STUDY MATERIAL

QUESTIONS BASED ON HIGH ORDER

THINKING SKILL
1 MARK QUESTIONS
Q. 1. Name a liquefied metal which expands on solidification.
Ans. Gallium (Ga) is a silvery white metal, liquid at room temp. It expands by 3.1%
on solidifica-tion.
Q. 2. How many number of molecules per unit cell which crystallizes in the form
of end face centred (monoclinic) lattice with a molecule at each lattice.
Ans. 2.
Q. 3. What is the coordination number of carbon, in diamond ?
Ans. 4 and its unit cell has 8 atoms.
[The space lattice of diamond is FCC]
Q. 4. Name the solid which has weakest intermolecular force ?
Ans. Ice
Q. 5. Arrange the following types of interactions in correct order of their
increasing strength :
Covalent, hydrogen bonding, Vander Waals, dipole dipole
Ans. Vander Waals < dipole dipole < hydrogen bonding < covalent.
Q. 6. Give reason for the appearance of colour in alkali metal halides.
Ans. Due to F-centres.
Q. 7. Which type of defect occur in Ag Br ?
Ans. Schottky defect and Frekel defect.
Q. 8. Give one example of doping which produces p-type of semi-conductors.
1
UNIT:-1
( SOLID STATE )
Ans. Ge doped with Al.
Q. 9. Out of (a) Graphite and (b) Carborundum which one is harder ?
Ans. Carborundum.
Q. 10. How can a material be made amorphous ?
Ans. By melting the material and by cooling it rapidly.
2 MARKS QUESTIONS
Q. 1. Give Reason :
The energy required to vaporize one mol of copper is smaller than that of
energy required to vaporize 1 mol of diamond.
Ans. Copper is a metallic solid having metallic bonds while diamond is a covalent
solid having covalent bonds. Metallic bonds are weaker than covalent bonds
and thus less amount of energy is required to break metallic bonds than
covalent bonds.
Q. 2. The unit cube length for LiCl (NaCl) is 5.14 A. Assuming anion-anion
contact. Calculate the ionic radius for Chloride ion.
Ans.
Interionic distance of LiCl = 5.14 / 2 = 2.57 A
AC =
2 2
AB BC +
=
2 2
2.57 2.57 +
= 3.63
therefore, radius of Cl

= 3.63 = 1.81 A
Q. 3. Give reasons :
(a) Diamond and rhombic Sulphur are covalent solids, but the latter
has lower melting points.
(b) Among NaCl and CsCl, CsCl is quite stable.
Ans. (a) Due to weak Vander Waals Force in Sulphur molecule.
2
Cl

Li
+
A
B
C
(b) CsCl coordination number is 8. It is surrounded by 8 anion tightly.
Q. 4. How many unit cells are present in a cube shaped ideal crystal of NaCl of mass 1
gm ?
Ans. Mass of 1 unit cell = volume density
= a d
=
3
0 3
a M Z
N a

=
23
58.5 4
6.023 10

No. of unit cells in 1 gm = 1/M

= 6.023 10
23
/ 58.5 4
= 2.57 10
21
Q. 5. In the mineral spinal; having the formula MgAl
2
O
4
. The oxide ions are arranged
in CCP, Mg
2+
ions occupy the tetrahedral voids. While Al
3+
ions occupy the
octahedral voids.
(i) What percentage of tetrahedral voids is occupied by Mg
2+
ions ?
(ii) What percentage of octahedral voids is occupied by Al
3+
ions ?
Ans. According to the formula, MgAl
2
O
4
. If there are 4 oxide ions, there will be 1 Mg
2+
ions and 2 Al
3+
. But if the 4 O
2
ions are ccp in arrangement, there will be 4 octahedral
and 8 tetrahedral voids.
(i) Percentage of tetrahedral voids occupied by Mg
2+
= (1 / 8) 100
= 12.5%
(ii) Percentage of octahedral voids occupied by Al
3+
= (2 / 4) 100
= 50%
Q. 6. Give reasons :
(a) Window glass of old building look milky.
b) Window glass of old building is thick at bottom.
(c) CaCl
2
will introduce Schottky defect if added to AgCl crystal.
Ans. (a) Due to annealing over a number of years glass acquires some crystalline
character.
3
(b) Glass is not a true solid. But a super-cooled liquid of high viscosity. It has the
property to flow.
(c) 2 Ag
+
will be replaced by 1 Ca
2+
ions to maintain electrical neutrality. Thus a
hole is created and lattice site for every Ca
2+
ion introduced.
Q. 7. Analysis shows that nickel oxide has the formula NiO
.98
O
1.00
. What fractions of
nickel exist as Ni
2+
and Ni
3+
ions ?
Ans. NiO
.98
O
1.00
Let Ni
2+
be x and Ni
3+
be 0.98 x
Total charge on compd. is equal to zero.
[2 (Ni
2+
) + 3 (Ni
3+
) 2 (O
2
)] = 0
2 x + 3 (0.98 x) 2 = 0
x = 0.94
Therefore Ni
2+
% =
0.94
0.98
100 = 96%
Ni
3+
= 4%
Q. 8. What type of defect can arise when a solid is heated ? Which physical property is
affected by this and in what way ?
Ans. When a solid is heated vacancy defect arises. This is because on heating some atoms
or ions leacve the lattice site completely some lattice sites are vacant. As a result of
this defect the density of the substance decreases, because some atoms leave the
structure completely.
Q. 9. (a) What happens when a Ferromagnetic or Ferrimagnetic solid is heated ?
(b) The ions of MgO and NaF all have the same number of electrons and
intermolecular distance are about the same (235 & 215 pm). Why are the
melting points are so different (2642 C & 992 C ?
Ans. (a) It changes into paramagnetic at hight temperature due to randomization of
spins.
(b) The ions in MgO carry two unit charges. In NaCl only one unit charge. Hence
electrostatic forces of attraction in MgO are stronger.
Q. 10. (a) If the radius of the Br ion is 0.182 nm, how large a cation can fit in each of
the tetrahedral hole.
4
(b) AgI crystallizes in a cubic closed packed ZnS structure. What fraction of
tetrahedral site is occupied by Ag ion ?
(c) At what temp. range, most of the metals becomes super conductors ?
Ans. (a) For a tetrahedron the limiting ratio is 0.225 0.414
For largest cation highest value 0.414 would be considered.
r
+
/ r

= 0.414
r
+
= 0.414 0.182 = 0.075 nm.
(b) In FCC there are 8 tetrahedral voids. Out of this is occupied by Ag cation.
(c) 2 k 5 k.
Q1. Examine the illustration of a portion of the defective crystal given below and answer the
following questions:

(i) What are these type of vacancy defect called?

(ii) How is the density of a crystal affected by these defects?

(iii) Name one ionic compound which can show this type of defect in the crystalline state.

(iv) How is the stoichiometry of the compound affected? (2 marks)

Q2. Analysis shows that a metal oxide has the empirical formula M0.96O1.00. Calculate the
percentage of M
2+
and M
3+
ions in this crystal. (2 marks)

Q3. In an ionic compound the anion (N
-
) forms cubic close packing, while the cation (M
+
)
occupy one third of the tetrahedral voids.
5

Deduce the empirical formula of the compound and the coordination number of (M
+
) ions. (2
marks)
Q4. The radius of copper atom is 118 pm. If copper crystallizes in a face-centered cubic
lattice, what is the size of the unit cell? (2 marks)

Q5. Why are amorphous solids to be considered as supercooled liquids? (2 marks)
6
Q1. What is meant by the term Co-ordination no?
Ans:- No of atoms (sphere) by which the central atom is surrounded.
Q2. What is the co-ordination no of atoms:-
(a) In a cubic close packet structure -12
(b) In a body centred cubic structure:-8
Q3. A cubic solid is made of two elements P and Q. Atoms of Q are at the corner of the
cube and P at the body centre. What is the formula of the compound? What are the co-
ordination No. of P and Q.
Ans:-PQ
Q5. Analysis shows that nickel oxide has the formula Ni
0.98
as I
1.00
. What fraction of Ni
exit as Ni
2+
and Ni
3+
ions?
Ans:- Let the no of Ni
2+
ion = X
Ni
3+
ion = 0.98 X
As per the question
2 X + 3(0.98- X) = 2
2 X + 3 X 0.98 -3 X =2
2 X 3 X = 2 - 3 X 0.98=2-2.94
X = 0.94
X =94
So fraction of Ni
2+
= 94%
And Ni
3+
= 06%
Q4. What is difference between Frenkel and schottky defect? (any two)
Ans:-
Frenkel defect Schottky defect
(a) In this defect shifting of icon
from its position to interstitial site.
(a) In this defect there is missing of equal
no of cation and anion.
(b) Density remain same. (b)Density decreases.
Q5. Silver Crystallises in fcc lattice. If edge length of the cell is 4.077 X 10
-8
cmand
density is 10.5 g cm
-3
. Calculate the atomic mass of silver.
Ans:- density =10.5 gm/cm3, Z=4
We Know
gm
x x x x
M
x x x
xM
xa N
zxM
d
14 . 107
4
10 ) 077 . 4 ( 5 . 10 10 022 . 6
) 10 077 . 4 ( 10 022 . 6
4
24 3 23
3 8 23 3
0
=
=
= =

Hence atomic mass of silver=107.14 gm.

Q6. Classify each of the following as being either a p-type or an n-type Semiconductor.
(a) Ge dopped with In----p-type.
(b) B dopped with Si----n-type.
Q7. Zinc oxide is white but it turns yellow on heating. Explain?
Ans:- When Zinc oxide is heated it loses oxygen.
ZnO-------- Zn
2+
+ 1/2 O
2
+ 2e
-
Zn
2+
adopt the interstitial void and electron in the neighbouring voids. Due to
presence of electron in void, the colour is yellow.
7
Q8. If NaCl is doped with 10-3 mole % SrCl2.What is the concentration of cation
vacancies?
Ans:- Since 100 mole of NaCl are doped with 10
-3
mol of SrCl
2
1 mole of NaCl are doped with =10
-3
/100 mol=10
-5
mol
As Sr
2+
ion introduced one cation vacancy
Conc. Of cation Vacancy=10-
5
X 6.022X10
23
mol
-1
=6.022X10
18
mol
-1
Q9. What type of defect arise when a solid is heated? Which physical property is affected
by it and what way ?
Ans:- Vacancy defect is created, it is because on heating some atoms leaved the lattice site
completely also the density decreases.
Q10. What is the affect of pressure on NaCl type crystals ?
Ans:- The coordination No. of NaCl increases from 6 to 8 .
Q11. Al crystallizes in a CCP structure. Its metallic radius is 125 pm.
(i) What is the length of side of the unit cell?
(ii) How many unit cells are there in 1cm
3
of Al?
Ans:- (i) In CCP a = 2 2 r
=2 X 4.14 X 125 pm = 354 pm

(ii) Volume of 1 unit cell = (3.54X10
-10
)
3
= 4.44 X 10
-23
cm
3
unit cell in 1cm
3
=
22
23
10 25 . 2
10 44 . 4
1
X
x
=

Q12. What happens when ferrimagnetic Fe

3
O
4
is heated to 850 K and why?
Ans:- Fe
3
O
4
on heating to 850 K becomes paramagnetic. This is due to greater alignment
of domains in one direction on heating.
FOR BELOW AVERAGE
01 Mark Question
1. What is the number of atoms per unit cell in a
i) Simple cube/primitive cube.
ii) Body centered cube.
iii) Face centered cube.
2. Name the element with which silicon can be doped to give a (i) p-type semi conductor
(ii) n-type semi conductor
3. A cube solid is made of two elements P and Q. Atoms of Q are at the corner of the
cube and P at the body centre. What is the formula of the compound? What are the co-
ordination number of P and Q.
8
4. What makes the crystal of KCl appear some time violet?
5. What is the effect of Schottky and Frenkel defects on the density of crystalline solid?
6. Name a substance which on addition to AgCl causes cation vacancy in it.
7. What happens when ferromagnetic Fe3O4 is heated at 850 K and why?
8. What is curie temperature?
9. What is ferromagnetism different from paramagnetism?
10. What structural changes will occur if NaCl crystal is subjected to high pressure?
FOR AVERAGE
1. An element (at. Mass=60) having fcc structure has a density of 6.23 g cm
-3
. What is
the edge length of the unit cell? (Avg. const. N = 6.02 x 10
23
mol
-1
)
2. The density of CsBr, which has a BCC structure, is 4.4 g cm
-3
. The edge length of the
unit cell is 400 pm. Calculate the interionic distance in crystal of CsBr (NA= 6.023 x
10
23
, At. Mass of Cs= 133, Br= 80)
3. The composition of a sample wustite is Fe0.93 O1.00, what percentage of the iron is
present in the form of Fe(III)?
4. NaCl crystallizes in FCC structure. Its density is 2.165 gm cm
-3
. If the distance
between Na
+
and its nearest Cl
-
is 281 pm. Find out the Avog. No. (Na=23 g mol
-1,
Cl
= 35.5 g mol
-1
)
5. The compound CuCl has ZnS structure and the edge length of its unit cell is 500 pm.
Calculate the density. (At. Mass, Cu=63, Cl=35.5, NA=6.02 x 10
23
)
FOR BELOW AVERAGE
02 or 03 Marks Questions
1. Calculate the efficiency of packing in a case of metal crystals for simple cube or body
centered cube or face centered cube (with the assumption that atoms are touching
each other)
2. How can you determine the atomic mass of an unknown metal if you know its
density and the dimension of its unit cell? Explain.
3. If the radius of the octahedral void is r and radius of the atoms in close packing is R.
derive relationship between r and R.
4. Explain the following with suitable examples:
(a) Ferromagnetism (b) Paramagnetism (c) Ferrimagnetism
9
(d) Anti ferromagnetism (e) 12-16 groups (f) 13-15 groups
(g) Schottky defect (h) Frenkel defect (i) F-centre
(j) Doping (k) n-type semiconductor (l) p-type semiconductor
(m) Conductor/ Insulator/ Semiconductors.
NUMERICAL PROBLEMS
1. If NaCl is doped with 10
-3
mol%. What is the concentration of cation vacancies?
2. Aluminum crystallizes in a cubic close packed structure. Its metallic radius is 125pm.
(a) what is the edge length of unit cell? (b) How many unit cells are there in 1.00 cm
3
of aluminum?
3. Silver forms ccp lattice and x-ray studies of its crystal show that edge length of its
unit cell is 408.6pm. Calculate the density of silver (Atomic mass = 107.9 u)
4. Niobium crystallizes in body centre cubic structure. If density is 8.55 gm/cc.
Calculate atomic radius of niobium using its atomic mass 93.
5. Silver crystallizes in face lattice. If edge length of the cell in 4.07 x 10-8 cm and
density is 10.5 gm/cc. Calculate the atomic mass of silver.
6. Gold (atomic radius = 0.144 nm) crystallizes in a fcc unit cell. What is the length of a
side of the cell?
7. An element (Atomic mass = 60) having fcc structure has a cell edge of 400 pm. What
is its density? NA = 6.023 x 10
23
.
FOR ABOVE AVERAGE
1. Analysis shows that nikel oxide has the formula Ni.98O1.00. What fraction of nickel
exists as Ni
+2
and Ni
+3
ions?
2. An element (atomic mass = 60) having face centred cubic unit cell has a density of
6.23 gm/cc. what is edge length of unit cell?
3. Metallic gold crystallizes in a fcc structure and has a density of 19.3 gm/cc. Calculate
the radius of gold atom. [atomic mass of Au=197, NA= 6.023 x 10
23
]
4. Unit cell of an element (Atomic mass = 108 and density 10.5 gm/cc) has an edge
length 409 pm. Deduce the type of crystal lattice.
5. An element has a body centred cubic structure with a cell edge of 288 pm. The
density of the element in 7.2 gm/cc. How many atoms are present in 208 gm of the
elements?
10
STUDY MATERIAL
1. Solution : Homogeneous mixture of two or more pure substances.
2. Types of solutions :
a) Solid in solid solution. Eg: Bronze, Brass.
b) Liquid in solid solution. Eg: Zinc-amalgam.
c) Gas in solid solution. Eg: Solution of hydrogen in palladium.
d) Solid in liquid solution. Eg: Aqueous Sodium Chloride sol.
e) Liquid in liquid solution. Eg: Ethanol dissolved in water.
f) Gas in liquid solution. Eg: Carbondioxide dissolved in water, ammonia dissolved in
water.
g) Solid in gas solution. Eg: Iodine vapour in nitrogen .
h) Liquid in gas solution. Eg: Water vapoursin air, Chloroform vapour in nitrogen.
i) Gas in gas solution. Eg: Water gas, Producer gas.
3. Concentrations of solution :
a) Mole fraction ( X):
X
solvent
= n
solvent
/n
solvent
+ n
solute
X
solute
= n
solute
/n
solvent
+ n
solute
b) Normality (N) :
N = W
B
/E
B
x 1000/V
c) Molarity (M) :
M = W
B
/M
B
x 1000/V
d) Molality (m) :
m = W
B
/M
B
x 1000/W
A
W
B
= Mass of solute in gram.
W
A
= Mass of solvent in gram.
M
B
= Molar mass of solute.
V = Volume of the solution.
E
B
= Equivalent weight of the solution.
4. Henerys Law : Mass of gas dissolved per unit volume of the solvent is directly
proportional to the pressure of the gas in equilibrium with the solution.
Limitations : Not applicable when pressure is very high.
11
UNIT:-2
SOLUTION
Not applicable when the temperature is too low.
Not applicable when the gas is highly soluble.
Not applicable when the gas react chemically with solvent and dissociate and associate in
the solvent.
5. Colligative Properties : Properties of solution which depends upon the number of
solute particles dissolved in it. Eg: R.L.V.P, Osmotic pressure, Elevation of boiling
point.
6. Vapour Pressure : Pressure exerted by vapours in equilibrium with its liquids at a
given temperature.
7. Lowering of vapour Pressure :
P = P
A
0
P (P
A
0
= v.p of pure solvent, p = v.p of sol.)
8. Relative lowering of vapour pressure : Ratio of lowering of vapour pressure of pure
solvent.
R.L.V.P = (P
A
0
P)/ P
A
0

9. Raults Law :
a) Partial pressures of components in the
solutions are directly proportional to their mole fractions.
b) R.L.V.P. of solution containing non volatile solute is equal to mole fraction of the
solute.
10. Limitations of Raults Law;
a) Applicable only to dilute solution.
b) Applicable only to homogeneous solution.
c) Applicable to the solution in which solute doesnot undergo association or dissociation.
11. Boiling Point : Temperature at which vapour pressure of the liquid is equal to
atmos[heric pressure.
12. Elevation of boiling Point :
T
b
= T
0
T = k
b
x m.
Here T
0
and T are Boiling points of pure solvent and solution.
m = molality , k
b
= Ebullioscopic constant.
1. Freezing points : Temperature at which liquids and its solid phase have same vapour
pressure.
2. Depression of freezing point :
T
f
= T - T
0
= k
f
x m.
Here T
0
and T are freezing points of pure solvent and solution
m = molality , k
f
= Cryoscopic constant.
3. Osmotic pressure : External pressure applied to the solution to just prevent osmosis.
4. Osmosis : Spontaneous flow of solvent molecule from lower concentrated solution
to higher concentrated solution through semi permeable membrane.
5. Reverse Osmosis : When the applied pressure is greater than osmosis pressure, the
reverse osmosis take place. (used in desalination plants to meet potable water)
6. Isotonic solution : The solutions having same osmotic pressure.
7. Azeotropic mixture : Binary mixture of liquids having same composition in liquid
and vapour phase and boils at the constant temperature.
12
a) Maximum Boiling Azeotropes : Azeotropes boils at the temperature higher than the
boiling point of its components. Eg: Mixture of HNO
3
(68 %) and water (32%)
b) Minimum Boiling Azeotropes : Azeotropes boils at the temperature lower than the
boiling point of its components. Eg: Mixture of Ethanol (95%) and water .
8. Ideal Solutions: Solutions obeying Raults Law and solvent solute molecular
forces are same as that of solvent solvent and solute solute molecular forces.
Eg: Solution of N- Hexane and N- Heptane, Solution of Benzene and Toluene etc.
9. Positive Deviation from Raults Law : Solutions having solvent solute molecular
forces are weaker than that of solvent solvent of solute solute molecular forces .
H
mix
= + ve, V
mix
= +ve and P > P
A
+ P
B .
Eg: solution of ethanol and acetone, solution of carbondisulphide and acetone.
10. Negative Deviation from Raults Law : Solutions having solvent solute molecular
forces are stronger than that of solvent solvent or solute solute molecular forces.
H
mix
= - ve, V
mix
= - ve and P < P
A
+ P
B
11. Abnormal molecular mass : Molecular mass calculated by measurement of
colligative properties differ from normal value due to association or dissociation of
solutes in solution.
Modified equation for colligative properties are
a) P/ P
A
0
= i X
B

b) T
b
= i k
b
x m.
c) T
f
= i k
f
x m.
d) = i C R T.
12. Vanthoff factor :
i = M
normal
/ M
observed

ratio of observed value of colligative properties and normal value of colligative properties
is called vanthoff factor.
13. Degree of dissociation () = (i -1) / (n-1).
n = no. of particles formed from dissociation of 1 molecule.
i = vant hoff factor.
14. Degree of association () = (i -1) / (1/n-1).
n = no. of simple molecule to form an associated molecule.
15. a) i >1 (solute undergoes dissociation).
b) i <1 (solute undergoes association).
c) i =1 (solute undergoes neither dissociation nor association).
13
Important Questions:
1. Define the Mole Fraction of a substances in a solution. What is sum of mole
fraction of all components in a three component system?
2. How is the molality of a solution different from its molarity?
3. Calculate the density of H
2
SO
4
solution if molality and molarity are 94.5 and 11.5
respectively.
4. How many ml of 0.1 (M) HCl required to react completely with a 1 gm mixture of
sodium carbonate and sodium bicarbonate containing equimolar amount of both.
5. State Henerys Law for a solubility of a gas in a liquid. Give its applications
(three) and limitations?
6. Explain the significance of Henerys Law constant K
H
. At the same temperature
hydrogen is more soluble in water than Helium. Which of them will have a higher
value of K
H
and Why?
7. What concentration of nitrogen should be present in a glass of water at room
temperature? Assume a temperature of 25
0
celcius. A total pressure of 1 atm and
mole fraction of nitrogen in air is 0,78 (K
H
for nitrogen is 8.42 x 10
-7
M/mm Hg).
8. Henerys Law constant for CO
2
in water is 1.67 x 10
8
Pa at 298 K. calculate the
quantity of CO
2
in 500 ml of soda water when packed under 2.5 atm CO
2
pressure
at 298 K.
9. Mention some limitations of Raults Law.
10. Urea form ideal solution of water. Determine the vapour pressure an aqueous
solution containing 10 % by mass of urea at 40
0
C. (V.P of water at 40
0
C = 55.3
mm Hg.).
11. Derive the equation to express the relative lowering of vapour pressure for a
solution is equal to its mole fraction of the solute in it when the solvent alone is
volatile.
12. Two liquids X and Y boil at 110
0
C and 130
0
C, which one of them has higher
vapour pressure at 50
0
C.
13. Benzene and Toluene forms ideal solution over entire range of composition. The
vapour pressure of pure Benzene and Toluene at 300 K are 50.71 mm Hg and
32.06 mm Hg respectively. Calculate the mole fraction of Benzene in vapour
phase if 80 gm of Benzene is mixed with 100 gm Toluene.
14. An aquous solution of 2 % non volatile solute exerts a pressure of 1.004 bar at
normal boiling point of solvent. What will be the molar mass of solute. (V.P of
pure water = 1.013 bar).
14
15. A person suffering from high blood pressure is advised to take minimum quantity
of salt.
16. Write the name of two inorganic substance (compounds) which can be used as
semipermiable membrane.
17. 100 mg protein is dissolved in enough water to make 10 ml of solution if this
solution has an osmotic pressure of 33.3 mm Hg at 25
0
C . what is the molar mass
of protein. ( R = 0.0821 L atm mol
-1
K
-1
and 760 mmHg = 1 atm).
18. State condition resulting in reverse osmosis. Give one of its application.
19. Define the following with a suitable example :
a) Maximum and minimum boiling azeotropes.
b) Desalination
c) Ideal solution
d) Abnormal molecular mass
20. a) Define Vanthoff factor.
b) What is the Vanthoff factor for a compound which
undergoes tetramerisation in an organic solvent.
c) What would be the value of Vanthoff factor for
1) dilute solution of K
2
SO
4
in water
2) Na
2
SO
4
.10H
2
O in water
3) Ethanoic acid in Benzene
d) When is the value of Vanthoff factor
1) more than one
2) less than one
3) equal to one
Hints:
3. m = 1000 M / (1000d MM
B
) ,
M=molarity, M
B
= molar mass of solute, d= density of sol.
d = 1.24 gm/cm
3
4. 157.8 ml
7. Partial pressure of nitrogen in atmosphere (P
N2
) = P
total
x X
N2
P
N2
= 592.8 mm Hg
Solubility of N
2
= K
H
x P
N2
= 4.99 x 10
-4
(M)
8. K
H
= 1.67 x 10
8
Pa , P
CO2
= 2.5 atm = 2.5 x 1.01325 x 10
-5
Pa
P
CO2
= K
H
x X
CO2
, X
CO2
= 1.517 x 10
-3

n
CO2
/(n
CO2
+ n
H2O
) = 1.517 x 10
-3

n
CO2
= 42.14 x 10
-3
mole.
15
10. From Raults Law : (P
A
0
P)/P
A
0
= X
B
= n
B
/n
A
P = 53.46 mm Hg.
12. X has higher vapour pressure than Y.
13. n
benzene
= 80/78 = 1.026 moles
n
toluene
= 100/92 = 1.087 moles
X
benzene
= 0.486 , X
toluene
= 0.514
From Raults Law : P
Ben
= P
Ben
0
x X
Ben
= 24.65 mm Hg
P
Tol
= P
Tol
0
x X
Tol
= 16.48 mm Hg
Mole fraction of Benzene in vapour phase =
P
Ben
/P
Ben
+ P
Tol
= 0.60.
14. (P
A
0
P)/P
A
0
= X
B
= n
B
/n
A
M
B
= 41.34 gm mol
-1
16. Calcium phosphate , Copper Ferrocyanide
17. = C x R x T
= W
B
x R x T/M
B
V
M
B
= 13980.45 gm Mol
-1
18. External pressure greater than osmotic pressure
Desalination plant .
20. a) Ratio of observed value of colligative properties to the
normal value of colligative properties is called Vanthoff factor.
b) i =
c) 1) 3,
2) 3,
3)
d) 1) solute undergoes dissociation in the solution
2) solute undergoes association in the solution
3) solute undergoes neither dissociation nor association
1 MARK QUESTIONS
Q. 1.The vapour pressure of deliquescent substance is less or more than that of water
vapours in air ?
Ans. Less than that of water vapours in air.
Q. 2. If is the degree of dissociation of Na
2
SO
4
then write the Vant Hoff factor used
for calculating the molecular mass.
Ans. = i 1 / m 1, => (m 1) = i 1, => 1 + (m 1) = i, => i = 1 + (3 1),
=> i = 1 + 2 .
Q. 3. If 6.023 10
20
molecules of urea are present in 10 ml of its soln. then what is the
conc. of urea soln.?
Ans. N
0
= 6.023 10
23
= 1 mol
6.023 10
20
molecules = 0.001 mol in 10 ml
M =
N 1000
v

=
.001 1000
10 1000

= 0.01 M.
Q. 4.Why camphor is used in molecular mass determination ?
Ans. Because it has very high cryoscopic constant.
It has large depression in m. p. when an organic solute is dissolved in it.
Q. 5.0.004 M soln of Na
2
SO
4
is isotonic with 0.01 M soln of glucose at the temp. What is
the apparent degree of dissociation of Na
2
SO
4
?
16
Ans. 75%
Q. 6.What happen when mango is placed in dilute aqueous soln. of HCl?
Ans. When mango is placed in dilute aqueous soln. of HCl it swells.
Q. 7. Out of (a) 200 ml of 2 M NaCl Soln. and (b) 200 ml of 1 M glucose Soln. which one
has higher osmotic pressure?
Ans.: (a) 200 ml of 2 M NaCl Soln.
NaCl is an electrolyte which dissolve to give ions. Glucose and urea are non electrolytes.
Thus glucose has minimum conc. and hence minimum osmotic pressure.
Q. 8.Out of (a) 0.01 M KNO
3
, (b) 0.01 M Na
2
SO
4
which aqueous soln. will exhibit high
B. P.?
Ans. (a) 0.01 M Na
2
SO
4
Q. 9.Out of (a) 1 M CaCl
2
(b) 1 M AlCl
3
which aqueous soln. will show max. vapour
pressure at 300 K ?
Ans. (a) 1 M CaCl
3
, if we assume 100% dissociation, i for CaCl
2
= 3 and AlCl
3
= 4 and
relative lowering of V. P. is directly proportional to i.
Q. 10. Out of (a) HNO
3
+ H
2
O and (b) C
6
H
6
+ C
6
H
5
CH
3
which will form max. boiling
azeotrope ?
Ans. (a) HNO
3
+ H
2
O.
2 MARKS QUESTIONS
Q. 1.Two solns of a substance (non-electrolyte) are mixed in the following manner 480
ml of 1.5 M (First Soln) + 520 ml of 1.2 M (Second Soln). What is the molarity of the
final mixture ?
Ans. Total molarity =
1 1 2 2
1 2
MV M V
V V
+
+
=
1.5 480 1.2 520
480 520
+
+
= 1.344 M
Q. 2.To get the hard boiled eggs, why common salt is added to water before boiling the
eggs?
Ans. Due to addition of common salt the B. P. of the salt containing water elevated, hence
the egg at high temperature becomes hard.
Q. 3.Equimolar Soln. of NaCl and BaCl
2
are prepared in H
2
O. D. F. pt. of NaCl is
found to be 2 C. What freezing point do you expect from BaCl
2
soln ?
Ans. i for NaCl = 2 i for BaCl
2
= 3
Therefore T `
F
(BaCl
2
) =
3 2
3
2

=
,
T `
F
for BaCl
2
= 3 C ,
Freezing Point of BaCl
2
Solution is T
F
= 3 C.
Q. 4.Why water cannot be separated completely from ethyl alcohol by fractional
distillation?
Ans. Ethyl alcohol and water (95.4% ethyl alcohol and 4.6% water) form constant boiling
mixture (azeotrope) boiling at 351.1 K. Hence, further water cannot be separated completely
from ethyl alcohol by fractional distillation.
Q. 5.Why a person suffering from high blood pressure is advised to take minimum
quantity of common salt ?
Ans. Osmotic pressure is directly proportional to the conc. of solutes. Our body fluid contains
a number of solutes. On taking large amount of salts, ions enter the body fluid there by
17
raising the conc. of the solutes. As a result osmotic pressure increases which may rapture the
blood cells.
Q. 6.Chloro acetic acid is a monoprotic acid and has K
a
= 1.36 10
3
. Calculate b. p. of
0.01 M aqueous solution? (K
b
= 0.51 k kg/mol)
Q. 7.Which colligative property is preferred for the molar mass determination of macro
molecules ? Why ?
Ans. Osmotic pressure is preferred over all other colligative properties because :
(a) even in dil. soln the o. p.values are appreciably high and can be measured accurately.
(b) o. p.can be measured at room temp. on the other hand elevation in B. P. is measured
at high temp. where the solute may decompose. The depression in freezing point is measured
at low temp.
Q. 8. How much ethyl alcohol must be added to 1 litre of water so that the solution will
freeze at 14 F ?
(K
f
for water = 1.86 C/mol)
Ans. (14 32) / 9 = C / 5
C = 5 ( 18) / 9
= 10 C
T `
F
=
F b
a b
K 1000 W
W M

W
b
= mass of solute
M
b
= molar mass of solute
W
a
= mass of solvent
10 =
b
1.86 1000 W
1000 46

W
b
= 247.31 g
Q. 9. 75.2 g of phenol is dissolved in solvent of K
F
= 14, if the depression in freezing
point is 7 k. What is the % of phenol ?
Ans. K
b
= 0.51 k kg/mol
= K
a
/ C
= 1.36 10
3
/ 0.01
= 0.3687
i = 1 +
= 1 + 0.3687 = 1.3687
T `
b
= i K
b
m
= 1.36 10
2
.51
= 0.0069 C
Ans. K
F
= 14
M
b
=
F 2
1 F
1000 K W
W T


Taking the solvent as 1 kg
M
b
=
1000 14 75.2
1000 7k

= 150.4 g per mol

phenol (molar mass) 94 g/mol
i =
Calculated molar mass
Observed molar mass
= 94 / 150.4 = 0.625
2 C
6
H
5
OH (C `
6
H
5
OH)
2
1 0
1 / 2
Total = 1 + / 2
= 1 / 2
i = 1 + / 2
= 1 / 2 = 0.625
/ 2 = 0.375
= 0.75
% of association = 75%
18
Q. 10. How many ml of 0.1 M HCl are required to react completely with 1 gm mixture
of Na
2
CO
3
& NaHCO
3
containing equimolar amounts of both ?
Ans.
Q.11 Given below is the sketch of a plant for carrying out a process.
Ans. (i) The process is called Reverse Osmosis. [Reverse Osmosis: If the pressure applied
on solution side exceeds the osmotic pressure then the osmosis can be reversed (i.e. pure
solvent can be forced out of the solution to pass through the pores of membrane in opposite
direction). This is called Reverse osmosis].
(ii) The solvent moves from sea water container to fresh water container.
(iii) Cellophane (It is one of the semi-permeable membranes that can be used)
(iv) This process is used for desalination of sea water.
Q.12 On increasing the temperature the solubility of most of the gases in water
decreases. An important consequence of this effect is the thermal pollution of water, such
as occurs around power plants cooled by a river or stream. How is the survival of fish
affected by thermal pollution of water?
Ans.: When the water temperature of the river or stream is increases the solubility of oxygen
in water decreases. Due to this decrease in dissolved oxygen the survival of fish becomes
difficult.
Q.13 How much NaOH is required to preapre 50 ml of aqueous solution with 70mg of
Na+ ions per ml. of the solution?
Ans. : Na+ ions in 1 ml = 70 mg
Na+ ions in 50 ml = 70 50 = 3.5g
Let the amount of Na
2
CO
3
be x
Let the amount of NaHCO
3
be 1 x
Since no. of moles of both are equal
2 3 3
x 1 x
N(Na CO ) M(NaHCO )

=
x 1 x
106 84

=
84 x = 106 106 x
x = 0.5578
xNa
2
CO
3
= 0.5578 / 106
= 0.00526
xNaHCO
3
= 0.00526
Na
2
CO
3
+ 2 HCl 2 NaCl + CO
2
+ H
2
NaHCO
3
+ HCl NaCl + CO
2
+
H
2
O
M
1
V
1
= 2 M
2
V
2
+ M
3
V
3
0.1 V
1
= 2 0.00526 + 0.00526
V
1
=
0.01578
0.1
= 0.1578 L
V = 157.8 ml.
(i) Name the process occurring in the
above plant
(ii) To which container does the net flow
of solvent take place
(iii) Name one SPM which can be used
in this plant
(iv) Give one practical use of the plant
19
Q.4 Volatile hydrocarbons are not used in the brakes of automobile as lubricants, but
non-volatile hydrocarbons are used as lubricants.
Ans.: The vapour pressure of volatile hydrocarbons is very high and they get evaporated
leaving behind the system. Due to this they are not used as lubricants in automobiles. Non-
volatile hydrocarbons having low vapour pressure are used as lubricants.
Q.5 When fruits and vegetables that have dried are placed in water, they slowly swell
and return to the original form. Explain why ? Would a temperature increase accelerate
the process ? Explain.
Ans.: The cell walls of the fruits and vegetables have semi-permeable membrane. When they
have dried, concentration inside is higher. On placing in water, water enters into the cells, i.e.,
osmosis takes place. Hence, they swell and return to the original form. The process will be
accelerated with increase of temperature because osmosis becomes faster with increase of
temperature.
Q1. Define osmotic pressure.
Ans:- The extra pressure that must be applied to the solution side to prevent the flow of
solvent molecules into solution through a semi permeable membrane is called
osmotic pressure.
Q2. State Raoults Law for a binary solution containing volatile components.
Ans:- At a particular temperature the partial vapour pressure of each component of a
solution containing volatile liquid is directly propositional to its mole fraction.
Q3. Define Vant Hoff factor.
Ans:-It is the ratio of experimental value of a colligative property to the theoretical value.
Q4. What do you understand by colligative properties?
Ans:- Properties of solutions which depend on the number of solute and solvent particles
but not on the nature of solute are called colligative properties.
Q5. State any two characteristics of ideal solution.
Ans:- Characteristics of an Ideal solution .
(i)
0 = H
mix
(ii)
B B B A
A
A
p p P p
0 0
, = =
Q6. Mention a large scale use of the phenomenon called reverse osmosis
Ans:- In desalination of sea water.
Q7. When is the value of Vant Hoff factor less than 1?
Ans:- Value of Vant Hoff factor is less than 1 in case of association of solute in solution.
Q8. When is the value of Vant Hoff factor more than 1?
Ans:- Value of vant Hoff factor is more than 1 in case of dissociation of solute in solution.
Q9. Why does molality of a solution remain unchanged with change in temperature while
its molarity changes?
20
Ans:- Molality of a solution depends on the mass of solvent and man does not vary with
change in temp. where as molarity depends on volume of solution and volume
change with change in temp.
Q10. What are azotropes?
Ans:- A liquide mixture which distills over without changes in composition is called
ozeotropes or ozeotropic mixture.
Q11. What are maximum boiling azeotropes? Give one example?
Ans:- A mixture which boils at temp. brighter than the boiling point of its components the
mixture is known as maximum boiling azeotropes. Eg- a mixture of HCl and H
2
O
containing 20.2% of HCl by weight.
Q12. What are minimum boiling azeotropes? Give one example?
Ans:- A mixture which boils at temp. lower than boiling point of its components the
mixture is known as minimum boiling azeotropes. E.g water and Benzene.
Q13. What is expected value of i for K
4
[Fe(CN)
6
] in dilute solution?
Ans:- Expected value of n in K4(Fe(CN)6) is 5.
Q14. What are isotonic solutions?
Ans:- Those solutions are said to be isotonic which have the same osmotic pressure.
Q15. Define molal elevation constant or ebullioscopic constant.
Ans:- It is equal to the elevation in boiling point of1 molar soln. i.e one mole of a solute
dissolved in 1 kg of the solvent.
Q16. What are non-ideal solutions? Explain as to why non-ideal solutions deviate from
Raoults Law.
Ans:- Non ideal solution are those which do not obey Raoults law.
When the molecular interaction between solute molecules solvent. Solvent molecules
is not same as the molecular interaction between solute & solvent molecules then
deviotion occurs.
Q17. What are colligative properties? Mention them.
Ans:-these are the colligative properties.
(a) Osmotic pressure (b) Relative lowering of vapour pressure
(b) Elevation in B.P (d) Depression in F.P
NUMERICALS
Q1. Calculate the mole fraction of ethylene glycol (C
2
H
6
O
2
) in solution containing 20 %
of ethylene glycol by mass.
Ans:-
Mole fraction of ethylene glycol =
2 6 2
. . . . . . .
. . . . .
O H ofC moles of No water of moles of No
glycol thelene of mole of no
+

21
i.e
0676 . 0
133
9
5320 62
18 62 20
18 / 80 62 / 20
62 / 20
/
= = =
+
= + =
X
X X
n n n
glycol water glycol glycol

So
9323 . 0 0676 . 0 1 1
2
= = =
glycol O H

Q2. An aqueous solution of glucose made by dissolving 10 g of glucose (C
6
H
12
O
6
) in 90 g
of water at 303 K. if vapor pressure of pure water at 303 K be 32.8 mmHg. What
would be the vapor pressure of solution
Ans:-
Hence w
B
= 10 g, M
B
=180, W
A
=90 g, M
A
=18
P
0
A
=32.8 mmHg.
P
S
=?
mmHg P P
P
P
P
p
P
P P
P
P P
A
S
A
S
A
S
A
S
A
B
A
S
A
43 . 32
90
89
8 . 32
90
89
90
1
1
90 / 1 1
18 / 90
180
0
0
0
0 0
0
0
0
= = = =
= = =

= =

Q3. A solution 3.8 g of sulphur in 100 g of CS2 (Boiling point=46.3

0
C) boils at 46.66
0
c.
what is the formula of sulphur molecules in the solution .(Atomic mass of sulphur is
32 g mol
-1
and K
b
= 2.4 K kg mol
-1
)
Ans:-
We have :-
A b
B B
B
W T
K W
M


=
1000
Here
3 . 253
3
760
100 36 . 0
4 . 2 1000 8 . 3
36 . 0 ) 3 . 46 273 ( ) 66 . 46 273 (
= =

=
= + + =
B
b
M
K T
No of atoms of sulphur S=Molecualar wt./Atomic Wt. = 253.33/32 8
Hence the formula of sulphur = S
8
Q4. Calculate the osmotic pressure of a solution obtained by mixing 100 cm
3
of 0.25 M
Solution of urea and 100 cm
3
of 0.1M soln of cane sugar at 293 K (R=0.082 L atm
22
mol
-1
K
-1
)
Ans:-
We know nRT V =
Or
atm 022 . 21
2 . 0 2
293 0821 . 0 35 . 0
293 0821 . 0 )
2
1 . 0 25 . 0
( 2 . 0
=

=

+
=
Q5. 2 g of benzoic acid (C
6
H
5
COOH) dissolved in 25 g of benzene shows a depression in
freezing point equal to 1.62 K. Molal depression constant for benzene is 4.9 K kg mol
-
1
. what is the percentage association of acid if it forms dimmer in soln.?
Ans:-
Given that
W
B
=2g , K
f
=4.9 KKgmol
-1
, W
A
=25 g,
K T
f
62 . 1 =
We have
1
98 . 241
25 62 . 1
9 . 4 1000 2
1000

=

=


= gmol
W T
K W
M
A f
f B
B
Also 2C
6
H
5
COOH (C
6
H
5
COOH)
2
Initially 1 0
( 1-x) x/2 mole
Total no. of particles at equilibrium. =
2
1
2
) 1 (
x x
x = +
2
1
x
i =
Now i=(Normal molecular mass/Abnormal molecular mass)
=122/241.98
Thus 122/241.98=1- x/2
Or x/2 =1- (122/241.98) =0.4958
So x = 0.9916
The degree of association of benzoic acid in benzene is 99.16 %
***************
FOR BELOW AVERAGE
01 Mark questions
23
1. State Henrys law.
2. Define osmotic pressure.
3. How pressure effect the solubility of a solid in a liquid.
4. State Raoults Law for a binary solution containing volatile components.
5. Define Henrys law about solubility of a gas in a liquid.
6. Define Vant Hoff factor.
7. What do you understand by colligative properties?
8. Define an ideal solution.
9. State any two characteristics of ideal solution.
10. Distinguish between molarity and molality.
11. What is a non- ideal solution?
12. Mention a large scale use of the phenomenon called reverse osmosis.
13. What is antifreeze? Give one example.
14. When is the value of Vant Hoff factor less than 1?
15. Name the two factors on which the vapour pressure of the liquids depend.
16. Define mole fraction of a substance in a solution
17. When is the value of Vant Hoff factor more than 1?
FOR AVERAGE
1. Why is the elevation in b.p. of water different in the following solutions? (i) 0.1 M
NaCl solution (ii) 0.1 M Sugar solution.
2. What are azotropes?
3. What happens when blood cells are placed in pure water?
4. Why is the cooking temperature in pressure cooker higher than in open pan?
5. Why does molality of a solution remain unchanged with change in temperature while
its molarity changes?
6. Why is ether not miscible in water?
7. What are maximum boiling azeotropes? Give one example?
8. What are minimum boiling azeotropes? Give one example?
9. Why do doctors advice gargles by saline water in case of sore throat?
10. Why is boiling point elevated when a non volatile solute is added?
11. A person suffering from high blood pressure should take less common salt, why?
12. Why do gases always tend to be less soluble in liquids as the temperature is raised?
FOR ABOVE AVERAGE
1. How mole fraction of a solute and molality are related?
24
2. Two liquids A and B boil at 145C and 190C respectively. Which of them has a
higher V.P. at 80C?
3. What is expected value of i for K
4
[Fe(CN)
6
] in dilute solution?
4. How molarity and molality of solute are related.
5. What possible value of i will it have if solute molecules undergo association in
solution.
6. Define molal elevation constant or ebullioscopic constant?
7. Define molal depression constant or cryoscopic constant?
8. Why is osmotic pressure considered as a colligative property?
9. On mixing equal volumes of water and ethanol what type of deviation would you
expect from Raoults Law?
10. What are isotonic solutions?
FOR BELOW AVERAGE
02 Marks question
1. Under what condition Vant Hoff factor is (i) equal to one, (ii) greater than 1, (iii) less
than 1.
2. Two liquid A and B on mixing produce a warm solution. Which type of deviation
from Raoults Law does it show?
3. What are non-ideal solutions? Explain as to why non-ideal solutions deviate from
Raoults Law.
4. What are colligative properties? Mention them.
5. Differentiate between molarity and molality of a solution. When and why is molality
preferred over molarity in handling solutions in chemistry?
FOR AVERAGE
1 Name the factors which affect the vapour pressure.
2. Amongst the following compounds, identify which are insoluble, partially soluble and
highly soluble in water.
(a) Phenol (b)Toluene (c) Formic Acid (d)Ethylene Glycol
(e)Chloroform (f) Pentanol
3. What do you mean by relative lowering of vapor pressure ? How is relative lowering
of vapor pressure related with mole fraction of non volatile solute in a solution?
4. With the help of a suitable diagram show that the vapour pressure of a solution is
lower than the pure solvent, causes a lowering of freezing point for the solution
compared to that of the pure solvent.
25
5. Carbon tetra chloride and water are immiscible where as ethanol and water are
miscible in all proportions. Correlate this behaviour with molecular structures of these
compounds.
FOR ABOVE AVERAGE
1. What do you mean by abnormal molecular mass? What are its cause?
2. With the help of suitable diagrams, illustrate the two types of non ideal solutions.
3. State Raoults law for solutions of non volatile solutes in volatile solvents. Derive a
mathematical expression for this law.
4. What is osmotic pressure and how is it related with the molecular mass of non-volatile
solute?
5. What is meant by abnormal molecular mass of solute? Discuss the factors which bring
abnormality in the experimentally determined molecular masses of solutes using
colligative properties.
6. State Raoults Law. Discuss the factor responsible for the deviation from this law.
7. State Henrys Law and mentions some important application.
8. Explain the significance of Henrys Constant (K
H
). At the same temperature,
hydrogen is more soluble in water than helium. Which of them will have a higher
value of K
H
and why?
9. Explain the difference between osmotic pressure and vapour pressure of a solution.
10. Give one example each of miscible liquid pairs showing positive and negative
deviation from Raoults Law. Give one reason each for such deviations.
FOR AVERAGE/BELOW AVERAGE
02 Marks question (Numerical)
1. The vapour pressure of pure liquid A and B are 450 and 700 mm Hg respectively at
350 K. Find out the composition of the liquid mixture if total vapour pressure is 600
mm Hg.
2. Calculate the mass percentage of aspirine(C
9
H
8
O
4
) in acetonitrile(CH
3
CN) when 6.5 g
of C
9
H
8
O
4
is dissolved in 450 g of CH3CN.
3. H
2
S, toxic gas with rotten a like smell, is used for qualitative analysis. If the solubility
of H
2
S in water at STP is 0.19 m. Calculate Henrys law constant.
4. 18 g of glucose is dissolve in 1 kg of water in a saucepan. At what temperature will
water boil at 1.03 bar? K
b
for water is 0.52 K kg mol
-1
.
5. An aqueous solution of 2% non-volatile solute exerts a pressure of 1.004 bar at the
normal point of the solvent. What is the molar mass of the solute?
26
6. The boiling point of benzene is 353.23 K. When 1.08 gm of non-volatile solute was
dissolved in 90 gm of benzene. The boiling point is reached to 354.11 K. Calculate
the molar mass of solute. Kb for benzene is 2.53 K kg mol
-1
.
7. 45 g of ethylene glycol is mixed with 600 g of water. Calculate (a) the freezing point
depression and (b) the freezing point of the solution.
8. 200 cm
3
of an aqueous solution of a protein contains 1.26 g of protein. The osmotic
pressure of such a solution at 300 K is found to be 2.57 x 10
-3
bar. Calculate the molar
mass of the protein.
9. A 5% solution (by mass) of cane sugar in water has freezing point of 271 K. Calculate
the freezing point of 5% glucose in water if the freezing point of pure water is 273.15
K.
FOR ABOVE AVERAGE
03 Marks Questions (Numerical)
1. If N
2
gas is bubbled through water at 293K, how many millimoles of nitrogen gas
would dissolved in 1 ltr. of water. Assume that N
2
exerts a partial pressure of 0.987
bars. Given that Henrys law constant for N
2
at 293 K is 76.48 kbar.
2. 0.6 mL of acetic acid having density 1.06 g mL
-1
, is dissolve in 1 litre of water. The
depression in freezing point observed for this strength of acid was 0.0205C.
Calculate the Vant Hoff factor and the dissociation constant of acid.
3. 100 g of liquid A (molar mass 140 g/mol) was dissolved in 1000 g of liquid B (molar
mass 180 g mol
-1
). The vapour pressure of pure liquid B was found to be 500 torr.
Calculate the vapour pressure of pure liquid A and its vapour pressure in the solution
if the total vapour pressure of the solution is 475 Torr.
4. 2 g of benzoic acid dissolved in 25 g of benzene shows a depression in freezing point
equal to 1.62 K. Molal depression constant for benzene is 4.9 K kg mol
-1
. What is the
percentage association of acid if it forms dimmer in solution?
5. Determine the osmotic pressure of solution prepared by dissolving 25 mg of K
2
SO
4
in
2 litre of water at 25C. Assuming that it is completely dissociated.
6. Two elements A and B from compounds having formula AB
2
and AB
4
. When
dissolved in 20 g of benzene, 1 g of AB
2
lowers the freezing point by 2.3 K where as
1.0 g of AB
4
lowers it by 1.3 K. The molar depression constant for benzene is 5.1 K
kg mol
-1
. Calculate atomic mass of A and B.
7. An antifreeze solution is prepared from 222.6 g of ethylene glycol and 200 g of water.
Calculate the molality of solution. If the density of the solution is 1.072 g/mol, then
what shall be the molarity of the solution?
27
*************************
STUDY MATERIAL
28
UNIT :-3
ELECTRO CHEMISTRY
Q1. Define molar conductivity. How does it varies with dilution ?
Ans:- Molar conductivity:-
It is the product of specific conductivity and volume of solution containing 1 g molecular
mass of the electrolyte.
C
K
mol
1000
=
Unit= Sm
2
mol
-1
* Variation :-
Strong Electrolyte:-Molar conductivity increases slowly with decrease in concentration.
Weak Electrolyte:- Molar Conductivity increases sharply for weak electrolyte on dilution
.Q2. States Koahlrausch law.
Ans:- Limiting molar conductivity of an electrolyte is the sum of molar conductivity of cation
and anion at concentration approaches zero.
0 0 0

