Solid State

1. Choose the most correct answer.

Question i.
Molecular solids are
(a) crystalline solids
(b) amorphous solids
(c) ionic solids
(d) metallic solids
Answer:
(b) amorphous solids

Question ii.
Which of the following is n-type semiconductor?
(a) Pure Si
(b) Si doped with As
(c) Si doped with Ga
(d) Ge doped with In
Answer:
(b) Si doped with As

Question iii.
In Frenkel defect
(a) electrical neutrality of the substance is changed.
(b) density of the substance is changed.
(c) both cation and anion are missing
(d) overall electrical neutrality is preserved
Answer:
(d) overall electrical neutrality is preserved

Question iv.
In crystal lattice formed by bcc unit cell the void volume is
(a) 68%
(b) 74%
(c) 32%
(d) 26%
Answer:
(c) 32%

Question v.
The coordination number of atoms in bcc crystal lattice is
(a) 2
(b) 4
(c) 6
(d) 8
Answer:
(d) 8

Question vi.
Which of the following is not correct ?
(a) Four spheres are involved in the formation of tetrahedral void.
(b) The centres of spheres in octahedral voids are at the a pices of a regular
tetrahedron.
(c) If the number of atoms is N the number of octahedral voids is 2N.
(d) If the number of atoms is N/2, the number of tetrahedral voids is N.
Answer:
(c) If the number of atoms is N the number of octahedral voids is 2N.

Question vii.
A compound forms hcp structure. Number of octahedral and tetrahedral voids
in 0.5 mole of substance is respectively
(a) 3.011 × 1023, 6.022 × 1023
(b) 6.022 × 1023, 3.011 × 1023
(c) 4.011 × 1023, 2.011 × 1023
(d) 6.011 × 1023, 12.022 × 1023
Answer:
(a) 3.011 × 1023, 6.022 × 1023

Question viii.
Pb has fcc structure with edge length of unit cell 495 pm. Radius of Pb atom is
(a) 205 pm
(b) 185 pm
(c) 260 pm
(d) 175 pm
Answer:
(d) 175 pm

2. Answer the following in one or two sentences.

Question i.
What are the types of particles in each of the four main classes of crystalline
solids?
Answer:
The smallest constituents or particles of various solids are atoms, ions or
molecules.

Question ii.
Which of the three types of packing used by metals makes the most efficient
use of space and which makes the least efficient use ?
Answer:
fcc has the most efficient packing of particles while scc has the least efficient
packing.

Question iii.
The following pictures show population of bands for materials having different
electrical properties. Classify them as insulator, semiconductor or a metal.

Answer:
Picture A represents metal conductor,
Picture B represents insulator,
Picture C represents semiconductor.

Question iv.
What is a unit cell?
Answer:

 Unit cell : It is the smallest repeating structural unit of a crystalline solid

(or crystal lattice) which when repeated in different directions produces
the crystalline solid (lattice).
 The crystal is considered to consist of an infinite number of unit cells.
 The unit cell possesses all the characteristics of the crystalline solid.

Question v.
How does electrical conductivity of a semiconductor change with
temperature ? Why?
Answer:

 Since the energy difference between valence band and conduction band
in semiconductor is not large, the electrons from valence band can be
promoted to conduction by heating.
 Hence electrical conductivity of a semiconductor increases with
temperature.

Question vi.
The picture represents bands of MOs for Si. Label valence band, conduction
band and band gap.
Answer:

Question vii.
A solid is hard, brittle and electrically non-conductor. Its melt conducts
electricity. What type of solid is it?
Answer:
A solid crystalline electrolyte like NaCl is hard, brittle and electrically
nonconductor. But its melt conducts electricity.

Question viii.
Mention two properties that are common to both hep and ccp lattices.
Answer:
In hcp and ccp crystal lattices coordination number is 12 and packing
efficiency is 74%.

Question ix.
Sketch a tetrahedral void.
Answer:
Question x.
What are ferromagnetic substances?
Answer:

1. The substances which possess unpaired electrons and high

paramagnetic character and when placed in a magnetic field are
strongly attracted and show permanent magnetic moment even when
the external magnetic field is removed are said to be ferromagnetic.
They can be permanently magnetised.
2. In the solid state, the metal ions of ferromagnetic substance are
grouped together into small regions called domains, where each
domain acts as a tiny magnet.

For example : Fe, Co, Gd, Ni, CrO2, etc.

3. Answer the following in brief.

Question i.
What are valence band and conduction band?
Answer:
There are two types of bands of molecular orbitals as follows :

 Valence band : The atomic orbitals with filled electrons from the inner
shells form valence bands, where there are no free mobile electrons
since they are involved in bonding.
 Conduction band : Atomic orbitals which are partially filled or empty on
overlapping form closely placed molecular orbitals giving conduction
bands where electrons are delocalised and can conduct, heat and
electricity.
Question ii.
Distinguish between ionic solids and molecular solids.
Answer:

Type/ Property Ionic solids Molecular solids

Monoatomic or polyatom
1. Particles of unit cell Cations and anions
molecules
London, dipole-dipole fo
2. Interparticle forces Electrostatic
and/or hydrogen bonds
3. Hardness Hard and brittle Soft
4. Melting points High 600 °C to 3000 °C Low (-272 °C to 400 °C)
Poor electrical conductors in
5. Thermal and electrical solid state. Good conductors Poor conductor of heat a
conductivity when melted or dissolved in electricity
water.
6. Examples NaCl, CaF2 ice, benzoic acid

Question iii.
Calculate the number of atoms in fcc unit cell.
Answer:
Number of atoms in face-centred cubic (fcc) unit cell :
In this unit cell, there are 8 atoms at 8 corners and 6 atoms at 6 face centres.
Each corner contributes 1/8th atom to the unit cell, hence due to 8 corners,
Number of atoms = 18 × 8 = 1.
Each face centre contributes half of the atom to the unit cell, hence due to 6
face centres,
Number of atoms = 12 × 6 = 3.
∴ Total number of atoms present in fee unit cell = 1 + 3 = 4.
Hence the volume of the unit cell is equal to the volume of four atoms.
Face centered unit cell

Question iv.
How are the spheres arranged in first layer of simple cubic close-packed
structures? How are the successive layers of spheres placed above this layer ?
Answer:
(i) Stacking of square close packed layers :

Stacking of square close packed layers

In this arrangement, the two dimensional AAAA type square closed packed
layers are placed one over the other in such a way that the crests of all spheres
are in contact with successive layers in all directions. All spheres of different
layers are perfectly aligned horizontally and vertically forming unit cells having
primitive or simple cubic structure. Since all the layers are identical and if each
layer is labelled as layer A, then whole three dimensional crystal lattice will be
of AAAA… type.
Each sphere is in contact with six surrounded spheres, hence the coordination
number of each sphere is six.

(ii) Stacking of two hexagonal close packed layers :

A close packed three dimensional structure can be generated by arranging
hexagonal close packed layers in a particular manner.

In this the spheres of second layer are placed in the depression of the first
layer.
In this if first layer is labelled as A then second layer is labelled as B since they
are aligned differently.

Two layers of closed packed spheres

In this, all triangular voids of the first layers are not covered by the spheres of
the second layer. The triangular voids which are covered by second layer
spheres generate tetrahedral void which is surrounded by four spheres. The
triangular voids in one layer have above them triangular voids of successive
layers.

The overlapping triangular voids from two layers together form an octahedral
void which is surrounded by six spheres.

Question v.
Calculate the packing efficiency of metal crystal that has simple cubic
structure.
Answer:
Step 1 : Radius of sphere : In simple cubic lattice, the atoms (spheres) are
present at eight corners and in contact along the edge in the unit cell.
If ‘a’ is the edge length of the unit cell and ‘r’ is the radius of the atom, then
a = 2r or r = a/2

scc structure

Step 2 : Volume of sphere :

Volume of one particle = 4π3 × r3
= 4π3 × (a/2)3 = πa36

Step 3 : Total volume of particles : Since the unit cell contains one particle.
Volume occupied by one particle in unit cell = πa36

Step 4 : Packing efficiency :

Packing efficiency

∴ Packing efficiency = 52.36%

Percentage of void space = 100 – 52.36
= 47.64%

Question vi.
What are paramagnetic substances? Give examples.
Answer:
(1) The magnetic properties of a substance arise due to the presence of
electrons.
(2) An electron while revolving around the nucleus, also spins around its own
axis and generates a magnetic moment and magnetic properties.
(3) If an atom or a molecule contains one or more unpaired electrons spinning
in same direction, clockwise or anticlockwise, then the substance is associated
with net magnetic moment and magnetic properties. They experience a net
force of attraction when placed in the magnetic field. This phenomenon is
called paramagnetism and the substance is said to be paramagnetic.
For example, O2, Cu2+, Fe3+ , Cr3+ , NO, etc.

Question vii.
What are the consequences of Schottky defect?
Answer:
Consequences of Schottky defect :

 Since the number of ions (cations and anions) decreases but volume
remains unchanged, the density of a substance decreases.
 As the number of missing cations and anions is equal, the electrical
neutrality of the compound remains same.
 This defect arises in ionic crystals like NaCl, AgBr, KCl, etc.

Question viii.
Cesium chloride crystallizes in cubic unit cell with Cl – ions at the corners and
Cs+ ion in the centre of the cube. How many CsCl molecules are there in the
unit cell ?
Answer:
Number of Cs+ ion at body centre = 1
Number of Cl– ions due to 8 comers = 8 × 18 = 1
Hence unit cell contains 1 CsCl molecule.

Question ix.
Cu crystallizes in fee unit cell with edge length of 495 pm. What is the radius
of Cu atom ?
Answer:
Given : a = 495 pm
Radius, r = ?
For fee structure,
radius = r = a22√=4952×2√ = 175 cm.
Radius of Cu atom = 175 pm

Question x.
Obtain the relationship between density of a substance and the edge length
of unit cell.
Answer:
(1) Consider a cubic unit cell of edge length ‘a’.
The volume of unit cell = a3

(2) If there are ‘n’ particles per unit cell and the mass of particle is ‘m’, then
Mass of unit cell = m × n.

(3) If the density of the unit cell of the substance is p then

Density of unit cell = Mass of unit cell Volume of unit cell
ρ = m×na3

Question 4.
The density of iridium is 22.4 g/cm3. The unit cell of iridium is fcc. Calculate the
radius of iridium atom. Molar mass of iridium is 192.2 g/mol.
Answer:
Given : Crystal structure of iridium = fcc
Molar mass of iridium = 192.2 gmol-1
Density = ρ = 22.4 gcm-3
Radius of iridium = ?
In fcc structure, there are 8 Ir atoms at 8 comers and 6 Ir atoms at 6 face
centres.
∴ Total number of Ir atoms = 18 × 8 + 12 × 6
=1+3
=4
Mass of Ir atom = 192.26.022×1023
= 31.92 × 10-23 g
∴ Mass of 4 Ir atoms = 4 × 31.92 × 10-23
= 1.277 × 10-21 g
∴ Mass of unit cell = 1.277 × 10-21 g
Density of unit cell = Mass of unit cell Volume of unit cell
22.4 = 1.277×10−21a3
∴ a3 = 1.277×10−2122.4
= 57 × 10-24 cm3
∴ a = (57 × 10-24)3 = 3.848 × 10-8 cm
If r is the radius of iridium atom, then for fcc structure,
r = a22√
= 3.848×10−82×1.414
= 1.36 × 10-8 cm
= 136 pm
Radius of iridium atom = 136 pm

Question 5.
Aluminium crystallizes in cubic close packed structure with unit cell edge
length of 353.6 pm. What is the radius of Al atom ? How many unit cells are
there in 1.00 cm3 of Al ?
Answer:
Given : Structure of Al
= Cubic close packed structure
= ccp structure
Edge length of unit cell = a = 353.6 pm
= 3.536 × 10-8 cm
r=?
Number of unit cells in 1.00 cm3 of Al = ?
Radius of Al atom = r = a22√=353.622√
= 353.62×1.414 = 125 pm
Volume of one unit cell = a3 = (3.536 × 10-8)3
= 4.421 × 10-23 cm3
Number of unit cells = 1.004.421×10−23
= 2.26 × 1022
Radius of Al atom = 125 pm
Number of unit cells = 2.26 × 1022
Question 6.
In an ionic crystalline solid atoms of element Y form hcp lattice. The atoms of
element X occupy one third of tetrahedral voids. What is the formula of the
compound?
Answer:
In the given hcp lattice, Y atoms are present at 12 corners and 2 face centres.
∴ Number of Y atoms = 12 × 12 + 2 × 12 = 3
There are 6 tetrahedral voids, the number of X atoms = 13 × 6 = 2
∴ Formula of the compound is X2Y3.

Question 7.
How are tetrahedral and octahedral voids formed?
Answer:
Tetrahedral void : The vacant space or void among four constituent particles
having tetrahedral arrangement in the crystal lattice is called tetrahedral void.

The arrangement of four spheres around the void is tetrahedral. A tetrahedral

void is formed when a triangular void made by three coplanar spheres is in
contact with fourth sphere above or below it.
Octahedral void : The vacant space or void at the centre of six spheres (or
atoms) which are placed octahedrally is called octahedral void.

Question 8.
Third layer of spheres is added to second layer so as to form hcp or ccp
structure. What is the difference between the addition of third layer to form
these hexagonal close-packed structures?
Answer:

1. In the formation of hexagonal closed-packed (hcp) structure, the first

one dimensional row shows depressions between neighbouring atoms.
2. When a second row is arranged so that spheres fit in these depressions
then a staggered arrangement is obtained. If the first row is A then the
second row is B.
3. When third row is placed in staggered manner in contact with second
row then A type arrangement is obtained.
4. Similarly, the spheres in fourth row can be arranged as B type layer. This
results in ABAB… type setting of the layers. This gives hexagonal close
packing (hcp) structure.
Hexagonal close packing (hcp)

Question 9.
An element with molar mass 27 g/mol forms cubic unit cell with edge length
of 405 pm. If density of the element is 2.7 g/cm 3, what is the nature of cubic
unit cell ? (fcc or ccp)
Answer:
Given : Molar mass = M = 27 g mol-1
Nature of crystal = cubic unit cell
Edge length = a = 405 pm = 4.05 × 10-8 cm
Density = ρ = 2.7 g cm-3
Nature of unit cell = ?

= 3.997
≅4
Hence the nature of unit cell = face-centred cubic unit cell
Radius of Al atom = 125 pm
The nature of cubic unit cell is fcc.

Question 10.
An element has a bcc structure with unit cell edge length of 288 pm. How
many unit cells and number of atoms are present in 200 g of the element?
(1.16 × 1024, 2.32 × 1024)

Question 11.
Distinguish with the help of diagrams metal conductors, insulators and
semiconductors from each other.
Answer:
Conductor:

1. A substance which conducts heat and electricity to a greater extent is

called conductor.
2. In this, conduction bands and valence bands overlap or are very closely
spaced.
3. There is no energy difference or very less energy difference between
valence bands and conduction bands.
4. There are free electrons in the conduction bands.
5. The conductance decreases with the increase in temperature.
6. E.g., Metals, alloys.
7. The conducting properties can’t be improved by adding third substance.

Insulator:
 1. A substance which cannot conduct heat and electricity under any
conditions is called insulator.
2. In this, conduction bands and valence bands are far apart.
3. The energy difference between conduction bands and valence bands is
very large.
4. There are no free electrons in the conduction bands and electrons can’t
be excited from valence bands to conduction bands due to large energy
difference.
5. No effect of temperature on conducting properties.
6. E.g., Wood, rubber, plastics.
7. No effect of addition of any substance.

Semiconductor:

1. A substance that has poor electrical conductance at low temperature

but higher conductance at higher temperature is called semiconductor.
2. In this, conduction bands and valence bands are spaced closely.
3. The energy difference between conduction bands and valence bands is
small.
4. The electrons can be easily excited from valence bands to conduction
bands by heating.
5. Conductance increases with the increase in temperature.
6. E.g., Si, Ge
7. By doping, conducting properties improve. E.g. n-type, p-type
semiconductors.
Question 12.
What are n-type semiconductors? Why is the conductivity of doped n-type
semiconductor higher than that of pure semiconductor ? Explain with diagram.
Answer:
n-type semiconductor:

 n-type semiconductor contains increased number of electrons in the

conduction band.
 When Si semiconductor is doped with 15th group element phosphorus,
P, the new atoms occupy some vacant sites in the lattice in place of Si
atoms.
 P has five valence electrons, out of which four are involved in covalent
bonding with neighboring Si atoms while one electrons remains free
and delocalised.
 These free electrons increase the electrical conductivity of the
semiconductor.
 The semiconductors with extra non-bonding free electrons are called n-
type semiconductors.
P atom occupying regular site of Si atom

Question 13.
Explain with diagram. Frenkel defect. What are the conditions for its
formation? What is its effect on density and electrical neutrality of the crystal?
Answer:

1. Frenkel defect : This defect arises when an ion of an ionic compound is

missing from its regular site and occupies interstitial vacant position
between lattice points.
2. Cations have smaller size than anions, hence generally cations occupy
the interstitial sites.
3. This creates a vacancy defect at its original position and interstitial
defect at new position.
 4. Frenkel defect is regarded as the combination of interstitial defect and
vacancy defect.

Conditions for the formation of Frenkel defect :

1. This defect arises in ionic compounds with a large difference between

the sizes of cation and anion.
2. The ionic compounds must have ions with low coordination number.

Consequences of Frenkel defect :

1. Since there is no loss of ions from the crystal lattice, the density of the
solid remains unchanged.
2. The crystal remains electrically neutral.
3. This defect is observed in ZnS, AgCl, AgBr, Agl, CaF 2, etc.

Question 14.
What is an impurity defect? What are its types? Explain the formation of
vacancies through aliovalent impurity with example.
Answer:
Impurity defect : This defect arises when foreign atoms, that is, atoms different
from the host atoms are present in the crystal lattice.

There are two types of impurity defects namely

1. Substitutional defects and

2. Interstitial defects.

(1) Substitutional defects : These defects arises when foreign atoms occupy the
lattice sites in place of host atoms, due to their displacements.
Examples : Solid solutions of metals (alloys). For example. Brass in which host
atoms are of Cu which are replaced by impurity of Zn atoms. In this Zn atoms
occupy regular sites while Cu atoms occupy substituted sites.
Brass

Vacancy through aliovalent impurity :

By addition of impurities of aliovalent ions :

Vacancy through aliovalent ion

When aliovalent ion like Sr2+ in small amount is added by additing SrCl2 to
NaCl during its crystallisation, each Sr2+ ion (oxidation state 2+) removes 2
Na+ ions from their lattice points, to maintain electrical neutrality. Hence one
of vacant lattice site is occupied by Sr2+ ion while other site remains vacant.

Interstitial impurity defect :

Stainless steel
A defect in solid in which the impurity atoms occupy interstitial vacant spaces
of lattice structure is called interstitial impurity defect.

For example, in steel, normal lattice sites are occupied by Fe atoms but
interstitial spaces are occupied by carbon atoms.

12th Chemistry Digest Chapter 1 Solid State Intext Questions and

Answers

Try this… (Textbook Page No. 1)

Observe the above figure carefully. The two types of circles in this figure
represent two types of constituent particles of a solid.

Question 1.
Will you call the arrangement of particles in this solid regular or irregular ?
Answer:
The arrangement of particles in this solid is regular.

Question 2.
Is the arrangement of constituent particles in
directions AB−→−, CD−→− and EF−→− same or different?
Answer:
AB−→− represents arrangement of identical particles of one type.
CD−→− represents arrangement of identical particles of another type.
EF−→− represents regular arrangement of two different particles in
alternate positions.

Use your brain power ! (Textbook Page No. 2)

Question 1.
Identify the arrangements A and B as crystalline or amorphous.

Answer:
Arrangement in image A indicates the substance is crystalline.
Arrangement in image B indicates the substance is amorphous.

Try this… (Textbook Page No. 3)

Question 1.
Graphite is a covalent solid yet soft and good conductor of electricity. Explain.
Answer:

1. Each carbon atom in graphite is sp2 hybridised and covalently bonded to

other three sp2 hybridised carbon atoms forming σ bonds and the
fourth electron in 2pz orbital of each carbon atom is used in the
formation of a π bond. This results in the formation of hexagonal rings
in two dimensions.
2. In graphite, the layers consisting of hexagonal carbon network are held
together by weak van der Waal’s forces imparting softness.
3. The electrons in π bonds in the ring are delocalised and free to move in
the delocalised molecular orbitals giving good electrical conductance.

Use your brain power ! (Textbook Page No. 13)

Question 1.
Which of the three lattices scc, bcc and fcc has the most efficient packing of
particles ? Which one has the least efficient packing ?
Answer:
fcc has the most efficient packing of particles while see has the least efficient
packing.

Can you think ? (Textbook Page No. 20)

Question 1.
When ZnO is heated it turns yellow and returns back to original white colour
on cooling. What could be the reason ?
Answer:
When colourless ZnO is strongly heated, the metal atoms are deposited on
crystal surface and anions O2- migrate to the surface producing vacancies at
anion lattice points.

These anions combine with Zn atoms forming ZnO and release electrons.
Zn + O2- → ZnO + 2e–

These released electrons diffuse into the crystal and occupy vacant sites of
anions and produce F- centres. Due to these colour centres, ZnO turns yellow.

