 × 10–6
[Ni ]+ [Ni (NH 3 ) 4 ]2+
2+
F– < H2O < NH3 < CN–. (Co is in +3 oxidation state in
all complexes). Thus the (B) option is correct. Ni 2+
or | 1.6 × 10–6
Ex. 16 S-bonding is not involved in : [Ni (NH 3 ) 4 ]2+
(A) ferrocene 106
? k= = 107
(B) dibenzenechromium 1.6× (0.5) 4
(C) Zeise’s salt Hence instability constant = 10–7
(D) Grignard‘s reagent
Ex. 20 In metal carbonyls the metal carbon bond length is
Ans. (D)
found to be less than the expected bond length.
Sol. RMgX i.e. Grignard’s reagent is V bonded complex. Explain why ?
Ex. 17 Wilkinson's catalyst contains : Sol. It is due to synergic interaction between metal and
(A) rhodium (B) iron CO which develops partial double bond character
(C) aluminium (D) cobalt between metal and CO.
Ans. (A) S
S
Sol. Wilkinson’s catalyst is [Rh(I)Cl(PPh3) 3]. So it
contains rhodium. V
M C O
o

Among [Ni(CN)4]4–, [Ni(PPh3)3Br] and [Ni(dmg)2]

o

Ex. 18
o o

species, the hybridisation states of the Ni-atoms

S
are respectively:
(A) dsp2, dsp2, sp3 (B*) sp3, sp3, dsp2 Synergic bonding
(C) sp3, dsp2, dsp2 (D) dsp2, sp3, dsp2 Ex. 21 Which of the following complexes formed by Cu2+
Sol. [Ni(CN)4] - Ni is in zero oxidation state. The CN– is
4–
ions is most stable
strong field ligand and, therefore, rearrangement of
(A) Cu 2   4NH 3 
o[Cu(NH 3 ) 4 ]2  , log K 11.6
electrons occur. So,
3d 4s 4p (B) Cu 2   4CN  
o[Cu(CN) 4 ]2  , log K 27.3
[Ni(CN)4]4– (C) Cu 2   2en  
o[Cu(en) 2 ]2  , log K 15.4
sp3 hybridisation
[Ni(PPh3)3Br] - Ni is in +1 oxidation state with 3d9 (D) Cu 2   4H 2 O  o[Cu(H 2 O) 4 ]2  , log K 8.9
configuration (PPh3 is a strong field ligand). So, Sol. (B) Greater the value of log K greater will be stability
3d 4s 4p of complex compound formed For reaction,
[Ni(PPh3)3Br] Cu 2  4CN  
o[Cu(CN) 4 ]2 
3
sp hybridisation
[(Cu(CN) 4 ) 2  ]
[Ni(dmg)2] - Ni is in +2 oxidation state with 3d8 K and log K 27.3
configuration. (dmg is a chelating ligand). So, [Cu 2  ][CN  ]4
3d 4s 4p For this reaction, log K has highest value among
[Ni(dmg)2] the given four reactions. Hence, K will also be higher
2
among these four reactions. Hence, K will also be
dsp hybridisation
higher among these four complexes.

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CHEMISTRY FOR NEET & AIIMS
Ex. 22 The colour of the coordination compounds depends Ex.2 5 The CFSE for octahedral [CoCl6]4– is 18,000 cm–1.
on the crystal field splitting. What will be the correct The CFSE for tetrahedral [CoCl4]2– will be
order of absorption of wavelength of light in the
visible region, for the complexes, (A) 18,000 cm–1 (B) 16,000 cm–1
[Co(NH 3 )6 ]3 ,[Co(CN)6 ]3 ,[Co(H 2 O)6 ]3 (C) 8,000 cm–1 (D) 20,000 cm–1
Sol. (C) CFSE for octahedral and tetrahedral complexes
(A) [Co(CN) 6 ]3 ! [Co(NH 3 ) 6 ]3 ! [Co(H 2 O) 6 ]3
4
(B) [Co(NH 3 )6 ]3 ! [Co(H 2 O) 6 ]3 ! [Co(CN) 6 ]3 are closely related to each other by formula 't '0 .
9
(C) [Co(H 2 O)6 ]3 ! [Co(NH 3 ) 6 ]3 ! [Co(CN) 6 ]3 where ' 0 CFSE for octahedral complex,
3 3 3
(D) [Co(CN) 6 ] ! [Co(NH 3 ) 6 ] ! [Co(H 2 O) 6 ]
't CFSE for tetrahedral complex
Sol. (C) As we know that, strong field ligand split the
five degenerate energy levels with more energy According to question, ' 0 18, 000cm 1
separation than weak field ligand, i.e., as strength of
ligand increases crystal field splitting energy
increases 4 4
? 't '0 u 18, 000cm 1
hc 9 9
Hence, 'E = 4 × 2,000 cm–1 = 8,000 cm–1
O
1 1 Ex.2 6 Due to the presence of ambidentate ligands
Ÿ 'E v Ÿ O v
O 'E coordination compounds show isomerism. Palladium
As energy separation increases, the wavelength
decreases. complexes of the type [pd(C 6 H 5 )2 (SCN)2 ] and
Thus, the correct order is [pd(C 6 H 5 )2 (NCS) 2 ] are
[Co(H 2 O)6 ]3 ! [Co(NH 3 ) 6 ]3 ! [Co(CN) 6 ]3
(A) Linkage isomers (B) Coordination isomers
Here strength of ligand increases 'E increases, CFSE
increases and O absored decreases. (C) Ionisation isomers (D) Geometrical isomers
Sol. (A) The ligand(s) which has two different bonding
Ex. 23 When 0.1 mol CoCl3(NH3)5 is treated with excess of
AgNO 3, 0.2 mol of AgCl are obtained. The sites are knwon as ambident ligands e.g., NCS, NO2
conductivity of solution will correspond to etc.
(A) 1 : 3 electrolyte (B) 1 : 2 electrolyte Here, NCS has two binding sites at N and S
(C) 1 : 1 electrolyte (D) 3 : 1 electrolyte Hence, NCS (thiocyanate) can bind to the metal ion
Sol. (B) One mole of AgNO3 precipitates one mole of in two ways
chloride ion. In the above reaction, when 0.1 mole
CoCl3(NH3)5 is treated with excess of AgNO3, 0.2 M m
 NCS or M 
o SNC
mole of AgCl are obtained thus, there must be two
free chloride ions in the solution of electrolyte. Thus, coordination compounds containing NCS as
So, molecular formula of complex will be a ligand can show linkage isomerism i.e.,
[Co(NH 3 )5 Cl]Cl 2 and electrolytic solution must [Pd(C6 H 5 )2 (SCN)2 ] and [Pd(C6 H 5 )2 (NCS) 2 ] are
2
contain [Co(NH 3 )5 Cl] and two Cl as constituent
–
linkage iosmers.
ions. Thus, it is 1 : 2 electrolyte
o[Co(NH 3 )5 Cl]2  (aq)  2Cl  (aq)
[Co(NH 3 ) 5 Cl]Cl 2  Ex. 27 The compounds [Co(SO 4 )(NH 3 )5 ]Br
Ex. 24 When 1 mole of CrCl3.6H2O is treated with excess of and [Co(SO 4 )(NH 3 )5 ]Cl represent
AgNO3, 3 molesof AgCl are obtained. The formula
of the complex is (A) Linkage isomerism
(A) [CrCl3 (H 2 O)3 ].3H 2 O (B) Ionisation isomerism
(B) [CrCl2 (H 2 O) 4 ]Cl.2H 2 O (C) Coordination isomerism
(C) [CrCl(H 2 O)5 ]Cl 2 .H 2 O (D) No isomerism
Sol. (D) Compounds having same molecular formula but
(D) [Cr(H 2 O) 6 ]Cl3
different structural formula are known as isomers.
Sol. (D) 1 mole of AgNO3 precipitates one free chloride
ion (Cl–) [Co(SO 4 ) 2 (NH 3 )5 ]Br and [Co(SO 4 )(NH 3 )5 ]Cl
Here, 3 moles of AgCl are precipitated by exess of have not same molecular formula. Hence, they are
AgNO3. Hence, there must be three free Cl– ions
not isomers.
So, the formula of the complex can be [Cr(H2O)6]Cl3.

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CHEMISTRY FOR NEET & AIIMS

Exercise PART - 1 PREVIOUS YEAR (NEET/AIPMT)

1. Which one of the folloiwng octahedral complexes

will not show geemetrical isomerism? (A and B are
monodentate ligands) [CBSE AlPMT 2003] H3N CI
(A) [MA4B2] (B) [MA5B] (C) Pt
(C) [MA2B4] (D) [MA3B3] H3N CI

2. According to IUPAC nomenclature sodium

nitroprusside is named as [CBSE AlPMT 2003]
(A) sodium pentacyanonitrosyl ferrate (II) H3N CI
(B) sodium pentacyanonitrosyl ferrate (III) (D) Pt
(C) sodium nitoferricyanide H3N CI
(D) sodium nitroferrocyanide

3. The number of unpaired electrons in the complex 7. Which of the following does not have a metal-carbon
ion [COF6]3- is (At.no.of Co =27) bond ? [CBSE AlPMT 2004]
[CBSE AlPMT 2003] (A) Al(OC2H5)3 (B) C2H5MgBr
(A) 3 (B) 2 (C) K[Pt(C2H4)Cl3] (D) Ni (CO)4
(C) 2 (D) 0
8. CN- is strong field ligand. This is due to the fact that
4. Among the following which is not the Sbonded [CBSE AlPMT 2004]
organometallic compound ? [CBSE AlPMT 2003] (A) it carries negative charge
(A) K[PtCl3 (K- C2H4)] (B) Fe (K-C5H5)2 (B) it is a pseudohalide
(C) Cr (K-C6H6)2 (D) (CH3)4 Sn (C) it can accept electrons form metal species
5. Which of the following coordination compounds (D) if forms high spin complexes with metal species
would exhibit optical isomerism ?
9. Considering H2O as weak field ligand, the number
(A) Pentaamminenitrocobalt (III) iodide
of unpaired electrons in [Mn(H2O)6]2+ will be (At.
(B) Diamminedichloroplatinum (ii) no. of Mn=25) [CBSE AlPMT 2004]
(C) Trans-Dicyanobis (ethylenediamine) chromium (A) 3 (B) 5
(III) chloride (C) 2 (D) 4
(D) Tris- (ethylenediamine) cobalt (III) bromide
10. Among [Ni(CO)4], [Ni(CN)4]2-, [NiCl4]-2 species, the
6. Which of the following is considered to be an hybridisation states of the Ni atom are, arespectively
anticancer species? [CBSE AlPMT 2004] (At no.of Ni=28) [CBSE AlPMT 2004]
CH2 (A) sp3, dsp2. dsp2 (B) sp3, dsp2. sp2
CI (C) sp3, sp3. dsp2 (D) dsp2, sp3. sp3
Pt CH2
(A)
CI CI 11. Which one of the following is an inner orbital
complex as well as diamagnetic in behaviour?
(At.No. Of Zn = 30, Cr =24, Co =27, Ni=28)
CI CI [CBSE AlPMT 2005]
(B) Pt (A) [Zn (NH3)6] 2+
(B) [Cr (NH3)6]3+
CI CI (C) [Co (NH3)6]3+ (D) [Ni (NH3)6]2+

172
 COORDINATION COMPOUNDS
12. Which one of the following is expected to exhibit (A) [V(gly) 2(OH)2 (NH3)2]+
optical isomerism? [CBSE AlPMT 2005] (B) [Fe (en) (py) (NH3)2]2+
(en = ethylenediamine) (C) [Co(ox)2 (OH)2]-
(A) Cis- [Pt(NH3)2Cl2] (D) [Ti(NH3)6]3+
(B) Trans - [Co(en)2 Cl2] +

(C) Trans- [ Pt (NH3)2 Cl2] 18. In which of the following coordination entities the
magnitude of '(CFSE in octahedral field) will be
(D) Cis - [Co(en)2 Cl2]+
maximum? [CBSE AlPMT 2008]
13. [Co(NH3]4 (NO2)2] Cl exhibits [CBSE AlPMT 2006] (A) [Co (H2O)6]3+ (B) [Co (NH3)6]3+
(A) linkage isomerism, geometrical isomerism and (C) [Co (CN)6]3- (D) [Co (C2O4)3]3-
optical isomerism
19. Which of the following does not show optical
(B) linkage isomerism, ionisation isomerism and
isomerism ? [CBSE AlPMT 2009]
optical isomerism
(A) [Co(en)2 Cl2]+ (B) [Co(NH3)3 Cl3]0
(C) linkage isomerism, ionisation isomerism and
geometrical isomerism (C) [Co)en) Cl2 (NH3)2]+ (D) [Co(en)3]3+

(D) ionisation isomerism, geometrical isomerism and 20. Which of the following does not show optical
optical isomerism isomerism ? (en= ethylenediammine)

14. [Cr (H2O)6] CL3 (at no. of Cr=24) has a magnetic [CBSE AlPMT 2009]
moment of 3.83 BM. the correct distribution of 3d (A) [Sc(H2O)3 (NH3)3]3+ (B) [Ti(en)2 (NH3)2]4+
electrons in the chromium of the complex is (C) [Cr (NH3)6]3+ (D) (Zn(NH3)3+
[CBSE AlPMT 2006]
1 1 1 1 1
21. Out of TIF62  , CoF63 , Cu 2 Cl 2 and NiCl24  (At. no. Z
(A) 3d ,3 ,3d
xy yz z2
(B) 3d x2  y2  ,3d z2 ,3d yz
of Ti=22, Co=27, Cu=29, Ni= 28) the colourless
1 species are [CBSE AlPMT 2009]
(C) 3d xy ,3d ( x 2 y2 ) , 3d yz
1
(D) 3d ,3d ,3d
xy
1
yz
1
zx
(A) TIF62  and CoF63
15. The d electron configurations of Cr2+ ,Mn2+ ,Fe2+
and Ni2+ are 3d4, 3d5,3d6 respectively. Which one of (B) Cu 2 Cl 2 and NiCl 24 
the following aqua complexes will exhibit the
(C) TIF62  and Cu 2 Cl2
minimum paramagetic behaviour (At. No of Cr = 24,
Mn=25, Fe=26, Ni=28) [CBSE AlPMT 2007] (D) CoF63 and NiC 42 
(A) [Fe(H2O)6]2+ (B) [Ni(H2O)6]2+
(C) [Cr(H2O)6]2+ (D) [Mn (H2O)6]2+ 22. The existence of two different coloured complexes
with the composition of [Co(NH3)4 Cl2]+ is due to
16. Which of the following will give a pair of enantiomers [CBSE AlPMT 2010]
? (en = NH2CH2CH2NH2) [CBSE AlPMT 2007]
(A) linkage isomerism
(A) [Cr (NH3)6] [Co(CN)6]
(B) geometrical isomerism
(B) [Co(en)2 Cl2]Cl
(C) coordination isomerism
(C) [Pt (NH3)4] [PtCl6]
(D) ionisation isomerism
(D) [Co(NH3)4 Cl2] NO2
23. Crystel field stabilisation energey for high spin d4
17. Which of the following complexes exhibits the octahedral comple is [CBSE AlPMT 2010]
highest paramagnetic behaviour ?
(A) -1.8'0 (B)-1.6'0 +P
Where, gly = glycine, en = ethylendiamine and bpy
(C) -1.2'0 (D) -0.6'0
= bipyridyl moities [CBSE AlPMT 2008]

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CHEMISTRY FOR NEET & AIIMS
24. Which of the following comlex ions is not expected 32. The name of complex ion [Fe(CN6)]3- is
to absorb visible light? [CBSE AlPMT 2010] [CBSE AlPMT 2015]
(A) [Ni (CN)4]2- (B) [Cr (NH3)6]3- (A) hexacyanoiron (III) ion
(C) [Fe (H2O6)4]2+ (D) [Ni (H2O6)4]2+ (B) hexacyanitoferrate (III) ion
(C) tricyanoferrate (III) ion
25. The complex, [Pt(Py)(NH3)BrCl] will have how many
geometrical isomers [CBSE AlPMT 2011] (D) hexacyanidoferrate (III) ion
(A) 4 (B) 0
33. The sum of coordination number and oxidation
(C) 2 (D) 3 number of the metal M in the complex [M(en)2 (C2O4)
Cl (Where, en is ethylendediamine) is
26. The complex [Co (NH3)6] [Cr(CN)6] and [Cr(NH3)6]
[CBSE AlPMT 2015]
[Co(CN) 6] are the examples of which type of
isomerism ? [CBSE AlPMT 2011] (A) 9 (B) 6
(A) lonisation isomerism (C) 7 (D) 8
(B) Coordination isomerism
34. The hybridisation involved incomplex [Ni(CN)4]2- is
(C) Geometrical isomerism (Atomic number of Ni=28) [CBSE AlPMT 2015]
(D) Linkage isomerism (A) dsp2 (B) sp3
(C) d2sp2 (D) d2sp3
27. Of the following complex ions ions which is
diamagnetic in nature [CBSE AlPMT 2011]
35. Number of possible isomers for the complex [Co(en)2
(A) [Ni(CN)4]2- (B) [CUCl4]2- Cl will be (en ethylendiamine)[CBSE AlPMT 2015]
(C) [COF6]3- (D) [NiCl4]2- (A) 2 (B) 1
(C) 3 (D) 4
28. Which one of the follwoing is an outer orbital
complex and exhibits paramagenetic behaviour?
36. Which of these statements about [Co(CN)6]3- is ture ?
[CBSE AlPMT 2012]
[CBSE AlPMT 2015]
(A) [Ni (NH3)6] 2+
(B) [Zn (NH3)6]2+
(A) [Co(CN)6] has no unpaired electrons and will
3-

(C)[Cr(NH3)6]3+ (D)[Co (NH3)6]3+ be in a low-spin configuration.

