CHAPTER 1

SOLID STATE
1 mk Q
Q 1. Crystalline Solids are anisotropic in nature. What does this Statement
mean?
A 1. The statement means that some of the physical properties like electrical
resistance or refractive index of Crystalline Solids show different values when measured
along different directions in the same crystal.
Q 2.

Why does the presence of excess of lithium make LiCl crystals pink?

A 2. The presence of excess of lithium makes LiCl crystals pink due to e -s trapped in
anionic vacancies (F centers). These electrons absorb some energy of the white light
giving pink colour to LiCl crystal.6
Q3. What is meant by anti-ferromagnetism? What type of substances exhibit
anti ferromagnetism?
A3.
Substance like MnO, MnO2 in which magnetic domains are oppositely oriented
and cancel out each others magnetic moment exhibit anti ferromagnetism. Magnetic.
Alignment of magnetic moments in antiferromagnetic substance:OR
Q3
What type of substance would make better magnets, ferromagnetic or
ferromagnetic?
A3.
Ferromagnetic substance would make better magnets because when
ferromagnetic substance is placed in magnetic field all the domains get oriented in the
direction of the magnetic field and a strong magnetic effect is produced eg : Co, Ni
Q4. In a compound nitrogen atoms (N) make ccp and metal atoms (M) occupy
one third of the tetrahedral voids present. Determine the formula of the
compound formed by M & N?
A4.

Let the no of nitrogen atoms (N) be x

No of tetrahedral voids = 2x
No of metal atoms = 2/3 x.

Ratio of M:N = 2/3x : x

Therefore the formula of the compound is M2 N3
Q 5. Classify each of the following as being either a p type or n type semi
conductor?
(i)
(ii)
A 5.

Ge doped with In.

B doped with Si.

(i)
P type semiconductor because when group 14 element is doped with
group 13 element, an electron deficit hole is created.
(ii)
n type semiconductor because when group 13 element is doped wih group
14 element , free electrons will become available.

Q 6.

Write a distinguishing feature between a metallic solid and an ionic solid?

A 6.
Ionic Solids

Metallic Solids

In solid state ionic solids are Metallic Solids are good electrical
electrical insulator :- ions are not conductors in solid state because of the
free to move. Eg NaCl, CuSO4 etc
presence of free electrons , Eg :- Copper,
Iron etc
2 mk
Q 1. Analysis shows that nickel oxide has the formula Ni
fractions of nickel exist as Ni2+ and Ni3+ ions?
A1.

The formula of the oxide is Ni 0.98 0 1.00

Let the number of O2- ions be 100.
Then number of nickel ions = 98
Let the number of Ni2+ be x
Then number of Ni3+ = 98 - x
Since total charge on cations = total charge on anions.
X x (2) + (98-x) x (3) = 100 x 2
2x + 294 3x = 200
x = 94
% of Ni2+ =

94
98

x 100 = 96%

0.98

1.00

. What

% of Ni3+ = 100 -96 = 4%

Q 2. A compound forms hcp structure. What is the total number of voids in 0.5
mol of it? How many of these are tetrahedral voids?
A2.

No of atoms = 0.5 mol = 0.5 x 6.022 x 1023

= 3.011 x 1023
No of octahedral voids = no of atoms in hcp structure
= 3.011 x 1023
No of tetrahedral voids = 2 x no of atoms in hcp structure
= 2 x 3.011 x 1023
= 6.022 x 1023
Total no of voids

Q3.

= 6.022 x 10 23 + 3.011 x 10 23
= 9.033 x 10 23

Examine the given defective crystal:-

A+
BA+
BBA+
BA+
BA+
BAnswer the following questions

BA+

A+
BA+
B-

A+

(i)

What type of stoichiometric defect is shown by the crystal? (1/2)

(ii)

How is the density of crystal affected by this defect?

(iii)

What type of ionic substance show such defect?

(1/2)
(1)

A 3. (i)
Schotty defect is shown by the crystals, since equal number of cations and
anions are missing from the crystal lattice.
(ii)

Due to this defect, the density of the crystal decreases.

(iii)

This defect is shown by those ionic substance in which cations and anions
are of almost similar size eg :- NaCl, KCl etc.

Q 4. If NaCl crystals are doped with 2 x 10

cation vacancies per mole?

-3

mol percent of SrCl2 , calculate the

A 4. Doping of NaCl with 2 x 10 -3 mol percent of SrCl 2 means 100 moles of NaCl is
doped with 2 x 10 -3 mole of SrCl2 or 1 mole of NaCl is doped with 2 x 10-5 mole of SrCl2

Each Sr2+ will occupy the place of Na+ and displace one Na+ from crystal lattice to
create cation vacancies.
Cation vacancies = Number of Sr 2+ ion added.
= 2 x 10 -5 mol = 2 x 10 -5 x 6.022 x 10 23. = 12.046 x 10 18 mol -1

Q 5. Calculate the packing efficiency of a metal crystal for a simple cubic

lattice?
A 5.

Packing efficiency in simple cubic lattice

rr
r

a
Volume of one atom x 100
Volume of cubic unit cell (a3)
Since a= 2r for simple cubic
Vol of one atom =4/3 r3
=

4/3 r3 x 100
(2 r) 3

4 x 3.14 x r3 x 100
3 x 8 x r3

52.36%

52.4%

Q 6 (a) In reference to a crystal structure, explain the meaning of coordination

number?
(b) What is the number of atoms in a unit cell of
(i)

Face centered cubic structure?

(ii)

Body centered cubic structure?

A6
(a)
The number of nearest neighbours of any constituted particle in the crystal
lattice is called its coordination number.
(b)

Number of atoms in a unit cell of

(i)

Face centered cubic cell structure is 4.

(ii)

Body centered cubic structure is 2.

3 mk
Q1.

In terms of band theory. What is the difference?

(a)

between a conductor and an insulator.

(b)

between a conductor and a semi conductor.

Empty conduction band

Filled (valence band)

_____

Partially
filled band

Over lappling band

Conductors

A1

(a)
In conductors, energy band is partially filled or it overlaps with a higher
energy unoccupied conduction band. Due to this electrons can flow easily under
an applied electric field and show conductivity
In insulators, the gap between filled valence band and the next higher
unoccupied band is large, hence electrons cannot jump to it and substance has
very small conductivity and behaves as an insulator.
Empty band
(conduction band)

Filled band
(Valence band)

(b)
In semiconductors the gap between valence band and conduction band is
small. Therefore some electrons may jump from valence band to conduction
band and show some conductivity eg Si and Ge

Q2 )

A 2)

Aluminum crystallizes in a cubic close packed structure. Its metallic radius

is 125 pm.
(a)

What is the length of the side of the unit cell?

(b)

How many unit cells are there in 1 cm3 of aluminum?

(a)

In a cubic close packed structure :4r=

2a

Given r = 125 x 10 -12 m

a=

4r
2

or 2

2 r

a = 125 x 10 -12 x 2 x 1.414 m = 354 pm.

(c)

a3 = (354)3 x (10-12) 3
= 44.21 x 10-30 m 3
No of unit cells in 1 cm3

= Total Volume
=
Vol of one unit cell

10-6
44.21 x 10-30

= 2.261x 10 22 unit cells.

Q3

How will you distinguish between the following pairs of terms :(a)

Hexagonal close packing and Cubic close packing?

(b)

Crystal lattice and unit cell?

(c)

Tetrahedral void and Octahedral void?

Hexagonal close packing

AB ABtype packing is called
hexagonal close packing. i.e spheres of
the third layer are exactly aligned with
those of the first layer . eg : Mg and
Zn

Q4

Cubic close packing

ABC ABCtype packing is called cubic
close packing. i.e spheres of the third layer
are not aligned with those of 1 st or 2nd.
When 4th layer is placed its spheres are
aligned with those of 1st layer. eg :- Cu and
Ag
Tetrahedral void
Octahedral void
A tetrahedral
void lattice
is surrounded An octahedral void
surrounded by
Crystal
Unit is
cell
The
three whichdimensional
crystal by
lattice
by 4 spheres
lie at the The
six smallest
spheres portion
and of
formed
a
arrangement
of tetrahedron.
constituent which
whenof 2repeated
different
vertices of a regular
combination
triangular in
voids
of the
st
nd
particles in the space which directions,
generates the entire lattice.
1 and 2 layer
There are 2 how
tetrahedral
voids per There is one octahedral void per atom
represents
the constituent
atom in a crystal
particles
(atoms,
ions
or in a crystal
molecules) are arranged in a
Account
crystalfor the following :(i)

Table salt, NaCl sometimes appears yellow in colour.

(ii)

FeO(s) is not formed in stoichiometric composition.

(iii)

Some of the very old glass objects appear slightly milky instead of being
transparent.

A4.

(i)
Yellow colour in NaCl is due to metal excess defect due to which unpaired
electrons occupy anionic vacancies. These sites are called F centers. These
electrons absorb energy from the visible region and transmits yellow colour.

(ii)
In the crystal of FeO, some of the Fe2+ cations are replaced by Fe3+ ions.
Three Fe2+ ions are replaced by two Fe 3+ ions to make up for the loss of positive
charge. Thus there would be less amount of metal as compared to stoichiometric
properties.
(iii)
Very old glass objects become slightly milky, because of heating during
the day & cooling at nights i.e annealing. Over a number of years, glass acquires
some crystalline character.
Q5.

The density of copper is 8.95 gcm -3. It has a face centered cubic structure.
What is the radius of copper atom? (Atomic mass Cu = 63.5 g mol -1 . NA =
6.022 x 1023 mol -1) ?

A5.

Mass per unit cell

Atomic mass of Cu x 4
NA

______63.5__x 4______
6.022 x 1023

4.22 x 10 -22 g

Volume of unit cell =

__Mass__
Density

4.22 x 10 -22
8.95

4.7 x 10-23 cm3

(Volume )1/3

(4.7 x10 -23)1/3

3.61 x 10-8 cm or 361pm

For fcc, r

___a___
2 2

Edge

361
2 x 1.41
128 pm

CHAPTER 2
SOLUTIONS
1 mk
Q 1.

Define an ideal solution and write one of its characteristics?

A1

The solutions which obey Raoults law over the entire range of concentration are
known as ideal solutions. i.e P = PoA x and P = PoB x
A

For ideal solutions

H mix = 0 and

B.

V mix = 0.

eg ;- Solution of n hexane and n- heptane

Q 2.

What is meant by reverse osmosis ?

A2
The process in which the solvent flows from the solution into the pure solvent
through the semi permeable membrane when a pressure higher than the osmotic
pressure is applied on the solution is called reverse osmosis.
Application :- The technique is used in the desalination of sea water.
Q3.

Define mole fraction.

A3
The mole fraction of a component is the ratio of the number of moles of that
component to the total number of moles of all the components present in the solution.
For a binary solution consisting of 2 components A and B if n A is the number of
moles of A and nB is the number of moles of B then.
x

= __nA___
nA + nB

Q 4.

= _ nB___

nA + nB

Define the term azeotrope?

A4
The constant boiling mixture which distill out unchanged in their composition are
called azeotropes.
Eg :- A mixture of ethanol and water containing 95.4% of ethanol forms an
azeotrope with boiling point 351.15 K.

Q5. Explain boiling point elevation constant for a solvent / Define ebullioscopic
constant?
A5

Since

Tb = Kb.m where m is molality

When m = 1
Kb =

Tb

Therefore Ebullioscopic constant is defined as the elevation in boiling point of a

solution when 1 mole of a solute is dissolved in 1 Kg of solvent .
Q6

What are isotonic solutions ?

A6
The solutions of equimolar concentrations having same osmotic pressure at
given temperature are called isotonic solutions.
eg :- A 0.9% solution of pure NaCl is isotonic with human red blood cells.

Q7
Explain why aquatic species are more comfortable in cold water rather than
in warm water?
A7
Aquatic species need dissolved oxygen for breathing. As solubility of gases
decrease with increase of temperature, less oxygen is available in summers in lakes.
Hence they feel more comfortable in winter when the solubility is higher.
OR
Q7
Why do gases nearly always tend to be less soluble in liquid as the
temperature is raised?
A7
Dissolution of gas in liquid is an exothermic process. Gas + Solvent
Solution + heat.
Therefore as per Lechatliers principle if the temperature is increased, equilibrium
shifts backward i.e the solubility decreases.
2 mk
Q1
How is the vapour pressure of a solvent affected when a non volatile solute
is dissolved in it?

A1
When a non volatile solute is added to a solvent, its vapour pressure decreases
because some of the surface sites are occupied by solute molecules. Thus less space
is available for the solvent molecules to vaporize.
Q2. The depression in freezing point of water observed for the same molar
concentrations of acetic acid, trichloro acetic acid and trifluoroacetic acid
increases in the order as stated above. Explain?
A2
As depression in f.pt (
Tf) is dependent on degree of dissociation () and
fluorine exerts the highest I effect. So trifluoro acetic acid is the strongest acid and
ionizes to a greater extent while acetic acid ionises to the minimum extent. Thus greater
the number of ions produced, greater is the depression in freezing point.

Q3. Differentiate between molarity and molality for a solution. How does a
change in temperature influence their values?
Or
Q3. State the main advantage of molality over molarity as the unit of
concentration?