+ =
mol
0
+
=Molar Conductivity of cation
0

=Molar Conductivity of anion

Q3. Wat do you mean by fuel cell? Write cathode and anode reaction in fuel cell.
Ans:- Fuel Cell:- These are electrical cells which can convert the energy of combustion of
a fuel like (H
2
, CO etc.) directly into electrical energy
Ex:-H
2
-O
2
fuel cell.
Reaction :-
Anode reaction:- H
2
(g)+2OH
-
(aq) --- 2H
2
O+2e.X 2
Cathode reaction:- O
2
(g) +2H
2
O+4e ---- 4OH
-
29
Overall reaction :-2H
2
(g) + O
2
(g) ------ 2H
2
O(l)
Q3. What do you mean by Corrosion? How it is a electrochemical phenomena?
Ans:- in corrosion a metal is oxidized by a lose of electrons to oxygen and metal oxide is
formed. It is an electrochemical phenomenon.
Chemistry of corrosion of iron:-
The sport where iron under goes oxidation is considered as anode.
At anode: 2Fe ---- 2Fe
2+
+ 4e
-
At another sport on the metal these electrons reduce oxygen in presence of
H
+
.
At anode :O
2
(
g
) + 4H
+
+ 4e
-
---- 2H
2
O(L)
The overall reaction is
2Fe + O
2
+ 4H+ ----- 2Fe
2+
+ 2H
2
O
The ferrous ions formed are further oxidized to ferric ions by atmospheric oxygen and
products comes out as rust in the form of Fe
2
O
3
XH
2
O(hydrated Ferric oxide)
Q4. A solution of CuSO
4
is electolysed for 10 minutes with a current of 1.5 amperes. What is
the mass of copper deposited at cathode?
Ans:- t= 10X60=600 Sec.
I=1.5 amperes.
Q=nF
(Cu
2+
+2e --- Cu)
=2X96500C
Q=It=1.5X600
=900 C
2 X 96500 C charge deposited 63 g of copper
900 C charge deposited
96500 2
900 63

gm of copper
=0.2938 gm.
Q5. The resistance of a conductivity cell containing 0.001 M Kcl solution at 298 K is 1500
. What is the cell constant If conductivity of 0.001 M Kcl solution 298 K is 0.148 X
10
-3
S cm
-1.
Ans:- R=1500
K=0.148 X 10
-3
S cm
-1
30
=
a
l
Cell Constant = ?
=
a
l
RK
=1500 X 0. 148 X 10
-3
=0.222 Cm
-1
Q6. Conductivity of 0.00241 M acetic acid is 7.896 X 10
-5
Scm
-1
. Calculate its molar
conductivity and if
0

for acetic acid 390.5 Scm

2
mol
-1
. what is its dissociation
constant?
Ans:-
K=7.896 X 10-5 S cm-1
2 0
5 . 390 Scm =
C
K
C
1000
=
93 . 32
241
7896
00241 . 0
1000 10 896 . 7
5
= =

=

5 2 2
0
10 85 . 1 00241 . 0 ) 0838 . 0 (
0838 . 0
5 . 390
93 . 32

= = =
= =

=
C K
C

Q7. Represent the cell in which the following reaction takes place.
Mg(S) + 2Ag
+
(0.0001 M) ----- Mg
2+
(0.130M) + 2Ag(s)
Calculate its E.M.F when E
0
=3.17V
Ans:- Cell reaction
Mg ----- Mg
2+
+ 2e -- - - - - Oxidation at anode
2Ag+ + 2e --- 2 Ag --- - - - - - -Reduction at cathode
Representation of cell
MgMg
2+
(0.130 M) Ag
+
(0.0001 M) Ag
C
1
C
2
E.M.F of the cell E= 1
2
log
591 . 0
C
C
n
E +
=3.17 +
[ ]
[ ]
+
+
2
2
log
2
0591 . 0
Mg
Ag
31
=3.17 +
( ) 130 . 0
) 0001 . 0 (
log
2
0591 . 0
2
=3.17 -0.21
E=2.96 V
Q8.
mol
0

for NaCl, HCl and Na AC(CH

3
COONa) are 126.4, 425.9 and 91.0 Scm2 mol-1
respectively. Calculate
mol
0

for HAC(CH
3
COOH, Acetic Acid).
Ans:-
4 . 126 9 . 516 4 . 126 9 . 425 0 . 91
0 0 0 0 0
#
0 0
= + =
+ + + =

+ + +
Cl Na Cl H Na COO CH HAC
=390.5 Scm
2
mol
-1
Q9. States Faradays laws of electrolysis.
Ans: 1
st
law:- The amount of substance deposited during electrolysis is directly
proportional to quantity of electricity passed.
m

Q, m=Z Q
=Zit
Where Z=electrochemical equivalent.
2
nd
law:- If same change is passed through different electrolytes, the mass of substance
deposited at each electrodes will be propositional to their equivalent weights.
W
1
/E
1
=W
2
/E
2
Where W is mass of substance and E is its equivalent weight.
Q10. Calculate G
0
for Zn-Cu cell at standard conditions.
Given C F V E V E
Cu
Cu
n
Zn 96500 , 34 . 0 / , 76 . 0 /
2 2
0
2
0
= + = =
+ +

Ans:-
1
0
0 0 0
2 . 212
96500 10 . 1 2 0
10 . 1
76 . 0 34 . 0 ) 76 . 0 ( 34 . 0

=
= =
=
+ = + =
=
kjmol
c V F nE G
V
E E E anode Cathode cell
Q11. Depict the galvanic cell in which the reaction
32
Zn(s)+2Ag
+
(aq) --- Zn
2+
(aq) + 2Ag(s) takes place.
(a) Which of the electrode is negative chage.
(b) The carries of the current in the cell.
(c) Individual reaction at each electrode.
Ans: Cell Reaction
Ag Zn Ag Zn
duction Ag e Ag
cathode AT
oxidation e Zn Zn
anode AT
2 2
Re 2 2 2
2
2
2
+ +

+
+
+
+
+
Cell representation
anode cathode
E E E E E
Ag Ag Zn Zn
aq
= =
+
+
+
) (
2
(c) Ag electrode is negative charged.
(d) Ag
+
and Zn
2+
ions carries the current in the cell. Current flow from Ag
electrode to Zn electrode.
(e) At anode
Oxidation e Zn Zn +
+
2
2
At cathode.
duction Ag e Ag Re 2 2 2 +
+
1 MARK QUESTIONS
Q. 1. Which solution will allow greater conductance of electricity, 1 M NaCl at 293 K
or 1 M NaCl at 323 K and why ?
Ans. 1 M NaCl at 323 K as the ionic mobilities increase with increase in temperature.
Q. 2. What does the negative value of E
cell
indicate ?
Ans. G will be positive, the cell will not work. `
Q. 3. Why is the equilibrium constant K, related to only E
cell
and not E
cell
?
Ans. This is because E
cell
is zero at equilibrium.
Q. 4. What is the sign of G for an electrolytic cell ?
Ans. Positive.
33
Q. 5. Rusting of iron is quicker in saline water than in ordinary water. Why is it so ?
Ans. In saline water, NaCl helps water to dissociate into H
+
and OH

. Greater the number

of H
+
, quicker will be rusting of Iron.
Q. 6. What would happen if the protective tin coating over an iron bucket is broken in
some places ?
Ans. Iron will corrode faster as the oxidation potential of Fe is higher than that of tin.
Q. 7. Can a nickel spatula be used to stir a solution of Copper Sulphate ? Justify your
answer.
(E
Ni+/Ni
= 0.25 V E
Cu+/Cu
= 0.34 V)
Ans. Reduction potential of Ni is less than Cu. Ni will replace the Cu from CuSO
4
. Thus Ni
spatula cannot be used to stir a solution of CuSO
4
.
Q. 8. Which out of 0.1 M HCl and 0.1 M NaCl, do you expect have greater

m
and
why ?
Ans. 0.1 M HCl will have greater
_
m
because H
+
(aq) being smaller in size than Na
+
(aq)
and have greater mobility.
Q. 9. Three iron sheets have been coated separately with three metals A, B, C whose
standard electrode potentials are given below :
A B C Iron
E
value
0.46 V 0.66 V 0.20 V 0.44 V
Identify in which rusting will take place faster when coating is damaged.
Ans. Rusting of iron will take place when coated with metal C as it is placed above iron
more than other metal.
Q. 10. Which will have greater molar conductivity ? Solution containing 1 mol KCl in
200 cc or 1 mol of KCl in 500 cc.
Ans. 1 mol of KCl in 500 cc.
2 MARKS QUESTIONS
Q. 1. (a) How will the value of E
cell
change in an electrochemical cell involving the
following reaction of the concentration of Ag
+
(aq) is increased ?
34
(b) What will be e. m. f. when the cell reaches equilibrium :
Mg (s) + 2 Ag
+
(aq) Mg
2+
(aq) + Ag

(s)
Ans. (a) E
cell
= E
cell

0.059
2
log
2
2
Mg
Ag
+
+




As the concentration of [Ag
+
] ion increases, E
cell
increases.
(b) e.m.f. = 0
Q. 2. (a) In a cell reaction, the equilibrium constant K is less than one. Is E for the
cell positive or negative ?
(b) What will be the value of K of E
cell
= 0 ?
Ans. For a cell E =
0.0591
n
log K
K < 0 log K < 0
i.e. log K is ve.
Then E
cell
will be negative.
(b) If E
cell
= 9 then 0 =
0.0591
n
log K
log K = 0 K = 1
Q. 3. Knowing that :
Cu
2+
(aq) + 2 e

Cu (s) E = + 0.34 V
2 Ag
+
(aq) + 2 e

2 Ag (s) E = + 0.80 V
Reason out whether, 1 M AgNO
3
solution can be stored in Copper Vessel or 1 M
CuSO
4
solution in Silver Vessel.
Ans. A solution of an electrolyte can be stored in a particular vessel only in case there is no
chemical reaction taking place with the material of the vessel.
Cu is a strong reducing agent and can lose electrons to Ag
+
as E of Cu is less than
that of Cu. So AgNO
3
cannot be kept in Copper Vessel.
CuSO
4
solution can be stored in Ag Vessel as no chemical reaction will take place as
Ag is placed above Cu in the activity series and Ag is less reactive than Copper.
35
A
B
400
200
0.2 0.4
C

m
Q. 4. What is the number of electrons in one Coloumb of electricity ?
Ans. Charge on one mole of electrons = 1 F = 96500 C
96500 C of Charge is present on electrons = 6.022 10
23
1 C of Charge is present on electrons = '
23
6.022 10
96500 C

1 C
= 6.24 10
18
Q. 5. Which of the following pairs will have greater conduction and why ?
(a) Copper wire at 25 C and Copper wire at 50 C.
(b) 0.1 M acetic acid solution or 1 M acetic acid solution ?
Ans. (a) Copper wire at 25 C because with increase in temperature metallic
conduction decreases due to vibration of kernels.
(b) 0.1 M acetic acid solution because with dilution degree of dissosciation
increases and hence no. of ions.
3 MARKS QUESTIONS
Q. 1. The following curve is obtained when molar conductivity (
m
) is plotted against
the square root of concentration for 2 electrolytes A and B.
(a) What can you say about the nature of the two electroyltes A and B ?
(b) How do you account for the increase in molar conductivity
m
for the
electrolytes A and B on dilution ?
Ans. (a) A is a strong electrolyte and B is a weak electrolyte.
(b) Molar conductivity of a strong electrolyte (A) increases with dilution as ionic
mobility increases. In a weak electrolyte molar conductivity increases steeply
with dilution as degree of dissociation increases and hence no. of ions
increases.
36
Q. 2. Iron and nickel are used to make electrochemical cell by using a salt bridge to
join a half cell containing 1 M Fe
2+
(aq) in which a strip of iron has been
immersed to a second half cell which contains 1 M Ni
2+
(aq) in which a strip of Ni
has been immersed ? A voltmeter is connected between the two metal strips :
E
Fe+/Fe
= 0.44 V E
Ni+/Ni
= 0.25 V
(a) Write the name of the cathode and anode.
(b) Write the half reactions involved ?
(c) What would be the effect on the Voltmeter reading if Fe
2+
concentration
were increased ?
Ans. (a) Anode : Fe
Cathode : Ni
(b) Reaction at anode : Fe Fe
2+
+ 2 e

Reaction at cathode : Ni
2+
+ 2 e

Ni
(c) Voltmeter reading decreases.
Q. 3. Consider the electrochemical cell :
Zn (s) / Zn
2+
(aq) // Cu
2+
(aq) / Cu. It has an electrical potential of 1.1 V when
concentration of Zn
2+
and Cu
2+
ions is unity.
State the direction of flow of electrones and also specify if Zinc and Copper are
deposited or dissolved at their respective electrodes. When :
(a) an external opposite potential of 0.8 V is applied.
(b) an external opposite potential of 1.1 V is applied.
(c) an external opposite potential of 1.4 V is applied.
Ans. (a) Electrons flow from Zn rod to Cu rod.
Zinc dissolved and Copper gets deposited.
(b) No flow of electrons and current.
No change observed at Zinc and Copper electrodes (system is at equilibrium).
(c) Electrons flow from Cu rod to Zn rod.
Zinc is deposited and Copper gets dissolved.
Q. 4. Given that :
CO
3+
+ e

CO
2+
E = 1.82 V
2 H
2
O O
2
+ 4 H
+
+4 e

E = 1.23 V
37
Explain why CO
3+
is not stable in aqueous solution ?
Ans. The E
cell
can be calculated as :
4 [CO
3+
+ e

CO
2+
] E = 1.82 V
2 H
2
O O
2
+ 4 H
+
+4 e

E = 1.23 V

Cell reaction : 4 CO
3+
+ 2 H
2
O CO
2+
O
2
+ 4 H
+
E
cell
= 1.82 V ( 1.23 V) = 3.05 V
Since E
cell
is positive, the cell reaction is spontaneous. CO
3+
iron will take part in the
reaction and hence unstable in aqueous solution.
Q. 5. For the reaction :
Ag
+
+ Hg Ag + Hg
2
2+
E = 0.80 V E = 0.79 V
Predict the direction in which the reaction will proceed if :
[Ag
+
] = 10
1
mol/h [Hg
2+
] = 10
3
mol/h
Ans. Cell reaction is :
2 Ag
+
+ 2 Hg 2 Hg + Hg
2
2+
E
cell
= E
cell

0.0591
2
log
2
2
2
Hg
Ag
+
+




= (0.80 V 0.79 V)
0.0591
2
log
( )
3
2
1
10
10

= 0.01 V
0.0591
2
( 1) = 0.01 + 0.0295
= 0.0395 V
Since E
cell
is positive, the reaction will be spontaneous in the forward direction.
FOR ABOVE AVERAGE
01 Marks Questions
1. Express mathematical relationship among resistance(R), Specific conductivity (K)
and cell constant.
2. Write relation between specific conductance and molecular conductivity of an
electrolytic.
3. State the Kohlrausch law.
4. Name a metal that can be used for the cathodic protection of iron against rusting.

38
5. How are secondary cells different from primary cells?
6. Write the reaction occurs in fuel cell.
7. What do you mean by standard electrode potential?
8. What is galvanization of iron?
9. Define strong electrolytes.
10. Define molar conductivity.
02 Marks Questions
1. What is corrosion? How is rusting of iron protected by cathodic protection.
2. How is cathodic protection different from galvanization in protection of iron from
rusting?
3. What do you understand by equilibrium constant? Calculate the equilibrium
constant of the reaction
Cu (s ) + 2Ag
+
(aq) Cu
2
+ (aq) + 2Ag (s) E = 0.46 v .
4. Represent Zn Cu cell and write Nernst equation for the calculation of emf of the
cell.
5. The conductivity of 0.2M solution of NaCl at 298 K is 0.0248 S cm
-1
. Calculate its
molar conductivity.
6. The standard electrode potential for Daniell cell is 1.1v. Calculate the standard
Gibbs energy for the reaction
Zn (s) + Cu
2+
(aq) Zn
2+
(aq) + cu (s)
7. State and explain the Faradays laws of electrolysis. What is the value of
Faradays constant?
8. State reasons for the following
Rusting of iron is said to be an electrochemical phenomena.
Rusting of iron is quicker in saline water than in ordinary water.
Arrange the following metals in the order in which they displace each from
the solution of their salts.
Al, Mg, Fe, Cu, Zn
03 Marks Questions
1. Write the Nernst equation and calculate the emf of the following cell at 298 K.
Cu(s) / Cu
2+
( 0.130 M ) // Ag
+
( 1 x 10
-4
M ) / Ag (s). Given that E
0
Cu
+2
/ Cu =
0.34 V and E
0
Ag
+
/ Ag = 0.80 V, F = 95500 C Mol
-1

2. What is standard hydrogen electrode? How it measures the electrode potential of an
electrode? Explain.
39
3. What are secondary cells? Explain lead storage battery with electrode reactions.
4. A galvanic cell is constructed in which the cell reaction is
Zn(s) + 2 Ag
+
(aq) Zn
2+
(aq) + 2 Ag (s),
Now write:
(a) Which of the metal electrode is negatively charged?
(b) The direction of the current (either anode to cathode or cathode to anode)
(c) Individual half electrode reaction for cathode
5. What are electrode potential and emf of a cell?
Calculate the emf of the cell
Mg(s) / Mg
2+
( 0.1 M ) // Ag
+
( 0.01 M ) / Ag at 250 C
Given that E
0
Ag
+
/ Ag = 0.8 V, E
0
Mg
2+
/ Mg = - 2.37 V
05 Marks Question
1. What is EMF of a cell?
Calculate the emf of the cell
Mg(s) / Mg
2+
( 0.1 M ) // Ag
+
( 1 x 10
-4
M) / Ag (s) at 250 C,
Given that E
0
Ag
+
/ Ag = 0.8 V , E
0
Mg
2+
/ Mg = -2.37v
2. What will be the effect on EMF of the cell if concentration of Ag
+
is increased to 1 x 10
-
3
M?
3. Explain the product of electrolysis of molten NaCl and aqueous NaCl. Explain the
difference between these two phenomena and list two other application of electrolysis.
4. A cell is formed as
Ni (s) / Ni
2+
( 0.01 M ) // Cu
2+
( 0.1 M ) / Cu(s)
The E
0
values for Ni
2+
/ Ni and Cu
2+
/ Cu electrodes are -0.25 V and 0.34 V
respectively.
Calculate the cell potential, equilibrium constant and work done by the cell.
5. Electrolysis of aqueous sodium chloride gives H2 gas at cathode instead of sodium metal
and Cl2 gas anode while electrolysis of molten NaCl gives sodium metal at cathode.
How is this difference in results explained? Give electrode reactions for anode and
cathode.
FOR BELOW AVERAGE
01 Mark Questions
1. What is over voltage in an electrolytic reaction?
2. What is Nickel- Cadmium cell?
3. How is unit of molar conductivity arrived at?
40
4. How many faradays of electricity are required to liberate 2 moles of hydrogen gas in
electrolysis of a solution ?
5. Why does cu not displace Fe from FeSO4 Solution?
6. Why does an alkaline solution enhance the rusting of iron?
7. What is concentration cell? Give an example.
8. In function of a galvanic cell, one of its electrodes does oxidation reaction. What is
the name of the electrode and what is its polarity?
9. What is the electrolyte used in a fuel cell?
10. Suggest one method to operate galvanic cell if the salt bridge is absent.
11. The standard reduction potential for the Zn
2+
aq/Zn (s) half cell is -0.76 V. Write the
electrode reactions of the cell when it is coupled with standard hydrogen electrode
(SHE). Also give the standard cell potential.
02 Marks Questions
1. Why is it not allowed to determine the molar conductivity at infinite dilution of a weak
electrolyte by extrapolating is allowed in the graph of strong electrolytes. Explain.

2. If E
0
for copper electrode is +0.34V; how will you calculate its emf when the solution in
contact with it is 0.1 M in copper ions? How does emf of copper electrode change when
concentration of Cu
2+
ions in solution is decreased?
3. Calculate the potential of a zinc - zinc ion electrode in which the zinc ion activity is
0.001M
[E
0
Zn
2+
/Zn = -0.76 V, R= 8.314 JK
-1
mo1
-1
, F=96500 Cmo1
-1
]
4. The molar conductance of sodiumacetate, hydrogenchloride and sodiumchloride at
infinite dilutions are 91, 426 and 126 Simen cm
2
mol
-1
. Calculate the molar conductance
of acetic acid at infinite dilution.
5. Estimate the minimum potential difference needed to reduce Al2O3 at 500c. The G
for the decomposition reaction 2/3 Al2O3 4/3 Al + O2 is G = 960 KJ.
6. The E
0
Values for two metal electrodes are given below
(i) Cr
3+
/Cr
2+
= -0.4V (ii) Fe
3+
/Fe
2+
= 0.8V
Comment on the result of treating a solution of Cr (II) with a solution containing
Fe (III) ions
7. Calculate the standard free energy change for the reaction occurring in the cell
Zn|Zn
2+
(IM) // Cu
2+
(IM) / Cu
Given E
0
zn
2+
/zn = -0.76V and E
0
cu
2+
/Cu= 0.34V.
19. Explain the electrolysis of aqueous NaCl and molten NaCl with their Chemical
reactions. Give reasons for this difference and deduce criteria for product formation.
41
20. Explain the electrode reaction of a fuel cell. Discuss the advantage of fuel cell in
space programme.
03 Marks Question
1. Predict the products of electrolysis in each of the following:
(i) An aqueous solution of AgNO3 With Ag electrodes.
(ii) A Dilute solution of H2SO4 With platinum electrodes.
(iii) An aqueous solution of CuCl2 with platinum electrodes.
2. The resistance of a conductivity cell containing 0.001 M KCl Solution at 298 K is
1500 ohms. What is the cell constant if conductivity of 0.001 M KCl Solution at 298
K is 0.146X10
-3
S cm
-1
.
3. Conductivity of 0.00241 M acetic acid is 7.896X10
-5
S cm
-1
, calculate its molar
conductivity and if ^
0
m for acetic acid is 390.5 S cm
2
mol
-1
. What is its dissociation
constant?
4.. Rusting is an electrochemical phenomena. Explain this phenomena with the help
of rusting of iron with reactions involved.
5. Silver is electrodeposited on a metallic vessel of surface area 800 cm
2
by passing
current of 0.2 ampere for 3 hours. Calculate the thickness of Silver deposited.
(Density of Ag =10.47 g cm
-3
, Atomic mass of Ag=108 amu)
05 Marks Question
6. Calculate the potential of following cell reaction at 298 K
Sn
4+
(1.50 M)+ Zn Sn
2+
(0.5M)+ Zn
2+
(2M)
The standard potential E
0
; of the cell is 0.89V, whether the potential of the cell
increase or decease (R=8.314 JK
-1
mol
-1
, F=96500 C mol
-1
) if the concentration of Sn
2+

is increased in the cell.
7. The conductivity of NaCl at 298 K has been determined at different concen-tration and the
results are given below:
Conc
n
/ M 0.001 0.010 0.020 0.050 0.100
102 x K/S m
-1
1.237 11.58 23.15 55.53 106.74
Calculate ^m for all concentrations and draw a plot between ^m and C1/2. Find the
value of ^m.
8. (a) State the reasons for the following :-
a. Iron does not rust even if Zinc coating is broken in a galvanized iron
pipe.
b. Electrolysis of KBr (aq) gives Br2 at anode, but that of KF (aq) does
not give F2.
(b) Write the electrode reaction of H2-O2 Cell.
42
(c) Calculate the EMF of the following cell at 298 K
Sn/Sn
2+
(0.1M) // Ag
+
(0.1M) / Ag
Given E
0
Sn
2+
/Sn = -0.14V, E
0
Ag
+
/Ag = 0.8V
9. (a) State Kholrauschs law for electrical conductance of an electrolyte at infinite
dilution.
(b) Give the composition and reaction of cathode and anode in a mercury cell?
Give one use.
(c) Silver is electrodeposited on a metallic vessel by passing a current of 0.2
ampere for 3 hours. Calculate the weight of silver deposited.
(Atomic mass of Ag=108 amu)
FOR AVERAGE
01 Mark Question
1. Define the molar conductivity of an electrolytic solution.
2. Express the relation between degree of dissociation of an electrolyte and its molar
conductivities.
3. What does the standard electrode potential of a metal being negative E
0

Zn
2+
/Zn = - 0.76 v shows?
4. What happens when the protective coating of galvanized iron is broken?
5. How is electroplating different from galvanization?
6. How does a fuel cell operate?
7. How much charge is required for the following reduction of 1 mol of Cu
2+
ions to cu
(s)?
8. Which type of metal can be used for the cathodic protection of iron?
9. Give one difference between primary and secondary cells.
10. What are uses of salt bridge in a galvanic cell?
02 Marks Question
1. What is mercury cell? Give an electrode reaction?
2. Make difference between molar conductivity and equivalent conductivity.
3. Suggest a cell to determine molar conductivity experimentally.
4. How will you explain the sharp increase in molar conductivity of a week electrolyte
on dilution? How is molar conductivity related to the degree of dissociation?
5. The conductivity of 0.20 M solution of potassium chloride 298 K is 2.48 x 10
-2
ohm
-1
cm
-1
calculate the molar conductivity ?
6. A solution of Ni (NO3)2 is electrolyzed between platinum electrodes using a current
of 5 A for 20 minutes? What mass of Nickel is deposited at the cathode?
43
7. The Zinc - silver oxide cell has the following reactions.
Zn Zn
2+
+ 2 e- E
0
= 0.76 v
Ag
2
O + H
2
O + 2e- 2Ag
+
+ 2OH
-
E
0
=0.34V
Calculate the standard free energy in joules
8. Give reason for the following phenomena:
(i) Iron does not rust if coating is broken in a galvanized iron pipe.
(ii) Rusting is said to be an electrochemical phenomena
9. Molar conductance of a 1.5 M solution of an electrolyte is found to be 138 simen cm
2
.
What would be specific conductance of this solution?
10. What is rusting? Explain how galvanization gives better protection than electroplating
for an iron object from rusting?
11. Describe the characteristics of variation in molar conductivities (^m) strong and weak
electrolytes on dilution.
03 Marks Question
1. Given E
0
Cu
2+
/ Cu = 0.34 volt and E
0
Ag
+
/Ag = 0.80 volt for a cell
a) Calculate cell potential for the cell containing 0.1 M Ag
+
and 4 M Cu
2+
at 25C.
b) How many hours does it take to reduce 3 moles of Fe
2+
with 2 amp current.
2. Calculate the standard cell potential, standard free energy charge rG
0
and equilibrium
constant for the Galvanic cell 2Cr(s) + 3 Cd
2+
2Cr
3+
+ Cd
Given that E
0
Cr
3+
/Cr = -0.74 v, E
0
Cd
2+
/Cd= -0.40 v
3. Define conductivity and molar conductivity for the solution of an electrolyte. Discuss
their variation with concentration.
4. The resistance of a conductance cell containing 7.5 x 10
-3
M solution of KCl at 250 C.
was 1005 ohms.
Calculate the specific conductance and molar conductance of the solution if cell
constant is 1.25 Cm
-1
.
5. What happens during the corrosion of a metal? Explain the electro-chemical basis of
corrosion of iron with chemical equation involved?
05 Marks Question
1 What is EMF of a cell? How is it different from cell potential (Ecell)? Calculate the
EMF of the cell reaction
Sn
4+
(1.5M) + Zn Sn
2+
(0.5 M) + Zn
2+
(2M )
The standard cell potential of the cell is 0.89 v.
2. Explain the primary and secondary batteries. How are secondary cells different from
primary cells? Give the composition and reaction of cathode and anode in a mercury
cell?
44
3.. What do you mean by molar conductivity and equivalent conductivity? Explain the
experimental Determination of molar conductivity with help of conductivity cell.
4 In the electrolysis of aqueous solution of sodium chloride, there are two possible
anode reactions.
2Cl
-
(aq) Cl
2
+ 2e- E
0
= 1.36 v
2 H
2
O (l) O
2
(g) + 4H
+
(aq) + 4e
-
E
0
= 1.23 v
Which of the above reaction actually takes place and why? Also give other utilities of
electrolysis?
********************

STUDY MATERIAL
Chemical Kinetics : Study of chemical reactions w.r.t. reaction rate, effect of various
variables, rearrangement of atoms and formation of intermediates.
Rate of Reaction : It is concerned with decrease in concentration of reactant per unit time.
Rate = - d[c]/ dt
It can also be defined as increase in concentration of products per unit time.
Rate= d[p]/ dt
Average Rate: It is rate of reaction measured over a long time interval.
Average Rate = X/ t
45
UNIT 04
CHEMICAL KINETICS
Instantaneous Rate
dT
dX
T
X
t
Lt
=

0
i.e. rate of reaction when the average rate is taken over a very small interval of time.
Rate law or Rate equation : Rate law is relation between Rate of reaction and concentration
of reactants.
[ ] [ ]
y x
B A K tion Rateofreac =
Mind always, it is not theoretical but it is written when order of reactions w.r.t. A & order of
reaction w.r.t. B are known experimentally.
Rate Constant : It is defined as rate of reaction when molar concentration of reactant is
unity.
Molecularity : Total number of molecules of the reactants in an elementary reaction
(Single step reaction) is called molecularity of reaction.
Unimolecular reaction : When molecularity is one.
NH
4
NO
2
N
2
+ 2 H
2
O
BiMolecular Reaction : When molecularity is two.
2HI H
2
+ I
2
Trimolecular or Termolecular reactions : When three species collide
2NO + O
2
2NO
2
Note that Molecularity greater than three is not observed? It is due to the probability
that more than three molecules can collide and react simultaneously is very small. Hence, the
molecularity greater than three is not observed.
Order of Reaction : The sum of the powers of the concentration of reactants in the rate law
is termed as order of the reaction. It can be in fraction. It can be Zero.
Order of a reaction is an experimental quantity. It is applicable to elementary as well
as complex reactions where as molecularity is applicable only for elementary reactions.
For complex reaction, Order is given by the slowest step and generally, molecularity
of the slowest step is same as the order of the overall reaction.
Zero order Reaction :
Rate = K[A]
o
The rate of a reaction does not change with the concentration of reactants.
First Order Reaction : The reaction in which the rate of reaction is directly proportionate to
the concentration of reacting substance.

Rate constant of first order reaction is
x a
a
t
K

= log
303 . 2
46
Rate = dx = k[A]
dt
or
[ ]
[ ] A
A
t
K
0
log
303 . 2
=
Where a is initial concentration, (a-x) is the concentration of reactants after time t.
The unit of K is s
-1
or Min
-1
.
Half Life of a reaction : The time taken for a reaction when half of the starting material has
reduced is called half life of a reaction.
K
t
693 . 0
2
1
= Where K= rate constant
Second Order Reaction :
[ ] [ ]
1 1
B A K
dT
dX
Rate = =
The reaction in which sum of powers of concentration terms in rate law or rate equation is
equal to 2.
Third Order Reaction : The reaction in which sum of powers of concentration terms in
rate law is equal to 3 i.e.
[ ] [ ]
y x
B A K
dT
dX
Rate = =
, Where x+y =3
Pseudo First Order Reaction : The reaction which is bimolecular but order is one is called
Pseudo first order reaction.
OH H C COOH CH O H H COOC CH
H
5 2 3 2 5 2 3
+ +
+
Large Excess
Factors affecting rate of reactions :
Rate of reaction is affected by
Nature of Physical Surface Concentration Temp.
Reactants State Area
Reactions of fraction order :
HBr Br H 2
2 2
+
[ ] [ ]
2
1
2
1
2
Br H K Rate =
Half life of Reaction of nth Order :
In general,
[ ]
1
0
2
1
1
n
A
t
where n is order of reaction.
For
a t
2
1 for Zero order
t

is independent for first order.

a
t
1
2
1
for second order.
47
2
2
1
1
a
t for 3
rd
order.
Activation Energy (E
a
) : It is extra energy which must be possessed by reactant
molecules so that collision between reactant molecules is effective and leads to formation
of product molecules.
Arrhenius equation of reaction rate :
RT
E
a
e A K

= .
Where K = rate constant
A= frequency factor,
E
a
= Energy of activation,
R = gas constant,
T= temperature in Kelvin
l
n
K = l
n
A E
a
/ RT
log K = log A- E
a
/ 2.303 RT
Rate determining step :
The slowest step in the reaction mechanism is called rate determining step.
Temperature coefficient :
It is the ratio of rate costant at temperature 308 K to the rate constant at
temperature 298 K,
Temperature Coefficient = Rate ConstantK at 308 K / Rate ConstantK at 298 K
48
CHEMICAL KINETICS
Below Average Students : 01 Mark
Q1. Define rate of chemical reaction?
Ans.: It is defined as change in concentration of reactants or products per Unit time.
Q2. What is the unit of rate of chemical reaction.
Ans. ML
-1
S
-1
.
Q3. Defineaverage rate of chemical reaction?
Ans.: When change in concentration is measured over bigger interval of time. It is called
average rate. It is denoted by X/ T where T is bigger time interval.
Q4. Define instantaneous rate of chemical reaction ?
Ans.: When change in concentration is measured over very small interval of time. It is
called instantaneous rate. It is denoted by dx/dt where X is small change in
concentration and dt is small interval of time.
Q5. Write the expression of rate constant for first order reaction
Ans.:
[ ]
[ ] R
R
t
K
0
log
303 . 2
=
Where [R
0
] is the original concentration of reactants
[R] is the concentration of reactant after time t.
Q6. Write the half life time expression for first order.
Ans.
K
t
693 . 0
2
1
=
Q7. Is half life time independent to initial concentration in first order reaction.
Ans.: Yes
Q8. Write the Arrhennius equation of reaction rate.
Ans.: RT
Ea
e A K

= .
where A is frequency factor,
E
a
is activation Energy.
Q9. What is elementary reaction.
Ans.: When reaction is compelled in single step.
Q10. What do you mean by molecularity of reaction.
Ans.: It is the number of molecules taking part in each act of leading chemical reaction.
Example : (1) decomposition of NH
4
NO
2.
O H N NO NH
2 2 2 4
2 + i.e. Unimolecular
(2)
2 2
2 I H HI + i.e. Bimolecular reaction
Q11. What do you mean by order of reaction.
Ans. : Sum of powers of the comcentarion of the reactants in the rate law expression is
called the order of that chemical reaction.
Suppose, Rate = K[A]
x
[B]
y
Hence, Order of reaction = x+y
Q.12. Calculate the overall order ofn a reaction which has the rate expression.
Ans. Rate = K[A]

[B]
3/2
Hence, Order of reaction = + 3/2 = 2 ( i.e. Second Order)
49
Q13. Write the Unit of K in Zero Order reaction.
Ans.: M
0
L
-1
S
-1
Q14. What is the Unit of K in first order reaction.
Ans. K=S
-1
Q15. What is the unit of K in Second Order reaction?
Ans. K=Mol
-1
.L.S
-1
Q16. Write the determination of second order reaction?
Ans. Molecularity is two & order of reaction is one.
Ex : OH H C COOH CH O H H COOC CH
H
5 2 3 2 5 2 3
+ +
+
Q17. Identify the reaction order if the unit of rate constant is Sec
-1
.
Ans. First order reaction.
Q18. What is the order of reaction of Nuclear reaction.
Ans.: First Order reaction
For Average Students :01 Mark
Q1. State any one condition under which a bimolecular reaction may be kinetically of first order?
Ans.:
0
2
1
5 2 3
5 2 3 5 2 3
] [ ] [ O H H COOC CH K Rate
OH H C COOH CH HOH H COOC CH
=
+ +
i.e. H
2
O is in excess.
Q2. Define activation energy.
Ans.: It is defined as extra energy to be supplied to the reactants so that they can
change into products.
Q3. A reaction is 50% complete in 2 Hrs and 75% complete in 4 Hrs.What is the order
of the reaction?
Ans. First Order.
Q4. The plot of log K versus X is linear with a slope = -E
a
/ 2.303 R. What is X?
Ans. X is 1/T.
Q5. The rate constant of a reaction is 1.2 x 10
-2
L.Mol
-1
S
-1
. What is the order of the
reaction ?
Ans.: Order =2
For Above Average Students : 01 Mark
Q1. What is temperature coefficient ?
Ans.:
298
308
R
R
Q2. Fill up the blanks :
.... ..........
.
1 2
2 1

=
T T
T T
R
E
a
Ans.:
1
2
R
R
Ln
50
Q3. A catalyst provides a path of . Activation energy.
Ans. Lower
Q4. In a photochemical reaction, the energy of activation is provided by
Ans.: Radiation
Q5. Which of the following graphs correspond to first order reaction ?
Ans.: (a)
Q6. Photochemical reaction between hydrogen & Chlorine on the Surface of water is a reaction of
(a) Zero Order, (b) First Order, (c) Second Order, (d) Third Order
Ans. : Zero Order
Q7. For a chemical reaction XA yM.
The rate law is r=K[A]
3
. If the concentration of A is doubled the reaction rate will be (a)
Doubled, (b) Quadrupled, (c) Increased by 8 times, (d) Unchanged
Ans.: (c)
CHEMICAL KINETICS
Below Average Students :02 Marks
Q1. Differentiate between order of reaction and molecularity of reaction.
Ans.
Order of reaction Molecularity
1. It is defined as sum of powers to which
concentration terms are raised in rate law
1. It is the number of molecules taking part in
chemical reaction.
2. It is determined experimentally 2. It is determined theoretically
3. It can be zero or even in fraction 3. It is always in whole number except Zero.
4. Order of complex reaction can be determined, 4. Molecularity of complex reaction can not be
determined.
Q2. For a reaction A+H
2
O B, rate TA. What is its
i) Molecularity, ii) Order of reactions ?
Ans. I) Its molecularity is 2
ii) Its order is 1.
Q3. Define pseudo unimolecular reaction. Give two examples.
Ans.: The reaction which is molecular but its order is one is called pseudo unimolecular
reaction. Eg.:
6 12 6 6 12 6 2 11 22 12
5 2 3 2 5 2 3
.) 2
.) 1
O H C O H C O H O H C
OH H C COOH CH O H H COOC CH
invertage
H
+ +
+ +
+
Glucose Fructose
Q4. Name four factors affecting rate of reduction.
51
(a) (b) (c) (D)
Rate Rate Rate Rate
C 1/c C C
2
Ans.: 1) Nature of reactants
2) Temperature
3) Concentration
4) Catalyst
Q5. When could order an molecularity of a reaction i) be Same ii) be different
Ans.: i) Order and molecularity will be same in single step reaction.
ii) They will be different if reaction is of two or more steps.
For Average Students : 02 Marks
Q1. Plot a graph between log cone Vs time and give expression value of K.
Ans. Slope= -K/2.303
Q2. The rate constant for a first order reaction is 0.005 min
-1
. Calculate its half life.
Ans.: Min
K
t 1386
05 . 0
693 . 0 693 . 0
2
1
= = =
Q.3. What is meant by effective collision?
Ans.: The collision which leads to formation of product. Molecules is called effective
collision.
Q4. When do molecules undergo effective collision?
Ans.: Molecules undergo effective collision if they cross energy barrier and orientation
barrier, that is they possess activation energy and collide in proper orientation.
Q5. How does concentration effect the rate of reaction?
Ans,: When we increase concentration of reactants, total no. of collision will increase, therefore,
probability of effective collision will increase, hence the rate of reaction will increase.
For Above Average Students : 02 Marks
Q1. An increase of 10 K in temp. rarely doubles the kinetic energy of particles but
doubles the rate of reaction, why?
Ans.: When temp. is increased 10 K , kinetic energy of molecules increases, no. of
molecules possessing activation energy become double, therefore no. of effective
collision doubles hence rate of reaction.
Q2. The rate of constants of a reaction at 500 K & 700 K are 0.02 Sec
-1
and 0.07 Sec
-
1
respectively. Calculate the values of Ea & A.
Ans.
61 . 1
012 . 0
02 . 0
. 02 . 0
,
8 . 18230
10 714 . 5
15 . 19
544 . 0
15 . 19
10
714 . 5 544 . 0
500 700
500 700
314 . 8 303 . 2 02 . 0
07 . 0
log
. 303 . 2
log
500 314 . 8
8 . 18230
14
4
1 1
2 1
1 2
1
2
= =
=
=
=

=
=

A
e A
Ae K Since
J Ea
Ea
mol JK
Ea
T T
T T
R
Ea
K
K
RT
Ea
Log
(Conc.)
time
52
FOR BELOW AVERAGE STUDENTS :03 Marks
Q1. Drive the relation
[ ]
[ ] R
o R
t
K log
303 . 2
=
Ans.: We know that rate of reaction is proportional to the first power of concentration of
the reactant R. For Ex.
[ ]
[ ]
[ ]
[ ]
dt K
R
R d
or
R K
dt
R d
Rate
P R
. , =
= =

Integrating this equation, we get

Ln[R]=-Kt+ I -------------------(1)
Again;
I is the constant of integration and its value can be determined easily,
When t=0, R=[R
0
], where [R
0
] is the initial concentration of the reactant.
Ln[R
0
]=-K x 0 +I
So, Ln[R
0
]=I
Substituting the value of I in Equation (1)
Ln[R]= -Kt + Ln [R
0
]
Rearranging this equation,
[ ]
[ ]
[ ]
[ ]
R
R
Log
t
K or
R
R
Ln
t
K or
Kt
R
R
Ln
0
0
0
303 . 2
,
1
,
=
=
=
Q2. Derive the expression t

= 0.693/ K for first order reaction.

