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UNIT:-1

( SOLID STATE )

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 ?
1
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.
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 :
2
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.
Cl A

+
Li B C

Interionic distance of LiCl = 5.14 / 2 = 2.57 A


AC = AB + BC
2 2

= 2.57 + 2.57
2 2

= 3.63
therefore, radius of Cl = 3.63 = 1.81 A
Q. 3. Give reasons :

3
(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.
(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
a3 M Z
= N0a3
58.5 4
= 6.023 1023

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


= 6.023 1023 / 58.5 4
= 2.57 1021
Q. 5. In the mineral spinal; having the
formula MgAl2O4. The oxide ions are
arranged in CCP, Mg2+ ions occupy the
tetrahedral voids. While Al3+ ions occupy
the octahedral voids.
4
(i) What percentage of tetrahedral voids is
occupied by Mg2+ ions ?
(ii) What percentage of octahedral voids is
occupied by Al3+ ions ?
Ans. According to the formula, MgAl2O4. If
there are 4 oxide ions, there will be 1 Mg 2+
ions and 2 Al3+. But if the 4 O2 ions are ccp
in arrangement, there will be 4 octahedral and
8 tetrahedral voids.
(i) Percentage of tetrahedral voids occupied
by Mg2+ = (1 / 8) 100
= 12.5%
(ii) Percentage of octahedral voids occupied
by Al3+ = (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) CaCl2 will introduce Schottky defect if
added to AgCl crystal.
Ans. (a) Due to annealing over a number of
years glass acquires some crystalline character.

5
(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 Ca2+ 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.98O1.00. What fractions of
nickel exist as Ni2+ and Ni3+ ions ?
Ans. NiO.98O1.00
Let Ni2+ be x and Ni3+ be 0.98 x
Total charge on compd. is equal to zero.
[2 (Ni2+) + 3 (Ni3+) 2 (O2)] = 0
2 x + 3 (0.98 x) 2 = 0
x = 0.94
0.94
Therefore Ni2+ % = 0.98 100 = 96%
Ni3+ = 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
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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.
(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 ?

7
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?

8
(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 M2+ and M3+ 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.

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)

9
Q5. Why are amorphous solids to be considered as
supercooled liquids? (2 marks)

Q1. What is meant by the term Co-ordination no?

10
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 Ni0.98 as I1.00. What fraction of Ni
exit as Ni2+ and Ni3+ ions?
Ans:- Let the no of Ni2+ ion = X
Ni3+ 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 Ni3+ = 06%

Q4. What is difference between Frenkel and


schottky defect? (any two)
11
Ans:-
Frenkel defect Schottky defect
(a) In this defect (a) In this defect there
shifting of icon is missing of equal no
from its position to of cation and anion.
interstitial site.
(b) Density remain (b)Density decreases.
same.

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
zxM 4 xM
d
N 0 xa 3
6.022 x10 x( 4.077 x10 8 )3
23

We Know M
6.022 x10 23 x10.5 x( 4.077)3 x10 24
4
107.14 gm

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-------- Zn2+ + 1/2 O2 + 2e-
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Zn2+ adopt the interstitial void and electron in
the neighbouring voids. Due to presence of
electron in void, the colour is yellow.

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 SrCl2
1 mole of NaCl are doped with =10-3/100
mol=10-5 mol
As Sr2+ ion introduced one cation vacancy
Conc. Of cation Vacancy=10-5 X 6.022X1023
mol-1
=6.022X1018 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 .

13
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 cm3
1
unit cell in 1cm3 = 4.44 x10 2.25 X 10
23
22

Q12. What happens when ferrimagnetic Fe 3O4 is


heated to 850 K and why?

Ans:- Fe3O4 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.


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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.
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?

15
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
1023 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 1023,
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+
16
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 1023)

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.

17
4. Explain the following with suitable examples:
(a) Ferromagnetism (b) Paramagnetism (c)
Ferrimagnetism
(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?

18
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 1023.
19
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 1023]
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?

UNIT:-2
SOLUTION

STUDY MATERIAL
20
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 :
21
a) Mole fraction ( X):
Xsolvent = nsolvent /nsolvent + nsolute
Xsolute = nsolute /nsolvent + nsolute
b) Normality (N) :
N = WB/EB x 1000/V
c) Molarity (M) :
M = WB/MB x 1000/V
d) Molality (m) :
m = WB/MB x 1000/WA
WB = Mass of solute in gram.
WA = Mass of solvent in gram.
MB = Molar mass of solute.
V = Volume of the solution.
EB = 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.
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.
22
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 = PA0 P (PA0 = 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 = (PA0 P)/ PA0
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.

23
11. Boiling Point : Temperature at which vapour
pressure of the liquid is equal to atmos[heric
pressure.
12. Elevation of boiling Point :
Tb = T0 T = kb x m.
Here T0 and T are Boiling points of pure solvent
and solution.
m = molality , kb = Ebullioscopic constant.
1. Freezing points : Temperature at which
liquids and its solid phase have same vapour
pressure.
2. Depression of freezing point :
Tf = T - T0 = kf x m.
Here T0 and T are freezing points of pure solvent
and solution
m = molality , kf = 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

24
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.
a) Maximum Boiling Azeotropes : Azeotropes
boils at the temperature higher than the
boiling point of its components. Eg: Mixture
of HNO3 (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.

25
9. Positive Deviation from Raults Law :
Solutions having solvent solute molecular
forces are weaker than that of solvent
solvent of solute solute molecular forces .
Hmix = + ve, Vmix = +ve and P > PA + PB .
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.
Hmix = - ve, Vmix = - ve and P < PA + PB
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/ PA0 = i XB
b) Tb = i kb x m.
c) Tf = i kf x m.
d) = i C R T.
12. Vanthoff factor :
26
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).

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?
27
2. How is the molality of a solution different
from its molarity?
3. Calculate the density of H2SO4 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 KH . At the same temperature
hydrogen is more soluble in water than
Helium. Which of them will have a higher
value of KH and Why?
7. What concentration of nitrogen should be
present in a glass of water at room
temperature? Assume a temperature of 250
celcius. A total pressure of 1 atm and mole
fraction of nitrogen in air is 0,78 (KH for
nitrogen is 8.42 x 10-7 M/mm Hg).

28
8. Henerys Law constant for CO2 in water is
1.67 x 108 Pa at 298 K. calculate the quantity
of CO2 in 500 ml of soda water when packed
under 2.5 atm CO2 pressure at 298 K.
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
400 C. (V.P of water at 400 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 1100 C and
1300 C, which one of them has higher
vapour pressure at 500 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

29
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).
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 250 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 :

30
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 K2SO4 in water
2) Na2SO4.10H2O 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 MMB) ,
31
M=molarity, MB = molar mass of solute, d=
density of sol.
d = 1.24 gm/cm3
4. 157.8 ml
7. Partial pressure of nitrogen in atmosphere (PN2)
= Ptotal x XN2
PN2 = 592.8 mm Hg
Solubility of N2 = KH x PN2 = 4.99 x 10-4 (M)
8. KH = 1.67 x 108 Pa , PCO2 = 2.5 atm = 2.5 x
1.01325 x 10-5 Pa
PCO2 = KH x XCO2 , XCO2 = 1.517 x 10-3
nCO2/(nCO2 + nH2O) = 1.517 x 10-3
nCO2 = 42.14 x 10-3 mole.
10. From Raults Law : (PA0 P)/PA0 = XB = nB/nA
P = 53.46 mm Hg.
12. X has higher vapour pressure than Y.
13. nbenzene = 80/78 = 1.026 moles
ntoluene = 100/92 = 1.087 moles
Xbenzene = 0.486 , Xtoluene = 0.514
From Raults Law : PBen = PBen0 x XBen = 24.65
mm Hg
PTol = PTol0 x XTol = 16.48
mm Hg
Mole fraction of Benzene in vapour phase =
PBen/PBen + PTol = 0.60.
14. (PA0 P)/PA0 = XB = nB/nA
MB = 41.34 gm mol-1
16. Calcium phosphate , Copper Ferrocyanide
17. = C x R x T
32
= WB x R x T/MBV
MB = 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
Na2SO4 then write the Vant Hoff factor used
for calculating the molecular mass.

33
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 1020 molecules of urea are
present in 10 ml of its soln. then what is the
conc. of urea soln.?
Ans. N0 = 6.023 1023 = 1 mol
6.023 1020 molecules = 0.001 mol in 10 ml
N 1000 .001 1000
M= v = 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 Na2SO4 is isotonic with
0.01 M soln of glucose at the temp. What is the
apparent degree of dissociation of Na2SO4 ?
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.

34
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 KNO3, (b) 0.01 M
Na2SO4 which aqueous soln. will exhibit high
B. P.?
Ans. (a) 0.01 M Na2SO4
Q. 9.Out of (a) 1 M CaCl2 (b) 1 M AlCl3 which
aqueous soln. will show max. vapour pressure
at 300 K ?
Ans. (a) 1 M CaCl3, if we assume 100%
dissociation, i for CaCl2 = 3 and AlCl3 = 4 and
relative lowering of V. P. is directly proportional to
i.
Q. 10. Out of (a) HNO3 + H2O and (b) C6H6 +
C6H5CH3 which will form max. boiling
azeotrope ?
Ans. (a) HNO3 + H2O.

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 ?

35
M1V1 + M2 V2 1.5 480 + 1.2 520
Ans. Total molarity = V + V = 1 2 480 + 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 BaCl2 are
prepared in H2O. D. F. pt. of NaCl is found to
be 2 C. What freezing point do you expect
from BaCl2 soln ?
Ans. i for NaCl = 2 i for BaCl2 = 3
3 2
Therefore TF (BaCl2) = 2 3 ,
TF for BaCl2 = 3 C ,
Freezing Point of BaCl2 Solution is TF = 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 ?
36
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 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 Ka = 1.36 103. Calculate b. p. of 0.01 M
aqueous solution? (Kb = 0.51 k kg/mol)
Ans. Kb = 0.51 k i=1+
kg/mol = 1 + 0.3687 =
= Ka / C 1.3687
Tb = i Kb m
= 1.36 103 /
0.01 = 1.36 102
= 0.3687 .51
= 0.0069 C

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

37
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 ?
(Kf for water = 1.86 C/mol)
Ans. (14 32) / 9 =C/5
C = 5 ( 18) / 9
= 10 C
K 1000 W
TF = W M
F

a b
b
Wb = mass of
solute
Mb = molar mass
of solute
Wa = mass of
solvent
1.86 1000 W
10 = 1000 46 b

Wb = 247.31 g
Q. 9. 75.2 g of phenol is dissolved in solvent of
KF = 14, if the depression in freezing point is 7
k. What is the % of phenol ?

38
Ans. KF = 14 2 C6H5OH
(C6H5OH)2
1000 K W
Mb = W DT1
F

F
2
1
Taking the solvent as 0
1 kg 1
Mb = 10001000 14 75.2 /2
7k
Total = 1 +
= 150.4 g per mol
/2
phenol (molar mass)
=1/2
94 g/mol
Calculated molar mass i =1+/
i = Observed molar mass 2
= 94 / 150.4 = =1/2=
0.625 0.625
/ 2 = 0.375
= 0.75
% of association =
75%

Q. 10. How many ml of 0.1 M HCl are


required to react completely with 1 gm mixture
of Na2CO3 & NaHCO3 containing equimolar
amounts of both ?
Ans.
39
Let the amount of
Na2CO3 be x xNaHCO3 = 0.00526
Let the amount of
NaHCO3 be 1 x Na2CO3 + 2 HCl
Since no. of moles 2 NaCl + CO2 + H2
of both are equal NaHCO3 + HCl
x 1 x
NaCl + CO2 + H2O

N(Na CO ) M(NaHCO )
2 3 3 M1V1 = 2 M2V2 +
x 1 x
106

84 M3V3
84 x = 106 106 0.1 V1 = 2 0.00526
x + 0.00526
x = 0.5578 V1 = 0.01578
0.1
xNa2CO3 = 0.5578 /
= 0.1578 L
106 V = 157.8 ml.
= 0.00526

Q.11 Given below is the sketch of a plant for


carrying out a process.
(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
40
this plant
(iv) Give one
practical use of the
plant

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

41
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

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
42
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.

43
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) D mix H 0 (ii) p A P A A , pB pB B
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?
44
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?
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 H2O
45
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 K4[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.

46
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
(C2H6O2) in solution containing 20 %
of ethylene glycol by mass.
Ans:-
Mole fraction of ethylene glycol =
no.of .mole.of .thelene.glycol
No.of .moles.of .water + No.of .moles.ofC2 H 6O2
47
i.e
20 / 62
glycol nglycol / nwater + nglycol
20 / 62 + 80 / 18
20 X 62 X 18 9
0.0676
62 X 5320 133

So H 2 O 1 glycol 1 0.0676 0.9323

Q2. An aqueous solution of glucose made by


dissolving 10 g of glucose (C6H12O6) 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 wB= 10 g, MB=180, WA=90 g, MA=18
P0A=32.8 mmHg.
PS=?
10
P A PS
0
P A PS
0
p
0
B 0
180 1 0S 1 / 90
P A P A 90 / 18 P A
PS 1 89 89
0
1 PS P 0 A 32.8 32.43mmHg
P A 90 90 90

48
Q3. A solution 3.8 g of sulphur in 100 g of CS2
(Boiling point=46.3 0 C) boils at 46.66 0c.
what is the formula of sulphur molecules in
the solution .(Atomic mass of sulphur is
32 g mol-1 and Kb= 2.4 K kg mol-1)
Ans:-
WB 1000 K B
We have :- MB
DTb WA

Here
DTb ( 273 + 46.66) (273 + 46.3) 0.36 K

3.8 1000 2.4 760


MB 253.3
0.36 100 3

No of atoms of sulphur S=Molecualar wt./Atomic


Wt. = 253.33/32 8
Hence the formula of sulphur = S8

Q4. Calculate the osmotic pressure of a solution


obtained by mixing 100 cm3 of 0.25 M
Solution of urea and 100 cm3 of 0.1M soln of
cane sugar at 293 K (R=0.082 L atm

49
mol -1K-1)
Ans:-

We know V nRT

0.25 + 0.1
0.2 ( ) 0.0821 293
2
Or
0.35 0.0821 293
21.022atm
2 0.2

Q5. 2 g of benzoic acid (C6H5COOH) 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

WB=2g , Kf=4.9 KKgmol-1, WA=25 g,


DT f 1.62 K

We have
WB 1000 K f 2 1000 4.9
MB 241.98 gmol 1
DT f W A 1.62 25

50
Also 2C6H5COOH (C6H5COOH)2
Initially 1 0
( 1-x) x/2 mole
x x
Total no. of particles at equilibrium. = (1 x) +
2
1
2

x
i 1
2

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

1. State Henrys law.


51
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?

52
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?

53
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?
2. Two liquids A and B boil at 145C and 190C
respectively. Which of them has a higher V.P.
at 80C?

54
3. What is expected value of i for K4[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

55
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.

56
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.
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
57
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.

58
8. Explain the significance of Henrys Constant
(KH). At the same temperature, hydrogen is
more soluble in water than helium. Which of
them will have a higher value of KH 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(C9H8O4) in acetonitrile(CH3CN) when

59
6.5 g of C9H8O4 is dissolved in 450 g of
CH3CN.
3. H2S, toxic gas with rotten a like smell, is used
for qualitative analysis. If the solubility of H 2S
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? Kb 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?
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.
60
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 cm3 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 N2 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

61
that Henrys law constant for N2 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

62
percentage association of acid if it forms
dimmer in solution?
5. Determine the osmotic pressure of solution
prepared by dissolving 25 mg of K2SO4 in 2
litre of water at 25C. Assuming that it is
completely dissociated.
6. Two elements A and B from compounds
having formula AB2and AB4. 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?

63
*************************

64
UNIT :-3
ELECTRO CHEMISTRY

STUDY MATERIAL

Q1. Define molar conductivity. How does it varies


with dilution ?
Ans:- Molar conductivity:-

65
It is the product of specific conductivity and
volume of solution containing 1 g molecular mass
of the electrolyte.

K 1000
mol
C

Unit= Sm2 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.

66
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 (H2, CO etc.) directly into
electrical energy
Ex:-H2-O2 fuel cell.

