(NCERT CBSE 12th Class XII Standard 12 Chemistry Solved Exemplary Problems) BookBank Teachers - NCERT CBSE 12th Class XII Standard 12 Chemistry Solved Exemplary Problems BookBank Publication-BookBank .pdf

1 NCERT 12th Chemistry Solution
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Table of Content
1. The Solid State
2. Solutions
3. Electrochemistry
4. Chemical Kinetics
5. Surface Chemistry
6. Principles and Processes of Elements
Isolation
7. The p-Block Elements
8. The d - and f -Block Elements
9. Coordination Compounds
10. Haloalkanes and Haloarenes
11. Alcohols, Phenols and Ethers
12. Aldehydes, Ketones and Carboxylic Acids
13. Amines
14. Biomolecules
15. Polymers
16. Chemistry in Daily Life
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Chapter 1
The Solid State
Summary
Solids have definite mass, volume and shape. This is due to the fixed position of
their constituent particles, short distances and strong interactions between them.
In amorphous solids, the arrangement of constituent particles has only short
range order and consequently they behave like super cooled liquids, do not have
sharp melting points and are isotropic in nature. In crystalline solids there is long
range order in the arrangement of their constituent particles. They have sharp
melting points, are anisotropic in nature and their particles have characteristic
shapes. Properties of crystalline solids depend upon the nature of interactions
between their constituent particles. On this basis, they can be divided into four
categories, namely: molecular, ionic, metallic and covalent solids. They differ
widely in their properties.
The constituent particles in crystalline solids are arranged in a regular pattern
which extends throughout the crystal. This arrangement is often depicted in the
form of a three dimensional array of points which is called crystal lattice. Each
lattice point gives the location of one particle in space. In all, fourteen different
types of lattices are possible which are called Bravais lattices. Each lattice can be
generated by repeating its small characteristic portion called unit cell. A unit cell
is characterised by its edge lengths and three angles between these edges. Unit
cells can be either primitive which have particles only at their corner positions or
centred. The centred unit cells have additional particles at their body centre (body-
centred), at the centre of each face (face-centred) or at the centre of two opposite
faces (end-centred). There are seven types of primitive unit cells. Taking centred
unit cells also into account, there are fourteen types of unit cells in all, which
result in fourteen Bravais lattices.
Close-packing of particles result in two highly efficient lattices, hexagonal
close-packed (hcp) and cubic close-packed (ccp). The latter is also called face-
centred cubic (fcc) lattice. In both of these packings 74% space is filled. The
remaining space is present in the form of two types of voids-octahedral voids and
tetrahedral voids. Other types of packing are not close-packings and have less
efficient packing of particles. While in body-centred cubic lattice (bcc) 68% space
is filled, in simple cubic lattice only 52.4 % space is filled.
Solids are not perfect in structure. There are different types of imperfections
or defects in them. Point defects and line defects are common types of defects.
Point defects are of three types - stoichiometric defects, impurity defects and
non-stoichiometric defects. Vacancy defects and interstitial defects are the
two basic types of stoichiometric point defects. In ionic solids, these defects are
present as Frenkel and Schottky defects. Impurity defects are caused by the
presence of an impurity in the crystal. In ionic solids, when the ionic impurity has
a different valence than the main compound, some vacancies are created. Non-
stoichiometric defects are of metal excess type and metal deficient type.
Sometimes calculated amounts of impurities are introduced by doping in
semiconductors that change their electrical properties. Such materials are widely
used in electronics industry. Solids show many types of magnetic properties like
paramagnetism, diamagnetism, ferromagnetism, antiferromagnetism and
ferrimagnetism. These properties are used in audio, video and other recording
devices. All these properties can be correlated with their electronic configurations
or structures.
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1. Define the term ‘amorphous’. Give a few examples of amorphous

solids.
Soln. A solid is said to be amorphous if the constituent particles are not
arranged in any regular fashion. They may have only short range order.
Amorphous solids are generally obtained when the melts are rapidly
cooled, e.g., glass, plastics, amorphous silica, etc.
2. What makes a glass different from a solid such as quartz? Under what
conditions could quartz be converted into glass?
Soln. Glass is an amorphous solid in which the constituent particles (SiO4

tetrahedra) have only a short range order and there is no long range order.
In quartz, the constituent particles (SiO4 tetrahedra) have both short range
as well as long range orders. On melting quartz and then cooling it rapidly,
it is converted into glass.
3. Classify each of the following solids as ionic, metallic, molecular,

network (covalent) or amorphous.
(i) Tetraphosphorus decoxide, P4O10

(ii) Ammonium phosphate, (NH4)3PO4
(iii) SiC (iv) I2 (v) P4
(vi) Plastic (vii) Graphite (viii) Brass
(ix) Rb (x) LiBr (xi) Si
Soln. P4O10 - molecular, (NH4)3PO4 - ionic, SiC - network(covalent),

I2 - molecular, P4 - molecular, plastic - amorphous, graphite - covalent,
brass - metallic, Rb - metallic, LiBr - ionic, Si - covalent
4. (i) What is meant by the term ‘coordination number’?

(ii) What is the coordination number of atoms :
(a) in a cubic close-packed structure?

(b) in a body-centred cubic structure?
Soln. (i) Coordination number is defined as the number of nearest
neighbours in a close packing. In ionic crystals, coordination number of
an ion in the crystal is the number of oppositely charged ions surrounding
that particular ion.
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(ii) (a) Coordination number of atoms in a cubic close-packed structure
is 12.
(b) Coordination number of atoms in a body-centred cubic structure
is 8.
5. How can you determine the atomic mass of an unknown metal if you
know its density and the dimension of its unit cell? Explain.
Soln. Suppose the edge of the unit cell = a pm
Number of atoms present per unit cell = Z
Atomic mass of the element = M
∴ Volume of the unit cell = (a pm)3 = (a × 10–10 cm)3
= a3 × 10–30 cm3
Mass of the unit cell a pm
Density of the unit cell =
Volume of the unit cell
Mass of the unit cell
= Number of atoms in the unit cell × Mass of each atom = Z × m
where m = mass of each atom
Atomic mass M
m= =
Avogadro's number N 0
Z×M
∴ Density of the unit cell, ρ = 3 −30
g/cm 3
a × N 0 × 10
where edge, a is in pm and molar mass, M in g mol–1.
Atomic mass can be calculated by using the expression
ρ × a 3 × N 0 × 10 −30
M= g mol −1
Z
6. ‘Stability of a crystal is reflected in the magnitude of its melting point’.
Comment. Collect melting points of solid water, ethyl alcohol, diethyl ether
and methane from a data book. What can you say about the intermolecular
forces between these molecules?
Soln. The melting points of some compounds are given below :
Water = 273 K, Ethyl alcohol = 155.7 K, Diethyl ether = 156.8 K,
Methane = 90.5 K
Higher the melting point, stronger are the forces holding the constituent
particles together and hence greater is the stability.
The intermolecular forces in water and ethyl alcohol are mainly hydrogen
bonding. Higher melting point of water as compared to alcohol shows
that hydrogen bonding in ethyl alcohol molecules is not as strong as in
water molecules. Diethyl ether is a polar molecule. The intermolecular
forces present in them are dipole-dipole attraction. Methane is a non-
polar molecule. The only forces present in them are the weak van der
Waals forces (London dispersion forces).
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7. How will you distinguish between the following pairs of terms ?
(i) Hexagonal close-packing and cubic close-packing
(ii) Crystal lattice and unit cells
(iii) Tetrahedral void and octahedral void
Soln. (i) Hexagonal close-packing (hcp) : The first layer is formed
utilizing maximum space, thus wasting minimum space. In every
second row, the particles occupy the depressions (also called voids)
between the particles of the row (fig.). In the third row, the particles
are vertically aligned with those in the first row giving AB AB AB.......
arrangement. This structure has hexagonal symmetry and is known
as hexagonal close-packing (hcp) structure. This packing is more
efficient and leaves small space which is unoccupied by spheres. In
two dimension central sphere is in contact with six other spheres. Only
26% space is free. In three dimension, the coordination number is 12.
A single unit cell has 4 atoms.
Cubic close-packing (ccp) : Again, if we start with hexagonal layer of
spheres and second layer of spheres is arranged by placing the spheres
over the voids of the first layer, half of these holes can be filled by these
spheres. Presume that spheres in the third layer are arranged to cover
octahedral holes. This arrangement leaves third layer not resembling with
either first or second layer, but fourth layer is similar to first, fifth layer
to second, sixth to third and so on giving pattern ABC ABC ABC....... This
arrangement has cubic symmetry and is known as cubic close-packed
(ccp) arrangement. This is also called face centred cubic (fcc).
(ii) Crystal lattice : A regular arrangement of the constituent particles
(i.e., atoms, ions or molecules) of a crystal in three dimensional space is
called crystal lattice or space lattice.
Unit cells : The smallest three dimensional portion of a complete space
lattice which when repeated over and over again in different directions
produces the complete space lattice is called the unit cell.
(iii) The empty spaces left between closed packed spheres are called voids
or holes.
T T T T T T
O O O O O O
T T T T T
O O O O O O
(a) Octahedral voids : This void is surrounded by six spheres and

formed by a combination of two triangular voids of the first and second
layer. There is one octahedral void per atom in a crystal. The radius ratio
 r 
void
  is 0.414.
 rsphere 
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(b) Tetrahedral voids : These voids are surrounded by four spheres which
lie at the vertices of a regular tetrahedron. There are two tetrahedral voids
 r 
per atom in a crystal and the radius ratio  void  is 0.225.
 rsphere 
 
8. How many lattice points are there in one unit cell of each of the following
lattice?
(i) Face-centred cubic
(ii) Face-centred tetragonal
(iii) Body-centred
Soln. Lattice points in face-centred cubic or face-centred tetragonal
= 8 (at corners) + 6 (at face-centres) = 14
Lattice points in body-centred cube
= 8 (at corners) + 1 (at body-centre) = 9
9. Explain :
(i) The basis of similarities and differences between metallic and ionic
crystals.
(ii) Ionic solids are hard and brittle.
Soln. (i) Similarities : Both ionic and metallic crystals have electrostatic
forces of attraction. In ionic crystals, these are between the oppositely
charged ions. In metals, these are among the valence electrons and the
kernels. That is why both have non-directional bonds.
Differences : (a) In ionic crystals, the ions are not free to move. Hence,
they cannot conduct electricity in the solid state. They can do so only in
the molten state or in aqueous solution. In metals, the valence electrons
are free to move. Hence, they can conduct electricity in the solid state.
(b) Ionic bond is strong due to electrostatic forces of attraction. Metallic
bond may be weak or strong depending upon the number of valence
electrons and the size of the kernels.
(ii) Ionic crystals are hard because they have strong electrostatic forces
of attraction among the oppositely charged ions. They are brittle because
ionic bond is non-directional.
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10. Calculate the efficiency of packing in case of a metal crystal for
(i) simple cubic
(ii) face-centred cubic (with the assumptions that atoms are touching each
other).
(iii) body-centred cubic
Soln. (i) In a simple cubic unit cell :
Suppose the edge length of the unit cell = a and radius of the sphere = r
As spheres are touching each other, evidently, a = 2r

1
No. of spheres per unit cell = × 8 = 1
8
4 3 r r
Volume of the sphere = pr
3
Volume of the cube = a = (2r)3 = 8r3
3 a
4 
∴ Fraction occupied, i.e., packing fraction =  pr 3  / 8r 3 = 0.524
3 
or % occupied i.e., packing efficiency = 52.4%
(ii) In face-centred cubic structure : As sphere A
on the face-centre is touching the spheres at
the corners, evidently AC = 4r.
B C
But from right angled triangle ABC,
AC = AB2 + BC 2 = a2 + a2 = 2a
4
∴ 2 a = 4r or a = r
2 3
 4  32 3
∴ Volume of the unit cell = a =  r = 3
r A a B
 2  2
C
1 1
No. of spheres in the unit cell = 8 × +6× =4
8 2
4 3 16 3
Volume of four spheres = 4 × pr = pr
3 3
16 pr 3 / 3
∴ Fraction occupied i.e., packing fraction = = 0.74
32r 3 / 2
or % occupied i.e., packing efficiency = 74%
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(iii) In body-centred cubic structure : As the C
sphere at the body-centre touches the spheres at
the corners, body diagonal, AD = 4r. A B
Further, face diagonal,
D
AC = AB2 + BC 2 = a2 + a2 = 2a
and body diagonal,
AD = AC 2 + CD 2 = 2a2 + a2 = 3a
4r
∴ 3 a = 4r or a =
3 3
 4r  64r 3
∴ Volume of the unit cell = a =   = 3
 3 3 3
1
No. of spheres per unit cell = 8 × +1= 2
8
4 3 8 3
Volume of two spheres = 2 × pr = pr
3 3
8 3
pr
∴ Fraction occupied i.e., packing fraction = 3 3 = 0.68
64r
3 3
or % occupied i.e., packing efficiency = 68%
11. Silver crystallises in fcc lattice. If edge length of the cell is 4.07 × 10–8 cm
and density is 10.5 g cm–3, calculate the atomic mass of silver.
d × a 3 × NA 10.5 × ( 4.07 × 10 −8 )3 × ( 6.02 × 10 23 )
Soln. M = =
Z 4
= 106.5 g mol –1
12. A cubic solid is made of two elements P and Q. Atoms of Q are at the
corners of the cube and P at the body-centre. What is the formula of the
compound? What are the coordination numbers of P and Q ?
Soln. As atoms Q are present at the eight corners of the cube, therefore
1
number of atoms of Q in the unit cell = ×8=1
8
As atoms P are present at the body-centre, therefore, number of atoms of
P in the unit cell = 1
Hence, the formula of the compound is PQ.
Coordination number of each of P and Q = 8
13. Niobium crystallises in body-centred cubic structure. If density is

8.55 g cm–3, calculate atomic radius of niobium using its atomic mass 93 u.
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Soln. Given d = 8.55 g cm–3, M = 93 g mol–1, Z = 2 (for bcc), NA = 6.022 × 1023,
r=?
Using formula
M×Z 93 × 2
a3 = = ⇒ a3 = 3.61 × 10–23 = 36.1 × 10–24
d × N A 8.55 × 6.022 × 10 23
∴ a = 3.304 × 10–8 cm = 330.4 × 10–12 m = 330.4 pm
For body-centred cubic,
3
r= a = 0.433 a = 0.433 × 330.4 pm = 143.1 pm
4
14. If the radius of the octahedral void is r and radius of the atoms in close-
packing is R, derive relation between r and R.
Soln. R and r are the radii of the octahedral site and atoms respectively,
then from Pythagoras theorem we get
AC2 = AB2 + BC2
(2R)2 = (R + r)2 + (R + r)2 r Br
R R
or 2R = R + r ⇒ ( 2 − 1) R = r
A R R C
∴ r = 0.414 R
15. Copper crystallises into a fcc lattice with edge length 3.61 × 10–8 cm.
Show that the calculated density is in agreement with its measured value of
8.92 g cm–3.
Soln. Given a = 3.61 × 10–8 cm, Z = 4 (for fcc), M = 63.5 (for Cu),
NA = 6.022 × 1023, d = ?
Z×M 4 × 63.5
Using formula, d = 3 = = 8.97 g cm–3
a × NA ( 3.61 × 10 ) × ( 6.022 × 10 23 )
−8 3
This value is in close agreement with the measured value (8.92 g cm–3).
16. Analysis shows that nickel oxide has the formula Ni0.98O1.00. What
fractions of nickel exist as Ni2+ and Ni3+ ions?
Soln. 98 Ni-atoms are associated with 100 O-atoms. Out of 98 Ni-atoms,
suppose Ni present as Ni2+ = x
Then Ni present as Ni3+ = 98 – x
Total charge on x Ni2+ and (98 – x) Ni3+ should be equal to charge on 100
O2– ions.
Hence, x × 2 + (98 – x) × 3 = 100 × 2
or 2x + 294 – 3x = 200 or x = 94
94
∴ Fraction of Ni present as Ni2+ = × 100 = 96%
98
4
Fraction of Ni present as Ni3+ = × 100 = 4%
98
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17. What is a semiconductor? Describe the two main types of semiconductors
and contrast their conduction mechanism.
Soln. Those solids which have intermediate conductivities ranging from
10–6 to 104 ohm–1 m–1 are classified as semiconductors. As the temperature
rises, there is a rise in conductivity value because electrons from the
valence band jump to conduction band.
(i) n-type semiconductor : When a silicon or germanium crystal is doped
with group 15 element like P or As, the dopant atom forms four covalent
bonds like Si or Ge atom but the fifth electron, not used in bonding, becomes
delocalised and continues its share towards electrical conduction. Thus
silicon or germanium doped with P or As is called n-type semiconductor,
n-indicative of negative since it is the electron that conducts electricity.
(ii) p-type semiconductor : When a silicon or germanium is doped with
group 13 element like B or Al, the dopant is present only with three
valence electrons. An electron vacancy or a hole is created at the place
of missing fourth electron. Here, this hole moves throughout the crystal
like a positive charge giving rise to electrical conductivity. Thus Si or Ge
doped with B or Al is called p-type semiconductor, p stands for positive
hole, since it is the positive hole that is responsible for conduction.
Positive hole
Silicon atom Mobile electron (no electron)
As B
Perfect crystal n-type p -type
18. Non-stoichiometric cuprous oxide, Cu2O can be prepared in laboratory.

In this oxide, copper to oxygen ratio is slightly less than 2 : 1. Can you
account for the fact that this substance is a p-type semiconductor?
Soln. The ratio less than 2 : 1 in Cu2O shows cuprous (Cu+) ions have been
replaced by cupric (Cu2+) ions. For maintaining electrical neutrality, every
two Cu+ ions will be replaced by one Cu2+ ion thereby creating a hole. As
conduction will be due to the presence of these positive holes, hence it is
a p-type semiconductor.
19. Ferric oxide crystallises in a hexagonal close-packed array of oxide ions

with two out of every three octahedral holes occupied by ferric ions. Derive
the formula of the ferric oxide.
Soln. Suppose the number of oxide ions (O2–) in the packing = 90
∴ Number of octahedral voids = 90
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As 2/3rd of the octahedral voids are occupied by ferric ions, therefore,
2
number of ferric ions present = × 90 = 60
3
∴ Ratio of Fe3+ : O2– = 60 : 90 = 2 : 3
Hence, the formula of ferric oxide is Fe2O3.
20. Classify each of the following as being either a p-type or n-type

semiconductor :
(i) Ge doped with In (ii) B doped with Si.
Soln. (i) Ge is group 14 element and In is group 13 element. Hence, an
electron deficient hole is created and therefore, it is a p-type semiconductor.
(ii) B is group 13 element and Si is group 14 element, there will be a free
electron, So, it is an n-type semiconductor.
21. Gold (atomic radius = 0.144 nm) crystallises in a face-centred unit cell.
What is the length of a side of the cell?
Soln. Given r = 0.144 nm, a = ?
For fcc, a = 2 2 r = 2 × 1.414 × 0.144 nm = 0.407 nm
22. In terms of band theory, what is the difference
(i) between a conductor and an insulator
(ii) between a conductor and a semiconductor?
Soln. In most of the solids and in many insulating solids conduction
takes place due to migration of electrons under the influence of electric
field. However, in ionic solids, it is the ions that are responsible for the
conducting behaviour due to their movement.
(i) In metals, conductivity strongly depends upon the number of valence
electrons available in an atom. The atomic orbitals of metal atoms form
molecular orbitals which are so close in energy to each other, as to form a
band. If this band is partially filled or it overlaps with the higher energy
unoccupied conduction band, then electrons can flow easily under an
applied electric field and the metal behaves as a conductor.
Conduction band
Empty Empty
band band
Forbidden zone Small energy gap

(Large energy gap)
Energy
Filled
band
Partially Overlapping
filled bands
band
Metal Insulator Semiconductor
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If the gap between valence band and next higher unoccupied conduction
band is large, electrons cannot jump into it and such a substance behaves
as insulator.
(ii) If the gap between the valence band and conduction band is
small, some electrons may jump from valence band to the conduction
band. Such a substance shows some conductivity and it behaves as a
semiconductor. Electrical conductivity of semiconductors increases with
increase in temperature, since more electrons can jump to the conduction
band. Silicon and germanium show this type of behaviour and are called
intrinsic semiconductors. Conductors have no forbidden band.
23. Explain the following terms with suitable examples :

(i) Schottky defect (ii) Frenkel defect
(iii) Interstitial defect (iv) F-centres.
Soln. (i) Schottky defect : In Schottky defect a pair of vacancies or holes
exist in the crystal lattice due to the absence of equal number of cations and
anions from their lattice points. It is a common defect in ionic compounds
of high coordination number where both cations and anions are of the
same size, e.g., KCl, NaCl, KBr, etc. Due to this defect density of crystal
decreases and it begins to conduct electricity to a smaller extent.
(ii) Frenkel defect : This defect arises when some of the ions in the lattice
occupy interstitial sites leaving lattice sites vacant. This defect is generally
found in ionic crystals where anion is much larger in size than the cation,
e.g., AgBr, ZnS, etc. Due to this defect density does not change, electrical
conductivity increases to a small extent and there is no change in overall
chemical composition of the crystal.
A+ B– A+ A+ A+ B– A+ B– A+
A+
B– B– A+ B– B– B– A+ B–
A+ B– A+ B– A+ A+ B– A+ B– A+
B– A+ B– A+ B– B– A+ B– A+ B–
Schottky defect in crystals Frenkel defect in crystals
(iii) Interstitial defect : When some constituent particles (atoms or

molecules) occupy an interstitial site of the crystal, it is said to have
interstitial defect. Due to this defect the density of the substance
increases.
(iv) F-Centres : These are the anionic sites occupied by unpaired electrons.
F-centres impart colour to crystals. The colour results by the excitation of
electrons when they absorb energy from the visible light falling on the
crystal.
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24. Aluminium crystallises in a cubic close packed structure. Its metallic
radius is 125 pm.
(i) What is the length of the side of the unit cell?
(ii) How many unit cells are there in 1.00 cm3 of aluminium?
Soln. Given r = 125 pm, a = ?, structure = ccp (fcc)
(i) For ccp (fcc), a = 2 2 r
= 2 × 1.414 × 125 pm = 354 pm
(ii) Volume of one unit cell = a3
= (354 × 10–10 cm)3 = 4.44 × 10–23 cm3
1 cm 3
Number of unit cells in 1 cm = 3
= 2.25 × 1022
4.44 × 10 −23 cm 3
25. IfNaCl is doped with 10–3 mol % SrCl2, what is the concentration of
cation vacancies ?
Soln. Let moles of NaCl = 100
∴ Moles of SrCl2 doped = 10–3
Each Sr2+ will replace two Na+ ions. To maintain electrical neutrality it
occupies one position and thus creates one cation vacancy.
∴ Moles of cation vacancy in 100 moles NaCl = 10–3
Moles of cation vacancy in one mole NaCl = 10–3 × 10–2 = 10–5
∴ Number of cation vacancies = 10–5 × 6.022 × 1023 = 6.022 × 1018 mol–1
26. Explain the following with suitable example :

(i) Ferromagnetism (ii) Paramagnetism
(iii) Ferrimagnetism (iv) Antiferromagnetism
(v) 12-16 and 13-15 group compounds.
Soln. (i) Ferromagnetic substances :
Substances which are attracted very strongly by a magnetic field are called
ferromagnetic substances, e.g., Fe, Ni, Co and CrO2 show ferromagnetism.
Such substances remain permanently magnetised, once they have been
magnetised. This type of magnetic moments are due to unpaired electrons
in the same direction.
The ferromagnetic material, CrO2, is used to make magnetic tapes used
for audio recording.
(ii) Paramagnetic substances : Substances which are weakly attracted

by the external magnetic field are called paramagnetic substances. The
property thus exhibited is called paramagnetism. They are magnetised
in the same direction as that of the applied field. This property is shown
by those substances whose atoms, ions or molecules contain unpaired
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electrons, e.g., O2, Cu2+, Fe3+, etc. These substances, however, lose their
magnetism in the absence of the magnetic field.
(iii) Ferrimagnetic substances : Substances which are expected to possess
large magnetism on the basis of the unpaired electrons but actually
have small net magnetic moment are called ferrimagnetic substances,
e.g., Fe3O4, ferrites of the formula M2+Fe2O4 where M = Mg, Cu, Zn, etc.
Ferrimagnetism arises due to the unequal number of magnetic moments
in opposite direction resulting in some net magnetic moment.
(iv) Antiferromagnetic substances : Substances which are expected

to possess paramagnetism or ferromagnetism on the basis of unpaired
electrons but actually they possess zero net magnetic moment are called
antiferromagnetic substances, e.g., MnO. Antiferromagnetism is due
to the presence of equal number of magnetic moments in the opposite
directions.
(v) 13-15 group compounds : When the solid state materials are produced
by combination of elements of groups 13 and 15, the compounds thus
obtained are called 13-15 compounds. For example, InSb, AlP, GaAs, etc.
12-16 group compounds : Combination of elements of groups
12 and 16 yield some solid compounds which are referred to as
12-16 compounds. For example, ZnS, CdS, CdSe, HgTe, etc. In these
compounds, the bonds have ionic character.
Chapter Intext Question

1. Why are solids rigid?
Soln. Unlike gases and liquids in which the molecules are free to move
about and hence constitute fluid state, in a solid, the constituent particles
are not free to move but oscillate about their fixed positions providing
them a rigid structure.
2. Why do solids have a definite volume?

Soln. The constituent particles in solids are bound to their mean positions
by strong cohesive forces of attraction. The interparticle distances remain
unchanged at a given temperature and thus solids have a definite
volume.
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3. Classify the following as amorphous or crystalline solids: Polyurethane,
naphthalene, benzoic acid, teflon, potassium nitrate, cellophane, polyvinyl
chloride, fibre glass, copper.
Soln. Amorphous solids : Polyurethane, teflon, cellophane, polyvinyl
chloride and fibre glass
Crystalline solids : Naphthalene, benzoic acid, potassium nitrate and
copper
4. Why is glass considered a supercooled liquid?

Soln. Glass is an amorphous solid. Like liquids, it has a tendency to flow,
though very slowly. This is evident from the fact that the glass panes in
the windows or doors of old buildings are invariably found to be slightly
thicker at the bottom than at the top. This is because the glass flows down
very slowly and makes the bottom portion slightly thicker.
5. Refractive index of a solid is observed to have the same value along

all directions. Comment on the nature of this solid. Would it show cleavage
property?
Soln. Since the solid has the same value of refractive index along all
directions, it is isotropic in nature. It is because there is no long range
order and the arrangement is irregular along all the directions and hence,
amorphous. Being an amorphous solid, it would not show a clean cleavage
when cut with a knife. Instead, it would break into pieces with irregular
surfaces.
6. Classify the following solids in different categories based on the nature

of intermolecular forces operating in them :
potassium sulphate, tin, benzene, urea, ammonia, water, zinc sulphide,
graphite, rubidium, argon, silicon carbide.
Soln. Ionic solids : Potassium sulphate, zinc sulphide
Covalent solids : Graphite, silicon carbide
Molecular solids : Benzene, urea, ammonia, water, argon
Metallic solids : Rubidium, tin
7. Solid A is a very hard electrical insulator in solid as well as in molten

state and melts at extremely high temperature. What type of solid is it?
Soln. Covalent or network solid
8. Ionic solids conduct electricity in molten state but not in solid state.
Explain.
Soln. Ionic solids conduct electricity in molten state since in the molten
state, ionic solids dissociate to give free ions. However, in the solid state,
since the ions are not free to move about but remain held together by
strong electrostatic forces of attraction, they do not conduct electricity.
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9. What type of solids are electrical conductors, malleable and ductile?
Soln. Metallic solids conduct electricity in solid state and are malleable
and ductile.
10. Give the significance of a ‘lattice point’.

Soln. Constituent particles of a crystalline solid are arranged in a definite
fashion in a three dimensional crystal lattice. Each position which is
occupied by the atoms, ions or molecules in the crystal lattice is called a
lattice point.
11. Name the parameters that characterise a unit cell.

Soln. The size and shape of a unit cell is determined by the lengths
of the edges of the unit cell (a, b and c) which may or may not be
mutually perpendicular and by the angles α, β and γ between the edges
b and c, c and a and a and b respectively.
12. Distinguish between

(i) Hexagonal and monoclinic unit cells
(ii) Face-centred and end-centred unit cells.
Soln. (i) (a) Hexagonal unit cell : a = b ≠ c
α = β = 90°, γ = 120°
Examples are graphite, ZnO.
(b) Monoclinic unit cell : a ≠ b ≠ c
α = γ = 90°, β ≠ 90°
Examples are Na2SO4·10H2O, monoclinic S.
(ii) (a) Face-centred unit cell : Lattice points are at the corners and centre
of each face.
1 1
No. of atoms per unit cell = 8 × + 6× = 4
8 2
(b) End-centred unit cell : Lattice points are at the corners and at the
centres of two end faces.
1 1
No. of atoms per unit cell = 8 × + 2× = 2
8 2
13. Explain how much portion of an atom located at (i) corner and (ii) body-
centre of a cubic unit cell is part of its neighbouring unit cell.
Soln. (i) A point lying at the corner of a unit cell is shared equally by eight
unit cells and therefore, only one-eighth (1/8) of each such point belongs
to the given unit cell.
(ii) A body-centred point belongs entirely to one unit cell since it is not
shared by any other unit cell.
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14. What is the two dimensional coordination number of a molecule in
square close-packed layer?
Soln. In such an arrangement, each sphere is in contact with four of its
neighbours. Thus, the two dimensional coordination number is four.
15. A compound forms hexagonal close-packed structure. What is the total

number of voids in 0.5 mol of it? How many of these are tetrahedral voids?
Soln. Number of atoms in 0.5 mol close packing = 0.5 × 6.022 × 1023
= 3.011 × 1023
Number of octahedral voids = Number of atoms in the packing
= 3.011 × 1023
Number of tetrahedral voids = 2 × Number of atoms in the packing
= 2 × 3.011 × 1023 = 6.022 × 1023
Total number of voids = 3.011 × 1023 + 6.022 × 1023 = 9.033 × 1023
16. A compound is formed by two elements M and N. The element N forms

ccp and atoms of M occupy 1/3rd of tetrahedral voids. What is the formula of
the compound?
Soln. Suppose no. of atoms of element N = a
Number of tetrahedral voids = 2a
Number of atoms of element M = 1 × 2 a = 2 a

3 3
2a
Ratio of M and N = :a= 2:3
3
Formula of the compound = M2N3
17. Which of the following lattices has the highest packing efficiency
(i) simple cubic (ii) body-centred cubic and (iii) hexagonal close-packed
lattice?
Soln. (i) Simple cubic - 52%
(ii) Body-centred cubic - 68%
(iii) Hexagonal close-packed - 74%
Hence hcp lattice has the highest packing efficiency.
18. An element with molar mass 2.7 × 10–2 kg mol–1 forms a cubic unit cell
with edge length 405 pm. If its density is 2.7 × 103 kg m–3, what is the nature
of the cubic unit cell?
Soln. Given M (molar mass of the element) = 2.7 × 10–2 kg mol–1
a (edge length) = 405 pm = 405 × 10–12 m = 4.05 × 10–10 m
d (density) = 2.7 × 103 kg m–3
NA (Avogadro’s number) = 6.022 × 1023 mol–1
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Using formula,
Z×M d × a3 × N A
Density (d) = or, Z =
a3 × N A M
( 2.7 × 10 3 )( 4.05 × 10 −10 )3 ( 6.022 × 10 23 )
or, Z = =4
2.7 × 10 −2
Number of atoms of the element present per unit cell = 4. Hence, the cubic
unit cell must be face-centred or cubic close packed (ccp).
19. What type of defect can arise when a solid is heated? Which physical
property is affected by it and in what way?
Soln. On heating a solid, vacancy defect is produced in the crystal. This
is because on heating, some lattice sites become vacant. As a result of this
defect, the density of the substance decreases because some atoms or ions
leave the crystal completely.
20. What type of stoichiometric defect is shown by :

(i) ZnS (ii) AgBr
Soln. (i) ZnS - Frenkel defect
(ii) AgBr - Both Frenkel and Schottky defect
21. Explain how vacancies are introduced in an ionic solid when a cation of
higher valency is added as an impurity in it.
Soln. When a cation of higher valency is added as an impurity in the ionic
solid, some of the sites of the original cations are occupied by the cations
of higher valency. Each cation of higher valency replaces two or more
original cations and occupies the site of one original cation and the other
site(s) remains vacant.
22. Ionic solids, which have anionic vacancies due to metal excess defect,
develop colour. Explain with the help of a suitable example.
Soln. A negative ion may be missing from its lattice site, leaving a hole which
is occupied by an electron, thereby maintaining the electrical balance. The
electrons thus trapped in the anion vacancies are called F-centres because
they are responsible for imparting colour to the crystals.
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For example, when NaCl is heated in an atmosphere of Na vapour, the
excess of Na atoms deposit on the surface of NaCl crystal.
The Cl– ions diffuse to the surface of the crystal and combine with Na
atoms to give NaCl. This happens by loss of electrons by sodium atoms to
form Na+ ions. The released electrons diffuse into the crystal and occupy
anionic sites. As a result the crystal now has an excess of sodium. The
anionic sites are occupied by unpaired electrons.
They impart yellow colour to the crystals of NaCl. The colour results by
the excitation of these electrons when they absorb energy from the visible
light falling on crystals.
23. A group 14 element is to be converted into n-type semiconductor by

doping it with a suitable impurity. To which group should this impurity
belong?
Soln. n-type semicondcutor means conduction due to presence of
excess of electrons. Therefore, to convert group 14 element into n-type
semicondutor, it should be doped with group 15 element.
24. What type of substances would make better permanent magnets,
ferromagnetic or ferrimagnetic. Justify your answer.
Soln. Ferromagnetic substances make better permanent magnets. This
is because the metal ions of a ferromagnetic substance are grouped into
small regions called ‘domains’. Each domain acts as a tiny magnet. These
domains are randomly oriented. When a ferromagnetic substance is
placed in a magnetic field, all the domains get oriented in the direction
of the magnetic field and a strong magnetic field is produced. Such order
of domains persists even when the external magnetic field is removed.
Hence, the ferromagnetic substance becomes a permanent magnet.
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Chapter 2
Solutions
Summary
A solution is a homogeneous mixture of two or more substances. Solutions are
classified as solid, liquid and gaseous solutions. The concentration of a solution is
expressed in terms of mole fraction, molarity, molality and in percentages. The
dissolution of a gas in a liquid is governed by Henry’s law, according to which, at a
given temperature, the solubility of a gas in a liquid is directly proportional to
the partial pressure of the gas. The vapour pressure of the solvent is lowered by
the presence of a non-volatile solute in the solution and this lowering of vapour
pressure of the solvent is governed by Raoult’s law, according to which the relative
lowering of vapour pressure of the solvent over a solution is equal to the mole
fraction of a non-volatile solute present in the solution. However, in a binary
liquid solution, if both the components of the solution are volatile then another
form of Raoult’s law is used. Mathematically, this form of the Raoult’s law is stated
0 0
as: p total = p1 x 1 + p 2 x 2 . Solutions which obey Raoult’s law over the entire range
of concentration are called ideal solutions. Two types of deviations from Raoult’s
law, called positive and negative deviations are observed. Azeotropes arise due to
very large deviations from Raoult’s law.
The properties of solutions which depend on the number of solute particles and
are independent of their chemical identity are called colligative properties. These
are lowering of vapour pressure, elevation of boiling point, depression of freezing
point and osmotic pressure. The process of osmosis can be reversed if a pressure
higher than the osmotic pressure is applied to the solution. Colligative properties
have been used to determine the molar mass of solutes. Solutes which dissociate in
solution exhibit molar mass lower than the actual molar mass and those which
associate show higher molar mass than their actual values.
Quantitatively, the extent to which a solute is dissociated or associated can be
expressed by van’t Hoff factor i. This factor has been defined as ratio of normal
molar mass to experimentally determined molar mass or as the ratio of observed
colligative property to the calculated colligative property.
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1. Define the term solution. How many types of solutions are formed?
Write briefly about each type with an example.
Soln. Solution - A solution is a homogeneous mixture of two or more

pure substances which are chemically non-reacting, whose composition
can be varied within certain limits. The component which is present in
a large proportion in the solution is called solvent and the component
present in relatively small proportion is called solute.
Types of solutions : Depending upon the physical state of solvent,
solutions can be divided into three main groups :
(a) Gaseous solutions :
(i) Solvent - gas, solute - gas. e.g., air (oxygen and nitrogen).
(ii) Solvent - gas, solute - liquid. e.g., humidity in air.
(iii) Solvent - gas, solute - solid. e.g., camphor in nitrogen.
(b) Liquid solutions :
(i) Solvent - liquid, solute - gas. e.g., aerated drinks.

(ii) Solvent - liquid, solute - liquid. e.g., ethanol in water.
(iii) Solvent - liquid, solute - solid. e.g., salt solution in water.
(c) Solid solutions :
(i) Solvent - solid, solute - gas. e.g., H2 in palladium.

(ii) Solvent - solid, solute - liquid. e.g., amalgam of Hg with Na.
(iii) Solvent - solid, solute - solid. e.g., alloys.
2. Give an example of a solid solution in which the solute is a gas.
Soln. Solution of hydrogen in palladium and dissolved gases in minerals.
3. Define the following terms :
(i) Mole fraction (ii) Molality

(iii) Molarity (iv) Mass percentage.
Soln. (i) Mole fraction : Mole fraction of a constituent (solute as well as
solvent) is the ratio of the number of moles of one component to the total
number of moles of all the components present in the solution. If nA and
nB are the number of moles of solvent and solute respectively then
nA nB
x = and x =
A nA + nB B nA + nB
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(ii) Molality : Molality of a solution is defined as the number of moles of
the solute dissolved in one kilogram of the solvent. It is denoted by m. It
is expressed as
Number of moles of solute Number of moles of solute
m= or × 1000
Mass of solvent in kg Mass of solvent in grams
(iii) Molarity : Molarity of a solution is defined as the number of moles of
the solute dissolved in one litre or one dm3 of the solution. It is denoted by
M and is expressed as
Number of moles of solute
M=
Volume of solution in litres
(iv) Mass percentage : It may be defined as mass of solute in grams per
100 g of solution.
w Mass of solute
or mass percentage = × 100
W Total mass of solution
4. Concentrated nitric acid used in the laboratory is 68% nitric acid by
mass in aqueous solution. What should be the molarity of such a sample of
the acid if the density of the solution is 1.504 g mL–1?
Soln. Let mass of solution = 100 g
Then mass of nitric acid = 68 g
Molar mass of HNO3 = 63 g mol–1
68
Number of moles of HNO3 = = 1.079 mole
63
Density of solution = 1.504 g mL–1
100 g
∴ Volume of solution = = 66.5 mL = 0.0665 L
1.504 g mL−1
Number of moles of the solute 1.079
Molarity of the solution = =
Volume of solution in L 0.0665
= 16.23 M
5. A solution of glucose in water is labelled as 10% w/w. What would be

the molality and mole fraction of each component in the solution? If the
density of the solution is 1.2 g mL–1, then what shall be the molarity of the
solution?
∴ Mass of glucose = 10 g
Mass of water = 90 g = 0.09 kg
10
No. of moles in 10 g glucose = = 0.0555 mol
180
90
No. of moles in 90g H2O = = 5 moles
18
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100 g
Volume of solution = = 83.33 mL = 0.0833 L
1.2 g mL−1
Number of moles of solute 0.0555 mol
(a) Molality = = = 0.617 m
Mass of solvent in kg 0.09 kg
(b) x (Glucose) = Number of moles of solute = 0.0555 = 0.01

Number of moles of solution 5.0555
∴ x (H2O) = 1 – 0.01 = 0.99
Number of moles of solute 0.0555
(c) Molarity = = = 0.666 M
Volume of solution in L 0.0833
6. How many mL of a 0.1 M HCl are required to react completely with 1 g
mixture of Na2CO3 and NaHCO3 containing equimolar amounts of both?
Soln. Step 1 : Calculation of the number of moles of the components in
the mixture.
Let Na2CO3 present in the mixture = x g
∴ NaHCO3 present in the mixture = (1 – x) g
Molar mass of Na2CO3 = 2 × 23 + 12 + 3 × 16 = 106 g mol–1
Molar mass of NaHCO3 = 23 + 1 + 12 + 3 × 16 = 84 g mol–1
x
∴ No. of moles of Na2CO3 in x g =
106
1− x
No. of moles of NaHCO3 in (1 – x) g =
84
As mixture contains equimolar amounts of the two,
x 1− x 106
= or, 106 – 106x = 84x or x = g = 0.558 g
106 84 190
0.558
Thus, moles of Na2CO3 = = 0.00526
106
∴ Moles of NaHCO3 = 0.00526
Step 2 : To calculate the moles of HCl required.
Na2CO3 + 2HCl → 2NaCl + H2O + CO2
NaHCO3 + HCl → NaCl + H2O + CO2
1 mole of Na2CO3, requires HCl = 2 moles
∴ 0.00526 mole of Na2CO3 requires HCl = 0.00526 × 2 = 0.01052 mole
1 mole of NaHCO3 requires HCl = 1 mole
∴ 0.00526 mole of NaHCO3 requires HCl = 0.00526 mole
∴ Total HCl required = 0.01052 + 0.00526 = 0.01578 mole
Step 3 : To calculate volume of 0.1 M HCl
Number of moles 0.01578
Volume of acid = = = 157.8 mL
Molarity 0.1
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7. A solution is obtained by mixing 300 g of 25% and 400 g of 40% solution
by mass. Calculate the percentage of the resulting solution.
Soln. 300 g of 25% solution contains solute = 75 g
400 g of 40% solution contains solute = 160 g
Total solute = 160 + 75 = 235 g
Total solution = 300 + 400 = 700 g
235
% of solute in the final solution = × 100 = 33.5%
700
% of water in the final solution = 100 – 33.5 = 66.5%
8. An antifreeze solution is prepared from 222.6 g of ethylene glycol,
C2H4(OH)2 and 200 g of water. Calculate the molality of the solution. If the
density of the solution is 1.072 g mL–1, then what shall be the molarity of the
solution?
Soln. Mass of the solute, C2H4(OH)2 = 222.6 g
Molar mass of solute, C2H4(OH)2 = 62 g mol–1
222.6 g
∴ Moles of the solute = = 3.59
62 g mol −1
Mass of the solvent = 200 g = 0.200 kg
422.6
Volume of solution = = 394.2 mL = 0.3942 L
1.072 g mL−1
Number of moles of solute 3.59
Molality = = = 17.95 m
Mass of solvent in kg 0.2
3.59 moles
Molarity = = 9.11 mol L–1
0.3942 L
9. A sample of drinking water was found to be severely contaminated with
chloroform, CHCl3, supposed to be a carcinogen. The level of contamination
was 15 ppm (by mass):
(i) Express this in percent by mass.
(ii) Determine the molality of chloroform in the water sample.
Soln. (i) 15 ppm means 15 parts in million (106) parts by mass in the
solution.
15
% by mass = × 100 = 1.5 × 10–3
106
(ii) Mass of solvent = 106 g (Mass of solute is negligible)
Molar mass of CHCl3 = 12 + 1 + 3 × 35.5 = 119.5 g mol–1
Mass in g 15
No. of moles of CHCl3 = =
Molar mass 119.5
15 / 119.5
∴ Molality = × 1000 = 1.25 × 10–4 m
106
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10. What role does the molecular interaction play in a solution of alcohol
and water ?
Soln. There is a strong hydrogen bonding in water as well as in alcohol
molecules. When alcohol and water are mixed the intermolecular hydrogen
bonding between the alcohol and water molecules in the mixture is weak.
Due to weaker interactions, the solution shows positive deviations from
ideal behaviour. As a result, the solution will have higher vapour pressure
and lower boiling point than alcohol and water separately.
11. Why do gases always tend to be less soluble in liquids as the temperature
is raised ?
Soln. As the temperature is increased, the equilibrium in a gas in liquid
solution shifts in backward direction since dissolution of gas in liquid is
an exothermic process. Hence the solubility of the gases decreases.
12. State Henry’s law and mention some important applications.

Soln. Henry’s law : The solubility of a gas in a liquid at a particular
temperature is directly proportional to the pressure of the gas in
equilibrium with the liquid at that temperature.
or
The partial pressure of a gas in vapour phase is proportional to the mole
fraction of the gas (x) in the solution.
p = KHx
where KH is Henry’s law constant.
Applications of Henry’s law :
(i) To increase the solubility of CO2 in soft drinks, soda, etc., the bottles
are sealed under high pressure.
(ii) In deep sea diving, increased pressure increases the solubility of
atmospheric gases in blood. Oxygen is used up in the metabolism but N2
remains dissolved and forms bubbles in the blood, when diver comes to
the surface. To reduce this danger, N2 is replaced by He which is much
less soluble in biological fluids.
(iii) In the functions of lungs - when air enters the lungs, partial pressure
of oxygen is high. This oxygen combines with haemoglobin to form
oxyhaemoglobin. Partial pressure of O2 in tissues is low, hence O2 is
released from oxyhaemoglobin which is used for the functions of the
cells.
13. The partial pressure of ethane over a saturated solution containing

6.56×10 g of ethane is 1 bar. If the solution contains 5.00 × 10–2 g of ethane,
–3
then what shall be the partial pressure of the gas?

Soln. Applying the relationship, m = KH × p
In the first case, 6.56 × 10–3 g = KH × 1 bar or KH = 6.56 × 10–3 g bar–1
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In the second case, 5.00 × 10–2 g = (6.56 × 10–3 g bar–1) × p
5.00 × 10 −2 g
or, p = = 7.62 bar
6.56×10 −3 g bar −1
14. What is meant by positive and negative deviations from Raoult’s law
and how is the sign of ∆mixH related to positive and negative deviations
from Raoult’s law ?
Soln. There are two types of liquid solutions : (I) Ideal solution and
(II) Non-ideal solution.
0
PB PB
I. Ideal solution : A solution which obeys P +
P= A
Raoult’s law of vapour pressure is called an ideal
PA0 PB
solution.
PA
In these solutions, intermolecular forces between
A-A and B-B molecules are same as that of between
xA = 1 xA = 0
A and B.
xB = 0 xB = 1
∆Hmixing = 0; ∆Vmixing = 0
Ideal solution
Examples :
(i) Benzene + toluene (ii) n-Hexane + n-heptane
(iii) Chlorobenzene + bromobenzene (iv) Ethyl bromide + ethyl iodide
II. Non-ideal solution : A solution which does not obey Raoult’s law of
vapour pressure is called non-ideal solution. They are of two types.
(a) Non-ideal solution with negative deviation: PB 0
PB
When intermolecular forces between A and B = PA +
P
are stronger than between A-A and B-B, then PA0
PB
intermolecular force increases, volume decreases, PA
vapour pressure decreases and heat is released.
Hence, DV= –ve, DH = –ve, DP = –ve xA = 1 xA = 0
This is why, the solution is known as non-ideal xB = 0 xB = 1
solution with –ve deviation.
Non-ideal solution with
PA < xA P0A , PB < xB P0B and PS < xA P0A + xB P0B negative deviation
Examples :
(i) Chloroform + acetone (ii) Water + sulphuric acid
(iii) HCl + water (iv) Acetone + aniline
(b) Non-ideal solution with positive deviation: PB
= PA + PB
0
When intermolecular forces between A and B are P
weaker than that of A-A and B-B. PA
PA0
In this case intermolecular force decreases, volume
PB
increases, vapour pressure increases, enthalpy
increases.
xA = 1 xA = 0
DV = +ve, DH = + ve, DP = +ve
xB = 0 xB = 1
So, it is called non-ideal solution with positive
Non-ideal solution with
deviation.
positive deviation
PA > xA P0A, PB > xB P0B and PS > xA P0A + xB P0B
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Examples :
(i) Ethanol + water (ii) Chloroform + ethanol
15. An aqueous solution of 2% non-volatile solute exerts a pressure of

1.004 bar at the normal boiling point of the solvent. What is the molecular
mass of the solute ?
Soln. Vapour pressure of pure water at the boiling point (P0) = 1 atm
= 1.013 bar
Vapour pressure of solution (Ps) = 1.004 bar
Let mass of solution = 100 g, then, mass of solute = (w2) = 2 g
Mass of solvent (w1) = 100 – 2 = 98 g
Applying Raoult’s law for dilute solution,
P 0 − Ps n2 n w / M2 w M
0
= = 2 = 2 = 2 × 1
P n1 + n2 n1 w1 / M1 M 2 w1
1.013 − 1.004 2 g 18 g mol −1
= ×
1.013 M2 98 g
2 × 18 1.013
or, M2 = × g mol −1 = 41.35 g mol–1
98 0.009
16. Heptane and octane form ideal solution. At 373 K, the vapour pressure
of the two liquid components are 105.2 kPa and 46.8 kPa respectively. What
will be the vapour pressure of a mixture of 26.0 g of heptane and 35.0 g of
octane?
Soln. Molar mass of heptane (C7H16) = 100 g mol–1
Molar mass of octane (C8H18) = 114 g mol–1
26.0 g
Number of moles of heptane = = 0.26 mol
100 g mol −1
35.0 g
No. of moles of octane = = 0.31 mol
114 g mol −1
0.26
x (heptane) = = 0.456
0.26 + 0.31
x (octane) = 1– 0.456 = 0.544
p(heptane) = 0.456 × 105.2 kPa = 47.97 kPa
p(octane) = 0.544 × 46.8 kPa = 25.46 kPa
PTotal = 47.97 + 25.46 = 73.43 kPa
17. The vapour pressure of water is 12.3 kPa at 300 K. Calculate the vapour
pressure of 1 molal solution of a solute in it.
Soln. Given P0 = 12.3 kPa, Ps = ? m = 1, No. of moles of solute = 1,
1000
No. of moles of water = = 55.5
18
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1
∴ Mole fraction of solute = = 0.0177
1 + 55.5
P 0 − Ps
From Raoult’s law, = x2 ,
P0
i.e., 12.3 − Ps = 0.0177 or Ps = 12.08 kPa
12.3
18. Calculate the mass of a non-volatile solute (molar mass 40 g mol–1)
which should be dissolved in 114 g octane to reduce its vapour pressure to
80%.
w
Soln. Number of moles of solute = mol
40
Let P0 = 100 then Ps = 80, DP = 20
114 g
No. of moles of solvent (octane) = = 1 mol
114 g mol −1
[molar mass of C8H18 = 114 g mol–1]
∆P 20 w / 40
Now, = x2 ∴ =
P0 100 w
+1
40
 w  w 0.8 w
or, 0.2  + 1 = or, = 0.2 or w = 10 g
 40  40 40
19. A solution containing 30 g of non-volatile solute exactly in 90 g
water has a vapour pressure of 2.8 kPa at 298 K. Further 18 g of water is
then added to the solution, the new vapour pressure becomes 2.9 kPa at
298 K. Calculate
(i) molar mass of the solute (ii) vapour pressure of water at 298 K.
Soln. (i) Suppose the molar mass of the solute = M g mol–1
30
No. of moles of solute, n2= moles
M
90 g
No. of moles of solvent, H2O, n1 = = 5 moles
18 g mol −1
30
P 0 − Ps n2 P 0 − 2.8
From Raoult’s law, = , i.e., = M
P0 n1 + n2 P0 30
5+
M
30 30 30 30
2.8 5+ − 5
M 2.8 M M M =
or, 1 − 0 = or = 1− =
P 30 P 0 30 30 30
5+ 5+ 5+ 5+
M M M M
||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
30
5+
P0 M = 1+ 6
or, = ... (i)
2.8 5 M
After adding 18 g of water, n1 = 6 moles
30 30
P 0 − 2.9 2 . 9
= M or, 1 − 0 = M
P0 30 P 30
6+ 6+
M M
30 30 30 30
6+ − 6 6+
2.9 M M M P 0
M = 1+ 5
or, = 1− = = or = …(ii)
P 0 30 30 30 2.9 6 M
6+ 6+ 6+
M M M
Dividing eqn. (i) by eqn. (ii), we get
6
2.9 1 + M  5  6 
= or, 2.9  1 +  = 2.8  1 +
2.8 5  M  M 
1+
M
14.5 16.8 2.3
or, 2.9 + = 2.8 + or, = 0.1 or M = 23 u
M M M
(ii) Putting M = 23 in eqn. (i) we get
P0 6 29 29
= 1+ = or P 0 = × 2.8 = 3.53 kPa
2.8 23 23 23
20. A 5% solution (by mass) of cane sugar in water has freezing point of
271 K. Calculate the freezing point of a 5% glucose in water if freezing point
of pure water is 273.15 K.
5 1000
Soln. Molality of sugar solution = × = 0.146 m
342 100
∆Tf for sugar solution = 273.15 – 271 = 2.15
∆T f 2.15
DTf = Kf × m ∴ Kf = =
m 0.146
5 1000
Molality of glucose solution = × = 0.278 m
180 100
2.15
∴ DTf (Glucose) = × 0.278 = 4.09°
0.146
∴ Freezing point of glucose solution = 273.15 – 4.09 = 269.06 K
21. Two elements A and B form compounds having molecular formula AB2
and AB4. When dissolved in 20.0 g of benzene (C6H6), 1.0 g AB2 lowers the
freezing point by 2.3°C whereas 1.0 g of AB4 lowers the freezing point by
1.3 °C. The molal depression constant for benzene is 5.1 K kg mol–1. Calculate
atomic mass of A and B.
||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
w2 × 1000 1 × 1000
Soln. For AB2, DTf = K f × or, 2.3 = 5.1 ×
M 2 × w1 M 2 × 20
50 × 5.1
∴ M2 = = 110.86 g mol–1
2.3
1 × 1000
Similarly for AB4 , 1.3 = 5.1 ×
M 2 × 20
50 × 5.1
∴ M2 = = 196.15 g mol–1
1.3
Now, molecular weight of AB2 = 110.86, molecular weight of AB4 = 196.15
AB4 = A + 4B = 196.15 ... (i)
AB2 = A + 2B = 110.86 ... (ii)
(i) – (ii) gives 2B = 85.29
∴ B = 42.645 u
Putting the value of B in equation (ii),
A + 2 × 42.645 = 110.86 or, A = 110.86 – 85.29 = 25.57 u
22. At 300 K, 36 g of glucose present in a litre of its solution has an osmotic
pressure of 4.98 bar. If the osmotic pressure of the solution is 1.52 bar at the
same temperature, what would be its concentration?
Soln. p = CRT
36
∴ In the first case, 4.98 = × R × 300 = 60R ... (i)
180
In the second case, 1.52 = C × R × 300 ... (ii)
Dividing (ii) by (i) we get, C = 0.061 M
23. Suggest the most important type of intermolecular attractive interaction
in the following pairs.
(i) n-Hexane and n-octane (ii) I2 and CCl4
(iii) NaClO4 and water (iv) Methanol and acetone
(v) Acetonitrile (CH3CN) and acetone (C3H6O).
Soln. (i) n-Hexane and n-octane : London dispersion forces as both the
molecules are non-polar.
(ii) I2 and CCl4 : London dispersion forces as both the molecules are non-
polar.
(iii) NaClO4 and water : Ion-dipole interactions as NaClO4 in water gives
–
Na+ and ClO 4 Ions. These ions interact with polar water molecules.
(iv) Methanol and acetone : Dipole-dipole interactions as both the
molecules are polar.
(v) Acetonitrile and acetone : Dipole-dipole interactions as both the
molecules are polar.
24. Based on solute-solvent interactions, arrange the following in order of
increasing solubility in n-octane and explain.
Cyclohexane, KCl, CH3OH, CH3CN.
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Soln. (i) Cyclohexane and n-octane both are non-polar. Hence, they mix
completely in all proportions.
(ii) KCl is an ionic compound while n-octane is non-polar. Hence, KCl
will not dissolve at all in n-octane.
(iii) CH3OH and CH3CN both are polar but CH3CN is less polar than
CH3OH. As the solvent is non-polar, CH3CN will dissolve more than
CH3OH in n-octane.
Thus, the order of solubility will be KCl < CH3OH < CH3CN < Cyclohexane.
25. Amongst the following compounds, identify which are insoluble,

partially soluble and highly soluble in water ?
(i) Phenol, (ii) Toluene, (iii) Formic acid,
(iv) Ethylene glycol, (v) Chloroform, (vi) Pentanol.
Soln. (i) Partially soluble because phenol has polar –OH group and non-
polar C6H5 group.
(ii) Insoluble because toluene is non-polar while water is polar.
(iii) Highly soluble because formic acid can form hydrogen bonds with
water.
(iv) Highly soluble because ethylene glycol can form hydrogen bonds
with water.
(v) Insoluble because chloroform is an organic liquid.
(vi) Partially soluble because –OH group is polar but the large hydrocarbon
part (C5H11) is non-polar.
26. If the density of some lake water is 1.25 g mL–1 and contains 92 g of Na+
ions per kg of water, calculate the molality of Na+ ions in the lake.
Soln. Number of moles in 92 g of Na+ ions
92 g
= = 4 mole (as atomic mass of Na = 23)
23 g mol −1
As these are present in 1 kg of water, by definition molality = 4 m
27. If the solubility product of CuS is 6 × 10–16, calculate the maximum

molarity of CuS in aqueous solution.
Soln. Maximum molarity of CuS in aqueous solution = Solubility of CuS
in mol L–1
If S is the solubility of CuS in mol L–1, then
CuS Cu2+ + S2–, Ksp = [Cu2+][S2–] = S × S = S2
∴ S2 = 6 × 10–16 or S = 6 × 10 −16 = 2.45 × 10–8 mol L–1
28. Calculate the mass percentage of aspirin (C9H8O4) in acetonitrile (CH3CN)

when 6.5 of C9H8O4 is dissolved in 450 g of CH3CN.
Soln. Given, Mass of aspirin = 6.5 g, Mass of acetonitrile = 450 g
||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
Mass of aspirin
Mass percent of aspirin = × 100
Mass of aspirin + Mass of acetonitrile
6.5
= × 100 = 1.424%
6.5 + 450
29. Nalorphene (C19H21NO3), similar to morphine, is used to combat
withdrawal symptoms in narcotic users. Dose of nalorphene generally given
is 1.5 mg. Calculate the mass of 1.5 × 10–3 m aqueous solution required for the
above dose.
Soln. Given, m = 1.5 × 10–3
Mass of solvent = 1 kg
Molar mass of C19H21NO3 = 19 × 12 + 21 + 14 + 48 = 311 g mol–1
∴ 1.5 × 10–3 mole of C19H21NO3 = 1.5 × 10–3 × 311g = 0.467 g = 467 mg
∴ Mass of solution = 1000 g + 0.467 g = 1000.467 g
Thus, for 467 mg of nalorphene, solution required = 1000.467 g
1000.467
For 1.5 mg of nalorphene, solution required = × 1.5 = 3.21 g
467
30. Calculate the amount of benzoic acid (C6H5COOH) required for preparing
250 mL of 0.15 M solution in methanol.
w × 1000 w × 1000 1.5 × 122
Soln. M = 2 ⇒ 0.15 = 2 or, w2 = = 4.57 g
M2 × V 122 × 250 4
31. The depression in freezing point of water observed for the same amount
of acetic acid, trichloroacetic acid and trifluoroacetic acid increases in the
order as given above. Explain briefly.
Soln. The depression in freezing point is in the order :
Acetic acid (CH3 – COOH) < trichloroacetic acid (Cl3C – COOH)
< trifluoroacetic acid (F3C – COOH)
Fluorine, being most electronegative, has the highest electron withdrawing
inductive effect. Consequently, trifluoroacetic acid is the strongest acid
while acetic acid is the weakest acid. Hence, trifluoroacetic acid ionizes to
the largest extent while acetic acid ionizes to the minimum extent to give
ions in their solutions in water. Greater the ions produced, greater is the
depression in freezing point. Hence, the depression in freezing point is
the maximum for the fluoroacetic acid and minimum for acetic acid.
32. Calculate the depression in the freezing point of water when 10 g of