Can you tell ? (Textbook Page No. 23)

Let a small quantity of phosphorus be doped into pure silicon.

Question 1.
Will the resulting material contain the same number of total number of
electrons as the original pure silicon ?
Answer:
Total number of electrons in doped silicon will be more than in original silicon.

Question 2.
Will the material be electrically neutral or charged ?
Answer:
Material will be electrically neutral.
Solutions
1. Choose the most correct answer.

Question i.
The vapour pressure of a solution containing 2 moles of a solute in 2 moles of
water (vapour pressure of pure water = 24 mm Hg) is
(a) 24 mm Hg
(b) 32 mm Hg
(c) 48 mm Hg
(d) 12 mm Hg
Answer:
(d) 12 mm Hg

Question ii.
The colligative property of a solution is
(a) vapour pressure
(b) boiling point
(c) osmotic pressure
(d) freezing point
Answer:
(c) osmotic pressure

Question iii.
In calculating osmotic pressure the concentration of solute is expressed in
(a) molarity
(b) molality
(c) mole fraction
(d) mass per cent
Answer:
(a) molarity

Question iv.
Ebullioscopic constant is the boiling point elevation when the concentration of
solution is
(a) 1 m
(b) 1 M
(c) 1 mass%
(d) 1 mole fraction of solute
Answer:
(a) 1 m

Question v.
Cryoscopic constant depends on
(a) nature of solvent
(b) nature of solute
(c) nature of solution
(d) number of solvent molecules
Answer:
(a) nature of solvent

Question vi.
Identify the correct statement
(a) vapour pressure of solution is higher than that of pure solvent.
(b) boiling point of solvent is lower than that of solution
(c) osmotic pressure of solution is lower than that of solvent
(d) osmosis is a colligative property.
Answer:
(b) boiling point of solvent is lower than that of solution

Question vii.
A living cell contains a solution which is isotonic with 0.3 M sugar solution.
What osmotic pressure develops when the cell is placed in 0.1 M KCl solution
at body temperature ?
(a) 5.08 atm
(b) 2.54 atm
(c) 4.92 atm
(d) 2.46 atm
Answer:
(c) 4.92 atm
Question viii.
The osmotic pressure of blood is 7.65 atm at 310 K. An aqueous solution of
glucose isotonic with blood has the percentage (by volume)
(a) 5.41%
(b) 3.54%
(c) 4.53%
(d) 53.4%
Answer:
(a) 5.41%

Question ix.
Vapour pressure of a solution is
(a) directly proportional to the mole fraction of the solute
(b) inversely proportional to the mole fraction of the solute
(c) inversely proportional to the mole fraction of the solvent
(d) directly proportional to the mole fraction of the solvent
Answer:
(d) directly proportional to the mole fraction of the solvent

Question x.
Pressure cooker reduces cooking time for food because
(a) boiling point of water involved in cooking is increased
(b) heat is more evenly distributed in the cooking space
(c) the higher pressure inside the cooker crushes the food material
(d) cooking involves chemical changes helped by a rise in temperature
Answer:
(a) boiling point of water involved in cooking is increased

Question xi.
Henry’s law constant for a gas CH3Br is 0.159 mol dm-3 atm at 250°C. What is
the solubility of CH3Br in water at 25 °C and a partial pressure of 0.164 atm?
(a) 0.0159 mol L-1
(b) 0.164 mol L-1
(c) 0.026 M
(d) 0.042 M
Answer:
(c) 0.026 M

Question xii.
Which of the following statement is NOT correct for 0.1 M urea solution and
0.05 M sucrose solution ?
(a) osmotic pressure exhibited by urea solution is higher than that exhibited by
sucrose solution
(b) urea solution is hypertonic to sucrose solution
(c) they are isotonic solutions
(d) sucrose solution is hypotonic to urea solution
Answer:
(c) they are isotonic solutions

2. Answer the following in one or two sentences

Question i.
What is osmotic pressure ?
Answer:
(1) Definition : The osmotic pressure is defined as the excess mechanical
pressure required to be applied to a solution separated by a semipermeable
membrane from pure solvent or a dilute solution to prevent the osmosis or
free passage of the solvent molecules at a given temperature. The osmotic
pressure is a colligative property.
Osmosis and osmotic pressure

(2) Explanation : Consider an inverted thistle funnel on the mouth of which a

semipermeable membrane is firmly fastened. It is filled with the experimental
solution and immersed in a solvent like water. As a result, solvent molecules
pass through the membrane into the solution in the funnel causing rising of
level in the arm of thistle funnel. This increases the hydrostatic pressure. At a
certain stage this rising level stops indicating an equilibrium between the rates
of flow of solvent molecules from solvent to solution and from solution to
solvent. The hydrostatic pressure at this stage represents osmotic pressure of
the solution in the thistle funnel.

Question ii.
A solution concentration is expressed in molarity and not in molality while
considering osmotic pressure. Why ?
Answer:

1. While calculating osmotic pressure by equation, π = CRT, the

concentration is expressed in molarity but not in molality.
2. This is because the measurements of osmotic pressure are made at a
certain constant temperature.
3. Molarity depends upon temperature but molality is independent of
temperature.
 4. Hence in osmotic pressure measurements, concentration is expressed in
molarity.

Question iii.
Write the equation relating boiling point elevation to the concentration of
solution.
Answer:
The elevation in the boiling point of a solution is directly proportional to the
molal concentration (expressed in mol kg-1) of the solution.
Hence, if ΔTb is the elevation in the boiling point of a solution of molal
concentration m then,
ΔTb ∝ m
∴ ΔTb = Kb m
where Kb is a proportionality constant.
If m = 1 molal,
ΔTb = Kb
Kb is called the ebullioscopic constant or molal elevation constant. K b is
characteristic of the solvent.

Question iv.
A 0.1 m solution of K2SO4 in water has freezing point of -0.43 °C. What is the
value of van’t Hoff factor if Kf for water is 1.86 K kg mol-1?
Answer:
Given : m = 0.1 m, ΔTf = 0 – (-0.43) = 0.43 °C
Kf = 1.86 K kg mol-1, i = ?
ΔTf = i × Kf × m
∴ i = ΔTfKf×m=0.431.86×0.1 = 2.312
van’t Hoff factor = i = 2.312

Question v.
What is van’t Hoff factor?
Answer:
Definition of the van’t Hoff factor, i : It is defined as a ratio of the observed
colligative property of the solution to the theoretically calculated colligative
property of the solution without considering molecular change.
The van’t Hoff factor can be represented as,

This colligative property may be the lowering of vapour pressure of a solution,

the osmotic pressure, the elevation in the boiling point or the depression in
the freezing point of the solution. Hence,

 When the solute neither undergoes dissociation or association in the

solution, then, i = 1
 When the solute undergoes dissociation in the solution, then, i > 1
 When the solute undergoes association in the solution, then i < 1

From the value of the van’t Hoff factor, the degree of dissociation of
electrolytes, degree of association of nonelectrolytes can be obtained.

van’t Hoff factor gives the important information about the solute molecules
in the solution and chemical bonding in them.
Question vi.
How is van’t Hoff factor related to degree of ionization?
Answer:
Consider 1 dm3 of a solution containing m moles of an electrolyte AxBy. The
electrolyte on dissociation gives x number of A y+ ions and y number of Bx- ions.
Let α be the degree of dissociation.

At equilibrium,
AxBy ⇌ xAy+ + yBx-
For 1 mole of electrolyte : 1 – α, xα, yα
and For ‘m’ moles of an electrolyte : m(1 – α), mxα, myα are the number of
particles.
Total number of moles at equilibrium, will be,
Total moles = m(1 – α) + mxα + myα
= m[(1 – α) + xα + yα]
= m[1 + xα + yα – α]
= m[1 + α(x + y – 1)]

The van’t Hoff factor i will be,

If total number of ions from one mole of electrolyte is denoted by n, then (x +

y) = n
∴ i = 1 + α(n – 1)
∴ α(n – 1) = i – 1
∴ α = i−1n−1 ……(1)
This is a relation between van’t Hoff factor i and degree of dissociation of an
electrolyte.

Question vii.
Which of the following solutions will have higher freezing point depression
and why ?
a. 0.1 m NaCl b. 0.05 m Al2(SO4)3
Answer:
(1) Freezing point depression is a colligative property, hence depends on the
number of particles in the solution.
(2) More the number of particles in the solution, higher is the depression in
freezing point.
(3) The number of particles (ions) from electrolytes are,

(4) Therefore Al2(SO4)3 solution will have higher freezing point depression.

Question viii.
State Raoult’s law for a solution containing a nonvolatile solute.
Answer:
Statement of Raoult’s law : The law states that the vapour pressure of a solvent
over the solution of a nonvolatile solute is equal to the vapour pressure of the
pure solvent multiplied by mole fraction of the solvent at constant
temperature.

Question ix.
What is the effect on the boiling point of water if 1 mole of methyl alcohol is
added to 1 dm3 of water? Why?
Answer:

 The boiling point of water (or any liquid) depends on its vapour
pressure.
 Higher the vapour pressure, lower is the boiling point.
 When 1 mole of volatile methyl alcohol is added to 1 dm 3 of water, its
vapour pressure is increased decreasing the boiling point of water.
Question x.
Which of the four colligative properties is most often used for molecular mass
determination? Why?
Answer:

1. Since osmotic pressure has large values, it can be measured more

precisely.
2. The osmotic pressure can be measured at a suitable constant
temperature.
3. The molecular masses can be measured more accurately.
4. Therefore, it is more useful to determine molecular masses of expensive
substances by osmotic pressure.

3. Answer the following.

Question i.
How vapour pressure lowering is related to a rise in boiling point of solution?
Answer:
(1) The boiling point of a liquid is the temperature at which the vapour
pressure of the liquid becomes equal to the external pressure, generally 1 atm
(101.3 × 103 Nm-2).

(2) When a liquid is heated, its vapour pressure rises till it becomes equal to
the external pressure.
If the liquid has a low vapour pressure, it has a higher boiling point.

Vapour pressure curve showing elevation in boiling point

(3) When a nonvolatile solute is added to a solvent, its vapour pressure
decreases, hence the boiling point increases.
This is explained by graphical representation of the vapour pressure and the
boiling point of the pure solvent and the solution.

If T0 and T are the boiling points of a pure solvent and a solution, then the
elevation in the boiling point is given by,
ΔTb = T – T0
The curve AB, represents the variation in the vapour pressure of a pure solvent
with temperature while curve CD represents the variation in the vapour
pressure of the solution.

(4) This elevation in the boiling point is proportional to the lowering of the
vapour pressure, i.e., P0 – P, where P0 and P are the vapour pressures of the
pure solvent and the solution.
[ΔTb ∝ (P0 – P) or ΔTb ∝ ΔP]

Question ii.
What are isotonic and hypertonic solutions?
Answer:
(1) Isotonic solutions : The solutions having the same osmotic pressure at a
given temperature are called isotonic solutions.

Explanation : If two solutions of substances A and B contain n A and nB moles

dissolved in volume V (in dm3) of the solutions, then their concentrations are,
CA = nAV (in mol dm-3) and
CB = nBV (in mol dm-3)

If the absolute temperature of both the solutions is T, then by the van’t Hoff
equation,
πA = CART and πB = CBRT, where πA and πB are their osmotic pressures.
For the isotonic solutions,
πA = πB
∴ CA = C B
∴ nAV=nBV
∴ nA = nB
Hence, equal volumes of the isotonic solutions at the same temperature will
contain equal number of moles (hence, equal number of molecules) of the
substances.

(2) Hypertonic solutions : When two solutions have different osmotic

pressures, then the solution having higher osmotic pressure is said to be a
hypertonic solution with respect to the other solution.

Explanation : Consider two solutions of substances A and B having osmotic

pressures πA and πB. If πB is greater than πA, then the solution B is a hypertonic
solution with respect to the solution A.
Hence, if CA and CB are their concentrations, then CB > CA. Hence, for equal
volume of the solutions, nB > nA.

Question iii.
A solvent and its solution containing a nonvolatile solute are separated by a
semipermable membrane. Does the flow of solvent occur in both directions?
Comment giving reason.
Answer:

1. When a solvent and a solution containing a non-volatile solute are

separated by a semipermeable membrane, there arises a flow of solvent
molecules from solvent to solution as well as from solution to solvent.
2. Due to higher vapour pressure of solvent than solution, the rate of flow
of solvent molecules from solvent to solution is higher.
3. As more and more solvent passes into solution due to osmosis, the
solvent content increases, and the rate of backward flow increases.
4. At a certain stage an equilibrium is reached where both the opposing
rates become equal attaining an equilibrium.

Question iv.
The osmotic pressure of CaCl2 and urea solutions of the same concentration at
the same temperature are respectively 0.605 atm and 0.245 atm. Calculate
van’t Hoff factor for CaCl2.
Answer:
Given : πCacl2 = 0.605 atm;
πUrea = 0.245 atm
For urea solution, van’t Hoff factor, i = 1
πCacl2 = i × (CRT)Cacl2
πUrea = (CRT)Urea

van’t Hoff factor = i = 2.47

Question v.
Explain reverse osmosis.
Answer:
Reverse osmosis : The phenomenon of the passage of solvent like water under
high pressure from the concentrated aqueous solution like seawater into pure
water through a semipermeable membrane is called reverse osmosis.

The osmotic pressure of seawater is about 30 atmospheres. Hence when

pressure more than 30 atmospheres is applied on the solution side, regular
osmosis stops and reverse osmosis starts. Hence pure water from seawater
enters the other side of pure water.

Purification of seawater by reverse osmosis

For this purpose of suitable semipermeable membrane is required which can

withstand high pressure conditions over a long period.
This method is used successfully in Florida since 1981 producing more than 10
million litres of pure water per day.
Question vi.
How molar mass of a solute is determined by osmotic pressure measurement?
Answer:
Consider V dm3 (litres) of a solution containing W2 mass of a solute of molar
mass M2 at a temperature T.
Number of moles of solute, n2 = W2M2
The osmotic pressure π is given by,
π = W2RTM2V
∴ M2 = W2RTπV
By measuring osmotic pressure of a solution, the molar mass of a solute can
be calculated.
Since osmotic pressure can be measured more precisely, it is widely used to
measure molar masses of the substances.

Question vii.
Why vapour pressure of a solvent is lowered by dissolving a nonvolatile solute
into it?
Answer:
Lowering of vapour pressure of a solution :
When a nonvolatile solute is added to a pure solvent, the surface area is
covered by the solute molecule decreasing the rate of evaporation, hence its
vapour pressure decreases. This decrease in vapour pressure is called lowering
of vapour pressure.

If P0 is the vapour pressure of a pure solvent (liquid) and P is the vapour

pressure of the solution, where P < P0, then, (P0 – P) is the lowering of the
vapour pressure.

Question viii.
Using Raoult’s law, how will you show that ∆P = P01x2 ? Where x2 is the mole
fraction of solute in the solution and P01 vapour pressure of pure solvent.
Answer:
If x1 and x2 are the mole fractions of solvent and solute respectively, then
x1 + x 2
By Raoult’s law,
P = x 1 × P0
where P0 is the vapour pressure of a pure solvent and P is the vapour pressure
of the solution at given temperature.

Question ix.
While considering boiling point elevation and freezing point depression a
solution concentration is expressed in molality and not in molarity. Why?
Answer:

 Boiling point elevation and freezing point depression involve

temperature changes, (ΔTb and ΔTf).
 Since molarity depends on temperature but molality is independent of
temperature we use molality and not molarity in considering boiling
point elevation and freezing point depression.

Question 4.
Derive the relationship between degree of dissociation of an electrolyte and
van’t Hoff factor.
Answer:
Consider 1 dm3 of a solution containing m moles of an electrolyte AxBy. The
electrolyte on dissociation gives number of Ay+ ions and y number of Bx- ions.
Let α be the degree of dissociation.

At equilibrium,
AxBy ⇌ xAy+ + yBx-
For 1 mole of electrolyte : 1 – α, xα, yα and
For ‘m’ moles of an electrolyte : m(1 – α), mxα, myα are the number of
particles.
Total number of moles at equilibrium, will be,
Total moles = m(1 – α) + mxα + myα
= m[(1 – α) + xα + yα]
= m[1 – xα + yα – α]
= m[1 + α(x + y – 1)]
The van’t Hoff factor i will be,

If total number of ions from one mole of electrolyte is denoted by n, then (x +

y) = n
∴ i = 1 + α(n – 1)
∴ α(n – 1) = i – 1
∴ α = i−1n−1 ……..(1)
This is a relation between van’t Hoff factor i and degree of dissociation of an
electrolyte.

Question 5.
What is effect of temperature on solubility of solids in water? Give examples.
Answer:
The solubility of a solid solute depends upon temperature.
Variation of solubilities of some ionic solids with temperature

 Generally rise in temperature increases the solubility. This is due to

expansion of holes or empty spaces in the liquid solvent. Generally 10 °C
rise in temperature, increases the solubility of solids two fold.
 Dissolution process may be endothermic or exothermic.
 The solubility of the substances like NaBr, NaCl, KCl, etc. changes slightly
with the increase in temperature.
 The solubility of the salts like NaNO3, KNO3, KBr, etc. increases
appreciably with the increase in temperature.
 The solubility of Na2SO4 first increases and after 30 °C decreases with the
increase in temperature.

This variation in solubility with temperature can be used to separate the salts
from the mixture by fractional crystallisation.

Question 6.
Obtain the relationship between freezing point depression of a solution
containing nonvolatile nonelectrolyte and its molar mass.
Answer:
The freezing point depression, ΔTf of a solution is directly proportional to
molality (m) of the solution.
∴ ΔTf ∝ m
∴ ΔTf = Kf m
where Kf is a molal depression constant.
The molality of a solution is given by,

If W1 grams of a solvent contain W2 grams of a solute of the molar mass M2,

then the molality m of the solution is given by,

If the weights are expressed in kg then,

ΔTf = Kf × W2W1M2
The unit of Kf is K kg mol-1
Hence, from the measurement of the depression in the freezing point of the
solution, the molar mass of the substance can be determined.

Question 7.
Explain with diagram the boiling point elevation in terms of vapour pressure
lowering.
Answer:
(1) The boiling point of a liquid is the temperature at which the vapour
pressure of the liquid becomes equal to the external pressure, generally 1 atm
(101.3 × 103 Nm-2).

(2) When a liquid is heated, its vapour pressure rises till it becomes equal to
the external pressure.
If the liquid has a low vapour pressure, it has a higher boiling point.
Vapour pressure curve showing elevation in boiling point

(3) When a nonvolatile solute is added to a solvent, its vapour pressure

decreases, hence the boiling point increases.
This is explained by graphical representation of the vapour pressure and the
boiling point of the pure solvent and the solution.

If T0 and T are the boiling points of a pure solvent and a solution, then the
elevation in the boiling point is given by,
ΔTb = T – T0
The curve AB, represents the variation in the vapour pressure of a pure solvent
with temperature while curve CD represents the variation in the vapour
pressure of the solution.

(4) This elevation in the boiling point is proportional to the lowering of the
vapour pressure, i.e., P0 – P, where P0 and P are the vapour pressures of the
pure solvent and the solution.
[ΔTb ∝ (P0 – P) or ΔTb ∝ ΔP]

Question 8.
Fish generally needs O2 concentration in water at least 3.8 mg/L for survival.
What partial pressure of O2 above the water is needed for the survival of fish?
Given the solubility of O2 in water at 0 °C and 1 atm partial pressure is 2.2 × 10 -
3
mol/L (0.054 atm)
Answer:
Given : Required concentration of O2
= 3.8 mg/L
= 3.8×10−332 mol L−1
Solubility of O2 = 2.2 × 10-3 mol L-1
P = 1 atm
Partial pressure of O2 needed = Po2 = ?

Pressure needed = Po2 = 0.05397 atm.

Question 9.
The vapour pressure of water at 20 °C is 17 mm Hg. What is the vapour
pressure of solution containing 2.8 g urea in 50 g of water? (16.17 mm Hg)
Answer:
Given : Vapour pressure of pure solvent (water) = P0
= 17 mm Hg
Weight of solvent = W1 = 50 g
Weight of solute (urea) = 2.8 g
Molecular weight of a solvent = M1 = 18
Molecular weight of a solute (urea) = M2
= 60 g mol-1
P0−PP0=W2×M1W1×M2
∴ 17−P17=2.8×1850×60 = 0.0168
∴ 17 – P = 17 × 0.0168
17 – P = 0.2856
∴ P= 17 – 0.2856
= 16.7144 mm Hg
Vapour pressure of solution = 16.7144 mm Hg
Question 10.
A 5% aqueous solution (by mass) of cane sugar (molar mass 342 g/mol) has
freezing point of 271K. Calculate the freezing point of 5% aqueous glucose
solution.
Answer:
Given : W2 = 5 g cane sugar; W1 = 100 – 5 = 95 g
M2 = 342 g mol-1; Tf1 = 271 K;
ΔTf1 = 273 – 271 = 2 K; Tf = ?
W2 = 5 g glucose, W’1 = 100 – 5 = 95 g,
M’2 = 180 g mol-1, ΔTf2 = ?