Reaction :-
Anode reaction:- H2(g)+2OH-(aq) ---
2H2O+2e.X 2
Cathode reaction:- O2(g) +2H2O+4e ---- 4OH-
Overall reaction :-2H2(g) + O2(g) ------ 2H2O(l)
67
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 ---- 2Fe2+ + 4e-
At another sport on the metal these
electrons reduce oxygen in presence of H+.
At anode :O2(g) + 4H+ + 4e- ---- 2H2O(L)

The overall reaction is


2Fe + O2 + 4H+ ----- 2Fe2+ + 2H2O
The ferrous ions formed are further oxidized to
ferric ions by atmospheric oxygen and products
comes out as rust in the form of
Fe2O3XH2O(hydrated Ferric oxide)
68
Q4. A solution of CuSO4 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
(Cu2+ +2e --- Cu)
=2X96500C
Q=It=1.5X600
=900 C
2 X 96500 C charge deposited 63 g of copper

63 900
900 C charge deposited 2 96500 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.
69
Ans:- R=1500

K=0.148 X 10-3 S cm-1


l
a
Cell Constant = ?
l
a
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
Scm2 mol-1. what is its dissociation constant?
Ans:-
K=7.896 X 10-5 S cm-1

0 390.5Scm 2

K 1000
C
C

7.896 105 1000 7896


32.93
0.00241 241

C 32.93
0.0838
0
390.5
K 2C (0.0838) 2 0.00241 1.85 10 5

70
Q7. Represent the cell in which the following
reaction takes place.

Mg(S) + 2Ag +(0.0001 M) -----


Mg2+(0.130M) + 2Ag(s)
Calculate its E.M.F when E0=3.17V
Ans:- Cell reaction
Mg ----- Mg2+ + 2e -- - - - - Oxidation at
anode
2Ag+ + 2e --- 2 Ag --- - - - - - -Reduction at
cathode
Representation of cell

MgMg2+ (0.130 M) Ag+(0.0001 M) Ag


C1 C2

0.591 C
E + log 2
E.M.F of the cell E= n C1

0.0591
Ag + 2

=3.17 + 2
log

Mg 2 +
0.0591 (0.0001) 2
=3.17 + 2
log
0.130
71
=3.17 -0.21
E=2.96 V
Q8. 0 mol for NaCl, HCl and Na AC(CH3COONa)
are 126.4, 425.9 and 91.0 Scm2 mol-1
respectively. Calculate 0 mol for HAC(CH3COOH,
Acetic Acid).
Ans:-


0 HAC 0 CH # COO + 0 Na + + 0 H + + 0 Cl 0 Na + 0 Cl
91.0 + 425.9 126.4 516.9 126.4

=390.5 Scm2 mol -1

Q9. States Faradays laws of electrolysis.


Ans: 1st 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.
72
2nd law:- If same change is passed through
different electrolytes, the mass of substance
deposited at each electrodes will be
propositional to their equivalent weights.
W1/E1=W2/E2
Where W is mass of substance and E is its
equivalent weight.

Q10. Calculate G0 for Zn-Cu cell at standard


conditions.
Given E 0 Zn 2 + / 2 n 0.76V , E 0Cu 2 + / Cu +0.34V , F 96500C

Ans:-
E 0 cell E 0 Cathode E 0 anode
+0.34 (0.76) 0.34 + 0.76
1.10V

DG 0 nE 0 F 2 1.10V 96500c
212.2kjmol 1

Q11. Depict the galvanic cell in which the reaction


Zn(s)+2Ag+(aq) --- Zn2+(aq) + 2Ag(s) takes
place.

73
(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


AT anode
Zn Zn 2 + + 2e oxidation
AT cathode
2 Ag + + 2e 2 Ag Re duction

Zn + 2 Ag Zn 2 + + 2 Ag

Cell representation
2 + ( aq )
Zn Zn Ag + Ag

E E+ E Ecathode Eanode

(c) Ag electrode is negative charged.


(d) Ag+ and Zn2+ ions carries the current
in the cell. Current flow from Ag
electrode to Zn electrode.
(e) At anode

Zn Zn 2 + + 2e Oxidation

At cathode.

74
2 Ag + + 2e 2 Ag Re duction

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 Ecell
indicate ?
Ans. G will be positive, the cell will not
work.
Q. 3. Why is the equilibrium constant K,
related to only Ecell and not Ecell ?
Ans. This is because Ecell is zero at
equilibrium.
Q. 4. What is the sign of G for an
electrolytic cell ?
Ans. Positive.
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 ?
75
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.
(ENi+/Ni = 0.25 V ECu+/Cu =
0.34 V)
Ans. Reduction potential of Ni is less than Cu.
Ni will replace the Cu from CuSO4. Thus Ni
spatula cannot be used to stir a solution of
CuSO4.
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
Evalue 0.46 V 0.66 V 0.20 V
0.44 V

76
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 Ecell change
in an electrochemical cell involving the
following reaction of the concentration
of Ag+ (aq) is increased ?
(b) What will be e. m. f. when the cell
reaches equilibrium :
Mg (s) + 2 Ag+ (aq) Mg2+ (aq) +
Ag (s)
0.059 Mg2+


Ans. (a) Ecell = Ecell 2
log Ag+

2

As the concentration of [Ag+] ion increases,


Ecell increases.
(b) e.m.f. = 0
77
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 Ecell = 0
?
0.0591
Ans. For a cell E = n log K
K < 0 log K < 0
i.e. log K is ve.
Then Ecell will be negative.
0.0591
(b) If Ecell = 9 then 0 = n
log K
log K = 0 K = 1

Q. 3. Knowing that :
Cu2+ (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 AgNO3 solution
can be stored in Copper Vessel or 1 M
CuSO4 solution in Silver Vessel.
Ans. A solution of an electrolyte can be stored
in a particular vessel only in case there is no

78
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 AgNO3 cannot be kept in Copper
Vessel.
CuSO4 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.
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 1023
1 C of Charge is present on electrons =
23
6.022 10
96500 C 1 C

= 6.24 1018
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
79
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 ?

400
lm
200
A
B
0.2 0.4
C

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
80
mobility increases. In a weak electrolyte
molar conductivity increases steeply with
dilution as degree of dissociation increases
and hence no. of ions increases.
Q. 2. Iron and nickel are used to make
electrochemical cell by using a salt bridge to
join a half cell containing 1 M Fe2+ (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 :
EFe+/Fe = 0.44 V ENi+/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 Fe2+ concentration
were increased ?
Ans. (a) Anode : Fe
Cathode : Ni
(b) Reaction at anode : Fe Fe2+ + 2
e
Reaction at cathode : Ni2+ + 2 e
Ni
(c) Voltmeter reading decreases.
81
Q. 3. Consider the electrochemical cell :
Zn (s) / Zn2+ (aq) // Cu2+ (aq) / Cu. It has
an electrical potential of 1.1 V when
concentration of Zn2+ and Cu2+ 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 :
CO3+ + e CO2+E = 1.82 V

82
2 H2O O2 + 4 H+ +4 e E =
1.23 V
Explain why CO3+ is not stable in aqueous
solution ?
Ans. The Ecell can be calculated as :
4 [CO3+ + e CO2+] E = 1.82 V
2 H2O O2 + 4 H+ +4 e E =
1.23 V



Cell reaction : 4 CO3+ + 2 H2O
CO2+ O2 + 4 H+
Ecell = 1.82 V ( 1.23 V) = 3.05 V
Since Ecell is positive, the cell reaction is
spontaneous. CO3+ iron will take part in the
reaction and hence unstable in aqueous
solution.
Q. 5. For the reaction :
Ag+ + Hg Ag + Hg22+
E = 0.80 VE = 0.79 V
Predict the direction in which the reaction
will proceed if :
[Ag+] = 101 mol/h [Hg2+] = 103 mol/h
Ans. Cell reaction is :
83
2 Ag+ + 2 Hg 2 Hg + Hg22+
0.0591 Hg2 2+


Ecell = Ecell 2
log + 2
Ag

0.0591 103
= (0.80 V 0.79 V) 2 log 10
1 2

0.0591
= 0.01 V 2 ( 1) = 0.01 + 0.0295
= 0.0395 V
Since Ecell 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.

5.How are secondary cells different from


primary cells?
84
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 .

85
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.

86
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) /
2+
Cu ( 0.130 M ) // Ag+ ( 1 x 10-4 M ) / Ag
(s). Given that E0 Cu+2 / Cu = 0.34 V and E0
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.

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) Zn2+ (aq) + 2 Ag (s),

87
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 E0 Ag+ / Ag = 0.8 V, E0 Mg2+ /
Mg = - 2.37 V
05 Marks Question
1. What is EMF of a cell?
Calculate the emf of the cell
Mg(s) / Mg2+ ( 0.1 M ) // Ag+ ( 1 x 10-4 M) /
Ag (s) at 250 C,
Given that E0 Ag+ / Ag = 0.8 V , E0 Mg2+ / Mg
= -2.37v
88
2.What will be the effect on EMF of the cell if
concentration of Ag+ is increased to 1 x 10-3M?
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) / Ni2+ ( 0.01 M ) // Cu2+ ( 0.1 M ) /
Cu(s)
The E0 values for Ni2+ / Ni and Cu2+ / 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.
89
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?

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

90
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 E0 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
91
concentration of Cu2+ ions in solution is
decreased?
3. Calculate the potential of a zinc - zinc ion
electrode in which the zinc ion activity is
0.001M
[E0 Zn2+ /Zn = -0.76 V, R= 8.314 JK-1mo1-1,
F=96500 Cmo1-1]
4. The molar conductance of sodiumacetate,
hydrogenchloride and sodiumchloride at infinite
dilutions are 91, 426 and 126 Simen cm2 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 E0 Values for two metal electrodes are
given below
(i) Cr3+/Cr2+= -0.4V (ii) Fe3+/Fe2+ = 0.8V

92
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|Zn2+ (IM) // Cu2+ (IM) / Cu
Given E0zn2+/zn = -0.76V and E0 cu2+/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.

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:

93
(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 ^0m for acetic acid is
390.5 S cm2 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.

94
5. Silver is electrodeposited on a metallic vessel
of surface area 800 cm2 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
Sn4+(1.50 M)+ Zn Sn2+(0.5M)+
Zn2+(2M)
The standard potential E0; of the cell is 0.89V,
whether the potential of the cell increase or
decease (R=8.314 JK-1mol-1, F=96500 C mol-1)
if the concentration of Sn2+ 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:

95
Concn / 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.
(c) Calculate the EMF of the following
cell at 298 K
Sn/Sn2+(0.1M) // Ag+(0.1M) / Ag
Given E0 Sn2+/Sn = -0.14V, E0 Ag+/Ag =
0.8V
96
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.

97
3. What does the standard electrode potential of a
metal being negative E0 Zn2+/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 Cu2+ 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.
98
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?

7. The Zinc - silver oxide cell has the following


reactions.
Zn Zn 2+ + 2 e- E0= 0.76 v
Ag2O + H2O + 2e- 2Ag+ + 2OH-
E0=0.34V
Calculate the standard free energy in joules
99
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 E0 Cu2+ / Cu = 0.34 volt and E0 Ag+ /Ag
= 0.80 volt for a cell
a) Calculate cell potential for the cell
containing 0.1 M Ag+ and 4 M Cu2+ at 25C.
100
b) How many hours does it take to reduce 3
moles of Fe2+ with 2 amp current.
2. Calculate the standard cell potential, standard
free energy charge rG0 and equilibrium
constant for the Galvanic cell 2Cr(s) + 3 Cd 2+
2Cr3+ + Cd
Given that E0Cr3+ /Cr = -0.74 v, E0 Cd2+ /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

101
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
Sn4+ (1.5M) + Zn Sn2+ (0.5 M) + Zn2+ (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?
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.
102
2Cl- (aq) Cl2 + 2e- E0 = 1.36 v
2 H2O (l) O2 (g) + 4H+ (aq) + 4e- E0=
1.23 v
Which of the above reaction actually takes
place and why? Also give other utilities of
electrolysis?
********************

103
UNIT 04
CHEMICAL KINETICS

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
Lt DX dX
Instantaneous Rate Dt 0
DT dT

104
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.
Rateofreaction K A B
x y

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.
NH4NO2 N2 + 2 H2O
BiMolecular Reaction : When molecularity is
two.
2HI H2+ I2

Trimolecular or Termolecular reactions : When


three species collide
105
2NO + O2 2NO2

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.
106
Rate = dx = k[A]
dt

Rate constant of first order reaction is


2.303 a
K log
t ax

2.303 A
or K
t
log 0
A

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.
0.693
t1
2 K Where K= rate constant

Second Order Reaction :


dX
K A B
1 1
Rate
dT

The reaction in which sum of powers of


concentration terms in rate law or rate equation is
equal to 2.

107
Third Order Reaction : The reaction in which
sum of powers of concentration terms in rate law
is equal to 3 i.e.
dX
K A B , Where x+y =3
x y
Rate
dT

Pseudo First Order Reaction : The reaction


which is bimolecular but order is one is called
Pseudo first order reaction.
+
CH 3 COOC 2 H 5 + H 2 O

H
CH 3 COOH + C 2 H 5 OH

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 :


H 2 + Br2 2 HBr

Rate K H 2 Br2
1 1
2

Half life of Reaction of nth Order :


1
In general, t
A where n is order of reaction.
1
2
0
n 1

For t a for Zero order


1
2

108
t is independent for first order.
1
t for second order.
1
a2

1 rd
a for 3 order.
t
1 2
2

Activation Energy (Ea) : 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 :


Ea

K A.e RT

Where K = rate constant


A= frequency factor,
Ea= Energy of activation,
R = gas constant,
T= temperature in Kelvin

lnK = lnA Ea/ RT


log K = log A- Ea / 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
109
110
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-1S-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
2.303 R
Ans.: K
t
0
log
R
111
Where [R0] 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.
0.693
Ans. t
1
2K

Q7. Is half life time independent to initial


concentration in first order reaction.
Ans.: Yes

Q8. Write the Arrhennius equation of reaction rate.


Ans.: K A.e where A is frequency factor,
Ea
RT

Ea 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 NH4NO2.
NH NO N + 2 H O i.e. Unimolecular
4 2 2 2

(2) 2HI H + I i.e. Bimolecular reaction


2 2

112
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)

Q13. Write the Unit of K in Zero Order


reaction.
Ans.: M0L-1S-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

113
Q16. Write the determination of second order
reaction?
Ans. Molecularity is two & order of reaction is
one.
Ex : CH COOC H + H O CH COOH + C H OH
3 2 5 2
H+
3 2 5

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.:
CH 3 COOC 2 H 5 + HOH CH 3 COOH + C 2 H 5 OH
Rate K [CH 3 COOC 2 H 5 ]1 [ H 2 O ]0

i.e. H2O 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.

114
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 = -Ea/ 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-1S-1. What is the order of the
reaction ?
Ans.: Order =2
For Above Average Students :
01 Mark

Q1. What is temperature coefficient ?


R
Ans.: R 308

298

Q2. Fill up the blanks :


Ea T .T
1 2 .......... ....
R T2 T1
R
Ans.: Ln 2
R1

115
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 ?
(a) (b) (c) (D)

Rate Rate Rate Rate

C 1/c C C2

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)
116
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 1. It is the number of
powers to which molecules taking part in
concentration terms are chemical reaction.
raised in rate law
2. It is determined 2. It is determined
experimentally theoretically
3. It can be zero or even 3. It is always in whole
in fraction number except Zero.
4. Order of complex 4. Molecularity of
reaction can be complex reaction can
determined, not be determined.

Q2. For a reaction A+H2O B, rate TA. What is


its
i) Molecularity, ii) Order of reactions ?

Ans. I) Its molecularity is 2


117
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.: +
1.)CH 3COOC 2 H 5 + H 2 O
H
CH 3 COOH + C 2 H 5 OH
2.)C12 H 22 O11 + H 2 O invertage
C 6 H 12 O6 + C 6 H 12 O6

Glucose Fructose

Q4. Name four factors affecting rate of reduction.


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

118
Log
(Conc.)
time

Q2. The rate constant for a first order reaction is


0.005 min-1. Calculate its half life.
0.693 0.693
Ans.: t K 0.05 1386Min
1
2

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
119
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.
K2 Ea T2 T1
log
K1 2.303R T1 .T 2
0.07 Ea 700 500
log
0.02 2.303 8.314 JK mol 700 500
1 1

10 4
0.544 Ea 5.714
19.15
Ans. Ea 0.544
19.15
18230.8 J
5.714 10 14
Ea RT
Since, K Ae
18230.8

0.02 A.e 8.314500

0.02
A 1.61
0.012

FOR BELOW AVERAGE STUDENTS :03


Marks
2.303 R o
Q1. Drive the relation K t log R
Ans.: We know that rate of reaction is
proportional to the first power of concentration of
the reactant R. For Ex.