Ans,:
[ ]
[ ]
K
t
t
K
R
R
t
K
R
R
Log
t
K
O
O
693 . 0
2 log
303 . 2
2
log
303 . 2
303 . 2
2
1
2
1
2
1
0
=
=
=
=
FOR AVERAGE STUDENTS :03 Marks
Q1. Derive the relationship between activation energy & rate constant.
Ans. Arrhenius equation RT
E
e A K

= .
where A is frequency factor, Ea is activation
energy, R= 8.314 JK
-1
mol
-1
, T is temp. in Kelvin.
53

=
=
=
=
2 1
1 2
1
2
2 1 1
2
2
1
. 303 . 2
log
1 1
ln
ln ln
ln ln
ln ln
T T
T T
R
Ea
K
K
T T R
Ea
K
K
RT
Ea
A k
RT
EG
A K
RT
Ea
A K
For Above Average Students : 03 Marks
Q1. The following results have been obtained during the kinetic studies of the reaction.
2A + B C + D
Experimental [A] M [B] M Initial rate of formation of D/M min
-1
1 0.1 0.1 6.0 x 10
-3
2 0.3 0.2 7.2 x 10
-2
3 0.3 0.4 2.88 x 10
-1
4 0.4 0.1 2.4 x 10
-2
Determined the rate law and the rate constant for the reaction.
Ans.:
) 4 ( ] 1 . 0 [ ] 4 . 0 [ 10 40 . 2
) 3 ( ] 1 . 0 [ ] 1 . 0 [ 10 0 . 6
2
2 2
2
1
4
1
, ), 2 /( ) 1 (
) 2 ( ] 4 . 0 [ ] 3 . 0 [ 10 2 . 7
) 1 ( ] [ ] [
2
3
2
2
=
=
=
= =
=
=

y x
y x
y
y x
y x
K
K
y
Y
weget Dividing
K
B A K
dt
dx
Dividing (3) by (2), we get,
1 2
2 1 3
2 1
0 . 6
] 1 . 0 [ ] 1 . 0 [ 10 0 . 6
] [ ] [ ] [ ] [
1
4
1
4
1

=
=
= =
= =
S M K
K
B A K B A K
dt
dx
x
x
y x
Q2. Calculate the half life of a first order reaction from their rate constants given below :
(a) 200 S
-1
(b) 2 Min
-1
(c) 4 year
-1
Ans.: (a) . 10 465 . 3
200
693 . 0 693 . 0
3
1
2
1
Sec
S K
t

= = =
(b) .. min 35 . 0 min 465 . 3
2
693 . 0
1
2
1
= = =

Min
t
(c) years t 173 . 0
4
693 . 0
2
1
= =
54
Q3. Give the mechanism of the reaction
) ( 2 ) ( ) (
2 2
g HCl g Cl g H
Sunlight
+
Ans.: Chain initiation step :
Cl Cl Cl
HN
2 +
Chain propagation step
Cl HCl Cl H
HCl H Cl H
+ +
+ +
2
2
Chain termination step
Q4. State the role of activated complex in a reaction and state the relation with energy of
activation.
Ans.: When the colliding reactant molecules possess the kinetic energy equal to energy of activation
then the configuration of atoms of the species at this state is different from the reactants as well as the
products.This state is called activated or transition state and specific configuration of this state is
called activated complex.
The reactant molecules do not change directly into products, first they absorb energy
equivalent to the energy of activation and form an activated complex. The activated complex formed
has a very short life spam and splits into the products. The activated complex is at the top of the
energy barrier graph and possess the highest energy. In this activated complex, all the bonds are in the
transition state.
Low energy activation barrier means the activated complex is readily formed and it is fast
reaction.
High energy of activation barrier means the activated complex is difficult to form and it is a
slow reaction.
55
A.B
Activated complex
E
af
Energy
P R
S
o
E E H =
ER JH
o
S
Reaction condition
UNIT 05
SURFACE
CHEMISTRY
STUDY MATERIAL
1. Adsorption:- It is the process of attracting molecular species on the surface of solid
or liquid .
2. Adsorbate:- The molecular species which concentrates or accumulates on the
surface known as Adsorbate.
3. Adsorbent:- The solid or liquid substance on which adsorption takes place known
as adsorbent .
4. Desorption:- The process of removal of adsorbed substance from a surface of solid
or liquid known as desorption.
5. Absorption:- The uniform distribution of molecular throughout the bulk of the solid
known as absorption.
6. Sorption:- The process in which both adsorption and absorption takes place
simultaneously known as sorption.
7. Enthalpy of Adsorption:- The amount of energy released by the attraction of one
mole of adsorbate on the adsorbent.
8. Types of adsorption :- There are two types of adsorption :
(a) Physisorption or Physical adsorption:- When the gas molecules are attracted or
accumulated on the solid by Vander waals forces.
(b) Chemisorption or Chemical adsorption:- When the gas molecules are accumulated on the
solid by chemical bonds.
9. Freundlich adsorption isotherm:- He gave a relation between the quantity of gas
adsorbed by unit mass of solid adsorbent and pressure at a particular temperature
x/m=k P
1/n
(n>1)
Where x be the mass of adsorbate ,m be the mass of adsorbent k & n be the constants
P be the pressure .This relation can be changed at different Pressure:-
At low pressure x/m=k P
1
At high pressure x/m=k P
0
At intermediate pressure x/m=k P
1/n

10. Adsorption from solution phase:- It has similar relation with Freundlich adsorption
isotherm .Only in place of pressure ,concentration of solution is taken.
Therefore x/m=k C
1/n

11. Catalyst:- A substance which increase or decrease the rate of chemical reaction
and quantitatively unchanged after the reaction known as catalyst. There are two types of
catalyst:- (i) Positive Catalyst and (ii) Negative Catalyst.
12. Promters:- A substance enhances the activity of catalyst.
13. Poisons:- A substance decreases the activity of catalyst.
14. Homogeneous catalysis:- When reactants and catalysts are in same phase ,the
process is known as Homogeneous catalysis.
Eg.
) ( 2 ) ( ) ( 2
3
) (
2 2
g SO g O g SO
g NO
+

56

15. Heterogeneous catalysis :- When reactants and catalysts are in different phases,
this process is known as Heterogeneous Catalysis.
Eg.: N
2
(g)

+ 3 H
2
(g)

Fe(S) 2 NH
3
(g)
16. Mechanism of heterogeneous catalysis :- The steps are as follows :
(i) Diffusion of reactants on the surface of catalyst.
(ii) Adsorption of reactants on the surface of catalyst.
(iii) Chemical reaction between reactants on the solid surface to form intermediate
product.
(ii) Desorption of product from solid surface.
(iii) Diffusion of products away from solid surface.
17. Shape-selective catalysis : A catalytic reaction that depends upon the pore structure
of catalyst as well as the size of reactant & product molecules is called Shape-selective
catalysis.
18. Enzyme Catalysis : Enzymes are biological catalyst which catalyse specific
biochemical reactions. They are complex nitrogenous organic compounds which are
produced by living plants and animals having high molecular mass. They are highly efficient
because they increase the rate of reaction by 10
8
to 10
20
times.
Eg.
2 3 2 2 2
2 CO NH O H CONH NH
Urease
+ +
Urease is an enzyme used for the decomposition of Urea only.
19. Colloids or Colloidal Solution : A heterogeneous solution in which dispersed
phase mixed in dispersion medium.
20. Lyophilic Colloids : Those colloids which are solvents loving or attracting they are
reversible Sols.
21. Lyophobic Colloids :- Those colloids which are solvent hating. It is
irreversible Sols.
22. Multimolecular Colloids: A colloid in which large no. of atoms or smaller
molecules aggregate together to form species having size in colloidal range for eg. A sulphur
sol consists of particles containing about a thousand of S
8
molecule.
23. Macromolecular colloids : A colloid in which the size of dispersed particles are in
a colloidal range. Such dispersed phase in dispersion medium is called Macromolecular
colloids. For Eg. Proteins, Starch and Cellulose form macromolecular colloids.
24. Associated Colloids : Those colloids which behave as strong electrolyte at low
concentration but at high concentration behave like colloids due to formation of aggregated
particle of colloidal dimensions. For eg. Micelles are associated colloids.
25. Kraft Temperature : The formation of Micelles takes place only above a particular
temp. is called Kraft temp.
26. Peptization : The process of converting precipitate into colloidal sol by mixing
small amount of electrolyte into dispersion medium known as peptization and the electrolyte
known as peptizing agent.
27. Dialysis : It is the process of purification of colloids by diffusion through a semi
permeable membrane.
57
28. Ultra filtration: It is the process of separating the colloidal particles from the
solvent and the solute present in colloida solution by ultra filter paper.
29. Tyndal effect : The process of scattering of light in colloidal solution by
colloidal solute known as Tyndal effect. The bright cone of light is called Tyndal cone.
30. Brownian Movement : The continuous zig zag motion of dispersed
phase in dispersion medium is called Brownian Movement. It is due to the unbalanced
bombardment of the particles by the molecules of the dispersion medium.
31. Helmholtz Electrical double layer : The combination of the two layers of
opposite charges around the colloidal solute is called Helmholtz Electrical double layer.
When the colloidal particles acquire +ve or ve charge by selective adsorption of one of the
ions, It attracts counter ions from the medium forming a second layer like.
Ag I / I
-
K
+
AgI / Ag
+
I

32. Zeta potential or Electro kinetic potential : The potential difference between
the fixed layer and the diffused layer of colloidal solution having opposite charges.
33. Electrophoresis : The process of migration of charged colloidal solute towards
the oppositely charged electrode in colloidal solution is known as Electrophoresis.
34. Coagulation : The process of converting colloidal solution into precipitate by mixing
small amount of oppositely charged electrolyte known as Coagulation.
35. Coagulative Value : The minimum no. of a milli moles of electrolyte requires to
coagulate one litre colloidal solutions.
36. Hardy-Schultz Rules: It has two rules :
a) Oppositely charged ions are effective for coagulation.
b) The coagulative power of electrolyte increases with increase in charged on the
ion used for coagulation. For Eg. :
Al
3+
> Ca
++
> Na
+
for negatively charged colloids. Similarly
[ Fe(CN)
6
]
4-
> PO
4
3-
>SO
4
2-
> Cl
-
for positively charged colloids.
37. Emulsion : A colloids contain dispersed phase and dispersion medium both in
liquid state is known as Emulsion.
There are two types of emulsion.
(i) Oil in water & (ii) water in oil.
38. Cottrell Smoke precipitator : Smoke is a colloidal solution of solid particles
like C, As compounds and dust in air. It comes out through the chimneys of industrial plants.
It consists of two metal discs charged to high potential. The charged dust and C , As particles
get discharged towards oppositely charged metal disc in form of precipitate while gases come
out through chimney.
1 MARK QUESTIONS
58
Q. 1. What kind of adsorption is represented by the following graph :
T
x
M
Ans. Chemisorption.
Q. 2. In the titration of oxalic acid by acidified KMnO
4
, the oxidation of oxalic acid is
slow in the beginning but becomes fast as the reaction progresses. Why ?
Ans. Autocatalysis by Mn
+2
.
Q. 3. Out of PO
4
3,
, SO
4
2,
, Cl
,
, which wil act as the best coagulating agent for for Fe
(OH)
3
?
Ans. PO
4
3
.
Q. 4. Arrange the following in correct order of their coagulating power :
Na
+
, Al
3+
, Ba
2+
Ans. Na
+
< Ba
2+
< Al
3+
Q. 5. Which type of charged particles are adsorbed on the surface of As
2
S
3
during its
preparation ?
As
2
O
3
+ 3 H
2
S As
2
S
3
+ 3 HOH
Ans. S
2
.
Q. 6. Which type of metals act as effective catalysts ?
Ans. Transition metals.
Q. 7. The colloidal solution of gold prepared by different methods have different
colours. Why ?
Ans. Due to difference in the size of colloidal particles.
Q. 8. At high pressure, the entire metal surface gets covered by a mono molecular
layer of the gas. What is the order of the process ?
Ans. Zero order.
59
Q. 9. What is the term used for minimum concentration of an electrolyte which is able
to cause coagulation of a sol ?
Ans. Flocculation value.
Q. 10. A liquid is found to scatter a beam of light but leaves no residue when passed
through the filter paper. What can the liquid be described as ?
Ans. Colloid.
Q. 11. If an electric field is applied to a colloidal sol, the dispersed phase particles are
found to move towards the electrode of opposite charge. If however, the
dispersed phase is made stationary, the dispersion medium is found to move in
the opposite direction. What is the term used for such movement of dispersion
medium ?
Ans. Electro osmosis.
Q. 12. Out of glucose, urea and dodecyl trimethyl ammonium chloride, which one
forms micelles in aqueous solution above certain concentration ?
Ans. Dodecyl trimethyl ammonium chloride.
Q. 13. A plot of log versus log p for the adsorption of a gas on a solid gives a straight
line. What is the slope equal to ?
Ans.
1
n
Q. 14. The formation of micelles occurs only beyond a certain temperature. What is the
temperature called ?
Ans. Kraft temperature
Q. 15. What are the signs of H, S and G for the process of adsorption ?
Ans. H = ve `
S = ve `
G = ve `
Q. 16. Out of CO and NH
3
which is adsorbed on activated charcoal to a large extent
and why ?
Ans. Ammonia; because more easily liquefiable gas undergoes adsorption to a greater
extent.
Q. 17. On passing H
2
S through dilute HNO
3
the colourless solution becomes turbid. Why ?
Ans. Due to formation of colloidal sol of Sulphur.
Q. 18. A sol is prepared by addition to excess AgNO
3
solution in KI solution. What
charge is likely to develop on the colloidal particles ?
60
Ans. Positive.
Q. 19. If we add equimolar amounts of ferric hydroxide sol and arsenic sulphide sol,
what will happen ?
Ans. Both the sols will get coagulated.
Q. 20. What happens when freshly precipitated Fe (OH)
3
is shaken with a little amount
of dilute solution of FeCl
3
?
Ans. It causes peptization leading to the formation of a positively charged sol of Fe (OH)
3
.
Q. 21. What happens to a gold sol if gelatin is added to it ?
Ans. It causes stabilisation of gold sol.
Q. 22. Out of NaCl, MgSO
4
, Al
2
(SO
4
)
3
, K
4
[Fe(CN)
6
], which one will bring about the
coagulation of a gold sol quickest and in the least of concentration ?
Ans. Al
2
(SO
4
)
3
.
Q. 23. What is the unit for expressing flocculation value ?
Ans. millimole per litre.
Q. 24. Out of PO
4
3
, SO
4
2
, Al
3+
and Na
+
, which will have the highest coagulating power
for As
2
S
3
colloid ?
Ans. Al
3+
.
2 MARKS QUESTIONS
Q. 1. Bleeding is stopped by the application of alum to a wound. Why ?
Ans. Blood is a colloid alum being an electrolyte, makes the blood to coagulate and form
clot.
Q. 2. What is the purpose of adding gelatin to ice cream ?
Ans. Ice cream is a colloid. Gelatin imparts stability to it because gelatin is a protective
colloid.
Q. 3. Dialysis is a method of purification of sols. But prolonged dialysis of the sol
makes it unstable. Why ?
Ans. Traces of electrolytes in the sol, impart charge to dispersed phase particles making it
stable. Prolonged dialysis removes all electrolytes thus making the sol unstable.
Q. 4. What is the function of gum arabic in the preparation of Indian ink ?
Ans. Gum arabic is a protective colloid and thus provides stability to Indian ink.
Q. 5. What is collodion ? What is its use ?
61
Ans. Cellulose dispersed in ethanol, is called collodion. It is used for making membranes
for ultrafiltration.
Q. 6. Why the sun looks red at the time of setting ? Explain on the basis of colloidal
properties.
Ans. At the time of setting, the sun is at the horizon. The light emitted by the sun has to
travel a longer distance through the atmosphere. As a result, blue part of the light is
scattered away by the dust particles in the atmosphere. Hence the red part is visible.
Q. 7. Addition of H
2
to acetylene gives ethane in presence of palladium but if BaSO
4
and quinoline or sulphur are also added, the product is ethane. Why ?
Ans. BaSO
4
+ quinoline / s poison the catalyst. Hence, the efficiency of the catalyst
decreases and the reaction stops at the first stage of reduction.
Q. 8. SnO
2
forms a positively charged colloidal sol in acidic medium and a negatively
charged sol in the basic medium. Why ?
Ans. SnO
2
is amphoteric in nature. It reacts with acid eg. HCl to form SnCl
4
in the solution.
The common Sn
4+
ions are adsorbed on the surface of SnO
2
particles giving them a
positive charge.
SnO
2
reacts with a base eg. NaOH to form Sodium Stannate in the solution. The
stannate ions are adsorbed on the surface of SnO
2
particles giving them a negative
charge.
Q. 9. Why physical adsorption is multimolecular whereas chemisorption is
unimolecular ?
Ans. Chemisorption takes place as a result of reaction between adsorbent and adsorbate.
When the surface of the adsorbent is covered with one layer, no further reaction can
take place.
Physical adsorption is simply by Vander Waals forces. So any number of layers may
be formed one over the other on the surface of the adsorbent.
Q. 10. What is meant by induced catalysis ? Give an example.
Ans. It is a phenomenon in which a chemical reaction increases the rate of another reaction
which otherwise may not occur in similar conditions.
Eg. Sodium arsenite (Na
3
AsO
3
) is not oxidised in air but if air is blown into a solution
containing Na
3
AsO
3
and Na
2
SO
3
, then both AsO
3
3
and SO
3
2
ions are oxidised.
Q. 11. What type of colloidal sols are formed in the following ?
(i) Sulphur vapours are passed through cold water.
(ii) White of an egg is mixed with water.
(iii) Concentration of soap solution is increased.
62
Ans. (i) Multimolecular colloid
(ii) Macromolecular colloid
(iii) Associated colloid.
Q. 12. What is common to aquasol and aerosol ? In what respect do they differ ?
Ans. Both are colloids.
In aquasol, water acts as dispersion medium.
In aerosol, air acts as dispersion medium.
Q. 13. Explain as to why SnO
2
forms a positively charged sol in solutions with pH < 7
and negatively charged sol in solutions with pH > 7.
Ans. Refer Ans. 8.
For average
Q.1 Why does physisorption decrease with increase of temperature ?
Ans.: Because the attraction between gas molecules and solid surface is very weak
which easily over come by increase of temperature.
Q2. Why are powdered substances more effective absorbents than their crystalline
forms?
Ans. Due to increase of surface area of powered substances.
Q.3. What do you mean by activation of adsorbant? How is it achieved?
Ans.: Activation of adsorbent means increase the extent of adsorption. It is achieved by
the increase of surface area.
Q4. Discuss the effect of pressure and temperature on the adsorption of gases on
solids.
Ans: Effect of pressure : By the increase of temp., extent of adsorption decreases
uniformly for physisorption but for chemisorption initially increases then
decreases.
Q5. What is observed
(i) When a beam of light is pressed through a colloidal sol
(ii) An electrolyte, NaCl is added to hydrated ferric oxide sol.
(iii) Electric current is passed through colloidal sol.
Ans.: (i) Tyndal Effect
(iv) Coagulation
(v) Electrophoresis
Q6. What do you mean by activity and selectivity of catalysis?
Ans. Activity of catalyst means to increase the extent of chemisorption.
Selectivity of Catalyst means to direct a reaction to form selective product.
Q7. What is ZSM-5? What is its formula?
Ans.: ZSM-5 is a zeoli8te seine of molecular porosity5. Its formula is
H
x
[(AlO
2
)
x
(SiO
2
)
96-x
] . 16H
2
O
Q8. Why adsorption is always exothermic?
Ans.: In Adsorption, change of entropy S is ve i.e. non favourable condition for exothermic
change where as change of enthalpy H is ve i.e. favourable condition for exothermic
change. Overall G becomes ve in adsorption; therefore adsorption is always exothermic.
Q9. Explain the following terms :
(i) Electrophoresis, (ii) Coagulation, (iii) Dialysis (iV) Tyndal Effect
63
Ans.: (i) Electrophoresis :- The immigration of colloidal solute towards oppositely charged
electrode under an electric potential is called Electrophoresis.
(ii) Coagulation :- The process of settling down of colloidal partcles is known as
coagulation.
(iii) Dialysis :- It is a process of removing dissolved impurities from colloidal solution by
means of diffusion through a suitable membrane.
(iv) Tyndal effect :- The scattering of light in colloidal solution by colloidal solute is
known as Tyndal effect.
Q10. Comment on the statement that colloid is not a substance but state of a substance .
Ans. A substance shows different physical properties in different medium. It may exist as colloid
or crystalloids under certain conditions. Eg. NaCl in water behaves like crystalloid while in
benzene behaves like colloid. Similarly dilute soap solution behaves like crystalloid whereas
concentrated soap solution like colloids. It is the size of particles which matters i.e. the state
in which the substances exists. If the size of the particles lies in the range 1 to 1000 no., it is
in colloidal state.
Q11. Why are substances like Platinum and Palladium offer used for carrying out electrolysis in
aqueous solution ?
Ans.: Platinum and palladium is inert electrodes. They are not react with the ions of electrolyte and
products of electrolysis. Hence they are used as electrodes during electrolysis. Hence they are
used as electrodes during electrolysis. Hence they are used as electrodes during electrolysis in
aqueous solution.
Q12. Why it is necessary to remove CO when ammonia is obtained by Habers process?
Ans.: Because CO acts as poison for the catalyst in the manufacture of NH
3
by Habers process.
Q13. Which will be adsorbed more readily on the surface of charcoal and why NH
3
or CO
2
?
Ans: The critical temperature NH
3
is more CO
2
, therefore NH
3
is liquefied more easily than CO
2
.
Hence NH
3
has higher intermolecular forces of attraction and hence it adsorbed more readily.
Q14. What is similarity and dissimilarity in aqua solution and solid aerosols?
Ans. Aqua Sols and solid aerosols both have solid as dispersed phase and have different dispersion
medium. Aqua solution contain water and aerosol contain air as dispersion medium.
Q15. How can a colloidal solution and true solution of the same colour be distinguished from each
other?
Ans.: By Tyndal effect( colloidal solution will scatter light and path becomes lighted where as no
such phenomena is observed in true solution.)
Q16. Why is ferric chloride preferred over potassium chloride in case of a cut leading to bleeding?
Ans.: Blood is negatively charge colloidal particles. It is coagulated by +ve ions. As Fe
++
ions has
greater number of charges than K
+
ions. Therefore on the basis of Hardy-Schulze rule,
Coagulation with Fe
+++
is faster and hence it is preferred.
BELOW AVERAGE STUDENTS :01 Mark Questions
1. Define Adsorption with one example.
2. What is physisorption and chemisorption ?
3. What is Freundlich adsorption isotheorem ?
4. Write the relation between quantity of gas adsorbed by unit mass of Solid adsorbent
and pressure at a particular temperature.
5. Draw a graph between rate of adsorption and pressure at different temperature like
T
1
>T
2
>T
3
.
64
6. Define catalysis with one example.
7. Write the use of ZSM-5.
8. What is Biochemical catalysis?
9. What is Colloids?
10. Define Dispersed phase and Dispersion medium.
11. Define Micelle.
12. What is Peptization?
13. What is Tyndal effect?
14. Define Coagulation and Precipitation of Sol.
15. What is Gel?
16. Define Peptizing agent.
AVERAGE STUDENTS :01 MARK QUESTIONS
1 Why the pressure of gas is decreased when a gas like O
2
, H
2
, CO, Cl
2
, NH
3
or
SO
2
is taken in closed vessels containing powdered charcoal ?
2. Why does physisorption decreases with increase of temperature?
3. Why are powdered substances are more effective adsorbents than their crystalline
forms?
4. Write the process by which vegetable oil converted into vegetable Ghee.
5. What is shape-selective catalysis?
6. Write two examples of heterogeneous catalysis.
ABOVE AVERAGE STUDENTS : 01 Mark
1. Define Enthalpy of Adsorption.
2. What is the role of desorption in the process of catalysis?
3. Define Tyndal Cone.
4. What is Electrokinetic Potential or Zeta Potential?
5. Define Coagulating Value.
SURFACE CHEMISTRY
Below Average Students :02 Marks Questions
1. Explain Desorption and Sorption.
2. Write two differences between physisorption and chemisorption.
3. What is homogeneous and Heterogeneous catalysis? Give one example each.
4. Define Promoters and Poisons.
5. Write two applications of catalyst in Industry.
6. Explain cleansing action of soap.
65
7. What are the methods for the preparation of colloids.
8. What is purification of colloidal solution? Name the process of purification of
colloids.
9. Write brief notes on
(a) Brownian Movement and
(b) Electrophoresis.
10. State Hardy-Schulze Rule. What is its application?
11. Write the example of colloids which is being used in our daily life.
AVERAGE STUDENTS :
02 Marks Question
1. Write the mechanism of Adsorption.
2. Why are substances like Platinum and Palladium often used for carrying out
electrolysis of aqueous solution?
3. What is function of promoters and Poisons?
4. Write the name of process and catalyst used for the preparation of NH
3

5. How can be Lyophobic colloids prepared?
6. Give two examples for preparation of colloids by chemical methods.
7. What is demulsification? Name two demulsifiers .
ABOVE AVERAGE STUDENTS :
02 Marks Questions
1. Write the mechanism of Homogeneous catalysis reaction
( ) ( )
( )
( ) g SO g O g SO
g NO
3 2 2
2 2 +
2. Define Kraft temperature (T
K
) and critical Micelle concentration (CMC).
3. What is the role of electrolyte in coagulation or precipitation?
4. Write the cause of formation of delta in brief.
5. Define Intrinsic and Extrinsic colloids with example.
BELOW AVERAGE STUDENTS :
03 Marks Questions
1 Define Adsorption, Adsorbent and Adsorbate.
2. Write three characteristics of physisorption and chemisorption.
3. Write at least three factors on which rate of adsorption depends.
4. Write three applications of Adsorption.
5. What are the characteristics of Enzyme catalysis?
66
6. Write three differences between Lyophilic and Lyophobic colloids.
7. Define Multimolecular, Associated and Macro molecular colloids.
8. Define Dialysis, Electro dialysis and Ultra filtration.
9. What is Emulsion. Write the types of Emulsions. How can be tested?
10. Write at least three applications of colloids.
AVERAGE STUDENTS :
03 Marks Questions
1. Draw a graph between
m
x
log
and log P.
Write the value of intercept and slope.
2. Write a brief notes on activity and selectivity of solid catalyst with example.
3. What is Zeolite? Write its structure and use.
4. What are Enzymes. Write the mechanism of Enzyme catalysis.
5. Write at least three differences between true solution , colloidal solution and
suspension.
6. Write the causes for the creation of charge on colloidal particles.
7. Explain the terms with suitable examples
(a) Alcosol, (b) Aerosol, (c) Hydrosol
8. Name the catalyst for Habers Process, Ostwalds Process and Contact Process.
ABOVE AVERAGE STUDENTS :
03 Marks Questions
1. Write the steps involve for mechanism of Heterogeneous catalysis?
2. Write a brief note on mechanism on Micelle formation.
3. What do you mean by Cottrell smoke precipitator.
67
STUDY MATERIAL
Important Points :
Mode of occurrence of elements : Elements are found in nature either in the free state is also called
the native state, or in the combined state i.e. found in the form of compounds. This is mainly due to
the reason that different elements have different chemical reactivities.
Native States : Elements or metals which are not attacked by moisture, oxygen and carbon dioxide of
the air occur in the native state. Examples: Carbon, Sulphur, Gold, Platinum, Noble Gases etc.
Combined States: The elements which are readily / easily attacked by moisture, Oxygen and Carbon
dioxide of air, occur in the combined state in form of their compounds are called minerals.
In the combined state, non-metals are found in the reduced form i.e.

X
( where x= F,Cl,Br,
I) while metals are found in the oxidized form i.e. is oxides eg. Fe
2
O
3
, Al
2
O
3
, SnO
2
, MnO
2
etc.
Minerals : The naturally occurring chemical substances in the form of which the metal occurs in
the earth along with impurities are called minerals.
Ores: The minerals from which the metal is conveniently and economically extracted is called an
Ores. Thus all ores are minerals but all minerals are not Ores.
Gangue or Matrix : The Earthy and silicious impurities with ores are known as matrix or Gangue.
Principal ores of some Important Metals :
Metal Ores Composition
Aluminium Bauxite
Kaolinite ( a form of Clay)
AlO
x
(OH)
3-2x

[ where 0 < x<1]
Iron Hematite Fe
2
O
3
Magnetite Fe
3
O
4
Iron Pyrite FeS
2
Copper Copper Pyrite CuFeS
2
Malachite CuCO
3
.Cu(OH)
2
Cuprite Cu
2
O
Zinc Zinc Blend ZnS
Sintering : It is a process of crushing ores to reasonable size before concentration of ores. It is
followed by heating of solid particles below its m.p. to change it into single mass.
Concentration : The process of removal of unwanted materials like sand, clay , rock etc from
ore is known as concentration or benefication or enrichment or dressing.
Leaching or chemical separation : It is a process in which ore is treated with suitable reagent which
dissolves ores but not the impurities.
Beayers Process or purification of bauxite by leaching : Bauxite ore is treated with caustic
soda (NaOH) , Al
2
O
3
dissolves in concentrated solution leaving behind impurities.
( ) ( ) ( ) ( ) aq l aq S
OH Al Na O H NaOH O Al ] ) ( [ 2 3 2
4 2 3 2
+ +
68
UNIT 06 :
GENERAL PRINCIPLES
AND PROCESS OF
ISOLATION OF ELEMENTS
The aluminate in solution is neutralized by passing CO
2
gas and hydrated Al
2
O
3
is precipitated. At this
stage the solution is seeded with freshly prepared samples of hydrated Al
2
O
3
, which induces the
precipitation.
( ) ( ) aq aq
NaHCO O xH O Al CO OH Al Na
3 2 3 2 2 4
2 . ] ) ( [ 2 + +
The precipitate of Al(OH)
3
is filtered, dried and finally heated to about 1470 K to obtain pure
Al
2
O
3
.
( ) ( ) g s
K
O xH O Al O xH O Al
2 3 2
1470
2 3 2
. +
Concentration of Gold & Silver ores by leaching : In the metallurgy of Ag & Au the respective
metal is leached with a dilute solution NaCN or KCN in the presence of air for oxygen from which a
metal is obtained later by replacement.
( )
( )
( )
( )
( ) ( ) aq aq
g
aq
s
OH CN M O O H CN M

+ + + + 4 ] [ 4 2 8 4
2 2 2
Where M= Ag or Au
( )
( )
( )
( )
( ) s
aq
s
aq
M CN Zn Zn CN M 2 ] ) ( [ ] [ 4
2
4 2
+ +

EXTRACTION OF CRUDE METAL FROM CONCENTRATED ORES :-

Conversion of ore into oxide i.e. de-electronation of ores : It is achieved by calcination and
roasting.
Calcination : It is the process of converting an ore into its oxide by heating it strongly below
its m.p. either in absence or limited supply of air.
This method is commonly used to convert metal carbonates and hydroxides to their
respective oxides.During the process of calcination, the following chemical changes occurs.
1) Moisture is driven out.
2) Volatile impurities of S, As & P are removed as their volatile oxides.
3) Water is removed from hydrated oxides and hydroxides ores.
O H O Al O H O Al
Heat
2 3 2 2 3 2
2 2 . +
Bauxite Alumina
O H O Fe O H O Fe
2 3 2 2 3 2
3 3 . +

Limonite Ferric oxide

4) Carbonate ores are converted into their respective oxides by loss of carbon dioxides.
2 3
CO CaO CaCO +

Limestone Calcium Oxide

( )
2 2 2 3
2 . CO O H CuO OH Cu CuCO + +

Malachite
4) It makes the ore porous and hence easily workable in subsequent stages. Calcination is
usually carried out in a reverberatory furnace.
Roasting : It is the process of converting an ore into its metallic oxide by heating strongly at temp. is
sufficient to melt in excess of air. This process is commonly used for sulphide ores. The following
changes occurs during roasting.
1.Moisture is removed
2.Organic matter is destroyed
3.Non-Metallic impurities like that of sulphur, Phosphorous and Arsenic are oxidized
and are removed as volatile gases.
69
+
+
+
3 2 2
10 4 2 4
2 2 8
2 3 4
5
8 8
O Al O As
O P O P
SO O S
4. Ores are generally converted into metallic oxides.

3 2 2 2
2 2
2 2
2 2 3 2
2 2 3 2
2 2 3 2
SO O Cu O S Cu
SO PbO O PbS
SO ZnO O ZnS
+ +
+ +
+ +
5 .It makes the ore porous & hence easily workable in subsequence stage.
1 MARK QUESTIONS
Q. 1. Why carbon reduction process is not applied for reducing
aluminium oxide to aluminium ?
Ans. Because aluminium metal itself a very powerful agent and can easily
reduce CO formed during the reaction back to carbon.
Q. 2. Explain why thermit process is quite useful for repairing the
broken parts of a machine ?
Ans. In thermit process, oxides of metals are reduced by aluminium in
which large amount of beat is evolved, metal is in the motten state & is '
allowed to fall between the broken parts of a machine.
heat
Fe
2
O
3
(s) + 2 Al (s) Al
2
O
3
+ 2 Fe (l) + heat
molen
Q. 3. Free energies of formation (
f
G) of MgO (s) and CO (g) at 1273 K and
2273 K are given below :
`
f
G MgO (s) = 941 KJ/mol at 1273 K
= 344 KJ/mol at 2273 K
`
f
G CO (g) = 439 KJ/mol at 1273 K
= 628 KJ/mol at 2273 K
On the basis of the above data, predict the temperature at which carbon
can be used as reducing agent for MgO (s).
Ans. The redox reaction is :
70
MgO (s) + C (s) Mg (s) + CO (g)
G = ` `
f
G
(Products)
`
f
G
reactant
At 1273 K G = 439 ( 941) = 502 KJ mol `
1
At 2273 K G = 628 ( 314) = 314 KJ mol `
1
The reaction is feasible at 2273 K.
Q. 4. Why is Zinc and not Copper used for the recovery of Silver from
the complex [Ag (CN)
2
] ?
Ans. Zinc is stronger reducing agent and more electropositive than Copper.
(E = + 0.34V)
Q. 5. Graphite is used as anode and not diamond. Assign reason.
Ans. In graphite there are free electrons which helps in
electricalconductivity.
Q. 6. How is granular zinc & zinc dust obtained ?
Ans. Granular zinc is obtained by pouring molten zinc in cold water & zinc dust by
melting zinc & then atomising it with blast of air.
Q. 7. How does NaCN act as a depressant in preventing ZnS from forming the
froth ?
Ans. NaCN forms a layer of zinc complex, Na
2
[Zn (CN)
4
] on the surface of ZnS
and thereby prevents it from the formation of froth.
Q. 8. In the process of extraction of gold, Roasted gold ore :
O
2
Roasted gold ore + CN

+ H
2
O [X] + OH

[X] + Zn [Y] + Au
Identify the complexes [X] & [Y].
Ans. [X] = [Au (CN)
2
]

, [Y] = [Zn (CN)

4
]
2
Q. 9. Why is the reduction of a metal oxide easier if the metal formed is in
liquid state at the temp. of reduction ?
Ans. The reduction of metal oxide is as :
M
2
O (s) + xM
1
(s or l) x M (s or l) + M
1
x
O (s)
The entropy of liquid metal is more than entropy of the metal in solid state. '
G for the reduction become more on negative side. `
G = H T S ` ` `
71
Q. 10. What is the role of collector in froth floatation process ?
Ans. Collector enhances non-wettability of the mineral particles.
Q. 11. At which temperature direct reduction of Fe
2
O
3
by carbon is possible ?
Ans. Above 1123 K, carbon can reduce Fe
2
O
3
.
Q. 12. Why a very high cosmic abundance of iron is there ?
Ans. A very high cosmic abundance of iron is due to its high nuclear binding
energy.
Q. 13. Why refractory metals are used in construction of furnaces ?
Ans. Refractory metals are used in construction of furnaces because they can
withstand high temperature.
Q. 14. What is pyrometallurgy ?
Ans. Extraction of metals using heat is called pyrometallurgy. It involves
concentration of ores, roasting calcination, smelting, reduction and refining of metals.
Sulphide, carbonate, oxide ores etc. are subjected to pyrometallurgy.
Q. 15. How the most electropositive metals are isolated from their ores ?
Ans. The most electropositive metals are isolated from their ores by electrolysis of
fused ionic salts.
SOME IMORTANT QUESTIONS
Q.1. In general which metals do you expect to occur in the nature in native state? Give examples.
Ans. : Metals such as Cu, Ag, Au, Pt etc. which lie below hudrogen in electrochemical series are not
readily attached by Oxygen, moisture and Carbon dioxide of the atmosphere and hence occur
in the native state in nature.
Q.2. Copper and Silver lie below in the electrochemical series and yet they are found in the
combined state as sulphide in nature.Comment.
Ans. : Due to high polarizing power of Cu and Ag ions, their sulphides are even more stable than the
metals.
Q.3. Which metals are generally extracted by electrolyte process? Which positions these metals
generally occupy in the periodic table?
Ans. : Electrolytic process is used for the extraction of active metals like Na, Ca, Mg, K, Al etc.
where all other methods fail. Except Al and few other metals, these metals belongs to S-block
elements of periodic table.
Q.4. Although thermodynamically feasible, in practice, Magnesium metal is not used for the
reduction of Alumina in the metallurgy of aluminium.Why?
Ans. : Below the temperature(1623 K) correspoinding to the point of intersection of Al
2
O
3
and MgO
curves in Ellingham diagram, Magnesium can reduce Alumina because the
f
G
o
value of
Al
2
O
3
at temperatures below 1623 K, is less negative than that of MgO. Therefore below 1623
K Mg can reduce Al
2
O
3
to Al. But Magnesium is much costier metal than Aluminium and
hence the process will be uneconomical.
72
Q.5. Why is the reduction od a metal oxide easier if the metal formed is in the liquid state at the
temperature of reduction?
Ans. : Entropy is higher when a metal is in the liquid state than when it is in the solid state.
Therefore, the value of entropy change (s) of the reduction process is more on the +ve side
when the metal formed is in the liquid state and the metal oxide being reduced is in the solid
state. Since the value of T S increase and that of H remains constant, therefore the value of
G
o
(
0 0 0
S T H G = _) becomes more on the ve side and the reduction becomes
easier.
Q.6. At a site, low grade copper ores are available and zinc and iron seraps are also available.
Which of the two seraps will be more suitable for reducing the leached copper ore and why ?
Ans. : The E
0
value for the redox couple Zn
2+
/ Zn(-0.76V) is more negative than that of Fe
2+
/ Fe(-
0.44) redox couple. Therefore, Zinc is more reactive than iron and hence reduction will be
faster in case if Zinc seraps are used, But Zinc is a costier metal than iron so using iron scraps
would be more economical.
Q.7. (A). Name the method used for refining of (i) Nickel (ii) Zirconium
(B). The Extarction of Au by leaching with NaCN envolves both Oxidation and Reduction.
Justify giving equations.
Ans. ; (A) [ i ] Mond Process : It is used to refine Nickel metal. When impure Nickel is heated in a
current of CO at 330-350 K, it forms volatile nickel tetracarbonyl complex leaving behind the
impurities. This complex again on heating at higher (450-470K) it undergoes thermal
decomposition giving pure Nickel.
( )
4
350 330
4 CO Ni CO Ni
K
+

Impure Nickel tetracarbonyl
Nickel
( ) CO Ni CO Ni
K
4
470 450
4
+

Pure Nickel
[ ii ] Van Arkel method : This method is very useful for preparing ultra pure metals by
removing all the Oxygen and Nitrogen present in the form of impurity in certain metals such as
Zirconium and titanium which are used in space technology.
In this method, crude Zirconium is heated in a evacuated vessels with iodine at 870 K, the
covalent volatile ZrI
4
thus formed is separated. It is then decomposed by heating over a tungsten
filament at 2075 K to give pure Zirconium.
( ) ( ) ( ) ( ) ( ) g s
K
g g s
I Zr ZrI I Zr
2
2075
4
870
2
2 2 + +
Impure Tungsten Pure
filament
(B) During the leaching process, Au is first oxidized to Au
+
by Oxygen (O
2
) of the air which then
combines with CN
-
(Cyanide) ion to form the soluble complex, Sodium dicyanoaurate(I).
( )
( )
( )
( ) [ ]
( ) ( ) aq aq g s
NaOH CN Au Na O O H aq NaCN Au 4 4 2 8 4
2 2 2
+ + + +
Impure Soluble Complex
Gold is then extracted from this complex, by displacement method using a more electropositive Zinc
metal, In this reaction, Zn acts as a reducing agent. It reduces Au
+
Au while it itself gets oxidized to
Zn
2+
which combines with CN
-
ions to form soluble complex, sodium tetracy anozincate(II)
( ) [ ]
( ) ( ) ( )
( ) [ ]
( ) aq s s aq
CN Zn Na Au Zn CN Au Na
4 2 2
2 2 + +
Thus extraction of Au by leaching with NaCN involved both oxidation and reduction.
Q.8. Free energies of formation (
f
G) of MgO
(s)
and CO
(g)
at 1273 K and 2273 K are given below :
73

f
G(MgO)
(s)
= -941 KJ/mol at 1273 K

f
G(MgO)
(s)
= -314 KJ/mol at 2273 K

f
G(CO
(g)
) = -439 KJ/mol at 1273 K

f
G(CO
(g)
) = -628 KJ/mol at 2273 K
On the basis of above data, predict the temperature at which carbon can be used as a reducing agent
for MgO
(s)
.
Ans. : (a) At 1273 K
i)
( ) ( )
mol Kj G MgO O Mg
f s s
/ 941 ;
2
1
2
= +
ii)
( ) ( )
mol Kj G CO O C
f s s
/ 439 ;
2
1
2
= +
The equation for reduction of MgO to Mg by C can be obtained by substracting equation (i) from
equation (ii). Thus
( ) ( ) ( ) ( ) g s s s
CO Mg C MgO + +
mol KJ G
r
/ 602 + =
Since
r
G of the above reduction reaction is +ve; therefore, reduction of MgO by C is not feasible at
1273 K.
(b) At 2273 K
iii)
( ) ( )
mol KJ G MgO O Mg
f s s
/ 314 ;
2
1
2
= +
iv)
( ) ( )
mol KJ G CO O C
f s s
/ 628 ;
2
1
2
= +
On substarcting Eq.(III) from Eq.(IV), we have
( ) ( ) ( ) ( )
mol KJ G CO Mg C MgO
r g s s s
/ 314 ; = + +
Since
r
G for the above reduction reaction is ve; therefore reduction of MgO by carbon at 2273 is
feasible.
Q.9. Metal sulphides occur mainly in rocks and metal halides in lakes and seas. Explain.
Ans.: Metal halides being soluble in water, get dissolved in rain water and are carried to lakes and
seas during weathering of rocks. On the otherhand, metal sulphides being insoluble are left behind in
the rocks as residue.
Q10. What are fluxes? How are they useful ?
Ans. : Flux is a substance that combines with gangue which may still be present in the roasted on the
calcined ore to form an easily fusible material called the slag.
Q.11. What is a slag?
Ans: A slag is an easily fusible material which is formed when gangue still present in the roasted or
the calcined ore combines with the flux. For example: in the metallurgy of Iron, CaO(flux) combines
with silica(SiO
2
) gangue to form easily fusible calcium silicate (CaSiO
3
) slag.
2 3
CO CaO CaCo +

( ) Slag
CaSiO SiO CaO
3 2
+
Q.12. What is the Principle of Zone refining ?
Ans. : When the molten solution of an impure metal is allowed to cool, the pure metal crystallizes
out while the impurities remains in the solution.
Q.13. What is a depressant? Give one example.
74
Ans. Compounds which prevent the formation of froth in froth flotation process are called
depressants. For example, NaCN can be used as a depressant for ZnS in the separation of ZnS from
PbS ore. It forms a layer of Zinc complex, Na
2
[Zn(CN)
4
] on the surface of ZnS and thus prevents it
from forming the froth.
Q.14. What is the role of a stabilizer in froth floatation process?
Ans.: Chemical compounds like cresols and aniline which tend to stabilize the froth are called
stabilizers.
Q.15. What types of Ores are roasted?
Ans. : Sulphides ores are roasted to convert them into their oxides since Oxides are more easily
reduced to metal than sulphides.
Short Questions :01 Mark
Very Short answer questions :
FOR BELOW AVERAGE STUDENTS: 01 Mark
1. How does minerals different from an Ore ?
2. What do you mean by benefication process or concentration or enrichment or dressing ?
3. What is a slag? Give one example of basic flux.
4. Why do a few elements occurs in the native state while others do not ?
5. Write constituents of bronze with their use.
6. Why is Zinc not extracted from Zinc Oxide through reduction using CO?
7. What is the role of cryolite in the metallurgy of Aluminium?
8. Which type of metals are refined by distillation method?
FOR AVERAGE STUDENTS :01 Mark
1. Name the chief form of occurrence of the following in the earths crust :
a) Aluminium, b) Iron, c) Copper, d) Zinc
2. An Ore sample of galena (PbS) is contaminated with Zinc blende(ZnS). Name ore
chemical which can be used to concentrated galena selectively by froth floatation process.
3. How is cast iron different from pig iron?
4. What is copper matte?
5. Why pine oil is used in the froth floatation method?
For Bright Students: 01 Mark
1. Copper and Silver lies below in the electrochemical series and yet they are found in the
combined state as sulphides in nature. Comment.
2. Name the common element present in the anode mud in electrolytic refining of copper.
Why are they so present?
3. What is meant by the term chromatography?
4. What is the role of depressant in froth floatation process?
5. What criterion is followed for selection of the stationary phase in chromatography?
6. What is the role of collector & froth stabilizer in froth floatation process?
75
For Below Average Students:
02 Marks Questions
1. Why copper metal is put in Silica lined converter ?
2. Giving examples, differentiate between roasting and calcinations.
3. Describe the method of refining of Nickel.
4. Explain the Leaching of Silver or Gold.
5. Write two important ores of Iron, Aluminium, coppere & Zinc with their chemical
formula.
6. What is aluminothermy? Explain with an example.
FOR AVERAGE STUDENTS:
02 Marks Questions
1. State the role of silica in the metallurgy of copper.
2. Why is the extraction of copper from pyrite difficult than that from its oxide ore through
reduction?
3. Write chemical reactions taking place in the extraction of Zinc from Zinc blend.
4. Silver Ores and native gold have to be leached with metal cyanides. Suggest a reason for
this.
5. What do you mean by vapour phase refining? Describe with suitable example.
6. The extraction of Au by leaching with NaCN envolves both oxidation and reduction.
Justify giving equations?
7. Copper can be extracted by hydrometallurgy but not Zinc explain.
FOR BRIGHT STUDENTS:
02 Marks Questions
1. Out of C and CO, which is a better reducing agent for ZnO?
2. What is the role of graphite in the electrometallurgy of Aluminium?
3. What do you mean by leaching? Explain with an example.
4. The Choice of a reducing agent in a particular case depends on thermodynamic factor,
how far do you agree with this statements? Support your opinion with two examples.
5. Discuss some of the factors which need consideration before deciding on the method of
extraction of metal from its ore.
FOR BELOW AVERAGE STUDENTS:
03 Marks Questions
2. What is the chief ore of iron? Write chemical reactions taking place in the
extraction of Iron from its Ores.
3. Give the important uses of
a) Aluminium, b) Copper, c) Iron
3. Differentiate between (i) Gangue and Flux (ii) Minerals & Ores
4. What do you mean by following terms :
76
(i) Electro metallurgy (ii) Hydrometallurgy (iii) Smelting
5. What is the significance of leading in the extraction of aluminium?
6. Explain the term :
(i) Distellation
(ii) Liquation
(iii) Poling in term of refining of metals.
FOR AVERAGE STUDENTS:
03 Marks Question
1. Name the processes from which chlorine is obtained as a bye-product. What will
happen if an aqueous solution of NaCl is subjected to electrolysed.
2. Explain how the following metals are obtained from their oxides by the reduction
process.
a) Metal X which is low in the reactivity series.
b) Metal Y which is in the middle of the reactivity series.
c) Metal Z which is high up in the reactivity series
3. a) Describe a method for refining of Nickel.
b) The extraction of Ag by leaching with NaCN involves both oxidation &
reduction.
For Bright Students: 03 Marks
1. Account for the following :
i) The reduction of metal oxide is easier if the metal formed is in liquid state
at the temperature of reduction.
ii) the reduction of Cr
2
O
3
with Al is thermodynamically feasible yet it does
not occur at room temperature.
iii) Is Carbon is satisfactory reducing agent for all metal Oxides ?
2. Name the main ore of lead metal, write its formula. How is this metal obtained
from its oxides ?
3. Discuss briefly the chromatographic method used for purification of elements.
4. The value of
f
G
0
for formation of Cr
2
O
3
is -540 KJ/mol and that of Al
2
O
3
is -827
KJ/mol. Is the reduction of Cr
2
O
3
possible with aluminium?
5. How can you separate alumina from Silica in Bauxite ore associated with Silica?
Give equations if any.
77