= 12.996 K kg mol-1
≅ 13 K kg mol-1

∴ Freezing point of solution = Tf

= 273 – 3.801 = 269.2 K
Freezing point of solution = 269.2 K.

Question 11.
A solution of citric acid C6H8O7 in 50 g of acetic acid has a boiling point
elevation of 1.76 K. If Kb for acetic acid is 3.07 K kg mol-1, what is the molality of
solution?
Answer:
Given : W1 = 50 g acetic acid
ΔTb = 1.76 K
Kb = 3.07 K kg mol-1
m=?
ΔTb = Kb × m
∴ m = ΔTbKb
= 1.763.07
= 0.5733 m
Molality of solution = 0.5733 m

Question 12.
An aqueous solution of a certain organic compound has a density of 1.063
gmL-1, an osmotic pressure of 12.16 atm at 25°C and a freezing point of -
1.03°C. What is the molar mass of the compound? (334 g/mol)

Question 13.
A mixture of benzene and toluene contains 30% by mass of toluene. At 30°C,
vapour pressure of pure toluene is 36.7 mm Hg and that of pure benzene is
118.2 mm Hg. Assuming that the two liquids form ideal solutions, calculate the
total pressure and partial pressure of each constituent above the solution at
30°C.
Answer:
Given : 30% by mass of toluene (T) and 70% by mass of benzene (B).
WT = 30 g; WB = 70g
P0T = 36.7 mm Hg; P0B = 118.2 mm Hg
MT = 92 g mol-1; MB = 78 g mol-1
PT = ?, PB = ?, Psoln = ?

Total number of moles = nTotal = nT + nB

= 0.326 + 0.8974
= 1.2234 mol

Mole fractions :
xT = nTnTotal =0.3261.2234 = 0.2665
xB = 1 – 0.2665 = 0.7335
Psoln = xT + P0T + xB × P0B
= 0.2665 × 36.7 + 0.7335 × 118.2
= 9.780 + 86.7
= 96.48 mm Hg

Partial pressures :
PT = xT × Psoln
= 0.2665 × 96.48
= 25.71 mm Hg
PB = xB × Psoln
= 0.7335 × 96.48
= 70.77 mm Hg
Total pressure Psoln = 96.48 mm Hg
Partial pressures : PToluene = 25.71 mm Hg
PBenzene = 70.77 mm Hg

Question 14.
At 25 °C a 0.1 molal solution of CH3COOH is 1.35% dissociated in an aqueous
solution. Calculate freezing point and osmotic pressure of the solution
assuming molality and molarity to be identical.
Answer:
Given : T = 273 + 25 = 298 K
C = 0.1 m ≅ 0.1 M; Kf = 1.86 K kg mol-1
Per cent dissociation = 1.35
Freezing point = tf = ?
π=?
α = 1.35100 = 0.0135

i = 1 – α + α + α = 1 + α = 1 + 0.0135 = 1.0135
(i) ΔTf = i × Kf × m
= 1.0135 × 1.86 × 0.1
= 0.1885 °C
∴ Freezing point of solution = 0 – 0.1885
= – 0.1885 °C
(ii) n = iCRT
= 1.035 × 0.1 × 0.08206 × 298
= 2.53 atm

(i) Freezing point of solution = – 0.1885 °C

(ii) Osmotic pressure = π = 2.53 atm

Question 15.
A 0.15 m aqueous solution of KCl freezes at -0.510 °C. Calculate i and osmotic
pressure at 0 °C. Assume volume of solution equal to that of water.
Answer:
Given : c = 0.15 m KCl ≅ 0.15 M KCl
ΔTf = 0 – Tf = 0 – (-0.510) = 0.510 °C
T = 273 K; Kf = 1.86 K kg mol-1
i = ?; π = ?
ΔTf = i × Kf × m
∴ i = ΔTfKf×m
= 0.5101.86×0.15
= 1.828
π = iCRT
= 1.828 × 0.15 × 0.08206 × 273
= 6.143 atm
i = 1.828, Osmotic pressure = π = 6.143 atm

12th Chemistry Digest Chapter 2 Solutions Intext Questions and Answers

Can you tell ? (Textbook Page No. 29)

Question 1.
Why naphthalene dissolves in benzene but not in water ?
Answer:
Since naphthalene is a covalent nonpolar substance, it is soluble in a nonpolar
solvent like benzene but insoluble in polar solvent like water.

Question 2.
Anhydrous sodium sulphate dissolves in water with the evolution of heat.
What is the effect of temperature on its solubility ?
Answer:
Since the dissolution of anhydrous sodium sulphate in water is an exothermic
process due to evolution of heat, according to Le Chatelier’s principle its
solubility decreases with the increase in temperature.

(Textbook Page No. 42)

Question 1.
If 1.25 m sucrose solution has ΔTf of 2.32 °C, what will be the expected value of
ΔTf for 1.25 m CaCl2 solution?
Answer:
Sucrose being nonelectrolyte, it has i = 1 but for CaCl 2,
(CaCl2 → Ca2+ + 2Cl–) the value of i = 3.
Hence
ΔTf = i × 2.32
= 3 × 2.32
= 6.92 °C
∴ ΔTf = 6.92 °C.

(Textbook Page No. 44)

Question 1.
Which of the following solutions will have maximum boiling point elevation
and which have minimum freezing point depression assuming the complete
dissociation? (a) 0.1m KCl (b) 0.05 m NaCl (c) 1 m AlPO4 (d) 0.1 m MgSO4.
Solution :
Boiling point elevation and freezing point depression are colligative properties
that depend on number of particles in solution. The solution having more
number of particles will have large boiling point elevation and that having less
number of particles would show minimum freezing point depression.
AlPO4 solution contains highest moles and hence highest number particles and
in turn, the maximum ΔTb. NaCl solution has minimum moles and particles, it
has minimum ΔTf.

Question 2.
Arrange the following solutions in order of increasing osmotic pressure.
Assume complete ionization. (a) 0.5 m Li2SO4 (b) 0.5 m KCl (c) 0.5 m Al2(SO4)3 (d)
0.1 m BaCl2.
Answer:
Consider 1 dm3 of each solution.
Osmotic pressure being a colligative property, it depends on number of
particles in the solution.
Therefore, increasing order of osmotic pressure is,
Ionic Equilibria
1. Choose the most correct answer :

Question i.
The pH of 10-8 M of HCl is
(a) 8
(b) 7
(c) less than 7
(d) greater than 7
Answer:
(c) less than 7

Question ii.
Which of the following solution will have pH value equal to 1.0?
(a) 50 mL of 0.1M HCl + 50mL of 0.1 M NaOH
(b) 60 mL of 0.1M HCl + 40mL of 0.1 M NaOH
(c) 20 mL of 0.1M HCl + 80mL of 0.1 M NaOH
(d) 75 mL of 0.2M HCl + 25mL of 0.2 M NaOH
Answer:
(d) 75 mL of 0.2M HCl + 25mL of 0.2 M NaOH

Question iii.
Which of the following is a buffer solution ?
(a) CH3COONa + NaCl in water
(b) CH3COOH + HCl in water
(c) CH3COOH + CH3COONa in water
(d) HCl + NH4Cl in water
Answer:
(c) CH3COOH + CH3COONa in water

Question iv.
The solubility product of a sparingly soluble salt AX is 5.2 x 10 -13. Its solubility in
mol dm-3 is
(a) 7.2 × 10-7
(b) 1.35 × 10-4
(c) 7.2 × 10-8
(d) 13.5 × 10-8
Answer:
(a) 7.2 × 10-7

Question v.
Blood in human body is highly buffered at pH of
(a) 7.4
(b) 7.0
(c) 6.9
(d) 8.1
Answer:
(a) 7.4

Question vi.
The conjugate base of [Zn(H2O)4]2+ is
(a) [Zn(H2O)4]2+ NH3
(b) [Zn(H2O)3]2+
(c) [Zn(H2O)3OH]+
(d) [Zn(H2O)H]3+
Answer:
(c) [Zn(H2O)3OH]+

Question vii.
For pH > 7 the hydronium ion concentration would be
(a) 10-7 M
(b) < 10-7 M
(c) > 10-7 M
(d) ≥ 10-7 M
Answer:
(b) < 10-7 M

2. Answer the following in one sentence :

Question i.
Why cations are Lewis acids ?
Answer:
Since cations are deficient of electrons they accept a pair of electrons, hence
they are Lewis acids.

Question ii.
Why is KCl solution neutral to litmus?
Answer:

1. Since KCl is a salt of strong base KOH and strong acid HCl, it does not
undergo hydrolysis in its aqueous solution.
2. Due to strong acid and strong base, concentrations [H 3O+] = [OH–] and
the solution is neutral.

Question iii.
How are basic buffer solutions prepared?
Answer:

1. Basic buffer solution is prepared by mixing aqueous solutions of a weak

base like NH4OH and its salt of a strong acid like NH4Cl.
2. A weak base is selected according to the required pH or pOH of the
solution and dissociation constant of the weak base.

Question iv.
Dissociation constant of acetic acid is 1.8 × 10-5. Calculate percent dissociation
of acetic acid in 0.01 M solution.
Answer:
Given : Ka = 1.8 x 10-5; C = 0.01 M
Percent dissociation = ?
∴ Percent dissociation = α × 100
= 4.242 × 10-2 × 102
= 4.242%
Percent dissociation = 4.242%

Question v.
Write one property of a buffer solution.
Answer:
Properties (or advantages) of a buffer solution :

 The pH of a buffer solution is maintained appreciably constant.

 By addition of a small amount of an acid or a base pH does not change.
 On dilution with water, pH of the solution doesn’t change.

Question vi.
The pH of a solution is 6.06. Calculate its H + ion concentration.

Question vii.
Calculate the pH of 0.01 M sulphuric acid.
Answer:
Given : C = 0.01 M H2SO4, pH = ?
H2SO4(aq)⟶2H+(aq)+SO2−4(aq)
∴ [H3O+] = 2 × 0.01 = 0.02 M
PH = -log10 [H3O+]
= -log10 0.02
= –(2¯¯¯.3010)
= 2 – 0.3010
= 1.6990
pH = 1.6990.

Question viii.
The dissociation of H2S is suppressed in the presence of HCl. Name the
phenomenon.
Answer:
The weak dibasic acid H2S is dissociated as follows :

When HCl is added, it increases the concentration of common ion H 3O+.

HCl(aq)+H2O(l)→H3O+(aq)+Cl−(aq)
Hence by Le Chaterlier’s principle, the equilibrium is shifted from right to left,
suppressing the dissociation of weak electrolyte H 2S.

Question ix.
Why is it necessary to add H2SO4 while preparing the solution of CuSO4?
Answer:
CuSO4 is a salt of strong acid H2SO4 and weak base Cu(OH)2. CuSO4 in aqueous
solution undergoes hydrolysis and forms a precipitate of Cu(OH) 2 and solution
becomes turbid.
CuSO4 + 2H2O ⇌ CU(OH)2↓ + H2SO4
OR
CuSO4 + 4H2O ⇌ Cu(OH)2 + 2H3O+ + SO2−4
When H2SO4 is added, the hydrolysis equilibrium is shifted to left hand side
and Cu(OH)2 dissolves giving clear solution.

Question x.
Classify the following buffers into different types :
a. CH3COOH + CH3COONa
b. NH4OH + NH4Cl
c. Sodium benzoate + benzoic acid
d. Cu(OH)2 + CuCl2
Answer:
(a) Acidic buffer (CH3COOH + CH3COONa)
(b) Basic buffer (NH4OH + NH4Cl)
(c) Acidic buffer (Sodium benzoate + benzoic acid)
(d) Basic buffer (Cu(OH)2 + CuCl2)
[Note : Cu(OH)2 being insoluble is not used to prepare a buffer solution.]

3. Answer the following in brief :

Question i.
What are acids and bases according to Arrhenius theory ?
Answer:
According to Arrhenius theory :
Acid : It is a substance which contains hydrogen and on dissolving in water
produces hydrogen ions (H+) E.g. HCl
HCl(aq)⇌H+(aq)+Cl−(aq)

Base : It is a substance which contains OH group and on dissolving in water

produces hydroxyl ions (OH–). E.g. NaOH
NaOH(aq)⇌Na+(aq)+OH−(aq)

Question ii.
What is meant by conjugate acid-base pair?
Answer:
Conjugate acid-base pair : A pair of an acid and a base differing by a proton is
called a conjugate acid-base pair.

Question iii.
Label the conjugate acid-base pair in the following reactions
a. HCl + H2O ⇌ H3O+ + Cl–
b. CO2−3 + H2O ⇌ OH– + HCO−3
Answer:

Question iv.
Write a reaction in which water acts as a base.
Answer:

Since water accepts a proton, it acts as a base.

Question v.
Ammonia serves as a Lewis base whereas AlCl3 is Lewis acid. Explain.
Answer:

 Since ammonia molecule, NH3 has a lone pair of electrons to donate it

acts as a Lewis base.
 AlCl3 is a molecule with incomplete octet hence it is electron deficient
and acts as a Lewis acid.

Question vi.
Acetic acid is 5% ionised in its decimolar solution. Calculate the dissociation
constant of acid.
Answer:
Given : C = 0.1 M; Dissociation = 5%, Ka=2 Percent dissociation
Dissociation constant of acid = Ka = 2.63 × 10-4

Question vii.
Derive the relation pH + pOH = 14.
Answer:
The ionic product of water, Kw is given by,
Kw = [H3O+] × [OH–]
At 298 K, Kw = 1 × 10-14
∴ pKw = -log10Kw = log10 1 x 10-14 = 14
∵ [H3O+] × [OH–] = 1 × 10-14
Taking logarithm to base 10 of both sides,
log10 [H3O+] + log10 [OH–] = log10 1 x 10-14
Multiplying both the sides by -1,
-log10 [H3O+] -log10 [OH–] = -log10 1 x 10-14
∵ pH = -log10 [H3O+]; pOH = -log10 [OH–];
pKw = – log10 Kw
∴ pH + pOH = pKw
OR pH + pOH =14

Question viii.
Aqueous solution of sodium carbonate is alkaline whereas aqueous solution of
ammonium chloride is acidic. Explain.
Answer:
(A) (i) Sodium carbonate is a salt of weak acid and strong base.
(ii) In aqueous solution it undergoes hydrolysis.
(iii) Strong base dissociates completely while weak acid dissociates partially
since [OH–] > [H3O+], the solution is basic.

(B) (i) Ammonium chloride is a salt of strong acid and weak base.
(ii) In aqueous solution it undergoes hydrolysis

(iii) Since [H+] or [H3O+ ] > [OH–] the solution is acidic.

Question ix.
pH of a weak monobasic acid is 3.2 in its 0.02 M solution. Calculate its
dissociation constant.
Answer:
Given : pH = 3.2; C = 0.02 M; Ka = ?
pH = -log10 [H+]
∴ [H+] = Antilog – pH
= Antilog – 3.2
= Antilog 4¯¯¯.8
= 6.31 × 10-4M

Ka = cα2
= 0.02 × (0.0315)2
= 1.984 × 10-5
Dissociation constant = Ka = 1.984 × 10-5
Question x.
In NaOH solution [OH–] is 2.87 × 10-4. Calculate the pH of solution.
Answer:
Given : [OH–] = 2.87 × 10-4 M, pH = ?
pOH = -log10 [OH–]
= -log10 2.87 × 10-4
= –(4¯¯¯.4579)
= (4 – 0.4579)
= 3.5421
∵ pH + pOH = 14
∴ pH = 14 – pOH = 14 – 3.5421 = 10.4579
pH = 10.4579.

4. Answer the following :

Question i.
Define degree of dissociation. Derive Ostwald’s dilution law for the CH 3COOH.
Answer:
(A) Degree of dissociation :
It is defined as a fraction of total number of moles of an electrolyte that
dissociate into its ions at equilibrium.
It is denoted by a and represented by,
α = number of moles dissociated total number of moles of an electrolyte
Or α = Per cent dissociation 100
∴ Per cent dissociation = α × 100

(B) Consider V dm3 of a solution containing one mole of CH3COOH. Then the
concentration of acid is, C = 1V mol dm3. Let α be the degree of dissociation
This is Ostwald’s dilution law.

Question ii.
Define pH and pOH. Derive relationship between pH and pOH.
Answer:
(1) pH : The negative logarithm, to the base 10, of the molar concentration of
hydrogen ions, H+ is known as the pH of a solution.
pH = -log10 [H+]

(2) pOH : The negative logarithm, to the base 10, of the molar concentration
of hydroxyl ions, OH– is known as the pOH of a solution.
pOH = -log10 [OH–]

Relationship between pH and pOH:

The ionic product of water, Kw is given by,
Kw = [H3O+] × [OH–]
At 298 K, Kw = 1 × 10-14
∴ pKw = -log10Kw = log10 1 x 10-14 = 14
∵ [H3O+] × [OH–] = 1 × 10-14
Taking logarithm to base 10 of both sides,
log10 [H3O+] + log10 [OH–] = log10 1 x 10-14
Multiplying both the sides by -1,
-log10 [H3O+] – log10 [OH–] = -log10 1 x 10-14
∵ pH = -log10 [H3O+]; pOH = -log10 [OH–];
pKw = – log10 Kw
∴ pH + pOH = pKw
OR pH + pOH =14

Question iii.
What is meant by hydrolysis ? A solution of CH 3COONH4 is neutral. why ?
Answer:
Hydrolysis : A reaction in which the cations or anions or both the ions of a salt
react with water to produce acidity or basicity or sometimes neutrality is called
hydrolysis.

A salt of weak acid and weak base for which K a = Kb:

Consider hydrolysis of CH3COONH4.

Since Ka = Kb, the weak acid CH3COOH and weak base NH4OH dissociate to the
same extent, hence, [H3O+] = [OH–] and the solution reacts neutral after
hydrolysis.

Question iv.
Dissociation of HCN is suppressed by the addition of HCl. Explain.
Answer:
The weak acid HCN is dissociated as follows :
HCN(aq)+H2O(l)⇌H3O+(aq)+CN−(aq)
The dissociation constant Ka is represented as,
Ka = [H3O+]×[CN−][HCN]
When HCl is added, it increases the concentration of H 3O+, hence in order to
keep the ratio constant, then by Le Chatelier’s principle, the equilibrium is
shifted from right to left, suppressing the dissociation of HCN.

Question v.
Derive the relationship between degree of dissociation and dissociation
constant in weak electrolytes.
Answer:
Expression of Ostwald’s dilution law in the case of a weak electrolyte :
Consider the dissociation of a weak electrolyte BA. Let V dm 3 of a solution
contain one mole of the electrolyte. Then the concentration of a solution is, C
= 1Vmol dm-3. Let α be the degree of dissociation of the electrolyte.

Applying the law of mass action to this dissociation equilibrium, we have,

As the electrolyte is weak, α is very small as compared to unity, ∴ (1 – α) ≈ 1.

This is the expression of Ostwald’s dilution law. Thus, the degree of
dissociation of a weak electrolyte is directly proportional to the square root of
the volume of the solution containing 1 mole of an electrolyte.

Question vi.
Sulfides of cation of group II are precipitated in acidic solution (H 2S + HCl)
whereas sulfides of cations of group IIIB are precipitated in ammoniacal
solution of H2S. Comment on the relative values of solubility product of
sulfides of these.
Answer:
(1) In qualitative analysis, the cations of group II are precipitated as sulphides,
namely HgS, CuS, PbS, etc., while cations of group IIIB are precipitated as
sulphides, namely, CoS, NiS, ZnS.

(2) The sulphides of group II have extremely low solubility product (K sp) about
10-29 to 10-53 while the sulphides of group IIIB have slightly higher K sp values
about 10-20 to 10-23.

(3) In group II, sulphides are precipitated by adding H 2S in acidic solution while
in IIIB group they are precipitated in a basic solution like ammonical solution.

(4) In acidic medium due to common ion H+, H2S is dissociated to very less
extent but gives sufficient S2- ion to exceed solubility product of group II
sulphides of cations and precipitate them.
HCl(aq)⟶H+(aq)+Cl−(aq);H2 S(aq)⇌2H+(aq)+S2−(aq)

(5) In basic medium, H+ from H2S are removed by OH– in solution, or by

NH4OH, increasing the dissociation of H2S and concentration of S2-, so that IP >
Ksp.

(6) Therefore group II cations are precipitated in an acidic medium while

cations of group IIIB are precipitated in ammonical solution.

Question vii.
Solubility of a sparingly soluble salt get affected in presence of a soluble salt
having one common ion. Explain.
Answer:
Consider the solubility equilibrium of a sparingly soluble salt, AgCl.
AgCl(s)⇌Ag+(aq)+Cl−(aq)
The solubility product, Ksp is given by,
Ksp = [Ag+] × [Cl–]
Consider addition of a strong electrolyte AgNO 3 with a common ion Ag+.
AgNO3(aq)⟶Ag+(aq)+NO−3(aq)
The concentration Ag+ in the solution is increased, hence by Le Chatelier’s
principle the equilibrium of AgCl is shifted to left hand side since the value of
Ksp is constant.
Thus in the presence of a common ion, the solubility of a sparingly soluble salt
is suppressed.