Molarity
It is defined as the number of moles of
solute dissolved in one litre of the solution
Mathematically
Molarity (M) =No of moles of solute x 1000
Vol of Solution (ml)

Molality
It is defined as the number of moles of
solute dissolved in 1 Kg of the solvent
Mathematically
Molality (M) =No of moles of solute x 1000
Mass of Solvent (g)

It decreases with increase in temperature It does not change with change in

(as V T)
temperature
Since molality does not change with a change in temperature therefore it is a
better method to express the concentration of a solution.
Q4. What is meant by colligative property. List any four factors on which
colligative properties of a solution depend?

A4.
The properties of solutions which depend upon the number of solute particles
and not upon the nature of the solute are known as colligative properties eg :- Osmotic
pressure.
Factors :(i)
(ii)
(iii)
(iv)

Number of particles of solute.

Concentration of solution.
Temperature.
Association or dissociation of solute.

An aqueous solution of sodium chloride freezes below 273K. Explain the

lowering in freezing point of water with the help of a suitable diagram?
Q5.

A5.
Freezing point of a substance is the temperature
at which solid and liquid phases of a substance coexist
i.e they have the same vapour pressure. As the vapour
pressure of the solution is less than that of pure solvent
For solution its vapour pressure will become equal to Vapour
that of a solid solvent only at a lower temperature.

liquid solvent

solution
pressuresolid solvent

Tf

Tfo

Temperature

3 mk
Q1. A sample of drinking water was found to be severely contaminated with
chloroform CHCl3 , supposed to be carcinogen. The level of contamination was
15ppm (by mass)?

A1.

(i)

Express this in percent by mass.

(ii)

Determine the molality of CHCl3 in water sample.

15 ppm means 15 parts in 106 parts by mass in the solution.

i.e

106 parts by mass of solution = 15 parts of solute.

or 100 parts (Mass %) =

Mass of solvent

15 x 100
106

15 x 10 -4

(106 -15) g


Therefore Molality

106 g
nB
wA

where nB = no of moles of solute

wA = Mass of the solvent

Molality

15/119.5 X 1000
106

= 1.25 x 10-4m
Q2
State Raoults law for a solution containing volatile components. How does
Raoults law becomes as special case of Henrys law?
A2
For a solution of volatile liquids, the partial vapour pressure of each component in
the solution is directly proportional to its mole fraction?
i.e

PA

and

PB

or

PA = P0A

or

PB

P0B

A
B

Where PA and PB are the partial pressure of A and B, P 0A , P0B are the vapour
pressure of pure component and x and x are their mole fractions.
A

If gas is the solute and liquid is the solvent then according to Henrys law
PA = K H x

Thus Raoults laws and Henrys law become identical except that their
proportionality constants are different.
Q3
Some ethylene glycol is added to your cars cooling system along with 5kg
of water. If the freezing point of water-glycol solution is -15 0c, what is the boiling
point of the solution?
Kb = 0.52 K Kgmol-1 and Kf = 1.86 K Kg mol-1
A3

Tf = 15oc Kf = 1.86 k/m

Molality =

Tf
Kf

15/1.86 = 8.06 m

Tb

=
=
=

Kb x m
0.52 x 8.06
4.190c

Boiling point of pure water = 100oc

Therefore Tb =
Tb +
Tbo
Tb = 100 + 4.19
= 104.19oC
Q4
Assuming complete dissociation. Calculate the expected freezing point of a
solution prepared by dissolving 6 g of Glaubers salt, Na 2SO4.10 H2O in 0.1 Kg
mol-1 of water. Kf of water = 1.86 K Kg mol -1.
A4

Kf
WB
MB

=
=
=

1.86 K Kgmol-1
6g
WA = 0.1 Kg mol-1
322 g mol-1

Since there is a complete dissociation

Therefore i = 3
Tf =

i K f WB
MB x W A

3 x 1.86 x 6
322 x 0.1

1.04o

Q5. Calculate the mass of a nonvolatile solute (molar mass 40g mol -1) which
should be dissolved in 114 g octane to reduce its vapour its pressure to 80%?
A5.

Ps= 80% of Po = 0.80 Po

No of moles of solute

W
40

No of moles of solvent
(octane)

114
114

Po Ps
Po

XB

Po 0.8 Po
Po

W /40
W /40 + 1

W
40

therefore

or

0.2

W +1
40

0.8 W
40
or

0.2

W = 10g

Q6
19.5g of CH2FCOOH is dissolved in 500g of water. The depression in
freezing point observed is 1oc. Calculate the Vant Hoff factor and dissociation
constant of fluoroacetic acid .Kf for water is1.86 K Kg mol-1.
A6

Kf= 1.86K Kgmol-1

WB = 19.5g WA = 500g
(ATf) obs = 1o.
MB (obs) =

1000 Kf WB
W T
A

= 72.54 g mol-1

1000 X1.86 X 19.5

500 X 1

MB (cal) = 14 + 19 + 45 = 78 g mol-1
L = M(cal)
MB (Obs)

= _78__
72.54

1.0753

Calculation of dissociation const (K)

Ka = _C2
1-
CH2FCOO -+ H+

CH2 FCOOH
Initial C MOL L-1
C(1-)
i = C (1+)
C

O
C
=
=

O
C

1 + or = i - 1
1.0753 1 = 0.0753

Taking volume of solution as 500 ml

C =19.5 x _1_ x 1000
78 500
Ka = C2
1-

= 0.5 M

= 0.5 x (0.0753)2
1-0.0753

Ka = 3.07 x 10-3
Q7. Non ideal solutions exhibit either positive or negative deviations from
Raoults law. What are these deviations and why are they caused? Explain with
one example for each type?
A7
For non ideal solutions, vapour pressure is either higher or lower than that
predicted by Raoults law. If it is higher the solution exhibits positive deviation and if it is
lower it exhibits negative deviation from Raoults law.
Positive Deviation
When solute solvent interactions are
weaker than solute solute or solvent
solvent interactions, vapour pressure
increases which result in positive
deviation.
Eg :- Ethanol +Acetone.
for a solution showing +ve deviation
PA > PoA XA and PB > PoB XB
H mix = +ve
Vmix = +ve

Negative Deviation
When solute solvent interactions are
stronger than solute solute or solvent
solvent interactions, vapour pressure
decreases which result in negative
deviation.
eg :- Chloroform + Acetone.
for a solution showing ve deviation
PA < PoA XA PB < P0B XB
H mix = - ve
Vmix = - ve

For plots of non ideal solution showing +ve and ve deviation refer NCERT pg 56

5 mk
Q1. (i)
What is Vant Hoff factor? What types of values can it have if in
forming the solution the solute molecules undergo

(ii)

(a)

Dissociation?

(b)

Association?

How many ml of 0.1M HCl solution are required to react completely with
1g of a mixture of Na 2CO3 containing equimolar amounts of both ? (Molar
Mass Na2CO3 = 106g and NaHC03 = 84g)

A1.
(i)
Vant Hoff factor (i) is defined as the ratio of the experimental value of
colligative property to the calculated value of colligative property .
i
Also, i =

Observed Colligative property

Calculated Colligative property

Total number of moles of particles after dissociation/ association

Number of moles of particles before association/ dissociation

Therefore , For (a) dissociation i > 1

And (b) Association i < 1
(ii)

Let x g of Na2CO3 be present in the mixture

So amt of Na HCO3 = 1 x
Moles of Na2CO3 in x g =

x_
106

Moles of NaHCO3 in (1-x) = _1-x_

84
As mixture contains equimolar amounts of the two.
x_ = 1-x_
106
84
106 106 x = 84x
X = _106__ = 0.558g
190
Moles of Na2 CO3 = __0.558__

= 0.00526

106
Moles of NaHCO3 = 1- 0.558 = 0.442
84
84

= 0.00526

To calculate the moles of HCl required.

Na2CO3 + 2 HCl
NaHCO3 + HCl

2 NaCl + H2O + CO2

NaCl + H2O + CO2

1 mole of Na2CO3 requires 2 moles of HCl

Therefore 0.00526 mole of
0.0152 moles of HCl.

Na 2 CO3

requires 2 x 0.00526 moles or

1 mole of NaHCO3 requires 1 mole of HCl

Therefore 0.00526 mole of NaHCO3 requires 0.00526 moles of HCl.
Total moles of HCl required = 0.01052 + 0.00526 = 0.01578 moles
To calculate volume of 0.1M HCl
1.1 mole of 0.1M HCl are present m 1000ml HCl
Therefore 0.01578 mole of 0.1M HCl will be present in
1000 x 0.01578
0.1
= 157.8 ml
Q2. (i)
The molecular masses of polymers are determined by osmotic
pressure method and not by measuring other colligative properties. Give two
reasons?
(ii)
At 300k, 36g of glucose C6H12O6 present per litre in its solution has a
pressure pf 4.98 bar. If the osmotic pressure of another glucose solution is
1.52 bar at the same temperature, calculate the concentration of the other
solution?
A2.
(i)
because :-

The osmotic pressure method has the advantage over other methods
(a)
It uses molarities instead of molalities and it can be measured at
room temperature.
(b)
Its magnitude is large as compared to other colligative properties.

(ii)

1 = C1 RT, 2 = C2 RT
Therefore _1 = C1
2 C 2

Q3

(i)

or

4.98
1.52

= 36/180
C2

or

C2

= 0.061 moll-1
= 0.061 x 180 gl-1
= 10.98 gl-1

Define the terms osmosis and osmotic pressure?

(ii)
An aqueous solution containing 12.48g of barium chloride in 1.0 kg
of water boils at 373.0832 k. Calculate the degree of dissociation of barium
chloride?
(Given Kb for H2O = 0.52 Km-1 molar mass of Ba Cl2 = 208.34 gmol-1)
A3.
(i)
The net spontaneous flow of the solvent molecules from the solvent to the
solution or from a less concentrated solution to a more concentrated solution through a
semipermeable membrane is called osmosis.
Osmotic pressure :- The minimum excess pressure that has to be applied on
the solution to prevent the entry of the solvent into the solution through the
semipermeable membrane is called osmotic pressure.
(iii)
(iv)

Given W2 = 12.48g , W1 = 1 Kg = 1000g

Tb (solution) = 373.0832 K
Kb for H2O = 0.52 Km-1 and M2 = (Ba Cl2) = 208.34
Tb = Tb - Tbo = 373.0832 373 = 0.0832 K
M2 (Observed) = Kb x W2 x 1000
Tb x W1
= 0.52 x 12.48 x 1000
0.0832 x 1000
= 78 g mol-1
i

= M2 (calculated) =

208.34 = 2.67

M2 (observed)
For BaCl2

78

= 3 as it gives 3 ions on dissociation

i-1
m-1

= 2.67 -1 = 1.67 = 0.835

3-1
2

= 83.5%
Q4. (a)
What type of deviation is shown by a mixture of ethanol and
acetone? Give reason.
(b)

What do you expect to happen when RBCs are placed in

(i)

1% NaCl solution (ii) 0.5 % NaCl solution

(c)
Calculate the molarity of 68% (w/w) solution of nitric acid , if the
density of the solution is 1.504 g ml-1

A4.
(a)
Ethanol and acetone shows positive deviation because on mixing the two
the forces of attraction decreases and the vapour pressure increases.
(b)

(c)

Since RBCs are isotonic with 0.9% NaCl solution therefore

(i)

In 1% solution of NaCl they will shrink due to plasmolysis

(ii)

In 0.5% solution of NaCl they will swell or may even burst.

Molarity

% x density x 10
Molar mass

Mass %
=
68 , d = 1.504 Molar mass of HNO3 = 63 gmol-1
Therefore Molarity = 68 x 1.504 x 10
63
= 16.23 M
Q5.

(a)

State Henrys law and mention two of its important applications

(b)
The partial pressure of ethane over a saturated solution containing
6.56 x 10-2g of ethane is 1bar. If the solution were to contain 5 x 10 -2 g of
ethane, then what will be the partial pressure of the gas.

A5.

(a)

Henrys law states that at a constant temperature , the solubility

x of a

gas in a liquid is directly proportional to the pressure of the gas

P = KH

Applications :-

To increase thje solubility of CO 2 in soda water, the bottle is sealed under high
pressure

There is a low concentration of oxygen in the blood and tissues of the people
living at high altitudes due to which they feel weak and are unable to think
clearly (anoxia).

(b) M = KH x P
For the 1st case 6.56 x 10-2 = KH x 1 bar or KH = 6.56 x 10-2 g bar -1
In the 2nd case 5 x 10 -2 = (6.56 x 10-2) x P
or P = 5 x 10 -2
6.56 x 10 -2
P = 0.762 bar

CHAPTER 5

SURFACE CHEMISTRY
01 MARK
Q1).

What is meant by shape selective catalysis?

A1) The catalytic reaction that depends upon the pore structure of the catalyst and
the size of the reactant and product molecules is called shape selective catalysis.
eg:-

zeolites (eg ZSM 5) converts alcohol directly into gasoline.

Q2)

What are the dispersed phase and dispersion medium in milk?

A2)

Dispersed phase : Fat

Dispersion medium : water

Q3)

What is Collodion?

A3)

Collodion is 4% solution of nitro cellulose in a mixture of alcohol and ether.

Q4)

Define Kraft temperature?

A4) The formation of micelles from the ionic surfactant can take place only above a
certain temperature which is called Kraft temperature.
Q5)

Why is adsorption always exothermic ?