120
RP
d R
Rate K R
dt
d R
or , K .dt
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=[R0], where [R0] is the initial
concentration of the reactant.
Ln[R0]=-K x 0 +I
So, Ln[R0]=I
Substituting the value of I in Equation (1)
Ln[R]= -Kt + Ln [R0]
Rearranging this equation,
Ln
R Kt
R 0
1
or , K Ln
R 0
t R
or , K
2.303 R
Log 0
t R

Q2. Derive the expression t = 0.693/ K for first


order reaction.
K
2.303
Log 0
R
t R
K
2.303 R
log O
t1 RO
2
Ans,: 2.303
2
K log 2
t1
2

0.693
t 1
2 K

121
FOR AVERAGE STUDENTS :03 Marks

Q1. Derive the relationship between activation


energy & rate constant.
Ans. Arrhenius equation K A.e where A is
E
RT

frequency factor, Ea is activation


energy, R= 8.314 JK-1mol-1, T is temp. in
Kelvin.
Ea
ln K ln A
RT
EG
ln K ln A
RT1
Ea
ln k ln A
RT2
K2 Ea 1 1
ln
K1 R T1 T2
K2 Ea T2 T1
log
K1 2.303R T1 .T2

For Above Average Students :


03 Marks
Q1. The following results have been obtained
during the kinetic studies of the reaction.
2A + B C + D

Experime [A] M [B] M Initial rate of


ntal 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
122
Determined the rate law and the rate constant
for the reaction.
Ans.:
dx
K [ A] x [ B ] y (1)
dt
7.2 10 2 K [0.3] x [0.4] y (2)
Dividing(1) /(2), weget ,
1 1
2 y 22
4 2Y
y2
6.0 10 3 K [0.1] x [0.1] y (3)
2.40 10 2 K [0.4] x [0.1] y (4)

Dividing (3) by (2), we get,


1 1
x 1
4 4x
dx
K [ A] x [ B ] y K [ A]1 [ B ] 2
dt
6.0 10 3 K [0.1]1 [0.1] 2
K 6.0 M 2 S 1

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
0.693 0.693
Ans.: (a) t K 200S 3.465 10 Sec.
1
2
1
3

0.693
(b) t1
2 2 Min 1
3.465 min 0.35 min ..

0.693
(c) t1
2 4
0.173 years

Q3. Give the mechanism of the reaction


H 2 ( g ) + Cl 2 ( g ) Sunlight
2 HCl ( g )

123
Ans.: Chain initiation step :
Cl + Cl HN
2Cl

Chain propagation step


H 2 + Cl H + HCl
H + Cl 2 HCl + Cl

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.
124
High energy of activation barrier means the
activated complex is difficult to form and it is a
slow reaction.
A.B
Activated complex

Eaf
Energy DH o S E R E P

ER JHoS
Reaction condition

125
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.

126
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 P1/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

127
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. 2SO ( g ) + O ( g ) 2SO ( g )
2 2
NO ( g )
3

15. Heterogeneous catalysis :- When reactants


and catalysts are in different phases, this process
is known as Heterogeneous Catalysis.

Eg.: N2(g) + 3 H2(g) Fe(S) 2 NH3(g)

16. Mechanism of heterogeneous catalysis :-


The steps are as follows :
(i) Diffusion of reactants on the surface of
catalyst.
128
(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 108 to 1020 times.
Eg. NH CONH + H O 2 NH + CO
2 2 2
Urease
3 2

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.

129
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 S8 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.
130
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.

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
131
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.
132
b) The coagulative power of electrolyte
increases with increase in charged on the ion used
for coagulation. For Eg. :
Al3+> Ca++ > Na+ for negatively charged
colloids. Similarly
[ Fe(CN)6]4- > PO43- >SO42- > 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
Q. 1. What kind of adsorption is represented
by the following graph :
133
x
M

Ans. Chemisorption.
Q. 2. In the titration of oxalic acid by
acidified KMnO4, 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 PO43,, SO42,, Cl,, which wil
act as the best coagulating agent for for Fe
(OH)3 ?

Ans. PO43.
Q. 4. Arrange the following in correct order
of their coagulating power :
Na+, Al3+, Ba2+
Ans. Na+ < Ba2+ < Al3+
Q. 5. Which type of charged particles are
adsorbed on the surface of As2S3 during its
preparation ?
As2O3 + 3 H2S As2S3 + 3 HOH
134
Ans. S2.
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.
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
135
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 ?
1
Ans. 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 NH3 which is adsorbed
on activated charcoal to a large extent and
why ?

136
Ans. Ammonia; because more easily liquefiable
gas undergoes adsorption to a greater extent.
Q. 17. On passing H2S through dilute HNO3 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
AgNO3 solution in KI solution. What
charge is likely to develop on the colloidal
particles ?
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 FeCl3 ?
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, MgSO4, Al2 (SO4)3,
K4[Fe(CN)6], which one will bring about

137
the coagulation of a gold sol quickest and in
the least of concentration ?
Ans. Al2 (SO4)3.
Q. 23. What is the unit for expressing
flocculation value ?
Ans. millimole per litre.
Q. 24. Out of PO43, SO42, Al3+ and Na+,
which will have the highest coagulating
power for As2S3 colloid ?
Ans. Al3+.

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
138
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 ?
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 H2 to acetylene gives ethane
in presence of palladium but if BaSO4 and
quinoline or sulphur are also added, the
product is ethane. Why ?
Ans. BaSO4 + quinoline / s poison the catalyst.
Hence, the efficiency of the catalyst decreases
and the reaction stops at the first stage of
reduction.

139
Q. 8. SnO2 forms a positively charged
colloidal sol in acidic medium and a
negatively charged sol in the basic medium.
Why ?
Ans. SnO2 is amphoteric in nature. It reacts
with acid eg. HCl to form SnCl4 in the
solution. The common Sn4+ ions are adsorbed
on the surface of SnO2 particles giving them a
positive charge.
SnO2 reacts with a base eg. NaOH to form
Sodium Stannate in the solution. The stannate
ions are adsorbed on the surface of SnO2
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.

140
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 (Na3AsO3) is not
oxidised in air but if air is blown into a
solution containing Na3AsO3 and Na2SO3,
then both AsO33 and SO32 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.
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 SnO2 forms a
positively charged sol in solutions with pH <
7 and negatively charged sol in solutions
with pH > 7.
141
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.
142
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
Hx[(AlO2)x(SiO2)96-x ] . 16H2O

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
143
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
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
144
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 NH3 by Habers process.

Q13. Which will be adsorbed more readily on


the surface of charcoal and why NH3 or CO2?
Ans: The critical temperature NH3 is more CO2,
therefore NH3 is liquefied more easily than
CO2. Hence NH3 has higher intermolecular
145
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.

146
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
T1>T2>T3.
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?
147
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 O2, H2, CO, Cl2, NH3 or
SO2 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?

148
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.

149
5. Write two applications of catalyst in
Industry.
6. Explain cleansing action of soap.
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.

150
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 NH3
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
2SO2 g + O2 g NO
g
2SO3 g

2. Define Kraft temperature (TK) and critical


Micelle concentration (CMC).

151
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?

152
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
x
1. Draw a graph between log
m 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.
153
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.

154
UNIT 06 :
GENERAL PRINCIPLES AND
PROCESS OF ISOLATION
OF ELEMENTS

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.
155
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. Fe2O3, Al2O3, SnO2, MnO2 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


Alumini Bauxite AlOx(OH)3-2x
um Kaolinite ( a form of [ where 0 <
Clay) x<1]
Iron Hematite Fe2O3
Magnetite Fe3O4
Iron Pyrite FeS2
Copper Copper Pyrite CuFeS2

156
Malachite CuCO3.Cu(OH)
2
Cuprite Cu2O
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) , Al2O3 dissolves in concentrated
solution leaving behind impurities.
Al 2 O3 S + 2 NaOH aq + 3H 2 O l 2 Na[ Al (OH ) 4 ] aq

The aluminate in solution is neutralized by passing


CO2 gas and hydrated Al2O3 is precipitated. At this
stage the solution is seeded with freshly prepared
samples of hydrated Al2O3, which induces the
precipitation.
157
2 Na[ Al (OH ) 4 ] aq + CO2 Al 2 O3 .xH 2 O + 2 NaHCO3 aq

The precipitate of Al(OH)3 is filtered, dried


and finally heated to about 1470 K to obtain pure
Al2O3.
Al 2 O3 .xH 2 O 1470
K
Al 2 O3 s + xH 2 O g

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.
4M s + 8CN aq + 2H 2O + O2 g 4[M CN 2 ]

aq + 4OH aq
Where M= Ag or Au

4[M CN 2 ]
2
aq + Zn s [Zn(CN ) 4 ] aq + 2M s

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

158
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.
Al 2 O3 .2 H 2 O Heat
Al 2 O3 + 2 H 2 O

Bauxite Alumina
D
Fe2 O3 .3H 2 O
Fe2 O3 + 3H 2 O

Limonite Ferric oxide

4) Carbonate ores are converted into their


respective oxides by loss of carbon dioxides.
D
CaCO3
CaO + CO2

Limestone Calcium Oxide


CuCO3 .Cu OH 2 D
2CuO + H 2 O + CO2

Malachite

4) It makes the ore porous and hence


easily workable in subsequent stages.
Calcination is usually carried out in a
reverberatory furnace.
159
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.
S 8 + 8O2 8SO2
P4 + 5O2 P4 O10
4 As + 3O2 2 Al 2 O3

4. Ores are generally converted into metallic


oxides.
2 ZnS + 3O2 2 ZnO + 2 SO2
2 PbS + 3O2 2 PbO + 2 SO2
2Cu 2 S + 3O2 2Cu 2 O + 2 SO3

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 ?

160
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
Fe2O3 (s) + 2 Al (s)
Al2O3 + 2 Fe (l) + heat
molen
Q. 3. Free energies of formation (fG) of
MgO (s) and CO (g) at 1273 K and 2273 K
are given below :
fG MgO (s) = 941 KJ/mol at 1273 K
= 344 KJ/mol at 2273 K
fG CO (g) = 439 KJ/mol at 1273 K
= 628 KJ/mol at 2273 K

161
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 :


MgO (s) + C (s) Mg (s) + CO
(g)
G = fG(Products) fGreactant
At 1273 K G = 439 ( 941) = 502 KJ
mol1
At 2273 K G = 628 ( 314) = 314
KJ mol1
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 ?

162
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, Na2
[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 :
O2
Roasted gold ore + CN + H2O
[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 :
M2O (s) + xM1 (s or l) x M (s or l)
+ M1xO (s)

163
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 TS
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 Fe2O3 by carbon is possible ?
Ans. Above 1123 K, carbon can reduce Fe2O3.
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

164
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?
165
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
Al2O3 and MgO curves in Ellingham diagram,
Magnesium can reduce Alumina because the
fGo value of Al2O3 at temperatures below
1623 K, is less negative than that of MgO.
Therefore below 1623 K Mg can reduce Al2O3
to Al. But Magnesium is much costier metal
than Aluminium and hence the process will be
uneconomical.

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
166
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 Go ( DG DH TDS _) becomes more on
0 0 0

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 E0 value for the redox couple Zn2+/
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
167
leaving behind the impurities. This complex
again on heating at higher (450-470K) it
undergoes thermal decomposition giving pure
Nickel.


Ni + 4CO 330 Ni CO 4
350 K

Impure Nickel tetracarbonyl


Nickel
Ni CO 4 450
Ni + 4CO
470 K

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 ZrI4 thus formed is separated. It is
then decomposed by heating over a tungsten
filament at 2075 K to give pure Zirconium.

Zr s + 2 I 2 g 870
ZrI 4 g 2075
K
Zr s + 2 I 2 g

Impure Tungsten Pure


filament

(B) During the leaching process, Au is first


oxidized to Au+ by Oxygen (O2) of the air which
168
then combines with CN- (Cyanide) ion to form the
soluble complex, Sodium dicyanoaurate(I).
4 Au s + 8 NaCN aq + 2 H 2 O + O2 g 4 Na Au CN 2 aq + 4 NaOH aq

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 Zn2+ which combines with CN- ions to
form soluble complex, sodium tetracy
anozincate(II)
2 Na Au CN 2 aq + Zn s 2 Au s + Na 2 Zn CN 4 aq

Thus extraction of Au by leaching with NaCN


involved both oxidation and reduction.

Q.8. Free energies of formation (fG) of MgO(s)


and CO(g) at 1273 K and 2273 K are given below :
fG(MgO)(s) = -941 KJ/mol at 1273 K
fG(MgO)(s) = -314 KJ/mol at 2273 K
fG(CO(g)) = -439 KJ/mol at 1273 K
fG(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


169
1
i) Mg s +
2
O2 MgO s ; D f G 941Kj / mol

1
ii) C + 2 O CO ; D G 439Kj / mol
s 2 s f

The equation for reduction of MgO to Mg by C


can be obtained by substracting equation (i) from
equation (ii). Thus
MgO s + C s Mg s + CO g

D r G +602 KJ / mol

Since rG of the above reduction reaction is +ve;


therefore, reduction of MgO by C is not feasible at
1273 K.
(b) At 2273 K
1
iii) Mg + 2 O MgO ; D G 314KJ / mol
s 2 s f

1
iv) C + 2 O CO ; D G 628KJ / mol
s 2 s f

On substarcting Eq.(III) from Eq.(IV), we have


MgO s + C s Mg s + CO g ; D r G 314 KJ / mol

Since rG 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.

170
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(SiO2) gangue to form easily
fusible calcium silicate (CaSiO3) slag.
D
CaCo3
CaO + CO2

CaO + SiO2 CaSiO3 Slag

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.


171
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,
Na2[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
172
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
173
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?

174
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?

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.
175
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.

176
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

177
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 :


(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.

178
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 Cr2O3 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 fG0 for formation of Cr2O3 is
-540 KJ/mol and that of Al2O3 is -827
179
KJ/mol. Is the reduction of Cr2O3 possible
with aluminium?
5. How can you separate alumina from Silica
in Bauxite ore associated with Silica? Give
equations if any.

180
UNIT 07
THE p-BLOCK
ELEMENTS

Nitrogen family (Group 15 Elements)

Members: Nitrogen, Phosphorous, Arsenic,


Antimony, Bismuth

General electronic configuration:- ns2np3, 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
181
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 NH3 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 down the
group. In terms of basic strength NH3 is more
182
basic than PH3 because in P we have larger size
& vacant d- orbital. Therefore in spite of lone pair
electrons in both cases PH3 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 P4
structure with lesser no of bonds while in later we
have larger no. of bonds with repeating P4 units.

(v) Anomalous character of N:


(a) Because of smaller size N is able to make
P P multiple bonds. This also causes N2 to
remain as discrete molecules and associated by
weak Vander Waals forces. This is why N 2 is
possible but P2 is not. This also causes N2 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 PCl3 & PCl5 both. PCl5 is


unstable because of two longer axial bonds. PCl 3
fumes in moisture.

(vii) Oxo acids:


183
(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 FeSO4 solution followed by
adding 1-2 drop conc. H2SO4 by the side of test
tube below tap water. This makes a brown ring.

(b) P:- Three important oxo acids viz H3PO4,


H3PO3, and H3PO2 . 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 k2O, Al2O3 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


sp3d- hybridized and structure is trigonal
bipyramidal.

OXYGEN FAMILY(Group 16 Elements)

184
MEMBERS:- Oxygen is the 1st element of the
group and other members are sulphur, Selenium,
Tellurium and Polonium.
General Electronic configuration, Valency &
oxidation state: The general electronic
configuration is ns2np4. 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.

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.

185
d) Valency:- Only oxygen is divalent, others are
tetravalent and hexavalent also.

e) Electronegativity: Only oxygen is able in


making effective H- bonding. Hence H2O is a
liquid and H2S 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.

186
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 (ns2np5) 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.
187
(6) Colour - All halogens are coloured . F2
yellow, Cl2 greenish yellow , Br2
red , I2 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.
(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 OF2 and O2F2
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

188
XX , XX3 , XX5 , XX7 (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.
(1) Absence of vacant d- orbital in the
outermost shell.
(2) 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

189
make compounds with highly electronegative
elements like fluorine & oxygen.

