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 ?

Ans. Ice

Q. 5. Arrange the following types of interactions in correct order of their

increasing strength :

Covalent, hydrogen bonding, Vander Waals, dipole dipole

Ans. Vander Waals < dipole dipole < hydrogen bonding < covalent.

Q. 6. Give reason for the appearance of colour in alkali metal halides.

Ans. Due to F-centres.

Q. 7. Which type of defect occur in Ag Br ?

Ans. Schottky defect and Frekel defect.

Q. 8. Give one example of doping which produces p-type of semi-

conductors.
1
Ans. Ge doped with Al.

Q. 9. Out of (a) Graphite and (b) Carborundum which one is harder ?

Ans. Carborundum.
Q. 10.How can a material be made amorphous ?
Ans. By melting the material and by cooling it rapidly.
2 MARKS QUESTIONS
Q. 1. Give Reason :
The energy required to vaporize one mol of copper is smaller than
that of energy required to vaporize 1 mol of diamond.
Ans. Copper is a metallic solid having metallic bonds while diamond is a
covalent solid having covalent bonds. Metallic bonds are weaker than
covalent bonds and thus less amount of energy is required to break
metallic bonds than covalent bonds.
Q. 2. The unit cube length for LiCl (NaCl) is 5.14 A. Assuming anion-
anion contact. Calculate the ionic radius for Chloride ion.
Ans.

Cl A

+
Li B C

Interionic distance of LiCl = 5.14 / 2 = 2.57 A

AC = AB 2 + BC 2

= 2.572 + 2.572
= 3.63
therefore, radius of Cl = 3.63 = 1.81 A
Q. 3. Give reasons :
(a) Diamond and rhombic Sulphur are covalent solids, but the
latter has lower melting points.
(b) Among NaCl and CsCl, CsCl is quite stable.

Ans. (a) Due to weak Vander Waals Force in Sulphur molecule.

2
 (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 MgAl 2O4. The oxide
ions are arranged in CCP, Mg2+ ions occupy the tetrahedral
voids. While Al3+ ions occupy the octahedral voids.

(i) What percentage of tetrahedral voids is occupied by Mg 2+ ions

?

(ii) What percentage of octahedral voids is occupied by Al3+ ions ?

Ans. According to the formula, MgAl2O4. If there are 4 oxide ions, there will
be 1 Mg2+ 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.

3
Ans. (a) Due to annealing over a number of years glass acquires some
crystalline character.
(b) Glass is not a true solid. But a super-cooled liquid of high viscosity.
It has the property to flow.
(c) 2 Ag+ will be replaced by 1 Ca 2+ ions to maintain electrical
neutrality. Thus a hole is created and lattice site for every Ca 2+ ion
introduced.
Q. 7. Analysis shows that nickel oxide has the formula NiO .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 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.

4
 (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 ?

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?

5
(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)

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

marks)

6
Q1. What is meant by the term Co-ordination no?
Ans:- No of atoms (sphere) by which the central atom is surrounded.

Q2. What is the co-ordination no of atoms:-

(a) In a cubic close packet structure -12
(b) In a body centred cubic structure:-8
Q3. A cubic solid is made of two elements P and Q. Atoms of Q are at the corner
of the

7
 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)
Ans:-
Frenkel defect Schottky defect
(a) In this defect shifting of (a) In this defect there is missing of
icon from its position to equal no of cation and anion.
interstitial site.
(b) Density remain same. (b)Density decreases.

Q5. Silver Crystallises in fcc lattice. If edge length of the cell is 4.077 X 10 -8
cmand
density is 10.5 g cm-3. Calculate the atomic mass of silver.
Ans:- density =10.5 gm/cm3, Z=4

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.

8
 ZnO-------- Zn2+ + 1/2 O2 + 2e-
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 .

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 1cm3 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 = 2.25 X 1022
4.44 x10 23

Q12. What happens when ferrimagnetic Fe3O4 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
9
 i) Simple cube/primitive cube.

ii) Body centered cube.

iii) Face centered cube.

2. Name the element with which silicon can be doped to give a (i) p-type
semi conductor (ii) n-type semi conductor

3. A cube solid is made of two elements P and Q. Atoms of Q are at the

corner of the cube and P at the body centre. What is the formula of the
compound? What are the co-ordination number of P and Q.

4. What makes the crystal of KCl appear some time violet?

5. What is the effect of Schottky and Frenkel defects on the density of

crystalline solid?

6. Name a substance which on addition to AgCl causes cation vacancy in it.

7. What happens when ferromagnetic Fe3O4 is heated at 850 K and why?

8. What is curie temperature?

9. What is ferromagnetism different from paramagnetism?

10. What structural changes will occur if NaCl crystal is subjected to high
pressure?

FOR AVERAGE
1. An element (at. Mass=60) having fcc structure has a density of 6.23 g cm -
3
. What is the edge length of the unit cell? (Avg. const. N = 6.02 x 10 23
mol-1)

2. The density of CsBr, which has a BCC structure, is 4.4 g cm-3. The edge
length of the unit cell is 400 pm. Calculate the interionic distance in
crystal of CsBr (NA= 6.023 x 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)?

10
4. NaCl crystallizes in FCC structure. Its density is 2.165 gm cm -3. If the
distance between Na+ and its nearest Cl- is 281 pm. Find out the Avog.
No. (Na=23 g mol-1, Cl = 35.5 g mol-1)

5. The compound CuCl has ZnS structure and the edge length of its unit cell is
500 pm. Calculate the density. (At. Mass, Cu=63, Cl=35.5, NA=6.02 x 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.

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 cm3 of aluminum?

11
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.

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

12
1. Solution : Homogeneous mixture of two or more pure substances.

2. Types of solutions :

a) Solid in solid solution. Eg: Bronze, Brass.

b) Liquid in solid solution. Eg: Zinc-amalgam.

c) Gas in solid solution. Eg: Solution of hydrogen in palladium.

d) Solid in liquid solution. Eg: Aqueous Sodium Chloride sol.

e) Liquid in liquid solution. Eg: Ethanol dissolved in water.

f) Gas in liquid solution. Eg: Carbondioxide dissolved in water, ammonia

dissolved in water.

g) Solid in gas solution. Eg: Iodine vapour in nitrogen .

h) Liquid in gas solution. Eg: Water vapoursin air, Chloroform vapour in

nitrogen.

i) Gas in gas solution. Eg: Water gas, Producer gas.

3. Concentrations of solution :

a) Mole fraction ( X):

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.

13
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.
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.
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.

14
4. Osmosis : Spontaneous flow of solvent molecule from lower
concentrated solution to higher concentrated solution through semi
permeable membrane.

5. Reverse Osmosis : When the applied pressure is greater than osmosis

pressure, the reverse osmosis take place. (used in desalination plants to
meet potable water)

6. Isotonic solution : The solutions having same osmotic pressure.

7. Azeotropic mixture : Binary mixture of liquids having same

composition in liquid and vapour phase and boils at the constant
temperature.

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.

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.

15
 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 :

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?

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?
16
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).

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 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).
17
 18. State condition resulting in reverse osmosis. Give one of its
application.

19. Define the following with a suitable example :

a) Maximum and minimum boiling azeotropes.

b) Desalination

c) Ideal solution

d) Abnormal molecular mass

20. a) Define Vanthoff factor.

b) What is the Vanthoff factor for a compound which

undergoes tetramerisation in an organic solvent.

c) What would be the value of Vanthoff factor for

1) dilute solution of 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) ,
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.
18
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.
0 0
14. (PA P)/PA = XB = nB/nA
MB = 41.34 gm mol-1
16. Calcium phosphate , Copper Ferrocyanide
17. =CxRxT

= 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.
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= = = 0.01 M.
v 10 1000
Q. 4.Why camphor is used in molecular mass determination ?
Ans. Because it has very high cryoscopic constant.

19
 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.
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 ?
M1V1 + M2 V2 1.5 480 + 1.2 520
Ans. Total molarity = V1 + V2
= = 1.344 M
480 + 520
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 BaCl 2
soln ?
Ans. i for NaCl = 2 i for BaCl2 = 3
3 2
Therefore TF (BaCl2) = 3,
2
TF for BaCl2 = 3 C ,
Freezing Point of BaCl2 Solution is TF = 3 C.

20
Q. 4.Why water cannot be separated completely from ethyl alcohol by
fractional distillation?
Ans. Ethyl alcohol and water (95.4% ethyl alcohol and 4.6% water) form
constant boiling mixture (azeotrope) boiling at 351.1 K. Hence, further water
cannot be separated completely from ethyl alcohol by fractional distillation.
Q. 5.Why a person suffering from high blood pressure is advised to take
minimum quantity of common salt ?
Ans. Osmotic pressure is directly proportional to the conc. of solutes. Our body
fluid contains a number of solutes. On taking large amount of salts, ions enter
the body fluid there by 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 kg/mol i=1+
= Ka / C = 1 + 0.3687 = 1.3687
Tb = i Kb m
= 1.36 103 / 0.01
= 0.3687 = 1.36 102 .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 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 F 1000 Wb
TF = Wb = mass of solute
Wa Mb
Mb = molar mass of solute
Wa = mass of solvent
1.86 1000 Wb
10 =
1000 46
Wb = 247.31 g

21
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 ?
Ans. KF = 14 2 C6H5OH (C6H5OH)2
1 0
1000 K F W2 1 /2
Mb =
W1 DTF Total = 1 + / 2
Taking the solvent as 1 kg =1/2
i =1+/2
Mb = 1000 14 75.2
1000 7k = 1 / 2 = 0.625
= 150.4 g per mol / 2 = 0.375
phenol (molar mass) 94 g/mol = 0.75
Calculated molar mass % of association = 75%
i=
Observed molar mass
= 94 / 150.4 = 0.625

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.
Let the amount of Na2CO3 be x
Let the amount of NaHCO3 be 1 xNaHCO3 = 0.00526
x
Since no. of moles of both are Na2CO3 + 2 HCl 2 NaCl + CO2
equal + H2
NaHCO3 + HCl NaCl +
x 1 x
CO2 + H2O
N(Na2CO3 ) M(NaHCO3 )
x 1 x
M1V1 = 2 M2V2 + M3V3

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

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

22
(i) Name the process occurring in
the above plant
(ii) To which container does the
net flow of solvent take place
(iii) Name one SPM which can be
used in this plant
(iv) Give one practical use of the
plant

Ans. (i) The process is called Reverse Osmosis. [Reverse Osmosis: If the
pressure applied on solution side exceeds the osmotic pressure then the osmosis
can be reversed (i.e. pure solvent can be forced out of the solution to pass
through the pores of membrane in opposite direction). This is called Reverse
osmosis].
(ii) The solvent moves from sea water container to fresh water container.
(iii) Cellophane (It is one of the semi-permeable membranes that can be used)
(iv) This process is used for desalination of sea water.
Q.12 On increasing the temperature the solubility of most of the gases in
water decreases. An important consequence of this effect is the thermal
pollution of water, such as occurs around power plants cooled by a river or
stream. How is the survival of fish affected by thermal pollution of water?
Ans.: When the water temperature of the river or stream is increases the
solubility of oxygen in water decreases. Due to this decrease in dissolved
oxygen the survival of fish becomes difficult.
Q.13 How much NaOH is required to preapre 50 ml of aqueous solution
with 70mg of Na+ ions per ml. of the solution?
Ans. : Na+ ions in 1 ml = 70 mg
Na+ ions in 50 ml = 70 50 = 3.5g

Q.4 Volatile hydrocarbons are not used in the brakes of automobile as

lubricants, but non-volatile hydrocarbons are used as lubricants.
Ans.: The vapour pressure of volatile hydrocarbons is very high and they get
evaporated leaving behind the system. Due to this they are not used as
lubricants in automobiles. Non-volatile hydrocarbons having low vapour
pressure are used as lubricants.
Q.5 When fruits and vegetables that have dried are placed in water, they
slowly swell and return to the original form. Explain why ? Would a
temperature increase accelerate the process ? Explain.
Ans.: The cell walls of the fruits and vegetables have semi-permeable
membrane. When they have dried, concentration inside is higher. On placing in
water, water enters into the cells, i.e., osmosis takes place. Hence, they swell
and return to the original form. The process will be accelerated with increase of
temperature because osmosis becomes faster with increase of temperature.
23
Q1. Define osmotic pressure.
Ans:- The extra pressure that must be applied to the solution side to prevent the
flow of
solvent molecules into solution through a semi permeable membrane is
called
osmotic pressure.

Q2. State Raoults Law for a binary solution containing volatile components.
Ans:- At a particular temperature the partial vapour pressure of each component
of a
solution containing volatile liquid is directly propositional to its mole
fraction.

Q3. Define Vant Hoff factor.

Ans:-It is the ratio of experimental value of a colligative property to the
theoretical value.

Q4. What do you understand by colligative properties?

Ans:- Properties of solutions which depend on the number of solute and solvent
particles
but not on the nature of solute are called colligative properties.

Q5. State any two characteristics of ideal solution.

Ans:- Characteristics of an Ideal solution .
(i) 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?

24
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
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.