Or
What is the sign of

A5)

H&

S when a gas is adsorbed by adsorbent ?

When a gas is adsorbed in the surface of solid, its entropy decreased i.e.
S =-ve. From Gibbs Helmholtz equation : G = H T
S for the process
to be spontaneous ,
G must be negative, which is possible only
when
H = -ve . Hence adsorption is always exothermic.

Q6) Why is it essential to wash the precipitate with water before estimating it
quantitatively?
A6) Some amount of the electrolytes mixed to form the precipitate remains adsorbed
on the surface of the particles of the precipitate. Hence it is essential to wash it with
water before it quantitatively.
Q7)

What happens when persistent dialysis of colloidal solution is carried out?

A7) The stability of a colloidal sol is due to the presence of a small amount of the
electrolyte. On persistent dialysis, the electrolyte is completely removed, so the colloidal
sol becomes unstable and gets coagulated.

Q8)

What causes Brownian movement in a colloidal solution?

A8) Brownian movement ie zigzag movement of the colloidal particles is due to hitting
of these particles by the molecules of the dispersion medium with different forces from
different directions.
Q 9)

Why it is important to have clean surface in surface studies?

A 9)

It facilitates the adsorption of species on the adsorbent.

Q 10) What happens when gelatin is mixed with gold sol?

A 10) Gold sol is a lyophobic sol. On addition of gelatin, the sol is stabilized..
Q 11) Gelatin which is a peptide is added in ice creams. What can be it s role?
A 11) Ice creams are emulsion which get stabilized by emulsifying agents like gelatin.
Q 12) What is the role of activated charcoal in gas mask used in coal mine?
A 12) Activated charcoal adsorbs poisonous gases present in coal mine.
Q 13) In what way is a sol different from a gel?
A 13) Sols are colloidal solutions of solid dispersed in liquid while gels are colloidal
solutions of liquid dispersed in solid.
Q 14) Of NH3 and N2, which gas will be adsorbed more readily on the surface of
charcoal and why?
A 14) NH3 is adsorbed more readily as it is more easily liquefiable compared to N2,
Moreover, NH3 molecule has greater molecular size.
Q 15) How does it become possible to cause artificial rain by spraying silver
iodide on the clouds?
A 15) Clouds are colloidal in nature and carry a charge. On spraying silver iodide which
is an electrolyte, the charge on the colloidal particles is neutralized. Clouds coagulate to
form rain.
Q 16) What is the role of diffusion in heterogeneous catalysis?
A 16) The gas molecules diffuse onto the surface of the catalyst and get adsorbed.
After the chemical change, the products formed diffuse away from the surface of the
catalyst setting the surface free for other reactant molecules to adsorb on the surface
and give the product.

02 MARKS
Q1)
Write the differences between physisorption and chemisorption with respect to
the following :(i) Specificity

(ii)

Temperature dependence

(iii) Reversibility

(iv)

Enthalpy change

Criteria

Chemisorption

Specificity

It is not specific in nature

It is highly specific in nature

Temperature
dependence

It decreases with increase in

temperature.
Thus,
low
temperature is favorable for
physisorption
Reversible in nature

It increases with increase in

temperature. Thus, highly
temperature is favorable for
chemisorption
Irreversible in nature

Low enthalpy of adsorption

High enthalpy of adsorption

Reversibility
Enthalpy
change

Q2)

Physisorption

Distinguish between homogeneous and heterogeneous catalysis.

A2)
When reactants and the catalysts are in the same phase (i.e. liquid or gas) the
catalysis is known as homogeneous catalysis.
3
O2 ( g ) NO
( g ) O3 ( g )
2

When reactants and the catalysts are in the different phase (i.e. liquid or gas) the
catalysis is known as heterogeneous catalysis.
4NH3(g) + 5O2(g)

Pt
( s ) 4 NO( g ) 6 H 2 O ( g )

Q3)
What is meant by coagulation of a colloidal solution? Describe briefly any three
methods by which coagulation of lyophobic sols can be carried out?
A3)
The process of aggregating together the colloidal particles is called coagulation
of the sol. It is also known as precipitation. Following are the three methods by which
coagulation of lyophobic sols can be carried out.

Q4)

(i)

Electrophoresis. In this process, the colloidal particles move towards

oppositely charged electrodes and get discharged resulting in
coagulation.

(ii)

Mixing of two oppositely charges sols.

When equal proportions of
positively charges sols are mixed, they neutralize each other resulting in
coagulation.

(iii)

Dialysis. By this method, electrolytes present in sol are removed

completely and colloid becomes unstable resulting in coagulation colloid
is a heterogeneous system, e.g gold sol, sulphur sol, soap, etc.

What are emulsions ? Discuss the role of an emulsifier in forming emulsion.

A4)
Emulsions are one of the types of colloidal system, in which both the dispersed
phase and dispersion medium are liquids, e.g milk.

Role of emulsifier Emulsifying agents are added to emulsions to stabilize them. The
emulsifying agent forms an interfacial film between suspended particles and the
medium. For oil in water emulsions, the principal emulsifying agents are gums, proteins,
natural and synthetic soaps.
Q 5)

A5)

How are the following colloidal solutions prepared?

(i)

Sulphur in water

(ii)

Gold in water

(i)

Sulphur sol is prepared by the oxidation of H 2S with SO2.

SO2 + 2H2S

(ii)

3S + 2H2O
(Sol)
Gold sol is prepared by Bredigs arc process or by the reduction of AuCl 3 with
HCHO.
oxidation

2AuCl3 + 3HCHO + 3H20

Reduction

2Au + 3HCOOH + 6HCI

(Sol)

Q6)

What are enzymes? Write in brief the mechanism of enzyme catalysis.

A6)

Enzymes are biochemical catalysts whih are globular proteins and form
macromolecular colloidal solution in water.

The mechanism of enzyme catalysis may be explained on the basis of

lock and key theory. Acc to the theory , Enzymes are highly specific due to the
presence of active sites on their surface. The shape of active site of any given
enzyme is such that only a specific substrate can fit in to it just as one key can fit
into a particular lock enzyme catalyzed reactions takes place in two steps as
follows :Step I :E

Formation of Enzyme substrate complex

+

Enzyme
Step II :-

ES

(fast and reversible)

Substrate

Enzyme substrate complex

Dissociation of enzyme substrate complex to form the products

ES

[EP]

P (slow and rate

determining)
Enzyme
Substrate
Complex
Q7)

Enzyme
Product
association

Enzyme
(Regenerated)

Product

What do you mean by activity and selectivity of catalysts?

A7) Activity : Ability of a catalyst to accelerate chemical reactions is known as its

activity . For example, Pt catalyses the combination of H 2 and O2 to form water. It has
been found that for hydrogenation reactions, the catalytic activity increases from Group
5 to Group 11 metals with maximum activity being shown by Group 7-9 elements of the
periodic table.
Selectivity : The ability of a catalyst to direct a reaction to yield a particular
product is called its selectivity. Combination of CO and H 2 yields different products with
different catalysts as given below :CO (g) + 3H2 (g)

Ni

CH4 (g) + H2O (g)

CO (g) + H2 (g)

Cu

CO (g) + H2 (g)

Cu I ZnO Cr O
2 3

HCHO (g)
CH3OH (g).

Q8)

Describe some features of catalysis by zeolites?

A8)

(i)
Zeolites are hydrated alumino-silicates which have a three- dimensional
network structure containing water molecules in their pores.

(ii)
On heating, water of hydration present in the pores is lost and the pores
become vacant to carry out catalysis.
(iii)
The size of the pores varies from 260 to 740 pm. Thus, only those
molecules can be adsorbed in these pores and catalyzed whose size fits these
pores. Hence, they act as molecular sieves or shape selective catalysts.
An important catalyst used in petroleum industry is ZSM -5 (Zeolite sieve
of molecular porosity 5). It converts alcohols into petrol by dehydrating them to
form a mixture of hydrocarbons.
ZSM -5
Alcohols
Hydrocarbons
Dehydration

03 MARKS
Q1)

Account for the following :(a)

Medicines are more effective in the colloidal form/ colloidal gold is used for
intramuscular injection.
(b)

Sky appears blue in colour.

(c)

Alum is added to purify water.

OR

Bleeding stops on rubbing moist alum on the cut surface.

A1)

(a)
Medicines are more effective in the colloidal form because they have a
large surface area and are easily assimilated in this form.
(b)
There are dust particles in the atmosphere. These dust particles are of
colloidal size and scatter the light. Blue light coming from the sun is scattered
and the sky appears blue.
(c)

Alum coagulates colloidal impurities present in water.

or
Alum brings about and coagulation of blood and stops further bleeding.

Q2)

Explain clearly how the phenomenon of adsorption finds application in

(i)

Production of vacuum in a vessel

(ii)

Heterogeneous catalysis

(iii)

Froth floatation process in metallurgy.

A 2)

(i)
Production of high vacuum. The traces of air can be adsorbed by
charcoal from a vessel evacuated by a vacuum pump to give a very high
vacuum.
(ii)
Heterogeneous catalysis.
Adsorption of reactants on the solid
surface of the catalyst increases the rate of reaction.
(iii)
Froth floatation process. A low grade sulphine ore is concentrated by
this method using pine oil and frothing agent. The mineral particles become wet
by oils while the gangue particles by water.

Q3)

What is an adsorption isotherm? Describe Freundlich adsorption isotherm.

A 3) Adsorption isotherm. It is the variation in the amount of gas adsorbed by the

adsorbent with pressure at constant temperature.
Freundlichs adsorption isotherm. It is an empirical relationship between the
quantity of gas adsorbed by unit mass of solid adsorbent and pressure at a particular
temperature.
1
x
kp n (n 1)
m

n 1,

When,

x
kp
m

or

. (i)
x

Where x is the mass of gas adsorbed on mass m of the adsorbent at pressure

p.k and n are constants which depend on the nature of the adsorbent and the gas at a
particular temperature.
Taking log in Eq. (i), gives
log

x
1
log k log p
m
n

log

x
m

The validity of Freundlich isotherm can be verified by plotting

on Y-axis and
log p on X-axis. If, it comes to be a straight line, the Freundlich isotherm is valid.

Q4)

Explain the terms with suitable examples :(i)

A4)

Alcosol

(ii)

Aerosol

(iii)

Hydrosol

(i)
Alcosol :It is a colloidal dispersion having alcohol as the dispersion
medium. For eg :- Collodion, which is a colloidal sol, of cellulose nitrate in ethyl
alcohol.
(ii)

Aerosol :-

It is a colloidal dispersion of a liquid in a gas eg:- fog.

(iii)
Hydrosol :- IT is a colloidal dispersion of a solid in water as the
dispersion medium.eg :- starch sol.
Q5)

Explain the following observations :-

(a) Cotrells smoke precipitator is fitted at the mouth of the Chimneys use is
factories.
(b)

Physical adsorption is multilayered, while chemisorption is monolayered.

(c)
A white precipitate of silver halide becomes coloured in presence of the
dye eosin.
A5)

(a)
The charged collodial particles of carbon after coming in contact with
oppositely charges electrode in Cottrell precipitator lose their charge and settle
down at the bottom.
(b)
In physical adsorption, there are Weak Vander Waals forces. Therefore it
forms multilayers. In Chemisorption, adsorbate is attached by chemical bond.
There is a strong force of attraction. Therefore, only one layer is obtained.
(c)
Eosin is adsorbed on the surface of silver halide precipitate making it look
coloured.

CHAPTER 6
GENERAL PRINCIPLES OF EXTRACTION
01 MARK
Q1.

Name the chief ores of aluminium and zinc.

A1.

Chief ores of Aluminium Bauxite. A

l0 x

(OH) 3- 2x [Where O<X<1]

Zinc :- zinc blende (ZnS)

Q2. What is the function of collectors in the froth floatation process for the
concentration of ores?
or
What is the role of collectors in froth floatation process?
A2.
Collectors such as pine oils, fatty acids, xanthates etc, enhance non wettability
of the mineral particles.
Q3.

What is the role of flux in metallurgical processes?

A3.
Flux is a substance that chemically combines with gangue (earthy impurities)
which may still be present in the roasted or the calcined ore to form an easily fusible
material called the slag.
Q4.

What types of ores can be concentrated by magnetic separation method?

A4.
Those ores which are magnetic in nature and associated impurities are nonmagnetic in nature or vice-versa, are concentrated by magnetic separation method.
Q5.

Differentiate between a mineral and an ore?

A5.
Naturally occurring substances from which metal may or may not be extracted
profitably is known as mineral. The minerals from which metal can be extracted chiefly,
easily and profitably are known as ores.
Q6.

Why is it that only sulphide ores are concentrated by froth floatation process?
or
Why is the froth floatation method selected for the concentration of sulphide

ores?

A6.
Only sulphide ores are concentrated by froth floatation method because sulphide
ores are wetted preferentially by pine oil and impurities (gangue) are wetted by water.
Q7.

Why are sulphide ores converted to oxide before reduction?

A7.
It is more easy to reduce an oxide ore than a sulphide ore. This is why sulphide
ores are roasted and first converted to its oxide form.

Q8. Although carbon and hydrogen are better reducing agents, but they are not used
to reduce metallic oxides are at high temperature. Why?
A8.
This is because carbon and hydrogen react with metals to form carbides and
hydrides respectively at high temperature.
Q9.