3. Important compounds of xenon with its shape,


hybridization & structure :-

sp3d sp3d2

Sp3d3 sp3d2
sp3
OXO- ACIDS
OF PHOSPHORUS

190
OXO- ACIDS OF
SULPHUR

4. The compounds which led to discovery of


inert gas compounds are O2+PtF6 & Xe+ PtF6
5. The xenon fluorides hydrolyse completely &
partially leading to the formation of different
compounds like:-
XeF6 + H2O XeO3 +HF (complete
hydrolysis)
XeF6 + H2O XeOF4 +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,
191
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 MxHy and not
necessarily to indicate that any compounds listed
behave chemically as hydrides.
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 MxHy 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?


192
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.
193
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.
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.
N2 + 3H2 2NH3

06. Complete the following reactions :-


i) XeF6 + H2O --- + ---- ( partial hydrolysis)

194
ii) XeF6 + H2O --- + ---- ( Complete
hydrolysis )
iii) Cl2 + H2O --- + ----
Ans: i) XeOF4 + HF
ii) XeO3 + HF
iii) HOCl + HCl
07. Arrange the following in decreasing order :-
i) NaF, NaI, NaCl,NaBr( Ionic nature)
ii) PH3, NH3, ,AsH3,SbH3 ( Basic Strength)
iii) HF,HBr,HCl,HI ( Acid Strength)
Ans i) NaF> NaCl > NaBr> NaI
ii) NH3> PH3> AsH3> SbH3
iii) HI> HBr> HCl> HI

08. Find hybridization and shape i) XeF 2 ii) XeO3


iii) XeF4
Ans: i) sp3d, Linear
ii) sp3, Pyramidal
iii) sp3d2, Square planar
09. Give reasons
i) H2O is a liquid but H2S a gas.
ii) Ammonia has higher boiling point than
phosphine
ii) Krypton & xenon make compounds.
Ans: i) Hydrogen bond is found in H2O but not in
H2S.
ii) Hydrogen bond is found in NH3 but not in
PH3.
iii) Because they have low ionization energy.
195
10. Write down the chemical reactions that take
place in the manufacture of sulphuric acid by
contacts process.
Ans: i) S + O2 SO2
V2O5
ii) SO2 + O2 SO3
iii) SO3 + H2SO4 H2S2O7
iv) H2S2O7 + H2O 2H2SO4

SOME IMPORTANT QUESTIONS WITH


ANSWERS

Q.1. Why does O3 act as powerful Oxidising


agent ?
Ans: Due to ease with Which it liberates atoms of
nascent oxygen (O3 O2 +0)
2Pbs (S) + 4O3 (g) PbSO4(S) + 4O2 (g)

Q.2. Which forms of Sulphur show paramagnetic


behaviour ?
Ans : In Vapour State sulphurPartly exists as S2
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 ?

196
Ans Due to smallest size and high effective
nuclear charge , readily accept one electron
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 SO2 detected ?


Ans : 1. It has pungent characteristic smell .
2. It decolourises KMn O4 solution
3. It turns acidified K2 Cr2 O7 green

Q.6. Are all the five bonds in PCl5 molecule


equivalent ?
Ans PCl5 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 H3 PO3 is dibasic and H3PO4 is tribasic ?


Ans In H3PO3 only two replacable hydrogen but
inH3PO4 , three hydrogens are replacable .

Q.8. Why is helium used in diving apparatus ?


Ans: Because heliun is very low solubility in
blood
197
Q.9. Give reason for bleaching action of Cl2
Ans Due to oxidation
Cl2+H2O 2HCl+ O
Coloured substance +O colourless
substance

Q10 Write the formula of tear gas .


Ans : CCl3 NO2

Q11. Which aerosol deplete ozone layer ?


Ans C.F.C

FOR BELOW AVERAGE


[01 Mark Question:]

A. Give reasons
01. N2 is relatively inert in terms of reactivity.
02. NH3 is a good complexing agent.
03. O3 acts as a powerful oxidizing agent.
04. NH3 forms hydrogen bond but PH3 does not.
05. Bond angle of NH4+ is higher than NH3.
06. H2S is less acidic than H2Te.
07. H2O is a liquid but H2S is a gas.
08. NH3 acts as a lewis base.
198
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 NCl5 whereas
phosphorous does.
12. N2 is a gas but phosphorous is a solid.
13. N2 is possible but P2 is not,Why?
14. NH3 is more basic than PH33
15. F2 and Cl2 are gases but I2 is a solid
16. NH3 is soluble in water but PH3 is not.
17. PH3 has lower boiling point than NH3.
18. PCl5 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.
199
23. NH3 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. H3PO3 is a diprotic acid.
03. Bond angle in PH3 is less than NH3
04. Noble gases form compound with fluorine
and oxygen only.
05. White P is more reactive than red P.
06. PCl5 is more covalent than PCl3.
07. SO2 is air pollutant.
08. Basic character among the hydrides of
group 15 elements decreases with increasing
atomic nos.
09. H3PO4 is triprotic but H3PO2 is
monoprotic
10. BiH3 is a reducing agent.

200
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. H3PO3 and H3PO2 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.
6. NH3 has higher dipole moment than NF3.
7. Trimethylamine is pyramidal but trisilylamine
is planar.
8. High concentration of ozone can be
dangerously explosive.

201
9. Identify the neutral molecule which is
isoelectronic with ClO-. Is that molecule a
lewis base?
10. PKa(I) for H2SO4 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
1. NaOH +Cl2
2. F2 + H2O
3. PCl3 + H2O
4. PCl5 + H2O
5. C + H2SO4
6. Ca(OCl)Cl+HCl

FOR ABOVE AVERAGE


202
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, N2O5,
XeOF4, XeOF2, H2S2O8.

203
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:
204
1. M-F, M-Cl, M-Br, M-I. (Decreasing order
of ionic nature)
2. F2, Cl2, Br2, I2. (Increasing order of
bond energy)
3. H2O, H2S, H2Se, H2Te. (Decreasing order
of boiling points)
4. NH3, PH3, AsH3, SbH3. (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, HOClO2, HOClO3.
(Increasing order of acid strength)
8. H2O, H2S, H2Se, H2Te. (Increasing order
of acid strength)
9. HClO4, HBrO4, HIO4. (Decreasing order of
acid strength)

205
F. Some more additional questions; (3 & 5
marks each)
1. Explain the process and necessary conditions
involved in the preparation of NH3, H2SO4 or
HNO3.
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 .

206
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 H2SO4 in contaqct process ?
9. How can H2SO4 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 HNO3 .
14. How HNO3 is prepared by ostwalds process
? Write reaction only at diff . stages
15. Balance the following equation :-
(i) I2 + HNO3 HIO3+NO2+H2O (ii) C+
HNO3 CO2 +NO2 +H2O

207
(iii) S + HNO3(conc.) H2SO4 +NO2+ H2O
(iv) P4+ HNO3 (conc.) H3PO4+ NO2+H2O
(V) HNO3 HNO3+ NO+ H2O

UNIT 08
THE d- BLOCK AND
f-BLOCK ELEMENTS
208
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.

209
CHARACTERISTICS OF TRANSITION
ELEMENTS:-

Properties of transition Reason due to


metals
i. metallic in nature High enthalpy of
atomization
ii. show variables Presence of vacant d-
oxidation states. orbitals
iii. complex Small size, High charge
compounds. density
iv. coloured compounds. d-d Transition
v. good catalyst Suitable surface area in
d-orbital
vi. paramagnetic Unpaired electron in d-
compounds. orbital
vii. Interstitial Similar atomic size &
compounds 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 :-
210
Basic Oxide :- Sc2O3,TiO, Due to lowest
Ti2O3, VO,V2O3, MnO oxidation states
,FeO, CuO, CoO, NiO,
Cu2O
Acidic Oxide:- Due to highest
V2O5,Mn2O7,CrO3, OsO4 oxidation states
AmphotericOxide:- Due to intermediate
CuO,TiO2,ZnO,CrO3, oxidation states
Cr2O3,
Mn2O3,MnO2,Mn3O4Fe3O4
Spinel:- ZnFe2O4, Tri & divalent
occupies octa & tetra-
hedral hole
Non stoichiometric Due to defects in
compounds:Fe0.91O or lattice crystal
Fe0.95O
Ionic Halides;All flouoro Due to lower
i.e. CuF2,AgF oxidation states
Covalent Halides:- Due to higher
CuI2,CuCl2,CuBr2,AgCl,Ag oxidation states
Br

Application of d- & f- block elements:-


1.Iron and steel used in construction,as catalyst
in Habers process
2.CrO2 is used in magnetic tapes
3.Ni is in hydrogenation
211
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 HNO3
8.V2O5 is catalyst in contact process
9.Titanium is in nuclear reactions.
10. PdCl2 is in Wackers process.

Differences between Lanthanoids and


Actinoids:-

Actinoids
Lanthanoids
Common oxidation state Common oxidation state
is +3, besides this +2 ,+4 is +3, besides this
+4,+5,+6, &+7 also.+2
quite rare
Have smaller tendency Strong tendency of
of complex forming complex forming
Dont form oxo- ions Do form oxo-ions i.e.
UO2+, PuO2,UO+
Non-Radioactive Except All are Radio-active
Promethium
Compounds are less Compounds are more
basic basic

Important compounds of transition metals:-


212
1.Potassium dichromate K2Cr2O7
Ore:- Chromate FeCr2O4

Preparation:-

4FeCr2O4+ 8Na2CO3 + 7O2 8Na2CrO4+ 2Fe2O3 +


8CO2

2Na2CrO4+ H2SO4 Na2Cr2O7 + Na2SO4


+ H2O

Na2Cr2O7 + 2KCl K2Cr2O7 + 2NaCl

Structure:-

Properties:-

1. Oxidising property:

(a) Iodide to iodine:

213
Cr2O7 2- + 14H+ + 6e- 2Cr 3+ + 7H2O
6I- 3I2 + 6e-
-------------------------------------------------------------
--
Cr2O7 2- + 14H+ + 6I- 2Cr3+ + 3I2 + 7H2O
(b)Ferrous to ferric:

Cr2O7 2- + 14H+ + 6e- 2Cr 3+ + 7H2O


6Fe2+ 6Fe3+ + 6e-
Cr2O7 2- + 6Fe2+ + 14 H+ 2Cr3+ + 6Fe3+ + 7H2O

2.Chromyl Chloride test:-

K2Cr2O7 + 4NaCl + 6H2SO4 2KHSO4 +


4NaHSO4 + 2CrO2Cl2 + 3H2O
Uses:
It is used as an oxidizing agent
For tanning of leather
As disinfectant
In volumetric analysis
In chromyl chloride test.

2. Potassium permanaganate KMnO4

Ore:- Pyrolusite - MnO2

Preparation:-
2MnO2+ 4KOH + O2 2K2MnO4 + 2H2O
4H+ + 3MnO42- 2MnO4- + MnO2 +2H2O
214
Structure:

Below

Properties:-
1.In acidic solutions:-
Iodine is liberated from potassium iodide
10 I - + 2MnO4- + 16 H+ 2Mn 2+ + 8H2O
+5I2

Fe 2+ ion(green) is converted to Fe 3+
(yellow)
Uses:
5Fe 2+ +MnO4 - + 8 H+ Mn 2+ + 4H2O + 5
Fe3+

2.In neutral or faintly alkaline solution:-


Oxidation of iodide to iodine
2MnO4-+ H2O + I- 8MnO2 + 6SO4 2- +
2OH-

Uses:-
As disinfectant
As oxidizing agent
For qualitative detection of halides,
sulphites, tartarate
215
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) d1-10 ns1-2
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
216
configuration is (n-2) f1-14 (n-1)d 0-1 ns2
2. For Some of first row of transition
elements the E o value are

V Cr Mn Fe Co Ni Cu
- - -1.18 -0.44 -0.28 -0.25 +0.34
1.1 0.91v v v v v V
8v

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 K2Cr2O7 turns


yellow on adding Na OH ?
Ans : It changes to Cr O4-2 ions which are yellow
in colour .
Cr2O7-2+2OH-1 2CrO4-2 yellow + H2O

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

217
due to force of attraction between them
and metal ions .
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 : 4FeCr2O4 + 16 NaOH + 7O2 8 Na2CrO4
+ Na2SO4+ 2Fe2O3
2Na CrO4 + 2H2SO4 + (Conc)
Na2Cr2O7 + H2O + Na2SO4
Na2Cr2O7 + 2KCl K2 Cr2 O7 + 2 NaCl
(i) 6Fe +2 + Cr2 O7-2 + 14 H+ 6Fe+3 + 2Cr+3
+7H2O

green
(ii) 3H2S + Cr2 O7-2 + 8H+3S+ 2Cr+3 + 7H2O

2.Describe the preparation of KMnO4 . How


does the acidified permanganate Soln. reacts
with (i) Iron (ii) Sulphurdioxide (iii)Oxalic
acid ?Write the ionic eqn for the reactions
Ans : 2MnO2 + 4KOH + O2K2MnO4 + 2H2O
218
MnO4-2 MnO4-1 +e-
(a) [ Fe +2 Fe +3 + e-]x 5
5e-+8H+ MnO4-1 Mn+2 + 4H2O
5 Fe +2 + 8H+ MnO4- 5Fe+3 + Mn+2+ 4H2O

(b) 2KMnO4 + 2H20 +5SO2 K2SO4 + 2MnSO4 +


2H2SO4
-
COO
- 2CO2 + 2e x 5
COO
{5e- + 8H+ + MnO4-1 Mn +2 + 4 H2O) }x
2
16 H+ + 2 MnO4 -1 + 5C2O4-2 5CO2)2 +
2Mn+2 + 8H20

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 :-

219
(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 V2O5 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 ?
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 .

220
(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

221
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 + 4H20
(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 .
222
Above Average : 01 mark
(i)Why is K2Cr2O7 generally preferred over
Na2Cr2O7 in a volumetric
analysis .Give reason .
Ans : It is because Na2Cr2O7 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 ?
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.


TiCl4+H2O -----------+----------
Ans : TiO2+4HCl

(v) Which trivalent cation is largest in lanthanoid


series ?
Ans La+3

223
Marks 02
(1) Write an equation in ionic form to
represent oxidizing action of Cr2 O7-
2
ion in acidic
Medium and draw its structure . Draw
structure of CrO4 -2 also .
Ans- ionic equation 6 e- + 14 H+ + Cr207-
2
2Cr+3 +7H2O

(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 MnO4-1 + 5 Fe +2 + 8H+ Mn+2 +5Fe+3
+4H2O
The colour of KMnO4 becomes coloursless and
Fe+2 is oxidized to Fe+3

Above Average 03 Marks


224
(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

************************

UNIT -09
CO-ORDINATION
COMPOUND

STUDY MATERIAL
225
1 MARK & 2 MARKS QUESTIONS
Q. 1. A cationic complex has two isomers A &
B. Each has one Co3+, five NH3, one Br and
one SO42. A gives a white precipitate with
BaCl2 solution while B gives a yellow
precipitate with AgNO3 solution.
(a) What are the possible structures of the
complexes A and B ?
(a) Will the two complexes have same
colour ?
Ans. (a) [CO (NH3)5 Br] SO4 and [CO
(NH3)5 SO4] Br
(b) NO
Q. 2. FeSO4 solution mixed with (NH4)2SO4
solution in 1 : 1 molar ratio gives the test of
Fe2+ ion but CuSO4 solution mixed with
aqueous ammonia in 1 : 4 molar ratio does
not give the test of Cu2+ ion. Explain why ?
Ans. When FeSO4 and (NH4)2SO4 solution are
mixed in 1 : 1 molar ratio, a double salt is
formed. It has the formula FeSO4 (NH4)2SO4
. 6 H2O. In aqueous solution, the salt
dissociates.