(B) [Co(CN)6]3- has four unpaired electrons and
29. A magnetic moment of 1.73 BM will be shown by
willbe ina low-spin configuration.
one among the following [CBSE AlPMT 2013]
(C) [Co(CN)6]3- has four unpaired electrons and will
(A) [Cu(NH3)4]2+ (B) [Ni (CN)4]2-
be in a low -spin configuration
(C) TiCl4 (D) [CoCl6]4-
(D) [Co(CN)6]3- has no unpaired electrons and will
30. Which of the following complexes is used ot be as be in high -spin configuration.
an anticancer agent [CBSE AlPMT 2014]
37. Cobalt (III) chloride forms several octahedral
(A) Mer - [Co(NH3)3Cl3] (B) Cis- [Ptcl2(NH3)2] complexes with ammonia. Which of the following
(C) Cis-K2 [PtCl2 Br2] (D)Na2CoCl4 will not give test for chloride ions with silver nitrate
at 250C ? [CBSE AlPMT 2015]
31. Among the following complexes, the one which
(A) CoCl3. 3NH3 (B) CoCl3. 4NH3
shows zero crystal field stabilasation energy (CFSE)
(C) CoCl3.5NH3 (D) CoCl3. 6NH3
is [CBSE AlPMT 2014]
(A) [Mn(H2O6]3+ (B) [Fe(H2O6]3+ 38. Jahn-Teller effectg is not observed in high spin
(C) [Co(H2O6] 2+
(D) [Co(H2O6] 3+ complexes of [NEET 2016, Phase II]
(A) d7 (B) d8
(C) 84 (D) d9

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 COORDINATION COMPOUNDS

39. The correct increasin order of trans-effect of the 45. An example of a sigma bonded organometallic
following species is [NEET 2016, Phase II] compound is [NEET 2017]

(A) NH3 > CN= > Br- > C6 H 5 (A) ruthenocene (B) Gignard’s reagent
(C) ferrocence (D) cobaltocene
(B) CN- > C6H5- > Br- NH3

(C) Br  ! CN  ! NH 3 ! C 6 H 5 46. The type of isomerism shown by the complex

(D) CN- > Br- > C6H5 > NH3 [CoCl2 (en)2] is [NEET 2018]
(A) Ionization isomerism
40. Which of the follwing pairs of d-orbitals will have (B) Coordination isomerism
electrondensity along teh axis ? (C) Geometrical isomerism
[NEET 2016, phase II] (D) Linkage isomerism
(A) dz2 ,dxz (B) dxz, dyz
(C) d2, d (D) dxy, dx2-y2 47. The geometry and magnetic behaviour of the
complex [Ni(CO)4 ] are [NEET 2018]
41. Which of the following has longest C-O bond (A) square planar geometry and paramagnetic
length? (Free C-O bond length in CO is 1.128A.) (B) tetrahedral geometry and diamagnetic
[NEET 2016, phase I] (C) square planar geometry and diamagnetic
(A) [Co(CO)4] -
(B) [Fe (CO)4]2- (D) tetrahedral geometry and paramagnetic
(C) [Mn(CO)6]+ (D) Ni (CO)4

42. Pick out the correct statement with respect to 48. Iron carbonyl, Fe(CO)5 is [NEET 2018]
[Mn(CN)6]3- [NEET2017] (A) trinuclear (B) mononuclear
(A) It is sp3d2 hybridised and octahedral (C) tetranuclear (D) dinuclear
(B) It is sp3 d2 hybridised and tetrahedral
(C) It is d2sp3 hybridised and octahedral
(D) It is dsp2 hybridised and square planar

43. Correct increasing order for the wavelengths of

absorption in the visible region for the complexes of
CO3+ is [NEET 2017]
(A) [Co(en)3]3+ ,[Co(NH3)6]3+ [Co(H2O6)]3+
(B) [Co(H2O)6]3+ ,[CO(en3)]]3+, [Co(NH3)6]3+
(C) [Co(H2O6)3]3+ ,[Co(NH3)3+], [Co(NH3)6]3+
(D) [Co(NH3)6]3+ ,[Co(en3)3+], [Co(H2O)6]3+

44. The correct order of the stoichiometrics of AgCl

formed when AgNO3 in excess is treated with the
complexes : CoCl3 6NH3 , CoCl3. 5NH3 . 4NH3
respectively is [NEET 2017]
(A) 1 AgCl, 3AgCl, 2AgCl
(B) 3AgCl, 1AgCl, 2AgCl
(C) 3AgCl, 2Agcl, 1AgCl
(D) 2AgCl, 3AgCl, 1AgCl

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CHEMISTRY FOR NEET & AIIMS

Exercise PART - 2 PREVIOUS YEAR (AIIMS)

1. The ion which is not tetrahedral in shap is 9. The diamagnetic species is

(A) BF4– (B) NH4+ (A) [Ni(CN)4]2– (B) [NiCl4]2–
(C) [Cu(NH3)4]2+ (D) [NiCl4]2– [2003] (C) [CoCl4]2– (D) [CoF6]2– [2005]

2. The complex used as an anti-cancer agent is 10. The correct order for the wavelength of absorption
in the visible region is
(A) mer-[Co(NH3)3Cl3] (B) cis-[PtCl2(NH3)2]
(A) [Ni(NO2)6]4– < [Ni(NH3)6]2+ < [Ni(H2O)6]2+
(C) cis-K2[PtCl2Br2] (D) Na2[CoCl4] [2003]
(B) [Ni(NO2)6]4– < [Ni(H2O)6]2+ < [Ni(NH3)6]2+
3. The ligand called S-acid is (C) [Ni(H2O)6]2+ < [Ni(NH3)6]2+ < [Ni(NO2)6]4–
(A) Co (B) NH3 (D) [Ni(NH3)6]2+ < [Ni(H2O)6]2+ < [Ni(NO2)6]4–
(C) C2O42– (D) ethylendiamine [2005]

[2003]
11. The pair in which both species have same magnetic
moment (spin only value) is
4. Which one of the following forms with an excess oc
CN– (cyanide) a complex having coordination (A) [Cr(H2O)6]2+, [CoCl4]2–
number two ? (B) [Cr(H2O)6]2+, [Fe(H2O)6]2+
(A) Cu+ (B) Ag+ (C) [Mn(H2O)6]2+, [Cr(H2O)6]2+
(C) Ni2+ (D) Fe2+ [2004] (D)[CoCl6]2–, [Fe(H2O)6]2+ [2006]

5. Which of the following is not considered as an 12. The number of possible isomers of an octahedral
organometallic compound ? complex [Co(C2O4)2(NH3)2]– is
(A) cis-Platin (B) Ferrocene (A) 1 (B) 2
(C) Zeise’s salt (D) Grignard reagent (C) 3 (D) 4 [2006]

[2004] 13. Which of the following metal ions will form

6. Which of the following does not have optical complexes with the same magnetic moment and
isomerism ? geometry irrespective of the nature of ligands ?
(A) [Co(NH3)3Cl3] (B) [Co(en)3]Cl3 (A) Ni2+ (B) Fe2+
(C) [Co(en)2Cl2]Cl (D) [Co(en)(NH3)2Cl2]Cl (C) Cu2+ (D) Co2+ [2007]

[2004] 14. Wavelength of red light is absorbed by the complex

(A) [Cu(CN)4]2– (B) [Cu(NH3)4]2+
7. An aqueous solution of CoCl2 on addition of excess (C) CuSO4 (D) Cu(CN)2 [2007]
of concentrated HCl turns blue due to formation of
(A) [Co(H2O)4Cl2] (B) [Co(H2O)2Cl4]2– 15. In the change [Cu(H2O)6]2+  
HCl
o [CuCl(H2O)5] ,
+

(C) [CoCl4]2– (D) [Co(H2O)2Cl2] the colour changes from

[2005] (A) blue to green (B) blue to pink
(C) pink to green (D) pink to blue [2007]
8. In which of the following pairs both the complexes
16. Which statement is true for ferrocene ?
show optical isomerism ?
(A) All Fe-C are of equal length
(A) cis-[Cr(C2O4)4Cl2]3–, cis-[Co(NH3)4Cl2]
(B) C are sp2 hybridized
(B) [Co(en)3]Cl3, cis-[Co(en)2Cl2]Cl
(C) It was the first discovered organometallic
(C) [PtCl(dien)]Cl, [NiCl2Br2]2–
compound
(D) [Co(NO3)3(NH3)3], cis-[Pt(en)2Cl2] [2005]
(D) All of these [2007]

176
 COORDINATION COMPOUNDS
25. Select the correct statement.
17. Which of the following is considered as an
(A) Geometrical isomer may differ in dipole moment
anticancer species ?
and visible/UV spectra.
H3N Cl H3N Cl (B) Complexes of the type [Ma3b3] can also have
(A) Pt (B) Pt facial (fac) and meridional (mer) isomer.
H3N Cl Cl NH3
(C) No optical isomer exists for the complex trans-
[Co(en)2Cl2]+.
CH2 (D) All of these.
Cl Cl Cl [2016]
(C) Pt CH2 (D) Pt
Cl Cl Cl Cl
26. Which of the following coordination compounds
[2008] would exhibit optical isomerism? [2017]
(A) pentamminenitrocobalt(III) iodide
18. A complex PtCl4.5NH3 shows a molar conductance
(B) diamminedichloroplatinum(II)
of 402 ohm–1 cm2 mol–1 in water and precipitates three
moles of AgCl with AgNO3 solution. The formula of (C) trans-dicyanobis (ethylenediamine)
the complex is chromium (III) chloride
(A) [Pt(NH3)6]Cl4 (B) [Pt(NH3)4Cl2]Cl2 (D) tris-(ethylendiamine) cobalt (III) bromide
(C) [Pt(NH3)5Cl]Cl3 (D) [Pt(NH3)3Cl3]Cl
[2010] 27. Trien is [2018]
(A) Hexa dentate, Mono anionic
19. The wavelength of light absorbed is highest in
(B) tetradentate, neutral
(A) [Co(NH3)5Cl]2+ (B) [Co(NH3)5H2O]3+
(C) tetradentate, dianion
(C) [Co(NH3)6]3+ (D) [Co(en)3]3+ [2011]
(D) Mono dentate, anion
20. Which of the following is diamagentic ?
(A) [Cu(NH3)4]2+ (B) [NiCl4]2– 28. Which of the following is diamagnetic complex
(C) [PtCl4]2– (D) [Cu(H2O)4]2+ [2011] (A) [Co(OX)3]3– , [Fe(CN)6]3–
(B) [Co(Ox)3]3– , [FeF6]3–
21. Which of the following metal ion forms unstable
(C) [Fe(Ox)3]3– , [FeF6]3–
complex with CN– ?
(D) [Fe(CN)6]3– , [CoF6]3– [2018]
(A) Ag(I) (B) Zn(II)
(C) Cu(II) (D) Cr(II) [2013]
29. Which of the following can be reduce easily
22. Least coording number is shown by (A) V(CO)6 (B) Mo(CO)6
(A) Co2(CO)8 (B) Mn2(CO)10 (C) [Co(CO)4] –
(D) Fe(CO)5 [2018]
(C) [Fe(en)2NH3] (D) [Cr(OH)3(NH3)3]
[2014]
ASSERTION AND REASON
23. The diamagnetic species is
In each of the following questions, two statement
(A) [Ni(CN)4]2– (B) [NiCl4]2–
are given one is assertion and the other is reason.
(C) [CoCl4]2– (D) [CoF6]3– [2015] Examine the statement carefully and mark the correct
answer according to the instruction given below
24. Amongst the following the most stable complex is
(A) If both the assertion and reason are true and
(A) [Fe(H2O)6]3+ (B) [Fe(NH3)6]3+
reason explains the assertion
(C) [Fe(C2O4)3]3– (D) [FeCl6]3– [2015]
(B) If both the assertion and reason are true but
reason does not explain the assertion

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CHEMISTRY FOR NEET & AIIMS
(C) If assertion is true but reason is false and dzx orbitals of the same shell. [2012]
(D) If assertion is false but reason in true
38. Assertion : [Fe(H2O)5NO]SO4 is paramagnetic.
(E) Both assertion and reason are false
Reason : The Fe in [Fe(H2O)5NO]SO4 has three
30. Assertion : NF3 is a weaker ligand than N(CH3)3. unpaired electrons. [2012]

Reason : NF3 ionizes to give F– ions in aqueous

39. Assertion : EDTA forms complex with divalent
solution. [2003, 2015]
metals of 3d-series in the ratio of 1:1
31. Assertion : The [Ni(en)3]Cl2 (en = ethylenediamine) Reason : EDTA has 4 – COOH groups.
has lower stability than [Ni(NH3)6]Cl2. [2013]

Reason : In [Ni(en)3]Cl2 the geometry of Ni is trigonal

40. Assertion : In a mixture of Cd(II) and Cu(II), Cd2+
bipyramidal. [2004]
gets precipitated in presence of KCN by H2S.
32. Assertion : [Co(NO2)3(NH3)3] does not show optical Reason : The stability constant of [Cu(CN)4]3– is
isomerism greater than [Cd(CN)4]2–. [2013]

Reason : It has a plane of symmetry.[2006]

41. Assertion : Linkage isomerism arises in coordination
compounds containing ambidentate ligand.
33. Assertion : C – O bond in metal carbonyl is long.
Reason : Ambidentate ligand has two different
Reason : There is delocalisation of electrons from
donor atoms. [2014]
filled d orbitals into the empty orbitals on the CO
ligands. [2007]
42. Assertion : CO[Hg(SCN)6] and Hg[Co(SCN)6] are
isomers.
34. Assertion : In high spin situation, configuration of
d5 ions will be t32 g e2g . Reason : SCN– is a stronger ligand as compared to
NCS–. [2016]
Reason : In high spin situation, pairing energy is
less than crystal field energy. [2008]
43. Assertion : [Fe(CN)6]3– is weakly paramagnetic while
35. Assertion : Cu(OH)2 is soluble in NH4OH but not in [Fe(CN)6]4– is diamagnetic.
NaOH. Reason : [Fe(CN)6]3– has +3 oxidation state while
Reason : Cu(OH)2 forms a soluble complex with NH3. [Fe(CN)6]4– has +2 oxidation state. [2017]
[2009] 44. Assertion : NF3 is a weaker ligand than N(CH3)3.
Reason : NF3 ionizes to give F– ions in aqueous
3+ solution. [2017]
NH
36. Assertion : (en)2 Co Co(en)2
45. Assertion : In zieses salt coordination no. of Pt is
OH
five [2018]
is named as tetrakis (ethylenediamine) μ-hydroxo- Reason : ethene is bidentate ligand
μimido dicobalt (III) ion.
Reason : In naming polynuclear complexes i.e.,
containing two or more metal atoms joined by
bridging ligands, the word μ is added with hyphen
before the name of such ligands. [2010]

37. Assertion : F– ion is a weak ligand and forms outer

orbital complex.
Reason : F– ion cannot force the electrons of dz2 and
dx2 – y2 orbitals of the inner shell to occupy dxy, dyz

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CHEMISTRY FOR NEET & AIIMS

ANSWER KEY

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

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

179
 40-65*0/4
CHEMISTRY FOR NEET & AIIMS

EXERCISE 6. (C) Cis-platin is the isomer of [Pt (NH3)2 Cl2 which is

used as an anticancer drug for treating several types of
P-1 (NEET/AIPMT)
malignanet tumours.
1. (B) [MA5B] due to absence of synmetry of B cannot
exist in the form of cis-trans isomer. H3N Cl

2. (B) IUPAC name of sodium nitroprusside Na2 [Fe(CN)5 Pt

NO] is sodium pentacyanoni trosyl ferrate (III) because
in it No is neutral ligand and the oxidation number of Fe
H3N Cl
is +3. which is calculated as Cis- platin
Na2 [Fe(CN)5 NO]
2 × (+1) + x +5 × (-1) + 1 ×0=0
7. (A) Al(OC2H5)3 does not have metal- carbon bond. (i.e.
[where x = oxidation state of Fe] it is not an example of organometallic compound)
2+x-5=0 Structure
x-3=0
x=+3 H H

3. (C) In complex ion [CpF6]3- , Co is present in +3 oxidation H H

O C C H

state H H
H C C O Al
H
27
Co = 1s2,2s2 2p6,3s2 3p6 3d7,4s2 H

H H O C C H
Co3+ = 1s2, 2s2 2p6,3s2 3p6 3d6
Thereefore, the number of unpaired electrons in H H

3dsubshell of [CoF6]3- is 4.
8. (B) CN- is a strong field ligand because it is an example
4. (D) In (CH3)4 Sn (organometallic compounds of tin) single
of pseudohalide. Pseudohalide ions are stronger
bonds are present in form of sigma bond. pi-bonded
coordinating ligands and they have the ability to V and S
organometallic compound includes alkenes, alkynes and
- bonds.
some other carbon containing compounds having pi-
electrons in their molecular orbitals.
9. (B) In [Mn (H2O6)]2+ Mn is present as Mn2+ or Mn (II)
so its electronic congiguration
CH3
1s2, 2s2 2p6, 3s2 3p6, 3d5
Sn d

H3C CH3
CH3 S p d

5. (D) Tris - (ethylendediamine) cobalt (III) bromide [Co(en)3

Br3 exhibits optical ismerism: Sp3 d2

In [Mn(H2O5) the coordination number of Mn is six,

2+

Mirror
3+
and in presence of weak field, ligand there will be no
En 3+ En
pairing of electrons in 3d. so it will from high spin complex
En Co Co En due to presence of five unpaired electrons.