25
Ans:- It is equal to the elevation in boiling point of1 molar soln. i.e one mole of
a solute
dissolved in 1 kg of the solvent.
Q16. What are non-ideal solutions? Explain as to why non-ideal solutions
deviate from
Raoults Law.
Ans:- Non ideal solution are those which do not obey Raoults law.
When the molecular interaction between solute molecules solvent. Solvent
molecules
is not same as the molecular interaction between solute & solvent
molecules then
deviotion occurs.
Q17. What are colligative properties? Mention them.
Ans:-these are the colligative properties.
(a) Osmotic pressure (b) Relative lowering of vapour pressure
(b) Elevation in B.P (d) Depression in F.P
NUMERICALS
Q1. Calculate the mole fraction of ethylene glycol (C2H6O2) in solution
containing 20 %
of ethylene glycol by mass.
Ans:-
no.of .mole.of .thelene.glycol
Mole fraction of ethylene glycol = No.of .moles.of .water + No.of .moles.ofC H 6O2
2

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 O 1 glycol 1 0.0676 0.9323

2

26
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

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 :- M B 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

27
Q4. Calculate the osmotic pressure of a solution obtained by mixing 100 cm 3 of
0.25 M
Solution of urea and 100 cm 3 of 0.1M soln of cane sugar at 293 K
(R=0.082 L atm
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

Also 2C6H5COOH (C6H5COOH)2

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

Now i=(Normal molecular mass/Abnormal molecular mass)

=122/241.98
28
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.

2. Define osmotic pressure.
3. How pressure effect the solubility of a solid in a liquid.
4. State Raoults Law for a binary solution containing volatile components.
5. Define Henrys law about solubility of a gas in a liquid.
6. Define Vant Hoff factor.
7. What do you understand by colligative properties?
8. Define an ideal solution.
9. State any two characteristics of ideal solution.
10. Distinguish between molarity and molality.
11. What is a non- ideal solution?
12. Mention a large scale use of the phenomenon called reverse osmosis.
13. What is antifreeze? Give one example.
14. When is the value of Vant Hoff factor less than 1?
15. Name the two factors on which the vapour pressure of the liquids depend.
16. Define mole fraction of a substance in a solution
17. When is the value of Vant Hoff factor more than 1?

FOR AVERAGE

1. Why is the elevation in b.p. of water different in the following solutions?

(i) 0.1 M NaCl solution (ii) 0.1 M Sugar solution.

29
2. What are azotropes?
3. What happens when blood cells are placed in pure water?
4. Why is the cooking temperature in pressure cooker higher than in open
pan?
5. Why does molality of a solution remain unchanged with change in
temperature while its molarity changes?
6. Why is ether not miscible in water?
7. What are maximum boiling azeotropes? Give one example?
8. What are minimum boiling azeotropes? Give one example?
9. Why do doctors advice gargles by saline water in case of sore throat?
10. Why is boiling point elevated when a non volatile solute is added?
11. A person suffering from high blood pressure should take less common
salt, why?
12. Why do gases always tend to be less soluble in liquids as the temperature
is raised?

FOR ABOVE AVERAGE

1. How mole fraction of a solute and molality are related?

2. Two liquids A and B boil at 145C and 190C respectively. Which of
them has a higher V.P. at 80C?
3. What is expected value of i for 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?

30
FOR BELOW AVERAGE
02 Marks question

1. Under what condition Vant Hoff factor is (i) equal to one, (ii) greater
than 1, (iii) less than 1.
2. Two liquid A and B on mixing produce a warm solution. Which type of
deviation from Raoults Law does it show?
3. What are non-ideal solutions? Explain as to why non-ideal solutions
deviate from Raoults Law.
4. What are colligative properties? Mention them.
5. Differentiate between molarity and molality of a solution. When and why
is molality preferred over molarity in handling solutions in chemistry?

FOR AVERAGE
1 Name the factors which affect the vapour pressure.
2. Amongst the following compounds, identify which are insoluble,
partially soluble and highly soluble in water.
(a) Phenol (b)Toluene (c) Formic Acid (d)Ethylene Glycol
(e)Chloroform (f) Pentanol
3. What do you mean by relative lowering of vapor pressure ? How is
relative lowering of vapor pressure related with mole fraction of non
volatile solute in a solution?
4. With the help of a suitable diagram show that the vapour pressure of a
solution is lower than the pure solvent, causes a lowering of freezing
point for the solution compared to that of the pure solvent.
5. Carbon tetra chloride and water are immiscible where as ethanol and
water are miscible in all proportions. Correlate this behaviour with
molecular structures of these compounds.

FOR ABOVE AVERAGE

1. What do you mean by abnormal molecular mass? What are its cause?
2. With the help of suitable diagrams, illustrate the two types of non ideal
solutions.

31
3. State Raoults law for solutions of non volatile solutes in volatile
solvents. Derive a mathematical expression for this law.
4. What is osmotic pressure and how is it related with the molecular mass of
non-volatile solute?
5. What is meant by abnormal molecular mass of solute? Discuss the factors
which bring abnormality in the experimentally determined molecular
masses of solutes using colligative properties.
6. State Raoults Law. Discuss the factor responsible for the deviation from
this law.
7. State Henrys Law and mentions some important application.
8. Explain the significance of Henrys Constant (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 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 H2S in water at STP is 0.19 m. Calculate Henrys law
constant.

32
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.
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 N2 exerts a
partial pressure of 0.987 bars. Given that Henrys law constant for N 2 at
293 K is 76.48 kbar.
2. 0.6 mL of acetic acid having density 1.06 g mL -1, is dissolve in 1 litre of
water. The depression in freezing point observed for this strength of acid
was 0.0205C. Calculate the Vant Hoff factor and the dissociation
constant of acid.
3. 100 g of liquid A (molar mass 140 g/mol) was dissolved in 1000 g of
liquid B (molar mass 180 g mol-1). The vapour pressure of pure liquid B
was found to be 500 torr. Calculate the vapour pressure of pure liquid A

33
 and its vapour pressure in the solution if the total vapour pressure of the
solution is 475 Torr.
4. 2 g of benzoic acid dissolved in 25 g of benzene shows a depression in
freezing point equal to 1.62 K. Molal depression constant for benzene is
4.9 K kg mol-1. What is the percentage association of acid if it forms
dimmer in solution?
5. Determine the osmotic pressure of solution prepared by dissolving 25 mg
of K2SO4 in 2 litre of water at 25C. Assuming that it is completely
dissociated.
6. Two elements A and B from compounds having formula AB 2and 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?

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

34
 UNIT :-3
ELECTRO CHEMISTRY

STUDY MATERIAL

Q1. Define molar conductivity. How does it varies with dilution ?

Ans:- Molar conductivity:-
It is the product of specific conductivity and volume of solution containing 1 g
molecular mass of the electrolyte.

K 1000
mol
C

Unit= Sm2 mol-1

35
* Variation :-

Strong Electrolyte:-Molar conductivity increases slowly with decrease in

concentration.

Weak Electrolyte:- Molar Conductivity increases sharply for weak electrolyte

on dilution .Q2. States Koahlrausch law.
Ans:- Limiting molar conductivity of an electrolyte is the sum of molar
conductivity of cation and anion at concentration approaches zero.
0 0 0
mol +
0
+ =Molar Conductivity of cation
0
=Molar Conductivity of anion

Q3. Wat do you mean by fuel cell? Write cathode and anode reaction in fuel
cell.
Ans:- Fuel Cell:- These are electrical cells which can convert the energy of
combustion of
a fuel like (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)

36
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)

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
37
 . What is the cell constant If conductivity of 0.001 M Kcl solution 298 K

is 0.148 X
10-3 S cm-1.

Ans:- R=1500
K=0.148 X 10-3 S cm-1
l
Cell Constant = ?
a
l
RK
a

=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

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
38
 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

=3.17 +
0.0591
log

Ag + 2

2
Mg 2 +
0.0591 (0.0001) 2
=3.17 + log
2 0.130
=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.

39
 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 Zn 2 + / 2 n 0.76V , E Cu 2 + / Cu +0.34V , F 96500C
0 0

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.

(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.

40
 (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.
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 E cell 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 ?
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)

41
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

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 log + 2
2
Ag

As the concentration of [Ag+] ion increases, Ecell increases.

(b) e.m.f. = 0
42
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 = log K
n

K < 0 log K < 0

i.e. log K is ve.

Then Ecell will be negative.

(b) If Ecell = 9 then 0 = 0.0591 log K

n

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 AgNO 3 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 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
6.022 1023
1 C of Charge is present on electrons = 1C
96500 C

= 6.24 1018
43
Q. 5. Which of the following pairs will have greater conduction and why ?
(a) Copper wire at 25 C and Copper wire at 50 C.
(b) 0.1 M acetic acid solution or 1 M acetic acid solution ?
Ans. (a) Copper wire at 25 C because with increase in temperature metallic
conduction decreases due to vibration of kernels.
(b) 0.1 M acetic acid solution because with dilution degree of
dissosciation increases and hence no. of ions.

3 MARKS QUESTIONS
Q. 1. The following curve is obtained when molar conductivity ( m) is
plotted against the square root of concentration for 2 electrolytes A
and B.
(a) What can you say about the nature of the two electroyltes A
and B ?
(b) How do you account for the increase in molar conductivity m
for the electrolytes A and B on dilution ?

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 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 Fe 2+ (aq) in which a strip of
iron has been immersed to a second half cell which contains 1 M Ni 2+
(aq) in which a strip of Ni has been immersed ? A voltmeter is
connected between the two metal strips :

44
 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 Fe 2+
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.
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
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 :

45
 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 V E = 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 :
2 Ag+ + 2 Hg 2 Hg + Hg22+

0.0591 Hg2 2+


Ecell = Ecell log + 2
2
Ag
0.0591 103
= (0.80 V 0.79 V) log

2
2 101
0.0591
= 0.01 V ( 1) = 0.01 + 0.0295
2
= 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.

46
 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?
6. Write the reaction occurs in fuel cell.

7. What do you mean by standard electrode potential?

8. What is galvanization of iron?
9. Define strong electrolytes.

10.Define molar conductivity.

02 Marks Questions
1. What is corrosion? How is rusting of iron protected by cathodic

protection.
2. How is cathodic protection different from galvanization in protection of

iron from rusting?

3. What do you understand by equilibrium constant? Calculate the

equilibrium constant of the reaction

Cu (s ) + 2Ag + (aq) Cu 2+ (aq) + 2Ag (s) E = 0.46 v .
4. Represent Zn Cu cell and write Nernst equation for the calculation of

emf of the cell.

5. The conductivity of 0.2M solution of NaCl at 298 K is 0.0248 S cm -1.

Calculate its molar conductivity.

6. The standard electrode potential for Daniell cell is 1.1v. Calculate the

standard Gibbs energy for the reaction

Zn (s) + Cu 2+ (aq) Zn 2+ (aq) + cu (s)
7. State and explain the Faradays laws of electrolysis. What is the value of

Faradays constant?
8. State reasons for the following

Rusting of iron is said to be an electrochemical phenomena.

Rusting of iron is quicker in saline water than in ordinary water.
Arrange the following metals in the order in which they
displace each from the solution of their salts.

47
 Al, Mg, Fe, Cu, Zn
03 Marks Questions
1. Write the Nernst equation and calculate the emf of the following cell
at 298 K. Cu(s) / Cu 2+ ( 0.130 M ) // Ag+ ( 1 x 10-4 M ) / Ag (s). Given
that 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),

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
2. What will be the effect on EMF of the cell if concentration of Ag + is
increased to 1 x 10-3M?

48
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.

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 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.

49
11. The standard reduction potential for the Zn2+ 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 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 cm 2 mol-1.
Calculate the molar conductance of acetic acid at infinite dilution.

5. Estimate the minimum potential difference needed to reduce Al2O3 at

500c. The G for the decomposition reaction 2/3 Al2O3 4/3 Al + O2
is G = 960 KJ.
6. The E0 Values for two metal electrodes are given below
(i) Cr3+/Cr2+= -0.4V (ii) Fe3+/Fe2+ = 0.8V
Comment on the result of treating a solution of Cr (II) with a solution
containing Fe (III) ions
7. Calculate the standard free energy change for the reaction occurring in
the cell
Zn|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.

50
20. Explain the electrode reaction of a fuel cell. Discuss the advantage of fuel
cell in space programme.
03 Marks Question
1. Predict the products of electrolysis in each of the following:

(i) An aqueous solution of AgNO3 With Ag electrodes.

(ii) A Dilute solution of H2SO4 With platinum electrodes.
(iii) An aqueous solution of CuCl2 with platinum electrodes.
2. The resistance of a conductivity cell containing 0.001 M KCl Solution at
298 K is 1500 ohms. What is the cell constant if conductivity of 0.001 M
KCl Solution at 298 K is 0.146X10-3 S cm-1.

3. Conductivity of 0.00241 M acetic acid is 7.896X10-5 S cm-1, calculate its

molar conductivity and if ^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.