Nitrogen family (Group 15 Elements)
Members: Nitrogen, Phosphorous, Arsenic, Antimony, Bismuth
General electronic configuration:- ns
2
np
3
, valance electrons is five, the valency may be 3 and
5 both. Nitrogen is only trivalent but phosphorous forms pentavalent because of vacant d-
orbital. The oxidation states are mainly +3 & +5. Down the group +5 oxidation states
especially is unstable due to inert pair effect (i) the stability of higher oxidation state
decreases down the group. (ii) As stated in (i) is due to reluctance of ns
2
electrons in bond
making process.]
General characteristics:
(i) Catenation: Increases down the group. Phosphorous has greater power of catenation than
nitrogen because in former the size is larger and availability of vacant d-orbitals, while in
later the size is smaller and stability is achieved through P P bonding. Single N N bond
is weaker than p p bond.
(ii) Electro negativity trend: N because of higher electro negativity is able to make
effective H- bond. Therefore NH
3
has higher B.pt than phosphine. Also this property causes
ammonia to be water soluble when ammonia makes H-bond with water.
(iii) Stability of Hydrides/ Basic characteristics: As size increases down the group the bond
length increases and hence stability of hydride decreases. Therefore acidic character increases
78
UNIT 07
THE p-BLOCK
ELEMENTS
down the group. In terms of basic strength NH3

is more basic than PH
3
because in P we
have larger size & vacant d- orbital. Therefore in spite of lone pair electrons in both cases
PH
3
is less basic.
iv) Reactivity of Elements: Molecular Nitrogen has a triple bond and with very high bond
energy it is relatively inert. White p is more reactive than red p because in former we
have only P
4
structure with lesser no of bonds while in later we have larger no. of bonds with
repeating P
4
units.
(v) Anomalous character of N:
(a) Because of smaller size N is able to make P P multiple bonds. This also causes N
2
to
remain as discrete molecules and associated by weak Vander Waals forces. This is why N
2
is
possible but P
2
is

not. This also causes N
2
to remain in gaseous form.
(b) N has no vacant d-orbital hence only valency of three is found while other in the
group like P is trivalent and pentavalent both.
(vi) Halides: P forms PCl
3
& PCl
5
both. PCl
5
is unstable because of two longer axial bonds.
PCl
3
fumes in moisture.
(vii) Oxo acids:
(a) N:- Two important oxo acids viz Nitric acid and Nitrous acid. Both are mono
protic.
The presence of nitrate ion can be detected by adding freshly prepare FeSO
4
solution
followed by adding 1-2 drop conc. H
2
SO
4
by the side of test tube below tap water. This
makes a brown ring.
(b) P:- Three important oxo acids viz H
3
PO
4
, H
3
PO
3
, and H
3
PO
2
. They are triprotic,
diprotic and monoprotic because of their structures.
(viii) Important compounds: Ammonia is prepared by Habers process.
Requirement for good yield of ammonia are high pressure, low tempt as per Le-chateliers
principle with iron oxide as catalyst and k
2
O, Al
2
O
3
as promoters. Ammonia has sp3
hybridization. Lone pair electrons on N makes its shape pyramidal. Ammonia is a good
complexing agent because of lone pair electron on nitrogen atom.
(d) Phosphorous penta Chloride: P is sp
3
d- hybridized and structure is trigonal
bipyramidal.
OXYGEN FAMILY(Group 16 Elements)
MEMBERS:- Oxygen is the 1
st
element of the group and other members are sulphur,
Selenium, Tellurium and Polonium.
General Electronic configuration, Valency & oxidation state: The general electronic
configuration is ns
2
np
4
. The valence electrons are six and valency varies from 2 to 6. The
oxidation state varies from -2 to +6. The maximum oxidation state of oxygen is +2.
General Characteristics:
(i) Anomalous character of oxygen:
a) Because of smaller size it makes effective P P bond. Therefore remains as discrete
molecule. But sulphur because of expansion of valency on account of vacant d- orbital exists
as solid.
79
b) Catenation: Oxygen has lesser ability of Catenation than sulphur because in later we have
vacant d-orbital. Therefore valency of sulphur goes from two to six. The single bond energy
in sulphur is larger than that of oxygen.
c) Paramagnetic behaviour: Because of two unpaired electrons in antibonding molecular
orbitals of oxygen it is paramagnetic. However sulphur is also paramagnetic in vapour-state.
d) Valency:- Only oxygen is divalent, others are tetravalent and hexavalent also.
e) Electronegativity: Only oxygen is able in making effective H- bonding. Hence H
2
O is a
liquid and H
2
S is gas.
ii) Stability of hydride/ Acidic character of hydride:- As size increases down the group,
the bond length between hydrogen and group member increases. This causes decreasing bond
energy down the group and acidic character of hydrides increases.
iii) Oxo acids: Sulphuric acid is the most important oxo- acid of sulphur, which is prepared
by contact processes:
iv) Allotropy:
a) Ozone is the allotrope of oxygen. High conc
n
. Of ozone is dangerously explosive. Ozone is
thermodynamically unstable and converts into dioxygen. The free energy for this is highly
negative.
Because of this nascent oxygen so produced, Ozone acts as powerful oxidizing agent. Ozone
has two resonating structures.
b) Sulphur has two allotropes viz Rhombic (State at room temp) and Mono clinic (Prepared
by heating rhombic sulphur).
Halogen Family (Group 17 Elements)
Members:- F, Cl, Br , I and At .
General properties:
(1) Electronic configuration - All these members have electrons (ns
2
np
5
) in
their valence shell.
(2) Atomic and ionic radii - They have the smallest radii in their respective
periods. However size increases downward the group due to increase in
no. of shells.
(3) Ionization enthalpy - They have very high ionization enthalpy. It
decreases down the group due to increase in size.
(4) Electron gain enthalpy - They have maximum negative electron gain
enthalpy in their periods as they have one electron short to attain stable
electronic configuration. These values become less negative downwards
the group.
(5) Electronegativity - They are highly electronegative in nature. It decreases
down the group.
(6) Colour - All halogens are coloured . F
2
yellow, Cl
2
greenish yellow ,
Br
2
red , I
2
violet.
(7) Oxidation state All the members show -1 oxidation-state but Cl , Br and
I shows +1 , +3 , +5 and +7 in addition to -1 state.
(8) Oxidising properties The ready acceptance of electron by halogen make
them strong oxidizing agent. Fluorine is known to be the strongest
oxidizing agent among halogens.
80
(9) Reactivity towards hydrogen :- With hydrogen they form hydride of the
type H- X. The acidic nature of these varies in the order HF < HCl < HBr
<HI .
(10) Reactivity towards oxygen With oxygen they form different oxides.
Fluorine forms two oxides OF
2
and O
2
F
2
but chlorine , bromine and iodine
form oxides using oxidation state of +1 to +7. The higher oxides are more
stable than lower oxides.
(11) Reactivity towards other halogens With other halogen they form
interhalogen compounds of the types XX , XX
3
, XX
5
, XX
7
(where X
is larger in size than X)
(12) Reactivity towards metal They form metal halides . Their ionic nature
decreases as follows
MF > MCl > MBr >MI
Anomalous behaviour of fluorine
Fluorine is anomalous in many properties due to following reasons;
(1) Small size and high charge density.
(2) Absence of vacant d- orbital in the outermost shell.
(3) The highest electronegativity.
INERT GASES (Group 18 Elements)
MEMBERS:- He , Ne, Ar, Kr,Xe & Rn
General Properties:-
1. All elements have octet configuration except He, which has duet. This makes them stable
in comparison to other elements.
2. Ionization enthalpy decreases down the group. Kr & Xe have low ionization energy &
hence they make compounds with highly electronegative elements like fluorine & oxygen.
3. Important compounds of xenon with its shape, hybridization & structure :-
sp
3
d sp
3
d
2

81
Sp
3
d
3
sp
3
d
2
sp
3
OXO- ACIDS OF PHOSPHORUS

OXO- ACIDS OF SULPHUR
4. The compounds which led to discovery of inert gas compounds are O
2
+
PtF
6

&
Xe
+
PtF
6

5. The xenon fluorides hydrolyse completely & partially leading to the formation of different
compounds like:-
XeF
6
+ H
2
O XeO
3
+HF (complete hydrolysis)
XeF
6
+ H
2
O XeOF
4
+HF (partial hydrolysis)
Binary Compounds
This section lists some binary compounds with halogens (known as halides), oxygen (known
as oxides), hydrogen (known as hydrides), and some other compounds of sulphur. For each
compound, a formal oxidation number for sulphur is given, but the usefulness of this number
is limited for p-block elements in particular. Based upon that oxidation number, an electronic
configuration is also given but note that for more exotic compounds you should view this as a
guide only. The term hydride is used in a generic sense to indicate compounds of the type
M
x
H
y
and not necessarily to indicate that any compounds listed behave chemically as
hydrides.
82
In compounds of sulphur (where known), the most common oxidation numbers of sulphur
are: 6, 4, 2, and -2.
Hydrides
The term hydride is used to indicate compounds of the type M
x
H
y
and not necessarily to
indicate that any compounds listed behave as hydrides chemically.
IMPORTANT QUESTIONS WITH MODEL ANSWER
(1 mark questions)
1. Why is phosphine weaker base than Ammonia?
Ans: P is bigger than N, therefore lone pair of electrons are less available on P than N.
2. Why is Ammonia a good complexing agent?
Ans: Because of lone pair of electrons on N.
3. Why Nitrogen is a gas whereas Phosphorous is a solid?
Ans: Nitrogen molecules have less Vander Waals forces of attraction whereas molecular
phosphorous has more Vander Waals forces of attraction.
4. Why is Nitrogen relatively inert?
Ans: Because of a triple bond with high bond energy.
5. Ammonia is water soluble. Why?
Ans: It forms hydrogen bond with water.
(2 marks questions)
1. Write shape of following molecules:
a) Ammonia
b) Phosphorous Pentachloride
Ans: a) Pyramidal
b) Trigonal bipyramidal
2. Ortho phosphoric acid is triprotic but phosphoric acid is diprotic. Why?
Ans: Because of their structures ortho phosphoric acid and phosphoric acid have three and
two ionisable hydrogen.
3. Give reasons:
a) Phosphorous pentachloride is unstable.
b) Phosphorous trichloride fumes in moisture.
Ans: a) Because of two longer axial bonds.
b) Because it reacts with water and forms hydrochloric acid.
(3 marks questions)
4. Nitrogen shows anomalous behaviour in the group. Why?
Ans: i) Small size
ii) High electro negativity
iii) Absence of vacant d-orbital.
5. How is ammonia prepared? Write chemical reaction involved in the Habers
process.
83
Ans: i) Ammonia is prepared by the combination of hydrogen and nitrogen in the ratio of 3:1.
ii) The used catalyst is iron oxide. The promotors are potassium and aluminium oxides.
iii) The required conditions are high pressure and moderate temperature.
N
2
+ 3H
2
2NH
3
06. Complete the following reactions :-
i) XeF
6
+ H
2
O --- + ---- ( partial hydrolysis)
ii) XeF
6
+ H
2
O --- + ---- ( Complete hydrolysis )
iii) Cl
2
+ H
2
O --- + ----
Ans: i) XeOF
4
+ HF
ii) XeO
3
+ HF
iii) HOCl + HCl
07. Arrange the following in decreasing order :-
i) NaF, NaI, NaCl,NaBr( Ionic nature)
ii) PH
3
, NH
3
, ,AsH
3
,SbH
3
( Basic Strength)
iii) HF,HBr,HCl,HI ( Acid Strength)
Ans i) NaF> NaCl > NaBr> NaI
ii) NH
3
> PH
3
> AsH
3
> SbH
3
iii) HI> HBr> HCl> HI
08. Find hybridization and shape i) XeF
2
ii) XeO
3
iii) XeF
4
Ans: i) sp3d, Linear
ii) sp3, Pyramidal
iii) sp3d
2
, Square planar
09. Give reasons
i) H
2
O is a liquid but H
2
S a gas.
ii) Ammonia has higher boiling point than phosphine
ii) Krypton & xenon make compounds.
Ans: i) Hydrogen bond is found in H
2
O but not in H
2
S.
ii) Hydrogen bond is found in NH
3
but not in PH
3
.
iii) Because they have low ionization energy.
10. Write down the chemical reactions that take place in the manufacture of sulphuric acid by
contacts process.
Ans: i) S + O
2
SO
2
V
2
O
5
ii) SO
2
+ O
2
SO
3
iii) SO
3
+ H
2
SO
4
H
2
S
2
O
7
iv) H
2
S
2
O
7
+ H
2
O 2H
2
SO
4
SOME IMPORTANT QUESTIONS WITH ANSWERS
Q.1. Why does O
3
act as powerful Oxidising agent ?
Ans: Due to ease with Which it liberates atoms of nascent oxygen (O
3
O
2
+0)
2Pbs (S) + 4O
3
(g) PbSO
4
(S) + 4O
2
(g)
Q.2. Which forms of Sulphur show paramagnetic behaviour ?
Ans : In Vapour State sulphurPartly exists as S
2
molecule which has two unpaired electrons
in the *
Orbitals hence exhibit paramagnetic
Q.3. Halogens have maximum negative electron gain enthalpy in the respective periods
in the P. T Why ?
Ans Due to smallest size and high effective nuclear charge , readily accept one electron
84
to acquire noble gas electronic configuration
Q4. Why is fluorine stronger Oxidising agent ?
Ans: Due to (a) Low enthalpy of dissociation
(b) high enthalpy of Hydration of F
-
Q.5. How is the presence of SO
2
detected ?
Ans : 1. It has pungent characteristic smell .
2. It decolourises KMn O
4
solution
3. It turns acidified K
2
Cr
2
O
7
green
Q.6. Are all the five bonds in PCl
5
molecule equivalent ?
Ans PCl
5
has a trigonal bipyramidal structure and the three equatorial p-cl bonds are
equivalent . while trhe
two axial bonds are different and longer than equatorial bonds.
Q.7. Why H
3
PO
3
is dibasic and H
3
PO
4
is tribasic ?
Ans In H
3
PO
3
only two replacable hydrogen but inH
3
PO
4
, three hydrogens are replacable .
Q.8. Why is helium used in diving apparatus ?
Ans: Because heliun is very low solubility in blood
Q.9. Give reason for bleaching action of Cl
2
Ans Due to oxidation
Cl
2
+H
2
O 2HCl+ O
Coloured substance +O colourless substance
Q10 Write the formula of tear gas .
Ans : CCl
3
NO
2
Q11. Which aerosol deplete ozone layer ?
Ans C.F.C
FOR BELOW AVERAGE
[01 Mark Question:]
A. Give reasons
01. N
2
is relatively inert in terms of reactivity.
02. NH
3
is a good complexing agent.
03. O
3
acts as a powerful oxidizing agent.
04. NH
3
forms hydrogen bond but PH3 does not.
05. Bond angle of NH
4
+
is higher than NH
3
.
06. H
2
S is less acidic than H
2
Te.
07. H
2
O is a liquid but H
2
S is a gas.
08. NH
3
acts as a lewis base.
09. Halogens act as strong oxidizing agent.
10. Dioxygen is a gas but sulphur is a solid at room temperature.
11. Nitrogen does not form NCl
5
whereas phosphorous does.
85
12. N
2
is a gas but phosphorous is a solid.
13. N2 is possible but P
2
is not,Why?
14. NH
3
is more basic than PH
33

15. F
2
and Cl
2
are gases but I
2
is a solid
16. NH
3
is soluble in water but PH
3
is not.
17. PH
3
has lower boiling point than NH
3
.
18. PCl
5
is unstable.
19. Catenation in nitrogen is weaker than phosphorous.
20. Stability of hydride of group 15 decreases down the group.
21. The +5 oxidation state of Bi is less stable than +3.
22. The basic character of hydride of group 15 decreases down the group.
23. NH
3
is pyramidal.
24. One of the noble gases only xenon is known to form real chemical compounds.
FOR AVERAGE
01. Fluorine is the strongest oxidizing agent among halogens.
02. H
3
PO
3
is a diprotic acid.
03. Bond angle in PH
3
is less than NH
3
04. Noble gases form compound with fluorine and oxygen only.
05. White P is more reactive than red P.
06. PC
l5
is more covalent than PC
l3
.
07. SO
2
is air pollutant.
08. Basic character among the hydrides of group 15 elements decreases with increasing
atomic nos.
09. H3PO4 is triprotic but H3PO
2
is monoprotic
10. BiH3 is a reducing agent.
11. Electron affinity of fluorine is less than that of chlorine.
12. Sulphur vapours show paramagnetic behaviour.
13. Halogens are coloured.
FOR ABOVE AVERAGE
01. H
3
PO
3
and H
3
PO
2
show reducing character.
2. Catenation in oxygen is lesser than sulphur.
3. Group 16 members are called chalcogens.
4. PKa value of HOCl is higher than that of HOClO.
5. Nitrogen shows Maximum covalency of four.
86
6. NH3 has higher dipole moment than NF
3
.
7. Trimethylamine is pyramidal but trisilylamine is planar.
8. High concentration of ozone can be dangerously explosive.
9. Identify the neutral molecule which is isoelectronic with ClO
-
. Is that molecule a
lewis base?
10. PKa(I) for H
2
SO
4
is larger than PKa(II).
FOR BELOW AVERAGE
B. Complete the following reactions:-
1. XeF2 + H2O
2. XeF2 +PF5
3. XeF4 +H2O
4. XeF6 +H2O
5. XeF4 +SbF5
6. I2+H2O+Cl2
FOR AVERAGE
1. CaF2+H2SO4
2. NaOH +Cl2
3. F2 + H2O
4. PCl3 + H2O
5. PCl5 + H2O
6. C + H2SO4
7. Ca(OCl)Cl+HCl
FOR ABOVE AVERAGE
01. P4 + KOH +H2O
02. XeF4 + O2F2
03. Ca3P2 + H2O
04. POCl3 + H2O
05. PH3 +HNO3
06. CuO +NH3
07. BrO3
-
+F2 +OH
-

C. Deduce structural formula of the following;
For below average:- NH3, PCl5, XeF2, XeF4, XeF6, SF6, IF7
For average:- H3PO4, H3PO2, H3PO3, SF4, XeO3
For above average:- Cl2O7, P4O10, N2O
5
, XeOF4, XeOF2, H2S2O
8
.
87
FOR BELOW AVERAGE
D. What happens when;

1. Conc. H2SO4 is added to CaF2.
2. SO3 is passed into water.
3. Chlorine is passed through a hot and conc. Solution of alkali, like Ba(OH)2.
4. XeF4 undergoes hydrolysis.
5. XeF6 undergoes hydrolysis.
6. PCl5 is heated.
7. NaCl is heated with H2SO4 in presence of MnO2.
8. Cl2 is passed through a solution of NaI in water.
9. SO2 gas is passed through a solution of Fe(III) salt.
10 White P is heated with NaOH solution in an inert atmosphere of CO2.
FOR BELOW AVERAGE & AVERAGE
E. Arrange the following as mentioned:
1. M-F, M-Cl, M-Br, M-I. (Decreasing order of ionic nature)
2. F
2
, Cl
2
, Br
2
, I
2
. (Increasing order of bond energy)
3. H
2
O, H
2
S, H
2
Se, H
2
Te. (Decreasing order of boiling points)
4. NH
3
, PH
3
, AsH
3
, SbH
3
. (Increasing order of basic nature)
5. HI, HBr, HCl, HF. (Increasing order of thermal stability)
6. HI, HBr, HCl, HF. (Increasing order of reducing power)
7. HOCl, HOClO, HOClO
2
, HOClO
3
. (Increasing order of acid strength)
8. H
2
O, H
2
S, H
2
Se, H
2
Te. (Increasing order of acid strength)
9. HClO
4
, HBrO
4
, HIO
4
. (Decreasing order of acid strength)

F. Some more additional questions; (3 & 5 marks each)
1. Explain the process and necessary conditions involved in the preparation of NH
3
,
H
2
SO
4
or HNO
3
.
2. What are interhalogen compounds? How are they classified?
3. Describe the chemistry of ring test.
4. Why do noble gases have comparatively larger atomic size? Give the reasons which
prompted Bartlett to prepare first noble gas compound.
5. Explain the chemistry of group 15 elements with respect to catenation, stability of
hydrides, and relative stability of oxidation states.
6. Describe the chief uses of fluorine, chlorine and their compounds.
How is bleaching powder prepared? Mention two of its uses .
88
7. Write the three steps involved in the manufacture of sulphuric acid by the contact
process
8. What are the condition to maximize the yield of H
2
SO
4
in contaqct process ?
9. How can H
2
SO
4
reacts with cu metals ?
10. How ammonia is manufactured by Habers process on large scale ?
11. Mention the Conditions to maximize the yield of ammonia .
12. How does amminia acts as a Lewis base ,show it with the help of a chemical .
13. Illustrate how copper metal can give diff. products on reaction with HNO
3
.
14. How HNO
3
is prepared by ostwalds process ? Write reaction only at diff . stages
15. Balance the following equation :-
(i) I
2
+ HNO
3
HIO
3
+NO
2
+H2O (ii) C+ HNO
3
CO
2
+NO2 +H
2
O
(iii) S + HNO
3
(conc.) H2SO4 +NO
2
+ H2O (iv) P4+ HNO
3
(conc.) H3PO
4
+
NO2+H2O
(V) HNO3 HNO3+ NO+ H2O

89
STUDY MATERIAL
Transition elements:-The elements lying in the middle of periodic table belonging to gr.3 to
12 are known as transition elements.
Electronic configuration :- (n-1)d
1-10
ns
1-2
.
Lanthanoids:-The 14 elements immediately following lanthanum, i.e .Cerium(58) to
Lutetium(71) are called lanthanoids.
Actinoids:-The 14 elements immediately following Actinium(89),with atomic no.90 to 103
are called actinoids.
Inner transition elements: Elments in which last electron inter in f-sub-shell of
antipenultimate energy level.
Solvation energy or energy of hydration:-The amount of energy change when 1 mole of
solid substance is changed into vapour state.
CHARACTERISTICS OF TRANSITION ELEMENTS:-
Properties of transition metals Reason due to
i. metallic in nature High enthalpy of atomization
ii. show variables oxidation states. Presence of vacant d- orbitals
iii. complex compounds. Small size, High charge density
iv. coloured compounds. d-d Transition
v. good catalyst Suitable surface area in d-orbital
vi. paramagnetic compounds. Unpaired electron in d-orbital
vii. Interstitial compounds Similar atomic size & Vacant space in lattice
Lanthanoid Contraction:-There is steadly decrease in the atomic and ionic radii as the
atomic no, increases. It is because ,for every additional proton in the nucleus ,the
corresponding electron goes into the 4f shell which is too diffused to screen the nucleus as
effectively as more localized for the outermost electron increases steadily with the atomic no.
of lanthaoids. This contraction in size is called lanthanoid contraction.
TRANSITION ELEMENTS FORM :-
Basic Oxide :- Sc
2
O
3
,TiO, Ti
2
O
3,
VO,V
2
O
3
,
MnO ,FeO, CuO, CoO, NiO, Cu
2
O
Due to lowest oxidation states
Acidic Oxide:-V
2
O
5
,Mn
2
O
7
,CrO
3
, OsO
4
Due to highest oxidation states
AmphotericOxide:-CuO,TiO
2
,ZnO,CrO
3
, Cr
2
O
3
,
Mn
2
O
3
,MnO
2
,Mn
3
O
4
Fe
3
O
4
Due to intermediate oxidation states
Spinel:- ZnFe
2
O
4
, Tri & divalent occupies octa & tetra-
hedral hole
Non stoichiometric compounds:Fe
0.91
O or Fe
0.95
O Due to defects in lattice crystal
Ionic Halides;All flouoro i.e. CuF
2
,AgF Due to lower oxidation states
90
UNIT 08
THE d- BLOCK
AND f-BLOCK
ELEMENTS
Covalent Halides:-CuI
2
,CuCl
2
,CuBr
2
,AgCl,AgBr Due to higher oxidation states
Application of d- & f- block elements:-
1. Iron and steel used in construction,as catalyst in Habers process
2. CrO
2
is used in magnetic tapes
3. Ni is in hydrogenation
4. W (Tunguston) in making electrical filament
5. AgBr in photography
6. Cu , Ag, Au are coinage metals
7. Pt is catalyst in manufacture of HNO
3
8. V
2
O
5
is catalyst in contact process
9. Titanium is in nuclear reactions.
10. PdCl
2
is in Wackers process.
Differences between Lanthanoids and Actinoids:-
Lanthanoids Actinoids
Common oxidation state is +3, besides this
+2 ,+4
Common oxidation state is +3, besides this
+4,+5,+6, &+7 also.+2 quite rare
Have smaller tendency of complex forming Strong tendency of complex forming
Dont form oxo- ions Do form oxo-ions i.e. UO
2
+
, PuO
2
,UO
+
Non-Radioactive Except Promethium All are Radio-active
Compounds are less basic Compounds are more basic
Important compounds of transition metals:-
1.Potassium dichromate K
2
Cr
2
O
7
Ore:- Chromate
FeCr
2
O
4
Preparation:-
4FeCr
2
O
4
+ 8Na
2
CO
3
+ 7O
2
8Na
2
CrO
4
+ 2Fe
2
O
3
+ 8CO
2
2Na
2
CrO
4
+ H
2
SO
4
Na
2
Cr
2
O
7
+ Na
2
SO
4
+ H
2
O
Na
2
Cr
2
O
7
+ 2KCl K
2
Cr
2
O
7
+ 2NaCl
Structure:-
91
Properties:-
1. Oxidising property:
(a) Iodide to iodine:
Cr
2
O
7

2-
+ 14H
+
+ 6e
-
2Cr
3+
+ 7H
2
O
6I
-
3I
2
+ 6e
-
---------------------------------------------------------------
Cr
2
O
7
2-
+ 14H
+
+ 6I
-
2Cr
3+
+ 3I
2
+ 7H
2
O
(b)Ferrous to ferric:
Cr
2
O
7

2-
+ 14H
+
+ 6e
-
2Cr
3+
+ 7H
2
O
6Fe
2+
6Fe
3+
+ 6e
-
Cr
2
O
7
2-
+ 6Fe
2+
+ 14 H
+


2Cr
3+
+ 6Fe
3+
+ 7H
2
O
2.Chromyl Chloride test:-
K
2
Cr
2
O
7
+ 4NaCl + 6H
2
SO
4
2KHSO
4
+ 4NaHSO
4
+ 2CrO
2
Cl
2
+ 3H
2
O
Uses:
It is used as an oxidizing agent
For tanning of leather
As disinfectant
In volumetric analysis
In chromyl chloride test.
2. Potassium permanaganate KMnO
4
Ore:- Pyrolusite - MnO
2
Preparation:-
2MnO
2
+ 4KOH + O
2
2K
2
MnO
4
+ 2H
2
O
4H
+
+ 3MnO
4
2-
2MnO
4
-
+ MnO
2
+2H
2
O
Structure:
Below
Properties:-
1. In acidic solutions:-
Iodine is liberated from potassium iodide
10 I
-
+ 2MnO
4
-
+ 16 H
+
2Mn
2+
+ 8H
2
O + 5 I
2
Fe
2+
ion(green) is converted to Fe
3+
(yellow)
92
Uses:
5Fe
2+
+MnO
4

-
+ 8 H
+
Mn
2+
+ 4H
2
O + 5 Fe
3+
2. In neutral or faintly alkaline solution:-
Oxidation of iodide to iodine
2MnO
4
-
+ H
2
O + I
-
8MnO
2 +
6SO
4

2-
+ 2OH
-
Uses:-
As disinfectant
As oxidizing agent
For qualitative detection of halides, sulphites, tartarate
In dry cell

QUESTION BANK
Below Average : 01 Marks
1. What are d Block Elements ?
Ans: Those elements in which d-orbital are progressively filled up are known as
d-orbital.
2. What is general electronic configuration of d Block elements ?
Ans: (n-i) d
1-10
ns
1-2
3. Why are Zn , Cd , Hg are not regarded as transition metals ?
Ans: It is because neither they nor their ions have incompletely filled d- orbitals .
4. What is the highest oxidation state shown by Cr. (24) , Mn(25) ?
Ans: Cr. Shows (+6) and Mn Shows (+7) Oxidation state .
5. Why do transition metals have high enthalpy of atomization ?
Ans : it is due to strong metallic bonds and additional covalent bonds
02 Marks
1. What are lanthanides ? Write electronic configuration of lanthanides .
Ans The 14 elements after lanthanum (57) are called lanthanides . There outer
electronic
configuration is (n-2) f
1-14
(n-1)d
0-1
ns
2
2. For Some of first row of transition elements the E
o
value are

V Cr Mn Fe Co Ni Cu
-1.18
v
-0.91v -1.18 v -0.44 v -0.28 v -0.25 v +0.34V
Give suitable explanation for the irregular trend in their values .
Ans it is due to irregular variation of sum of sublimation and ionization
energy in these elements .
3. Why is orange solution of K
2
Cr
2
O
7
turns yellow on adding Na OH ?
Ans : It changes to Cr O4-2 ions which are yellow in colour .
Cr
2
O
7
-2
+2OH
-1
2CrO4
-2
yellow + H
2
O
4. Co (II) is stable in aqueous solution but in the presence of strong ligands
and in air get oxidized
Co
+3
, Why ?

Ans:- Strong ligands and air Oxidized Co
+2
to Co
+3
by providing energy released
due to force of attraction between them and metal ions .
93
5. Why Ce
+3
Can be easily Oxidised to Ce
+4
?
Ans : It is because Ce
+4
has stable electronic configuration .

03 Marks
1. Give balanced equation for the preparation of K2Cr2O7 from chromate ores . What
happens when acidified dichromate soln. react with (i) FeSo4 (ii) H2s gas ?
Ans : 4FeCr
2
O
4
+ 16 NaOH + 7O
2
8 Na
2
CrO
4
+ Na
2
SO
4
+ 2Fe
2
O
3
2Na CrO
4
+ 2H
2
SO
4
+ (Conc) Na
2
Cr
2
O
7
+ H
2
O + Na
2
SO
4

Na
2
Cr
2
O
7
+ 2KCl K
2
Cr
2
O
7
+ 2 NaCl
(i) 6Fe +2 + Cr
2
O
7
-2
+ 14 H+ 6Fe
+3
+ 2Cr
+3
+7H
2
O
green
(ii) 3H
2
S + Cr
2
O
7
-2
+ 8H+3S+ 2Cr
+3
+ 7H
2
O
2. Describe the preparation of KMnO
4
. How does the acidified permanganate Soln.
reacts with (i) Iron (ii) Sulphurdioxide (iii)Oxalic acid ?Write the ionic eqn for the
reactions
Ans : 2MnO
2
+ 4KOH + O
2
K
2
MnO
4
+ 2H
2
O
MnO
4
-2
MnO
4
-1
+e-
(a) [ Fe
+2
Fe
+3
+ e-]x 5
5e-+8H+ MnO
4
-1
Mn
+2
+ 4H
2
O
5 Fe
+2
+ 8H+ MnO4
-
5Fe
+3
+ Mn
+2
+ 4H2O

(b) 2KMnO
4
+ 2H
2
0 +5SO
2
K
2
SO
4
+ 2MnSO
4
+ 2H
2
SO
4

-
COO
- 2CO
2
+ 2e x 5
COO
{5e- + 8H+ + MnO
4
-1
Mn
+2
+ 4 H
2
O) }x 2
16 H+ + 2 MnO4
-1
+ 5C
2
O
4
-2
5CO
2
)2 + 2Mn+2 + 8H
2
0
3. What is an lanthanoid contraction ? What is its cause ? Give its consequences .
Ans The decrease in atomic and ionic size with increase in atomic no. in lanthanoid series
is called lanthanoid contraction . The cause of lanthanoid contraction is poor shielding
effect of d and f electron , due to which effective nuclear charge increases .
. consequences :-
(i) The ion ic size of lanthanoid is similar to each other , they occur , together and their
separation becomes difficult .
(ii) The ionization energy of 5 d transition series are higher than 4 d transition series .
(iii)There is close resemblance between elements of 4 d and 5 d transition series . due to
similar ionic

Average 01 Mark
(i) Why does V
2
O
5
acts as catalyst ?
Ans : It is because V shows variable O.S .
(ii) Why are transition metals and there compounds generally coloured ?
Ans It is due to present of unpaired electrons in transition metals and their ions ,
that is why they absorbed light from visible region and undergoes d-d
transition and radiate complementary colour .
(iii) Why are Cr+ , Ag+ & Sc
+3
Colour less ?
94
Ans It is because they do not have unpaired electrons ,therefore can not under goes d-d
transition .
(iv) Why do Zr and Hf show similar properties ?
Ans It is due to similar ionic size which due to lanthanide contraction .
(v) Why is Cu
+1
diamagnetic and Cu
+2
paramagnetic ?
It is because Cu+ does not have unpaired electrons where as Cu+2 has unpaired
electrons in d-sub cell .

02 Marks
(i) Why are transition metal fluorides are ionic in nature where as chlorides and
bromides are covalent in nature .
Ans - It is because of fluorine is most electronegative where as Cl and Br are
less electro negative .
Greater the difference in electro negativity more will be ionic character .
(ii) Why Mn+2 is more stable than Mn+3 but Fe +3 is more stable than Fe+2 ?
Ans Mn+2 has half filled d- orbital ,therefore it is more stable than Mn+3
Fe+3 has half filled d- orbital, therefore it is more stable than Fe +2 .
(iii) Why are lanthanoid colored and paramagnetic L
Ans It is due to presence of unpaired electrons, they are paramagnetic and they absorb
light
From visible region and undergoes f-f transition and radiate complementary
colour .


03 Marks
(i) What is meant by disproportionation ? Give two examples of above reaction
in aqn. Solution .
Ans Disproportionation means the same substance get oxidized and
reduced, examples
Cu+ Cu+2 + Cu
3CrO4
-3
+ 8H+ 2CrO4
-2
+ Cr
+3
+ 4H
2
0
(ii) Explain the following , giving reason .
(a) Transition metal and many of their compounds show paramagnetic behavior
(b) The enthalpy of atomisation of the transition metal is high .
(c) The Transition metal generally form coloured compounds .
Ans(a) It is due to unpaired electrons .
(b) It is due to strong metallic bond and additional Covalent bonds due to presence of
unpaired electron in d- orbitals
(c) It is due to presence of unpaired electrons ,they undergo d-d transition .
Above Average : 01 mark
(i)Why is K
2
Cr
2
O
7
generally preferred over Na
2
Cr
2
O
7
in a volumetric
analysis .Give reason .
Ans : It is because Na
2
Cr
2
O
7
is hygroscopic in nature that is why it absorbs moisture from
atmosphere , therefore its standard solution can not be prepared .

(ii) Why do transition metals have higher I.E than s block elements ?
95
Ans: It is due to smaller atomic size than s-block elements , effective nuclear charge is
more , terefore I.E is high.

(iii) Why are Ti+2 and other transition metals and their ions paramagnetic ?
Ans: These ions have unpaired electrons in d- subshell.
(iv) Complete the following eqn.
TiCl
4
+H
2
O -----------+----------
Ans : TiO
2
+4HCl
(v) Which trivalent cation is largest in lanthanoid series ?
Ans La+3
Marks 02
(1) Write an equation in ionic form to represent oxidizing action of Cr
2
O
7
-
2
ion in acidic
Medium and draw its structure . Draw structure of CrO
4

-2
also .
Ans- ionic equation 6 e
-
+ 14 H+ + Cr
2
0
7
-2
2Cr
+3
+7H
2
O

(2) Co(ii) is stable in aquous soln. but in presence of strong ligands and in air get
Oxidised to CO +3 , Why ?
Ans Stronger ligands and air Oxidised Co
+2
To Co
+3
by providing energy released due to
force of attraction
Between them and metal ions .
(3)What happen when acidified KMnO4 is added to ferrous sulphate soln.?
Ans MnO
4
-1
+ 5 Fe
+2
+ 8H
+
Mn
+
2 +5Fe
+3
+4H
2
O
The colour of KMnO
4
becomes coloursless and Fe
+2
is oxidized to Fe
+3

Above Average 03 Marks
(1) Compare the chemistry of actinoids with that of lanthanoids with reference to (i)
electronic
configuration
(ii) Oxidation state (iii) Chemical reactivity .
Ans : Electronic config. In lanthanoids 4f orbitals are progressively filled whereas in
actinoids
5f orbitals are progressively filled up .
(ii) Oxidation state lanthanoids Show +3 oxidation state & same elements of this series
show
+2 & +4 oxidation state also .
Actinoids show +3 , +4, +5,+7 O.S. Although +3 , +4are the most common .
(iii) Chemical reactivity :- Actinoids are more reactive then lanthanoids due to bigger
atomic
size and lower I.E
96
************************
STUDY MATERIAL
1 MARK & 2 MARKS QUESTIONS
Q. 1. A cationic complex has two isomers A & B. Each has one Co
3+
, five NH
3
, one Br
and one SO
4
2
. A gives a white precipitate with BaCl
2
solution while B gives a
yellow precipitate with AgNO
3
solution.
(a) What are the possible structures of the complexes A and B ?
(a) Will the two complexes have same colour ?
Ans. (a) [CO (NH
3
)
5
Br] SO
4
and [CO (NH
3
)
5
SO
4
] Br
(b) NO
Q. 2. FeSO
4
solution mixed with (NH
4
)
2
SO
4
solution in 1 : 1 molar ratio gives the test of
Fe
2+
ion but CuSO
4
solution mixed with aqueous ammonia in 1 : 4 molar ratio
does not give the test of Cu
2+
ion. Explain why ?
Ans. When FeSO
4
and (NH
4
)
2
SO
4
solution are mixed in 1 : 1 molar ratio, a double salt is
formed. It has the formula FeSO
4
(NH
4
)
2
SO
4
. 6 H
2
O. In aqueous solution, the salt
dissociates.
When CuSO
4
and NH
3
are mixed in the molar ratio of 1 : 4 in solution, a complex
[Cu (NH
3
)
4
] SO
4
is formed.
Q. 3. If to an aqueous solution of CuSO
4
in two tubes, we add ammonia solution in one
tube and HCl (aq) to the other tube, how the colour of the solutions will change ?
Explain with the help of reaction.
Ans. In first case, colour will change from blue to deep blue.
[Cu (H
2
O)
4
]
2+
+ 4 NH
3
[Cu (NH
3
)
4
]
2+
+ 4 H
2
O
deep blue
While in second case, its colour will change to yellow.
[Cu (H
2
O)
4
]
2+
+ 4 Cl

[CuCl
4
]
2+
+ 4 H
2
O
yellow
97
UNIT -09
CO-ORDINATION
COMPOUND
Q. 4. A, B and C are three complexes of Chromioum with the empirical formula
H
12
O
6
Cl
3
Cr. All the three complexes have Cl and H
2
O molecules as the ligands.
Complex A does not react with conc. H
2
SO
4
. Complexes B and C lose 6.75% and
13.5% of their original weight respectively on heating with conc. H
2
SO
4
. Identify
A, B and C.
Ans. Data suggests that the complexes are hydrate isomers.
As comples A does not lose any molecule of H
2
O on heating which shows that no
water molecule of H
2
O is outside the co-ordination sphere.
A = [Cr (H '
2
O]
0
] Cl
3
As B loses 6.75% actual loss in wt. '
= 266.5 = 18 au
B = [Cr (H
2
O)
5
Cl] Cl
2
. H
2
O
As C loses 13.5% of wt. on heating which is twice the loss in the first case, C '
isomer exists as a dihydrate :
[Cr (H
2
O)
4
Cl
2
] Cl . 2 H
2
O
SCN

Q. 5. Fe
3+
(A) (B)
excess excess
What are (A) and (B) ? Give IUPAC name of (A). Find the spin only magnetic
moment of (B).
Ans. A = Fe (SCN)
3
, B = [FeF
6
]
3
IUPAC name of A = trithiocyanato iron (III)
E. C. of Fe (III) = d
5
, unpaired e

s = 5
Spin only magnetic moment = 5(5 2) + B. M.
= 5.916 B. M.
Q. 6. A complex is prepared by mixing COCl
3
and NH
3
in the molar ratio of 1 : 4, 0.1
M solution of this complex was found to freeze at 0.372 C. What is the formula
of the complex ? Given that molal depression constant of water K
f
= 1.86 C/m.
Ans. The oretical T `
f
= K
f
. m
98
= 1.86 0.1
= 0.186
observed T `
f
= 0.372
As observed T `
f
is double of the theoretical value this shows that each molecule of
the complex dissociates to form two ions. formula is : '
[CO (NH
3
)
4
Cl
2
] Cl
Q. 7. How t
2g
and eg orbitals are formed in an octahedral complex ?
Ans. In an octahedral complex, positive metal ion is considered to be present at the centre
and negative ligands at the corners. As lobes of dx y and dz lie along the axes, i.
e. along the ligands repulsions are more and so is the energy. The lobes of the
remaining three d-orbitals lie between the axes i. e. between the ligands, the
repulsions between them are less and so is the energy.
Q. 8. Dimethyl glyoxime is added to alcoholic solution of NiCl
2
. When ammonium
hydroxide is slowly added to it, a rosy red precipitate of a complex appears.
(a) Give the str. of the complex showing hydrogen bond.
(b) Give oxidation state and hybridisation of central metal ion.
(c) Identify whether it is paramagnetic or diamagnetic.
Ans. (a)
(b) O. S. = + 2
bybridisation = dsp
(c) diamagnetic as no unpaired electron.
Q. 9. Explain the reason behind a colour of some gem stone with the help of example.
Ans. The colours of many gem stones are due to the presence of transition metal ions &
colour are produced due to d-d transition. For example the mineral corundum Al
2
O
3
is
colourless when pure but when various M
3+
transition metal ions are present in trace
99
amounts various gem stones are formed. Ruby is Al
2
O
3
containing about 0.5 1%
Cr
3+
.
Q. 10. How many EDTA (lethylendiamine tetra acetic acid) molecules are required to
make an octahedral complex with a Ca
2+
ion.
Ans. EDTA is a hexadentate ligand therefore only one EDTA molecule is required to form
octahedral complex.
Q. 11. What is the hybridisation of central metal ion and shape of Wilkinsons
catalyst ?
Ans. Wilkinsons catalyst is (PH
3
P)
3
RhCl. In this Rh has dsp hybridisation and square
planar shape.
Q. 12. Which vitamin is a complex compound of cobalt ?
Ans. Vitamin B
12
is a complex compound in which central metal atom is cobalt.
Q. 13. Write the IUPAC name of [CO (NH
3
)
4
B
12
]
2
[ZnCl
4
].
Ans. Tetraamminedibromocobalt (III) tetrachlorozincate (II)
Q. 14. What is the value of x in the complex HxCO (CO)
4
on the basis of EAN rule. (At.
No. Co` = 27)
Ans. x = 36 (27 + 4 2)
= 36 35
= 1
Q. 15. Why is the silver plating of copper, K [Ag (CN)
2
] is used instead of AgNO
3
?
Ans. This is because if AgNO
3
is used Cu will displace Ag
+
from AgNO
3
. The deposit so
obtained is black, soft, non-adhering. To get a good shining deposit, [Ag (CN)
2
]

are
used as it is a stable complex, the conc. of Ag
+
is very small in the solution. As such
no displacement of Ag
+
ions with Cu is possible.
Short answer type question
Q. 1 Write the formula of the following compound.
(a) Tetraamineaquachlorido Cobalt (III) chloride .
(b) Potassium tetrahydrooxozincate (II)
(c)Potassium trioxalatoaluminate (II)
(d) Pentaaminecarbonato cobalt (III) chloride
Ans- (a) Co (NH
3
)
4
(H
2
O) a} Cl
2
(b) K
2
[Zn (OH)
4
]
(c) K
3
(Al (C
2
O
4
)
3
) (d) [Co (NH
3
)
3
(CO)
3
] Cl
Q2 Write the IUPAC name of the following Co-Ordination compound.
(a)[ Pt (NH
3
)
2
Cl (NO
2
) Cl(NO
2
)] (b) K
3
[Cr(C
2
O
4
)
3
]
(c)[Co(NH
3
)
5
CO
3
] Cl (d) [ Co Cl
2
(en)
2
] Cl
Ans-
a) Dammie chloridonitrito N-Platinum(II)
b) Pottassium trioxalato chromate (III)
100
c) Pentaamine carbonato cobalt (III) chloride
d) Dichloroidobis (ethane -1, 2 diamine) cobalt (III) chloride
Q.3 [NiCl
4
]
2
is paramagnetic while [Ni (CO)
4
] is diamagnetic through both one
tetrahedral Why?
(i) In [ Ni (CO)
4
] Ni is in Zero Oxidation state but [NiCl
4
]
2
it is in +2
oxidation state
(ii) In the presence of Co ligand , the unpaired d electronics of Ni pair up but Cl being a
weak legand is
unable to pair up the unpaired electron
Q4 Explain [Co (NH
3
)
6
]
3+
is an inner oriental complex when [Ni (NH
3
)
6
]
2+
is an outer
oriental
Complex.
Ans : In [Co (NH
3
)
3+
Complex d
2
SP
3
hybridisation involved forming inner d orbital
Where as In Ni (NH
3
)
6
complex involved in SP
3
d
2
Hybridiasation forming outer d orbitals
Q5 What is meant by unidentate , didentate and ambidentate ligands . give two
example of each
Ans: When a legend is bound to a metal ion through a single diner atom, is said to be
unidentate for ex- Cl
-
, H
2
O & NH
3
When a legande can bound through two donor atoms as in H
2
N CH
2
CH
2
NH
2
, or
C
2
O
4
(oxalate) is said to be didentate legend. When several donor atoms
are present in a single ligand, the ligand is said to be polydentate ligand which can
ligate through two different atoms is called ambidenate ligand Ex-NO
2
, SCN
Q6. What are difference between double salt and a complex salt.
Ans: (1) both double salts as well as complex are formed by the combination of two or
more stable compounds in stiochometric ratio
(2) They differ in the fact that double salts such as carnallite KCl. MgCl
2
. 6H
2
0
, Mohrs salt FeSO
4
(NH
4
)
2
SO
4
. 6 H
2
0 & Potash alum K
2
SO
4
Al
2
(SO
4
)
3

.12H
2
O etc dissociatic into simple ions when dissolve in water .
However when complex ions such as [Fe (CN)
6
]
4
of
K
4
Fe (CN)
6
do not dissociate into Fe
2+
and CN
-
ions
Q. 7. Discuss the nature of bonding in metal carbonyls
Ans: The homoleptic carbonyls are formed by most of the transition metal. These
Carbonyls. Show Simple tetrahedral , trigonal bypyramidal and octahydral
Structure .
It is Shown on poge no. 255 of unit 9 NCERT Vol I
Q. 8. Mention any four characteristics of Co- Ordination Compound
Ans (1) Hard ness of water is estimated by simple titration with Na
2
EDTA.
(2) Extraction of metals like Ag and Au make use of complex formation .
(3) Purification of metals by the formation of Co- Ordination compounds
(4) Biological application like pigment formation photosynthesis, Chloropyll.
Haemoglobin pigment of blood .
Q9. List various types of isomerism possible for Co- ordination compounds .
given an example .
Ans A)Stereoisomerism
(a) Geometrical isomerism Cis & trans of [ Pt (NH
3
)
2
cl
2
]
(b) Optical isomerism d & l of [Co (en)
3
]3+
(B) Structural isomerism
101
(a) Linkage isomerism [ Co (NH
3
)
5
(NO
2
)]Cl
2
(b) Co ordination isomerism [ Co(NH
3
)
6
] [Cr(CN)
6
]
(c) Ionisation [Co(NH
3
)
5
SO
4
] Br & [Co(NH
3
)
5
Br ] SO
4

(d)Solvate isomerism [Cr (H
2
0)
6
] Cl
3
.
Q10 (Fe ( H
2
O)
6
)
3 +
is strongly paramagnetic whereas [ Fe(CN )
6
]
3
is weakly
paramagnetic . Explain .
In [Fe (CN)
6
]
3
only one electron is unpaired & is strong ligand forms d
2
sp
3

hbridisation shows weekly paramagnetic where as in presence of H
2
O in
(Fe(H
2
0)
6
)
3+
weak ligand and five electron are unpaired and forms SP
3
d
2
hybridization shows strongly panamagnetic .
Q11 Calculate the ovelall complex dissociation equilibrium constant for cu
(NH
3
)
4

2+
ion , given that
4
for this complex is 2.1x10
13
Ans : The over all dissociation constant is the reciprocal of over all stability
constant i.e
1 /4 = 4.7X 10
-14
.
01 Marks Question (For Below Average )

1. Define ligands
2. What do yoy mean by complex compounds
3. Explain Co-ordination number.
4. Calculate Co-ordination no. of [Co(NH
3
)
4
(Cl) (NO
2
) ] cl complex
5. What do you mean by oxidation no/state of co-ordination compounds .?
6. Write the example of linkage ammonium
7. Write two use / application of Co-ordination compounds .
8. Write example of chelating lingads
9. What do you mean by chelate effect?
10. Write the IUPAC name of [Cu (NH
3
)
5
Cl] Cl
2
complex

Marks Question (For Below Averege )
1. How will you distinwich Homoleptic & hetroleptic complex
2. What are the limitation of VBT
3. What are the merits of CFT
4. Explain t
2
g and eg in the field of CFT Splitting.
5. What is meant by stability at a Co-ordination Compound in solution? State the
factor on which stability Of the complex depends.
6. What is spectrochemical serious? Explain the difference between strong field ligand
weak field ligand.
7. Give reason why FeSO
4
Soln mixed with (NH
4
)
2
SO
4
soln in 1:1 molar ratio given
102
the test of Fe
2+
ion but cuso4 soln mixed with aqueas ammonia in 1:4 molar ratio
does not given the test of Cu
2+
ion
8. out of given two Co-ordination compound which is Chiral & why explain
(a) cis [CrCl
2
(ox)
2
]
3-
(b) [Cr Cl
2
(ox)
2
]
3-
9. Give evidence that
[Cu (NH
3
)
5
Cl SO
4
and [Co (NH
3
)
5
SO
4
]Cl are ionization isomerism .
AVERAGE & ABOVE AVERAGE STUDENTS
01 Marks question
1. [NiCl
4
]
2-
paramagnetic which [ Ni(C0
4
)] is diamaqgnetic why .
2. Predict the no of unfaired electron in [Pt (CN)
4
]
2-

3. Predict the oxidation no of cobalt in K [ Co (CO)
4
]
4. Explain magnetic moment of the complex
5. Calculate Co- ordination no. of the complex
cis [ Cr (en )
2
Cl
2
] Cl
6. Discuss role of Co-ordination compound in the field of medicinal chemistry
7 Discuss nature of bonding in (Ni(CO))
4
8. How many Co-ordination numbers are there in ethylenediamine ?
9. Name two factors that fever a metal ions forming complex .
10. What is meant by the denticity of a ligand .
02 Marks (Bright achiever)
1. Explain giving one examples role of Co-ordination Compound in biological system
& Analytical system
2. (A) How many ions are present / formed from the complex [CuNH
3
)
6
] Cl
2
(b) Amongst the following which one has the highest magnetic moment value?
3. [Fe (CN
6
]
4
and [Fe (H
2
0)
6
]
2
are of different colour in dilute solution. why?
(b) Draw figure to show the splitting at d-orbital in an octahedral crystal field.
4. Explain Aqueous copper Sulphate Solution gives
(a) A green ppt with aqueous potassium fluoride.
(b) A bright green solution with aqueous potassium chloride
5. A Co- ordination compound has the formula CoCl
3
4NH
3
. it does not liberate ammonia
but precipitate chloride ion as ACL. Give the IUPAC name of the complex and write
its structural formula.
6. Explain why chelating complex is more stable than unchealated complex
103
7. Name two complexes which are used in medicines.