CH3CH2CHClCOOH is added to 250 g of water.
(Ka = 1.4 × 10–3, Kf = 1.86 K kg mol–1)
Soln. Number of moles of CH3CH2CHClCOOH
10
= mole = 8.16 × 10–2 mole
122.5
||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
8.16 × 10 −2 mol
∴ Molality of the solution (m) = × 1000 kg −1 = 0.3264 m
250
If a is the degree of dissociation of CH3CH2CHClCOOH, then
–
CH3CH2CHClCOOH  CH3CH2CHClCOO + H+
Initial conc. C mol L–1 0 0
At equilibrium C(1 – a) Ca Ca
Cα × Cα 1.4 × 10 −3 = 0.065
∴ Ka = = Cα 2 or, a = Ka / C =
C(1 − α ) 0.3264
To calculate van’t Hoff factor:
–
CH3CH2CHClCOOH  CH3CH2CHClCOO + H+
Initial moles 1 0 0
Moles at eqm. 1 – a a a
Total moles = 1 + a ∴ i = 1 + 0.065 = 1.065
DTf = iKf m = (1.065)(1.86)(0.3264) = 0.65°
33. 19.5 g of CH2FCOOH is dissolved in 500 g of water. The depression in

the freezing point observed is 1.0°C. Calculate the van’t Hoff factor and
dissociation constant of fluoroacetic acid. Kf for water is 1.86 K kg mol–1.
Soln. Given, w2 = 19.5 g, w1 = 500 g,
Kf = 1.86 K kg mol–1, (DTf)obs = 1.0°C, M2 = ?
1000 K f w2 1000 × 1.86 × 19.5
∴ M2 (observed) = = = 72.54 g mol −1
w1∆T f 500 × 1.0
M2 (calculated) for CH2FCOOH = 78 g mol–1
( M 2 )cal 78
van’t Hoff factor (i) = = = 1.0753
( M 2 )obs 72.54
Calculation of dissociation constant :
Suppose degree of dissociation at the given concentration is a.
–
Then, CH2FCOOH → CH2FCOO + H+
Initial C 0 0
At eqm. C(1 – α) Cα Cα
Total = C(1 + α)
C(1 + α )
∴ i= = 1 + α or, α = i – 1 = 1.0753 – 1 = 0.0753
C
[CH 2 FCOO¯ ][H + ] Cα × Cα Cα 2
Again Ka = = =
[CH 2 FCOOH] C(1 − α ) 1 − α
Taking volume of the solution as 500 mL,
19.5 1 Cα 2 ( 0.5)( 0.0753)2
C= × × 1000 = 0.5 M ∴ K a = = = 3.07 × 10 −3
78 500 1− α 1 − 0.0753
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34. Vapour pressure of water at 293 K is 17.535 mm Hg. Calculate the vapour
pressure of water at 293 K when 25 g of glucose is dissolved in 450 g water.
Soln. Given, P0 = 17.535 mm Hg, w2 = 25 g, w1 = 450 g, Ps = ?
For solute (glucose, C6H12O6), M2 = 180 g mol–1,
For solvent (H2O), M1 = 18 g mol–1
P 0 − Ps n2
Applying Raoult’s law, 0
= ,
P n1 + n2
w2
P 0 − Ps n2 M 2 or, P w M
= = 1 − s0 = 2 1 ( n2<<n1)
P 0 n1 w1 P w1M 2
M1
Substituting the given value, we get
Ps 25 × 18 Ps 1
1− = or, 1 − =
17.535 450 × 180 17.535 180
1 Ps 179 Ps
1− = or, =
180 17.535 180 17.535
179
or, Ps = 17.535 × = 17.437 mm Hg
180
35. Henry’s law constant for the molality of methane in benzene at 298 K is
4.27 × 105 mm Hg. Calculate the solubility of methane in benzene at 298 K
under 760 mm Hg.
Soln. Here, KH = 4.27 × 105 mm Hg, p = 760 mm Hg
p 760
Applying Henry’s law, p = KHx ∴ x = = 5
= 1.78 × 10 −3
KH 4.27 × 10
i.e., solubility in terms of mole fraction of methane in benzene = 1.78 × 10–3
36. 100 g of liquid A (molar mass 140 g mol–1) was dissolved in 1000 g of
liquid B (molar mass 180 g mol–1). The vapour pressure of pure liquid B was
found to be 500 torr. Calculate the vapour pressure of pure liquid A and its
vapour pressure in the solution if the total vapour pressure of the solution
is 475 torr.
100 g 5
Soln. Number of moles of liquid A (solute) = −1
= mole
140 g mol 7
1000 g 50
Number of moles of liquid B (solvent) = −1
= mole
180 g mol 9
∴ Mole fraction of A in the solution (xA)
5 5
5 63 45
= 7 = 7 = × = = 0.114
5 50 395 7 395 395
+
7 9 63
||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
∴ Mole fraction of B in the solution (xB) = 1 – 0.114 = 0.886
Also, given P0B = 500 torr
Applying Raoult’s law, PA = xA P0A = 0.114 × P0A ... (i)
PB = xB P B = 0.886 × 500 = 443 torr
0
PTotal = PA + PB
475 − 443
475 = 0.114 P0A + 443 or P0A = = 280.7 torr
0.114
Substituting this value in eqn. (i), we get PA = 0.114 × 280.7 torr = 32 torr
37. Vapour pressure of pure acetone and chloroform at 328 K are
741.8 mm Hg and 632.8 mm Hg respectively. Assuming that they form
ideal solution over the entire range of composition, plot Ptotal, Pchloroform
and Pacetone as a function of xacetone. The experimental data observed for
different compositions of mixtures is :
100 × xacetone 0 11.8 23.4 36.0 50.8 58.2 64.5 72.1
Pacetone/mm Hg 0 54.9 110.1 202.4 322.7 405.9 454.1 521.1
Pchloroform/mm Hg 632.8 548.1 469.4 359.7 257.7 193.6 161.2 120.7
Plot this data also on the same graph paper. Indicate whether it has positive
deviation or negative deviation from the ideal solution.
Soln. xacetone 0.0 0.118 0.234 0.360 0.508 0.582 0.645 0.721
Pacetone/mm Hg 0 54.9 110.1 202.4 322.7 405.9 454.1 521.1
Pchloroform/mm Hg 632.8 548.1 469.4 359.7 257.7 193.6 161.2 120.7
Ptotal 632.8 603.0 579.5 562.1 580.4 599.5 615.3 641.8
700
Ptotal
600
500
400
300
Pchloroform
200
Pacetone
100
0
0 x acetone 0.2 0.4 0.6 0.8
As the plot for Ptotal dips downwards, hence the solution shows negative
deviation from the ideal behaviour.
38. Benzene and naphthalene form ideal solution over the entire range of
composition. The vapour pressures of pure benzene and naphthalene at
300 K are 50.71 mm Hg and 32.06 mm Hg respectively. Calculate the mole
fraction of benzene in the vapour phase if 80 g of benzene is mixed with
100 g of naphthalene.
Soln. Molar mass of benzene (C6H6) = 78 g mol–1
Molar mass of naphthalene (C10H8) = 128 g mol–1
80 g
∴ Number of moles in 80 g of benzene = = 1.026 mole
78 g mol −1
||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
100 g
∴ Number of moles in 100 g of naphthalene =
128 g mol −1
= 0.78125 mole
1.026 1.026
∴ In the solution, mole fraction of benzene = =
1.026 + 0.78125 1.80725

Mole fraction of naphthalene = 1 – 0.567= 0.433 = 0.567
P0Benzene = 50.71 mm Hg, P0naphthalene = 32.06 mm Hg
Applying Raoult’s law of vapour pressure
PBenzene = xBenzene × P0Benzene = 0.567 × 50.71 mm Hg = 28.75 mm Hg
Pnaphthalene = xnaphthalene × P0naphthalene
= 0.433 × 32.06 mm Hg = 13.88 mm Hg
∴ From Dalton’s law, mole fraction of benzene in the vapour phase
PBenzene 28.75 28.75
= = = = 0.6744
PBenzene + Pnaphthalene 28.75 + 13.88 42.63
39. The air is a mixture of a number of gases. The major components are
oxygen and nitrogen with approximate proportion of 20% and 79% by
volume at 298 K. The water is in equilibrium with air at a pressure of 10 atm.
At 298 K, if the Henry’s law constants for oxygen and nitrogen are 3.30 × 107
mm Hg and 6.51 × 107 mm Hg respectively, calculate the composition of
these gases in water.
Soln. Total pressure of air in equilibrium with water = 10 atmosphere
As air contains 20% oxygen and 79% nitrogen by volume,
20
∴ Partial pressure of oxygen (pO2) = × 10 atm
100
= 2 atm = 2 × 760 mm Hg = 1520 mm Hg
79
Partial pressure of nitrogen (pN2) = ×10 atm
100
= 7.9 atm = 7.9 × 760 mm Hg = 6004 mm Hg
KH(O2) = 3.30 × 10 mm Hg, KH(N2) = 6.51 × 107 mm Hg
7
Applying Henry’s law , pO2 = KH × xO2

pO 1520 mm Hg
or, xO = 2
= = 4.61 × 10–5
2 KH 3.30×107 mm Hg
pN = KH × xN
2 2
pN 6004 mm Hg
xN = 2
= 7
= 9.22 × 10–5
2 KH 6.51×10 mm Hg
40. Determine the amount of CaCl2 (i = 2.47) dissolved in 2.5 litre of water
such that its osmotic pressure is 0.75 atm at 27°C.
n p×V
Soln. From the expression, π = iCRT = i RT or, n =
V i × R×T
||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
0.75 atm × 2.5 L

=
2.47 × 0.0821 L atm K −1 mol −1 × 300 K = 0.0308 mole
Molar mass of CaCl2 = 40 + 2 × 35.5 = 111g mol–1
∴ Amount of CaCl2 dissolved = 0.0308 × 111 = 3.42 g
41. Determine the osmotic pressure of a solution prepared by dissolving
25 mg of K2SO4 in 2 litre of water at 25°C, assuming that it is completely
dissociated.
Soln. K2SO4 dissolved = 25 mg = 0.025 g
Volume of solution = 2 L, T = 25°C = 298 K
Molar mass of K2SO4 = 2 × 39 + 32 + 4 × 16 = 174 g mol–1
K2SO4 dissociates completely as, K2SO4 → 2K+ + SO42–
i.e., ions produced = 3, ∴ i = 3
n w 1
∴ π = iCRT = i RT = i × × RT
V M V
0.025 g 1
= 3× −1
× × 0.0821 L atm K −1 mol −1 × 298 K = 5.27 × 10 −3 atm
174 g mol 2L

1. Calculate the mass percentage of benzene (C6H6) and carbon
tetrachloride (CCl4) if 22 g of benzene is dissolved in 122 g of carbon
tetrachloride.
Soln. Mass of solution = Mass of benzene + Mass of carbon tetrachloride
= 22 g + 122 g = 144 g
Mass of benzene 22 g
Mass percentage of benzene = × 100 = × 100
Mass of solution 144 g
Mass of benzene 22 g
× 100 = × 100 = 15.28%
Mass of solution 144 g
∴ Mass percentage of CCl4 = 100 – Mass percentage of benzene
= 100 – 15.28 = 84.72%
2. Calculate the mole fraction of benzene in solution containing 30% by
mass in carbon tetrachloride.
∴ Mass of benzene in the solution = 30 g
∴ Mass of carbon tetrachloride = 100 – 30 g = 70 g
Molar mass of benzene (C6H6) = 78 g mol–1
Molar mass of CCl4 = 12 + 4 × 35.5 = 154 g mol–1
Mass 30 g
∴ No. of moles of benzene = = = 0.385
Molar mass 78 g mol −1
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Mass 70 g
No. of moles of CCl4 = = = 0.455
Molar mass 154 g mol −1
Total number of moles of solution = 0.385 + 0.455 = 0.84
Moles of benzene 0.385
Mole fraction of benzene = = = 0.458
Total moles in the solution 0.84
∴ Mole fraction of CCl4 = 1 – 0.458 = 0.542
3. Calculate the molarity of each of the following solutions :
(a) 30 g of Co(NO3)2·6H2O in 4.3 L of solution (b) 30 mL of 0.5 M H2SO4
diluted to 500 mL (atomic mass of cobalt = 58.7)
Soln. (a) Molar mass of Co(NO3)2·6H2O = 58.7 + 2(14 + 48) + 6 × 18
= 290.7 g mol–1
Mass 30 g
Number of moles of Co(NO3)2·6H2O = = = 0.103
Molar mass 290.7 g mol −1
Volume of solution = 4.3 L
Number of moles of solute 0.103 mole
Molarity of solution = = = 0.024 M
Volume of solution in L 4.3 L
(b) Given V1 = 30 mL, M1 = 0.5, V2 = 500 mL, M2 = ?
Using formula, V1M1 = V2M2 or, 30 × 0.5 = 500 × M2 or, M2 = 0.03
Molarity of solution = 0.03 M
4. Calculate the mass of urea (NH2CONH2) required in making 2.5 kg of
0.25 molal aqueous solution.
Soln. Moles of urea = 0.25 mole
Mass of solvent (water) = 1 kg = 1000 g
Molar mass of urea (NH2CONH2) = 14 + 2 + 12 + 16 + 14 + 2 = 60 g mol–1
∴ Mass of urea in 1000 g of water = 0.25 mol × 60 g mol–1 = 15 g
Total mass of solution = 1000 + 15 g = 1015 g = 1.015 kg
Thus, 1.015 kg of solution contain urea = 15 g
15 g
∴ 2.5 kg of solution will require urea = × 2.5 kg = 37 g
1.015 kg
5. Calculate (a) molality (b) molarity and (c) mole fraction of KI if the
density of 20% (mass/mass) aqueous KI is 1.202 g mL–1.
Soln. Given : Let mass of solution in water = 100 g, then mass of KI = 20 g
∴ Mass of solvent (water) 100 – 20 = 80 g = 0.080 kg
(a) Calculation of molality
Molar mass of KI = 39 + 127 = 166 g mol–1
20 g
∴ Moles of KI = = 0.120
166 g mol −1
Number of moles of KI 0.120 mol
Molality of solution = = = 1.5 mol kg–1
Mass of solvent in kg 0.080 kg
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(b) Calculation of molarity
Density of solution = 1.202 g mL–1
100 g
∴ Volume of solution = = 83.2 mL = 0.0832 L
1.202 g mL−1
Number of moles of solute 0.120 mole
Molarity of solution = = = 1.44 M
Volume of solution in L 0.0832 L
(c) Calculation of mole fraction of KI
No. of moles of KI = 0.120
Mass of water 80 g
No. of moles of water = = = 4.44
Molar mass of water 18 g mol −1
Number of moles of KI
Mole fraction of KI =
Total number of moles in solution
0.120 0.120
= = = 0.0263
0.120+4.44 4.560
6. H2S a toxic gas with rotten egg like smell, is used for qualitative analysis.
If the solubility of H2S in water at STP is 0.195 m, calculate Henry’s law
constant.
Soln. Solubility of H2S gas = 0.195 m
∴ Moles of H2S = 0.195, Mass of water = 1000 g
1000 g
No. of moles of water = = 55.55 moles
18 g mol −1
∴ Mole fraction of H2S gas in the solution (x)
0.195 0.195
= = = 0.0035
0.195 + 55.55 55.745
Pressure at STP = 1 bar
Applying Henry’s law, P(H2S) = KH × xH2S
PH S 1 bar
or, K H = 2
= = 285.7 bar
xH S 0.0035
2
7. Henry’s law constant for CO2 in water is 1.67 × 108 Pa at 298 K. Calculate
the quantity of CO2 in 500 mL of soda water when packed under 2.5 atm CO2
pressure at 298 K.
Soln. Given, KH = 1.67 × 108 Pa, PCO2 = 2.5 atm = 2.5 × 101325 Pa
Applying Henry’s law, PCO2 = KH × xCO2
PCO 2.5 × 101325 Pa
∴ xCO = 2
= 8
= 1.517 × 10–3
2 KH 1.67 × 10 Pa
nCO nCO
i.e., xCO2 = 2
= 2
= 1.517 × 10 −3
nH O + nCO nH O
2 2 2 [nCO2 is negligible w.r.t. nH2O]
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For 500 mL of soda water,
Volume of water = 500 mL; mass of water = 500 g,
500
moles of water = = 27.78 i.e., nH2O = 27.78
18
nCO
∴ 2
= 1.517 × 10 −3 or nCO2 = 42.14 × 10–3 mole,
27.78
Mass of CO2 = 42.14 × 10–3 × 44 g = 1.854 g
8. The vapour pressures of pure liquids A and B are 450 and 700 mm Hg
at 350 K respectively. Find out the composition of the liquid mixture if total
vapour pressure is 600 mm Hg. Also find the composition of the vapour
phase.
Soln. Given : P0A = 450 mm Hg, P0B = 700 mm Hg, PTotal = 600 mm Hg, xA = ?
Applying Raoult’s law, PA = xA × P0A
PB = xB × PB0 = (1 – xA)P0B
PTotal = PA + PB = xA × P0A + (1 – xA)P0B = P0B + (P0A – P0B)xA
Substituting the given values, we get
100
600 = 700 + (450 – 700)xA or, 250xA = 100 or xA = = 0.40
250
Thus, composition of the liquid mixture will be
xA (mole fraction of A) = 0.40
xB (mole fraction of B) = 1 – 0.40 = 0.60
Calculation of composition in the vapour phase
PA = xA × P0A = 0.40 × 450 mm Hg = 180 mm Hg
PB = xB × P0B = 0.60 × 700 mm Hg = 420 mm Hg
PA 180
Mole fraction of A in the vapour phase = = = 0.30
PA + PB 180 + 420
Mole fraction of B in the vapour phase = 1 – 0.30 = 0.70
9. Vapour pressure of pure water at 298 K is 23.8 mm Hg. 50 g of urea
(NH2CONH2) is dissolved in 850 g of water. Calculate the vapour pressure of
water for this solution and its relative lowering.
Soln. Given, P0 = 23.8 mm Hg
P 0 − Ps
w2 = 50 g, M2 (urea) = 60 g mol , Ps = ? –1
=?
P0
w1 = 850 g, M1(water ) = 18 g mol –1
50 850
∴ n2 = = 0.83 ∴ n1 = = 47.22
60 18
P 0 − Ps n2
Applying Raoult’s law, =
0 n1 + n2
P
0
P − Ps 0.83 0.83
or, 0
= = = 0.017
P 47.22 + 0.83 48.05
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Thus, relative lowering of vapour pressure = 0.017
∆P
Again, 0 = 0.017 ⇒ ∆P = 0.017 × 23.8
P
or, P0 – Ps = 0.017 × 23.8 or, Ps = 23.8 – 0.017 × 23.8 or Ps = 23.4 mm Hg
Thus, vapour pressure of water in the solution = 23.4 mm Hg
10. Boiling point of water at 750 mm Hg is 99.63°C. How much sucrose is
to be added to 500 g of water such that it boils at 100°C ? Molal elevation
constant for water is 0.52 K kg mol–1.
Soln. Elevation in boiling point (∆Tb) = 100 – 99.63 = 0.37° C
Mass of solvent (water), w1 = 500 g, Mass of solute w2 = ?
Molar mass of solvent, M1 = 18 g mol–1
Molar mass of solute, C12H22O11 = 342 g mol–1
w × 1000
Applying the formula, ∆Tb = Kb × 2
M 2 × w1
M 2 × w1 × ∆Tb 342 × 500 × 0.37
or, w2 = = = 122 g
1000 × Kb 1000 × 0.52
11. Calculate the mass of ascorbic acid (vitamin C, C6H8O6) to be dissolved
in 75 g acetic acid to lower its melting point by 1.5°C, Kf = 3.9 K kg mol–1.
Soln. Lowering in melting point (∆Tf ) = 1.5°
Mass of solvent (CH3COOH ), w1 = 75 g, Mass of solute, w2 = ?
Molar mass of solvent (CH3COOH ), M1 = 60 g mol–1
Molar mass of solute, C6H8O6 = 72 + 8 + 96 = 176 g mol–1
w × 1000
Applying the formula, ∆Tf = K f × 2
M 2 × w1
M 2 × w1 × ∆T f 176 × 75 × 1.5
or w2 = = = 5.08 g
1000 × K f 1000 × 3.9
12. Calculate the osmotic pressure in pascals exerted by a solution
prepared by dissolving 1.0 g of polymer of molar mass 185,000 in
450 mL of water at 37°C.
Soln. Given, Number of moles of solute dissolved (n)
1.0 g 1
= −1
= mol
185,000 g mol 185 , 000
V = 450 mL = 0.450 L, T = 37°C = 37 + 273 = 310 K
R = 8.314 kPa L K–1mol–1 = 8.314 ×103 Pa L K–1 mol–1
n
π = CRT = RT
V
Substituting these values, we get
1 1
π= × × 8.314 × 10 3 × 310 = 30.96 Pa
185 , 000 0.45
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Chapter 3
Electrochemistry
Summary
An electrochemical cell consists of two metallic electrodes dipping in electrolytic
solution(s). Thus an important component of the electrochemical cell is the ionic
conductor or electrolyte. Electrochemical cells are of two types. In galvanic cell,
the chemical energy of a spontaneous redox reaction is converted into electrical
work, whereas in an electrolytic cell, electrical energy is used to carry out a non-
spontaneous redox reaction. The standard electrode potential for any electrode
dipping in an appropriate solution is defined with respect to standard electrode
potential of hydrogen electrode taken as zero. The standard potential of the cell
can be obtained by taking the difference of the standard potentials of cathode and
V V V
anode ( E ( cell ) = E cathode – E anode). The standard potential of the cells are
V V
related to standard Gibbs energy (∆rG = –nF E ( cell ) ) and equilibrium constant
V
(∆rG = – RT ln K) of the reaction taking place in the cell. Concentration dependence
of the potentials of the electrodes and the cells are given by Nernst equation.
The conductivity, κ, of an electrolytic solution depends on the concentration
of the electrolyte, nature of solvent and temperature. Molar conductivity, Λ m, is
defined by = κ/c where c is the concentration. Conductivity decreases but molar
conductivity increases with decrease in concentration. It increases slowly with
decrease in concentration for strong electrolytes while the increase is very steep
for weak electrolytes in very dilute solutions. Kohlrausch found that molar
conductivity at infinite dilution, for an electrolyte is sum of the contribution of the
molar conductivity of the ions in which it dissociates. It is known as law of

independent migration of ions and has many applications. Ions conduct electricity
through the solution but oxidation and reduction of the ions take place at the
electrodes in an electrochemical cell. Batteries and fuel cells are very useful
forms of galvanic cell. Corrosion of metals is essentially an electrochemical
phenomenon. Electrochemical principles are relevant to the Hydrogen Economy.
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1. Arrange the following metals in the order in which they displace each
other from the solution of their salts.
Al, Cu, Fe, Mg and Zn.
Soln. Mg, Al, Zn, Fe, Cu
2. Given the standard electrode potentials,

K /K = –2.93 V, Ag+/Ag = 0.80 V, Hg2+/Hg = 0.79 V, Mg2+/Mg = –2.37 V,
+
Cr3+/Cr = – 0.74 V
Arrange these metals in their increasing order of reducing power.
Soln. Higher the oxidation potential, more easily it is oxidized and hence
greater is the reducing power. Thus, increasing order of reducing power
will be Ag < Hg < Cr < Mg < K.
3. Depict the galvanic cell in which the reaction :

Zn(s) + 2Ag+(aq) → Zn2+(aq) + 2Ag(s) takes place.
Further show:
(i) Which of the electrode is negatively charged?
(ii) The carriers of the current in the cell.
(iii) Individual reaction at each electrode.
Soln. The cell will be represented as
Zn(s) | Zn2+(aq) ||Ag+(aq) | Ag(s)
(i) Anode, i.e., zinc electrode will be negatively charged.

(ii) Electrons are current carriers. The current will flow from silver to zinc
in the external circuit.
(iii) At anode : Zn(s) → Zn2+(aq) + 2e–
At cathode : Ag+(aq) + e– → Ag(s)
4. Calculate the standard cell potentials of galvanic cell in which the

following reactions take place:
(i) 2Cr(s) + 3Cd2+(aq) → 2Cr3+(aq) + 3Cd(s)

(ii) Fe2+(aq) + Ag+(aq) → Fe3+(aq) + Ag(s)
Calculate the DrG° and equilibrium constant of the reactions.
Given : E°Cr3+/Cr = – 0.74 V, E°Cd2+/Cd = – 0.40 V
E°Ag+/Ag = 0.80 V, E°Fe3+/Fe2+ = 0.77 V

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Soln. (i) E°cell = E°cathode – E°anode = – 0.40 V – (– 0.74V) = + 0.34V
DG° = –nFE°cell = – 6 × 96500 × 0.34 = –196860 J mol–1 = –196.86 kJ mol–1
–DG° = 2.303 RT log K
196860 = 2.303 × 8.314 × 298 × log K or log K = 34.5014
K = Antilog 34.5014 = 3.172 × 1034
(ii) E°cell = +0.80 V – 0.77 V = +0.03 V
DG° = –nFE°cell = – 1 × 96500 × 0.03 = –2895 J mol–1 = –2.895 kJ mol–1
DG° = –2.303 RT log K
–2895 = –2.303 × 8.314 × 298 × log K
or log K = 0.5074
K = Antilog (0.5074) = 3.22
5. Write the Nernst equation and emf of the following cells at 298 K:
(i) Mg(s)| Mg2+(0.001M)||Cu2+(0.0001 M)|Cu(s)
(ii) Fe(s)|Fe2+(0.001M)||H+(1M)|H2(g)(1bar)|Pt(s)
(iii) Sn(s)|Sn2+(0.050 M)||H+(0.020 M)|H2(g) (1 bar)|Pt(s)
(iv) Pt(s)|Br2(l)|Br–(0.010 M)||H+(0.030 M)| H2(g) (1 bar)|Pt(s)
Given : E°Mg2+/Mg = – 2.37 V, E°Cu2+/Cu = + 0.34 V
E°Fe2+/Fe = – 0.44 V, E°Sn2+/Sn = – 0.14 V
E°Br /Br– = + 1.08 V
2
Soln. (i) The electrode reactions are
At anode : Mg(s) → Mg2+ (0.001 M) + 2e–
At cathode : Cu2+ (0.0001 M) + 2e– → Cu(s)
Net reaction : Mg(s) + Cu2+ (0.001 M) → Mg2+ (0.0001 M) + Cu(s)
The Nernst equation for this cell at 25°C
 0.0591 [Mg 2+ ]
Ecell = Ecell − log
2 [Cu 2+ ]

Where Eanode 
= –2.37 V; Ecathode = +0.34 V
\    = (+0.34 V) – (–2.37 V) = +2.71 V
Ecell = Ecathode − Eanode
The cell emf is then given by
0.0591  0.001 
Ecell = 2.71 − log 
2  0.0001 
 0.0591   0.0591 
Ecell =  2.71 − log10  V =  2.71 − V = 2.71 – 0.03 = 2.68 V
 2   2 
(ii) The electrode reactions are
At anode : Fe(s) → Fe2+ (0.001 M) + 2e–
At cathode : 2H+ (1M) + 2e– → H2 (1 bar)
Net reaction : Fe(s) + 2H+ (1M) → Fe2+ (0.001 M) + H2 (1 bar)
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The Nernst equation of this cell at 25°C
 0.0591 [Fe 2+ ](pH 2 )
2 [H + ]2
  
Ecell = Ecathode − Eanode = E − E = 0.000 V – (–0.44 V) = +0.44 V
H+|H2 Fe 2+|Fe
The cell emf is then given by
0.0591 0.001 × 1  1 
Ecell = 0.44 − log = 0.44 − 0.0296 log  1000 
2 (1)2
= 0.44 – 0.0296 log(10–3) = 0.44 + (3 × 0.0296) = 0.44 + 0.0888
Therefore, Ecell = +0.53 V
(iii) The electrode reactions are
At anode : Sn(s) → Sn2+ (0.05 M) + 2e–
At cathode : 2H+ (0.02 M) + 2e– → H2 (1 bar)
Net reaction : Sn(s) + 2H+ (0.02 M) → Sn2+ (0.05 M) + H2 (1 bar)
The Nernst equation of this cell at 25°C
 0.0591 [Sn 2+ ](pH 2 )
2 [H + ]2

Ecell = E − E = 0.000 V – (–0.14 V) = +0.14 V
H+|H2 Sn 2+|Sn
 0.05 × 1   0.05 
or, Ecell = Ecell − 0.0296 log = Ecell – 0.0296 log 
(0.02) 2
 0.0004 
  
= Ecell – 0.0296 (log 125) = Ecell – 0.0296 × 2.0969 = Ecell – 0.06
Ecell = 0.14 – 0.06 = 0.08 V
(iv) The electrode reactions are
At anode : 2Br– (0.01 M) → Br2(l) + 2e–
At cathode : 2H+ (0.03 M) + 2e– → H2 (1 bar)
Net reaction : 2H+ (0.03 M) + 2Br¯ (0.01 M) → Br2(l) + H2 (1 bar)
The Nernst equation of this cell at 25°C is
 0.0591 [Br2( l ) ](pH 2 )
2 [H + ]2 [Br − ]2
 1
Ecell = E 
− EBr |Br¯ = 0 − 1.08 = –1.08 – 0.0296 × log
H+|H2 2
(0.03) (0.01)2
2
 1 
= –1.08 – 0.0296 log  V
−4 −4 
 (9 × 10 )(1 × 10 ) 
 108 
= –1.08 – 0.0296 × log   = –1.08 – 0.0296 (log 10 – log 9) V
8
 9 
= –1.08 – 0.0296 (8 – 0.9542) V = –1.08 – 0.0296 (7.0457)
Ecell = –1.08 – 0.21 = –1.29 V
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6. In the button cells widely used in watches and other devices the
following reaction takes place :
Zn(s) + Ag2O(s) + H2O(l) → Zn2+(aq) + 2Ag(s) + 2OH–(aq)
Determine DrG° and E° for the reaction.
Given : E°Ag O/Ag = 0.344 V, E°Zn2+/Zn = –0.76 V,
2
Soln. Zn is oxidised and Ag2O is reduced (as Ag+ ions change into Ag)
E°cell = E°Ag O/Ag – E°Zn2+/Zn = 0.344 – (– 0.76) = 1.104 V
2
DrG° = –nFE°cell = –2 × 96500 × 1.104 = – 2.13 × 105 J
7. Define conductivity and molar conductivity for the solution of an

electrolyte. Discuss their variation with concentration.
Soln. The reciprocal of resistivity is known as specific conductance or
simply conductivity. It is denoted by k (kappa). Thus, if k is the specific
conductance and G is the conductance of the solution, then
1 1 1 1 l l
= R = and ρ = ∴ = × , k =G×
G k G k A A
Now, if l = 1 cm and A = 1sq.cm, then k = G.
Hence, conductivity of a solution is defined as the conductance of a
solution of 1 cm length and having 1 sq. cm as the area of cross-section.
Alternatively, it may be defined as conductance of one centimetre cube of
the solution of the electrolyte.
Molar conductivity of a solution at a dilution V is the conductance of all
the ions produced from 1 mole of the electrolyte dissolved in V cm3 of
the solution when the electrodes are one cm apart and the area of the
electrodes is so large that the whole of the solution is contained between
them. It is represented by Lm.
kA
Lm =
l
Since l = 1 cm and A = V (volume containing 1 mole of electrolyte)
L m = kV
Variation of conductivity
and molar conductivity with
concentration : Conductivity
always decreases with
decrease in concentration,
for both weak and strong
electrolytes. This is because
the number of ions per unit
volume that carry the current
in a solution decreases on
dilution.
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Molar conductivity increases with decrease in concentration. This is
because that total volume, V, of solution containing one mole of electrolyte
also increases. It has been found that decrease in k on dilution of a solution
is more than compensated by increase in its volume.
8. The conductivity of 0.20 M solution of KCl at 298 K is 0.0248 S cm–1.

Calculate its molar conductivity.
Soln. Given k = 2.48 × 10–2 W–1 cm–1, M = 0.20 mol L–1
k × 1000 1000 × 2.48 × 10 −2
Lm = = = 124 W–1 cm2 mol–1
M 0.20
9. The resistance of a conductivity cell containing 0.001M KCl solution
at 298 K is 1500 W. What is the cell constant if conductivity of 0.001M KCl
solution at 298 K is 0.146 × 10–3 S cm–1.
Soln. Cell constant = k × R = 0.146 × 10–3 × 1500 = 0.219 cm–1
10. The conductivity of sodium chloride at 298 K has been determined at

different concentrations and the results are given below :
Concentration/M 0.001 0.010 0.020 0.050 0.100
102 × k/S m–1 1.237 11.85 23.15 55.53 106.74
Calculate Lm for all concentrations and draw a plot between Lm and c1/2.
Find the value of L0m.
1 S cm −1
Soln. 1 S cm –1
= 100 S m–1
, = 1 (unit conversion factor)
100 S m −1
Conc. 1000 × k
k(S m–1) k(S cm–1) Lm = (S cm2 mol−1) c1/2(M1/2)
(M) Molarity
1.237 × 1.237 × 1000 × 1.237 × 10 −4

10–3 = 123.7 0.0316
10–2 10–4
10 −3
11.85 × 11.85 × 1000 × 11.85 × 10 −4

10–2 = 118.5 0.100
10–2 10–4 10 −2
23.15 × 23.15 × 1000 × 23.15 × 10 −4

2 × 10–2 = 115.8 0.141
10–2 10–4 2 × 10 −2
55.53 × 55.53 × 1000 × 55.53 × 10 −4

5 × 10–2 = 111.1 0.224
10–2 10–4 5 × 10 −2
106.74 × 106.74 × 1000 × 106.74 × 10 −4

10–1 = 106.7 0.316
10–2 10–4 10 −1
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124.0 (0.032, 123.7)
122.0
120.0
(0.10, 118.5)
118.0
m(S cm2 mol–1)
116.0 (0.14, 115.8)

114.0
112.0 (0.22, 111.1)
110.0
108.0 (0.32, 106.7)
106.0
0.0 0.05 0.10 0.15 0.20 0.25 0.30 0.35
c1/2(mol L–1)1/2
L0 = Intercept on the Lm axis = 124.0 S cm2 mol–1 (on extrapolation to zero

concentration).
11. Conductivity of 0.00241 M acetic acid is 7.896 × 10–5 S cm–1. Calculate

its molar conductivity. If L0m for acetic acid is 390.5 S cm2 mol–1, what is its
dissociation constant?
c k × 1000 (7.896 × 10 −5 ) × 1000
Soln. L m = = = 32.76 S cm2 mol–1
M 0.00241
L cm 32.76
α= = = 8.4 × 10 −2
L 0m 390.5
cα 2 0.00241 × (8.4 × 10 −2 )2
Ka = = = 1.86 × 10–5
1− α 1 − 0.084
12. How much charge is required for the following reductions:

(i) 1 mol of Al3+ to Al ? (ii) 1 mol of Cu2+ to Cu ?
(iii) 1 mol of MnO 4– to Mn2+ ?
Soln. (i) The given reaction is
Al3+ + 3e– → Al
1 mole 3 mole
\ 3 mole electrons are needed for reduction of 1 mole of Al3+ to Al.
3 mole electrons = 3 Faraday = 3 × 96500 coulombs
= 2.895 × 105 coulombs
(ii) The given reaction is
Cu2+ + 2e– → Cu
1 mole 2 mole
\ 2 mole electrons are needed for reduction of 1 mole of Cu2+ to Cu.

2 mole electrons = 2 Faraday = 2 × 96500 coulombs = 1.93 × 105 coulombs
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(iii) The given reaction is
MnO4–(aq) + 8H+ + 5e– → Mn2+(aq) + 4H2O(l)
1 mole 5 mole
\ 5 mole electrons are needed for reduction of 1 mole of MnO4– to Mn2+.
5 mole electrons = 5 Faradays = 5 × 96500 coulombs
= 4.825 × 105 coulombs
13. How much electricity in terms of Faraday is required to produce

(i) 20.0 g of Ca from molten CaCl2? (ii) 40.0 g of Al from molten Al2O3?
Soln. (i) CaCl2 → Ca2+ + 2Cl–
or, Ca2+ + 2e– → Ca
2 mol 1 mol (40 g)
Q 40 g of calcium needs = 2 mole of electrons = 2 × 96500 coulombs
\ 20 g of calcium needs = 96500 coulombs (1F).
(ii) Al2O3 → 2Al3+ + 3O2–
or, Al3+ + 3e– → Al
3 mole 1 mole (27 g)
Q 27 g of aluminium needs = 3 mole of electrons = 3 × 96500 coulombs
3 × 96500 × 40.0
\ 40.0 g of aluminium needs = coulombs
27
= 4.28888 × 105 coulombs (4.44 F)
14. How much electricity is required in coulomb for the oxidation of

(i) 1 mol of H2O to O2? (ii) 1 mol of FeO to Fe2O3?
Soln. (i) The electrode reaction for 1 mol of H2O is given as
1
H 2 O  → O2
2
1
i.e., O 2 − → O2 + 2e −
2

\ Quantity of electricity required = 2 F = 2 × 96500 C = 193000 C
(ii) The electrode reaction for 1 mol of FeO is given as
1
FeO  → Fe 2O 3
2
i.e., Fe 2+ → Fe 3+ + e −

\ Quantity of electricity required = 1 F = 96500 C
15. A solution of Ni(NO3)2 is electrolysed between platinum electrodes

using a current of 5 amperes for 20 minutes. What mass of Ni is deposited at
the cathode? (At. mass of Ni = 58.7)
–
Soln. Ni(NO3)2 → Ni2+ + 2NO 3
At cathode : Ni2+ + 2e– → Ni
For getting 1 mole of Ni, we require 2 Faradays of electricity.
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I = 5 A, t = 20 min = 20 × 60 = 1200 sec,
(Q = I × t = 5 × 20 × 60 = 6000 C)
Q 2 × 96500 C of electricity will produce 58.7 g of nickel
58.7×6000
\ 6000 C of electricity will produce = = 1.825 g of nickel
2×96500
16. Three electrolytic cells A, B, C containing solutions of ZnSO4, AgNO3 and
CuSO4, respectively are connected in series. A steady current of 1.5 amperes
was passed through them until 1.45 g of silver deposited at the cathode of
cell B. How long did the current flow? What mass of copper and zinc were
deposited? (At. wt. of Ag = 108, Cu = 63.5, Zn = 65.3)
Soln. Given : I = 1.5 A, W = 1.45 g Ag, t = ?, E = 108, n = 1
E
Using Faraday’s 1st law of electrolysis, W = ZIt or, W = It
nF
108
or, 1.45 g = × 1.5t
1 × 96500
1.45 × 96500
or, t = = 863.73 seconds
1.5 × 108
63.5
Now for Cu, W1 = 1.45 g Ag, E1 = 108, W2 = ?, E2 = = 31.75
2
From Faraday’s 2nd law of electrolysis
W1 E
Using formula, = 1
W2 E2
1.45 108 1.45 × 31.75
= \ W2 = = 0.426 g of Cu
W2 31.75 108
65.3
Similarly, for Zn, W1 = 1.45 g Ag, E1 = 108, W2 = ?, E2 = = 32.65
2
W1 E 1.45 108 1.45 × 32.65
Using formula, = 1 = = ⇒ W2 = = 0.438 g of Zn
W2 E2 W2 32.65 108
17. Using the standard electrode potentials predict if the reaction between
the following is feasible :
(i) Fe3+(aq) and I–(aq) (ii) Ag+(aq) and Cu(s)
3+ –
(iii) Fe (aq) and Br (aq) (iv) Ag(s) and Fe3+(aq)
(v) Br2(aq) and Fe2+(aq)
Given : E°½I / I– = 0.54 V, E°Cu2+/Cu = 0.34 V, E°½Br /Br– = 1.09 V,
2 2
E°Ag+/Ag = 0.80 V, E°Fe3+/Fe2+ = 0.77 V
Soln. A reaction is feasible if EMF of the cell reaction is positive.
1
(i) Fe3+(aq) + I–(aq) → Fe2+(aq) + I2,
2
i.e., Pt|I2|I–(aq)||Fe3+(aq)|Fe2+(aq)|Pt
\ E°cell = E°Fe3+/ Fe2+ – E°1/2I / I– = 0.77 – 0.54 = 0.23 V(Feasible)
2
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(ii) Ag+(aq) + Cu(s) Ag(s) + Cu2+(aq),
i.e., Cu |Cu2+(aq)||Ag+(aq)|Ag
E°cell = E°Ag+ / Ag – E°Cu2+/Cu = 0.80 – 0.34 = 0.46 V(Feasible)
1
(iii) Fe3+(aq) + Br–(aq) Fe2+(aq) + Br2,
2
i.e., Br2|Br–(aq)||Fe3+(aq)|Fe2+(aq)
E°cell = E°Fe3+/ Fe2+ – E°1/2Br / Br– = 0.77 – 1.09 = – 0.32 V (Not feasible)
2
(iv) Ag(s) + Fe3+(aq) Ag+(aq) + Fe2+(aq)
i.e., Ag(s) |Ag+(aq)||Fe3+(aq)|Fe2+(aq)
E°cell = E°Fe3+ / Fe2+ – E°Ag+ / Ag = 0.77 – 0.80 = – 0.03 V (Not feasible)
1
(v) Br2( aq ) + Fe2+(aq) Br–(aq) + Fe3+(aq),
2
i.e., Fe2+(aq)|Fe3+(aq)||Br2|Br–
E°cell = E°1/2Br / Br– – E°Fe3+ / Fe2+ = 1.09 – 0.77 = 0.32 V (Feasible)
2
18. Predict the product of electrolysis in each of the following:

(i) An aqueous solution of AgNO3 with silver electrodes.
(ii)an aqueous solution of AgNO3 with platinum electrodes.
(iii)
A dilute solution of H2SO4 with platinum electrodes.
(iv)An aqueous solution of CuCl2 with platinum electrodes.
Soln. (i) Electrolysis of aqueous solution of AgNO3 with silver
electrodes,
AgNO3(s) + aq Ag+(aq) + NO–3(aq)
H 2 O H + + OH −
At cathode: Ag+ ions have lower discharge potential than H+ ions. Hence,
Ag+ ions will be deposited as Ag in preference to H+ ions.
At anode: As Ag anode is attacked by NO3– ions, Ag of the anode will
dissolve to form Ag+ ions in the solution.
Ag Ag+ + e–
(ii) Electrolysis of aqueous solution of AgNO3 using platinum electrodes,
At cathode: Ag will be deposited.
– –
At anode: As anode is not attacked, out of OH and NO–3 ions, OH ions
have lower discharge potential. Hence, OH– ions will be discharged in
preference to NO–3 ions, and OH– will then decompose to give out O2.
OH–(aq) OH + e–,
4OH 2H2O(l) + O2(g)
(iii) Electrolysis of dilute H2SO4 with platinum electrodes,
H2SO4(aq) 2H+(aq) + SO2–
4(aq)
H2O H+ + OH–
At cathode: H+ + e– H,
H+H H2(g)
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At anode: OH– OH + e–,
4OH 2H2O + O2(g)
Thus, H2 is liberated at the cathode and O2 at the anode.
(iv) Electrolysis of aqueous solution of CuCl2 with platinum electrodes,
–
CuCl2(s) + aq Cu2+(aq) + 2Cl (aq)
H2O H+ + OH–
At cathode: Cu2+ ions will be reduced in preference to H+ ions.
Cu2+ + 2e– Cu
At anode: Cl ions will be oxidized in preference to OH– ions.
–
Cl– Cl + e–,
Cl + Cl Cl2(g)
Thus, Cu will be deposited on the cathode and Cl2 will be liberated at the
anode.

1. How would you determine the standard electrode potential of the
system Mg2+ | Mg?
Soln. Set up an electrochemical cell consisting of Mg|MgSO4(1 M) as
one electrode by dipping a magnesium wire in 1 M MgSO4 solution and
standard hydrogen electrode Pt, H2 (1 atm)|H+(1 M) as the second electrode.
Measure the EMF of the cell and also note the direction of deflection in the
voltmeter. The direction of deflection shows that the electrons flow from
magnesium electrode to hydrogen electrode, i.e., oxidation takes place on
magnesium electrode and reduction on hydrogen electrode.
Voltmeter
e
Mg – +
Salt bridge e
rod H2 gas at
1 atm
pressure
1 M HCl
Pt foil
solution
1M MgSO4
solution
Thus, the cell may be represented as follows :
Mg|Mg2+ (1 M) || H+ (1 M)|H2, (1 atm), Pt(s)
E°cell = E° + − E° 2+
H /H2 Mg /Mg
Put E° =0
H+ /H2

Hence E° = − E°cell
Mg 2+ /Mg
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It is observed that EMF of the cell comes out to be 2.36 V.
Hence standard electrode potential for Mg2+|Mg system will be E° = –2.36 V.
2. Can you store copper sulphate solution in a zinc pot ?

Soln. E° 2+ = −0.76 V, E° 2+ = 0.34 V
Zn /Zn Cu /Cu
We have to check whether the following reaction takes place or not.
Zn(s) + CuSO4(aq) ZnSO4(aq) + Cu(s)
E°cell = E° − E° = 0.34 V – (–0.76 V) = 1.1 V
Cu 2+ /Cu Zn 2+ / Zn
Since E°cell is positive, the reaction takes place and we cannot store CuSO4
solution in a zinc pot.
3. Consult the table of standard electrode potentials and suggest three

substances that can oxidise ferrous ions under suitable conditions.
Soln. Oxidation of ferrous ions means:
Fe2+ Fe3+ + e–; E° 3+ 2+ = 0.77 V
Fe /Fe
Only those substances can oxidise Fe2+ to Fe3+ which are stronger oxidising
agents and have positive reduction potentials greater than 0.77 V so
that EMF of the cell reaction is positive. This is for elements lying below
Fe3+/Fe2+ in the electrochemical series, for example, Br2, Cl2 and F2.
4. Calculate the potential of hydrogen electrode in contact with a solution

whose pH is 10.
+ − 1
Soln. For hydrogen electrode, H + e  → H2
2
From Nernst equation,
0.0591 1 0.0591 1
E + = E° + − log + = 0− log −10
H /H2 H /H2 n [H ] 1 10
= –0.0591 × 10 = –0.591 V
5. Calculate the emf of the cell in which the following reaction takes place:
Ni(s) + 2Ag+(0.002 M) Ni2+(0.160 M) + 2Ag(s)
Given that E°cell = 1.05 V
Soln. Ni( s) → Ni 2(aq
+
) + 2e
−
2Ag +(aq ) + 2e − → 2Ag( s)
Ni( s) + 2Ag(+aq ) → Ni(2aq

+
) + 2Ag (s )
0.0591 [Ni 2+ ] 0.0591 0.16

Ecell = E°cell − log 2
= 1.05 − log
2 [Ag ]+ 2 (0.002)2
0.0591 0.16 0.0591
= 1.05 − log 6
= 1.05 − log 4 × 10 4
2 4 × 10 − 2
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0.0591 0.0591
= 1.05 − (log 4 + log10 4 ) = 1.05 − (0.602 + 4.0000)
2 2
0.0591 × 4.602
= 1.05 − = 1.05 – 0.1358 = 0.9142
2
6. The cell in which the following reaction occurs:
2Fe (aq) + 2I–(aq)
3+
2Fe2+(aq) + I2(s) has E°cell = 0.236 V at 298 K. Calculate the
standard Gibb’s energy and the equilibrium constant of the cell reaction.
Soln. 2Fe 3+ + 2e − → 2Fe 2 +
2I − → I 2 + 2e −
2Fe 3+ + 2I − → I 2 + 2Fe 2 + ; E°cell = 0.236 V
DG° = – nE°F = –2 × 0.236 × 96500 = – 45548 J mol–1 = – 45.54 kJ mol–1

DG° = – 2.303 RT log K
∆G° −( −45548)
log K = − = = 7.98 ⇒ K = 9.61 × 107
2.303 RT 2.303 × 8.314 × 298
7. Why does the conductivity of a solution decrease with dilution?
Soln. Conductivity of solution decreases with dilution because number of
ions per unit volume decreases.
8. Suggest a way to determine the L0m value of water.

Soln. Water is a weak electrolyte. Its L0m value can be determined with the
help of Kohlrausch’s law.
L0m(HCl) = L0m(H+) + L0m(Cl–) ... (i)
L m(NaOH) = L m(Na ) + L m(OH )
0 0 + 0 –
... (ii)
L m(NaCl) = L m(Na ) + L m(Cl )
0 0 + 0 –
... (iii)
Adding (i) and (ii) and subtracting (iii) we get
L0m(H2O) = L0m(H+) + L0m(OH–) = L0m(HCl) + L0m(NaOH) – L0m(NaCl)
9. The molar conductivity of 0.025 mol L–1 methanoic acid is

46.1 S cm2 mol–1. Calculate its degree of dissociation and dissociation
constant. Given l(H+) = 349.6 S cm2 mol–1 and l(HCOO–) = 54.6 S cm2 mol–1
Soln. L0m(HCOOH) = l0(H+) + l0(HCOO–) = 349.6 + 54.6 = 404.2 S cm2 mol–1
l 46.1
α = 0m = = 0.114 ⇒ α = 11.4%
l m 404.2
Cα 2 0.025 × (0.114)2 0.025 × 0.114 × 0.114
Ka = = = = 3.67 × 10 −4
1− α 1 − 0.114 0.886
10. If a current of 0.5 ampere flows through a metallic wire for 2 hours, then
how many electrons would flow though the wire?
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Soln. Q = I × t = 0.5 × 2 × 60 × 60 = 3600 C
Charge on 1 electron is 1.602 × 10–19 C.
1
3600 C is charge on × 3600
1.602 × 10 −19
3600
= × 1019 = 2.25 × 10 22 electrons
1.602
11. Suggest a list of metals that are extracted electrolytically.
Soln. Ca, Na, K, Al are extracted electrolytically.
12. Consider the reaction: Cr2O72– + 14H+ + 6e– → 2Cr3+ + 7H2O

What is the quantity of electricity in coulombs needed to reduce 1 mol of
Cr2O2–
7 ?
2–
Soln. Cr2O7 + 14H+ + 6e– 2Cr3+ + 7H2O,
6 × 96500 C = 579000 C of electricity is required to reduce 1 mol of Cr2O2–
7.
13. Write the chemistry of recharging the lead storage battery, highlighting
all the materials that are involved during recharging.
Soln. Chemical reactions while recharging:
2PbSO4 + 2H2O PbO2 + Pb + 2H2SO4
Electricity is passed through the electrolyte PbSO4 which is converted into
PbO2 and Pb.
14. Suggest two materials other than hydrogen that can be used as fuels in
fuel cells.
Soln. CH4 and CO can be used in fuel cell instead of hydrogen.
15. Explain how rusting of iron is envisaged as setting up of an

electrochemical cell.
Soln. The following reactions take place at the surface of iron metal which
acts as an electrochemical cell.
Fe( s) → Fe(2aq + + −
) 2e Oxidation
O 2( g ) + 4H +( aq) + 4 e − → 2H 2O( l) Reduction
2Fe 2 + + 2Fe
2H 2O + + 1 / 2O + 1→ Fe O → Fe + 4H + +
( aq) 2( aq()l)+ 2H 2O( l2(
) g ) / 2O 2(
2 g )3( s) 2O(3(aqs) + 4H ( aq)
Atmospheric oxidation
The water layer present on the surface of iron dissolves acidic oxides of
air like CO2 to form acids which dissociate to give H+ ions. Fe starts losing
electrons in presence of H+ ions.
H2O + CO2 H2CO3 2H+ + CO32–
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Chapter 4
Chemical Kinetics
Summary
Chemical kinetics is the study of chemical reactions with respect to reaction
rates, effect of various variables, rearrangement of atoms and formation of
intermediates. The rate of a reaction is concerned with decrease in concentration
of reactants or increase in the concentration of products per unit time. It can
be expressed as instantaneous rate at a particular instant of time and average
rate over a large interval of time. A number of factors such as temperature,
concentration of reactants, catalyst, affect the rate of a reaction. Mathematical
representation of rate of a reaction is given by rate law. It has to be determined
experimentally and cannot be predicted. Order of a reaction with respect to a
reactant is the power of its concentration which appears in the rate law equation.
The order of a reaction is the sum of all such powers of concentration of terms
for different reactants. Rate constant is the proportionality factor in the rate law.
Rate constant and order of a reaction can be determined from rate law or its
integrated rate equation. Molecularity is defined only for an elementary reaction.
Its values are limited from 1 to 3 whereas order can be 0, 1, 2, 3 or even a
fraction. Molecularity and order of an elementary reaction are same.
Temperature dependence of rate constants is described by Arrhenius equation
(k = Ae–Ea/RT). Ea corresponds to the activation energy and is given by the energy
difference between activated complex and the reactant molecules, and A (Arrhenius
factor or pre-exponential factor) corresponds to the collision frequency. The
equation clearly shows that increase of temperature or lowering of Ea will lead to
an increase in the rate of reaction and presence of a catalyst lowers the activation
energy by providing an alternate path for the reaction. According to collision
theory, another factor P called steric factor which refers to the orientation of
molecules which collide, is important and contributes to effective collisions, thus,
modifying the Arrhenius equation to k = P Z ABe − E a / RT .
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1. From the rate expression for the following reactions, determine their
order of reaction and the dimensions of the rate constants.
(i) 3NO(g) → N2O(g); Rate = k[NO]2

(ii) H2O2(aq) + 3I–(aq) + 2H+ → 2H2O(l) + I–3 ; Rate = k[H2O2][I–]
(iii) CH3CHO(g) → CH4(g) + CO(g); Rate = k[CH3CHO]3/2
(iv) C2H5Cl(g) → C2H4(g) + HCl(g); Rate = k[C2H5Cl]
Rate mol L−1 s −1
Soln. (i) Order = 2,Dimensions of k = 2
= −1 2
= L mol–1 s–1
(mol L )
[NO]
(ii) Order = 2, Dimensions of k = L mol–1 s–1
3
(iii) Order = ,
2
Dimensions of k = = = L1/2 mol–1/2 s–1
[CH 3CHO]3/2 (mol L−1 )3/2

(iv) Order = 1, Dimensions of k = = 1
= s −1
[C 2 H 5Cl] mol L −
2. For the reaction : 2A + B → A2B the rate = k[A][B]2 with

k = 2.0 × 10–6 mol–2 L2 s–1. Calculate the initial rate of the reaction
when [A] = 0.1 mol L–1, [B] = 0.2 mol L–1. Calculate the rate of reaction
after [A] is reduced to 0.06 mol L–1.
Soln. Initial rate = k[A][B]2 = (2.0 × 10–6) × (0.1) × (0.2)2 = 8 × 10–9 mol L–1 s–1
When [A] is reduced from 0.10 mol L–1 to 0.06 mol L–1, i.e. 0.04 mol L–1 of
A has reacted. Then according to equation, amount of B reacted is half
of A.
1
[B] = × 0.04 mol L–1 = 0.02 mol L–1
2
Hence, [B] left = 0.2 – 0.02 = 0.18 mol L–1
Now, again rate = k[A][B]2
\ Rate = (2.0 × 10–6) × (0.06) × (0.18)2 = 3.89 × 10–9 mol L–1 s–1
3. The decomposition of NH3 on platinum surface is zero order reaction.

What are the rates of production of N2 and H2 if k = 2.5 × 10–4 mol L–1 s–1?
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Soln. For the reaction, 2NH3 → N2 + 3H2
1 d[NH 3 ] d[N 2 ] 1 d[H 2 ] ...(1)
Rate = − = =
2 dt dt 3 dt
For zero order reaction
Rate = k ...(2)
From equation (1) and (2)
1 d[NH 3 ] d[N 2 ] 1 d[H 2 ]
Rate = − = = =k ...(3)
2 dt dt 3 dt
d[N 2 ]
\ Rate of production of N2 = =k
dt
k = 2.5 × 10–4 mol L–1 s–1
\ Rate of production of N2 = k = 2.5 × 10–4 mol L–1 s–1
From equation (3)
d[H 2 ]
Rate of production of H2 = = 3k = 3 × 2.5 × 10–4 mol L–1 s–1
dt
= 7.5 × 10–4 mol L–1 s–1
4. The decomposition of dimethyl ether leads to the formation of CH4, H2
and CO and the reaction rate is given by
Rate = k[CH3OCH3]3/2
The rate of reaction is followed by increase in pressure in closed vessel, so
the rate can also be expressed in terms of the partial pressure of dimethyl
ether, i.e.,
Rate = k(pCH3OCH3)3/2
If the pressure is measured in bar and time in minutes, then what are the
units of rate and rate constants ?
Soln. In terms of pressure,
Units of rate = bar min–1
−1
Rate bar min
Units of k = = = bar–1/2 min–1
( )
3/ 2 3/ 2
pCH bar
3OCH 3
5. Mention the factors that affect the rate of a chemical reaction.