5. Silver is electrodeposited on a metallic vessel of surface area 800 cm 2 by

passing current of 0.2 ampere for 3 hours. Calculate the thickness of
Silver deposited.
(Density of Ag =10.47 g cm-3, Atomic mass of Ag=108 amu)
05 Marks Question
6. Calculate the potential of following cell reaction at 298 K
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:
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
51
 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
9. (a) State Kholrauschs law for electrical conductance of an electrolyte
at infinite dilution.
(b) Give the composition and reaction of cathode and anode in a
mercury cell? Give one use.
(c) Silver is electrodeposited on a metallic vessel by passing a current
of 0.2 ampere for 3 hours. Calculate the weight of silver deposited.
(Atomic mass of Ag=108 amu)

FOR AVERAGE
01 Mark Question
1. Define the molar conductivity of an electrolytic solution.
2. Express the relation between degree of dissociation of an electrolyte and
its molar conductivities.
3. What does the standard electrode potential of a metal being negative 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)?

52
8. Which type of metal can be used for the cathodic protection of iron?
9. Give one difference between primary and secondary cells.
10. What are uses of salt bridge in a galvanic cell?
02 Marks Question
1. What is mercury cell? Give an electrode reaction?
2. Make difference between molar conductivity and equivalent conductivity.
3. Suggest a cell to determine molar conductivity experimentally.
4. How will you explain the sharp increase in molar conductivity of a week
electrolyte on dilution? How is molar conductivity related to the degree
of dissociation?
5. The conductivity of 0.20 M solution of potassium chloride 298 K is 2.48
x 10-2 ohm-1 cm-1 calculate the molar conductivity ?
6. A solution of Ni (NO3)2 is electrolyzed between platinum electrodes
using a current of 5 A for 20 minutes? What mass of Nickel is deposited
at the cathode?

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
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 cm2. 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

53
 a) Calculate cell potential for the cell containing 0.1 M Ag+ and 4 M Cu2+
at 25C.
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 Cd2+ 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 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.
2Cl- (aq) Cl2 + 2e- E0 = 1.36 v
2 H2O (l) O2 (g) + 4H+ (aq) + 4e- E0= 1.23 v

54
 Which of the above reaction actually takes place and why? Also give
other utilities of electrolysis?
********************

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.

55
 Average Rate = X/ t
Lt DX dX
Instantaneous Rate Dt 0
DT dT

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

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.

56
First Order Reaction : The reaction in which the rate of reaction is directly
proportionate to the concentration of reacting substance.

Rate = dx = k[A]
dt

Rate constant of first order reaction is

2.303 a
K log
t ax

2.303 A
or K log 0
t 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 Where K= rate constant
2 K

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.

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 ,
x y
Rate Where x+y =3
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

57
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 12 A n 1 where n is order of reaction.
0

For t 1 a for Zero order

2

t is independent for first order.

1
t1 for second order.
2 a
1
t1 2 for 3rd order.
2 a

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

58
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
K
2.303 R
log 0
Ans.:
t R

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. t1
2 K

Q7. Is half life time independent to initial concentration in first order reaction.
Ans.: Yes

Q8. Write the Arrhennius equation of reaction rate.

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

59
Ans.: It is the number of molecules taking part in each act of leading chemical
reaction.
Example : (1) decomposition of NH4NO2.
NH 4 NO2 N 2 + 2 H 2 O i.e. Unimolecular
(2) 2 HI H 2 + I 2 i.e. Bimolecular reaction

Q11. What do you mean by order of reaction.

Ans. : Sum of powers of the comcentarion of the reactants in the rate law
expression is
called the order of that chemical reaction.
Suppose, Rate = K[A]x[B]y
Hence, Order of reaction = x+y

Q.12. Calculate the overall order ofn a reaction which has the rate expression.
Ans. Rate = K[A][B]3/2
Hence, Order of reaction = + 3/2 = 2 ( i.e. Second Order)

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

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

60
 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.

Q3. A reaction is 50% complete in 2 Hrs and 75% complete in 4 Hrs.What is

the order
of the reaction?
Ans. First Order.

Q4. The plot of log K versus X is linear with a slope = -E a/ 2.303 R. What is
X?
Ans. X is 1/T.

Q5. The rate constant of a reaction is 1.2 x 10 -2 L.Mol-1S-1. What is the order
of the
reaction ?
Ans.: Order =2
For Above Average Students : 01 Mark

Q1. What is temperature coefficient ?

R308
Ans.: R
298

Q2. Fill up the blanks :

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

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 61 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.

3
The rate law is r=K[A] . If the concentration of A is doubled the reaction
rate will be (a) Doubled, (b) Quadrupled, (c) Increased by 8 times, (d)
Unchanged
Ans.: (c)

CHEMICAL KINETICS
Below Average Students :02 Marks

Q1. Differentiate between order of reaction and molecularity of reaction.

Ans.
Order of reaction Molecularity
1. It is defined as sum of powers to 1. It is the number of molecules taking
which concentration terms are raised part in chemical reaction.
in rate law
2. It is determined experimentally 2. It is determined theoretically
3. It can be zero or even in fraction 3. It is always in whole number
except Zero.
4. Order of complex reaction can be 4. Molecularity of complex reaction
determined, can 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

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.:

62
 +
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

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 1 1386Min
2 K 0.05

Q.3. What is meant by effective collision?

Ans.: The collision which leads to formation of product. Molecules is called
effective
collision.
Q4. When do molecules undergo effective collision?
Ans.: Molecules undergo effective collision if they cross energy barrier and
orientation
barrier, that is they possess activation energy and collide in proper
orientation.

Q5. How does concentration effect the rate of reaction?

Ans,: When we increase concentration of reactants, total no. of collision will
increase, therefore, probability of effective collision will increase, hence the rate
of reaction will increase.
For Above Average Students : 02 Marks
Q1. An increase of 10 K in temp. rarely doubles the kinetic energy of particles
but
doubles the rate of reaction, why?

63
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. 19.15
Ea 0.544 18230.8 J
5.714 10 14
Ea
Since, K Ae RT

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.
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]
64
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
2.303
K log 2
t1
2

0.693
t 1
2 K

FOR AVERAGE STUDENTS :03 Marks

Q1. Derive the relationship between activation energy & rate constant.
E
Ans. Arrhenius equation K A.e RT where A is 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

Experiment [A] M [B] M Initial rate of formation of D/M

al min-1
1 0.1 0.1 6.0 x 10-3
2 0.3 0.2 7.2 x 10-2
65
3 0.3 0.4 2.88 x 10-1
4 0.4 0.1 2.4 x 10-2

Determined the rate law and the rate constant for the reaction.
Ans.:
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) t1 1
3.465 10 3 Sec.
2 K 200 S

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

0.693
(c) t1 0.173 years
2 4

Q3. Give the mechanism of the reaction

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

Ans.: Chain initiation step :

Cl + Cl HN
2Cl
Chain propagation step
H 2 + Cl H + HCl
H + Cl 2 HCl + Cl
Chain termination step

66
Q4. State the role of activated complex in a reaction and state the relation
with energy of activation.
Ans.: When the colliding reactant molecules possess the kinetic energy equal to
energy of activation then the configuration of atoms of the species at this state is
different from the reactants as well as the products.This state is called activated
or transition state and specific configuration of this state is called activated
complex.
The reactant molecules do not change directly into products, first they
absorb energy equivalent to the energy of activation and form an activated
complex. The activated complex formed has a very short life spam and splits
into the products. The activated complex is at the top of the energy barrier graph
and possess the highest energy. In this activated complex, all the bonds are in
the transition state.
Low energy activation barrier means the activated complex is readily
formed and it is fast reaction.
High energy of activation barrier means the activated complex is difficult
to form and it is a slow reaction.

A.B
Activated complex

Eaf
Energy DH o S E R E P

ER JHoS
Reaction condition

UNIT 05
SURFACE CHEMISTRY

67
 STUDY MATERIAL

1. Adsorption:- It is the process of attracting molecular species on the

surface of solid or liquid .

2. Adsorbate:- The molecular species which concentrates or accumulates on

the surface known as Adsorbate.

3. Adsorbent:- The solid or liquid substance on which adsorption takes

place known as adsorbent .

4. Desorption:- The process of removal of adsorbed substance from a surface

of solid or liquid known as desorption.

5. Absorption:- The uniform distribution of molecular throughout the bulk of

the solid known as absorption.

6. Sorption:- The process in which both adsorption and absorption

takes place simultaneously known as sorption.

7. Enthalpy of Adsorption:- The amount of energy released by the

attraction of one mole of adsorbate on the adsorbent.

8. Types of adsorption :- There are two types of adsorption :

(a) Physisorption or Physical adsorption:- When the gas molecules are
attracted or accumulated on the solid by Vander waals forces.
(b) Chemisorption or Chemical adsorption:- When the gas molecules are
accumulated on the solid by chemical bonds.

9. Freundlich adsorption isotherm:- He gave a relation between the

quantity of gas adsorbed by unit mass of solid adsorbent and pressure at a
particular temperature
x/m=k 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 isotherm .Only in place of pressure ,concentration of
solution is taken.
Therefore x/m=k C 1/n

68
11. Catalyst:- A substance which increase or decrease the rate of
chemical reaction and quantitatively unchanged after the reaction known as
catalyst. There are two types of catalyst:- (i) Positive Catalyst and (ii) Negative
Catalyst.

12. Promters:- A substance enhances the activity of catalyst.

13. Poisons:- A substance decreases the activity of catalyst.
14. Homogeneous catalysis:- When reactants and catalysts are in same
phase ,the process is known as Homogeneous catalysis.
Eg. 2 SO2 ( g ) + O2 ( g ) NO
(g)
2 SO3 ( g )

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.
(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 2 CONH 2 + H 2 O Urease
2 NH 3 + CO2

Urease is an enzyme used for the decomposition of Urea only.

19. Colloids or Colloidal Solution : A heterogeneous solution in which

dispersed phase mixed in dispersion medium.

20. Lyophilic Colloids : Those colloids which are solvents loving or

attracting they are reversible Sols.

21. Lyophobic Colloids :- Those colloids which are solvent hating. It is

irreversible Sols.

69
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.

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 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.

70
33. Electrophoresis : The process of migration of charged colloidal solute
towards the oppositely charged electrode in colloidal solution is known as
Electrophoresis.

34. Coagulation : The process of converting colloidal solution into

precipitate by mixing small amount of oppositely charged electrolyte known as
Coagulation.

35. Coagulative Value : The minimum no. of a milli moles of electrolyte

requires to coagulate one litre colloidal solutions.

36. Hardy-Schultz Rules: It has two rules :

a) Oppositely charged ions are effective for coagulation.
b) The coagulative power of electrolyte increases with increase in
charged on the ion used for coagulation. For Eg. :
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 :

71
 x
M

Ans. Chemisorption.

Q. 2. In the titration of oxalic acid by acidified KMnO 4, the oxidation of

oxalic acid is slow in the beginning but becomes fast as the reaction
progresses. Why ?

Ans. Autocatalysis by Mn+2.

Q. 3. Out of 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

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.

72
Q. 9. What is the term used for minimum concentration of an electrolyte
which is able to cause coagulation of a sol ?
Ans. Flocculation value.
Q. 10.A liquid is found to scatter a beam of light but leaves no residue when
passed through the filter paper. What can the liquid be described as ?
Ans. Colloid.
Q. 11. If an electric field is applied to a colloidal sol, the dispersed phase
particles are found to move towards the electrode of opposite charge.
If however, the dispersed phase is made stationary, the dispersion
medium is found to move in the opposite direction. What is the term
used for such movement of dispersion medium ?
Ans. Electro osmosis.
Q. 12.Out of glucose, urea and dodecyl trimethyl ammonium chloride,
which one forms micelles in aqueous solution above certain
concentration ?
Ans. Dodecyl trimethyl ammonium chloride.
Q. 13.A plot of log versus log p for the adsorption of a gas on a solid gives a
straight line. What is the slope equal to ?
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 ?
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.
73
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 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 ?

74
Ans. Traces of electrolytes in the sol, impart charge to dispersed phase
particles making it stable. Prolonged dialysis removes all electrolytes thus
making the sol unstable.
Q. 4. What is the function of gum arabic in the preparation of Indian ink ?
Ans. Gum arabic is a protective colloid and thus provides stability to Indian
ink.
Q. 5. What is collodion ? What is its use ?
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.
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 SnCl 4
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 SnO 2 particles
giving them a negative charge.
Q. 9. Why physical adsorption is multimolecular whereas chemisorption is
unimolecular ?
Ans. Chemisorption takes place as a result of reaction between adsorbent and
adsorbate. When the surface of the adsorbent is covered with one layer,
no further reaction can take place.
Physical adsorption is simply by Vander Waals forces. So any number of
layers may be formed one over the other on the surface of the adsorbent.
75
Q. 10.What is meant by induced catalysis ? Give an example.
Ans. It is a phenomenon in which a chemical reaction increases the rate of
another reaction which otherwise may not occur in similar conditions.
Eg. Sodium arsenite (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.
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
76
 solids.
Ans: Effect of pressure : By the increase of temp., extent of adsorption
decreases
uniformly for physisorption but for chemisorption initially increases
then
decreases.

Q5. What is observed

(i) When a beam of light is pressed through a colloidal sol
(ii) An electrolyte, NaCl is added to hydrated ferric oxide sol.
(iii) Electric current is passed through colloidal sol.
Ans.: (i) Tyndal Effect
(iv) Coagulation
(v) Electrophoresis

Q6. What do you mean by activity and selectivity of catalysis?