***********

FOR AVERAGE
01 mark questions
Q.1. Write down the IUPAC name of the following organic compounds: -
(a) CH
3
CHCl
2
(b) CH
3
CH
2
CH
2
CH(C(CH
3
)
3
)CH(I)CH
2
CH
3
(c)
H
5
C
2
Cl
Ans: - (a) 1,1- Dichloroethane
(b) 3-Iodo 4 (1,1 dimethyl ethyl ) heptane
(c) 1- Chloro 4 ethyl cyclo hexane
Q.2. Write down the structures of the following organic compounds
(a) 1- Bromo 4 sec. butyl 2 methyl benzene
(b) 2 Chloro 3 methyl pentane
(c ) Vinyl chloride
Ans:- (a)
C
2
H
5
CH Br

CH
3
CH
3
(b) CH
3
CH
2
CH(CH
3
)CH(Cl)CH
3
( c) CH
2
= CHCl
Q.3.Write down the structures of the following organic compounds: -
(a) Allyl Chloride
(b) Teflon
( c) D.D.T.
(d) P.V.C.
Ans: - (a) CH
2
=CH-CH
2
Cl
( b) [-CF
2
-CF
2
-]
n

Cl
(c ) CCl
3
CH
Cl
104
UNIT -10
HALO ALKANE AND HALO
ARENE
(d) [-CH2 CH - ]
n
Cl
Q.4.Which one of the following has the highest dipole moment, and
why?
(a) CH
2
Cl
2
(b) CHCl
3
( c) CCl
4
Ans:- CH
2
Cl
2
has the highest dipole moment since both the Cl- atoms are
present on one side (on the head) of c atom and therefore cause a maximum
dipole moment. In CHCl
3
and CCl
4,
two Cl atoms and four Cl atoms cancel
out their dipole moments.
Q.5. What happens when
a) Methyl Chloride is treated with KCN
b) ChloroBenzene is subjected to hydrolysis
c) Propene is treated with Cl
2
in the presence of U.V. light OR is heated.
d) Chlorobenzene is treated with acetyl chloride in presence
e) of anhyd. AlCl
3
f) Chloroform is slowly oxidized by air in presence of light.
Ans:-
a) CH
3
Cl + KCN CH
3
CN + Kcl
Methyl cyanide
b)
Cl + HOH H
+
OH + HCL

Phenol
U.V. Light or
( c) CH
3
CH = CH
2
+ Cl
2
CH
2
CH= CH
2
+ HCL
Heat
Cl
Allyl Chloride
O Cl Cl
(d) anhyd. COCH
3
Cl + CH3-C-Cl +
AlCl
3
COCH
3
Air
(e) CHCl
3
+
2
1
O2 COCl
2
+ HCl
FOR AVERAGE
2 marks questions
105

Q.1. Which are the possible mono chloro structural isomers expected to be
formed
on free radical mono chlorination of (CH
3
)
2
CHCH
2
CH
3
.
Ans:- There are four possible product as follows
CH
2
(Cl) CH CH
2
CH
3
,
CH
3
(CH
3
)
2
C CH
2
CH
3
,
CH
3
(CH
3
)
2
CH CH CH
3
and
Cl
(CH
3
)
2
CH CH
2
CH
2
Cl
Q.2. Explain the following reactions :
(a) Sandmeyers reaction
(b) Elimination reaction
Q.3. Arrange the compounds in increasing order of their boiling pts.
(a) CH
3
CH
2
CH
2
CH
2
Br, CH
3
CH
2
CHBrCH
3
, (CH
3
)
3
C Br
(b) CH
3
Br, CH
2
Br
2,
CHBr
3
Ans:
(a) (CH
3
)
3
C-Br< CH
3
CH
2
CHBrCH
3
< CH
3
CH
2
CH
2
CH
2
Br
Boiling point increases.
Boiling point decreasing on increasing the branching

(b) CH
3
Br< CH
2
Br
2
< CHBr
3
Boiling point increases
Boiling point increases due increasing molecular mass.
Q.4. Write the mechanism of the following reaction:
Frideal Craft Acylation ( in Chlorobenzene)
106
Ans:-
Reaction Cl Cl Cl
Anhy. COCH
3
+ CH
3
COCl +
AlCl
3

COCH
3
Reaction Mechanism:
O Cl
CH3-COCl + AlCl
3
CH
3
C
+
+
-AlCl
4
-
Cl Cl
+ CH
3
CO
H +AlCl
4
-
+
HCl
CH
3
CO - AlCl
3
Q.5. Explain why: -
(a) H
2
SO
4
cannot be used along with KI in the conversion of an
alcohol to an alkyl halide.
(b) Alkyl halide though polar are immiscible with water.
Ans: -
(a) H
2
SO
4
converts KI to corresponding HI and then oxidise it into
iodine.
(b) When halo alkane interacts with water molecule , less amount of
energy is released which is not sufficient to break the original H-
bond between water molecule and to form new H-bond with halo
alkane and water.
For Average
3 marks questions
Q.1. Identify A,B,C,D,E and R in the following chemical reaction .
Organic Peroxide Aq. KOH Alk.
KMnO
4
a) CH
3
CH=CH
2
+ HBr A
B
C
b) CH3 CH3
Na/Dry ether Mg
107
CH3 CH3 RX
D
H
2
O
CH3 CH3

E
Ans:-
(a) A CH
3
CH
2
CH
2
Br
B CH
3
CH
2
CH
2
OH
C CH
3
CH
2
COOH

(b) R (CH
3
)
3
C-
D (CH
3
)
3
CMgX
E (CH
3
)
3
CH
Q.2. Write down the IUPAC name of the following organic compounds:
(a) Br
Br
b) O- Br- C
6
H
4
CH(CH
3
)CH
2
CH
3
c) (CH
3
)
3
CCH=CHC
6
H
4
I-p
Ans:-
a) 4,4-Dibromo pentene
b) 2-methyl- 2-(o-bromophenyl) butane
c) 3,3-Dimethyl-1-(p-iodophenyl) butane
Q.3. How can the following interconversions are carried out
(a) Ethanol to but-1-yne
(b) Benzene to 4-bromo nitro benzene
( c) Toluene to benzyl alcohol
Ans:- Conc. H
2
SO
4
1. Br
2
a) CH
3
CH
2
OH CH
2
=CH
2
CH= CH
160-170
0
C 2.Alc.KOH
NaNH
2
C
2
H
5
Cl
CH
3
CH
2
C= CH CH=
CNa
NO
2
NO
2

b) Conc.HNO
3
Br
2
/ CCl
4
108
Br
CH3 CH
2
Cl
c) U.V.Light
Q.4.Identify the following pair of structures :
a) CH
3
CH
3
HO H HO H

H Cl Cl H
C
6
H
5
C
6
H
5
b) Br H H Br
CH
3
CH
3
CH
3
CH
3
Ans:-
a) Dia stereomers
b) Structural isomers
Q.5. What is the formula of tartaric acid? Does it show optical isomerism or not.
Draw the structures of its optical isomers.
Ans: -
Tartaric acid exists in three optical isomeric form.

COOH COOH
COOH
HO H H OH H
OH
H OH HO H H
OH
COOH COOH
COOH
109
l-T.A d-T.A.
Meso-T.A.
FOR ABOVE AVERAGE
MARKS QUESTION:-

Q1. Write down the IUPAC name of the following organic compound.
(a)CH
3
CH=C (Cl) CH
2
CH (CH3)
2
(b)CH
3
CH Br CH Cl CH
3
(c) CH
3
C (Cl) (C2H
5
) CH
2
CH
3
(d) CH
3
C(P-Cl-C6H
4
)
2
CH (Br)CH
3
Ans:- (a) 3-chloro-5-methyle hex-2-ene
(b) 2-Choloro-2-ethyl butane.
(C) 2-Bromo-3-chloro butane.
(d) 3-Bromo-2,2-bis(p-chloro phenyl) butane
Q2. Write down the structure of the following organic compounds.
(a) 1-chloro-3-ethyl cyclohexane.
(b) P-bromo chloro benzene.
(c) Ethylene di chloride.
(d) Ethylidene di chloride.
(e) Benzoyl chloride.
Ans:- (a) (b) CH
2
-Cl
CH
2
-Cl
Cl
C
2
H
5
Cl
(c)Br Cl (d) CH
3
-CH
Cl

COCl
(e)
FOR ABOVE AVERAGE
02 Marks
110
Q1. Write the structure of the major organic product in each of the following
reaction.
(a) Br

+ NaSH
CH
2
Br
Cl
(b) + C
2
H
5
ONa
+Heat ethanol
O
2
N NO
2
Ans:- Br OC
2
H
5
(b)
(a)
CH
2
SH NO
2
O
2
N
Q2. Give the Preparation and uses of chloropicrin chlorotone.
Q3. Explain the formation of two products in the following reaction.
CH
3
Ch
2
Cl + H
2
O CH
3
CH=CH CH
2
OH + CH
3
Ch(OH)CH=CH
2
Q4. (a) Write all Possible isomers of C
7
H
7
Cl
(b) Write the Structural formula of optical isomer.
Of the component having molecular formula C
4
H
9
Br.
Ans:- (a) 4 isomers
(b) H
CH
3
-C-C
2
H
5
Br
Q5.What mass of propene is obtained from 34.0 gm of 1-iosopropane on
treating with ethanolic KOH if yield is 36%
Ans:-3.02 gm.
Q6. Arrange the following compound according to reactivity towards
nucleophilic substitution reaction with reagent mentioned.
111
4 nitro chlorobenzene, 2, 4 dinitro chloro benzene, and 2, 4, 6 trinitro
chloro benzene with Ch
3
ONa
For Above Average
03 Marks
Q1. An Organic compound A having molecular formula C4H8 on treatment
with dil H2SO4 gives B B on treatment with ione Hcl and anhydrous
Zncl2 gives C and on treatment with sodium ethoxide gives back A . Identify
the compound A , B and C and write equation involved.
Ans:
A CH
3
C = CH
2
|
CH
3
B CH
3
C(OH) CH
3
|
CH
3
C CH
3
C(Cl) CH
3
|
CH
3

Q2. Although chlorine is an electron withdrawing group, yet it is ortho, para-
directing in
electrophilic aromatic substitution reactions why ?
Ans: Chlorin because of its I- effect withdraws electron from the benzene ring
and hence tends
to destabilize the intermediate carbocation formed during the electrophilic
substitution.
Q3.Predict the order of reactivity of the following compound in SN
1
and SN
2
reaction.
(a) The four isomeric bromobutone
(b) C
6
H
5
CH
2
Br, C
6
H
5
CH(C
6
H
5
)Br, C
6
H
5
CH(CH
3
)Br, C
6
H
5
C(CH
3
)C
6
H
5
Br
Ans:-
CH
3
CH
2
CH
2
CH
2
Br<(CH
3
)
2
CH CH
2
Br<CH
3
CH
2
CH(Br)CH
3
<(CH
3
)
3
C-Br
Reactivity towards SN
1
Reaction
112
CH
3
CH
2
CH
2
CH
2
Br>(CH
3
)
2
CH CH
2
Br>CH
3
CH
2
CH(Br)CH
3
>(CH
3
)
3
C-Br
Reactivity towards SN
2
Reaction
(b) Reactivity towards SN1 Reaction
C
6
H
5
C(CH
3
)(C
6
H
5
)Br>C
6
H
5
(CH(C
6
H
5
)Br>C
6
H
5
CH(CH
3
)Br>C
6
H
5
CH
2
Br
Reactivity towards SN
2
Reaction
C
6
H
5
C(CH
3
)(C
6
H
5
)Br<C
6
H
5
(CH(C
6
H
5
)Br<C
6
H
5
CH(CH
3
)Br<C
6
H
5
CH
2
Br
Q4. Explain the following .
(a) Allyl chloride is hydrolysed more readily than n-propyl chloride.
(b) Vinyl chloride is hyolrolysed more slowly than ethyl chloride
Ans:- (a) Allyl chloride readily undergoes ionization tpo produce sesonance
stabilized allye
carbocation. Science carbocation are rective species, therefore
allyle cotion reading combines with OH ions to form allyl alcohol.
In contrast n-propyl chloride does not undergo ionization to
produce n- propyl chloride.
a. Vinyl chloride get reacting stabilization Carbon-chlorine bond
acquires some double bond character. In contrast in ethyl chloride,
the carbon-chlorine bond is a pure single bond. This Vinyl chloride
under goes hydrolysis more slowly than ethyl chloride.
113
)

1 MARK QUESTIONS
Q. 1. What is the main product obtained when vapours of t-butyl alcohol are passed
over copper at 300 ?
Ans. Isobutylene (2-Methyl propene)
Q. 2. What is usually added to ethyl alcohol to make it unfit for drinking purposes ?
Ans. Methanol and Pyridine.
Q. 3. Phenol has smaller dipole moment than methanol.
(OR)
Why are dipole moments of phenols smaller than dipole moments of alcohols ?
Ans. Due to electron-withdrawing effect of the benzene ring, the C O bond in phenol is
less polar but in case of methanol due to electron-donating effect of CH
3
group, C
O bond is more polar.
Q. 4. Name the products obtained when anisole is treated with HI.
Ans. Phenol and methyl iodide.
Q. 5. Why are Grignard reagents soluble in ether but not in benzene ?
Ans. Grignard reagents from co-ordination complexes with ether but not benzene since the
former has lone pair of electrons but the later does not.
Q. 6. Alcohols are easily protonated than phenols. Justify.
Ans. In phenols lone pair of electrons on the oxygen atom are delocalised over the benzene
ring due to resonance and hence are not easily available for protonation. In contrast in
alcohols, the lone pairs of electrons on the oxygen atom are localized due to absence
of resonance and hence are easily available for protonation.
Q. 7. Di-tert butyl ether cannot be made by Williamsons synthesis. Explain why ?
Ans. To prepare di tert-butyl ether by Williamsons synthesis, we need tert-butyl bromide
and Sodium tertiary butoxide. Since tert-butyl bromide being 3-alkyl halide prefers
114
UNIT 11
ALCOHOLS, PHENOLS
AND ETHERS
to undergo elimination rather than substitution, therefore the product obtained is
isobutylene rather than ditertiary butyl ether.
Q. 8. While separating a mixture of ortho and para-nitro phenols by steam distillation,
name the isomer which will be steam volatile. Give reasons.
Ans. In o-nitrophenol, there is intramolecular hydrogen bonding as follows :
In p-nitrophenol, there is intramolecular hydrogen bonding as follows :
Due to intermolecular H bonding in p-nitrophenol, its b. p. is much higher than that of
o-nitrophenol. Hence o-nitraphenol due to its lower b. p. is steam volatile while p-
nitrophenol is not.
Q. 9. How an OH group attached to carbon in the benzene ring activates benzene
towards electrophilic substitution ?
Ans.
The lone pair of electrons present on oxygen atom enter into resonance with the
benzene ring. As a result, the electron density becomes higher at o- and p- position
115
and due to higher electron density, the ring gets activated towards electrophilic
substitution.
Q. 10. Ethers are cleaved by acids not by based. Why ?
Ans. The C O C bond in ethers like the C OH bond in alcohols is quite strong. In
order to weaken it, the oxygen atom must be protonated. A subsequent nucleophile
attack by a strong nucleophile such as Br

as I

ion on the less hindered carbon atom

of the protonated :
+
C O C
|
H
bond brings about the cleavage of ethers to form an alcohol and an alkyl halide. The
acids only can provide the H
+
ion required for protonation of O atom of ether and
therefore only acids can bring about the cleavage of ethers and not bases.
Q. 11. Phenols do not undergo substitution of the OH group like alcohols. Explain.
Ans. The C O bond in phenols has some double bond character due to resonance and
hence cannot be easily cleaved by a nucleophile. In contrast, the C O bond in
alcohols is a pure single bond and hence can be easily cleaved by a nucleo phile.
Q. 12. Alcohols acts as weak bases. Explain.
Ans. The oxygen atom of the hydroxyl group has two lone pairs of electrons. Therefore
alcohols accept a proton from strong mineral acid to form oxonium ions. Hence act as
weak bases.
Q. 13. Write the mechanism of hydration of ethene to yield ethanol.
Ans. H
2
O + H
+
H
3
O
+
Step (i) : Protonation of alkene to form carbocation by electrophilic attack :
C = C + H O H C C + H O
+ +

2
H H
Step (ii) : Nucleophilic attack of water on carbocation :
C C + H O C C O H
+ +
2

H H
H
Step (iii) : Deprotonation to form an alcohol :
C C O H + H O
+
2
C C + H O
3
+
H O H
H
H
116

Q.1 Why is it that secondary alcohols can only undergo a single oxidation step in contrast to primary
alcohols? (2 marks)
1. Once the oxidation has reached the ketone stage, (primary alcohols on oxidation yield aldehyde where as
secondary alcohols on oxidation yield a ketone), it is impossible to put more oxygen atoms on the relevant
carbon atom without rupturing the backbone of the molecule.
Q1. Why phenol is acidic ?
Ans: In phenol dissociation takes place as follows.
OH O

+H
+
(Phenol) ( Phenoxideion )

The conjugate base of phenol ie. Phenoxide ion is resonance stabilized. This is why
the negative charge on oxygen atom is delocalized through out the ring. So, the oxygen
117
present in phenoxide ion has less tendency to form undissociated phenol molecule and
equilibrium lies towards right direction.
Q2. While separating a mixture of ortho and para nitrophenols by steam distillation, name
the
isomes which will be steam volatile. Give reason.
Ans: O- nitro phenol will be steam volatile because there is intramolecular. H-bonding in its
molecule.
O
OH
N Intramolecular hydrogen bonding
\\
O

But in case of p- nitro phenol there is association of molecules of p-
nitro phenol due to intermolecular hydrogen bonding.
O O O O
\\ //
N OH N
| | |

| | |
OH N OH
\\
O O
Q.1 Give the mechanism of formation of alkene from alwhol in preserve of acid catalyst.
H H H H
| | | |
H-C-C-O-H H- C C - OH
2

| | | |
H H H H

Ethyl alcohol (Protonated alcohol)
-H
2
O

H H
| |
H-C=C-H -H+ H-C-C-+
| | | |
H H H H
(Ethene) (Carbocation)
Q2. Discuss the mechanism of fornsation of ether from alcohol in presence of aid catalyst.
H H
| |
H-C-C-O-H + H
+
H
3
CCH
2
-
+
OH
2

| |
H H
Ethylacohol (Pronated alcocol)
118
H H H H H H
| | | | | |
H-C-C-O-H + H
3
CCH
2
-O
+
H
2
H-C-C-O
+
-C-C-H
| | | | | | |
H H H H H H H
-H
+

H H H H
| | | |
H-C-C-O-C-C-H
| | | | |
H H H H H
Q3. Discuss Williamson systhecis.
Ans:- In this method symmetrical and unsymmehical ethers are formed. In this synthesis an
alkyle is allowed to react with sodium alkoxide.
R X + R O Na R O R + NaX
Ethers contains substitutes alkylgsoups can be prepared by this
method. The reaction involveds SN2 attack of an alkoxide ion on primary alkyl halide.
CH
3
CH
3
| |
H
3
C O
-
Na
+
+ CH
3
Br H
3
C O C-CH
3
+ NaBr
| |
CH
3
CH
3

In case of secondary and tertiany holides elimination completes over substitution. It a
3 alkyl holide is used an alkene is the only reaction product and no ether is formaed.
CH
3
|
H
3
C-C-Br + Na+OCH
3
H
3
C-C=CH
2
+NaBr+CH
3
OH
| |
CH
3
CH
3
( 2- methyl propene )
Q4. Ortho and paranitrophenols are more acidic than phanel. Draw the resonance structures
of the corresponding phonoxide ion.
Ans:- Electronwithdrawal by nitro group makes the plenoxide ion more resonance stabilized
and so the strength of phenel increases.
SOME MORE IMPORTANT QUESTIONS WITH ANSWERS
BELOW AVERAGE
1 mark questions:-
119
Q.1. Give the IUPAC name of CH
3
O CH CH
3
CH3
Ans:- 2- Methoxypropane
Q.2. Give the IUPAC name of C
6
H
5
--O CH
2
CH
2
CH CH
3
1 2 3 4
CH3
Ans:- 3- Methyl butoxy benzene
1 CH
2
OH

Q.3. Give the IUPAC name of H
3
C -- CH CH
2
CH-- CH

- CH
3
6 5 4 3 2
CH
3
OH
Ans : - 2,5 Dimethyl hexane 1,3 - diol
Q.4 . Give the IUPAC name of

CH
3

CH
3
-- C -- OH

CH
3



Ans : - 2-Methyl propanol

Q.5. Give the IUPAC name of OH

Ans:- Benzene 1,4- diol OH
Q.6. Write the structures of 1- Ethoxypropane

H H H
Ans: -
C
2
H
5
O - C - C C - H

H H H
120
Q.7. Write the structure of 2- Ethoxy 3 methyl pentane
H H CH
3
OC
2
H
5
H

Ans: - H - C - C C - C -- C - H

H H H H H
Q.8. Illustrate Riemer Tiemann reaction with one example
Ans :-
OH OH
CHO
KOH, CHCl
3

(Phenol) H
+
(2- hydroxy benzaldehyde)
Q.9. Why phenol is acidic ?
Ans:- Due to resonance stabilization of its conjugate base phenoxide ion.
Q.10. Convert anisole to phenol?
OCH
3
+ HI OH
Ans:-
+ CH
3
I
(Anisole) (Phenol)
2 Marks Questions:-
Q.1. Give the equations of reaction for the preparation of phenol from cumene.
Q.2. Why phenol is more acidic than etanol.
Q.3. Explain the following with an example: -
(i) Kolbes reaction
(ii) Williamsons ether synthesis
Q.4. Show how will you synthesise pentan- 1- ol using a suitable alkyl halide?
Q.5. Write chemical reaction for the preparation of phenol from cumene?
Q.6. Write the equation of hydration of ethane to yield ethanol.
121
Q.7. Convert the following :-
(i) Ethyl alcohol and Acetic acid
(ii) Propan 2 ol to propene
Q.8. Explain esterification with example.
Q.9. Convert the following : -
(i) Aniline to Phenol
(ii) Phenol to picric acid
Q.10. Alcohols are comparatively more soluble in water than hydrocarbons of
comparable molecular masses. Explain this fact.
3 marks questions
Q.1. The following is not an appropriate reaction for the preparation of t-butyl
ether.
C H
3
C H
3


C
2
H
5
ONa + CH
3
- C - CH
3
CH
3
-- C --
OC
2
H
5

CH
3
CH
3

(i) What would be the major product of this reaction?
(ii) Write a suitable reaction for the preparation of t- butyl ether.
Q.2.
(i) Explain why is ortho - nitro phenol more acidic than methoxy
phenol ?
(ii) Why o-nitro phenol is steam volatile while p-nitro phenol has
higher boiling point.
(iii) Give reason for the higher boiling point of ethanol in comparison
to Methoxy methane.
Q.3.
(i) What happens when phenol is treated with FeCl
3
?
(ii) Distinguish between phenol and benzyl alcohol.
(iii) Explain the coupling reaction with one example.

Q.4. Account for the following : -

(i) Alcohols act as weak bases.
(ii) Phenol has smaller dipole moment than methanol.
(iii)Phenols do not give protonation reaction easily.
Q.5.
(i) Draw the structures of all isomeric alcohols of molecular formula
122
C
5
H
12
O.
(iii) Classify the isomers of alcohols as Primary, Secondary and
Tertiary alcohols.
Q.6. While separating a mixture of ortho and para nitro phenols by
steam
distillation, name the isomers which will be steam volatile. Give
reason.
Q.7. Convert the following: -
(i) Acetaldehyde to Isopropylalcohol
(ii) Acetone to t - butyl alcohol.
Q.8. Arrange the following set of compounds in order of their increasing
boiling points.
(a) Pentan 1 ol, Butan 1- ol, Butan 2- ol, ethanol, Propan

1- ol,
(b) Pentan -1-ol, n- butane, pentanal, ethoxyethane and
methanol.
Q.9.
(i) What is the Lucas test?
(ii) Distinguish Primary, Secondary and tertiary alcohols with
the
help of Lucas test.
Q.10.
(i) Why the presence of OH group attracted to benzene ring
activates the ring towards electrophilic substitution?
AVERAGE
01 mark questions : -
Q.1. Write down the IUPAC name of
H
3
C CH
3
OC
2
H
5
Q.2. Write down the IUPAC name of
OH
CH
3
CH
3

Q. 3. Write down the structure of the product of the following reaction: -
123
H
3
C-CH= CH
2
H
2
O/ H
+
.
Q.4. Distinguish between
OH COOH
and
Q.5. Distinguish between O

COCH
3
C-C
6
H
5
and
Q6. Write the structure of the product of the following reaction: -
O
NaBH
4
H
3
C CH
2
- CH- C -H

.
CH
3
Q.7. Give the mechanism of dehydration of alcohols to alkenes.
Q.8. Explain Williiamsons synthesis with one example.
Q.9. Alcohols are comparatively more soluble in water than hydrocarbons of
comparable
molecular masses.
2 marks questions
Q.1. How is 1-propoxypropane synthesized form propan 1- ol. Write
mechanism of this
reaction.
Q.2. Write the equation of the following reactions : -
(i) Friedel Craft reaction
(ii) Nitration of anisole
Q.3. Explain the following with an example :
(i) Kolbe reaction
124
(ii) Reimer Tiemanns reaction
Q. 4. Convert the following: -
(i) Phenol to bezene
(ii) Phenol to benzoquinone
Q.5. Distinguish between the following pair of compounds :

CH
2
OH OH
(i)
and
(ii) O
C
and
O H
C C- H
H
Q.6. Write the reactions of Williamsons synthesis of 2- ethoxy- 3-
methylpentane. Starting from ethanol and 3- methylpentan-2-ol.
Q.7. You are given benzene , Conc.H
2
SO
4
and NaOH. Write the equations for
the
preparation of Phenol using these reagents.
Q.8. Name the reagents used in the following reactions:
(i) Benzyl alcohol and Benzoic Acid
(ii) Butan- 2- one to Butan 2- ol
Q.9. Explain the acidity of phenol in the light of resonance structures.
Q.10. Distinguish primary, secondary and tertiary alcohols using Copper as
catalyst.
3 marks questions
Q.1. (a) When 3- methyl butan 2 ol is treated with HBr, then following
reaction takes place
Br

125
H
3
C CH CH CH
3
HBr H
3
C CH CH
2

CH
3


H
3
C OH H
3
C
(b) Explain the nitration of anisole
Q.2. Write the equations of the following reactions: -
(i) Bromination of anisole in ethanoic acid medium.
(ii) Friedel-Crafts acetylation of anisole.

Q.3.
(i) Explain why is ortho - nitro phenol more acidic than o- methoxy
phenol?
(ii) Write the mechanism of the reaction of HI with methoxy
methane.
Q.4. How are the following conversions carried out?
(i) Ethyl magnesium chloride Propan 1- ol
(ii) Benzyl chloride Benzyl alcohol
(iii) Propane Propan 2- ol
Q.5.
(i) Explain the preparation of ethers by acid dehydration of secondary
or
tertiary Alcohols is not a suitable method.
(iii) Explain why propanol has higher boiling point than that of the
hydrocarbon , butane?
ABOVE AVERAGE
01 mark questions
Q.1. What is meant by hydrocarbonation-oxidation reaction?
Illustrate with an example.

Q.2. Ortho and para nitrophenols are more acidic than phenol. Draw the
resonance structures of the corresponding phenoxide ions.

Q.3. Distinguish between anisole and phenol?

Q.4. Preparation of ethers by acid dehydration of secondary or tertiary alcohol
is
126
not a suitable method. Why?

Q.5. Convert Salicylic acid to Aspirin.
Q.6. Predict the product of the following reaction.
OH
CCl
4
/ OH
--

H
+
Phenols
Q.7. Predict the major product of acidic catalysed dehydration of butan-1-ol.
Q. 8.
CH
3

CH
3
-- C O -- CH3 + HI

CH
3
Predict the product in the above
reaction
(t-butyl methyl ether )
2 marks questions: -
Q.1. Give the major products that are formed by heating each of the
following ethers unit HI.
(i)

CH
2
-O
(ii) CH
3


H
3
C -- CH2 CH
2
O-- CH

CH
2
CH
3

CH3
Q.2. Why anisole undergoes bromination with bromine in ethanoic
acid
127
even in absence of iron (III) bromide catalyst.
Q.3. During dehydration of alcohols to ethers, the method is suitable
for
the preparation of ethers having primary alkyl groups only,
why?
Q.4. Explain the fact that in aryl alkyl ethers
(i) The alkoxy group activates the benzene ring towards the
electrophilic substitution.
(iii) It directs the incoming substituents to ortho and para
positions
in benzene ring.
Q.5. Show how could you synthesise the following alcohols from
appropriate alkenes?
CH
3
OH
(i) OH (ii)
Q.6. Write Structures of the products of the following reactions:
O
(i)
NaBH
4
CH
2
-C-OCH
3
O
(ii)
NaBH
4
H
3
C CH
2
- CH-- C HO

.
CH
3
3 marks questions: -
Q.1.
(a) Show how the following alcohols prepared by the reaction of
a
128
suitable are Grignard reagent on methanol?

(i) H
3
C CH- CH
2
OH

.
CH
3
(ii) CH
2
OH
(c) Give the mechanism of conversion of alkene into alcohol in
presence of acid catalyst.
Q.2.
(a) Which of the following is an appropriate set of reactants for
the preparation of 1- methoxy-4 nitrobenzene and why?
(i) (ii)
Br ONa
+ H
3
COONa + CH
3
Br
NO
2
NO
2
c) The bond angle in alcohols is slightly less than the
tetrahedral angle.
Q.3.
(i) Arrange the following compounds in the increasing order of
their acidic strength :
Propan 1 ol ; 2,4,6 trinitrophenol; 3 nitrophenol; 3,5
dinitro-phenol; Phenol; 4-methyl phenol
(ii) Predict the product of the reaction given below:-
129
CH
3

CH
3
-- C -- Br + Na
+
CH
3
..

CH
3

Q.4.
(i) What is the cause of large difference of B.P.s between ethyl
alcohol, Ethylene glycol and glycerol?
(ii) Of benzene and phenol, which is more easily nitrated and
why?
Q.5. Give the structures and IUPAC names of the products expected
from the following reactions:
(a) Catalytic reduction of butanal.
(b) Hydration of propene in the presence of dilute sulphuric
acid.
(c) Reaction of propanone with methylmagnesium bromide followed
by hydrolysis.

130
ALDEHYDES, KETONES AND CARBOXYLIC ACIDS
BASIC CONCEPTS:
1. Aldehydes and ketones :These are carbonyl compounds and
contain carbonyl ( >C=O) functional group.They have
general formula RCHO and RCOR

respectively. The carbon
atom of the carbonyl group is SP
3
Hybridised. The >C=O
bond is polar due to the different electronegativities of the
constituent atoms. Aldehydes (RCHO), ketones(R
2
C=O) and
carboxylic acids (RCOOH) are most important and widely
used compounds in organic chemistry. They play an
important role in biochemical processes of life.These
compounds and their derivatives are used in many food
products, pharmaceuticals, for artificial flavouring, as
solvents and for preparing a number of materials.
The structure of carbonyl group is given below

2. PREPARATION OF ALDEHYDES:
(a) By oxidation of alcohols

(b) By Dehydrogenation of alcohols
131
UNIT 12
TH

ALDEHYDE, KETONS AND
CARBOXYLIC ACIDS
(c) By ozonolysis of alkenes

(d) By hydration of alkynes
(e) Rosenmunds reaction
(f) Treatment of acid chloride with dialkylcadmium gives
ketones
(g)From nitriles and esters
This rection is called Stephens reaction.
132
Nitriles are selectively reduced by isobutylaluminium
hydride (DIBAL-H) to imines followed by hydrolysis to give
aldehydes.
Esters are also reduced to aldeydes with DIBAL-H.
Nitriles react with Grignard reagent which on hydrolysis
gives ketones.
(h) Aromatic aldeydes are prepared from aromatic
hydrocarbons by the following methods:
( a) Etards reaction: Toluene reacts with chromyl chloride
(CrO
2
Cl
2
) in Cs
2
or CCl
4
to form benzaldehyde.
133
(b) Gatterman- Koch reaction: When a mixture of CO and HCl gas
is passed through benzene in presence of anhydrous AlCl
3
+ CuCl,
benzaldehyde is formed.
(c) Friedel- Crafts acylation:
Physical Properties of Aldehydes and Ketones
(a) Physical State : Most of the aldehydes ( except
formaldehyde which is gas ) are liquid at room
temperature. The lower ketones are colourless liquids
and have a pleasant smell. The higher members are
colourless solids. Aromatic ketones are usually solids
with a pleasant smell.
(b) Boiling Points : Aldehydes and ketones have relatively
high boiling points as compared to hydrocarbons of
comparable moleculer masses. It is due to the reason
that aldehydes and ketones contain polar carbonyl
group and therefore they have stronger interactions
dipole dipole interactions between the opposite ends of
C=O dipoles.
These dipole dipole interactions are however , weaker
than intermolecular H-bonding in alcohols.Consequently
boiling points of aldehydes and ketones are relatively
lower than the alcohols of comparable molecular
masses.
134
Dipole- Dipole interaction between two carbonyl
groups
(C) Solubility :
The lower members of aldehydes and ketones (upto four
carbon atoms) are soluble in water . It is due to their
capability of forming hydrogen bonds with water
molecules . The solubility of these compounds in water
decreases with the increase in the size of alkyl group. It
is because of the increase in the magnitude of non polar
parts in the molecule. However higher homologous are
soluble in organic solvents.
CHEMICAL PROPERTIES OF ALDEHYDES AND KETONES:
Aldehydes and ketones are highly reactive compounds. Both
Aldehydes and ketones undergo nucleophilic addition reactions.
Explanation: The reactive nature of aldehydes and ketones is
because of the presence of a polar carbonyl group. As the oxygen
atom is more electronegative, therefore, it pulls the electron
density around itself acquiring a partial negative charge whereas
a partial positive is developed on the carbon atom. The positively
charged carbon atom of carbonyl is then readily attacked by the
nucleophilic species for initiation of the raction. This leads to the
formayion of an intermediate anion which further undergoes the
attack of H
+
ion or other positively charged species to form the
final product. The nucloephilic recation may be catalysed by acids
or bases. The reaction in general , may be represented as:
135
Aldehydes are generally more reactive than ketones due to the
following reasons:
i) Presence of two alkyt groups cause more steric hindrance
in the approach of nucleophile to carbonyl carbon. In
aldehydes only one alkyl group is present.
ii) In ketones +I effect of two alkyl groups reduce the
positive charge of carbonyl carbon and reduces its
electrophilicity.
SOME IMPORTANT NUCELOPHILIC ADDITION REACTIONS:
a) Addition of hydrogen cyanide( HCN)
Presence of base catalyses the reaction
b) Addition of sodium hydrogensulphite( NaHSO
3
)


c)Addition of alcohols:

d)Addition of ammonia and its derivatives:
136
e) Reduction reactions:
i) Using LiAlH
4
or NaBH
4
to alcohols
137

iii) Reduction to Hydrocarbons:
Clemmensen reduction
Wolf- Kishner reduction

f) Oxidation :Aldehydes are easily oxidized to carboxylic acids
with common oxidizing agents like KMnO
4,
K
2
Cr
2
O
7
, Nitric acid and
even with mild oxidizing agents like Tollens reagent and Fehling
solution also.

Ketones are generally oxidized under vigorous conditions with
strong oxidizing agents. Oxidation of ketones involve C-C bond
cleavage and as a result a mixture of carboxylic acids are formed.
Tollens Test: The test is used to distinguish between aldehydes
and ketones. Aldehydes form silver mirror with ammonical silver
nitrate( Tollens reagent). Ketones do not react with it.
138
Fehlings test: Fehling reagent= fehling solution A (aq CuSO
4
) +
Fehling solution B( Alk. Sodium potassium tartarate)
Haloform reaction: Aldehydes and ketones Having atleast one
CH
3
Group linked to the carbonyl carbon give this reaction.


Iodoform test: ( using the reagent NaOH+I
2
) is used to identify
the presence of group or in a
compound.
g) Condensation reactions:
i) Aldol condensation: This recation is given by those aldehydes
and ketones which have -hydrogen atom. -hydrogen of carbonyl
compounds is acidic due to strong electron withdrawing nature of
carbonyl group in presence of a base.

139
Aldols have both -OH group and carbonyl group.
ii) Cross aldol condensation:
iv) Cannizaros reaction:
140
This is a disproportionation reaction in which aldehyde undergoes
self reduction and oxidation.
h) Electrophilic substitution reaction: When carbonyl group is
attached to benzene ring, it deactivates the ring and it is meta-
directing.
Uses of aldehydes and ketones:
i) Used as solvents and flavouring agents.
ii) Formaldehyde is used as formalin( 40% solution) to
preserve biological specimens.
iii) Used as starting material for the preparation of a number
of organic compounds, Dyes, polymers etc.
CARBOXYLIC ACIDS
(i) PREPARATION:
a) From primary alcohols and aldehydes
b) From alkylbenzene :
The alkyl chain in alkyl substituted benzene is completely
oxidized to COOH irrespective of the length of the chain.
Primary and secondary alkyl groups also get oxidized, only
tertiary group remains unaffected.
141
c) From nitriles and amides :
d) From Grignard reagent:

e) From acyl halides and anhydrides :
f) From esters :
(ii) PHYSICAL PROPERTIES:
a) Lower members of carboxylic acids (upto 9-C) are liquids at
room temperature, and have foul odour.
b) Higher members are solid and odourless.
142
c) Carboxylic acids remain associated (dimer) form in vapour
state and in aprotic solvents(like organic solvents).

d) In protic solvents like H
2
O carboxylic acids remain in
dissociate form.

e) The solubility of carboxylic acids decreases with increasing
number of C-atoms as the non-polar hydrophobic alkyl part
gets bigger.
f) Carboxylic acids are soluble organic solvents like benzene,
ether, chloroform, etc.
CHEMICAL REACTIONS OF CARBOXYLIC ACIDS:
Acidic character of carboxylic acids:- carboxylic acids are weaker
than mineral acids but stronger than alcohols and simple phenols.
Carboxylic acids are stronger acids than phenols because
carboxylate ion is more resonance stabilised than phenoxide ion.
As in carboxylate ion resonance structure ve charge is on
electronegative O-atoms while it is on lesser electronegative C-
atoms in phenoxide ion resonance structure.
Alcohols are even less acidic as alkoxide ion shows no resonance.

Carboxylic acids dissociates in water to give carboxylate ion and
hydronium ion.
143

Higher the P
ka
value less is the acidic strength.


Effect of Substituents on the Acidic Strength of Carboxylic Acids :-
Electron withdrawing group (EWG) increases the acidic strength
as it increases the polarity (-I effect) of O-H bond facilitating the
release of H
+
ion.

Electron withdrawing group stabilizes the carboxylate ion by
dispersing ve charge. Presence of electron donating group(EDG)
decreases the acidic strength as it decreases the polarity of O-H
bond due to its +I effect. Also EDG destablishes the carboxylate
ion by further increase e-density towards the carboxylate ion. The
effect of some EWG
s
is as follows:

Closer the presence of EWG to the carboxylic group more is the
acidic strength.
When carboxylic group is attached to vinyl or phenyl group its
acidic strength is due to resonance.

The presence of EWG increases the acidic strength in benzene
ring while presence of EDG decreases acidic strength.

Reactions
(i) Formation of anhydrides
(ii) Esterification
144
(iii) Formation of acyl chlorides

Thionyl chloride (SOCl
2
) method is preferred because both the
by-products are gaseous as a result pure product is obtained.
(iv) Reaction with Ammonia
(V) Reduction
(v) Sodalime decarboxylation
(vi) Kolbes electrolysis
145
(vii) Hell Volhard Zelinsky (HVZ) reaction: By this method -
substituted carboxylic acids can be prepared.
This reaction is given by only those carboxylic acids which have -
H. X in - position of carboxylic acid can be replaced by any
group in its reaction with aq KOH, alc.KCN, etc.
(viii) Aromatic carboxylic acids undergo electrophilic
substitution reaction. The COOH group attached to
benzene ring is a deactivating group and is m-directing.