What is the role of

CO2

in the extractive metallurgy of aluminium from its ore?

or
CO2

What role is played by

in the getting pure alumina (

Al 2

O3

) in the

extraction of aluminium?
A9.
O3

The aluminate in solution is neutralized by passing

CO2

and hydrate

Al 2

is precipitated
2 Na [Al (OH)4] (aq) +

CO2

(g)

Al 2 O3

xH 2 O (s)

+ 2Na

HCO3

(aq)

Q10. Why is electrolytic reduction preferred over chemical reduction for the isolation of
certain metals?
A10. More reactive metals, i.e. alkali metals and alkaline earth metals are usually
extracted by electrolysis of their fused salts because in electrolytic reduction, by
applying external potential from outside source, reduction can be brought easily.
Further, more reactive metals have more affinity with oxygen than that of carbon. Thats
why electrolytic reduction is preferred over chemical reduction.
02 MARKS
Q1.

How is copper extracted from a low grade ore of it?

A1.

Copper is extracted by hydrometallurgy from low grade ores. It is leached out

2+
H2
using acid or bacteria. The solution containing Cu is treated with scrap iron or
.
2+

Cu

(aq) +

H2

.(aq)

2+

Cu (aq) + Fe(s)

+
Cu(s ) + 2 H (aq)

Cu(s ) +

2+

Fe (aq)

Q2. How do we separate two sulphide ores by Froth floatation method? Explain with
an example?
Or
State the role of depresent in froth floatation process?
A2.
Two sulphide ores can be separated by adjusting properties of oil to water or by
using depressants which prevent one type of sulphide ore particles from forming the
froth with air bubbles.
Eg :-In case of an ore containing Zns and Pbs, the depresent NaCN is used. It
forms complex with ZnS and thus prevents it from forming a froth while Pbs
forms the froth and hence can be separated from ZnS.
4NaCN + ZnS
Q3.

A3.

Na 2

[Zn CN)4] +

Na 2

sodiumtetracyanidozincate(II)complex
State Write the reactions involved in the following process :
(i)

Leaching of bauxite ore to prepare pure alumina.

(ii)

Recovery of gold after gold ore has been leached with NaCN solution.
O2

Leaching of alumina from bauxite ore Bauxite usually contains Si

oxide and titanium oxide (Ti

O2

, iron

) as impurities. Powered ore is digested with conc

NaOH solution at 473-523Kand 35-36 bar pressure.

dissolved in the solution while impurities do not.
3536
Al 2
O3
H2
(s) + 2NaOH (aq) + 3
O(l) 473523 K

Al 2

O3

and

SiO 2

2Na [Al(OH)4](aq)

are

Filtrate is neutralized by passing

CO2

gas and hydrated

Al 2

O3

is

precipitated.Some fresh alumina is also added to solution to induce precipitation.

2CO 2
Al 2 O3
HCO3
2 Na [Al (OH)4] (aq) +
(g)
. xH 2 O( s) + 2Na
(aq).
ppt
Precipitate is filtered, washed, dried and heated to give back pure
Al 2 O 3

s
. xH 2 O ) 1470K

Al 2 O3 ( s ) +

Al 2

O3

xH 2 O ( g )

Alumina

Recovery of gold

H2
O2
4Au(s)+ 8 CN (aq) +2
O (aq) +
(g)
(aq)
2[Au(CN)2]- (aq) + Zn (s)

4[Au(CN)2]2-(aq) + 4 OH

[Zn(CN)42- ] (aq) +2Au(s)

Soluble gold complex

In this reaction, zinc acts as a reducing agent.
Q4.

A4.

Define the following terms :

(i)

Roasting

(ii)

Calcination

(i)
Roasting. The process of heating of metal ore below its melting point in
the presence of air is called roasting.
(ii)
Calcination. The process of heating of metal ore in the absence of air is
called calcination.

Q5.

Why is an external emf of more than 2.2V required for the extraction of

CL2

from brine?
A5.
Cl2

H2
For the reaction 2 Cl (aq) + 2
O (l)
(g)

2 OH

(aq) +

H2

(g)

Value of
E

is + 422kJ. Using the equation

A6.

= -n FE

, the value of

comes out to be -2.2V. Therefore an external emf of more than 2.2V is

required for the extraction of

Q6.

Cl2

from brine.

(a)

What is the composition of copper matte?

(b)

What is the function of

SiO 2

(a)

Copper matte contains

Cu2

(b)

SiO

Silica ) is added in the reverberatory furnace during the extraction of

in the metallurgy of copper?

s and FeS.

Cu to remove impurities of iron oxide (FeO) present in the ore. Silica here acts as
flux and reacts with iron oxide gangue to remove it as slag, iron silicate.
FeO +
Iron oxide

Q7.

A7.

SiO 2

Silica

Fe

SiO 3

Iron silica slag

Give reason for the following :(i)

Alumina is dissolved in cryolite instead of being electrolysed directly.

(ii)

Zinc oxide can be reduced to the metal by heating with carbon but
not Cr 2 O 3
.

(i)
Melting point of alumina is very high and it is a bad conductor of electricity.
Cryolite is added to alumina to lower its melting point and to make it conductor of
electricity.
(ii)

Reduction of zinc oxide is done by using coke ZnO +C

1673K

Chromium oxide is reduced through alumina (thermic reduction process}.

Cr 2 O3

+ 2Al

Al 2 O 3 + 2Cr

Zn + CO

This is because, the free energy change for the formation of

Cr 2 O3

is

more negative than that of ZnO.

Q8. State the basis of refining a substance by chromatographic method. Under what
circumstances is this method specially useful?
A8.
Chromatographic Method.
This method is based on the principle that
different components of a mixture are differently adsorbed on an adsorbent. Adsorbed
components are removed by using suitable solvent (eluent).
This method is very useful for the purification of the elements which are available
in minute quantities and the impurities are not different in chemical properties
from the element to be purified.
Q9.

What chemical principle is involved in choosing a reducing agent for getting the
Al 2 O 3
Fe2 O3
metal from its oxide ore? Consider the metal oxides,
and
, and justify
the choice of reducing agent in each case?
A9.
Thermodynamic factor helps us in choosing a suitable reducing agent for the
reduction of a particular metal oxide to metal. From Ellingham diagram, it is evident that
o
metals which have more negative f G of their oxide can reduce those metal oxide for
which
Fe2 O3

Go

is less negative. Since, the free energy change for the formation of

is less negative than CO, CO is a good reducing agent for it.

Fe2 O3

G = -ve [because

+ 3CO 823K 2Fe + 3

G(

Fe2 O3

CO2

) is less negative then

The free energy change for the formation of

Al 2 O3

G (CO)]

is highly negative (~ 1000

to 1100), thus, no reducing agent is suitable for its reduction. It is thus,reduced by

electrolysis of its oxide.
Q10. How is wrought iron different from steel?
A10. Pig iron contains 4% C and trace elements like, S, P,Si and Mn as impurity. It is
heated strongly (in excess of oxygen) in Bessemer converter. By this, volatile impurities
P2 O5
SO 2
like C,P,S are removed as CO,
and
repectively. Si amd Mn are also
oxidised into their oxides which combine to form MnSi

O3

(slag). The iron so obtained

is called wrought iron. When, it is heated with 0.5% C, it gives steel. Thus, steel is less
pure3 than wrought iron.
03 MARKS
Q1.

Explain the basic principles of following metallurgical operatins :

(i)

Zone refining

(ii)

Vapour phase refining

(iii)

Electrolytic refining

A1.
(i)
Zone refining It is based on the fact that the impurities are more soluble in
the melt than in the solid state of the metal. When one end of the impure metal rod is
heated with the help of mobile heater, the molten zone moves forward along with
impurities.
In this way impurities are concentrated at the other end of the rod. This end is cut off.
The process is repeated several times to obtain ultrapure metals for producing
semiconductors. Ge,Si,Ga and In are purified by this method.

Noble gas atmosphere

Metal rod
shown

Induction coil heaters moving as

Molten zone
Zone refining process
(ii)
Vapour phase refining In this method, the metal is converted into its
volatile compound and is collected elsewhere. It is then decomposed to give pure
metal. So the two requirements are
(a)

the metal should form a volatile compound with an available

reagent.

(b)

The volatile compound should be easily decomposable, for the

recovery of metal.

(iii)
Electrolytic refining In this method, the impure metals is made anode
and a strip of pure form of same metal is made cathode. Aqueous solution of salt
of same metal is taken as electrolyte. On passing electric current, metal ions
from the electrolyte are deposited at the cathode in the form of pure metal while
an equivalent amount of metal dissolves from the anode and goes into the
electrolyte solution as metal ions, i.e. pure metal is dissolved from anode and
deposited at cathode through electrolyte in equivalent amount.
Q2. Write down the reactions which occur in upper, middle and lower zones in the
blast furnace during the extraction of iron from iron ore?
A2.

Reduction of iron oxide in blast furnace

(i)

Lower zone of the blast furnace

C+

O2

C+

CO2

CO2

+ Heat

2CO

Coke is burnt to give temperature upto 2200K at lower part of the blast
furnace.
(ii)

Middle zone of the blast furnace

CO and heat move up in the furnace. The temperature range on the
middle zone of the blast furnace is 900 1500 K.
FeO + CO

Fe +

CO2

Limestone is also decomposed to CaO which removes silicate impurity of

the one as slag.
Ca
C+

CO3

1100K

CO2

CaO +

CaO +

CO2

2CO

SiO 2

Ca
Slag

SiO 3

(iii)

Upper zone of the blast furnace

Temperature range in this zone is 500-800K. Following reactions take
place in this zone.
Fe2 O3

+ CO

Fe3 O 4

+ 4CO

Fe2 O3

+ CO

Fe3 O 4

3Fe + 4

CO2

CO2

2FeO +

CO2

The iron obtained from blast furnace is known as pig iron. It contains
about 4% carbon.
Q3.

(a)

The reaction :

Cr 2 O3

Al 2 O 3

+ 2Al

+ 2Cr (

Go

= -

421kJ) is thermodynamically feasible as is apparent from the Gibbs energy value. Why
does it not take place at room temperature?

(b)
that of

The value of
Al 2 O 3

o
f G

for formation of

Cr 2 O3

1
is - 827 kJ mol . Is the reduction

is -540kJ
Cr 2 O3

mol1

and

possible with AI?

A3.
(a) In the given redox reaction, all the reactants and the products are solids at
room temperature, therefore, there does not exist any equilibrium between the reactants
and the products and hence the reaction does not occur at room temperature. The
interpretation of

Go

is based on K (

Go

= -RT in K) where K is the equilibrium

constant. Where there is no equilibrium in the solid state and the value of K becomes
insignificant. However, at high temperature, when chromium melts, the value of T S
increases. As a result, the value of

G o becomes more ve and hence the reaction

proceeds rapidly.
(b).

The two thermochemical equations can be written as :

4
3
-827kJ mol

Al (s) +

O2

(g)

2
3

Al 2 O3

(s) ;

(g)

2
3

Cr 2 O3

(s):

Go

AI,

Al 2 O 3

(i)
4
3

Cr (s) +

mol1

O2

Go

= -540 kJ

(ii)
Subtracting equation (ii) from equation (i), we get
4
3

Go

2
3

Al (s) +

Cr 2 O3

2
3

(s)

Al 2 O3

(s) +

4
3

Cr (s) ;

1
= -287 kJ mol

As

Go

Cr 2 O3

of the combined redox reaction is ve, therefore , reduction of

by AI is possible.

Q4.

Write chemical reactions taking place in the extraction of zinc from zinc blende.

A4.

The various steps involved in the extraction of zinc from zinc blende are :
(a)
Concentration.
floatation process.
(b)

The ore is crushed and then concentrated by froth

Roasting.

The concentrated ore is roasted in presence of excess of air

SO 2
at about 1200 K when zinc oxide (ZnO) is formed and
is evolved.
2ZnS + 3
Zinc blende

O2

1200K

2ZnO + 2S

O2

Zinc oxide

(c)
Reduction Zinc oxide obtained in step (b) is mixed with powdered coke
and heated to 1673 K in a fire clay retort when it is reduced to zinc metal.
ZnO + C 1673K Zn + CO

At 1673 K, zinc metal being volatile (b.p 1180K), distils over and is condensed.
(d)
Electrolytic refining
The metal obtained as above is impure. It is
purified by electrolytic method. Impure zinc is made the anode while cathode
SO 4
consists of a sheet of pure zinc. The electrolyte consists of Zn
solution
H 2 SO 4

acidified with dil.

. On passing electric current, pure Zn is deposited on

the cathode.
Q5.

(a)

Describe the principle involved in each of the following process :-

(i)

Mond process for refining of nickel.

(ii)

Liquation method

(b)

What is the role of graphite rod in the electrometallurgy of aluminium?

A5.
(a)
(i)
Mond process for refining of nickel. (vapour phase refining) is
based upon the principle that nickel is heated in the presence of carbon monoxide to
form nickel tetra carbonyl, which is a volatile complex.
Ni+ 4CO

330-350 K

Ni(CO)4

Nickel tetra carbonyl

Then, the obtained nickel tetra carbonyl decomposed by subjecting it to a higher

temperature (450 470K) to obtain pure nickel metal.
Ni(CO)4
Nickel tetra
carbonyl

Ni + 4CO
Nickel

(ii)
Liquation method In this method a low melting metal like tin can
be made to flow on a sloping surface. In this way, it is separated from
higher melting impurities.