10. (B) In Ni (CO)4 , nickel is sp3 hybridised because in it

En En
oxidation state of Ni is zero. So. configuaration of
D-form Mirror I-form
28Ni = 1s2, 2s2 2p6, 3s2 3p6 3d6 3d8, 4s2

180
 COORDINATION COMPOUNDS
d s p mirror image

×× ×× ×× ×× Cl

3
en Co en
Sp

(CO is a strong field ligand, ligand, hence pairing of Cl

electrons will occur)
It gives super imposable structure.
In [Ni(CN) 4] 2- , nickel iw present as Ni 2+ , so its
but trans-form is optically inactive.
configuration = 1s2,2s2 2p6, 3s2 3p6 3d8
Cl
d s p

×× ×× ×× ×× Transform en Co en

2
dsp
Cl
Optically active form
CN is strong field ligand, hence it makes Ni electrons
- 2+

to be pairs up. 13. (C) The compound [Co(NH3)4 (NO2)2]Cl exhibits linkage,
In [NiCl4) nickel is present ass Ni , so its configuration
2- 2+ ionisation and geometrical isomerism Hence,
= 1s2,2s2 2p6, 3s2 3p6, 3d8 (i) its linkage isomers are

d s p
[Co (NH3)4 (NO2)2] Cl and [Co (NH3)4 (ONO2)2 ] Cl
(ii) its ionisation isomers are
×× ×× ×× ××
[Co (NH3)4 (NO2) Cl ]NO2and [Co (NH3)4 (NO2)2 ] Cl

Sp3
(iii) its geometrical isomers are
NH3 + NO2 +
H3N H3N
Cl- is a weak field ligand, hence in Ni2+ electrons are not NO2 NH3

paired
Co And Co
11. (C) In [Co(NH3)6]3+ , oxidation state of Co = +3 and its
NH3
coordination number is six. H3N NO2 H3N
NH3 NO2
27
C0 = 1s2, 2s2 2p6, 3s2 3p6 3d7, 4s2 Cis-isomer Trans-isomer
Co3+ = 1s2, 2s2 2p6, 3s2 3p6 3d6

d s p
14. (D) Magnetic moment  P  n  n  2  BM

×× ×× ×× ×× ×× ××
or 3.83 n  n  2
2
d
3
Sp or 3.83 × 8.83 = n2 +2n
14.6689 = n2 +2n
[Co (NH3)6]3+ is an inner orbital complex as well as
diamagnetic in behaviour (due to absence of unpaired n=3
electrons. ) Hence, number of unpaired electrons in d-subshell of
[Zn(NH3)6] o sp d hybridisation (outer orbital
2+ 3 2 chromium (Cr =24+ = 3
complex and diamagnetic in nature). So, the configuration of chromium ion is
[Ce(NH3)6] o d sp hybridisation (inner orbital
3+ 2 3
Cr3+ = 1s2, 2s2 2p6, 3s2 3p6 3d3
complex and paramagnetic in nature). In [Cr(H2O6)] Cl2 , oxidation state of Cr is +3.

12. (D) Cis- [Co(en)2]+ is able to show the phenomenon of Hence, in 3d3 the distribution of electrons
optical isomerism b ecause it can form a superimposable 3d1xy .3d1yz ,3d1zx , 3d 0x 2  y2 3d 0z2

181
CHEMISTRY FOR NEET & AIIMS
15. (B) As the number of unpaired electron increases, the Co5+ = [Ar], 3d4 [4 unpaired electrons]
magnetic moment increases and hence, the paramagnetic ox and OH are weak field ligands, thus pairing of electron
behaviour increases. units does not occur.
So, Cr2+ (22) = 3d4 (4 unpaired electrons) The electronic configuration of
Mn2+ (23) = 3d5 (5 unpaired electrons) Ti (22) = [Ar] 4s2 ,3d2
Fe (24) = 3d (4 unpaired electrons)
2+ 6
Oxidation state of Ti in [Ti(NH3)5]3+ is 3.
Ni (26) = 3d (2 unpaired electrons)
2+ 8
Ti3+ =[Ar]3d1 (one unpaired electron) Hence, complex
So, [Ni(H2O) 6 ] 2+
exhibit miniumum paramagnetic [Co(ox)2 (OH)2]- has maximum number of unpaired
behaviour. electrons, thus show maximim paramagnetism

16. (B) Enantiomorphs or Enantiomers A pair of molecules 18. (C) As in all the given complex the central metal atom is
related to each other as an object and its mirror images same and contains same number of d electrons, thus
are known as enantiomorphs or enantiomers. These are CFSE is decided by ligands. In case of strong field ligand,
not superimposable on its mirror image. CFSE is maximum. CN- is a strong field ligand. Hence, in
The example is [Co(en)2 Cl2]+ [Co(CN)6]3- magnitude of CFSE i.e ' is maximum.
Dichlorobis (ethylene diamine) cobalt (III)
19. (B) Optical istomerism is exhibited only by those
Mirror complexes in which plance of symmetry are absent.
en En
Cl Octahedral complexes of the types [M(aa)3] [M(aa)x2, y2]
Cl
and [M(aa)2 x2 ] have absence of plane of symmetry, thus
Co Co exhibit optical isomerism. Here, aa represents bidentate
ligand, x or y represents monodentate ligand and M
Cl Cl represents central metal ion Hence, [Co(NH3)3 Cl3]0 due
En to presence of symmetry elements does not exhibit optical
en Mirror image
isomerism. or Octahedral complexes of [M(AA)2 B2] type,
e.g [Co(en)2 Cl2]+ , [M (AA)B2C2] type e.g [Co(en)Cl2
Enantiomorphs
(NH3)2] and [M(AA)3] type. e.g. [Co(en)3]3+ show optical
17. (C) The electronic configuration of V(23) = [Ar] 4s2,3d3 isomensim, whereas complexes of [MA3B3] type. e.g. [Co
(NH3) Cl2]0 do not show optical isomerism.
` Let in [V(gly)2 (OH)2 (NH3)2]+ oxidation state of V is X.
x + (-1) × 2 + (-1) 2 + (0 × 2) = + 1
20. (C) In [Cr (Cr (NH3)6]3+, Cr is present as Cr3+
x=+5
Cr3+ = [Ar]3d3 , 4s0
V5+ = [Ar] 4s0,3d0 (no unpaired electrons)
The electronic configuration of 3d 4s
Fe (26) = [Ar] 4 s2 , 3d6
Let the oxidation state of Fe in [Fe (en) (ppy) (NH3)2]2+ is x
[ x + (0) + (0) +(0) ×2] = + 2 [Cr (NH3)6]3+ = [Ar]3d3

x =+2
Fe2+ = [Ar],3d6 ('
4 unpaired electron) 3d 4s 4p

but, bpy, en and NH3 all are strong field ligands, so pairing ×× ×× ×× ×× ××
occurs and thus, Fe2+ contains no unpaired electron Nh3 Nh3 NH3 NH3 NH3 NH3

The electronic configuration of Electron donated by NH3 ligand

hybridisation d2 sp3
Co (27) = [Ar] 4s , 3d
2 7

Let the oxidation state of Co in [Co (ox)2 (OH)2]- is x Since, this complex has three unpaired electrons,
x + (-2) × + (-1) × 2 = - 1 excitation of electrons is possible and thus, it is expected
x = +5 that this complex will absorb visible light.

182
 COORDINATION COMPOUNDS

eg
21. (C) TiF62  , Ti is present as Ti4+
0.6'
0.4?
Ti4+ = [Ar] 3d0 4s0 Degenerate
d-orbitals
t2g
Hence. TiF62  is colourless due to the absence of unpaired
? Crystal field stabilsation energy
electrons.
= (-3 × 0.4 + 1×0.6) '
In Cu2Cu2 . Cu is present as Cu+
4s = (-1.2 + 0.6) '= - 0.6 '
3d10
Cu+ = [Ar] 24. (A) Key Idea the absorption of visible light, presence of
unpaired d-electrons is the necessity.
Due to absence of unpaired electrons, Cu 2 C 2 is (A) In [Ni (CN)4]2- Ni is present as Ni2+
colourless. Ni2+ , Ni is present as Ni2+
22. (B) Key Idea Complexes of [MA4B 2] type exhibit Ni2+ = [Ar] 3d8 4s0
geometrical isomerism. ? [Ni(CN4]2-
3d 4s 4p
The complex [Co (NH3)4 Cl2]+ is a [MA4B2 ] type complex
and thus, fulfills the conditions that are necessary to ×× ×× ×× ××
exhibit eometrical isomerism.
The complex [Co(NH3)4 Cl2]+ is a [MA4B2] type complex Dsp2 hybridisation
and thus, fulfils the conditions that are necessary to (Pairing occurs because CN- is a strong field ligand).
exhibit geometrical isomerism. Hence, it has two Since, in [Ni(CN)4]2-, no unpaired electron is present in
geometrical isomers of different colours as : the structure d- orbitals so it does not absorb visible light.
of the geometrical isomers is as (B) In [Cr (NH3)6]3+, Cr is present as Cr3+
Cl Cl
H3N
Cl
H3N NH3 Cr3+ =[Ar] 3d34s0 (Three unpaired electrons)
(C) In [Fe(H2O6)3+ , Fe is present as Fe2+
Co Co
[Ar]3d6 4s0 (Four unpaired elections)
NH3
H3 N
H3N NH3
(D) In [Ni (H2O)6]2+ , Ni is present as Ni2+
NH3 Cl
Cis -form Trans -form Ni2+ [Ar]3d8 4s0 (Two paired electrons)
For linkage isomerism, presence of ambidentate ligand The complex given in option (B), (C),(D) have unpaired
is necessary. electrons, thus absorb visible light.
For coordination ismerisem, both the cation and anion NOTE :
of the complex must be complex ions. In presence of NH3 and H2O pairing does not occur as
For ionisation isomerism, an aniom different to the they are stronge field ligand.
ligands must be present outside the coordination sphere.
All these conditions are not satisfies by this complex. 25. (B) The complex is square planar and is of the type [M
Hence.it does not exhibit other given isomerisms. (abcd)]. It has three geometrical isomers.
Py NH3 Py Br
23. (D) Key Idea In case of high spin complex 'is small.
than the pairing energy. That means. the energy required Pt Pt
to pair up the fourth electron with the electrons of lower
Cl Br ; Cl NH3 ;
energy d-orbitals would be higher than that required to
Py NH3
place the electrons in the higher d-orbital. Thus, pairing
does not occur. Pt
For high spin d4 octahedral complex.
Br Cl

183
CHEMISTRY FOR NEET & AIIMS
26. (A) The complexes [Co (NH3)6 ] [Cr (CN)6] and [Cr (NH3)6] 4s 4p 4d
[Co (CN)6] are the examples of coordination isomerisms.
this isomerism occurs only in those complexes in which ×× ×× ×× ×× ×× ××
both cation adn anionare complex. It occurs due to
exchane of ligands between cotaion and anion Sp3d2 hybridisation

Thus, it is also an outer obrbital complex as it involve 4d-

27. (A) Electronic congfiguration of Ni2+ in [Ni (CN)4]2- is
orbitals for bonding but it is diamagnetic as all the
Ni2+ = 3d8 4s0
electrons are paired.
(C) In [Cr )NH3)6]3+
3d 4s 4p
Cr3+ = [Ar] 3d3
Ni2+ has dsp2 hybridisation, as CN- is a strong field ligand. [Cr(NH3)6]3+ =

3d 4s 4p

×× ×× ×× ×× ×× ×× ×× ××
××
- -
CN CN
-
CN
-
CN 2 3
Three d sp hybridisation
unpaired
28. (A) Outer orbital complex utilises (n-1) d-orbitals for electrons

bonding and exhibit paramagnetic behaviour, only if there

Because of the involvement of (n-1) d. i.e 3d- orbital in
present unpaired electrons.
hybridisation. it is an inner orbital complex. its nature is
(A) In [Ni (NH3)6]2+
paramagnetic because of the presence of three nupaired
Ni2+ = [Ar] 3d8 4s0 electrons.
3d 4s (D) In [Co(NH3)6]3+ :
Co3+ [Ar] 3d6
3d
3d

[Ni(NH3)6] = 2+

Two
Unpaired [CO (NH3)6]3+ =
electrons

4s 4p 4d 3d 4s 4p

×× ×× ×× ×× ×× ×× ×× ×× ×× ×× ×× ××
2 3
Ds p
Sp3d2 hybridisation
ŸInner orbital complex
So, this is an outer orbitl complex as it involve 4d- orbitals
for bonding. but having paramagnetic character. Because of the involvement of (n-1) d orbital in
(B) In [Zn (NH3)6] : 2+ hybridisation. it is an inner orbital complex. As all the
Zn2+ =[Ar] = (Ar) 3d10 electrons are paired, it is a dimagnetic complex.
3d
29. (A) Magentic moment, P is related with number of
unpaired electrons as

P n  n  2 BM
[Zn (NH3)6] 2+
(1.73)2 = n (n+2)
3d
On solving n = 1
Thus, the complex / compound having one uppaited
electron exhibit a magnetic moment of 1.73 BM

184
 COORDINATION COMPOUNDS
(A) In [Cu(NH3)4]2+ CFSE = [(-0.4 × 4)+(2×0.6)]
CU = [Ar] 3d
2+ 9
= - 0.4

32. (D) Key Concept When complex ion is an anion, the

name of the metal ends with suffix -ate along with its
(Although in the presence of strong field ligand NH3 the oxidation number in the complex ion.
unpaired electron gets excited to higher energy level but [Fe(CN)6]3- = Hexacyanoferrate (III) ion
it still remains unpaired )
33. (B) Given complex compound is [ M(en)2(C2O4)] Cl
(B) In [Ni (CN)4]2- let oxidation number of M is x.
Ni2+ = [Ar] 3d8 ? x-2-2=-1
or x=33
Now, as coordination number is defined as the total
But CN being strong field ligand pair up the unpaired
- number of binding sites attached to the metal. Hence, in
electrons and hence in this complex, number of unpaired the given complex coordination number is 6.
electrons =0
34. (A) [Ni (CN)4]2-
(C) In (TiCl4]
Let oxidation state of Ni in [Ni (CN)4]2- is x.
Ti4+ = [Ar]
? x-4=-2
(D) In [CoCl6]4-
or x=2
Co2+ = [Ar] 3d7
Now, Ni2+ = [Ar] 3d8 4 s0 d

It contains three unpaired electrons. 3d 3s 4p

Thus, [Cu(NH3)4] is the complex that exhibits a magnetic

2+
'
CN- is a strong field ligand. Hence, all unpaired
moment 1.73 BM. electrons are paired up.
30. (B) Cis - plath in known as anticancer agent. The formula 3d 3s 4p
of cis-platin is cis [PtCl2 (NH3)2]. Here, the word cis refers
to cis geometrical isomer of [PtCl2 (NH3)2]. it is used as
an antitumour agent.
CN
-
CN- CN
-
CN-

31. (B) The CFSE for octahedral complex is given by ? Hybridisation of ) [Ni (CN)4]2- is dsp2
CFSE = [-0.4t2 ge- + 0.6 ege-]
35. (C) [Co (en)2 Cl2]
For Mn 3 ,[3d 4 ] o t 32 e1g Cl
Cl Cl Cl
? CFSE = [(-0.4 ×3) +(0.6 ×1) = -0.6]
En Co en Co En
For Fe3+ , [3d6] o t 32 eg2
en Cl
CFSE = [-(0.4 ×3) + (0.6 ×2)] = 0 Cis trans
Optically active Optically inactive
For Co2+ , [3d7] t 52 eg2 Stereoisomers =2 Stereoisomers =2
Hence, total number of stereoisomers = 2+1 =3
CFSE = [ (-0.4 ×5) +(2×0.6)]
= - 0.8

For Co3+, [3d6]o t 42 eg2

185
CHEMISTRY FOR NEET & AIIMS
36. (A) [Co(CN)6]3-
Co3+ = 1s2 2s2 2p6 3s23p6 3d6
40. (C)
CN- is a strong field ligand and as it approaches the
metal ion, the electrons must pair up.
The splitting of the d-orbitals into two sets of orbitals in y Z Z
an octahedral [Co (CN)6]3- , may be represented as dxy dzyx dzx

Thus, dxy ,dyz and dyz orbitals have maximum electron

3d e2g orbital
density between the axis
dx2 -y2 dz2 '0

t2g orbital Y
Z
dxy dyz dxz

Here, for d6 ions, thee electrons first enter orbitals with Y

parallel spin put the remaining may pair up in t2g orbital X
giving rise to low spin complex (stronge) ligand) field X