Ans. Activity of catalyst means to increase the extent of chemisorption.
Selectivity of Catalyst means to direct a reaction to form selective
product.

Q7. What is ZSM-5? What is its formula?

Ans.: ZSM-5 is a zeoli8te seine of molecular porosity5. Its formula is
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 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 .

77
Ans. A substance shows different physical properties in different medium. It
may exist as colloid or crystalloids under certain conditions. Eg. NaCl in
water behaves like crystalloid while in benzene behaves like colloid.
Similarly dilute soap solution behaves like crystalloid whereas
concentrated soap solution like colloids. It is the size of particles which
matters i.e. the state in which the substances exists. If the size of the
particles lies in the range 1 to 1000 no., it is in colloidal state.

Q11. Why are substances like Platinum and Palladium offer used for carrying
out electrolysis in aqueous solution ?
Ans.: Platinum and palladium is inert electrodes. They are not react with the
ions of electrolyte and products of electrolysis. Hence they are used as
electrodes during electrolysis. Hence they are used as electrodes during
electrolysis. Hence they are used as electrodes during electrolysis in
aqueous solution.

Q12. Why it is necessary to remove CO when ammonia is obtained by Habers

process?
Ans.: Because CO acts as poison for the catalyst in the manufacture of NH 3 by
Habers process.

Q13. Which will be adsorbed more readily on the surface of charcoal and why
NH3 or CO2?
Ans: The critical temperature NH3 is more CO2, therefore NH3 is liquefied
more easily than CO2. Hence NH3 has higher intermolecular forces of
attraction and hence it adsorbed more readily.

Q14. What is similarity and dissimilarity in aqua solution and solid aerosols?
Ans. Aqua Sols and solid aerosols both have solid as dispersed phase and have
different dispersion medium. Aqua solution contain water and aerosol
contain air as dispersion medium.

Q15. How can a colloidal solution and true solution of the same colour be
distinguished from each other?
Ans.: By Tyndal effect( colloidal solution will scatter light and path becomes
lighted where as no such phenomena is observed in true solution.)

Q16. Why is ferric chloride preferred over potassium chloride in case of a cut
leading to bleeding?
Ans.: Blood is negatively charge colloidal particles. It is coagulated by +ve
ions. As Fe++ ions has greater number of charges than K + ions. Therefore
on the basis of Hardy-Schulze rule, Coagulation with Fe +++ is faster and
hence it is preferred.

BELOW AVERAGE STUDENTS :01 Mark Questions

78
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?
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?
6. Write two examples of heterogeneous catalysis.

ABOVE AVERAGE STUDENTS : 01 Mark

79
 1. Define Enthalpy of Adsorption.
2. What is the role of desorption in the process of catalysis?
3. Define Tyndal Cone.
4. What is Electrokinetic Potential or Zeta Potential?
5. Define Coagulating Value.

SURFACE CHEMISTRY
Below Average Students :02 Marks Questions

1. Explain Desorption and Sorption.

2. Write two differences between physisorption and chemisorption.
3. What is homogeneous and Heterogeneous catalysis? Give one
example each.
4. Define Promoters and Poisons.
5. Write two applications of catalyst in Industry.
6. Explain cleansing action of soap.
7. What are the methods for the preparation of colloids.
8. What is purification of colloidal solution? Name the process of
purification of colloids.
9. Write brief notes on
(a) Brownian Movement and
(b) Electrophoresis.
10. State Hardy-Schulze Rule. What is its application?
11. Write the example of colloids which is being used in our daily life.

AVERAGE STUDENTS :
02 Marks Question
1. Write the mechanism of Adsorption.
2. Why are substances like Platinum and Palladium often used for
carrying out electrolysis of aqueous solution?
3. What is function of promoters and Poisons?
4. Write the name of process and catalyst used for the preparation of NH3

80
 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).
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?
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

81
 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.
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.

82
 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.
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

Aluminium Bauxite AlOx(OH)3-2x
Kaolinite ( a form of Clay) [ where 0 < x<1]
Iron Hematite Fe2O3
Magnetite Fe3O4
Iron Pyrite FeS2
83
Copper Copper Pyrite CuFeS2
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.

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.

84
 Calcination : It is the process of converting an ore into its oxide by
heating it strongly below its m.p. either in absence or limited supply of
air.
This method is commonly used to convert metal carbonates and
hydroxides to their respective oxides.During the process of calcination,
the following chemical changes occurs.
1) Moisture is driven out.
2) Volatile impurities of S, As & P are removed as their volatile oxides.
3) Water is removed from hydrated oxides and hydroxides ores.
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.

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.

85
1 MARK QUESTIONS

Q. 1. Why carbon reduction process is not applied for

reducing aluminium oxide to aluminium ?

Ans. Because aluminium metal itself a very powerful agent and

can easily reduce CO formed during the reaction back to carbon.

Q. 2. Explain why thermit process is quite useful for repairing

the broken parts of a machine ?

Ans. In thermit process, oxides of metals are reduced by

aluminium in which large amount of beat is evolved, metal is in
the motten state & is allowed to fall between the broken parts of a
machine.
heat
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

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

86
 The reaction is feasible at 2273 K.
Q. 4. Why is Zinc and not Copper used for the recovery of
Silver from the complex [Ag (CN)2] ?

Ans. Zinc is stronger reducing agent and more electropositive

than Copper. (E = + 0.34V)
Q. 5. Graphite is used as anode and not diamond. Assign
reason.
Ans. In graphite there are free electrons which helps in
electricalconductivity.
Q. 6. How is granular zinc & zinc dust obtained ?
Ans. Granular zinc is obtained by pouring molten zinc in cold water &
zinc dust by melting zinc & then atomising it with blast of air.
Q. 7. How does NaCN act as a depressant in preventing ZnS from
forming the froth ?
Ans. NaCN forms a layer of zinc complex, 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)

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.
87
 Q. 11. At which temperature direct reduction of Fe 2O3 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 and refining
of metals. Sulphide, carbonate, oxide ores etc. are subjected to
pyrometallurgy.
Q. 15. How the most electropositive metals are isolated from their
ores ?
Ans. The most electropositive metals are isolated from their ores by
electrolysis of fused ionic salts.
SOME IMORTANT QUESTIONS

Q.1. In general which metals do you expect to occur in the nature in native
state? Give examples.
Ans. : Metals such as Cu, Ag, Au, Pt etc. which lie below hudrogen in
electrochemical series are not readily attached by Oxygen, moisture and
Carbon dioxide of the atmosphere and hence occur in the native state in
nature.

Q.2. Copper and Silver lie below in the electrochemical series and yet they are
found in the combined state as sulphide in nature.Comment.
Ans. : Due to high polarizing power of Cu and Ag ions, their sulphides are even
more stable than the metals.

Q.3. Which metals are generally extracted by electrolyte process? Which

positions these metals generally occupy in the periodic table?
Ans. : Electrolytic process is used for the extraction of active metals like Na, Ca,
Mg, K, Al etc. where all other methods fail. Except Al and few other
metals, these metals belongs to S-block elements of periodic table.

88
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 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 0 DH 0 TDS 0 _) becomes more on the ve side and the
reduction becomes easier.

Q.6. At a site, low grade copper ores are available and zinc and iron seraps are
also available. Which of the two seraps will be more suitable for reducing
the leached copper ore and why ?
Ans. : The E0 value for the redox couple Zn2+/ Zn(-0.76V) is more negative than
that of Fe2+/ Fe(-0.44) redox couple. Therefore, Zinc is more reactive than
iron and hence reduction will be faster in case if Zinc seraps are used, But
Zinc is a costier metal than iron so using iron scraps would be more
economical.

Q.7. (A). Name the method used for refining of (i) Nickel (ii) Zirconium
(B). The Extarction of Au by leaching with NaCN envolves both
Oxidation and Reduction. Justify giving equations.

Ans. ; (A) [ i ] Mond Process : It is used to refine Nickel metal. When impure
Nickel is heated in a current of CO at 330-350 K, it forms volatile nickel
tetracarbonyl complex leaving behind the impurities. This complex again
on heating at higher (450-470K) it undergoes thermal decomposition
giving pure Nickel.

Ni + 4CO 330 Ni CO 4
350 K

Impure Nickel tetracarbonyl

Nickel
Ni CO 4 450
Ni + 4CO
470 K

Pure Nickel

89
[ 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 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

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

1
ii) C s + O2 CO s ; D f G 439 Kj / mol
2
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
90
 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 s + O2 MgO s ; D f G 314KJ / mol
2
1
iv) C s + O2 CO s ; D f G 628KJ / mol
2
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.

Q10. What are fluxes? How are they useful ?

Ans. : Flux is a substance that combines with gangue which may still be present
in the roasted on the calcined ore to form an easily fusible material called the
slag.

Q.11. What is a slag?

Ans: A slag is an easily fusible material which is formed when gangue still
present in the roasted or the calcined ore combines with the flux. For example:
in the metallurgy of Iron, CaO(flux) combines with silica(SiO 2) gangue to form
easily fusible calcium silicate (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.

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
91
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
1. How does minerals different from an Ore ?
2. What do you mean by benefication process or concentration or
enrichment or dressing ?
3. What is a slag? Give one example of basic flux.
4. Why do a few elements occurs in the native state while others do not ?
5. Write constituents of bronze with their use.
6. Why is Zinc not extracted from Zinc Oxide through reduction using
CO?
7. What is the role of cryolite in the metallurgy of Aluminium?
8. Which type of metals are refined by distillation method?

FOR AVERAGE STUDENTS :01 Mark

1. Name the chief form of occurrence of the following in the earths crust
:
a) Aluminium, b) Iron, c) Copper, d) Zinc
2. An Ore sample of galena (PbS) is contaminated with Zinc
blende(ZnS). Name ore chemical which can be used to concentrated
galena selectively by froth floatation process.
3. How is cast iron different from pig iron?
4. What is copper matte?

92
 5. Why pine oil is used in the froth floatation method?
For Bright Students: 01 Mark
1. Copper and Silver lies below in the electrochemical series and yet they
are found in the combined state as sulphides in nature. Comment.
2. Name the common element present in the anode mud in electrolytic
refining of copper. Why are they so present?
3. What is meant by the term chromatography?
4. What is the role of depressant in froth floatation process?
5. What criterion is followed for selection of the stationary phase in
chromatography?
6. What is the role of collector & froth stabilizer in froth floatation
process?

For Below Average Students:

02 Marks Questions

1. Why copper metal is put in Silica lined converter ?

2. Giving examples, differentiate between roasting and calcinations.
3. Describe the method of refining of Nickel.
4. Explain the Leaching of Silver or Gold.
5. Write two important ores of Iron, Aluminium, coppere & Zinc with
their chemical formula.
6. What is aluminothermy? Explain with an example.
FOR AVERAGE STUDENTS:
02 Marks Questions
1. State the role of silica in the metallurgy of copper.
2. Why is the extraction of copper from pyrite difficult than that from its
oxide ore through reduction?
3. Write chemical reactions taking place in the extraction of Zinc from
Zinc blend.
4. Silver Ores and native gold have to be leached with metal cyanides.
Suggest a reason for this.

93
 5. What do you mean by vapour phase refining? Describe with suitable
example.
6. The extraction of Au by leaching with NaCN envolves both oxidation
and reduction. Justify giving equations?
7. Copper can be extracted by hydrometallurgy but not Zinc explain.

FOR BRIGHT STUDENTS:

02 Marks Questions
1. Out of C and CO, which is a better reducing agent for ZnO?
2. What is the role of graphite in the electrometallurgy of Aluminium?
3. What do you mean by leaching? Explain with an example.
4. The Choice of a reducing agent in a particular case depends on
thermodynamic factor, how far do you agree with this statements?
Support your opinion with two examples.
5. Discuss some of the factors which need consideration before deciding
on the method of extraction of metal from its ore.

FOR BELOW AVERAGE STUDENTS:

03 Marks Questions
2. What is the chief ore of iron? Write chemical reactions taking place in
the extraction of Iron from its Ores.
3. Give the important uses of
a) Aluminium, b) Copper, c) Iron
3. Differentiate between (i) Gangue and Flux (ii) Minerals & Ores

4. What do you mean by following terms :

(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

94
 1. Name the processes from which chlorine is obtained as a bye-product.
What will happen if an aqueous solution of NaCl is subjected to
electrolysed.
2. Explain how the following metals are obtained from their oxides by
the reduction process.
a) Metal X which is low in the reactivity series.
b) Metal Y which is in the middle of the reactivity series.
c) Metal Z which is high up in the reactivity series
3. a) Describe a method for refining of Nickel.
b) The extraction of Ag by leaching with NaCN involves both
oxidation & reduction.

For Bright Students: 03 Marks

1. Account for the following :
i) The reduction of metal oxide is easier if the metal formed is in
liquid state at the temperature of reduction.
ii) the reduction of 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 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.

95
 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 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 ns2 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
96
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 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 N2 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. PCl3 fumes in moisture.