Soln. Following are the factors on which rate of reaction depends.
(i) Nature of the reactant : Rate of reaction depends on nature of
reactant.
Example : Reactions of ionic compounds are faster than that of covalent
compounds.
(ii) State of reactants : Solid reactions are slow, reactions of liquids are
fast whereas that of gases are very fast.
(iii) Temperature : Rate of reaction largely depends on temperature. It
has been observed that every 10°C rise in temperature increases rate of
reaction by 2-3 times.
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rt +10
= 2 - 3 . This ratio is called temperature coefficient.
rt
There are two reasons for increasing rate of reaction with increasing
temperature.
(a) Increase in temperature increases average kinetic energy of reactant
molecules. Hence, rate of collision increases.
(b) With increase in temperature number of molecules having threshold
energy also increases i.e. number of active molecules increases. As a result,
number of effective collisions increases. Hence, rate of reaction increases.
(iv) Concentration : Rate of reaction also depends on concentration of
reactants.
Rate = k × Cn, where n = order of reaction, C = concentration of reactant.
(v) Presence of catalyst : Rate of reaction also depends on presence
of catalyst. Catalyst increases rate of reaction by any of the following
ways :
(a) Increasing surface area of reaction.
(b) Adsorbing the reactants on its surface and thus increasing chance of
collision.
(c) By forming unstable intermediate with the substrate.
(d) By providing alternate path of lower activation energy.
6. A reaction is second order with respect to a reactant. How is the rate of

reaction affected if the concentration of the reactant is
(i) doubled (ii) reduced to half ?
Soln. Rate = kR2
(i) If [A] = 2R, rate = k(2R)2 = 4kR2 i.e. rate of reaction increases 4 times
when concentration is doubled.
2
1 R 1 1
(ii) If [A] = R, rate = k   = kR 2 i.e. rate becomes th
when
2 2 4 4
1
concentration is reduced to .
2
7. What is the effect of temperature on the rate constant of a reaction?
How can this temperature effect on rate constant be represented
quantitatively?
Soln. The rate constant increases with increase in temperature and becomes
almost double for every 10° increase in temperature. Swedish chemist,
Arrhenius derived a quantitative relation between rate of reaction and
temperature. According to Arrhenius,
Ea
− Ea k Ea  1 1
k = Ae RT
or, log k = log A – or, log 2 =  − 
RT k1 2.303 R  T1 T2 
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where k1 = rate constant at temperature T1,
k2 = rate constant at temperature T2,
Ea = energy of activation, R = universal gas constant.
8. In a pseudo first order hydrolysis of ester in water, the following results

were obtained :
t/s 0 30 60 90
[Ester]/mol L –1
0.55 0.31 0.17 0.085
(i) Calculate the average rate of reaction between the time interval 30 to 60
seconds.
(ii) Calculate the pseudo first order rate constant for the hydrolysis of
ester.
Soln. (i) Average rate during the interval 30-60 sec
C − C1 0.17 − 0.31 0.14
Rate = − 2 =− = mol L−1 s −1 = 4.67 × 10–3 mol L–1 s–1
t2 − t1 60 − 30 30
2.303 [R ]
(ii) Using formula, k′ = log 0 in which [R0] = 0.55 M
t [ R]
At t = 30 sec, [R] = 0.31 mol L–1
2.303 0.55
\ k′ = log = 1.91 × 10 −2 s −1
30 0.31

At t = 60 sec, [R] = 0.17 mol L–1
2.303 0.55
k′ = log = 1.96 × 10 −2 s −1
60 0.17
\
At t = 90 sec, [R] = 0.085 mol L–1
2.303 0.55
\ k′ = log = 2.07 × 10 −2 s −1
90 0.085

1.91 + 1.96 + 2.07
Hence, average k′ = × 10 −2 = 1.98 × 10–2 s–1
3
9. A reaction is first order in A and second order in B.
(i) Write the differential rate equation.
(ii) How is the rate affected on increasing the concentration of B three
times?
(iii) How is the rate affected when the concentrations of both A and B are
doubled?
Soln. (i) Reaction is first order in A and second order in B, hence differential
rate equation is
dx
= k[A][B]2
dt
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(ii) Let rate = kab2
If [B] is tripled, Rate = ka (3b)2 = 9kab2
i.e. Rate increases 9 times.
(iii) If both [A] and [B] are doubled, Rate = k (2a) (2b)2 = 8kab2
i.e. Rate of reaction increases 8 times.
10. In a reaction between A and B, the initial rate of reaction (r0) was
measured for different initial concentrations of A and B as given below :
A/mol L–1 B/mol L–1 r0/mol L–1s–1

0.20 0.30 5.07 × 10–5
0.20 0.10 5.07 × 10–5
0.40 0.05 1.43 × 10–4
What is the order of the reaction with respect to A and B ?

dx
Soln. = k[ A]x [ B]y
dt
5.07 × 10–5 = k(0.2)x (0.3)y …(i)
5.07 × 10–5 = k(0.2)x (0.10)y …(ii)
Dividing (i) by (ii), we get
1 = 3y ⇒ 30 = 3y ⇒ y = 0
5.07 × 10–5 = k(0.2)x (0.1)0 …(iii)
1.43 × 10 = k(0.4) (0.05)
–4 x 0
…(iv)
Dividing (iv) by (iii), we get 2.8 = 2 x
log 2.8 = x log 2

log 2.8 0.4472
or x = = = 1.48 ≈ 1.5
log 2.0 0.3010

The order of reaction is 1.5 with respect to ‘A’ and zero with respect to ‘B’.
11. The following results have been obtained during the kinetic studies of
the reaction :
2A + B → C + D
Experiment [A]/ mol L–1 [B]/ mol L–1 Initial rate of formation of
D/ mol L–1 min–1
I 0.1 0.1 6.0 × 10–3
II 0.3 0.2 7.2 × 10–2
III 0.3 0.4 2.88 × 10–1
IV 0.4 0.1 2.40 × 10–2
Determine the rate law and the rate constant for the reaction.
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Soln. Suppose order with respect to A is m and with respect to B is n.
Then the rate law will be
Rate = k[A]m[B]n
Substituting the value of experiments I to IV, we get
Expt. I: Rate = 6.0 × 10–3 = k (0.1)m (0.1)n …(i)
Expt. II: Rate = 7.2 × 10–2 = k (0.3)m (0.2)n …(ii)
Expt. III: Rate = 2.88 × 10–1 = k (0.3)m (0.4)n …(iii)
Expt. IV: Rate = 2.4 × 10 = k (0.4) (0.1)
–2 m n
…(iv)
Comparing equation (i) and equation (iv)
(Rate)I 6.0 × 10 −3 k(0.1)m (0.1)n
\ = =
(Rate)IV 2.4 × 10 −2 k(0.4)m (0.1)n

m
1 (0.1)m  1 
or, = = \ m=1
4 (0.4)m  4 

Comparing equation (ii) and equation (iii)
(Rate)II 7.2 × 10 −2 k(0.3)m (0.2)n
= =
(Rate)III 2.88 × 10 −1 k(0.3)m (0.4)n
n2 n
or,  1  = (0.2) =  1  \ n=2
 2   
(0.4)n  2 

\ Rate law expression is : Rate = k[A][B]2.
The rate constant can be calculated from the given data of any experiment
using expression:
Rate
k=
[A][B]2
6.0 × 10 −3
From Expt. I, k = = 6.0
0.1 × (0.1)2
\ Rate constant k = 6.0 mol–2 L2 min–1
Rate mol L−1 min −1
Unit of k, k = 2
= −1 −1 2
= mol–2 L2 min–1
[A][B] (mol L )(mol L )
12. The reaction between A and B is first order with respect to A and zero
order with respect to B. Fill in the blanks in the following table :
Experiment [A]/ mol L–1 [B]/ mol L–1 Initial rate/mol L–1 min–1
I 0.1 0.1 2.0 × 10–2
II – 0.2 4.0 × 10–2
III 0.4 0.4 _
IV – 0.2 2.0× 10–2
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Soln. The reaction is first order with respect to A and zero order with
respect to B, hence the rate expression will be = k[A]1 [B]0 = k[A]
–2
From expt. I: 2.0 × 10 = k(0.1) or, k = 0.2 min–1
–2
From expt. II: 4.0 × 10 = (0.2) × [A] ⇒ [A] = 0.2 mol L–1
From expt. III: Rate = (0.2)(0.4) = 0.08 mol L–1 min–1 = 8 × 10–2 mol L–1 min–1
From expt. IV: 2.0 × 10–2 = (0.2) × [A] ⇒ [A] = 0.1 mol L–1
13. Calculate the half-life of the first order reaction from their rate constants
given below :
(i) 200 s–1 (ii) 2 min–1 (iii) 4 year–1
0.693
Soln. Half-life period of a first order reaction is given by t1/2 = ,
hence k
0.693 0.693
(i) t1/2 = = 3.46 × 10–3 s (ii) t1/2 = = 0.346 min
200 2

0.693
(iii) t1/2 = = 0.173 year
4
14. The half-life for radioactive decay of 14C is 5730 years. An archaeological
artifact containing wood had only 80% of the 14C found in a living tree.
Estimate the age of the sample.
Soln. Radioactive decay follows first order kinetics. Therefore,
0.693 0.693
Decay constant (l) = = yr −1
t1/2 5730
Given, [R]0 = 100 \ [R] = 80
2.303 [ R]0 2.303 100
and t = log = log
l [ R]  0.693  80
 5730 
2.303 × 5730
= × 0.0969 yr = 1845 years
0.693
15. The experimental data for the decomposition of N2O5
[2N2O5 → 4NO2 + O2]
in gas phase at 318K are given below :
t/s 0 400 800 1200 1600 2000 2400 2800 3200
10 × [N2O5]/mol L
2 –1
1.63 1.36 1.14 0.93 0.78 0.64 0.53 0.43 0.35
(i) Plot [N2O5] against t.
(ii) Find the half-life period for the reaction.
(iii) Draw a graph between log [N2O5] and t.
(iv) What is the rate law?
(v) Calculate the rate constant.
(vi) Calculate the half-life period from k and compare it with (ii).
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Soln. t/s [N2O5] × 102/ mol L–1 log[N2O5]
0 1.63 –1.79
400 1.36 –1.87
800 1.14 –1.94
1200 0.93 –2.03
1600 0.78 –2.11
2000 0.64 –2.19
2400 0.53 –2.28
2800 0.43 –2.37
3200 0.35 –2.46
(i) Plot of [N2O5] vs time
1.6
1.4
1.2
102 × [N2O5]/mol L–1
1.0
0.8
0.6
0.4
0.2
0
400 800 1200 1600 2000 2400 2800 3200
Time/ (s)
(ii) Initial conc. of N2O5 = 1.63 × 10–2 M

Half of this concentration = 0.815 × 10–2 M
Time corresponding to this concentration = 1440 s. Hence, t½ = 1440 s
(iii) Plot of log [N2O5] vs time
–1.80
–1.90
–2.00
–2.10
log [N2O5]
–2.20
–2.30
–2.40
–2.50
0
400 800 1200 1600 2000 2400 2800 3200
Time/ (s)
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(iv) As plot of log [N2O5] vs time is a straight line. Hence it is a reaction of
first order, i.e. rate law is:
Rate = k[N2O5]
(v) For first order reaction,
k
log R = − t + log R0
2.303
−k
Therefore slope of the graph drawn between log R and t will be .
2.303
k y − y1
\ Slope of the line = − = 2
2.303 t2 − t1
−2.46 − ( −1.79) 0.67 k 0.67
or, Slope = =− or, =
3200 − 0 3200 2.303 3200
0.67
or, k = × 2.303 = 4.82 × 10–4 s–1
3200
0.693 0.693
(vi) t1/2 = = = 1438 s
k 4.82 × 10 −4
The value of t1/2 calculated from the value of k is very close to that obtained
from graph.
16. The rate constant for a first order reaction is 60 s–1. How much time will
it take to reduce the initial concentration of the reactant to its 1/16th value?
[ R0 ]
Soln. Given, k = 60 s–1, [R0] = [R0], [R] = ,t=?
16
2.303 [ R ] 2.303 −2
Using formula, t = log 0 = log 16 = 4.62 × 10 s
k [ R] 60
Alternatively, In general, amount of the substance left after n half lives,
[ R0 ] [ R0 ]
R= =
2n 16
0.693 0.693
\ n = 4 and t = n × t1/2; t = n × =4× = 0.0462 s
k 60
17. During nuclear explosion, one of the products is 90Sr with half-life of
28.1 years. If 1 mg of 90Sr was absorbed in the bones of a newly born baby
instead of calcium, how much of it will remain after 10 years and 60 years if
it is not lost metabolically ?
Soln. As radioactive disintegration follows first order kinetics. Hence
0.693 0.693
Decay constant of 90Sr, (l) = = = 2.466 × 10 −2 yr −1
t1/ 2 28.1
To calculate the amount left after 10 years
Given, [R0] = 1 mg, t = 10 years, k = 2.466 × 10–2 yr–1, [R] = ?
2.303 [R ] 2.303 1
Using formula, l = log 0 or 2.466 × 10–2 = log
t [ R] 10 [ R]
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−2
or, 2.466 × 10 × 10 = − log[ R]
2.303
or, log [R] = –0.1071 or, [R] = Antilog (–0.1071) = 0.7814 mg
To calculate the amount left after 60 years, t = 60 years, [R0] = 1 mg, [R] = ?
2.303 1 2.466 × 10 −2 × 60
or, 2.466 × 10–2 = log or, = –log [R]
60 [ R] 2.303
or, log [R] = – 0.6425 or, [R] = Antilog (–0.6425) = 0.2278 mg
18. For a first order reaction, show that time required for 99% completion is
twice the time required for the completion of 90% of reaction.
Soln. 99% completion means that x = 99% of [R0]
or, [R] = [R0] – 0.99[R0] = 0.01[R0]
2.303 [R ]
For first order reaction, t = log 0
k [ R]
2.303 [ R0 ] 2.303 2.303
∴ t99% = log = log 10 2 = 2 ×
k 0.01[ R0 ] k k
90% completion means that [R] = [R0] – 0.90[R0] = 0.1[R0]
[ R0 ]
\ t90% = 2.303 log =
2.303
log 10 =
2.303
k 0.1[ R0 ] k k
t99%  2 × 2.303   2.303 
\ =
t90%  k   k  = 2 or, t99% = 2 × t90%
19. A first order reaction takes 40 min for 30% decomposition. Calculate t1/2.
Soln. 30% decomposition means that x = 30% of [R0]
or, [R] = [R0] – 0.3[R0] = 0.7[R0]
2.303 [ R]0 2.303 [ R0 ]
For reaction of 1st order, k = log = log
t [ R] 40 0.70[ R0 ]
2.303 10 2.303
= log min −1 = × 0.1549 min −1 = 8.918 × 10 −3 min −1
40 7 40
0. 693 0.693
For a 1st order reaction, t1/2 = = = 77.7 min
k 8.918 × 10 −3 min −1
20. For the decomposition of azoisopropane to hexane and nitrogen at
543 K, the following data are obtained.
t (sec) P(mm of Hg)
0 35.0
360 54.0
720 63.0
Calculate the rate constant.
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Soln. (CH 3)2 CHN = NCH(CH 3)2(g ) 

→ N 2(g ) + C6 H14(g )
Azoisopropane Hexane
Initial pressure P0 0 0
Pressure P0 – p p p
after time t
Total pressure after time t (Pt) = (P0 – p) + p + p = P0 + p or p = Pt – P0
[R]0 ∝ P0 and [R] ∝ P0 – p
On substituting the value of p, [R] ∝ P0 – (Pt – P0), i.e. [R] ∝ 2P0 – Pt
As decomposition of azoisopropane is a first order reaction
2.303 [ R]0 2.303 P0
\ k= log = log
t [ R] t 2 P0 − Pt
When t = 360 sec,
2.303 35.0 2.303 35.0
k= log = log = 2.175 × 10–3 s–1
360 2 × 35.0 − 54.0 360 16
2.303 35.0 2.303
When t = 720 sec, k = log = log 5 = 2.235 × 10–3 s–1
720 2 × 35.0 − 63 720
2.175 + 2.235
\ Average value of k = × 10 −3 s −1 = 2.20 × 10–3 s–1
2
21. The following data were obtained during the first order thermal
decomposition of SO2Cl2 at a constant volume.
SO2Cl2(g) → SO2(g) + Cl2(g)
Experiment Time/s–1 Total pressure/atm
1 0 0.5
2 100 0.6
Calculate the rate of the reaction when total pressure is 0.65 atm.
Soln. SO2Cl2(g) SO2(g) + Cl2(g)
Let initial pressure P0 0 0
Pressure at time t P0 – p p p
Let initial pressure P0 ∝ R0
Pressure at time t, Pt = P0 – p + p + p = P0 + p
\ Pressure of reactant at time t = P0 – p = 2P0 – Pt ∝ R
2.303 P0
Using formula, k = log
t 2 P0 − Pt
2.303 0.5 2.303
When t = 100 s, k = log = log(1.25)
100 2 × 0.5 − 0.6 100
2.303
= ( 0.0969) = 2.2316 × 10 −3 s −1
100
When Pt = 0.65 atm, \ Pressure of SO2Cl2 at time t (pSO2Cl2),
R = 2P0 – pt = 2 × 0.50 – 0.65 atm = 0.35 atm
Rate at that time = k × pSO2Cl2 = (2.2316 × 10–3) × (0.35) = 7.8 × 10–4 atm s–1
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22. The rate constant for the decomposition of N2O5 at various temperatures
is given below:
T/°C 0 20 40 60 80
10 × k/s–1
5
0.0787 1.70 25.7 178 2140
Draw a graph between ln k and 1/T and calculate the value of A and Ea.
Predict the rate constant at 30°C and 50°C.
Soln. The values of rate constants for the decomposition of N2O5 at various
temperatures are given below :
T(°C) T (K) 1/T k (s–1) ln k (= 2.303 log k)
0 273 3.6 × 10 –3
7.87 × 10 –7
–14.06
20 293 3.4 × 10–3 1.70 × 10–5 –10.98
40 313 3.19 × 10–3 25.7 × 10–5 –8.266
60 333 3.00 × 10–3 178 × 10–5 –6.332
80 353 2.8 × 10–3 2140 × 10–5 –3.844
–2
–4
–6
ln k –8
– 10
– 12
– 14
– 16
– 18
– 20
2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 3.8 4.0
10 3 × 1/T
Graph between ln k and 1/T
Slope of the line = tan q
y2 − y1 −10.98 − ( −14.08)
= = × 10 3 = –15.5 × 103
x2 − x1 3.4 − 3.6
Ea = –slope × R = – (–15.5 × 103 × 8.314) = 128.86 kJ K–1 mol–1
Ea 128.86 × 10 3 J K −1mol −1
Again ln A = ln k + = −14.06 +
RT 8.314 × 273
= –14.06 + 56.77 = 42.71 or, log A = 18.53
or, A = antilog 18.53 = 0.3388 × 1019 or, A = 3.388 × 1018
Value of rate constant k at 303 K and 323 K can be obtained from graph.
1 1
First of all ln k is obtained corresponding to and and then
303 K 323 K
k is calculated.
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23. The rate constant for the decomposition of a hydrocarbon is
2.418 × 10–5 s–1 at 546 K. If the energy of activation is 179.9 kJ/mol, what will
be the value of pre-exponential factor.
Soln. Here, k = 2.418 × 10–5 s–1, Ea = 179.9 kJ mol–1, T = 546 K, A = ?
According to Arrhenius equation,
Ea 179.9
log A = log k + = log(2.418 × 10–5) +
2.303 RT 2.303 × 8.314 × 10 −3 × 546
= (–5 + 0.3834) + 17.2081 = 12.5924 s–1
or, A = Antilog (12.5924) s–1 = 3.912 × 1012 s–1
24. Consider a certain reaction A → Products with k = 2.0 × 10–2 s–1. Calculate
the concentration of A remaining after 100 s if the initial concentration of A
is 1.0 mol L–1.
Soln. The units of k show that the reaction is of first order.
2.303 [R ] –2 2.303 1.0
Hence, k = log 0 or, 2.0 × 10 = log
t [ R] 100 [ R]
or, log [R] = –0.8684 ⇒ [R] = Antilog (–0.8684) = 0.1354 mol L–1
25. Sucrose decomposes in acid solution into glucose and fructose according
to the first order rate law, with t1/2 = 3.00 hours. What fraction of sample of
sucrose remains after 8 hours ?
Soln. Sucrose decomposes according to first order rate law, hence
2.303 [R ] [ R]
k= log 0 , t1/2 = 3 hrs, t = 8 hrs, =?
t [ R] [ R0 ]
0.693 0.693
t1/2 = 3.0 hrs, \ k = = = 0.231 hr −1
t1/ 2 3
2.303 [R ] [R ]
Hence, 0.231 = log 0 or, log 0 = 0.8024
8 [ R] [ R]
[ R0 ] [ R] 1
or, = Antilog ( 0.8024) = 6.345 or, = = 0.158
[ R] [ R0 ] 6.345
26. The decomposition of a hydrocarbon follows the equation

k = (4.5 × 1011s–1)e–28000K/T. Calculate Ea.
Soln. Arrhenius equation, k = Ae–Ea/RT
Given equation is k = (4.5 × 1011 s–1)e–28000K/T
Comparing both the equations, we get
E 28000 K
− a =−
RT T
or, Ea = 28000 K × R = 28000 × 8.314 = 232.79 kJ mol–1
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27. The rate constant for the first order decomposition of H2O2 is given by
the following equation:
log k = 14.34 – 1.25 × 104K/T
Calculate Ea for this reaction and at what temperature will its half-period be
256 minutes?
Soln. According to Arrhenius equation, k = Ae–Ea/RT
Ea Ea
or, ln k = ln A – or, log k = log A – …(i)
RT 2.303 RT
Given equation is
log k = 14.34 – 1.25 × 104 K/T ....(ii)
Ea 1.25 × 10 4 K
Comparing (i) with (ii), =
2.303 RT T
or, Ea = 2.303R × 1.25 × 10 K = 2.303 × (8.314) × 1.25 × 104 = 239.34 kJ mol–1
4
0.693
When t1/2 = 256 min, k = = 4.51 × 10–5 s–1
256 × 60
Substituting this value in the given equation,
1.25 × 10 4 K
log(4.51 × 10–5) = 14.34 –
T
1.25 × 10 4 K
i.e., (–5 + 0.6542) = 14.34 –
T
4
1.25 × 10 K
or, = 18.6858 or, T = 669 K
T

28. The decomposition of A into product has value of k as 4.5 × 103 s–1 at
10°C and energy of activation 60 kJ mol–1. At what temperature would k be
1.5 × 104 s–1?
Soln. Given k1 = 4.5 × 103 s–1,
T1 = 10 + 273 K = 283 K; k2 = 1.5 × 104 s–1, T2 = ?, Ea = 60 kJ mol–1
Applying Arrhenius equation,
k2 Ea  T2 − T1 
log =  
k1 2.303R  T1T2 
1.5 × 10 4 60000  T2 − 283 
log =
4.5 × 10 3 2.303 × 8.314  283T2 
 T − 283  0.5228 T − 283
or, log 3.333 = 3133.63  2  or, = 2
 283T2  3133.63 283T2
or, 0.0472T2 = T2 – 283 or 0.9528T2 = 283
283
or, T2 = = 297 K = 297 – 273 = 24°C
0.9528
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29. The time required for 10% completion of the first order reaction at
298 K is equal to that required for its 25% completion at 308 K. If the value
of A is 4 × 1010 s–1, calculate k at 318 K and Ea.
2.303  R  0 2.303  R  0
Soln. t= log , t= log
k1 90 k2 75
 R  0  R
100 100   0
2.303 10 2.303 4 2.303 10 2.303 4
t= log ,t= log = log = log
k1 9 k2 3 k1 9 k2 3
4
k2 log
⇒ = 3 = log 1.333 = 0.1249 = 2.733
k1 10 log 1.111 0.0457
log
9
k2 Ea  T2 − T1  Ea  308 − 298 
log = ⇒ log 2.733 =
 
k1 2.303 R  T1T2  2.303 × 8.314  298 × 308 
2.303 × 8.314 × 308 × 298 19.147 × 308 × 298
Ea = × 0.4367 = × 0.4367
10 10
= 76.75 kJ mol–1
E
ln k = ln A − a
RT
Ea 76.75 × 1000
log k = log A − = log( 4 × 1010 ) −
2.303 RT 2.303 × 8.314 × 318
76750
= 10.6021 − = 10.6021 − 12.6051 = −2.003
6088.746
k = Antilog (–2.003) = 9.93 × 10–3
30. The rate of a reaction quadruples when the temperature changes from
293 K to 313 K. Calculate the energy of activation of the reaction assuming
that it does not change with temperature.
Soln. Given r2 = 4r1, T1 = 293, T2 = 313 K, Ea = ?
r k 4
We know, 2 = 2 =
r1 k1 1
Using Arrhenius equation,
k2 Ea  1 1 
log = −
k1 2.303 R  T1 T2 

Ea  1 1 
log 4 = −
2.303 × 8.314  293 313 

2.303 × 8.314 × 293 × 313

or, Ea = log 4 × or, Ea = 52.864 kJ
20
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1. For the reaction R → P, the concentration of a reactant changes from
0.03 M to 0.02 M in 25 minutes. Calculate the average rate of reaction using
units of time both in minutes and seconds.
Soln. In units of minute,
∆[ R] [ R]2 − [ R]1 0.02 − 0.03 ( −0.01)
Average rate = – =− =− =−
∆t t2 − t1 25 25
= 4 × 10–4 M min–1
In units of second,
∆[ R] 0.01
Average rate = – =− = 6.66 × 10 −6 M s −1
∆t 25×60
2. In a reaction, 2A → products, the concentration of A decreases from
0.5 mol L–1 to 0.4 mol L–1 in 10 minutes. Calculate the rate during this interval.
1 ∆[ R] 1 [ R]2 − [ R]1
Soln. Average rate = − =−
2 ∆t 2 t2 − t1
1 0.4 − 0.5 1 −0.1 M
=− × =− × = 5 × 10–3 M min–1
2 10 2 10
3. For a reaction, A + B → product; the rate law is given by, = k[A]1/2 [ ]2.
What is the order of the reaction?
1 1
Soln. Order of reaction = + 2 = 2 = 2.5
2 2
4. The conversion of molecules X to Y follows second order kinetics. If
concentration of X is increased to three times how will it affect the rate of
formation of Y?
Soln. The reaction, X → Y, follows second order kinetics hence the rate
law equation will be
Rate = kC2, where C = [X]
If concentration of X increases three times, now, [X] = 3C mol L–1
\ Rate = k(3C)2 = 9kC2
Thus the rate of reaction will become 9 times. Hence, the rate of formation
of Y will increase 9 times.
5. A first order reaction has a rate constant 1.15 × 10–3 s–1. How long will
5 g of this reactant take to reduce to 3 g?
Soln. Here, [R]0 = 5 g, [R] = 3 g, k = 1.15 × 10–3 s–1
2.303 [ R]0 2.303 5
For first order reaction, t = log = 3
log
k [ R] 1.15 × 10 − 3
= 2.00 × 10 (log 1.667) = 2.0 × 10 × 0.2219 s = 443.8 ≈ 444 s
3 3
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6. Time required to decompose SO2Cl2 to half of its initial amount is
60 minutes. If the decomposition is a first order reaction, calculate the rate
constant of the reaction.
0.693 0.693
Soln. For a first order reaction, k = = = 1.155 × 10–2 min–1
t1/ 2 60
0.693
or, k = = 1.925 × 10 −4 s −1
60 × 60
7. What will be the effect of temperature on rate constant?
Soln. It has been found that for a chemical reaction, with rise in temperature
by 10°, the rate constant is nearly doubled.
The temperature dependence of the rate of a chemical reaction can be
accurately explained by Arrhenius equation.
k = Ae–Ea/RT
Where A is the Arrhenius factor or the frequency factor. It is also called
pre-exponential factor. It is a constant specific to a particular reaction.
R is gas constant and Ea is activation energy measured in joules/mole
(J mol–1).
8. The rate of the chemical reaction doubles for an increase of 10 K in
absolute temperature from 298 K. Calculate Ea.
Soln. Given : T1 = 298 K, T2 = 308 K, Ea = ?, r1 = r (say) then r2 = 2r
k Ea  1 1
Using Arrhenius equation log 2 =  − 
k1 2.303 R  T1 T2 
2 Ea  1 1 
Putting the values log = −
1 2.303 × 8.314  298 308 

Ea  10 
0.3010 =
2.303 × 8.314  298 × 308 

0.3010 × 2.303 × 8.314 × 298 × 308
or, Ea = or, Ea = 52.897 kJ mol–1
10
9. The activation energy for the reaction 2HI(g) → H2(g) + I2(g) is 209.5 kJ mol–1
at 581 K. Calculate the fraction of molecules of reactants having energy
equal to or greater than activation energy.
Soln. Fraction of molecules having energy equal to or greater than
activation energy is given as
n − E / RT E Ea
x= =e a \ ln x = − a or, log x = −
N RT 2.303 RT
3
209.5 × 10
or, log x = − = −18.8323
2.303 × 8.314 × 581
\ x = Antilog (–18.8323) = 1.471 × 10–19
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Chapter 5
Surface Chemistry
Summary
Adsorption is the phenomenon of attracting and retaining the molecules of a
substance on the surface of a solid resulting into a higher concentration on the
surface than in the bulk. The substance adsorbed is known as adsorbate and the
substance on which adsorption takes place is called adsorbent. In physisorption,
adsorbate is held to the adsorbent by weak van der Waals forces, and in
chemisorption, adsorbate is held to the adsorbent by strong chemical bond. Almost
all solids adsorb gases. The extent of adsorption of a gas on a solid depends upon
nature of gas, nature of solid, surface area of the solid, pressure of gas and
temperature of gas. The relationship between the extent of adsorption (x/m) and
pressure of the gas at constant temperature is known as adsorption isotherm.
A catalyst is a substance which enhances the rate of a chemical reaction without
itself getting used up in the reaction. The phenomenon using catalyst is known as
catalysis. In homogeneous catalysis, the catalyst is in the same phase as are the
reactants, and in heterogeneous catalysis the catalyst is in a different phase from
that of the reactants.
Colloidal solutions are intermediate between true solutions and suspensions.
The size of the colloidal particles range from 1 to 1000 nm. A colloidal system consists
of two phases - the dispersed phase and the dispersion medium. Colloidal systems
are classified in three ways depending upon (i) physical states of the dispersed phase
and dispersion medium (ii) nature of interaction between the dispersed phase and
dispersion medium and (iii) nature of particles of dispersed phase. The colloidal
systems show interesting optical, mechanical and electrical properties. The process
of changing the colloidal particles in a sol into the insoluble precipitate by addition
of some suitable electrolytes is known as coagulation. Emulsions are colloidal systems
in which both dispersed phase and dispersion medium are liquids. These can be of:
(i) oil in water type and (ii) water in oil type. The process of making emulsion is
known as emulsification. To stabilise an emulsion, an emulsifying agent or emulsifier
is added. Soaps and detergents are most frequently used as emulsifiers. Colloids find
several applications in industry as well as in daily life.
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1. Distinguish between the meaning of the terms adsorption and

absorption. Give one example of each.
Soln. The phenomenon of accumulation of the molecules of a substance

on a solid or liquid surface resulting in the increased concentration of
the molecules on the surface is called adsorption. In absorption, the
substance is uniformly distributed throughout the bulk of the solution.
A distinction can be made by taking an example of water vapours. Water
vapours are absorbed by anhydrous calcium chloride but adsorbed by
silica gel.
Adsorption Absorption
It is a surface phenomenon, i.e., It occurs throughout the body
it occurs only on the adsorbent of the material. It is called bulk
surface. phenomenon.
The concentration on the The concentration is same
adsorbent’s surface is different throughout.
from that in the bulk.
The rate varies throughout the The rate remains the same.
process.
2. What is the difference between physisorption and chemisorption?

Soln.
Physisorption Chemisorption
The adsorbate and adsorbent The adsorbate and adsorbent are
are held by weak van der Waals held by forces similar to a chemical
forces. bond.
Heat of adsorption is of the Heat of adsorption is of the order of
order of 20 kJ/mol. 200 kJ/mol.
It is reversible. It is irreversible.
It decreases with increase in It increases with temperature and
temperature and occurs at lower occurs at high temperature.
temperatures.
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It is not specific in nature, i.e., all It is specific in nature and occurs

gases are adsorbed on all solids only when a chemical bond is
to some extent. formed between the adsorbate and
adsorbent.
Multimolecular layers may be Usually unimolecular layer is formed
formed on the adsorbent. on the adsorbent.
3. Give reason why a finely divided substance is more effective as an

adsorbent.
Soln. The extent of adsorption increases with increase in surface area of
the adsorbent. Thus, finely divided metals and porous substances having
large surface areas are good adsorbents.
4. What are the factors which influence the adsorption of a gas on a

solid?
Soln. Factors affecting adsorption of a gas on solids are :
Nature of the adsorbent : The same gas is adsorbed to different extents by
different solids at the same temperature. Also, greater the surface area of
the adsorbent, more is the gas adsorbed.
Nature of the adsorbate : Different gases are adsorbed to different
extents by different solids at the same temperature. Higher the critical
temperature of the gas, greater is its amount adsorbed.
Temperature : Since adsorption is an exothermic process, applying Le
Chatelier’s principle, we can find out that adsorption decreases with an
increase in temperature.
Specific area of the adsorbent : Surface area available for adsorption
per gram of the adsorbent increases the extent of adsorption. Greater
the surface area, higher would be the adsorption therefore, porous or
powdered adsorbents are used.
Pressure : At constant temperature, the adsorption of gas increases with
pressure.
Activation of adsorbent : It means increasing the adsorbing power of an
adsorbent by increasing its surface area. It is done by:
(i) making the adsorbent’s surface rough
(ii) removing gases already adsorbed
(iii) subdividing the adsorbent into smaller pieces.
5. What is an adsorption isotherm? Describe Freundlich adsorption

isotherm.
Soln. Adsorption isotherm is a graph between the amount of the gas
adsorbed by an adsorbent and equilibrium pressure of the adsorbate at
constant temperature.
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Freundlich obtained an empirical relationship between the quantity of
gas adsorbed by unit mass of solid adsorbent and pressure at a particular
temperature. It is mathematically represented in the following way :
x
= kP1/ n where k and n are constants
m
P is pressure,
m is mass of the adsorbent, slope = 1/n
log x/m
x is mass of the adsorbate.
Taking log on both sides log k
x 1
log = log k + log P log P
m n
1
A graph between x and log P is a straight line with slope equal to and
m n
ordinate intercept equal to log k.
6. What do you understand by activation of adsorbent? How is it

achieved?
Soln. Activation of an adsorbent means increasing its adsorbing power by
increasing the surface area of the adsorbent by making its surface rough,
and removing adsorbed gases from it. With an increase in surface area the
adsorption increases.
7. What role does adsorption play in heterogenous catalysis?

Soln. Adsorption of reactants on solid surface of the catalysts increases
the rate of reaction. There are many gaseous reactions of industrial
importance involving solid catalysts. Manufacture of ammonia using
iron as a catalyst, manufacture of H2SO4 by Contact process and use of
finely divided nickel in the hydrogenation of oils are excellent examples
of heterogeneous catalysis.
8. Why is adsorption always exothermic?

Soln. During adsorption, there is always a decrease in residual forces of
the surface, i.e., there is decrease in surface energy which appears as heat.
Adsorption therefore, is invariably an exothermic process. In other words,
DH of adsorption is always negative to keep the value of DG negative for
the reaction to be spontaneous as DS decreases during adsorption.
9. How are the colloidal solutions classified on the basis of physical states
of the dispersed phase and dispersion medium?
Soln. Colloids can be classified into eight types depending upon the
physical state of the dispersed phase and the dispersion medium.
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Dispersed Dispersion Types of

Examples
phase medium colloid
Solid Solid Solid sol Coloured glasses, gem stones
Solid Liquid Sol Paints, cell fluid
Solid Gas Aerosol Smoke, dust
Liquid Solid Gel Cheese, butter, jellies
Liquid Liquid Emulsion Milk, hair cream
Liquid Gas Aerosol Fog, mist, cloud
Gas Solid Solid sol Pumice stone, foam rubber
Gas Liquid Foam Froth, whipped cream
10. Discuss the effect of pressure and temperature on the adsorption of

gases on solids.
Soln. (i) Adsorption decreases with an increase in temperature because
it is an exothermic process and according to Le Chatelier’s principle
the reaction will proceed in backward direction with increase in
temperature.
(ii) At a constant temperature, adsorption increases with pressure.
11. What are lyophilic and lyophobic sols? Give one example of each type.
Why are hydrophobic sols easily coagulated?
Soln. There are two types of colloidal sols:
(i) Lyophilic sols : The word lyophilic means solvent loving. They are
obtained by directly mixing the dispersed phase and the dispersion
medium, e.g., sols of gum, gelatin, starch, etc. They are solvent attracting
hence quite stable and cannot be coagulated easily.
(ii) Lyophobic sols : They cannot be prepared by directly mixing the
dispersed phase and dispersion medium but are prepared by special
methods, e.g., sols of metals. They are solvent repelling. Hydrophobic
sols are easily coagulated due to repulsion between water and dispersed
phase.
12. What is the difference between multimolecular and macromolecular

colloids? Give one example of each. How are associated colloids different
from these two types of colloids?
Soln. Depending upon the type of particles of the dispersed phase,
colloids are classified as : multimolecular, macromolecular and associated
colloids.
(i) Multimolecular colloids: On dissolution, a large number of atoms
or smaller molecules of a substance aggregate together to form species
having size in the colloidal range (diameter < 1nm). The species thus
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formed are called multimolecular colloids. For example, a gold sol may
contain particles of various sizes having many atoms. Sulphur sol consists
of particles containing a thousand or more of S8 sulphur molecules.
(ii) Macromolecular colloids: Macromolecules in suitable solvents form
solutions in which the size of the macromolecules may be in the colloidal
range. Such systems are called macromolecular colloids. These colloids
are quite stable and resemble true solutions in many respects. Examples
of naturally occurring macromolecules are starch, cellulose, proteins and
enzymes; and those of man-made macromolecules are polythene, nylon,
polystyrene, synthetic rubber, etc.
(iii) Associated colloids (Micelles) : There are some substances which at
low concentrations behave as normal strong electrolytes but, at higher
concentrations exhibit colloidal behaviour due to the formation of
aggregates. The aggregated particles thus formed are called micelles. These
are also known as associated colloids. The formation of micelles takes
place only above a particular temperature called Kraft temperature (Tk)
and above a particular concentration called critical micelle concentration
(CMC). On dilution, these colloids revert back to individual ions. Surface
active agents such as soaps and synthetic detergents belong to this class.
For soaps, the CMC is 10–4 to 10–3 mol L–1. These colloids have both
lyophobic and lyophilic parts. Micelles may contain as many as 100
molecules or more.
13. What are enzymes? Write in brief the mechanism of enzyme catalysis.
Soln. Enzymes are complex nitrogenous organic compounds which act as
biological catalysts and increase the rate of cellular processes. According
to the lock and key model, like every lock has a specific key, similarly
every enzyme acts at a specific substrate.
enzyme changes
shape slightly as
substrate enters products
active site, making
substrate the site more precise
active site
enzyme
enzyme + enzyme/substrate enzyme/products enzyme +
substrate complex complex products
entering active site leaving active site
Lock-and-key model
Substrates Product
Fast Enzyme- Slow

Enzyme substrate
complex
Induced-fit model
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When the substrate fits the active site (lock) of the enzyme, the chemical
change begins. But it has also been noticed that enzyme changes shape,
when substrate lands at the active site. This induced-fit model of enzyme
action pictures the substrate inducing the active site to adopt a perfect
fit, rather than a rigid shaped lock and key. Therefore, the new model for
enzyme action is called induced fit model.
14. How are colloids classified on the basis of

(i) physical states of components
(ii) nature of dispersion medium and
(iii) interaction between dispersed phase and dispersion medium?
Soln. (i) Refer answer number 9.
(ii) Depending upon the nature of dispersion medium colloids can be
classified as sol if the dispersion medium is liquid, gel if the dispersion
medium is solid. If the dispersion medium is water, the sol is called
hydrosol and if the dispersion medium is alcohol, it is called alcosol. A
colloid in which the dispersion medium as well as dispersed phase are
liquids, is called emulsion.
(iii) Refer answer number 11.
15. Explain what is observed
(i) when a beam of light is passed through a colloidal sol.
(ii) an electrolyte, NaCl is added to hydrated ferric oxide sol.
(iii) electric current is passed through a colloidal sol?
Soln. (i) When a beam of light is Eye
passed through colloidal particles, Microscope
Tyndall cone
its path becomes clearly visible and Scattered light
Light
is known as Tyndall effect. It is due source
to scattering of light by colloidal
particles. The bright cone of the light
is called Tyndall cone. Colloidal solution
Tyndall effect
(ii) When NaCl is added to hydrated
ferric oxide sol coagulation takes
place. Since ferric oxide is a positive
sol, it is coagulated by the negative Reservoir
chloride ions. Anode Cathode
(iii) When electric potential is applied
across two platinum electrodes
dipped in a colloidal solution, the Initial level
Water
colloidal particles move towards (dispersion Colloidal
one or the other electrode. The medium) solution
movement of colloidal particles under
an applied electric potential is called
electrophoresis. Stop cock
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Positively charged particles move towards the cathode while negatively
charged particles move towards the anode. Since all the colloidal particles
in a given colloidal solution carry the same charge, the particles move to
one or the other electrode depending on the charge.
16. What are emulsions? What are their different types? Give example of
each type.
Soln. These are liquid-liquid colloidal systems, i.e., the dispersion of
finely divided droplets in another liquid. If a mixture of two immiscible
or partially miscible liquids is shaken, a coarse dispersion of one liquid in
the other is obtained which is called emulsion. Generally, one of the two
liquids is water. There are two types of emulsions:
(i) Oil dispersed in water (O/W type) and
(ii) Water dispersed in oil (W/O type).
Oil in water Water in oil
In the first system, water acts as dispersion medium. Examples of this type
of emulsion are milk and vanishing cream. In milk, liquid fat is dispersed
in water. In the second system, oil acts as dispersion medium. Common
examples of this type are butter and cream.
17. What is demulsification? Name two demulsifiers.

Soln. The process of converting the emulsion back into two distinct
components, oil and water is called demulsification. This can be done by
(i) boiling (ii) freezing
(iii) changing pH (iv) electrostatic precipitation.
18. Action of soap is due to emulsificationand micelle formation. Comment.

Soln. Soap is sodium or potassium salt of a higher fatty acid and may
be represented as RCOO–Na+ (e.g., sodium stearate CH3(CH2)16COO–Na+,
which is a major component of many bar soaps). When dissolved in water,
it dissociates into RCOO– and Na+ ions. The RCOO– ions, however, consist
of two parts – a long hydrocarbon chain R (also called non-polar ‘tail’)
which is hydrophobic (water repelling), and a polar group COO– (also
called polar-ionic ‘head’), which is hydrophilic (water loving).
The RCOO– ions are, therefore, present on the surface with their COO–
groups in water and the hydrocarbon chains R staying away from it and
remain at the surface. But at critical micelle concentration, the anions are
pulled into the bulk of the solution and aggregate to form a spherical
shape with their hydrocarbon chains pointing towards the centre of the
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sphere with COO– part remaining outward on the surface of the sphere.
An aggregate thus formed is known as ‘ionic micelle’.
The cleansing action of soap is due
to the fact that soap molecules form
micelle around the oil droplet in such
(a) (b)
a way that hydrophobic part of the
stearate ions is in the oil droplet and
hydrophilic part projects out of the
grease droplet like the bristles.
(a) Grease on cloth
(b) Stearate ions (from soap) arranging (c)
around the grease droplets
(c) Micelle formed
Since the polar groups can interact with water, the oil droplet surrounded
by stearate ions is now pulled in water and removed from the dirty
surface. Thus soap helps in emulsification and washing away of oils and
fats. The negatively charged sheath around the globules prevents them
from coming together and forming aggregates.
19. Give four examples of heterogeneous catalysis.
Soln. (a) CH == CH Pt
2 2( g ) + H 2( g ) → CH 3 − CH 3( g )
Fe
(b) N 2( g ) + 3H 2( g ) → 2 NH 3( g )
(c) CO( g ) + 2H 2( g ) ZnO


+ Cr 2O 3
→ CH 3OH( l )
(d) 2SO 2( g ) + O 2( g ) Pt

→ 2SO 3( g )
20. What do you mean by activity and selectivity of catalysts?

Soln. (a) Activity : The activity of a catalyst depends upon the strength
of chemisorption to a large extent. The reactants must get adsorbed
reasonably strongly on to the catalyst to become active. But adsorption
must not be so strong that they are immobilised. It is observed that
maximum activity is shown by elements of groups 7-9 of the periodic
table e.g., 2H 2 + O 2 Pt
→ 2H 2 O
(b) Selectivity : The selectivity of a calatyst is its ability to yield a particular
product in the reaction e.g.,
CO + 3H 2 Ni
→ CH 4 + H 2 O
Cu/ZnO-Cr O
CO + 2H 2 
2 3
→ CH 3OH
CO + H 2 Cu
→ HCHO
Thus, a selective catalyst can act as a catalyst in one reaction and may fail
to catalyse another reaction.
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21. Describe some features of catalysis by zeolites.
Soln. (a) Zeolites are hydrated aluminosilicates which have a three
dimensional network structure containing water molecules in their
pores.
(b) The pores are made vacant by heating before catalysis.
(c) The reactions taking place in zeolites depend upon the size and shape
of reactant and product molecules and also on the pores and cavities
in them. e.g., ZSM-5 converts alcohols to hydrocarbons by dehydrating
them.
Alcohols ZSM−
 5
→ Hydrocarbons
22. What is shape selective catalysis?
Soln. The catalytic reaction that depends upon the pore structure of the
catalyst and the size of the reactant and product molecules is called shape-
selective catalysis. Zeolites are good shape-selective catalysts because of
their honeycomb-like structures. They are microporous aluminosilicates
with three dimensional network of silicates in which some silicon atoms
are replaced by aluminium atoms giving Al –O–Si framework. The
reactions taking place in zeolites depend upon the size and shape of
reactant and product molecules as well as upon the pores and cavities of
the zeolites. They are found in nature as well as synthesised for catalytic
selectivity.
23. Explain the following terms :

(i) Electrophoresis (ii) Coagulation
(iii) Dialysis (iv) Tyndall effect
Soln. (i) Electrophoresis : Refer answer number 15 (iii)
(ii) Coagulation or precipitation : The stability of the lyophobic sols
is due to the presence of charge on colloidal particles. If somehow, the
charge is removed, the particles will come nearer to each other to form
aggregates (or coagulate) and settle down under the force of gravity. The
process of settling down of colloidal particles is called coagulation.
(iii) Dialysis : It is the process of removing dissolved substances from a
colloidal solution by means of diffusion through a suitable membrane.
Since particles (ions or smaller molecules) in a true solution can pass
through animal membrane (bladder) or parchment paper or cellophane
sheet but not the colloidal particles, the membrane can be used for dialysis.
The apparatus used for this purpose is called dialyser. A bag of suitable
membrane containing the colloidal solution is suspended in a vessel
through which fresh water is continuously flowing. The molecules and
ions diffuse through membrane into the outer water and pure colloidal
solution is left behind.
(iv) Tyndall effect : Refer answer number 15 (i)
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24. Give four uses of emulsions.
Soln. (i) Some of the medicines are effective as emulsions.
(ii) Paints are emulsions which are used in our daily life.
(iii) Soaps and detergents act as cleansing agents, action of which is based
on emulsification.
(iv) Photographic films are coated with emulsion of AgBr on its surface.
25. What are micelles? Give an example of a micelle system.

Soln. Micelles are substances that behave as normal strong electrolytes
at low concentration but at high concentrations behave as colloids due
to formation of aggregates. They are also called associated colloids, e.g.,
soaps and detergents. They can form ions and may contain 100 or more
molecules to form a micelle.
26. Explain the terms with suitable examples:

(i) Alcosol (ii) Aerosol (iii) Hydrosol
Soln. (i) Alcosol : The sol in which alcohol is used as dispersion medium
is called alcosol e.g., sol of cellulose nitrate in ethyl alcohol.
(ii) Aerosol : The sol in which dispersion medium is gas and dispersed
phase is either solid or liquid, the colloidal system is called aerosol e.g.,
fog, insecticides, sprays, etc.
(iii) Hydrosol : The sol in which dispersion medium is water is called
hydrosol e.g., starch sol.
27. Comment on the statement that ‘colloid is not a substance but a state of
substance’.
Soln. Colloid is not a substance, but a state of substance because the
same substance may exist as a colloid or crystalloid under different
conditions e.g., sulphur. Colloidal solution of sulphur consists of sulphur
molecules dispersed in water. In this state, sulphur atoms combine
to form multimolecules whose size lies between 1 nm to 1000 nm and
form colloidal state. Sulphur forms true solution in carbon disulphide.
Similarly soap is a solution at low concentration but a colloid at higher
concentration.

1. Why are substances like platinum and palladium often used for carrying
out electrolysis of aqueous solutions?
Soln. Due to their inert nature, these metals do not affect the products of
electrolysis. They have good adsorbing capacity for hydrogen.
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2. Why does physisorption decrease with the increase of temperature?
Soln. Physical adsorption of a gas by a solid is generally reversible. Thus,
 Gas/ Solid + Heat
Solid + Gas 
Since the adsorption process is exothermic, the physical adsorption occurs
readily at low temperature and decreases with increasing temperature
(Le Chatelier’s principle).
3. Why are powdered substances more effective adsorbents than their

crystalline forms?
Soln. The extent of adsorption increases with increase in surface area of the
adsorbent. Finely powdered substances have large, porous areas and act
as good adsorbents.
4. Why is it necessary to remove CO when ammonia is obtained by Haber’s

process?
Soln. CO is a catalytic poison. It reacts with iron to form iron carbonyl
thus inhibiting the activity of catalyst.
5. Why is the ester hydrolysis slow in the beginning and becomes faster
after sometime?
Soln. The acid formed during the reaction provides hydrogen ions which
act as catalyst for the reaction and it becomes faster.
6. What is the role of desorption in the process of catalysis?

Soln. In catalysis the products formed are desorbed and detached from
the surface so that, more reactants can get adsorbed on the surface of
catalyst.
7. What modification can you suggest in the Hardy Schulze law?

Soln. The Hardy Schulze law considers the coagulation of sols
because of neutralisation of their charges. Since coagulation can
also occur by mixing two oppositely charged sols, it should also include
“when oppositely charged sols are mixed in proper proportions to
neutralize the charges of each other, the coagulation of both the sols
occurs.”
8. Why is it essential to wash the precipitate with water before estimating

it quantitatively?
Soln. Few impurities which are soluble in water and are adsorbed on the
surface of the precipitate are removed by washing them with water.
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Chapter 6
Principles and Processes of
Elements Isolation
Summary
Metals are required for a variety of purposes. For this, we need their extraction from
the minerals in which they are present and from which their extraction is
commercially feasible.These minerals are known as ores. Ores of the metal are
associated with many impurities. Removal of these impurities to certain extent is
achieved in concentration steps. The concentrated ore is then treated chemically
for obtaining the metal. Usually the metal compounds (e.g., oxides, sulphides) are
reduced to the metal. The reducing agents used are carbon, CO or even some metals.
In these reduction processes, the thermodynamic and electrochemical concepts
are given due consideration. The metal oxide reacts with a reducing agent; the
oxide is reduced to the metal and the reducing agent is oxidised. In the two reactions,
the net Gibbs energy change is negative, which becomes more negative on raising
the temperature. Conversion of the physical states from solid to liquid or to gas,
and formation of gaseous states favours decrease in the Gibbs energy for the entire
system. This concept is graphically displayed in plots of ∆G0 vs T (Ellingham diagram)
for such oxidation/reduction reactions at different temperatures. The concept of
electrode potential is useful in the isolation of metals (e.g., Al, Ag, Au) where the
sum of the two redox couples is +ve so that the Gibbs energy change is negative.
The metals obtained by usual methods still contain minor impurities. Getting pure
metals require refining. Refining process depends upon the differences in properties
of the metal and the impurities. Extraction of aluminium is usually carried out from
its bauxite ore by leaching it with NaOH. Sodium aluminate, thus formed, is separated
and then neutralised to give back the hydrated oxide, which is then electrolysed
using cryolite as a flux. Extraction of iron is done by reduction of its oxide ore in
blast furnace. Copper is extracted by smelting and heating in a reverberatory furnace.
Extraction of zinc from zinc oxides is done using coke. Several methods are employed
Aluminium 1. Bauxite, Al2O3. x H2O Electrolysis of For the extraction, a

2. Cryolite, Na3AlF6 Al2O3 dissolved in good source of
molten Na3AlF6 electricity is required.
Iron 1. Haematite, Fe2O3 Reduction of the Temperature

2. Magnetite, Fe3O4 oxide with CO approaching 2170 K
and coke in Blast is required.
furnace
Copper 1. Copper pyrites, CuFeS2 Roasting of It is self reduction in a
2. Copper glance, Cu2S sulphide specially designed
3. Malachite, partially and converter. The
CuCO3.Cu(OH)2 reduction reduction takes place
4. Cuprite, Cu2O easily. Sulphuric acid
leaching is also used
in hydrometallurgy
from low grade ores.
Zinc 1. Zinc blende or Roasting followed The metal may be

Sphalerite, ZnS by reduction with purified by fractional
2. Calamine, ZnCO3 coke distillation.
3. Zincite, ZnO
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1. Copper can be extracted by hydrometallurgy but not zinc. Explain.
Soln. The E° of zinc (Zn2+/Zn = – 0.76 V) is lower than that of copper

(Cu2+/Cu = +0.34 V). Hence, zinc can displace Cu from solutions of
Cu2+ ions.
Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)
But to displace zinc from solution of Zn2+ ions, we need a metal more
reactive than it, i.e., Al (E°Al3+/Al = –1.66V), Mg (E°Mg2+/Mg = –2.37 V),
Ca(E°Ca2+/Ca = –2.87 V), K(E°K+/K = –2.93 V) etc.
But all these metals react with water forming their corresponding ions
with the evolution of H2 gas. Hence, Al, Mg, etc. cannot be used to
displace zinc from the solution of Zn2+ ions. Thus, copper can be extracted
by hydrometallurgy but not zinc.
2. What is the role of depressant in froth-floatation process?

Soln. In froth -floatation process, the role of the depressant is to prevent
one type of sulphide ore particles from forming the froth with air bubbles.
For example, NaCN is used as a depressant to separate lead sulphide
(PbS) ore from zinc sulphide (ZnS) ore. The reason is that NaCN forms a
zinc complex, Na2[Zn(CN)4] on the surface of ZnS preventing it from the
formation of the froth. Under these conditions, only PbS forms froth and
therefore, it can be separated from ZnS ore.
3. Why is the extraction of copper from pyrites more difficult than that
from its oxide ore through reduction?
Soln. In the Ellingham diagram, the Cu2O line is almost at the top. So it is
quite easy to reduce oxide ores of copper directly to the metal by heating
with coke (as can be seen in graph that the lines of C, CO and C, CO2 are
at much lower positions). But most of the ores are sulphide and some
may also contain iron. So, the sulphide ores are roasted/smelted to give
oxides :
2Cu2S + 3O2 2Cu2O + 2SO2
The oxide can then be easily reduced to metallic copper using coke :
Cu2O + C 2Cu + CO
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4. Explain : (i) Zone refining (ii) Column chromatography.

Soln. (i) This method is based on the principle that the impurities are
more soluble in the melt than in the solid state of the metal. A circular
mobile heater is fixed at one end of a rod of the impure metal. The molten
zone moves along with the heater which is moved forward. As the
heater moves forward, the pure metal crystallises out of the melt and the
impurities pass on into the 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. This method is very useful
for producing semiconductor and other metals of very high purity, e.g.,
germanium, silicon, boron, gallium and indium.
Noble-gas atmosphere
Metal rod Induction-coil

Molten zone heaters moving
as shown
Zone refining process
(ii) Chromatographic method is based on the principle that different
components of a mixture are differently adsorbed on an adsorbent.
The adsorbed components are removed (eluted) by using suitable
(eluant). There are several chromatogrpahic techniques such as paper
chromatography, column chromatography, gas chromatography, etc.
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Column chromatography : Column chromatography involves separation
of a mixture over a column of adsorbent (stationary phase) packed in a
glass tube. The column is fitted with a stopcock at its lower end (fig).
The mixture adsorbed on adsorbent is placed on the top of the adsorbent
column packed in a glass tube.
solvent
mixture of
compounds
(a + b + c) a a
adsorbent b+c
b
(stationary
phase) c
glass wool
Column chromatography
Different stages of separation of
components of a mixture
An appropriate eluant which is a liquid or a mixture of liquids is allowed

to flow the column slowly. Depending upon the degree to which the
compounds are adsored, complete separation takes place. The most
readily adsorbed substances are retained near the top and others come
down to various distance in the column.
5. Out of C and CO, which is a better reducing agent at 673 K?

Soln. When carbon acts as a reducing agent, it is either converted into CO
or CO2 or both.
2C + O2 2CO
C + O2 CO2
CO is oxidised to CO2 when it is used as a reducing agent.
2CO + O2 2CO2
From the Ellingham diagram (refer answer number 3), it is clear that
at the temperature 673 K, the DG° of the formation of CO2 from CO is
more negative than the formation of CO or CO2 from carbon. Hence, at
temperature 673 K, CO is a better reducing agent than C.
6. Name the common elements present in the anode mud in electrolytic

refining of copper. Why are they so present?
Soln. Many of the metals such as copper, silver, gold, aluminium, lead, etc.,
are purified by this method. This is perhaps the most important method.
The impure metal is made anode while a thin sheet of pure metal acts
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as a cathode. The electrolytic solution consists of generally an aqueous
solution of a salt or a complex of the metal. On passing the current, the
pure metal is deposited on the cathode and equivalent amount of the metal
gets dissolved from the anode. Thus, the metal is transferred from anode
to cathode through solution. The soluble impurities pass into the solution
while the insoluble one, especially less electropositive impurities collect
below the anode as anodic mud or anode sludge. Impurities from the
blister copper deposit as anode mud which contains antimony, selenium,
tellurium, silver, gold and platinum.
7. Write down the reactions taking place in different zones in the blast
furnace during the extraction of iron.
Soln. Near the bottom of the furnace (zone of combustion, 2170 K), coke
first combines with air to form CO2 which then combines with more coke
(zone of heat absorption, 1423 K) to form CO. The CO thus produced acts
as the reducing agent and reduces iron oxide to spongy iron near the top
of the furnace (zone of reduction, 823 K).
Charge
cup and cone

arrangement 200 - 250°C waste gases
400°C
600°C
700°C refractory
800 -1000°C bricks
1300°C
1600°C hot air
Tuyeres
molten
slag molten metal
Blast furnace
C + O2 CO2; ∆H = – 393.3 kJ (Exothermic)
CO2 + C 2CO; ∆H = + 163.2 kJ (Endothermic)
823 K
3Fe2O3 + CO → 2Fe3O4 + CO2
823 K
Fe3O4 + CO → 3FeO + CO2
But the further reduction of FeO to Fe by CO occurs around 1123 K.
~1123 K
FeO + CO → Fe + CO2
However, direct reduction of iron ores (haematite, magnetite, etc.) left
unreduced (around 823 K) get converted completely to iron by carbon
(above 1123 K).
> 1123 K
Fe2O3 + 3C → 2Fe + 3CO
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Limestone which acts as flux, decomposes at 1123 K (zone of slag
formation) to form CaO which then combines with silica to form slag.
1123 K
CaCO3 
→ CaO + CO2;
1123 K
CaO + SiO 2 
→ CaSiO 3
(slag)
Silicates, phosphates and manganates present as impurities in ore, are
reduced to Si, P and Mn, respectively.
P4O10 + 10C 4P + 10CO
SiO2 + 2C Si + 2CO
MnO2 + 2C Mn + 2CO
At the lower part of the furnace (zone of fusion, 1423-1673 K) the spongy
iron melts and dissolves some carbon, S, P, SiO2, Mn, etc.
The molten slag being less dense floats over the surface of the molten iron.
The molten iron is then tapped off from the furnace and is then solidified
to give blocks of iron called cast iron or pig iron.
8. Write chemical reactions taking place in the extraction of zinc from zinc
blende.
Soln. Concentration : When zinc blende is used, the powdered ore is
concentrated by froth-floatation process.
Roasting : The concentrated ore is heated in excess of oxygen at about
900°C. Zinc sulphide is oxidised to zinc oxide. If some of the ore is oxidised
to zinc sulphate, it also decomposes at 900°C into ZnO.
900°C
2ZnS + 3O2 2ZnO + 2SO2
900°C
ZnS + 2O2 ZnSO4
For roasting, a reverberatory furnace may be used.
Reduction : The principal reaction that takes place during reduction is the
conversion of the oxide into the metal with the help of carbon.
ZnO + C Zn + CO
Electrolytic refining : Purification of zinc is done by electrolytic refining
using pure Zn as cathode and impure Zn as anode. The electrolyte is
ZnSO4.
Reaction at cathode : Zn2+(aq) + 2e– → Zn(s)
Reaction at anode : 2H2O(l) → O2(g) + 4H+(aq) + 4e–
ZnSO4 electrolyte is added from time to time.
9. State the role of silica in the metallurgy of copper.
Soln. Iron present in pyrites has greater affinity for oxygen than copper.
The copper oxide formed reacts with unchanged iron sulphide to form
iron oxide so, most of the iron sulphide is oxidised to ferrous oxide.
2FeS + 3O2 2FeO + 2SO2
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Ferrous oxide combines with silica which acts as flux and forms ferrous
silicate. By this reaction most of the iron is removed as slag.
FeO + SiO2 FeSiO3
Flux Ferrous silicate
(slag)
10. What is meant by the term “chromatography”?