? [Co(CN)6]3- has no unpaired electron and will be in a

low spin configuration. dz2
dx2-y2

37. (A) [Co (NH3)6 Cl3] o [Co (NH3)6]3+ +3CI-

[Co (NH3)3 Cl3] o [Co (NH3)3 +CI3] dx2 and d x2-y2 orbitals have maximum electron density
along the axes.
[Co (NH3)4 Cl2]Cl o [Co (NH3)4 Cl2]+ +CI-
[Co (NH3)5 Cl Cl o [Co (NH3)5]2+ +2CI- 41. (B) As negative charge on metal carbonyl complex
So, [Co (NH3)5 Cl Cl2@ does not ionise so does not give increases, back S -bonding increases and hence bond
test for chloride ions. legth of C-O bond increases while bond length of metal-
carbon bond decreases.
38. (B) Key Idea Jahn-Teller distortion is observed in those
Hence, [Fe(CO)4]2- has longest C-O bond length among
octahedra complexe in which d-electrons are filled
the given complexes.
unsymmetrically.
[Mn(CO)6]+ < [Ni(CO)4] < [Co(CO)4]- < [Fe (CO)4]2-

eg eg 42. (C) [Mn (CN)6] 3- is d2sp3 - hybridised and octahedral

complex. In [Mn (CN)6]3- Mn is in +3 ixudatuib state Mn3+
t2g t2g =3d4 4s0
d4 d7
3d 4s 4p
Orbitals of
Eg eg Mn3+ ion =
3d 4s 4p
3-
t2g t2g [Mn(CN)6] =
9
d8 d
d2sp3 -hybridised
Except d3, all are unsymmetrically filled, thus d8 complex (Octahedral)
will not show jahn-Teller distortion

39. (B) Trans effect is the effect of a coordinated group 43. (A) Key concept Weavlegth (O) of absorption is inversely
upon the rate of substitution at the position trans to proportional to CFSE ('0value) of ligands attached with
itself in a square or octahedral complex. As the rate of the central metal ion
substitution of the trans ligand increases. the intensity
of trans effect also increases . Thus, correct order is 1
i.e O v '
0
CN  ! C6H 5 ! Br  NH 3

186
 COORDINATION COMPOUNDS
According to spectochemical series 46. (C) [MA2 (a – a)2] geometrical & Optical
I < Br < S < SCN < CI < F < OH
- - 2- - - - -

 C 2 O 42   O 2   H 2 O  NSS  NH 3  en  NO 2  CN  47. (B) Ni (CO)4

Strong 3d10 4sq 4pq

Weak field Increasing order of '0 field  

ligands ligands sp3

The CFSE of ligands attached with Co3+ ion is in the

48. (B) Fe(CO)5 Only one central metal atom
order
en > NH3> > H2O (From spectrochemical series)
' For ligand the order of wavelength of wavelength of
absorption in the visible region will be : en < NH3 < H2O
or, [Co(en)3]3+ < [Co(NH3]6]3+ < [Co(H2O)6]3+

44. (C) According to Wener’s theory

CoCl3 . 6NH3 o [Co (NH3)6]3+ 3CI-
CoCl3 . 5NH3 o [Co (NH3)5]2+ 2CI-
CoCl3 . 4NH3 o [Co (NH3)4]+ CI-
When AgNO3 in excess in treated with these complexes
then following reactions takes place:
3
[Co(NH3 )6 ]3 3CI   AgNO3 o 3AgCl  [Co(NH3 ) 6 ]
(Excess)

2
[Co(NH3 )CI]2  2CI   AgNO3 o 2AgCI  [Co(NH 3 ) 5 Cl]
(Excess)

[Co(NH 3 )CI2 ]2  CI  AgNO3 o AgCI  [Co(NH 3 ) 4 Cl 2 ]

(Excess)

45. (B) The organometallic compounds having sigma bond

between carbon and metal are sigma bonded
organometallic . An example of a sigma bonded
organometallic compound is Grignard’ reagent.

R  Mg  X

 

V bond

Whereas, rnthenocene, ferrocene and cobaltocene are

not sigma bonded organometallic compound.

Ru Fe Co

Rethenocene Cobaltocene
Ferrocene

187
CHEMISTRY FOR NEET & AIIMS
8. (B) : [Co(en)3]Cl3
EXERCISE
3+
en 3+ en
P-2 (AIIMS)
1. (C) : [Cu(NH3)4]2+, Cu2+ o 3d94s0 en en
3d 4s 4p
en en
[Cu(NH3)4] o 2+
xx xx xx xx
mirror
dsp2 cis-[Co(en)2Co2]Cl
square planar +
+ en
One electron is shifted from 3d to 4p orbital. en
Cl Cl
2. (B) : cis-[PtCl2(NH3)2] is used as an anti-cancer agent, Co Co
called as cis-platin and is highly toxic. On injecting, the
Cl Cl
more reactive Cl groups are lost so the Pt atom bonds to en
en
a N atoms in guanodine (part of the DNA molecule).
Those cells which are undergoing cell division are mirror
attacked by cis-platin. 9. (A) :
3. (A) : Carbon monoxide is S - acid ligand as it characterises [Ni(CN)4]2- xx xx xx x x
both metal to carbon and carbon to metal bonding. The diamagnetic
latter is known as S-acidic character.
[NiCl4 ]2- xx xx x x x x

4. (B) : Ag+ of AgCN is soluble in excess cyanide ion to paramagnetic

form [Ag(CN)2]– complex. 2-
[CoCl4 ] xx xx x x x x

H3N Cl paramagnetic
5. (A) : Pt is not an organometallic compound [CoF6]2- xx x x xx xx x x xx
H3N Cl
paramagnetic
as it does not contain carbon-metal bond.
cis-Platin is an inorganic compound, used as an anti- 10. (A) : The absorption of energy or the observation of
cancer drug and falls into calls of DNA damaging agents. colour in a complex compound depends on the charge of
the metal ion and the nature of the ligands attached. The
6. (A) : Optical isomerism is very common in octahedral same metal ion with different ligands shows different
complexes of general formulae, absorption depending upon the type of ligand. The
[Ma2b2c2]n ±, [MaBcdef ], [M(AA)3]n ±, [M(AA)2a2]n ±, presence of weak field ligands make the central metal ion
[M(AA)a2b2]n ±, [M(AA)2ab]n + and [M(AB)3]n +, to absord low energies i.e., of higher wavelength. The
where AA is symmetrical bidentate ligand and AB is strength of ligands can be obtained from spectrochemical
unsymmetrical bidentate ligang. series. i.e. (Weak field) I– < Br– < S2– < Cl– <NO3– < F– < OH–
Octahedral complex of the type Ma4b2 and Ma3b3 exhibit < H2O < NH3 < NO2– < CN– < CO (strong field)
geometrical isomerism.
11. (B) : Spin only magnetic moment, Ps n(n  2) where,
7. (C) : CoCl2 is a weak Lewis acid, reacting with chloride n = number of unpaired electrons.
ion to produce salt containing the tetrahedral [CoCl4]2–
ion. CoCl2 is blue when hydrated, for this reason it is Number of unpaired electrons in Cr2+ ([Ar] 3d4) is 4, in
widely used as an indicator for water. Co2+ ([Ar] 3d5) is 5.
As the number of unpaired electrons in Cr2+ and Fe2+ are
same, hence [Cr(H2O)6]2+ and [Fe(H2O)6]2+ will have same
magnetic moment.
12. (C) : [Co(C2O4)2(NH3)2]–

188
 COORDINATION COMPOUNDS
ox ox So, [Cu(NH3)4]2+ is paramagnetic.
NH3 H3N
[NiCl4]2– : x
x
x
x
x
x
x
x
Co Co
sp3
NH3 H3N No. of unpaired electrons = 2
ox ox
So, [NiCl4]2– is paramagnetic,
cis-isomer (1) cis-isomer (2)
mirror [PtCl4]2– : x
x
x
x
x x
x x
(d-and l-form)
NH3
dsp2
No. of unpaired electrons = 0
So, [PtCl4]2– is demagnetic.
ox Co ox
x x x x
[Cu(H2O)4]2+ : x x x x

sp3
NH3
No. of unpaired electrons = 1
trans-isomer (3)
So. [Cu(H2O)4]2+ is paramagnetic.
13. (C) : In presence of either strong field or weak field, the 21. (A) : Except Ag(l). all ions form stable complexes with
number of unpaired electron remains the same in case of CN–.
Cu2+ ion. 22. (A) :
Cu o 3d104s1 Complex Coordination no.
Cu2+ o 3d9 Co2(CO8) 4
Mn2(CO)10 5
14. (B) : When NH4OH is added to the solution containing [Fe(en)2NH3] 5
Cu2+ ions, deep blue solution is obtained. [Cr(OH)3(NH3)3] 6
Cu2+ + 4NH4OH o [Cu(NH3)4]2+ + 4H2O
deep blue solution 23. (A) :
Hydrated cupric compounds absorb radiations [Ni(CN)4]2– : xx xx xx xx

corresponding to red light and the transmitted colour is Diamagnetic

greenish blue (which is complementary to red colour). [NiCl4]2– : xx x x x x xx
Thus, cupric compounds give greenish-blue colour. Paramagnetic
15. (B) : Blue to pink [CoCl4]2– : xx x x x x xx

Paramagnetic
[CoF6]2– : xx x x x x xx xx xx
16. (D) : Fe Paramagnetic
Ferrocene 24. (C) : [Fe(C2O4)3]3– is the most stable complex due to
17. (A) : Cis-Platin is effective in curing cancer chelate formation as C2O42– is a bidentate chelating ligand.
H3N Cl 25. (D)
Pt
H3N Cl 26. (D) : The optical isomers are pair of molecules which are
18. (C) : The complex PtCl 4 .5NH 3 is designated as non superimposable mirror images of each other.
[Pt(NH3)5Cl]Cl3 which ionizes to [Pt(NH3)5Cl]3+ + 3Cl– ions.
en
Thus, total ions produced are four but three moles of
AgCl are produced from 3Cl– ions with AgNO3.
19. (A) : As in complex [Co(NH3)5Cl]2+, Cl– is present as en
en Co Co
ligand which is weakest among ligands present in other
complexes, so it requires less energy for excitation. Thus,
the wavelength of light absorbed will be highest (i.e., E
v 1/O).
en
20. (C) : [Cu(NH3)4]2+ en
x x x x 3+
x x x x [Co(en)3] [Co(en)3]
3+

dsp 2
(dextro) (laevo)
No. of unpaired electrons = 1 The two optically active isomers are collectivily called
enantiomers.

189
CHEMISTRY FOR NEET & AIIMS
27. (B)
37. (A)
28. (A) : Diamagnetic complex is are
[Co(Ox)3]3– and [Fe(CN)6]3– 38. (A) : Fe+ : [Ar] 3d6 4s1
29. (A) : V(CO)6 easily reduces to [V(CO)6]– When the weak field ligand H2O and strong field ligand
No attack, the congiuration changes as follows :
30. (C) : Due to high electronegativity of F-atoms, the lone Fe+ : [Ar] 3d7 4s0
pair of N-atom is NF3 molecule cannot be ligated easily.
Whereas in N(CH3)3, CH3 group is a electron releasing
group, thus lone pair of N-atom in N(CH3) molecule can 3d7
be ligated easily. ? Fe+ has 3 unpaired electrons.
.. .. 39. (B) : EDTA is a hexadentate ligand. It forms complex with
central metal in the ratio 1 : 1 in which it binds through
tow nitrogen atoms and four oxygen atoms.
N N
40. (A) : Cd2+ + 2CN– o Cd(CN)2–
F F CH3 CH3 Cd(CN)2 p + 2CN– o [Cd(CN)4]2–
F CH3
[Cd(CN)4]2– is colourless compound and not too stable.
Except, nitrogen fluoride, all other halides hydrolyse in When hydrogen sulphide gas is added, cadmimum
water. sulphide is precipitated.
NCl3 + 3H2O o NH3 + 3HClO [Cd(CN)4]2– is colourless compound and not too stable.
31. (D) : [Ni(en)3]Cl2 is a chelating compound and chelated when hydrogen sulphide gas is added, cadmium sulphide
complexes are more stable than similar complexes with is precipitated.
unidentate ligands as dissociation of the complex [Cd(CN)4]2– + H2S o CdSp + 2H+ + 4CN–
involves breaking of two bonds rather than one. But in case of Cu2+,
In [Ni(en)3]Cl2, Ni with d8 configuration shows octahedral Cu2+ + 2CN– o Cu(CN)2p
geometry. Six electrons will occupy the t2g orbitals and Quickly
two electrons will occupy the eg orbitals. 2Cu(CN)2p decompose
2CuCNp + (CN)2 n
32. (A) : The essential requirement for a substance to be CuCNp + 3CN o [Cu(CN)4]3–
–

optically active is that the substance should not have a This complex is so stable (i.e., [Cu+] is too low) that H2S
plane of symmetry in its structure. cannot precipitate Cu(I) sulphide (Cu2S).
33. (A) : C – O bond in metal carbonyl is long as ligated CO 41. (A)
has lower bond order. The lower B.O. is due to the
42. (C) : Co[Hg(SCN)6] and Hg[Co(SCN)6] are ionisation
transfer of metal dS electrons into the S* orbitals of ligated
isomers. NCS– is stronger than SCN–.
CO.
[ eg
43. (B) : Both Assertion and Reason are true but Reason is
not the correct explanation of statement-1. [Fe(CN)6]3– is
weakly paramagnetic as it has unpaired electrons while
[Fe(CN)6]2– has no unpaired electron. 'It is diamagnetic.
d-orbitals 44. (C) : It is correct statement that NF3 is a weaker ligand
34. (C) : than N(CH3) 3, the reason is that fluorine is highly
[ t2g
electronegative therefore, it with draw electrons from
d-orbital splitting in an
nitrogen atom. Hence, the lone pair ofnitrogen atom
octahedral crystal field
? In high spin situation, '0 < P, in d5 configuration, 4th cannot be ligated. While N(CH3)3 is a strong ligand
and 5th electron are added to eg rather than t2g. So, because CH3 is electron releasing group.
configuration of d5 ion will be t32 g e2g . 45. (D) : Zieses salt :
Cl
35. (A) H2C
3+ Pt Cl
NH H2C
Cl
36. (A) : (en)2 Co Co(en)2 is named as tetrakis Co-ordination no. is 4
OH Ethane is monodentate
(ethylenediamine)-μ-hydroxo-μ-imido dicobalt (III) ion.
For more than one bridging group the word μ is repeated
before each bridging group.

190
METALLURGY
CHAPTER
09
All parts of the material universe are in constant motion and though
some of the changes may appear to be cyclical, nothing ever exactly
returns, so far as human experience extends, to precisely the same
condition.

''JOSEPH HENRY''

INTRODUCTION

T
he branch of chemistry which deals with the method of extraction of metals from their
ores. A few elements like carbon, sulphur, gold and noble gases, occur in free state
while others in combined forms in the earth’s crust. The extraction and isolation of an
element from its combined form involves various principles of chemistry. A particular
element may occur in a variety of compounds. The process of metallurgy and isolation
should be such that it is chemically feasible and commericially viable. Still, some
general principles are common to all the extraction processes of metals. For obtaining
a particular metal, first we look for minerals which are naturally occurring chemical
substances in the earth’s crust obtainable by mining. Out of many minerals in which
a metal may be found, only a few are viable to be used as sources of that metal. Such
minerals are known as ores.
Rarely, an ore contains only a desired substance. It is usually contaminated with
earthly or undesired materials known as gangue. The extractin and isolation of metals
from ores involve the following major steps:
y Concentration of the ore,
y Isolation of the metal from its concentrated ore, and
y Purification of the metal.
The entire scientific and technological process used for isolation of the metal
from its ores is known as metallurgy.

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CHEMISTRY FOR NEET & AIIMS
Metal
The element which tends to form positive ion is called a metal.

Minerals
The various compounds of metals which occur in the earth's crust and are obtained by mining are called minerals.
In earth crust order of abundance of elements is. O > Si > Al > Fe
A mineral may be single compound or a mixture of compounds having fixed chemical composition.

Ore
The mineral from which a metal can be profitably and easily extracted is called an ore.
Types of Ores :
(i) Combined Ore : Metals placed above H in electrochemical series are generally reactive i.e. why they generally
found in combined state.
(a) Halide ore / Sulphate ore / Oxy ore : Metals are highly reactive (Li o Mg)
(b) Oxide ore : Reactive metal (Al to Sn)
(c) Sulphide ore : Metal placed near H or below H. (Pb, Hg, Cu, Ag)

(ii) Native Ore : Metal placed below H in electrochemical series are generally found in native state.
(Ag, Au, Cu, Pt etc.)

Gangue or Matrix
The undesirable impurities present in an ore are called gangue.

Mining Process
Process of taking out ore from earth crust is called mining.

Types of Metallurgy
(a) Pyro Metallurgy : Extraction of metal from ore by using heat energy.
Steps involved are : Calcination, roasting, reduction etc.
Ex. Less reactive metals : Cu, Fe, CO, Ni, Zn, Sn, Pb etc.
(b) Hydro Metallurgy : (Ag, Au, Cu) – This is wet metallurgy process.
Cu o Pyro + Hydro
Ag and Auo By cynide process.
Steps are : (i) Complex formation (ii) Metal displacement
(i) AgCl or AuCl NaCN Na[Ag(CN)2]
(Sodium argento cynide)
(ii) 2Na [Ag(CN)2] Zn Agp + Na2 [Zn(CN)4]
(Impure)
(c) Electrical Metallurgy : This process used for highly electro positive metal (s-block and AA) metal obtained by
electrolysis of fused salt/anhydrous medium. Ex. - IA, IIA, IIIA
(d) Ion Exchange Metallurgy : Trans-Uranic (elements after Uranium in periodic table) elements are obtained by
this method.

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 METALLURGY
Steps Involved in The Extraction of Metals
The extraction of a metal from its ore is completed in the following four steps.
(I) Concentration of the ore (II) Conversion of concentrated Ore into Oxide form
(III) Reduction to the metal (IV) Refining of the metal.