Question viii.
The pH of rain water collected in a certain region of Maharashtra on particular
day was 5.1. Calculate the H3O+ ion concentration of the rain water and its
percent dissociation.
Answer:
Given : pH = 5.1, [H3O+] = ?
PH = -log10 [H3O+]
∴ log10 [H3O+] = -pH
∴ [H3O+] = Antilog – pH
= Antilog – 5.1
= Antilog 6¯¯¯.9
= 7.943 × 10-6 M
(H3O+ in rainwater is due to dissolved gases, CO2, SO2, etc. forming acids which
dissociate giving H3O+ and acidity to rainwater.)
[H3O+] = 7.943 × 10-4 M

Question ix.
Explain the relation between ionic product and solubility product to predict
whether a precipitate will form when two solutions are mixed?
Answer:
If ionic product and solubility product are indicated by IP and K sp respectively
then,
(I) When IP = Ksp, the solution is saturated.
(II) When IP > Ksp, the solution is supersaturated and hence precipitation will
occur, when two solutions are mixed.
(Ill) When IP < Ksp, the solution is unsaturated and precipitation will not occur,
when two solutions are mixed.

12th Chemistry Digest Chapter 3 Ionic Equilibria Intext Questions and

Answers

Use your brain power (Textbook Page No. 47)

Question 1.
Which of the following is a strong electrolyte ?
HF, AgCl, CuSO4, CH3COONH4, H3PO4.
Answer:
CH3COONH4 is a strong electrolyte since in aqueous solution it dissociates
completely. Sparingly soluble salts AgCl, CuSO4 are also strong electrolytes.

Use your brain power (Textbook Page No. 49)

Question 1.
All Bronsted bases are also Lewis bases, but all Bronsted acids are not Lewis
acids. Explain.
Answer:
NH3 is a Bronsted base since it can accept a proton while it is also a Lewis base
since it has a lone pair of electrons to donate.

(2) HCl is a Bronsted acid since it can donate a proton but it is not a Lewis acid
since it can’t accept a pair of electrons.

Use your brain power (Textbook Page No. 53)

Question 1.
Suppose that pH of monobasic and dibasic acid is the same. Does this mean
that the molar concentrations of both acids are identical ?
Answer:
Even if monobasic acid and dibasic acid give same pH, their molar
concentrations are different. One mole of monobasic acid like HCl gives 1 mol
of H+ while one mole of dibasic acid gives 2 mol of H+ in solution. Hence the
concentration of dibasic acid will be half of the concentration of monobasic
acid. For example, for same pH. [Monobasic acid] = [Dibasic acid]/2

Question 2.
How does pH of pure water vary with temperature ? Explain.
Answer:
Since the increase in temperature, increases the dissociation of water, its pH
decreases.

Can you tell ? (Textbook Page No. 54)

Question 1.
Why (i) an aqueous solution of NH4Cl is acidic.
(ii) while that of HCOOK basic ?
Answer:
(i) (i) Ammonium chloride is a salt of strong acid and weak base.
(ii) In aqueous solution it undergoes hydrolysis

(iii) Since [H+] or [H3O+] > [OH–] the solution is acidic.

(ii) HCOOK is a salt of weak acid HCOOH and strong base KOH. In aqueous
solution it undergoes hydrolysis giving weak acid and strong base KOH which
dissociates completely,

∴ [OH–] > [H3O+], and the solution reacts basic.

Can you think ? (Textbook Page No. 56)

Question 1.
Home made jams and jellies without any added chemical preservative
additives spoil in a few days whereas commercial jams and jellies have a long
shelf life. Explain. What role does added sodium benzoate play ?
Answer:
Sodium benzoate added to jams and jellies in commercial products maintains
the pH constant and acts as a preservative. Hence jams and jellies are not
spoiled for a very long time unlike homemade products.

Can you tell ? (Textbook Page No. 56)

Question 1.
It is enough to add a few mL of a buffer solution to maintain its pH. Which
property of buffer is used here ?
Answer:
The important property of reserve acidity and reserve basicity of a buffer
solution is used to maintain constant pH. Weak acid or weak base along with
ions (cations or anions) from salt react with excess of added acid (H +) or base
[OH–] and maintain pH constant.

Use your brain power (Textbook Page No. 59)

Question 1.
What is the relationship between molar solubility and solubility product for
salts given below : (i) Ag2CrO4 (ii) Ca3(PO4)2 (iii) Cr(OH)3.
Answer:
Can you tell ? (Textbook Page No. 60)

Question 1.
How is the ionization of NH4OH suppressed by addition of NH4Cl to the
solution of NH4OH ?
Answer:
Ionisation of NH4OH is represented as follows :
NH4OH(aq)⇌NH+4(aq)+OH−(aq)
It has ionisation constant,
Kb = [NH4+]×[OH−][NH4OH]
Kb has constant value at constant temperature. When strong electrolyte NH 4Cl
is added to its solution, it dissociates completely.
NH4Cl(aq)⟶NH+4(aq)+Cl−(aq)
Due to common ion NH+4, by Le Chatelier’s principle, the equilibrium is
shifted from right to left, suppressing the ionisation of NH 4OH.
Electrochemistry
1. Choose the most correct option.

Question i.
Two solutions have the ratio of their concentrations 0.4 and ratio of their
conductivities 0.216. The ratio of their molar conductivities will be
(a) 0.54
(b) 11.574
(c) 0.0864
(d) 1.852
Answer:
(a) 0.54

Question ii.
On diluting the solution of an electrolyte,
(a) both ∧ and κ increase
(b) both ∧ and κ decrease
(c) ∧ increases and κ decreases
(d) ∧ decreases and κ increases
Answer:
(c) ∧ increases and κ decreases

Question iii.
1 S m2 mol-1 is equal to
(a) 10-4 S m2 mol-1
(b) 104 Ω-1 cm2 mol-1
(c) 10-2 S cm2 mol-1
(d) 102 Ω-1 cm2 mol-1
Answer:
(b) 104Ω-1 cm2 mol-1

Question iv.
The standard potential of the cell in which the following reaction occurs
H2+ (g, 1 atm) + Cu2+ (1 M) → 2H (1 M) + Cu(s), (E0Cu = 0.34 V) is
(a) – 0.34 V
(b) 0.34 V
(c) 0.17 V
(d) -0.17 V
Answer:
(b) 0.34 V

Question v.
For the cell, Pb(s)|Pb2+ (1 M)|| Ag+ (1 M)|Ag(s), if concentration of an ion in the
anode compartment is increased by a factor of 10, the emf of the cell will
(a) increase by 10 V
(b) increase by 0.0296 V
(c) decrease by 10 V
(d) decrease by 0.0296 V
Answer:
(d) decrease by 0.0296 V

Question vi.
Consider the half reactions with standard potentials

The strongest oxidising and reducing agents respectively are

(a) Ag and Fe2+
(b) Ag+ and Fe
(c) Pb2+ and I–
(d) I2 and Fe2+
Answer:
(b) Ag+ and Fe

Question vii.
For the reaction
Ni(s) + Cu2+ (1 M) → Ni2+ (1 M) + Cu(s), E0cell = 0.57 V. Hence ΔG0 of the reaction
is
(a) 110 kJ
(b) -110 kJ
(c) 55 kJ
(d) -55 kJ
Answer:
(b) -110 kJ

Question viii.
Which of the following is not correct ?
(a) Gibbs energy is an extensive property
(b) Electrode potential or cell potential is an intensive property.
(c) Electrical work = -ΔG
(d) If half reaction is multiplied by a numerical factor, the corresponding
E0 value is also multiplied by the same factor.
Answer:
(d) If half reaction is multiplied by a numerical factor, the corresponding
E0 value is also multiplied by the same factor.

Question ix.
The oxidation reaction that takes place in lead storage battery during
discharge is

Answer:
(c) Pb(s)+SO4(aq)2−⟶PbSO4( s)+2e−

Question x.
Which of the following expressions represent molar conductivity of Al 2(SO4)3 ?
Answer:
(b) 2λ0Al3++3λ0SO2−4

2. Answer the following in one or two sentences.

Question i.
What is a cell constant ?
Answer:
(A) Cell constant of a conductivity cell is defined as the ratio of the distance
between the electrodes divided by the area of cross section of the electrodes.

In SI units it is expressed as m-1.

Question ii.
Write the relationship between conductivity and molar conductivity and hence
unit of molar conductivity.
Answer:
If k is conductivity and ∧m is molar conductivity then, ∧m = κ×1000C
Unit of molar conductivity is, Ω-1 cm2 mol-1 or S cm2 mol-1.

Question iii.
Write the electrode reactions during electrolysis of molten KCl.
Answer:
Question iv.
Write any two functions of salt bridge.
Answer:
The functions of a salt bridge are :

 It maintains the electrical contact between the two electrode solutions

of the half cells.
 It prevents the mixing of electrode solutions.
 It maintains the electrical neutrality in both the solutions of two half cells
by a flow of ions.
 It eliminates the liquid junction potential.

Question v.
What is standard cell potential for the reaction
3Ni(s) + 2Al3+ (1M) → 3NI2+ (1M) + 2Al(s)
if E0Ni = – 0.25 V and E0Al = -1.66V?
Solution :
Given : E0Ni /Ni = -0.25 V
2+

E0Al /Al = – 1.66 V; E0cell = ?

3+

Since Ni is oxidised and Al3+ is reduced,

E0cell =E0Al3+/Al−E0Ni2+/Ni
= – 1.66 – (-0.25)
= – 1.41 V
Ans. E0cell = -1.41 V
[Note : Since E0cell is negative, the given reaction is not possible but reverse
reaction is possible.]

Question vi.
Write Nerst equation. What part of it represents the correction factor for
nonstandard state conditions ?
Answer:
(1) Nernst equation for cell potential is,

(2) The part of equation namely,

represents the correction factor for nonstandard state conditions.

Question vii.
Under what conditions the cell potential is called standard cell potential ?
Answer:
In the standard cell, the active masses of the substances taking part in the
electrochemical reaction have unit value, i.e., 1 M solution or ions and 1 atm
gas.

Question viii.
Formulate a cell from the following electrode reactions :
Au3+(aq)+3e−⟶Au(s)
Mg(s)⟶Mg2+(aq)+2e−
Answer:
An electrochemical cell from above electrode reactions is,

Question ix.
How many electrons would have a total charge of 1 coulomb ?
Answer:
Given : 1 Faraday = charge on 1 mol of electrons
= 6.022 × 1023 electrons and 1 Faraday = 96500 C
∵ 96500 C = 6.022 × 1023 electrons 6 022 × 1023
∴ 1 C ≡ 6.022×102396500 = 6.24 × 1018 electrons
Ans. Number of electrons = 6.24 × 1018

Question x.
What is the significance of the single vertical line and double vertical line in
the formulation galvanic cell.
Answer:
(i) Consider representation of Daniell cell,

Single vertical line represents separation of two phases, solid Zn (s) and solution
of ions.
(ii) Double vertical lines represent a salt bridge.

3. Answer the following in brief

Question i.
Explain the effect of dilution of solution on conductivity ?
Answer:

 The conductance of a solution is due to the presence of ions in the

solution. More the ions, higher is the conductance of the solution.
 Conductivity or the specific conductance is the conductance of unit
volume (1 cm3) of the electrolytic solution.
 The conductivity of the electrolytic solution always decreases with the
decrease in the concentration of the electrolyte or the increase in
dilution of the solution.
 On dilution, the concentration of the solution decreases, hence the
number of (current carrying) ions per unit volume decreases. Therefore
the conductivity of the solution decreases, with the decrease
concentration or increase in dilution. (It is to be noted here that, molar
conductivity increases with dilution.)

Question ii.
What is a salt bridge ?
Answer:
A salt bridge is a U-shaped glass tube containing a saturated solution of a
strong electrolyte, like KCl, NH4NO3, Na2SO4 in a solidified agar-agar gel. A hot
saturated solution of these electrolytes in 5% agar solution is filled in the U-
shaped tube and allowed it to cool and solidify forming a gel.
Fig. 5.9 : Salt bridge
It is used to connect two half cells or electrodes forming a galvanic or voltaic
cell.

Question iii.
Write electrode reactions for the electrolysis of aqueous NaCl.
Answer:
Reactions in electrolytic cell :
(i) Reduction half reaction at cathode : There are Na + and H+ions but since
H+ are more reducible than Na+, they undergo reduction liberating hydrogen
and Na+ are left in the solution.
2H2O(l) + 2e– → H2(g) + 2OH–(aq) (reduction) E0 = -0.83 V

(ii) Oxidation half reaction at anode : At anode there are Cl – and OH–. But
Cl– ions are preferably oxidised due to less decomposition potential.

Net cell reaction : Since two electrons are gained at cathode and two electrons
are released at anode for each redox step, the electrical neutrality is
maintained. Hence we can write,
Since Na+ and OH– are left in the solution, they form NaOH(aq).

Question iv.
How many moles of electrons are passed when 0.8 ampere current is passed
for 1 hour through molten CaCl2 ?
Answer:
Given : I = 0.8 A; t = 1 × 60 × 60 = 3600 s
Number of moles of electrons = ?
Q=I×t
= 0.8 × 3600
= 2880 C
1 Faraday = 1 mol electrons
1 Faraday = 96500 C
∵ 96500 C = 1 mol electrons
∴ 2880 C ≡ 288096500
= 0.02984 mol electrons
Ans. Number of moles of electrons = 0.02984

Question v.
Construct a galvanic cell from the electrodes Co 3+|Co and Mn2+|Mn. E0Co = 1.82
V,
E0Mn = – 1.18V. Calculate E0cell .
Answer:

Question vi.
Using the relationsip between ∆G0 of cell reaction and the standard potential
associated with it, how will you show that the electrical potential is an
intensive property ?
Answer:
(1) For an electrochemical cell involving n number of electrons in the overall
cell reaction,
ΔG0 = -nFE0cell
where ΔG0 is standard Gibbs energy change and E0cell is a standard cell
potential.
(2) ∴ E0cell=−ΔG0nF
Since ΔG0 changes according to number of moles of electrons involved in the
cell reaction, the ratio, ΔG0/nF remains constant.
(3) Therefore E0cell is independent of the amount of substance and it
represents the intensive property.

Question vii.
Derive the relationship between standard cell potential and equilibrium
constant of cell reaction.
Answer:
For any galvanic cell, the overall cell reaction at equilibrium can be
represented as,
Reactants ⇌ Products.
[For example for Daniell cell,
Zn(s)+Cu2+(aq)⇌Zn2+(aq)+Cu(s) ]
The equilibrium constant, K for the reversible reaction will be, K=[ Products ]
[ Reactants ]

The equilibrium constant is related to the stan-dard free energy change Δ G 0,

as follows,
ΔG0 = -RTlnK
If E0cell is the standard cell potential (or emf) of the galvanic cell, then ΔG 0 = -
nFE0cell
By comparing above equations,

Question viii.
It is impossible to measure the potential of a single electrode. Comment.
Answer:
(1)
Fig 5.12(a) : Measurement of single electrode potential

Fig 5.12(b) : Measurement of cell potential

According to Nemst theory, electrode potential is the potential difference
between the metal and ionic layer around it at equilibrium, i.e. the potential
across the electric double layer.

(2) For measuring the single electrode potential, one part of the double layer,
that is metallic layer can be connected to the potentiometer but not the ionic
layer. Hence, single electrode potential can’t be measured experimentally.

(3) When an electrochemical cell is developed by combining two half cells or

electrodes, they can be connected to the potentiometer and the potential
difference or cell potential can be measured.
Ecell = E2 – E1
where E1 and E2 are reduction potentials of two electrodes.

Question ix.
Why do the cell potential of lead accumulators decrease when it generates
electricity ? How the cell potential can be increased ?
Answer:
Working of a lead accumulator :
(1) Discharging : When the electric current is withdrawn from lead
accumulator, the following reactions take place :

(2) Net cell reaction :

(i) Thus, the overall cell reaction during discharging is

OR
Pb(s) + PbO2(s) + 2H2SO4(aq) → 2PbSO4(s) + 2H2O(l)
The cell potential or emf of the cell depends upon the concentration of
sulphuric acid. During the operation, the acid is consumed and its
concentration decreases and specific gravity decreases from 1.28 to 1.17. As a
result, the emf of the cell decreases. The emf of a fully charged cell is about
2.0 V.

(ii) Recharging of the cell : When the discharged battery is connected to

external electric source and a higher external potential is applied the cell
reaction gets reversed generating H2SO4.
Reduction at the -ve electrode or cathode :
PbSO4(s) + 2e– → Pb(s) + SO2−4(aq)
Oxidation at the + ve electrode or anode :

The emf of the accumulator depends only on the concentration of H 2SO4.

Question x.
Write the electrode reactions and net cell reaction in NICAD battery.
Answer:
Reactions in the cell :
(i) Oxidation at cadmium anode :
Cd(s) + 2OH–(aq) → Cd(OH)2(s) + 2e–
(ii) Reduction at NiO2(s) cathode :
NiO2(s) + 2H2O(l) + 2e– → Ni(OH)2(s) + 2OH–(aq)
The overall cell reaction is the combination of above two reactions.
Cd(s) + NiO2(s) + 2H2O(l) → Cd(OH)2(s) + Ni(OH)2(s)

4. Answer the following :

Question i.
What is Kohrausch law of independent migration of ions? How is it useful in
obtaining molar conductivity at zero concentration of a weak electrolyte ?
Explain with an example.
Answer:
(A) Statement of Kohlrausch’s law : This states that at infinite dilution of the
solution, each ion of an electrolyte migrates independently of its co-ions and
contributes independently to the total molar conductivity of the electrolyte,
irrespective of the nature of other ions present in the solution.

(B) Explanation : Both the ions, cation and anion of the electrolyte make a
definite contribution to the molar conductivity of the electrolyte at infinite
dilution or zero concentration (∧0).
If λ0+ and λ0− are the molar ionic conductivities of cation and anion
respectively at infinite dilution, then
∧0 = λ0+ + λ0−.
This is known as Kohlrausch’s law of independent migration of ions.
For an electrolyte, BxAy giving x number of cations and y number of anions,
∧0 = xλ0+ + yλ0−.

(C) Applications of Kohlrausch’s law :

(1) With this law, the molar conductivity of a strong electrolyte at zero
concentration can be determined. For example,
∧0(KCl)=λ0K+−λ0Cl−
(2) ∧0 values of weak electrolyte with those of strong electrolytes can be
obtained. For example,

Molar conductivity of a weak electrolyte at infinite dilution or zero

concentration cannot be measured experimentally.
Consider the molar conductivity (∧0) of a weak acid, CH3COOH at zero
concentration. By Kohlrausch s law,

where λ0CH3COO– and λ0H are the molar ionic conductivities of CH3COO– and
+

H+ ions respectively.
If ∧0CH3COONa, ∧0HCl and ∧0NaCl are molar conductivities of CH3COONa, HCl and NaCl
respectively at zero concentration, then by
Kohlrausch’s law,
Hence, from ∧0 values of strong electrolytes, ∧0 of a weak electrolyte
CH3COOH, at infinite dilution can be calculated.

Question ii.
Explain electrolysis of molten NaCl.
Answer:
(1) Construction of an electrolytic cell : It consists of a vessel containing
molten (fused) NaCl. Two graphite (carbon) inert electrodes are dipped in it,
and connected to an external source of direct electric current (battery). The
electrode connected to a negative terminal of the battery is a cathode and
that connected to a positive terminal is an anode.

(2) Working of the cell :

(A) In the external circuit, the electrons flow through the wires from anode to
cathode of the cell.
(B) The fused NaCl dissociates to form cations (Na +) and anions (Cl–).
NaCl(fused) ⟶Na+(l)+Cl−(l)
Na+ migrate towards cathode and Cl– migrate towards anode.
Fig. 5.7 : Electrolysis of fused sodium chloride

(C) Reactions in electrolytic cell :

(i) Reduction half reaction at cathode : The Na + ions get reduced by accepting
electrons from a cathode supplied by a battery and form metallic sodium.
Na++e−⟶Na(s) (reduction)

(ii) Oxidation half reaction at anode : The Cl – ions get oxidised by giving up
electrons to the anode forming neutral Cl atoms in the primary process, and
these Cl atoms combine forming Cl2 gas in the secondary process.

The released electrons in the anodic oxidation half reaction return to battery
through the metallic wires.

Net cell reaction : In order to maintain the electrical neutrality, the number of
electrons gained at cathode must be equal to the number of electrons
released at anode. Hence the reduction half reaction is multiplied by 2 and
both reactions, oxidation half reaction and reduction half reaction are added
to obtain a net cell reaction.
Results of electrolysis :

 A molten silvery white Na is formed at cathode which floats on the

surface of molten NaCl.
 A pale green Cl2 gas is liberated at anode.

Question iii.
What current strength in amperes will be required to produce 2.4g of Cu from
CuSO4 solution in 1 hour ? Molar mass of Cu = 63.5 g mol-1.
Answer:
Given : WCu = 2.4 g; t = 1 hr = 1 × 60 × 60 s
MCu = 63.5 g mol-1; I = ?