226
When CuSO4 and NH3 are mixed in the molar
ratio of 1 : 4 in solution, a complex
[Cu (NH3)4] SO4 is formed.
Q. 3. If to an aqueous solution of CuSO4 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 (H2O)4]2+ + 4 NH3 [Cu
(NH3)4]2+ + 4 H2O
deep blue
While in second case, its colour will change to
yellow.
[Cu (H2O)4]2+ + 4 Cl [CuCl4]2+
+ 4 H2O
yellow
Q. 4. A, B and C are three complexes of
Chromioum with the empirical formula
H12O6Cl3Cr. All the three complexes have
Cl and H2O molecules as the ligands.
Complex A does not react with conc.
H2SO4. Complexes B and C lose 6.75% and
13.5% of their original weight respectively

227
on heating with conc. H2SO4. Identify A, B
and C.
Ans. Data suggests that the complexes are
hydrate isomers.
As comples A does not lose any molecule of
H2O on heating which shows that no water
molecule of H2O is outside the co-ordination
sphere.
A = [Cr (H2O]0] Cl3
As B loses 6.75% actual loss in wt.
= 266.5 = 18 au
B = [Cr (H2O)5 Cl] Cl2 . H2O
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 (H2O)4 Cl2] Cl . 2 H2O
SCN F
Q. 5. Fe3+ (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 = [FeF6]3
228
IUPAC name of A = trithiocyanato iron (III)
E. C. of Fe (III) = d5, unpaired es = 5
Spin only magnetic moment = 5(5 + 2) B. M.
= 5.916 B. M.
Q. 6. A complex is prepared by mixing
COCl3 and NH3 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 Kf = 1.86 C/m.
Ans. The oretical Tf = Kf . m
= 1.86 0.1
= 0.186
observed Tf = 0.372
As observed Tf is double of the theoretical
value this shows that each molecule of the
complex dissociates to form two ions.
formula is :
[CO (NH3)4 Cl2] Cl
Q. 7. How t2g 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
229
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 NiCl2. 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)

230
(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 Al2O3 is
colourless when pure but when various M3+
transition metal ions are present in trace
amounts various gem stones are formed. Ruby
is Al2O3 containing about 0.5 1% Cr3+.
Q. 10. How many EDTA (lethylendiamine
tetra acetic acid) molecules are required to
231
make an octahedral complex with a Ca2+
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 (PH3P)3 RhCl. In
this Rh has dsp hybridisation and square
planar shape.
Q. 12. Which vitamin is a complex compound
of cobalt ?
Ans. Vitamin B12 is a complex compound in
which central metal atom is cobalt.
Q. 13. Write the IUPAC name of [CO (NH3)4
B12]2 [ZnCl4].
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 AgNO3 ?
232
Ans. This is because if AgNO3 is used Cu will
displace Ag+ from AgNO3. 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 (NH3)4 (H2O) a} Cl2 (b) K2 [Zn (OH)
4]
(c) K3 (Al (C2O4)3) (d) [Co (NH3)3 (CO) 3]
Cl

Q2 Write the IUPAC name of the following


Co-Ordination compound.
(a)[ Pt (NH3)2 Cl (NO2) Cl(NO2)] (b) K3
[Cr(C2O4)3]
(c)[Co(NH3)5CO3 ] Cl (d) [ Co Cl2 (en)2] Cl
Ans-
a)Dammie chloridonitrito N-Platinum(II)
233
b) Pottassium trioxalato chromate (III)
c)Pentaamine carbonato cobalt (III) chloride
d) Dichloroidobis (ethane -1, 2 diamine)
cobalt (III) chloride

Q.3 [NiCl4]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 [NiCl4]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 (NH3) 6]3+ is an inner
oriental complex when [Ni (NH3)6]2+ is an
outer oriental
Complex.
Ans : In [Co (NH3) 3+ Complex d2 SP3
hybridisation involved forming inner d orbital
Where as In Ni (NH3) 6 complex involved
in SP3d2
Hybridiasation forming outer d orbitals
Q5 What is meant by unidentate , didentate
and ambidentate ligands . give two
example of each

234
Ans: When a legend is bound to a metal ion
through a single diner atom, is said to be
unidentate for ex- Cl-, H2O & NH3
When a legande can bound through two
donor atoms as in H2N CH2 CH2NH2, or
C2 O4 (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-NO2, 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. MgCl2. 6H20
, Mohrs salt FeSO4 (NH4) 2 SO4 . 6
H20 & Potash alum K2SO4 Al2(SO4) 3
.12H2O etc dissociatic into simple
ions when dissolve in water .
However when complex ions such as [Fe
(CN) 6]4 of
K4 Fe (CN) 6 do not dissociate into Fe2+
and CN- ions

235
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 Na2 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 (NH3)2cl2]

236
(b) Optical isomerism d & l of [Co
(en)3]3+
(B) Structural isomerism
(a) Linkage isomerism [ Co (NH3) 5
(NO2)]Cl2
(b) Co ordination isomerism
[ Co(NH3)6] [Cr(CN)6]
(c) Ionisation [Co(NH3)5 SO4] Br &
[Co(NH3) 5 Br ] SO4
(d)Solvate isomerism [Cr (H20) 6 ] Cl3 .

Q10 (Fe ( H2O)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 d2 sp3
hbridisation shows weekly paramagnetic
where as in presence of H2O in
(Fe(H20)6)3+ weak ligand and five electron
are unpaired and forms SP3 d2
hybridization shows strongly
panamagnetic .

Q11 Calculate the ovelall complex


dissociation equilibrium constant for cu
(NH3)4 2+ ion , given that 4 for this
complex is 2.1x10 13

237
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(NH3)4 (Cl)
(NO2) ] 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 (NH3)5Cl]
Cl2 complex
238
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 t2g 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 FeSO4 Soln mixed with
(NH4) 2SO4 soln in 1:1 molar ratio given
the test of Fe2+ ion but cuso4 soln mixed
with aqueas ammonia in 1:4 molar ratio
does not given the test of Cu2+ ion

239
8. out of given two Co-ordination compound
which is Chiral & why explain
(a) cis [CrCl2 (ox)2]3- (b) [Cr Cl2(ox)2]3-
9. Give evidence that
[Cu (NH3)5Cl SO4 and [Co (NH3)5 SO4]Cl are
ionization isomerism .

AVERAGE & ABOVE AVERAGE


STUDENTS
01 Marks question
1. [NiCl4]2- paramagnetic which [ Ni(C04)] 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 )2Cl2] Cl
6. Discuss role of Co-ordination compound in
the field of medicinal chemistry
7 Discuss nature of bonding in (Ni(CO))4
240
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 [CuNH3)6] Cl2
(b) Amongst the following which one has the
highest magnetic moment value?

3. [Fe (CN6] 4 and [Fe (H20) 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.

241
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


CoCl3 4NH3. 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
7. Name two complexes which are used in
medicines.

***********
UNIT -10
HALO ALKANE AND HALO
ARENE
242
FOR AVERAGE
01 mark questions
Q.1. Write down the IUPAC name of the following
organic compounds: -
(a) CH3CHCl2
(b) CH3CH2CH2CH(C(CH3)3)CH(I)CH2CH3
(c)
H5C2 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)
C2H5
CH Br
CH3 CH3
(b) CH3CH2CH(CH3)CH(Cl)CH3
243
( c) CH2= 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) CH2=CH-CH2Cl
( b) [-CF2-CF2-]n

Cl

(c ) CCl3CH
Cl

(d) [-CH2 CH - ]n

Cl

Q.4.Which one of the following has the highest


dipole moment, and
why?
(a) CH2Cl2
(b) CHCl3
( c) CCl4
Ans:- CH2Cl2 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
244
dipole moment. In CHCl3 and CCl4, 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 Cl2 in the presence of
U.V. light OR is heated.
d) Chlorobenzene is treated with acetyl
chloride in presence
e)of anhyd. AlCl3
f) Chloroform is slowly oxidized by air in
presence of light.
Ans:-
a) CH3 Cl + KCN CH3 CN +
Kcl
Methyl cyanide

b)
Cl + HOH H+
OH + HCL
Phenol

U.V. Light or
( c) CH3 CH = CH2 + Cl2
CH2 CH= CH2 + HCL
Heat
Cl
Allyl Chloride
245
O Cl
Cl
(d) anhyd.
COCH3
Cl + CH3-C-Cl +
AlCl3
COC
H3
Air
1
(e) CHCl3 + 2 O2 COCl2 + HCl

FOR AVERAGE
2 marks questions

Q.1. Which are the possible mono chloro structural


isomers expected to be formed
on free radical mono chlorination of
(CH3)2CHCH2CH3.

Ans:- There are four possible product as follows

CH2(Cl) CH CH2 CH3,

CH3
(CH3)2 C CH2 CH3,

CH3
246
(CH3)2 CH CH CH3 and

Cl

(CH3)2 CH CH2 CH2Cl

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) CH3CH2CH2CH2Br, CH3CH2CHBrCH3
, (CH3)3C Br
(b) CH3Br, CH2Br2, CHBr3

Ans:
(a) (CH3)3C-Br< CH3CH2CHBrCH3<
CH3CH2CH2CH2Br

Boiling point increases.

Boiling point decreasing on increasing


the branching

247
(b) CH3Br< CH2Br2< CHBr3

Boiling point increases


Boiling point increases due increasing
molecular mass.
Q.4. Write the mechanism of the following
reaction:
Frideal Craft Acylation ( in Chlorobenzene)
Ans:-
Reaction Cl Cl
Cl
Anhy. COCH3
+ CH3COCl +
AlCl3
COCH3
Reaction Mechanism:
O Cl

CH3-COCl + AlCl3 CH3C+


+
-AlCl4-
Cl Cl
+
CH3CO
H
+AlCl4- + HCl
CH3CO
- AlCl3
248
Q.5. Explain why: -
(a) H2SO4 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) H2SO4 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. KMnO4

249
a) CH3CH=CH2 + HBr A
B
C

b) CH3 CH3
Na/Dry ether
Mg
CH3 CH3 RX
D
H2O
CH3 CH3

E
Ans:-
(a) A CH3CH2CH2Br
B CH3CH2CH2OH
C CH3CH2COOH

(b) R (CH3)3C-
D (CH3)3CMgX
E (CH3)3CH
Q.2. Write down the IUPAC name of the following
organic compounds:

(a) Br

Br

250
b) O- Br- C6H4CH(CH3)CH2CH3
c)(CH3)3CCH=CHC6H4I-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. H2SO4 1. Br2


a) CH3CH2OH CH2=CH2 CH=
CH
160-1700C 2.Alc.KOH
NaNH2
C2H5Cl
CH3CH2C= CH
CH= CNa

NO2
NO2
b) Conc.HNO3 Br2/ CCl4

Br

CH3 CH2Cl
251
c) U.V.Light

Q.4.Identify the following pair of structures :


a) CH3 CH3

HO H HO
H

H Cl Cl H

C6H5 C6H5

b) Br H H
Br

CH3 CH3 CH3


CH3
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: -
252
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

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)CH3 CH=C (Cl) CH2 CH (CH3)2 (b)CH3CH


Br CH Cl CH3

253
(c) CH3 C (Cl) (C2H5) CH2 CH3 (d) CH3
C(P-Cl-C6H4)2 CH (Br)CH3

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) CH2-Cl

CH2-Cl
Cl

C2H5

Cl
(c) Br Cl (d) CH3-CH
Cl
254
COCl

(e)

FOR ABOVE AVERAGE


02 Marks
Q1. Write the structure of the major organic
product in each of the following reaction.

(a) Br
+NaSH

CH2Br

Cl

(b) + C2H5ONa +
ethanol
Heat

O2N NO2

Ans:- Br OC2H5
(b)
(a)
CH2SH NO2
O2N
255
Q2. Give the Preparation and uses of chloropicrin
chlorotone.

Q3. Explain the formation of two products in the


following reaction.

CH3Ch2Cl + H2O CH3CH=CH CH2OH +


CH3 Ch(OH)CH=CH2
Q4. (a) Write all Possible isomers of C7H7Cl
(b) Write the Structural formula of optical
isomer.
Of the component having molecular formula
C4H9Br.

Ans:- (a) 4 isomers


(b) H

CH3-C-C2H5

Br

256
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.
4 nitro chlorobenzene, 2, 4 dinitro chloro
benzene, and 2, 4, 6 trinitro chloro benzene with
Ch3ONa

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 CH3 C = CH2
|
CH3

B CH3 C(OH) CH3


257
|
CH3

C CH3 C(Cl) CH3


|
CH3

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 SN1 and SN2 reaction.
(a) The four isomeric bromobutone
(b) C6H5CH2Br, C6H5CH(C6H5)Br,
C6H5CH(CH3)Br, C6H5C(CH3)C6H5Br

Ans:-

CH3CH2CH2CH2Br<(CH3)2CH CH2Br<CH3 CH2


CH(Br)CH3<(CH3)3C-Br
258
Reactivity towards SN1 Reaction

CH3CH2CH2CH2Br>(CH3)2CH CH2Br>CH3 CH2


CH(Br)CH3>(CH3)3C-Br

Reactivity towards SN2 Reaction

(b) Reactivity towards SN1 Reaction

C6H5C(CH3)
(C6H5)Br>C6H5(CH(C6H5)Br>C6H5CH(CH3)Br>C6
H5CH2Br
Reactivity towards SN2 Reaction

C6H5C(CH3)
(C6H5)Br<C6H5(CH(C6H5)Br<C6H5CH(CH3)Br<C6
H5CH2Br

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

259
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.

260
UNIT 11
ALCOHOLS, PHENOLS
AND ETHERS

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)

261
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 CH3 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.

262
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 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 :

263
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
264
ring. As a result, the electron density becomes
higher at o- and p- position 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 :
+
COC
|
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
265
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. H2O + H+ H3O+
Step (i) : Protonation of alkene to form
carbocation by electrophilic attack :
H H
C = C + H O
+
H C C
+
+ H 2O

Step (ii) : Nucleophilic attack of water on


carbocation :
H H
C C +
+ H 2O C C O +
H
H

Step (iii) : Deprotonation to form an


alcohol :
H H OH
C C O
+
H + H 2O C C + H 3O
+

266
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.

267
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 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.
268
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
269
| | | |
H-C-C-O-H H- C C -
OH2
| | | |
HH H H

Ethyl alcohol
(Protonated alcohol)
-H2O

HH
| |
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+
H3CCH2 - +OH2
| |
HH
Ethylacohol
(Pronated alcocol)
270
H H
HH HH
| |
| | | |
H-C-C-O-H + H3CCH2-O+H2
H-C-C-O+-C-C-H
| |
| | | | |
HH
H HH HH

-H+

HH HH

| | | |

H-C-C-O-C-C-H

| | | | |

H HH HH

Q3. Discuss Williamson systhecis.

271
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.

CH3
CH3
|
|
H3 C O-Na+ + CH3 Br H 3C O
C-CH3 + NaBr
|
|
CH3
CH3

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.
272
CH3
|
H3C-C-Br + Na+OCH3 H3C-
C=CH2+NaBr+CH3OH
| |
CH3 CH3
( 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:-

Q.1. Give the IUPAC name of CH3O CH


CH3

273
CH3
Ans:- 2- Methoxypropane

Q.2. Give the IUPAC name of C6H5--O CH2


CH2 CH CH3
1 2 3 4
CH3
Ans:- 3- Methyl butoxy benzene

1 CH2OH

Q.3. Give the IUPAC name of H3C -- CH


CH2 CH-- CH - CH3
6 5
4 3 2
CH3 OH

Ans : - 2,5 Dimethyl hexane 1,3 - diol

Q.4 . Give the IUPAC name of

CH3

CH3 -- C -- OH

CH3

274
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: -
C2H5O - C - C C - H

H H H

Q.7. Write the structure of 2- Ethoxy 3 methyl


pentane

H H
CH3 OC2H5 H

275
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, CHCl3

(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?

OCH3 + HI OH
Ans:-
+ CH3 I

(Anisole) (Phenol)
276
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.

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 : -


277
(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
H3 C H3

C2H5 ONa + CH3 - C - CH3


CH3 -- C -- OC2H5

CH3
CH3
(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.
278
(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 FeCl3?
(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
C5H12O.
(iii) Classify the isomers of alcohols as
Primary, Secondary and
Tertiary alcohols.

279
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?

280
AVERAGE
01 mark questions : -

Q.1. Write down the IUPAC name of


H3C CH3
OC2H5

Q.2. Write down the IUPAC name of


OH
CH3 CH3

Q. 3. Write down the structure of the product of


the following reaction: -
H3C-CH= CH2 H2O/ H+
.

Q.4. Distinguish between


OH
COOH

and

281
Q.5. Distinguish between
O

COCH3 C-
C6H5

and

Q6. Write the structure of the product of the


following reaction: -
O
NaBH4
H3C CH2 - CH- C -H
.

CH3

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.

282
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
(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 :

CH2OH OH
(i)
and
(ii) O

and
283
O H

C C- 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.H2SO4 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.

284
3 marks questions
Q.1. (a) When 3- methyl butan 2 ol is treated
with HBr, then following
reaction takes place
Br

H3C CH CH CH3 HBr


H3C CH CH2 CH3
H3C OH
H3C

(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?