Recap: Summary
Aldehydes, ketones and carboxylic acids have carboxyl
group and are highly polar compounds.
Carboxylic acids although contain group but do not give the
reactions given by aldehydes and ketones.
Aldehydes and ketones have higher boiling points than the
corresponding hydrocarbons and ethers due to higher polarity
(stronger dipole-dipole interactions)
Carboxylic acids have also higher boiling points due to
extensive H-bonding.
Carboxylic acids are stronger acids than phenols and
alcohols but weaker than mineral acids.
Aromatic acids are in general more acidic than aliphatic
acids due to the presence of electron withdrawing benzene
ring.
146
Higher the pKa value of an acid weaker is the acid, i.e., it is
poor proton donor.
Ketones are more polar and have higher boiling point than
aldehydes of comparable molecular mass.
Aldehydes are more reactive towards nucleophilic
substitution reactions than ketones.
Aldehydes oxidise to give carboxylic acids.
Aldehydes on reduction give 1 alcohols.
Ketones on reduction give 2 alcohols.
Ketones are oxidised only under drastic conditions and
breaking of CC bond takes place at the carboxyl group.
Aldol condensation is given by only those aldehydes and
ketones which have
Cannizaros reaction is given by only those aldehydes which
do not have
Aldehydes and ketones can be converted to corresponding
hydrocarbons (having same number of C-atoms) by
Clemensons reduction and Wolf-Kishner reduction.
Carboxylic acids on reduction give 1 alcohols.
Sodalime decarboxylation method can be used to reduce a
C-atom in carboxylic acids.
Hell Volhard Zelinsky reaction is used to introduce a
substitute like CN, X, OH, etc., at in a carboxylic acid.
Carbonyl group and carboxylic group both are ring
deactivating and m-directing groups when attached to
benzene ring.
Aldehydes can be oxidised with mild oxidising agents like
Tollens reagent and Fehlings solution but not ketones.
Aromatic aldehydes are oxidised by Tollens reagent but not
with Fehlings solution.
Formic acid is the only acid which gives the tests given by
aldehyde groups.
1 MARK QUESTIONS
Q. 1. Name the reaction and the reagent used for the conversion of acid chlorides to
the corresponding aldehydes.
Ans. Name : Rosenmunds reaction
Reagent : H
2
in the presence of Pd (supported over BaSO
4
) and partially poisoned by
addition of Sulphur or quinoline.
O O
|| Pd/BaSO
4
||
R C Cl + H
2
R C H + HCl
147
+ S or quinoline
Q. 2. Suggest a reason for the large difference in the boiling points of butanol and
butanal, although they have same solubility in water.
Ans. The b. pt. of butanol is higher than that of butanal because butanol has strong
intermolecular H-bonding while butanal has weak dipole-dipole interaction. However
both of them form H-bonds with water and hence are soluble.
Q. 3. What type of aldehydes undergo Cannizaro reaction ?
Ans. Aromatic and aliphatic aldehydes which do not contain hydrogens.
Q. 4. Out of acetophenone and benzophenone, which gives iodoform test ? Write the
reaction involved.
(The compound should have CH
3
CO-group to show the iodoform test.)
Ans. Acetophenone (C
6
H
5
COCH
3
) contains the grouping (CH
3
CO attached to carbon) and
hence given iodoform test while benzophenone does not contain this group and hence
does not give iodoform test.
C
6
H
5
COCH
3
+ 3 I
2
+ 4 NaOH CHI
3
+ C
6
H
5
COONa + 3 NaI + 3 H
2
O
Acetophenane Iodoform
I
2
/NaOH
C
6
H
5
COC
6
H
5
No reaction
Q. 5. Give Fehling solution test for identification of aldehyde gp (only equations).
Name the aldehyde which does not give Fehlings soln. test.
Ans. R CHO 2 Cu
2+
+ 50 H

RCOO

+ Cu
2
O 3 H `
2
O
Benzaldehyde does not give Fehling soln. test.
(Aromatic aldehydes do not give this test.)
Q. 6. What makes acetic acid a stronger acid than phenol ?
Ans. Greater resonance stabilization of acetate ion over phenoxide ion.
Q. 7. Why HCOOH does not give HVZ (Hell Volhand Zelinsky) reaction but
CH
3
COOH does ?
Ans. CH
3
COOH contains hydrogens and hence give HVZ reaction but HCOOH does
not contain -hydrogen and hence does not give HVZ reaction.
Q. 8. During preparation of esters from a carboxylic acid and an alcohol in the
presence of an acid catalyst, water or the ester formed should be removed as
soon as it is formed.
148
Ans. The formation of esters from a carboxylic acid and an alcohol in the presence of acid
catalyst in a reversible reaction.
H
2
SO
4
RCOOH + ROH RCOOR + H
2
O
Carboxylic acid alcohol Ester
To shift the equilibrium in the forward direction, the water or ester formed should be
removed as fast as it is formed.
Q. 9. Arrange the following compounds in increasing order of their acid strength.
Benzoic acid, 4-Nitrobenzoic acid, 3, 4-dinitrobenzoic acid, 4-methoxy benzoic
acid.
Ans. Since electron donating gps. decrease the acid strength therefore 4-methoxybenzoic
acid is a weaker acid because methoxy sp. is E. D. G. than benzoic acid. Further since
electron withdrawing gps. increase the acid strength, therefore both 4 nitrobenzoic
acid and 3, 4-dinitrobenzoic acids are stronger acid than benzoic acid. Further due to
the presence of additional NO
2
gp at m-position wrt COOH gt, 3, 4-dinitrobenzoic
acid is a lattice stronger acid than 4-nitrobenzoic acid. Thus the increasing order of
acid strength will be :
4-methoxybenzoic acid < benzoic acid < 4-nitrobenzoic acid < 3, 4, dinitrobenzoic
acid.
Q. 10. How is tert-butyl alcohol obtained from acetone ?
Ans.
Q. 11. Give IUPAC name of the following compound :
Ans. 2-methylcyclopent-3-ene-1-oic acid
Q. 12. How will you distinguish between methanol and ethanol ?
Ans. By Iodoform test :
Ethanol having -methyl gp will give yellow ppt. of iodoform whereas methanol
does not have -methyl gp will not give ppt. of iodoform.
149
Q. 13. Distinguish between :
(i) Acetaldehyde and acetone
(ii) Methanoic acid and Ethanoic acid.
Ans. (i) Acetaldehyde will give positive tests with Tollens reagent and Fehling Solns.
whereas acetone will not give these test.
(ii) Methanoic acid gives Tollens reagent test whereas ethanoic acid does not due
to difference in their boiling points.
Q. 14. Why are aldehydes more reactive than ketones ?
Ans. It is because of 2 reasons :
The carboxyl compounds (both aldehydes & ketones) undergo nucleophilic addition
reaction.
(i) + I effect : The alkyl group in ketones due to their e

releasing character
decrease the electrophilicity / + ve charge on c-atom and thus reduce its
reactivity.
(ii) Steric hindrance : Due to steric hindrance in ketones, they are less reactive.
Q. 15. Give the composition of Fehling A and Fehling B ?
Ans. Fehling A = aq. CuSO
4
Fehling B = alkaline sodium potassium tartarate
(Rochelle Salt)
Q. 16. Name one reagent which can distiguish between 2-pentanone and 3-pentanone ?
Ans. 2-pentanone has a CH
3
CO-group, hence gives positive iodoform test.
3-pentanone does not have a CH
3
CO-group, hence does not give positive iodoform
test.
Iodoform test I
2
/NaOH
O
|| I
2
CH
3
CH
2
CH
2
C CH
3
+ NaOH CHI
3
(yellow ppt.)
O
||
CH
3
CH
2
C CH
2
CH
3
No rxn.
Q. 17. Why pcc cannot oxidise methanol to methane and while KMnO
4
can ?
Ans. This is because pcc is a mild oxidising agent and can oxide methanol to methanal
only.
While KMnO
4
being strong oxidising agent oxidises it to methanoic acid.
150
Q. 18. Would you expect benzaldehyde to be more reactive or less reactive in
nucleophlic addition reaction than propanal ? Explain.
Ans. C-atom of carbonyl group of benzaldehyde is less electrophilic than C-atom of
carbonyl group in propanal. Polarity of carbonyl group is in benzaldehyde reduced
due to resonance making it less reactive in nucleophilic addition reactions.
+
O
| |
C
H
O

H
There is no such resonance effect in propanal and so the polarity of carboxyl group in
it is more than in benzaldehyde. This makes propanal more reactive than
benzaldehyde.
Q. 19. What are Hemiacetal and acetal ?
Ans. Hemiacetal and acetals are formed by addition of alcohols on carboxyl compounds.
Q. 20. Why does methanal not give aldol condensation while ethanol gives ?
Ans. This is because only those compounds which have hydrogen atoms can undergo
aldol reaction. Ethanol possesses -hydrogen and undergoes aldol condensation. '
Methanal has no hydrogen atoms, hence does not undergo aldol condensation.
Q. 21. Why does methanal undergoes Cannizaros rxn ?
Ans. Because it does not possesses hydrogen atom. Only those aldehydes can undergo
Cannizaro reaction which do not possess hydrogen atoms.
Q. 22. Arrange the following in order of increasing boiling points :
CH
3
CH
2
CH
2
OH, CH
3
CH
2
CH
2
CH
3
, CH
3
CH
2
OCH
2
CH
3
, CH
3
CH
2
CH
2
CHO
Ans. CH
3
CH
2
CH
2
CH
3
< C
2
H
5
OC
2
H
5
< CH
3
CH
2
CH
2
CHO < CH
3
(CH
2
)
2
OH
(hydrogen) (ether) (aldehyde) (alcohol)

increase in bond polarity.

Q. 23. Why does solubility decreases with increasing molecular mass in carboxylic
acid ?
151
Ans. Because of increase in alkyl chain length which is hydrophobic in nature.
Q. 24. Although phenoxide ion has more no. of resonating structures than carboxylate
ion, carboxylic acid is a stronger acid. Why ?
Ans. Conjugate base of phenol phenoxide ion has non equivalent resonance structures
in which ve charge is at less electronegative C-atom and +ve charge is at more
electronegative O-atom.
Resonance is not so effective. '
O O
+
O
+
O
+

In carboxylate ion, ve charge is delocalised on two electronegative O-atoms hence

resonance is more effective.
R C R C R C
O
O
O
O
O

]
Q. 25. There are two NH
2
group in semicarbazide. However, only one is involved in
formation of semicarbazones. Why ?
Ans. Although semicarbazide has two NH
2
groups but one of them is involved in
resonance.
O O

|| + | . . | +
H
2
N C NH
2
NH
2
H `
2
N = C NH NH
2
H `
2
N C = NH
NH
2
As a result, e

density on one of the NH
2
group is reduced and hence it does not act
as nucleophile.
Lone pair of other NH '
2
group is not involved in resonance and is available for
nucleophilic attack.
2 MARKS QUESTIONS
Q. 1. Arrange the following carboxyl compounds in increasing order of their reactivity
in nucleophilic addition reactions. Explain with proper reasoning :
Benzaldehyde. p-tolualdeyde, p-nitrobenzaldehyde, Acetophenone.
152
Ans. Acetophenone is a ketone while all others are aldehydes, therefore it is least reactive.
In p-tolualdehyde, there is methyl group (CH
3
) at para position w.r.t. to the carboxyl
gp, which increases electron density on the carbon of the carboxyl gp by
hyperconjugation effect thereby making it less reactive than benzaldehyde.
H C C H
O

H C = = C e t c .
H
H
H
H
H
On the other hand, in p-nitrobenzaldehyde, the NO
2
gp is a powerfuil electron-
withdrawing gp. It withdraws electrons both by inductive and resonance effect
thereby decreasing the electron density on the carbon atom of carboxyl gp. This
facilitates the attack of the nucleophile and hence makes it more reactive than
benzaldehyde.
Therefore, the overall order of increasing reactivity :
acetophenone < p-tolualdehyde < benzaldehyde < p-nitrobenzaldehyde.
Q. 2. Arrange the following compounds in increasing order of their boiling points.
Explain by giving reasons.
CH
3
CHO, CH
3
CH
2
OH, CH
3
OCH
3
, CH
3
CH
2
CH
3
.
Ans. The molecular masses of all these compounds are comparable :
CH
3
CHO (44), CH
3
CH
2
OH (46), CH
3
COCH
3
(46), CH
3
CH
2
CH
3
(44).
CH
3
CH
2
OH exists as associated molecule due to extensive intermolecular hydrogen
bonding and hence its boiling point is the highest (351 K). Since dipole-dipole
interaction are stronger in CH
3
CHO than in CH
3
OCH
3
, hence boiling point of
CH
3
CHO (293 K) is much higher than that of CH
3
OCH
3
(249 K). Further, molecules
of CH
3
CH
2
CH
3
have only weak Vander Waals forces while the molecules of
CH
3
OCH
3
have little stronger dipole-dipole interactions and hence the boiling point of
CH
3
OCH
3
is higher (249 K) than that of CH
3
CH
2
CH
3
(231 K). Thus the over all
increasing order of boiling points is :
CH
3
CH
2
CH
3
< CH
3
OCH
3
< CH
3
CHO < CH
3
CH
2
OH
Q. 3. Which acid of each pair shown here would you expect to be stronger ?
CH
3
CO
2
H or FCH
2
CO
2
H
153
Ans.
increases the electron the electron density in the lizes the carboxylate the
carboxyate
density in the O H O H bond thereby ion by intensifying ion by
dispersing
bond thereby making making the release of a the ve charge. the ve
charge.
the relase of a proton proton easier.
difficult.
Thus due to lesser electron density in the O H bond and greater stability of
FCH
2
COO

ion over CH
3
COO

ion FCH
2
COOH is a stronger acid than CH
3
COOH.
Q. 4. Which acid is stronger and why ?
F
3
C COOH or H
3
C COOH
Ans. F
3
C C CH
3
C
CF
3
has a strong I effect. CH
3
has a weak + I effect.
It stabilises the carboxylate ion It stabilises the carboxylate ion
by dispersing the ve charge. by intensifying the ve charge.
Therefore due to greater stability of F
3
C C
6
H
4
COO

(p) ion over CH

3

C
6
H
4
COO

(p) ion, F
3
C C
6
H
4
COOH is a much stronger acid than CH
3
C
6
H
4
COOH.
Q. 5. Arrange the following compounds in increasing order of their reactivity towards
HCN. Explain it with proper reasoning.
Acetaldehyde, Acetone, Di-tert-butyl ketone, Methyl tert-butyl ketone.
Ans. Addition of HCN to the carboxyl compounds is a nucleophilic addition reaction.
The reactivity towards HCN addition decreases as the + I effect of the alkyl gp/s
increases and/or the steric hindrance to the nucleophilic attack by CN

at the carboxyl
carbon increases. Thus the reactivity decreases in the order.
154
+ I effect increases
Steric hindrance increases
Reactivity towards HCN addition decreases
In other words, reactivity increases in the reverse order, i. e.,
Ditert-butyl Ketone < tert-Butyl methyl Ketone < Acetone < Acetaldehyde
Q. 6. Write structural formulae and names of four possible aldol condensation
products from propanal and butanal. In each case, indicate which aldehyde acts
as nucleophile and which as electrophile.
Ans. (i) Propanal as nucleophile as well as elecrophile.
OH CH
3
5 4 3 | 2 | 1
CH
3
CH
2
CHO + CH
3
CH
2
CHO CH
3
CH
2
CH CH CHO
Propanal Propanal 3-hydroxy-2-methyl pentanal
(ii) Propanal as electrophile and butanal as nucleophile.
OH CH
2
CH
3
5 4 3 | 2 | 1
CH
3
CH
2
CHO + CH
3
CH
2
CH
2
CHO CH
3
CH
2
CH CH CHO
Propanal Butanal 2-ethyl-3-hydroxy pentanal
(Electrophile) (Nucleophile)
(iii) Butanal as electrophile and propanal as nucleophile.
OH CH
3
6 5 4 3 | 2 | 1
CH
3
CH
2
CH
2
CHO + CH
3
CH
2
CHO + CH
3
CH
2
CH
2
CH CH CHO
Butanal Propanal 3-hydroxy-2-methyl pentanal
(Electrophile) (Nucleophile)
(iv) Butanal both as nucleophile as well as an elecrophile.
OH CH
2
CH
3
6 5 4 3 | 2 | 1
CH
3
CH
2
CH
2
CHO + CH
3
CH
2
CH
2
CHO + CH
3
CH
2
CH
2
CH CH CHO
Butanal Butanal 2-ethyl-3-hydroxy hexanal
(Electrophile) (Nucleophile)
155
Q. 7. An organic compound with the molecular formula C
9
H
10
O forms 2, 4-DNP
derivative, reduces Tollens reagent and undergoes Cannizaro reaction. On
vigorous oxidation, it gives 1, 2-benzenedicarboxylic acid. Identify the
compound.
Ans. (i) Since the given compound with M. F. C
9
H
10
O forms a 2, 4-DNP derivative and
reduces Tollens reagent, it must be an aldehyde.
(ii) Since it undergoes Cannizaro reaction, therefore CHO gp. is directly attached
to the benzene ring.
(iii) Since on vigorous oxidation, it gives 1, 2-benzene dicarboxylic acid, therefore
it must be an ortho substituted benzaldehyde. The only o-substituted aromatic
aldehyde having M. F. C
9
H
10
O is 2-ethyl benzaldehyde. All the reactions can
now be explained on the basis of this structure.
[Ag (NH
3
)
2
]
+
OH

[O]
Ag + ` `
Tollens reagent
Silver
mirror 2-ethyl benzoate 2-ethyl benzaldehyde 1, 2-benzene dicarboxylic acid
(M. F. C
9
H
10
O)
2, 4-dinitrophenyl hydrozene

2, 4-DNP derivative
Q. 8. Explain why o-hydroxybenzaldehyde is a liquid at room temperature while
p-hydroxybenzaldehyde is a high melting solid.
Ans. Due to interamolecular H-bonding ortho-hydroxy benzaldehyde exists as discrete
molecule whereas due to intermolecular H-bonding, p-hydroxybenzaldehyde exists as
associated molecules. To break these intermolecular H-bonds, a large amount of
156
C H O
C H
5 2
C O O H
C O O H
C H = N N H N O + H O
2 2
C H
2 5
N O
2
C O O

C H
5 2
energy is needed. Consequently, p-hydroxybenzaldehyde has a much higher m. pt.
and b. pt. than that of o-hydroxy benzaldehyde. As a result, o-hydroxy benzaldehyde
is a liquid at room temperature while p-hydroxy benzaldehyde is a high melting solid.
Q. 9. Identify A, B and C and give their structures :
Br
2
H
+
A + B C (C
17
H
12
O)
NaOh
Ans. The given compound (I) contains CH
3
CO gp and hence in the presence of Br
2
/NaOH
undergoes haloform reaction to give sodium salt of carboxylic acid (A) and
bromoform CHBR
3
(B). (A) on protonation gives the corresponding acid (II). (II)
being a -ketoacid readily undergoes decarboxylation to give 2-methylcylohexanane
(C).
Br
2
/NaOH H
+
CHBr
3
+
Haloform reac
n
(B)
(A)
H
+
( CO `
2
)

Dexcarboxylation
(A -keto acid) 2-methyl cyclo
hexanone
(C) M. F. = C
7
H
12
O

1 Write the structure of the following compounds

(i) 4-OXO pentanal
(ii) 2, 4 Dimethyl pent 3-one.
(iii) 3-Methylbutanal
(iv) 4-chloropentane -2-one
(v) 3-brome-4-Phenyl pentanoic acid
(vi) Para-methyl Benzaldehyde
(vii) 4-Methyl pent-3-ene-2-one
157
C H
3
C O C H
3
O
I
C H
3
C O C H
3
O
I
C H
3
C O O

O
Ans:- (i)
H O H H O
| || | | ||
H-C-C-C-C-C-H
| | |
H H H
(ii)
CH
3
O CH
3
| || |
H
3
C-C ----C-C-CH
3
| |
H H

(iii) CH
3
-CH-CH
2
-CHO

Ch
3
(iv) CH
3
-CH-CH
2
-C-CH
3

Cl O
(v) CH
3
- CH - CH - CH
2
- COOH
C
6
H
5
- Br
(vi) CH3 - -CHO
(vii) CH
3
-C-CH=C-CH
3
|| |
O CH
3
2 Write IUPAC Names of the followings:-
(i) CH
3
CHO (ii) O
CH
3
(iii) (CH
3
)
2
CHCOCH((CH
3
)
2
(iv) CH
3
CH (OCH
3
) CHO
(v) CH
3
-CH-CH
2
CH
2
-CHO
|
CH
3
(vi) PHCOPH
(vii) CH
3
-CH
2
-CH-CH
2
-CH-CHO
| |
Br CH
3
(viii) C
6
H
5
CH=CH-CHO
(ix) (CH
3
)
3
-CCH
2
COOH
158
Ans: (i) 3- Methyl cyclohexane carbaldehyde
(ii) 2- Methyl Cyclo hexanone
(iii) 2,4 Dimethyl Pantan -3- One
(iv) 2- Methoxy Propanal
(v) 4-Methyl pertanal
(vi) Diphenylmethanone
(vii) 4-Bromo-2-Methyl Hexanal.
(viii) 3-Dhehyl Propernal
(ix) 3,3-dimethyl Bytasnance acid
3. Arrange the following compound in increasing order of their boiling points.
(a) CH
3
-CHO
(b) CH
3
-CH
2
-OH
(c) CH
3
-O-CH
3
(d) CH
3
-CH
3
(e) CH
4
ANS:- CH
4
< CH
3
-CH
3
<CH
3
-O-CH
3
<CH
3
-CHO<CH
3
-CH
2
-OH
4. Arrange the following compound in the increasing order of their properties as
indicated
(i) Acetaldehyde, Acetone, Di-tert-Butyl Ketone(Reaction towards HCN)
(ii) Benzoic acid, 4 Nitro benzoic acid, 3, 4 Dinitro benzoic acid, 4-methoxy benzoic
acid (acid strength)
Ans:- (1) Di-tert-Butyl < Ketone < Acetone< Acetaldehyde
(2) 4-methoxy Benzoic Acid< Benzoic Acid<4 Nitro benzoic acid<3, 4
Dinitro benzoic acid
5 Give simple chemical test to distinguish between the following pair of compounds:-
(i) Propanal & propanone
(ii) Benzaldehyde and Acetophenone
(iii) Ethanal & Propanal
(iv) Acetophenone & Benzophenone
Ans:-
(i) Propanal & propanone
(ii) Benzaldehyde and Acetophenone Tollens reagent Test
(i) Ethanal & Propanal
(ii) Acetophenone & Benzophenone By Iodoform Test.
6. How will you distinguish?
(i) Phenol & Benzoic Acid
(ii) Benzoic Acid & Ethyl benzoate.
Ans:- By Sodiumbicarbonate test, Benzoic acid gives effervescence.
COOH COONa
|
+ NaHCO
3
+ CO
2
+ H
2
O
159
Phenol and ethyl benzoate do not give this Test.
7. How will you distinguish the following pairs:-
(i) Pentan- 2-one and Pentan- 3-one
(ii) Propanol & Propanal
(iii) Methanal & Ethanal
O O
|| ||
Ans:- CH
3
-CH
2
-CH
2
-C-CH
3
, CH
3
-CH
2
- C-CH
2
-CH
2
Will Give +ve Iodoform test Do not give +ve Iodoform test

(iii) Propanol will give sodium metal test.
Propanol will give +ve Fehlings Solution Test
8. Arrange them in the increasing order of reactivity in esterification reaction
i. CH
3
OH, (CH
3
)
3
COH, (CH
3
)
2
-CH-OH, CH
3
CH
2
OH
ii. (CH
3
)
3
CCOOH, CH
3
COOH, (CH
3
)
2
-CHCOOH,HCOOH
Ans:- (i) (CH
3
)
3
COH<(CH
3
)
2
-CH-OH< CH
3
CH
2
OH< CH
3
OH
(ii) (CH
3
)
3
CCOOH< (CH
3
)
2
-CHCOOH< CH
3
COOH< HCOOH
9 Arrange the following acid derivatives towards increasing order of nucleophelic
Substituion reaction
(a) RCONH
2
, RCOOCOR, RCOCI & RCOOR
(b) Acid derivative unlike aldehyde and ketones show mucleophic substitution
Ans:- (a) RCONH
2
< RCOOR <R.CO.O.COR <RCOCl
AMIDE ESTER ACID ANHYDRIDE ACID CHLORIDE

(b) Acid derivatives although contain >C=O group, yet do not under go the
usual properties of carbonyl groups due to the presence of resonance.
9. What happens :-
01. When primary alcohol vapours are passed over Cu metal at 573 k
Cu,573K
Ans:- RCH2-OH RCHO
Corresponding Aldehyde is formed.

02. When secondary alcohols treated with chromic anhydride (CrO
3
)
CrO3
Ans:-R-CH-R R-C-R
| [O]
OH O
Corresponding Ketone is formed.

03. Ethyne treated with H
2
O in the presence of H
2
SO
4
& HgSO
4
160
H2O
Ans: CH = CH CH
3
-CHO
H2SO4-HgSO4
Corresponding Acetaldehyde is formed.
04. Toulene is treated with chromyl chloride (CrO
2
Cl
2
) followed by hydrolysis.
Ans:
CH
3
CHO
| (i) CrO
2
Cl
2
|
(ii) H
2
O
Corresponding Benzaldeiyde is formed.
05. Propanone is treated with HCN
Ans:- CN
|
CH
3
-C-CH
3
+HCN CH
3
-C-CH
3
|| |
O OH
Corresponding Cyanohydrim of problem is formed.
06. Ethanal is treated with NaHSO
3.
Ans:-
CH
3
CHO+NaHSO
3
CH
3
-CH-SO
3
H
|
ONa
CH
3
-CH-SO
3
Na
|
OH
Corresponding Sodiumbisulphite of ethanol is formed.
07. Proponal is treated with Methyl magnesium bromide.
Ans:-
H
|
CH
3
-CH
2
CHO+CH
3
MgBr [CH
3
CH
2
-C-OMgBr]
|
CH
3
H
2
O
CH
3
-CH
2
CH-OH
|
CH
3
Corresponding Butane 20% is formed.
08. 3- Pentanone is treated with KMnO
4
at high pressure
Ans:- O
|| KMnO4
CH
3
-CH
2
CHO-C-CH
2
CH
3
CH
3
-CH
2
-COOH+CH
3
-COOH
161
High Press
Corresponding A mixene of ethonoic acid and propanoic and propanoic and is formed
09. Ethanal is treated with dil NaOH.
Ans:-
dilNaOH
2CH
3
CHO CH
3
-CH-CH
2
-CHO CH
3
-CH=CH-CHO
| -H
2
O
OH
Aldol:Condensation taken-place giving rise to a mixume of salt of Bemoic and
Benzylalcohal.
10. Benzaldehyde is treated with hot Alkali
Ans:-
2 CHO COONa CH
2
OH
+
Disproportionation rection takes place giving rise to a mixture of salt of Benzoic
acid and Benzylalcohol.
10. Acetic acid is treated with PCl
5.
Ans:-
PCl
5
CH
3
COOH CH
3
COCl
Acetylchloride is formed.
11. Benzoic acid is treated with NH
3
Ans:-
COOH (i) NH
3
CONH
2
(ii)
Benzamide is formed.
11. COMPLETE THE FOLLOWINGS
(i) O
||
C-Cl H
2
CHO
Pd- BaSO
4
1. AlH(i-Bu)
2
(ii)CH
3
-CN CH
3
CHO
2 H
2
O
NH
2
NC
(iii) CHCl
3
+ alc. KOH
162
COC
2
H
5
O
(iv) || AlCl
3
+ C
2
H
5
-C-Cl
CS
2
Hg
2+,
H
2
SO
4
(v) CH
3
-C = C-H H
2
O CH
3
COCH
3
(vi)
H
Conc NaOH HCOONa + CH
3
OH
2 C =0
H
O
(vii) || NO
2
NO
2
| |
+ H
2
N -NH =N-NH-- -NO
2
NO
2
(viii) CH
2
-CH
2
-CH
3
COH
1. KMnO
4
KOH
2. H
2
O
I LiAlH
4
(ix) CH
3
-COOH CH
3
CH
2
OH
2. H
3
O
+
12. Transformation:
i. Ethanol to butane 1,3 diol;
Ans:- H
[O] dil NaOH |
C
2
H
5
OH CH
3
CHO CH
3
-C-CH
2
-CHO
|
OH
[H]
CH
3
-CH-CH
2
-CH
2
-OH
|
OH
Butane 1,3,-diol
ii. 3 nitro brome benzene to 3 - nitro benzoic acid
Ans:- NO2 NO2 NO2 NO2
| | | |
163
Mg/dryether CO2
Br MgBr C-O-MgBr COOH
||
O 3- Nitro
Benzoic acid


(iii) Butanal to butanoic acid
Ans:-
[O]
CH
3
-CH
2
-CH
2
-CHO CH
3
-CH
2
-CH
2
-COOH
KMnO4
(iv) Acetic acid to Ethan amine
Ans:- NH
3
(i) LiAlH
4
CH
3
COOH CH
3
CONH
2
CH
3
CH
2
NH
2
(ii) H
2
O
(v) Bromo benzene to benzoic acid
Ans:- O
|| COOH
Br MgBr C-OMgBr |
Mg CO
2
H
2
O
Dry ether
(vi) Benzene to m-nitro acetophenone
Ans:-
NO
2
NO
2
Conc conc
HNO3-H2SO4 CH3COCl
AlCl
3
(Anhy)
COCH
3
(vii) Benzoic acid to benzaldehyde.
Ans:- O
||
COOH C-Cl CHO
PCl5 H2
Pd-BaSO
4
QUESTION BANK FOR BRIGHT STUDENTS
Q.1
Complete each synthesis by giving missing starting material,
reagent or products
(i)
164
(ii)
(iii)
(iv)
(v)
(vi)
(vii)
(viii)
(ix)
165
(x)
(xi)
Ans: Try yourself

Q.2
Predict the products of the following reactions:
(i)
(ii)
(iii)
(iv)
ANS: (i)
166
(ii)
(iii)
(iv)
Q.3
Write the structures of products of the following reactions;
(i)
(ii)
167
(iii)
(iv)
ANS: (i)
(ii)
(iii)
(iv)
168
Q.4
Write structural formulas and names of four possible aldol
condensation products from propanal and butanal. In each case,
indicate which aldehyde acts as nucleophile and which as
electrophile.
ANS:(i) Taking two molecules of propanal, one which acts as a
nucleophile and the other as an electrophile.
(ii) Taking two molecules of butanal, one which acts as a
nucleophile and the other as an electrophile.
(iii) Taking one molecule each of propanal and butanal in which
propanal acts as a nucleophile and butanal acts as an
electrophile.
169
(iv) Taking one molecule each of propanal and butanal in which
propanal acts as an electrophile and butanal acts as a
nucleophile.
Question 5:
An organic compound contains 69.77% carbon, 11.63% hydrogen
and rest oxygen. The molecular mass of the compound is 86. It
does not reduce Tollens reagent but forms an addition compound
with sodium hydrogensulphite and give positive iodoform test. On
vigorous oxidation it gives ethanoic and propanoic acid. Write the
possible structure of the compound.
ANS: % of carbon = 69.77 %
% of hydrogen = 11.63 %
% of oxygen = {100 (69.77 + 11.63)}%
= 18.6 %
Thus, the ratio of the number of carbon, hydrogen, and oxygen
atoms in the organic compound can be given as:
Therefore, the empirical formula of the compound is C
5
H
10
O. Now,
the empirical formula mass of the compound can be given as:
5 12 + 10 1 + 1 16
= 86
Molecular mass of the compound = 86
Therefore, the molecular formula of the compound is given by
C
5
H
10
O.
170
Since the given compound does not reduce Tollens reagent, it is
not an aldehyde. Again, the compound forms sodium hydrogen
sulphate addition products and gives a positive iodoform test.
Since the compound is not an aldehyde, it must be a methyl
ketone.
The given compound also gives a mixture of ethanoic acid and
propanoic acid.
Hence, the given compound is pentan2ol.
The given reactions can be explained by the following equations:
Q.5
Arrange the following compounds in increasing order of their
property as indicated:
(i) Acetaldehyde, Acetone, Di-tert-butyl ketone, Methyl tert-butyl
ketone (reactivity towards HCN)
(ii) CH
3
CH
2
CH(Br)COOH, CH
3
CH(Br)CH
2
COOH, (CH
3
)
2
CHCOOH,
CH
3
CH
2
CH
2
COOH (acid strength)
(iii) Benzoic acid, 4-Nitrobenzoic acid, 3,4-Dinitrobenzoic acid, 4-
Methoxybenzoic acid (acid strength)
ANS:(i) When HCN reacts with a compound, the attacking species
is a nucleophile, CN

. Therefore, as the negative charge on the

compound increases, its reactivity with HCN decreases. In the
171
given compounds, the +I effect increases as shown below. It can
be observed that steric hindrance also increases in the same
Hence, the given compounds can be arranged according to their
increasing reactivities toward HCN as:
Di-tert-butyl ketone < Methyl tert-butyl ketone < Acetone <
Acetaldehyde
(ii) After losing a proton, carboxylic acids gain a negative charge
as shown:
Now, any group that will help stabilise the negative charge will
increase the stability of the carboxyl ion and as a result, will
increase the strength of the acid. Thus, groups having +I effect
will decrease the strength of the acids and groups having I
effect will increase the strength of the acids. In the given
compounds, CH
3
group has +I effect and Br

group has I effect.

Thus, acids containing Br

are stronger.
Now, the +I effect of isopropyl group is more than that of n-
propyl group. Hence, (CH
3
)
2
CHCOOH is a weaker acid than
CH
3
CH
2
CH
2
COOH.
Also, the I effect grows weaker as distance increases. Hence,
CH
3
CH(Br)CH
2
COOH is a weaker acid than CH
3
CH
2
CH(Br)COOH.
Hence, the strengths of the given acids increase as:
(CH
3
)
2
CHCOOH < CH
3
CH
2
CH
2
COOH < CH
3
CH(Br)CH
2
COOH <
CH
3
CH
2
CH(Br)COOH
(iii) As we have seen in the previous case, electron-donating
groups decrease the strengths of acids, while electron-
withdrawing groups increase the strengths of acids. As methoxy
172
group is an electron-donating group, 4-methoxybenzoic acid is a
weaker acid than benzoic acid. Nitro group is an electron-
withdrawing group and will increase the strengths of acids. As
3,4-dinitrobenzoic acid contains two nitro groups, it is a slightly
stronger acid than 4-nitrobenzoic acid. Hence, the strengths of
the given acids increase as:
4-Methoxybenzoic acid < Benzoic acid < 4-Nitrobenzoic acid
< 3,4-Dinitrobenzoic acid
Q.6
Predict the products formed when cyclohexanecarbaldehyde
reacts with following reagents.
(i) PhMgBr and then H
3
O
+
(ii)Tollens reagent
(iii) Semicarbazide and weak acid
(iv)Excess ethanol and acid
(v) Zinc amalgam and dilute hydrochloric acid
ANS:(i)
(ii)
(iii)
173
(iv)
(v)
Q.7
How will you prepare the following compounds from benzene?
You may use any inorganic reagent and any organic reagent
having not more than one carbon atom
(i) Methyl benzoate (ii) m-Nitrobenzoic acid
(iii) p-Nitrobenzoic acid (iv) Phenylacetic acid
(v) p-Nitrobenzaldehyde.
ANS:(i)
174
(ii)
(iii)
175
(iv)
(v)

Q. 8
Name the reaction and the reagent used for the conversion
of acid chlorides to the corresponding aldehydes.
Ans. Name : Rosenmunds reaction
Reagent : H2 in the presence of Pd (supported over BaSO4) and
partially poisoned byaddition of Sulphur or quinoline.

Q.9 How is tert-butyl alcohol obtained from acetone?
176
Ans.
Q. 10. Why pcc cannot oxidise methanol to methane and while
KMnO4 can ?
Ans. This is because pcc is a mild oxidising agent and can oxide methanol
to methanal only. While KMnO4 being strong oxidising agent oxidises it to
methanoic acid.
Q. 11. What are Hemiacetal and acetal ?
Ans. Hemiacetal and acetals are formed by addition of alcohols on
carboxyl compounds.
Q. 12. Which acid is stronger and why ?
F3C C
6
H
4
COOH or H3C C
6
H
4
COOH
Ans.
CF3 has a strong I effect. CH3 has a weak + I effect.
It stabilises the carboxylate ion It stabilises the carboxylate ion
by dispersing the ve charge. by intensifying the ve charge.
Therefore due to greater stability of F3C C6H4 COO (p) ion over CH3
C6H4COO (p) ion, F3C C6H4 COOH is a much stronger acid than CH3
C6H4 COOH.
Q. 13. An organic compound with the molecular formula C9H10O forms 2, 4-DNP
derivative, reduces Tollens reagent and undergoes Cannizaro reaction. On vigorous
oxidation, it gives 1, 2-benzenedicarboxylic acid. Identify the compound.
Ans. (i) Since the given compound with M. F. C9H10O forms a 2, 4-DNP derivative and
reduces Tollens reagent, it must be an aldehyde.
(ii) Since it undergoes Cannizaro reaction, therefore CHO gp. is directly
attached to the benzene ring.
(iii) Since on vigorous oxidation, it gives 1, 2-benzene dicarboxylic acid, therefore it must be
an ortho substituted benzaldehyde. The only o-substituted aromatic aldehyde having M. F.
C9H10O is 2-ethyl benzaldehyde. All the reactions can now be explained on the basis of this
structure.
[Ag (NH3)2]
+
OH
-
[O]
Ag + C
2
H
5
C
6
H
4
COO
-
-CHOC
6
H
4
C
2
H
5
> COOHC
6
H
4
Tollens reagent 2-ethyl benzaldehyde |
Silver mirror 2-ethyl benzoate
COOH

177
1, 2-benzene dicarboxylic
acid
FOR BELOW AVERAGE
01 Marks QUESTIONS
1. Write the structure of the following compounds
(viii) 4-OXO pentanal
(ix) 2,4 Dimethyl pent 3-one.
(x) 3-Methylbutanal
(iv) 4-chloropentane -2-one
(v) 3-brome-4-Phenyl pentanoic acid
(vi) Para-methyl Benzaldehyde
(vii) 4-Methyl pent-3-ene-2-on

2. Write IUPAC Names of the followings:-
O

(i) CH
3
CHO (ii)
CH
3
(iii) (CH
3
)
2
CHCOCH((CH
3
)
2
(iv) CH
3
CH (OCH
3
) CHO
(v) CH
3
-CH-CH
2
CH
2
-CHO
|
CH
3
(vi) PHCOPH
(vii) CH
3
-CH
2
-CH-CH
2
-CH-CHO
| |
Br CH
3
(viii) C
6
H
5
CH=CH-CHO
(ix) (CH
3
)
3
-CCH
2
COOH
FOR AVERAGE
02 Marks QUESTIONS
3. Arrange the following compound in increasing order of their boiling points.
(f) CH
3
-CHO
(g) CH
3
-CH
2
-OH
(h) CH
3
-O-CH
3
(i) CH
3
-CH
3
(j) CH
4
4. Arrange the following compound in the increasing order of their properties as indicated
178
(iii) Acetaldehyde, Acetone, and Di-tert-Butyl Ketone (Reaction towards HCN)
(iv) Benzoic Acid, 4Nitro benzoic acid, 3, 4 Dinitro benzoic acid, and 4-methoxy
benzoic acid (acid strength)
FOR ABOVE AVERAGE
02 Marks QUESTIONS
5. Give simple chemical test to distinguish between the following pair of compounds:-
(v) Propanal & propanone
(vi) Benzaldehyde and Acetophenone
(vii) Ethanal & Propanal
(viii) Acetophenone & Benzophenone
6. How will you distinguish?
(iv) Phenol & Benzoic Acid
(v) Benzoic Acid & Ethyl benzoate.
7. How will you distinguish the following pairs:
(i) Pentan 2-one and Pentan 3-one
(ii) Propanol & Propanal
(iii) Methanal & Ethanal
FOR AVERAGE
02 Marks QUESTIONS

8. Arrange them in the increasing order of reactivity in esterification reaction.
iii. CH
3
OH, (CH
3
)
3
COH, (CH
3
)
2
-CH-OH, CH
3
CH
2
OH
iv. (CH
3
)
3
CCOOH, CH
3
COOH, (CH
3
)
2
-CHCOOH,HCOOH
12. Arrange the following acid derivatives towards increasing order of nucleophelic
Substituion reaction
(a) RCONH
2
, RCOOCOR, RCOCI & RCOOR
(b) Acid derivative unlike aldehyde and ketones show mucleophic substitution

FOR ABOVE AVERAGE
02 Marks QUESTIONS
10. Write mechanism for the followings:-
(a) Nucleophilic addition in aldehydes and Ketones
(b) Aldol condensation
(c) Esterification of carboxylic acids
11. What happens:-
1. When primary alcohol vapours are passed over Cu metal at 573 k
2. When secondary alcohols is treated with chromic anhydride (CrO
3
)
179
3. Ethyne is treated with H
2
O in the presence of H
2
SO
4
& HgSO
4
4. Toulene is treated with chromyl chloride (CrO
2
Cl
2
) followed by hydrolysis.
5. Propanone is treated with HCN
6. Ethanal is treated with NaHSO
3.
7. Proponal is treated with Methyl magnesium bromide.
8. 3- Pentanone is treated with KMnO
4
at high pressure
9. Ethanal is treated with dil NaOH.
10. Benzaldehyde is treated with hot Alkali.
11. Acetic acid is treated with PCl
5.
12. Benzoic acid is treated with NH
3.
12. COMPLETE THE FOLLOWING.
(i) O

C-Cl H
2
?
Pd- BaSO
4
1. AlH(t-Bu)
2
(ii) CH
3
-CN ?
2 H
2
O
NH
2
| CHCl
3
+ Alc KOH
(iii) ?
O
(iv) AlCl
3
+ C
2
H
5
-C-Cl ?
CS
2
Hg
2+,
H
2
SO
4
(v) CH
3
-C = C-H ?
(vi)
H
Conc NaOH ?
2 C =0
H
O
(vii) NO
2
180
||
|
+ H
2
N -NH NH
2
(viii) CH
2
-CH
2
-CH
3
1. KMnO
4
KOH
2. H
2
O
I LiAlH
4
(ix) CH
3
-COOH
2. H
3
O
+
13. Road Map problems Identity A & B.
O
NH
3
H
2
|

Ni

(i) R
2
C A B
Cu di NaOH
(ii) CH
3
-CH
2
-OH A B
573 K
O
1. CH
3
MgBr 2,4,DNP
(iii) CH
3
-C H A
B
2. H
2
O
O
1. CH
3
MgBr Cu
(iv) CH
3
-C-CH
3
A B.
2. H
2
O 753 K
HgSO
4
CH
3
MgX
[o]
(v) HC = CH A B C
H
2
SO
4
FOR ABOVE AVERAGE
02 Marks QUESTIONS
181
||
||
||
14. Transformation
(i) Ethanol to butane 1, 3 diol;
(ii) 3- nitro bromobenzene to 3- nitro benzoic acid
(iii) Butanal to butanoic acid
(iv) Acetic acid to Ethan amine
(v) Bromo benzene to benzoic acid
(vi) Benzene to m-nitro acetophenone
(vii) Benzoic acid to benzaldehyde
15. IDENTIFICATION TYPE QUESTIONS
(a) An organic compound A molecular formula C
3
H
6
O is resistant to oxidation
but forms a compound B (C
3
H
8
O) on reaction. B reacts with HBr to form bromide C
with an treated with alcoholic KOH form an alkene D C
3
H
6
deduce the structure A,B,C,D.
(b) An organic compound A with molecular formula C
8
H
8
O forms an orange
red precipitate with 2-4 DNP reagent & with yellow precipitate with on heating with iodine
in the presence of sodium hydroxide. It neither reduce Tollens or fehling reagent nor does it
decolorize bromine water. On drastic oxidation with chromic acid, it gives a carboxylic acid
(B) having molecular formula n C
7
H
6
O
2
. Identify the compound A and B and explain the
reaction involved.
(c) An organic compound A C
8
H
6
on treatment with dilute H
2
SO
4
containing
HgSO
4
gives compound B which can also be obtained from a reaction of benzene with acid
chloride in presence of AlCl
3
? B on treated with I
2
in aq KOH gives C and yellow
compound D identify A,B,C,and D . Give the chemical reaction involved
FOR BELOW AVERAGE
01 Marks QUESTIONS
16. NAME REACTIONS: (Write Notes on)
(i) Rosen mund reduction
(ii) Cannizaro reaction
(iii) Cross aldol condensation
(iv) Aldol Condensation
(v) Clemensens reduction
(vi) Wolff Kishner reaction
17. DESCRIBE THE FOLLOWING TERMS:
(i) Acetylation
(ii) Decarboxylation
(iii) Silver mirror test
FOR ABOVE AVERAGE
01 Marks QUESTIONS
18. GIVE THE REASON FOR THE FOLLOWINGS:
(i) The boiling points of aldehyde and ketones are lower than the corresponding
alcohols and carboxylic acid .
(ii) The boiling point of carboxylic acid is higher than the Corresponding esters
(iii) Aldehydes and ketones under goes a number of nucleophlic addition reaction
(iv) Aldehydes under go nucleophlic addition reaction more readily than ketones
(v) Formaldehyde gives Cannizaro reaction where as acetaldehyde gives aldol
condensation
182
(vi) Di- tert. butyl ketone does not give NaHSO
3
adduct but acetone gives
(vii) Floroacetic acid is a stronger acid than chloroacetic acid.
(viii) The PKa value of chloroacetic acid is lower than PKa value of acetic acid
(ix) >C = O group behaves differently in aldehyde and acid .
(x) The melting point of an aliphatic carboxylic acid containing an even number of
carbon atoms is higher than next lower and next higher homologues containing
Odd number of carbon atoms.
(xi) Electrophilic substitution on benzoic acid takes place at meta position.
**********************************************