Soln. Chromatographic method is based on the principle that different
components of a mixture are differently adsorbed on an adsorbent.
The adsorbed components are removed (eluted) by using suitable
(eluant). There are several chromatogrpahic techniques such as paper
chromatography, column chromatography, gas chromatography, etc.
11. What criterion is followed for the selection of the stationary phase in
chromatography?
Soln. The stationary phase is selected in such a way that the impurities
are more strongly adsorbed or are more soluble in the stationary phase
than element to be purified. Under these conditions, when the column is
extracted, the impurities will be retained by the stationary phase whereas
the pure component is easily removed.
12. Describe a method for refining nickel.

Soln. Nickel is purified by Mond’s process. Impure nickel is treated with
carbon monoxide at 60-80°C when volatile compound nickel carbonyl is
formed. Nickel carbonyl decomposes at 180°C to form pure nickel and
carbon monoxide.
60 - 80°C 180°C
Ni + CO Ni(CO)4 Ni + 4CO
Impure Gaseous Pure
compound
13. How can you separate alumina from silica in a bauxite ore associated
with silica? Give equations, if any.
Soln. Serpeck’s process is used when silica is present in considerable
amounts in bauxite ore. The ore is mixed with coke and heated at 1800°C
in presence of nitrogen, where AlN is formed.
Al2O3 + 3C + N2 2AlN + 3CO
Silica is reduced to silicon which volatilises off at this temperature.
SiO2 + 2C Si + 2CO
14. Giving examples, differentiate between ‘roasting’ and ‘calcination’.

Soln. Calcination : It is the process of converting an ore into its oxide by
heating it strongly below its melting point either in absence or limited
supply of air.
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∆
Fe2O3·xH2O → Fe2O3 + xH2O
∆
ZnCO3(s) → ZnO(s) + CO2(g)
Roasting : In roasting, the ore is heated in a regular supply of air in a

furnace at a temperature below the melting point of the metal.
2ZnS + 3O2 2ZnO + 2SO2
2PbS + 3O2 2PbO + 2SO2
15. How is ‘cast iron’ different from ‘pig iron’?

Soln. The iron obtained from Blast furnace contains about 4% carbon and
many impurities in smaller amount (e.g., S, P, Si, Mn). This is known as
pig iron and cast into variety of shapes.
Cast iron is different from pig iron and is made by melting pig iron with
scrap iron and coke using hot air blast. It has slightly lower carbon content
(about 3%) and is extremely hard and brittle.
16. Differentiate between “minerals” and “ores’.
Soln. The natural substances in which the metal or their compounds occur
in the earth are called minerals. The mineral has a definite composition. It
may be a single compound or complex mixture. The minerals from which
the metals can be conveniently and economically extracted are known
as ores. All the ores are minerals but all minerals cannot be ores, e.g.,
both bauxite (Al2O3.xH2O) and clay (Al2O3.2SiO2.2H2O) are minerals of
aluminium. It is bauxite which is used for extraction of aluminium and
not clay. Thus bauxite is an ore of aluminium.
17. Why copper matte is put in silica lined converter ?

Soln. Copper matte consists of Cu2S and FeS. When a blast of hot air is
passed through molten matte taken in a silica lined converter, FeS present
in matte is oxidised to FeO which combines with silica (SiO2) to form
FeSiO3 (slag).
2FeS + 3O2 2FeO + 2SO2
FeO + SiO2 FeSiO3
Silica Slag
When complete iron has been removed as slag, some of the Cu2S undergoes
oxidation to form Cu2O which then reacts with more Cu2S to form copper
metal.
2Cu2S + 3O2 2Cu2O + 2SO2
2Cu2O + Cu2S 6Cu + SO2
Thus, copper matte is heated in silica lined converter to remove FeS
present in matte as FeSiO3 (slag).
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18. What is the role of cryolite in the metallurgy of aluminium?
Soln. The role of cryolite is as follows :
(i) It makes alumina a good conductor of electricity.
(ii) It lowers the fusion temperature of the bath from 2323 K to about
1140 K.
19. How is leaching carried out in case of low grade copper ores?
Soln. The leaching of the low grade copper ores is carried out with
acids in the presence of air when copper goes into solution as Cu2+ ions.
Therefore,
2Cu(s) + 2H2SO4(aq) + O2(g) 2CuSO4(aq) + 2H2O(l)
or Cu(s) + 2H+(aq) + 1/2O2(g) Cu2+(aq) + H2O(l)
20. Why is zinc not extracted from zinc oxide through reduction using CO?
Soln. The standard free energy of formation (∆fG°) of CO2 from CO is
higher than that of the formation of ZnO from Zn. Hence, CO cannot be
used to reduce ZnO to Zn.
21. The value of ∆f G° for formation of Cr2O3 is – 540 kJ mol–1 and that of
Al2O3 is – 827 kJ mol–1. Is the reduction of Cr2O3 possible with Al?
Soln. The two equations are :
4 2
Al(s) + O2(g) Al2O3(s) ; ∆f G°Al, Al2O3 = –827 kJ mol–1
3 3
4 2
3 Cr(s) + O2(g) Cr2O3(s) ; ∆f G° = –540 kJ mol–1
3
Subtracting equation (ii) from equation (i), we get
4 2 2 4
Al(s) + Cr2O3(g) Al2O3(s) + Cr(s) ; ∆rG° = –287 kJ mol–1
3 3 3 3
Since ∆f G° of the combined redox reaction is negative, therefore, reduction
of Cr2O3 by Al is possible.
22. Out of C and CO, which is a better reducing agent for ZnO?
Soln. The free energy of formation (∆f G°) of CO from C becomes lower
at temperatures above 1120 K whereas that of CO2 from C becomes lower
above 1323 K than ∆fG° of ZnO. However, ∆fG° of CO2 from CO is always
higher than that of ZnO. Therefore, C can reduce ZnO to Zn but not CO.
Therefore, out of C and CO, C is a better reducing agent than CO for
ZnO.
Reduction of Zn is usually carried out around 1673 K,
1673 K
ZnO + C Zn + CO
23. The choice of a reducing agent in a particular case depends on

thermodynamic factor. How far do you agree with this statement? Support
your opinion with two examples.
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Soln. Some basic concepts of thermodynamics help us in understanding
the theory of metallurgical transformations. Gibb’s energy is the most
significant term.
The graphical representation of Gibb’s 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. (For diagram refer answer number 3) Such diagrams help us
in predicting the feasibility of thermal reduction of an ore. The criterion
of feasibility is that at a given temperature Gibb’s energy of the reaction
must be negative.
Examples :
(i) Thermodynamics helps us to understand how coke reduces the oxide
and why blast furnace is chosen. One of the main reduction steps in this
process is :
FeO(s) + C(s) Fe(s/l) + CO(g) …(1)
It can be seen as a couple of two simpler reactions. In one, the reduction of
FeO is taking place and in the other, C is being oxidised to CO:
1
FeO(s) Fe(s) + O [∆G(FeO, Fe)] …(2)
2 2(g)
1
C(s) + O CO(g) [∆G(C, CO)] …(3)
2 2(g)
When both the reactions take place to yield the equation (1), the net Gibb’s
energy change becomes :
∆G(C, CO) + ∆G(FeO, Fe) = ∆rG …(4)
Naturally, the resultant reaction will take place when the right hand side
in equation (3) is negative. In ∆G° vs T plot representing reaction 2, the
plot goes upward and that representing the change C → CO (C, CO) goes
downward. At temperatures above 1073 K (approx), the C, CO line comes
below the Fe, FeO line [∆G(C, CO) < ∆G(Fe, FeO)]. So in this range, coke will
be reducing the FeO and will itself be oxidised to CO. In a similar way
the reduction of Fe3O4 and Fe2O3 at relatively lower temperatures by CO
can be explained on the basis of lower lying points of intersection of their
curves with the CO, CO2 curve in Ellinghan diagram.
(ii) In the graph of ∆rG° vs T for formation of oxides, the Cu2O line is
almost at the top. So it is quite easy to reduce oxide ores of copper directly
to the metal by heating with coke (both the lines of C, CO and C, CO2
are at much lower position in the graph particularly after 500 - 600 K).
However most of the ores are sulphide and some may also contain iron.
The sulphide ores are roasted/smelted to give oxides:
2Cu2S + 3O2 2Cu2O + 2SO2
The oxide can then be easily reduced to metallic copper using coke.
Cu2O + C 2Cu + CO
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24. Name the processes from which chlorine is obtained as a by-
product. What will happen if an aqueous solution of NaCl is subjected to
electrolysis?
Soln. Sodium metal is prepared by Down’s process. This process involves
the electrolysis of a fused mixture of NaCl and CaCl2 at 873 K. During
electrolysis, sodium is discharged at the cathode and Cl2 is obtained at
the anode as a by-product.
Electrolysis
NaCl(l)  → Na+(melt) + Cl–(melt)
Cathode : Na+(melt) + e– Na(s)
Anode : Cl (melt)
–
Cl(g) + e–
2Cl(g) Cl2(g)
If an aqueous solution of NaCl is electrolysed, H2 is evolved at the
cathode and Cl2 is obtained at the anode. The reason being that the E°
of Na+/Na redox couple is much lower (E° = –2.71V) than that of H2O
( E °Η O/ H ) = − 0.83 V) and hence water is reduced to H2 in preference to
2 2
Na+ ions. However, NaOH is obtained in the solution.
Electrolysis
NaCl(aq)  → Na+(aq) + Cl–(aq)
Anode : Cl–(aq) Cl(g) + e–
2Cl(g) Cl2(g)
Cathode : 2H2O(l) + 2e– H2(g) + 2OH–(aq)
25. What is the role of graphite rod in the electrometallurgy of aluminium?

Soln. In this process, a fused mixture of alumina, cryolite and fluorspar
(CaF2) is electrolysed using graphite as anode and steel as cathode.
During electrolysis, Al is liberated at the cathode whereas CO and CO2
are liberated at the anode.
Cathode : Al3+(melt) Al(l)
Anode : C(s) + O (melt)
2–
CO(g) + 2e–
C(s) + 2O2–(melt) CO2(g) + 4e–
If some other metal is used as the anode other than graphite, then O2
liberated will not only oxidise the metal of the electrode but would also
convert some of the Al liberated at the cathode back to Al2O3. Since graphite
is much cheaper than any metal, graphite is used as the anode. So, the role
of graphite in electrometallurgy of Al is to prevent the liberation of O2 at
the anode which may otherwise oxidise some of the liberated Al back to
Al2O3.
26. Outline the principles of refining of metals by the following methods:

(i) Zone refining (ii) Electrolytic refining
(iii) Vapour phase refining
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Soln. (i) Refer answer number 4(i).
(ii) In this method, the impure metal is made to act as anode. A strip of
the same metal in pure form is used as cathode. They are put in a suitable
electrolytic bath containing soluble salt of the same metal. The more basic
metal remains in the solution and the less basic ones go to the anode
mud.
Anode : M M n+ + ne–
Cathode : M + ne–
n+
M
Copper is refined using an electrolytic method. Anodes are of impure
copper and pure copper strips are taken as cathode. The electrolyte is
acidified solution of copper sulphate and the net result of electrolysis is
the transfer of copper in pure form from the anode to the cathode:
Anode : Cu Cu2+ + 2e–
Cathode : Cu2+ + 2e– Cu
Impurities from the blister copper deposit as anode mud which contains
antimony, selenium, tellurium, silver, gold and platinum; recovery of
these elements may meet the cost of refining.
Zinc may also be refined this way.
(iii) In this method, the metal is converted into its volatile compound and
collected elsewhere. It is then decomposed to give pure metal. So, the two
requirements are:
(a) The metal should form a volatile compound with an available
reagent.
(b) The volatile compound should be easily decomposable, so that the
recovery is easy.
Following example will illustrate this technique.
Mond process for Refining Nickel : In this process, nickel is heated
in a stream of carbon monoxide forming a volatile complex, nickel
tetracarbonyl:
Ni + 4CO 330 − 350 K
→ Ni(CO)4
The carbonyl is subjected to higher temperature so that it is decomposed
giving the pure metal :
450 − 470 K
Ni(CO)4 → Ni + 4CO
27. Predict conditions under which Al might be expected to reduce MgO.

Soln. The two equations are :
4 2
(a) Al + O2 Al2O3
3 3
(b) 2Mg + O2 2MgO
At the point of intersection of Al2O3 and MgO curves the ∆G° becomes
zero for the reaction.
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For the reduction of MgO by Al consider the reaction :
3MgO(s) + 2Al(s) → 3Mg(s, l, g) + Al2O3(s)
For this reaction the temperature should be chosen so that,
DfG°(Al2O3) < DfG°(MgO)
Around 2000 K the line for Al2O3 lies below that of MgO, therefore, Al can
reduce MgO. However, at a temperature below the intersection point of
two lines MgO is more stable and cannot be reduced by Al.

1. Which of the ores mentioned in Table 6.1 (NCERT Textbook) can be
concentrated by magnetic separation method?
Soln. Ores in which one of the components (either the impurity or the
actual ore) is magnetic can be concentrated by magnetic separation, e.g.,
ores containing iron (haematite, magnetite, siderite and iron pyrites).
2. What is the significance of leaching in the extraction of aluminium?

Soln. Leaching is significant as it helps in removing the impurities like
SiO2, Fe2O3, etc. from the bauxite ore.
Al2O3(s) + 2NaOH(aq) + 3H2O(l)
Alumina
473-523 K
SiO2(l) + 2NaOH(aq) Na2SiO3(aq) + H2O(l)
Silica Sodium silicate
2Na[Al(OH)4](aq) + 2CO2(g) Al2O3 · xH2O (s) ↓ + 2NaHCO3(aq)

1473 K
Al2O3 · xH2O(s) Al2O3(s) + xH2O(g)
3. The reaction, Cr2O3 + 2Al Al2O3 + 2Cr (∆G° = –421 kJ) is

thermodynamically feasible as is apparent from the Gibbs energy value.
Why does it not take place at room temperature?
Soln. Certain amount of activation energy is essential even for such
reactions which are thermodynamically feasible, therefore heating is
required.
4. Is it true that under certain conditions, Mg can reduce Al2O3 and Al can
reduce MgO? What are those conditions?
Soln. Yes, below 1350°C, Mg can reduce Al2O3 and above 1350°C, Al can
reduce MgO. This can be inferred from ∆G° vs T plots.
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Chapter 7
The p-Block Elements
Summary
Groups 13 to 18 of the periodic table consist of p-block elements with their valence
shell electronic configuration ns2np1–6. Groups 13 and 14 were dealt with in Class
XI. In this Unit remaining groups of the p-block have been discussed.
Group 15 consists of five elements namely, N, P, As, Sb and Bi which have
general electronic configuration ns2np3. Nitrogen differs from other elements of this
group due to small size, formation of pπ–pπ multiple bonds with itself and with
highly electronegative atom like O or C and non-availability of d orbitals to expand
its valence shell. Elements of group 15 show gradation in properties. They react with
oxygen, hydrogen and halogens. They exhibit two important oxidation states, + 3
and + 5 but +3 oxidation is favoured by heavier elements due to ‘inert pair effect’.
Dinitrogen can be prepared in laboratory as well as on industrial scale. It forms
oxides in various oxidation states as N2O, NO, N2O3, NO2, N2O4 and N2O5. These
oxides have resonating structures and have multiple bonds. Ammonia can be
prepared on large scale by Haber’s process. HNO 3 is an important industrial
chemical. It is a strong monobasic acid and is a powerful oxidising agent. Metals
and non-metals react with HNO3 under different conditions to give NO or NO2.
Phosphorus exists as P4 in elemental form. It exists in several allotropic forms.
It forms hydride, PH3 which is a highly poisonous gas. It forms two types of halides as
PX3 and PX5. PCl3 is prepared by the reaction of white phosphorus with dry chlorine
while PCl5 is prepared by the reaction of phosphorus with SO2Cl2. Phosphorus forms
a number of oxoacids. Depending upon the number of P–OH groups, their basicity
varies. The oxoacids which have P–H bonds are good reducing agents.
The Group 16 elements have general electronic configuration ns2np4. They show
maximum oxidation state, +6. Gradation in physical and chemical properties is
observed in the group 16 elements. In laboratory, dioxygen is prepared by heating
KClO3 in presence of MnO2. It forms a number of oxides with metals. Allotropic form
of oxygen is O3 which is a highly oxidising agent. Sulphur forms a number of allotropes.
Of these, α– and β– forms of sulphur are the most important. Sulphur combines with
oxygen to give oxides such as SO2 and SO3. SO2 is prepared by the direct union of
sulphur with oxygen. SO2 is used in the manufacture of H2SO4. Sulphur forms a
number of oxoacids. Amongst them, the most important is H2SO4. It is prepared by
contact process. It is a dehydrating and oxidising agent. It is used in the manufacture
of several compounds.
Group 17 of the periodic table consists of the following elements F, Cl, Br, I and
At.These elements are extremely reactive and as such they are found in the
combined state only. The common oxidation state of these elements is –1. However,
highest oxidation state can be +7. They show regular gradation in physical and
chemical properties. They form oxides, hydrogen halides, interhalogen compounds
and oxoacids. Chlorine is conveniently obtained by the reaction of HCl with KMnO4.
HCl is prepared by heating NaCl with concentrated H2SO4. Halogens combine with
one another to form interhalogen compounds of the type XX1n (n = 1, 3, 5, 7)
where X1 is lighter than X. A number of oxoacids of halogens are known. In the
structures of these oxoacids, halogen is the central atom which is bonded in each
case with one OH bond as X–OH. In some cases X = 0 bonds are also found.
Group 18 of the periodic table consists of noble gases. They have ns2 np6 valence
shell electronic configuration except He which has 1s2. All the gases except Rn
occur in atmosphere. Rn is obtained as the decay product of 226Ra.
Due to complete octet of outermost shell, they have less tendency to form
compounds. The best characterised compounds are those of xenon with fluorine
and oxygen only under certain conditions. These gases have several uses. Argon is
used to provide inert atmosphere, helium is used in filling balloons for meteorological
observations, neon is used in discharge tubes and fluorescent bulbs.
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1. Discuss the general characteristics of Group 15 elements with reference

to their electronic configuration, oxidation state, atomic size, ionisation
enthalpy and electronegativity.
Soln. The valence shell electronic configuration of group 15 elements is
ns2np3. Due to half-filled p-orbitals, these elements have extra stability
associated with them.
The common oxidation states of these elements are – 3, +3 and +5. The
tendency to exhibit –3 oxidation state decreases down the group. The
stability of +5 state decreases and that of +3 state increases down the
group due to inert pair effect.
The size of group 15 elements increases down the group. There is a
considerable increase in covalent radius from N to P. However, from As
to Bi only a small increase in covalent radius is observed. This is due to
presence of completely filled d and or f orbitals in heavier members.
Down the group, ionisation enthalpy decreases due to increase in atomic
size. Due to stable half-filled configuration, they have much greater value
than that of group 14 elements.
The electronegativity value, in general, decreases down the group with
increasing atomic size. However, amongst the heavier elements, the
difference is not that much pronounced.
2. Why does the reactivity of nitrogen differ from phosphorus?

Soln. Nitrogen has a unique ability to form pπ – pπ multiple bonds with
itself and with other elements having small size and high electronegativity.
Consequently, its bond enthalpy is very high and reactivity is less.
Another factor which affects the chemistry of N is the absence of
d-orbitals in its valence shell. As a result, not only the covalency of

N is restricted to four, it can also not form dπ – pπ bonds. P on the other
hand, does not form pπ – pπ bonds and hence it only forms a P – P single
bond, which can easily be broken. Also, phosphorus has vacant d-orbitals
and can form dπ – dπ bond with transition metals to form compounds
which can act as ligands.
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3. Discuss the trends in chemical reactivity of group 15 elements.
Soln. Nitrogen has very low reactivity due to unavailability of vacant
d-orbital and high bond dissociation energy of N N bond.
(a) Hydrides : General formula for hydrides is MH3, e.g., NH3, PH3, AsH3,
SbH3, BiH3. All these hydrides are covalent in nature and have pyramidal
structure (sp3 hybridized).
Property Down the Reason

group
Basic decreases The size of central atom increases, electron
strength of density decreases.
MH3
Thermal decreases The size of the central atom increases,
stability of its tendency to form stable M – H bonds
MH3 decreases.
Reducing increases The stability of hydrides decreases, thus the
character reducing character increases.
Melting and increases NH3 has high melting point and boiling
boiling point (except in N) point than PH3 due to hydrogen bonding.
As the molecular size increases van der
Waals forces increases.
(b) Halides : Elements of group 15 form two types of halides viz. trihalides
and pentahalides. The halides are predominantly basic (Lewis bases) in
nature and have lone pair of electrons (central atom is sp3 hybridized).
The pentahalides are thermally less stable than the trihalides.
Property Gradation Reason

Stability of trihalides NF3 > NCl3 Large size difference between N
of nitrogen > NBr3 and the halogens
Lewis base strength NF3 < NCl3 Decreasing electronegativity of

< NBr3 < NI3 halogens
Bond angle among PF3 < PCl3 < Due to decreased bond pair-bond
the halides of PBr3 < PI3 pair repulsion
phosphorus
(c) Oxides : All the elements of this group form two types of oxides i.e.,
M2O3 and M2O5 and are called trioxides and pentoxides.
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Property Gradation Reason

Acidic strength N2O3 > P2O3 > Electronegativity of central atom
of trioxides As2O3 decreases
Acidic strength N2O5 > P2O5 > Electronegativity of central atom
of pentoxide As2O5 > Sb2O5 > decreases.
Bi2O5
Acidic strength N2O < NO < N2O3 Oxidation state of central atom
of oxides of < N2O4< N2O5 increases
nitrogen
Stability of P2O5 > As2O5 > Stability of oxides of a higher
pentoxide Sb2O5 > N2O5 > oxidation state i.e., M2O5 decreases
Bi2O5 with increasing atomic number
(d) Oxoacids : The elements of this group form a number of oxoacids out
of which those of N and P are more common.
Oxoacids of N :
Formula (Name) Ox. state of N
H2N2O2 (Hyponitrous acid) +1
HNO2 (Nitrous acid) +3
HNO3 (Nitric acid) +5
Oxo-acids of P :
Formula (Name) Ox. state Basicity
H3PO3 (Phosphorous acid) O +3 2
H3PO4 (Orthophosphoric acid) P
+5 3
HPO3 (Metaphosphoric acid) HO +5 O 1
H4P2O6 (Hypophosphoric acid) +4
Metaphosphoric acid
4
H2P2O7 (Pyrophosphoric acid) +5
HPO3 (P = +5) (Monobasic) 4
O O O O
2 molecules
P P P P
HO O O
HO OH HO OH
OH OH OH
Metaphosphoric acid
Orthophosphoric acid Diphosphoric acid
HPO (P = +5) (Monobasic)
3 (or Pyrophosphoric acid)
H3PO4 (P = +5) (Tribasic)
H4P2O7 (P = +5) (Tetrabasic)
O O O
2 molecules
P P P
O O O
O
HO OH HO OH
OH OH OH P P P
Orthophosphoric acid Diphosphoric acid OH
H3PO4 (P = +5) (Tribasic) (or PyrophosphoricH acid) HO OH
H4P2O7 (P = +5) (Tetrabasic)OH OH OH
Phosphorous acid Hypophosphoric acid
H3PO3 (P = +3)(Diabasic) H4P2O6 (P = +4) (Tetrabasic)
O O O
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4. Why does NH3 form hydrogen bond but PH3 does not?
Soln. Hydrogen bond is formed between electronegative atom and
hydrogen atom. Nitrogen is an electronegative atom and electronegativity
decreases down the group so PH3 cannot form H-bond.
5. How is nitrogen prepared in the laboratory? Write the chemical

equations of the reactions involved.
Soln. In the laboratory, dinitrogen is prepared by treating an aqueous
solution of ammonium chloride with sodium nitrite.
NH4Cl(aq) + NaNO2(aq) → N2(g) + 2H2O(l) + NaCl(aq)
Small amounts of NO and HNO3 are also formed in this reaction. These
impurities can be removed by passing the gas through aqueous sulphuric
acid containing potassium dichromate. It can also be obtained by the
thermal decomposition of ammonium dichromate.
Heat
(NH4)2Cr2O7  → N2 + 4H2O + Cr2O3
Very pure nitrogen can be obtained by the thermal decomposition of
sodium or barium azide.
Heat
Ba(N3)2 
→ Ba + 3N2
6. How is ammonia manufactured industrially?

Soln. Industrially ammonia is manufactured by Haber’s process.
N2(g) + 3H2(g) → 2NH3(g); ∆f H° = –46.1 kJ/mol
In accordance with Le-Chatelier’s principle, high pressure and low
temperature would favour the formation of ammonia. The optimum
conditions for production of 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.
H2
Pump
N2
N2 + H2
Compressor
at
20 MPa
700 K
Catalyst
iron oxide +
Al2O3 + K2O (N2 + H2 + NH3) liquid NH3
The manufacture of ammonia
7. Illustrate how copper metal can give different products on reaction

with HNO3.
Soln. Nitric acid is a strong oxidising agent and attacks most metals.
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The products of oxidation depend upon the concentration of the acid,
temperature and the nature of the material undergoing oxidation. Copper
with cold dil. HNO3 forms nitric oxide (NO).
3Cu + 8HNO3 → 3Cu(NO3)2 + 2NO + 4H2O
(Cold, dil.)
Copper with hot conc. HNO3 forms nitrogen dioxide (NO2).
Cu + 4HNO3 → Cu(NO3)2 + 2NO2 + 2H2O
(Hot conc.)
8. Give the resonating structures of NO2 and N2O5.

Soln. Resonating structures
NO2 : N N
O O O O
N2 O 5 : O O O O O O
N N N N
O O O O
9. The HNH angle value is higher than HPH, HAsH and HSbH angles. Why?
[Hint : Can be explained on the basis of sp3 hybridisation in NH3 and only s–p
bonding between hydrogen and other elements of the group].
Soln. The actual bond angles are
NH3 PH3 AsH3 SbH3
106.5° 93.5° 91.5° 91.3°
The decreased bond angle in other hydrides can be explained by
the fact that the sp3 hybridisation becomes less and less distinct with
increasing size of the central atom i.e., pure p-orbitals are utilised in M-H
bonding.
10. Why does R3P O exist but R3N O does not (R = alkyl group)?
Soln. In R3N O, covalency required is five. The maximum covalency of
nitrogen is four as it does not possess d-orbitals in the valence shell i.e., it
cannot extend its valency beyond four. On the other hand, other members
have d-orbitals and can utilise these orbitals to show covalency of five or
six e.g., R3P O, PCl5, [SbF6]–, etc. These can form dπ – pπ bonds.
11. Explain why NH3 is basic while BiH3 is only feebly basic.
Soln. The basic character decreases from NH3 to BiH3. The basic nature
is due to the presence of lone pair of electrons on the central atom. NH3
is the strongest electron pair donor due to its small size as the electron
density of the electron pair is concentrated over a small region. As the size
increases the electron density gets diffused over a large region and hence
the ability to donate the electron pair (basic nature) decreases.
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12. Nitrogen exists as diatomic molecule and phosphorus as P4. Why?
Soln. Nitrogen is diatomic gaseous molecule at ordinary temperature
due to its ability to form pπ – pπ multiple bonds. The molecule has one
σ and two π-bonds. Phosphorus exists as discrete tetratomic tetrahedral
molecules as these are not capable of forming multiple bonds due to
repulsion between non-bonded electrons of the inner core.
13. Write main differences between the properties of white phosphorus

and red phosphorus.
Soln.
Property White Phosphorus Red Phosphorus
State Translucent Brittle substance
(crystalline)
Colour White, gets yellowish on Red
exposure to light
Odour Garlic like odour Odourless
Hardness Soft like wax and can be cut Hard
by knife
Poisonous nature Poisonous Non-poisonous
Solubility Soluble in CS2 Insoluble in CS2
Chemilumi- Glows in dark Does not glow in dark
nescence
Density 1.80 2.10
Reactivity Very reactive Less reactive
P Covalent
Action of Burns readily in Cl2 forming Combines
Bond with Cl2
chlorine PCl3 and PCl5 only on heating
forming first PCl3 and
P then PPCl5.
P
Structure of white and red phosphorus(i)are givenofbelow
Structure :
white phosphorus
P Covalent P
P Covalent Bond
Bond
P P P P
P P
P P
P
(i) Structure of white phosphorus (ii) Structure of red phosphorus
Covalent
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14. Why does nitrogen show catenation properties less than phosphorus?
Soln. The single N–N bond is weaker than the single P–P bond because
of high interelectronic repulsion of the non-bonding electrons, owing to
the small bond length. As a result the catenation tendency is weaker in
nitrogen.
15. Give the disproportionation reaction of H3PO3.
Soln. The acids in +3 oxidation state of phosphorus tend to disproportionate
to higher and lower oxidation states, e.g., phosphorous acid on heating
disproportionates to give orthophosphoric acid and phosphine.
4H3PO3 → 3H3PO4 + PH3
16. Can PCl5 act as an oxidising as well as a reducing agent? Justify.
Soln. The oxidation state of P in PCl5 is +5. As P has five electrons in its
valence shell, it cannot increase its oxidation state beyond +5 by donating
electrons, therefore, PCl5 cannot act as a reducing agent. However, it can
decrease its oxidation number from +5 to +3 or some lower value, so,
PCl5 acts as an oxidising agent. For example, it oxidises Ag to AgCl, Sn
to SnCl4.
0 +5 +1 +3 0 +5 +4 +3
→ 2AgCl + PCl 3 ; Sn + 2PCl 5 
2Ag + PCl 5  → SnCl 4 + 2PCl 3
17. Justify the placement of O, S, Se, Te and Po in the same group of the
periodic table in terms of electronic configuration, oxidation state and
hydride formation.
Soln. (i) Electronic configuration :
8O = [He]2s 2p ; 16S = [Ne]3s 3p ;
2 4 2 4
34Se = [Ar]3d 4s 4p
10 2 4
52Te = [Kr]4d 5s 5p and 84Po = [Xe]4f 5d 6s 6p

10 2 4 14 10 2 4
All these elements have same ns2np4 (n = 2 to 6) valence shell electronic

configuration and hence are justified to be placed in group 16 of the
periodic table.
(ii) Oxidation states : They need two more electrons to form dinegative
ions by acquiring the nearest noble gas configuration. So, the minimum
oxidation state of these elements should be –2. Oxygen predominantly
and sulphur to some extent being electronegative show an oxidation
state of –2. Since these elements have six electrons in the valence shell,
therefore, the maximum oxidation state they can show is, + 6. Other
positive oxidation states shown by these elements are +2 and +4. Although,
oxygen due to the absence of d-orbitals does not show oxidation states of
+4 and +6. Thus, on the basis of minimum and maximum oxidation states,
these elements are justified to be placed in the same group i.e., group 16
of the periodic table.
(iii) Formation of hydrides : All the elements complete their respective
octets by sharing two of their valence electrons with 1s-orbital of hydrogen
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to form hydrides of the general formula EH2 i.e., H2O, H2S, H2Se, H2Te
and H2Po. Therefore, on the basis of formation of hydrides of the general
formula, EH2, these elements are justified to be placed in group 16 of the
periodic table.
18. Why is dioxygen a gas but sulphur a solid?

Soln. Oxygen atom has the tendency to form multiple bonds (pπ – pπ
interaction) with other oxygen atom on account of small size while this
tendency is missing in sulphur atom. The bond energy of oxygen-oxygen
double bond (O O) is quite large (about three times that of oxygen-
oxygen single bond, O – O = 34.9 kcal mol–1) while sulphur-sulphur double
bond (S S) is not so large (less than double of sulphur-sulphur single
bond, S–S = 63.8 kcal mol–1). As a result, —O—O—O— chains are less
stable as compared to O O molecule while —S—S—S— chains are more
stable than S S molecule. Therefore, at room temperature, while oxygen
exists as a diatomic gas molecule, sulphur exists as S8 solid.
19. Knowing the electron gain enthalpy values for O → O– and O → O2– as
–141 and 702 kJ mol–1 respectively, how can you account for the formation
of large number of oxides having O2– species and not O– ?
Hint : Consider lattice energy factor in the formation of compound.
Soln. This can be explained with the help of electronic configuration.
1s2 2s2
O
O–
2–
O
As O2– has most stable configuration amongst these. So, formation of O2– is
much more easier. In solid state, large amount of energy (lattice enthalpy)
is released to form divalent O2– ions. It is greater lattice enthalpy of O2–
which compensates for the high energy required to remove the second
electron.
20. Which aerosols deplete ozone?
Soln. CFC – Chlorofluorocarbon (freons) : These compounds commonly
known as freons are introduced into the atmosphere from aerosol
sprays and refrigerating equipments. They undergo photochemical
decomposition and destroy ozone as shown by the following sequence
of reactions.
hυ • •
CF2Cl2 → CF2Cl + Cl (free radical)
hυ • • • •
CFCl3 → CFCl2 + Cl ; Cl + O3 ClO + O2
• • • • • •
ClO slow
 → Cl + O; ClO + O Cl + O2
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21. Describe the manufacture of H2SO4 by Contact process?
Soln. Sulphuric acid is manufactured by the Contact process which
involves three steps :
(i) burning of sulphur or sulphide ores in air to generate SO2.
(ii) conversion of SO2 to SO3 by the reaction with oxygen in the presence
of a catalyst (V2O5), and
(iii) absorption of SO3 in H2SO4 to give oleum (H2S2O7).
A flow diagram for the manufacture of sulphuric acid is shown in
the figure. The SO2 produced is purified by removing dust and other
impurities such as arsenic compounds.
The key step in the manufacture of H2SO4 is the catalytic oxidation of
SO2 with O2 to give SO3 in the presence of V2O5 (catalyst).
V O
2 5 → 2SO
2SO2(g) + O2(g)  3(g)
DrH = – 196.6 kJ mol–1

The reaction is exothermic, reversible and the forward reaction leads to
a decrease in volume. Therefore, low temperature and high pressure are
the favourable conditions for maximum yield. But the temperature should
not be very low otherwise rate of reaction will become slow.
In practice, the plant is operated at a pressure of 2 bar and a temperature
of 720 K. The SO3 gas from the catalytic converter is absorbed in
concentrated H2SO4 to produce oleum. Dilution of oleum with water give
H2SO4 of the desired concentration. In the industry, two steps are carried
out simultaneously to make the process a continuous one and also to
reduce the cost.
SO3 + H2SO4 → H2S2O7
(Oleum)
The sulphuric acid obtained by Contact process is 96 – 98% pure.
Waste Conc. H2S O4
Impure spray spray Conc. H2 SO4
SO 2 + O2 Dry
SO 2 + O2
SO3
V2 O5
Quartz
Sulphur
Preheater
Air
Sulphur Waste Waste Catalytic

water acid Arsenic purifier converter Oleum
burner containing (H2 S2O7)
Washing and Drying
tower gelatinous hydrated
Dust cooling tower ferric oxide
precipitator
Flow diagram for the manufacture of sulphuric acid
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22. How is SO2 an air pollutant?
Soln. SO2 present in atmosphere combines with water to give sulphuric
acid.
2SO2 + O2 + 2H2O → 2H2SO4
This is called acid rain. Acid rain causes extensive damage to building and
statues made of marble, limestone, etc. due to its reaction to give CaSO4.
CaCO3 + H2SO4 → CaSO4 + CO2 + H2O
This way SO2 acts as pollutant.
23. Why are halogens strong oxidising agents?

Soln. General electronic configuration of halogen is
ns np
It will easily accept one electron to fulfill its shell. This easily acceptance
of electron makes halogens strong oxidising agents.
24. Explain why fluorine forms only one oxoacid, HOF.

Soln. Due to high electronegativity and absence of d orbitals, F does not
form oxoacids such as HOFO, HOFO2 and HOFO3 in which the oxidation
state of F is +3, +5 and +7. It just forms one oxoacid, i.e., HOF in which the
oxidation state of F is + 1.
25. Explain why inspite of nearly the same electronegativity, oxygen forms
hydrogen bonding while chlorine does not.
Soln. Although O and Cl have about the same electronegativity, yet their
atomic size (covalent radii) are much different : O = 66 pm and Cl = 99 pm.
Thus, electron density per unit volume of oxygen atom is much higher
than that of chlorine atom. Hence, oxygen forms hydrogen bonds while
chlorine does not though both have approx. the same electronegativity.
26. Write two uses of ClO2.

Soln. ClO2 is a powerful oxidising agent. ClO2 is used as a bleaching agent
for paper pulp and textiles and in water treatment.
27. Why are halogens coloured?

Soln. All halogens are coloured because of absorption of radiations in
visible region which results in the excitation of outer electrons to higher
level. By absorbing different quanta of radiation, they display different
colours as
F2 → yellow
Cl2 → greenish yellow
Br2 → red
I2 → violet
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28. Write the reactions of F2 and Cl2 with water.
Soln. Fluorine reacts vigorously with water and oxidises water to
oxygen.
2H2O + 2F2 → 4HF + O2
Chlorine dissolves in water to form chlorine water. It slowly reacts with
the water to form a mixture of hydrochloric acid and hypochlorous acid.
H2O + Cl2 → HCl + HOCl
Hypochlorous acid is very unstable. In presence of sunlight, it decomposes
to give HCl and nascent oxygen.
hυ
HOCl → HCl + O
This oxygen is responsible for oxidising and bleaching properties of
chlorine.
29. How can you prepare Cl2 from HCl and HCl from Cl2? Write reactions
only.
Soln. Preparation of chlorine by Deacon’s process : By oxidation of
hydrogen chloride gas by atmospheric oxygen in the presence of CuCl2
at 723 K
2→ CuCl
4HCl + O2  2Cl2 + 2H2O
Preparation of HCl : Cl2 can be reduced to HCl by reaction of H2 in the
presence of diffused sunlight.
Diffused
H 2 + Cl 2 Sunlight
 → 2HCl
30. What inspired N. Bartlett for carrying out reaction between Xe and
PtF6?
Soln. Neil Bartlett observed that PtF6 reacts with O2 to yield an ionic solid,
O2+ PtF6–.
Here, O2 gets oxidised to O2+ by PtF6.
Since the first ionisation enthalpy of Xe(1170 kJ mol–1) is fairly close to
that of O2 molecule (1175 kJ mol–1), Bartlett thought that PtF6 should also
oxidise Xe. When Xe and PtF6 were mixed, a rapid reaction took place and
a red solid with the formula, Xe+PtF6– was obtained.
278 K
→ Xe +[PtF6 ]−
Xe + PtF6 
31. What are the oxidation states of phosphorus in the following :
(i) H3PO3 (ii) PCl3 (iii) Ca3P2
(iv) Na3PO4 (v) POF3?
Soln. Let the oxidation state of P be x.
+1 x −2
(i) H 3 P O 3 ∴ 3(+1) + x + 3(–2) = 0 or x = +3
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x −1
(ii) P Cl 3 ∴ x + 3(–1) = 0 or x = +3
+2 x
(iii) Ca 3 P2 ∴ 3(+2) + 2 × x = 0 or x = –3
+1 x −2
(iv) Na 3 P O 4 ∴ 3(+1) + x + 4(–2) = 0 or x = +5
x −2 −1
(v) P O F3 ∴ x + 1(–2) + 3(–1) = 0 or x = +5.
32. Write balanced equations for the following :

(i) NaCl is heated with sulphuric acid in the presence of MnO2.
(ii) Chlorine gas is passed into a solution of NaI in water.
Soln. (i) MnO2 + H2SO4 → MnSO4 + H2O + O
[NaCl + H2SO4 → NaHSO4 + HCl] × 2
2HCl + O → H2O + Cl2
2NaCl + MnO2 + 3H2SO4 → 2NaHSO4 + MnSO4 + 2H2O + Cl2
(ii) Cl will replace I
2NaI(aq) + Cl2(g) → 2NaCl(aq) + I2(s)
33. How are xenon fluorides XeF2, XeF4 and XeF6 obtained?
Soln. Xenon forms three binary fluorides, XeF2, XeF4 and XeF6 by the
direct reaction of elements under appropriate experimental conditions.
673 K
Xe( g) + F2( g) 
1 bar
→ XeF2(s)
(xenon in excess)
873 K
Xe( g) + 2F2( g) 
7 bar
→ XeF4(s)
(1 : 5 ratio)
573 K
Xe( g) + 3F2( g) 60-70
 bar
→ XeF6(s)
(1 : 20 ratio)
34. With what neutral molecule is ClO– isoelectronic? Is that molecule a

Lewis base?
Soln. Replace O– (9 electrons) in ClO– by F (9 electrons). The resulting
neutral molecule is ClF. Since ClF can combine further with F to form
ClF3, so, ClF is a Lewis base.
35. How are XeO3 and XeOF4 prepared?

Soln. Hydrolysis of XeF4 and XeF6 with water gives XeO3.
6XeF4 + 12H2O → 4Xe + 2XeO3 + 24 HF + 3O2
XeF6 + 3H2O → XeO3 + 6HF
Partial hydrolysis of XeF6 gives oxyfluorides, XeOF4 and XeO2F2.
XeF6 + H2O → XeOF4 + 2HF
XeF6 + 2H2O → XeO2F2 + 4HF
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36. Arrange the following in the order of property indicated for each set :
(i) F2, Cl2, Br2, I2 – increasing bond dissociation enthalpy.
(ii) HF, HCl, HBr, HI – increasing acid strength.
(iii) NH3, PH3, AsH3, SbH3, BiH3 – increasing base strength.
Soln. (i) I2 < Br2 < F2 < Cl2 (ii) HF < HCl < HBr < HI
(iii) NH3 > PH3 > AsH3 > SbH3 > BiH3
37. Which one of the following does not exist?

(i) XeOF4 (ii) NeF2
(iii) XeF2 (iv) XeF6
Soln. (ii) Amongst all noble gases, only Xe (except KrF2) forms
compounds.
38. Give the formula and describe the structure of a noble gas species
which is isostructural with:
(i) ICl –4 (ii) IBr2– (iii) BrO3–
–
Soln. (i) Structure of ICl4 : I in ICl4– has four bond pairs and two lone
pairs. Therefore, according to VSEPR theory, it should be square planar
as shown.
–
Here, ICl4 has (7 + 4 × 7 + 1) = 36 valence electrons. A noble gas species
having 36 valence electrons is
–
XeF4(8 + 4 × 7 = 36). Therefore, like ICl4 , XeF
Cl4
is also squareCl
planar. Br
– –
(ii) Structure of IBr2 : I in IBr2 has two bond pairs and three lone pairs.
So, according to VSEPR theory, it should be linear.
I I
Here, IBr2– has 22 (7 + 2 × 7 + 1) valence electrons.
A noble gas species having 22 valence electrons is XeF2 (8 + 2 × 7 = 22).
Thus, like IBr2–, XeF2 is also linear : Cl Cl
Br
BrSquare planar Linear
Cl Cl
I I Br
Cl O O–
Cl O
Br
Square planar Linear Pyramidal
–
(iii) Structure of BrO3 : The central atom Br has seven electrons. Four of
these electrons form two double bonds or coordinate bonds with two
Br
oxygen atoms while the fifth electron forms a single bond with O– ion.
The remaining two electrons formOone – lone pair. Hence, in all there are
O –
three bond pairs and one lone O pair around Br atom in BrO3 . Therefore,
according to VSEPR theory, BrO3–should be pyramidal.
Pyramidal
–
Here, BrO3 has 26(7 + 3 × 6 + 1 = 26) valence electrons. A noble gas species
having 26 valence electrons is XeO3(8 + 3 × 6 = 26). Thus, like BrO3–, XeO3
is also pyramidal.
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39. Why do noble gases have comparatively large atomic sizes?
Soln. The atomic radii of noble gases are by far the largest in their
respective periods. This is due to the reason that noble gases have only
van der Waals radii while others have covalent radii. van der Waals radii,
by definition are larger than covalent radii.
40. List the uses of neon and argon gases.

Soln. Uses of neon :
– Neon is used in discharge tubes and fluorescent bulbs for advertisement
display purposes.
– Glow of different colours ‘neon signs’ can be produced by mixing
neon with other gases.
– Neon bulbs and used in botanical gardens and in green houses.
Uses of argon :
– Argon is used mainly to provide an inert atmosphere in high
temperature metallurgical processes such as arc welding of metals and
alloys. In the laboratory, it is used for handling substance which are air
sensitive.
– It is used in filling incandescent and fluorescent lamps where its
presence retards the sublimation of the filament and thus increases the
life of the lamp.
– It is also used in “neon signs” for obtaining lights of different
colours.
1. Why are pentahalides more covalent than trihalides?

Soln. Higher the positive oxidation state of central atom, more will be its
polarising power which, in turn, increases the covalent character of bond
formed between the central atom and the other atom.
2. Why is BiH3 the strongest reducing agent amongst all the hydrides of
group 15 element?
Soln. Because BiH3 is the least stable among the hydrides of group 15.
3. Why is N2 less reactive at room temperature?

Soln. Because of strong pπ – pπ overlap resulting into the triple bond.
N N due to which the bond dissociation energy of N2 is very high
rendering it less reactive.
4. Mention the conditions required to maximise the yield of ammonia.

Soln. N2 + 3H2 2NH3; ∆fH = –46.1 kJ mol–1
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In accordance with Le Chatelier’s principle high pressure and low
temperature would favour formation of ammonia. The optimum
conditions for the production of ammonia are a pressure of about
200 atm, a temperature of about 700K and use of a catalyst such as iron
oxide with small amount of K2O and Al2O3 as promoters.
5. How does ammonia react with a solution of Cu2+?

Soln. NH3 in the form of solution reacts with Cu2+ to form a complex with
deep blue colour.
2+
Cu2+
(aq) + 4NH3(aq) [Cu(NH3)4 ](aq)
(deep blue)
6. What is the covalence of nitrogen in N2O5?

Soln. From the structure of N2O5, it is evident that covalence of nitrogen
is four.
N 2O 5 : O O O
N N
O O
7. Bond angle in PH4+ is higher than in PH3. Why?
+
Soln. Both are sp3 hybridised. In PH4 all the four orbitals are bonded
whereas in PH3 there is a lone pair of electrons on P, which is responsible
for lone pair-bond pair repulsion in PH3 reducing the bond angle to less
than 109° 28′.
8. What happens when white phosphorus is heated with concentrated

NaOH solution in an inert atmosphere of CO2?
Soln. When white phosphorus is heated with concentrated NaOH solution
in an inert atmosphere of CO2, phosphine gas is liberated.
P4 + 3 NaOH + 3 H 2 O → PH 3 + 3 NaH 2 PO 2
Phosphine
9. What happens when PCl5 is heated?

Soln. On heating PCl5 sublimes and is converted to PCl3 on stronger
heating.
heat
PCl 5 
→ PCl 3 + Cl 2
10. Write a balanced equation for the hydrolytic reaction of PCl5 in heavy
water.
Soln. PCl5 + D2O → POCl3 + 2DCl
11. What is the basicity of H3PO4?

Soln. Three P — OH groups are present in the molecule of H3PO4.
Therefore, its basicity is three.
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12. What happens when H3PO3 is heated?
Soln. On heating phosphorous acid dispropotionates to give
orthophosphoric acid and phosphine.
4H 3PO 3 → 3H 3PO 4 + PH 3
13. List the important sources of sulphur.

Soln. Combined sulphur exists as sulphates, such as gypsum, epsom,
baryte and sulphides such as galena, zinc blende, copper pyrites, etc.
Traces of sulphur occur as hydrogen sulphide in volcanoes. Few organic
materials like eggs, proteins, garlic, onion, mustard, hair and wool contain
sulphur. 0.03 – 0.1% sulphur is present in the earth’s crust.
14. Write the order of thermal stability of the hydrides of group 16

element.
Soln. H2O > H2S > H2Se > H2Te
15. Why is H2O a liquid and H2S a gas?

Soln. Because of small size and high electronegativity of oxygen, molecules
of water are highly associated through hydrogen bonding resulting in its
liquid state.
16. Which of the following does not react with oxygen directly? Zn, Ti, Pt,
Fe.
Soln. Platinum does not react with oxygen directly.
17 Complete the following reactions:

(i) C2H4 + O2 →
(ii) 4Al + 3O2 →
Soln. (i) C2H4 + 3O2 → 2CO2 + 2H2O
(ii) 4Al + 3O2 → 2Al2O3
18. Why does O3 act as a powerful oxidising agent?

Soln. Due to the ease with which ozone liberates nascent oxygen atoms, it
acts as a powerful oxidising agent.
O3 → O2 + O
19. How is O3 estimated quantitatively?

Soln. When ozone reacts with an excess of KI solution buffered with a
borate buffer (pH = 9.2), iodine is liberated which can be titrated against
standard solution of sodium thiosulphate. This is used as a method of
estimation of ozone quantitatively.
20. What happens when sulphur dioxide is passed through an aqueous

solution of Fe(III) salt?
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Soln. When sulphur dioxide is passed through an aqueous solution of
ferric ions, ferric ions are reduced to ferrous ions.
Fe 3 + + SO 2 + 2H 2O → 2Fe 2 + + SO 24 − + 4H +
21. Comment on the nature of two S — O bonds formed in SO2 molecule.
Are the two S — O bonds in this molecule equal?
Soln. Both the S—O bonds are covalent and have equal strength due to
resonating structures.
S S
O O O O
22. How is the presence of SO2 detected?
Soln. Presence of SO2 is detected by bringing a paper dipped in acidified
potassium dichromate near the gas. If the paper turns green, it shows the
presence of SO2 gas.
K2Cr2O7 + H2SO4 + 3SO2 → K2SO4 + Cr2(SO4)3 + H2O
(Orange) (Green)
23. Mention three areas in which H2SO4 plays an important role.

Soln. (i) In manufacture of fertilisers.
(ii) In manufacture of pigments, paints and dyestuff intermediates.
(iii) In detergent industry.
24. Write the conditions to maximise the yield of H2SO4 by Contact

process.
Soln. The key step in the manufacture of sulphuric acid is oxidation of
SO2 to SO3 in presence of V2O5 catalyst.
V2O5
2SO2 + O2 2SO3 , H = – 196.6 kJ mol–1.
The reaction is exothermic and reversible. Hence, low temperature and
high pressure are the favourable conditions for maximum yield of SO3. In
practice a pressure of 2 bar and temperature of 720 K is maintained.
25. Why is Ka2 << Ka1 for H2SO4 in water?

Soln. H2SO4 is a very strong acid in water largely because of its first
– –
ionisation to H3O+ and HSO4 . The ionisation of HSO4 to H3O+ and SO42– is
very very small. That is why, Ka2 << Ka1.
26. Considering the parameters such as bond dissociation enthalpy,

electron gain enthalpy and hydration enthalpy, compare the oxidising
power of F2 and Cl2.
Soln. Fluorine is a better oxidising agent than chlorine because E°F /F – is
2
higher than E°Cl2/Cl–. It is mainly due to low bond dissociation energy,
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high hydration energy and lower electron gain enthalpy, non-availability
of d-orbitals in valence shell, that results in higher reduction potential of
F2 than chlorine.
27. Give two examples to show the anomalous behaviour of fluorine.

Soln. (i) Ionisation enthalpy, electro-negativity and electrode potential
are higher for fluorine than the expected trends of other halogen.
(ii) Fluorine does not show any positive oxidation state except in HOF.
28. Sea is the greatest source of some halogens. Comment.

Soln. Sea water contains chlorides, bromides and iodides of sodium,
potassium, magnesium and calcium but sodium chloride being the
maximum makes sea water saline. Various sea weeds contain upto 0.5%
iodine.
29. Give the reason for bleaching action of Cl2.

Soln. Chlorine bleaches by oxidation
Cl2 + H2O → HCl + HOCl → HCl + [O]
The nascent oxygen reacts with dye to make it colourless.
30. Name two poisonous gases which can be prepared from chlorine gas.
Soln. COCl2 (phosgene), CCl3NO2 (tear gas).
31. Why is ICI more reactive than I2?

Soln. In general, interhalogen compounds are more reactive than halogens
due to weaker X–X′ bonding than X–X bond. Thus, ICl is more reactive
than I2.
32. Why is helium used in diving apparatus?

Soln. A mixture of helium and oxygen does not cause pain due to very
low solubility of helium in blood as compared to nitrogen.
33. Balance the following equation:

XeF6 + H2O → XeO2F2 + HF
Soln. XeF6 + 2H2O → XeO2F2 + 4HF
34. Why has it been difficult to study the chemistry of radon?