(vii) Oxo acids:

(a) N:- Two important oxo acids viz Nitric acid and Nitrous acid. Both
are mono protic.
The presence of nitrate ion can be detected by adding freshly prepare FeSO 4
solution followed by adding 1-2 drop conc. 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.

97
OXYGEN FAMILY(Group 16 Elements)

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.

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.

98
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.
(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 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;

99
 (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 make compounds with highly electronegative elements
like fluorine & oxygen.

3. Important compounds of xenon with its shape, hybridization & structure :-

sp3d sp3d2

100
 Sp3d3 sp3d2 sp3
OXO- ACIDS OF PHOSPHORUS

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, 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

101
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?

Ans: Because of lone pair of electrons on N.

3. Why Nitrogen is a gas whereas Phosphorous is a solid?

Ans: Nitrogen molecules have less Vander Waals forces of attraction whereas
molecular phosphorous has more Vander Waals forces of attraction.

4. Why is Nitrogen relatively inert?

Ans: Because of a triple bond with high bond energy.

5. Ammonia is water soluble. Why?

Ans: It forms hydrogen bond with water.

(2 marks questions)
1. Write shape of following molecules:
a) Ammonia
b) Phosphorous Pentachloride

Ans: a) Pyramidal
b) Trigonal bipyramidal

2. Ortho phosphoric acid is triprotic but phosphoric acid is diprotic. Why?

Ans: Because of their structures ortho phosphoric acid and phosphoric acid have
three and two ionisable hydrogen.

3. Give reasons:
a) Phosphorous pentachloride is unstable.
b) Phosphorous trichloride fumes in moisture.
Ans: a) Because of two longer axial bonds.
b) Because it reacts with water and forms hydrochloric acid.

(3 marks questions)
4. Nitrogen shows anomalous behaviour in the group. Why?
Ans: i) Small size
ii) High electro negativity
102
 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)
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) XeF2 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.

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

103
 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 ?
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

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

104
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.
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.
23. NH3 is pyramidal.
24. One of the noble gases only xenon is known to form real chemical
compounds.
FOR AVERAGE

105
 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.
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.
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
106
 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

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.

107
FOR BELOW AVERAGE
D. What happens when;

1. Conc. H2SO4 is added to CaF2.

2. SO3 is passed into water.
3. Chlorine is passed through a hot and conc. Solution of alkali, like
Ba(OH)2.
4. XeF4 undergoes hydrolysis.
5. XeF6 undergoes hydrolysis.
6. PCl5 is heated.
7. NaCl is heated with H2SO4 in presence of MnO2.
8. Cl2 is passed through a solution of NaI in water.
9. SO2 gas is passed through a solution of Fe(III) salt.
10 White P is heated with NaOH solution in an inert atmosphere of CO2.

FOR BELOW AVERAGE & AVERAGE

E. Arrange the following as mentioned:

1. M-F, M-Cl, M-Br, M-I. (Decreasing order of ionic nature)

2. 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)

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.

108
 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 .
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
(iii) S + HNO3(conc.) H2SO4 +NO2+ H2O (iv) P4+ HNO3 (conc.)
H3PO4+ NO2+H2O
(V) HNO3 HNO3+ NO+ H2O

109
 UNIT 08
THE d- BLOCK AND
f-BLOCK ELEMENTS
STUDY MATERIAL

Transition elements:-The elements lying in the middle of periodic table

belonging to gr.3 to 12 are known as transition elements.

Electronic configuration :- (n-1)d 1-10 ns 1-2 .

Lanthanoids:-The 14 elements immediately following lanthanum, i.e

.Cerium(58) to Lutetium(71) are called lanthanoids.

Actinoids:-The 14 elements immediately following Actinium(89),with atomic

no.90 to 103 are called actinoids.

Inner transition elements: Elments in which last electron inter in f-sub-shell of

antipenultimate energy level.

Solvation energy or energy of hydration:-The amount of energy change when

1 mole of solid substance is changed into vapour state.

CHARACTERISTICS OF TRANSITION ELEMENTS:-

Properties of transition metals Reason due to

i. metallic in nature High enthalpy of atomization
ii. show variables oxidation states. Presence of vacant d- orbitals
iii. complex compounds. Small size, High charge density
iv. coloured compounds. d-d Transition
v. good catalyst Suitable surface area in d-orbital
vi. paramagnetic compounds. Unpaired electron in d-orbital
110
vii. Interstitial compounds Similar atomic size & Vacant space in
lattice
Lanthanoid Contraction:-There is steadly decrease in the atomic and ionic
radii as the atomic no, increases. It is because ,for every additional proton in the
nucleus ,the corresponding electron goes into the 4f shell which is too diffused
to screen the nucleus as effectively as more localized for the outermost electron
increases steadily with the atomic no. of lanthaoids. This contraction in size is
called lanthanoid contraction.
TRANSITION ELEMENTS FORM :-

Basic Oxide :- Sc2O3,TiO, Ti2O3, VO,V2O3, Due to lowest oxidation states

MnO ,FeO, CuO, CoO, NiO, Cu2O
Acidic Oxide:-V2O5,Mn2O7,CrO3, OsO4 Due to highest oxidation states
AmphotericOxide:-CuO,TiO2,ZnO,CrO3, Due to intermediate oxidation
Cr2O3, Mn2O3,MnO2,Mn3O4Fe3O4 states
Spinel:- ZnFe2O4, Tri & divalent occupies octa &
tetra-hedral hole
Non stoichiometric compounds:Fe0.91O or Due to defects in lattice crystal
Fe0.95O
Ionic Halides;All flouoro i.e. CuF2,AgF Due to lower oxidation states
Covalent Halides:- Due to higher oxidation states
CuI2,CuCl2,CuBr2,AgCl,AgBr

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
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:-

Lanthanoids Actinoids

Common oxidation state is +3, besides Common oxidation state is +3, besides
this +2 ,+4 this +4,+5,+6, &+7 also.+2 quite rare
Have smaller tendency of complex Strong tendency of complex forming
forming
Dont form oxo- ions Do form oxo-ions i.e. UO2+, PuO2,UO+
111
Non-Radioactive Except Promethium All are Radio-active
Compounds are less basic Compounds are more basic

Important compounds of transition metals:-

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:

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:-

112
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
Structure:

Below

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

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
In dry cell

113
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
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 -0.91v -1.18 v -0.44 v -0.28 v -0.25 v +0.34V
v

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
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 .

114
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
-2 +3
(ii) 3H2S + Cr2 O7 + 8H+3S+ 2Cr + 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
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 :-
(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

115
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 .
(v) Why is Cu+1 diamagnetic and Cu +2 paramagnetic ?
It is because Cu+ does not have unpaired electrons where as Cu+2 has
unpaired electrons in d-sub cell .

02 Marks

(i) Why are transition metal fluorides are ionic in nature where as
chlorides and bromides are covalent in nature .
Ans - It is because of fluorine is most electronegative where as Cl and Br are
less electro negative .
Greater the difference in electro negativity more will be ionic
character .
(ii) Why Mn+2 is more stable than Mn+3 but Fe +3 is more stable
than Fe+2 ?
Ans Mn+2 has half filled d- orbital ,therefore it is more stable than Mn+3
Fe+3 has half filled d- orbital, therefore it is more stable than Fe
+2 .

(iii) Why are lanthanoid colored and paramagnetic L

Ans It is due to presence of unpaired electrons, they are paramagnetic and
they absorb light
From visible region and undergoes f-f transition and radiate
complementary colour .

03 Marks

(i) What is meant by disproportionation ? Give two examples of

above reaction in aqn. Solution .
Ans Disproportionation means the same substance get oxidized and
reduced, examples
116
 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 .

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

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+ + Cr207-22Cr+3 +7H2O

117
(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

(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

1 MARK & 2 MARKS QUESTIONS

118
Q. 1. A cationic complex has two isomers A & B. Each has one Co 3+, five
NH3, one Br and one SO42. A gives a white precipitate with BaCl 2
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 Cu 2+ 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 FeSO 4 (NH4)2SO4 . 6 H2O. In
aqueous solution, the salt dissociates.
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 CuSO 4 in two tubes, we add ammonia
solution in one tube and HCl (aq) to the other tube, how the colour of
the solutions will change ? Explain with the help of reaction.
Ans. In first case, colour will change from blue to deep blue.
[Cu (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 H 2O
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 on heating with conc. H2SO4. Identify A, B and
C.

Ans. Data suggests that the complexes are hydrate isomers.

119
 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

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 COCl 3 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

120
 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 the ligands repulsions are more and so is the
energy. The lobes of the remaining three d-orbitals lie between the axes i.
e. between the ligands, the repulsions between them are less and so is the
energy.

Q. 8. Dimethyl glyoxime is added to alcoholic solution of NiCl 2. When

ammonium hydroxide is slowly added to it, a rosy red precipitate of a
complex appears.
(a) Give the str. of the complex showing hydrogen bond.
(b) Give oxidation state and hybridisation of central metal ion.
(c) Identify whether it is paramagnetic or diamagnetic.
Ans. (a)

121
 (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 M 3+
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 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 ?
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

122
 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)
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
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

123
 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

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]
(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]

124
 (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

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

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

125
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 Fe 2+ ion but cuso4 soln mixed with aqueas ammonia in 1:4
molar ratio
does not given the test of Cu2+ ion
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
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)

126
 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.

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

FOR AVERAGE
01 mark questions
Q.1. Write down the IUPAC name of the following organic compounds: -
127
 (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
( 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
dipole moment. In CHCl3 and CCl4, two Cl atoms and four Cl atoms cancel
out their dipole moments.
128
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
O Cl Cl
(d) anhyd. COCH3
Cl + CH3-C-Cl +
AlCl3
COCH3
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
129
(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

(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

130
 H +AlCl4-
+ HCl
CH3CO - AlCl3

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
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
131
Q.2. Write down the IUPAC name of the following organic compounds:

(a) Br

Br

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
0
160-170 C 2.Alc.KOH

NaNH2
C2H5Cl
CH3CH2C= CH CH=
CNa

NO2 NO2

b) Conc.HNO3 Br2/ CCl4

Br

CH3 CH2Cl
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
132
 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: -
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

(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.

133
 (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

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

134
 O2N

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

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

135
 |
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 SN 1 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

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>C6H5CH2Br
Reactivity towards SN2 Reaction

C6H5C(CH3)(C6H5)Br<C6H5(CH(C6H5)Br<C6H5CH(CH3)Br<C6H5CH2Br

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

136
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.

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)

137
Q. 2. What is usually added to ethyl alcohol to make it unfit for drinking
purposes ?

Ans. Methanol and Pyridine.

Q. 3. Phenol has smaller dipole moment than methanol.

(OR)

Why are dipole moments of phenols smaller than dipole moments of

alcohols ?

Ans. Due to electron-withdrawing effect of the benzene ring, the C O bond

in phenol is less polar but in case of methanol due to electron-donating
effect of 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.

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 :
138
 In p-nitrophenol, there is intramolecular hydrogen bonding as follows :

Due to intermolecular H bonding in p-nitrophenol, its b. p. is much higher

than that of o-nitrophenol. Hence o-nitraphenol due to its lower b. p. is
steam volatile while p-nitrophenol is not.
Q. 9. How an OH group attached to carbon in the benzene ring
activates benzene towards electrophilic substitution ?

Ans.

The lone pair of electrons present on oxygen atom enter into resonance
with the benzene ring. As a result, the electron density becomes higher at
o- and p- position and due to higher electron density, the ring gets
activated towards electrophilic substitution.
Q. 10.Ethers are cleaved by acids not by based. Why ?
139
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 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 :

140
 H H OH
C C O
+
H + H 2O C C + H 3O
+

H

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

Q1. Why phenol is acidic ?

141
 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.

Ans: O- nitro phenol will be steam volatile because there is intramolecular. H-

bonding in its
molecule.
O
OH
N Intramolecular hydrogen bonding
\\
O

But in case of p- nitro phenol there is association of

molecules of p- nitro phenol due to intermolecular hydrogen bonding.
O O O O
\\ //
N OH N
| | |

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

H H H H
| | | |
H-C-C-O-H H- C C - OH2
| | | |
HH H H
142
 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)

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.

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

143
 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 H3C 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.

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

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

144
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

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

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

H H H H H

Q.8. Illustrate Riemer Tiemann reaction with one example

145
 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)

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 : -

(i) Aniline to Phenol
(ii) Phenol to picric acid

146
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.
(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.

Q.6. While separating a mixture of ortho and para nitro phenols by

steam

147
 distillation, name the isomers which will be steam volatile. Give
reason.

Q.7. Convert the following: -

(i) Acetaldehyde to Isopropylalcohol
(ii) Acetone to t - butyl alcohol.

Q.8. Arrange the following set of compounds in order of their increasing

boiling points.
(a) Pentan 1 ol, Butan 1- ol, Butan 2- ol, ethanol, Propan

1- ol,
(b) Pentan -1-ol, n- butane, pentanal, ethoxyethane and
methanol.

Q.9.
(i) What is the Lucas test?
(ii) Distinguish Primary, Secondary and tertiary alcohols with
the
help of Lucas test.
Q.10.
(i) Why the presence of OH group attracted to benzene ring
activates the ring towards electrophilic substitution?