(b)
In the electrometallurgy of alumina, a fused mixture of alumina, cryolite
and fluorspar (CaF2) is electrolysed using graphite as anode and graphite lined
as cathode. During electrolysis, Al is liberated at the cathode while CO and CO2
are liberated at the anode. The relevant equations are as under :
Al 3 3e Al (l )

At cathode :

At anode :

C (s) +

2
O

(melt)

CO(g) +

C (s) +

2
2 O

(melt)

CO2

2e

(g) + 4 e

Oxygen evolved at the anode burns, the anode material (graphite).

If instead of graphite, some other metal is used as the anode, then

O2

liberated will oxidise the metal of the electrode. Since graphite is much cheaper
than any metal, therefore, graphite is used as the anode.

CHAPTER 7
P-BLOCK ELEMENTS
01 MARK
1)
Ans:

Why does PCl3 fume in moisture?

PCl3 hydrolyses in the presence of moisture giving fumes of HCl.
PCl3 + 3H2O - H3PO3 + 3HCl

2)
PH3 forms bubbles when passed slowly in water but NH3 dissolves. Explain why?
Ans:- Due to high electronegativity & small size of N, NH3 forms H- bonds with water and
hence it is water soluble. On the other hand, due to its lower electronegativity and its bigger size.
PH3 does not form H-bonds with H2O. As a result, it does not dissolve in H2O and hence escapes
as bubbles.
3)
Solid Phosphorus pentachoride behaves as an ionic compound. Explain why?
Ans In the solid state PCl5 exists as an ionic solid [PCl4]+ [PCl6]- in which the cation [PCl4]+
tetrahedral and the anion [PCl6]- is octahedral.
4)
Sulphur in vapour state exhibits paramagnetic behavior. Give reason.
Ans In vapour state, sulphur partly exists as S2 molecule which has two unpaired electrons in
the antibonding -orbitals like O2 and hence, exhibits paramagnetism.
5)
In solution of H2SO4 in water, the second dissociation constant, Ka 2 is less than the first
dissociation constant, Ka 1. Explain.
Ans Ka2 is less than Ka1 because the negatively charged HSO4- ion has much less tendency to
donate a proton to H2O as compared to neutral H2SO4.
6)
Draw the structure of SO2 molecule. Comment on the nature of two S-O bonds formed in
it. Are the two S-O bonds in this molecule equal?
Ans Structure of SO2 molecule is given below:

In
SO
2,
sulphur is sp2 hybridised. The molecule of SO2 is angular. It is resonance hybrid of the above two

canonical forms. In SO2, both the S-O bonds are covalent and have equal strength due to
resonance.

7)
Ans

Write the balanced chemical equation for the following reaction :

Excess of SO2 reacts with sodium hydroxide solution.
Chemical equation for sodium hydrogen sulphite.
2NaOH + SO2 - Na2SO3 + H2O
Na2SO3 + H2O + SO2 - 2NaHSO3
Sodium hydrogen sulphite

8)
Name two poisonous gases which can be prepared from chlorine gas.
Ans Phosgene (COCl2), tear gas (CCl3NO2), mustard gas (ClCH2CH2SCH2CH2Cl) all are
obtained from chlorine gas..
9)
Ans

Write two uses of ClO2

i)
ClO2 is a powerful oxidizing agent & chlorinating agent
ii)
It is an excellent bleaching agent.

10)
What inspired N Bartlett for carrying out reaction between Xe and PtF6?
Ans Bartlett found that the first ionization enthalpy of molecular oxygen is almost similar
with that of xenon. Thus, after preparing red coloured compound O2+ [PtF6]- , he got inspired for
carrying out reaction between Xe and PtF6 and made efforts to prepare Xe+ [PtF6]- by mixing Xe
and PtF6.
02 MARKS
1)

Arrange the following NH3, PH3, A3H3, SbH3 BiH3

in order of
a)
Increasing basic strength
b)
Increasing reducing character.
Ans a)
On moving down the group, size of the elements increases. As the size increases,
tendency to attract a proton decreases and thus, the basic character decreases. Hence the
increasing order of basic strength is BiH3 < Sbh3 < AsH3 < Ph3 < NH3
b)
The stability of hydrides decreases from NH3 to BiH3 which can be observed from
their bond dissociation enthalpy. Thus the reducing character of hydrides increases in the order
NH3 < PH3 < AsH3 < SbH3 < BiH3
2)

Explain the following :

i)
NO2 readily forms a dimer.

ii)
BiCl3 is more stable than BiCl5.
Ans
i)
NO2 is an odd molecule due to the presence of odd number of valence electrons.
Hence, it readily dimerises to give more stable N2O4 molecule with even number of electrons.
ii)
Due to inert pair effect, +3 oxidation state of Bi is more stable than its +5
oxidation state. Thus, BiCl3 is more stable than BiCl5.
3)
Draw the structures of white phosphorus and red phosphorus. Which one of these two
types of phosphorus is more reactive and why?

Ans

Structure of white phosphorus is given below :

Structure of red phosphorus is given below:

White phosphorus is more reactive because of its discrete tetrahedral structure and
angular strain.
4)
Ans

Write the conditions to maximize the yield of H2SO4 by contact process.

The key step in the production of H2SO4 is the oxidation of SO2 to SO3.
SO2(g) + O2(g)

2SO3 (9)

Ho = - 196.6 KJmol-1

The reaction is exothermic & reversible and the forward reaction proceeds with decrease in
volume. Therefore in accordance with Le chatliers; principle, to maximize the yield of SO3 &
hence of H2SO4, a low temperature (720 K), a high pressure (2 bar) & V2O5 is used as a catalyst.
5)

Assign reasons for the following.

a)
H2S is more acidic than H2O.
b)
Sulphur has a greater tendency for catenation than oxygen.
Ans a)
Due to decrease in (E-H) bond dissociation enthalpy down the group, acidic
character increases. Thus, H2S is more acidic than H2O.
b)
Bond energy of S-S bond (213 kJ mol-1) is greater than O-O bond (138 kJ mol-1).
Due to small size of oxygen atom, there is greater lp-bp repulsion in O-O, resulting in weakening
of O-O bond more than in S-S bond. Therefore, the tendency of catenation in oxygen is lower
than sulphur.
6)

Draw the structure of each of the following.

a)
H2S2O8
b)
H2SO4

Ans

7)

Ans

a)

Structure of H2S2O8 is given below:

b)

The structure of H2SO4

Complete the following chemical equations:a)

NaOH (hot & Conc.) + Cl2
b)
Cl2 + F2 (excess)
a)
3Cl2 + 6NaOH 5NaCl + NaClO3 + 3H2O
(hot & conc)
b)
Cl2 + 3F2 (excess) 2ClF3

Which neutral molecule would be isoelectronic with ClO-?

How are interhalogen compounds formulated and how are they prepared?
Ans
ClO- has 26 electrons. A neutral molecule with 26 electrons is OF2.
|
|
XX | XX 3 XX 5
b)
Interhalogen compounds are formulated as
, etc.
The interhalogen compounds can be prepared by direct combination or by the action of
halogen on lower interhalogen compounds. The product formed depends upon some specific
conditions, eg:
437
K
Cl2 + F2
2ClF
(Equal volume)
8)

a)
b)
a)

Cl2 + 3F2
2CIF3
(Excess)

9)

Ans

a)
i)
ii)
i)
ii)

573K

How are the following compounds prepared from XeF6?

XeOF4
XeO3
XeF6 + H2O XeOF4 + 2HF
XeF6 + 3H2O XeO3 + 6HF

9)
b)
XeF2 is linear molecule without a bent. Explain.
Ans XeF2 is linear molecule. According to VSEPR theory, the three lone pairs will occupy the
equalorial positions and two bond pairs will occupy axial positions to minimize lp-lp and lp-bp
repulsions.

10)

Explain Why
a)
Noble gases have comparatively large atomic sizes.
b)
Noble gases form compounds with fluorine & oxygen only.
Ans a)
It is due to the reason that noble gases have only vander waals radii while others
have covalent radii & by definition, Vander waals radii are larger than covalent radii.
b)
Fluorine and oxygen are the most electronegative elements and hence, are very
reactive. Therefore, they form compounds with noble gases particularly with xenon.
03 MARKS:
1)
What happens when
a)
White phosphorus is heated with conc. NaOH solution in an inert gas
atmosphere?
b)
Orthophosphorous acid is heated?
c)
PCl5 is heated.
Ans a)
When white phosphorus is heated with Conc. NaOH solution in an inert gas
atmosphere, phosphine gas is produced.
P4 + 3NaOH + 3H2O PH3 + 3NaH2PO2

2)

Ans

b)

On heating, H3PO3 disproportionate into H3PO4 and phosphine.

4H3PO3 3H3PO4 + PH3

c)

When PCl5 is heated, it decomposes into PCl3 and Cl2.

PCl5 PCl3 + Cl2

Complete the following chemical reaction

i)
I2 + conc.HNO3
ii)
HgCl2 + PH3
iii)
AgCl(s) + NH3 (aq)
i)
I2 + 10HNO3 2HIO3 + 10NO2 +4H2O
ii)
3HgCl2 + 2PH3 Hg3P2 + 6HCl
iii)
AgCl(s) + 2NH3 (aq) [Ag(NH3)2] cl (aq)

3)
On heating compound (A) gives a gas (B) which is a constituent of air. This gas when
treated with 3 mol of hydrogen (H2) in the presence of a catalyst gives another gas (C) which is
basic in nature. Gas C on further oxidation in moist condition gives a compound (D) which is a
part of acid rain. Identify compounds (A) to (D) and also give necessary equations of all the steps
involved.
Ans Compounds (A) to (D) are as follows :
(A) = NH2NO2
(B) = N2
(C) = NH3
(D) = HNO3
The reactions are given as under :

i)
NH4NO2
N2 + 2H2O
ii)
N2 + 3H2 2NH3
iii)
4NH3 + 5O2 4NO + 6H2O
iv)
2NO + O2 2NO2
v)
3NO2 + H2O 2HNO3 + NO
4)
On reaction with Cl2, phosphorus forms two types of halides A and B. Halide A is
yellowish-white powder but halide B is colourless oily liquid. Identify A and B and write the
formulas of their hydrolysis products.
Ans A is PCl5 (It is yellowish-white powder)
P4 + 10Cl2 4PCl5
B is PCl3 (It is a colourless oily liquid)
P4+6Cl2 4PCl3
Hydrolysis products are formed as follows:
PCl3 + 3H2O H3PO3 + 3HCl
PCl5 + 4H2O H3PO4 + 5HCl
5)
An amorphous solid A burns in air to form a gas B which turns lime water milky.
The gas is also produced as a by-product during roasting of sulphide ore. This gas decolourises
acidified aqueous KMnO4 solution and reduces Fe3+ to Fe2+. Identify the solid A and the gas
B and write the reactions involved.
Ans The solid A is sulphur, S8 and the gas B is SO2.
The reactions are given as under:

S8 + 8O2
8SO2
2MnO 4 + 5SO2 + 2H2O 5SO42- + 4H+ + 2Mn2+
2Fe3+ + SO2 + 2H2O 2Fe2+ + SO42- + 2H+
SO2 is produced as a by product during roasting of sulphide ore. The sulphides are converted into
oxides with the evolution of SO2.
6)

Complete the following chemical equation

i)
C + H2SO4 (conc.)

Ans

ii)
iii)
i)
ii)

SO3 + H2SO4 (conc.)