Alkyl amines are more basic than ammonia and aryl amines are less basic than alkyl amines
due to presence of electron density on N-atom.
This is as follows:
.. .. ..
NH
3
< R-NH
2
> Ar-NH
2
In alkyl amines magnitude of electron density on N-atom is increased
By presence of electron releasing group ie alkyl groups whereas the magnitude of electron
density is decreaed on N atom in aryl amines
Due to electron withdrawing group ie aryl group .
183
UNIT -13
ORGANIC COMPOUNDS
CONTAINING NITROGEN
AMINIES
The less basicity of aryl amine is due to resonatig structures.
+
NH
2
184
BASICITY AMONG PRIMARY, SECONDARY & TERTIARY AMINES:
Basicity among alkyl amines is found as secondary amines > pr.amines> tert. Amines
. The irregular trends among amines is explained on the basis of electron doner alkyl group
attached to an atom. Pr. Amines have less no. of alkyl group,hence less basic in secondary
amines presence of two alkyl groups make more basic than pr. Amines but in tert. Amines
presence of three alkyl groups creats steric hindrance resulting in repulsion between elctrons
makes low electron density on N-atom.
.. .. ..
R---N---R > R---NH
2
> R
2
---N----R
The above basicity of amines can be explained on the basis of K
b
&
pK
b
. higher the K
b
values or lower the pK
b
value shows higher basic characters .
Sec. amines > tert. Amines < pr. Amines
pK
b
3.00 3.29 3.25

PREPARATION OF AMINES:-
I. REDUCTION OF NITRO COMPOUNDS
H
2
/Pd
(a) ArNO
2
------------------------ ArNH
2
Ethanol


(b) ArNO
2
--------------------ArNH
2


II. Ammonolysis of alkyl halides---
An alkyl or aryl halides react with ethanolic solution of ammonia undergo nucleophilic
substitution in which halogen atom is replaced by amino gr.
RX RX
RNH
2
----------- R
2
NH ------------ R
3
N
PR Amine. SEC. TERT.
DISADVANTAGEBy this method a mixture of amines are prepared and not separated
easily.
III. Reduction of nitriles --
H
2
/Ni
RCN------------------ RCH
2
NH
2

a. Reduction of amides-----
LAH
RCONH
2
--------------------- RCH
2
NH
2
WATER
V. Hoffmann bromamide degradation reaction
Pr. amines are prepared by this reaction in which amide combines with bromine in aq. Or
ethanolic solution of sodium hydroxide.
RCONH
2
+ Br
2
+4 NaOH ------ RNH
2
+Byproducts
185
Sn/ HCl
Important chemical properties---
(i) Basic properties-- Presence of electron density on N atom is the reason of basic
property. Higher the electron density on N atom , higher the basic character .
(ii) Solubility in water--- Lower alkyl amines are soluble in water due to H- bonding .
Hihger akyl amines are insoluble in water.
v. Acylation reaction --- Amines combines with acyl halides to form N-alkyl ethanamine.
C
2
H
5
NH
2
+ CH
3
COCl ------ C
2
H
5
NHCOC H
3
vi. Carbylamine reaction ---Primary amine combines with chloroform in ethanolic
potassium hydroxide to form isocyanide with pungent smell.
Heat
RNH
2
+CHCl
3
+ 3 KOH -------- RNC + 3 KCl + 3H
2
O
vii. Reaction with nitrous acid ------
NaNO
2
+HCl
RNH
2
+ HNO
2
-------------ROH + N
2
+HCl
HOH
DIAZOTIZATION REACTION & DIAZONIUM SALTS :-
The conversion of primary aromatic amines into diazonium salt is known as diazotization
reaction.The diazotization reaction is characterize in the joining two N-atoms (diazo)through
double bonds.
PREPARATION:- The commonly known diazonium saltie benzene diazonium chloride is
repared by reacting aniline with sodium nitrite and hydrochloric acid.
273278 K
ArNH
2
+ NaNO
2
+HCl ---------------------ArN
2
+
Cl
-
+NaCl +2H
2
O

PROPERTIES OF DIAZONIUM SALTS:--
It is a colourless crystalline solid. It is in soluble in water .It is easily decomposable in dry
state.
IMPORTANT REACTIONS:--
(I) Sandmeyers reaction :- The reaction of diazonium salt with halo acid in
presence of copper halide to have halobenzene is called sandmeyers reaction.
Ar-N
2
Cl + CuCl + HCl ------- Ar-Cl + N
2

(II) Gatterman reaction :--- The reaction of diazonium salt with halo acid in
presence of copper powder is called Gatterman reaction.
Ar-N
2
Cl + Cu + HCl ---------- Ar-Cl + N
2
+ CuCl
(III) Hydrolysis reaction ----- Diazonium salt on hydrolysis upon 283 K gives
phenol.
HOH, 283K
Ar-N
2
Cl -------------------------- Ar-OH + N
2
+ HCl
(IV) Reduction of diazonium salt ----- Diazonium salts on reduction with mild
reducing agent like phosphorous acid or ethanol reduced to arene .
Ar-N
2
Cl + H
3
PO
2
+ HOH --------- ArH + N
2
+ H
3
PO
3
+ HCl
(V) Nitration reaction ------ Diazonium salt on treatment with
186
HBF
4
followed by sodium nitrite & copper at high temperature gives nitroarene.
+ - NaNO
2
Ar-N
2
Cl + HBF
4
-- Ar-N
2
BF
4
--------- ArNO
2
+ N
2
+ NaBF
4
(V) Coupling reaction ----The reaction between diazonium salt with aryl
compounds through N=N- is called coupling reaction.
Ex.Benzene diazonium chloride reacts with phenol in basic medium , phenol coupled
with diazonium salt to the para position of phenol to produce p-hydroxy azobenzene( orange
dye).
OH

Ar-N
2
Cl + ArOH -------------- Ar-N=N-ArOH + Cl
-
+ HOH
1 MARK QUESTIONS
Q. 1. Why the presence of a base is essential in the ammonolysis of alkyl halides ?
Ans. During ammonolysis of alkyl halides, the acid liberated during the reaction combines
with the amine formed to form amine salt. To liberate free amine from the amine salt,
a base is needed.
Q. 2. Although NH
2
gp is an ortho and para directing gp, nitration of aniline gives
along with ortho and para, meta derivatives also.
Ans. Nitration is carried out with a mixture of Conc. NO
3
+ Conc. H
2
SO
4
(nitrating mix). In
the presence of these acids, most of aniline gets protonated to form anilinium ion.
Therefore, in the presence of acids, the reaction mixture consists of aniline and
anilinium ion. Now NH
2
gp in aniline is O, p-directing and activating while N
+
H
3
gp in anilinium ion is m-directing and deactivating hence a mixture of all threeortho,
para and meta derivatives is formed.
Q. 3. Pk
b
of aniline is more than that of methyl amine.
Ans. In aniline, the lone pair of electrons on the N-atom are delocalized over the benzene
ring. As a result electron density on the nitrogen decreases. In contrast in CH
2
NH
2
, + I
effect of CH
3
increase the electron density on the N-atom. Therefore, aniline is a
weaker base than methylamine and hence its Pk
b
value is higher than that of
methylamine.
Q. 4. Aniline gets coloured on standing in air for a long time. Why ?
Ans. Due to strong electron-donating effect (+ R effect) of NH
2
gp, the electron density on
the benzene ring increases. As a result, aniline is easily oxidised on standing in air for
a long time to form coloured products.
187
Q. 5. CH
3
CONH
2
is a weaker base than CH
3
CH
2
NH
2
.
Ans. Due to resonance, the lone pair of electrons on the nitrogen atom in CH
3
CONH
2
is
delocalised over the keto gp. There is no such effect in CH
3
CH
2
NH
2
. Due to reduction
in electron density on N of CH
3
CONH
2
, it is a weaker base than CH
3
CH
2
NH
2
.
Q. 6. Aromatic primary aminies cant be prepared by Gabriel phthalimide synthesis.
Ans. The preparation of aromatic primary amines (Aniline) by Gabriel phthalimide reaction
requires the treatment of pot. phthalimide with C
6
H
5
Cl or C
6
H
5
Br, which is a
nucleophilic substitution Rx
n
. Since aryl halides do not undergo nucleophilic
substitution under ordinary laboratory conditions, therefore C
6
H
5
Cl or C
6
H
5
Br does
not react with pot. phthalimide to give N-phenyl. Phthalimide and hence aromatic
primary amines cant be prepared by this method.
Q. 7. Accomplish the following conversions :
(i) Nitrobenzene to benzoic acid
(ii) Benzyl Chloride to 2-phenylethanamine
Ans. (i) NaNO
2
+ HCl
(i) Fe/HCl 273 278 K CuCN/HCN

(ii) NaOH Diazotization Benzene
Diazanium
Aniline Chloride
Benzonitrile
H
3
+
O

Hydrolysis
Benzoic acid
(ii)
KCN (aq) ` LaAlH
4

KCl Redue
Benzyl Chloride Phenyl ethanenitrite 2-
phenylethanamine
Q. 8. Give the structures of A, B and C in the following compounds :
NaCN OH

NaOH + Br
2
(i) CH
3
CH
2
I A B C
Partial Hydrolysis
NH
3
NaOBr NaNO
2
/HCl
(ii) CH
3
COOH A B C
188
N O
2
O
N H
2
O
N N C l
+

O
C N
O
C O O H
O
C H C l
2 2
O
C H C N
2
O
C H C H N H
1 2
2 2 2
O
D
Ans. O
NaCN OH

||
(i) CH
3
CH
2
I CH
3
CH
2
CN CH
3
C NH
2
(Partial Hydrolysis)
Propanenitrile (A) Ethanamide (B)
NaOH + Br
2
CH
3
NH
2
Hofmann bromamide reac
n
Methanamine (C)
NH
3
NaOBr NaNO
2
/HCl
(ii) CH
3
COOH CH
3
CONH
2
CH
3
NH
2

CH
3
OH
D (Hofmann bromamide
`
Ethanoic acid Ethanoimide (A) reac.) Methanamine (B)
Methanol (C)
Q. 9. Why is it difficult to prepare pure amines by ammonolysis of alkyl halides ?
Ans. By ammonolysis of alkyl halides, a mixture of primary, secondary and tertiary amines
is formed. So it is difficult to separate it.
Rx Rx Rx Rx
NH
3
R NH
2
R
2
NH R
3
N R
4
N
+
X

1 amine 2 amine 3 amine Quaternary

Salt
Q. 10. Can tertiary amines undergo acetylation reactions ? Explain.
Ans. For an amine to undergo acetylation, it should have a replaceable hydrogen atom.
Tertiary amines cannot undergo acetylation reactions because these do not have
replaceable hydrogen atom.
Q. 11. Sulphanilic acid has acidic as well as basic group; but it is soluble in alkali but
insoluble in mineral acids. Explain.
Ans. Sulphanilic acid exists as Zwitter ion as :
N H
3
+
O
S O
3

In the presence of dil. NaOH the weakly acidic NH

3
+
group transfers its H
+
to OH

to form soluble salt P NH
2
C
6
H
4
SO
3

Na
+
. On the other hand, SO
3
+
group is a very
weak base and does not accept H
+
from dil HCl to form NH
3
C
6
H
4
SO
3
H and therefore,
it does not dissolve in dil HCl.
Q. 12. Why are aliphatic amines more basic than aromatic amines ?
189
Ans. In Aromatic amines, due to resonance, N-atom acquries +ve charge and lone pair '
of N-atom is less available.
N H
2
N H
2
+
N H
2
+
N H
2
+

N H
2
In aliphatic amines, due to e

releasing nature of alkyl groups lone pair of e

on N-
atom is more available.
More basic. '
Q. 13. Explain why :
(i) Ethylamine is soluble in water but aniline is not.
(ii) Aniline does not undergo Friedel Crafts reaction.
(iii) Diazonium salts of aromatic amines are more stable than that of aliphatic
amines.
Ans. (i) Ethyl amine dissolves in water due to formation of H-bonding with water
molecules.
H H
| |
H N - - - - - - - - - - - - H O - - - - - - - H N - - - - - - - - H O - - - - -
-
| | | |
C
2
H
5
H C
2
H
5
H
H N H
|
C
2
H
5
However in Aniline, due to larger hydrophobic alkyl part extent of H-bonding
decreases considerably
insoluble in water. '
(ii) Aniline being a Lewis base reacts with Lewis acid AlCl
3
or FeCl
3
to form a
salt.
C
6
H
5
NH
2
+ AlCl
3
C
6
H
5
NH
2
+
AlCl
3

Lewis base Lewis acid

190
As a result, N-atom acquires + ve charge and hence acts as a strong
deactivating group for electrophilic reaction.
(iii) Diazonium salts of aromatic amines are more stable due to dispersal of +ve
charge on benzene ring due to resonance.
N = N
+
+
N = N

+
N = N
+
+
N N
+
+
+
N N

In aliphatic amines, there is no such dispersal of + ve charge due to absence of

resonance.
Q. 14. Why 1 amines have got higher boiling point than 3 amines ?
Ans. Due to presence of two H-atoms, in 1 amines they undergo extensive hydrogen
bonding while due to absence of H-atom in 3 amines do not undergo H-bonding.
- - - - - - - - H R H - - - - - - - -
| | |
R N H - - - - - - - - N H - - - - - - - - N R
| |
H H - - - - - - - -
- - - - - - - - H N R
|
H
Due to extensive hydrogen bonding in 1 amines, they have higher boiling point 7
than 3 amines.
Q. 15. How can you distinguish between 1 and 2 amine ?
Ans. (i) Carbylamine test :
R NH
2
+ CHCl
3
+ 3 KOH R NC + 3 KCl + H
2
O

(pungent smelling)
2 amines do not give this test.
(ii) Aryl sulphonyl chloride test :
191
Q. 16. How can you distinguish between aromatic and aliphatic amines ?
Ans. The diaronium salts of Aromatic amines undergo coupling reactions with phneol or
andine to form coloured compounds used as dyes.
No such reactions are given by aliphatic amines.
Q. 17. How can tri substitution of Bromine be prevented in aniline ?
OR
How can we prepare mono bromo aniline ?
Ans. Because of high reactivity of aromatic amines substitution tends to occur at o- and p-
positions. Monosubstituted aniline can be prepared by protecting NH
2
group by
acetylation with acetic anhydride, then carrying out substitution followed by
hydrolysis of substituted amide.
2 MARKS QUESTIONS
Q. 1. Give increasing order of reactivity towarads electrophilic substitution reaction of
the following compounds :
C H
3
O

N
O
C H
3
C H
3

C H N C H
3 3
+
O
C H
3

C H N ( C H
2
+
3 3
)
O
Ans. Higher the electron density in the benzene ring, more reactive is the aromatic
compound towards electrophilic substitution reaction. Now due to the presence of a
192
|
H
lone pair of electrons on the N-atom which it can directly donate to the benzene ring.
N (CH
3
)
2
(due to two alkyl groups on N) is a much stronger electron donating gp than
CH
3
gp. (only one alkyl group on N). The remaining two gps contain a positive charge
on the N-atom and hence act as electron withdrawing gps. But in (CH
3
)
3
N
+
gp, the
+vely charged N is directly attached to the benzene ring, therefore, its electron
withdrawing ability is much stronger than CH
2
N
+
(CH
3
)
2
. From the above, it
follows that the electron density in the benzene ring increases in the order :
Therefore, their reactivity towards elecrophilic substitution reactions also increases in
the same order.
Q. 2. Which one is more acidic ? Explain :
Ans. Due to powerful I effect to the F-atom, it withdraws electrons from N
+
H
2
gp. As a
result, electron density in the N H bond of p-fluoroanilinium ion decreases and
hence release of a proton from p-fluoroanilinium ion is much more easier than from
anilinium ion. Therefore, p-fluoroanilinium ion is more acidic than anilinium ion.
Q. 3. Explain the order of basicity of the following compounds in (i) Gaseous phase
and (ii) inaqueous soln. :
(CH
3
)
3
N, (CH
3
)
2
NH, CH
3
NH
2
, NH
3
Ans. Due to + I effect of alkyl gps, the electron density on the N-atom of 1, 2 and 3
amines is higher than that on the N-atom in NH
3
. Therefore, all amines are more basic
than NH
3
.
(i) In gaseous phase, solvation effects are absent and hence the relative basicity of
amines depends only on + I effect of the alkyl gps. Now since + I effect
193
increases in going from 1 to 2 to 3 amine, so the basicity of amines
decreases in the order :
3 amine > 2 amine > 1 amine
(CH
3
)
3
N > (CH
3
)
2
NH > CH
3
NH
2
> NH
3
(ii) In aq. soln, the basicity depends upon two factors :
(a) + I effect of CH
3
gp and
(b) Solvation effect.
Stabilization of the conjugate acid (formed addition of a proton to amine) by
H-bonding explained above on the basis of + I effect, the order will be :
(CH
3
)
3
N > (CH
3
)
2
NH > CH
3
NH
2
On the basis of Stabilisation of conjugate acids by H-bonding alone as explained
below :
The order will be :
CH
3
NH
2
> (CH
3
)
2
NH > (CH
3
)
3
N
The combined effect of these two opposing factors is that (CH
3
)
2
NH is the strongest
base. In case of CH
3
NH
2
and (CH
3
)
3
NH, the stability due to H-bonding predeminates
over stability due to + I effect of CH
3
gp, thereby making CH
3
NH
2
stronger than
(CH
3
)
3
NH. So the overall order in aq. soln will be :
(CH
3
)
2
NH > CH
3
NH
2
> (CH
3
)
3
N > NH
3
Conceptual Questions
Q 1. Give reasons:---
a. Primary amines are more basic than ammonia.
b . Sec. amines are more basic than pr.amines.
194
Ans a. In pr. Amines, alkyl group increases electron density on the N-atom making
it more basic than ammo
b. In sec. amine, there are two alkyl groups increase electron density on N-atom more
than N-atom in pr. amines in which there is one alkyl group.
Q.2. Why are amines always less acidic than comparable alcohols?
Ans.--- Amines are less acidic than alcohols because of oxygen higher electronegative
& smaller size. Therefore O-H breakes easily than N-H bond.
Q.3. Why is amide more acidic than an amine ?
Ans.In amide there is C=O group attached NH
2
, electron withdrawing & increases
acidic nature of amide whereas in amines there is alkyl group which is electron
releasing and makes it more basic & hence less acidic.
Q.4. How is aniline distinguished from N-methyl aniline ?
Ans.On adding CHCl
3
& KOH , aniline gives offensive smell forming isocyanide
compound whereas N-methyle aniline not.
Q.5. Why cyanide ion act as ambident nucleophile ?
Ans.---- Cyanide ion can link through either carbon or nitrogen, therefore it is an
ambident nuclophile.
Q6. How would you remove nonpolar impurities from an amine ?
Ans.--- Adding HCl , amine will form salt whereas nonpolar impurities will not react .
Amines can be regenerated by adding NaOH .
Q7. Why tert. Amines donot undergo acylation reaction ?
Ans.-- Tert. Amines donot undergo acylation reaction because they donot have N-
attached to H- atom.
Q8. How will you convert the following.
(a) Aniline to acetanilide
(b) Benzene to aniline
Ans:- (a) C
6
H
5
NH
2
+CH
3
COCl NaOH C
6
H
5
NHCOCH
3
+HCL
(b) C
6
H
6
+HNO
3
Conc
ConeH
2
So4
C
6
H
5
NO
2

3H
2
C
6
H
5
NH
2

333K

Sn/Hcl

Q9. Why does the boiling point of CH
3
NH
2
less than HCOOH?
Ans:- HCOOH is associated with intermolecular H-bonding in greater extent then
CH
3
NH
2
and therefore HCOOH has higher boiling point than CH
3
NH
2 .
Q10. What is Zwitter ion? Write the formula of Zwitter ion of alanine.
Ans:- The ion of a molecule having +ve change at one end and ve charge at other
is called zwitter ion.
CH
3
CH-COOH CH
3
-CH-COO
-

CH
2
NH
2
Q11. How will you prepare aniline from nitrobenzene industrially?
195
Ans:- Aniline is prepared industrially by reduction of nitrobenzene in presence o of H
2
and
Fe/Hcl.
NO
2
NH
2
+ 6[H]
Fe/Hcl
+ 2H
2
O
Q12. Aromatic primary amines are not prepared by gabrial phthalimide
synthesis. Why?
Ans:- Because aryl halides donot undergo nucleophilic substitution reaction.
Q13. Convert the following-
(i) Acetamide to ethanamine
(ii) Benzene to autophenone
(iii) Anitine to 4- bromo aniline
(iv) Methanamine to ethanamine
(v) Phenol to aniline
(vi) Ethyl alcohol ( ethanol) to ethanamine
Ans:- (i) CH
2
CONH
2

Na/C
2
H
5
OH
CH
3
CH
2
NH
2
(ii) C
6
H
5
+ CH
3
COCl
Alcl3
C
6
H
5
COCH
3
(iii) C
6
H
5
NH
2
+ CH
3
cocl
H2O/H+
C
6
H
5
NHCOCH
3

CH
3
COOH

Br C
6
H
4
NHCOCH
3

H
2
O/H
BrC
6
H
4
NH
2

NH
2
OR

Br
(iv) CH
3
NH
2
CH
3
OH CH
3
Cl CH
3
CN
CH
3
CH
2
NH
2
(v) OH or C
6
H
6
OH
NH
3
C
6
H
5
NH
2


Zncl
2
(vi) C
6
H
5
OH + NH
3

Al
2
O
3
C
6
H
5
NH
2
Heat
14. Account for the following-
(i) Nitration of toluene is easier than benzene
(ii) Ethylanmine is soluble in water where as aniline is not.
(iii) pKh of aniline is more than that of methylamine.
(iv) Diazonium salts of aromatic amines are more stable than these of
aliphatic amines.
(v)Methylamice in water reacts with ferric chloride to precipitate hydrated
ferric oxide.
(vi) Primary amires have higher boiling point then tertiary amines.
(vii) Silver chloride dissolves in aqeous methylamine solution.
(viii) Aniline readily reacts with bromine to give 2,4,6 tribromo-aniline.
Ans:- (i) The methyl group of toluene is electron releasing group and releases
eleases electron density to the benzene ring and hence makes the joining of
electrophile NO
2
+
more easier and faster.
(ii) Ethylamine has more electron density on the N-atam with electron releasing nature of
ethyl group while aniline has electron gainer benzene ring & deereaus electron density on
the N-atom & hemee formation of H-bond with water becomes difficult and hence not
soluble.
196
(iii) Aniline is less basic than methylamine due to electron releasing benzene ring and
hence pKb value is more & Kb value is less.
(iv) Diazonium salt of aromatic amines have dipolar N
2
-cl group which shows more
intermolecular attraction than those of aliphatic amines and hemee more stable.
(v) Methylamine is basic in nature and have attracts to the cl group of Fecl
3
in presence of
H of water and hence precipitate the Ferric oxide hydrated.
(vi) Primary amires have less surface and less spherical shape and hence expericnce
greate varder waals force of attraction and hence greater boiling point
(vii) Silver chloride has tendency to form complex compound with aqeous methyl amine
and hence dissolves.
(vii) Aniline has electron releasing amine group, NH
2
and increases electron density on
the ortho- and para- positions of the benzene ring and hence form 2,4,6 tribromo-aniline.
Amines are basic even more basic than ammonia among amines, alkyl amines are more basic
than aryl amines.
Explanation:- The basic nature of amines is because of lone pair of electrons on the N-atom
which can be donated to other.
.. ..
R NH
2
NH
2
Alkyl amines have electron donor alkyl group ( R ) that increases the electron density on the N-
atem and makes the alkyl amines more basic while aryl amines the alkyl amines more basic
while aryl amines have electron gainer benzene ring. Benzene is rich in electrons but having
tendency to gain electrons instead of donating to the N-atom & hence the electon density on the
N- atom becomes less and hence less basic. The low basicity of aryl amines may be explained
broadly by ellustrating resonating structures of anyl amines ie aniline.
The low basicity of anylamires is with resonance stabilization of the compound i.e
.. + + + ..
NH
2
NH
2
NH
2
NH
2
NH
2
I II III IV V
Out of I--V resonating structures the figures II ,III and IV are involved in the
charge separation. The fig. II electrons are always rotating between 6 carbon atoms
and not available permanently to the N-atom for strong basic nature.
In comparision to the aryl amires the alkyl amines have no such type of resonance and
hence the movement of electrons is always alkyl group to the N-atom of the functional
group amino group (NH
2
).
R NH
2
This phenomena makes the permanent displacement of the electrons towards N-atom
makes it more basic.
197
FOR BELOW AVERAGE
01 Mark Questions

1. Write IUPAC Name - (CH
3
)
2
CHNH
2

2. Write IUPAC Name - CH
3
NHCH(CH
3
)
2
3. Write IUPAC Name - CH
3
CH
2
N( CH
3
)
2

4. Classify the given amines into primary, secondary& tertiary.
(CH
3
)
2
CHNH
2
,( CH
3
)
2
CHNH
2
, CH
3
CH
2
N(CH
3
)
2

5. Arrange the following in decreasing order of PKb values
(CH
3
)
2
CHNH
2
,( CH
3
)
2
CH NHCH
3
, CH
3
CH
2
N(CH
3
)
2

6. Arrange the following in increasing order of basic strength
Aniline, Dimethylaniline, Diethyl amine &Methyl amine
7. Which of the compounds is most basic
Aniline, p-Nitroaniline & p-Toludine
8. Which of the following compounds is more soluble in water-
Aniline, Diethyl aniline & Ethyl amine
9. Write the hybridized state of amines.
10. What is the geometry of amines?
11. What is the structural formula of Zwitter ion of Sulphanilic acid
12. Complete the following
CuCN
ArN
2
+
X
-
+CN
-
------------- --------+N
2
+ X

13. Convert
Aniline to benzonitrile
14. Convert
Aniline to sulphanilic acid.
15. What do you mean by ambident Nucleophiles ? Give an example.
02 Marks Questions
1. Give reasons ---
a. Amines are basic in nature.
b. Aryl amines are less basic than ethyl amines.
2. How would you distinguish between Primary & secondary amines?
3. Out of ethyl alcohol & ethyl amine, which has higher boiling point and why?
4. Illustrate each of the following with an example
a Sandmayer reaction
b. Diazotization reaction.
5. How will you convert ---
a. Nitrobenzene to phenol
b. Aniline to chlorobenzene
6. Account for the following---
(i) Primary amines are higher boilng points than comparable tertiary amines.
(ii) Conc. Sulphuric acid used in nitration of Benzene.
7. Write the chemical equations for one example of each the following---
(i) Coupling reaction
(ii) Hoffmann bromamide reaction.
8. How will you convert---
198
(i) Methanamine to ethanamine
(ii) Ethanamine to methanamine.
9. Complete the following
NaCN OH
-
NaOH/ Br
2

(i) CH
3
CH
2
I--------- A------------B--------------------- C
NH
3
NaOBr NaNO
2
/ HCl
(ii) CH
3
COOH------------ A------------- B ------------------ C

heat
10. How will you convert ---
(i) Ethanoic acid into methanamine
(ii) Methanol to ethanoic acid
11. Write short notes on the following-
(i) Carbylamine reaction
(ii) Acetylation reaction
12. Why cannot aromatic primary amine be prepared by Gabrial phthalimide synthesis?
13. Explain, Why it difficult to prepare pure amines by ammonolysis of alkyl halides?
14. Silver chloride dissolve in methylamine solution, Give reason.
15. Write the structure of the following compounds (i) TNT (ii) picric acid
03. Marks Questions
1. Give reasons-
a. Aniline is weaker base than cyclohexaamine.
b. Alkylamines have less PKb value than arylamines.
c. Methylamine in water reacts with ferric chloride to precipitate
ferrichydroxide.
2. What happens when
a. Aliphatic/aromatic amines react with chloroform in alcoholic potash.
b. Aniline combines with bromine water at room temperature.
c. Arene diazonium chloride combines with fluoroboric acid.
3. Predict the products
(i) Arene diazonium chlorides react with phenol in presence of alkali.
(ii) 4-Nitrotoluene combines with bromine & further reduced by tin in
Presence of acid.
(iii) Aniline is treated with Acetylchloride in presence of pyridine.
4. Give one chemical test to distinguish between them-
(i) Ethylamine and aniline
(ii) Ethylamine and dimethylamine
(iii) Aniline and benzylamine.
5. Identify the compound A, B, C in the following reactions-

(i) Br
2
/NaOH HNO
2
A----------------- B ---------------C

Sn/ HCl NaNO
2
/ HCl
199
(ii) A---------------- B ----------------------- C

Br
2
/ KOH
(iii) A------------------ B -------------------- C
Heat
6. Comment on the following-
a. Hoffmanns bromamide reaction.
b. Carbylamine reaction
c. Diazotization reaction
7. Write the chemical reactions -
a. Hinsbergs test for all amines.
b. Test to distinguish aliphatic amines & aromatic amines.
8. Write the reactions & mention the product with IUPAC name
(i) Aniline combines with nitric acid in presence of sulphuric acid.
(ii) Aniline combines with sulphuric acid at 453473K.
(iii) Arene diazonium chloride combines with ethanol.
9. Give reasons-
(i) Silver chloride dissolves in aqeous methyl amine solution.
(ii) Tertiary amines do not undergo acylation reaction.
(iii) Aniline readily reacts with bromine to give 2,4,6-tribromoaniline.
10. What is the Gabrial phthalamide synthesis ?
11. Condensation of aniline and benzaldehyde gives compound A that is
hydrogenated to give compound B .Identify A and B .
12. What happens when
(i) Nitropropane reduced with LiAlH
4

(ii) Ethyl isocyanide undergoes hydrolysis
(iii) Benzene diazonium chloride reacts with phenol in basic medium.
FOR AVERAGE
01. Mark Questions
1 Why do amines react as Nucleophiles?
2. How is m-nitroaniline obtained from nitroarene?
3. Write IUPAC name of the compound


4. Give chemical test to distinguish between benzyl amine & aniline .
5. Complete the following reactions
Conc. H
2
SO
4
ArNH
2
--------------------- -------------------
6. How would convert, aniline to benzonitrile?
7. What is Mendius reaction?
8. Why does ammonolysis of alkyl halides not give pure Amines?
9. How will you convert aniline to phenol?

H
2
N OCH
3
200
02.
Marks Questions
1. Accompalish the following conversions
a. Chlorobenzene to p-chloroaniline
b. Nitromethane to dimethyl amine
2. Give reasons-
a. Aliphatic amines are stronger base than aromatic amines.
b. Diazonium salts of aromatic amines are more stable than aliphatic
amines.
3. Write the chemical reaction for the following with one example.
a. Coupling reaction
b. Sandmeyer reaction.
4. How will you carry the following conversions
a. Aniline to benzonitrile
b. Aniline to 2, 4, 6-tribromo aniline
5. Describe the test of primary amines & secondary amines with chemical
equations.
03. Marks Questions
1. Starting the necessary chemical reactions, conditions write the chemical Equations to obtained
chlorobenzene from aniline.
2. Identify X & Y.
NH
3
H
2
/Ni
RCOR -------------- X -------------- Y
3. Write short notes on the following---
a. Carbylamine reaction.
b. Diazotisation reaction.
c. Hoffmann Bromamide reaction.
4. Describe a chemical test to identify pr. Amines, sec, amines and tert. Amines
5. An aromatic compound A on treatment with aq. Ammonia & heating forms
compound B which on further heating with bromine and KOH forms another
compound, Formula C
6
H
7
N. Identify the compounds A, B and C.
6. Account for the following---
a. pK
b
value of aniline is more than that of methyl amine
b. Ethylamine is soluble in water but aniline is not.
a. Aqueous methyl amine reacts with Ferric chloride to give precipitate
hydrated ferric oxide.
FOR ABOVE AVERAGE
01. Mark Questions.
1. An organic compound X having molecular formula C
2
H
7
N On treatment nitrous acid
gives an oily yellow substance. Identify X
2. Name the product obtained by action of aniline with Bromine.
3. What happens when ethyl amine dissolves in liq. Ammonia?
4. How would you prepare Orange Dye?
5. Give the reagents used in Gatterman reaction.
02 Marks Questions.
1. Give reasons
a. Tert. Amines do not undergo acylation reaction.
b. Aniline cannot be prepared by Gabrial synthesis
2. Accomplish the conversions
201
b. Benzoic acid to aniline
c. Propanoic acid to ethanoic acid
3. What happens when-
b. Aromatic amines react with nitrous acid.
c. Aryl diazonium chloride reacts with phenolic in basic medium.
4. Distinguish between the pair of the compounds
a. Ethanamine & diethylamine
b. Phenol & aniline.
5. Write the product for the following reactions-
a. Nitroethane is treated with lithium Aluminium Hydride.
b. Ethyl-isonitrile is hydrolysed in the presence of acid

03. Marks Questions.
1. Write short on the following
a. Gattermann reaction.
b. Hoffman bromamide reaction
c. Gabrial phthalamide reaction.
2. An organic compound A with molecular formula C
2
H
5
NO
2
, reacts with nitrous acid
to give C
2
H
4
O
3
N, B. On reduction A Gives another compound C with molecular
formula C
2
H
7
N On treatment with nitrous acid gives D which shows iodoform test,
Identify A.
3. Distinguish between.
(A) Aliphatic amines & aromatic amines.
(B) Aniline & phenol
(C) Diethylamine & triethylamine
4. Accomplish the conversions
a. Nitrobenzene to benzoic acid.
b. Benzene diazonium chloride to p-hydroxy azobenzene.
c. Chlorobenzene to p-chloroaniline.
5. An aliphatic compound X, molecular formula C
3
H
7
NO, reacts with bromine in
presence of KOH to produce another compound Y . The compound Y further reacts
with nitrous acid to form Ethanol & nitrogen gas. Identify X & Y and write chemical
reactions involved.

6. Give suitable reasons
(A) Ethylamine dissolves in liquid ammonia.
(B) Aniline does not undergo Friedel Crafts reaction
(C) Gabriel phthalamide synthesis is preferred for synthesizing
Primary amines.
************
202


A biomolecule is a molecule that naturally occurs in living organisms. Biomolecules
consist primarily of carbon and hydrogen, along with nitrogen, oxygen, phosphorus and
sulfur. Other elements sometimes are incorporated but are much less common.
A diverse range of biomolecules exist, including:
Small molecules:
o Lipid , Phospholipid, Glycolipid, Sterol
o Vitamin
o Hormone , Neurotransmitter
o Carbohydrate , Sugar
o Disaccharide
Monomers :
o Amino acid
o Nucleotide
o Phosphate
o Monosaccharide
Polymers :
o Peptide , Oligopeptide, Polypeptide, Protein
o Nucleic acid , i.e. DNA, RNA
o Oligosaccharide , Polysaccharide
Saccharides
Monosaccharides are carbohydrates in the form of simple sugars. Examples of
monosaccharides are the hexoses glucose, fructose, and galactose and pentoses, ribose, and
deoxyribose
Disaccharides are formed from two monosaccharides joined together. Examples of
disaccharides include sucrose, maltose, and lactose
Monosaccharides and disaccharides are sweet, water soluble, and crystalline.
Polysaccharides are polymerized monosaccharides, complex, unsweet carbohydrates.
Examples are starch, cellulose, and glycogen. They are generally large and often have a
complex, branched, connectivity. They are insoluble in water and do not form crystals.
Shorter polysaccharides, with 2-15 monomers, are sometimes known as oligosaccharides.
Amino acids
Amino acids are molecules that contain both amino and carboxylic acid functional groups. (In
biochemistry, the term amino acid is used when referring to those amino acids in which the
203
UNIT -14
BIOMOLECULES
amino and carboxylate functionalities are attached to the same carbon, plus proline which is
not actually an amino acid).
Amino acids are the building blocks of long polymer chains. With 2-10 amino acids such
chains are called peptides, with 10-100 they are often called polypeptides, and longer chains
are known as proteins. These protein structures have many structural and functional roles in
organisms.
There are twenty amino acids that are encoded by the standard genetic code, but there are
more than 500 natural amino acids. When amino acids other than the set of twenty are
observed in proteins, this is usually the result of modification after translation (protein
synthesis). Only two amino acids other than the standard twenty are known to be
incorporated into proteins during translation, in certain organisms:
Selenocysteine is incorporated into some proteins at a UGA codon, which is normally
a stop codon.
Pyrrolysine is incorporated into some proteins at a UAG codon. For instance, in some
methanogens in enzymes that are used to produce methane.
Besides those used in protein synthesis, other biologically important amino acids include
carnitine (used in lipid transport within a cell), ornithine, GABA and taurine.
Protein structure
The particular series of amino acids that form a protein is known as that protein's primary
structure. Proteins have several, well-classified, elements of local structure and these are
termed secondary structure. The overall 3D structure of a protein is termed its tertiary
structure. Proteins often aggregate into macromolecular structures, or quaternary structure.
Metalloproteins
A metalloprotein is a molecule that contains a metal cofactor. The metal attached to the
protein may be an isolated ion or may be a complex organometallic compound or organic
compound, such as the porphyrin group found in hemoproteins. In some cases, the metal is
coordinated with both a side chain of the protein and an inorganic nonmetallic ion. This type
of protein-metal-nonmetal structure is found in iron-sulfur clusters.
Vitamins
A vitamin is a compound that cannot be synthesized by a given organism but is nonetheless
vital to its survival or health (for example coenzymes). These compounds must be absorbed,
or eaten, but typically only in trace quantities. When originally discovered by a Polish doctor,
he believed them to all be basic. He therefore named them vital amines. The l was dropped to
form the word vitamines.
1. Carbohydrates Carbohydrate is a class of compounds that include polyhydroxy
aldehyde, polyhydroxy ketone and large polymeric molecules that can be broken
down to polyhydroxy aldehyde and ketones. Example: sugar, glucose, starch, gums
etc. They are derived mainly from plants.
2. Monosaccharides These include non-hydrolysable carbohydrates. These are
soluble in water e.g. glucose, fructose, etc.
204
3. Aldose The monosaccharides contaning a aldehydic group are called aldose.
Example: glucose.
4. Ketose - The monosaccharides contaning a ketonic group are called ketose. Example:
fructose.
5. Disaccharides These carbohydrates, which on hydrolyses yield two molecules of
monosaccharides are called disacchaides. They are crystalline solid. Soluble in water
and sweet in taste. Example: cane sugar, maltose, lactose.
6. Oligosaccharides Those carbohydrates which yields 2 to 10 monosaccharides
molecules on hydrolysis are called oligosaccharides. Example: Raffinose. On
hydrolysis it gives glucose, fructose and galactose.
7. Polysaccharides - Those carbohydrates, which produce large no, of monosaccharides
units are called polysaccharides. They are formed by linking together a large no. of
monosaccharide units through glycosidic linkage. e.g starch, amylose, glycogen,
cellulose, etc.
8. Sugars - In general, monosaccharides and oligosaccharides are crystalline solids,
soluble in water and sweet in taste. These are collectively called sugars. e.g glucose,
sucrose.
9. Non-sugars The polysaccharides are amorphous, insoluble in water and tasteless
are known as non-sugars e.gss starch and cellulose.
10. Reducing sugars Those carbohydrates which contains free aldehydic or ketonic
group and reduces Fehlings solution and Tollens reagent are called reducing sugars.
e.g. all monosaccharides, maltose and lactose.
11. Non-reducing sugars Those sugars which do not have free aldehydic or ketonic
group and do not reduce Fehlings solution and Tollens reagent are called non-
reducing sugars. e.g. sucrose.
12. Glucose Glucose has one aldehydic group, one primary alcoholic ( - CH
2
OH ) and
four secondary alcoholic group ( - CHOH ) and gives reaction with
(i) HCN Glucose reacts with hydrogen cyanide to give glucose cyanohydrin
CH
2
OH (CHOH)
4
CHO + HCN CH
2
OH - (CHOH)
4
CH(OH)(CN)
(ii) Tollens reagent Glucose reduces Tollens reagent to metallic silver.
CH
2
OH (CHOH)
4
CHO + Ag
2
O CH
2
OH - (CHOH)
4
COOH + 2Ag
(iii) Glucose on prolong heating with HI forms n-hexane. Suggesting all the
six carbon atoms in glucose are linked linearly.
HI
CH
2
OH (CHOH)
4
CHO CH
3
- (CH
2
)
4
CH
3
Red P n-hexane
13. Proteins Proteins are complex ployamides formed from amino acids. They are
essential for proper growth and maintenance of body. They are long polymers of
amino acids linked by peptide bonds.
205
14. Myoglobin It is a protein which stores oxygen in muscle tissue. It consists of only
single polypeptide chain associated with heme unit.
15. Amino acids The compounds, which contain carboxylic acid group and amino
group, are called amino acid. It forms proteins.
16. Essential amino acids Those amino acid which are not synthesized by our body
called essential amino acid. Example: valine, lysine, etc.
17. Non- Essential amino acids Those amino acid which are synthesized by our body
called non-essential amino acid. It is also called dispersible amino acids. Example:
glycine, alanine, etc.
18. Enzymes They are essential biological catalysts, which are needed to catalyse
biochemical reaction. Example: maltase, lactase. Almost all enzymes are globular
proteins. They are highly specific for a particular reaction and for a particular
substrate.
1 MARK QUESTIONS
Q. 1. Which carbohydrate is called grape-sugar ? Give its condensed structural
formula.
Ans. Glucose is called grape-sugar ? Its condensed structural formula is :
CHO
|
(CHOH)
4
|
CH
2
OH
Q. 2. Which of the following is not an -amino acid ?
Histidine, trypsin, cysteine, proline
Ans. Trypsin, it is a protein made from amino acids.
Q. 3. Write the structure of Zwitter ion formed from Alanine.
Ans. COO

|
CH
3
C H
|
NH
3
+
Q. 4. Wreite the name and structure of the simplest amino acid which can show
optical activity.
Ans COOH Alanine
|
CH
3
C H
|
NH
2
206
Q. 5. How many hydrogen bonds are present between (i) A and T (ii) C and G in a
double helix structure ?
Ans. (i) between A and T there exist two hydrogen bonds :
A - - - - - - - - - - T
- - - - - - - - - -
(ii) between C and G there exist three hydrogen bonds :
- - - - - - - - - -
C - - - - - - - - - - G
- - - - - - - - - -
Q. 6. When RNA in hydrolysed there is no relationship among the quantities of four
bases obtained like DNA. What does this fact indicate about structure of RNA ?
Ans. This indicate that RNA has a single strand structure.
Q. 7. Where does the water present in the egg go after boiling the egg ?
Ans. After boiling, the water soluble globular protein of egg while get denatured and it
cogulates into hard and rubbery insoluble mass.
Q. 8. Which vitamin is helpful in healing wound and cuts ? What is the chemical name
of this vitamin ?
Ans. Vitamin-C is helpful in healing wounds and cuts, its chemical name is Ascorbic acid.
2 MARKS QUESTIONS
Q. 1. What type of bonding helps in stabilising the -helix structure of proteins ?
Ans. In a -helix structure, polypeptide chain of amino acids coils as a right handed screw
because of the formation of all possible Hydrogen bonds between NH group at
each amino residue and > C = 0 group of adjacent turn of helix.
Q. 2. Name the water insoluble fraction of Starch. Name the monomer of this.
Ans. Amylopectin is water insoluble fraction of starch. It is a polymer of -glucose.
Q. 3. What are the products of hydrolysis of (i) lactose (ii) sucrose. Also name the
enzyme used for reaction.
Lactase
Ans. (i) C
12
H
22
O
11
+ H
2
O C
6
H
12
O
6
+ C
6
H
12
O
6
Lactose glucose glactose
Invertase
(ii) C
12
H
22
O
11
+ H
2
O C
6
H
12
O
6
+ C
6
H
12
O
6
Sucrose glucose fructose
Q. 4. How will you prove that all the carbon atoms of glucose are in straight chain ?
207
Ans. The reaction of glucose with HI gives n-hexane and it proves that all sin-carbon-atom
are in straight chain.
HI
Ho CH
2
(CHOH)
4
CHO CH
3
(CH
2
)
4
CH
3
Heat n-hexane
Q. 5. Enumerate two reactions of glucose which cannot be explained by its open chain
structure.
Ans. (i) Glucose does not give Schiffs Test although it contains aldehyde group.
(ii) Glucose does not form crystaline product with NaHSO
3
.
Q. 6. B-complex is an often prescribed Vitamin. What is complex about it ? What is its
usefulness ?
Ans. It is a type of Vitamin which contains B
1
, B
2
, B
6
and B
12
. It required to release energy
from food and to promote healthy skin and muscles. Its deficiency causes beri-beri
(Vitamin B
1
) and Anaemia (Vitamin B
12
).
Q. 7. What are anomers ? Give two points of difference between two anomer of
glucose.
Ans. The pair of optical Isomers which differ in the orientation of H and OH gp only at C
1
Carbon atom are called anomers.
Difference between two anomers of glucose :
-D (+) glucose -D (+) glucose
(1) The specific rotation is + 111. (1) The specific rotation is +
19.2.
(2) The OH gp at C
1
is below the plane. (2) The OH gp at C
1
is above the
plane.
Q1. What monosaccharides could be obtained from the hydrolysis of each of the following:

(a) Sucrose (b) Cellulose (c) Starch (d) Glycogen (2 marks)

Q2. Why is ATP an energy rich molecules? (2 marks)

Q3. Shown below is a molecule of ATP. ATP on hydrolysis form ADP. Indicate the point of
cleavage in ATP molecule when it forms ADP on hydrolysis. (2 marks)
208


Q4. Why is sucrose a non-reducing sugar? (2 marks)

Q5. Why are maltose and lactose reducing sugars? (2 marks)
Q.1 What monosaccharides could be obtained from the hydrolysis of each of the following:
(a) Sucrose (b) Cellulose
(c) Starch (d) Glycogen (2 marks)
1. (a) Glucose and fructose
(b) Glucose
(c) Glucose
(d) Glucose
Q.2 Why is ATP an energy rich molecules? (2 marks)
2. ATP is energy rich molecule because of the presence of four negatively charged oxygen
atom very close
to each other. These four negatively charged oxygen atoms experience very high repulsive
energy. When
ATP is hydrolysed, the hydrolysis of bonds results in decrease in repulsive forces and
consequently a
large amount of energy is released.
Q.3 Shown below is a molecule of ATP. ATP on hydrolysis form ADP. Indicate the point of
cleavage in ATP
209
molecule when it forms ADP on hydrolysis.
(2 marks)
3. During hydrolysis, the bond between second and third phosphate can be easily broken to
form ADP the
point of cleavage is shown in diagram below. Point of cleavageto form ADP.
Q.4 Why is sucrose a non-reducing sugar? (2 marks)
4. Sucrose is a non-reducing sugar because anomeric carbon of both monosaccharides are
involved in
glycoside or acetal formation.
Q.5 Why are maltose and lactose reducing sugars? (2 marks)
5. Maltose and lactose are reducing sugars because in one of the monosaccharide units there
is a homiacetal
group that can be opened to give free CHO group.
FOR BELOW AVERAGE
Questions of one mark
Q 1. What are biomolecules ?
2. Give two examples of monosaccharies.
3. Give name the monomers which constitutes lactose .
4. Give the name of linkage which found between the monomer units of sucrose
5. Name the two essential amino acids.
6. Name the source of vit. E.
7. Who proposed the double helical structure of DNA ?
FOR AVERAGE
1. What are monosaccharides ?
210
2. Give an example of branched polysaccharide .
3. What are non-reducing sugars ?
4. What happen when glucose is treated with HI ?
5. Draw the pyranose structure of alpha-D-glucose
6. Name the components of starch .
7. Where glycogen is present in human body ?
8. Name the primary constituents of proteins.
9. What are the expected products of hydrolysis of maltoses10.Which type of proteins constitute enzymes ?
FOR ABOVE AVERAGE
1. Why is maltose a reducing sugar?
2. Give the name of most abundant carbohydrate present on the earth.
3. Write down the reaction between acetic anhydride and glucose.
4. Give the formula of glycine .
5. What is the function of glycogen in human body.
6. Draw the structure of zwitter ion.
7. What do you mean by denaturation of proteins ?
8. What is the activation energy for acidic hydrolysis of sucrose ?
FOR BELOW AVERAGE
Questions of two marks
1. What are main functions of hexose sugars?
2. Give two applications of carbohydrates in plants.
3. Give the functions of cellulose.
4. How we classify the amino acids according to the need in the body ?
5. What happen when denaturation of proteins takes place? Explain with examples
6. Give importance and source of vit. B.
7. Explain peptide linkage
FOR AVERAGE
1. Draw the furanose and pyranose structure of hexose sugar.
2. Explain acidic and basic amino acids with examples
3. Differentiate between fibrous and globular proteins.
4. What is the difference between nucleoside and nucleotide.
5. How can we classify the vitamins .Give source of vit A & C.
211
FOR ABOVE AVERAGE
1. Draw the hawarth projection formula for maltose.
2. Differentiate between tertiary and quaternary structure of
proteins
3. Differentiate amylase and amylopectin
4. What are functional difference between DNA and RNA.
5. Name the factors affecting enzymatic activity.
FOR BELOW AVERAGE
Questions of three marks
1. How carbohydrates are classified according to monomer units present in them ?
2. Give two chemical reaction for preparation of glucose.
3 .How starch is different from cellulose ?
4. What do you mean by secondary structure of proteins ? Explain.
5. Give main source of and function of vit. B & vit. D
FOR AVERAGE
1. Give the reaction of glucose with (i) Br
2
(ii) NH
2
OH (iii) HNO
3.
2. How can you show that glucose have cyclic structure?
3. Explain the alpha helical and beta pleated structure of proteins.
4. Explain the mechanism of enzyme catalysis.
5. Give difference between DNA & RNA. Give applications of RNA
FOR ABOVE AVERAGE
1. What do you mean by DNA finger-printing ? Enlist their uses.
2. How do you explain the amphoteric nature of amino acids ?
3. Give biological application of DNA.
4. Two strands of DNA are not identical but complimentary. Explain.
5. Supply of vit. C needs continue for human body. Why ?
Some Important Questions with Answers
1. Give one example of branched polysaccharide.
Ans. - Starch
2. Why sucrose is known as invert sugar ?
Ans- Because after hydrolysis optical rotation is changed.
212
3. What D &L denotes ?
Ans- Relative configuration of particular hydrocarbon with respect to glyceraldehydes.
4.Amino acids have relatively high melting point as compared to corresponding
haloacids. Explain.
Ans: Amino acids have relatively higher m.p as compared to corresponding haloacids.
We know that amino acids have amino (basic) group and carboxylic (acid) group. A
proton which comes from carboxylic group is accepted by amino group. Thus amino
acid exists in the form of dipolar ion i.e. zwitter ion. Due to this ionic form amino
acids become crystalline solids and due to this salt like structure show higher melting
point.
5 Amino acids are amphoteric in nature/behavior. Explain.
Ans: Due to presence of dipolar ion i.e. zwitter ion, amino acid can reacts with acid and
bases.
6 Why cant vitamin C be stored in our body? Or
Why except B
12
or vitamin B and C cant be stored in our body?
Ans: Vitamin B except B
12
& C are water soluble vitamins. Therefore these vitamins are
regularly supplied from outside because they are readily excreted in urine and cant be
store in our body.
7 What is glycogen? Why glycogen is also known as animal starch?
Ans: Glycogen is polysaccharide of glucose. Carbohydrates are stored in animal body as
glycogen. It is found in liver, brain. It is also known as animal starch because its
structure is similar to amylopectin and is highly branded.
8. What is DNA fingerprinting? Enlist their uses.
Ans: It is well known fact that every individual has unique fingerprints. These occur at the
tips of the fingers and have been used for identification for a long time. But these can
be altered by surgery. A sequence of base on DNA is also unique for a person and
information regarding this is called DNA fingerprinting. Following are the uses of
DNA printing.
a) in forensic laboratories for identification of criminals.
b) To determine paternity of an individual.
c) To identify the dead bodies in any accident by comparing the DNAs of parent or
children.
d) To identify racial groups to rewrite biological evolution.