AVERAGE
01 mark questions : -

Q.1. Write down the IUPAC name of

H3 C 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

148
 and

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.

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 :

149
 CH2OH OH
(i)

and

(ii) O

and
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.

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.
150
 (ii) Friedel-Crafts acetylation of anisole.

Q.3.
(i) Explain why is ortho - nitro phenol more acidic than o- methoxy
phenol?
(ii) Write the mechanism of the reaction of HI with methoxy
methane.

Q.4. How are the following conversions carried out?

(i) Ethyl magnesium chloride Propan 1- ol

(ii) Benzyl chloride Benzyl alcohol
(iii) Propane Propan 2- ol
Q.5.
(i) Explain the preparation of ethers by acid dehydration of secondary
or
tertiary Alcohols is not a suitable method.

(iii) Explain why propanol has higher boiling point than that of the
hydrocarbon , butane?

ABOVE AVERAGE
01 mark questions
Q.1. What is meant by hydrocarbonation-oxidation reaction?
Illustrate with an example.

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

Q.3. Distinguish between anisole and phenol?

Q.4. Preparation of ethers by acid dehydration of secondary or tertiary alcohol

is
not a suitable method. Why?

Q.5. Convert Salicylic acid to Aspirin.

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

151
 OH
CCl4/ OH --

H+
Phenols

Q.7. Predict the major product of acidic catalysed dehydration of butan-1-ol.

Q. 8.

CH3

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.

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

152
 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
(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

(c) Give the mechanism of conversion of alkene into alcohol in

presence of acid catalyst.

153
 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

(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.

154
 UNIT 12TH
ALDEHYDE, KETONS AND
CARBOXYLIC ACIDS

ALDEHYDES, KETONES AND CARBOXYLIC ACIDS

BASIC CONCEPTS:
1. Aldehydes and ketones :These are carbonyl compounds and contain
carbonyl ( >C=O) functional group.They have general formula RCHO and
RCOR respectively. The carbon atom of the carbonyl group is SP 3
Hybridised. The >C=O bond is polar due to the different
electronegativities of the constituent atoms. Aldehydes (RCHO),
ketones(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.

155
 The structure of carbonyl group is given below

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

(b) By Dehydrogenation of alcohols

(c) By ozonolysis of alkenes

(d) By hydration of alkynes

156
 (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.

Nitriles react with Grignard reagent which on hydrolysis gives ketones.

(h) Aromatic aldeydes are prepared from aromatic hydrocarbons by the

following methods:
( a) Etards reaction: Toluene reacts with chromyl chloride (CrO 2Cl2) in
Cs2 or CCl4 to form benzaldehyde.

157
(b) Gatterman- Koch reaction: When a mixture of CO and HCl gas is passed
through benzene in presence of anhydrous AlCl3 + CuCl, benzaldehyde is
formed.

(c) Friedel- Crafts acylation:

Physical Properties of Aldehydes and Ketones

158
 (a) Physical State : Most of the aldehydes ( except formaldehyde
which is gas ) are liquid at room temperature. The lower ketones
are colourless liquids and have a pleasant smell. The higher
members are colourless solids. Aromatic ketones are usually
solids with a pleasant smell.
(b) Boiling Points : Aldehydes and ketones have relatively high boiling
points as compared to hydrocarbons of comparable moleculer
masses. It is due to the reason that aldehydes and ketones
contain polar carbonyl group and therefore they have stronger
interactions dipole dipole interactions between the opposite ends
of C=O dipoles.

These dipole dipole interactions are however , weaker than

intermolecular H-bonding in alcohols.Consequently boiling points
of aldehydes and ketones are relatively lower than the alcohols of
comparable molecular masses.

Dipole- Dipole interaction between two carbonyl groups

(C) Solubility :
The lower members of aldehydes and ketones (upto four carbon
atoms) are soluble in water . It is due to their capability of forming
hydrogen bonds with water molecules . The solubility of these
compounds in water decreases with the increase in the size of
alkyl group. It is because of the increase in the magnitude of non
polar parts in the molecule. However higher homologous are
soluble in organic solvents.

159
CHEMICAL PROPERTIES OF ALDEHYDES AND KETONES:
Aldehydes and ketones are highly reactive compounds. Both Aldehydes and
ketones undergo nucleophilic addition reactions.
Explanation: The reactive nature of aldehydes and ketones is because of the
presence of a polar carbonyl group. As the oxygen atom is more
electronegative, therefore, it pulls the electron density around itself acquiring
a partial negative charge whereas a partial positive is developed on the
carbon atom. The positively charged carbon atom of carbonyl is then readily
attacked by the nucleophilic species for initiation of the raction. This leads to
the formayion of an intermediate anion which further undergoes the attack
of H+ ion or other positively charged species to form the final product. The
nucloephilic recation may be catalysed by acids or bases. The reaction in
general , may be represented as:

Aldehydes are generally more reactive than ketones due to the following
reasons:
i) Presence of two alkyt groups cause more steric hindrance in the
approach of nucleophile to carbonyl carbon. In aldehydes only one
alkyl group is present.
ii) In ketones +I effect of two alkyl groups reduce the positive charge of
carbonyl carbon and reduces its electrophilicity.

SOME IMPORTANT NUCELOPHILIC ADDITION REACTIONS:

a) Addition of hydrogen cyanide( HCN)

Presence of base catalyses the reaction

b) Addition of sodium hydrogensulphite( NaHSO3)

160
c)Addition of alcohols:

d)Addition of ammonia and its derivatives:

161
e) Reduction reactions:
i) Using LiAlH4 or NaBH4 to alcohols

iii) Reduction to Hydrocarbons:

162
 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.

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)

163
Haloform reaction: Aldehydes and ketones Having atleast one CH 3 Group
linked to the carbonyl carbon give this reaction.

Iodoform test: ( using the reagent NaOH+I2) 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.

164
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.

Uses of aldehydes and ketones:

i) Used as solvents and flavouring agents.
ii) Formaldehyde is used as formalin( 40% solution) to preserve
biological specimens.

165
iii) Used as starting material for the preparation of a number of organic
compounds, Dyes, polymers etc.

CARBOXYLIC ACIDS
(i) PREPARATION:
a) From primary alcohols and aldehydes

b) From alkylbenzene :

The alkyl chain in alkyl substituted benzene is completely oxidized to

COOH irrespective of the length of the chain. Primary and secondary
alkyl groups also get oxidized, only tertiary group remains unaffected.

c) From nitriles and amides :

d) From Grignard reagent:

e) From acyl halides and anhydrides :

166
 f) From esters :

(ii) PHYSICAL PROPERTIES:

a) Lower members of carboxylic acids (upto 9-C) are liquids at room
temperature, and have foul odour.
b) Higher members are solid and odourless.
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.
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
167
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.

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:

168
Closer the presence of EWG to the carboxylic group more is the acidic
strength.

When carboxylic group is attached to vinyl or phenyl group its acidic strength
is due to resonance.

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

Reactions
(i) Formation of anhydrides

(ii) Esterification

(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

169
 (V) Reduction

(v) Sodalime decarboxylation

(vi) Kolbes electrolysis

(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.

170
 (viii) Aromatic carboxylic acids undergo electrophilic substitution
reaction. The COOH group attached to benzene ring is a
deactivating group and is m-directing.

Recap: Summary
Aldehydes, ketones and carboxylic acids have carboxyl group and are
highly polar compounds.
Carboxylic acids although contain group but do not give the reactions
given by aldehydes and ketones.
Aldehydes and ketones have higher boiling points than the
corresponding hydrocarbons and ethers due to higher polarity (stronger
dipole-dipole interactions)
Carboxylic acids have also higher boiling points due to extensive H-
bonding.
Carboxylic acids are stronger acids than phenols and alcohols but
weaker than mineral acids.
Aromatic acids are in general more acidic than aliphatic acids due to
the presence of electron withdrawing benzene ring.

Higher the pKa value of an acid weaker is the acid, i.e., it is poor proton
donor.
Ketones are more polar and have higher boiling point than aldehydes
of comparable molecular mass.
Aldehydes are more reactive towards nucleophilic substitution
reactions than ketones.
171
 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 C
C bond takes place at the carboxyl group.
Aldol condensation is given by only those aldehydes and ketones which
have
Cannizaros reaction is given by only those aldehydes which do not
have
Aldehydes and ketones can be converted to corresponding
hydrocarbons (having same number of C-atoms) by Clemensons
reduction and Wolf-Kishner reduction.
Carboxylic acids on reduction give 1 alcohols.
Sodalime decarboxylation method can be used to reduce a C-atom in
carboxylic acids.
Hell Volhard Zelinsky reaction is used to introduce a substitute like CN,
X, OH, etc., at in a carboxylic acid.
Carbonyl group and carboxylic group both are ring deactivating and m-
directing groups when attached to benzene ring.
Aldehydes can be oxidised with mild oxidising agents like Tollens
reagent and Fehlings solution but not ketones.
Aromatic aldehydes are oxidised by Tollens reagent but not with
Fehlings solution.
Formic acid is the only acid which gives the tests given by aldehyde
groups.

1 MARK QUESTIONS
Q. 1. Name the reaction and the reagent used for the conversion of acid
chlorides to the corresponding aldehydes.
Ans. Name : Rosenmunds reaction
Reagent : H2 in the presence of Pd (supported over BaSO 4) and partially
poisoned by addition of Sulphur or quinoline.
O O
|| Pd/BaSO4 ||
R C Cl + H2 R C H + HCl
+ S or quinoline

172
Q. 2. Suggest a reason for the large difference in the boiling points of
butanol and butanal, although they have same solubility in water.
Ans. The b. pt. of butanol is higher than that of butanal because butanol has
strong intermolecular H-bonding while butanal has weak dipole-dipole
interaction. However both of them form H-bonds with water and hence
are soluble.
Q. 3. What type of aldehydes undergo Cannizaro reaction ?
Ans. Aromatic and aliphatic aldehydes which do not contain hydrogens.
Q. 4. Out of acetophenone and benzophenone, which gives iodoform test ?
Write the reaction involved.
(The compound should have 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
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 ?

173
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.
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 ?
Ans.

Q. 11. Give IUPAC name of the following compound :

174
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.
(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.
175
 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 KMnO 4
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.
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 ?

176
Ans. This is because only those compounds which have hydrogen atoms
can undergo aldol reaction. Ethanol possesses -hydrogen and
undergoes aldol condensation. Methanal has no hydrogen atoms,
hence does not undergo aldol condensation.
Q. 21.Why does methanal undergoes Cannizaros rxn ?
Ans. Because it does not possesses hydrogen atom. Only those aldehydes
can undergo Cannizaro reaction which do not possess hydrogen atoms.
Q. 22.Arrange the following in order of increasing boiling points :
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-
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.

177
 R C
O

O
R C
O

O
] R C

Q. 25.There are two NH2 group in semicarbazide. However, only one is

O

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
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 (CH 3) at para
position w.r.t. to the carboxyl gp, which increases electron density on the
carbon of the carboxyl gp by hyperconjugation effect thereby making it
less reactive than benzaldehyde.

H 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 gp. It withdraws electrons both by inductive and
resonance effect thereby decreasing the electron density on the carbon

178
 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 stronger in CH 3CHO
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 electronthe electron density in the lizes the carboxylate the
carboxyate
179
 density in the O HO 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.
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. 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.

180
 + I effect increases
Steric hindrance increases
Reactivity towards HCN addition decreases

In other words, reactivity increases in the reverse order, i. e.,
Ditert-butyl Ketone < tert-Butyl methyl Ketone < Acetone <
Acetaldehyde
Q. 6. Write structural formulae and names of four possible aldol
condensation products from propanal and butanal. In each case,
indicate which aldehyde acts as nucleophile and which as
electrophile.
Ans. (i) Propanal as nucleophile as well as elecrophile.
OH 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
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.

181
 OH
CH2CH3
6 5 4 3| 2|
1
CH3CH2CH2CHO + CH3CH2CH2CHO + CH3CH2CH2 CH
CH CHO
Butanal Butanal 2-ethyl-3-hydroxy hexanal
(Electrophile) (Nucleophile)

Q. 7. An organic compound with the molecular formula C 9H10O 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.

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

COO H
5 2 5
Tollens reagent

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

2, 4-dinitrophenyl hydrozene

182
 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 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 3 Br2 H+
CO CH 3
A + B C (C17H12O)
I NaOh

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 CHBR 3 (B). (A) on protonation

183
 gives the corresponding acid (II). (II) being a -ketoacid readily
undergoes decarboxylation to give 2-methylcylohexanane (C).
O O
CH 3 Br2/NaOH CH 3 H+
COCH 3 CHBr3 + COO

I Haloform reacn (B)

(A)

H+ ( CO2)

Dexcarboxylation

(A -keto acid) 2-methyl

cyclo hexanone
(C) M. F. =
C7H12O

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
| |
184
 H H

(iii) CH3-CH-CH2-CHO

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
(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

185
 (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

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

(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.

186
 COOH COONa
|

+ NaHCO3 + CO2 + H2O

Phenol and ethyl benzoate do not give this Test.

7. How will you distinguish the following pairs:-

(i) Pentan- 2-one and Pentan- 3-one

(ii) Propanol & Propanal
(iii) Methanal & Ethanal
O O
|| ||
Ans:- 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

(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.