O3(9) + I-(aq) + H2O (e)
C + 2H2SO4 (conc.) CO2 + 2SO2 + 2H2O
SO3 + H2SO4 (conc.) H2S2O7
Oleum
O3 (g)+ 2I (aq) + H2O(l) 2OH-(aq) + I2(s) + O2(g)

iii)
7)

Account for the following:

a)
Iron on reaction with HCl forms FeCl2 & not FeCl3.
b)
O2 & F2 both stabilize higher oxidation states of metals but O2 exceeds F2 in doing
so.
c)
ICl is more reactive than I2?
Ans a)
HCl reacts with Fe and produces H2.
Fe + 2HCl FeCl2 + H2
Liberation of hydrogen prevents the formation of ferric chloride
Ans b)
O2 and F2 both stabilize higher oxidation states of metal but O2 exceeds F2 in
doing so due to ability of oxygen to form multiple bonds with metals.
Ans

c)

Interhalogen compounds are more reactive than halogens (except fluorine)

|

XX
because
bond (I-Cl bond in question) in interhalogens is weaker than X-X bond (I-I bond)
in halogens, except F-F bond. In other words, I-Cl bond is weaker than I-I bond. Thats why, ICl
is more reactive than I2.
8)

Ans

(ii)

a)
i)
ii)
iii)
i)

Draw the structure of

XeOF4 Molecule.
HClO4 Molecule
BrF3

(iii)

9)
How are xenon fluorides XeF2, XeF4 and XeF6 obtained ?
Ans These xenon fluorides are obtained by direct reaction between Xe and F2, under different
conditions as shown below:
673 k , 1

Xe (g) + F2 (g)
XeF2 (s)

(excess)
873 k , 7

Xe (g) + 2F2 (g)

XeF4 (s)

(1:5 ratio)
573 k , 6070

Xe (g) + 3F2 (g)

XeF6 (s)

(1: 20 ratio)

10)

Account for the following

a)
Helium is used in diving equipments.
b)
Structure of xenon fluorides cannot be explained by valence bond approach.
c)
Bleaching of flowers by chlorine is permanent while that by sulphur dioxide is
temporary.
Ans a)
Helium is used as a diluent for oxygen in modern diving apparatus because of its
very low solubility in blood.
b)
According to the valence bond approach, covalent bonds are formed by the
overlapping of half-filled atomic orbitals. But xenon has fully-filled electronic configuration.
Hence, the structure of xenon fluorides cannot be explained by VBT.
c)
Cl2 bleaches coloured material by oxidation. Cl2 + H2O 2HCl + [O]
hence bleaching is permanent.
On the other hand, SO2 bleaches coloured material by reduction & hence bleaching is
temporary SO2 + 2H2O 2H2SO4 + 2[H]

05 MARKS
1)
On heating lead (II) nitrate gives a brown gas A. The gas A on cooling changes to
colourless solid B. Solid B on heating with NO changes to a blue solid C. Identify A, B
and C and also write reactions involved and draw the structures of B and C.
Ans The gas A is NO2
The reactions are explained as under :

2Pb(NO3)2
2PbO + 4NO2 + O2
A
(brown colour)
Oncooling

2NO2
N2O4

2NO + N2O4

(Colourless solid)
250 K

2N2O3

C
(Brown colour solid)

Structure of N2O4

Structure of N2O5
2)

i)
How would you account for the following ?
a)
NF3 is an exothermic compound whereas NCl3 is not. Explain.
b)
All the P-Cl bonds in PCl5 molecule are not equivalent. Explain why?
c)
Why nitrogen gas is very unreactive ?
Ans a)
In case of nitrogen, only NF3 is known to be stable. N-F bond strength is greater
than F-F bond strength, therefore formation of NF3 is spontaneous. In case of NCl3, N-Cl bond
strength is lesser than CL-Cl bond strength. Thus, energy has to be supplied during the formation
of NCl3.
Ans b)
PCl5 has a trigonal bipyramidal structure and the three equatorial P-Cl bonds are
equivalent while the two axial bonds are different and longer than equatorial bonds. This is
because the axial bond pairs suffer more repulsion as compared to equatorial bond pairs.
Ans c)
Nitrogen is chemically less reactive. This is due to the presence of a more stable
triple bond in N2 molecule whereas phosphorus forms only P-P single bond. Therefore,
phosphorus is more reactive than nitrogen.
ii)

Draw the structures of the following

a)
(HPO3)3
b)
H4P2O7

Ans

3)

a)

Structure of (HPO3)3 is given below:

b)

Structure of H4P2O7 is given below:

a)

P4O6 reacts with water according to equation P4O6 + 6H2O

4H3PO3, Calculate

the volume of 0.1 M NaOH solution required to neutralize the acid formed by dissolving 1.1 g of
P4O6 in H2O.
Ans

P4O6 + 6H2O
H3PO3 + 2NaOH

4H3PO3
Na2HPO3 + 2H2O] x 4

---------------------------------------------------------------------------P4O6 + 8NaOH

4Na2HPO3 + 2H2O

1 mol

8 mol
1.1
No. of moles in P4O6 = 220
1 mol P4O6 requires = 8 mol NaOH
1.1
1.1

220 mol P4O6 requires = 8

220 mol NaOH

8.8
220 =0.04 mol NaOH

Molarity of NaOH solution is 0.1 M

1.1 mol NaOH is present in = 1 litre
1
0.04 mol NaOH is present in = 0.1

x 0.04 litre

= 400 ml.
b)
Give an example to show the effect of concentration of nitric acid on the
formation of oxidation product.
Ans Dilute and concentrated nitric acid gives different oxidation products on reaction with
copper metal.
3Cu + 8HNO3 (dil.)

3Cu(NO3)2 + 2NO + 4H2O

Cu + 4HNO3 (conc.)

Cu(NO3)2 + 2NO2 + 2H2O

NO and NO2 are the oxidation products obtained wilh dil. HNO3 and conc. HNO3 respectively.
4)

Give reasons for the following.

i)
Decomposition of O3 molecule is a spontaneous process.
ii)
SF6 is inert towards hydrolysis.
iii)
(CH3)3 P=O exists but (CH3)3 N=O does not.
iv)
Oxygen has less electron gain enthalpy with negative sign than sulphur.
v)
SO2 is an air pollutant.
Ans i)
Decomposition of O3 is an exothermic process (H = -ve) and occurs with
increase in entropy (S = +ve). These two effects reinforce each other which results in large
negative Gibbs energy change. It favours its decomposition into oxygen.

ii)
In SF6, S is surrounded by 6 F- octahedrally. Therefore, attack of water molecule
on S is sterically hindered.
iii)
Due to absence of d-orbitals,N cannot form p-d multiple bonds.As a result,N
cannot expand its covalency more than four,but in R3N=O,N has its covalency 5,therefore,the
compound R3N=O doesnot exist.On the other hand,due to the presence of d-orbitals in P,it forms
p-d multiple bonds,therefore can expand its covalency more than four.As a result P can form
(CH3)3 P=O.In this compound the covalency of P is 5.
iv)
The electron gain enthalpy of oxygen is less negative than sulphur due to its
compact size. As a result of which, the electron repulsions in the relatively compact 2p subshell
are comparatively large hence the incoming electrons are not accepted with the same ease as in
case of sulphur.
v)
SO2 is water soluble, therefore it dissolves in rainwater causing acid rain.
Moreover, when released in air, it mixes with it and leads to several diseases like eye irritation,
redness, asthma, bronchitis, etc. Thus, it is considered as an air pollutant.
5)
a)
Name the two most important allotropes of sulphur. Which one of the two is
stable at room temperature? What happens when the stable form is heated above 370 K?
Ans Two most important allotropes of sulphur are
i)
Rhombic sulphur (-sulphur)
ii)
Monoclinic sulphur
The stable form at room temperature is rhombic sulphur which transforms to monoclinic sulphur
when heated above 369K
370K
Rhombic sulphur
Monoclinic Sulphur
b)
i)
Ans

ii)

i)

Draw the structures of

H4S2O7 ii)
O3

iii)

S8

iii)

Crown Shape

6)

a)
i)
ii)
iv)

How would you account for the following

The oxidizing Power of oxoacids of chlorine follows the order
HClO4 < HClO3 < HClO2 < HClO
The halogens are coloured.
F2 is a stronger oxidizing agent than Cl2

b)

Complete the following chemical equations.

i)

I2 + NaClO3

ii)

I2 + H2O + Cl2

Ans a)
As the oxidation number of halogen atom in oxoacid increases, its oxidizing
power decreases. Therefore, HClO is least stable and gives [O] most easily, so its oxidizing
power is greater than HClO4.
b)
All halogens are coloured due to the absorption of raditions in visible region
which results in the excitation of outer electrons to higher energy level. By absorbing different
quanta of radiation, they display different colours.

c)
Since Eo for F2/F- eleclrode is higher than that of Cl2/Cl- electrode F2 is more
easily reduced than Cl2 & is a stronger oxidizing agent than Cl2.
Ans

b)

i)

I2 + 2NaClO3

ii)

I2 + 6H2O + 5Cl2

2NaI+2ClO2 + O2

2HIO3 + 10HCl

Iodic acid.
2)

a)
How can you prepare Cl2 from HCl & HCl from Cl2. Write reactions only.
b)
Write the reactions of F2 & Cl2 with water.
Ans a)
HCl can be oxidized to Cl2 by a number of oxidizing agents such as MnO2,
KMnO4, K2Cr2O7, etc.
Reaction with MnO2 is given below:
MnO2 + 4HCl

MnCl2 + Cl2+ 2H2O

Cl2 can be reduced to HCl by reaction of H2 in presence of diffused sunlight.

Diffused sunlight
H2 + Cl2
> 2HCl
220
b)
F2 being a stronger oxidizing agent oxidises H2O to O2 or O3. The reactions are
given as under:
2F2 (g) + 2H2O (l)

4H+ (aq) + 4F- (aq) + O2 (g)

2F2 (g) + 3H2O (l)

6H+ (aq) + 6F- (aq) + O3 (g)

Cl2, on the other hand, reacts with H2O to form hydrochloric acid and hypochlorous acid as per
the following equation :
Cl2(g) + H2O (l)

HCl (aq)
Hydrochloric acid

8)

HOCl (aq)
Hypochlorous acid

a)
i)
ii)
iii)

Give reason for the following.

F2 is more reactive than ClF3 but ClF3 is more reactive than Cl2.
H3PO2 is a stronger reducing agent than H3PO3.
PCl5 is more covalent than PCl3.

b)

Complete the following chemical equation.

i)

XeF4 + O2F2

ii)

XeF4 + SbF5

Ans a) i) Fluorine due to its small size, high electronegativity and low bond energy is more
reactive than ClF3 but bond energy of C-Cl bond is higher than Cl-F bond, therefore ClF3 is more
reactive than Cl2.
ii)

The structure of H3PO2 ,H3PO3 & H3PO4 are as follows:

The acids which contain P-H bond, have strong reducing properties. Hypophosphorous
acid (H3PO2) contains two P-H bonds, whereas orthophosphorous acid (H3PO3) has one P-H
bond. Hence, H3PO2 is a stronger reducing agent than H3PO3.
iii)
Since, pentavalent metal ion has higher polarizing power than trivalent metal ion.
Thus, PCl5 is more covalent than PCl3.

b) i)

XeF4 + O2F2

ii)

XeF4 + SbF5

XeF6 + O2

[XeF3]+ [SbF6]-

CHAPTER 9
COORDINATION CHEMISTRY
01 MARK
Q1.

Define ambidentate ligand with an example ?

A1.

Ligand that can ligate through two different atoms eg

NO2

ion can ligate

through N or through oxygen.

Q2.

NH 3

A2.

NC

Fe
NC

CN

NC

trans isomer
2+
Mn

Calculate the magnetic moment of

2+

Mn

3 d 3 45o

Q4.

Give the IUPAC name of [Ni

A4.

Tetrachloridonickelate (II)

Q5.

Out of [Fe(

A5.

[Fe(

02 MARKS

CN
NH 3

cis isomer

C2 O4

CN

Fe

CN

A3.

)2 (CN)4]-

NH 3
NH 3

NC

Q3.

NH 3

Draw structures of geometrical isomers of [Fe (

C2 O4

Cl 4

)3]3- and [Fe

ion?

n(n+2)

5(7)

35 BM

]2-

CL6

]3-, which is more stable and why?

)3]3-, as it is a chelate complex.

Q1. What is spectro chemical series? What is the difference between a strong field
ligand and a weak field ligand?
A1.
Arrangement of ligands in increasing orde of field strength is called spectro
chemical series.
A strong field ligand produces greater splitting in the d-orbitals, the complex is
likely to be low spin. A weak field ligand, on the other hand produces lesser splitting,
and complex is likely to be high spin.
Q2.

Using valence bond, approach, deduce the shape and magnetic character of
NH 3
[Co (
) 6]3+ ion. (Atomic no of Co = 27)

A2.

27

2
3d7 4 s

Co
3+

CO

3d64so

3+
CO

3d

4s

4p

Co3+ assumes d2sp3 hybridization and accepts six pairs of e - from 6

NH 3

molecules Shape octahedral Magnetic nature Diamagnetic

Q3. How is coordination chemistry useful in medicine? Where is Wilkinsons catalyst
used?
A3.

Chelates are being used to beat metal poisoning. E.g EDTA is used to treat lead
Ph3 P
poisoning. Wilkinsons catalyst [(
3 Rh Cl] is used for hydrogenation of alkenes.
Q4. Write the structure of the complex Pentaamminenitrito N Cobalt (III). Which
isomerism can this complex exhibit?
NH 3

)5 (

NO2

)] 2+, Linkage isomerism.

A4.

[Co (

Q5.

A solution of [Ni(H2O)6]2+ is green , but a solution of [Ni(CN)4]2- is colorless. Why?

2+

A5.
H2

3d 8 4s o

O is a weak ligand, so high-spin complex is formed (sp 3d2), leaving

two unpaired e-.

CN

being a strong ligand, produces a low spin square planar (dsp 2)complex

leaving no unpaired e-.

03 MARKS
Q1.

List the postulates of Werners Theory for coordination compounds on the basis
NH 3
of the theory, assign primary and secondary valencies to Pd in [Pd (
4]Cl2

A1.

(a)
In coordination compounds metals show two types of linkages (valences)
primary and secondary.
(b)

Primary valencies are ionisable and satisfied by ve ions.

(c)
Secondary valencies are non-ionisable and satisfied by neutral or ve
ions. Secondary valency is equal to coordination number and is fixed for a metal.
(d)
The ions/groups bound by secondary linkages to the metal having
characteristic spatial arrangements corresponding to different coordination
numbers.
[Pd (

NH 3

]Cl2

Primary valence - +2
Secondary valence 4
Q2.

Discuss the nature of bonding in metal carbonyls?

A2.