(I) Concentration of the ore

The removal of impurities from the ore is called its concentration. It is carried out in one or more of the following
steps. These undesired impurity are gangue or matrix.
By physicals separation :
(a) Gravity Separation (Lavigation)
This method of concentration of the ore is based on the difference in the specific lavigation gravities of the ore
and the gangue particles.
Powdered ore is agitated with a running stream of water. The lighter gangue particles are taken away by water
while heavier ore particles settle down. Ex. Oxygenated Ores.
(b) Froth Floatation Method
This method is mainly employed for the concentration of sulphide ores.
The method is based on the different wetting characteristics of the gangue and the sulphide ore with water and
oil. The gangue preferentially wetted by water and the ore by oil.
The crushed ore along with water is taken in a floatation cell. Various substances are added depending on the
nature of the ore and a current of air is blown in. The substances added are usually of three types.
(i) Frothers
They generate a stable froth which rises to the top of the tank. Example of frother is pine oil, Eucalyptus oil,
etc.
(ii) Collectors or Floating Agents
These attach themselves by polar group to the grains of the ores which then become water repellant and
pass on into the froth. Example: sodiumethyl /ethyly xanthate.
(iii) Activators or Depressants
These reagents activate or depress the flotation properly and help in the separation of different sulphide
ores present in a mixture.
An example of depressant is NaCN. An activator is CuSO4.
(iv) Froth stabliser : To stablise froth.
Ex. cresol , Aniline etc.
(c) Magnetic Separation
If the ore and not the gangue or the gangue and not the ore is attracted by a magnet, the two can be separated
by this method.
Magnetite (Fe3O4) is concentrated by this method,(FeWO4) wolframite removed from SnO2, FeO removed
from chromite (FeCr2O4 Ÿ Cr2O3˜FeO).

By Chemical separation :
Some of the ores are concentrated by means of chemical treatment.
Leaching : It involves the treatment of the ore with a suitable reagent. as to make it soluble while impurity remain
insoluble. The ore is recovered from the solution by suitable chemical method.

(a) Aluminium :

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CHEMISTRY FOR NEET & AIIMS
(I) RED BAUXITE : Two processes
(i) Bayer's Process
Ex. Bauxite ore contain impurity Fe2O3, TiO2, SiO2 when it dissolve in aq. NaOH/pressure + 150°C T bauxite is
dissolve but other are not dissolve.
Al2O3 + 2NaOH o 2NaAlO2 + H2O
NaAlO2 + 2H2O o Al(OH)3 + NaOH

'
Al2O3 + 3H2O

(ii) Hall’s Process : Na2CO3 is used.

HOH
Al2O3 + Na2CO3 o 2NaAlO2 CO2
Al(OH)3 + Na2CO3

(II) WHITE BAUXITE : One processes.

(i) Serpek’s process : (C+N2) is used.
H2O
Al2O3 + N2 AlN Al(OH)3 + NH3 n

C + SiO2 o CO2n + Sin .

(ii) Cyanide Process : Their process used for Au, Ag by (Mac-Arthur forrest cyanide process).
(i) Ag Ag2S + 4NaCN 2 o 2Na [Ag (CN)2] + Na2SO4 [in absence of O2, reaction become reversible]
2O

2Na[Ag(CN)2] + Zn o Na2[Zn (CN)4] + 2Agp

(ii) Au Au + KCN + H2O  o K [Au (CN)2] + KOH
O2

K[Au (CN)2] + KOH + Zn o K2 ZnO2 + KCN + H2O + Aup

(II) Conversion of concentrated ore into oxide form

Calcination :
Calcination is a process in which ore is heated, generally in the absence of air, to expel water from a hydrated oxide
or carbon dioxide from a carbonate at temperature below their melting points.
For Example (All carbonate, hydrated ore and hydroxide ore)
(i) Al2O3. 2H2O o Al2O3 + 2H2O,2Al(OH)3 oAl2O3 + 3H2O (Bauxite)
(ii) 2Fe2O3. 3H2O o 2Fe2O3 + 3H2O (Haematities)
(iii) CaCO3 oCaO + CO2 (Lime stone)
(iv) CaCO3. MgCO3 oCaO + MgO + 2CO2n
(v) MgCO3 o MgO + CO2n (Magnisia alba)
(vi) ZnCO3 oZnO + CO2n (Calamine)
(vii) FeCO3 o FeO + CO2n (Siderite)

Advantages of Calcination :
y Moisture is removed.
y Organic matter is destroyed
y The hydroxide and carbonates ores are converted into their oxides.
y The metal become porous and easily workable

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 METALLURGY
ROASTING
(Metal sulphides o Metal oxide + SO2)
The removal of the excess sulphur contained in sulphide ores by heating in an excess of air is called roasting.
The concentrated sulphide ore is heated in reverberatory furnace, below its melting point or fusion temperature in
the presence of an excess of air with or without the addition of an external substance.
In roasting definite chemical like oxidation, chlorination etc. take place but in calcination does not occur any major
chemical changes.
(i) 2ZnS + 3O2 o 2ZnO + 2SO2
(ii) ZnS + 2O2 o ZnSO4
(iii) 2PbS + 3O2 o 2PbO + 2SO2
(iv) PbS + 2O2 o PbSO4

Thermal reduction
Some less stable metal oxide further decompose into metal and oxygen.

1
Ag2O  o 2Ag  O 2 n
300q C
Ag2S + O2
2

1
HgS + O2 HgO 
400q C
o Hg  O 2
2

Partial roasting

2CuFeS2 + O2

Cu2O 2FeO
after roasting Cu2S + FeS + Cu2O + FeO

Roasting in Fe metallurgy
Fe2O3 + FeO
Haematite
Fe3O4 = Fe2O3 + FeO
Magnetite

FeCO3  o FeO + CO n
'
2
Siderite
Roasting o to prevent wastage of Fe as slag in reduction step

1
2FeO  O 2 o Fe 2 O3 (It does not form slage)
2

In reduction step FeO  SiO 2 FeSiO 3

(Flux ) (Impurity) (Slage)

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CHEMISTRY FOR NEET & AIIMS
Advantages of Roasting
y Excess of sulphur is removed as volatile oxide.
S + O2 o SO2 n
(air)
y The metal sulphide is converted into metal oxide.
y Impurities of arsenic and antimony are removed as their volatile oxides.
Sb4 + 3O2 o 2Sb2O3
As4 + 3O2 o 2As2O3

(III) Reduction of Ore to the Metal

The calcined or roasted ore is then reduced to the metallic state in either of the following ways.
(A) Reduction by Carbon (Smelting) : (This is common method of reduction)
"Reduction of the oxide with carbon at high temperature is known as smelting".
The oxides of less electropositive metals like Pb, Zn, Fe, Sn, Cu etc. are reduced by strongly heating them with
coal or coke, in the blast furnace.
Slag : Fusible metarial during reduction process.
Slag : Gangue + substance (for remove gangue)
Flux : Substance used to convert non fusible impurities into fusible one.

KEY POINTS

Three types of flux :

(a) Acidic Flux : Substance used to remove basic impurities (metal oxide)
For example CaO  SiO 2 o CaSiO 3
( basic impurity) (acidic flux ) (Slag)

Acidic flux are non metal oxide (SiO2, P2O5 etc.)

(b) Basic flux : Substance used to remove acidic impurities (non metal oxide)
From example

Basic flux are metal oxide. (CaO, MgO, etc.)

(c) Neutral flux : Substance used in electrolytic reduction to decrease the fusion temperature and to increase the
conductivity of the solution by providing free ions.
For example (Na 3 AlF6  CaF2 ), CaCl2 etc.
Cryolite Flourspar

Smelting :
y Concentrate ore (ore + gangue) + RA (carbon) + Flux (RA Ÿ Reducing agent)
p
Metal + Slag + gases

}
Cr2O3
y Mn3O4 Carbon is not used
MnO2 for reduction
y Coke is not used for reduction of s-block oxide Al2O3 (due to formation of metal carbides)
CaO + 2C oCaC2 + CO

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 METALLURGY
Some reactions
(i) CuO + CO o CO2 + Cu
PbO + C o Pb + CO
Fe2O3 + 3C o Fe + 3CO
ZnO + C o Zn + CO
ZnO + CO o Zn + CO2
(ii) (gangue) acidic impurity (flux) (slag)
SiO2 + CaCO3 o CaSiO3 + CO2 n
P2O5 + 3CaO o Ca3 (PO4)2
(iii) Basic impurity + Flux o slag
MgCO3 + SiO2 o MgSiO3 + CO2 n
FeO + SiO2 o FeSiO3
Note : Blue flame is obtained by burning of CO in smelting process.

(B) Self Reduction :

Compounds of certain metals are reduced to metal without using any additional reducing agent. ores of Cu,
Pb, Hg etc.
Their sulphide ores are partially roasted to give some oxide. This oxide is now reduced to the metal by the
remaining sulphide ore at elevated temperatures in the absence of air. The process is known as self reduction.

Self Reduction for Pb

(i) 2PbS + 3O2 Roasting 2PbO + 2SO2 n
(Galena) (air)

High temp.
PbS + 2PbO Absence of air
3Pb + SO2 n
(unroasted ore) (roasted ore) (Self reduction)

'
(ii) 2Cu O + Cu S 
2 2 o 6 Cu + SO2

(C) Metal Displacement Method :

In this method, a water soluble compound is obtained from the ore. The aqueous solution of the compound
is reacted with a more electropositive metal which displaces, the metal from the solution.
(i) Ziervogel process for silver.
Ag2S + 2O2 85°C Ag2SO4
Argentite
Ag2SO4 (aq) + Cu o CuSO4 (aq) + 2Ag (S)
(Scrap Copper)
(ii) Separation Ag by Complex formation (Cyanide process)
Silver and gold are extracted by a method involving complex formation.
Ag2S + 4NaCN air 2Na [Ag(CN)2] + Na2SO4
(Powdered argentite)
2Na [Ag(CN)2] + Zn o Na2 [Zn(CN)4] (aq) + 2Ag p
Black ppt.

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CHEMISTRY FOR NEET & AIIMS
(D) Electrolytic Reduction :
This process is mainly used for the extraction of highly electropositive metals.
Electrolysis is carried out in a large cells and a small amount of another suitable electrolyte is added which:
(i) Lowers the melting point of the main electrolyte
(ii) Enhances its conductivity
(iii) Reduces corrosion troubles
Ex. Na, K, Mg, Ca, Al, etc.
e.g. Manufacture of metallic sodium (Down's process)
Molten NaCl containing a little CaCl 2 is electrolyzed between graphite anode and iron cathode. The
various reactions that take place are
On Fusion : NaCl Na+ + Cl– (Ions become mobile)
On Electrolysis : At Cathode : Na+ + e– o Na (reduction)
(Metallic sodium)
At Anode : 2Cl– o Cl2 (g) + 2e–

(E) Reduction by Al :
This process is employed in the case of those metals which have very high melting points and are to be
extracted from their oxides
Cr2O3 + 2Al o2Cr + Al2O3
3Mn3O4 + 8Al o9Mn + 4Al2O3

(IV) Purification or Refining of Metals

Metals obtained by reduction processes still contain some objectionable impurities and have to be refined. Numerous
techniques are available, including the following :
Physical methods :
These methods include the following processes :
(i) Liquation Process : This process is used for the purification of the metal, which itself is readily fusible, but the
impurities are infusible.
Examples : (a) Purification of impure tin metal
(b) Purification of crude zinc
(ii) Fractional Distillation Process : This process is used to purify those metals which themselves are volatile and
the impurities in them are nonvolatile and vice-versa. Zn, Cd and Hg are purified by this process.
(iii) Zone Refining Method (Fractional Crystallisation Method) : This process is used when metals are required in
very high purity. For example pure Si and Ge are used in semiconductors and hence are purified by this method.
Zone refining method is based on the principle that an impure molten metal on gradual cooling will deposit
crystals of the pure metal, while the impurities will be left in the remaining part of the molten metal.
(iv) Chromatographic Methods : This method is based on the principle that different components of a mixture are
differently adsorbed on an adsorbent. The mixture is put in a liquid or gaseous medium which is moved through
the adsorbent.

Chemical Methods :
These methods include the following methods :
(A) OXIDATIVE REFINING :
The method is used when the impurities present in the metal have a greater affinity for oxygen and are more readily
oxidized than the metal.

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 METALLURGY
(i) Bessemerisation (Purification of iron) :
The iron obtained from a blast furnace is a brittle material called cast iron or pig iron. Molten iron from blast
furnace is exposed to a jet of pure O2 gas for about 20 minutes in a furnace that is lined with basic oxide such as
CaO. The impurities in the iron are oxidized and the acidic oxides that form react with basic CaO to yield a molten
slag that can be poured off. Phosphorous, for example, is oxidized to P4O10, which then reacts with CaO to give
molten Ca3 (PO4)2.
P4(l) + 5 O2(g) o P4O10(l)

6 CaO (g) + P4O10(l) o 2 Ca3(PO4)2(l)

Basic oxide acidic oxide slag

(ii) Cupellation (Removal of Lead) :

In this process the molten impure metal is heated in a cupel, which is boat-shaped dish made of bone ash or
cement, and a blast of air is passed over the molten metal. The impurities are oxidized and the volatile oxides
thus produced escape with the blast of air. The pure metal remains behind in the cupel. Pb present in silver is
removed by cupellation process.
2 Pb(g) + O2 o 2 PbO(g)

(B) PARTING PROCESS :

Crude gold obtained by MacArthur-Forrest cyanide and chlorination process contains Ag, Cu, Zn, and sometimes
Pb as impurity. Zn and Pb are removed by cupellation process. Cu and Ag are removed by parting process.
(i) Parting with sulfuric acid or nitric acid: Gold is not attacked by these acids while Cu and Ag dissolve. If,
however, the Au content in an impure sample is more than 30%, the Cu and Ag are also not attacked by the acid
of any strength. Hence, before the acid treatment, the impure sample is melted with necessary amount of Ag to
reduce its gold content to about 25% (quartation). The resulting alloy, after being granulated in water, is boiled
with H2SO4 or nitric acid when Cu and Ag pass into solution, leaving Au undissolved . Au is separated and
fused again with borax and nitre when 100% Au is obtained.
(ii) Parting with CI2 : Sometimes chlorine is used for the purification of Au. The impure sample of Au is fused with
borax and CI2 gas is forced through it. The base metals are converted into chlorides that pass out as fumes at
this high temperature, and AgCI forms a separate layer between the fused layer of Au and borax, which is
skimmed off and the Au left behind cast into ingots.

(C) POLING PROCESS :

This process is used for the purification of copper and tin.
(i) Purification of Impure Copper : Impure copper is remelted in a reverberatory furnace lined with SiO2 and a blast
of O2 is blows into the furnace. O2 oxidises S, Sb and As to their respective oxides which, being, volatile, get
volatilised and are thus removed. Fe is oxidised to FeO which forms a slag of FeSiO3 with SiO2 lining of the
furnace. Molten copper left behind contains CuO as impurity. This molten copper is treated with powdered
anthracite and then stirred with a pole of green wood. Green wood, at high temperature, liberates hydrocarbon
gases, which are converted into methane (CH4). Methane thus obtained reduces CuO to free Cu–metal, which
is about 99.5% pure and is called tough pitch copper.
Green wood o Hydrocarbons o CH4
4CuO + CH4 o 4Cu (pure metal) + CO2 + 2H2O

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CHEMISTRY FOR NEET & AIIMS
(ii) Purification of Impure Tin : Impure tin metal contains the impurities of Cu, Fe, W and SnO2. The impurity of
SnO2 is due to the incomplete reduction of tin stone ore (SnO2) during smelting. In order to remove these
impurities, the impure molten tin metal is taken in a big pot and stirred with a pole of green wood. Green wood,
at high temperature liberates hydrocarbon gases, which are converted into methane CH4. Methane thus obtained
reduces SnO2 to pure metal while the impurities of Cu, Fe, W etc. come up to the surface, where they come in
contact with air and are oxidised to their respective oxides. The oxides form a scum on the surface of pure tin
metal. This scum is removed from the surface. Tin metal obtained by this method is 99% pure.
Green wood o Hydrocarbon o CH4
2SnO2 + CH4 o 2Sn + CO2 + 2H2O

(D) ELECTROLYTIC REFINING:

Some metals such as Cu, Ni, and Al are refined electrolytically. The Hooper process is a process for the electrolytic
refining of aluminum. Impure Al forms the anode and pure Al forms the cathode of the Hooper’s cell which contains
three liquid layers. The bottom layer is molten impure Al, the middle is a fused salt layer containing aluminum
fluoride, and the top layer is pure Al. At the anode (bottom layer), Al passes with solution as aluminum ion (Al3+),
and at the cathode (top layer), these ions are reduced to the pure metal. In operation, molten metal is added to the
bottom of the cell and pure aluminum is drawn off the top.
At anode : Al o Al3+ + 3e–

At cathode : Al3+ + 3e– o Al

Copper obtained from the reduction of ores must be purified for use in making electrical wiring because impurities
increase its electrical resistance. The method used is electro-refining.
Impure Cu obtained from ores is converted to pure Cu in an electrolyte cell that the impure copper as the anode an
pure copper as the cathode. The electrolyte is an aqueous solution of CuSO4. At the impure Cu anode, Cu is oxidized
along with the more easily oxidized metallic impurities such as Zn and Fe. The less easily oxidized impurities such as
Ag, Au, and Pt fall to the bottom of the cell as anode mud, which is reprocessed to recover the precious metals. At
the pure Cu cathode, Cu2+ ions get reduced to pure copper metal, but the less easily reduced metal ions (Zn2+, Fe2+
etc.) remain in the solution.
Anode (oxidation) : M (s) o M2+ (aq) + 2e– (M = Cu, Zn, Fe)

Cathode (reduction) : Cu2+ (aq) + 2e– o Cu(s)

Thus, the net cell reaction simply involves transfer of Cu metal from the impure anode to the pure cathode, Cu
obtained by this process is 99.95% pure.