285
(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.
286
Q.3. Distinguish between anisole and phenol?

Q.4. Preparation of ethers by acid dehydration of


secondary or tertiary alcohol is
not a suitable method. Why?

Q.5. Convert Salicylic acid to Aspirin.


Q.6. Predict the product of the following reaction.

OH
CCl4/
OH --

H+
Phenols

Q.7. Predict the major product of acidic catalysed


dehydration of butan-1-ol.

Q. 8.

CH3

287
CH3 -- C O -- CH3 + HI

CH3
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)

CH2-O

(ii) CH3

H3C -- CH2 CH2 O-- CH


CH2CH3

CH3

Q.2. Why anisole undergoes bromination with


bromine in ethanoic acid
even in absence of iron (III) bromide catalyst.
288
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?

CH3 OH
(i) OH (ii)

Q.6. Write Structures of the products of the


following reactions:
O
(i)
NaBH4
CH2-C-OCH3
O
289
(ii)
NaBH4
H3C CH2 - CH-- C HO
.

CH3

3 marks questions: -

Q.1.
(a) Show how the following alcohols prepared
by the reaction of a
suitable are Grignard reagent on
methanol?

(i) H3C CH- CH2OH


.

CH3

(ii) CH2OH

290
(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

+ H3COONa + CH3Br

NO2 NO2

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
291
(ii) Predict the product of the reaction given
below:-

CH3

CH3 -- C -- Br + Na+CH3
..

CH3
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.

292
UNIT 12TH
ALDEHYDE, KETONS AND
CARBOXYLIC ACIDS

293
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 SP3 Hybridised.
The >C=O bond is polar due to the different
electronegativities of the constituent atoms.
Aldehydes (RCHO), ketones(R2C=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

294
2.PREPARATION OF ALDEHYDES:
(a) By oxidation of alcohols

(b) By Dehydrogenation of alcohols

(c) By ozonolysis of alkenes

(d) By hydration of alkynes

295
(e) Rosenmunds reaction

(f) Treatment of acid chloride with


dialkylcadmium gives ketones

(g)From nitriles and esters

This rection is called Stephens reaction.


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.

296
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 (CrO2Cl2) in Cs2 or CCl4 to form
benzaldehyde.

(b) Gatterman- Koch reaction: When a mixture of


CO and HCl gas is passed through benzene in
297
presence of anhydrous AlCl3 + 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
298
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.

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
299
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
300
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:

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)
301
Presence of base catalyses the reaction

b) Addition of sodium
hydrogensulphite( NaHSO3)

c)Addition of alcohols:

d)Addition of ammonia and its derivatives:

302
e) Reduction reactions:
i) Using LiAlH4 or NaBH4 to alcohols

303
iii) Reduction to Hydrocarbons:
Clemmensen reduction

Wolf- Kishner reduction

f) Oxidation :Aldehydes are easily oxidized to


carboxylic acids with common oxidizing agents
like KMnO4, K2Cr2O 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.

304
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.

Fehlings test: Fehling reagent= fehling solution


A (aq CuSO4) + Fehling solution B( Alk. Sodium
potassium tartarate)

Haloform reaction: Aldehydes and ketones


Having atleast one CH3 Group linked to the
carbonyl carbon give this reaction.

305
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.

Aldols have both -OH group and carbonyl group.


306
ii) Cross aldol condensation:

iv) Cannizaros reaction:

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.
307
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

308
secondary alkyl groups also get oxidized, only
tertiary group remains unaffected.

c)From nitriles and amides :

d) From
Grignard reagent:

e)From acyl halides and anhydrides :

f) From esters :
309
(ii) PHYSICAL PROPERTIES:
a)Lower members of carboxylic acids (upto 9-C)
are liquids at room temperature, and have
foul odour.
b) High
er members are solid and odourless.
c)Carboxylic acids remain associated (dimer)
form in vapour state and in aprotic
solvents(like organic solvents).

d) In
protic solvents like H2O 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.

310
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.

311
Higher the Pka 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 EWGs is as follows:

Closer the presence of EWG to the carboxylic


group more is the acidic strength.

312
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

(iii) Formation of acyl chlorides

Thionyl chloride (SOCl2) method is preferred


because both the by-products are gaseous as a
result pure product is obtained.
(iv) Reaction with Ammonia

313
(V) Reduction

(v) Sodalime decarboxylation

(vi) Kolbes electrolysis

314
(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) Aro
matic carboxylic acids undergo electrophilic
substitution reaction. The COOH group
attached to benzene ring is a deactivating
group and is m-directing.

315
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.

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.

316
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.

317
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 : H2 in the presence of Pd (supported
over BaSO4) and partially poisoned by
addition of Sulphur or quinoline.
O O
|| Pd/BaSO4 ||
R C Cl + H2 R
C H + HCl
+ 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.

318
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 CH3CO-group
to show the iodoform test.)
Ans. Acetophenone (C6H5COCH3) contains
the grouping (CH3CO attached to carbon) and
hence given iodoform test while
benzophenone does not contain this group and
hence does not give iodoform test.
C6H5COCH3 + 3 I2 + 4 NaOH
CHI3 + C6H5COONa + 3 NaI + 3 H2O
Acetophenane Iodoform
I2/NaOH
C6H5COC6H5 No reaction

319
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 Cu2+ + 50 H
RCOO + Cu2O 3 H2O
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 CH3COOH
does ?
Ans. CH3COOH 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.
Ans. The formation of esters from a carboxylic
acid and an alcohol in the presence of acid
catalyst in a reversible reaction.
320
H2SO4
RCOOH + ROH RCOOR +
H2O
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 NO2 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 ?
321
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.
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.

322
(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. CuSO4
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 CH3CO-group, hence
gives positive iodoform test.
3-pentanone does not have a CH3CO-group,
hence does not give positive iodoform test.
323
Iodoform test I2/NaOH
O
|| I2
CH3CH2CH2 C CH3 + NaOH
CHI3
(yellow ppt.)
O
||
CH3 CH2 C CH2 CH3
No rxn.
Q. 17. 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. 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.

324
O
||
C O

H
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
325
Cannizaro reaction which do not possess
hydrogen atoms.
Q. 22. Arrange the following in order of
increasing boiling points :
CH3CH2CH2OH, CH3CH2CH2CH3,
CH3CH2 OCH2CH3,
CH3CH2CH2CHO
Ans. CH3CH2CH2CH3 < C2H5OC2H5 <
CH3CH2CH2CHO < CH3 (CH2)2 OH
(hydrogen) (ether) (aldehyde)
(alcohol)



increase in bond polarity.
Q. 23. Why does solubility decreases with
increasing molecular mass in carboxylic
acid ?
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-
326
atom and +ve charge is at more
electronegative O-atom.
Resonance is not so effective.
+ + +
O
O O O O

In carboxylate ion, ve charge is delocalised


on two electronegative O-atoms hence
resonance is more effective.

R C
O

O
R C

Q. 25. There are two NH2 group in


O

O
] R C
O

semicarbazide. However, only one is


involved in formation of semicarbazones.
Why ?
Ans. Although semicarbazide has two NH2
groups but one of them is involved in
resonance.
O O
O
|| + | .. |
+
H2N C NH2NH2 H2N = C
NH NH2 H2 N C = NH NH2
327
As a result, e density on one of the NH2
group is reduced and hence it does not act as
nucleophile.
Lone pair of other NH2 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.
Ans. Acetophenone is a ketone while all others
are aldehydes, therefore it is least reactive. In
p-tolualdehyde, there is methyl group (CH3) 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 H
O

H C C H H C = = C e tc .
H H H

On the other hand, in p-nitrobenzaldehyde, the


NO2 gp is a powerfuil electron-withdrawing
328
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.
CH3CHO, CH3CH2OH, CH3OCH3,
CH3CH2CH3.
Ans. The molecular masses of all these
compounds are comparable :
CH3CHO (44), CH3CH2OH (46),
CH3COCH3 (46), CH3CH2CH3 (44).
CH3CH2OH 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
329
stronger in CH3CHO than in CH3OCH3,
hence boiling point of CH3CHO (293 K) is
much higher than that of CH3OCH3 (249 K).
Further, molecules of CH3CH2CH3 have only
weak Vander Waals forces while the molecules
of CH3OCH3 have little stronger dipole-
dipole interactions and hence the boiling point
of CH3OCH3 is higher (249 K) than that of
CH3CH2CH3 (231 K). Thus the over all
increasing order of boiling points is :
CH3CH2CH3 < CH3OCH3 < CH3CHO <
CH3CH2OH
Q. 3. Which acid of each pair shown here
would you expect to be stronger ?
CH3CO2H or FCH2CO2H

Ans.

increases the electron the electron


density in the lizes the carboxylate the
carboxyate

330
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 FCH2COO
ion over CH3COO ion FCH2COOH is a
stronger acid than CH3COOH.
Q. 4. Which acid is stronger and why ?
F3C COOH or
H3C COOH

Ans. F3C C CH3


C

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.

331
Therefore due to greater stability of F 3C
C6H4 COO (p) ion over CH3
C6H4COO (p) ion, F3C C6H4 COOH
is a much stronger acid than CH3 C6H4
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.

+ I effect increases

332
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 CH3
5 4 3| 2|
1
CH3CH2CHO + CH3CH2CHO
CH3CH2 CH CH CHO
Propanal Propanal 3-hydroxy-2-
methyl pentanal
(ii) Propanal as electrophile and butanal as
nucleophile.
OH
CH2 CH3
5 4 3| 2| 1

333
CH3CH2CHO + CH3CH2CH2CHO
CH3CH2CH CH CHO
Propanal Butanal 2-ethyl-3-
hydroxy pentanal
(Electrophile) (Nucleophile)
(iii) Butanal as electrophile and propanal as
nucleophile.
OH
CH3
6 5 4 3|
2| 1
CH3CH2CH2CHO + CH3CH2CHO +
CH3CH2CH2 CH CH CHO
Butanal Propanal 3-
hydroxy-2-methyl pentanal
(Electrophile) (Nucleophile)
(iv) Butanal both as nucleophile as well as an
elecrophile.
OH
CH2CH3
6 5 4 3 |
2| 1
CH3CH2CH2CHO + CH3CH2CH2CHO +
CH3CH2CH2 CH CH CHO
Butanal Butanal 2-ethyl-3-
hydroxy hexanal
(Electrophile) (Nucleophile)
334
Q. 7. 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.

335
COO
CHO COO H
[Ag (NH3)2]+ OH
C 2H
[O] 5 C H
COO H 2 5

Ag +

Tollens reagent

Silver
mirror 2-ethyl benzoate 2-ethyl benzaldehyde
1, 2-benzene dicarboxylic acid
(M. F. C9H10O)

2, 4-dinitrophenyl
hydrozene
NO 2

CH = NNH NO 2 + H 2O

C 2H 5

2, 4-DNP derivative

Q. 8. Explain why o-hydroxybenzaldehyde is


a liquid at room temperature while
336
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
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 :
O
CH
H+
3

CO CH
Br2
3

I A + B C
(C17H12O)
NaOh

337
Ans. The given compound (I) contains CH3CO
gp and hence in the presence of Br2/NaOH
undergoes haloform reaction to give sodium
salt of carboxylic acid (A) and bromoform
CHBR3 (B). (A) on protonation gives the
corresponding acid (II). (II) being a -
ketoacid readily undergoes decarboxylation to
give 2-methylcylohexanane (C).
O O
CH CH
Br2/NaOH
3 3

COCH 3 COO

HI +
CHBr3 +

Haloform reacn (B)

(A)

H+ ( CO2)


Dexcarboxylation

(A -keto acid) 2-
methyl cyclo hexanone
(C) M. F. =
C7H12O
338

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

Ans:- (i)

HOHH O
| || | | ||
H-C-C-C-C-C-H
| | |
H H H

(ii)

CH3 O CH3
| || |
H3C-C ----C-C-CH3
| |
H H

(iii) CH3-CH-CH2-CHO
339
Ch3
(iv) CH3-CH-CH2-C-CH3

Cl O

(v) CH3 - CH - CH - CH2 - COOH

C6H5 - Br

(vi) CH3 - -CHO

(vii) CH3-C-CH=C-CH3
|| |
O CH3

2 Write IUPAC Names of the followings:-

(i) CH3 CHO


(ii) O
CH3

(iii) (CH3 )2 CHCOCH((CH3 )2


(iv) CH 3 CH (OCH3) CHO
(v) CH3-CH-CH2CH2-CHO
|
CH3
340
(vi) PHCOPH
(vii) CH3-CH2-CH-CH2-CH-CHO
| |
Br CH3
(viii) C6H5CH=CH-CHO
(ix) (CH3)3-CCH2COOH

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) CH3-CHO
(b) CH3-CH2-OH
(c) CH3-O-CH3
(d) CH3-CH3
(e) CH4

341
ANS:- CH4 < CH3-CH3<CH3-O-CH3<CH3-
CHO<CH3-CH2-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
342
(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
|

+ NaHCO3 + CO2 + H 2O

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
|| ||

343
Ans:- CH3-CH2-CH2-C-CH3, CH3-CH2- C-
CH2-CH2
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. CH3OH, (CH3)3COH, (CH3) 2-CH-OH,


CH3CH2OH
ii. (CH3) 3CCOOH, CH3COOH, (CH3) 2-
CHCOOH,HCOOH

Ans:- (i) (CH3)3COH<(CH3) 2-CH-OH<


CH3CH2OH< CH3OH

(ii) (CH3) 3CCOOH< (CH3) 2-CHCOOH<


CH3COOH< HCOOH
9 Arrange the following acid derivatives towards
increasing order of nucleophelic Substituion
reaction

(a) RCONH2, RCOOCOR, RCOCI &


RCOOR

344
(b) Acid derivative unlike aldehyde and
ketones show mucleophic substitution

Ans:- (a) RCONH2 < 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 (CrO3)
CrO3
Ans:-R-CH-R R-C-R
| [O]
OH O
Corresponding Ketone is formed.

345
03. Ethyne treated with H2O in the presence of
H2SO4 & HgSO4

H2O
Ans: CH = CH CH3-CHO
H2SO4-HgSO4
Corresponding Acetaldehyde is formed.

04. Toulene is treated with chromyl chloride


(CrO2Cl2) followed by hydrolysis.
Ans:
CH3 CHO
| (i) CrO2Cl2 |

(ii) H2O

Corresponding Benzaldeiyde is formed.

05. Propanone is treated with HCN


Ans:-
CN

|
CH3-C-CH3+HCN CH3-
C-CH3
||
|

346
O
OH

Corresponding Cyanohydrim of problem is


formed.

06. Ethanal is treated with NaHSO3.


Ans:-
CH3CHO+NaHSO3
CH3-CH-SO3H

ONa

CH3-CH-SO3Na

OH
Corresponding Sodiumbisulphite of ethanol
is formed.

07. Proponal is treated with Methyl magnesium


bromide.
Ans:-

H
347
|
CH3-CH2CHO+CH3MgBr
[CH3CH2-C-OMgBr]

|
CH3
H2O
CH3-CH2CH-OH

|
CH3

Corresponding Butane 20%


is formed.

08. 3- Pentanone is treated with KMnO4 at high


pressure
Ans:- O
|| KMnO4
CH3-CH2CHO-C-CH2CH3 CH3-
CH2-COOH+CH3-COOH
High Press

Corresponding A mixene of ethonoic acid and


propanoic and propanoic and is formed

348
09. Ethanal is treated with dil NaOH.
Ans:-
dilNaOH
2CH3CHO CH3-CH-CH2-CHO
CH3-CH=CH-CHO
|
-H2O
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
CH2OH
+
Disproportionation rection takes place giving
rise to a mixture of salt of Benzoic acid and
Benzylalcohol.

10. Acetic acid is treated with PCl5.


Ans:-
PCl5
CH3COOH CH3COCl
Acetylchloride is formed.

349
11.Benzoic acid is treated with NH3
Ans:-

COOH (i) NH3


CONH2
(ii)

Benzamide is formed.