Soln. Radon is radioactive with very short half-life which makes the study
of chemistry of radon difficult.
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Chapter 8
The d - and f -Block
Elements
Summary
The d-block consisting of Groups 3-12 occupies the large middle section of the periodic
table. In these elements the inner d orbitals are progressively filled. The f-block is placed
outside at the bottom of the periodic table and in the elements of this block, 4f and
5f orbitals are progressively filled.
Corresponding to the filling of 3d, 4d and 5d orbitals, three series of transition
elements are well recognised. All the transition elements exhibit typical metallic properties
such as –high tensile strength, ductility, malleability, thermal and electrical conductivity
and metallic character. Their melting and boiling points are high which are attributed
to the involvement of (n –1) d electrons resulting into strong interatomic bonding. In
many of these properties, the maxima occur at about the middle of each series which
indicates that one unpaired electron per d orbital is particularly a favourable configuration
for strong interatomic interaction.
Successive ionisation enthalpies do not increase as steeply as in the main group
elements with increasing atomic number. Hence, the loss of variable number of electrons
from (n –1) d orbitals is not energetically unfavourable. The involvement of (n –1) d electrons
in the behaviour of transition elements impart certain distinct characteristics to these
elements. Thus, in addition to variable oxidation states, they exhibit paramagnetic
behaviour, catalytic properties and tendency for the formation of coloured ions, interstitial
compounds and complexes.
The transition elements vary widely in their chemical behaviour. Many of them are
sufficiently electropositive to dissolve in mineral acids, although a few are ‘noble’. Of the
first series, with the exception of copper, all the metals are relatively reactive.
The transition metals react with a number of non-metals like oxygen, nitrogen,
sulphur and halogens to form binary compounds. The first series transition metal oxides
are generally formed from the reaction of metals with oxygen at high temperatures. These
oxides dissolve in acids and bases to form oxometallic salts. Potassium dichromate and
potassium permanganate are common examples. Potassium dichromate is prepared from
the chromite ore by fusion with alkali in presence of air and acidifying the extract.
Pyrolusite ore (MnO2) is used for the preparation of potassium permanganate. Both the
dichromate and the permanganate ions are strong oxidising agents.
The two series of inner transition elements, lanthanoids and actinoids constitute
the f-block of the periodic table. With the successive filling of the inner orbitals, 4f, there
is a gradual decrease in the atomic and ionic sizes of these metals along the series
(lanthanoid contraction). This has far reaching consequences in the chemistry of the
elements succeeding them. Lanthanum and all the lanthanoids are rather soft white
metals. They react easily with water to give solutions giving +3 ions. The principal
oxidation state is +3, although +4 and +2 oxidation states are also exhibited by some
occasionally. The chemistry of the actinoids is more complex in view of their ability to
exist in different oxidation states. Furthermore, many of the actinoid elements are radioactive
which make the study of these elements rather difficult.
There are many useful applications of the d- and f-block elements and their
compounds, notable among them being in varieties of steels, catalysts, complexes,
organic syntheses, etc.
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1. Write down the electronic configuration of
(i) Cr3+ (ii) Pm3+ (iii) Cu+ (iv) Ce4+

(v) Co2+ (vi) Lu2+ (vii) Mn2+ (viii) Th4+
Soln. (i) Cr3+(24) : 1s22s22p63s23p63d3
(ii) Pm3+(61) : 1s22s22p63s23p64s23d104p65s24d105p64f 4

(iii) Cu+(29) : 1s22s22p63s23p63d10
(iv) Ce4+(58) : 1s22s22p63s23p64s23d104p65s24d105p6
(v) Co2+(27) : 1s22s22p63s23p63d7
(vi) Lu2+(71) : 1s22s22p63s23p64s23d104p65s24d105p64f145d1
(vii) Mn2+(25) : 1s22s22p63s23p63d5
(viii) Th4+(90) : 1s22s22p63s23p63d104s24p64d105s25p64f145d106s26p6
2. Why are Mn2+ compounds more stable than Fe2+ towards oxidation of
their +3 state?
Soln. Mn2+ has an electronic configuration of 1s22s22p63s23p63d54s0. To go
to Mn3+ state the electron has to be taken out from stable d5 orbital which
is half filled and requires very high ionisation energy. In case of Fe2+ ion,
the third electron is taken out from 3d6 configuration which results in
more stable 3d5 configuration.
3. Explain briefly how +2 state becomes more and more stable in the first
half of the first row transition elements with increasing atomic numbers?
Soln. With increasing atomic number the effective nuclear charge increases
after losing two electrons from s-orbital. The ionic size decreases which
results in more stability. The stability is less in the beginning due to too
few electrons to lose or share.
4. To what extent do the electronic configurations decide the stability of
oxidation states in the first series of the transition elements? Illustrate your
answer with examples.
Soln. Sc3+ has stable electronic configuration (vacant d-orbital), therefore
Sc3+ is more stable than Sc+.
Fe3+ is more stable than Fe2+ due to half filled d-orbitals.
Mn2+ is more stable than Mn3+ due to half filled d-orbitals.
V5+ is more stable (due to vacant d-orbital) than V3+.
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5. What may be the stable oxidation state of the transition element with
the following d-electron configurations in the ground state of their atoms :
3d3, 3d5, 3d8 and 3d4 ?
Soln. (i) 3d3 : Stable oxidation state will be +5 due to outer electronic
configuration 3d34s2 (+2, +3, +4, +5).
(ii) 3d5 : Stable oxidation state will be +2 and +7 due to outer electronic
configuration 3d54s2 (+2, +3, +4, +6, +7).
(iii) 3d8 : Stable oxidation state will be +2 due to outer electronic
configuration 3d84s2 (+2, +3, +4).
(iv) 3d4 : Stable oxidation state will be +3 and +6 due to outer electronic
configuration 3d44s2. There is no d4 configuration in ground state, as it
becomes 3d54s1.
6. Name the oxometal anions of the first series of the transition metals in
which the metal exhibits the oxidation state equal to its group number.
Soln. Manganese shows oxidation state of +7 in its oxometal anion MnO4–
which is equivalent to its group number 7. Cr in Cr2O72– and CrO42– show
oxidation state +6 which is equivalent to its group number 6.
7. What is lanthanoid contraction? What are the consequences of

lanthanoid contraction?
Soln. The overall decrease in atomic and ionic radii from lanthanum to
lutetium is a unique feature in the chemistry of the lanthanoids. It has far
reaching consequences in the chemistry of the third transition series of
the elements.
This contraction is attributed to the imperfect shielding of one electron by
another in the same sub-shell. However, the shielding of one 4f electron by
another is less than one 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 lanthanoid series, known
as lanthanoid 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), a consequence of the lanthanoid contraction, account for
their occurrence together in nature and for the difficulty faced in their
separation.
8. What are the characteristics of the transition elements and why are
they called transition elements? Which of the d-block elements may not be
regarded as the transition elements?
Soln. General characteristics of transition elements.
(i) Electronic configuration – (n – 1) d1-10ns1-2
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(ii) Metallic character - With the exceptions of Zn, Cd and Hg, they have
typical metallic structures.
(iii) Atomic and ionic size - Ions of same charge in a given series show
progressive decrease in radius with increasing atomic number.
(iv) Oxidation state - Variable ; ranging from +2 to +7.
(v) Paramagnetism - The ions with unpaired electrons are paramagnetic.
(vi) Ionisation enthalpy - Increases due to increase in molecular charge.
(vii) Formation of coloured ions - Due to unpaired electrons.
(viii) Formation of complex compounds - Due to small size and high
charge density of metal ions.
(ix) They possess catalytic properties - Due to their ability to adopt
multiple oxidation states.
(x) Formation of interstitial compounds.
(xi) Alloy formation.
They are called transition elements due to their incompletely filled
d-orbitals in ground state or any stable oxidation state and they are
placed between s and p-block elements. Zn, Cd and Hg have fully filled
d0 configuration in their ground state hence may not be regarded as the
transition elements.
9. In what way is the electronic configuration of the transition elements

different from that of the non-transition elements?.
Soln. The electronic configuration of the transition elements is
(n – 1)d1-10ns1-2. (n–1) stands for penultimate shell and d-orbitals may
have one to ten d electrons and n denotes valence s or the outermost
shell which can have one or two electrons. Hence the basic difference
in electronic configuration of transition metals is that their penultimate
shell is incomplete and progressively filled and not the valence shell.
10. What are the different oxidation states exhibited by the lanthanoids?
Soln. In lanthanoids +3 oxidation state is predominant. However
occasionally +2 and +4 ions in the solution or in solid compounds are
also obtained. e.g. Ce4+, Tb4+, Eu2+, Yb2+, etc. +2 and +4 oxidation states
are exhibited due to extra stability of empty, half-filled or fully filled
f-subshells.
11. Explain giving reasons :

(i) Transition metals and many of their compounds show paramagnetic
behaviour.
(ii) The enthalpies of atomisation of the transition metals are high.
(iii) The transition metals generally form coloured compounds.
(iv) Transition metals and their many compounds act as good catalysts.
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Soln. (i) Paramagnetism arises from the presence of unpaired electrons,
each such electron has magnetic moment associated with its spin angular
momentum and orbital angular momentum. For the compounds of the
first series of transition metals, the contribution of the orbital angular
momentum is effectively quenched and hence is of no significance. For
these, the magnetic moment is determined by the number of unpaired
electrons and is calculated by using the ‘spin-only’ formula, i.e.,
m = n( n + 2) B.M
Where n is the number of unpaired electrons and µ is the magnetic
moment in units of Bohr magneton (BM). A single unpaired electron has
a magnetic moment of 1.73 Bohr magneton (BM).
(ii) Because of large number of unpaired electrons in their atoms they
have stronger interatomic interactions and hence stronger metallic
bonding between atoms resulting in higher enthalpies of atomisation.
(iii) Due to presence of unpaired electrons and d-d transitions, the
transition metals are generally coloured. When an electron from a lower
energy d orbital is excited to a higher energy d-orbital, the energy of
excitation corresponds to the frequency of light absorbed. This frequency
generally lies in the visible region. The colour observed corresponds to
the complementary colour of the light absorbed. The frequency of the
light absorbed is determined by the nature of the ligand.
(iv) The transition metals and their compounds are known for their
catalytic activity. This activity is ascribed to their ability to adopt multiple
oxidation states and to form complexes. Vanadium(V) oxide (in Contact
Process), finely divided iron (in Haber’s Process), and nickel (in Catalytic
Hydrogenation) are some of the examples. Catalysts at a solid surface
involve the formation of bonds between reactant molecules and atoms of
the surface of the catalyst.
12. What are interstitial compounds? Why are such compounds well known for
transitions metals ?
Soln. Interstitial compounds are those which are formed when small
atoms like H, C or N are trapped inside the crystal lattices of metals. They
are usually non stoichiometric and are neither typically ionic nor covalent,
for example, TiC, Mn4N, Fe3H, VH0.56 and TiH1.7, etc.
These do not correspond to any normal oxidation state of the metal.
Because of the nature of their composition, these compounds are
referred to as interstitial compounds.The principal physical and chemical
characteristics of these compounds are as follows :
(i) They have high melting points, higher than those of pure metals.
(ii) They are very hard, some borides approach diamond in hardness.
(iii) They retain metallic conductivity
(iv) They are chemically inert.
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13. How is the variability in oxidation states of transition metals different
from that of the non-transition metals ? Illustrate with examples.
Soln. The variability of oxidation states, a characteristic of transition
elements, arises out of incomplete filling of d-orbitals in such a way that
their oxidation states differ from each other by unity, e.g., VII, VIII, VIV, VV.
This is in contrast with the variability of oxidation sates of non transition
elements where oxidation states normally differ by a unit of two.
In the p-block the lower oxidation states are favoured by the heavier
members (due to inert pair effect), the opposite is true in the groups
of d-block. For example, in group 6, Mo(VI) and W(VI) are found to be
more stable than Cr(VI). Thus Cr(VI) in the form of dichromate in acidic
medium is a strong oxidising agent, whereas MoO3 and WO3 are not.
14. Describe the preparation of potassium dichromate from iron chromite

ore. What is the effect of increasing pH on a solution of potassium dichromate?
Soln. Potassium dichromate is prepared from chromate, which in turn is
obtained by the fusion of chromite ore (FeCr2O4) with sodium or potassium
carbonate in free access of air. The reaction with sodium carbonate occurs
as follows:
4FeCr2O4 + 8Na2CO3 + 7O2 → 8Na2CrO4 + 2Fe2O3 + 8CO2
The yellow solution of sodium chromate is filtered and acidified with
sulphuric acid to give a solution from which orange sodium dichromate,
Na2Cr2O7⋅2H2O can be crystallised.
2Na2CrO4 + 2H+ → Na2Cr2O7 + 2Na+ + H2O
Sodium dichromate is more soluble than potassium dichromate. The latter
is therefore, prepared by treating the solution of sodium dichromate with
potassium chloride.
Na2Cr2O7 + 2KCl → K2Cr2O7 + 2NaCl
Orange crystals of potassium dichromate crystallise out. The chromates
and dichromates are interconvertible in aqueous solution depending
upon pH of the solution. If pH of potassium dichromate is increased it is
converted to yellow potassium chromate.
2CrO42– + 2H+ → Cr2O72– + H2O
Cr2O72– + 2OH– → 2CrO42– + H2O
15. Describe the oxidising action of potassium dichromate and write the
ionic equations for its reaction with
(i) iodide (ii) iron(II) solution and (iii) H2S.
Soln. K2Cr2O7 is a powerful oxidising agent. In dilute sulphuric acid
medium the oxidation state of Cr changes from +6 to +3. The oxidising
action can be represented as follows:
Cr2O72– + 14H+ + 6e– → 2Cr3+ + 7H2O
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(i) Iodide : Iodide ion (I–) is oxidised to I2 by the acidfied solution of
K2Cr2O7.
Reaction :
Cr2O72– + 14H+ + 6e– → 2Cr3+ + 7H2O
6I– → 3I2 + 6e–
Cr2O72– + 14H+ + 6I– → 3I2 + 2Cr3+ + 7H2O
(ii) Iron(II) solution : Ferrous salts (Fe2+) are oxidised to ferric (Fe3+) salts
when they are treated with acidified K2Cr2O7.
Reaction :
Cr2O72– + 14H+ + 6e– → 2Cr3+ + 7H2O
6Fe2+ → 6Fe3+ + 6e–
Cr2O72– + 6Fe2+ +14H+ → 2Cr3+ + 6Fe3+ + 7H2O
(iii) H2S : H2S is oxidised to sulphur.
Cr2O72– + 3H2S + 8H+ → 2Cr3+ + 7H2O + 3S
16. Describe the preparation of potassium permanganate. How does the
acidified permanganate solution react with (i) iron (ii) ions (ii) SO2 and (iii)
oxalic acid ? Write the ionic equations for the reactions.
Soln. Potassium permanganate (KMnO4) is prepared by the fusion of a
mixture of pyrolusite (MnO2), potassium hydroxide and oxygen, first
green coloured potassium manganate is formed.
2MnO2 + 4KOH + O2 → 2K2MnO4 + 2H2O
The potassium manganate is extracted by water, which then undergoes
disproportionation in neutral or acidic solution to give potassium
permanganate.
Electrolytically :
3MnO42– + 4H+ → 2MnO4– + MnO2 + 2H2O
In acidic medium of dilute sulphuric acid, KMnO4 acts as strong oxidising
agent and it reacts as:
MnO4– + 8H+ + 5e– → Mn2+ + 4H2O
(i) Iron(II) solution : Ferrous (Fe2+) ion solution to ferric (Fe3+) ion
solution.
MnO4– + 8H+ + 5e– → Mn2+ + 4H2O
5Fe2+ → 5Fe3+ + 5e–
MnO4– + 5Fe2+ + 8H+ → Mn2+ + 5Fe3+ + 4H2O
(ii) Sulphur dioxide (SO2)
MnO4– + 8H+ + 5e– → Mn2+ + 4H2O] × 2
10H2O + 5SO2 → 5SO42– + 20H+ + 10e–
2MnO4 –+ 5SO2 + 2H2O → 5SO42– + 2Mn2+ + 4H+
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(iii) Oxalic acid
MnO4– + 8H+ + 5e– → Mn2+ + 4H2O] × 2
COO –
5  10CO2 + 10e–
COO –
2MnO4– + 16H+ + 5C2O42– → 2Mn2+ + 10CO2 + 8H2O
17. For M2+/M and M3+/M2+ systems the E° values for some metals are as
follows
Cr2+/Cr –0.9 V Cr3+/Cr2+ –0.4 V
Mn /Mn
2+
–1.2 V Mn3+/Mn2+ +1.5 V
Fe2+/Fe –0.4 V Fe3+/Fe2+ +0.8 V
Use this data to comment upon
(i) the stability of Fe3+ in acid solution as compared to that of Cr3+ or Mn3+
and
(ii) the ease with which iron can be oxidised as compared to a similar
process for either chromium or manganese metal.
Soln. (i) From the E° values for M3+/M2+ for Cr, Mn and Fe, it is very
clear that Fe3+ is more stable than Mn3+ in an acidic medium, whereas less
stable than Cr3+ because of the higher reduction potential in comparison to
Cr3+/Cr2+ and lower reduction potential than Mn3+/Mn2+.
(ii) Reduction potential for Mn2+/Mn is most negative and therefore,
it will be most easily oxidised and ease of getting oxidised will be
Mn > Cr > Fe.
18. Predict which of the following will be coloured in aqueous solution?

Ti3+, V3+, Cu+, Sc3+, Mn2+, Fe3+ and Co2+. Give reasons for each.
Soln. The configuration of the given metal ions can be given as
Ti3+ – 3d1 4s0 1 unpaired electron
V – 3d 4s
3+ 2 0
2 unpaired electrons
Cu – 3d 4s
+ 10 0
No unpaired electron
Sc – 3d 4s
3+ 0 0
No unpaired electron
Mn2+ – 3d5 4s0 5 unpaired electrons
Fe – 3d 4s
3+ 5 0
Co – 3d 4s
2+ 7 0
Out of these only Cu+ and Sc3+ are colourless. All other ions are coloured
due to presence of unpaired electrons.
19. Compare the stability of +2 oxidation state for the elements of the first
transition series.
Soln. The common oxidation state of 3d series elements is + 2 which arises
due to participation of only 4s electrons. The tendency to show highest
oxidation state increases from Sc to Mn, then decreases due to pairing of
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electrons in 3d subshell. Thus in the series Sc(II) does not exist, Ti(II) is
less stable than Ti(IV). At the other end of the series, oxidation state of Zn
is +2 only.
20. Compare the chemistry of actinoids with that of the lanthanoids with
special reference to
(i) electronic configuration (ii) atomic and ionic sizes
(iii) oxidation state and (iv) chemical reactivity.
Soln. (i) Electronic configuration : Lanthanoids have general electronic
configuration of [Xe] 4f 1-14 5d0-1 6s2 and actinoids have general electronic
configuration of [Rn]5f1-14 6d0-1 7s2. Thus, lanthanoids belong to 4 f-series
whereas actinoids belong to 5f-series.
(ii) Atomic and ionic sizes : The atomic size of lanthanoids decreases
from lanthanum to lutetium. Though the decrease is not regular, in case
of atomic radii, the decrease in the ionic size (M3+) is regular. Decrease in
size between two successive elements is higher in actinoids due to poor
screening by 5f electrons.
(iii) Oxidation state : The most common oxidation state of lanthanoids is
+3 while actinoids show more variable oxidation states than lanthanoids
ranging from +3 to +7. The tendency of showing greater range of oxidation
states can be attributed to the fact that the 5f, 6d and 7s levels are of
comparable energies and larger distance of 5f as compared to 4f from the
nucleus.
(iv) Chemical reactivity : Actinoids are far more reactive than lanthanoids.
They react with non-metals at moderate temperatures whereas lanthanoids
react at high temperatures. Most actinoids are attacked by HCl but are
slightly affected by HNO3 due to formation of a protective layer of oxide
and alkalies give no reaction.
Lanthanoids liberate hydrogen from dilute acids and burn in halogens to
form halides.
21. How would you account for the following?

(i) Of the d4 species, Cr2+ is strongly reducing while manganese(III) is
strongly oxidising.
(ii) Cobalt(II) is stable in aqueous solution but in the presence of complexing
reagents it is easily oxidised.
(iii) The d1 configuration is very unstable in ions.
Soln. (i) Both Cr2+ and Mn3+ have d4 configuration, Cr2+ is reducing
since its configuration is converted to d3 from d4. d3 has half filled t2g
configuration with higher stability. Mn3+ is oxidising since in changing
from d4 to d5 the configuration becomes half filled which has extra stability.
(ii) Co(II) gets oxidised to Co(III) in presence of complexing agent because
Co(III) is more stable than Co(II). Most of the strong field ligands cause
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pairing of electrons forming diamagnetic octahedral complexes which are
very stable due to very large crystal field stabilization energy.
(iii) d1 configuration is very unstable in ions because after losing one more
electron it will become more stable due to vacant d-orbital. All elements
with d1 configuration are either reduced or undergo disproportionation.
e.g.,
+6 +7 +4
3MnO4 2–
+ 4H → 2MnO4 + MnO2 + 2H2O
+ –
3d1 3d0
22. What is meant by ‘disproportionation’? Give two examples of
disproportionation reaction in aqueous solution.
Soln. Disproportionation reaction involves the oxidation and reduction of the
same substance. The two examples of disproportionation reaction are
(i) 2Cu+ → Cu2+ + Cu
(ii) 3MnO42– + 4H+ → 2MnO4– + MnO2 + 2H2O
23. Which metal in the first series of transition metals exhibits +1 oxidation
state most frequently and why?
Soln. Copper exhibits +1 oxidation state in the first series of transition
metals because when one electron is lost, the configuration becomes stable
due to fully filled d10 configuration.
24. Calculate the number of unpaired electrons in the following gaseous

ions : Mn3+, Cr3+, V3+ and Ti3+. Which one of these is the most stable in
aqueous solution ?
Soln. Mn3+ – 3d4 4s0 4 unpaired electrons
Cr3+ – 3d3 4s0 3 unpaired electrons
V3+ – 3d2 4s0 2 unpaired electrons
Ti – 3d 4s
3+ 1 0
Cr3+ is most stable in aqueous solution due to half filled t2g level.
25. Give examples and suggest reasons for the following features of the
transition metal chemistry :
(i) The lowest oxide of transition metal is basic, the highest is amphoteric/
acidic.
(ii) A transition metal exhibits highest oxidation state in oxides and
fluorides.
(iii) The highest oxidation state is exhibited in oxoanions of a metal.
Soln. (i) Lowest oxidation compounds of transition metals are basic due
to their ability to get oxidised to higher oxidation states. Whereas the
higher oxidation state of metal and compounds gets reduced to lower
ones and hence acts as acidic in nature.
e.g. MnO is basic whereas Mn2O7 is acidic.
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(ii) Due to high electronegativities of oxygen and fluorine, the oxides and
fluorides of transition metals exhibit highest oxidation state.
e.g. OsF6, V2O5
(iii) In oxoanions of metals, the metals from bonds with oxygen and
hence are present in their highest oxidation states. For example : Cr forms
CrO42– and Cr2O72–, both contain chromium in +6 oxidation state.
Permanganate ion, MnO4– contains Mn in its highest oxidation state
of +7.
26. Indicate the steps in the preparation of
(i) K2Cr2O7 from chromite ore
(ii) KMnO4 from pyrolusite ore.
Soln. (i) 4FeCr2O4 + 8Na2CO3 + 7O2 → 8Na2CrO4 + 2Fe2O3 + 8CO2
2Na2CrO4 + 2H+ → Na2Cr2O7 + 2Na+ + H2O
Na2Cr2O7 + 2KCl → K2Cr2O7 + 2NaCl
(ii) 2MnO2 + 4KOH + O2 ∆ → 2K2MnO4 + 2H2O
3MnO42– + 4H+ → 2MnO4– + MnO2 + 2H2O
27. What are alloys? Name an important alloy which contains some of the
lanthanoid metals. Mention its uses.
Soln. An alloy is a blend of metals prepared by mixing the components.
Alloys are homogeneous solid solutions in which the atoms of one metal
are distributed randomly among the atoms of other. Misch metal is an
alloy which contains some of the lanthanoid metals. It contains 95%
lanthanoid metals, 5% iron and traces of S, C, Ca and Al. Mischmetall is
used in Mg-based alloy to produce bullets, shell and lighter flint.
28. What are inner transition elements? Decide which of the following
atomic numbers are the atomic numbers of the inner transition element :
29, 59, 74, 95, 102, 104.
Soln. Lanthanoids and actinoids are called inner transition elements
because inner f-orbitals are progressively filled and the last electron goes
to anti-penultimate f orbital.
Elements with atomic number 59, 95, 102 are inner transition metals
because they belong to lanthanoids and actinoids.
Pr (59) 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 5p6 6s2 4f3
Am (95) 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 5p6 6s2 4f14 5d10 6p6 7s2 5f7
No (102) 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d10 4f14 5s2 5p6 5d10 5f14 6s2 6p6 7s2
29. The chemistry of the actinoid elements is not so smooth as that of
the lanthanoids. Justify this statement by giving some examples from the
oxidation state of these elements.
Soln. The actinoids are radioactive elements and the earlier members have
relatively long half-lives, the latter ones have half-life values ranging from
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a day to 3 minutes for lawrencium (Z = 103). The latter members could
be prepared only in nanogram quantities. These facts render their study
more difficult.
There is a greater range of oxidation states, which is 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 of the series frequently
exhibit higher oxidation states. For example, 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 tend to hydrolyse. Because the distribution of oxidation states among
the actinoids is so uneven and so different for the earlier and latter elements.
It is unsatisfactory to review their chemistry in terms of oxidation states.
30. Which is the last element in the series of the actinoids? Write the
electronic configuration of this element. Comment on the possible oxidation
state of this element.
Soln. Lawrencium (Lr) is the last element of actinoids. Its outer electronic
configuration is 5f14 6d1 7s2 and its possible oxidation state is +3.
31. Use Hund’s rule to derive the electronic configuration of Ce3+ ion, and
calculate its magnetic moment on the basis of ‘spin-only’ formula.
Soln. The electronic configuration of Ce3+ is 4f 1.
m= n( n + 2) = 1(1 + 2) = 3 = 1.732 BM.
32. Name the members of the lanthanoid series which exhibit +4 oxidation
state and those which exhibit +2 oxidation state. Try to correlate this type of
behaviour with the electronic configurations of these elements.
Soln. All lanthanoids show Ln3+ oxidation state. But some of them show
+2 and +4 states also in solution and solid form like Ce4+, Eu2+, Yb2+, Tb4+,
etc. The variable oxidation state is related to electronic configuration due
to extra stability of half filled, fully filled or empty orbitals. e.g., Ce4+ has
4f 0 , Eu2+ has 4f 7 Tb4+ has 4f 7 and Yb2+ has 4f14 configuration.
33. Compare the chemistry of the actinoids with that of lanthanoids with
reference to (i) electronic configuration (ii) oxidation states and (iii) chemical
reactivity.
Soln. Refer answer number 20.
34. Write the electronic configurations of the elements with the atomic
numbers 61, 91, 101, and 109.
Soln. Z = 61 : 4f 5 6s2 Z = 91 : 5f 2 6d1 7s2
Z = 101 : 5f 7s
13 2
Z = 109 : 6d 7 7s2
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35. Compare the general characteristics of the first series of transition
metals with those of the second and third series metals in the respective
vertical columns. Give special emphasis on the following points
(i) electronic configurations (ii) oxidation states
(iii) ionisation enthalpies and (iv) atomic sizes.
Soln. (i) Electronic configurations : In lst transition series, 3d-orbitals
are progressively filled whereas in 2nd transition series, 4d-orbitals are
progressively filled and in 3rd transition series, 5d-orbitals are progressively
filled.
(ii) Oxidations states : Elements show variable oxidation states in both
the series. The highest oxidation state is equal to total number of electrons
in ‘s’ as well as ‘d’ orbitals. The number of oxidation states shown are less
in 5d transition series than 4d series. In 3d series +2 and +3 oxidation states
are common and they form stable complexes in these oxidation states. In
other series OsO4 and PtF6 are formed which are quite stable in higher
oxidation state.
(iii) Ionisation enthalpies : The ionisation enthalpies in each series
generally increases gradually from left to right. The ionisation enthalpy
of 5d series do not differ appreciably due to lanthanoid contraction.
(iv) Atomic sizes : The atomic sizes of 4d and 5d-series do not differ
appreciably due to lanthanoid contraction. The atomic radii of second
and third series are larger than 3d series.
36. Write down the number of 3d electrons in each of the following ions : Ti2+,
V2+, Cr3+, Mn2+, Fe2+, Fe3+, Co2+, Ni2+ and Cu2+. Indicate how would you expect
the five 3d orbitals to be occupied for these hydrated ions (octahedral).
Soln. Ti2+ – 3d2 V2+ – 3d3 Cr3+ – 3d3
Mn2+ – 3d5 Fe2+ – 3d6 Fe3+ – 3d5
Co2+ – 3d7 Ni2+ – 3d8 Cu2+ – 3d9
Filling of orbitals in octahedral hydrated ions
Ti 2+ : t 22 g ; V 2+ : t 23 g



Cr 3+ : t 23 g ; Mn 2+ : t 23 g e g2





Fe 2+ : t 24 g e g2 ; Fe 3+ : t 23 g e g2






Co 2+ : t 25 g e g2 ; Ni 2+ : t 26 g e g2







Cu 2+ : t 26 g e g3




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37. Comment on the statement that elements of the first transition
series possess many properties different from those of heavier transition
elements.
Soln. (i) In first transition series lower oxidation state is more stable
whereas in heavier transition elements higher oxidation states are more
stable.
(ii) The ionisation enthalpy of 5d transition series is higher than 3d and 4d
transition series.
(iii) M–M bonding is most common in heavier transition metals but less in
first series.
(iv) The elements of first transition series do not form complexes with
higher coordination number of 7 and 8.
(v) The elements of first series can form high spin or low spin complexes
depending upon strength of ligands but elements of other series form low
spin complexes irrespective of strength of ligands.
38. What can be inferred from the magnetic moment values of the following
complex species?
Example Magnetic Moment (BM)
K4[Mn(CN)6] 2.2
[Fe(H2O)6]2+ 5.3
K2[MnCl4] 5.9
Soln. Magnetic Moment ( m ) = n( n + 2) BM
When n = 1, m = 1(1 + 2) = 3 = 1.73 BM ≈ 2
When n = 2, m = 2( 2 + 2) = 8 = 2.83 BM ≈ 3
When n = 3, m = 3( 3 + 2) = 15 = 3.87 BM ≈ 4
When n = 4, m = 4( 4 + 2) = 24 = 4.90 BM ≈ 5
When n = 5, m = 5( 5 + 2) = 35 = 5.92 BM ≈ 6
K4[Mn(CN)6] : Oxidation state of Mn is +2, Mn2+ has an electronic
configuration of [Ar]3d5.
As m = 2.2 BM which corresponds to one unpaired electron. The orbital
diagram for Mn2+ is
3d





[Fe(H2O)6]2+ : m = 5.3 BM corresponds to 4 unpaired electrons. The

configuration of Fe2+ ions is [Ar]3d6 and orbital diagram is
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3d
K2[MnCl4], : m = 5.9 BM, Mn2+ ion has 5 unpaired electrons. Its orbital
diagram is
3d

1. Silver atom has completely filled d-orbitals (4d10) in its ground state.
How can you say that it is a transition element?
Soln. Silver (Z = 47) can exhibit +2 oxidation state wherein it will have
incompletely filled d-orbitals (4d), hence it is a transition element.
2. In the series Sc (Z = 21) to Zn (Z = 30), the enthalpy of atomisation of zinc

is the lowest, i.e., 126 kJ mol–1. Why?
Soln. In the formation of metallic bonds, no electrons from 3d-
orbitals are involved in case of zinc, while in all other metals of the
3d-series, electrons from the d-orbitals are always involved in the formation
of metallic bonds.
3. Which of the 3d-series of the transition metals exhibits the largest

number of oxidation states and why?
Soln. Manganese (Z = 25), as its atom has the maximum number of
unpaired electrons.
4. The E°(M2+/M) value for copper is positive (+0.34 V). What is possibly the
reason for this? (Hint: consider its high DaH° and low DhydH°)
Soln. The high energy to transform Cu(s) to Cu2+(aq) is not found balanced
by its hydration energy. Hydration energy and lattice energy of Cu2+ is
more than Cu.
5. How would you account for the irregular variation of ionisation

enthalpies (first and second) in the first series of the transition elements?
Soln. Irregular variation of ionisation enthalpies is mainly attributed to
varying degree of stability of different 3d-configurations (e.g., d0, d5, d10 are
exceptionally stable).
6. Why is the highest oxidation state of a metal exhibited in its oxide or

fluoride only?
Soln. Because of small size and high electronegativity oxygen or fluorine
can oxidise the metal to its highest oxidation state.
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7. Which is a stronger reducing agent Cr2+ or Fe2+ and why?
Soln. Cr2+ is stronger reducing agent than Fe2+
Reason: d4 → d3 occurs in case of Cr2+ to Cr3+.
But d6 → d5 occurs in case of Fe2+ to Fe3+.
In a medium (like water) d3 is more stable as compared to d5.
8. Calculate the ‘spin only’ magnetic moment of M2+(aq) ion (Z = 27).

Soln. Z = 27
Electronic configuration of M2+ is 3d7
No. of unpaired electrons = 3
m= n( n + 2) = 3( 3 + 2) = 15 = 3.87 BM.
9. Explain why Cu+ ion is not stable in aqueous solutions?
Soln. Cu+ in aqueous solution undergoes disproportionation, i.e.,
2Cu+(aq) → Cu2+(aq) + Cu(s)
The stability of Cu2+(aq) rather than Cu+(aq) is due to the much more negative
DhydH° of Cu2+(aq) than Cu+, which more than compensates for the second
ionisation enthalpy of Cu.
10. Actinoid contraction is greater from element to element than lanthanoid

contraction. Why?
Soln. The 5f electrons are more effectively shielded from nuclear charge.
In other words the 5f electrons themselves provide poor shielding from
element to element in the seriest.
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Chapter 9
Coordination Compounds
Summary
The chemistry of coordination compounds is an important and challenging
area of modern inorganic chemistry. During the last fifty years, advances in this
area, have provided development of new concepts and models of bonding and
molecular structure, novel breakthroughs in chemical industry and vital insights
into the functioning of critical components of biological systems.
The first systematic attempt at explaining the formation, reactions, structure
and bonding of a coordination compound was made by A. Werner. His theory
postulated the use of two types of linkages (primary and secondary) by a metal
atom/ion in a coordination compound. In the modern language of chemistry
these linkages are recognised as the ionisable (ionic) and non-ionisable (covalent)
bonds, respectively. Using the property of isomerism, Werner predicted the
geometrical shapes of a large number of coordination entities.
The Valence Bond Theory (VBT) explains with reasonable success, the
formation, magnetic behaviour and geometrical shapes of coordination compounds.
It, however, fails to provide a quantitative interpretation of magnetic behaviour
and has nothing to say about the optical properties of these compounds.
The Crystal Field Theory (CFT) to coordination compounds is based on the
effect of different crystal fields (provided by the ligands taken as point charges),
on the degeneracy of d orbital energies of the central metal atom/ion. The
splitting of the d orbitals provides different electronic arrangements in strong
and weak crystal fields. The treatment provides for quantitative estimations of
orbital separation energies, magnetic moments and spectral and stability
parameters. However, the assumption that ligands consititute point charges
creates many theoretical difficulties.
The metal–carbon bond in metal carbonyls possesses both σ and π character.
The ligand to metal is σ bond and metal to ligand is π bond. This unique synergic
bonding provides stability to metal carbonyls.
The stability of coordination compounds is measured in terms of stepwise
stability (or formation) constant (K) or overall stability constant (β β ). The
stabilisation of coordination compound due to chelation is called the chelate effect.
The stability of coordination compounds is related to Gibbs energy, enthalpy and
entropy terms.
Coordination compounds are of great importance. These compounds provide
critical insights into the functioning and structures of vital components of
biological systems. Coordination compounds also find extensive applications in
metallurgical processes, analytical and medicinal chemistry.
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1. Explain the bonding in coordination compounds in terms of Werner’s

postulates.
Soln. The main postulates are :
(i) In coordination compounds metals show two types of linkages

(valencies)-primary and secondary.
(ii) The primary valencies are normally ionisable and are satisfied by
negative ions.
(iii) The secondary valencies are non ionisable. These are satisfied by
neutral molecules or negative ions. The secondary valency is equal to the
coordination number and is fixed for a metal.
(iv) The ions/groups bound by the secondary linkages to the metal
have characteristic spatial arrangements corresponding to different
coordination numbers.
2. FeSO4 solution mixed with (NH4)2SO4 solution in 1:1 molar ratio gives
the test of Fe2+ ion but CuSO4 solution mixed with aqueous ammonia in
1:4 molar ratio does not give the test of Cu2+ ion. Explain why?
Soln. FeSO4 solution when mixed with (NH4)2SO4 solution in 1:1 molar
ratio forms a double salt FeSO4⋅(NH4)2SO4⋅6H2O which when dissolved
in water dissociates into simple ions to give tests for its constituent ions.
When CuSO4 is mixed with aqueous ammonia a complex ion [Cu(NH3)4]2+
is formed which does not give Cu2+ in the solution.
3. Explain with two examples each of the following: coordination entity,

ligand, coordination number, coordination polyhedron, homoleptic and
heteroleptic.
Soln. (i) Coordination entity : A coordination entity constitutes a central

metal atom or ion bonded to a fixed number of ions or molecules. For
example, [CoCl3(NH3)3] is a coordination entity in which the cobalt ion is
surrounded by three ammonia molecules and three chloride ions. Other
examples are [Ni(CO)4], [PtCl2(NH3)2], [Fe(CN)6]4–, [Co(NH3)6]3+.
(ii) Ligand : The ions or molecules bound to the central atom/ion in the
coordination entity are called ligands. These may be simple ions such
as Cl–, small molecules such as H2O or NH3, larger molecules such as
H2NCH2CH2NH2 or N(CH2CH2NH2)3 or even macromolecules, such as
proteins.
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(iii) Coordination number : The coordination number [C.N.] of a metal
ion in a complex can be defined as the number of ligand or donor atoms
to which the metal is directly bonded. For example, in the complex ions,
[PtCl6]2– and [Ni(NH3)4]2+, the coordination number of Pt and Ni are 6 and
4 respectively. Similarly, in the complex ions, [Fe(C2O4)3]3– and [Co(en)3]3+,
the coordination number of both, Fe and Co, is 6 because C2O42– and en
(ethane-1,2-diamine) are bidentate ligands.
(iv) Coordination polyhedron : The spatial arrangement of the
ligand atoms which are directly attached to the central atom/ion
defines a coordination polyhedron about the central atom. The most
common coordination polyhedra are octahedral, square planar and
tetrahedral. For example, [Co(NH3)6]3+ is octahedral, [Ni(CO)4] is
tetrahedral and [PtCl4]2– is square planar.
(v) Homoleptic and heteroleptic complexe : Complexes in which a metal
is bound to only one kind of donor groups, e.g., [Co(NH3)6]3+, are known
as homoleptic. Complexes in which a metal is bound to more than one
kind of donor groups, e.g., [Co(NH3)4Cl2]+, are known as heteroleptic.
4. What is meant by unidentate, bidentate and ambidentate ligands? Give

two examples for each.
Soln. Unidentate ligands are those which bind to the metal ion through a
single donor atom. e.g., Cl–, H2O.
Bidentate ligands are those which bind to the metal ion through two donor
atoms. e.g., ethane-1,2-diamine (H2NCH2CH2NH2), oxalate (C2O42–) ion.
Ambidentate ligands are those which can bind to metal ion through two
different donor atoms. e.g., NO2– and SCN– ion.
5. Specify the oxidation numbers of the metals in the following

coordination entities :
(i) [Co(H2O)(CN)(en)2]2+ (ii) [CoBr2(en)2]+
(iii) [PtCl4]2–
(iv) K3[Fe(CN)6]
(v) [Cr(NH3)3Cl3]
Soln. (i) [Co(H2O)(CN)(en)2]2+ : +3; (ii) [CoBr2(en)2]+ : +3
(iii) [PtCl4]2– : +2; (iv) K3[Fe(CN)6] : +3; (v) [Cr(NH3)3Cl3] : +3
6. Using IUPAC norms write the formulas for the following :

(i) Tetrahydroxozincate(II)
(ii) Potassium tetrachloridopalladate(II)
(iii) Diamminedichloridoplatinum(II)
(iv) Potassium tetracyanonickelate(II)
(v) Pentaamminenitritio-O-cobalt(III)
(vi) Hexaamminecobalt(III) sulphate
(vii) Potassium tri(oxalato)chromate(III)
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(viii) Hexaammineplatinum (IV)
(ix) Tetrabromidocuprate(II)
(x) Pentaamminenitrito-N-cobalt(III)
Soln. (i) Tetrahydroxozincate(II) – [Zn(OH)4]2–
(ii) Potassium tetrachloridopalladate(II) – K2[PdCl4]
(iii) Diamminedichloridoplatinum(II) – [Pt(NH3)2Cl2]
(iv) Potassium tetracyanonickelate(II) – K2[Ni(CN)4]
(v) Pentaamminenitrito-O-cobalt(III) – [Co(NH3)5ONO]2+
(vi) Hexaamminecobalt(III) sulphate – [Co(NH3)6]2(SO4)3
(vii) Potassium tri(oxalato)chromate(III) – K3[Cr(C2O4)3]
(viii) Hexaammineplatinum(IV) – [Pt(NH3)6]4+
(ix) Tetrabromidocuprate(II) – [Cu(Br)4]2+
(x) Pentaamminenitrito-N-cobalt(III) – [Co(NH3)5NO2]2+
7. Using IUPAC norms write the systematic names of the following:
(i) [Co(NH3)6]Cl3 (ii) [Pt(NH3)2Cl(NH2CH3)]Cl
(iii) [Ti(H2O)6] 3+
(iv) [Co(NH3)4Cl(NO2)]Cl
(v) [Mn(H2O)6]2+ (vi) [NiCl4]2–
(vii) [Ni(NH3)6]Cl2 (viii) [Co(en)3]3+
(ix) [Ni(CO)4]
Soln. (i) Hexaamminecobalt (III) chloride
(ii) Diamminechloridomethylamine platinum (II) chloride
(iii) Hexaaquatitanium (III) ion
(iv) Tetraamminechloridonitrito-N-cobalt (III)chloride
(v) Hexaaquamanganese (II) ion
(vi) Tetrachloridonickelate (II) ion
(vii) Hexaammine nickel(II) chloride
(viii) Tris (ethane-1, 2-diamine) cobalt(III) ion
(ix) Tetracarbonylnickel (0)
8. List various types of isomerism possible for coordination compounds,
giving an example of each.
Soln. (i) Geometrical isomerism : This type of isomerism arises in
heteroleptic complexes due to different possible geometric arrangements
of the ligands. Important examples of this behaviour are found with
coordination numbers 4 and 6. In a square planar complex of formula [MX2L2]
(X and L are unidentate), the two identical ligands may be arranged adjacent
to each other in a cis-isomer, or opposite to each other in a trans isomer.
Another type of geometrical isomerism occurs in octahedral coordination
entities of the type [Ma3b3] like [Co(NH3)3(NO2)3]. If three donor atoms of
the same ligands occupy adjacent positions at the corners of an octahedral
face, we have the facial (fac) isomer. When the positions are around the
meridian of the octahedron, we get the meridional (mer) isomer.
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Cl NH3 Cl NH3
Pt Pt
Cl NH3 NH3 Cl
cis trans
Geometrical isomers
cis and trans of Pt[NH3)2Cl2]
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]
(ii) Optical isomerism : Optical isomerism is common in octahedral
complexes involving bidentate ligands. In a coordination entity of the
[PtCl2(en)2]2+, only the cis-isomer shows optical activity.

(iii) Linkage isomerism : Linkage isomerism arises in a coordination
compound containing ambidentate ligand. A simple example is provided
by complexes containing the thiocyanate ligand, NCS–, which may bind
through the nitrogen to give M-NCS or through sulphur to give M-SCN.
This behaviour was seen in the complex [Co(NH3)5(NO2)]Cl2, which is
obtained as the red form, in which the nitrite ligand is bound through
oxygen (–ONO), and as the yellow form, in which the nitrite ligand is
bound through nitrogen (–NO2).
(iv) Coordination isomerism : This type of isomerism arises from the
interchange of ligands between cationic and anionic entities of different
metal ions present in a complex. An example is provided by [Co(NH3)6]
[Cr(CN)6], in which the NH3 ligands are bound to Co3+ and the CN–
ligands to Cr3+. In its coordination isomer [Cr(NH3)6][Co(CN)6], the NH3
ligands are bound to Cr3+ and the CN– ligands to Co3+.
(v) Ionisation isomerism : This form of isomerism arises when the counter
ion in a complex salt is itself a potential ligand and can displace a ligand
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which can then become the counter ion. An example is provided by the
ionisation isomers [Co(NH3)5SO4]Br and [Co(NH3)5Br]SO4.
(vi) Solvate isomerism : This form of isomerism is known as ‘hydrate
isomerism’ in case where water is involved as a solvent. This is similar
to ionisation isomerism. Solvate isomers differ by whether or not a
solvent molecule is directly bonded to the metal ion or merely
present as free solvent molecules in the crystal lattice. An example is
provided by the aqua complex [Cr(H2O)6]Cl3 (violet) and its solvate
isomer [Cr(H2O)5Cl]Cl2⋅H2O (grey-green).
9. How many geometrical isomers are possible in the following

coordination entities?
(i) [Cr(C2O4)3]3– (ii) [Co(NH3)3Cl3]
Soln. (i) Zero
(ii) Two - Facial and meridional.
NH3 NH3
Cl NH3 NH3 Cl
Co Co
Cl NH3 Cl Cl
Cl NH3
fac- mer-
10. Draw the structures of optical isomers of :

(i) [Cr(C2O4)3]3– (ii) [PtCl2(en)2]2+ (iii) [Cr(NH3)2Cl2(en)]+
Soln. (i) ox 3– ox 3–
Cr ox ox Cr
ox ox
(ii) en 2+
en 2+
Cl Cl
Pt Pt
Cl Cl
en en
(iii) en + en +
H3N NH3
Cr Cr
H3N Cl Cl NH3
Cl Cl
11. Draw all the isomers (geometrical and optical) of :

(i) [CoCl2(en)2]+ (ii) [Co(NH3)Cl(en)2]2+
(iii) [Co(NH3)2Cl2(en)]+
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Soln. (i)
(ii)
+ + +
Cl Cl en
Cl NH3 Cl
(iii) en Co en Co Co
NH3 NH3 NH3 Cl
NH3 Cl NH3
All isomers are optically
active isomers
12. Write all the geometrical isomers of [Pt(NH3)(Br)(Cl)(py)] and how many
of these will exhibit optical isomerism?
NH3 Br H3N Py H3N Cl
Soln. Pt Pt Pt
Py Cl Cl Br Br Py
All will show optical
isomerism
13. Aqueous copper sulphate solution (blue in colour) gives :
(i) a green precipitate with aqueous potassium fluoride and
(ii) a bright green solution with aqueous potassium chloride. Explain these
experimental results.
Soln. (i) Aqueous CuSO4 solution contains [Cu(H2O)4]2+ ions which
impart blue colour. When KF is added, H2O being weak field ligand can
be replaced by F– forming [CuF4]2– ions which impart green colour.
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[Cu(H 2 O)4 ]2 + + 4 F− → [Cu F4 ]2 − + 4 H 2 O

[From KF( aq ) ] (Green ppt.)
(ii) When KCl is added, Cl– ligand replaces H2O forming [CuCl4]2– ions
which has bright green colour.
[Cu(H2O)4 ]2 + + 4 Cl − → [Cu Cl 4 ]2 − + 4 H 2 O
[From K Cl( aq ) ] (Bright green solution)
14. What is the coordination entity formed when excess of aqueous KCN
is added to an aqueous solution of copper sulphate? Why is it that no
precipitate of copper sulphide is obtained when H2S(g) is passed through
this solution?
Soln. [Cu(H 2 O)4 ]2 + + 4 CN − → [Cu(CN)4 ]2 − + 4 H 2 O
highly stable
CN– is a strong field ligand, therefore, [Cu(CN)4]2– is highly stable and
has large value of stability constant. On passing H2S, CuS is not formed
because this coordination entity does not give Cu2+ ion.
15. Discuss the nature of bonding in the following coordination entities on
the basis of valence bond theory :
(i) [Fe(CN)6]4– (ii) [FeF6]3–
(iii) [Co(C2O4)3]
3–
(iv) [CoF6]3–
Soln. (i) [Fe(CN)6]4– : Fe(26) has electronic configuration [Ar] 4s23d6.
Fe2+ has electronic configuration [Ar] 4s23d6
CN– ion causes pairing of electrons because it is a strong field ligand.
3d 4s 4p
Fe2+
[Fe(CN)6]4–
d2sp3 hybridisation
It has octahedral shape and is diamagnetic in nature due to absence of
electrons.
(ii) [FeF6]3– : Fe(26) has electronic configuration [Ar] 4s23d6. Fe3+ : [Ar] 4s03d5
F being a weak field ligand, does not cause pairing of electrons.
(iii) [Co(C2O4)3]3– : Co(27) has electronic configuration [Ar] 4s23d7.

Co3+ : [Ar]4s03d6
C2O42– being a strong field ligand causes pairing of electrons.
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(iv) [CoF6]3– : Co(27) has electronic configuration [Ar] 4s23d7.
Co3+ : [Ar]4s03d6.
F– being a weak field ligand, cannot cause pairing of electrons.
16. Draw figure to show the splitting of d-orbitals in an octahedral crystal

field.
Soln. Let us assume that the six ligands are positioned symmetrically
along the Cartesian axes, with metal atom at the origin.
dx2 – y2 , dz2
eg
Energy o
[ t2g
Average energy of d ,d ,d
xy yz xz
the d-orbitals in a
d-orbitals spherical crystal Splitting of d-orbitals in an
in free ion field octahedral crystal field
d-orbital splitting in an octahedral crystal field
As the ligands approach, first there is an increase in energy of d-orbitals

relative to that of the free ion just as would be the case in a spherical
field.
The orbitals lying along the axes (dz2 and dx2 – y2) get repelled more strongly
than dxy, dyz and dzx orbitals which have lobes directed between the axes.
The dz2 and dx2 – y2 orbitals get raised in energy and dxy dyz, dxz orbitals are
lowered in energy relative to the average energy in the spherical crystal
field. Thus, the degenerate set of d-orbitals get split into two sets : the
lower energy orbitals set, t2g and the higher energy orbitals set, eg. The
energy is separated by Do.
17. What is spectrochemical series? Explain the difference between a weak

field ligand and a strong field ligand.
Soln. The crystal field splitting, Do, depends upon the field produced by
the ligand and charge on the metal ion. Some ligands are able to produce
strong fields in which, the splitting will be large whereas others produce
weak fields and consequently result in small splitting of d-orbitals. In
general, ligands can be arranged in a series in the order of increasing field
strength as given below :
I– < Br– < SCN– < Cl– < S2– < F– < OH– < C2O42– < H2O < NCS– < edta4– < NH3
< en < CN– < CO
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Such a series is termed as spectrochemical series.
If Do < P, the fourth electron enters one of the eg orbitals giving the
configuration t23 g e1g. Ligands for which Do < P are known as weak field
ligands and form high spin complexes. If Do > P, it becomes more
energetically favourable for the fourth electron to occupy a t2g orbital
with configuration t2g4eg0. Ligands which produce this effect are known as
strong field ligands and form low spin complexes.
18. What is crystal field splitting energy? How does the magnitude of Do
decide the actual configuration of d-orbitals in a coordination entity?
Soln. The difference in energies of two sets of d-orbitals t2g and eg is called
crystal field splitting energy (Do).
(i) If Do < P, the configuration will be t32ge1g and it is there in case of weak
field ligands and high spin complex will be formed.
(ii) If Do > P, the configuration will be t42ge0g and it is in case of a strong field
ligands and low spin complex will be formed.
19. [Cr(NH3)6]3+ is paramagnetic while [Ni(CN)4]2– is diamagnetic. Explain

why?
Soln. [Cr(NH3)6]3+ : Cr(24) : [Ar] 4s13d5, Cr3+(21) : [Ar] 4s03d3
It is paramagnetic due to presence of unpaired electrons

[Ni(CN)4]2– : Ni(28) : 4s23d8 , Ni2+ : 4s03d8
3d 4s 4p
[Ni(CN)4]2–
dsp2 hybridisation
It has square planar shape and is diamagnetic due to absence of unpaired

electrons.
20. A solution of [Ni(H2O)6]2+ is green but a solution of [Ni(CN)4]2– is

colourless. Explain.
Soln. [Ni(H2O)6]2+ has unpaired electrons due to weak H2O ligands which
absorb light from visible region and radiate complementary colour i.e.,
green whereas [Ni(CN)4]2– does not have any unpaired electron due to
strong CN– ligand, therefore, does not absorb light from visible region
hence, it is colourless.
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21. [Fe(CN)6]4– and [Fe(H2O)6]2+ are of different colours in dilute solutions.
Why?
Soln. In [Fe(CN)6]4–, CN– is a strong field ligand hence, pairing of electrons
takes place.
In [Fe(H2O)6]4–, H2O is a weak ligand hence, pairing does not take place
Both ligands show different magnitude of crystal field splitting energy

due to different nature hence, absorb different wavelengths and show
different colours.
22. Discuss the nature of bonding in metal carbonyls.
Soln. *
 

M C O

Synergic bonding
The metal-carbon bond in metal carbonyls possess both s and p character.
The M-C s bond is formed by the donation of lone pair of electrons on
the carbonyl carbon into a vacant orbital of the metal. The M-C p bond
is formed by the donation of a pair of electrons from a filled d-orbital
of metal into the vacant antibonding p* orbital of carbon monoxide. The
metal to ligand bonding creates a synergic effect which strengthens the
bond between CO and the metal.
23. Give the oxidation state, d-orbital occupation and coordination number
of the central metal ion in the following complexes :
(i) K3[Co(C2O4)3] (ii) cis-[Cr(en)2Cl2]Cl
(iii) (NH4)2[CoF4] (iv) [Mn(H2O)6]SO4
Soln. (i) K3[Co(C2O4)3] - O.S. = + 3, C.N. = 6, 3d6 configuration = t62geg0
(ii) cis-[Cr(en)2Cl2]Cl - O.S. = + 3, C.N. = 6, d3 configuration = t32g
(iii) (NH4)2[CoF4] - O.S. = + 2, C.N. = 4, d7 configuration = t52geg2
(iv) [Mn(H2O)6]SO4 - O.S. = + 2, C.N. = 6, d5 configuration = t23geg2 .
24. Write down the IUPAC name for each of the following complexes and
indicate the oxidation state, electronic configuration and coordination
number. Also give stereochemistry and magnetic moment of the
complex :
(i) K[Cr(H2O)2(C2O4)2].3H2O (ii) [Co(NH3)5Cl]Cl2
(iii) CrCl3(py)3 (iv) Cs[FeCl4]
(v) K4[Mn(CN)6]
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Soln. (i) K[Cr(H2O)2(C2O4)2].3H2O : Potassiumdiaquadioxalatochromate
(III) hydrate
Oxidation state = +3; C.N. = 6; configuration = t32g

m= n( n + 2) = 3×5 = 15 = 3.87 B.M.
(ii) [Co(NH3)5Cl]Cl2 : Pentaamminechloridocobalt(III) chloride
Co(27) : 4s23d7; Co3+ : 4s03d6

The oxidation state of Co = +3
C.N. = 6; Configuration = t62g; m = 0 B.M.
(iii) [CrCl3(py)3] : Trichloridotripyridinechromium (III)
Coordination No. of Cr = 6; Oxidation state = +3; Configuration = t32g;
Cr(24) : 4s1 3d5; Cr3+ : 4s03d3

m = n( n + 2) = 15 = 3.87 B.M.
(iv) Cs[FeCl4] : Caesiumtetrachloridoferrate III)
Oxidation state = +3; Coordination No. = 4; Configuration = t2g
3
eg2;
Fe (26) : 4s 3d ; Fe : 4s 3d
2 6 3+ 0 5

It is paramagnetic due to presence of 5 unpaired electrons.
m= n( n + 2) = 5×7 = 35 = 5.92 B.M.
(v) K4[Mn(CN)6] : Potassium hexacyanomanganese(II)
Oxidation state = +2; Coordination no. = 6; Configuration = t2g5 ; Mn(25)
: [Ar] 4s23d5; Mn2+ : [Ar] 4s03d5
m= n( n + 2) = 1 × 3 = 1.732 B.M.
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25. What is meant by stability of the coordination compound in solution?
State the factors which govern stability of complexes.
Soln. The stability of a complex in solution refers to the degree of association
between the two species involved in the state of equilibrium. The magnitude
of the (stability or formation) equilibrium constant for the association,
quantitatively expresses the stability. Thus, if we have a reaction of the
type : M + 4L ML4
then, larger the stability constant, the higher is the proportion of ML4
that exists in solution. Free metal ions rarely exist in the solution so that
M will usually be surrounded by solvent molecules which will compete
with the ligand molecules, L and be successively replaced by them. For
simplicity, we generally ignore these solvent molecules and write four
stability constants as follows :
M + L ML K1 = [ML]/[M][L]
ML + L ML2 K2 = [ML2]/[ML][L]
ML2 + L ML3 K3 = [ML3]/[ML2][L]
ML3 + L ML4 K4 = [ML4]/[ML3][L]
Where K1, K2, etc., are referred to as stepwise stability constants.
Alternatively, we can write the overall stability constant as :
M + 4L ML4 4 = [ML4]/[M][L]4
The stepwise and overall stability constant are therefore related as
follows:
b4 = K1 × K2 × K3 × K4 or more generally,
bn = K1 × K2 × K3 × K4 .................. Kn
Factors affecting stability of complexes :
(i) Smaller the size of cation, greater will be the stability of complex e.g.,
Fe3+ forms more stable complex than Fe2+.
(ii) Greater the charge on central metal ion, more stable will be the
complex e.g., Pt4+ forms more stable complex than Pt2+.
(iii) Stronger the ligand, more stable will be the complex formed e.g., CN–
forms more stable complex then NH3.
26. What is meant by the chelate effect? Give an example.
Soln. When a di-or polydentate ligand uses its two or more donor atoms
to bind a single metal ion, it is said to be a chelate ligand. The number of
such ligating groups is called the denticity of the ligand. Such complexes,
called chelate complexes tend to be more stable than similar complexes
containing unidentate ligands. Example : EDTA, DMG, etc.
27. Discuss briefly giving an example in each case the role of coordination
compound in :
(i) biological systems (ii) medicinal chemistry
(iii) analytical chemistry (iv) extraction/metallurgy of metals.
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Soln. (i) Coordination compounds are of great importance in biological
systems. The pigment responsible for photosynthesis, chlorophyll, is a
coordination compound of magnesium. Haemoglobin, the red pigment
of blood which acts as oxygen carrier is a coordination compound of
iron. Vitamin B12, cyanocobalamine, the anti- pernicious anaemia factor,
is a coordination compound of cobalt. Among the other compounds of
biological importance with coordinated metal ions are the enzymes
like, carboxypeptidase A and carbonic anhydrase (catalysts of biological
systems).
(ii) There is growing Interest in the use of chelate therapy in medicinal
chemistry. An example is the treatment of problems caused by the presence
of metals in toxic proportions in plant/animal systems. Thus, excess of
copper and iron are removed by the chelating ligands D-penicillamine
and desferrioxime B via the formation of coordination compounds. EDTA
is used in the treatment of lead poisoning. Some coordination compounds
of platinum effectively inhibit the growth of tumours. Examples are: cis-
platin and related compounds.
(iii) Coordination compounds find use in many qualitative and quantitative
chemical analysis. The familiar colour reactions given by metal ions with
a number of ligands (especially chelating ligands), as a result of formation
of coordination entities, form the basis for their detection and estimation
by classical and instrumental methods of analysis. Examples of such
reagents include EDTA, DMG (dimethylglyoxime), a-nitroso-b-naphthol,
cupron, etc.
(iv) Some important extraction processes of metals, like those of silver and
gold, make use of complex formation. Gold, for example, combines with
cyanide in the presence of oxygen and water to form the coordination
entity [Au(CN)2]– in aqueous solution. Gold can be separated in metallic
form from this solution by the addition of zinc.
28. How many ions are produced from the complex Co(NH3)6Cl2 in
solution?
(a) 6 (b) 4 (c) 3 (d) 2
Soln. (c) : 3 ions are produced by [Co(NH3)6]Cl2.
2+
 Co(NH 3 )6  Cl 2 → Co(NH 3 )6  + 2 Cl −
29. Amongst the following ions which one has the highest magnetic
moment value?
(a) [Cr(H2O)6]3+ (b) [Fe(H2O)6]2+ (c) [Zn(H2O)6]2+
Soln. (b) : Cr3+ – 3d3, Fe2+ – 3d6, Zn2+ – 3d10
Since Fe2+ has 4 unpaired electrons, it has highest magnetic moment.
30. The oxidation number of cobalt in K[Co(CO)4] is
(a) + 1 (b) +3 (c) –1 (d) –3
Soln. (c) : +1 + x + 4(0) = 0 \ x = –1.
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31. Amongst the following, the most stable complex is
(a) [Fe(H2O)6]3+ (b) [Fe(NH3)6]3+
(c) [Fe(C2O4)3]3– (d) [FeCl6]3–
Soln. (c) : Since C2O4 is a bidentate ligand, it forms the most stable
2–
complex.
32. What will be the correct order for the wavelengths of absorption in the
visible region for the following :
[Ni(NO2)6]4–, [Ni(NH3)6]2+, [Ni(H2O)6]2+?
Soln. In spectrochemical series the order of the given ligands is
H2O < NH3 < NO2–. Hence, the wave length of light will be absorbed
hc
in the opposite order since E = .
l
Hence, the order of absorption of light will be
[Ni(NO2)6]4– < [Ni(NH3)6]2+ < [Ni(H2O)6]2+.

1. Write the formulas for the following coordination compounds :
(i) Tetraamminediaquacobalt(III) chloride
(ii) Potassium tetracyanonickelate(II)
(iii) Tris(ethane-1,2-diamine) chromium(III) chloride
(iv) Amminebromidochloridonitrito-N-platinate(II)
(v) Dichloridobis(ethane-1,2-diamine) platinum(IV) nitrate
(vi) Iron(III) hexacyanoferrate(II)
Soln. (i) [Co(NH3)4(H2O)2]Cl3 (ii) K2[Ni(CN)4]
(iii) [Cr(en)3]Cl3 (iv) [Pt(NH3)BrCl(NO2)]–
(v) [PtCl2(en)2](NO3)2 (vi) Fe4[Fe(CN)6]3
2. Write the IUPAC names of the following coordination compounds :

(i) [Co(NH3)6]Cl3 (ii) [Co(NH3)5Cl]Cl2 (iii) K3[Fe(CN)6]
(iv) K3[Fe(C2O4)3] (v) K2[PdCl4] (vi) [Pt(NH3)2Cl(NH2CH3)]Cl
Soln. (i) Hexaamminecobalt(III) chloride
(ii) Pentaamminechloridocobalt(III) chloride (HO3)2
(iii) Potassium hexacyanoferrate(III)
(iv) Potassium trioxalatoferrate(III)
(v) Potassium tetrachloridopalladate(II)
(vi) Diamminechlorido (methylamine) platinum(II) chloride
3. Indicate the types of isomerism exhibited by the following complexes

and draw the structures for these isomers :
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(i) K[Cr(H2O)2(C2O4)2] (ii) [Co(en)3]Cl3
(iii) [Co(NH3)5(NO2)](NO3)2 (iv) [Pt(NH3)(H2O)Cl2]
Soln. (i) Both geometrical (cis-, trans-) and optical isomers (for cis) can
exist.
OH2 – OH2 –
OH2
K+ ox Cr K+ ox Cr ox
ox OH2
cis- trans-
OH2 – OH2 –
OH2 OH2
ox Cr Cr ox
ox ox
Mirror
(ii) Two optical isomers can exist.
3+ 3+
en en
en Co Co en
en en
Mirror
(iii) Ionization isomers :
[Co(NH3)5 (NO2)] (NO3)2, [Co(NH3)5 (NO3)](NO2)(NO3)
Linkage isomers : [Co(NH3)5(NO2)](NO3)2 , [Co(NH3)5 (ONO)](NO3)2
(iv) Geometrical (cis-, trans-) isomers can exist.
H3N Cl H3N Cl
Pt Pt
H2O Cl Cl OH2
cis- trans-
4. Give evidence that [Co(NH3)5Cl]SO4 and [Co(NH3)5SO4]Cl are ionisation

isomers.
Soln. The ionisation isomers dissolve in water to yield different ions and
thus react differently to various reagents:
[Co(NH3)5Cl]SO4 + Ba2+ → BaSO4(s)(white ppt.)
[Co(NH3)5SO4]Cl + Ba2+ → No reaction
[Co(NH3)5Cl]SO4 + Ag+ → No reaction
[Co(NH3)5SO4]Cl + Ag+ → AgCl(s) (white ppt.)
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5. Explain on the basis of valence bond theory that [Ni(CN)4]2– ion with
square planar structure is diamagnetic and the [NiCl4]2– ion with tetrahedral
geometry is paramagnetic.
Soln. [Ni(CN)4]2– : Ni(28) : 4s23d8; Ni2+(28) : 4s03d8
CN– is a strong field ligand so, it causes pairing of electrons.
It is diamagnetic due to absence of unpaired electrons.