(E) KROLL’S PROCESS :

TiCl4 + 2 Mg 10001500°C Ti + 2 MgCl2 (Kroll’s process)
TiCl4 + 4 Na under atmosphere of Argon Ti + 4 NaCl (Imperial metal industries (IMI) process)

NaCl is leached with H2O. Ti is in the form of small granules. Zr is also produced by Kroll’s process.
(F) VAPOUR PHASE REFINING :

(i) Extraction of Nickel (Mond’s process) :

Ni(s) + 4 CO(s) 50°C [Ni(CO4)] (g)
[Ni (CO)4](g) 200°C Ni + 4CO(g)

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 METALLURGY
(ii) Van Arkel–De Boer Process :
Small amounts of very pure metals (Ti, Zr, or Bi) can be produced by this method.
50 - 250°C 1400°C
Impure Ti + 2I2 TiI4 Tungsten filament
Ti + 2I2

(G) PARKES PROCESS :

The removal of the impurities of Ag from the commercial lead is called desilverisation of lead and is done by Parkes
Process . Thus, Parkes process is the desilverisation of lead.
In Parkes process, the commercial lead, which contains Ag as impurities, is melted in iron pots and 1% of Zn is added
to it. The molten mass is thoroughly agitated. Since Ag is about 300 times more soluble in Zn than in Pb, most of the
Ag present in the commercial lead as impurity mixes with Zn, to form Zn–Ag alloy. When the whole is cooled, two
layers are obtained. The upper layer contains Zn–Ag alloy in the solid state, while the lower layer has lead in the
molten state. This lead contains only 0.0004% of Ag and hence is almost pure. Lead obtained after removing most
of Ag from it (desilverisation of lead) by Parkes process, is called desilverised lead. This lead contains the impurities
of metals like Zn, Au, Sb etc. These metal impurities are removed from desilverised lead by Bett’s Electrolytic
Process.
Zn–Ag alloy, formed in the upper layer, is skimmed off from the surface of the molten lead by perforate ladles. This
alloy contains lead as impurity. This impurity of Pb is removed from the alloy by liquation process, in which Zn–Ag
alloy is heated in a slopping furnace, when the impurity of Pb melts and hence drains away from the solid alloy. Thus
purified Zn–Ag is obtained. Now Ag can be obtained from this purified Zn–Ag alloy by distillation process, in
which the alloy is heated strongly in presence of little carbon in a fire–clay retort. Zn, being more volatile, distills off
while Ag remains in the retort, carbon used in the process reuses the oxide of Zn, if formed. Ag obtained from Zn–
Ag alloy is contaminated with a little of Pb as impurity. This impurity of Pb placed in a cupel (cupel is a boat–shaped)
dish made of bone ash which is porous in nature) in a reverberatory furnace and heated in the presence of air. By
doing so, lead (impurity) is oxidised to PbO (litharge) which volatilises and pure Ag is left behind in the cupel. Last
traces of PbO are absorbed by the porous mass of the cupel.

(H) PUDDING PROCESS :

This process is used for the manufacture of wrought iron from cast iron. We know that cast iron contains the
impurities of C, S, Si, Mn and P. When these impurities are removed from cast iron, we get wrought iron. In this
process the impurities are oxidised to their oxides not by blast of air but by the hematite (Fe2O3) lining of the furnace.

Extraction of Some Metals

(I) Extraction of Copper
Copper is mainly extracted from copper pyrites. After the concentration of its ore by froth flotation process, the ore
is roasted in a current of air to remove arsenic, antimony and much of sulphur. The reactions occuring are
2CuFeS2 + O2 o Cu2S + 2FeS + SO2 n (major reaction)
2Cu2S + 3O2 o 2Cu2O + 2SO2
2FeS + 3O2 o 2FeO + 2SO2 (minor reactions)
The ore is then mixed with a little coke and sand and smelted in a water-jacketed blast furnace. The minor reactions
that occured during roasting continue here. Ferrous oxide combines with sand to form a fusible slag. Cuprous oxide
formed combines with ferrous sulphide to give ferrous oxide and cuprous sulphide. This is because iron has more
affinity for oxygen than copper.
FeO + SiO2 o FeSiO3 ; Cu2O + FeS o Cu2S + FeO

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CHEMISTRY FOR NEET & AIIMS
Molten mass collected from the bottom of furnace contains largely cuprous sulphide and a little ferrous sulphide.
This molten mass is known as matte.

Converter

SiO2 -- air
+ – + – + – +

Molten Matte

Bassemer Converter

The molten matte is finally transferred to Bessemer converter. A blast of sand and air is blown in the converter
through tuyeres which are situated a little above the bottom. This causes removal of S and As oxides and ferrous
oxide as slag. At the same time Cu2S is oxidized mostly into Cu2O and partly into CuO and CuSO4. All these react
with Cu2S giving copper.
The reactions are
2Cu2S + 3O2 o 2Cu2O + 2SO2 n
2Cu2S + 5O2 o 2CuSO4 + 2CuO
2Cu2O + Cu2S o 6Cu + SO2 n
CuSO4 + Cu2S o 3Cu + 2SO2 n
Cu2S + 2CuO o 4Cu + SO2 n
Finally, copper may be refined electrolytically (electrolyte; copper sulphate : anode; impure copper and cathode;
pure copper).

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 METALLURGY
(II) Extraction of Iron

Iron is extracted from its principal ore, heamatite. After the preliminary washing, concentration and roasting, the ore
is smelted in the presence of coke and limestone in a blast furnace.
Roasted ore (8 parts) with desulphurized coke (4 parts) and limestone pieces (1 part) is fed into the blast furnace from
the top. (Preheated air is blown in through water - jacketed pipes called tuyeres fixed in the lower part of the furnace).
There is a temperature gradient as we move from the bottom (temperature about 2000K) to the top (temperature
about 500K) of the blast furnace.

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CHEMISTRY FOR NEET & AIIMS
The blast furnace may be broadly divided into three main parts as described in the following.

Blast Furnace

(a) Zone of Fusion

The lower portion where coke burns and produced carbon dioxide and a lot of heating is known as zone of
fusion:
C + O2 o CO2 'H = –406 kJ mol–1
Here the temperature is about 1775 K. A little above this, where temperature is above this, where temperature
is about 1475 K – 1575 K, iron coming from above melts.

(b) Zone of Heat Absorption

The middle portion (temperature 1075 K – 1275 K), CO2 rising up is reduced to CO with the absorption of heat:
CO2 + C o 2CO 'H = 163 kJ mol–1
In this portion, limestone coming from above is decomposed and the resultant lime (CaO), which acts as flux,
combines with silica (present as impurity - gangue) to form calcium silicate (fusible slag) :
CaCO3 o CaO + CO2
CaO + SiO2 o CaSiO3

(c) Zone of Reduction

The upper portion (675K – 975 K) where iron oxide is reduced to spongy iron by carbon monoxide rising up to
furnace
Fe2O3 + 3CO o 2Fe + 3CO2

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 METALLURGY
The reduction is believed to take place in stages :
3Fe2O3 + CO o 2Fe3O4 + CO2
Fe3O4 + CO o 3FeO + CO2
FeO + CO o Fe + CO2
At the bottom of the furnace the molten iron sinks down while above this floats the fusible slag which protects the
molten iron form oxidation. These two can be removed from different holes (fig.). Waste gases escaping at the top
consists of about 30% CO, 10% CO2 and the rest nitrogen.
Iron obtained from the blast furnace is known as pig iron.
Pig iron contains about 2–5% carbon as well as other impurities (usually Si, Mn, S and P). Pig iron is converted into
cast iron by remelting in a vertical furnace heated by coke. Cast iron expands on solidification and is used for casting
various articles. Wrought iron, which is the purest form of iron can be obtained by heating cast iron in a reverberatory
furnace lined with iron oxide. Wrought iron contains about 0.2% carbon.

Types of Iron :
Cast Iron or Pig Iron
It is most impure form of Iron and contains the higest proportion of carbon (2.5 - 4 % ) along with traces of S, P,
Mn and Si. Cast iron contain 2.5 to 4.3 & pig contain 2.5 to 5%.
Wrought Iron (Fibrous Iron) or Malleable Iron
It is the purest form of iron and contains minimum amount of carbon (0.12 - 0.25%) and less than 5% of other
impurities.

(III) Manufacture of Steel : It is the most important form of iron and finds extensive applications. As far as carbon
content (impurity) is concerned it is mid-way between cast iron and wrought iron, it contains 0.25- 2% carbon.
Different method are used :–
(a) Bessemer Process
This process is based on the fact that impurity of the pig iron are completely oxidised in presence of hot air
blast.
This process involves the use of a large pear- shaped furnace (vessels) called Bessemer converter.
(b) BOP Method (Basic Oxygen Process)
The process is carried out in a steel vessel with a refractory lining (usually made of dolomite, CaCO3, MgCO3).
Oxygen gas at about 10 atm pressure and a stream of powdered limestone are fed through a water-cooled lance
and discharged above the molten pig iron.
2C + O2 o2CO
2FeO + Si o2Fe + SiO2
FeO + Mn oFe + MnO
FeO + SiO2 oFeO. SiO2
MnO + SiO2 oMnO.SiO2 (slag)
4P + 5O2 o 2P2O5
3CaO + P2O5 o Ca3 (PO4)2
The properties of steel depend on its chemical composition but also on heat treatment. At high temperatures, iron
and carbon in steel combine to form iron carbide, Fe3C, called cementite :
3Fe (s) + C (s) o Fe3C(s)
The forward reaction is endothermic, so that the formation of cemetite is favoured at high temperatures. When steel
containing cemetite is cooled slowly, the above equilibrium shifts to the left, and the carbon separates as small
particles of graphite, which give the steel a gray colour. If the steel is cooled rapidly, equilibrium is not attained and
the carbon remains large in the form of cementite, Fe3C. Steel containing cementite is light in colour, and is harder
and more brittle than that containing graphite.

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CHEMISTRY FOR NEET & AIIMS
(c) Heat Treatment of Steel
Quenching or Hardening :
Steel is heated to red hot temp. and is then cooled suddenly by plunging into either cold water or oil. It makes
steel hard and brittle.
Annealing :
The steel is heated to red hot temp. and then cooled slowly.
It makes steel soft.
Tempering :
If quenched steel is heated to temp. between 500 to 575 K and then cooled slowly, it becomes quite hard but
brittleness disappears. The process is called tempering.
Surface Treatment of Steel
(i) Nitriding - Process of heating steel at 1000 K in an atmosphere of NH3.
This gives hard coating of iron nitride on the surface.
(ii) Case hardening - Process of giving a thin coating of hardend steel, by heating steel in contact with
charcoal followed quenching in oil.

• It is used for axles of railway wagons.

Note : Thus all the three forms of iron differ in their carbon contents, both iron and steel are obtained from cast iron.
Order of M.P.WI > Steel > CI or PI

(IV) Extraction of Zinc (Zn)

ORE o Zinc blende or Black jack (ZnS)

A Physical (froth floating)

a Crushing or b Pulverisation c Concentration
grinding
B Chemical (Roasting)

e Refining d Reduction
(by electro refining) by smelting

Uses
(a) Zn–Cu couple, Zn- Hg, zinc dust etc. are used as reducing agent in organic reactions.
(b) large amounts of zinc are used for galvanizing iron. Zinc is deposited on the surface of iron articles. This
process is called galvanization.
(c) ZnSO4 .7H2O (White vitrol) issued as eye lotion.

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 METALLURGY

(V) Extraction of Silver and Gold

GOLD(Au)
Ore - Auriferrous Rock

Residue (impurity
Finely +0.5% NaCN sol. and O 2
divide filteration
ore Au Zn powder
Filterate Na[Au(CN)2]
Filteration

Filteration Residue
Na2[Zn(CN)4] Crude Au
Au + Zn
Pb+Cu+Ag

Au Cupellation Au + dil H2SO 4

pure Au
+Cu, Ag –PbO
+Pb,Cu,Ag –ZnSO4

Amalgamation –H2

pure Au Electro refining 99.99%

E – AuCl3 Au
C – pure gold
A – impure gold

Reaction involved :
(a) 4Au + 8NaCN + O2 + 2H2O o 4Na[Au(CN) 2 ]  4NaOH
(so lub le)

(b) 2Na[Au(CN) 2 ]  Zn o Na 2 [Zn(CN) 4 ]  2Au p

(soluble) (so lub le)

SILVER(Ag)
Ore - Argentite Ag2S

Residue (impurity)
Finely 5% NaCN sol.+O2
divided Zn powder
Filteration
ore Ag2S (excess and
Filterate Na[Ag(CN) 2] Filteration
soluble
complex
Filterate Residue
Na2[Zn(CN)4] Au + Zn
Crude Ag
purification

99.99% Electro refining + dil H2SO4

Pure Ag
Pure Ag E – AgNO3sol. – ZnSO4
C – Pure Ag – H2
A – Impure Ag

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CHEMISTRY FOR NEET & AIIMS

(VI) Extraction of Aluminium

Short chart of Al from Al2O3.2H2O (Bauxite)

A Calcination
a b c
B Roasting for [FeO] impurity
Beayer's
C Leaching
Hall's
e Electrolytic refining d Electrolytic reduction D Calcination Srepeck's
(Hoop's process)
Bauxite
p
Concentration of Bauxite ore
(a) Baeyer's Process : (Used for red bauxite in which main impurity is iron oxide)
Bauxite ore Roasted as to convert FeO into Fe2O3
150°C
Roasted ore + NaOH 8 atm
 NaAlO2 Hydrolysis Al(OH)3 + NaOH
solution in presence ppt.
of little Al(OH)3
(b) Hall's Process : (Red bauxite)
Bauxite ore + Na2CO3 Fused NaAlO2
p extracted with water
Solution
p warmed 50° – 60° C
CO2 is circulated
p
Al(OH)3 + Na2CO3
(c) Serpeck's Process : (Used for white bauxite in which main impurity is silica)
Bauxite ore + coke  1800°C AlN H2O Al(OH)3 + NH3
+ ppt.
(Nitrogen) N2 C + SiO2 (gangue) o CO2 + Si A A
p
CALCINATION
Al(OH)3 1500°C Al2O3
p
Electrolytic Reduction
Electrolyte Al2O3 dissolved in Na3AlF6 and CaF2
Cathode–Carbon lining Anode – Graphite rods
Al2O3  o Al + O2
Electrolysis
950 q C

p 99.8% pure
Electrolytic Refining
(Hoop's process)
Pure Al (99.98 % pure)

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 METALLURGY
Important points :
(i) Useful gas NH3 is evolved in the leaching of bauxite by Serpeck's process.
(ii) In the electrolytic reduction of Al2O3 cryolite (Na3AlF6) is added along with CaF2 (fluorspar) to–
• decrease m.p. of Al2O3
• decrease viscosity of electrolyte (CaF2 is used)
• increase conductivity
(iii) In the electrolytic reduction graphite anode get corrode or finished due to reaction with O 2 liberates at
anode, hence it had to be changed periodically.
(iv) In the electrolytic refining (4th step) no electrodes are used. In the Hoop's process molten pure Al is used
as cathode and molten impure Al is used as anode.
(v) In the Hoop's process carbon dust is sprayed over molten Al to
– avoid heat lose
– minimise metallic lusture (glaze) which is harmful for the eyes.

THERMODYNAMICS OF EXTRACTION : ELLINGHAM DIAGRAM OF A METAL

Some basic concepts of thermodynamics help us in understanding the theory of metallurgical transformations.
Gibbs energy is the most significant term here. The change in Gibbs energy, 'G for any process at any specified
temperature, is described by the equation:
'G = 'H – T'S .............(1)
where, 'H is the enthalpy change and 'S is the entropy change for the process. For any reaction, this change could
also be explained through the equation:
'GV = – RTlnK .............(2)
where, K is the equilibrium constant of the ‘reactant – product’ system at the temperature T. A negative 'G implies
a +ve K in equation (2) And this can happen only when reaction proceeds towards products. From these facts we
can make the following conclusions:
1. When the value of 'G is negative in equation (1) only then the reaction will proceed. If 'S is positive, on
increasing the temperature (T), the value of T'S would increase ('H < T'S) and then 'G will become –ve.
2. If reactants and products of two reactions are put together in a system and the net 'G of the two possible
reactions is –ve, the overall reaction will occur. So the process of interpretation involves coupling of the two
reactions, getting the sum of their 'G and looking for its magnitude and sign. Such coupling is easily understood
through Gibbs energy ('G–) vs T plots for formation of the oxides

Ellingham Diagram
The graphical representation of Gibbs energy was first used by H.J.T. Ellingham. This provides a sound basis for
considering the choice of reducing agent in the reduction of oxides. This is known as Ellingham Diagram. Such
diagrams help us in predicting the feasibility of thermal reduction of an ore. The criterion of feasibility is that at a
given temperature, Gibbs energy of the reaction must be negative.
(a) Ellingham diagram normally consists of plots of 'fG– vs T for formation of oxides of elements i.e., for the
reaction,
2xM(s) + O2(g) o 2Mx O(s)
In this reaction, the gaseous amount (hence molecular randomness) is decreasing from left to right due to the
consumption of gases leading to a –ve value of 'S which changes the sign of the second term in equation (1)
Subsequently 'G shifts towards higher side despite rising T (normally, 'G decreases i.e., goes to lower side
with increasing temperature). The result is +ve slope in the curve for most of the reactions shown above for
formation of Mx O(s).