11. COMPLETE THE FOLLOWINGS

(i) O
||
C-Cl H2 CHO

Pd- BaSO4

1. AlH(i-Bu)2
(ii)CH3-CN
CH3CHO
2 H2O

NH2 NC

(iii) CHCl3 + alc. KOH

350
COC2H5
O
(iv) || AlCl3
+ C2H5-C-Cl
CS2

Hg2+,H2SO4
(v) CH3-C = C-H H2O CH3COCH3

(vi)
H
Conc NaOH HCOONa + CH3OH
2 C =0

O
(vii) || NO2
NO2
| |
+ H2N -NH =N-NH-- -
NO2

NO2

(viii) CH2-CH2-CH3

351
COH
1. KMnO4
KOH
2. H2O

I LiAlH4
(ix) CH3-COOH CH3CH2OH
2. H3O+

12. Transformation:

i. Ethanol to butane 1,3 diol;


Ans:-
H
[O] dil
NaOH |
C2H5OH CH3CHO CH3-
C-CH2-CHO

OH

[H]

CH3-CH-CH2-CH2-OH

|
352
OH

Butane 1,3,-diol

ii. 3 nitro brome benzene to 3 - nitro benzoic


acid
Ans:- NO2 NO2
NO2 NO2
| | |
|
Mg/dryether CO2

Br MgBr
C-O-MgBr COOH
||

O 3- Nitro

Benzoic acid

(iii) Butanal to butanoic acid


Ans:-
[O]
CH3-CH2-CH2-CHO CH3-
CH2-CH2-COOH
KMnO4

353
(iv) Acetic acid to Ethan amine
Ans:- NH3 (i)
LiAlH4
CH3COOH CH3CONH2
CH3CH2NH2
(ii) H2O

(v) Bromo benzene to benzoic acid


Ans:-
O
|| COOH
Br MgBr
C-OMgBr |
Mg CO2
H2O
Dry ether

(vi) Benzene to m-nitro acetophenone


Ans:-
NO2
NO2
Conc conc
HNO3-H2SO4
CH3COCl
AlCl3(Anhy)
COCH3
354
(vii) Benzoic acid to benzaldehyde.
Ans:- O
||
COOH C-Cl
CHO
PCl5
H2
Pd-BaSO4

QUESTION BANK FOR BRIGHT STUDENTS


Q.1
Complete each synthesis by giving missing
starting material, reagent or products
(i)

(ii)

(iii)
355
(iv)

(v)

(vi)

(vii)

(viii)

(ix)

(x)

356
(xi)

Ans: Try yourself

Q.2
Predict the products of the following reactions:
(i)

(ii)

(iii)

(iv)

ANS: (i)

357
(ii)

(iii)

(iv)

Q.3
Write the structures of products of the following
reactions;
(i)
358
(ii)

(iii)

(iv)

ANS: (i)

(ii)

359
(iii)

(iv)

Q.4
Write structural formulas and names of four
possible aldol condensation products from
propanal and butanal. In each case, indicate

360
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.

(iv) Taking one molecule each of propanal and


butanal in which propanal acts as an electrophile
and butanal acts as a nucleophile.

361
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:

362
Therefore, the empirical formula of the
compound is C5H10O. 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 C5H10O.
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:

363
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) CH3CH2CH(Br)COOH, CH3CH(Br)CH2COOH,
(CH3)2CHCOOH, CH3CH2CH2COOH (acid strength)
(iii) Benzoic acid, 4-Nitrobenzoic acid, 3,4-
Dinitrobenzoic acid, 4-Methoxybenzoic acid (acid
strength)
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
364
the 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
365
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,
(CH3)2CHCOOH is a weaker acid than
CH3CH2CH2COOH.
Also, the I effect grows weaker as distance
increases. Hence, CH3CH(Br)CH2COOH is a weaker
acid than CH3CH2CH(Br)COOH.
Hence, the strengths of the given acids increase
as:
(CH3)2CHCOOH < CH3CH2CH2COOH <
CH3CH(Br)CH2COOH < CH3CH2CH(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
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

366
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 H3O+
(ii)Tollens reagent
(iii) Semicarbazide and weak acid
(iv)Excess ethanol and acid
(v) Zinc amalgam and dilute hydrochloric acid
ANS:(i)

(ii)

367
(iii)

(iv)

(v)

Q.7

368
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)

(ii)

369
(iii)

(iv)

370
(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.

371
Q.9 How is tert-butyl alcohol obtained from
acetone?
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.

372
Q. 12. Which acid is stronger and why ?
F3C C6H4 COOH or H3C C6H4 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-
373
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 + C2H5C6H4COO- -CHO
C6H4C2H5 > COOHC6H4
Tollens reagent 2-ethyl benzaldehyde
|
Silver mirror 2-ethyl benzoate
COOH

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
374
(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:-

(i) CH3 CHO (ii)

CH3

(iii) (CH3 )2 CHCOCH((CH3 )2 (iv) CH 3 CH


(OCH3) CHO
(v) CH3-CH-CH2CH2-CHO
|
CH3
(vi) PHCOPH
(vii) CH3-CH2-CH-CH2-CH-CHO
| |
Br CH3
(viii) C6H5CH=CH-CHO
(ix) (CH3)3-CCH2COOH

FOR AVERAGE
375
02 Marks QUESTIONS

3. Arrange the following compound in


increasing order of their boiling points.
(f) CH3-CHO
(g) CH3-CH2-OH
(h) CH3-O-CH3
(i) CH3-CH3
(j) CH4

4. Arrange the following compound in the


increasing order of their properties as
indicated

(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
376
(vii) Ethanal
& Propanal
(viii) Acetophe
none & 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. CH3OH, (CH3)3COH, (CH3) 2-CH-OH,


CH3CH2OH
iv. (CH3) 3CCOOH, CH3COOH, (CH3) 2-
CHCOOH,HCOOH

12. Arrange the following acid derivatives towards


increasing order of nucleophelic Substituion
reaction
377
(a) RCONH2, 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 (CrO3)
3.Ethyne is treated with H2O in the presence
of H2SO4 & HgSO4

378
4.Toulene is treated with chromyl chloride
(CrO2Cl2) followed by hydrolysis.
5.Propanone is treated with HCN
6.Ethanal is treated with NaHSO3.
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 PCl5.
12. Benzoic acid is treated with NH3.

12. COMPLETE THE FOLLOWING.


(i) O

C-Cl H2
?
Pd- BaSO4

1. AlH(t-Bu)2
(ii) CH3-CN ?
379
2 H2O
NH2
| CHCl3 + Alc KOH
(iii) ?

O
(iv) AlCl3
+ C2H5-C-Cl ?
CS2

Hg2+,H2SO4
(v) CH3-C = C-H ?

(vi)
H
Conc NaOH ?
2 C =0

|| O
(vii) NO2
380
|
+ H2N -NH NH2

(viii) CH2-CH2-CH3

1. KMnO4
KOH
2. H2O

I LiAlH4
(ix) CH3-COOH
2. H3O+

13. Road Map problems Identity A & B.

|| O
NH3 H2| Ni
(i) R2 C A B

381
Cu di NaOH
(ii) CH3-CH2-OH A B
573 K

|| O
1. CH3MgBr 2,4,DNP
(iii) CH3-C H A
B
2. H2O

|| O
1. CH3MgBr Cu
(iv) CH3-C-CH3 A B.
2. H2O 753 K

HgSO4 CH3MgX
[o]
(v) HC = CH A B C
H2SO4

FOR ABOVE AVERAGE


02 Marks QUESTIONS

14. Transformation
(i) Ethanol to butane 1, 3 diol;

382
(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 C3H6O is resistant to oxidation but forms a
compound B (C3H8O) on reaction. B reacts with
HBr to form bromide C with an treated with
alcoholic KOH form an alkene D C3H6 deduce the
structure A,B,C,D.
(b) An organic compound A with molecular
formula C8H8O 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 C7H6O2. Identify the compound A and
B and explain the reaction involved.

383
(c) An organic compound A C8H6 on
treatment with dilute H2SO4 containing HgSO4
gives compound B which can also be obtained
from a reaction of benzene with acid chloride in
presence of AlCl3? B on treated with I2 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:

384
(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
(vi) Di- tert. butyl ketone does not give NaHSO3
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.

385
***************************************
*******

UNIT -13
ORGANIC COMPOUNDS
CONTAINING NITROGEN
AMINIES

386
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:
.. .. ..
NH3 < R-NH2 > Ar-NH2

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 .
The less basicity of aryl amine is due to resonatig
structures.

387
+
NH2

388
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---NH2 > R2---N----R
The above basicity of amines can be explained on the basis
of Kb &
pKb. higher the Kb values or lower the pKb value shows
higher basic characters .
Sec. amines > tert. Amines < pr. Amines
pKb 3.00 3.29 3.25

PREPARATION OF AMINES:-

I. REDUCTION OF NITRO COMPOUNDS


H2/Pd
(a) ArNO2 ------------------------ ArNH2
Ethanol
389
Sn/ HCl

(b) ArNO2 --------------------ArNH2

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
RNH2----------- R2NH ------------ R3N
PR Amine. SEC. TERT.

DISADVANTAGEBy this method a mixture of


amines are prepared and not separated easily.

III. Reduction of nitriles --


H2/Ni
RCN------------------ RCH2 NH2

a. Reduction of amides-----

LAH
RCONH2 --------------------- RCH2NH2
WATER

390
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.

RCONH2 + Br2 +4 NaOH ------ RNH2


+Byproducts

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.

C2H5NH2 + CH3COCl ------ C2 H5


NHCOC H3
vi. Carbylamine reaction ---Primary amine
combines with chloroform in ethanolic
potassium hydroxide to form isocyanide with
pungent smell.
Heat
RNH2 +CHCl3 + 3 KOH -------- RNC + 3
KCl + 3H2O
391
vii. Reaction with nitrous acid ------
NaNO2+HCl
RNH2 + HNO2 -------------ROH + N2
+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
ArNH2 + NaNO2 +HCl ---------------------ArN2 +Cl- +NaC
+2H2O

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:--

392
(I) Sandmeyers reaction :- The reaction of
diazonium salt with halo acid in presence
of copper halide to have halobenzene is
called sandmeyers reaction.
Ar-N2Cl + CuCl + HCl ------- Ar-Cl + N2

(II) Gatterman reaction :--- The reaction of


diazonium salt with halo acid in presence
of copper powder is called Gatterman
reaction.
Ar-N2Cl + Cu + HCl ---------- Ar-Cl + N2
+ CuCl

(III) Hydrolysis reaction ----- Diazonium salt


on hydrolysis upon 283 K gives phenol.
HOH, 283K
Ar-N2Cl -------------------------- Ar-OH +
N2 + HCl

(IV) Reduction of diazonium salt -----


Diazonium salts on reduction with mild
reducing agent like phosphorous acid or
ethanol reduced to arene .

Ar-N2Cl + H3PO2 + HOH --------- ArH +


N2 + H3PO3 + HCl

(V) Nitration reaction ------ Diazonium salt


on treatment with
393
HBF4 followed by sodium nitrite & copper at
high temperature gives nitroarene.
+ - NaNO2
Ar-N2Cl + HBF4 -- Ar-N2BF4 ---------
ArNO2 + N2 + NaBF4
(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-N2Cl + 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.

394
Q. 2. Although NH2 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. NO3 + Conc. H2SO4 (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 NH2 gp in aniline is O,
p-directing and activating while N+H3 gp in
anilinium ion is m-directing and deactivating
hence a mixture of all threeortho, para and
meta derivatives is formed.
Q. 3. Pkb 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 CH2NH2, + I effect
of CH3 increase the electron density on the N-
atom. Therefore, aniline is a weaker base than
methylamine and hence its Pkb value is higher
than that of methylamine.
Q. 4. Aniline gets coloured on standing in air
for a long time. Why ?
395
Ans. Due to strong electron-donating effect (+
R effect) of NH2 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.

Q. 5. CH3CONH2 is a weaker base than


CH3CH2NH2.
Ans. Due to resonance, the lone pair of
electrons on the nitrogen atom in CH 3CONH2
is delocalised over the keto gp. There is no
such effect in CH3CH2NH2. Due to reduction
in electron density on N of CH3CONH2, it is a
weaker base than CH3CH2NH2.
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 C6H5Cl or C6H5Br, which
is a nucleophilic substitution Rxn. Since aryl
halides do not undergo nucleophilic
substitution under ordinary laboratory
conditions, therefore C6H5Cl or C6H5Br does
not react with pot. phthalimide to give N-
phenyl. Phthalimide and hence aromatic

396
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
N N C l
+
CN

NH
Ans. (i)NO 2
NaNO2 + HCl
2

O (i) Fe/HCl
O 273
O 278 K O

CuCN/HCN


(ii) NaOH Diazotization
Benzene

Diazanium
Aniline
Chloride Benzonitrile
COOH

H3+O O

Hydrolysis

Benzoic acid
C H 2C N 2 1
C H 2C l2 C H 2C H 2N H 2

(ii) O O O
KCN (aq) LaAlH4


KCl Redue
397
Benzyl Chloride Phenyl
ethanenitrite 2-phenylethanamine
Q. 8. Give the structures of A, B and C in the
following compounds :
NaCN OH
NaOH + Br2
(i) CH3CH2I A
B C
Partial Hydrolysis

NH3 NaOBr
NaNO2/HCl
(ii) CH3COOH A
B C
D
Ans. O
NaCN OH
||
(i) CH3CH2I CH3CH2CN
CH3 C NH2
(Partial Hydrolysis)
Propanenitrile (A)
Ethanamide (B)
NaOH + Br2
CH3 NH2
Hofmann bromamide reacn Methanamine
(C)
398
NH3 NaOBr
NaNO2/HCl
(ii) CH3COOH CH3CONH2
CH3NH2
CH3OH
D (Hofmann
bromamide
Ethanoic acidEthanoimide (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
NH3 R NH2 R2
NH R3 N R4 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.
399
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 :
NH 3
+


SO 3

In the presence of dil. NaOH the weakly acidic


NH3+ group transfers its H+ to OH to
form soluble salt P NH2C6H4SO3Na+.
On the other hand, SO3+ group is a very
weak base and does not accept H + from dil
HCl to form NH3C6H4SO3H and therefore, it
does not dissolve in dil HCl.
Q. 12. Why are aliphatic amines more basic
than aromatic amines ?
Ans. In Aromatic amines, due to resonance, N-
atom acquries +ve charge and lone pair of
N-atom is less available.
+ + +
NH 2 NH 2 NH 2 NH 2 NH 2

In aliphatic amines, due to e releasing nature


of alkyl groups lone pair of e on N-atom is
more available.
More basic.
400
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
| |
HN------------HO-------
HN--------HO------
| | |
|
C2H5 H C2H5
H

HNH
|
C2H5
However in Aniline, due to larger
hydrophobic alkyl part extent of H-
bonding decreases considerably
401
insoluble in water.
(ii) Aniline being a Lewis base reacts with
Lewis acid AlCl3 or FeCl3 to form a salt.
C6H5NH2 + AlCl 3
C6H5NH2+AlCl3
Lewis base Lewis acid
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.
402
-------- H R
H--------
| | |
RNH-------- NH------
--NR
| |
H H-----
---

--------HNR
|
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 NH2 + CHCl3 + 3 KOH R
NC + 3 KCl + H2O

(pungent smelling)
2 amines do not give this test.
403
(ii) Aryl sulphonyl chloride test :

|
H

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
404
prepared by protecting NH2 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 :

CH 3

CH
CH 3 N 3
CH3 N
+
CH 3
CH2 N +
( C H 3) 3
CH 3

O O O 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 lone pair of
electrons on the N-atom which it can directly
405
donate to the benzene ring. N (CH3)2 (due to
two alkyl groups on N) is a much stronger
electron donating gp than CH3 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
(CH3)3 N+ gp, the +vely charged N is
directly attached to the benzene ring,
therefore, its electron withdrawing ability is
much stronger than CH2N+ (CH3)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 :

406
Ans. Due to powerful I effect to the F-atom, it
withdraws electrons from N+H2 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. :
(CH3)3N, (CH3)2NH, CH3NH2, NH3
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
NH3.
(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 increases in
going from 1 to 2 to 3 amine, so the
basicity of amines decreases in the order :
407
3 amine > 2 amine > 1 amine
(CH3)3N > (CH3)2NH > CH3NH2 >
NH3
(ii) In aq. soln, the basicity depends upon two
factors :
(a) + I effect of CH3 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 :
(CH3)3N > (CH3)2NH > CH3NH2
On the basis of Stabilisation of conjugate acids
by H-bonding alone as explained below :

The order will be :


CH3NH2 > (CH3)2NH > (CH3)3N
408
The combined effect of these two opposing
factors is that (CH3)2 NH is the strongest
base. In case of CH3NH2 and (CH3)3 NH, the
stability due to H-bonding predeminates over
stability due to + I effect of CH 3 gp, thereby
making CH3NH2 stronger than (CH3)3 NH.
So the overall order in aq. soln will be :
(CH3)2 NH > CH3NH2 > (CH3)3N > NH3
Conceptual Questions
Q 1. Give reasons:---
a. Primary amines are more basic than
ammonia.
b . Sec. amines are more basic than pr.amines.