Ans. Current strength = I = 2.026 A

Question iv.
Equilibrium constant of the reaction,
2Cu+(aq) → Cu2+(aq) + Cu(s)
is 1.2 × 106. What is the standard potential of the cell in which the reaction
takes place ?
Answer:
For the cell reaction, n = 1

Question v.
Calculate emf of the cell
Zn(s)|Zn2+ (0.2M)||H+(1.6M)|H2(g, 1.8 atm)|Pt at 25°C.
Answer:
Given : Zn(s)|Zn2+(0.2M)||H+(1.6M)|H2(g, 1.8 atm)|Pt
= 0.763 – 0.0296 × (- 0.8521)
= 0.763 + 0.02522
= 0.7882
Ans. E0cell = 0.7882 V

Question vi.
Calculate emf of the following cell at 25°C.
Zn(s)| Zn2+(0.08M)||Cr3+(0.1M)|Cr
E0Zn = – 0.76 V, E0Cr = – 0.74 V
Answer:
Question vii.
What is a cell constant ? What are its units? How is it determined
experimentally?
Answer:
(A) Cell constant of a conductivity cell is defined as the ratio of the distance
between the electrodes divided by the area of cross section of the electrodes.
In SI units it is expected as m-1.

The resistance of an electrolytic solution is measured by using a conductivity

cell and Wheatstone

Fig. 5.6 : Measurement of conductance

The measurement of molar conductivity of a solution involves two steps as
follows :
Step I : Determination of cell constant of the conductivity cell :
KCl solution (0.01 M) whose conductivity is accurately known (κ = 0.00141 Ω -
1
cm-1) is taken in a beaker and the conductivity cell is dipped. The two
electrodes of the cell are connected to one arm while the variable known
resistance (R) is placed in another arm of Wheatstone bridge.

A current detector D’ which is a head phone or a magic eye is used. J is the

sliding jockey (contact) that slides on the arm AB which is a wire of uniform
cross section. A source of A.C. power (alternating power) is used to avoid
electrolysis of the solution.

By sliding the jockey on wire AB, a balance point (null point) is obtained at C.
Let AC and BC be the lengths of wire.
If Rsolution is the resistance of KCl solution and Rx is the known resistance then by
Wheatstone’s bridge principle,
Rsolution BC=RxAC
∴ Rsolution =BC×RxAC
Then the cell constant ‘ b ’ of the conductivity cell is obtained by, b = κ Kcl ×
Rsolution.

Step II : Determination of conductivity of the given solution :

KCl solution is replaced by the given electrolytic solution and its resistance (R s)
is measured by Wheatstone bridge method by similar manner by obtaining a
null point at D.
The conductivity (κ) of the given solution is,
κ = cell constant Rs=bRs

Step III: Calculation of molar conductivity :

The molar conductivity (∧m) is given by,

Since the concentration of the solution is known, ∧m can be calculated.

Question viii.
How will you calculate the moles of electrons passed and mass of the
substance produced during electrolysis of a salt solution using reaction
stoichiometry.
Answer:
Calculation of moles of electrons passed : The charge carried by one mole of
electrons is referred to as one faraday (F). If total charge passed is Q C, then
moles of electrons passed = Q(C)F(C/mole−)

Calculation of mass of product : Mass, W of product formed is given by,

W = moles of product × molar mass of product (M)
= Q96500 × mole ratio × M
= I×t96500 × mole ratio × M 96500
When two electrolytic cells containing different electrolytes are connected in
series so that same quantity of electricity is passed through them, then the
masses W1 and W2 of products produced are given by,

Question ix.
Write the electrode reactions when lead storage cell generates electricity.
What are the anode and cathode and the electrode reactions during its
recharging?
Answer:
Recharging of the cell : When the discharged battery is connected to external
electric source and a higher external potential is applied the cell reaction gets
reversed generating H2SO4.
Reduction at the – ve electrode or cathode :
PbSO4( s)+2e−→Pb(s)+SO2−4(aq)
Oxidation at the + ve electrode or anode :

The emf of the accumulator depends only on the concentration of H 2SO4.

Question x.
What are anode and cathode of H2-O2 fuel cell ? Name the electrolyte used in
it. Write electrode reactions and net cell reaction taking place in the fuel cell.
Answer:
Construction :
(i) In fuel cell the anode and cathode are porous electrodes with suitable
catalyst like finely divided platinum.

(iii) H2 is continuously bubbled through anode while O, gas is bubbled through

cathode.

Working (cell reactions) :

(i) Oxidation at anode : At anode, hydrogen gas is oxidised to H 2O.
2H2(g) + 4OH–(aq) → 4H2O(l) + 4e– (oxidation half reaction)
(ii) Reduction at cathode : The electrons released at anode travel to cathode
through external circuit and reduce oxygen gas to OH –.
O2(g) + 2H2O(l) + 4e– → 4OH–(aq) (reduction half reaction)

(iii) Net cell reaction: Addition of both the above reactions at anode and
cathode gives a net cell reaction.
2H2(g) + O2(g) → 2H2O(l) (overall cell reaction)

Question xi.
What are anode and cathode for Leclanche’ dry cell ? Write electrode
reactions and overall cell reaction when it generates electricity.
Answer:
A dry cell has zinc vessel as anode and graphite rod as cathode and moist
paste of ZnCl2, MnO2, NH4Cl as electrolytes.
At anode :
Zn(s) → Zn2+(aq) + 2e– (Oxidation half reaction)
At graphite (c) cathode :
2NH+4(e) + 2e– → 2NH3(aq) + H2(g) (Reduction half reaction)
2MnO2(s) + H2 → Mn2O3(s) + H2O(l)
There is a side reaction inside the cell, between Zn 2+ ions and aqueous NH3.
Zn2+(aq)+4NH3(aq)⟶[Zn(NH3)4]2+(aq)

Question xii.
Identify oxidising agents and arrange them in order of increasing strength
under standard state conditions. The standard potentials are given in
parenthesis.
Al(- 1.66 V), Cl2 (1.36 V), Cd2+ (-0.4 V), Fe (-0.44 V), I2 (0.54 V), Br– (1.09 V).
Answer:
The oxidising agents are I2, Br– and Cl2. The increasing strength is

(Note : Actually Br2 acts as an oxidising agent but not Br–.)

Question xiii.
Which of the following species are reducing agents? Arrange them in order of
increasing strength under standard state conditions. The standard potentials
are given in parenthesis.
K (-2.93V), Br2(1.09V), Mg(-2.36V), Co3+(1.61V), Ti2+(-0.37V), Ag+(0.8V), Ni (-
0.23V).
Answer:
Lower the standard reduction potential, higher is reducing power. The
reducing agents are Ni, Mg and K. Their increasing strength is,

(Note : Cations don’t act as reducing agent since they are already in oxidised
state.)

Question xiv.
Predict whether the following
reactions would occur spontaneously
under standard state conditions.
a. Ca(s) + Cd2+(aq) → Ca2+(aq) + Cd(s)
b. 2 Br-(s) + Sn2+(aq) → Br2(l) + Sn(s)
c. 2Ag(s) + Ni2+(aq) → 2 Ag+(aq) + Ni(s)
(use information of Table 5.1)
Answer:

12th Chemistry Digest Chapter 5 Electrochemistry Intext Questions and

Answers

Question 1.
How does electrical resistance depend on the dimensions of an electronic
(metallic) conductor?
Answer:
The electrical resistance of an electronic conductor is linearly proportional to
its length (l) and inversely proportional to its cross section area a.

Fig. 5.3 : Electronic conductor

Thus, R ∝ l; R ∝ 1a
∴ R ∝ la or R = ρ × la
where the proportionality constant p is called specific resistance. IUPAC
recommends the term resistivity for specific resistance.

Question 2.
What are the units of resistivity ?
Answer:
For an electronic conductor of length l, and cross section area a, the resistance
R is represented as
R = ρ × la
where ρ is the resistivity of the conductor.
∴ ρ = R × al
If l = 1 m, a = 1 m2, ρ = R

Hence, resistivity is the resistance of a conductor of volume of 1 m 3.

(In C.G.S. units, the units of ρ are ohm cm. Hence, ρ is the resistance of a
conductor of unit volume or 1 cm3.)

Question 3.
Define resistivity. What are its units ?
Answer:
Resistivity (or specific resistance) : It is the resistance of a conductor that is 1 m
in length and 1 m2 in cross section area in SI units. (In C.G.S. units, it is the
resistance of a conductor that is 1 cm in length and 1 cm 2 in cross section
area.) Hence, the resistivity is the resistance of a conductor of unit volume. (In
case of electrolytic solution, ρ is the resistivity i.e., resistance of a solution of
unit volume.)
It has SI units, ohm m and C.G.S. units, ohm cm.

Question 4.
Why is alternating current used in the measurement of conductivity of the
solution ?
Answer:
If direct current (D.C.) by battery is used, there will be electrolysis and the
concentration of the solution is changed. Hence alternating current (A.C.) with
high frequency is used.

Try this… (Textbook page No. 93)

Question 1.
What must be the concentration of a solution of silver nitrate to have the
molar conductivity of 121.4 Ω-1 cm2 mol-1 and the conductivity of 2.428 × 10-3 Ω-
1
cm-1 at 25 °C ?
Answer:

∴ Concentration of a Solution = 0.02 M

Try this… (Textbook page No. 96)

Question 1.
Obtain the expression for dissociation constant in terms of ∧c and ∧0 using
Ostwald’s dilution law.
Answer:
Consider a solution of a weak electrolyte, BA having concentration C mol dm -3.
If α is the degree of dissociation, then by Ostwald’s theory of weak
electrolytes,

If K is the dissociation constant of the weak electrolyte, then by Ostwald’s

dilution law,
K = α2C(1−α)
If ∧m is the molar conductivity of the electrolyte BA at the concentration C and
∧0 is the molar conductivity at zero concentration or infinite dilution, then

Hence by measuring ∧m at the concentration C and knowing ∧0, the

dissociation constant can be calculated.
If λ0+ and λ0− are the ionic conductivities, then by Kohlrauseh’s law,
∧0 = λ0+ + λ0−.

Learn this as well…

Question 1.
How is the cell constant of a conductivity cell determined?
Answer:
The cell constant of a given conductivity cell is obtained by measuring the
resistance (R) (or the conductance) of a standard solution whose conductivity
(fc) is accurately known by using Wheatstone’s bridge (discussed in Q. 37). For
this purpose, KCl solution of accurately known conductivity is used.
κKCl=1RKCl×la where la is a cell constant, represented by b.
∴ κKCl=bRKCl
or b = κKCl × RKCl
For example, the conductivity of 0.01 M KCl is 0.00141 Ω -1 cm-1 (S cm-1). Hence
by measuring R KCl the cell constant b can be obtained.

Try this… (Textbook page No. 95)

Question 1.
Calculate ∧0 (CH2ClCOOH) if ∧0 values for HCl, KCl and CH2ClCOOK are
respectively, 4.261, 1.499 and 1.132 Ω-1 m2 mol-1.
Solution :

Adding equations (i) and (ii) and subtracting equation (iii) we get equation (I).

Can you tell ? (Textbook page No. 103)

Question 1.
You have learnt Daniel cell in XIth standard. Write notations for anode and
cathode. Write the cell formula.
Answer:
Daniel cell is represented as,

Try this… (Textbook page No. 104)

Question 1.
Write electrode reactions and overall cell reaction for Daniel cell you learnt in
standard XI.
Answer:
Reactions for Daniell cell:

Question 1.
Describe different types of reversible electrodes with examples. (1 mark for
each type)
Answer:
A reversible electrochemical cell or a galvanic cell consists of two reversible
half cells or electrodes. There are four types of reversible electrodes according
to their compositions.
(1) Metal-metal ion electrode : This electrode is set up by dipping a metal in a
solution containing its own ions, e.g. Zn rod dipped into ZnSO 4 solution
containing Zn++ ions of concentration C.
It is represented as,
Zn2+(aq)∣Zn(s)
The reduction reaction at the electrode is,
Zn++(aq) + 2e– → Zn(s)
(2) Metal-sparingly soluble salt electrode : This electrode consists of a metal
coated with one of its sparingly soluble salts and immersed in a solution
containing an electrolyte having a common anion as that of the salt. For
example, silver electrode coated with sparingly soluble AgCl dipped in KCl
solution with common anion Cl–. This electrode is represented as,
Cl–(aq) | AgCl(s) | Ag(s)
The reduction reaction is,
AgCl(s) + e → Ag(s) + Cl–(aq)

(3) Gas electrode : This is developed by bubbling pure and dry gas around a
platinised platinum foil dipped in the solution containing ions (of the gas)
reversible with respect to the gas bubbled.
The gas is adsorbed on the surface of platinum foil and establishes an
equilibrium with its ions in the solution. Pt electrode provides electrical
contact and also acts as a catalyst.
Some of the gas electrodes are represented as follows :
(i) Hydrogen gas electrode :
H+(aq) | H2(g, PH2) | Pt
Reduction reaction : H+(aq) + e– → 12H2(g)
(ii) Chlorine gas electrode :
Cl–(aq) | Cl2(g, PCl2) | Pt
Reduction reaction : 12Cl2(g) + e- → Cl–(aq)

(4) Redox electrode (Oxidation reduction electrode) : This electrode consists of

a platinum wire dipped in a solution containing the ions of the same metal (or
a substance) in two different oxidation states, like Fe 2+ – Fe3+, Sn2+ – Sn4+, Mn++ –
MnO–4, etc.
A platinum electrode which provides an electrical contact and acts as catalyst
aquires an equilibrium between two ions in the solution, due to their tendency
to undergo a change from one oxidation state to another. The electrodes are
represented as,
Fe2+(aq), Fe3+(aq) | Pt
Reduction reaction : Fe3+(aq) + e– → Fe2+(aq)
SnCl2(aq), SnCl4(aq) | Pt
Reduction reaction : Sn4+(aq) + 2e– →Sn2+(aq)
Use your brain power! (Textbook page No. 98)

Question 1.
Distinguish between electrolytic and galvanic cells.
Answer:
Electrolytic cell:

1. This device is used to bring about a non-spontaneous chemical reaction

by passing an electric current.
2. It is used to bring about a chemical reaction generally for the
dissociation (electrolysis) of compounds.
3. In this cell, electrical energy is converted into chemical energy.
4. In this cell, the cathode is negative and the anode is positive.
5. Electrolytic cells are irreversible.
6. Oxidation takes place at the positive electrode and reduction at the
negative electrode.
7. The electrons are supplied by the external source and enter through
cathode and come out through anode.
8. It is used for electroplating, electrorefining, etc.

Electrochemical cell (Galvanic cell or Voltaic cell):

1. This device is used to produce electrical energy by a spontaneous

chemical reaction.
2. It is used to generate electricity.
3. In this cell, chemical energy is converted into electrical energy.
4. In this cell, the cathode is positive and the anode is negative.
5. Electrochernical cells are reversible.
6. Oxidation takes place at the negative electrode and reduction at the
positive electrode.
7. The electrons move from anode to cathode in the external circuit.
8. It is used as a source of electric current.

Try this… (Textbook page No. 107)

Question 1.
Write expressions to calculate equilibrium constant from
i. Concentration data
ii. Thermochemical data
iii. Electrochemical data
Answer:
(i) Consider following a reversible cell reaction.
aA + bB ⇌ cC + dD
If [A], [B], [C] and [D] represent concentrations of reactants and products then
the equilibrium constant K is,
K = [C]c×[D]d[ A]a×[B]b
(ii) If ΔG0 is the standard Gibbs free energy change at temperature T then,
ΔG0 = – RTlnK = – 2.303 RTlog10K
(iii) From electrochemical data,
if E0cell is the standard cell potential and K is the equilibrium constant for the
cell reaction at a temperature T, then,
E0cell =0.0592nlog10K

Learn this as well…

Question 1.
The construction and working of the calomel electrode.
Answer:
(1) Since standard hydrogen electrode (SHE) is not convenient for
experimental use, a secondary reference electrode like calomel electrode is
used.
(2) Construction : It consists of a glass vessel with side arm B for dipping in a
desired solution of another electrode like, ZnSO 4(aq) for an electric contact. The
vessel is filled with mercury, a paste of Hg and Hg 2Cl2 (calomel) and saturated
KCl solution.
Fig. 5.15 : Determination of standard electrode potential using calomel
electrode
(3) The potential developed depends upon the concentration of Cl – or KCl
solution. When saturated KCl solution is used, its reduction potential is 0.242
V.
(4) Consider following cell :
Zn(s) | ZnSO4(aq) || KCl(aq) | Hg2Cl2(s) | Hg
OR Zn(s) | ZnSO4(aq) || Calomel electrode
Reduction reaction for calomel electrode :
Hg2Cl2(s) + 2e– → 2Hg(l) + 2Cl–(aq)
Hence potential of calomel electrode depends on the concentration of Cl – or
KCl solution.

Can you tell ? (Textbook page No. 114)

Question 1.
In what ways are fuel cells and galvanic cells similar and in what ways are they
different ?
Answer:
Similarity between fuel cells and galvanic cells :

 In both the cells, there is oxidation at anode and j reduction at cathode.

 The cell potential is developed due to net redox reactions.
 Both are galvanic cells.
Difference in fuel cells and galvanic cells :

 Fuel cells involve electrodes with large surface area while galvanic cells
involve electrodes with j compact surface area.
 Fuel cells involve gaseous materials on a large scale while galvanic cells
involve gaseous materials at a definite pressures along with electrolytes
or there may not be gases.
 In fuel cells, the cell potential is developed due to exothermic
combustion reactions while in galvanic cell, cell potential is developed
due to normal redox reactions.
 In fuel cells gaseous electrode materials are continuously supplied from
outside while in galvanic cells electrode materials have constant
concentration or may change due to reactions.

Use your brain power (Textbook page No. 114)

Question 1.
Indentify the strongest and the weakest oxidizing agents from the
electrochemical series.
Answer:
From the electrochemical series,
(a) The strongest oxidising agent is fluorine since it has the highest standard
reduction potential (E0F2/F− = + 2.87 V).
(b) The weakest oxidising agent (or the strongest reducing agent) is lithium
since it has the lowest standard reduction potential, ( E0Li+/Li = -3.045 V).

Use your brainpower (Textbook page No. 115)

Question 1.
Identify the strongest and the weakest reducing agents from the
electrochemical series.
Answer:
(a) From the electrochemical series, the strongest reducing agent is lithium
since it has the lowest standard reduction potential ( E0Li+/Li = -3.045 V).
(b) The weakest reducing agent is fluorine since it has the highest standard
reduction potential,
(E0F2/F− = +2.87 V).

Question 2.
From E° values given in Table 5.1, predict whether Sn can reduce I 2 or Ni2+.
Answer:
From the electrochemical series,
Halogen Derivatives
1. Choose the most correct option.

Question i.
The correct order of increasing reactivity of C-X bond towards nucleophile in
the following compounds is

a. I < II < III < IV

b. II < I < III < IV
c. III < IV < II < I
d. IV < III < I < II
Answer:
(d) IV < III < I < II

Question ii.

The major product of the above reaction is,

Answer:
(c)

Question iii.
Which of the following is likely to undergo racemization during alkaline
hydrolysis?
Answer:
(a) Only I

Question iv.
The best method for preparation of alkyl fluorides is
a. Finkelstein reaction
b. Swartz reaction
c. Free radical fluorination
d. Sandmeyer’s reaction
Answer:
b. Swartz reaction

Question v.
Identify the chiral molecule from the following.
a. 1-Bromobutane
b. 1,1- Dibromobutane
c. 2,3- Dibromobutane
d. 2-Bromobutane
Answer:
(d) 2-Bromobutane

Question vi.
An alkyl chloride on Wurtz reaction gives 2,2,5,5-tetramethylhexane. The same
alkyl chloride on reduction with zinc-copper couple in alchol give hydrocarbon
with molecular formula C5H12. What is the structure of alkyl chloride

Answer:
(a)

Question vii.
Butanenitrile may be prepared by heating
a. propanol with KCN
b. butanol with KCN
c. n-butyl chloride with KCN
d. n-propyl chloride with KCN
Answer:
(d) n-propyl chloride with KCN

Question viii.
Choose the compound from the following that will react fastest by S N1
mechanism.
a. 1-iodobutane
b. 1-iodopropane
c. 2-iodo-2 methylbutane
d. 2-iodo-3-methylbutane
Answer:
(c) 2-iodo-2 methylbutane

Question ix.

The product ‘B’ in the above reaction sequence is,

Answer:
(d)

Question x.
Which of the following is used as source of dichlorocarbene
a. tetrachloromethane
b. chloroform
c. iodoform
d. DDT
Answer:
(b) chloroform

2. Do as directed.

Question i.
Write IUPAC name of the following compounds

Answer:
Question ii.
Write structure and IUPAC name of the major product in each of the following
reaction.

Answer:
Structure and IUPAC name
Question iii.
Identify chiral molecule/s from the following.

Answer:
Chiral molecule

Question iv.
Which one compound from the following pairs would undergo S N2 faster from
the?

Answer:

(1) Sincey is a primary halide it undergoes SN2 reaction faster

than .
(2) Since iodine is a better leaving group than chloride, 1-iodo propane
(CH3CH2CH2I) undergoes SN2 reaction faster than l-chloropropane
(CH3CH2CH2CI).

Question v.
Complete the following reactions giving major product.
Answer:

Answer:

Answer:
Answer:

Question vi.
Name the reagent used to bring about the following conversions.
a. Bromoethane to ethoxyethane
b. 1-Chloropropane to 1 nitropropane
c. Ethyl bromide to ethyl isocyanide
d. Chlorobenzene to biphenyl
Answer:

Question vii.
Arrange the following in the increase order of boiling points
a. 1-Bromopropane
b. 2- Bromopropane
c. 1- Bromobutane
d. 1-Bromo-2-methylpropane
Answer:
l-Bromo-2-methylpropane, 2-Bromopropane, 1-Bromopropane, 1-Bromo
butane

Question viii.
Match the pairs.