In [NiCl4]2–, Cl– is a weak field ligand so, it does not cause pairing of
electrons
It is paramagnetic due to presence of unpaired electrons.
6. [NiCl4]2– is paramagnetic while [Ni(CO)4] is diamagnetic though both are

tetrahedral. Why?
Soln. In Ni(CO)4, Ni is in zero oxidation state whereas in NiCl42–, it is in +2
oxidation state. In the presence of CO ligand, the unpaired d-electrons of
Ni pair up but Cl– being a weak ligand is unable to pair up the unpaired
electrons.
7. [Fe(H2O)6]3+ is strongly paramagnetic whereas [Fe(CN)6]3– is weakly

paramagnetic. Explain.
Soln. In presence of CN–, (a strong ligand), the 3d electrons pair up leaving
only one unpaired electron. The hybridisation is d2sp3 forming inner
orbital complex. In the presence of H2O, (a weak ligand), 3d electrons do
not pair up. The hybridisation is sp3d2 forming an outer orbital complex
containing five unpaired electrons hence, it is strongly paramagnetic.
8. Explain [Co(NH3)6]3+ is an inner orbital complex whereas [Ni(NH3)6]2+ is

an outer orbital complex.
Soln. In the presence of NH3, the 3d electrons pair up leaving two d orbitals
empty to be involved in d2sp3 hybridisation forming inner orbital complex
in case of [Co(NH3)6]3+.
In Ni(NH3)62+, Ni is in +2 oxidation state and has d3 configuration, the
hybridisation involved is sp3d2 forming outer orbital complex.
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9. Predict the number of unpaired electrons in the square planer [Pt(CN)4]2–
ion.
Soln. For square planer shape, the hybridisation is dsp2. Hence, the
unpaired electrons in 5d orbital pair up to make one d-orbital empty for
dsp2 hybridisation. Thus there is no unpaired electron.
[Pt(CN)4]2– : Pt(78) : 6s15d9 , Pt2+ : 6s05d8
10. The hexaaquomanganese(II) ion contains five unpaired electrons,

while the hexacyano ion contains only one unpaired electron. Explain using
Crystal Field Theory.
Soln. Mn(II) has 3d5 electronic configuration. Water is a weak field ligand
and therefore Do is small. Therefore, the hexaaqua complex will be high
spin complex containing 5 unpaired electrons. On the other hand, CN–
is a strong field ligand and therefore, Do is large. Therefore, in its cyano
complex, the electrons pair up and have only one unpaired electron.
o small o large
High spin [Mn(H2O)6]2+ Low spin [Mn(CN)6]4–
11. Calculate the overall complex dissociation equilibrium constant for the
Cu(NH3)42+ ion, given that b4 for this complex is 2.1 × 1013.
Soln. The overall dissociation constant is the reciprocal of overall stability
constant i.e. 1/ b4.
1
Overall dissociation constant = = 4.7 × 10 −14
13
2.1 × 10
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Chapter 10
Haloalkanes and Haloarenes
Summary
Alkyl/ Aryl halides may be classified as mono, di, or polyhalogen (tri-, tetra-, etc.)
compounds depending on whether they contain one, two or more halogen atoms in
their structures. Since halogen atoms are more electronegative than carbon, the carbon-
halogen bond of alkyl halide is polarised; the carbon atom bears a partial positive
charge, and the halogen atom bears a partial negative charge.
Alkyl halides are prepared by the free radical halogenation of alkanes, addition
of halogen acids to alkenes, replacement of –OH group of alcohols with halogens using
phosphorus halides, thionyl chloride or halogen acids. Aryl halides are prepared by
electrophilic substitution to arenes. Fluorides and iodides are best prepared by halogen
exchange method.
The boiling points of organohalogen compounds are comparatively higher than the
corresponding hydrocarbons because of strong dipole-dipole and van der Waals forces
of attraction. These are slightly soluble in water but completely soluble in organic
solvents.
The polarity of carbon-halogen bond of alkyl halides is responsible for their
nucleophilic substitution, elimination and their reaction with metal atoms to form
organometallic compounds. Nucleophilic substitution reactions are categorised into
SN1 and SN2 on the basis of their kinetic properties. Chirality has a profound role in
understanding the reaction mechanisms of SN1 and SN2 reactions. SN2 reactions of
chiral alkyl halides are characterised by the inversion of configuration while SN1 reactions
are characterised by racemisation.
A number of polyhalogen compounds e.g., dichloromethane, chloroform, iodoform,
carbon tetrachloride, freon and DDT have many industrial applications. However,
some of these compounds cannot be easily decomposed and even cause depletion of
ozone layer and are proving environmental hazards.
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1. Name the following halides according to IUPAC system and classify them
as alkyl, allyl, benzyl (primary, secondary, tertiary), vinyl or aryl halides:
(i) (CH3)2CHCH(Cl)CH3 (ii) CH3CH2CH (CH3)CH(C2H5)Cl

(iii) CH3CH2C(CH3)2CH2l (iv) (CH3)3CCH2CH(Br)C6H5
(v) CH3CH(CH3)CH(Br)CH3 (vi) CH3C(C2H5)2CH2Br
(vii) CH3C(Cl)(C2H5)CH2CH3 (viii) CH3CH = C(Cl)CH2CH(CH3)2
(ix) CH3CH = CHC(Br)(CH3)2 (x) p-ClC6H4CH2CH(CH3)2
(xi) m-ClCH2C6H4CH2C(CH3)3 (xii) o-BrC6H4CH(CH3)CH2CH3
CH3Cl CH3Cl
Soln. (i) : H3CCHCHCH3 (ii) CH3CH2CHCHCH2CH3
2-Chloro-3-methylbutane 3-Chloro-4-methylhexane
(2° alkyl halide) (2° alkyl halide)
(iii) (iv)
CH3Br CH2CH3
(v) CH3CHCHCH3 (vi) H3CCCH2Br
4 3 2 1
2-Bromo-3-methylbutane CH2CH3
(2° alkyl halide) 1-Bromo-2-ethyl-2-methylbutane
(1° alkyl halide)
Cl Cl CH3
(vii) H3CCCH2CH3 (viii) H CCH CCH CHCH
3 2 1 3 1 2 2 3
3 4 5 6
CH2CH3 3-Chloro-5-methylhex-2-ene
4 5
3-Chloro-3-methylpentane (vinyl halide)
(3° alkyl halide)
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(ix) (x)
(xi) ClCH2 (xii) Br

CH3
CH2CCH3 HCCH2CH3
CH3
CH3
1-Chloromethyl-3-(2,2-dimethylpropyl)
1-Bromo-2-(1-methylpropyl)
benzene (benzylic chloride)
benzene (aryl halide)
2. Give the IUPAC names of the following compounds :
(i) CH3CH(Cl)CH(Br) (CH3) (ii) CHF2CBrCIF
(iii) CICH2C CCH2Br (iv) (CCl3)3CCI
(v) CH3C(p-CIC6H4)2CH(Br)CH3 (vi) (CH3)3CCH C(Cl) C6H4I–p
Cl Br
Soln. (i) H3CCHCHCH3 (ii)
2-Bromo-3-chlorobutane
CCl3
(iii) ClCH2C CCH2Br (iv) Cl3CCCl
1-Bromo-4-chlorobut-2-yne CCl3
2-(Trichloromethyl)-
Cl 1,1,1,2,3,3,3-
heptachloropropane
H3CCCH(Br)CH3 CH3 Cl
(v) (vi) H3CCCH C I
CH3
1-Chloro-1-(4-iodophenyl)
Cl -3,3-dimethylbut-1-ene
2-Bromo-3,3-bis-
(4-chlorophenyl)butane
3. Write the structures of the following organic halogen compounds.
(i) 2-Chloro-3-methylpentane (ii) p-Bromochlorobenzene
(iii) 1-Chloro-4-ethylcyclohexane (iv) 2-(2-Chlorophenyl)-1-iodooctane
(v) Perfluorobenzene (vi) 4-tert-Butyl-3-iodoheptane
(vii) 1-Bromo-4-sec-butyl-2-methylbenzene
(viii) 1,4-Dibromobut-2-ene
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Soln. Structures of the given compounds are :
(i) H3CH2CHCCHCH3 (ii) Cl Br

H3C Cl
(iii) H5C2 Cl
(iv)
F
I
F F
(v) (vi) H3C(CH2)2CCHCH2CH3
F F H3CCCH3
F
CH3
CH3
(vii) CH3CH2HC Br (viii) BrCH2CH CHCH2Br
CH3
4. Which one of the following has the highest dipole moment?
(i) CH2Cl2 (ii) CHCl3 (iii) CCl4
Soln. CHCl3 has the highest dipole moment. The reason for it can be
understood by looking into the structure of the given compounds.
(i) CH2Cl2 has a symmetrical structure such that the C Cl bond
dipole moments cancel out each other while the C H dipole moments
reinforce each other and thus contribute to a net moment.
Cl
H
Net dipole C
moment
Cl H
(ii) CCl4 has a perfectly tetrahedral structure where the net dipole of 3
C – Cl bonds point in a direction opposite to the fourth C – Cl bond and
thus results in zero dipole moment.
Cl
C
Cl Cl
Cl
Net dipole moment 3C – Cl
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(iii) In CHCl3 net moment of 3C – Cl reinforces the dipole moment of
C – H and therefore has the highest dipole moment.
H
C
Cl Cl
Cl
Net dipole moment 3C – Cl
5. A hydrocarbon C5H10 does not react with chlorine in dark but gives
a single monochloro compound C5H9Cl in bright sunlight. Identify the
hydrocarbon.
Soln. A number of structural isomers are possible for molecular formula
C5H10. But, the given compound gives a single monochloro derivative
when reacted with Cl2 in sunlight suggests that, all the H-atoms in the
compound are equivalent. This is possible only if the compound is a cyclic
alkane.
Therefore, the compound is
6. Write the isomers of the compound having formula C4H9Br.

Soln. The possible isomers of C4H9Br are
(i) H3CCH2CH2CH2Br (ii) H3CCH2CH(Br)CH3
CH3 CH3
(iii) H3CCHCH2Br (iv) H3CCCH3
Br
7. Write the equations for the preparation of 1-iodobutane from
(i) 1-butanol (ii) 1-chlorobutane (iii) but-1-ene
Soln. (i) 1-Iodobutane may be prepared from 1-butanol as :
2 Red P/I
CH3 — (CH2)2 — CH2 — OH CH3 — (CH2)2 — CH2 — I
(ii) From 1-Chlorobutane
H3C — (CH2)2 — CH2 — Cl + NaI CH3 — (CH2)2 — CH2I + NaCl
NaCl formed is precipitated in dry acetone.
(iii) From but-1-ene as :
CH3 — H2C — HC CH2 + HI CH3 — CH2 — CH2 — CH2 — I
8. What are ambident nucleophiles? Explain with an example.
Soln. Ambident nucleophiles are nucleophiles that are capable of attacking
the substrate (alkyl halide) through two different atoms.
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It so happens due to the presence of two nucleophilic centres which arise
from the contributing (resonance) structures that are possible for the ion.
e.g., In NO2– ion, there is a lone pair of electrons on N and therefore makes
it nucleophilic while oxygen by virtue of the negative charge acts as a
nucleophile. Thus, NO2– can attack via O or N atom thereby making it
ambidentate.
.. ..
N N –
– O
O O O
RX + Ag O N O R NO2
nitroalkane
RX + KNO2 R O N O
alkyl nitrite
9. Which compound in each of the following pairs will react faster in SN2
reaction with OH– ?
(i) CH3Br or CH3I (ii) (CH3)3CCl or CH3Cl
Soln. (i) Between CH3Br and CH3I, CH3I will react faster via the SN2
mechanism. In SN2 mechanism, C – X bond breaks and the faster it breaks
faster is the reaction.
I– is a better leaving group. Owing to its large size, the C – I bond breaks
faster than the C – Br bond and reaction proceeds further at a greater
rate.
(ii) The order of reactivity in an SN2 reaction depends on minimal steric
hindrance around the carbon involved in the C – X bond. Lesser the steric
hindrance felt by the incoming nucleophile, more reactive will be the
alkyl halide towards SN2 reaction.
Based on this, CH3Cl will react faster than (CH3)3CCl.
10. Predict all the alkenes that would be formed by dehydrohalogenation
of the following halides with sodium ethoxide in ethanol and identify the
major alkene :
(i) 1-Bromo-1-methylcyclohexane
(ii) 2-Chloro-2-methylbutane
(iii) 2,2,3-Trimethyl-3-bromopentane.
–
Br C2H5O
Soln. (i) +
CH3 C2H5OH CH3 CH2
major minor
Cl
C2H5O–
(ii) H3CCCH2CH3 H2 C CCH2CH3 + H3CC CHCH3
C2H5OH
CH3 CH3 CH3
minor major
||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
CH3 CH3 CH3 CH2
C2H5O
(iii) H3C — C — C — CH2— CH3 H3C—C — C—CH2—CH3 +
C2H5OH
CH3 Br CH3
minor
CH3 CH3
H3C—C — C CH— CH3
CH3
major
11. How will you bring about the following conversions?
(i) Ethanol to but-1-yne (ii) Ethane to bromoethene
(iii) Propene to 1-nitropropane (iv) Toluene to benzyl alcohol
(v) Propene to propyne (vi) Ethanol to ethyl fluoride
(vii) Bromomethane to propanone (viii) But-1-ene to but-2-ene
(ix) 1-Chlorobutane to n-octane (x) Benzene to biphenyl
Red P/I2 Na
Soln. (i) C H CH OH 2CH 3CH2I C H3CH2CH2CH3
3 2 dry ether
Ethanol
H2/Ni
reduction
CH3C H2C CH
But-1-yne
Br2/UV light KOH(alc.), 
(ii) C2H6 C2H5Br CH2 CH2
Br2/CCl4
BrCH2CH2Br
–HBr
Ethene 1,2-Dibromoethane
KOH(alc.), 
CH2 CHBr
Bromoethene
HBr + AgNO2/EtOH/H2O
(iii) H3CHC CH2 CH3CH2CH2Br
benzoyl peroxide
Propene
CH3CH2CH2NO2
1-Nitropropane
CH3 CH2Cl CH2OH
Cl2/h aq. KOH/

(iv)
– HCl
Toluene Benzyl alcohol
Br2/CCl4 KOH/C2H5OH
(v) H3CHC CH2 CH3CHCH2  H3CC CH
Propene Propyne
Br Br
SOCl2 Hg2F2
(vi) CH3CH2OH CH3CH2Cl CH3CH2F
pyridine
Ethanol Ethyl fluoride
||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
(vii)
(viii)
(ix)
(x)
12. Explain why

(i) the dipole moment of chlorobenzene is lower than that of cyclohexyl
chloride?
(ii) alkyl halides, though polar, are immiscible with water?
(iii) Grignard reagents should be prepared under anhydrous conditions?
Soln. (i) (a) In order to understand the lower dipole moment of
chlorobenzene we need to look into the contributing structures of the
molecules.
.. .Cl
..
. .. Cl
+ . .. Cl
+ . .. Cl
+ . .. .
..Cl
. . . .
– –
–
I II III IV V
(b) From the above structures we find that the C – Cl bond in chlorobenzene
has a partial double bond character (structure II, III and IV). As a result, the
C – Cl bond length here is shorter than the C – Cl single bond but longer than
the C – Cl double bond.
(c) Also evident is the positive charge on Cl atom which reduces the
partial negative (d–) charge which it is expected to carry by the virtue of
its electronegativity.
(d) Consequently, the dipole moment, which is a product of bond length
and partial negative charge on Cl atom, reduces.
However, in cyclohexyl chloride this does not happen. It is an alkyl halide
and carbon is purely sp3 hybridised and C – Cl bond has the bond length
||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
of a single bond and d– appearing on Cl is also higher, thus, the greater
dipole moment.
(ii) Only those compounds which can form hydrogen bonds with water
are miscible with it. Alkyl halides, though polar due to the presence of
electronegative halogen atom, are immiscible since they cannot form
hydrogen bonds.
(iii) Grignard reagents R – Mg – X is a class of highly reactive compounds
which can extract a proton even from water molecule. They thus, turn
into the corresponding alkanes and render any other desired reaction
ineffective.
This is why Grignard reagents are prepared in the absolute absence of
water (anhydrous conditions). (e.g.,)
13. Give the uses of freon 12, DDT, carbon tetrachloride and iodoform.
Soln. (i) Freon 12 (CCl2F2) is
• used in aerosol propellants • refrigeration
• air-conditioning.
(ii) DDT (p, p′- dichlorodiphenyltrichloroethane) is
• used as an insecticide, • mainly used against mosquitoes.
(iii) Carbontetrachloride (CCl4) is used
• in manufacture of refrigerants and propellants for aerosol cans
• in synthesis of chlorofluorocarbons
• as degreasing agent • as cleansing agent
• as a solvent in laboratories
(iv) Iodoform (CHI3) is used as an antiseptic.
14. Write the structure of the major organic product in each of the following
reactions :
acetone
(i) CH3CH2CH2Cl + NaI
heat
ethanol
(ii) (CH3)3CBr + KOH
heat
Water
(iii) CH3CH(Br)CH2CH3 + NaOH
(iv) CH3CH2Br + KCN aq. ethanol
(v) C6H5ONa + C2H5Cl
(vi) CH3CH2CH2OH + SOCl2
peroxide
(vii) CH3CH2CH CH2 + HBr
(viii) CH3CH C(CH3)2 + HBr
acetone
Soln. (i) CH3CH2CH2Cl + NaI CH3CH2CH2I + NaCl

Propyl chloride Iodopropane
||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
(ii)
Br OH
water
(iii) CH3CHCH2CH3 + NaOH CH3CHCH2CH3 + NaBr + H2O
2-Bromobutane Butan-2-ol
(iv)
� +
(v) ONa + C2H5Cl O — C2H5 + NaCl
Sodium phenoxide Phenylethylether
(vi)
peroxide
(vii) CH3CH2CH CH2 + HBr CH2CH2CH2 — CH2 — Br
1-Bromobutane
CH3
(viii) CH3CH C(CH3)2 + HBr CH3 — CH2 — C — Br
CH3
2-Bromo-2-methylbutane
15. Write the mechanism of the following reaction
EtOH-H O
nBuBr + KCN
2
nBuCN
Soln. The given reaction is a nucleophilic substitution reaction of 1st order
i.e., SN1. The mechanism may be depicted as :
Step 1 : Generation of nucleophile
EtOH – H2O –
KCN K+ + C N
Step 2 : Nucleophilic attack and formation of transition state :
Step 3 : Generation of product:

||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
Thus, we have
EtOH/H2O
CH3CH2CH2CH2Br + KCN CH3CH2CH2CH2CN + KBr
16. Arrange the compounds of each set in order of reactivity towards SN2
displacement :
(i) 2-Bromo-2-methylbutane, 1-Bromopentane, 2-Bromopentane
(ii) 1-Bromo-3-methylbutane, 2-Bromo-2-methylbutane,
3-Bromo-2-methylbutane
(iii) 1-Bromobutane, 1-Bromo-2,2-dimethylpropane, 1-Bromo-2-methyl butane,
1-Bromo-3-methylbutane.
Soln. SN2 reaction proceeds via the formation of transition state where
the carbon atom is surrounded by 5 other atoms (groups). Thus, for such
a transition state to form, the steric interactions have to be minimum.
Therefore, the most favourable substrates for SN2 reactions are 1° alkyl
halides followed by 2° and 3° alkyl halide. Order of reactivity towards
SN2 : 1° > 2° > 3° > aryl halide.
Based on this, the order will be
Br Br
(i) H3C(CH2)3CH2Br > CH3CH(CH2)2CH3 > CH3C(CH2)2CH3
1-Bromopentane 2-Bromopentane
CH3
2-Bromo-2-methylpentane
CH3 CH3 CH3
(ii) H3CCHCH2CH2Br > CH3CHCHCH3 > CH3CCH2CH3
1-Bromo-3-methylbutane Br Br
2-Bromo-3- 2-Bromo-2-
methylbutane methylbutane
CH3
(iii) CH3(CH2)CH2Br > (CH3)2CHCH2CH2Br > CH3CH2CHCH2Br >
1-Bromobutane 1-Bromo-3-methylbutane 1-Bromo-2-methylbutane
(I) (II) (III)
CH3
CH3CCH2Br
CH3
1-Bromo-2,2-dimethylpropane
(IV)
In example (iii), although all the given alkyl halides are 1° but the steric
hindrance around the carbon bearing the –Br atom decides the order of
reactivity. More the number of bulky groups around this carbon lower
will be its reactivity towards SN2.
17. Out of C6H5CH2Cl and C6H5CHClC6H5, which is more easily hydrolysed by
aqueous KOH?
||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
Soln. C6H5CHClC6H5 is hydrolysed faster.
(a) Hydrolysis of an alkyl halide is an example of nucleophilic substitution
reaction. In case of aryl halides this follows the SN1 pathway i.e., via the
formation of carbocation.
(b) C6H5CH2Cl or benzyl chloride gives
+
CH2 (I) carbocation while C6H5CHClC6H5 generates
+
C (II).
H
(c) Out of I & II, carbocation II is more stable. The reason is the presence
of two phenyl rings attached to the carbon carrying the positive charge.
(d) As a result, the delocalisation of the +ve charge is greater and the
carbocation is more stable. Due to this, (II) is formed faster and the
corresponding halide is hydrolysed with greater ease as compared to
benzyl chloride.
18. p-Dichlorobenzene has higher m.p. and solubility than those of o- and
m-isomers. Discuss.
Soln. The para-isomers have high melting points and solubility as
compared to their ortho and meta isomers due to symmetry of para-isomers
that fits into crystal lattice better than ortho and para isomers.
19. How can the following conversions be carried out?

(i) Propene to propan-1-o1
(ii) Ethanol to but-1-yne
(iii) 1-Bromopropane to 2-bromopropane
(iv) Toluene to benzyl alcohol
(v) Benzene to 4-bromonitrobenzene
(vi) Benzyl alcohol to 2-phenylethanoic acid
(vii) Ethanol to propanenitrile
(viii) Aniline to chlorobenzene
(ix) 2-Chlorobutane to 3,4-dimethylhexane
(x) 2-Methyl-1-propene to 2-chloro-2-methylpropane
(xi) Ethyl chloride to propanoic acid
(xii) But-1-ene to n-butyliodide
(xiii) 2-Chloropropane to 1-propanol
(xiv) Isopropyl alcohol to iodoform (xv) Chlorobenzene to p-nitrophenol
(xvi) 2-Bromopropane to 1-bromopropane
(xvii) Chloroethane to butane (xviii) Benzene to diphenyl
(xix) tert-Butyl bromide to isobutyl bromide
(xx) Aniline to phenylisocyanide
||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
Soln.
HBr/ aq. KOH/
(i) CH3HC CH2 CH3CH2CH2Br CH3CH2CH2OH
peroxide
Propene Propanol
(ii) 2CH3CH2OH + SOCl2 2CH3CH2Cl + SO2↑ + HCl ↑

–
C2H5O/KOH
(iii) CH CH2CH2Br CH3CH CH2
HBr
CH3CHCH3
3 
1-Bromopropane Br
2-Bromopropane
(iv)
Br Br
Br2/FeBr3 conc. H2SO4 + conc. HNO3

(v)
Benzene Bromobenzene
NO2
4-Bromonitrobenzene
CH2OH CH2Cl CH2CN CH2COOH
SOCl2 KCN/EtOH-H2O H3O+
(vi)
Benzyl 2-Phenylethanoic
alcohol acid
SOCl2 KCN/
(vii) H3C CH2OH H3 C CH2Cl CH3 CH2OH
EtOH-H2O
Ethanol Propanenitrile
+ –
NH2 N NCl Cl
NaNO2 + HCl
(viii) CuCl/HCl
273 K
Aniline Benzene Chlorobenzene
diazonium
chloride
||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
(ix)
CH3 CH3
HCl
(x) H3C C CH2 H3C C CH3
2-Methylpropene
Cl
2-Chloro-2- methylpropane
KCN H3O+
(xi) CH3CH2Cl CH3CH2CN CH3CH2COOH
EtOH-H2O
(xii)
Cl
KOH/C2H5OH HBr, peroxide
(xiii) CH3CHCH3 CH3CH CH2

KOH,
CH3CH2CH2OH /H2O
CH3CH2CH2Br
Propanol
(xiv) CH CHOH + 4I + 6NaOH 

3 2 CHI3 + CH3COONa + 5NaI + 5H2O
CH3 Iodoform
Isopropylalcohol
Cl Cl OH
conc. HNO3 (i) 15% NaOH, 433 K
(xv)
conc. H2SO4 (ii) dil. H+
Chlorobenzene
NO2 NO2
p-Nitrophenol
KOH/C2H5OH HBr/
(xvi) H CCCH H3CCH CH2 H3CCH2CH2Br
3 3  peroxide
Br 1-Bromopropane
2-Bromopropane
dry ether
(xvii) 2H3CCH2Cl + 2Na H3CCH2CH2CH3 + 2NaCl
Chloroethane Butane
Cl
Cl2/FeCl3 Na/ether
(xviii)
Benzene Dipheynl
||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
CH3 CH3 CH3
KOH/C2H5OH HBr/
(xix) CH3—C—Br H3C—C peroxide
H3C—CH
CH3 CH2 CH2—Br
tert-Butylbromide
NH2
N C
warm + 3KCl + 3H2O
(xx) + CHCl3 + 3KOH/(alc.)
Phenylisocyanide
Aniline
20. The treatment of alkyl chlorides with aqueous KOH leads to the
formation of alcohols but in the presence of alcoholic KOH, alkenes are
major products. Explain.
Soln. Formation of alcohols from the reaction between alkyl chlorides and
aqueous KOH is an example of simple nucleophilic substitution.
H2O
CH3 CH2 Cl + KOH CH3 CH2 OH + KCl
But when aqueous KOH is replaced by alcoholic KOH, alkenes are formed
instead of alcohols due to elimination of HCl from an alkyl halide.
EtOH
CH3 CH2Cl + KOH CH2 CH2
This can be exaplained if we consider the size of the nucleophile in the
two reactions. In the aqueous medium the Nu is OH which is relatively
small while in the alcoholic medium the Nu is C2H5 which is bulky in
nature.
The bulky Nu will always find it easier to abstract a proton than to attack
a tetravalent carbon to produce a substitution product.
H H H H
–
–
H H
H5C2O + C C C—C — Cl + C2H5OH C C
H H
H H H Cl H H alkene
If C2H5O was to attack the carbon carrying halogen, steric repulsions

would hinder the attack and prevent substitution product.
21. Primary alkyl halide C4H9Br (A) reacted with alcoholic KOH to give
compound (B). Compound (B) is reacted with HBr to give (C) which is an
isomer of (A). When (A) is reacted with sodium metal it gives compound (D).
C8H18 which is different from the compound formed when n-butyl bromide
is reacted with sodium. Give the structural formula of (A) and write the
equations for all the reactions.
Soln. The given reaction
sequence is :
When (A) is treated with Na
metal, Wurtz reaction takes
||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
place. It is given that (A) is a primary alkyl halide.
\ The possible structures of C4H9Br (A) are
(I) H3C — CH — CH2Br (II) CH3 — CH2 — CH2 — CH2 — Br
CH3
However, it is given that (A) on reaction with Na metal gives alkane
C8H18 which is not the same as the one obtained from the Wurtz reaction
of n-butylbromide. Therefore (A) ≠ II.
Thus,
22. What happens when

(i) n-butyl chloride is treated with alcoholic KOH,
(ii) bromobenzene is treated with Mg in the presence of dry ether,
(iii) chlorobenzene is subjected to hydrolysis,
(iv) ethyl chloride is treated with aqueous KOH,
(v) methyl bromide is treated with sodium in the presence of dry ether,
(vi) methyl chloride is treated with KCN?
alc. KOH
Soln. (i) CH3CH2CH2CH2Cl CH3CH2CH CH2
n-Butylchloride But-1-ene
The reaction is an example of b-hydrogen elimination brought about by
C2H5O
(ii)
Preparation of Grignard reagent
NaOH, 623 K, 300 atm

(iii) Cl OH
Chlorobenzene Phenol
Chlorobenzene is highly unreactive towards nucleophilic substitution.
However, it can be hydrolysed to phenol by heating in aqueous sodium
hydroxide solution at a temperature of 623 K and 300 atm pressure. The
presence of an electron withdrawing group increases the reactivity of
haloarenes.
||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
KOH/H2O
(iv) CH3 CH2 Cl CH3 CH2 OH
( SN2 reaction)
dry ether
(v) 2CH3 Br + 2Na
KCN
(vi) CH3Cl CH3 CN
EtOH/H2O
Methylchloride Ethanenitrile

1. Write the structures of the following compounds :
(i) 2-Chloro-3-methylpentane (ii) 1-Chloro-4-ethylcyclohexane
(iii) 4-tert-Butyl-3-iodoheptane (iv) 1,4-Dibromobut-2-ene
(v) 1-Bromo-4-sec-butyl-2-methylbenzene
Cl
CH3Cl
Soln. (i) (ii)
C2H5
1-Chloro-4-ethylcyclohexane
(iii) (iv) H2CHC CHCH2
Br Br
1, 4-Dibromobut-2-ene
(v)
2. Why is sulphuric acid not used during the reaction of alcohols with KI ?
Soln.H2SO4 is a strong oxidising agent. Therefore, when it is used in
presence of KI, it tends to convert KI to HI and finally oxidises it to I2.
3. Write structures of different dihalogen derivatives of propane.
Soln. The structures of all possible dihalogen derivatives of propane are
||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
4. Among the isomeric alkanes of molecular formula C5H12, identify the
one that on photochemical chlorination yields
(i) A single monochloride
(ii) Three isomeric monochlorides
(iii) Four isomeric monochlorides.
Soln. An alkane with molecular formula C5H12 can exist in the following
isomeric forms :
CH3
(I) H3CCH2CH2CH2CH3 (II) H3CCHCH2CH3
n-pentane 2-methylbutane
CH3
(III) H3C C CH3
CH3
2, 2, dimethylpropane
Upon photochemical chlorination, the H atom in the alkane is replaced by
halogen atom. Looking at the structures we find that 3 different halogen
derivatives are possible for (I), while 4 are possible for (II) and only
I for (III).
(i) All the H atoms in (III) are equivalent. Therefore, we get only a single
monochloride from (III).
(ii) (I) yields 3 isomeric products due to presence of 3 different H atoms.
(iii) (II) yields 4 isomeric products due to presence of 4 different H
atoms.
(I) hv/Cl2
(Cl)CH (CH ) CH + H CCH(Cl)(CH ) CH
2 2 3 3 3 2 2 3
Cl
+ H3CCH2CHCH2CH3
CH3 CH3 Cl
hv/Cl2
(II) (Cl)H2CCHCH2CH3 + H3CCCH2CH3 + (H3C)2CHCHCH3
Cl
CH2Cl
hv/Cl2
(III) CH3 C CH3
CH3
5. Draw the structures of major monohalo products in each of the following
reactions :
OH
(i) + SOCl2
||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
CH2CH3
(ii) Br2 , heat or UV light
O2N
CH2OH CH3
heat + Hl
(iii) + HCl (iv)
OH
heat
(v) CH3CH2Br + Nal (vi) + Br2 UV light
Soln. The major haloderivatives formed in the given reactions are

Br
Cl CHCH3
(i) (ii)
O2N
CH2Cl CH3
(iii) (iv) I
HO
Br
(v) H C CH2 I (vi)

3
6. Arrange each set of compounds in order of increasing boiling points.

(i) Bromomethane, bromoform, chloromethane, dibromomethane.
(ii) 1-Chloropropane, isopropyl chloride, 1-chlorobutane.
Soln. The boiling points of organic compounds depend on the strength of
the intermolecular forces in them. These forces are :
(a) van der Waals forces and (b) dipole-dipole interactions
These forces are dependent on the
(i) molecular mass and (ii) surface area of the molecules
(i) As the molecular mass of the compound increases, the boiling point
also increases. Therefore the correct order is :
chloromethane < bromomethane < dibromomethane < bromoform
(ii) Amongst molecules with same mass, it is the size of the molecule that
determines the boiling point. Branched compounds are more compact
and therefore have less surface area as compared to their straight chain
counterparts and therefore lower boiling point. The order of boiling point
is :
iso-propyl chloride < 1-chloropropane < 1-chlorobutane
||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
7. Which alkyl halide from the following pairs would you expect to react
more rapidly by an SN2 mechanism? Explain your answer.
(i) CH3CH2CH2CH2Br or CH3CH2CHCH3
Br
CH3
(ii) CH3CH2CHCH3 or H3C C Br

Br CH3
(iii) CH3CHCH2CH2Br or CH3CH2CHCH2Br
CH3 CH3
Soln. We know that SN2 mechanism involves a transition state wherein
both, the incoming nucleophile as well as the leaving group are present
around the carbon atom. There are 5 atoms simultaneously bonded to it.
Thus, for such a transition state to be possible, there should be minimum
steric hindrance. Hence, 1° alkyl halides are most reactive towards SN2
followed by 2° and finally 3°.
1° RX > 2° RX > 3° RX
Based on the above order,
(i) CH3CH2CH2CH2Br is more reactive.
(ii) CH CH CHCH is more reactive.
3 2 3
Br
(iii) CH3 CH CH2 CH2 Br is more reactive.
CH3
In (iii), it is the proximity of the branched chain — CH3 that determines
the reactivity. In CH3CH2CH(CH3)CH2 the methyl group is closer to the
leaving group thereby hindering the transition state.
8. In the following pairs of halogen compounds, which compound
undergoes faster SN1 reaction?
Cl Cl
(i) and
Cl
(ii) and
Cl
Soln. SN1 reaction proceeds via the formation of a carbocation intermediate.
This intermediate is formed by the cleavage of the C — X bond. More
stable is the resultant carbocation faster is the SN1 reaction.
Order of stability of carbocation is
3° carbocation > 2° carbocation > 1° carbocation
||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
Cl
(i) will react faster. The carbocation will be more stable and
hence reaction will be faster.
Cl
(ii) reacts faster due to the greater stability of 2° carbocation
as compared to 1° carbocation.
9. Identify A, B, C, D, E, R and R′ in the following.

dry ether H2 O
(i) Br + Mg A B
dry ether D2 O
R
(ii) R Br + Mg C CH3CHCH3
D
(iii)
dry ether H2O

Soln. (i) Br + Mg MgBr
A B
Grignard reagent
CH3
(ii) R is CH3CHCH3
D
CH3
(iii) R′ is H3C C
CH3
CH3 CH3 CH3 CH3
Na/ether Mg
 CH3 CH3 X C CH3 H3C MgX
CH3 CH3
CH3 CH3 D H2O
CH3
H3C H
CH3
E
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Chapter 11
Alcohols, Phenols and Ethers
Summary
Alcohols and phenols are classified (i) on the basis of the number of hydroxyl
3 2
groups and (ii) according to the hybridisation of the carbon atom, sp or sp to
which the –OH group is attached. Ethers are classified on the basis of groups
attached to the oxygen atom.
Alcohols may be prepared (1) by hydration of alkenes (i) in presence of an
acid and (ii) by hydroboration-oxidation reaction (2) from carbonyl compounds by
(i) catalytic reduction and (ii) the action of Grignard reagents. Phenols may be
prepared by (1) substitution of (i) halogen atom in haloarenes and (ii) sulphonic
acid group in aryl sulphonic acids, by –OH group (2) by hydrolysis of diazonium
salts and (3) industrially from cumene.
Alcohols are higher boiling than other classes of compounds, namely
hydrocarbons, ethers and haloalkanes of comparable molecular masses. The
ability of alcohols, phenols and ethers to form intermolecular hydrogen bonding
with water makes them soluble in it.
Alcohols and phenols are acidic in nature. Electron withdrawing groups in
phenol increase its acidic strength and electron releasing groups decrease it.
Alcohols undergo nucleophilic substitution with hydrogen halides to yield
alkyl halides. Dehydration of alcohols gives alkenes. On oxidation, primary alcohols
yield aldehydes with mild oxidising agents and carboxylic acids with strong
oxidising agents while secondary alcohols yield ketones. Tertiary alcohols are
resistant to oxidation.
The presence of –OH group in phenols activates the aromatic ring towards
electrophilic substitution and directs the incoming group to ortho and para
positions due to resonance effect. Reimer-Tiemann reaction of phenol yields
salicylaldehyde. In presence of sodium hydroxide, phenol generates phenoxide
ion which is even more reactive than phenol. Thus, in alkaline medium, phenol
undergoes Kolbe’s reaction.
Ethers may be prepared by (i) dehydration of alcohols and (ii) Williamson
synthesis. The boiling points of ethers resemble those of alkanes while their
solubility is comparable to those of alcohols having same molecular mass. The
C–O bond in ethers can be cleaved by hydrogen halides. In electrophilic
substitution, the alkoxy group activates the aromatic ring and directs the incoming
group to ortho and para positions.
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1. Write IUPAC names of the following compounds :
CH3
(i) CH3—CH—CH—C—CH3 (ii) H3C—CH—CH2—CH—CH—CH2—CH3
CH3 OH CH3 OH OH C2H5
(iii) CH3—CH—CH—CH3 (iv) HO—CH2—CH—CH2—OH

OH OH OH
(v) (vi)
(vii) (viii)
(ix) CH3—O—CH2—CH—CH3 (x) C6H5—O—C2H5

CH3
(xi) C6H5—O—C7H15(n–) (xii)

CH3—CH2 —O—CH—CH2—CH3
CH 3
Soln. (i) 2,2,4-Trimethylpentan-3-ol
(ii) 5-Ethylheptan-2,4-diol (iii) Butane-2,3-diol

(iv) Propane-1,2,3-triol (v) 2-Methylphenol
(vi) 4-Methylphenol (vii) 2,5-Dimethylphenol
(viii) 2,6-Dimethylphenol (ix) 1-Methoxy-2-methylpropane
(x) Ethoxybenzene (xi) 1-Phenoxyheptane
(xii) 2-Ethoxybutane
2. Write structures of the compounds whose IUPAC names are as follows:
(i) 2-Methylbutan-2-ol (ii) 1-Phenylpropan-2-ol
(iii) 3,5-Dimethylhexane-1,3,5-triol (iv) 2,3-Diethylphenol
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(v) 1-Ethoxypropane (vi) 2-Ethoxy-3-methylpentane
(vii) Cyclohexylmethanol (viii) 3-Cyclohexylpentan-3-ol
(ix) Cyclopent-3-en-1-ol (x) 3-Chloromethylpentan-1-ol
Soln. (i) (ii)
OH
C2H5
(iii) (iv)
C2H5
(v) H3CCH2OCH2CH2CH3 (vi)
(vii) CH2 – OH (viii)
OH
(ix) (x)
3. (i) Draw the structures of all isomeric alcohols of molecular formula

C5H12O and give their IUPAC names.
(ii) Classify the isomers of alcohols in question 3 (i) as primary, secondary
and tertiary alcohols.
Soln. The isomeric alcohols with molecular formula C5H12O are :
(i) (a) (b)
Pentanol (1°)
Pentan-2-ol(2°)
(c) (d)
Pentan-3-ol(2°) 2-Methylbutan-1-ol(1°)
(e) (f)
2-Methylbutan-2-ol(3°)
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CH3 CH3 OH
(g) CH3 – C – CH2 – OH (h)
CH3 – CH – CH – CH3
*
CH3 3-Methylbutan-2-ol (2°)
2,2-Dimethylpropan-1-ol (1°)
Isomers (b), (d) and (h) contain chiral carbon atoms thus, they exhibit
enantiomerism.
(ii) Isomers (a), (d), (e) and (g) are primary alcohols.
Isomers (b), (c) and (h) are secondary alcohols.
Isomer (f) is a tertiary alcohol.
4. Explain why propanol has higher boiling point than that of the
hydrocarbon, butane.
Soln. The boiling point of any compound depends on the strength of
inter-molecular forces. Stronger is the inter-molecular attraction, higher
is the boiling point.
In butane, the molecules interact with each other through weak van der
Waals forces. These weak forces can be easily overcome by supplying
small amount of heat energy. Thus, they have low boiling point.
In propanol, the molecules are held together by strong hydrogen bonding.
These attractive forces operating between molecules are more difficult to
break and therefore higher amount of heat needs to be supplied, therefore,
the higher boiling point.
Hydrogen bonding
H7C3 – O H–O H–O

H C3H7 C3H7
5. Alcohols are comparatively more soluble in water than hydrocarbons of
comparable molecular masses. Explain this fact.
Soln. Organic compounds are soluble in water if they are able to form
hydrogen bonds with it. Alcohols are able to establish this interaction by
the virtue of their OH group and are therefore soluble in water. On the
other hand, other hydrocarbons of comparable mass do not dissolve in
water since they cannot form hydrogen bonds.
Hydrogen bonds
6. What is meant by hydroboration-oxidation reaction? Illustrate it with

an example.
Soln. Hydroboration-oxidation is a method of preparation of alcohols
from alkenes. The main advantage of this method is the high yield of
alcohol obtained. During hydroboration, diborane (BH3)2 is made to react
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with an alkene to form an addition product. This product is then treated
with hydrogen peroxide in the presence of sodium hydroxide to give
alcohol. For example,
CH3CH CH2
Propene
Propanol Addition product

7. Give the structure and IUPAC names of monohydric phenols of
molecular formula, C7H8O.
Soln. Given molecular formula : C7H8O
OH
Since, it is given that it is a phenol the basic skeleton will be .
This structure accounts for C6H6O. Remaining CH2 when added to the
phenol gives following structures :
2-Methylphenol
3-Methylphenol
(o-cresol)
(m-cresol) 4-Methylphenol
(p-cresol)
8. While separating a mixture of ortho and para nitrophenols by steam

distillation, name the isomer which will be steam volatile. Give reason.
Soln. During steam distillation, it is the lower boiling compound which
distills out first. Between ortho- and para-nitrophenol it is the ortho-isomer
which will be steam volatile since it has a lower boiling point.
The difference in boiling point between the two isomers can be
understood based on the structural difference. In ortho-isomer intra-
molecular hydrogen bonding takes place while in the para-isomer, inter-
molecular hydrogen bonding takes place.
O O H O O
O N O N
N
O
H
O
o-Nitrophenol O N O
H O O H
Inter-molecular H bonding
p-Nitrophenol
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As a result of the strong forces operating between the molecules of
p-isomer, the boiling point is higher and it is not steam volatile.
9. Give the equations of reactions for the preparation of phenol from

cumene.
Soln.
CH3
H3C – CH – CH3 H3C – C – O – OH OH
O2 H3O+
+ CH3COCH3
368-408K 323-363K
Propanone
Cumene Cumene Phenol
hydroperoxide
10. Write chemical reaction for the preparation of phenol from
chlorobenzene.
Cl ONa OH
Soln. 623 K H+
+ NaOH 300 atm
Chlorobenzene Phenol
11. Write the mechanism of hydration of ethene to yield ethanol.
Soln. The acid catalysed hydration of ethene may be represented as :
H H
H3O+/
C C H3C – CH2 – OH
H H Ethanol
Ethene
The mechanism followed by the above reaction may be depicted as
Step 1 : Generation of carbocation : Protonation of ethene yields a
carbocation as
Step 2 : Nucleophilic attack of water on carbocation : The carbocation

polarizes the lone pair electrons of O of water and hydration takes place.
H
:
H3C – CH2 + H2O: H3C – CH2 – O

H
Step 3 : Formation of product, Regeneration of the proton :
12. You are given benzene, conc. H2SO4 and NaOH. Write the equations for
the preparation of phenol using these reagents.
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Soln. Using the given reagents, phenol may be prepared as :
SO3H
ONa OH
Conc. H2SO4 NaOH Dil. H+
fuse, 573 K
Benzene Benzene sulphonic acid Sodium phenoxide Phenol
13. Show how will you synthesise :

(i) 1-Phenylethanol from a suitable alkene.
(ii) Cyclohexylmethanol using an alkyl halide by an SN2 reaction.
(iii) Pentan-1-ol using a suitable alkyl halide.
Soln. (i)

CH2OH
(ii)
Alkyl
halide
CH2OH

+ NaOH SN2

(iii)
Alkyl halide
14. Give two reactions that show the acidic nature of phenol. Compare
acidity of phenol with that of ethanol.
Soln. (a) Acids react with base and so does phenol.
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OH O Na
+ NaOH + H2O
Phenol Sodium
phenoxide
(b) Upon reaction with active metals such as Na, phenol liberates H2.
OH ONa
2 + 2Na 2 + H2↑

These two reactions demonstrate the acidic nature of phenol.
As compared to ethanol, phenols are more acidic. They lose their H atom
as H+ more readily than alcohols.
The reason for such a behaviour of phenol may be attributed to the
resonance stabilisation that arises from the contributing structures of
corresponding phenoxide ion.
C2H5OH C2H5O + H
Ethanol Ethoxide ion
OH O
+ H+
Phenol Phenoxide
:O : :O : : O: :O:
:
: O:
:
(I) (II) (III) (IV) (V)

Charge dispersal by resonance
The resonance stabilization provided by the contributing structures
(I)-(V) more than compensates for the bond breakage energy of O – H
bond and thus causes phenol to be acidic in nature.
No such resonance structures are possible for ethoxide ion and therefore
the conversion of ethanol to ethoxide is not favoured under normal
conditions. Therefore, ethanol is less acidic than phenol.
15. Explain why is ortho nitrophenol more acidic than methoxyphenol?
Soln.
o-Nitrophenol o-Methoxyphenol
(I) (II)
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The acidity of phenol arises from the loss of H of O – H group as H+. This
loss is facilitated if the polarity of the O – H bond increases and H carries
substantial d+ charge.
In (I), the presence of the highly electron withdrawing NO2 group at the
ortho position increases the polarity of the O – H bond.
– –
+ + +
– + – –
+
Resonance structure of o-nitrophenol

This helps in release of H+ and increases acidity. (II) is less acidic because
–OCH3 is an electron releasing group and increases the e– density on O of
OH and H+ release is suppressed.
This can be understood from the resonance structures of II which are
OH OH OH OH OH
+ + +
H3CO CH3O – CH3O CH3O H3CO
– –
Resonance structure of o-methoxyphenol
16. Explain how does the –OH group attached to a carbon of benzene ring
activates it towards electrophilic substitution.
Soln. In an electrophilic substitution reaction, an electron deficient species
attacks the benzene ring which is e– rich.
When an –OH group is attached to the benzene ring, by the virtue of
its electron releasing nature increases the e– density of the ring and thus
activates it, i.e., makes it a welcome site for electrophiles.
The increase in electron density can be visualised as :
:
:O – H O–H O–H
(I) (II) (III)

From structures (I) - (V), we find that the attachment of hydroxyl group
to benzene has increased the electron density (–ve charge) on the ring
carbon atoms (especially C-2, C-4 and C-6). It is therefore said to have
activated the ring towards electrophiles which are attracted to the
increased electron density.
17. Give equations of the following reactions :

(i) Oxidation of propan-1-ol with alkaline KMnO4 solution.
(ii) Bromine in CS2 with phenol. (iii) Dilute HNO3 with phenol.
(iv) Treating phenol with chloroform in presence of aqueous NaOH.
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alk. KMnO4
Soln. (i) CH3 – CH2 – CH2OH CH3CH2COOH + H2O
Propan-1-ol Propanoic acid
OH OH OH
Br2/CS2 Br
(ii) +
Phenol o-Bromophenol Br
p-Bromophenol
OH OH OH
Dil. HNO3 NO2
(iii) +
Phenol o-Nitrophenol NO2

p-Nitrophenol
OH ONa
aq. NaOH
CHO
(iv) + CHCl3
Phenol
18. Explain the following with an example.
(i) Kolbe’s reaction (ii) Reimer-Tiemann reaction
(iii) Williamson ether synthesis (iv) Unsymmetrical ether.
Soln. (i) Kolbe’s reaction : The fact that phenoxide ion is even more
reactive than phenol towards incoming electrophiles is made use of in
this reaction. Sodium phenoxide is reacted with CO2 followed by acid
treatment to yield o-hydroxybenzoic acid as the major product.
OH ONa OH
NaOH (i) CO2 COOH
(ii) H+
Phenol Salicylic acid
(ii) Reimer-Tiemann reaction : Treatment of phenol with chloroform
in the presence of aqueous alkali introduces a CHO group at the ortho
position. Acidification yields salicylaldehyde.
(iii) Williamson synthesis : In this method, an alkyl halides is reacted

with sodium alkoxide.
R – X + R – ONa R – O – R + NaX
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The reaction involves SN2 attack of an alkoxide ion on 1°RX.
CH3
H3C – C – ONa + CH3 – Br
CH3
Better results are obtained when RX is primary.
(iv) Unsymmetrical ethers : Unsymmetrical ethers are organic compounds
where the ethereal oxygen atom is attached to two different alkyl or aryl
groups. e.g.,
C2H5 – O – CH3, C6H5O – C2H5, etc.
19. Write the mechanism of acid dehydration of ethanol to yield ethene.

Soln. In the presence of conc. acids such as H3PO4 and H2SO4, alcohols
undergo dehydration to yield alkenes.
conc. H+/
H3C – CH2 – OH CH2 CH2 + H2O
Ethanol Ethene
The mechanism for this reaction is :
Step 1 : Protonation of ethanol
fast H
: :
H3C – CH2 – OH + H CH3 CH2 – O

H
Protonated ethanol
Step 2 : Formation of carbocation
H slow
H3C – CH2 – O H3C – CH2 + H2O
H Carbocation
Step 3 : Formation of ethene and regeneration of proton
H
H H
H – C – CH2 C C + H
H H
H Ethene
20. How are the following conversions carried out?
(i) Propene Propan-2-ol
(ii) Benzyl chloride Benzyl alcohol
(iii) Ethyl magnesium chloride Propan-1-ol
(iv) Methyl magnesium bromide 2-Methylpropan-2-ol.
H2O/H+
Soln. (i) H3C – CH CH2 CH3 – CH – CH3

Propene
OH
Propan-2-ol
(ii)
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O
C
(iii) H3C – CH2 – MgCl + H H
Ethyl magnesium formaldehyde
chloride Dry ether
H3O+
H3C–CH2–CH2–OMgCl CH3–CH2–CH2–OH
Propanol
CH3
(i) Dry ether
(iv) CH3 – C – OH
(ii) H3O+
CH3
2-Methylpropan-2-ol
21. Name the reagents used in the following reactions :

(i) Oxidation of primary alcohol to carboxylic acid.
(ii) Oxidation of primary alcohol to aldehyde.
(iii) Bromination of phenol to 2,4,6-tribromophenol.
(iv) Benzyl alcohol to benzoic acid.
(v) Dehydration of propan-2-ol to propene.
(vi) Butan-2-one to butan-2-ol.
Soln. (i) Alkaline KMnO4
(ii) Pyridinium chlorochromate in chloromethane (CH2Cl2)
(iii) Br2/H2O
(iv) Alkaline KMnO4
(v) Conc. H2SO4 or H3PO4 at 433-443 K
(vi) H2/Ni or NaBH4 or LiAlH4
22. Give reason for the higher boiling point of ethanol in comparison to
methoxymethane.
Soln. The higher boiling point of ethanol may be attributed to the presence
of intermolecular hydrogen bonding in it.
Due to such extensive bonding, more energy needs to be supplied to
ethanol to break these bonds and move it into the vapour phase.

Methoxymethane, an ether, lacks such hydrogen bonding and is therefore
a low boiling liquid.