The M-C bond in metal carbonyls possess both s and p character. M-C sigma

bond is formed by donation of lone pair of e

on the carbonyl carbon into a
vacant orbital of the metal. The M-C bond is formed by donation of a pair of

from a
e
filled d-orbital
of metal into
the vacant anti

bonding
orbital of CO.
The metal
ligand bonding
creates
a
synergic effect
which
strengthens the bond between CO and the metal

Q3.

A3.

Explain the following :(a)

Low spin octahedral complxes of Ni arent known.

(b)

- complexes are known only for transition elements.

(c)

CO is a stronger ligand than

(a)

For octahedral complex, coordination number should be 6. Since Ni has

[Ar]3d8 4 s

NH 3

for many metals.

configuration, i.e only one d orbital is empty, it can form only high

spin complexes.
(b)

Transition metals have empty d orbitals to accommodate

donated by

ligands.
(c)
Due to small size and ability to form -bonds alogwith normal sigma
bonds.
Q4.

A4.

For the complex [Fe(en)2 Cl2]Cl, identify the following :(i)

Oxidation number of iron.

(ii)

Hybrid orbitals and shape of the complex.

(iii)

Magnetic behaviour of the complex.

(iv)

Number of its geometrical isomers.

(v)

Whether there may be optical isomers

(vi)

Name of the complex.

(i)

x + 2(0) + 2 (-1) + (-1) = 0

(ii)

sp

octahedral geometry

oxidn no +3

(iii)

paramagnetic (1 unpaired e-)

(iv)

Two geometrical isomers (CIs, trans)

(v)

Yes, due to polydentate ligends

(vi)

Dichloridobis (ethane -1,2- diamine) iron (III) chloride.

Q5. What will be correct order of wavelengths of absorption in the visible region for
the following :[Ni(
A5.
H2

NO2

)6]4- , [Ni(

NH 3

)6]2+, [Ni(

H2

O)6]2+

The strength of ligands according to sepctrochemical series

NO2

>

NH 3

>

Therefore splitting produced bythem in d-orbitals will also be in the same oreder (or O
NO2 NH 3
H2
Will be maximum in
, followed by
and
O). Hence , energy
1
absorbed will be in the same order. Since E
opposite order. i.e
NO2
NH 3
H2
[Ni(
)6]4- < [Ni(
)6]2+< [Ni(
O)6]2+.

, wavelength absorbed will be in the

CHAPTER 10
HALOALKANES AND HALOARENES
1 Mk Questions:
1)

Write the IUPAC name of the following compound :

CH3
H3C C CH2Cl
CH3

Ans

1 Chloro 2, 2 dimethylpropane

2)
Ans

Draw the structure of 2-bromopentane

H3C CH2 CH2 CH CH3
Br

3)
Write a chemical reaction in which iodide ion replaces the diazonium group in a
diazonium salt.
warm
+
Ans
N2
Cl
+
KI(aq)
>
I + N2 + KCl
.
4)
Out of CH3 CH Cl CH2 CH3 and CH3 CH2 CH2 CH2 Cl which one is hydrolysed more
easily by aq. KOH?
Ans CH3 CH CH2 CH3 , as its a secondary halide
|
Cl
5)
Ans

How can you convert methylbromide to methylisocyanide in a single step?

Ag CN
CH3Br
alc . > CH3NC + Ag Br

2 Mks Questions
1)
Ans

What are ambident nucleophiles? Explain with an example.

Ambident nucleophiles have two nuclophilic sites through which they can attack.

Eg. [C
N : C = N] linking through C results in alkyl cyanides and through N
results in isocyanides.

2)

Write chemical equations when

i) ethylchloride is treated with aq.KOH
ii) chlorobenzene is treated with CH3COCl in presence of anhyd.AlCl3.

Ans

i) C2H5Cl

aq . KOH
> C2H5OH + KCl

COCH3

ii)
H3COC

CH 3 COCl
Anhyd AlCl 3 >

Cl

Cl +

Cl + HCl
2-chloroacetophenone

4-chloroacetophenone

3)

Write the mechanism of the following reaction:

E+ OH , H 2 O
N BuBr + KCN
> n BuCN

Ans

CN- is an ambident nucleophile it can attack through C and N

C-C bond is stronger than C-N bond, cyanide is formed.

4)

Ans

5)
Ans

Give reasons:
a)
The order of reactivity of haloalkanes is RI>RBr>RCl
b)
Neopentyl chloride, (CH3)3C CH3 Cl doesnt follow SN2 mechanism.
a)
Larger the size of halogen atom, weaker the C-X bond,
R group remaining same i.e; bond strength follows the order
R-I <R-Br<R-Cl, hence reactivity is opposite.
b)
R group being bulky, provides steric hindrance to the incoming nucleophile.
Why does Wurtz reaction fail in case of tertiary halides?
3o halides prefer to undergo dehydrohalogenation in presence of a base like Na metal.
CH3
CH3
|

(CH3)3 C-Na+ + H CH2 C Br

NaBr
> (CH3)3 CH + CH2 = C CH3

|
CH3

3 Mk Questions:
1)

Write a chemical test to distinguish between

a)
Chlorobenzene and benzyl chloride
b)
Chloroform and carbontetrochloride
c)
n-propyl bromide and isopropyl bromide

Ans

a)
Benzyl chloride gives a white ppt with AgNO3 Soln., chlorobenzene does not.
b)
Chloroform gives offensive smelling isocyanides, on heating with 1o amine and
KOH, CCl4 doesnt give this test.
c)
Isopropyl bromide, on treating with aq.KOH, gives Propan-2-ol which gives a
yellow ppt. on heating wiith NaOH and I2 n- propyl bromide doesnt answer this test

2)

Complete the following reactions:

i)
ii)

iii)
Ans

i)

ii)

iii)

3)

Give reasons:

a) p-dichlorobenzene has higher melting point than o- and m- isomers.

b) Haloarenes are less reactive than haloalkanes towards nucleophilic substitution
reactions.
c) Alkyl chloride gives alcohol with aq.KOH, but alkene with alc. KOH.
Ans

a)
p-isomer has more symmetric structure, so molecules can pack closely.
b)
The C-X bond has partial double bond character due to resonance. Also, in
haloalkanes, X is bonded to sp3 C while in haloarenes, X is bonded to sp2 C. sp3-C is less
electronegative, releases electrons to halogen more easily.
c)
In aq.solution, KOH is almost completely ionized to give OH- ions, which being a
strong nucleophile, gives a substitution product. An alcoholic soln. of KOH contains alkoxide
ions (RO-), which being a strong base, preferentially eliminates an HCl molecule to form
alkenes.
4)

Ans

Convert:
a)
Ethene to ethanol
b)
Chlorobenzene to toluene
c)
Chlorobenzene to diphenyl

a)

CH2 = CH2 + H2O

dil . H 2 SO 4
> CH3CH2OH
.

b)

c)

5)

What are enantiomers? Identify the asymmetric carbons in the following molecule:a b
c
d
HOOC CH (OH) CH (OH) COOH

Ans

Enantiomers are non-superimposable mirror images of an optically active compound.

b and c are asymmetric carbon atoms as they are bonded to 4 different groups.

6)

Write short notes on :

a) Gatterman reaction
b) Wurtz reaction
c) Peroxide effect or Kharasch effect

Ans a) Aromatic 1o amines produce benzene diazonium salts with HNO2 (produced in situ) at
273 K. Chloro arenes and bromoarenes can be prepared using Cu/HCl or Cu/HBr from these
diazonium salts.

b)
Alkyl halides, when treated with sodium in presence of dry ether, produce an
alkane with even number of C atoms.
dry
2 R-X + Na ether > R _ R + 2NaX
E.g. 2 CH3 Br + Na

dry .
ether > CH3 CH3 + 2NaBr

If a mix of two different alkyl halides is taken, then a mixture of alkanes is obtained which is
difficult to separate.
Na
E.g. CH3 Br + C2H5Br dry ether > CH3-CH3 + C2H5 + CH3-C2H5
c)
The addition of Hydrogen bromide to unsymmetrical alkenes in presence of a
peroxide takes place in such a way that H goes to that C which has lesser H atoms and Br goes to
the C with greater number of H atoms.
( C6 H 5 COO ) 2
CH3 CH = CH2 + H Br
> CH3 CH2 CH2 Br

This rule doesnt apply to addition of HCl or HI

7)

Explain the following with an example each

a)
Swarts reaction
b)
Finkelstein reaction
c)
Hunsdiecker reaction
Ans a) Flourination of hydrocarbons directly with F 2 occurs explosively due to the large
amount of energy released. Hence, they can be conveniently prepared indirectly by halogen
exchange with chloro and bromoalkanes.
CH3Br + AgF CH3F + AgBr
2 C2H5Cl + .Hg2F2 2C2H5F + Hg2Cl2
b) Iodoalkanes can be easily prepared from chloroalkanes or bromoalkanes by heating
with NaI in acetone.
acetone
R-Cl + NaI
> R I + NaCl

R Br + NaI

acetone
> R I + NaBr

c)
Bromoalkanes can be prepared by refluxing the silver salt of a carboxylic acid
with Bromine in CCl4.

CH3CH2COOAg + Br2

CCl 4
Reflux > CH3CH2Br + CO2 + AgBr

The yield of alkyl bromide is 1o>2o>3o

8)

Explain why.
a)
Vinyl chloride is unreactive in nuceophilic substation reaction
b)
3-Bromocyclohexene is more reactive than 4-Bromocyclohexene in hydrolysis
with aq.NaOH
c)
tert-butyl chloride reacts with aq.NaOH by SN 1 mechanism, while n-butyl
chloride reacts with aq.NaOH by SN2 mechanism.
Ans a)
Vinyl chloride is unreactive in nucleophikic substitution reactions due to
reasanance which results in a partial double bond character of C-Cl bond which is difficult to
break.

b)
3-bromocyclohexene forms allyl carbocation which is more stable than
carbocation formed by 4-Bromocycohexene
c)
Tertiary carbocation is stable, so tert-butyl chloride follows SN 1 mechanism. Nbutyl chloride would form 1o carbocation which isnt that stable. Hence it undergoes SN2
mechanism through formation of transition state.
9)

Identify the products A and B formed in the following reaction:

CH3CH2CH = CH CH3 + HCl A + B
Ans Since both the doubly-bonded C atoms have same number of H atoms, Markonikovs rule
becomes irrelevant.
So, products will be CH3 CH2 CH CH2 CH3
CH3CH2CH2CH CH3
|
(A) and
|
(B)
Cl
Cl
3-chloropentane
2-choropentane
10)

What happens when:

a)
n-butyl chloride is treated with alc.KOH

Ans

b)
c)
a)
a)

Bromobenzene is treated with Mg in presence of dry ether.

Chlorobenze is subjected to hydrolysis.
CH3CH2CH2CH2Cl - alc.KOH CH3-CH2-CH=CH2+KCl + H2O
But 1 ene
dry ether
Br
+
Mg
>
Mg Br

a)

Cl2 + aq.NaOH no reaction.

CHAPTER 11
ALCOHOLS, PHENOLS AND ETHERS
1 Mark Questions
1)

A)

Write the IUPAC name of CH3 CH= CH CH- CH2 CH3

|
OH
Hex 4 en 3 ol

2)
A)

Why is the boiling point of C2 H5 OH higher than that of CH3 OH ?

Due to more number of C atoms, van der waals forces increase.

3)
A)

Name the reagent used in bromination of phenol to 2,4, 6 tribromophenol.

Aqueous solution of bromine (Bomine water)

4)
A)

Name the alcohol used to prepare the ester CH3 C OOCH(CH3)CH3

Propan-2-ol CH3-CH(OH)-CH3

5)
A)

Which is more volatile o-nitrophenol or p-nitrophenol?

o-nitrophenol,, as it has intramolecular H-bonding, whereas p-nitrophenol has
intermolecular H-bonding.

O-Nitrophenol with intra molecular hydrogen bonding

02 MARKS
1)

A)

How will you convert:

a)
Propene to propan 2 ol
b)
Ethyl chloride to ethanol
a)
CH3-CH = CH2 H2O/H+ CH3 CH CH3

|
OH
Propan 2 ol
b)

2)

A)

CH3 -CH2- Cl aq NaOH CH3 CH2 OH [o] CH3 - CHO

-----------
------- Ethanal
CrO3/PCC
Write the mechanism for the following reaction:
HBr

CH3CH2OH
CH3CH2Br + H2O
1o alc undergoes the reaction by SN2 mechanism

Protonated Alcohol
3)

A)

How would you obtain

i)
Picric acid from phenol?
ii)
2- Methylpropan-2-ol from 2- Methylpropene?
i)

ii)

4)

A)

5)
A)

Give reasons :
a)
Boiling points of alcohols decrease with increase in branching of the alkyl chain.
b)
Phenol does not give protonation reaction readily
a)
Because increase in branching of the alkyl chain reduces surface area, so
intermolecular forces of attraction decrease.
b)
Because the lone pair on oxygen is delocalized over the benzene ring due to
resonance, hence not available for protonation easily.
Explain why cleavage of phenyl alkyl ether with HBr always gives phenol and alkyl
bromide.
Due to resonance, the O-C bond in phenyl alkyl ether has a partial double bond character,
hence it is difficult to break.
Also, phenoxide ion is stabilized by resonance, hence we get phenol and alkyl bromide.