Answer:

3. Give reasons

Question i.
Haloarenes are less reactive than haloalkanes.
Answer:
Haloarenes (Aryl halides) are less reactive than (alkyl halides) haloalkanes due
to the following reasons :

(1) Resonance effect : In haloarenes, the electron pairs on halogen atom are in
conjugation with 7r-electrons of the benzene ring. The delocalization of these
electrons C-Cl bond acquires partial double bond character.

Due to partial double bond character of C-Cl bond in aryl halides, the bond
cleavage in haloarene is difficult and are less reactive. On the other hand, in
alkyl halides, carbon is attached to chlorine by a single bond and it can be
easily broken.

(2) Aryl halides are stabilized by resonance but alkyl halides are not. Hence,
the energy of activation for the displacement of halogen from aryl halides is
much greater than that of alkyl halides.

(3) Different hybridization state of carbon atom in C-X bond :

(i) In alkyl halides, the carbon of C-X bond is sp 3-hybridized with less 5-
character and greater bond length of 178 pm, which requires less energy to
break the C-X bond.

(ii) In aryl halides, the carbon of C-X bond is sp 3-hybridized with more 5-
character and shorter bond length which requires more energy to break C-X
bond. Therefore, aryl halides are less reactive than alkyl halides.

(iii) Polarity of the C-X bond : In aryl halide C-X bond is less polar than in alkyl
halides. Because sp3-hybrid carbon of C-X bond has less tendency to release
electrons to the halogen than a sp3-hybrid carbon in alkyl halides. Thus
halogen atom in aryl halides cannot be easily displaced by nucleophile.

(2) Aryl halides are extremely less reactive towards nucleophilic substitution
reactions.
Answer:
Aryl halides are extremely less reactive towards nucleophilic substitution
reaction due to the following reasons : (1) Resonance effect : In haloarenes,
the electron pairs on halogen atom are in conjugation with 7r-electrons of the
benzene ring. The delocalization of these electrons C-Cl bond acquires partial
double bond character.

Due to partial double bond character of C-Cl bond in aryl halides, the bond
cleavage in haloarene is difficult and are less reactive towards nucleophilic
substitution.

(2) Sp2 hybrid state of C : Different hybridization state of carbon atom in C-X
bond : In aryl halides, the carbon of C-X bond is sp 2-hybridized with more 5-
character and shorter bond length of 169 pm which requires more energy to
break C-X bond. It is difficult to break a shorter bond than a longer bond, in
alkyl chloride (bond length 178 pm) therefore, aryl halides are less reactive
towards nucleophilic substitution reaction.

(3) Instability of phenyl cation : In aryl halides, the phenyl cation formed due to
self ionisation will not be stabilized by resonance which rules out possibility of
SN1 mechanism. Also backside attack of nucleophile is blocked by the aromatic
ring which rules out SN2 mechanism. Thus cations are not formed and hence
aryl halides do not undergo nucleophilic substitution reaction easily.

(4) As any halides are electron rich molecules due to the presence of re-bond,
they repel electron rich nucleophilic, attack. Hence, aryl halides are less
reactive towards nucleophilic substitution reactions. However, the presence of
electron withdrawing groups at o/p position activates the halogen of aryl
halides towards substitution.
(3) Aryl halides undergo electrophilic substitution reactions slowly.
Answer:
Aryl halides undergo electrophilic substitution reactions slowly and it can be
explained as follows :

(1) Inductive effect : The strongly electronegative halogen atom withdraws the
electrons from carbon, atom of the ring, hence aryl halides show reactivity
towards electrophilic attack.

(2) Resonance effect : The resonating structures of aryl halides show increase
in electron density at ortho and para position, hence it is o, p directing.

The inductive effect and resonance effect compete with each other. The
inductive effect is stronger than resonance effect. The reactivity of aryl halides
is controlled by stronger inductive effect and o, p orientation is controlled by
weaker resonating effect.

The attack of electrophile (Y) on haloarenes at ortho and para positions are
more stable due to formation of chloronium ion. The chloronium ion formed is
comparatively more stable than other hybrid structures of carbonium ion.

(4) Reactions involving Grignard reagent must be carried out under anhydrous
condition.
Answer:
(1) Grignard reagent (R Mg X) is an organometallic compound. The carbon-
magnesium bond is highly polar and magnesium halogen bond is in ionic in
nature. Grignard reagent is highly reactive.

(2) The reactions of Grignard reagent are carried out in dry conditions because
traces of moisture may spoil the reaction and Grignard reagent reacts with
water to produce alkane. Hence, reactions involving Grignard reagent must be
carried out under anhydrous condition.

(5) Alkyl halides are generally not prepared by free radical halogenation of
alkane.
Answer:
(1) Free radical halogenation of alkane gives a mixture of all different possible
Monohaloalkanes as well as polyhalogen alkanes.
(2) In this method, by changing the quantity of halogen the desired product
can be made to predominate over the other
products. Hence, alkyl halides are generally not prepared by free radical
halogenation of alkane.

Question ii.
Alkyl halides though polar are immiscible with water.
Answer:
(1) In alkyl halide, the halogen atom is more electronegative than carbon
atom, the C – X bond is polar.
(2) Though alkyl halide is polar, it is insoluble in water because alkyl halide is
not able to form hydrogen bonds with water. Attraction between alkyl halide
molecule is stronger than attraction between alkyl halide and water.

(2) C-F bond in CH3F is the strongest bond and C-I bond in CH 3I is the weakest
bond. Explain.
Answer:
(1) Methyl fluoride (CH3F) is highly polar molecule and has the shortest C-F
bond length (139 pm) and the strongest C-F bond due to greater overlap of
orbitals of the same principal quantum number i.e., overlap of 2sp 3 orbital of
carbon with 2pz orbital of fluorine.
(2) Methyl iodide (CH3I) is much less polar and has the longest (C-I) bond
length (214 pm) and the weakest C-I bond due to poor overlap of 2sp 3 orbital
carbon with 5pz orbital of iodine i.e., 2sp3 orbital of carbon cannot penetrate
into larger p-orbitals.

(3) The boiling point of alkyl iodide is higher than that of alkyl fluoride.
Answer:
For a given alkyl group, the boiling point increases with increasing atomic
mass of the halogen, because magnitude of van der Waals force increases with
increase in size and mass of halogen. Therefore, boiling point of alkyl iodide is
higher than that of alkyl fluoride.

(4) The boiling point of isopropyl bromide is lower than that of it-propyl
bromide.
Answer:
For isomeric alkyl halides (isopropyl bromide and n-propyl bromide), the
boiling point decreases as the branching increases, surface area decreases on
branching and van der Waals forces decrease, therefore, the boiling point of
isopropyl bromide is lower than that of n-propyl bromide.

(5) p-Dichlorobenzene has mp. higher than those of o-and rn-

isomers.
Answer:
p-Dichlorobenzene has higher melting point than those of o-and m-isomers.
This is because of its symmetrical structure which can easily fits in crystal
lattice. As a result intermolecular forces of attraction are stronger and
therefore greater energy is required to overcome its lattice energy.

Question iii.
Reactions involving Grignard reagent must be carried out under anhydrous
conditions.
Question iv.
Alkyl halides are generally not prepared by free radical halogenation of
alkanes.
Answer:
(1) Direct fluorination of alkanes is highly exothermic, explosive and invariably
leads to polyfluorination and decomposition of the alkanes. It is difficult to
control the reaction.
(2) Direct iodination of alkanes is highly reversible and difficult to carry out.
(3) In direct chlorination and bromination, the reaction is not selective. It can
lead to different isomeric monohalogenated alkanes (alkyl halides) as well as
polyhalogenated alkanes.
Hence, halogenation of alkanes is not a good method of preparation of alkyl
halides.

4. Distinguish between – SN1 and SN2 mechanism of substitution reaction ?

Answer:
5. Explain – Optical isomerism in 2-chlorobutane.
Answer:

(1) 2-Chlorobutane contains an asymmetric. carbon atom

(the starred carbon atom) which is attached to four different groups, i.e., ethyl
(-CH2 – CH3), methyl (CH3), chloro (Cl) and hydrogen (H) groups.

(2) Two different arrangements of these groups around the carbon atom are
possible as shown in the figure. Hence, it exists as a pair of enanti¬omers. The
two enantiomers are mirror images of each other and are not superimposable.

(3) One of the enantiomers will rotate the plane of plane-polarized light to the
left hand side and is called the laevorotatory isomer (/-isomer). The other
enantiomer will rotate the plane of plane-polarized light to the right hand side
and is called the dextrorotatory isomer (d-isomer).

(4) Equimolar mixture of the d- and the 1-isomers is optically inactive and is
called the racemic mixture or the racemate (dl-mixture). The optical inactivity
of the racemic mixture is due to external compensation.
6. Convert the following.

Question i.
Propene to propan-1-ol
Answer:

Question ii.
Benzyl alcohol to benzyl cyanide
Answer:

Question iii.
Ethanol to propane nitrile
Answer:

Question iv.
But-1-ene to n-butyl iodide
Answer:

Question v.
2-Chloropropane to propan-1-ol
Answer:

Question vi.
tert-Butyl bromide to isobutyl bromide
Answer:
Question vii.
Aniline to chlorobenzene
Answer:

Question viii.
Propene to 1-nitropropane
Answer:

7. Answer the following

Question i.
HCl is added to a hydrocarbon ‘A’ (C4H8) to give a compound ‘B’ which on
hydrolysis with aqueous alkali forms tertiary alcohol ‘C’ (C 4H10O). Identify ‘A’ ,
‘B’ and ‘C’.
Answer:

Question ii.
Complete the following reaction sequences by writing the structural formulae
of the organic compounds ‘A’, ‘B’ and ‘C’.

Answer:
Question iii.
Observe the following and answer the questions given below.

a. Name the type of halogen derivative

b. Comment on the bond length of C-X bond in it
c. Can react by SN1 mechanism? Justify your answer.
Answer:
a. Vinyl halide
b. C – X bond length shorter in vinyl halide than alkyl halide. Vinyl halide has
partial double bond character due to resonance.

In vinyl halide, carbon is sp hybridised. The bond is shorter and stronger and
the molecule is more stable.

c. Yes, It reacts by SN1 mechanism. SN1 mechanism involves formation of

carbocation intermediate. The vinylic carbocation intermediate formed is
resonance stabilized, hence SN1 mechanism is favoured.

Activity :
1. Collect detailed information about Freons and their uses.
2. Collect information about DDT as a persistent pesticide.
Reference books
i. Organic chemistry by Morrison, Boyd, Bhattacharjee, 7 th edition, Pearson
ii. Organic chemistry by Finar, Vol 1, 6th edition, Pearson

12th Chemistry Digest Chapter 9 Halogen Derivatives Intext Questions

and Answers

Use your brain power….. (Textbook page 212)

Question 1.
Write IUPAC names of the following:
Answer:

Question 10.1 : (Textbook page 213)

How will you obtain [Link].1-methylcyclohexane from alkene? Write

possible structures of alkene and the reaction involved.
Answer:

Use your brain power ….. (Textbook page 213)

Question 1.
Rewrite the following reaction by filling the blanks:

Answer:
Question 10.2 : (Textbook page 216)

Arrange the following compounds in order of increasing boiling points :

bromoform, chloromethane, dibromomethane, bromomethane.
Answer:
The comparative boiling points of halogen derivatives are mainly related with
van der Waals forces of attraction which depend upon the molecular size. In
the present case all the compounds contain only one carbon. Thus the
molecular size depends upon the size of halogen and number of halogen
atoms present.

Thus increasing order of boiling point is, CH 3CI < CH3Br < CH2Br2 < CHBr3

Try this ….. (Textbook page 2016)

Question 1.
(1) Make a three-dimensional model of 2-chlorobutane.
(2) Make another model which is a mirror image of the first model.
(3) Try to superimpose the two models on each other.
(4) Do they superimpose on each other exactly ?
(5) Comment on whether the two models are identical or not.
Answer:
(1) (2) and (3)

(4) Two models are non-superimposable mir ror images of each other called
enantiomers.

(5) Two enantiomers are identical. Theyhave the same physical properties
(such as melting points, boiling points, densities refractive index). They also
have identical chemical properties. The magnitude of their optical rotation is
equal but the sign of optical rotation is opposite.

Try this ….. (Textbook page 219)

Question 1.

1. Draw structares of enantiomers of lactic acid using

Fischer projection formulae.
2. Draw structures of enantiomers of 2-bromobutane using wedge formula.
Answer:
(1)

(2) Wedge formula : 2-brornobutane

Can you tell? (Textbook page 220)

Question 1.
Alkyl halides, when treated with alcoholic solution of silver nitrite, give
nitroalkanes whereas with sodium nitrite they give alkyl nitrites. Explain.
Answer:
Nitrite ion is an ambident nucleophile, which can attack through ‘O’ or ‘N’.

Both nitrogen and oxygen are capable of donating electron pair. C – N bond,
being stronger than N – O bond, attack occurs through C atom from alkyl
halide forming nitroalkane.
However, sodium nitrite (NaNO2) is an ionic compound and oxygen is free to
donate pair of electrons. Hence, attack occurs through oxygen resulting in the
formation of alkyl nitrite.

Use your brain power! (Textbook page 222)

Question 1.
Draw the Fischer projection formulae of two products obtained when
compound (A) reacts with OHe by SN1 mechanis.

Answer:

Question 2.
Draw the Fischer projection formula of the product formed when compound
(B) reacts with OHΘ by SN2 mechanism.

Answer:
Question 10.4 : (Textbook page 223)

Allylic and benzylic halides show high reactivity towards the S N1 mechanism
than other primary alkyl halides. Explain.
Answer:
In allylic and benzylic halide, the carbocation formed undergoes stabilization
through the resonance. Hence, allylic and benzylic halides show high reactivity
towards the SN1 reaction. The resonating structures are

Resonance stabilization of allylic carbocation

Resonance stabilization of benzylic carbocation

Question 10.5 : (Textbook page 224)

Which of the following two compounds would react faster by SN2 mechanism
and Why?

Answer :
In SN2 mechanism, a pentacoordinate T.S. is involved. The order of reactivity of
alkyl halides towards SN2 mechanism is.
Primary > Secondary > Tertiary, (due to increasing crowding in T.S. from
primary to tertiary halides.
1- Chlorobutane being primary halide will react faster by S N2 mechanism, than
the secondary halide 2- chlorobutane.)

Can you tell? (Textbook page 227)

Question 1.
Conversion of chlorobenzene to phenol by aqueous sodium hydroxide
requires a high temperature of about 623K and high pressure. Explain.

Answer:
Due to the partial double bond character in chlorobenzene, the bond cleavage
in chlorobenzene is difficult and is less reactive. Hence, during the conversion
of chlorobenzene to phenol by a question NaOH requires high temperature &
high pressure.
Alcohols, Phenols and Ethers
1. Choose the correct option.

Question i.
Which of the following represents the increasing order of boiling points of (1),
(2), and (3)?
(1) CH3 – CH2 – CH2 – CH2 – OH
(2) (CH3)2 CH – O – CH3
(3) (CH3)3COH
A. (1) < (2) < (3)
B. (2) < (1) < (3)
C. (3) < (2) < (1)
D. (2) < (3) < (1)
Answer:
(a) (1) < (2) < (3)

Question ii.
Which is the best reagent for carrying out following conversion ?

A. LiAlH4
B. Conc. H2SO4, H2O
C. H2/Pd
D. B2H6, H2O2 – NaOH
Answer:
B. Conc. H2SO4, H2O

Question iii.
Which of the following reaction will give ionic organic product on reaction ?
A. CH3 – CH2 – OH + Na
B. CH3 – CH2 – OH + SOCl2
C. CH3 – CH2 – OH + PCl5
D. CH3 – CH2 – OH + H2SO4
Answer:
C. CH3 – CH2 – OH + PCl5

Question iv.
Which is the most resistant alcohol towards oxidation reaction among the
follwoing ?

Answer:
(c)

Question v.
Resorcinol on distillation with zinc dust gives
A. Cyclohexane
B. Benzene
C. Toluene
D. Benzene-1, 3-diol
Answer:
(b) Benzene

Question vi.
Anisole on heating with concerntrated HI gives
A. Iodobenzene
B. Phenol + Methanol
C. Phenol + Iodomethane
D. Iodobenzene + methanol
Answer:
B. Phenol + Methanol

Question vii.
Which of the following is the least acidic compound ?
Answer:
(b)

Question viii.
The compound incapable of hydrogen bonding with water is ……

Answer:
(b)

Question ix.
Ethers are kept in air tight brown bottles because
A. Ethers absorb moisture
B. Ethers evaporate readily
C. Ethers oxidise to explosive peroxide
D. Ethers are inert
Answer:
C. Ethers oxidise to explosive peroxide
Question x.
Ethers reacts with cold and concentrated H 2SO4 to form
A. oxonium salt
B. alkene
C. alkoxides
D. alcohols
Answer:
A. oxonium salt

2. Answer in one sentence/ word.

Question i.
Hydroboration-oxidation of propene gives…..
Answer:
n-propyl alcohol (CH3 – CH2 – CH2 – OH)

Question ii.
Write the IUPAC name of alcohol having molecular formula C 4H10O which is
resistant towards oxidation.
Answer:

Question iii.
Write the structure of optically active alcohol having molecular formula C 4H10O
Answer:

Question iv.
Write name of the electrophile used in Kolbe’s Reaction.
Answer:
Electrophile : Carbon dioxide (O = C = O)

3. Answer in brief.
Question i.
Why phenol is more acidic than ethyl alcohol ?
Answer:
(1) In ethyl alcohol, the -OH group is attached to sp 3 – hybridised carbon while
in phenols, it is attached to sp2 – hybridised carbon.

(2) Due to higher electronegativity of sp2 – hybridised carbon, electron density

on oxygen decreases. This increases the polarity of O-H bond and results in
more ionization of phenol than that of alcohols.

(3) Electron donating inductive effect (+1 effect) of the alkyl group destabilizes
alkoxide ion. As a result alcohol does not ionize much in water, therefore
alcohol is neutral compound in aqueous medium.

(4) In alkoxide ion, the negative charge is localized on oxygen, while in

phenoxide ion the negative charge is delocalized. The delocalization of the
negative charge (structure I to V) makes phenoxide ion more stable than that
of phenol.

The delocalization of charge in phenol (structures VI to X), the resonating

structures have charge separation (where oxygen atom of OH group to be
positive and delocalization of negative charge over the ortho and para
positions of aromatic ring) due to which phenol molecule is less stable than
phenoxide ion. This favours ionization of phenol. Thus phenols are more acidic
than ethyl alcohol.

Question ii.
Why p-nitrophenol is a stronger acid than phenol ?
Answer:
(1) In p-nitrophenol, nitro group (NO2) is an electron withdrawing group
present at para position which enhances the acidic strength (-1 effect). The O-
H bond is under strain and release of proton (H +) becomes easy. Further p-
nitrophenoxide ion is more stabilised due to resonance.

(2) Since the absence of electron withdrawing group (like – NO 2) in phenol at

ortho and para position, the acidic strength of phenol is less than that of p-
nitrophenol.

Question iii.
Write two points of difference between properties of phenol and ethyl alcohol.
Answer:

Question iv.
Give the reagents and conditions necessary to prepare phenol from
a. Chlorobenzene
b. Benzene sulfonic acid.
Answer:
(1) From chlorobenzene : Reagents required : NaOH and dil. HC1
Temperature : 623 K, Pressure : 150 atm
(2) From Benzene sulphonic acid : Reagents required : aq NaOH, caustic soda,
dil. HC1 Temperature : 573 K

Question v.
Give the equations of the reactions for the preparation of phenol from
isopropyl benzene.
Answer:
Preparation of phenol from cumene (isopropylbenzene) : This is the
commercial method of preparation of phenol. When a stream of air is passed
through cumene (isopropylbenzene) suspended in aqueous Na 2CO3 solution in
the presence of cobalt naphthenate catalyst, isopropyl benzene hydroperoxide
or cumene hydroperoxide is formed. Isopropylbenzene hydroperoxide on
warming with dil. H2SO4 gives phenol and acetone. Acetone is an important
by-product of the reaction and is separated by distillation. The reaction is
called auto oxidation.

Question vi.
Give a simple chemical test to distinguish between ethanol and ethyl bromide.
Answer:
When ethyl bromide is heated with aq NaOH; ethyl alcohol is formed whereas
ethanol does not react with aq NaOH

4. An ether (A), C5H12O, when heated with excess of hot HI produce two alkyl
halides which on hydrolysis form compound (B)and (C), oxidation of (B) gave
and acid (D), whereas oxidation of (C) gave a ketone (E). Deduce the structural
formula of (A), (B), (C), (D) and (E).
Answer:

5. Write structural formulae for

a. 3-Methoxyhexane
b. Methyl vinyl ether
c. 1-Ethylcyclohexanol
d. Pentane-1,4-diol
e. Cyclohex-2-en-1-ol
Answer:

6. Write IUPAC names of the following

Answer:

Activity :
• Collect information about production of ethanol as byproduct in sugar
industry and its importance in fuel economy.
• Collect information about phenols used as antiseptics and polyphenols
having antioxidant activity.