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23. Give IUPAC names of the following ethers :
(i) (ii) CH3OCH2CH2Cl
(iii) O2N—C6H4—OCH3(p) (iv) CH3CH2CH2OCH3

H3 C CH3
(v) (vi)
OC2H5
OC2H5
Soln. (i) 1-Ethoxy-2-methylpropane (ii)
2-Chloro-1-methoxyethane
(iii) 4-Nitroanisole (iv) 1-Methoxypropane
(v) 1-Ethoxy-4, 4-dimethylcyclohexane (vi) Ethoxybenzene
24. Write the names of reagents and equations for the preparation of the
following ethers by Williamson’s synthesis :
(i) 1-Propoxypropane (ii) Ethoxybenzene
(iii) 2-Methyl-2-methoxypropane (iv) 1-Methoxyethane
Soln. (i)
CH3CH2CH2 – O – CH2CH2CH3 + NaBr

1-Propoxypropane
OCH2CH3
(ii) + NaBr
Ethoxybenzene
CH3 CH3
(iii) CH3 – C – ONa + CH3 – Br CH3 – C – OCH3 + NaBr
Bromomethane
CH3 CH3
2-Methyl-2-methoxypropane
(iv) CH3CH2ONa + CH3 – Br Heat CH3CH2 – O – CH3 + NaBr

Sodium ethoxide Bromomethane 1-Methoxyethane
25. Illustrate with examples the limitations of Williamson synthesis for the
preparation of certain types of ethers.
Soln. The main limitation of Williamson’s ether synthesis lies in its
unemployability for preparation of unsymmetrical ethers where the
compound contains secondary or tertiary alkyl groups.
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e.g., reaction between tert-butyl bromide and sodium methoxide yields
an alkene.
B
This is because the competing elimination reaction predominates over
SN2 and alkene is formed.
26. How is 1-propoxypropane synthesised from propan-1-ol? Write
mechanism of this reaction.
?
Soln. CH3CH2CH2OH (CH3CH2CH2)2O
Propanol Propoxypropane
This reaction can be brought about as:
CH3CH2CH2OH + SOCl2 CH3CH2CH2Cl + SO2 + HCl
Propanol
2CH3CH2CH2OH + 2Na CH3CH2CH2ONa + H2

metal
CH3CH2CH2Cl + CH3CH2CH2ONa (CH3CH2CH2)2O

1-Chloropropane Sodium Propoxypropane
propoxide
Mechanism : SN2 attack of propoxide on the halide
CH3CH2
CH2CH2CH2ONa + CH2 – Cl CH3CH2CH2 – O – CH2CH2CH3
27. Preparation of ethers by acid dehydration of secondary or tertiary
alcohols is not a suitable method. Give reason.
Soln. Consider the reaction between propan-2-ol molecules in the
presence of acid.
If an ether is to be formed, another alcohol molecule must carry out a

nucleophilic attack on the carbocation as
However, this does not happen because of

(a) the steric hindrance around the carbocation, and (b) bulky size of the
nucleophile which would further cause crowding.
As a result, the carbocation prefers to lose a proton and forms an alkene.
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H – CH2 CH2
–H+
HC CH
CH3 CH3
For the same reason 3° alcohols in the presence of acid do not form ethers
since 3° alcohols are even more sterically hindered than 2° alcohols.
28. Write the equation of the reaction of hydrogen iodide with:
(i) 1-propoxypropane (ii) methoxybenzene and
(iii) benzyl ethyl ether.
HI
Soln. (i) CH3CH2CH2 – O – CH2CH2CH3
373 K
1-Propoxypropane
Propan-1-ol
CH3CH2CH2 – OH + CH3CH2CH2 – I
Iodopropane
OCH3 OH
HI, 373 K
(ii) + CH3 – I
Iodomethane
Methoxybenzene Phenol
CH2 – O – C2H5 CH2I
HI, 373 K
(iii) + C2H5OH
Ethanol
Benzyl ethyl ether Benzyl iodide
29. Explain the fact that in aryl alkyl ethers (i) the alkoxy group activates
the benzene ring towards electrophilic substitution and (ii) it directs the
incoming substituents to ortho and para positions in benzene ring.
Soln. Consider the following resonance structures of aryl alkyl ethers :
:O – R O–R O–R O–R O–R
:
(I) (II) (III) (IV) (V)

(i) From the above structures we find that the presence of the OR group
has increased the electron density on the benzene ring and therefore the
ring is said to have been activated towards incoming electrophiles.
(ii) From structures (II), (III) and (IV) we find that and the electron density
has increased on C-2, C-4 and C-6, i.e., at the ortho and para positions. As a
result the electrophile (E ) attaches itself to these e– rich sites and the –OR
group is said to have directed the E to ortho and para positions.
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30. Write the mechanism of the reaction of HI with methoxymethane.
Soln. The reaction between methoxymethane and HI is :
CH3 – O – CH3 + HI CH3I + CH3OH
Step I : Generation of oxonium ion : Protonation of ether molecule
: :
O + H–I O + I
H3C CH3 H3C CH3
H
Step II : Nucleophilic attack on oxonium ion :
If excess HI is used, methanol formed above reacts with HI to form methyl

iodide.
31. Write equations of the following reactions :

(i) Friedel-Crafts reaction – alkylation of anisole.
(ii)Nitration of anisole.
(iii)
Bromination of anisole in ethanoic acid medium.
(iv)Friedel-Craft’s acetylation of anisole.
Soln. (i) Friedel-Crafts reaction (Alkylation) :
OCH3 OCH3 OCH3
Anhyd. AlCl3 CH3

+ CH3Cl +
CS2
2-Methoxytoluene
CH3
(Minor)
4-Methoxytoluene
(Major)
(ii) Nitration of anisole : Anisole reacts with a mixture of concentrated
sulphuric acid and nitric acid to yield a mixture of ortho and para
nitroanisole.
OCH3
Conc. H2SO4 +
Conc. HNO3
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(iii) Bromination

(iv) Friedel-Craft’s acetylation of anisole.
32. Show how would you synthesise the following alcohols from
appropriate alkenes.
CH3 OH
(i) OH (ii)
OH
(iii) (iv) OH
Soln. (i) or
H3O+ OH
(ii)
(iii) or
H3O+
(iv) OH
33. When 3-methylbutan-2-ol is treated with HBr, the following reaction
takes place:
Br
CH3—CH—CH—CH3 HBr CH3—C—CH2—CH3
CH3 OH CH3
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Give a mechanism for this reaction.
[Hint : The secondary carbocation formed in step II rearranges to a more
stable tertiary carbocation by a hydride ion shift from 3rd carbon atom.]
Soln. The given reaction is an example of carbocation rearrangement
which takes place by hydride shift. The mechanism for it is:
Step 1 : Formation of carbocation : Protonation of alcohol.
HBr H+ + Br
H3C – HC – HC – CH3 H3C – CH – CH – CH3 + H2O

CH3 OH2 CH3
2° Carbocation
Step 2 : 1,2-hydride shift : Formation of a more stable, 3° carbocation.
H
H3C – C – CH – CH3
CH3
I
Initially, a 2° carbocation (I) was formed. But, due to the higher stability
of its 3° counter part, the hydride shift takes place and the more stable
carbocation (II) is formed.
Step 3 : Attack of nucleophile : Generation of product
Br
CH3 – C – CH2 – CH3+ Br H3C – C – CH2 – CH3
CH3 CH3

1. Classify the following as primary, secondary and tertiary alcohols :
CH3
(i) CH3 – C – CH2OH (ii) H2 C CH – CH2OH
CH3
OH
(iii) CH3—CH2—CH2—OH (iv) CH – CH3
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CH3
CH2 – CH – CH3 CH CH – C – OH
(v) OH (vi) CH3
Soln. Primary alcohols : (i), (ii) and (iii)
Secondary alcohols : (iv) and (v)
Tertiary alcohols : (vi)
2. Identify allylic alcohols in the above examples.
Soln. Allylic alcohols : (ii) and (vi).
3. Name the following compounds according to IUPAC system.
(i) (ii)
OH
(iii) (iv)
Br
(v)
Soln. (i) 3-Chloromethyl-2-isopropylpentan-1-ol

(ii) 2, 5-Dimethylhexane-1,3-diol
(iii) 3-Bromocyclohexanol
(iv) Hex-1-en-3-ol
(v) 2-Bromo-3-methylbut-2-en-1-ol
4. Show how are the following alcohols prepared by the reaction of a
suitable Grignard reagent on methanal.
CH2OH
(i) CH3 – CH – CH2OH (ii)

CH3 OMgBr
H2 O
Soln. (i) CH3 – CH – MgBr + HCHO CH3 – CH – CH2
CH3 CH3
CH3 – CH – CH2OH + Mg(OH)Br
CH3
MgBr CH2OMgBr CH2OH
(ii) HCHO +
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5. Write structures of the products of the following reactions :
O
H O/H+ CH2 – C – OCH3
(i) CH3 – CH CH2 2 (ii) NaBH4
O
NaBH4
(iii) CH3 – CH2 – CH – CHO
CH3
OH
CH2 – C – OCH3
Soln. (i) CH3 – CH – CH3 (ii)
O
OH
(iii)
6. Give structures of the products you would expect when each of the
following alcohol reacts with (a) HCl – ZnCl2 (b) HBr and (c) SOCl2.
(i) Butan-1-ol (ii) 2-Methylbutan-2-ol
Soln.
Reagent HCl – ZnCl2 HBr SOCl2
Alcohol
CH3CH2CH2CH2OH No reaction at CH3(CH2)2CH2Br CH3(CH2)2CH2Cl
Butan-1-ol room
temperature.
CH3 CH3 CH3 CH3
H3CCH2 C CH3 H3CCH2 C CH3 H3CCH2 C CH3 H3CCH2 C CH3
OH Cl Br Cl
2-Methylbutan-2-ol (forms instantly)
7. Predict the major product of acid catalysed dehydration of

(i) 1-methylcyclohexanol and (ii) butan-1-ol
Soln. (i)
H+/
(ii) CH3 – CH2 – CH2 – CH2 – OH
2
8. Ortho and para nitrophenols are more acidic than phenol. Draw the
resonance structures of the corresponding phenoxide ions.
Soln. The attachment of the –NO2 group to the phenol molecule at o- and
p-positions decreases the electron density on oxygen atom. This causes
the oxygen atom to pull the bond pair of electrons of the O – H bond
towards itself thereby facilitating the release of H as H+.
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The resonance structures of the phenoxide ions are :
9. Write the equations involved in the following reactions :

(i) Reimer-Tiemann reaction (ii) Kolbe’s reaction
Soln. (i) Reimer-Tiemann reaction
(ii) Kolbe’s reaction

OH ONa OH
NaOH (i) CO2 COOH
(ii) H+

Phenol Salicylic acid
10. Write the reactions of Williamson synthesis of 2-ethoxy-3-
methylpentane starting from ethanol and 3-methylpentan-2-ol.
Soln.
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11. Which of the following is an appropriate set of reactants for the
preparation of 1-methoxy-4-nitrobenzene and why?
Br ONa
(i) + CH3 ONa (ii) + CH3Br
NO2 NO2
Soln. Set (ii) is more appropriate for preparation of the said compound.
In set (i) the CH3O acts as a nucleophile. But, the presence of bulky
NO2 group prevents the nucleophilic attack.
In set (ii) nucleophile, O2N O attacks CH3Br and the desired
product O2N OCH3 is formed.
12. Predict the products of the following reactions :

(i) CH3 – CH2 – CH2 – O – CH3 + HBr
OC2H5
(ii) + HBr
OC2H5
Conc. H2SO4 +
(iii)
Conc. HNO3
HI
(iv) (CH3)3C – OC2H5
Soln. (i) CH3CH2CH2OH + CH3Br

OH
(ii) + C2H5Br
OC2H5 OC2H5
(iii) +
NO2 O2N
(iv) (CH3)3C – I + C2H5OH
a
b
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Chapter 12
Aldehydes, Ketones and
Carboxylic Acids
Summary
Aldehydes, ketones and carboxylic acids are some of the important classes of
organic compounds containing carbonyl group. These are highly polar molecules.
Therefore, they boil at higher temperatures than the hydrocarbons and weakly
polar compounds such as ethers of comparable molecular masses. The lower
members are more soluble in water because they form hydrogen bonds with water.
The higher members, because of large size of hydrophobic chain of carbon atoms,
are insoluble in water but soluble in common organic solvents. Aldehydes are
prepared by dehydrogenation or controlled oxidation of primary alcohols and
controlled or selective reduction of acyl halides. Aromatic aldehydes may also be
prepared by oxidation of (i) methylbenzene with chromyl chloride or CrO3 in the
presence of acetic anhydride, (ii) formylation of arenes with carbon monoxide and
hydrochloric acid in the presence of anhydrous aluminium chloride, and (iii) cuprous
chloride or by hydrolysis of benzal chloride. Ketones are prepared by oxidation of
secondary alcohols and hydration of alkynes. Ketones are also prepared by reaction
of acyl chloride with dialkylcadmium. A good method for the preparation of aromatic
ketones is the Friedel-Crafts acylation of aromatic hydrocarbons with acyl chlorides
or anhydrides. Both aldehydes and ketones can be prepared by ozonolysis of alkenes.
Aldehydes and ketones undergo nucleophilic addition reactions onto the carbonyl
group with a number of nucleophiles such as, HCN, NaHSO3, alcohols (or diols),
ammonia derivatives, and Grignard reagents. The α-hydrogens in aldehydes and

ketones are acidic. Therefore, aldehydes and ketones having at least one α-hydrogen,
undergo Aldol condensation in the presence of a base to give α-hydroxyaldehydes
(aldol) and α-hydroxyketones(ketol), respectively. Aldehydes having no α-hydrogen
undergo Cannizzaro reaction in the presence of concentrated alkali. Aldehydes
and ketones are reduced to alcohols with NaBH4, LiAlH4, or by catalytic hydrogenation.
The carbonyl group of aldehydes and ketones can be reduced to a methylene group
by Clemmensen reduction or Wolff-Kishner reduction. Aldehydes are easily
oxidised to carboxylic acids by mild oxidising reagents such as Tollens’ reagent and
Fehling’s reagent. These oxidation reactions are used to distinguish aldehydes from
ketones. Carboxylic acids are prepared by the oxidation of primary alcohols, aldehydes
and alkenes by hydrolysis of nitriles, and by treatment of Grignard reagents with
carbon dioxide. Aromatic carboxylic acids are also prepared by side-chain oxidation
of alkylbenzenes. Carboxylic acids are considerably more acidic than alcohols and
most of simple phenols. Carboxylic acids are reduced to primary alcohols with LiAlH4,
or better with diborane in ether solution and also undergo α-halogenation with Cl2
and Br2 in the presence of red phosphorus (Hell-Volhard Zelinsky reaction).
Methanal, ethanal, propanone, benzaldehyde, formic acid, acetic acid and benzoic
acid are highly useful compounds in industry.
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1. What is meant by the following terms? Give an example of the reaction

in each case.
(i) Cyanohydrin (ii) Acetal (iii) Semicarbazone

(iv) Aldol (v) Hemiacetal (vi) Oxime
(vii) Ketal (viii) Imine
(ix) 2,4-DNP derivative (x) Schiff’s base
Soln. (i) Carbonyl compounds in the presence of an alkali, react with

HCN to form an addition product called cyanohydrin.
– –
HCN + OH H2O + CN
–
OH
O– H+ CN
O + HCN C C
CN OH
Tetrahedral Cyanohydrin
intermediate
(ii) Acetals are gem-dialkoxy compounds formed when aldehydes react

with monohydric alcohols in the presence of dry HCl gas.
ROH, HCl gas

OR ROH OR
H3C CHO H3C–CH CH3 CH + H2O
H+
OH OR
Hemiacetal Acetal
(iii) Semicarbazone is formed by the reaction between carbonyl compounds

and semicarbazide.
O O
O + H2 N NH NH2 N NH NH2
Semicarbazide Semicarbazone
(iv) b-Hydroxy aldehydes are called aldol. Aldehydes and ketones
containing at least one a-H atom undergo a reaction in the presence of
dilute alkali to form aldol compounds. e.g.,
(v) Hemiacetals are gem-alkoxyalcohols which are produced from the

addition of one molecule of monohydric alcohol to an aldehyde in the
presence of HCl gas.
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H3C Dry HCl(g) CH3 OH
C O+H OCH3 C
H H OCH3
Hemiacetal
(vi) Oximes are formed by reaction between aldehydes or ketones and
hydroxylamine. The reaction is carried out in mildly acidic condition.
H3 C
O + H2N OH
H Hydroxylamine
(vii) Ketals are cyclic products formed by the reaction of ketones with
ethylene glycol in the presence of dry HCl gas.
R HO CH2 R O CH2
dryHCl(g)
C O+ C + H2 O
R HO CH2 dil HCl R O CH2
Ethylene glycol Ketal
(viii) Imines are formed when carbonyl compounds react with ammonia
derivative.
C O + H2N Z N Z + H2O
Carbonyl Imine
compound
Z = R, , –NH2, –OH, etc.
(ix) 2, 4-DNP derivatives are formed when 2, 4-dinitrophenylhydrazine

reacts with aldehydes or ketones.
pH 3.5 H
O + H2NHN NO2 N N NO2
Aldehyde
or ketone O 2N O 2N
2, 4-DNP
DNP-derivative
(x) Reaction between aldehydes or ketones with 1° aliphatic or aromatic
amines yields a Schiff’s base.
very dil H +
R CHO + H2N R′ RCH N R′ + H2O
Schiff’s base
2. Name the following compounds according to IUPAC system of
nomenclature :
(i) CH3CH(CH3)CH2CH2CHO (ii) CH3CH2COCH(C2H5)CH2CH2Cl
(iii) CH3CH CHCHO (iv) CH3COCH2COCH3
(v) CH3CH(CH3)CH2C(CH3)2COCH3 (vi) (CH3)3CCH2COOH
(vii) OHCC6H4CHO-p
Soln. (i) 4-Methylpentanal (ii) 6-Chloro-4-ethylhexan-3-one
(iii) But-2-en-1-al (iv) Pentane-2, 4-dione
(v) 3, 3, 5-Trimethylhexan-2-one (vi) 3, 3-Dimethylbutanoic acid
(vii) Benzene-1, 4-dicarbaldehyde
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3. Draw the structures of the following compounds.
(i) 3-Methylbutanal (ii) p-Nitropropiophenone
(iii) p-Methylbenzaldehyde (iv) 4-Methylpent-3-en-2-one
(v) 4-Chloropentan-2-one (vi) 3-Bromo-4-phenylpentanoic acid
(vii) p, p′-Dihydroxybenzophenone (viii) Hex-2-en-4-ynoic acid
4 3 2 1
Soln. (i) CH3 CH CH2 CHO (ii) O 2N COCH2CH3
CH3
1 2 3 4 5
(iii) CH CHO (iv) CH3 C CH C CH3
3
1 2 3 4 5
O CH3
5 3 2
4 1
(v) CH3 C CH2 CH CH3 (vi) CH3CH CHCH2COOH
O Cl C6H5Br
O
(vii) HO C OH
6 5 4 3 2 1
(viii) CH3 C C CH CH COOH
4. Write the IUPAC names of the following ketones and aldehydes.
Wherever possible, give also common names.
(i) CH3CO(CH2)4CH3 (ii) CH3CH2CHBrCH2CH(CH3)CHO
(iii) CH3(CH2)5CHO (iv) Ph–CH=CH–CHO
(v) CHO (vi) PhCOPh
Soln.
IUPAC name Common name
(i) Heptan-2-one Methyl-n-pentyl ketone
(ii) 4-Bromo-2-methyl hexanal g-Bromo-a-methyl caproaldehyde
(iii) Heptanal –
(iv) 3-Phenylprop-2-enal b-Phenylacrolein
(v) Cyclopentane carbaldehyde –
(vi) Diphenylmethanone Benzophenone
5. Draw structures of the following derivatives.

(i) The 2,4-dinitrophenylhydrazone of benzaldehyde
(ii) Cyclopropanone oxime
(iii) Acetaldehydedimethylacetal
(iv) The semicarbazone of cyclobutanone
(v) The ethylene ketal of hexan-3-one
(vi) The methyl hemiacetal of formaldehyde
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NO2
Soln. (i) CH NNH NO2
NOH CH3 OCH3

(ii) (iii) C
H OCH3
CH2 CH2
O O O
(iv) NNH C NH2 (v) CH3 CH2 C CH2 CH2 CH3
H OH
(vi) C
H OCH3
6. Predict the products formed when cyclohexanecarbaldehyde reacts
with following reagents.
(i) PhMgBr and then H3O+ (ii) Tollens’ reagent
(iii) Semicarbazide and weak acid (iv) Excess ethanol and acid
(v) Zinc amalgam and dilute hydrochloric acid
Soln.
OMgBr OH
CH O C H3O+
C
Ph – MgBr H H
(i) Ph Hydrolysis Ph
Dry ether
Cyclohexanecarbaldehyde Cyclohexylphenylcarbinol
CH O COO–
+2 [Ag(NH3)2]+ + 3OH– + 2Ag + 4NH3 + 2H2O
(ii)
Tollens' reagent Silver
Cyclohexane mirror
carboxylate ion
O
CH O O CH NNHCNH2 + H2O
weak acid
(iii) + H2NNHCNH2
Cyclohexanecarbaldehyde
semicarbazone
OC2H5
CH O H OC2H5 C
H+ OC2H5 + H2O
(iv) +
H OC2H5 H
Cyclohexanecarbaldehyde
diethylacetal
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CHO CH3
Zn/Hg–HCl
(v)
(Clemmensen reduction)
Methylcyclohexane
7. Which of the following compounds would undergo aldol condensation,
which the Cannizzaro reaction and which neither? Write the structures of
the expected products of aldol condensation and Cannizzaro reaction.
(i) Methanal (ii) 2-Methylpentanal
(iii) Benzaldehyde (iv) Benzophenone
(v) Cyclohexanone (vi) 1-Phenylpropanone
(vii) Phenylacetaldehyde (viii) Butan-1-ol
(ix) 2,2-Dimethylbutanal
Soln. Aldol condensation is shown by those aldehydes or ketones which
have at least one a-H atom while Cannizzaro reaction is undergone by
aldehydes that have no a-H atom.
Therefore, the given compounds can be classified as:
Aldol Condensation Cannizzaro Condensation Neither
2-Methylpentanal Methanal Butan-1-ol
Cyclohexanone Benzaldehyde Benzophenone
1-Phenylpropanone 2, 2-Dimelthylbutanal
Phenylacetaldehyde
The aldol reactions undergone are :
–
dil OH
(ii) 2CH3 (CH2)2 CH CHO
CH3
2-Methylpentanal
CH3 CH3
CH3(CH2)2 C CH C (CH2)2 CH3

H OH CHO
O
–
dil OH
(v) 2 O
OH
Cyclohexanone
– OH CH3
dil OH
(vi) 2 COCH2CH3 C
1-Phenylpropanone H3C CH2 H O
– OH CHO
(vii) 2 CH2CHO dil OH
CH2
Phenyl acetaldehyde H H
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Cannizzaro reactions :
–
Conc. OH
(i) 2HCHO H3COH + HCOONa
Methanal
–
Conc. OH COONa
(iii) 2 CHO CH2OH +
Benzaldehyde
CH3
–
(ix) H3CCH2 C CHO Conc. OH
CH3
2, 2-Dimethylbutanal
CH3 CH3
H3CCH2 COONa + H3CCH2 CH2OH
CH3 CH3
8. How will you convert ethanal into the following compounds?
(i) Butane-1,3-diol (ii) But-2-enal (iii) But-2-enoic acid
Soln. (i)
(i) dil. NaOH

(ii) 2CH3CHO CH3CH CHCHO
(ii) H+, 
Ethanal But-2-enal
aq. NaoH [Ag(NH3)2]+OH–

2CH3CHO 
CH3CH CHCHO Tollens' reagent CH3CH CHCO2H
But-2-enoic acid
9. Write structural formulas and names of four possible aldol condensation
products from propanal and butanal. In each case, indicate which aldehyde
acts as nucleophile and which as an electrophile
Soln. The possible products of aldol condensation from propanal and
butanal are
OHCH3
–
dil OH
(i) 2CH3CH2CHO H3CCH2CHCHCHO
Propanal 3-Hydroxy-2-methylpentanal
OH CH2CH3
–
dil OH
(ii) 2CH3(CH2)2CHO H3C(CH2)2 CH CHCHO
Butanal 2-Ethyl-3-hydroxyhexanal
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(iii) When butanal acts as an electrophile and propanal as nucleophile :
–
OH
OH
H3C (CH2)2CHO + CH3CH2CHO H3C(CH2)2CHCHCHO
Butanal Propanal
CH3
3-Hydroxy-2-methylhexanal
(iv) When propanal serves as an electrophile and butanal as nucleophile :

OH C2H5
CH3CH2CHO + CH3(CH2)2CHO H3CCH2CH CHCHO
2-Ethyl-3-hydroxypentanal
10. An organic compound with the molecular formula C9H10O forms 2,4-DNP
derivative, reduces Tollens’ reagent and undergoes Cannizzaro reaction.
On vigorous oxidation, it gives 1, 2-benzenedicarboxylic acid. Identify the
compound.
Soln. (i) It is given that the compound reduces Tollens’ reagent. This proves
that the compound is an aldehyde. Further, the fact that it undergoes
Cannizzaro reaction shows that it lacks an a-H atom.
(ii) On oxidation it yields 1,2‑benzenedicarboxylic acid. This shows that it
is an o-substituted benzaldehyde.
The only possible structure for the compound is :
CHO
C2H5

The reactions undergone are :
11. An organic compound (A) (molecular formula C8H16O2) was hydrolysed

with dilute sulphuric acid to give a carboxylic acid (B) and an alcohol (C).
Oxidation of (C) with chromic acid produced (B). (C) on dehydration gives
but-1-ene. Write equations for the reactions involved.
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Soln. Given :
(i) Compound (A) upon hydrolysis produces one molecule each of a

carboxylic acid and alcohol. This indicates that (A) is an ester.
(ii) (C) upon oxidation produces (B) proving that (C) and (B) have same
no. of carbon atoms.
(iii) (C) on dehydration produces but-1-ene. This, coupled with the fact
that it gives a carboxylic acid (B) on oxidation shows that (C) is a primary
alcohol.
\ (C) is CH3 CH2 CH2 CH2OH (B) is H3C (CH2)2 COOH
Butan-1-ol Butanoic acid
and hence, (A) is
O
H3C (CH2)2 C O (CH2)3 CH3
Butyl butanaote
The reactions involved may be summarized as :
O
dil H +
CH3(CH2)2 C O (CH2)3CH3 CH3(CH2)2 COOH
(A) (B)
+ CH3(CH2)2CH2OH
CrO3/H+
(C) (B) (C)
H +/
CH3CH2CH CH2
But-1-ene
12. Arrange the following compounds in increasing order of their property

as indicated :
(i) Acetaldehyde, Acetone, Di-tert-butyl ketone, Methyl tert-butyl ketone
(reactivity towards HCN)
(ii) CH3CH2CH(Br)COOH, CH3CH(Br)CH2COOH, (CH3)2CHCOOH,
CH3CH2CH2COOH (acid strength)
(iii) Benzoic acid, 4-Nitrobenzoic acid, 3,4‑Dinitrobenzoic acid,
4-Methoxybenzoic acid (acid strength)
Soln. (i) The reaction between carbonyl compounds and HCN proceeds
via the nucleophilic attack of CN– on carbonyl carbon. Such an attack takes
place faster if the carbonyl carbon is not attached to large alkyl groups.
Less is the steric hindrance, more reactive is the compound.
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\ The order is :
O O O O
(CH3)3C C(CH3)3 < (H3C)3C CH3 < CH3 CH3 < CH3 H
Di-tert-butyl ketone Methyl-tert-butyl Acetone Acetaldehyde
ketone
(ii) The presence of any electron withdrawing group or electronegative
atom in carboxylic acid molecule increases the acidic strength of the acid.
Moreover, the acidity decreases if the atom/group is bonded further off
the a-carbon.
Therefore, the acid strength is :
(CH3)2CHCOOH < CH3(CH2)2COOH
I II
Br Br
< CH3CHCH2COOH < CH3CH2CHCOOH
III IV
Between I and II the higher acidity of II is due to lesser number of – CH3
groups on the a-carbon. –CH3 group increases the electron density by +I
effect on a-carbon which in turn exerts the same effect on COOH group
and hinders release of H+.
(iii) In benzoic acid, the attachment of electron withdrawing groups
(EWG) on the benzene ring makes the O—H bond of COOH group polar
and H is lost as H+.
Therefore, the order is,
COOH COOH COOH COOH
< < <

NO2
Benzoic acid NO2 NO2
OCH3
4-Methoxybenzoic acid 4-Nitrobenzoic acid 3, 4-Dinitrobenzoic acid
13. Give simple chemical tests to distinguish between the following pairs
of compounds.
(i) Propanal and Propanone
(ii) Acetophenone and Benzophenone
(iii) Phenol and Benzoic acid
(iv) Benzoic acid and Ethyl benzoate
(v) Pentan-2-one and Pentan-3-one
(vi) Benzaldehyde and Acetophenone
(vii) Ethanal and Propanal
Soln. The given set of compounds may be distinguish by the following
reaction.
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Compound Compound Compound
→ I II
Reagent ↓
Ammoniacal CH3—CH2—CHO
silver nitrate CH3CH2COO– + 2Ag +
2[Ag(NH3)2]+ 2H2O + 4NH3
(Tollens’ reagent)
No reaction
NaOI O
COONa
+ CHI3 Benzophenone
Yellow
Acetophenone ppt. No reaction
NaHCO3 COONa
Phenol Benzoic acid

+ H2O + CO2
Effervescence
NaHCO3
gives brisk
effervescence.
NaOI
CH3CH2CCH2CH3
No reaction gives iodoform test.
NaOI
gives iodoform test.

NaOI CH3CHO CH3CH2CHO No
Ethanal Propanal reaction
gives iodoform test.
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14. How will you prepare the following compounds from benzene? You
may use any inorganic reagent and any organic reagent having not more
than one carbon atom
(i) Methyl benzoate (ii) m-Nitrobenzoic acid
(iii) p-Nitrobenzoic acid (iv) Phenylacetic acid
(v) p-Nitrobenzaldehyde
O
C OCH3
?
Soln. (i)
Benzene Methyl benzoate

CH3 COOH
–
CH3Cl/AlCl3 KMnO4/OH Esterification
CH3OH(excess) + conc H2SO4, 
COOCH3
Methyl benzoate
COOH
?
(ii)
NO2
Benzene m-Nitrobenzoic acid
COOH COOH
as done Conc. HNO3
in solution (i) + Conc. H2SO4 NO2
Benzene m-Nitrobenzoic acid
COOH
?
(iii)
Benzene
NO2
p-Nitrobenzoic acid
CH3 CH3 CH3
CH3Cl/AlCl3 Conc. HNO3 NO2
+
+ Conc.H2SO4/
Benzene Toluene
NO2
p-Nitrotoluene
||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
CH3 COOH
(i) Alk.KMnO4
(ii) dil H +
NO2 NO2
(Separated from o-isomer p-Nitrobenzoic acid
by distillation)
CH2 COOH
?
(iv)
Benzene Phenylacetic acid

CH3 CH2Br CH2CN
CH3Cl Br2,  or h Alc. KCN, 

AlCl3
Benzene Toluene CH2COOH
H3O +
CHO
?
(v)
NO2
p-nitrobenzaldehyde
CH3 CHO
As in (solution iii) (i) CrO3/(CH3CO)2O

(ii) H3O+
Benzene
NO2 NO2
p-Nitrobenzaldehyde
15. How will you bring about the following conversions in not more than
two steps?
(i) Propanone to Propene
(ii) Benzoic acid to Benzaldehyde
(iii) Ethanol to 3-Hydroxybutanal
(iv) Benzene to m-Nitroacetophenone
(v) Benzaldehyde to Benzophenone
(vi) Bromobenzene to 1-Phenylethanol
(vii) Benzaldehyde to 3-Phenylpropan-1-ol
(viii) Benzaldehyde to a-Hydroxyphenylacetic acid
(ix) Benzoic acid to m-Nitrobenzyl alcohol
||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
Soln. (i) Propanone to Propene :
H2/Ni Conc. H2SO4
CH3 C CH3 CH3 CH CH3 CH3 CH CH2
443 K Propene
O OH
Propanone 2-Propanol
(ii) Benzoic acid to Benzaldehyde :
SOCl2 H2/Pd-BaSO4
COOH COCl CHO
–SO2, –HCl boiling xylene
Benzoic acid Benzoyl chloride Benzaldehyde
(iii) Ethanol to 3-Hydroxybutanal :
Mild oxidation Dil.OH –
CH3CH2OH CH3CHO Warm
CH3CH(OH)CH2CHO
KMnO4/dil. H2SO4
Ethanol Acetaldehyde 3-Hydroxybutanal
(Two molecules)
(iv) Benzene to m-Nitroacetophenone :
COCH3 Conc. HNO + COCH3
(CH CO) O/ 3 2 3
anhyd. AlCl3 Conc. H2SO4
Nitration NO2
(Friedel Craft's
Benzene acylation) Acetophenone m-Nitroacetophenone
(v) Benzaldehyde to Benzophenone :

KMnO4 573 K
CHO COOH + HOOC
(O) MnO
(Two molecules)
Benzaldehyde
O
C
Benzophenone
(vi) Bromobenzene to 1-Phenylethanol
Mg (i) CH3CHO
Br MgBr CH CH3
dry ether (ii) H3O+
Bromobenzene OH
1-Phenylethanol
(vii) Benzaldehyde to 3-Phenylpropan-1-ol :
||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
(viii) Benzaldehyde to a-Hydroxyphenylacetic acid :
(ix) Benzoic acid to m-Nitrobenzyl alcohol :

COOH COOH CH2 OH
Conc. HNO3 (i) LiAlH4
+ Conc. H2SO4 NO2 (ii) H2O/H + NO2

Benzoic acid 
m-Nitrobenzoic acid m-Nitrobenzyl
alcohol
16. Describe the following :
(i) Acetylation (ii) Cannizzaro reaction
(iii) Cross-aldol condensation (iv) Decarboxylation
O
Soln. (i) Acetylation : Acetylation is the process of introducing an R C
group in compounds that contain a replaceable hydrogen atom. The best
example of acetylation is Friedel-Crafts acylation reaction where RCO
group is introduced on the benzene ring.
Reagents employed for the purpose of acylation are acylchloride, acid
anhydride etc. e.g., Friedel‑crafts acylation :
COCH3
Anhyd. Pyridine
+ CH3COCl ; CH3COCl + C2H5OH
Acetyl chloride AlCl3
Acetophenone CH3COOC2H5 + HCl
Ethyl acetate
(ii) Cannizzaro reaction : Cannizzaro reaction is undergone by aldehydes
or ketones that lack an a-hydrogen atom. Such carbonyl compounds in the
presence of conc. NaOH and heat undergo disproportionation reaction to
produce the corresponding carboxylate ion and alcohol.
–
Conc. OH – +
e.g., CHO  CH2OH + COONa
Benzaldehyde Benzyl alcohol Sodium benzoate
(No -H)
(iii) Cross-aldol condensation : Aldol condensation is the reaction that
takes place, when aldehydes or ketones with at least one a-H atom react in
the presence of dilute alkali to produce b-hydroxy aldehydes or ketones.
||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
When two different aldehydes or ketones are taken, it gives a mixture of
products. Such a reaction is called cross-aldol condensation.
1. NaOH CH3CHO
+
2. Heat
CH3CH2CHO
CH3 CH CH CHO + CH3CH2 CH C CHO
But-2-enal
From two molecules of ethanal CH3
2-Methylpent-2-enal
From two molecules of propanal
Simple or self aldol products

CH3 CH C CHO + CH3CH2 CH CHCHO
CH3
2-Methylbut-2-enal Pent-2-enal
From one molecule of ethanal and one molecule of propanal
Cross aldol products
Ketones can also be used as one component in the cross aldol reactions
COCH3
(iv) Decarboxylation : Carboxylic acids lose carbon dioxide to form

hydrocarbons when their sodium salts are heated with sodalime (NaOH
and CaO in the ratio of 3 : 1). The reaction is
NaOH + CaO
R COONa R H + Na2CO3
Heat
17. Complete each synthesis by giving missing starting material, reagents
or products
CH2CH3 COOH
KMnO4 SOCl2
(i) (ii)
KOH, heat heat
COOH
H2NCONHNH2
(iii) C6H5CHO
O
C
(iv)
O CHO
[Ag(NH3)2]+ NaCN/HCl
(v) (vi)
CHO COOH
dil. NaOH
(vii) C6H5CHO + CH3CH2CHO
||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
(i) NaBH4 CrO3
(viii) CH3COCH2COOC2H5 (ix) OH
(ii) H +
(i) O3
(x) CH2 CHO (xi) 2 O
(ii) Zn-H2O
CH2CH3
COOK
Soln. (i) KMnO4
KOH, 
(ii)
O
O
N NH NH2
H2 N NHNH2
(iii) CHO H + H2O
O
O
Cl
(iv) + HCl
+ Anhyd. AlCl3
O O
[Ag(NH3)2] +
(v) + Ag
CHO COO–
OH
CHO CH CN
NaCN/HCl
(vi)
COOH COOH
dil. OH– CH3

(vii) CHO + CH3CH2CHO CH C
CHO
(Claisen-Schmidt reaction)
O OH
O
(i) NaBH4 CH
(viii) H3C CH2 C OC2H5 + H3C CH2COOC2H5
(ii) H
CrO3
(ix) OH O
||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
–
(BH3)2/THF H2O2/OH/H2O
(x) CH2 CH2 B
3
Pyridine
chlorochromate
CHO CH2OH
(i) O3
(xi) 2 O
(ii) Zn – H2O
18. Give plausible explanation for each of the following:

(i) Cyclohexanone forms cyanohydrin in good yield but 2,2,6
trimethylcyclohexanone does not.
(ii) There are two —NH2 groups in semicarbazide. However, only one is
involved in the formation of semicarbazones.
(iii) During the preparation of esters from a carboxylic acid and an alcohol
in the presence of an acid catalyst, the water or the ester should be removed
as soon as it is formed.
Soln. (i) Consider the following reactions :
O
HO CN
HCN/OH
(a)
(I)
Cyclohexanone
O
H3C CH3 –
HCN/OH
(b) CH3 No reaction
(II)
Reaction (a) is an example of cyanohydrin formation by the nucleophilic
attack of cyanide ion on the carbonyl carbon. In cyclohexanone, this attack
takes place easily and cyanohydrin is formed. But in II, attack of the Nu–
is sterically hindered due to the presence of the three methyl groups. As a
result, the reaction does not occur.
(ii) Semicarbazide has the following resonance structures arising due to
the electron withdrawing nature of the O atom.
||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
From the above structures we find that the lone pair of electrons on N atoms
on either side of C O group are delocalised, involved in resonance.
Therefore, they are not available for carrying out the nucleophilic attack
on the aldehyde or ketone.
But, the –NH2 (terminal one) is intact, i.e. it is not involved in resonance
and thus its, lone pair is available for attack on carbonyl compound.
This is why the semicarbazone is formed through this N atom only.
H+
(iii) RCOOH + ROH RCOOR + H2O
acid alcohol ester
The esterification reaction is a reversible reaction. If water and the ester
are allowed to remain in the reaction mixture the hydrolysis of the ester
would take place. Hence, water or ester should be removed as soon as it
is formed.
19. An organic compound contains 69.77% carbon, 11.63% hydrogen
and rest, oxygen. The molecular mass of the compound is 86. It does not
reduce Tollens’ reagent but forms an addition compound with sodium
hydrogensulphite and give positive iodoform test. On vigorous oxidation
it gives ethanoic and propanoic acid. Write the possible structure of the
compound.
Soln. (a) The given compound does not reduce Tollens’ reagent which
implies that it is not an aldehyde.
O
(b) Positive iodoform test proves that it has a CH3 C group.
(c) The oxidation products are indicative of the presence of 5 carbon
atoms.
To find the exact molecular formula
%C = 69.77%, %H = 11.63%, %O = 100 – (69.77 + 11.63) = 18.6 %
69.77 11.63 18.6
C:H:O= : :
12 1 16
The structure based on inferences a, b and c is
O
H3C C CH2CH2CH3
Reactions involved are :
O –+
OH SO3Na
H3C C (CH2)2CH3+ NaHSO3 C
CH3 (CH2)2CH3
Addition compound
O
Iodoform reaction
CH3 C (CH2)2CH3 + 3I2 + 4NaOH
CHI3 + CH3CH2CH2COONa + 3NaI + 3H2O
Yellow
||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
O
(O)
CH3 C (CH2)2CH3 CH3COOH + CH3CH2COOH
Ethanoic acid Propionic acid
20. Although phenoxide ion has more number of resonating structures

than carboxylate ion, carboxylic acid is a stronger acid than phenol. Why?
Soln. (i) Phenoxide ion has the following resonating structures :
–
O– O O O O O
– –
–
(I) (II) (III) (IV) (V)
Carboxylate ion has the following resonance structures.
O O– O
R C R C R – C
–
O O O
A B
(ii) Phenoxide ion is a resonance hybrid of structures I to V, where each
structure has a contribution of 20% in the resonance hybrid. On the other
hand, each of the two contributing structures of carboxylate ion contribute
50% towards the resonance hybrid. Therefore, the carboxylate ion tends
to be more stable than the phenoxide ion and hence has higher acidity.
(iii) The negative charge that rests on the electronegative O atom in
carboxylate ion. We know that the presence of negative charge on an
electronegative atom makes the ion more stable. For the same reason
RCOO– is more stable than the phenoxide ion where the oxygen has no
negative charge on it. For the above two reasons carboxylate ion is more
stable and has higher acidity than phenol.

1. Write the structures of the following compounds.
(i) a-Methoxypropionaldehyde (ii) 3-Hydroxybutanal
(iii) 2-Hydroxycyclopentanecarbaldehyde
(iv) 4-Oxopentanal (v) Di-sec.butyl ketone
(vi) 4-Fluoroacetophenone
Soln. (i) (ii)

||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
(iii) CHO (iv)
OH
O
(v) (vi) F C – CH3
2. Write the structures of the products of the following reactions :

O
C Anhyd.AlCl3
(i) + C2H5 Cl CS2
(ii) (C6H5CH2)2Cd + 2CH3COCl

CH3
Hg2+, H 1. CrO2Cl2
2SO4
(iii) (iv) 2. H3O+
NO2
O O
C CH2 – C – CH3
Soln. (i) C2H5 (ii)
O
CHO
C
(iii) H3C CH3 (iv)
NO2
3. Arrange the following compounds in increasing order of their boiling
points.
CH3CHO, CH3CH2OH, CH3OCH3, CH3CH2CH3
Soln. CH3CH2CH3 < CH3OCH3 < CH3CHO < CH3CH2OH
4. Arrange the following compounds in increasing order of their reactivity

in nucleophilic addition reactions.
(i) Ethanal, Propanal, Propanone, Butanone.
(ii) Benzaldehyde, p-Tolualdehyde, p-Nitrobenzaldehyde, Acetophenone.
Hint : Consider steric effect and electronic effect.
Soln. (i) Butanone < Propanone < Propanal < Ethanal
(ii) Acetophenone < p-Tolualdehyde, Benzaldehyde <
p-Nitrobenzaldehyde.
||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
5. Predict the products of the following reactions:
O
H+
(i) + HO – NH2
O2N
O
(ii) + NH2 – NH NO2
(iii)
O
C
(iv) CH3 H+
+ CH3CH2NH2
N – OH
Soln. (i)
O 2N
NNH NO2
(ii)
O
(iii)
H3 C
C N – CH2CH3
(iv)
6. Give the IUPAC names of the following compounds :

(i) PhCH2CH2COOH (ii) (CH3)2C CHCOOH
CH3 NO2
COOH COOH
(iii) (iv)
O2N NO2
Soln. (i) 3-Phenylpropanoic acid
(ii) 3-Methylbut-2-enoic acid
(iii) 2-Methylcyclopentanecarboxylic acid
(iv) 2,4,6-Trinitrobenzoic acid
7. Show how each of the following compounds can be converted to

benzoic acid.
(i) Ethylbenzene (ii) Acetophenone
(iii) Bromobenzene (iv) Phenylethene (Styrene)
||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
CH2CH3 COOK COOH
KMnO4-KOH H3O+
Soln. (i)
COCH3 COOK COOH

KMnO4-KOH H3O+
(ii)
O
COOH
Br MgBr C OMgBr
Mg O C O HOH
(iii)
COOK COOH
CH CH2
(iv) KMnO4-KOH H3O+
+ HCOOK
8. Which acid of each pair shown here would you expect to be stronger ?
(i) CH3CO2H or CH2FCO2H
(ii) CH2FCO2H or CH2ClCO2H
(iii) CH2FCH2CH2CO2H or CH3CHFCH2CO2H
(iv) F3C COOH or H3C COOH
Soln. (i) H2CFCOOH will be stronger of the two. The presence of

electronegative F atom at the a-C causes electron withdrawal from the
COOH and facilitates the release of H+.
(ii) CH2FCO2H is a stronger acid for the same reason as stated above. F is
more electronegative than Cl, so it withdraws electrons from the carboxyl
group to a greater extent.
(iii) CH3CHFCH2COOH is stronger. Although both the given acids have F
atom in them, it is the proximity of F in CH3CHFCH2COOH to the COOH
group which makes it more acidic.
(iv) F3C COOH is more acidic due to the presence of electron
withdrawing CF3 group in it.
||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
Chapter 13
Amines
Summary
Amines can be considered as derivatives of ammonia obtained by replacement of
hydrogen atoms with alkyl or aryl groups. Replacement of one hydrogen atom of
ammonia gives rise to structure of the type R-NH2, known as primary amine.
Secondary amines are characterised by the structure R2NH or R-NHR′′ and tertiary
amines by R3N, RNR′′R′′ ′′ or R2NR′.
′. Secondary and tertiary amines are known as
simple amines if the alkyl or aryl groups are the same and mixed amines if the
groups are different. Like ammonia, all the three types of amines have one unshared
electron pair on nitrogen atom due to which they behave as Lewis bases.
Amines are usually formed from nitro compounds, halides, amides, imides, etc.
They exhibit hydrogen bonding which influence their physical properties. In
alkylamines, a combination of electron releasing, steric and H-bonding factors
influence the stability of the substituted ammonium cations in protic polar solvents
and thus affect the basic nature of amines. Alkyl amines are found to be stronger
bases than ammonia. In aromatic amines, electron releasing and withdrawing groups,
respectively increase and decrease their basic character. Aniline is a weaker base
than ammonia. Reactions of amines are governed by availability of the unshared
pair of electrons on nitrogen. Influence of the number of hydrogen atoms at
nitrogen atom on the type of reactions and nature of products is responsible for
identification and distinction between primary, secondary and tertiary amines. p-
Toluenesulphonyl chloride is used for the identification of primary, secondary and
tertiary amines. Presence of amino group in aromatic ring enhances reactivity of
the aromatic amines. Reactivity of aromatic amines can be controlled by acylation
process, i.e., by treating with acetyl chloride or acetic anhydride. Tertiary amines
like trimethylamine are used as insect attractants.
Aryldiazonium salts, usually obtained from arylamines, undergo replacement
of the diazonium group with a variety of nucleophiles to provide advantageous
methods for producing aryl halides, cyanides, phenols and arenes by reductive
removal of the diazo group. Coupling reaction of aryldiazonium salts with phenols
or arylamines give rise to the formation of azo dyes.
||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
1. Write IUPAC names of the following compounds and classify them into
primary, secondary and tertiary amines.
(i) (CH3)2CHNH2 (ii) CH3(CH2)2NH2

(iii) CH3NHCH(CH3)2 (iv) (CH3)3CNH2
(v) C6H5NHCH3 (vi) (CH3CH2)2NCH3
(vii) m-BrC6H4NH2
Soln. (i) Propan-2-amine (primary), (ii) Propan-1-amine (primary),
(iii) N-Methylpropan-2-amine (secondary),

(iv) 2-Methylpropan-2-amine (primary),
(v) N-Methylbenzenamine or N-Methylaniline (secondary),
(vi) N-Ethyl-N-methylethanamine (tertiary),
(vii) 3-Bromobenzenamine or 3-Bromoaniline (primary).
2. Give one chemical test to distinguish between the following pairs of

compounds.
(i) Methylamine and dimethylamine (ii) Secondary and tertiary amine
(iii) Ethylamine and N-methylaniline (iv) Aniline and benzylamine
(v) Aniline and N-methylaniline
Soln.
Compounds Compound I Compound II
Reagent
Carbylamine test CH3NH2 (1° amine) (CH3)2NH (2° amine)
CHCl3 + alc. KOH + D Methylamine Dimethylamine
CH3NC + 3KCl + 3H2O No reaction

Methyl carbylamine
(offensive odour)
Hinsberg’s test R2NH + C6H5SO2Cl R3N + C6H5SO2Cl
C6H5SO2Cl
C6H5SO2NR2 + HCl No reaction

(Insoluble in alkali)
||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
Carbylamine reaction C2H5NH2

CHCl3 + alc. KOH + D Ethylamine (1° amine) NHCH3
N-methylamine (2° amine)

C2H5NC + 3KCl + 3H2O
Ethyl isocyanide
(foul smell) No reaction
Azo dye test
NaNO2 + dil. HCl NH3 CH2NH3
(0 – 5°C) Aniline Benzylamine
+ –
N NCl CH2OH
Benzenediazonium + N2 + HCl
chloride efferverscence
Carbylamine test
CHCl3 + alc. KOH + D NH2 NH CH3
Aniline (1° amine) N-methylaniline (2° amine)
No reaction
N C + 3KCl
+ 3H2O
(Unpleasant
odour)
3. Account for the following :

(i) pKb of aniline is more than that of methylamine.
(ii) Ethylamine is soluble in water whereas aniline is not.
(iii) Methylamine in water reacts with ferric chloride to precipitate hydrated
ferric oxide.
(iv) Although amino group is o- and p-directing in aromatic electrophilic
substitution reactions, aniline on nitration gives a substantial amount of
m-nitroaniline.
(v) Aniline does not undergo Friedel–Crafts reaction.
(vi) Diazonium salts of aromatic amines are more stable than those of
aliphatic amines.
(vii) Gabriel phthalimide synthesis is preferred for synthesising primary
amines.
Soln. (i) If the pKb value of any base or compound is higher than that
of another, it implies that the former is a weaker base than the latter. In
aniline, the N-atom is attached to the benzene ring and therefore the lone
||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
pair on N is delocalised over the entire benzene ring. As a result, it cannot
accept a proton or any other electrophile.
This is why it has a lower Kb value (lower basic strength) and high
corresponding pKb value.
In methylamine, CH3NH2, the electron density on nitrogen is greater
than that in case of aniline. This is because –CH3 group in methylamine,
by virtue of its +I effect, increases electron density on N, which is more
available for protonation.
(ii) Any compound capable of forming hydrogen bonds with water,
dissolves in it. Ethylamine is able to do the same and hence its solubility.
N H
H5C2 N H O H N C2H5
H H
However, in aniline, the bulky hydrocarbon part – C6H5 prevents the
formation of effective hydrogen bonding and therefore it is not soluble.
(iii) The formation of hydrated ferric oxide may be understood by taking
into consideration the basic strength of CH3NH2. In presence of CH3NH2,
water hydrolyses as
O
+
CH3 NH2 + H H CH3 NH3 + OH
These OH ions react with FeCl3 as:
2FeCl3 + 6OH 2Fe(OH)3 or Fe2O3 .3H2O
hydrated ferric
oxide
(iv) During nitration, the nitration mixture used (conc. HNO3 and conc.
H2SO4) protonates the NH2 group to produce anilinium ion as
NH2 NH3
conc. H2SO4
+ conc. HNO3
Aniline Anilinium ion

||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
This anilinium ion acts as a deactivating group and directs the incoming
nucleophile – NO2 to meta position and the meta-isomer of nitroaniline is
obtained.
m-Nitroaniline
(v) During Friedel-Crafts reaction, anhydrous AlCl3 is used as a Lewis

acid for generation of the electrophile from the electrophilic reagent.
CH3Cl + AlCl3 CH3 + [AlCl4]

electrophile
generated
But when this reaction is carried out with aniline, no electrophile generation
takes place. The reason being the presence of aniline as a base.
Aniline is a Lewis base, reacts with AlCl3 and hence deactivates it. The
Lewis acid is therefore no more available for electrophile generation and
hence reaction does not take place.
+ –
NH2 NH2AlCl3
+ AlCl3
Lewis
Lewis base acid Deactivated AlCl3
(vi) Diazonium salts carry a N atom with a positive charge. This positive
charge is well dispersed in aromatic diazonium salts through resonance
as shown below:
Such a charge delocalisation is not possible in aliphatic amines and hence

they are less stable.
(vii) Gabriel phthalimide reaction gives pure primary amines without any
contamination of secondary and tertiary amines. Therefore, it is preferred
for synthesising primary amines.
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4. Arrange the following :
(i) In decreasing order of the pKb values:
C2H5NH2, C6H5NHCH3, (C2H5)2NH and C6H5NH2
(ii) In increasing order of basic strength:
C6H5NH2, C6H5N(CH3)2, (C2H5)2NH and CH3NH2
(iii) In increasing order of basic strength:
(a) Aniline, p-nitroaniline and p-toluidine
(b) C6H5NH2, C6H5NHCH3, C6H5CH2NH2.
(iv) In decreasing order of basic strength in gas phase:
C2H5NH2, (C2H5)2NH, (C2H5)3N and NH3
(v) In increasing order of boiling point :
C2H5OH, (CH3)2NH, C2H5NH2
(vi) In increasing order of solubility in water :
C6H5NH2, (C2H5)2NH, C2H5NH2.
Soln. (i) The order of pKb will decrease as :
C6H5NH2 > C6H5NHCH3 > C2H5NH2 > (C2H5)2 NH
(ii) C6H5NH2 < C6H5N(CH3)2 < CH3NH2 < (C2H5)2NH
(iii) p-Nitroaniline <Aniline < p-Toluidine

O 2N NH2 NH2 H2 N CH3
The availability of l.p. on N of p-nitroaniline is drastically reduced by

presence of electron withdrawing –NO2 group on it.
In contrast, presence of electron releasing –CH3 group increases the
electron density on N atom and improves basicity in p-toluidine.
(b) C6H5NH2 < C6H5NHCH3 < C6H5CH2NH2
Involvement of l.p. of N in resonance causes aniline to have low basicity.
In II, the –Me group through its +I effect improves the electron density
on N and therefore its basic strength increases. In III, the –NH2 is farther
off from benzene ring and hence l.p. is localized on it and hence the basic
strength is highest.
(iv) In gas phase, basicity follows the order :
(C2H5)3N > (C2H5)2NH > C2H5NH2 > NH3
In gas phase, the stabilization by solvation is not present and hence basic
strength follows the expected order based on +I effect of alkyl groups.
(v) (CH3)2NH < C2H5NH2 < C2H5OH
(vi) C6H5NH2 < (C2H5)2NH < C2H5NH2
Amines can form hydrogen bonds with water and are therefore soluble in
it. However, the solubility decreases if the mass of the hydrocarbon part
increases.
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5. How will you convert :
(i) Ethanoic acid into methanamine
(ii) Hexanenitrile into 1-aminopentane
(iii) Methanol to ethanoic acid (iv) Ethanamine into methanamine
(v) Ethanoic acid into porpanoic acid (vi) Methanamine into ethanamine
(vii) Nitromethane into dimethylamine
(viii) Propanoic acid into ethanoic acid?
SOCl2 NH3 (excess)
Soln. (i) CH3COOH CH3COCl
Ethanoic acid Ethanoyl chloride
Br2 / KOH
CH3CONH2 CH3NH2
Ethanamide (Hofmann bromamide Methanamine
reaction)
H3O+ PCl5
(ii) CH3(CH2)4CN CH3(CH2)4COOH CH3(CH2)4COCl
Hydrolysis
Hexanenitrile Hexanoic acid Hexanoyl chloride
NH3 (excess) 
Br2 / KOH
CH3(CH2)4NH2 CH3(CH2)4CONH2
1-Aminopentane
(iii)
(iv)
(v)
(vi)
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(vii)
(viii)
Propanoic acid
dil. HCl
+ NaNO2
Ethanoic acid
6. Describe a method for the identification of primary, secondary and

tertiary amines. Also write chemical equations of the reactions involved.
Soln. 1°, 2° and 3° amines can be distinguished by Hinsberg’s reagent.
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7. Write short notes on the following :
(i) Carbylamine reaction (ii) Diazotisation
(iii) Hofmann’s bromamide reaction (iv) Coupling reaction
(v) Ammonolysis (vi) Gabriel phthalimide synthesis
(vii) Acetylation
Soln. (i) Carbylamine reaction : Aliphatic and aromatic primary
amines on heating with chloroform and ethanolic potassium hydroxide
form isocyanides or carbylamines which are foul smelling substances.
Secondary and tertiary amines do not show this reaction. This reaction is
known as carbylamine reaction or isocyanide test and is used as a test for
primary amines.
Heat
R NH2 + CHCl3 + 3KOH R NC + 3KCl + 3H2O
Carbylamine
(foul smell)
(ii) Diazotisation : The conversion of primary aromatic amines into
diazonium salts is known as diazotisation.
The conversion is brought about by reacting the amine with HNO2 which
is prepared in situ.
273-278 K
NH2 + NaNO2+ 2HCl
+ –
Aniline N NCl + NaCl + 2H2O
Diazonium salt
(iii) Hofmann’s bromamide reaction : Primary amides when heated with
Br2 and (aqueous or ethanoic solution of) NaOH lose a carbon atom and
are converted to the corresponding amines. It is an example of step-down
reaction.

CH3CONH2+ Br2 + 4NaOH CH3NH2 + 2NaBr + Na2CO3 + 2H2O
Acetamide
(iv) Coupling reaction : The reaction of diazonium salts with phenols and
aromatic amines to form azo compounds having an extended conjugate
system with both aromatic rings joined through the — N=N — bond, is
called coupling reaction. In this reaction, the nitrogen atoms of the diazo
group are retained in the product. The coupling with phenols takes place
in mildly alkaline medium while that with amines occurs under faintly
acidic conditions. For example,
+ 273-278 K, –OH
N NCl– + OH
(pH 9-10)
Benzenediazonium Phenol
chloride N N OH + HCl
p-Hydroxyazobenzene (orange dye)

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+ 273-278 K, H+
N NCl– + NH2
(pH 4-5)

Benzenediazonium Aniline
chloride N N NH2 + HCl
p-Aminoazobenzene
(yellow dye)
CH3
+ –
Na+O 3S N NCl + N
CH3
Diazonium salt of N, N-Dimethylaniline
sulphanilic acid
CH3
273-278 K, H+ + –
NaO3S N N N + HCl
Methyl orange CH3
Coupling generally occurs at the p-position with respect to the hydroxyl

or the amino group, if free, otherwise it takes place at the o-position.
(v) Ammonolysis : The process of cleavage of the C — X bond in alkyl
halides by ammonia molecule is called ammonolysis. 1° amine thus
obtained behaves as a nucleophile and further reacts with alkyl halide to
form 2°, 3° and finally quaternary ammonium salt.
+ R’X R’’X
NH3 + R X R NH3X– RNH2 RNHR’ RNR’R’’
(vi) Gabriel phthalimide synthesis : In this reaction phthalimide is
converted into its potassium salt by treating it with alcoholic potassium
hydroxide. Then potassium phthalimide is heated with an alkyl halide
to yield an N-alkylpthalimide which is hydrolysed to phthalic acid and
primary amine by alkaline hydrolysis.
CO CO
KOH (alc.) – + C2H5I
NH NK
–H2O –KI
CO CO
Phthalimide Potassium
phthalimide
CO COOH
NaOH(aq)
NC2H5 + C2H5NH2
(Hydrolysis)
CO COOH Ethyl amine
Phthalic acid
This synthesis is very useful for the preparation of pure aralkyl and
aliphatic primary amines. However, aromatic primary amines cannot be
prepared by this method.
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(vii) Acetylation : The process of introducing an acetyl group
O
(CH3 C ) into a molecule is called acetylation. The reaction occurs
by nucleophilic substitution. There occurs a replacement of hydrogen
atom of –NH2 or >NH by the acetyl group.
Common acetylating agents used are acetyl chloride and acetic
anhydride.
O
CH3CH2NH2 + CH3 C Cl
8. Accomplish the following conversions :

(i) Nitrobenzene to benzoic acid (ii) Benzene to m-bromophenol
(iii) Benzoic acid to aniline
(iv) Aniline to 2,4,6-tribromofluorobenzene
(v) Benzyl chloride to 2-phenylethanamine
(vi) Chlorobenzene to p-chloroaniline (vii) Aniline to p-bromoaniline
(viii) Benzamide to toluene (ix) Aniline to benzyl alcohol.
NO2 NH2
NaNO2/HCl,
(i) Fe/HCl 273-278 K
Soln. (i)
(ii) NaOH
Nitrobenzene Aniline
+
N NCl– CN COOH
CuCN/KCN H3O+
Hydrolysis
Benzenediazonium Benzonitrile Benzoic acid

chloride
(ii)
||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
(iii)
(iv)
(v)
(vi)
(vii)
||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
(viii)
(ix) Write reactions from aniline to toluene as given in (viii) and then,
9. Give the structures of A, B and C in the following reactions:

(i) CH3CH2 I
+
(ii) C6H5N2Cl CuCN

H2O/H
→ A 
NH
→ B 3→ C
D
KCN LiAlH HNO
→ A  4→ B  
(iii) CH3CH2Br   2→ C
0° C
Fe/HCl
Fe/HCl
22 22 NaNO +HCl
NaNO +HCl H O/H++
H O/H
(iv) C6H5NO2  → A   → B  →C
273 K
273 K DD
(v) CH3COOH
Fe/HCl HNO C H OH
Fe/HCl
→ B C
HNO2
(vi) C6H5NO2  → A 273K 6 H5 OH
→C
273K O
NaCN OH–
Soln. (i) CH3CH2I CH3CH2CN CH3 C NH2
(Partial hydrolysis)
Iodoethane Propane nitrile (A) Ethanamide (B)
NaOH + Br2
CH3 NH2
Methanamine (C)
Hydrolysis
(ii)
H2O/H+
Benzenediazonium Cyanobenzene (A)
chloride
Heat
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(iii)
NaNO2/HCl +
(iv) C6H5NO2 Fe/HCl C6H5NH2 C 6 H5 N NCl–
Nitrobenzene Aniline (A) 273 K Benzenediazonium H2O/H+
Heat
chloride (B)
C6H5OH
Phenol (C)
(v)
Fe/HCl HNO2 +
(vi) C6H5NO2 C6H5NH2 C6H5 N NCl–
273 K
Nitrobenzene Aniline (A) Benzendiazonium C6H5OH
chloride (B)
N N OH
p-Hydroxyazobenzene (C)
10. An aromatic compound ‘A’ on treatment with aqueous ammonia and

heating forms compound ‘B’ which on heating with Br2 and KOH forms a
compound ‘C’ of molecular formula C6H7N. Write the structures and IUPAC
names of compounds A, B and C.
Soln. Given scheme of reactions is
aq. NH3/ Br2/KOH
A B C
Aromatic compd. C6H7N
(i) Looking at the given scheme, we can clearly see that reaction B → C is
Hofmann bromamide reaction.
Thus, C is an amine (1°) while B must be an amide with molecular formula
C7H7NO.
(ii) Further, the ratio of C and H in B and C are indicative of the fact that
it is an aromatic compound.
O NH2
NH2 C
C= C6H7N ; B = C 7H7 N ;
Aniline Benzamide
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Since, B is formed by the action of ammonia on A, A must be a carboxylic
acid,
COOH
A=
Benzoic acid
The reactions are
COOH CONH2 NH2
NH3/H2O Br2/KOH
 
A B C
11. Complete the following reactions :
(i) C6H5NH2 + CHCl3 + alc.KOH → (ii) C6H5N2Cl + H3PO2 + H2O →
(iii) C6H5NH2 + H2SO4 (conc.) → (iv) C6H5N2Cl + C2H5OH →
(v) C6H5NH2 + Br2(aq) → (vi) C6H5NH2 + (CH3CO)2O →
(i) HBF
(vii) C6H5N2Cl (ii)NaNO
 4
/Cu, D
→
2
Soln. (i) NH2 + CHCl3 + 3KOH (alc.)

∆
N C+ 3KCl + 3H2O
Carbylamine reaction
Cu+
(ii) C6H5N2Cl + H3PO2 + H2O C6H6 + N2 + H3PO3 + HCl
(Reduction)
Benzenediazonium Benzene
chloride
+
(iii) C6H5NH2 + H2SO4 (conc.) C6H5NH3HSO4–
Aniline Anilinium hydrogen sulphate
Reduction
(iv) C6H5N2Cl + C2H5OH C6H6 + CH3CHO + N2 + HCl
Benzenediazonium Benzene Ethanal
chloride
NH2 NH2
Br Br
(v) + 3Br2(aq.) + 3HBr
Aniline
Br
2,4,6-Tribromoaniline
||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
O
CH3 C CH3COOH
(vi) C6H5NH2 + O C6H5NHCOCH3 + CH3COOH
or Pyridine
Aniline CH3 C Acetanilide
(Acetylation)
O
Acetic anhydride
HBF4 +
(vii) C6H5N2Cl C6H5N2BF4
–
Benzenediazonium Benzenediazonium
chloride fluoroborate
NaNO2/Cu
C6H5NO2 + N2 + NaBF4
Heat
Nitrobenzene
12. Why cannot aromatic primary amines be prepared by Gabriel
phthalimide synthesis?
Soln. (i) Gabriel phthalimide reaction involves the nucleophilic attack of
the phthalimide on the alkyl halide.
O O
N +R X N R
O O
(ii) Such a nucleophilic substitution reaction is not possible if the

substrate is an aryl halide.
(iii) The reason for it can be explained on the basis of
(a) Partial double bond character of C — X bond in aryl halide. Consider
the following structures :
X X X X X
I II IV III V
From the resonance structures we see that the C — X bond has a double
bond character in structures II, III and IV and this makes cleavage of
C — X bond difficult.
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(b) Also the steric hindrance by the bulkyaryl group prevents the
incoming nucleophile.
13. Write the reactions of (i) aromatic and (ii) aliphatic primary amines with
nitrous acid.
Soln. Amines do not directly react with nitrous acid, rather they react
with a mixture of dil. HCl and NaNO2 and HNO2 is produced in situ.
The reactions are :
+ –
NH2 273-278 K N NCl
(i) + NaNO2 + HCl + 2H2O
Diazonium salt
273-278 K +
(ii) CH3CH2NH2 + NaNO2 + HCl [CH3CH2 N N]Cl–
H2O
CH3CH2OH + N2+ HCl

14. Give plausible explanation for each of the following :
(i) Why are amines less acidic than alcohols of comparable molecular
masses?
(ii) Why do primary amines have higher boiling point than tertiary amines?
(iii) Why are aliphatic amines stronger bases than aromatic amines?
Soln. (i) Loss of a proton from an amine gives RNH– ion while loss of a
proton from alcohol gives RO– ion as shown below:
R NH2 R NH + H+
R O H R O + H+
As O is more electronegative than N, RO– can accommodate the negative
charge more easily than the RNH– can.
As, RO– is more stable than RNH– the former is formed more. As a result,
amines are less acidic than alcohols.
(ii) (a) At boiling point, the molecules in a compound break free from
their inter molecular forces and escape into the vapour phase.
Weaker the inter-molecular forces, lower will be the boiling point.
(b) In 1° amines, there is strong H-bonding that binds the amine molecules
together. Whereas in 3° amine absence of H on N atom prevents hydrogen
bonding completely.
This is why 1° amines have higher boiling point.
R R R
N H N H N H
H H H
H-bonding in 1° amines
||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
(iii) (a) The basic nature of amines is a result of the presence of l.p. of
electron on the N atom. Also the electron density is increased on N due to
the +I effect of alkyl group.
(b) In aryl amines the l.p. on N is involved in resonance with the benzene
ring and hence less available for protonation.
NH2 NH2 NH2 NH2 NH2
(I) (II) (III) (IV) (V)

(c) In aliphatic amines there is no such delocalisation and hence it is more
basic.