187
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.

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
|| |
O OH

Corresponding Cyanohydrim of problem is formed.

06. Ethanal is treated with NaHSO3.

Ans:-
CH3CHO+NaHSO3 CH3-CH-SO3H
|
ONa

188
 CH3-CH-SO3Na
|
OH
Corresponding Sodiumbisulphite of ethanol is formed.

07. Proponal is treated with Methyl magnesium bromide.

Ans:-
H
|
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

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.

189
 10.Acetic acid is treated with PCl5.
Ans:-
PCl5
CH3COOH CH3COCl
Acetylchloride is formed.

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

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

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

(vi)
H
Conc NaOH HCOONa + CH3OH

190
 2 C =0

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

NO2

(viii) CH2-CH2-CH3

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
|
OH
Butane 1,3,-diol

ii. 3 nitro brome benzene to 3 - nitro benzoic acid

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

191
 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

(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

(vii) Benzoic acid to benzaldehyde.

Ans:- O
||
COOH C-Cl CHO
PCl5 H2
Pd-BaSO4

192
QUESTION BANK FOR BRIGHT STUDENTS

Q.1

Complete each synthesis by giving missing starting material, reagent or

products

(i)

(ii)

(iii)

(iv)

(v)

(vi)

(vii)
193
(viii)

(ix)

(x)

(xi)

Ans: Try yourself

Q.2

Predict the products of the following reactions:

(i)

(ii)

(iii)

(iv)
194
ANS: (i)

(ii)

(iii)

(iv)

Q.3

Write the structures of products of the following reactions;

195
(i)

(ii)

(iii)

(iv)

ANS: (i)

(ii)

196
 (iii)

(iv)

Q.4

Write structural formulas and names of four possible aldol condensation

products from propanal and butanal. In each case, indicate which aldehyde
acts as nucleophile and which as electrophile.

ANS:(i) Taking two molecules of propanal, one which acts as a nucleophile

and the other as an electrophile.

(ii) Taking two molecules of butanal, one which acts as a nucleophile and the
other as an electrophile.

197
(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.

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:

198
Therefore, the empirical formula of the compound is C 5H10O. 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:

Q.5
199
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 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 of the acids. In the given

200
compounds, CH3 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 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)

201
(ii)

(iii)

(iv)

(v)

202
Q.7

How will you prepare the following compounds from benzene? You may use
any inorganic reagent and any organic reagent having not more than one
carbon atom

(i) Methyl benzoate (ii) m-Nitrobenzoic acid

(iii) p-Nitrobenzoic acid (iv) Phenylacetic acid

(v) p-Nitrobenzaldehyde.

ANS:(i)

(ii)

203
(iii)

(iv)

(v)

204
 Q. 8
Name the reaction and the reagent used for the conversion of acid
chlorides to the corresponding aldehydes.
Ans. Name : Rosenmunds reaction
Reagent : H2 in the presence of Pd (supported over BaSO4) and partially
poisoned byaddition of Sulphur or quinoline.

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

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 ?

205
Ans. Hemiacetal and acetals are formed by addition of alcohols on carboxyl
compounds.

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-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- -CHOC6H4C2H5 > COOH
C6H4 Tollens reagent 2-ethyl benzaldehyde
|
Silver mirror 2-ethyl benzoate
COOH

1, 2-benzene dicarboxylic
acid

206
FOR BELOW AVERAGE
01 Marks QUESTIONS
1. Write the structure of the following compounds

(viii) 4-OXO pentanal

(ix) 2,4 Dimethyl pent 3-one.
(x) 3-Methylbutanal
(iv) 4-chloropentane -2-one
(v) 3-brome-4-Phenyl pentanoic acid
(vi) Para-methyl Benzaldehyde
(vii) 4-Methyl pent-3-ene-2-on

2. Write IUPAC Names of the followings:-

(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
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

207
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
(vii) Ethanal & Propanal
(viii) Acetophenone & Benzophenone

6. How will you distinguish?

(iv) Phenol & Benzoic Acid
(v) Benzoic Acid & Ethyl benzoate.

7. How will you distinguish the following pairs:

(i) Pentan 2-one and Pentan 3-one
(ii) Propanol & Propanal
(iii) Methanal & Ethanal

FOR AVERAGE
02 Marks QUESTIONS

8. Arrange them in the increasing order of reactivity in esterification reaction.

iii. 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
(a) RCONH2, RCOOCOR, RCOCI & RCOOR
(b) Acid derivative unlike aldehyde and ketones show mucleophic
substitution

FOR ABOVE AVERAGE

02 Marks QUESTIONS

208
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
4. Toulene is treated with chromyl chloride (CrO 2Cl2) 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 KMnO4 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 ?
2 H2O
NH2
| CHCl3 + Alc KOH
(iii) ?

O
209
(iv) AlCl3
+ C2H5-C-Cl ?
CS2

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

(vi)
H
Conc NaOH ?
2 C =0

O
(vii) || NO2
|
+ 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

210
 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;
(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

211
to form bromide C with an treated with alcoholic KOH form an alkene D C 3H6
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.
(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 AlCl 3? 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:

(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.

212
 (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.

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

UNIT -13
ORGANIC COMPOUNDS
CONTAINING NITROGEN
AMINIES

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:
.. .. ..
213
 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.
+
NH2

214
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

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

215
 WATER

V. Hoffmann bromamide degradation reaction

Pr. amines are prepared by this reaction in which amide combines with
bromine in aq. Or ethanolic solution of sodium hydroxide.

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
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- +NaCl +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:--

216
(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

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.
Q. 2. Although NH2 gp is an ortho and para directing gp, nitration of
aniline gives along with ortho and para, meta derivatives also.

217
Ans. Nitration is carried out with a mixture of Conc. NO 3 + 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 ?

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
CH3CONH2 is delocalised over the keto gp. There is no such effect in
CH3CH2NH2. Due to reduction in electron density on N of CH 3CONH2,
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 Rx n. 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
primary amines cant be prepared by this method.
Q. 7. Accomplish the following conversions :
218
 (i) Nitrobenzene to benzoic acid
(ii) Benzyl Chloride to 2-phenylethanamine +
Ans. (i) N O 2 NH2 NaNO2 + HCl N N C l CN

(i) Fe/HCl 273 278 K CuCN/HCN

O O O O

(ii) NaOH Diazotization Benzene
Diazanium
Aniline Chloride
Benzonitrile
COOH
H3+O
O
Hydrolysis

Benzoic acid
2 1
C H 2C l2
C H 2C N C H 2C H 2N H 2
(ii)
KCN (aq) LaAlH4
O O O

KCl Redue

Benzyl Chloride Phenyl ethanenitrite 2-

phenylethanamine
Q. 8. Give the structures of A, B and C in the following compounds :
NaCN OH NaOH + 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
219
 Hofmann bromamide reacn Methanamine (C)
NH3 NaOBr
NaNO2/HCl
(ii) CH3COOH CH3CONH2 CH3NH2
CH3OH
D (Hofmann bromamide

Ethanoic acid Ethanoimide (A) reac.) Methanamine (B)
Methanol (C)
Q. 9. Why is it difficult to prepare pure amines by ammonolysis of alkyl
halides ?
Ans. By ammonolysis of alkyl halides, a mixture of primary, secondary and
tertiary amines is formed. So it is difficult to separate it.
Rx Rx Rx Rx
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.
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 NH 3+ 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 ?
220
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.
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--------H
O------
| | | |
C2H5 H C2H5
H

HNH
|
C2H5

However in Aniline, due to larger hydrophobic alkyl part extent of

H-bonding decreases considerably
insoluble in water.
(ii) Aniline being a Lewis base reacts with Lewis acid AlCl 3 or FeCl3
to form a salt.

C6H5NH2 + AlCl3 C6H5NH2+AlCl3

221
 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.
-------- 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

222
 (pungent smelling)
2 amines do not give this test.

(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 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 :

223
 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 donate to the benzene ring. N (CH3)2 (due to two alkyl groups on
N) is a much stronger electron donating gp than CH 3 gp. (only one alkyl
group on N). The remaining two gps contain a positive charge on the N-
atom and hence act as electron withdrawing gps. But in (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 :

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.

224
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 :
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 :

225
 CH3NH2 > (CH3)2NH > (CH3)3N
The combined effect of these two opposing factors is that (CH 3)2 NH is
the strongest base. In case of CH 3NH2 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.

Q.3. Why is amide more acidic than an amine ?

Ans.In amide there is C=O group attached NH 2 , electron withdrawing
& increases acidic nature of amide whereas in amines there is alkyl group
which is electron releasing and makes it more basic & hence less acidic.

Q.4. How is aniline distinguished from N-methyl aniline ?

Ans.On adding 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 ?

Ans.-- Tert. Amines donot undergo acylation reaction because they donot
have N- attached to H- atom.

Q8. How will you convert the following.

226
 (a) Aniline to acetanilide
(b) Benzene to aniline

Ans:- (a) C6H5NH2+CH3COCl NaOH C6H5NHCOCH3 +HCL

ConeH So4 3H
(b) C6H6+HNO3 Conc 2 C6H5NO2 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.

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

Ans:- (i) CH2CONH2 Na/C2H5OH CH3CH2NH2

Alcl3
(ii) C6H5 + CH3COCl C6H5COCH3
H2O/H+ CH COOH
(iii) C6H5NH2 + CH3cocl C6H5NHCOCH3 3
H O/H
Br C6H4NHCOCH3 2 BrC6H4NH2

227
 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.
(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 N 2-cl group which
shows more intermolecular attraction than those of aliphatic amines and
hemee more stable.
(v) Methylamine is basic in nature and have attracts to the cl group of Fecl 3
in presence of H of water and hence precipitate the Ferric oxide hydrated.
(vi) Primary amires have less surface and less spherical shape and hence
expericnce greate varder waals force of attraction and hence greater boiling
point
(vii) Silver chloride has tendency to form complex compound with aqeous
methyl amine and hence dissolves.
(vii) Aniline has electron releasing amine group, NH 2 and increases electron
density on the ortho- and para- positions of the benzene ring and hence form
2,4,6 tribromo-aniline.

228
Amines are basic even more basic than ammonia among amines, alkyl amines are
more basic than aryl amines.

Explanation:- The basic nature of amines is because of lone pair of electrons on

the N-atom which can be donated to other.

.. ..
R 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

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.

229
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
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.

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---

230
 (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

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

NH3 NaOBr NaNO2/ 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) TNT (ii) picric acid

03. Marks Questions

1. Give reasons-
a. Aniline is weaker base than cyclohexaamine.
b. Alkylamines have less PKb value than arylamines.
c. Methylamine in water reacts with ferric chloride to precipitate
ferrichydroxide.

2. What happens when

a. Aliphatic/aromatic amines react with chloroform in alcoholic potash.
b. Aniline combines with bromine water at room temperature.
c. Arene diazonium chloride combines with fluoroboric acid.

3. Predict the products

(i) Arene diazonium chlorides react with phenol in presence of alkali.
(ii) 4-Nitrotoluene combines with bromine & further reduced by tin in
Presence of acid.

231
 (iii) Aniline is treated with Acetylchloride in presence of pyridine.

4. Give one chemical test to distinguish between them-

(i) Ethylamine and aniline
(ii) Ethylamine and dimethylamine
(iii) Aniline and benzylamine.

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

(i) 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 of sulphuric acid.
(ii) Aniline combines with sulphuric acid at 453473K.
(iii) Arene diazonium chloride combines with ethanol.
9. Give reasons-
(i) Silver chloride dissolves in aqeous methyl amine
solution.
(ii) Tertiary amines do not undergo acylation reaction.
(iii) Aniline readily reacts with bromine to give 2,4,6-
tribromoaniline.
10. What is the Gabrial phthalamide synthesis ?
11. Condensation of aniline and benzaldehyde gives compound A that is
hydrogenated to give compound B .Identify A and B .
12. What happens when
(i) Nitropropane reduced with LiAlH4
(ii) Ethyl isocyanide undergoes hydrolysis
(iii) Benzene diazonium chloride reacts with phenol in basic medium.

232
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

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
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
233
3. Write short notes on the following---
a. Carbylamine reaction.
b. Diazotisation reaction.
c. Hoffmann Bromamide reaction.
4. Describe a chemical test to identify pr. Amines, sec, amines and tert. Amines
5. An aromatic compound A on treatment with aq. Ammonia & heating
forms compound B which on further heating with bromine and KOH
forms another compound, Formula 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.

FOR ABOVE AVERAGE

01. Mark Questions.
1. An organic compound X having molecular formula C 2H7N On treatment
nitrous acid gives an oily yellow substance. Identify X
2. Name the product obtained by action of aniline with Bromine.
3. What happens when ethyl amine dissolves in liq. Ammonia?
4. How would you prepare Orange Dye?
5. Give the reagents used in Gatterman reaction.