12th Chemistry Digest Chapter 11 Alcohols, Phenols and Ethers Intext

Questions and Answers

Use your brain power! (Textbook Page No 235)

Question 1.
Classify the following alcohols as l0/2°/3° and allylic/benzylic

Answer:
(1) Ally lie alcohol (primary)
(2) Allylic alcohol (secondary)
(3) Allylic alcohol (tertiary)
(4) Benzylic alcohol (primary)
(5) Benzylic alcohol (secondary)

Use your brain power ….. (Textbook Page No 236)

Question 1.
Name t-butyl alcohol using carbinol system of nomenclature.
Answer:
Trimethyl carbinol.

Problem 11.1 (Textbook Page No 238)

Question 1.
Draw structures of following compounds:
(i) 2,5-DiethIphenoI
(ii) Prop-2-en-I-oI
(iii) 2-methoxypropane
(iv) Phenylmethanol
Solution :
Try this ….. (Textbook Page No 238)

Write IUPAC names ol (he following compounds.

Do you know (Textbook Page No 238)

Question 1.
The mechanism of hydration of ethylcnc to ethyl alcohol.
Answer:
The mechanism of hydration of ethylene involves three steps:

Step 1: Ethylene gets protonated to form carbocation by electrophilic attack of

H3O (Formation of carbocation intermediate).

Step 2 : Nucleophilic attack of water on carbocation

Step 3 : Deprotonation to form an alcohol

Problem 11.2 : (Textbook Page No 239)

Question 1.
Predict the products for the following reaction.

Solution:

The substrate (A) contains an isolated and an aldehyde group.

H2/Ni can reduce both these functional groups while LiAlH 4 can reduce only –
CHO of the two, Hence

Try this ….. (Textbook page 240)

Question 1.
Arrange O – H, C – H and N – H bonds in increasing order of their bond
polarity.
Answer:
Increasing order of polarity :C – H, N – H, O – H

Problem 11.3 : (Textbook Page No 241)

Question 1.
The boiling point of n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol and
tert-butyl alcohol are 118 °C, 108 °C. 99 °C and 82 °C respectively. Explain.
Solution:
As branching increases, intermolecular van der Waal’s force become weaker
and the boiling point decreases. Therefore, n-butyl alcohol has highest boiling
point 118 °C and tert-butyl alcohol has lowest boiling point 83 °C. Isobutyl
alcohol is a primary alcohol and hence its boiling point is higher than that of
sec-butyl alcohol.

Problem 11.4 : (Textbook Page No 242)

The solubility of o-nitrophenol and p-nitrophenol is 0.2 g and 1.7 g/100 g of

H2O respectively. Explain the difference.
Solution :

p-Nitrophenol has strong intermolecular hydrogen bonding with solvent

water. On the other hand, o-nitrophenol has strong intramolecular hydrogen
bonding and therefore the intermolecular attraction towards solvent water is
weak. The stronger the intermolecular attraction between solute and solvent
higher is the solubility. Hence p-nitrophenol has higher solubility in water than
that of o-nitrophenol.

Problem 11.5 : (Textbook Page No 243 & 244)

Question 1.
Arrange the following compounds in decreasing order of acid strength and
justify.
(1) CH3 – CH2 – OH
(2) (CH3)3 C – OH
(3) C6H5 – OH
(4) p-NO2 – C6H4 – OH
Solution :
Compounds (3) and (4) are phenols and therefore are more acidic than the
alcohols (1) and (2). The acidic strengths of compounds depend upon
stabilization of the corresponding conjugate bases. Hence let us compare
electronic effects in the conjugate bases of these compounds :

The conjugate base of the alcohol (1) is destabilized by + 1 effect of one alkyl
group, whereas conjugate base of the alcohol (2) is destabilized by +1 effect
of three alkyl groups. Hence (2) is weaker acid than (1)

Phenols : The conjugate base of p-nitrophenol (4) is better resonance

stabilized due to six resonance structures compared to the five resonance
structure of conjugate base of phenol (3). The resonance structure VI has – ve
charge on only electronegative oxygens. Hence the phenol (4) is stronger acid
than (3). Thus the decreasing order of acid strength is (4), (3), (1), (2).

Use your brain power (Textbook Page No 244)

Question 1.
What are the electronic effects exerted by – OCH 3 and – Cl? Predict the acid
strength of

Answer:
The electronic effects exerted by – Cl and – O CH 3 are as follows :
(1) Cl being more electronegative atom it pulls the bonding electrons towards
itself. This is known as negative inductive effect (- I).

(2) – OCH3 is less electronegative group which repels the bonding electrons
away from it. This is known as positive inductive effect ( + I).

(3) The relative to parent phenol, is more acidic

than .

Problem 11.6 : (Textbook Page No 245)

Question 1.
Mechanism of acid catalyzed dehydration of ethanol to give ethene.
Answer:
The mechanism of dehydration of ethanol involves the following order :
Step 1 : Formation of protonated alcohols : Initially ethyl alcohol gets
protonated to form ethyl oxonium ion.

Step 2 : Formation of carbocation : It is the slowest step and hence, the rate
determining step of the reaction.

Steps 3: Formation of ethene: Removal of a proton (H +) from carbocation.

The acidused in step I is released in step 3, the equilibrium is shifted to the
right, ethene is removed as it is formed.

Problem 11.6 : (Textbook Page No 245)

Question 1.
Write the reaction showing major and minor products formed on heating
butan-2-ol with concentrrated sulphuric acid.
Solution :
In the reaction described butan-2-ol undergoes dehydration to give but-2-ene
(major) and but-l-ene (minor) in accordance with Saytzeff rule.

Problem 11.7 : (Textbook Page No 246)

Question 1.
Write and explain reactions to convert propan-l-ol into propan-2-ol.
Solution :
The dehydration of propane-l-ol to propene is the first step. Markownikoff
hydration of propene is the second step to get the product propan-2-ol. This
is brought about by reaction with concemtrated H 2SO4 followed by hydrolysis.

Problem 11.8 : (Textbook Page No 246)

Question 1.
An organic compound gives hydrogen on reaction with sodium metal. It forms
an aldehyde having molecular formula C2H4O on oxidation with pyridinium
chlorochromate. Name the compounds and give equations of these reactions.
Solution :
The given molecular formula C2H4O of aldehyde is written as CH3 – CHO. Hence
the formula of alcohol from which this is obtained by oxidation must be CH 3 –
CH2 – OH. The two reactions can, therefore, be represented as follows :

(Do you know? Textbook Page No 248)

Question 90.
Write the mechanism of dehydration of alcohol to give ether.
Answer:
Dehydration of alcohols to form ether is SN 2 reaction. The mechanism of
dehydration of ethanol involves the following steps.

Step 1 (Protonation) : Initially ethyl alcohol gets protonated in the presence of

acid to form ethyl oxonium ion.

Step 2 (SN2 mechanism) : Protonated alcohol species undergoes a backside

attack by second molecule of alcohol is a slow step.

Step 3 (Deprotonation) : Formation of diethyl ether by elimination of proton

Problem 11.9 : (Textbook Page No 249)

Question 1.
Ethyl isopropyl ether does not form on reaction of sodium ethoxide and
isopropyl chloride.

(i) What would be the main product of this reaction?

(ii) Write another reaction suitable for the preparation of ethyl isopropyl ether.
Solution :
(i) Isopropyl chloride is a secondary chloride. On treating with sodium
ethoxide it gives elimination reaction to form propene as the main product.

(ii) Ethyl isopropyl ether can be prepared as follows using ethyl chloride
(10 chloride) as substrate.

Do you know? (Textbook Page No 250)

Question 1.
The mechanism of the reaction of HI with methoxy ethane.
Answer:
The reaction mechanism takes place as follows :
Step 1 : Protonation of ether Initially the ether molecule (methoxy ethane)
protonated by cone. HI to form oxonium ion.

Step 2 : Iodide is a good nucleophile. It attacks the least substituted carbon of

the oxonium ion formed in step 1 and displaces an alcohol molecule by
SN2 mechanism.

For example :
• Use of excess HI converts the alcohol into alkyl iodide.
• In the case of ether having one tertiary alkyl group the reaction with hot HI
follows the SN1 mechanism, and tertiary iodide is formed rather than tertiary
alcohol.

Step 1 :

Step 2 :
Aldehydes, Ketones and Carboxylic Acids
1. Choose the most correct option.

Question i.
In the following resonating structures A and B, the number of unshared
electrons in valence shell present on oxygen respectively are

Answer:
c. 4, 6

Question ii.
In the Wolf -Kishner reduction, alkyl aryl ketones are reduced to
alkylbenzenes. During this change, ketones are first converted into
a. acids
b. alcohols
c. hydrazones
d. alkenes
Answer:
c. hydrazones

Question iii.
Aldol condensation is
a. electrophilic substitution reaction
b. nucleophilic substitution reaction
c. elimination reaction
d. addition – elimination reaction
Answer:
d. addition-elimination reaction
Question iv.
Which one of the following has the lowest acidity?

Answer:
(c)

Question v.
Diborane reduces
a. ester group
b. nitro group
c. halo group
d. acid group
Answer:
d. acid group

Question vi.
Benzaldehyde does NOT show positive test with
a. Schiff reagent
b. Tollens’ ragent
c. Sodium bisulphite solution
d. Fehling solution
Answer:
d. Fehling solution

2. Answer the following in one sentence

Question i.
What are aromatic ketones?
Answer:
The compounds in which group is attached to either two aryl
groups or one aryl and one alkyl group are called aromatic ketones.

For example :

Question ii.
Is phenylacetic acid an aromatic carboxylic acid?
Answer:
Phenylacetic acid is not an aromatic carboxylic acid.

Question iii.
Write reaction showing conversion of ethanenitrile into ethanol.
Answer:

Question iv.
Predict the product of the following reaction:
CH3−CH2−COOCH3i⋅AlH(i−Bu)2 ii. H3O⊕⟶?
Answer:

Question v.
Name the product obtained by reacting toluene with carbon monoxide and
hydrogen chloride in presence of anhydrous aluminium chloride.
Answer:

Question vi.
Write reaction showing conversion of Benzonitrile into benzoic acid.
Answer:

Question vii.
Name the product obtained by the oxidation of 1,2,3,4-tetrahydronaphthalene
with acidified potassium permanganate.
Answer:

Question viii.
What is formalin?
Answer:
The aqueous solution of formaldehyde (40%) is known as formalin.

Question ix.
Arrange the following compounds in the increasing order of their boiling
points : Formaldehyde, ethane, methyl alcohol.
Answer:
Ethane, formaldehyde, methyl alcohol.

Question x.
Acetic acid is prepared from methyl magnesium bromide and dry ice in
presence of dry ether. Name the compound which serves not only reagent but
also as cooling agent in the reaction.
Answer:
The cooling agent used in the above reaction is dry ice (O = C = O).

3. Answer in brief.

Question i.
Observe the following equation of reaction of Tollens’ reagent with aldehyde.
How do we know that a redox reaction has taken place. Explain.
R−CHO+2Ag(NH3)+2+OH−⟶ΔR−COO−+2Ag↓+4NH3+2H2O
Answer:
Tollen’s reagent oxidises acetaldehyde to acetic acid (carboxylate ion) and Ag
in Tollen’s reagent complex are reduced to silver. In this reaction, oxidation
and reduction takes place simultaneously hence, it is a redox reaction.
Question ii.
Formic acid is stronger than acetic acid. Explain.
Answer:

In acetic acid, the methyl group is an electron-donating group. The acetate ion
formed gets destabilized due to the electron releasing effect of methyl group (
+1 effect) which is higher than that of H-atom in the corresponding formic
acid. As a result, acetic acid dissociates to a lesser extent. Thus decreasing the
acidity of acetic acid.

Formic acid having lower pKa value than acetic acid. Hence, formic acid is a
stronger acid than acetic acid.

Question iii.
What is the action of hydrazine on cyclopentanone in presence of —. KOH in
ethylene glycol?
Answer:

Question iv.
Write reaction showing conversion of Acetaldehyde into acetaldehyde
dimethyl acetal.
Answer:

Question v.
Aldehydes are more reactive toward nucleophilic addition reactions than
ketones. Explain.
Answer:
The reactivity of aldehydes and keones is due to the polarity of carbonyl group
which results in electrophilicity of carbon. The reactivity is further explained on
the basis of electronic effect and steric effects.

(1) Influence of electronic effects: A ketone has two electron-donating [Link]

groups ( + I effect) bonded to carbonyl carbon which are responsible for
decreasing its positive polarity and electrophilicity. In contrast. aldehydes have
only electron-donating group bonded to carbonyl carbon. This shows
aldehydes are more electrophilic than ketones.

(2) Steric effects : Two bulky alkyl groups in ketone come in the way of the
incoming nucleophile. This is called steric hindrance to nucleophilic attack.

On the other hand. nucleophile can easily attack the carbonyl carbon in
aldehyde because has one alkyl group and is less crowded or sterically less
hindered.

Hence aldehydes are more reactive and can easily be attacked by

nucleophiles.

Question vi.
Write reaction showing the action of the following reagent on propane nitrile
a. Dilute NaOH
b. Dilute HCl ?
Answer:
(1) Action of dil NaOH:
(2) Action of dil HCl:

Question vi.
Arrange the following carboxylic acids with increasing order of their acidic
strength and justify your answer.

Answer:
The increasing order of acidity will be 1 <3 <2. Acidity depends on mainly two
factors : (1) ease of proton release (2) stability of conjugate base formed. In
example (3) the ether O exerts a I effect and is closer to COOH group than in 2
(1 effect diminishes). Also the conjugate base formed will be stabilized by the
same – I effect by delocalization of charge.

4. Answer the following

Question i.
Write a note on
a. Cannizaro reaction
b. Stephen reaction.
Answer:
(1) The carbon atom adjacent to carbonyl carbon atom is called a-carbon
atom (α – C) and the hydrogen atom attached to a-carbon atom is called α-
hydrogen atom (α – H).

(2) The α-hydrogen of aldehydes and ketones is acidic in nature due to (i) the
strong-I effect of carbonyl group (ii) resonance stabilization of the carbanion.

(3) Aldol condensation reaction is characteristic reaction of aldehydes and

ketones containing active α-hydrogen atom.

(4) When aldehydes or ketones containing α – H atoms are warmed with a

dilute base or dilute acid, two molecules of them undergo self condensation
to give β-hydroxy aldehyde (aldol) or β-hydroxy ketone (ketol) respectively.
The reaction is known as Aldol addition Reaction.

(5) In aldol condensation, the product is formed by the nucleophilic addition

of α-carbon atom of a second molecule which gets attached to carbonyl
carbon atom of the first molecule and α-hydrogen atom of the second
molecule gets attached to carbonyl oxygen atom of the first molecule forming
(- OH) group to give β-hydroxy aldehyde or ketone.

(6) This is a reversible reaction, establishing an equilibrium favouring aldol

formation to a greater extent than ketol formation.
(7) For aldehyde :

Acetaldol on heating undergoes subsequent elimination of water giving rise to

α, β unsaturated aldehyde.

The overall reaction is called aldol condensation. It is a nucleophilic addition-

elimination reaction. For ketone :

Diacetone alcohol on dehydration by heating forms α, β unsaturated ketone.

Question ii.
What is the action of the following reagents on toluene ?
a. Alkaline KMnO4, dil. HCl and heat
b. CrO2Cl2 in CS2
c. Acetyl chloride in presence of anhydrous AlCl 3.
Answer:
(1) Action of alkaline KMnO4 : When toluene is heated with alkaline KMnO 4.
(methyl group gets oxidised to earboxy lic group) benzoic acid is obtained

(2) Action of CrO2Cl2 in C2:

Answer:
When Loluenc is ircated with soluion of chromyl chloride (CrO 2Cl2) in Cs2,
brown chromium complex is obtained, which on acid hydrolysis gives
benzaldehyde.

(3) Action of acetyl chloride in presence of anhyd. AlCl 3.

Answer:
When toluene is treated with acetyl chloride in presence of anhydrous AlCl 3 4-
methyl acetophenone is obtained.
Question iii.
Write the IUPAC names of the following structures :

Question iv.
Write reaction showing conversion of p- bromoisopropyl benzene into p-
Isopropyl benzoic acid (3 steps).
Answer:
Question v.
Write reaction showing aldol condensation of cyclohexanone.
Answer:

Activity :
Draw and complete the following reaction scheme which starts with
acetaldehyde. In each empty box, write the structural formula of the organic
compound that would be formed.

12th Chemistry Digest Chapter 12 Aldehydes, Ketones and Carboxylic

Acids Intext Questions and Answers

Use your brain power! (Textbook Page No 254)

Question 1.
Classify the following as aliphatic and aromatic aldehydes.
Answer:

Use your brain power! (Textbook Page No 255)

Question 1.
Classify the following as simple and mixed ketones. Benzoplienone, acetoneq
hutanoneq acetophenone.

Compoun
Benzophenone ……………………………………………..
Acetone ……………………………………………..
Butanone ……………………………………………..
Acetophenone ……………………………………………..

Answer:

Compound
Benzophenone Simple ketone
Acetone Simple ketone
Butanone Mixed ketone
Acetophenone Mixed ketone
Use your brain power! (Textbook Page No 264)

Write IUPAC names for the following compounds.

Try this ….. (Textbook Page No 260)

Question 1.
Draw structures for the following :
(1) 2-Methylpentanal
(2) Hexan-2-one
Answer:

Can you tell? (Textbook Page No 260)

Question 1.
Which is the reagent that oxidizes primary alcohols to only aldehydes and
does not oxidize aldehydes further into carboxylic acid ?
Answer:
The reagent that is used to make only aldehydes is-heated Cu at 573 K.

Use your brain power! (Textbook Page No 261)

Question 1.
Write the structure of the product formed on Rosenmund reduction of
ethanoyl chloride and benzoyl chloride.
Answer:

Can you think? (Textbook Page No 261)

Question 1.
What is the alcohol formed when benzoyl chloride is reduced with pure
palladium as the catalyst ?
Answer:

Use your brain power! (Textbook Page No 262)

Question 1.
Name the compounds which are used for the preparation of benzophenone
by Friedel-Crafts acylation reaction. Draw their structures.
Answer:
The compounds which are used in preparation of benzophenone by Friedel –
Crafts reaction are :

Use your brain power! (Textbook Page No 263)

Identify the reagents necessary to achieve each of the following

transformations:
Answer:

Use your brain power! (TextBook Page No 264)

Predict the products (name and structure) in the following reactions.

Answer:

Problem 12.1 : (Textbook Page No 276)

Question 1.
Alcohols (R – OH), phenols (Ar – OH) and carboxylic acids (R – COOH) can
undergo ionization of O – H bond to give away proton H +; yet they have
different pKa values, which are 16, 10 and 4.5 respectively. Explain.
Solution :
pKa value is indicative of acid strength. Lower of pK a value stronger the acid.
Alcohols, phenols and carboxylic acids, all involve ionization of an O – H bond.
But their different pKa values indicate that their acid strengths are different.
This is because the resulting conjugate bases are stabilized to different
extents.
As the conjugate base of carboxylic acid is best stabilized, among the three,
carboxylic acids are strongest and have the lowest pKa value. As conjugate
base of alcohols is destabilized, alcohols are weakest acids and have highest
pIQ value. As conjugate base of phenols is moderately stabilized, phenols are
moderately acidic and have intermediate pBQ value.

Try this….. (Textbook Page No 277)

Question 1.
Compare the following two conjugate bases and answer.

(1) Indicate the inductive effects of CH3 – group in (a) and Cl-group in (b) by
putting arrowheads in the middle of appropriate covalent bonds.
(2) Which species is stabilized by inductive effect, (a) or (b) ?
(3) Which species is destabilized by inductive effect, (a) or (b) ?
Answer:

(2) The monochloroacetate ion formed gets stabilised due to electron-

withdrawing of Cl atom (- I effect).
(3) The acetate ion formed gets destabilised due to electron
releasing effect of methyl group

Use your brain power! (Textbook Page No 277)

Question 1.
(1) Compare the pKa values and arrange the following in an increasing order of
acid strength. CI3CCOOH, ClCH2COOH, CH3COOH, Cl2CHCOOH
(2) Draw structures of conjugate bases of monochloroacetic acid and
dichloroacetic acid. Which one is more stabilized by – 1 effect?
Answer:

The dichloroacetate ion formed gets stabilised due

electron-withdrawing effect of two chlorine atoms. (- 1 effect)

Try this….. (Textbook Page No 277)

Question 1.
Arrange the following acids in order of their decreasing acidity.
Answer:
Acidity in the decreasing order

Try this ….. (Textbook Page No 267)

Question 1.
Draw the structure of propanone and indicate its polarity.
Answer:

Can you tell? (Textbook Page No 268)

Question 1.
Simple hydrocarbons, ethers, ketones and alcohols do not get oxidized by
Tollen’s reagent. Explain, Why?
Answer:

(1) Due to the presence of hydrogen atom in aldehyde group , an

aldehyde is oxidised to carboxylic acid which is not possible in case

of ethers, ketones, alcohols and hydrocarbons.
(2) In ketones, carbonyl atom is attached to C-atom, hence C – C bond

in can’t be broken easily.