03 MARKS
1)
A)

Write a short note on Williamsons Synthesis.

An alkl halide, on treating with a suitable sodium alkoxide gives an ether
RONa + RX - R O R + NaX
Symmetric and unsymmetric ethers can be prepared by this method
Aryl alkyl ethers can be prepared as shown

But there is no reaction if arylhalide and sodium alkoxide are taken

Best yields of unsymmetrical ethers are obtained when alkyl halides are primary with 2 o
and 3o alkyl halide, dehydrohalogenation occurs to give alkene.

2)

Convert:
a)
Methyl magnesium chloride --2-methyl propan-2-ol
b)
Benzyl chloride --- Benzyl alcohol
c)
Phenol -- benzoquinone

A)
a)

propano
ne

b)

c)

3)

A)

Give reasons :
a) The boiling point of ethanol is higher than methoxymethane.
b) Phenol is more acidic than ethanol
c) O- and p-nitrophhenols are more acidic than phenol.
a)
Ethanol has intermolecular H-bonding while methoxymethane only has dipoledipole forces.

b)
by
effect of
c)

4)
A)

In phenols, O atom acquires a partial positive charge due to resonance, this

weakens O-H bond, release of H+ is easy. Also, phenoxide ion is stabilised
resonance. On the other hand, alkoxide ion is destabilized due to the +I
alkyl group.
-NO2 group, being electron-withdrawing, stabilizes the o- and p- nitrophenoxide
ions.

Describe the mechanism of hydration of ethene to yield ethanol.

Protonation of Alkene

Nucleophilic attack by water on the carbocation

Deprotonation
5)
Give equations for Reimer Tiemann reaction and Kolbes reaction.
A)
Reimer Tiemann reaction Phenol reacts with chloroform in the presence of alkali to
give o- and p-hydroxy aldehyde.

Kolbes reaction Phenoxide ion generated by treating phenol with NaOH undergoes
electrophilic substitution with CO2

6)

A)

7)

A)

Arrange the following compounds in increasing order of their acid strength.

Propan-1-ol, 2, 4, 6-Trinitrophenol, 3 Nitrophenol,
3, 5- Dinitrophenol, phenol, 4-Methylphenol, 4-Methoxyphenol
Propan-1-ol <4-Methoxyphenol<4-Methylphenol<phenol< 3-Nitrophenol
<3, 5 Dinitrophenol<2, 4, 6 Trinitro phenol
Propan 1 ol has R group, which destabilizes the propoxide ion due to +I effect, hence
weaker than all phenols.
All e- donating groups reduce acidity of phenols by destabilizing phenoxide ion and e withdrawing groups increase acidity.
Methoxy group is stronger e- - donating groups compared to methyl group.
Larger the number of e- withdrawing groups, greater the acidity. 2, 4, 6
Trinitrophenol is strongest, followed by 3, 5 Dinitrophenol and 3 Nitrophenol.
Give a simple chemical test to distinguish between:
a)
Phenol and cyclohexanol
b)
Propan-2-ol and Benzyl alcohol
c)
Propan-1-ol and 2-Methylpropan-2-ol
a)
Phenol produces a deep violet colour with neutral FeCl3 solution., cyclohexanol
doesnt.
b)
Propan-2-ol gives yellow ppt of iodoform with NaOH and I 2, benzyl alcohol
doesnt.

c)

8)

On treating with conc. HCl and anhydrous ZnCl 2 at room temperature, 2methylpropan-2-ol produces turbidity immediately while propan-1-ol doesnt
produce turbidity at room temperature.

Give the mechanism for the reaction:

2C2H5OH

Dilute H 2 SO 4 ( 413 K )

C2H5O C2H5

A)

Protonation of Alcohol

Nucleophillic attack by Alcohol

Deprotonation
9)
An organic compound A (C6H6O) gives a characteristic colour with aq. FeCl3 Solution.
when (A) is treated with CO2 and NaOH at 410 K under pressure, it gives compound (B) which
on acidification gives compound (C). Compound (C) reacts with acetyl chloride to give (D),
which is a popular pain killer. Deduce the strutures of A,B,C and D and explain all reactions
A)
(A) C6H6O must be phenol
Phenol gives sodium salicylate with CO2 which on acidification gives salicylic acid.
Salicylic acid forms aspirin with acetyl chloride.

10)
A

(a)

Explain hydroboration-oxidation reaction with an example

Diborane reacts with alkenes to give trialkyl boranes as addition product. This is
oxidized by H2O2 to alcohol, in the presence of aq.NaOH

(b)

Identify A B C in the following reaction.

LiAl H 4
HN O2 (273 k )
KCN

CH3Br
A
B
C

A
B
C

CH3CN
CH3CH2NH2
CH3CH2N2Cl (Unstable, so forms CH3CH2OH + N2 + HCl with Water

CHAPTER 12
ALDEHYDES KETONES AND CARBOXYLIC ACIDS
01 MARK
1)

Write the structure of p-methylbenzaldehyde.

A)
2)

Complete the reaction :

+ CH3COCl

Anh . Al Cl3

A)

Acetophenone
3)
Arrange the following in increasing order of their acid strength (CH3)2 CHCOOH,
CH3 CH2 CH(Br) COOH, CH3 CH(Br) CH2 COOH.
A)
(CH3)2 CHCOOH < CH3 CH(Br)CH2COOH<CH3CH2CH(Br)COOH
4)
Write IUPAC name of

A)

5 Bromo -3- chlorobenzoic acid

5)

Give a chemical test to distinguish between acetaldehyde and benzaldehyde.

A)

On heating with Na OH and I2, acetaldehyde gives a yellow ppt of iodoform,

benzaldehyde doesnt

02 MARKS
1)
a)
A)

Convert:
Ethanol to 1,2 Ethanediol
(b) Phenol to acetophenone
Cold Alkaline KMn O 4
Conc H 2 S O4 (443 k )
a) C2H5OH
CH2 = CH2 + H2O

Ethane 1, 2 - diol

b)

3)

Give reasons:

a)
b)

Monochloroethanoic acid is a weaker acid than dichloroethanoic acid.

Benzoic acid is stronger than ethanoic acid

A) a)

Cl has I effect, making release of protons easier. Also, it stabilises the carboxylate ion.
Monochloroacetic acid has one Cl atom. While dichloroacetic acid has two Cl atoms.
Hence it is a stronger acid.

b) Benzene ring is e- withdrawing, while CH3 group is e- donating. Hence, release of

protons is easier in benzoic acid than ethanoic acid. Also, the benzoate ion is much more
stable than ethanoate ion due to e- - withdrawing benzene ring.
4)
Describe Cannizaros reaction with example.
A)
Aldehydes without -H undergo self-oxidation and reduction (disproportionation) on
treatment with conc. Alkali. One molecule is reduced to alcohol while the other is oxidized to
salt of corresponding carboxylic acid

5)

Complete the equations

a)

A)
a)
03 MARKS

CH3CHO

LiAl H 4

CH3CH2OH

b) CH3COCH3

Conc . HCl

ZnHg

b) CH3CH2CH3

1)
Explain Aldol condensation with an example.
A)
Aldehydes or ketones having at least one -H undergo condensation to produce hydroxy aldehyde (aldol) in the presence of a dil. Base.
Eg.2CH3CHO

dil . NaOH

CH3CH(OH)CH2CHO

(H 2 O)

CH3CH=CH-CHO

3-Hydroxybutanal
Eg.
If two different molecules of aldehydes and/or ketones undergo aldol
condensation, the reaction is called CROSS ALDOL REACTION.
2)

Give reasons
a)
There are two NH2 groups in semicarbazide, but only one is involved in the
formation of semicarbazones:
b)
Cyclohexanone forms cyanohydrins in good yield, but 2,2,6Trimethylcyclohexanone doesn.t.

c)

Aldehydes are more reactive than ketones towards nucleophilic addition.

A)
a)
One of the NH2 groups is involved in resonance, hence it cannot act as a
nucleophile. Other one is free, it can act as a nucleophile.

b)

CN- can attack easily without any steric hindrance in cyclohexanone.

Lot of CH3 groups offer too much steric hindrance.

c) Aldehydes have one R group and ketones have two. Two R groups cause more steric
hindrance and greater +I effect reduces the electrophilicity of the carbonyl carbon.
3)

How will you convert:

a)
Propanone to propane
b)
Benzoyl chloride to benzaldehyde
c)
Ethanal to but-2-enal

A)
a)

b)

c)

4)

How will you bring about the following conversions?

a)
Benzene to Benzophenone
b)
Propyne to acetone
c)
p-nitrotoluene to p-nitrobenzaldehyde

Ans 4 a)

b)

c)

5)
An organic compound A contains 69.77% carbon, 11.63% hydrogen and rest oxygen. The
molecules mass of the compound is 86. It doesnt reduce Tollens reagent but forms an addition
compound with sodium hydrogen sulphite and gives positive iodoform test. On vigorous
oxidation, it gives ethanoic abd propanoic acids. What is the structure of compound A?
Ans

Element
C
H
O

%
Molar Mass
69.77
12
11.63
1
18.6
16

Moles
5.81
11.63
1.16

Simple ratio
5
10
1

Empirical formula C5H10O

Empirical formula mass = 5(12) + 10(1) + 1(16) = 86
86
n = 86
=1
Moecules formula C5H10O
Since it doesnt give Tollens test but gives positive iodoform test. It is a methyl ketone i.e it has
C CH3 group. Since on oxidation it gives ethanoic and propanoic acid, it must be pentan-2one.
CH3 CH2 CH2 CO CH3 CH3COOH + CH3 CH2 COOH
Pentan-2-one
05 MARKS
1)

a)

Draw the structures of:

Ans

i)
ii)

5-Chloro-3methyl-pentan-2-one
p-nitropropiophenone

b)
i)
ii)
iii)

Give simple chemical tests to distinguish between:

Ethanal and propanal
Phenol and benzoic acid
Benzaldehyde and acepopheone

a) i)

ii)

b)

2)

i) CH3 CHO gives a yellow ppt of iodoform with NaOH/I2 (positive iodoform test)
CH3CH2CHO doesnt answer this test.
ii) Phenol produces deep violet colour with aq-neutral FeCl 3 Soln., benzoic acid
doesnt answer the test.
iii) Acetophenone produces yellow ppt on heating with NaOH+I 2, benzaldehyde
doesnt.

Identify A,B,C,D and E in the following sequence:

A

Cl 2 CHC l 3 NaOH

C 6 H 5COCl

C 6 H 6/ AlCl 3

D+E

A) A CH4, B HCOONa, C C6H5COOOCH,

D

CHO E C6H5COOH

3)
An organic compound A (C3H2O) on treatment with Cu at 573 K gives B. B doesnt
reduce Fehlings solution. But gives a yellow ppt. of compound C with I 2/NaOH. Deduce the
structures of A, B and C.
A)
Since compound B gives iodoform test, it must be having CO-CH 3 group i.e it is a
ketone.
Since B is obtained by dehydrogenation of A, A is a 2o alcohol

A is R-CH CH3
|

OH
Comparing with the given molecules formula, R is CH3
A is CH3-CH-CH3
|
OH
Propan-2-ol
The reactions are:
O
Cu
Fehling ' s
CH3-CH-CH3 573 k > CH3-C-CH3
> no reactions
Soln .
OH
Acetone
(A)
(B)
CH3 COCH3 + 3I2 + 4NaOH CH3COONa + 3NaI+CHI3 + 3H2O
(C)
So, A = CH3CHCH3 Propan-2-ol
|
OH
B = CH3COCH3 Propan-2-one
C = CHI3 Iodoform
4)
a)
An organic compound A (C3H6O) is resistant to oxidation but forms a compound
B (C3H8O) on reduction. B reacts with H Br to form a bromide C which on treatment with
alcoholic KOH forms an alkene D (C3H6). Deduce the structures A,B,C and D.
b)
Carboxylic acids contain a carbonyl group, but do not show the nucleophilic
addition reaction like ketones or aldehydes. Why?

Ans

a)

CH3-CO-CH3

Acetone
A

LiAlH 4
reduction. > CH3-CH-CH3
OH
Propan-2-ol
B
H Br

CH3-CH=CH2 <
D
Propene

alc . KOH
.

CH3-CH-CH3

Br
2-Bromo propane
C

b)

This is due to resonance (for structures refer NCERT)

The carboxyl carbon of the resonance hybrid is less positive and hence less
electrophilic than carbonyl C of aldehydes and ketones

5)

a) Explain the following :

i) Cyanohydrin
ii) Acetal

iii) 2,4 DNP derivative

b) Complete the following:

KMnO 4
i)
CH2CH3
>
.
COOH

ii)

iii)
Ans

SOCl 2
>

COOH

C6H5CHO

H 2 NCONHNH 2
>

a) i) Formed addition of HCN to aldehydes or ketones

C O H CN

OH
CN

Cyanohydrin
ii) Formed on addition of two moles of alcohol to an aldehyde or ketone.
DryHC lg as

C = O + 2 R OH

OR
OR

C
Acetal

+ H2O

iii) Addition product of aldehydes or ketones with 2,4 Dinitro phenyl hydrazine in
weakly acidic medium.
NO2

NO2

C = O + H2N NH

b)

i)

NO2

C = NNH

NO2

ii)

iii) C6H5CH = NNHCONH2

Benzaldehyde semicarbazone