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CHEMISTRY FOR NEET & AIIMS
(b) Each plot is a straight line except when some change in phase (s oliq or liq o g) takes place. The temperature
at which such change occurs, is indicated by an increase in the slope on +ve side (e.g., in the Zn, ZnO plot, the
melting is indicated by an abrupt change in the curve).
(c) There is a point in a curve below which 'G is negative (So Mx O is stable). Above this point, Mx O will
decompose on its own.
(d) In an Ellingham diagram, the plots of 'G– for oxidation (and therefore reduction of the corresponding species)
of common metals and some reducing agents are given. The values of 'fG–, etc.(for formation of oxides) at
different temperatures are depicted which make the interpretation easy.
(e) Similar diagrams are also constructed for sulfides and halides and it becomes clear why reductions of Mx S is
difficult. There, the 'fGV of Mx S is not compensated.

Limitations of Ellingham Diagram :

1. The graph simply indicates whether a reaction is possible or not i.e., the tendency of reduction with a reducing
agent is indicated. This is so because it is based only on the thermodynamic concepts. It does not say about
the kinetics of the reduction process (Cannot answer questions like how fast it could be ?).
2. The interpretation of 'G– is based on K ('GV = – RT lnK). Thus it is presumed that the reactants and products
are in equilibrium:
MxO + Ared xM + AOox
This is not always true because the reactant/product may be solid. [However it explains how the reactions are
sluggish when every species is in solid state and smooth when the ore melts down. It is interesting to note here that
'H (enthalpy change) and the 'S (entropy change) values for any chemical reaction remain nearly constant even on
varying temperature. So the only dominant variable in equation (1) becomes T. However, 'S depends much on the
physical state of the compound. Since entropy depends on disorder or randomness in the system, it will increase if
a compound melts (s o l) or vapourises (l o g) since molecular randomness increases on changing the phase from
solid to liquid or from liquid to gas].
The reducing agent forms its oxide when the metal oxide is reduced. The role of reducing agent is to provide 'G–
negative and large enough to make the sum of 'G– of the two reactions (oxidation of the reducing agent and
reduction of the metal oxide) negative.

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 METALLURGY
As we know, during reduction, the oxide of a metal decomposes:

1
MxO(s) o xM (solid or liq) + O (g) .............(3)
2 2
The reducing agent takes away the oxygen. Equation (3) can be visualised as reverse of the oxidation of the metal.
And then, the 'fG– value is written in the usual way:

1
xM(s or l) + O (g) o MxO(s) ['G– (M,MxO)] .............(4 )
2 2
If reduction is being carried out through equation (3), the oxidation of the reducing agent (e.g., C or CO) will be there

1
C(s) + O (g) o CO(g) ['G(C.CO)]
2 2

1
CO(g) + O (g) o CO2(g) ['G(CO.CO )]
2 2 2

If carbon is taken, there may also be complete oxidation of the element to CO2:

1 1 1 1
C(s) + O2(s) o CO2(g) [ 'G(C.CO )]
2 2 2 2 2

On subtracting equation (4) [it means adding its negative or the reverse form as in equation (3) from one of the three
equations, we get:
MxO(s) + C(s) o xM(s or 1) + CO(g)
MxO(s) + CO(g) o xM(s or 1) + CO2(g)

1 1
MxO(s) + C(s) o xM(s or 1) + CO2(g)
2 2
These reactions describe the actual reduction of the metal oxide, MxO that we want to accomplish. The 'rG– values
for these reactions in general, can be obtained by similar subtraction of the corresponding 'f G– values.
As we have seen, heating (i.e., increasing T) favours a negative value of 'rG–. Therefore, the temperature is chosen
such that the sum of 'rG– in the two combined redox process is negative. In 'rG– vs T plots, this is indicated by
the point of intersection of the two curves (curve for MxO and that for the oxidation of the reducing substance).
After that point, the 'rG– value becomes more negative for the combined process including the reduction of MxO.
The difference in the two 'rG– values after that point determines whether reductions of the oxide of the upper line
is feasible by the element represented by the lower line. If the difference is large, the reduction is easier

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Mettallurgy at a Glance

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 METALLURGY
Flow chart for the Extraction of Fe

Finely divided ore

magnetite Fe3O4 Conc. ore Calcination and
Gravity separation Roasting Fe2O3+ Carbon reduction
haematite Fe2O3 +
–SiO2
Little SiO2 little SiO2
limonite Fe2O3, 3H2O
Blast Ore (8) part
Siderite Furnace +Coke (4) part
+CaCO3(l) part

(Pudding process)
Molten iron taken in
Wrought iron a furnace which Pig Iron or Slag
Fe + 0.1 to is lined with Haematite Cast Iron CaSiO3
0.25%C + 0.3 to
0.45%S, Mn, Si,P – CO2 Fe + C, S,
– SO2 Mn, Si, P
– MnSiO3
– Fe3(PO4)2

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CHEMISTRY FOR NEET & AIIMS

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 METALLURGY

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CHEMISTRY FOR NEET & AIIMS

Some Important Compound and their formulae

Lunar caustic (Highly photo sensensitive) AgNO3
Monozite ThO2
Calomal Hg2Cl2
Illumanite TiO2
Corrosive sublimate HgCl2
(does not give chromyl chloride test)
Type metal Pb+Sn+Sb
Constantan Cu(60%) +Ni (40%)
Litharge PbO
Red Lead (OR) Sindhur Pb3O4
Butter of tin SnCl4 .5H2O
Spelter (Impure Zn during extraction of Zn) Crude zinc metal called spelter
which contain nonfusible impurities and the impurities of Pb, Fe, Cd.
Green vitrol FeSO4 . 7H2O
Blue vitrol CuSO4 . 5H2O
White vitrol ZnSO4 .7H2O
Lithopone BaSO4+ ZnS
Nessler Reagent in basic medium K2HgI4
Mohr salt (ferrous Ammonium sulphate) FeSO4 · (NH3)2SO4 · 6H2O
Ignition mixture Mg powder + BaO2
Fusion mixture Na2CO3+ K2CO3
Freezing mixture NaCl is used with ice
Electron Mg (95%) + Zn (5%) used in aircraft

List of Ores and their names

Types of Ores S. N. Formla of the Ore Name
Oxide Ore 1. ZnO (Philosopher’s Wool) Zincite
2. MnO2 Pyrolusite
3. SnO2 Cassiterite (Tin stone)
4. Cu2O Cuprite (Ruby Copper)
5. Fe2O3 Haematite
6. Al2O3.2H2O Bauxite
7. FeO. Cr2O3 Chromite
8. Fe3O4 Magnetite
9. Fe2O3.3H2O Limonite
10. TiO2 Illumanite

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 METALLURGY

Sulphide Ore 1. ZnS Zinc Blende (Sphalerite)

2. HgS Cinnabar
3. PbS Galena
4. Ag2 S Argentite or Silver glance
5. FeS2 Iron pyrites (Fool’s gold)
6. CuFeS2, CuS.FeS Copper pyrites (Chalcopyrities)
7. Cu2S.Ag2S Copper silver glance
8. Ag2S.Sb2S3 Pyrargirite (Ruby silver)
9. Cu2S (Copper glance) Chalcocite

Halide Ore 1. NaCl Rock Salt

2. AgCl Horn Silver
3. CaF2 Flourspar
4. AlF3.3NaF Cryolite
5. KCl.MgCl2.6H2O Carnelite

Carbonate Ore 1. MgCO3 Magnesite

2. CaCO3 Lime stone
3. MgCO3.CaCO3 Dolomite
4. ZnCO3 (Smithosonite) Calamine
5. PbCO3 Cerrusite
6. FeCO3 Siderite
7. CuCO3. Cu(OH)2 Malachite
8. 2CuCO3.Cu(OH)2 Azurite

Sulphate Ore 1. CaSO4.2H2O Gypsum

2. MgSO4.7H2O Epsomite Or Epsom salt
3. K2SO4.Al2(SO4)3.24H2O Alum

Nitrate Ore 1. NaNO3 Chile- Salt Peter

2. KNO3 Salt peter or Indian salt peter

Phosphate Ore 1. Ca3(PO4)2 Rock Phosphate

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CHEMISTRY FOR NEET & AIIMS

SOLVED EXAMPLE
Ex. 1 Using data given below, predict whether the Ex. 5 A metal is extracted from its sulphide ore and the
reduction of MgO with C is spontaneous or not at process of extraction involves the following steps.
1500ºC. (A) (B)
Metal sulphide Concentrated ore
(C) (D)
2 C + O2  o 2 CO 'Go | – 530 kJ Matte Impure metal Pure metal
Identify the steps (A), (B), (C) and (D).
2 MgO o 2 Mg + O2 'Go | + 730 kJ Sol. (A) Froth floatation process. Sulphide ores are
Sol. The positive value of 'G o indicates that the concentrated by froth-floatation process.
reduction of MgO with C dose not occur to a (B) Roasting. Metal sulphides are roasted to
significant extent at 1500ºC convert into metal oxide and to remove
impurities.
2 C + O2 o 2 CO 'Go | – 530 kJ
In roasting ; 2CuFeS2 + O2 o Cu2S +
2 MgO o 2 Mg + O2 'G | + 730 kJ
o 2FeS + SO2.

2 MgO + 2C o 2Mg + 2CO 2FeS + 3O2 o 2FeO + 2SO2.
or MgO + C o Mg + CO 'Go positive value. 2Cu2S + 3O2 o 2Cu2O + 2SO2.

Ex. 2 Sea water

(A)
Mg(OH)2
(B)
Mg Cl2. 6H2O FeO + SiO2 o FeSiO3
(C) (D) (C) Bessemerisation / self reduction. Reduction of
MgCl2 Mg + Cl2n metal oxide by its sulphide takes place in
Identify the reagents and processes (A) to (D) and Bessemer converter.
give the name of this process.
In Bessemerisation ; 2Cu2O + Cu2S o
Sol. MgCl2 (from sea water) + Ca(OH)2 (A) o Mg(OH)2 6Cu + SO2 (self - reduction)
+ CaCl2 ; Mg(OH)2 + 2HCl (B) o MgCl2 (aq.) + 2H2O (D) Electro-refining. Pure metal is obtained at
Crystallisation of MgCl2(aq) yields MgCl2.6H2O cathode.
Calcination (C) Mn+ + n e– o m
MgCl2 6H2O
Dry HCl
MgCl2 + 6H2O
Ex. 6 Write chemical equations for metallurgical processes
MgCl2(A)
Electrolysis is (D)
Mg 2+
+ 2Cl – to represent :
(i) roasting of galena (PbS) in limited supply of air at
p +2e p Cl2
–
moderate temperature.
Mg Cl2 (ii) reduction of Cu2O using coke as a reducing agent.
(cathode) (anode) (iii) deposition of pure silver from an aqueous
solution of Ag+.
Name of the process is Dow’s process.
Sol. (i) 2PbS + 3O2 o 2PbO + 2SO2
Ex. 3 Convert magnesite into anhydrous MgCl2.
PbS + 2O2 o PbSO4
Sol. Mg CO3 MgO + CO2.
(ii) Cu2O + C o 2Cu + CO
MgO + C + Cl2 o MgCl2 + CO
Electrolysis
(iii) Ag+ + e– Ag (at cathode)
Ex. 4 At a site, low grade copper ores are available and
zinc and iron scraps are also available. Which of the Ex. 7 Which is not the correct process-mineral matching
in metallurgical extraction.
two scraps would be more suitable for reducing the
(A) Leaching : silver
leached copper ore and why?
(B) Zone refining : lead.
Sol. Since zinc lies above iron in electrochemical series,
(C) Liquation : tin
it is more reactive than iron. As a result, if zinc scraps
(D) Van Arkel : Zr
are used the reduction will be faster. However, zinc
Sol. Lead is purified by Electro-refining. Zone refining is
is a costlier metal than iron. Therefore, it will be used for the purification of Si and Ge.
advisable and advantageous to use iron scraps.
Therefore, (B) option is correct.

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 METALLURGY
Ex. 8 Tin stone, an oxide or of tin is amphoteric in nature. Ex. 11 Assertion : In the electrolytic reduction of Al2O3,
Explain. cryolite lowers the melting point of the mixture and
brings conductivity.
Sol. Tin stone is cassiterite i.e. SnO2. SnO2 dissolves in
Reason : Cryolite is an ore of aluminium.
acid and alkali both, hence amphoteric oxide.
(A) If both Assertion and Reason are true and
SnO2 + 4HCl o SnCl4 + 2H2O Reason is a correct explanation of Assertion.
(B) If both Assertion and Reason are true and
SnO2 + 2NaOH o Na2SnO3 + H2O Reason is not a correct explanation of
Assertion.
Ex. 9 Select the incorrect statement. (C) If Assertion is true but Reason is false.
(A) In the Bayer’s Al2O3 goes in to solution as (D) If Assertion is false but Reason is true.
Sol. Assertion : Cryolite as impurity reduces the melting
soluble [Al(OH)4]– while other basic oxides as
point of Al2O3 from 2200 K to approximately 930 K
TiO2 and Fe2O3 remain insoluble and being ionic compound dissociates to give ions
(B) Extraction of zinc from zinc blende is achieved which bring about the conductivity of the electrolyte.
by roasting followed by reduction with carbon. Reason : Cryolite is Na3AlF6 and is ore of aluminium.
(C) The methods chiefly used for the extraction of Therefore, (B) option is correct.
lead and tin are respectively carbon reduction Ex. 12 Assertion : Reduction of ZnO with carbon is done
and electrolytic reduction. at 1100ºC.
(D) Extractive metallurgy of magnesium involves Reason : 'Gº is negative at this temperature thus,
fused salt electrolysis. process is spontaneous.
(A) If both Assertion and Reason are true and
Sol. Lead o self reduction; 2PbO + PbS o 3Pb + Reason is a correct explanation of Assertion.
SO2 (B) If both Assertion and Reason are true and
Reason is not a correct explanation of
Tin o carbon reduction ; SnO2 + 2C o Sn + Assertion.
2CO (C) If Assertion is true but Reason is false.
Therefore, (C) option is correct. (D) If Assertion is false but Reason is true.
Sol. All three oxidation curves for the carbon system lie
Ex. 10 Assertion : In froth floatation process sodium ethyl above that for oxidation of zinc, until a temperature
xanthate is used as collector. of approximately 1000ºC is reached. At this point C
is thermodynamically capable of reducing ZnO to
Reason : Sulphide ores are water soluble.
Zn. Since this temperature is greater than the boiling
(A) If both Assertion and Reason are true and point of Zn (907ºC), it will be formed as a vapour.
Reason is a correct explanation of Assertion. The overall equation for reduction is
(B) If both Assertion and Reason are true and ZnO(s) + C (s) o Zn(g) + CO(g)
Reason is not a correct explanation of Therefore, (A) option is correct.
Assertion.
Ex. 13 Which of the following is not an ore of iron ?
(C) If Assertion is true but Reason is false.
(A) limonite (B) cassiterite
(D) If Assertion is false but Reason is true. (C) magnetite (D) none of these
Sol. Assertion : Potassium or sodium ethyl xanthate is Sol. SnO2 , cassiterite is an ore of tin.
used as a collector. These get attached with the Therefore, (B) option is correct.
particles of the sulphide ore and thus make them
Ex. 14 In the extraction of copper from sulphide ore the
water-repellant. Consequently the ore particles pass metal is formed by reduction of Cu2O with :
on into the froth. Collectors are always added in (A) FeS (B) CO
small quantity. (C) Cu2S (D) SO2
Reason : Sulphide ores are water insoluble. Sol. 2Cu2O + Cu2S 6Cu + SO2 .
Therefore, (C) option is correct. Therefore, (C) option is correct.