1. Classify the following amines as primary, secondary and tertiary :
NH N(CH3)2
2
(a) (b)
(c) (C2H5)2CHNH2 (d) (C2H5)2NH

Soln. (a) Primary (b) Tertiary (c) Primary (d) Secondary.
2. (a) Write structures of different isomeric amines corresponding to the

molecular formula, C4H11N.
(b) Write IUPAC names of all the isomers.
(c) What type of isomerism is exhibited by different pairs of amines?
Soln. (a and b)
Primary amines :
(i) CH 3CH 2 CH 2 CH 2 NH 2 (ii) CH3CH2 CH CH3
Butanamine
NH2
Butan-2-amine
CH3 CH3
(iii) CH3 C NH2 (iv) CH3 CH CH2 NH2
2-Methylpropan-1-amine
CH3
2-Methylpropan-2-amine
||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
Secondary amines :
(v) CH3CH2 NH CH2CH3 (vi) CH3CH2CH2 NH CH3
N-Ethylethanamine N-Methylpropanamine
CH3
(vii) CH3 CH NH CH3

N-Methylpropan-2-amine
Tertiary amine:
CH3
(viii) CH3 N CH2CH3

N, N-Dimethylethanamine
(c) Chain isomers : (i) & (iv), (ii) & (iii), (i) & (iii), (ii) & (iv)
Position isomers : (i) & (ii), (vi) & (vii)
Metamers : (v) & (vi), (v) & (vii)
Functional isomers: All primary amines are functional isomers of
secondary and tertiary amines and vice versa.
3. How will you convert: (i) Benzene into aniline, (ii) Benzene into N,N-
dimethylaniline, (iii) Cl(CH2)4Cl into hexan-1,6-diamine?
Soln. (i)
CH3
NH2 N
As in (i) CH3I (2 moles), ∆ CH3
(ii) Above –2HI
Benzene Nitrobenzene N,N-Dimethylaniline

2 mol NaCN
(iii) Cl (CH2)4 Cl NC (CH2)4 CN
EtOH
Reduction
H2NH2C (CH2)4 CH2NH2

Hexan-1,6-diamine
4. Arrange the following in increasing order of their basic strength.
(a) C2H5NH2, C6H5NH2, NH3, C6H5CH2NH2 and (C2H5)2NH
(b) C2H5NH2, (C2H5)2NH, (C2H5)3N, C6H5NH2
(c) CH3NH2, (CH3)2NH, (CH3)3N, C6H5NH2, C6H5CH2NH2.
Soln. (a) The order of basicity is
C6H5NH2 < NH3 < C6H5CH2NH2 < C2H5NH2 < (C2H5)2NH
||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
The basic nature of amine arises from their ability to donate the lone pair
of electrons on N to electrophiles. The availability of this l.p. depends on
two factors:
(i) Electron donating/withdrawing effect of the alkyl groups attached to
the N atom.
(ii) Steric hindrance posed by alkyl groups around N.
The presence of alkyl groups on the N atom increases the electron density
and makes the l.p. more available for electrophiles. This happens due to
the +I effect of the alkyl groups. But, if the alkyl groups are too bulky or
too many in number, they tend to sterically hinder the incoming proton
and the basic strength decreases. These two factors working in opposing
directions, tend to balance out each other in 2° amines, making them most
basic and the basic strength follows the order:
R2NH > R3N > RNH2 > NH3 > NH2
2° amines 3° amines 1° amines amines
Aryl amine
In aryl amine, the l.p. on N is involved in resonance and hence less
available to proton.
(b) C6H5NH2 < C2H5NH2 < (C2H5)3N < (C2H5)2NH
aryl amine 1° 3° 2°
(c) C6H5NH2 < C6H5CH2NH2 < (CH3)3N < CH3NH2 < (CH3)2NH
5. Complete the following acid-base reactions and name the products:

(i) CH3CH2CH2NH2 + HCl → (ii) (C2H5)3N + HCl →
+
Soln. (i) CH3CH2CH2NH2 + H+Cl– CH3(CH2)2NH3Cl–
+
(ii) (C2H5)3N + H+Cl– (C2H5)3NHCl–
6. Write the reactions of the final alkylation product of aniline with excess
of methyl iodide in the presence of sodium carbonate solution.
+
Soln. C6H5NH2 + CH3 I [C6H5NH2CH3]I–
Aniline N-Methylanilinum iodide
+
2[C6H5NH2CH3]I–+ Na2CO3 2C6H5NHCH3 + CO2 + 2NaI
N-Methylaniline
+ CH3I
C6H5NHCH3 C6H5N(CH3)2
Na2CO3
N,N-Dimethylaniline
||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
+ –
C6H5N(CH3)2 + CH3 I [ C6H5N(CH3)3 ] I
N,N,N-Trimethylanilinium iodide
+ + 2–
2C6H5N(CH3)3I– + Na2CO3 [C6H5N(CH3)3]2CO3 + 2NaI
N,N,N-Trimethylanilinium carbonate
7. Write the chemical reaction of aniline with benzoyl chloride and write
the name of the product obtained.
O Cl
H C
H O
N
H N C
aq.NaOH
Soln. + Na+
H Cl
Aniline Benzoyl chloride
H O
–NaCl N C
+
–H
N-Phenylbenzamide
8. Write structures of different isomers corresponding to the molecular

formula, C3H9N. Write IUPAC name of the isomers which will liberate nitrogen
gas on treatment with nitrous acid.
Soln. In all, four structural isomers are possible. These are as follows :
Primary amines : CH3CH2CH2NH2 CH3 CH CH3
Propan-1-amine
NH2
Propan-2-amine
Secondary amines : CH3 NH C2H5
N-Methylethanamine
CH3
Tertiary amines : CH3 N CH3

N,N-Dimethylmethanamine
Only primary amines react with HNO2 to liberate N2 gas.
CH3CH2CH2NH2 + HNO2 CH3CH2CH2OH + H2O + N2
Propan-1-amine Propan-1-ol
(major product)
CH3 CH3
CH NH2 + HNO2 CHOH + N2 + H2O
CH3 CH3
Propan-2-amine Propan-2-ol
(major product)
||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
9. Convert
(i) 3-Methylaniline into 3-nitrotoluene
(ii) Aniline into 1,3,5-tribromobenzene.
CH3 CH3
NaNO2/HBF4
Soln. (i) 273-278 K
Diazotization
+ –
NH2 N NBF4
3-Methylaniline 3-Methylbenzene CH3
diazonium fluoroborate
NaNO2/Cu
Heat
NO2
3-Nitrotoluene
NH2 NH2
Br2/H2O
Br Br
(ii) (Bromination)
Aniline
Br
2, 4, 6-Tribromoaniline
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Chapter 14
Biomolecules
Summary
Carbohydrates are optically active polyhydroxy aldehydes or ketones or molecules
which provide such units on hydrolysis. They are broadly classified into three groups
— monosaccharides, disaccharides and polysaccharides. Glucose, the most
important source of energy for mammals, is obtained by the digestion of starch.
Monosaccharides are held together by glycosidic linkages to form disaccharides or
polysaccharides.
Proteins are the polymers of about twenty different α-amino acids which
are linked by peptide bonds. Ten amino acids are called essential amino acids
because they cannot be synthesised by our body, hence must be provided through
diet. Proteins perform various structural and dynamic functions in the organisms.
Proteins which contain only α-amino acids are called simple proteins. The
secondary or tertiary structure of proteins get disturbed on change of pH or
temperature and they are not able to perform their functions. This is called
denaturation of proteins. Enzymes are biocatalysts which speed up the reactions
in biosystems. They are very specific and selective in their action and chemically
all enzymes are proteins.
Vitamins are accessory food factors required in the diet. They are classified
as fat soluble (A, D, E and K) and water soluble (Β group and C). Deficiency of
vitamins leads to many diseases.
Nucleic acids are the polymers of nucleotides which in turn consist of a base,
a pentose sugar and phosphate moiety. Nucleic acids are responsible for the transfer
of characters from parents to offsprings. There are two types of nucleic acids —
DNA and RNA. DNA contains a five carbon sugar molecule called 2-deoxyribose
whereas RNA contains ribose. Both DNA and RNA contain adenine, guanine and
cytosine. The fourth base is thymine in DNA and uracil in RNA. The structure of
DNA is a double strand whereas RNA is a single strand molecule. DNA is the
chemical basis of heredity and have the coded message for proteins to be synthesised
in the cell. There are three types of RNA — mRNA, rRNA and tRNA which actually
carry out the protein synthesis in the cell.
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1. What are monosaccharides?
Soln. A carbohydrate that cannot be hydrolysed further to give simpler
unit of polyhydroxy aldehyde or ketone is called a monosaccharide.

With a few exceptions they have general formula, CnH2nOn. About 20
monosaccharides are known to occur in nature. Some common examples
are glucose, fructose, ribose, etc.
2. What are reducing sugars?

Soln. All those carbohydrates which reduce Fehling’s solution and
Tollen’s reagent are referred to as reducing sugars. All monosaccharides
whether aldose or ketose are reducing sugars.
3. Write two main functions of carbohydrates in plants.

Soln. Two main functions of carbohydrates are
(i) Cell wall of bacteria and plants is made up of a polysaccharide, cellulose.

(ii) Starch is the major food reserve material in plants.
4. Classify the following into monosaccharides and disaccharides. Ribose,
2-deoxyribose, maltose, galactose, fructose and lactose.
Soln. Monosaccharides : Ribose, 2-deoxyribose, galactose and fructose

Disaccharides : Maltose and Lactose
5. What do you understand by the term glycosidic linkage?

Soln. Disaccharides on hydrolysis with dilute acids or enzymes yield
two molecules of either the same or different monosaccharides. The two
monosaccharides are joined together by an oxide linkage formed by the
loss of a water molecule. Such a linkage between two monosaccharides
units through oxygen atom is called glycosidic linkage.
6. What is glycogen? How is it different from starch ?
Soln. The carbohydrates are stored in animal body as glycogen. It is also

known as animal starch because its structure is similar to amylopectin.
It is present in liver, muscles and brain. When the body needs glucose,
enzymes break the glycogen down to glucose. Glycogen is also found in
yeast and fungi.
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Starch is the main storage polysaccharide of plants. It is the most important
dietary source for human being. High content of starch is found in cereals,
roots, tubers and some vegetables. It is a polymer of two components-
amylose (15-20%) which is water soluble and amylopectin(80-85%) which
is water insoluble.
7. What are the hydrolysis products of (i) sucrose and (ii) lactose ?
Soln. (i) Sucrose on hydrolysis gives one unit of glucose and one unit of
fructose.
Invertase
C12H 22O11 + H 2O → C6H12O6 + C6H12O6
Sucrose Glucose Fructose
(ii) Lactose on hydrolysis with dilute acids yields an equimolar mixture of

D-glucose and D-galactose.
8. What is the basic structural difference between starch and cellulose ?

Soln. The basic structural difference between starch and cellulose is of
linkage between the glucose units. In starch, there is a-D-glycosidic
linkage. Both the components of starch-amylose and amylopectine are
polymer of a-D-glucose. On the other hand, cellulose is a linear polymer
of b-D-glucose in which C1 of one glucose unit is connected to C4 of the
other through b-D-glycosidic linkage.
9. What happens when D-glucose is treated with the following reagents?

(i) HI (ii) Bromine water (iii) HNO3
CHO
Soln. (i) (CHOH)4 HI,
CH3CH2CH2CH2CH2CH3
n-hexane
CH2OH
Glucose
CHO COOH
(ii) (CHOH)4 Br2 water
(CHOH)4
CH2OH CH2OH
Glucose Gluconic acid
CHO COOH
(iii) (CHOH)4 HNO3
(CHOH)4
[O]
CH2OH COOH
Glucose Saccharic acid
10. Enumerate the reactions of D-glucose which cannot be explained by its

open chain structure.
Soln. The open chain structure of D-glucose OHC – (CHOH)4 – CH2OH
fails to explain the following reactions :
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(i) Though it contains the aldehyde (–CHO) group, glucose does not give
2,4-DNP test, Schiff’s test and it does not form the hydrogen sulphite
addition product with NaHSO3.
(ii) The pentaacetate of glucose does not react with hydroxylamine
(NH2OH) to form the oxime indicating the absence of free
–CHO group.
(iii) The formation of two anomeric methyl glycosides by glucose on
reaction with CH3OH and dry HCl can be explained in terms of the cyclic
structure. The equilibrium mixture of a-and b-glucose react separately
with methanol in the presence of dry HCl gas to form the corresponding
methyl D-glucosides.
α
CHOH H – C – OCH3
H – C – OH H – C – OH
HO – C – H CH3OH HO – C – H
O O
Dry HCl gas
H – C – OH H – C – OH
H–C H–C
CH2OH CH2OH
A mixture of α- and Methyl α-D-glucoside
β-D-glucose
(iv) Like methyl glycosides, glucose pentaacetate also exists in two
anomeric formes as explained below :
CHOH
H – C – OH
HO – C – H +5(CH3CO)2O
O
–5CH3COOH
H – C – OH
H–C α β
CH2OH H – C – OCOCH3 CH3OCO – C – H
A mixture of α- and H – C – OCOCH3 H – C – OCOCH3
β-D-glucose O O
CH3OCO – C – H CH3OCO – C – H
+
H – C – OCOCH3 H – C – OCOCH3
H–C H–C
CH2OCOCH3 CH2OCOCH3
α-D-Glucose β-D-Glucose
pentaacetate pentaacetate
These pentaacetates donot have a free –OH group at C1 and hence are not
hydrolysed in aqueous solution to produce the open chain aldehyde form
and hence do not react with NH2OH to form glucose oxime.
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(v) The existence of glucose in two crystalline forms termed as a and
b-D-glucose can again be explained on the basis of cyclic structure of
glucose and not by its open chain structure. It was proposed that one of
the –OH groups may add to – CHO group and form a cyclic hemiacetal
structure. It was found that glucose forms a 6-membered ring in which
–OH at C – 5 is involved in ring formation. This explains the absence of
–CHO group and also existence of glucose in two forms as shown below.
These two forms exist in equilibrium with open chain structure.
O
1
1
H – C – OH H–C
1
H–C–H
2
2
H – C – OH
2
H – C – OH H – C – OH
O O HO –3C – H O
HO –3C – H HO –3C – H
H –4C – OH H –4C – OH H –4C – OH
H –5C H –5C – OH H –5C
6 6 6
CH2OH CH2OH CH2OH
α-D-(+)-glucose β-D-(+)-glucose
11. What are essential and non-essential amino acids? Give two examples
of each type.
Soln. There are about 20 amino acids which make up the bio-proteins.
Out of these 10 amino acids (non-essential) are synthesised by our bodies
and rest are essential in the diet (essential amino acids) and supplied to
our bodies by food which we take because they cannot be synthesised in
our body.
e.g. Essential amino acid - Valine and Leucine
Non-essential amino acid - Glycine and Alanine
12. Define the following as related to proteins
(i) Peptide linkage (ii) Primary structure (iii) Denaturation.
Soln. (i) Peptide Linkage : Proteins are the polymers of a-amino acids
which are connected to each other by peptide bond or peptide linkage.
Chemically, peptide linkage is an amide formed between –COOH group
and –NH2 group. The reaction between two molecules of similar or
different amino acids, proceeds through the combination of the amino
group of one molecule with the carboxyl group of the other. This results
in the elimination of a water molecule and formation of a peptide bond
–CO–NH–. The product of the reaction is called a dipeptide because it
is made up of two amino acids. For example, when carboxyl group of
glycine combines with the amino group of alanine we get a dipeptide,
glycylalanine.
(ii) Primary Structure : Proteins may have one or more polypeptide
chains. Each polypeptide in a protein has amino acids linked with each
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other in a specific sequence and it is this sequence of amino acids that is
said to be the primary structure of that protein. Any change in this primary
structure i.e., the sequence of amine acids creates a different protein.
(iii) Denaturation : Protein found in a biological system with a unique
three-dimensional structure and biological activity is called a native
protein. When a protein in its native form, is subjected to physical change
like change in temperature or chemical change in pH, the hydrogen bonds
are disturbed. Due to this, globules unfold and helix get uncoiled and
protein loses its biological activity. This is called denaturation of protein.
During denaturation 2° and 3° structures are destroyed but 1° structure
remains intact. The coagulation of egg white on boiling is a common
example of denaturation. Another example is curdling of milk which is
caused due to the formation of lactic acid by the bacteria present in milk.
13. What are the common types of secondary structure of proteins?

Soln. The secondary structure of protein refers to the shape in which a long
polypeptide chain can exist. They are found to exist in two different types
of structures viz, a-helix and b-pleated sheet structure. These structures
arise due to the regular folding of the backbone of the polypeptide chain
O
due to hydrogen bonding between – C – and –NH– groups of the peptide
bond. a-Helix is one of the most common ways in which a polypeptide
chain forms all possible hydrogen bonds by twisting into a right handed
screw (helix) with the –NH group of each amino acid residue hydrogen
bonded to the C O of an adjacent turn of the helix. In b-structure all
peptide chains are stretched out to nearly maximum extension and then
laid side by side which are held together by intermolecular hydrogen
bonds. The structure resembles the pleated folds of drapery and therefore
is known as b-pleated sheet.

a-helix structure b-pleated sheet structure
of a protein of a protein
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14. What type of bonding helps in stabilising the a-helix structure of
proteins?
Soln. a-Helix is one of the most common ways in which a polypeptide
chain forms all possible hydrogen bonds by twisting into a right handed
screw (helix) with the –NH group of each amino acid residue hydrogen
bonded to the C O of an adjacent turn of the helix.
15. Differentiate between globular and fibrous proteins.
Soln. Characteristic differences between globular and fibrous proteins
can be given as :
Globular Proteins Fibrous Proteins
1. These are cross linked These are linear condensation
proteins and are condensation polymer
product of acidic and basic
amino acids.
2. These are soluble in water, These are insoluble in water but
mineral acids and bases. soluble in strong acids and bases.
3. These proteins have three These are linear polymers held
dimensional folded structure. together by intermolecular
These are stabilised by hydrogen bonds. e.g., hair, silk.
internal hydrogen bonding.
e.g., egg albumin enzymes.
16. How do you explain the amphoteric behaviour of amino acids?

Soln. Due to dipolar or Zwitter ionic structure, amino acids are amphoteric
in nature. The acidic character of the amino acids is due to the N+H3 group
while the basic character is due to the COO– group.
+
NH3 – CH – COO– + OH– H2N – CH – COO– + H2O
R R
Acidic part
+
NH3 – CH – COOH
R

17. What are enzymes?

Soln. Life is possible due to the coordination of various chemical processes
in living organisms. An example is the digestion of food, absorption of
appropriate molecules and ultimately production of energy. This process
involves a sequence of reactions and all these reactions occur in the body
under very mild conditions. This occurs with the help of certain biocatalysts
called enzymes. Almost all the enzymes are globular proteins. Enzymes
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are specific for a particular reaction and for a particular substrate. They
are generally named after the compound or class of compounds upon
which they work. For example, the enzyme that catalyses hydrolysis of
maltose into glucose is named as maltose.
18. What is the effect of denaturation on the structure of proteins?

Soln. Proteins are very sensitive to the action of heat, mineral acids,
alkalies etc. On heating or on treatment with mineral acids, soluble
forms of proteins such as globular proteins often undergo coagulation or
precipitation to give fibrous proteins which are insoluble in water. This
coagulation also results in the loss of the biological activity of the protein.
That is why the coagulated proteins so formed are called denatured
proteins.. Chemically, denaturation does not change the primary
structure but brings about changes in the secondary and tertiary structure
of proteins.
19. How are vitamins classified? Name the vitamin responsible for the
coagulation of blood.
Soln. Vitamins are classified into two groups depending upon their
solubility in water or fat.
(i) Fat soluble vitamins : Vitamins which are soluble in fats and oils but
insoluble in water are kept in this group. These are vitamins A, D, E and
K. They are stored in liver and adipose (fat storing) tissues.
(ii) Water soluble vitamins : B group vitamins and vitamin C are soluble
in water so they are grouped together. Water soluble vitamins must be
supplied regularly in diet because they are readily excreted in urine and
cannot be stored (except vitamin B12) in our body.
Vitamin K is responsible for coagulation of blood.
20. Why are vitamin A and vitamin C essential to us? Give their important
sources.
Soln. Deficiency of vitamin A causes Xerophthalmia (hardening of
cornea of the eye) and night blindness. So its use is essential to us. It is
available in fish liver oil, carrots, butter and milk. It promotes growth and
increases resistance to diseases. Vitamin C is very essential to us because
its deficiency causes Scurvy (bleeding of gums) and pyorrhea (loosening
and bleeding of teeth). Vitamin C increases resistance of the body towards
diseases. Maintains healthy skin and helps cuts and abrasions to heat
properly. It is soluble in water. It is present in citrus fruits, e.g.,oranges,
lemons, amla, tomatoes, green vegetables (Cabbage) chillies, sprouted
pulses and germinated grains.
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21. What are nucleic acids? Mention their two important functions.
Soln. Nucleic acids : They constitute an important class of biomolecules
which are found in the nuclei of all living cells in the form of nucleoproteins
(i.e., proteins containing nucleic acid as the prosthetic group). Nucleic acids
are the genetic materials of the cells and are responsible for transmission
of hereditary effect from one generation to the other and also carry out
the biosynthesis of proteins. Nucleic acids are biopolymers (i.e., polymers
present in the living system). The genetic information coded in nucleic
acids controls the structure of all proteins including enzymes and thus
governs the entire metabolic activity in the living organism.
Two important functions of nucleic acids are :
(i) Replication : The process by which a single DNA molecule produces
two identical copies of itself is called replication.
(ii) Protein Synthesis : DNA may be regarded as the instrument manual for
the synthesis of all proteins present in the cell.
22. What is the difference between a nucleoside and a nucleotide?
Soln. Nucleoside : A nucleoside contains only two basic components
of nucleic acids, i.e., a pentose sugar and a nitrogenous base. It may be
represented as Sugar-base.
Depending upon the type of sugar present, nucleosides are of two types :
(i) Ribonucleosides and (ii) Deoxyribonucleosides.
Nucleotides : A nucleotide contains all the three basic components
of nucleic acids, i.e., a phosphoric acid group, a pentose sugar and
a nitrogenous base. In other words, nucleotides are nucleoside
monophosphates.
Depending upon the type of sugar present, nucleotides like nucleosides
are of two types : (i) Ribonucleotides and (ii) Deoxyribonucleotides.
23. The two strands in DNA are not identical but are complementary.
Explain.
Soln. Two nucleic acid chains are wound about each other and held
together by hydrogen bonds between pairs of bases. The two strands are
complementary to each other because the hydrogen bonds are formed
between specific pairs of bases. Adenine forms hydrogen bonds with
thymine whereas cytosine forms hydrogen bonds with guanine.
24. Write the important structural and functional differences between
DNA and RNA.
Soln. Difference between DNA and RNA.
DNA RNA
1. It usually occurs inside nucleus Very little RNA occurs inside
and some cell organelles. nucleus. Most of it is found in the
cytoplasm.
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2. DNA is the genetic material. RNA is not the genetic material

except in certain viruses, e.g.,
TMV, Reovirus.
3. It is double stranded with RNA is single stranded with the
a-helix structure in which two exception of some viruses (e.g.,
strands are coiled spirally. double stranded in Reovirus).
4. DNA shows regular helical There is no regular coiling except
coiling. in parts of tRNA.
5. DNA is of only two types, There are at least three types of
nuclear and extra-nuclear. RNA-mRNA, rRNA and tRNA.
6. It contains deoxyribose sugar. It contains ribose sugar.
7. Nitrogen base thymine occurs Thymine is replaced by uracil
in DNA along with three in RNA. The other three are
other—adenine, cytosine and adenine, cytosine and guanine.
guanine.
8. It has a unique property of It does not replicate.
replication.
9. DNA transcribes genetic RNA translates the transcribed
information to RNA. message for forming
polypeptides.
10. DNA controls heredity, RNA controls only protein
evolution, metabolism, synthesis.
structure and differentiation.
11. DNA controls metabolism It only controls metabolism
and genetics including under instructions from DNA.
variations.
25. What are the different types of RNA found in the cell?
Soln. RNA molecules are of three types and they perform different
functions. They are named as messenger RNA (m-RNA), ribosomal RNA
(r-RNA) and transfer RNA (t-RNA).

1. Glucose or sucrose are soluble in water, but cyclohexane or benzene
(simple six membered ring compounds) are insoluble in water. Explain.
Soln. Glucose or sucrose contain several hydroxyl groups in their
molecules which form hydrogen bonding with water molecules due to
which they dissolve in water. On the other hand compounds like benzene
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or cyclohexane cannot form hydrogen bonds with water molecules, so
they are insoluble in water.
2. What products are expected when lactose is hydrolysed ?

Soln. Lactose (C12H22O11) on hydrolysis with dilute acid yields an
equimolar mixture of D-glucose and D-galactose.
3. How do you explain the absence of aldehyde group in pentaacetate of

glucose ?
Soln. The cyclic hemiacetal form of glucose contains an OH group at C-1
which gets hydrolysed in the aqueous solution to produce the open chain
aldehydic form which then reacts with NH2OH to form the corresponding
oxime. Therefore, glucose contains an aldehydic group. On the other
hand, when glucose is reacted with acetic anhydride, the OH group at
C-1, along with the four other OH groups at C-2, C-3, C-4 and C-6 form
a pentaacetate. As the pentaacetate of glucose does not contain a free OH
group at C-1, it cannot get hydrolysed in aqueous solution to produce the
open chain aldehydic form and thus glucose pentaacetate does not react
with NH2OH to form glucose oxime. Hence, glucose pentaacetate does
not contain the aldehdye group.
1 1
CH O CHOH CHOCOCH3
2
H OH H2 OH O H OCOCH3
+5(CH3CO)2O 3
HO H HO 3 H CH3OCO H
–5CH3COOH 4
H OH H4 OH H OCOCH3 O
5
H5 H
:
H OH 6
6
CH2OH CH2OH CH2OCOCH3
-Glucose -Glucose pentaacetate
Glucose
(open chain form) + +
-Glucose -Glucose pentaacetate
–H2O NH2OH
NH2OH
CH NOH No oxime
H OH
HO H
H OH
H OH
CH2OH
Glucose oxime
4. The melting points and solubility in water of amino acids are higher
than those of the corresponding haloacids. Explain.
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Soln. The amino acids exist as zwitter ions, H3N+—OHR—COO—.
Because of this dipolar salt like character they have strong dipole-dipole
attractions. So, their melting points are higher than halo acids which do
not have sail like character. Moreover, due to this salt like character, they
interact strongly with H2O. Thus, solubility of amino acids in water is
higher than that of the corresponding halo acids which do not have salt
like character.
5. Where does the water present in the egg go after boiling the egg.
Soln. The boiling of an egg is a common example of denaturation of
proteins present in the white portion of an egg.
The albumin present in the white of an egg gets coagulated when the
egg is boiled hard. The soluble globular protein present in it is denatured
resulting in the formation of insoluble fibrous protein.
6. Why vitamin C cannot be stored in our body?
Soln. Vitamin C is a water-soluble vitamin. Water-soluble vitamins when
supplied regularly in the diet cannot be stored in our body because they
are readily excreted in urine.
7. What products would be formed when a nucleotide from DNA
containing thymine is hydrolysed ?
Soln. When a nucleotide from DNA containing thymine is completely
hydrolysed, the products obtained are :
(i) 2-deoxy-D(–)ribose.
(ii) two pyrimidine i.e., guanine (G) and adenine (A).
(iii) two purines, i.e., thymine (T) and cytosine (C) and
(iv) phosphoric acid.
8. When RNA is hydrolysed, there is no relationship among the quantities
of different bases obtained ? What does this fact suggest about the structure
of RNA ?
Soln. A DNA molecule has two strands in which the four complementary
bases pair each other, viz. cytosine (C) always pairs with guanine (G)
while thymine (T) always pairs with adenine (A). Therefore, when a DNA
molecule is hydrolysed the molar amount of cytosine is always equal to
that of guanine and that of adenine is always equal to that of thymine
RNA also contains four bases, the first three are same as in DNA but the
fourth one is uracil (U).
As in RNA there is no relationship between the quantities of four bases
(C, G, A and U) obtained, therefore, the base-pairing principle, viz., (A)
pairs with (U) and (C) pairs with (G) is not followed. So, unlike DNA,
RNA has a single strand.
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Chapter 15
Polymers
Summary
Polymers are defined as high molecular mass macromolecules, which consist of
repeating structural units derived from the corresponding monomers. These polymers
may be of natural or synthetic origin and are classified in a number of ways.
In the presence of an organic peroxide initiator, the alkenes and their derivatives
undergo addition polymerisation or chain growth polymerisation through a free
radical mechanism. Polythene, teflon, orlon, etc. are formed by addition polymerisation
of an appropriate alkene or its derivative. Condensation polymerisation reactions are
shown by the interaction of bi – or poly functional monomers containing – NH2, –

OH and – COOH groups. This type of polymerisation proceeds through the
elimination of certain simple molecules as H2O, CH3OH, etc. Formaldehyde reacts
with phenol and melamine to form the corresponding condensation polymer
products. The condensation polymerisation progresses through step by step and is
also called as step growth polymerisation. Nylon, bakelite and dacron are some
of the important examples of condensation polymers. However, a mixture of two
unsaturated monomers exhibits copolymerisation and forms a co-polymer
containing multiple units of each monomer. Natural rubber is a cis 1, 4-polyisoprene
and can be made more tough by the process of vulcanisation with sulphur. Synthetic
rubbers are usually obtained by copolymerisation of alkene and 1, 3 butadiene
derivatives.
In view of the potential environmental hazards of synthetic polymeric wastes,
certain biodegradable polymers such as PHBV and Nylon-2- Nylon-6 are
developed as alternatives.
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1. Explain the terms polymer and monomer.

Soln. Polymers are very large molecules having high molecular mass,
which are formed by joining of repeating structural units on a large scale
derived from monomers. e.g., Polythene, PVC, Nylon-6, 6 etc.
Monomer is a simple molecule capable of undergoing polymerisation
and leading to the formation of the corresponding polymer e.g., Ethene,
Vinyl chloride, etc.
2. What are natural and synthetic polymers? Give two examples of each type.
Soln. Natural Polymers - These are substances of natural origin, i.e.,
these are found in nature mainly in plants and animals. The well known
natural polymers are proteins (polymers of amino acids), polysaccharides
(polymers of monosaccharides), etc.
Synthetic Polymers - These are man made polymers i.e., polymers
synthesised in laboratory. These include synthetic plastics, fibres and
synthetic rubber. Specific examples are polythene and dacron.
3. Distinguish between the terms homopolymer and copolymer and give

an example of each.
Soln. A polymer which is obtained from only one type of monomer
molecules is known as homopolymer e.g., Polythene, Polyvinyl chloride,
etc.
nCH2 CH2 ( CH2 CH2 )n

Ethene Polythene
A polymer made from more than one type of monomer molecules is

referred to as a co-polymer e.g., Nylon-6,6, Buna-S,Buna-N, etc.
nCH2 CH CH CH2 + nC6H5CH CH2

1, 3-Butadiene styrene
C6H5
( CH2 CH CH CH2 CH2 CH )n
Butadiene-styrene (Buna-S)
4. How do you explain the functionality of a monomer?
Soln. Functionality of a monomer is defined as the number of bonding sites

in the monomers.
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5. Define the term polymerisation.
Soln. The process of joining together of a large number of simple small
molecules (monomers) to make very large molecules (polymer) is termed
polymerisation.
Polymerisation
nCH2 CH2 n [ CH2 CH2 ] [ CH2 CH2 ]n
Ethene Repeating unit Polythene polymer
6. Is —( NH–CHR–CO )—
n , a homopolymer or copolymer?
Soln. Since the unit—NHCHRCO
( —is
)n obtained from the single monomer
unit NH2—CHR— COOH, it is a homopolymer.
7. In which classes, the polymers are classified on the basis of molecular

forces?
Soln. On the basis of molecular forces present between the chains of
various polymers, the polymers are classified into the following four
groups
(i) Elastomers (ii) Fibres
(iii) Thermoplastic polymers and (iv) Thermosetting polymers.
8. How can you differentiate between addition and condensation

polymerisation?
Soln. In addition polymerisation, the molecules of the same or different
monomers add together to form a large polymer molecule without
the elimination of simple molecules like H2O, HCl etc. Condensation
polymerisation is a process in which two or more bifunctional molecules
undergo a series of condensation reactions with the elimination of some
simple molecules like H2O, HCl, alcohol leading to the formation of
polymers.
9. Explain the term copolymerisation and give two examples.

Soln. Copolymerisation is a process in which a mixture of more than one
monomeric species is allowed to polymerise. The copolymer contains
multiple units of each monomer in the chain. The examples are copolymer
of 1, 3-butadiene and styrene. Another example is the copolymer of
1, 3-butadiene and acrylonitrile.
10. Write the free radical mechanism for the polymerisation of ethene.
Soln. The polymerisation of ethene to polythene consists of heating or
exposing to light a mixture of ethene with a small amount of benzoyl
peroxide initiator. The process starts with the addition of phenyl
free radical formed by the peroxide to the ethene double bond thus
regenerating a new and larger free radical. This step is called chain
initiating step. As this radical reacts with another molecule of ethene,
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another bigger sized radical is formed. The repetition of this sequence
with new and bigger radicals carries the reaction forward and the step is
termed as chain propagating step. Ultimately, at some stage the product
radical thus formed reacts with another radical to form the polymerised
product. This step is called the chain terminating step. The sequence of
steps may be depicted as follows :
Chain initiating steps :
O O O
. .
C6H5 C O O C C6H5 2C6H5 C O 2C6H5
Benzoyl peroxide Phenyl radical
. .
C6H5 + CH2 CH2 C6H5 CH2 CH2
Chain propagating step :
. .
C6H5 CH2 CH2 + CH2 CH2 C6H5 CH2 CH2 CH2 CH2
.
C6H5 ( CH2 CH2 )n CH2 CH2
Chain terminating step :
For termination of the long chain, these radicals can combine in different
ways to form polythene. One mode of termination of chain is shown as
under :
. .
C6H5 ( CH2 CH2 )n CH2 CH2 + C6H5 ( CH2 CH2 )n CH2 CH2
C6H5 ( CH2 CH2 )n CH2 CH2 CH2 ( CH2 CH2 )n C6H5

Polythene
11. Define thermoplastics and thermosetting polymers with two examples

of each.
Soln. Thermoplastic polymers : These are the linear or slightly branched
long chain molecules capable of repeatedly softening on heating and
hardening on cooling. These polymers possess intermolecular forces of
attraction intermediate between elastomers and fibres. Some common
thermoplastics are polythene, polystyrene, polyvinyls, etc.
Thermosetting polymers : These polymers are cross linked or heavily
branched molecules, which on heating undergo extensive cross linking
in moulds and become infusible. These cannot be reused. Some common
examples are bakelite, urea-formaldelyde resins, etc.
12. Write the monomers used for getting the following polymers.
(i) Polyvinyl chloride (ii) Teflon
(iii) Bakelite
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Soln. Polymer Monomer
(i) Polyvinyl chloride Vinyl chloride (CH2 CHCl)
(ii) Teflon Tetrafluoro ethylene (CF2 CF2)
(iii) Bakelite Phenol (C6H5OH) and Formaldehyde (HCHO)
13. Write the name and structure of one of the common initiators used in
free radical addition polymerisation.
O O
Soln. Benzoyl peroxide C H C O O CC6H5
6 5
14. How does the presence of double bonds in rubber molecules influence
their structure and reactivity?
Soln. Natural rubber is a linear polymer of isoprene i.e., 2-methyl-1,
3-butadiene.
H3C H CH2 CH2
C C C C
H2C CH2 H3C H
In the polymer double bonds are located between C2 and C3 isoprene
units. The cis-polyisoprene molecule consists of various chains held
together by weak van der Waals interactions and has coiled structure.
This cis-configuration about double bonds does not allow the chains to
come closer for effective attraction due to weak van der Waals interactions.
Thus, it can be stretched like a spring and exhibits elastic properties.
15. Discuss the main purpose of vulcanisation of rubber.

Soln. Natural rubber becomes soft at high temperature (> 335 K) and
brittle at low temperature (< 283 K) and shows high water absorption
capacity. It is soluble in non-polar solvents and is non-resistant to attack
by oxidising agents. To improve upon these physical properties, a process
of vulcanisation is carried out. This process consists of heating a mixture
of raw rubber with sulphur and an appropriate additive at a temperature
range between 373 K to 415 K. On vulcanisation, sulphur forms cross links
at the reactive sites of double bonds and thus the rubber gets stiffened.
16. What are the monomeric repeating units of Nylon-6 and Nylon-6,6?
(CH2)5 NH ]
Soln. The monomeric repeating unit of Nylon-6 is [ CO
which is obtained by heating caprolactam with water at a high
temperature.
NH O H
H2C C O 533-543 K
C (CH2)5 N
H2O n
H2C CH 2 Nylon-6
CH2 CH2
Caprolactam
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The monomeric units of Nylon-6,6 are hexamethylene diamine and
adipic acid. Both the units are condensed at high temperature under high
pressure.
HOOC(CH2)4COOH + nH2N(CH2)6NH2
Adipic acid Hexamethylene diamine
553 K High pressure
H H O O
N (CH2)6 N C (CH2)4 C
n
Nylon-6,6
17. Write the names and structures of the monomers of the following
polymers :
(i) Buna-S (ii) Buna-N
(iii) Dacron (iv) Neoprene.
Soln.
Monomers
Polymers
Name Structure
Buna-S (i) Styrene C6H5CH CH2
(ii) Buta-1, 3-diene CH2 CHCH CH2
Buna-N (i) Acrylonitrile CH2 CH—CN
(ii) Buta-1, 3-diene CH2 CHCH CH2
Dacron (i) Ethylene glycol HOCH2 CH2OH
(ii) Terephthalic acid
HOOC COOH
Neoprene Chloroprene Cl
CH2 C CH CH2
18. Identify the monomers in the following polymeric structures.

O O
(i) C (CH2)8 C NH (CH2)6 NH
n
HN N NH CH2
(ii) N N
NH n
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Soln. The monomers are
(i) Decanoic acid : HOOC – (CH2)8 – COOH and Hexamethylene diamine:
H2N(CH2)6NH2
H2N N NH2
(ii) Melamine : and Formaldehyde : HCHO
N N
NH2
19. How is dacron obtained from ethylene glycol and terephthalic acid?
Soln. Dacron is obtained from ethylene glycol and terephthalic acid by
condensation polymerisation reaction.
nHOOC COOH nHOH2CCH2OH

Ethylene glycol
Terephthalic acid
O O
OCH2 CH2 O C C
n
Terylene or Dacron
20. What is a biodegradable polymer? Give an example of a biodegradable

aliphatic polyester.
Soln. A large number of polymers are quite resistant to the
environmental degradation processes and are thus responsible for the
accumulation of polymeric solid waste materials. These solid wastes
cause acute environmental problems and remain undegraded for quite
a long time.
Aliphatic polyesters are one of the important classes of biodegradable
polymers. One such example is of PHBV.
Poly b-hydroxybutyrate-co-b-hydroxy valerate (PHBV) is obtained by
the copolymerisation of 3-hydroxybutanoic acid and 3-hydroxypentanoic
acid.
OH OH
CH3 CHCH2COOH + CH3CH2CHCH2COOH
3-Hydroxybutanoic acid 3-Hydroxypentanoic acid
CH3 O CH2CH3 O
( OCHCH2 C O CHCH2C n
PHBV
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1. What are polymers?
Soln. Polymers are high molecular mass substances consisting of
large number of repeating structural units. They are also called as
macromolecules. Some examples of polymers are polythene, bakelite,
rubber, nylon 6, 6 etc.
2. How are polymers classified on the basis of structure?

Soln. On the basis of structure, the polymers are classified as below :
(i) Linear polymers such as polythene, polyvinyl chloride, etc.
(ii) Branched chain polymers such as low density polythene.
(iii) Cross linked polymers such as bakelite, melamine, etc.
3. Write the names of monomers of the following polymers :

H H O O O H
(i) N (CH2)6 N C (CH2)4 C n (ii) C (CH2)5 N
n
(iii) [ CF2 CF2 ]n
Soln. (i) Hexamethylene diamine and adipic acid
(ii) Caprolactam
(iii) Tetrafluoroethene
4. Classify the following as addition and condensation polymers : Terylene,

Bakelite, Polyvinyl chloride, Polythene.
Soln. Addition polymers : Polyvinyl chloride, Polythene.
Condensation polymer : Terylene, Bakelite.
5. Explain the difference between Buna-N and Buna-S.

Soln. Buna-N is a copolymer of 1, 3-butadiene and acrylonitrile and
Buna-S is a copolymer of 1, 3-butadiene and styrene.
6. Arrange the following polymers in increasing order of their

intermolecular forces.
(i) Nylon 6,6, Buna-S, Polythene
(ii) Nylon 6, Neoprene, Polyvinyl chloride.
Soln. The increasing order of intermolecular forces is:
(i) Buna-S, Polythene, Nylon 6, 6
(ii) Neoprene, Polyvinyl chloride, Nylon 6.
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Chapter 16
Chemistry in Everyday Life
Summary
Chemistry is essentially the study of materials and the development of new
materials for the betterment of humanity. A drug is a chemical agent, which
affects human metabolism and provides cure from ailment. If taken in doses
higher than recommended, these may have poisonous effect. Use of chemicals
for therapeutic effect is called chemotherapy. Drugs usually interact with
biological macromolecules such as carbohydrates, proteins, lipids and nucleic
acids. These are called target molecules. Drugs are designed to interact with
specific targets so that these have the least chance of affecting other targets.
This minimises the side effects and localises the action of the drug. Drug chemistry
centres around arresting microbes/destroying microbes, preventing the body
from various infectious diseases, releasing mental stress, etc. Thus, drugs like
analgesics, antibiotics, antiseptics, disinfectants, antacids and tranquilizers are
used for specific purpose. To check the population explosion, antifertility drugs
have also become prominent in our life.
Food additives such as preservatives, sweetening agents, flavours,
antioxidants, edible colours and nutritional supplements are added to the
food to make it attractive, palatable and add nutritive value. Preservatives are
added to the food to prevent spoilage due to microbial growth. Artificial sweeteners
are used by those who need to check the calorie intake or are diabetic and want
to avoid taking sucrose.
These days, detergents are much in vogue and get preference over soaps
because they work even in hard water. Synthetic detergents are classified into
three main categories, namely: anionic, cationic and non-ionic, and each
category has its specific uses. Detergents with straight chain of hydrocarbons
are preferred over branched chain as the latter are non-biodegradable and
consequently cause environmental pollution.
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1. Why do we need to classify drugs in different ways?
Soln. In a general way, the drug may be defined as a substance

used in the prevention, diagnosis, treatment or cure of diseases.
We must classify the drug so as to understand its action on our
body. Drugs are classified on the basis of (a) pharmacological effect,
(b) drug action, (c) chemical structure and (d) molecular targets.
2. Explain the term, target molecules or drug targets as used in medicinal

chemistry.
Soln. Drugs usually interact with biomolecules such as carbohydrates,
lipids, proteins and nucleic acids. These are called target molecules or
drug targets. These perform various functions in the body. For example,
proteins which perform the role of biological catalysts in the body are
called enzymes and those which are crucial to communication system
in the body are called receptors. Nucleic acids have coded genetic
information for the cell. Lipids and carbohydrates are structural parts of
the cell membrane.
3. Name the macromolecules that are chosen as drug targets.

Soln. Macromolecules of biological origin such as carbohydrates, lipids,
proteins and nucleic acids.
4. Why should not medicines be taken without consulting doctors?

Soln. Drugs are designed to interact with specific targets so that these
have the least chance of affecting other targets. Only a doctor can diagnose
a disease properly and prescribe the correct medicine in proper dose
because excess of medicines may have harmful effects on our body. So we
should not take medicines without consulting doctors.
5. Define the term chemotherapy.

Soln. Chemotherapy (literally means chemical treatment) is the science
in which chemicals are used for the treatment of diseases. Chemotherapy
is defined as the use of chemicals (drugs) to injure or destroy infectious
microorganisms without causing any injury to the host. Chemotherapy
has developed into a vast subject today and efforts are being continuously
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made to search new drugs as to free human beings from various types of
diseases.
6. Which forces are involved in holding the drugs to the active site of
enzymes?
Soln. Substrates bind to the active site of the enzyme through a variety
of interactions such as ionic bonding, hydrogen bonding, van der Waals
interaction or dipole-dipole interaction.
7. While antacids and antiallergic drugs interfere with the function of

histamines, why do these not interfere with the function of each other?
Soln. Histamine stimulates the secretion of pepsin and hydrochloric acid
in the stomach. The drug cimetidine (antacid) was designed to prevent the
interaction of histamine with the receptors present in the stomach wall.
This resulted in release of lesser amount of acid. Antacid and antiallergic
drugs work on different receptors.
8. Low level of noradrenaline is the cause of depression. What type of

drugs are needed to cure this problem? Name two drugs.
Soln. Noradrenaline is one of the Neurotransmitters that plays a role in
mood changes. If the level of noradrenalines remains low for some reason,
then the signal-sending activity becomes low and the person suffers from
depression. In such situations, antidepressant drugs are required. These
drugs inhibit the enzymes which catalyse the degradation of noradrenaline.
If the enzyme is inhibited, this important neurotransmitter is slowly
metabolised and can activate its receptor for longer periods of time, thus
counteracting the effect of depression. Iproniazid and phenylzine are two
such drugs.
9. What is meant by the term ‘broad spectrum antibiotics’? Explain.

Soln. The range of bacteria or other microorganisms that are affected
by a certain antibiotic is expressed as its spectrum of action. Antibiotics
which kill or inhibit a wide range of Gram-positive and Gram-negative
bacteria are said to be broad spectrum antibiotics. e.g., Chloramphenicol,
Tetracycline, etc.
10. How do antiseptics differ from disinfectants? Give one example of

each.
Soln. Antiseptics and disinfectants are the chemicals which either kill
or prevent the growth of microorganisms. Antiseptics are applied to the
living tissues such as wounds, cuts, ulcers and diseased skin surfaces.
Examples are furacine, soframicine, etc. These are not ingested like
antibiotics. On the other hand, disinfectants are applied to inanimate
objects such as floors, drainage system, instruments, etc.
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Same substances can act as an antiseptic as well as disinfectant by varying
the concentration. For example, 0.2% solution of phenol is an antiseptic
while its 1% solution is disinfectant.
11. Why are cimetidine and ranitidine better antacids than sodium
hydrogencarbonate or magnesium or aluminium hydroxide?
Soln. Excessive hydrogencarbonate can make the stomach alkaline and
trigger the production of even more acid. Metal hydroxides are better
alternatives because being insoluble, these do not increase the pH above
neutrality. These treatments control only symptoms, and not the cause.
Therefore, with these metal salts, the patients cannot be treated easily.
The drugs cimetidine (Tegamet) and ranitidine (Zantac) prevent the
interaction of histamine with the receptors present in the stomach wall.
This resulted in release of lesser amount of acid.
12. Name a substance which can be used as an antiseptic as well as

disinfectant.
Soln. 0.2% solution of phenol is an antiseptic while its 1% solution is
disinfectant.
13. What are the main constituents of dettol?

Soln. Dettol is a mixture of chloroxylenol (4-chloro-3,5-dimethylphenol)
and terpineol.
14. What is tincture of iodine? What is its use?

Soln. 2-3% solution of iodine in alcohol-water mixture is known as tincture
of iodine. It is a powerful antiseptic.
15. What are food preservatives?

Soln. Food preservatives prevent spoilage of food due to microbial growth
or these may be defined as the substances which are capable of inhibiting
the process of fermentation, acidification or any other decomposition of
food. The most commonly used preservatives include table salt, sugar,
vegetable oils and sodium benzoate. Salts of sorbic acid and propanoic
acid are also used as preservatives.
16. Why is use of aspartame limited to cold foods and drinks?

Soln. Use of aspartame is limited to cold foods and soft drinks because it
in unstable to heat and decomposes at cooking temperature.
17. What are artificial sweetening agents? Give two examples.

Soln. The chemical substances which give sweetening effect to food but
do not add any calorie to our body are celled artificial sweetening agents.
e.g., aspartame, saccharin etc.
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18. Name the sweetening agent used in the preparation of sweets for a
diabetic patient.
Soln. Saccharin is of great value of diabetic persons and people
who need to control intake of calories because it is excreted from the
body in urine unchanged and appears to be entirely inert and harmless
when taken.
19. What problem arises in using alitame as artificial sweetener?

Soln. Alitame is high potency sweetener (2000 times as sweet as cane
sugar). The control of sweetness of food is difficult while using it.
20. How are synthetic detergents better than soaps?

Soln. Soaps when used in hard water form insoluble precipitates which
separate as scum in water and are useless as cleansing agent. In fact these
are hindrance to good washing, because the precipitate adheres onto the
fibre of the cloth as gummy mass. On the other hand, synthetic detergents
can be used both in soft and hard water as they give foam even in hard
water. Some of the detergents give foam even in ice cold water.
21. Explain the following terms with suitable examples

(i) cationic detergents
(ii) anionic detergents and
(iii) non-ionic detergents.
Soln. (i) Cationic detergents : Cationic detergents are quarternary
ammonium salts of amines with acetates, chlorides or bromides as
anions. Cationic part possess a long hydrocarbon chain and a positive
charge on nitrogen atom. Hence, these are called cationic detergents.
Cetyltrimethylammonium bromide is a popular cationic detergent and is
used in hair conditioners.
+
CH3
CH 3(CH 2 ) 15 N CH 3 Br–
CH3
Cetyltrimethyl ammonium bromide
Cationic detergents have germicidal properties and are expensive,
therefore these are of limited use.
(ii) Anionic detergents : Anionic detergents are sodium salts of
sulphonated long chain alcohols or hydrocarbons. Alkyl
hydrogensulphates formed by treating long chain alcohols with
concentrated sulphuric acid are neutralised with alkali to form anionic
detergents. Similarly alkyl benzene sulphonates are obtained by
neutralising alkyl benzene sulphonic acids with alkali.
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H2 SO 4 2 4 H SO
CH3(CH2 )10CH 2OH CHCH
3(CH 2 ) 102CH
3 (CH 2OH
)10CH 2OSO3H
CH3 (CH2 )10CH 2OSO3H
Lauryl alcohol Lauryl alcohol
Lauryl hydrogen Lauryl hydrogen
sulphate sulphate
NaOH (aq) NaOH (aq)

CH3 (CH2 )10CH 2OSO – + (CH2 )10CH 2OSO –
CH 3 Na
+
3 Na 3
sodium lauryl sulphate sodium lauryl sulphate
In anionic detergents, the anionic part of the molecule is involved in

the cleansing action. Sodium salts of alkylbenzenesulphonates are an
important class of anionic detergents.
They are mostly used for household work. Anionic detergents are also
used in toothpastes.
(iii) Non-ionic detergents : Non-ionic detergents do not contain any ion
in their constitution. One such detergent is formed when stearic acid
reacts with polyethyleneglycol.
Liquid dishwashing detergents are non-ionic type.
22. What are biodegradable and non-biodegradable detergents? Give one

example of each.
Soln. Biodegradable detergents : Detergents having straight hydrocarbon
chains are easily degraded by microorganisms and hence are called
biodegradable detergents. e.g.,
– –
CH 3(CH2 )10CH 2OSO 3 Na+ CH3 (CH 2)11 SO3 Na+
Sodium lauryl sulphate
Sodium p-(n-dodecyl) benzene sulphonate
Non-biodegradable detergents : Detergents containing branched
hydrocarbon chains are not easily degraded by the microorganisms and
hence are called non-biodegradable detergents.
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23. Why do soaps not work in hard water?
Soln. Hard water contains calcium and magnesium ions. These ions form
insoluble calcium and magnesium soaps respectively when sodium or
potassium soaps are dissolved in hard water.
These insoluble soaps separate as scum in water and are useless as

cleansing agent. In fact these are hindrance to good washing, because the
precipitate adheres onto the fibre of the cloth as gummy mass.
24. Can you use soaps and synthetic detergents to check the hardness of
water?
Soln. Soaps and detergents can be used to check the hardness of water.
Hard water forms curdy white precipitate with Ca2+ and Mg2+ ions present
in hard water whereas no such precipitates are formed by detergents in
hard water.
25. Explain the cleansing action of soaps.

Soln. Soap is sodium or potassium salt of a higher fatty acid and may
be represented as RCOO– Na+ (e.g., sodium stearate CH3(CH2)16COO– Na+.
When dissolved in water, it dissociates into RCOO– and Na+ ions. The
RCOO– ions, however, consist of two parts – a long hydrocarbon chain R
(also called non-polar ‘tail’) which is hydrophobic (water repelling), and
a polar group COO– (also called polar-ionic ‘head’), which is hydrophilic
(water loving).
The RCOO– ions are, therefore, present on the surface with their COO–
groups in water and the hydrocarbon chains R staying away from it and
remain at the surface. But at critical micelle concentration, the anions are
pulled into the bulk of the solution and aggregate to form a spherical
shape with their hydrocarbon chains pointing towards the centre of the
sphere with COO– part remaining outward on the surface of the sphere.
An aggregate thus formed is known as ‘ionic micelle’. These micelles may
contain as many as 100 such ions.
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The cleansing action of soap is due to the fact that soap molecules form
micelle around the oil droplet in such a way that hydrophobic part of the
stearate ions is in the oil droplet and hydrophilic part projects out of the
grease droplet like the bristles. Since the polar groups can interact with
water, the oil droplet surrounded by stearate ions is now pulled in water
and removed from the dirty surface. Thus soap helps in emulsification and
washing away of oils and fats. The negatively charged sheath around the
globules prevents them from coming together and forming aggregates.
(c)
26. Ifwater contains dissolved calcium hydrogen carbonate, out of soaps

and synthetic detergents which one will you use for cleaning clothes?
Soln. Synthetic detergents.
27. Label the hydrophilic and hydrophobic parts in the following

compounds.
–
(i) CH3(CH2)10CH2OSO3 Na+
+
(ii) CH3(CH2)15 N (CH3)3 Br–
(iii) CH3(CH2)16COO(CH2CH2O)nCH2CH2OH
Soln. Hydrophobic Hydrophilic
(i) CH3(CH2)10CH2 OSO3– Na+
(ii) CH3(CH2)15 N+(CH3)3Br–
(iii) CH3(CH2)16 COO(CH2CH2O)nCH2CH2OH

1. Sleeping pills are recommended by doctors to the patients suffering
from sleeplessness but it is not advisable to take its doses without
consultation with the doctor. Why ?
Soln. Most of the drugs taken in doses higher than recommended may
cause harmful effect and act as poison. Therefore, a doctor should always
be consulted before taking medicine.
2. With reference to which classification has the statement, “ranitidine is

an antacid” been given?
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Soln. This statement refers to the classification according to pharmacological
effect of the drug because any drug which will be used to counteract the
effect of excess acid in the stomach will be called antacid.
3. Why do we require artificial sweetening agents?

Soln. Those people who have diabetes or who need to control intake of
calories, they cannot take sugar. They need its substitute. These substitutes
are called artificial sweeteners. These are excreted from the body in urine
unchanged.
4. Write the chemical equation for preparing sodium soap from

glyceryloleate and glyceryl palmitate. Structural formulae of these
compounds are given below.
(i) (C15H31COO)3C3H5 – Glyceryl palmitate
(ii) (C17H33COO)3C3H5 – Glyceryl oleate.
Soln.
5. Following type of non-ionic detergents are present in liquid detergents,

emulsifying agents and wetting agents. Label the hydrophilic and
hydrophobic parts in the molecule. Identify the functional group(s) present
in the molecule.
C9H19 O(CH2CH2O)xCH2CH2OH
(x = 5 to 10)
Soln. C9H19 O(CH2CH2O)xCH2CH2OH
Hydrophobic or Hydrophilic or polar part

non polar part
The functional groups present in the molecule are alcoholic group
and ethereal linkage (—O—).

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1 NCERT 12th Chemistry Solution

1. Define the term ‘amorphous’. Give a few examples of amorphous

Soln. Glass is an amorphous solid in which the constituent particles (SiO4

3. Classify each of the following solids as ionic, metallic, molecular,

(i) Tetraphosphorus decoxide, P4O10

Soln. P4O10 - molecular, (NH4)3PO4 - ionic, SiC - network(covalent),

4. (i) What is meant by the term ‘coordination number’?

(a) in a cubic close-packed structure?

(a) Octahedral voids : This void is surrounded by six spheres and

As spheres are touching each other, evidently, a = 2r

13. Niobium crystallises in body-centred cubic structure. If density is

Perfect crystal n-type p -type

18. Non-stoichiometric cuprous oxide, Cu2O can be prepared in laboratory.

19. Ferric oxide crystallises in a hexagonal close-packed array of oxide ions

20. Classify each of the following as being either a p-type or n-type

Forbidden zone Small energy gap

23. Explain the following terms with suitable examples :

(iii) Interstitial defect : When some constituent particles (atoms or

26. Explain the following with suitable example :

(ii) Paramagnetic substances : Substances which are weakly attracted

(iv) Antiferromagnetic substances : Substances which are expected

Chapter Intext Question

2. Why do solids have a definite volume?

4. Why is glass considered a supercooled liquid?

5. Refractive index of a solid is observed to have the same value along

6. Classify the following solids in different categories based on the nature

7. Solid A is a very hard electrical insulator in solid as well as in molten

10. Give the significance of a ‘lattice point’.

11. Name the parameters that characterise a unit cell.

12. Distinguish between

15. A compound forms hexagonal close-packed structure. What is the total

16. A compound is formed by two elements M and N. The element N forms

Number of atoms of element M = 1 × 2 a = 2 a

20. What type of stoichiometric defect is shown by :

23. A group 14 element is to be converted into n-type semiconductor by

Soln. Solution - A solution is a homogeneous mixture of two or more

(b) Liquid solutions :

(i) Solvent - liquid, solute - gas. e.g., aerated drinks.

(c) Solid solutions :

(i) Solvent - solid, solute - gas. e.g., H2 in palladium.

3. Define the following terms :

(i) Mole fraction (ii) Molality

5. A solution of glucose in water is labelled as 10% w/w. What would be

(b) x (Glucose) = Number of moles of solute = 0.0555 = 0.01

12. State Henry’s law and mention some important applications.

13. The partial pressure of ethane over a saturated solution containing

then what shall be the partial pressure of the gas?

15. An aqueous solution of 2% non-volatile solute exerts a pressure of

25. Amongst the following compounds, identify which are insoluble,

27. If the solubility product of CuS is 6 × 10–16, calculate the maximum

28. Calculate the mass percentage of aspirin (C9H8O4) in acetonitrile (CH3CN)

32. Calculate the depression in the freezing point of water when 10 g of

33. 19.5 g of CH2FCOOH is dissolved in 500 g of water. The depression in

Applying Henry’s law , pO2 = KH × xO2

0.75 atm × 2.5 L

Chapter Intext Question

molar conductivity of the ions in which it dissociates. It is known as law of

2. Given the standard electrode potentials,

3. Depict the galvanic cell in which the reaction :

Zn(s) | Zn2+(aq) ||Ag+(aq) | Ag(s)

(i) Anode, i.e., zinc electrode will be negatively charged.

4. Calculate the standard cell potentials of galvanic cell in which the

(i) 2Cr(s) + 3Cd2+(aq) → 2Cr3+(aq) + 3Cd(s)