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.
409
Q.3. Why is amide more acidic than an amine ?
Ans.In amide there is C=O group attached
NH2 , 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 CHCl3 & 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 ?

410
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) C6H5NH2+CH3COCl NaOH


C6H5NHCOCH3 +HCL
ConeH So4
(b) C6H6+HNO3 Conc 2 C6H5NO2
3H
2 C6H5NH2
333K
Sn/Hcl

Q9. Why does the boiling point of CH3NH2 less


than HCOOH?
Ans:- HCOOH is associated with intermolecular
H-bonding in greater extent then
CH3NH2 and therefore HCOOH has higher
boiling point than CH3NH2 .
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.
411
CH3 CH-COOH CH3-CH-COO-

CH2 NH2

Q11. How will you prepare aniline from


nitrobenzene industrially?
Ans:- Aniline is prepared industrially by
reduction of nitrobenzene in presence o of H2 and
Fe/Hcl.

NO2 NH2
Fe/Hcl
+ 6[H] + 2H2O

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
412
Na/C H OH
Ans:- (i) CH2CONH2 2 5 CH3CH2NH2
Alcl3
(ii) C6H5 + CH3COCl
C6H5COCH3
H2O/H+
(iii) C6H5NH2 + CH3cocl
C6H5NHCOCH3 CH3COOH
Br C6H4NHCOCH3 H2O/H BrC6H4NH2

NH2
OR
Br

(iv) CH3NH2 CH3OH


CH3Cl CH3CN
CH3CH2NH2
NH
(v) OH or C6H6OH 3
C6H5NH2
Zncl
2
Al O
(vi) C6H5OH + NH3 2 3 C6H5NH2
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.
413
(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 NO2+ 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.
(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 N2-cl group which shows more
intermolecular attraction than those of aliphatic
amines and hemee more stable.

414
(v) Methylamine is basic in nature and have
attracts to the cl group of Fecl3 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,
NH2 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.

.. ..
415
R NH2 NH2

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

.. + +
+ ..
NH2 NH2 NH2 NH2
NH2

I II III IV V

416
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 (NH2).

R NH2
This phenomena makes the permanent
displacement of the electrons towards N-atom
makes it more basic.

FOR BELOW AVERAGE

01 Mark Questions

1. Write IUPAC Name - (CH3)2CHNH2


2. Write IUPAC Name - CH3NHCH(CH3)2
3. Write IUPAC Name - CH3CH2N( CH3)2
4. Classify the given amines into primary,
secondary& tertiary.
(CH3 )2CHNH2 ,( CH3 )2 CHNH2,
CH3CH2N(CH3)2
417
5. Arrange the following in decreasing order of
PKb values
(CH3 )2 CHNH2 ,( CH3 )2 CH NHCH3,
CH3CH2N(CH3)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
ArN2+X- +CN- ------------- --------+N2 + X
13. Convert
Aniline to benzonitrile
14. Convert
Aniline to sulphanilic acid.
15. What do you mean by ambident Nucleophiles ? Give an
example.

418
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---
(i) Methanamine to ethanamine
(ii) Ethanamine to methanamine.

9. Complete the following


419
NaCN OH- NaOH/ Br2
(i) CH3CH2I--------- A------------B--------------------
C

NH3 NaOBr NaNO


HCl
(ii) CH3COOH------------ 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) TN
(ii) picric acid

03. Marks Questions

1. Give reasons-
a. Aniline is weaker base than cyclohexaamine.
420
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 fluorobori
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.

421
5. Identify the compound A, B, C in the following
reactions-

(i) Br2/NaOH HNO2


A----------------- B ---------------C

Sn/ HCl NaNO2/ HCl


(ii) A---------------- B ----------------------- C

Br2/ 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 o
sulphuric acid.
(ii) Aniline combines with sulphuric acid at 453
473K.
422
(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 LiAlH4
(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

H2N OCH3

423
4. Give chemical test to distinguish between
benzyl amine & aniline .
5. Complete the following reactions
Conc. H2SO4
ArNH2 --------------------- -------------------
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?
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
424
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.
NH3 H2/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, se
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
C6H7N. Identify the compounds A, B and C.
6. Account for the following---
a. pKb 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.
425
FOR ABOVE AVERAGE
01. Mark Questions.
1. An organic compound X having molecular
formula C2H7N On treatment nitrous acid
gives an oily yellow substance. Identify X
2. Name the product obtained by action of aniline wi
Bromine.
3. What happens when ethyl amine dissolves in li
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
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
basic medium.
4. Distinguish between the pair of the compounds
a. Ethanamine & diethylamine
b.Phenol & aniline.
5. Write the product for the following reactions-

426
a. Nitroethane is treated with lithium Aluminiu
Hydride.
b. Ethyl-isonitrile is hydrolysed in the presence o
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 C2H5NO2 , reacts with nitrous acid to
give C2H4O3N, B. On reduction A Gives
another compound C with molecular formula
C2H7N 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.

427
5. An aliphatic compound X, molecular formula
C3H7NO, 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.

************

428
UNIT -14
BIOMOLECULES

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

429
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 amino
and carboxylate functionalities are attached to the
430
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

431
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
432
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.

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
433
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.
434
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 ( - CH2OH ) and
four secondary alcoholic group ( - CHOH )
and gives reaction with
(i) HCN Glucose reacts with hydrogen
cyanide to give glucose cyanohydrin

CH2OH (CHOH)4 CHO + HCN


CH2OH - (CHOH)4 CH(OH)(CN)
(ii) Tollens reagent Glucose reduces
Tollens reagent to metallic silver.

CH2OH (CHOH)4 CHO + Ag2O


CH2OH - (CHOH)4 COOH + 2Ag
(iii) Glucose on prolong heating with HI
forms n-hexane. Suggesting all the six
435
carbon atoms in glucose are linked
linearly.
HI
CH2OH (CHOH)4 CHO
CH3- (CH2)4 CH3
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.

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.

436
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
|
CH2OH
Q. 2. Which of the following is not an -
amino acid ?
437
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
|
CH3 C H
|
NH3+
Q. 4. Wreite the name and structure of the
simplest amino acid which can show optical
activity.
Ans COOH Alanine
|
CH3 C H
|
NH2
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 :
438
----------
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
439
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) C12H22O11 + H2O
C6H12O6 + C6H12O6
Lactose glucose glactose
Invertase
(ii) C12H22O11 + H2O
C6H12O6 + C6H12O6
Sucrose glucose fructose
Q. 4. How will you prove that all the carbon
atoms of glucose are in straight chain ?
Ans. The reaction of glucose with HI gives n-
hexane and it proves that all sin-carbon-atom
are in straight chain.
HI
Ho CH2 (CHOH)4 CHO CH3
(CH2)4 CH3
Heat n-hexane
440
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 NaHSO3.
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,
B2, B6 and B12. It required to release energy
from food and to promote healthy skin and
muscles. Its deficiency causes beri-beri
(Vitamin B1) and Anaemia (Vitamin B12).
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 C1
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 C1 is below the plane.
(2) The OH gp at C1 is above the plane.
441
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)

442
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
443
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
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.

444
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 .
445
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 ?


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


446
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 ?

447
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.

FOR ABOVE AVERAGE

1. Draw the hawarth projection formula for maltose.

448
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

449
1. Give the reaction of glucose with (i) Br2 (ii)
NH2OH (iii) HNO3.
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.

450
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.

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
451
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 B12 or vitamin B and C cant be
stored in our body?
Ans: Vitamin B except B12 & 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.
452
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.

UNIT 15
POLYMER

453
Polymer: - Polymer compounds are very high
molecular masses formed by the
combination of Simple molecules by
covalent bonds.
Ex. nCH2=CH2 ( CH2 CH2
)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
454
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
455
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.
(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

456
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
457
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.

458
Polymer (origion Greek) poly means many, mers
means part
459
Defination: Very large molecules having high
molecular mass (103-107 u)
Macromolecule: other name for polymer
Polymerization: the process of formation of
polymer
Classification of polymer:
1.Based on sources:
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
460
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
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

461
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

462
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(C6H5OCOOCOC6H5)
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 (C2H5)3Al and titanium
tetrachloride(TiCl4)
Condensation polymerization or step growth:
Since each step produces a functionalized species
and is independent of each other,this is called step
groth.

463
As,monomers with different functional groups are
condensed,so, it is Condensation polymerization.
e.g. Condensation between Hexamethylene-di-
amine[ NH2-(CH2)6-NH2] and Adipic
acid[HOOC-(CH2)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[ NH2-(CH2)6-NH2]
and Adipic acid [HOOC-(CH2)4-COOH.
Q. what is the monomer of nylon-6?
A. Caprolactum [NH2-(CH2)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 ?

464
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.
465
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 CH2=CH2 Carry
bags,toys,buckets
PTFE(Teflon) Tetraflouroetene CF2=CF2
Non -stick cookware,Oilseals,gasket
Polyacrylonitrile Acronitrile CH2=CHCN
Substitute for wool(mink)
Polypropene Propene CH2=CHCH3
ropes,pipes
Polystyrene Styrene CH2=CHC6H5
Insulator,Wrapping material
PVC Vinyl Chloride CH2=CHCl
Raincoats,flooring,water pipes
(Thermocol)

Condensation polymer
Nylon 6,6 Adpic Acid COOH-(CH2)4COOH
Parachute Rope, Socks, Stockings
Hexamethylene- di amine [ NH2-
(CH2)6-NH2]
Nylon 6 Caprolactum [NH2-(CH2)5-
COOH] Parachute Rope, Socks, Stockings
Dacron Ethylerne Glycol OH-(CH2)2OH
466
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 ?
467
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 (CH2 CH C6H5)n a homo
polymer or a copolymer.
Ans. It is a homo polymer and the monomer
from which it is obtained in styrene C6H5 CH
= CH2.
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.
2 MARKS QUESTIONS
Q. 8. Write the names of monomers and
structure used for getting the following
polymers ?
PmmA, PVC, Teflon

468
Ans. (i) PVC monomer Vinylchloride,
CH2 = CH Cl
(ii) Teflen monomer Tetrafluoro
ethylene, F2C = CF2
(iii) PMMA monomer Methyl
methacrylate,
CH3
|
CH2 = C COOCH3
Q. 9. Identify the monomer in the following
polymer structures :

O
Ans. (i) HOCH2 CH2OHand HOOC
COOH

ethane-1, 2-dial Benzene-1, 4-


dicarboxylic acid
(ii) Melamine Formaldehyde
H 2N N NH 2

N N

NH 2 and HCHO

469
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
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

470
for condensation polymers also eg. for
example.
(i) Addition polymerisation of styrene and
butadiene form copolymer styrene
butadiene rubber.
n CH2 = CH CH = CH2 + n C6H5CH
= CH2 >
C6H5
( CH2 CH = CH CH2)n CH2 CH
)n
(ii) Condensation polymer became thylene
diamine and adipic acid form nylon-6, 6.
n HOOC (CH2)4 COOH + n H2N
(CH6) NH2
adipic acid hexamethylene
n H2O
diamien
( NH (CH2)6 NH CO
(CH2)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.
471
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
Q3: Write the monomer of Glyptal polymer.
Ans: (a) Ethylene glycol (b) Phthalic acid
Q4: What is Synthetic polymer ? Give one
example.

472
Ans: Man made polymers are called Synthetic
polymers. Polyethene, PVC.
Q5: What is approximate molecular mass of
Polymer ?
Ans: It is approximate molecular mass 103-107u.
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
473
HDP. Buckets, dustbin, bottles.
02 Marks Questions
Q1. Differentiate between thermo plastic and
thermo setting Plastic.
Ans:

Thermo Plastic Thermo setting


Polymer Polymer

1.Liner or slightly 1.Cross linked or


branched long heavy branched
change molecules molecule
2.Posses 2.This can not be
intermediate inter reused
molecular force of 3.Ex. Bakelite,
attraction. Urea-Formal
3.Ex. Polythene, dehyde resins
Polystyrene
Q2: Give two Polymerisation reactionds for each.
(a) Addition polymers and
(b) Condensation Polymers
Ans: Addition Polymers :-
474
nCH2=C ( CH2
CH2)n
Condensation Polymers
n H2N(CH2)6 NH2 + n HOOC(CH2) COOH
[NH(CH2)2NHCO(CH2)4CO)]n+nH2O
Q3: What are elastomers ? Give one example.
Ans: The rubber like material which are elastic in
nature. Eg. Natural rubber.
Q4: Write the chemical structure of Glyptal
Ans: Ethylene Glycol-OHCH2CH2OH
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.
475
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:-
476
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;

CH3

CH2 C CH CH2

S S

CH2 C CH CH2
CH3
Q10: Explain the terms:-
477
(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 = CH2
Q3: Write the monomer of Neoprene?
Ans: Chloroprene.
Q4. Write the name of monomers of Melamine-
Formaldehyde.
478
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
479
Q1: Differntiate between addition polymer and
condensation polymer.
Ans:
Addition Polymer Condensation Polymer
1. Large no. of 1. Large no. of
unsaturated monomers monomers having
combine together to different functional
form polymers Eg. group with release of
Polythene and small molecule like
polystyrene water combine to form
polymers. Eg. Nylon
and Teflon

Q2: Distinguish between thermoplastic and


thermo setting polymers.

Thermo plastic Thermo setting plastic


polymer
1.The inter moliculer 1.The inter molecular
forces are force are
480
intermediate. maximum.
2.there are no cross 2.They are cross
linkage bond linkaged.
3.Eg. Polythene and 3.Eg. Bakelite
polystyrene

Q3: Distinguish between Homopolymers and


Copolymers.
Homopolymers Copolymers
1. The polymers which 1. The polymers which
are form by only one are form by two or
type of monomers Eg. more types of
Teflon & PVC monomers .Eg.
Terrylene & Buna-S

Q5: Depict a free radical mechanism of addition


polymerization of isoprene.
.

481
R* + CH2 = CCH = CH2 R CH2
CCH = CH2
|
|
CH3
CH3

.
R CH2
C=CH CH2

CH3

CH3 CH2 -----

482
and
C=C

R CH2 H

Trans
1, 4 structure
CH3 H

C=C

R CH2 CH2 ---

Cis
1, 4 structure

Q6: Why are the numbers 6, 6 and 6 put in the


name of Nylon 66 and Nylon 6?

483
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.
484
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:-
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.
485
(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.
486
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.
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
487
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

488
pentanoic acid.It is used in speciality
packaging , orthopaedic devices.

UNIT -16
CHEMISTRY IN
EVERYDAY LIFE

STUDY MATERIAL
489
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
490
disinfectants .example 1.% solution of phenol
(2)SO2 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.
491
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
(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(C6H5COONa) .

492
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.
493
O

CH2-O-C-C17H35
O CH2-OH
|
CH-O - C-C17H35 +3NaOH = CH-OH
+3C17H35COONa
O |
CH2-OH Sodium stearate
CH2-O-C-C17H35
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

494
Lauryl alcohol
Lauryl hydrogen sulphate Sodium
lauryl sulphate

(Anionic detergents)

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.
495
(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.

496
11.Anionic Detergents : Eg:
Sodiumdodecylsulphate.
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.
497
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.
498
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.
499
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 ?
Ans. Reserpine.
Q. 4. Which alkaloid is used to treat
malaria ?

500
Ans. Quinine.
Q. 5. Identify the following :

HO NHCOCH3
Ans. Paracetamol.
Q. 6. What is the use of the following
compound :
OCO CH 3

COO 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 :
501
Ans. Penicillin G.
Q. 13. Which antibiotic contains NO2 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 ?
O
CH3 (CH2)11 CH2 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.

502
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 ?

503
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.
Q. 6. What is tincture iodine ? What is its
use ?
Ans. Alcoholic Solution of I2.
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.

504
(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 NaHCO3 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.

505
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

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.
506
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
507
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- KMnO4 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.
508
A12. Bithional.
A13. Broad spectrum antibiotics.
A14. To make transparent the soap.
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

509
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

510
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
(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?

511
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.
512
(i) Antacids (ii) Antihistamines (iii)
Antibiotics
(iv) Antifertility drugs (v)
Foodpreservatives.

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