(3) H atom attached to carbonyl carbon can be oxidised to – OH group giving

carboxylic group Therefore, aldehyde reduces Tollen’s reagent,

whereas simple hydrocarbons, ethers, ketones and alcohols do not reduce
Tollen’s reagent.

Use your brain power! (Textbook Page No 269)

Question 1.
Sodium bisulfite is sodium salt of sulfurous acid, write down its detailed bond
structure.
Answer:

Bond structure of sodium bisulfite

Use your brain power! (Textbook Page No 270)

Predict the product of the following reaction:

Answer:

Use your brain power! (Textbook Page No 271)

Question 1.
Draw the structures of
(1) The semicarbazone of cyclohexanone
(2) The imine formed in the reaction between 2-methylhexanal and ethyl
amine
(3) 2, 4-dinitrophenyl hydrazone of acetaldehyde.
Answer:
(1) The semi carbazone of cyclohexanone.
(2) The imine formed between 2-methyl hexanal and ethyl amine.

(3) 2, 4-dinitrophenylhydrazone of acetaldehyde.

Try this….. (Textbook Page No 272)

Question 1.
Write chemical reactions taking place when propan-2-ol is treated with iodine
and sodium hydroxide.
Answer:

Question 2.
When acetaldehyde Is treated with dilute NaOH, the following reaction is
observed.
(1) What are the functional groups in the product?
(2) Can another product be formed during the same reaction? (Deduce the
answer by doing atomic audit of reactant and product)
(3) Is this an addition reaction or condensation reaction?
Answer:
(1) There arc two functiona’ groups in the product: -CRO and -OH
(2) No other product can be formed in the same reaction.
(3) This is an addition reaction.

Use your brain power! (Textbook Page No 273)

Question 1.
Observe the following reaction.
Answer:

Question 2.
Will this reaction give a mixture of products like a cross aldol reaction ?
Answer:

No, since benzaldehyde, does not have a-hydrogen atom, it

will not undergo self aldol condensation.

Use your brain power! (Textbook Page No 274)

Question 1.
Can isobutyraldehyde undergo a Cannizzaro reaction? Explain.
Answer:
Since isobutyraldehyde contains a-carbon atom, it cannot
undergo Cannizzaro reaction.

Can you tell? (Textbook Page No 279)

What is the term used for elimination of water molecule ?

Answer:
Dehydration.

Use your brain power! (Textbook Page No 278)

Question 1.
Fill in the blanks and rewrite the balanced equations.
Answer:
Amines
1. Choose the most correct option.

Question i.
The hybridization of nitrogen in primary amine is ………………………..
a. sp
b. sp2
c. sp3
d. sp3d
Answer:
c. sp3

Question ii.
Isobutylamine is an example of ………………………..
a. 2° amine
b. 3° amine
c. 1° amine
d. quaternary ammonium salt.
Answer:
a. 2° amine

Question iii.
Which one of the following compounds has the highest boiling point?
a. n-Butylamine
b. sec-Butylamine
c. isobutylamine
d. tert-Butylamine
Answer:
a. n-Butylamine

Question iv.
Which of the following has the highest basic strength?
a. Trimethylamine
b. Methylamine
c. Ammonia
d. Dimethylamine
Answer:
d. Dimethylamine

Question v.
Which type of amine does produce N2 when treated with HNO2?
a. Primary amine
b. Secondary amine
c. Tertiary amine
d. Both primary and secondary amines
Answer:
a. Primary amine

Question vi.
Carbylamine test is given by
a. Primary amine
b. Secondary amine
c. Tertiary amine
d. Both secondary and tertiary amines
Answer:
a. Primary amine

Question vii.
Which one of the following compounds does not react with acetyl chloride?
a. CH3-CH2-NH2
b. (CH3-CH2)2NH
c. (CH3-CH2)3N
d. C6H5-NH2
Answer:
Answer:
c. (CH3 – CH2)3N

Question viii.
Which of the following compounds will dissolve in aqueous NaOH after
undergoing reaction with Hinsberg reagent?
a. Ethylamine
b. Triethylamine
c. Trimethylamine
d. Diethylamine
Answer:
a. Ethyl amine

Question ix.
Identify ‘B’ in the following reactions

Answer:
d. CH3-CH2-OH

Question x.
Which one of the following compounds contains azo linkage?
a. Hydrazine
b. p-Hydroxyazobenzene
c. N-Nitrosodiethylamine
d. Ethylenediamine
Answer:
b. p-Hydroxyazobenzene

2. Answer in one sentence.

Question i.
Write reaction of p-toluenesulfonyl chloride with diethylamine.
Answer:
Question ii.
How many moles of methylbromide are required to convert ethanamine to N,
N-dimethyl ethanamine?
Answer:
2 moles of methylbromide are required to convert ethanamine to N, N-
dimethyl ethanamine.

Question iii.
Which amide does produce ethanamine by Hofmann bromamide degradation
reaction?
Answer:
Propanamide (CH3 – CH2 – CONH2) produces ethanamine by Hofmann
bromamide degradation reaction.

Question iv.
Write the order of basicity of aliphatic alkylamine in gaseous phase.
Answer:
The order of basicity of aliphatic alkyl amines in the gaseous follows the
order : tertiary amine > secondary amine > primary amine > NH 3.

Question v.
Why are primary aliphatic amines stronger bases than ammonia?
Answer:
The alkyl group tends to increase the electron density on the nitrogen atom.
As a result, amines can donate the lone f pair of electrons on nitrogen more
easily than ammonia. Hence, aliphatic amines are stronger bases than
ammonia.

Question vi.
Predict the product of the following reaction. Nitrobenzene Sn/Conc. HCl?
Answer:

The product is aniline/

Question vii.
Write the IUPAC name of benzylamine.
Answer:
The IUPAC name is Phenylmethanamine.

Question viii.
Arrange the following amines in an increasing order of boiling points. n-
propylamine, ethylmethyl amine, trimethylamine.
Answer:
Amines in an increasing order of boiling points : trimethyl amine, ethyl methyl
amine, n-propyl amine

Question ix.
Write the balanced chemical equations for the action of dil H 2SO4 on
diethylamine.
Answer:

Question x.
Arrange the following amines in the increasing order of their pKb values.
Aniline, Cyclohexylamine, 4-Nitroaniline
Answer:
Cyclohexyl amine (pKA 3.34), aniline (pKA 9.13) 4-nitroaniline (pKA 12.99)

3. Answer the following

Question i.
Identify A and B in the following reactions.

Answer:
Question ii.
Explain the basic nature of amines with suitable example.
Answer:
The basic strength of amines is expressed in terms of K b or pKb value. According
to Lowry-Bron-sted theory the basic nature of amines is explained by the
following equilibrium equation.

In this equilibrium amine accepts H+, hence an amine is a Lowry-Bronsted

base.

According to Lewis theory, the species which donates a pair of electrons is

called a base.

The nitrogen atom in amiqes has a lone pair of electrons, which can be
donated to suitable acceptor like proton H+.

The aqueous solutions of amines are basic in nature due to release of free
OH– ions in solutions. Hence amines are Lewis bases. There exists an
equilibrium in their aqueous solutions as follows :

R – NH2 + H2O ⇌ RNH3 + OH–

Since OH– is a stronger base, equilibrium shifts towards left-hand side giving
less concentration of OH–.

Here, Kb value is smaller and pKb value is larger.

Hence amines are weak bases.

Question iii.
What is diazotisation? Write diazotisation reaction of aniline.
Answer:
Aryl amines react with nitrous acid in cold condition (273 – 278 K) forms arene
diazonium salts. The conversion of primary aromatic amine into diazonium
salts is called diazotisation.
Diazotisation of aniline :

Question iv.
Write reaction to convert acetic acid into methylamine.
Answer:

Question v.
Write a short note on coupling reactions.
Answer:

Reactions involving retention of diazo group : (Coupling reactions) :

Question vi.
Explain Gabriel phthalimide synthesis.
Answer:
Phthalimide is reacted with alcoholic KOH to form potassium phthalimide.
Further potassium phthalimide is treated with an ethyl iodide. The product N-
ethylphthalimide is hydrolysed with aq NaOH to form ethyl amine. This
reaction is known Gabriel phthalimide synthesis.

Question vii.
Explain carbylamine reaction with suitable examples.
Answer:
Aliphatic or aromatic primary amines on heating with chloroform and
alcoholic potassium hydroxide solution form carbyl amines or isocyanides with
extremely unpleasant smell. This reaction is a test for primary amines.

Secondary and tertiary amines do not give this test.

Question viii.
Write reaction to convert
(i) methanamine into ethanamine
(ii) Aniline into p-bromoaniline.
Answer:
(1) Methanamine into ethanamine
(2) Aniline into p-bromo aniline

Question ix.
Complete the following reactions :
a. C6H5N2 Cl + C2H5OH →
b. C6H5NH2 + Br2(aq) → ?
Answer:
(a)

(b)

Question x.
Explain Ammonolysis of alkyl halides.
Answer:
When an alkyl halide is heated with alcoholic ammonia in a sealed tube under
pressure at 373 K, a mixture of primary, secondary, tertiary amines and a
quaternary ammonium salt is obtained. In this reaction, breaking of C – X
bond by ammonia is called ammonolysis of alkyl halides. The reaction is also
known as alkylation. For example, when methyl bromide is heated with
alcoholic ammonia at 373 K, it gives a mixture of methylamine (a primary
amine), dimethylamine (a secondary amine), trimethyl amine (a tertiary amine)
and tetramethylam- monium bromide (a quaternary ammonium salt).

The order of reactivity of alkyl halides with ammonia is R – I > R – Br > R – Cl.

Question xi.
Write reaction to convert ethylamine into methylamine.
Answer:

4. Answer the following.

Question i.
Write the IUPAC names of the following amines :
Answer:

Question ii.
What are amines? How are they classified?
Answer:
Amines are classified on the basis of the number of hydrogen atoms of
ammonia that are replaced by alkyl group. Amines are classified as primary
(1°), secondary (2°) and tertiary (3°).

(1) Primary amines (1° amines) : The amines in which only one hydrogen atom
of ammonia is replaced by an alkyl group or aryl group are called primary (1°)
amines.

Examples :
(i) CH3 – NH2 methylamine
(ii) CH3 – CH2 – NH2 ethylamine

(2) Secondary amines (2° amines) : The amines in which two hydrogen atoms
of ammonia are replaced by two, same or different alkyl or aryl groups are
called secondary (2°) amines.

Examples :
(i) C2H5 – NH – CH3 ethylmethylamine
(ii) CH3 – NH – CH3 dimethylamine

(3) Tertiary amines (3° amines) : The amines in which all the three hydrogen
atoms of ammonia are replaced by three same or different alkyl or aryl groups
are called tertiary (3°) amines.

Examples :

Secondary and tertiary amines are further classified as (1) Simple or

symmetrical amines (2) Mixed or unsymmetrical amines.

(i) Simple or symmetrical amines : In simple amines same alkyl groups are
attached to the nitrogen e.g.
(ii) Mixed or unsymmetrical amines : In mixed amines different alkyl groups are
attached to the nitrogen.

Question iii.
Write IUPAC names of the following amines.

Answer:

Question iv.
Write reactions to prepare ethanamine from
a. Acetonitrile
b. Nitroethane
c. Propionamide
Answer:
a. Ethanamine from acetonitrile :

b. Ethanamine from nitroethane :

c. Ethanamine from Propionamide :

Question v.
What is the action of acetic anhydride on ethylamine, diethylamine and
triethylamine?
Answer:
Acetylation of amines : The reaction in which the H atom attached to nitrogen

in amine is replaced by acetyl group is called acetylation of

amines.

(1) Ethylamine on reaction with acetic anhydride forms monoacetyl derivative,

N-acetylethylamine.

(2) Diethylamine (a secondary amine) on reaction with acetic anhydride forms

a monoacetyl derivative, N-acetyldiethyl amine (or N,N-diethyl acetamide).
(3) Triethylamine does not react with acetic anhydride as it does not have any
H atom attached nitrogen atom of amin e

Question vii.
Distinguish between ethylamine, diethylamine and triethylamine by using
Hinsberg’s reagent?
Answer:
This reaction is useful for the distinction of primary, secondary and tertiary
amines.

(i) Primary amine (like ethyl amine) is treated with Hinsberg’s reagent (benzene
sulphonyl chloride) forms N-alkyl benzene sulphonamide which dissolve in
aqueous KOH solution to form a clear solution of potassium salt and upon
acidification gives insoluble N-alkyl benzene sulphonamide.

(ii) Secondary amine like diethyl amine is treated with benzene sulphonyl
chloride forms N,N-diethyl benzene which sulphonyl amide remains insoluble
in aqueous KOH and does not dissolve in acid.

(iii) Tertiary amine like triethyl amine does not react with benzene sulphonyl
chloride and remains insoluble in KOH, however it dissolves in dil. HCl to give
a clear solution due to formation of ammonium salt.

Question viii.
Write reactions to bring about the following conversions :
a. Aniline into p-nitroaniline
b. Aniline into sulphanilic acid?
Answer:
(1) Aniline into p-nitroaniline

(2) Aniline into sulphanilic acid.

Activity :

 Prepare a chart of azodyes, colours and its application.

 Prepare a list of names and structures of N-containing ingredients of
diet.
12th Chemistry Digest Chapter 13 Amines Intext Questions and Answers

Use your brain power! (Textbook Page No 282)

Question 1.
Classify the following amines as simple/mixed; 1°, 2°, 3° and aliphatic or
aromatic. (C2H5)2NH, (CH3)3N, C2H5 – NH – CH3,

Answer:
(A) Common Names : Rules

1. According to common naming system, the amines are named as

alkylamines.
2. The common name of a primary amine is obtained by writing the name
of the alkyl group followed by the word ‘amine’.
Example : CH3 – NH2 : methyl-amine
3. The simple {symmetrical) secondary and tertiary amines are written by
adding prefix ‘di- (forpresence of two alkyl groups) and ‘tri’- (for
presence of three alkyl groups) respectively to the name of alkyl groups.
Examples: (i) CH3 – NH – CH3 dimethylamine, (ii) (C2H5)3 N triethylamine
4. The mixed (or unsymmetrical) secondary and tertiary amines are given
names by writing the names of alkyl groups in alphabetical order,
followed by the word ‘amine’.
Example : CH3 – CH2 – NH – CH3 ethyhnethylamine

(B) IUPAC names : Rules

1. According to IUPAC system of nomenclature of amines, aliphatic amines

are named as alkanarnines.
2. The name of the amine is obtained by replacing the suffix ‘e’ from
parent alkane’s name by ‘amine’.
3. The position of the amino group is indicated by the lowest possible
locant.
Example :

4. In case of secondary and tertiary amines, the largest alkyl group is

considered to be the parent alkane and other alkyl groups are written as
N-substituents.
Example : ClH5NH – CH3 N – Methylethanamine
5. A complete name of amine is written as one word.

Try this….. (Textbook Page No 283)

Question 1.
Draw possible structures of all the isomers of C4H11N. Write their common as
well as IUPAC names.
Answer:

Use your brain power! (Textbook Page No 283)

Question 1.
Write chemical equations for
(i) reaction of alc. NH with C2H5I.
Answer:

(ii) Amonolysis of benzyl chloride followed by the reaction with 2 moles of

CH3I.
Answer:

(2) Ammonolysis of alkyl halides is not suitable method to prepare primary

amines.
Answer:
In the laboratory, ammonolysis of alkyl halides is not a suitable method to
prepare primary amines as it gives a mixture of primary, secondary, tertiary
amines and quaternary ammonium salts. (Refer to the reaction in answer to
Question 16). The separation of primary amine becomes difficult.
Problem 13.1 : (Textbook Page No 285)

Question 1.
Write reaction to convert methyl bromide into ethyl amine? Also, comment on
the number of carbon atoms in the starting compound and the product.
Solution :
Methyl bromide can be converted into ethyl amine in two stage reaction
sequence as shown below.

The starting compound methyl bromide contains one carbon atom while the
product ethylamine contains two carbon atoms. A reaction in which number of
carbons increases involves a step up reaction. The overall conversion of methyl
bromide into ethyl amine is a step up conversion.

Use your brain power! (Textbook Page No 285)

Identify ‘A’ and ‘B’ in the following conversions.

Answer:

Use your brain power! (Textbook Page No 286)

Question 1.
Write the chemical equations for the following conversions :
(1) Methyl chloride to ethylamine.
(2) Benzamide to aniline.
(3) 1, 4-Dichlorobutane to hexane-1, 6-diamine.
(4) Benzamide to benzylamine.
Answer:
(1) Methyl chloride to ethylamine

(2) Benzamide to aniline

(3) 1, 4-Dichlorobutane to hexane-1, 6-diamine

(4) Benzamide to benzylamine

Use your brain power! (Textbook Page No 287)

Question 1.
Arrange the following :
(1) In decreasing order of the boiling point C 2H5 – OH, C2H5 – NH2, (CH3)2 NH
(2) In increasing order of solubility in water: C 2H5 – NH2, C3H7 – NH2, C6H5 – NH2
Answer:
(1) Decreasing order of the boiling point : C 2H5 — OH, C2H5 — NH2, (CH3)2 NH
(2) Increasing order of solubility in water : C 6H5NH2, C3H7 — NH2, C2H5 — NH2

Use your brain power! (Textbook Page No 288)

Question 1.
Refer to pKb values and answer which compound from the following pairs is
the stronger base?
(1) CH3 – NH2 and (CH3)2 NH
(2) (C2H5)2 NH and (C2H5)3 N
(3) NH3 and (CH3)2 CH – NH2
Answer:
(1) CH3 -NH2 and (CH3)2 NH
(CH3)2 NH is a stronger base

(2) (C2H5)2 NH and (C2H5)3 N

(C2H5)2 NH is a stronger base

(3) NH3 and (CH3)2 CHNH2

(CH3)2 CHNH2 is a stronger base

Use your brain power! (Textbook Page No 290)

Question 1.
Arrange the following amines in decreasing order of their basic strength :
NH3, CH3 – NH2, (CH3)2 NH, C6H5NH2
Answer:
Decreasing order of basic strength :
(CH3)2NH, CH3 -NH2, NH3, C6H5NH2

Use your brain power! (Textbook Page No 291)

Question 1.

Answer:
Use your brain power! (Textbook Page No 291)

Question 1.
Complete the following reaction :

Answer:

Use your brain power! (Textbook Page No 292)

Answer:

Use your brain power! (Textbook Page No 292)

Question 1.
Write the carbylamine reaction by using aniline as starting material.
Answer:

Can you tell? (Textbook Page No 292)

(1) What is the formula of nitrous acid ?

(2) Can nitrous acid be stored in bottle ?
Answer:
(1) Formula of nitrous acid : H – O – N = O
(2) Nitrous acid cannot be stored in bottle.

Use your brain power! (Textbook Page No 294)

Question 1.
How will you distinguish between methyl amine, dimethylamine and
trimethylamine by Hinsberg’s test?
Answer:
(1) Methyl amine (primary amine) reacts with benzene sulphonyl chloride to
form N-methylbenzene sulphona- mide
(2) Dimethyl amine reacts with benzene sulphonyl chloride to give N, N –
dimethylbenzene sulphonamide.

(3) Trimethyl amine does not react with benzene sulphonyl chloride and
remains insoluble in KOH

Problem 13.1 : (Textbook Page No 295)

Question 1.
Write the scheme for preparation of p-bromoaniline from aniline. Justify your
answer.
Solution :
NH2 – group in aniline is highly ring activating and o – /p – directing due to
involvement of the lone pair of electrons on ‘N’ in resonance with the ring. As
a result, on reaction with Br2 it gives 2,4,6-tribromoaniline. To get a
monobromo product, it is necessary to decrease the ring activating effect of –
NH2 group. This is done by acetylation of aniline. The lone pair of ‘N’ in
acetanilide is also involved in resonance in the acetyl group. To that extent,
ring activation decreases.
Hence, acetanilide on bromination gives a monobromo product p-
bromoacetanilide. After monobromination the original – NH 2 group is
regenerated. The protection of – NH2 group in the form of acetyl group is
removed by acid catalyzed hydrolysis to get p-bromoaniline, as shown in the
following scheme.

Use your brain power! (Textbook Page No 296)

Question 1.
(1) Can aniline react with a Lewis acid?
(2) Why aniline does not undergo Frledel – Craft’s reaction using aluminium
chloride?
Answer:
(1) Aniline reacts with a Lewis acid, forms salt.
(2) Aniline does not undergo Friedcl-Crafr’s reaction (alkylation and
acetylation) due to salt formation with aluminium chloride (Lewis acid), which
is used as catalyst. Due to this, nitrogen of anime acquires + ve charge and
hence acts as strong deactivating effect on the ring and makes it difficult for
the electrophilic attack.
Can you tell? (Textbook Page No 294)

(1) Do tertiary amines have ‘H’ bonded to ‘N?

(2) Why do tertiary amines not react with benzene sulfonyl chloride?
Answer:

(1) Tertiary amines do not have ‘H’ bonded to ‘N’.

(2) Tertiary amine does not undergo reaction with benzene sulphonyl chloride
as it does not have any H atom attached to the nitrogen atom of amine.