213

Polymer: - Polymer compounds are very high molecular masses formed by the
combination of Simple molecules by covalent bonds.
Ex. nCH
2
=CH
2
( CH
2
CH
2
)n
Ethene Polythene
( Monomer) ( Polymer)
Homopolymer :- A polymer from one type of monomers is called homopolymer
Ex. Polythene.
Copolymer :- A polymer from two or more type of monomers is called copolymer
Ex. Terylene or decron, Nylon 66.
Classification of polymers :- Polymer are classified in number of ways described as
follows
(A) Natural polymers :- The polymers obtained from nature (plants & animals ) are
called natural polymers. Eg. Strarch, Cellulose, Natural
rubber and Proteins etc.
(B) Synthetic Polymers :- The polymers which are prepared in laboratory are called
Synthetic or man made polymers. Eg. Polythene, PVC,
Nylon, Teflon.
Classification of polymers on the basis of structure
(a) Linear polymer :- These are polymers in which monomeric units are linked together
to form linear chains. Eg. Polythene, PVC, Teflon
(b) Cross linked polymers:- These are polymers in which the monomers unites are cross-
linked together to form a three- dimensional network. Ex. Bakelite, Synthetic rubber.
(c) Branch chain polymers:- The polymers in which monomers are joined to form long
chains with side chains. Ex. Low density polythene.
Classification of polymers on the basis of molecular forces.
214
UNIT 15
POLYMER
(a) Elastomers:- The polymers that have elastic character like rubber are called
elastomers.
Ex. Natural rubber
(b) Fibers:- They have strong intermolecular forces between the chains. These forces are
either H-bonding or dipole interactions.
Ex. Nylon-66, dacron, silk etc.
(c) Thermoplastics :- These are the polymers which can be easily softened repeatedly
heated and hardened when cooled with little change in their properties.
Ex. Polythene, PVC.
(d) Thermositting Polymers :- These are the polymers which undergo permanent
change on heating. They become hard and infusible on heating. Ex. Bakelite. Etc.
Classification of polymers on the basis of mode of synthesis.
(a) Addition polymers:- A polymers formed by direct addition of repeated
monomers without the elimination of by product molecule is called addition
polymers. Ex. Polythene, PVC,PTFE, etc
(b) Condensation polymers :- A polymer formed by the condensation of two or
more than two monomers with the elimination of simple molecules like water,
ammonia, hydrogen sulphide, alcohol, etc. is called condensation polymer. In
this each case monomer generally contains two functional groups. Ex. Nylon
66 and Nylon 6, Bakelite, Daecron, etc.
High density polythene (Zeiglar Natta catalyst)
It is prepared by heating of about 333- 343K under a pressure of 6-7 atm in the
presence of Zeiglar Natta catalyst ( Tri ethyel aluminium Titenium tetra chloride )
333-343K, 6-7 atam
n CH2 = CH2 ( CH2 CH2)n
Zeiglar Natta catalyst
Uses:- It is used in manufacture of containers ( buckets , Dust bin, etc)
It is used in manufacture of different house wares pipes etc.
215
Polymer (origion Greek) poly means many, mers means part
Defination: Very large molecules having high molecular mass (10
3
-10
7
u)
Macromolecule: other name for polymer
Polymerization: the process of formation of polymer
Classification of polymer:
1. Based on sources:
216
a. Natural: from plants and animal sources for example starch
cellulose rubber etc.
b. Semi synthetic: polymer with modification of natural polymer
for example rayon.
c. Synthetic prepared in laboratory for example nylon, ethylene
etc.
2. Based on structure of polymer:
a. Linear: long and straight change for example PVC
b. Branched: linear polymer with branches for example low
density plastic
c. Cross linked or network: contains strong covalent bond
between various linear polymer for example Bakelite, melamine
.
3. Based on mode of polymerization:
a. Addition polymerization: repeated unit of monomers having
unsaturation in its structure
217
i. Homo-polymer: when monomer is of same kind for
e.g. polyether, PVC
ii. Copolymer polymer having two different monomers
for e.g. Buna-S, Buna- N
b. Condensation polymerization: repeated condensation reaction
between mostly two different bi-functional monomer unit with
the elimination of water alcohol etc. for e.g. nylon 66, Dacron
4. Based on molecular forces
a. Elastomers: rubber like solid with stretchable property up to
some extant for e.g. Buna-S, Buna N.
The force between chains is weak Vanderwall force.
b. Fiber: thread like solid with high tensile strength
Force between chain is hydrogen bonding for e.g. polyester,
nylon 6, 6
c. Thermo plastic: linear or slightly branched long chain molecule,
soften on heating. For example polyethylene PVC. Etc.
d. Thermosetting: cross linked molecule once setup cant not be
soften on heating. for example Bakelite, melamine
Decreasing order of force of attraction between the chains
Thermosetting > Fiber> Thermoplastic> Elastomers
Difference between thermoplastic and thermosetting
Type of polymerization reaction:
Addition polymerization or chain growth:
Due to increase in the length of chain
Due to addition of similar monomer it is addition polymerization e.g. polythene
Steps of addition polymerization with free radical mechanism:
Chain initiation :by molecules like Benzoyl peroxide(C
6
H
5
OCOOCOC
6
H
5
)
Chain propagation : through free radical
Chain terminalisation :combination of free radicals.
Q .which catalyst is used in HDP like polythene?
A. Zeigler-Natta catalyst.
Q. what is Zeigler-Natta catalyst?
A. Triethylaluminium (C
2
H
5
)
3
Al and titanium tetrachloride(TiCl
4
)
Condensation polymerization or step growth:
Since each step produces a functionalized species and is independent of each other,this is
called step groth.
As,monomers with different functional groups are condensed,so, it is Condensation
polymerization.
218
e.g. Condensation between Hexamethylene-di-amine[ NH
2
-(CH
2
)
6
-NH
2
] and Adipic
acid[HOOC-(CH
2
)
4
-COOH in Nylon-6,6.
Q.why nylon is named as such?
A.It is Acroname of New-York and London.
Q .why is it called 6,6?
A. As the monomers contain six carbon each i.e. Hexamethylene- di - amine[ NH
2
-(CH
2
)
6
-
NH
2
] and Adipic acid [HOOC-(CH
2
)
4
-COOH.
Q. what is the monomer of nylon-6?
A. Caprolactum [NH
2
-(CH
2
)
5
-COOH].
Q. Which properties of polyester make it more usable fibre ?
A. Crease resistant, Dip dry, Blending with other natural fibre like cotton, wool etc.
Q. what are different kinds of blended polyester?
A. Tere-Cot (Terelene with Cotton)
Tere-Wool (Terelene with Wool)
Tere-Silk (Terelene with silk)
Q.A Tere-Cot shirt is marked as 60-40.What does it mean?
A. It contains 60% terelene and 40% cotton.
Q. What is the source of natural rubber?
A. Milky latex from rubber tree.
Q. Which countries are the greater producer of rubber ?
A. Sri Lanka, Malaysia, Indonesia, South America.
Q. What is the monomer of natural rubber?
A. Isoprene (2-Methylbut-1,3-diene).
Q. What is a vulcanized rubber?
A. When natural rubber is heated with sulphur, it forms cross-linkage of sulphur between
linear polymers. Such rubber is called vulcanized rubber.
Q. How is vulcanized rubber than natural rubber?
A. vulcanized rubber Natural rubber
1. Non sticky 1.Sticky
2. Linkage of sulphur 2.Linear chain
3. Less absorbent of water 3. Absorbs water
4. Easily oxidized 4. Less oxidized
5. Working temp. -40 to 120 0C 5. Working temp. 40 to 120 0C
6. Tough and hard 6. Soft
Q. What is Neoprene rubber?
A.2-Chlorobut -1,3-diene
Q. Why is Neoprene rubber non inflammable ?
A. Due to presence of chloro group .
Q. What is Bio-degradable polymer?
A. The polymers which can be degraded by microbes. e.g. PHBV and Nylon-2 ,Nylon-6.
Q. Give full form of PVC, PTFE,PHBV?
A. PVC: Poly Vinyl Chloride
PTFE : Polytetrafluoroethene
PHBV : poly--hydroxybutyrate-co--hydroxy valerate.
Name of polymer Monomer structure Uses
Addition polymer
Polythene Ethene CH
2
=CH
2
Carry bags,toys,buckets
PTFE(Teflon) Tetraflouroetene CF
2
=CF
2
Non -stick cookware,Oilseals,gasket
Polyacrylonitrile Acronitrile CH
2
=CHCN Substitute for wool(mink)
Polypropene Propene CH
2
=CHCH
3
ropes,pipes
Polystyrene Styrene CH
2
=CHC
6
H
5
Insulator,Wrapping material
PVC Vinyl Chloride CH
2
=CHCl Raincoats,flooring,water pipes
(Thermocol)
219
Condensation polymer
Nylon 6,6 Adpic Acid COOH-(CH2)4COOH Parachute Rope, Socks,
Stockings
Hexamethylene- di amine [ NH
2
-(CH
2
)
6
-NH
2
]
Nylon 6 Caprolactum [NH
2
-(CH
2
)
5
-COOH] Parachute Rope, Socks,
Stockings
Dacron Ethylerne Glycol OH-(CH2)2OH
Terephthalic Acid COOH-C6H4-COOH Blended Fibers, Socks, Stockings
Bakalite Formaldehyde HCHO Electric switches, Handel of
pressure cooker
Phenol C6H5OH
Melamine Formaldehyde HCHO Unbreakable Crockery
Melamine C3N6H6
1 MARK QUESTIONS
Q. 1. Write an equation for the Chemistry involved when a drop of hydrochloric acid
make a hole in nylon stockings.
Ans. The ( CO NH ) amide bond in nylon gets hydrolysed.
Q. 2. Fibres are of crystalline structure. Why ?
Ans. Fibres have strong intermolecular forces of attraction which leads to close packing of
their chains and impart crystalline structure.
Q. 3. Which artificial polymer is present in bubble gum or chewing gum ?
Ans. Bubble gum or chewing gum contains synthetic Styrene-butadiene rubber.
Q. 4. Name the polymer used for making medicinal Capsule.
Ans. PHBVUC Polyhydroxy butyrate-CO- -hydroxy valerated.
Q. 5. Which polymer is used in making electrical goods and why ?
Ans. Bakelite because of its electrical insulator property.
Q. 6. Is (CH
2
CH C
6
H
5
)
n
a homo polymer or a copolymer.
Ans. It is a homo polymer and the monomer from which it is obtained in styrene C
6
H
5
CH
= CH
2
.
Q. 7. Which colligative property is used to determine the molecular masses of the
polymers ?
Ans. Osmotic pressure is the colligative property used to determine the molecular masses
of polymer.
220
2 MARKS QUESTIONS
Q. 8. Write the names of monomers and structure used for getting the following
polymers ?
PmmA, PVC, Teflon
Ans. (i) PVC monomer Vinylchloride, CH
2
= CH Cl
(ii) Teflen monomer Tetrafluoro ethylene, F
2
C = CF
2
(iii) PMMA monomer Methyl methacrylate,
CH
3
|
CH
2
= C COOCH
3
Q. 9. Identify the monomer in the following polymer structures :
Ans. (i) HOCH
2
CH
2
OH and HOOC COOH
ethane-1, 2-dial Benzene-1, 4-dicarboxylic acid
(ii) Melamine Formaldehyde
and HCHO
Q. 10. How do double bonds in the rubber molecule influence their structure and
reactivity ?
Ans. Due to presence of double bond the rubber molecule show cis-configuration because
which the polymer chains can not come close to each other and get boiled but as they
have their hindrance problem. This causes them to have weak Vander Waals
intraction between the molecules consequently they get elastic property, solubility in
organic solvents etc.
Q. 11. Why are the No. of 6, 6 and 6 put in the names of nylon-6, 6 and nylon-6 ?
Ans. The no. of 6, 6 in nylon-6, 6 implies that both the monomers of nylon-6, 6 namely
hexamethylene diamine and adipic acid contain six carbon atom each. The no. of 6 in
221
O
N H
2
H N
2
N
N H
2
N N
nylon-6 contains six carbon atom each. The no. of 6 in nylon-6 indicates that its
monomer Caprolectum has six carbon atom in its molecule.
Q. 12. Could a copolymer be formed in both addition and condensation polymerisation
or not ? Explain.
Ans. Yes, though copolymers are mostly addition polymers like styrcue butadiene rubber
and butyl rubber, the term can be used for condensation polymers also eg. for
example.
(i) Addition polymerisation of styrene and butadiene form copolymer styrene
butadiene rubber.
n CH
2
= CH CH = CH
2
+ n C
6
H
5
CH = CH
2
>
C
6
H
5

( CH
2
CH = CH CH
2
)
n
CH
2
CH )
n
(ii) Condensation polymer became thylene diamine and adipic acid form nylon-6,
6.
n HOOC (CH
2
)
4
COOH + n H
2
N (CH
6
) NH
2

adipic acid hexamethylene n H
2
O
diamien
( NH (CH
2
)
6
NH CO (CH
2
)
4
CO )
n
Q. 13. Arrange the following polymer in increasing order of their molecular forces :
(a) nylon-6, 6, Buna-S, polythene.
(b) nylon-6, Neoprene, polyvinyl chloride.
Ans. (a) Buna S < Polythene < Nylon-6, 6.
(b) Neoprene < Polyvinyl Chloride < Nylon-6.
Q. 14. Explain the difference between Buna S and Buna N.
Ans. Buna N is a copolymer of 1, 3-butadiene and acrylo nitrile, Buna S is a
copolymer of 1, 3-butadiene and styrene.
Q. 15. Why should we always use purest monomer in free radical mechanism ?
Ans. Monomer has to be as pure as possible because the presence of any other molecule
during free radical polymerisation can act chain initiator or inhibitor which will
interfere with the normal polymerisation reaction.
BELOW AVERAGE
01 Marks Questions
Q1: Write the monomer of Polyvinyl chloride.
Ans: Vinyl chloride.
Q2: Write the polymer of phenol and formaldehyde that is used for making combs.
Ans: Bakelite, (a) Phenol (b) Formaldehyde
222
Q3: Write the monomer of Glyptal polymer.
Ans: (a) Ethylene glycol (b) Phthalic acid
Q4: What is Synthetic polymer ? Give one example.
Ans: Man made polymers are called Synthetic polymers. Polyethene, PVC.
Q5: What is approximate molecular mass of Polymer ?
Ans: It is approximate molecular mass 10
3
-10
7
u.
Q6: What are monomers of Nylon 6.6
Ans: (a) Hexamethylene diamine and adaipic acid.
Q7: Write the Mnomers of Buna-s.
Ans. 1, 3 butadine and styrene
Q8: What are carben fibers ? Give two examples.
Ans: A long thread solid posses high tensile strength. Eg. Terrylen and Nylon.
Q9: What is addition polymerization ?
Ans: A chemical reaction in which monomer unit is repeated to produce a molecule without
losing of molecule like water or ammonia. Ex. Polythene, Polyvinyl chloride
Q10: Give one example of each for low density polythene and high density polthene.
Ans: LDP. Squeze bottle and toys
HDP. Buckets, dustbin, bottles.
02 Marks Questions
Q1. Differentiate between thermo plastic and thermo setting Plastic.
Ans:
Thermo Plastic Polymer Thermo setting Polymer
1. Liner or slightly branched long
change molecules
2. Posses intermediate inter
molecular force of attraction.
3. Ex. Polythene, Polystyrene
1. Cross linked or heavy branched
molecule
2. This can not be reused
3. Ex. Bakelite, Urea-Formal dehyde
resins
Q2: Give two Polymerisation reactionds for each.
(a) Addition polymers and
(b) Condensation Polymers
Ans: Addition Polymers :-
nCH
2
=C ( CH
2
CH
2
)
n

Condensation Polymers
n H
2
N(CH
2
)
6
NH
2
+ n HOOC(CH
2
) COOH [NH(CH
2
)
2
NHCO(CH
2
)
4
CO)]
n
+nH
2
O
Q3: What are elastomers ? Give one example.
Ans: The rubber like material which are elastic in nature. Eg. Natural rubber.
223
Q4: Write the chemical structure of Glyptal
Ans: Ethylene Glycol-OHCH
2
CH
2
OH
Phthalic acid COOH
COOH
Q5 : Define Copolymers.Give two examples.
Ans: The Polymer in which repeating units are combined with two or more differents types of
monomers
Eg. Polyster and terrylene(Dacron)
Q6: What is Neoprene? Mention any two uses.
Ans: A synthetic rubber made by chloroprene. It is a synthetic rubbers.
Uses: Conveyor belts in coal mines & gaskets.
Q7: Define Synthetic rubbers. Whether it is homopolymer or co-polymer?
Ans: Any Vuclanised rubbers like polymers. Which is getting stretched to about twice lengths
and returns to the original shape and size as the external force is released.
Eg. Homopolymers.
Q8: Explain the difference between Buna-N and Buna-S.
Ans: Buna-N:-
1. It is obtained by the copolymerization of 1,3 butadiene and acrylonitrile in the
presence of a Peroxide Catalyst.
2. It is resistant to action of Petrol.
3. It is used in making in oil seals tank lining etc
Buna-S:-
1. It is obtained by the Copolymerisation of buta diene and styrene.
2. It is used for automobile tyres.
Q9: What do you understand by Vulcanised Rubbers?
Ans: When natural rubber is heated with sulpher at 373K to 415K. The vulcanized rubber
has excellent elasticity with low water absorption tendency. The probable structure of
vulcanized rubber molecule as follows;
CH
3

CH
2
C CH CH2
S S
224
CH
2
C CH CH
2
CH
3

Q10: Explain the terms:-
(a) PDI
(b) PMMA
Ans: PDI :- Polydispersity Index: The ratio of the mass average molecular mass is called
PDI
PMMA:- It is polymer of ethyl methylacrylate.
AVERAGE STUDENT
Very Short Answer 01 Marks
Q1: Write the monomer of Polystyrene?
Ans: Styrene.
Q2: Write the structure of monomer of Polystyrene?
Ans: Ar CH = CH
2
Q3: Write the monomer of Neoprene?
Ans: Chloroprene.
Q4. Write the name of monomers of Melamine-Formaldehyde.
Ans: Melamine and Formaldehyde.
Q5: What is the monomer of Polyacrylonitrile?
Ans: Acrylonitrile
Q6. Write the polymer of Tetrafluoro ethane.
Ans: Teflon.
Q7: Define Copolymers?
Ans: The polymer is obtained by two or more different monomers.
Q8: Is ( NH CHR CO )
n
is a homopolymer or a copolymer?
Ans: It is a Copolymer.
Q9: Why should one always use purest monomer in free radical polymerization?
Ans: The impurities present in monomer may combine with free radical that slow the rate
of polymerization.
Q10: What is meant by PTEE ? Give its popular name.
Ans: Polytetra fluoroethylene. Teflon.
02 Marks Questions
Q1: Differntiate between addition polymer and condensation polymer.
225
Ans:
Addition Polymer Condensation Polymer
1. Large no. of unsaturated monomers
combine together to form polymers Eg.
Polythene and polystyrene
1. Large no. of monomers having different
functional group with release of small
molecule like water combine to form
polymers. Eg. Nylon and Teflon
Q2: Distinguish between thermoplastic and thermo setting polymers.
Thermo plastic polymer Thermo setting plastic
1. The inter moliculer forces are
intermediate.
2. there are no cross linkage bond
3. Eg. Polythene and polystyrene
1. The inter molecular force are
maximum.
2. They are cross linkaged.
3. Eg. Bakelite
Q3: Distinguish between Homopolymers and Copolymers.
Homopolymers Copolymers
1. The polymers which are form by only
one type of monomers Eg. Teflon & PVC
1. The polymers which are form by two or
more types of monomers .Eg. Terrylene &
Buna-S
Q5: Depict a free radical mechanism of addition polymerization of isoprene.
.
R* + CH
2
= CCH = CH
2

R CH
2
CCH = CH
2
| |
CH
3
CH
3


.
R CH
2
C=CH CH
2
|
CH
3

CH
3
CH
2
-----
226
and
C = C

R CH
2
H

Trans 1, 4 structure
CH
3
H

C = C

R CH
2
CH
2
---

Cis 1, 4 structure
Q6: Why are the numbers 6, 6 and 6 put in the name of Nylon 66 and Nylon 6?
Ans: Nylon 66 means that it is formed by two monomers each containing six carbon
atoms. While in Nylon 6 means that it is formed by a monomer containing six carbon
atoms.
Q7: Explain the structural difference between polyacrylats and polyesters
Ans: Polyacrylate-
CH2 = CR
|
COOR
And Polyster
CO
| |
O
Q8: What is PHBV ?
Ans: It is a poly hydroxyl butyrate. Co-- hydroxyl Valerate.
It is copolymer of 3- hydroxyl butanoic acid and 3- hydroxyl pentanoic acid in which
monomer units linked by ester linkage.
Q9: Explain the difference between Buna-N and Buna-S.
Ans: Buna-N:-
227
1. It is optained by the copolymerization of 1,3 butadiene and acrylonitrile in the
presence of a Peroxide Cxtalyst.
2. It is resistant to action of Petrol.
3. It is used in making in oil seals tank lining etc
Buna-S:-
1. It is obtained by the Copolymerisation of buta diene and styrene.
2. It is used for automobile tyres.
Q10. Arrange the following Polymers in increasing order of inter molecular forces.
(a) Nylon 66, Buna-S and Polythene
(b) Nylon 6, Neoprene and PVC
Ans: (a) Buna-S, Polythene and Nylon 66.
(b) Neoprene, PVC and Nylon 6.
BRIGHT STUDENT
Very Short Answer Question: 01 Mark
Q1. What does stand for PDI
Ans: Polydispersity Index.
Q2. Write the name of neoprene polymer?
Ans: Chloroprene
Q3: Write the name of reagent use for initating a free radical chain reaction.
Ans: Tertiary Butyle peroxaide.
Q4: What are carbon fiber?
Ans: A long thread solid posses high tensile strength. Eg. Terrylen and Nylon
Q5: A polymer is use for making combs, name the polymer.
Ans : Baklite
Q6: A polymer is used for making paints and lacquers, name it.
Ans: Glyptal.
Q7: Name the monomer of polyvinylchloride.
Ans: Vinylcloride.
Q8: Arrange in increasing order of inter molecular forces.
Nylon 66, Buna-S and polyethene.
Ans: Nylon 66 > polyethene> Buna-S
Q10. Arrange the following Polymers in increasing order of inter molecular forces
Nylon 6, Neoprene and PVC
Ans : Nylon 6, PVC and. Neop
SHORT ANSWER 02 Marks
Q1: Write the structure of monomer of polystyrene.
228
Ans: Styrene. Ar CH=CH2
Q2: Clasify the polymers as addition and condenstation polymers.
Nylon 66, Buna-S, Polythene.
Ans: Nylon 66 condensation polymer.
Buna-S and polytheneAddition polymer.
Q3: Classify the polymers as addition and condensation polymer
Nylon 6, Neoprene and PVC.
Ans: Nylon 6 Condensation polymer
Neoprene and PVC Addition polymer.
Q4: What is Biodegradble polymer?
Ans: The polymers which are Biodegrable and not causes any environmental population is
called Biodegrable . Eg. PHBV and Nylon 2 Nylon 6.
Q5. Who do double bonds in rubber molecules influence there structure and reactivity.
Ans: Greater the number of double bound the rubber will be less reactive because of
greater inter molecular forces of attraction among the monomers.
Q6: What is PHBV? Give its one use.
Ans: It is a poly hydroxybutyrateco hydroxyl valerate .
It is obtain by the copolirisation of 3 hydroxyl butanoic acid and 3 hydroxy
pentanoic acid.It is used in speciality packaging , orthopaedic devices.



229
STUDY MATERIAL

1. Tranquilizers- they are chemicals which are used for treatment of mental diseases
.they act on higher centers of central nervous system. Example Equanil , Seconal
,luminal or Barbituric acid etc.
2. Antibiotics- Chemical substances which are produced by micro-organisms(such as
moulds and bacteria) and are capable of destroying other micro organism are called
antibiotics .Example penicillin ,Ampiciline.
3. Broad spectrum Antibiotics- Antibiotics which are effective against several different
types of harmful micro-organisms and thus, capable of curing several infections are
called broad spectrum antibiotics Example chloromycetin, Tetracycline .
4. Antihistamins :- Antihistamins are amines which are used as drugs to control the
allergy effects produced by histamines. Example diphenyl hydrazine or
promethazine .
5. Antipyritics :- Chemical substances which are used to bring down the body
temperature in high fevers are called antipyretic. Example Aspirin, paracetamole or
Analgin etc.
6. Disinfectants :- Chemical substances which kill micro organism or stop their
growth but are harmful to human tissue are called disinfectants .example 1.%
solution of phenol (2)SO
2
in

very low concentration.
7. Analgesics:- chemical substance used for relieving pain are called analgesics
.
Example
novalgin, profanes etc.

8. Antacids:- These substances react with hydrochloric acid present in the stomach
neutralize it partially. Example magnesium hydroxide , Aluminum hydroxide etc . it
can be used as tablet or in aqueous suspension .
9. Antifertility drug Those drug which control the birth of the child are called antifertility
drugs. Steroids are the active ingredients of the pill functioning as an antifertility
agents. some commonly used pills contains a combination of ethynlestradiol and
norethindrone.
10. Anticancer agents Those drugs which are used in treatment of cancer are used as
anticancer agents e.g cis-platin.
11. Antimicrobials Disease in man and animal which may be caused by bacteria, virus
and other micro-organisms microbes. Any organism that causes diseases is called a
pathogen.
Many body secretions either kill the microbes or inhibit their growth. Examples are
lysozyme in tears, nasal secretion and saliva, fatty acids and lactic acid in sweat and
sebaceous secretions and hydrochloric acid in stomach.
The control of microbial diseases can achieved in three ways by
(1)A drug which kills the organisms in the body(bacteria) e.g penicillin
230
UNIT -16
CHEMISTRY IN
EVERYDAY LIFE
(Bactricidal).
(2) A drug which inhibits or arrests the growth of the organism (bacteriostatic)
(3) Increasing immunity and resistance to infection of the body.
Antibiotics are the class of drugs used as antimicrobials.
12. Chemicals in food :- Many chemicals are added to food for their preservation and
enhancing their appeal. These include flavouring , sweetness, dyes, antioxidants, etc.
13. PreservativesThose chemicals which prevent undesirable changes in flavour,
colour, texture, appetitic appeal during a storage are called preservative. They delay
these changes and prevent spoilage of food due to microvial growth. The most
common preservative is sodium benzoate(C
6
H
5
COONa) .
Class 1 preservatives-includes table salts, sugar , vegetable oil.
Class 2 preservativesodium benzoate ,salts of sorbic acids and propanoic acid.
14. Antioxidants--- Antioxidants are the important class of compounds which prevent
oxidation of food materials.
These compounds retard the action of oxygen on the food and thereby help in
preservation. These act as sacrificial materials i.e. they are more reactive towards
oxygen than the materials they are protecting. Example
(1) Butylated hydroxyl anisole (BHA)
(2) Butylated hydroxyl toluene (BHT)
15. Artificial sweetness sweetness are another type of food additives e.g ortho
sulphobenzimide (saccharin) is marketed as soluble sodium or calcium salt. It is 300
times sweeter than cane sugar. It is lifesaver for diabetic patients and is to control
intake of calories
16. SoapThey are sodium or potassium salts of higher fatty acids like steric acids, oleic
acid and palmitic acid. Soaps are formed by heating fat with aqueous sodium
hydroxide solution the reaction is called saponification.
O

CH
2
-O-C-C
17
H
35
O CH
2
-OH
|
CH-O - C-C
17
H
35
+3NaOH = CH-OH+3C
17
H
35
COONa
O |
CH
2
-OH Sodium stearate
CH
2
-O-C-C
17
H
35
Glyceryl stearate Glycerol
17. Detergents: They are sodium or potassium salts of sulphonic acids e.g sodium alkyl
benzene sulphonate.
Types of Detergents:-
(i) Anionic detergents:- When detergents bears an anion at the soluble end of the
chain, it is called anionic detergents.ex. It is used in toothpastes and house
hold work.
NaOH(aq) - +
CH3(CH2)16CH2OH+H2SO4 CH3(CH2)16CH2OSO3H CH3(CH2)16CH2OSO3 Na
- H2O
Lauryl alcohol Lauryl hydrogen sulphate Sodium lauryl sulphate
(Anionic detergents)


231
18. Advantage of detergents:
(a) They work well even with hard water.
(b) They are more effective than soaps.
(c) They can work well even with acidic water.
(d) They can work well with woolen garments.
1. Chemotherapy : Treatment of diseases with the help of suitable drugs.
2. Antipyretic : Reduce body temperature. Eg: Aspirin, Analgin.
3. Analgesic : Pain Killer. Eg : Aspirin, Morphin, Heroin, Analgin.
4. Tranquiliser : Decreases anxiety. Eg: Luminal, Seconal.
5. Antibiotic : Cure infections. Eg: Penicilin, Tetracyclin,
Chloroamphenicol.
6. Antimalarial : Eg: Quinine, Chloroquinine.
7. Antifertility Drug : Birth control. Eg: A pill containing estrogen and
progesterone.
8. Preservatives : Chemicals used for preventing spoilage of food materials.
Eg: Sodium Benzoate.
9. Artificial sweetening agent : Eg: Sacharin, Aspartame (methyl ester).
10. Cationic Detergents : Eg: Trimethylstearylammoniumchloride.
11. Anionic Detergents : Eg: Sodiumdodecylsulphate.
232
12. Non-ionic Detergents : Eg: Pentaacrythritolmonostearate.
13. Biodegradable Detergents : Detergents having straight hydrocarbon
chain and easily decomposed by microorganisms. Eg:
Sodiumlaurylsulphate, sodiumdodecyl benzenesulphonate.
Important Questions :
16. What is understood by Chemotharepy.
17. Explain the terms with an example :
a) Antibiotic.
b) Tranquillizers.
c) Antihistamin.
d) Antipiratics.
e) Disinfactant.
18. Describe the following substances with one suitable examples :
a) Food Preservatives.
b) Sweetning agent.
c) Enzymes.
d) Antioxident.
19. Explain the following terms with one examples :
a) Biodegradable detergents.
b) Non-biodegradable detergents.
c) Anionic detergents.
d) Non- ionic detergents.
20. What are analgesic drugs. How are they classified and when are they usually
recommended for use.
21. Aspirin drugs help in preventing of heart attack, explain.
22. Diabetic patient are advised to take artificial sweeteners instead of natural
sweetener. Why?
23. Which type of detergent produce less foam.
24. Which type of detergent would you use to formulate toilet cleaner and Why?
25. Name the antiseptic you will add to soap to make it useful for control of pimples.
233
26. Discuss two ways in which drugs prevent attachment of natural substrate on active
site of enzymes.
27. Write one use of followings :
a) Zentac.
b) PCM.
c) Ranitidine.
d) Equanil.
e) Novestrol.
f) Morphin.
g) ChloroamPhenicol.
h) Bithional.
Hints :
5. Analgesics Pain Killer
Classification Narcotic Morphin (to relief post operative pain)
Non Narcotic Aspirin, PCM (to reduce fever , to prevent blood platelets coagulation)
6. Aspirin act as blood thiner and causes no coagulation.
7. The artificial sweetners are either non metabolized by body or do not produce
carbohydrate like glucose when metabolized.
8. Nonionic detergents
9. Cationic detergents
10. Bithional
12. Zentac Antacid
PCM Antipyretics, Analgesics
Ranitidin Antacids
Equanil Tranquillizer
NonVestrol Antifertility drugs
Morphine Analgesics
ChloroamPhenicol Antibiotics
Bithional Anticeptics
1 MARK QUESTIONS
Q. 1. Give an example of a chemical substance which can act both as an antiseptic and
disinfectant.
Ans. Phenol.
Q. 2. What is the chemical name of antiseptic chloroxylenol ?
Ans. 4-Chloro-3, 5-dimethyl phenol.
Q. 3. Which alkaloid is used to control hypertension ?
234
Ans. Reserpine.
Q. 4. Which alkaloid is used to treat malaria ?
Ans. Quinine.
Q. 5. Identify the following :
HO NHCOCH
3
Ans. Paracetamol.
Q. 6. What is the use of the following compound :
O C O C H
3
C O O H
Ans. Analgesic.
Q. 7. Which artificial sweetner has the lowest sweetness value ?
Ans. Aspartame.
Q. 8. Which artificial sweetner has the highest sweetness value ?
Ans. Alitame.
Q. 9. What kind of a drug is Chlorpheniramine maleate ?
Ans. Anti histamine drug.
Q. 10. What is the chemical name of aspirin ?
Ans. 2-Acetoxy benzoic acid.
Q. 11. Name the antibacterial present in toothpaste.
Ans. Triclosan.
Q. 12. Identify the drug :
Ans. Penicillin G.
235
Q. 13. Which antibiotic contains NO
2
group attached to aromatic nucleus in its
structure ?
Ans. Chloramphenicol.
Q. 14. What is the use of barbituric acid ?
Ans. Tranquilizer.
Q. 15. Name one analgesic drug which is also used to prevent heart attacks.
Ans. Aspirin.
Q. 16. What is the application of the following molecule in everyday life ?
CH
3
(CH
2
)
11
CH
2
SO
3

Na
+
Ans. It is a detergent.
Q. 17. Give an example of a drug that is antipyretic as well as analgesic.
Ans. Paracetamol.
Q. 18. Out of morphine, N-Acetyl-para-aminophenol, Diazepam and tetrahydrocatenol,
which can be used as analgesic without causing addiction ?
Ans. N-Acetyl-para-aminophenol.
Q. 19. Name a sugar substitute which is 160 times as sweet as surcrose.
Ans. Aspartame.
2 MARKS QUESTIONS
Q. 1. When a mixture of salicylic acid, acetic anhydride and acetic acid is refluxed,
what is the product obtained and what is its use in everyday life ?
Ans. Aspirin used as analgesic.
Q. 2. Distinguish between a narrow spectrum and broad spectrum antibiotic.
Ans. A narrow spectrum antibiotic works against a limited range of microbes whereas a
broad spectrum antibiotic works against a large variety of microbes.
Q. 3. What is Salvarson ? To which class of drugs does it belong ? For what distance is
it used ?
Ans. Antimicrobial agent.
Used for the treatment of STD called Syphilis.
Q. 4. How does apirin act as an analgesic ?
Ans. It inhibits the synthesis of prostaglandins which stimulates inflammation of the tissue
and cause pain.
Q. 5. What are barbiturates ? To which class of drugs do they belong ?
Ans. 5, 5-derivatives of barbituric acid are called barbiturates. They belong to the class of
tranquilizers. They also act as sleep producing agents.
Eg. Luminal, Veronal.
236
O
Q. 6. What is tincture iodine ? What is its use ?
Ans. Alcoholic Solution of I
2
.
Used as an antiseptic.
Q. 7. To what class of medicines does chloramphericol belong ? For what disease can
it be used ?
Ans. Broad spectrum antibiotic
Used to cure typhoid, dysentry, acute fever.
Q. 8. Pick the odd one amongst the following on the basis of their medicinal properties
mentioning the reason.
(i) Luminal, seconal, phenacetin, equanil
(ii) Chloroxylenol, phenol, chlorampherical, bithional
Ans. (i) Phenacetin is an antipyretic while all the rest are tranquilisers.
(ii) Chlorampherical is an antibiotic while all the remaining are antiseptics.
Q. 9. Why is bithional added to soap ?
Ans. Acts as an antiseptic and reduces the odours produced by bacterial decomposition of
organic matter on the skin.
Q. 10. Why are cimetidine or ranitidine better antacids than sodium bicarbonate or
magnesium or aluminium hydroxide ?
Ans. If excess of NaHCO
3
or Mg (OH)
2
or Al (OH)
3
is used, it makes the stomach alkaline
and thus triggers the release of even more HCl. In contrast, cimetidine or ranitidine
prevent the interaction of histamine with the receptor cells in the stomach wall and
thus release lesser amount of HCl.
Q. 11. Why is the use of aspartame limited to cold foods and drinks ?
Ans. It decomposes at baking or cooking temperatures and hence can be used only in cold
foods and drinks.
Q. 12. What problem arises in using alitane as artificial sweetener ?
Ans. It is a high potency artificial sweetener. Therefore it is difficult to control the
sweetness of the food to which it is added.
Q. 13. What is the purpose of adding antioxidants to food ? Give two examples of
antioxidants.
Ans. They are added to prevent oxidation of fats and oils present in food thus preventing
food from becoming rancid.
Eg. BHA (Butylated hydroxy anisole)
BHT (Butylated hydroxy toluene)
FOR BELOW AVERAGE
01 Mark Questions
237
1. Define the term chemotherapy
2. Define the term Tranquilizers and give one example.
3. Define the term Anti Oxidants and give one example.
4. Name a food preservative which is most commonly used by food products.
5. List two major classes of antibiotics and give one example of each class.
6. Why is bithional added to the toilet soap?
7. Give an example of a narcotic which is used as an analgesic.
8. Define antiseptic and give one example.
9. Name one medical compound each that is used to treat (1) hypertension (2) general
body pain.
10. What is function of wide spectrum antibiotics and give one example.
11. How are antiseptic different from disinfectant? Give one example of each of them.
12. Soap is a weak antiseptic itself. What may be added to soap to improve its antiseptic
action?
13. What type of drug is chloramphenicol?
14. Why ethanol is added to soap?
15. Name the medicine which can act as analgesic as well as antipyretic. Give its
chemical name.
16. Give one example of bactericidal antibiotic and bacteriostatic antibiotic.
17. Why is use of aspartame limited to cold foods and drinks
18. What type of drug is Phenacetin?
19. How are synthetic detergents better than soaps?
20. What is tincture of Iodine?
FOR BELOW AVERAGE STUDENTS
A1. The branch of science which deals with the treatment of diseases
using suitable chemicals is known as chemotherapy.
A2. They are chemicals which are used for treatment of mental diseases. Example
Equanil.
A3. Antioxidants are the compounds which prevent oxidation of food materials.
Examples, BHA (Butylated hydroxy anisol) and BHT( Butylated hydroxy
toluene.
A4. Class I- preservatives Table salt, sugar and vegetable oil.
Class II preservatives Sodium benzoate
A5. (a) Simple antibiotics- Penciline, Ampiciline
(b) Broad spectrum antibiotics Chloromycetin.
A6. Bithional is added to soaps to impart them antiseptic properties. Such soaps are used
to reduce odor due to bacterial action on skin surface.
A7. Morphine or heroin.
A8. They are chemicals which kill or prevent the growth of microorganisms. They are
applied to living tissues. Example- KMnO
4
Solution, 0.2 % solution of phenol etc.
A9. (i) Equanil (ii) Novalgin
A10. Antibiotics which are effective against several different types of harmful micro
organisms and capable of curing several infections are called broad spectrum
antibiotics. Example- Chloromycetin, tetracycline.
A11. Antiseptic is used in living tissue where as disinfectants are used in nonliving things.
Example of Anticeptic- Tincture of iodine ( 2-3 % iodine in alcohol water solution)
and iodoform act as antiseptic. Example of disinfectants 2% solution of phenols.
A12. Bithional.
A13. Broad spectrum antibiotics.
A14. To make transparent the soap.
238
A15. Aspirin.
A16. Ofloxacin and chloramphenicol respectively.
A17. It is unstable at cooking temperature.
A18. Antipyretics.
A19. Broad spectrum antibiotics.
A20. 2-3% Iodine in ethanol is called tincture of iodne.
FOR AVERAGE
01 Mark Questions
1. What are main constituents of Dettol?
2. What are food preservatives?
3. Name the sweetening agent used in the preparation of sweet for a diabetic patient.
4. Why do soaps not work in hard water?
5. If water contains dissolve calcium hydrogen carbonate, out of soaps and synthetic
detergents which one will you use for cleansing cloths?
6. Why should not medicine be taken without consulting doctors?
7. Name two narcotics which are used as analgesics?
8. What is an antipyretics ? Give an example.
9. What are antagonists and agonists ?
10. Pick out the odd amongst the following compounds on the basis of there
medicinal properties.
Luminal, Seconal, Phenacetin, Equanil.
FOR ABOVE AVERAGE
01 Mark Questions
1. Write the chemical formula of
(i) Sodium stearate (ii) Sodium palmitate
2. Write chemical equation of soaponification.
3. What is biodegradable detergents?
4. Write chemical formula of (i) Sodium dodecyl benzene sulphonate and (ii) Sodium
lauryl sulphate.
5. What are pathogens ?
6. What is the chemical formula of cataionic detergents ?
FOR BELOW AVERAGE
02 Mark Questions
1. Mention one important use of each of the following
(i) Equanil (ii) sucralose
2. Name a broad spectrum antibiotics and state two diseases for which it is prescribed.
3. State the function along with one example each of (i) Antihistamines (ii)
Antioxidents.
4. Describe the following with an example.
(i) Antimicrobials (ii) Analgesics
5. Name the medicines used for the treatment of the following diseases (i) Tuberculosis
(ii) Typhoid
6. Describe the following with example.
(i) Preservatives (ii) Biodegradable detergents
7. Describe the following with giving examples
239
(i) Edible colours (ii) Antifertility drugs
8. Define the followings and give one examples.
(i) Antipyrites (ii) Antibiotics
9. Give one important use of each of the following :
(i) Bithional (ii) Chloramphenicol (iii) Streptomycine
(iv) Paracetamol
FOR AVERAGE
02 Mark Questions
1. Why do we require artificial sweetening agents?
2. Which process is involved in holding the drugs to the active site of enzymes?
3. What are different types of synthetic detergents ? Explain with sutable
Examples.
4. How are synthetic detergents better than soap?
5. Describe the cleansing action of detergents.
FOR ABOVE AVERAGE
02 Mark Questions
1. What are biodegradable and non biodegradable detergents?
2. Explain the following terms with suitable examples.
(a) Cationic detergents (b) anionic detergents.
3. Why are detergents usually preferred to soap for washing cloths?
4. Why biodegradable detergents are more prefer now a days.
5. Define the following terms with suitable examples.
(i) Antacids (ii) Antihistamines (iii) Antibiotics
(iv) Antifertility drugs (v) Foodpreservatives.
THE END
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240