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Ex. 15 Which of the following is a carbonate ore ? Ex. 18 When copper ore is mixed with silica, in a
(A) pyrolusite (B) malachite
(C) diaspore (D) cassiterite reverberatory furnace copper matte is produced. The
Sol. CuCO3.Cu(OH)2 Malachite. copper matte contains
Therefore, (B) option is correct. (A) Sulphides of copper (II) and iron (II)
Ex. 16 Column-I and column-II contains four entries each. (B) Sulphides of copper (II) and iron (III)
Entries of column-I are to be matched with some (C) Sulphides of copper (I) and iron (II)
entries of column-II. Each entry of column-I may
have the matching with one or more than one entries (D) Sulphides of copper (I) and iron (III)
of column-II.
Sol . (C) When copper ore is mixed with sillica in a
Column-I Column-II
(A) Pb (p) Bessemerisation reverberatory furnace copper matte is produced. The
(B) Cu (q) Roasting copper matte contains sulphide of copper (I) and
(C) Zn (r) Pyrometallurgy iron (II)
(D) Fe (pig iron) (s) Self-reduction
method Copper matte 
o Cu 2S and FeS
Ans. (A) q, r, s; (B) p, q, r, s; (C) q, r; (D) r ;
Sol. (A) 2PbS + 3O2 o 2PbO + 2SO2 (Roasting) Ex. 19 Which of the following reactions is an exam ple of
PbS + PbO2 2Pb + SO2 (Self-reduction method) autoreduction

(B) 2Cu2S + 3O2 o 2Cu2O + 2SO2 (Roasting) (A) Fe3 O 4  4CO 
o 3Fe  4CO 2
Cu2S + 2Cu2O 6Cu + SO2 (Self-reduction takes
place in Bessemer converter) (B) Cu 2 O  C 
o 2Cu  CO

(C) 2ZnS + 3O2 o 2ZnO + 2SO2 (Roasting) (C) Cu 2  (aq)  Fe(s) 
o Cu(s)  Fe 2  (aq)
ZnO + C Zn + CO (Carbon reduction)
(D) Haematite ore is calcined. 1 1
3Fe2O3 + CO 2Fe3O4 + CO2 (D) Cu 2 O  Cu 2S 
o 3Cu  SO 2
2 2
Fe3O4 + CO 3FeO + CO2
FeO + CO Fe + CO2 1 1
Sol . (D) Cu 2 O  Cu 2S 
o 3Cu  SO 2
Ex. 17 In the extraction of chlorine by electrolysis of brine 2 2
........
This reaction includes reduction of copper (I) oxide
(A) Oxidation of Cl– ion to chlorine gas occurs
(B) Reduction of Cl– ion to chlorine gas occurs by copper (I) sulphide. In this process, copper is
(C) For overall reaction 'G has negative value reduced by itself hence this process is known as
(D) A displacement reaction takes place autoreduction and the solidified copper. So, obtained
Sol . (A) Following reaction takes place in the extraction is known as blister copper.
of chlorine by electrolysis
2H 2 O(l)  2Cl  (aq) o H 2 (g)  Cl 2 (g)  2OH  (aq) Ex. 20 A number of elements are available in earth’s crust
From the above reaction it is very clear that the but most abundant elements are ........
oxidation of Cl– ion to chlorine gas occurs. Thus,
option (a) is the correct answer. (A) Al and Fe (B) Al and Cu
'°G for this reaction is +422kJ. Therefore, (C) Fe and Cu (D) Cu and Ag
thermodynamically reaction is not feasible.
We know that Sol . (D) Among a number of elements which are vailable
'qG  nFEq in earth crust, the most abundant elements are
By using this equation value of E° can be calculated. aluminium and iron. Aluminium is third most
Thus,
abundant element in earth crust. i.e., 8.3% by weight
'G q
Eq  2.2V while iron present in earth crust with 4.2% by weight.
nF
Therefore for the occurrence of this reaction. external Copper and silver are also found in earth crust but
potential (emf) greater than 2.2 V is required. Due to their abundance percentage is low.
this fact (c) is not correct option.

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 METALLURGY
Ex. 21 Zone refining is based on the principle that ....... Ex. 23 Electrolytic refining is used to purify which of the
(A) Impurities of low boiling metals can be separated following metals
by distillation (A) Cu and Zn (B) Ge and Si
(B) Impurities are more soluble im molten metal than (C) Zr and Ti (D) Zn and Hg
in solid metal Sol . (A) Copper and zinc are two metals which are
(C) Different components of a mixture are generally purified by using electrolyte refining. In
differently absorbed on an absorbent this process impure metal is used as anode and pure
(D) Vapours of volatile compound can be metal is used as a cathode. Impurities from the blister
decomposed in pure metal copper or impure zinc deposit as anode mud.
Sol . (B) Zone refining is based on the principle that the
impurities are more soluble in molten state than in
solid state of the metal. A circular mobile heater fixed
at one end of impure metal rod. The molten zone
moves along with heater which is moved forward.
As the heater moves forward, the pure metal
crystallises out of the melt and the impurities pass
on into adjacent molten zone. The process is
repeated several times and the heater is moved in
the same direction.
At one end, impurities get concentrated. This end is
cut off. we.g., germanium, silicon, gallium etc. are
refined by this method.

Ex. 22 In the metallurgy of aluminium .....

(A) Al3+ is oxidised to Al (s)
(B) Graphide anode is oxidised to carbon monoxide
and carbon dioxide
(C) Oxidation state of oxygen changes in the
reaction at anode
(D) Oxidation state of oxygen changes in the overall
reaction involved in the process
Sol . (B) In the metallurigy of aluminium, electrolysis is
performed in a steel vessel with lining of carbon
acts as cathode and graphite acts as anode. During
this process graphite anode is oxidised to CO and
CO2
Chemical reaction occuring in this process is as
follows
2Al2O3 + 3C o 4Al + 3CO2
This process is known as Hall – Heroult process.
The electrolytic reactions are
At cathode Al3 (melt)  3e  
o Al(l)

At anode C(s)  O 2  (melt) 

o CO(g)  2e 

C(s)  2O 2  (melt) 
o CO 2 (g)  4e 

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CHEMISTRY FOR NEET & AIIMS

Exercise PART - 1 PREVIOUS YEAR (NEET/AIPMT)

1. The method of zone refining of metals is based on 8. Which one of the following is a mineral of iron?
the principle of [CBSE AlPMT 2003] [CBSE AlPMT 2012]
(A) Greater noble character of the solid metal than (A) Malachite (B) Cassiterite
that of the impurity
(C) Pyrolusite (D) Magnetite
(B) Greater solubility of the impurity in the molten
state than in the solid 9. Aluminium is extracted from alumina (Al2O3) by
(C) Greater mobility of the pure metal than that of electrolysis of a molten mixture of
impurity
[CBSE AlPMT 2012]
(D) Higher melting point of the impurity than that
of the pure metal (A) Al2O3+HF+NaAIF4
(B) Al2O3 +CaF2 +NaAIF4
2. A solid compount X on heating gives CO2 gas and a (C) Al2O3 +Na3AIF6 +CaF2 d
residue mixed with water forms Y. On passing an
excess of CO2 through Y inwater, a clear solution Z (D) Al2O3 +KF+Na3AIF6
is obtained. On boiling Z, compound X is reformed. 10. Roasting of sulphides gives the gas X as a by-
The compound X is [CBSE AlPMT 2004]
product. This is a colourless gas with choking smell
(A) Ca(HCO3)2 (B) CaCO3
of burnt sulphur and causes great damage to
(C) Na2 CO3 (D) K2 CO3
respiratory organs as a result of acid rain. Its aqueous
3. Which of the following statements, about the solution is acideic acts as a reducing agent and its
advantage of roasting of sulphide ore before acid has never been insolated. The gas X is
reduction is not true? [CBSE AlPMT 2007]
[NEET 2013]
(A) Carbon and hydrogen are suitable reducing
agents for metal sulphides (A) H2S (B) SO2
(B) The 'f G0 of the sulphide is greater than those (C) CO2 (D) SO3
for CS2 and H2S
(C) The 'f G0 is negative for roasting of sulphide 11. In the extraction of copper from its sulphide ore, the
ore to oxide metal finally obtained by the reduction of cuprous
(D) Roasting of the sulphide to the oxide is oxide with [CBSE AlPMT 2015]
thermodynamically feasible (A) iron (II) sulphide (B) carbon monoxide
(C) copper (I) sulphide (D) sulphur dioxide
4. Sulphide ores of metals are usually concentrated b
y froth floatation process. Which one of the 12. Match items of Column I with the items of Column II
following sulphide ores offers an exception and is and assign the correct code. [NEET 2016, Phase I]
concentrated by chemical leaching
[CBSE AlPMT 2007] Column I Column II
(A) Argentite (B) Galena (A) Cyanide process (1) Ultrapure Ge
(C) Copper pyrite (D) Sphalerite (B) Froth floatation process (2) Dressing of ZnS
(C) Electrolytic reduction (3) Extraction of Al
5. Which of the following pairs of metals is purified by
van Arkel method ? [CBSE AlPMT 2011] (D) Zone refining (4) Extraction of Au
(A) Zr and Ti (B) Ag and Au (5) Purification of Ni
(C) Ag and Au (D) Ni and Fe Codes
6. Which of the following elements is present as the a b c d
impurity to the maximum extent in the pig iron? (A) 2 3 1 5
[CBSE AlPMT 2011] (B) 1 2 3 4
(A) Carbon (B) Silion (C) 3 4 5 1
(C) Phosphorus (D) Manganese
(D) 4 2 3 1
7. In the extraction of copper from its sulphide ore, the
metal is finally obtained by the reduction of cuprus 13. Extraction of gold and silver involves leaching with
oxide with [CBSE AlPMT 2012] CN- ion. Silver is later recovered by [NEET 2017]
(A) copper (I) sulphide (Cu2S) (A) liquation (B) distillation
(B) Sulphur dioxide (C) zone refining (D) displacement with Zn
(C) Iron sulphide(FeS)
(D) Carbon Monoxide (CO)

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 METALLURGY

Exercise PART - 2 PREVIOUS YEAR (AIIMS)

ASSERTION AND REASON

1. In the extraction of copper from sulphide ore the
10. Assertion : Extraction of iron metal from iron oxide
mtal is formed by reduction of Cu2O with
ore is carried out by heating with coke only.
(A) FeS (B) CO Reason : The reaction Fe2O3(s) o Fe(s) + 3/2O2(g) is a
(C) Cu2S (D) SO2 [2003] spontaneous process. [2005]
2. Which of the following is a carbonate ore ? 11. Assertion : Magnesium is extracted by the
(A) Pyrolusite (B) Malachite electrolysis of fused mixtrue of MgCl2, NaCl and
(C) diaspore (D) Cassiterite [2005] CaCl2.
Reason : Calcium chloride acts as a reducing agent.
3. Carbon and CO gas are used to reduce which of the [2013]
following pairs of metal oxides for extraction of
metals ? 12. Assertion : Coke and flux are used in smelting.
(A) FeO, SnO (B) SnO, ZnO Reason : The phenomenon in which ore is mixed
(C) BaO, Na2O2 (D) FeO, ZnO [2007] with suitable flux and coke is heated to fusion is
known as smelting. [2017]
4. What is the rode of aniline or cresol when added in
a froth floatation process ? 13. Assertion : Fe+3 is not valid for Brown Ring Test.
(A) Stabilizer (B) Depressant Reason : Because NO3– first convert into NO2–
(C) Wetting agent (D) All of these [2013] [2018]
(A) If both assertion and reason are true and reason
5. Slag formed in blast furnace, removes the impurity is the correct explanation of assertion.
of (B) If both assertion and reason are true but reason
(A) SiO2 (B) CaO is not the correct explanation of assertion.
(C) CO2 (D) FeO [2014] (C) If assertion is true but reason is false.
(D) If both assertion and reason are false.
6. Which of the following is not the correct match ?
(E)Both assertion and reason are false
(A) Leaching : Ag
(B) Zone refining : Sn
(C) Liquation : Pb
(D) van Arkel : Zr [2015]

7. The composition of carnallite is

(A) KCl.MgCl2.6H2O (B) Na2Al2O3
(C) Fe3O4 (D) Na3AlF6
[2001, 2015]

8. Oil used as frothing agent in forth-floatation process

is
(A) pine oil (B) mustard oil
(C) coconut oil (D) olive oil [2016]

9. 2CuFeS2 + O2o Cu2S + 2FeS + SO2

Which process of metallurgy of copper is
represented by above equation? [2017]
(A) Concentration (B) Roasting
(C) Reduction (D) Purification

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CHEMISTRY FOR NEET & AIIMS

ANSWER KEY

EXERCISE : PART # I
1. B 2. B 3. A 4. D 5. A 6. A 7. A 8. D 9. C 10. B 11. C 12. D 13. D

PART # II
1. A 2. B 3. D 4. A 5. A 6. B 7. A 8. A 9. B 10. D 11. C 12. B 13. C

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CHEMISTRY FOR NEET & AIIMS 40-65*0/4

EXERCISE 9. (C) Alumina, Al2O3 is a bad conductor of electricity and

has very high melting point, So before subjecting to
P-1 (NEET/AIPMT) electrolysis, it is mixed with fluorspar (CaF2) and cryolite
1. (B) The method of zone refining of metals is based on (Na3 AlF6), which lower its melting point and make it
the principle of greater solubility of the impurity in the more conducting. Mainly CaF2 and Na3 AlF6 are mixed
molten state than inthe solid. Elements which are used with Al2O3 for converting Al2 O3 in molten state.
as semiconductors like Si. Ge.Ga etc, are refined by this
10. (B) So2 gas is obtained when any sulphide ore is roasted.
method. Gallium arsenide and indium antimonide (also
used as semiconductor) are also refined by this method. 2M S  3O  '
o 2M O  2SO
2 2 2 2
2. (B) Compound X is CaCO3 This gas exhibits all the characteristics that are given in
the question.
C aC O  '
o C aO  C O n
3 R e sidue 2
X
11. (C) Cu2S+2Cu2O o 6Cu+SO2 n
CaO  H O o Ca(OH)
Residue 2 2 12. (D) A-4, B-2, C-3, D-1
Y
x Cyanide process It is a metallurgical technique for
Ca(OH) CO  H O o Ca(HCO )
2 2 2 3 2 extracting Au(gold) from low grade ore by converting
Y Excess Z
the Au to a water-soluble coordination complex.
C a (H C O )  '
o C a C O  H O  C O n
3 2 3 2 2 x Froth floatstion process This process is used for
Z X
dressing of sulphide ore, i.e ZnS.
3. (A) Carbon and hydrogen are not suitable reducing x Electrolytic reduction This process is used for
agents for metal sulphides. extraction of Al which is carried out in a steel tank lined
inside with graphite. Here, graphite serves as cathode.
4. (D) Galena (PbS), copper pyrites (CuFeS2) and argentite
The electrolyte consists of alumina dissolved in fused
(Ag2S) are concentrated by froth floatation process but
cryolite (Na3 AlF6) and fluorspart (CaF2)
sphalerite (ZnS) is concentrated by chemical leaching.
x Zone refining This process is used for ultra pure Ge
5. (A) Zr and Ti are purified by van-Arkel method. element. An ingot of Ge is first purified by zone refining.
Then a small amount of antimony is placed in the molten
600 0 Co ZrI 
Zr  2I  1800 0 C o Zr  2 I zone which is passed through the pure Ge with the proper
2 4 2
Impure Pure choice of rate of heating and other variables.
This method is useful for removing all the oxygen and 13. (D) Extraction of gold and silver involves leaching with
nitrogen present in the form of impurity in certain metals CN- ion. Silver is later recovered by distillation of Zn.
like Zr and Ti. In the metallurgy of silver of gold, the respective metal is
6. (A) Pig iron contains about 4% carbon (major impurity) leached with a dilute solution of NaCN or KCN in the
and other impurities (S,P,Si, Mn) in trace amounts presence of air to obtain the metal in solution as complex.
From the complex, metal is obtained later by replacement.
7. (A) In the extraction of copper from its sulphide ore, In general
when ore is subjected to roasting, some of it is oxidised 4M(s) + 8CN- (aq) + 2H2O (aq) + O2 (g) o4[M(CN2)-
to Cu2O which reacts with the remaining Cu2S(sulphide
(aq) +4OH- (aq)
ore) to give copper metal.
2[M(CN)2 ]- (aq)+Zn(s) o [Zn(CN4)]2- (aq)+2M (s) M-
2Cu2 S + 3O2 o 2Cu2O +2SO2 n
Ag or Au
2Cu2 O + Cu2S o 6Cu +SO2 n
This method is known as Mac-Arthur Forest cyanide
In this process Cu2S behaves as reducing agent. process.
8. (D) Mineral Chemical Composition
Malachite CuCo3 Cu(OH)2
Cassiterite SnO2
Pyrolusite MnO2
Magnetite FeO4
Thus, magnetite is a mineral of iron.

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 METALLURGY

EXERCISE

P-2 (AIIMS) 11. (C) : NaCl and CaCl2 are added to provide conductivity
to the electrolyte and also to lower the fusion temperature
1. (A) : Iron has greater affinity for oxygen than copper. of anhydrous MgCl2.
Cu2O + FeS o FeO + Cu2S
FeO + SiO2 o FeSiO3 12. (B) : Both assertion and reason are true but reason is not
(slag) the correct explanation of assertion. Non fusible mass
2Cu2S + 3O2 o 2Cu2O + 2SO2 present in ore in mixing with suitable flux are fused which
2Cu 2 O  Cu 2S auto
o 6Cu  SO 2 are then reduced bycoke to give free metal.
reduction

13. (C) : In Brown ring test Fe2+ oxidizes to Fe3+, and NO3–
2. (B) : Pyrolusite -MnO2 reduces to NO.
Malachite - CuCO3.Cu(OH)2
Diaspore - Al2O3.H2O
Cassiterite - SnO2

reduction
+2
3. (D) : Fe O + C Fe0 + CO
FeO + C Fe + CO2
reduction

Similarly, Zn O + C+2 0
Zn + CO
ZnO + C Zn + CO2
4. (A)
5. (A) : In the blast furnace, Sio2 is removed as calcium
silicate.
CaO + SiO2 o CaSiO3
Flux Gangue (Slag)
(Impurity)

6. (B) : Zone refining method is used for the elements like

Si, Ge, Ga etc. which are used as semiconductors and are
required in highly pure form.

7. (A) : Carnallite is an ore of potassium and its formula is

KCl.MgCl2.6H2O.
8. (A)

9. (B)

10. (D) : Extraction of iron metal from iron oxide ore is carried
out by heating with coke and flux (calcium carbonate).
Flux is a slag forming substance. It converts infusible
impurities into fusible slag.
The reaction : Fe2O3(s) o Fe(s) + 3/2 O2(g) is not a
spontaneous process. Fe2O3 is converted in Feo at about
400°C.

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8PSL
3PVHI
8PSL