02 Marks Questions.
1. Give reasons
a. Tert. Amines do not undergo acylation reaction.
b. Aniline cannot be prepared by Gabrial synthesis
2. Accomplish the conversions
b. Benzoic acid to aniline
c. Propanoic acid to ethanoic acid
3. What happens when-
b. Aromatic amines react with nitrous acid.
c. Aryl diazonium chloride reacts with phenolic in basic medium.
4. Distinguish between the pair of the compounds
a. Ethanamine & diethylamine
b. Phenol & aniline.
5. Write the product for the following reactions-
a. Nitroethane is treated with lithium Aluminium Hydride.
b. Ethyl-isonitrile is hydrolysed in the presence of acid

03. Marks Questions.

1. Write short on the following

a. Gattermann reaction.

234
 b. Hoffman bromamide reaction
c. Gabrial phthalamide reaction.
2. An organic compound A with molecular formula C 2H5NO2 , 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.

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.

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

235
 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
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.

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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 same carbon, plus proline which is not actually an amino acid).

Amino acids are the building blocks of long polymer chains. With 2-10 amino
acids such chains are called peptides, with 10-100 they are often called
polypeptides, and longer chains are known as proteins. These protein structures
have many structural and functional roles in organisms.

There are twenty amino acids that are encoded by the standard genetic code, but
there are more than 500 natural amino acids. When amino acids other than the
set of twenty are observed in proteins, this is usually the result of modification
after translation (protein synthesis). Only two amino acids other than the
standard twenty are known to be incorporated into proteins during translation, in
certain organisms:

Selenocysteine is incorporated into some proteins at a UGA codon, which

is normally a stop codon.
Pyrrolysine is incorporated into some proteins at a UAG codon. For
instance, in some methanogens in enzymes that are used to produce
methane.

Besides those used in protein synthesis, other biologically important amino

acids include carnitine (used in lipid transport within a cell), ornithine, GABA
and taurine.

Protein structure

The particular series of amino acids that form a protein is known as that
protein's primary structure. Proteins have several, well-classified, elements of
local structure and these are termed secondary structure. The overall 3D
structure of a protein is termed its tertiary structure. Proteins often aggregate
into macromolecular structures, or quaternary structure.

Metalloproteins

A metalloprotein is a molecule that contains a metal cofactor. The metal

attached to the protein may be an isolated ion or may be a complex
organometallic compound or organic compound, such as the porphyrin group
found in hemoproteins. In some cases, the metal is coordinated with both a side
chain of the protein and an inorganic nonmetallic ion. This type of protein-
metal-nonmetal structure is found in iron-sulfur clusters.

Vitamins

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A vitamin is a compound that cannot be synthesized by a given organism but is
nonetheless vital to its survival or health (for example coenzymes). These
compounds must be absorbed, or eaten, but typically only in trace quantities.
When originally discovered by a Polish doctor, he believed them to all be basic.
He therefore named them vital amines. The l was dropped to form the word
vitamines.

1. Carbohydrates Carbohydrate is a class of compounds that include

polyhydroxy aldehyde, polyhydroxy ketone and large polymeric
molecules that can be broken down to polyhydroxy aldehyde and ketones.
Example: sugar, glucose, starch, gums etc. They are derived mainly from
plants.

2. Monosaccharides These include non-hydrolysable carbohydrates.

These are soluble in water e.g. glucose, fructose, etc.

3. Aldose The monosaccharides contaning a aldehydic group are called

aldose. Example: glucose.

4. Ketose - The monosaccharides contaning a ketonic group are called

ketose. Example: fructose.

5. Disaccharides These carbohydrates, which on hydrolyses yield two

molecules of monosaccharides are called disacchaides. They are
crystalline solid. Soluble in water and sweet in taste. Example: cane
sugar, maltose, lactose.

6. Oligosaccharides Those carbohydrates which yields 2 to 10

monosaccharides molecules on hydrolysis are called oligosaccharides.
Example: Raffinose. On hydrolysis it gives glucose, fructose and
galactose.

7. Polysaccharides - Those carbohydrates, which produce large no, of

monosaccharides units are called polysaccharides. They are formed by
linking together a large no. of monosaccharide units through glycosidic
linkage. e.g starch, amylose, glycogen, cellulose, etc.

8. Sugars - In general, monosaccharides and oligosaccharides are

crystalline solids, soluble in water and sweet in taste. These are
collectively called sugars. e.g glucose, sucrose.

9. Non-sugars The polysaccharides are amorphous, insoluble in water and

tasteless are known as non-sugars e.gss starch and cellulose.

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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 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.

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

239
 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 ?
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 :
----------
C---------- G
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 ----------
Q. 6. When RNA in hydrolysed there is no relationship among the
quantities of four bases obtained like DNA. What does this fact
indicate about structure of RNA ?
Ans. This indicate that RNA has a single strand structure.
Q. 7. Where does the water present in the egg go after boiling the egg ?
Ans. After boiling, the water soluble globular protein of egg while get
denatured and it cogulates into hard and rubbery insoluble mass.
Q. 8. Which vitamin is helpful in healing wound and cuts ? What is the
chemical name of this vitamin ?
Ans. Vitamin-C is helpful in healing wounds and cuts, its chemical name is
Ascorbic acid.

2 MARKS QUESTIONS
Q. 1. What type of bonding helps in stabilising the -helix structure of
proteins ?
Ans. In a -helix structure, polypeptide chain of amino acids coils as a right
handed screw because of the formation of all possible Hydrogen bonds
between NH group at each amino residue and > C = 0 group of
adjacent turn of helix.
Q. 2. Name the water insoluble fraction of Starch. Name the monomer of
this.
Ans. Amylopectin is water insoluble fraction of starch. It is a polymer of -
glucose.
Q. 3. What are the products of hydrolysis of (i) lactose (ii) sucrose. Also
name the enzyme used for reaction.
Lactase
Ans. (i) 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 ?

241
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
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.

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)

242
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)

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
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 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.

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 ?

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 2. Give two examples of monosaccharies.
3. Give name the monomers which constitutes lactose .
4. Give the name of linkage which found between the monomer units of sucrose
5. Name the two essential amino acids.
6. Name the source of vit. E.
7. Who proposed the double helical structure of DNA ?

FOR AVERAGE

1. What are monosaccharides ?

2. Give an example of branched polysaccharide .
3. What are non-reducing sugars ?
4. What happen when glucose is treated with HI ?
5. Draw the pyranose structure of alpha-D-glucose
6. Name the components of starch .
7. Where glycogen is present in human body ?
8. Name the primary constituents of proteins.
9. What are the expected products of hydrolysis of maltoses10.Which type of proteins constitute
enzymes ?

FOR ABOVE AVERAGE

1. Why is maltose a reducing sugar?
2. Give the name of most abundant carbohydrate present on the earth.
3. Write down the reaction between acetic anhydride and glucose.
4. Give the formula of glycine .
5. What is the function of glycogen in human body.
6. Draw the structure of zwitter ion.
7. What do you mean by denaturation of proteins ?
8. What is the activation energy for acidic hydrolysis of sucrose ?

FOR BELOW AVERAGE

Questions of two marks

245
 1. What are main functions of hexose sugars?
2. Give two applications of carbohydrates in plants.
3. Give the functions of cellulose.
4. How we classify the amino acids according to the need in the body ?
5. What happen when denaturation of proteins takes place? Explain with
examples
6. Give importance and source of vit. B.
7. Explain peptide linkage

FOR AVERAGE

1. Draw the furanose and pyranose structure of hexose sugar.

2. Explain acidic and basic amino acids with examples
3. Differentiate between fibrous and globular proteins.
4. What is the difference between nucleoside and nucleotide.
5. How can we classify the vitamins .Give source of vit A & C.

FOR ABOVE AVERAGE

1. Draw the hawarth projection formula for maltose.

2. Differentiate between tertiary and quaternary structure of
proteins
3. Differentiate amylase and amylopectin
4. What are functional difference between DNA and RNA.
5. Name the factors affecting enzymatic activity.
FOR BELOW AVERAGE
Questions of three marks

1. How carbohydrates are classified according to monomer units present in them ?

2. Give two chemical reaction for preparation of glucose.
3 .How starch is different from cellulose ?
4. What do you mean by secondary structure of proteins ? Explain.
5. Give main source of and function of vit. B & vit. D
FOR AVERAGE

246
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.
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 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.

247
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.

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

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
248
 ( Monomer) ( Polymer)
Homopolymer :- A polymer from one type of monomers is called
homopolymer
Ex. Polythene.
Copolymer :- A polymer from two or more type of monomers is called
copolymer
Ex. Terylene or decron, Nylon 66.
Classification of polymers :- Polymer are classified in number of ways
described as
follows
(A) Natural polymers :- The polymers obtained from nature (plants &
animals ) are
called natural polymers. Eg. Strarch, Cellulose,
Natural
rubber and Proteins etc.
(B)Synthetic Polymers :- The polymers which are prepared in laboratory
are called
Synthetic or man made polymers. Eg. Polythene,
PVC,
Nylon, Teflon.
Classification of polymers on the basis of structure
(a) Linear polymer :- These are polymers in which monomeric units are
linked together to form linear chains. Eg. Polythene, PVC, Teflon
(b) Cross linked polymers:- These are polymers in which the monomers
unites are cross-linked together to form a three- dimensional network. Ex.
Bakelite, Synthetic rubber.
(c) Branch chain polymers:- The polymers in which monomers are joined to
form long chains with side chains. Ex. Low density polythene.
Classification of polymers on the basis of molecular forces.
(a) Elastomers:- The polymers that have elastic character like rubber are
called elastomers.

249
 Ex. Natural rubber
(b) Fibers:- They have strong intermolecular forces between the chains.
These forces are either H-bonding or dipole interactions.
Ex. Nylon-66, dacron, silk etc.
(c) Thermoplastics :- These are the polymers which can be easily softened
repeatedly heated and hardened when cooled with little change in their
properties.
Ex. Polythene, PVC.
(d) Thermositting Polymers :- These are the polymers which undergo
permanent
change on heating. They become hard and infusible on heating. Ex.
Bakelite. Etc.
Classification of polymers on the basis of mode of synthesis.
(a) Addition polymers:- A polymers formed by direct addition of
repeated monomers without the elimination of by product molecule
is called addition polymers. Ex. Polythene, PVC,PTFE, etc
(b) Condensation polymers :- A polymer formed by the condensation
of two or more than two monomers with the elimination of simple
molecules like water, ammonia, hydrogen sulphide, alcohol, etc. is
called condensation polymer. In this each case monomer generally
contains two functional groups. Ex. Nylon 66 and Nylon 6,
Bakelite, Daecron, etc.
High density polythene (Zeiglar Natta catalyst)
It is prepared by heating of about 333- 343K under a pressure of 6-7 atm
in the
presence of Zeiglar Natta catalyst ( Tri ethyel aluminium Titenium tetra
chloride )
333-343K, 6-7 atam
n CH2 = CH2 ( CH2 CH2)n
Zeiglar Natta catalyst
Uses:- It is used in manufacture of containers ( buckets , Dust bin, etc)

250
 It is used in manufacture of different house wares pipes etc.

Polymer (origion Greek) poly means many, mers means part

Defination: Very large molecules having high molecular mass (103-107 u)
Macromolecule: other name for polymer
251
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

c. Cross linked or network: contains strong covalent bond

between various linear polymer for example Bakelite, melamine
.

3. Based on mode of polymerization:

252
 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

b. Condensation polymerization: repeated condensation reaction

between mostly two different bi-functional monomer unit with
the elimination of water alcohol etc. for e.g. nylon 66, Dacron

4. Based on molecular forces

a. Elastomers: rubber like solid with stretchable property up to

some extant for e.g. Buna-S, Buna N.

The force between chains is weak Vanderwall force.

b. Fiber: thread like solid with high tensile strength

Force between chain is hydrogen bonding for e.g. polyester,

nylon 6, 6

c. Thermo plastic: linear or slightly branched long chain molecule,

soften on heating. For example polyethylene PVC. Etc.

d. Thermosetting: cross linked molecule once setup cant not be

soften on heating. for example Bakelite, melamine

Decreasing order of force of attraction between the chains

Thermosetting > Fiber> Thermoplastic> Elastomers
Difference between thermoplastic and thermosetting
Type of polymerization reaction:
Addition polymerization or chain growth:
Due to increase in the length of chain

Due to addition of similar monomer it is addition polymerization e.g.

polythene

Steps of addition polymerization with free radical mechanism:

Chain initiation :by molecules like Benzoyl peroxide(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?
253
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.
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 ?
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 .

254
Q. What is Bio-degradable polymer?
A. The polymers which can be degraded by microbes. e.g. PHBV and Nylon-2
,Nylon-6.
Q. Give full form of PVC, PTFE,PHBV?
A. PVC: Poly Vinyl Chloride
PTFE : Polytetrafluoroethene
PHBV : poly--hydroxybutyrate-co--hydroxy valerate.
Name of polymer Monomer structure Uses
Addition polymer
Polythene Ethene 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
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.

255
Q. 2. Fibres are of crystalline structure. Why ?
Ans. Fibres have strong intermolecular forces of attraction which leads to close
packing of their chains and impart crystalline structure.
Q. 3. Which artificial polymer is present in bubble gum or chewing gum ?
Ans. Bubble gum or chewing gum contains synthetic Styrene-butadiene
rubber.
Q. 4. Name the polymer used for making medicinal Capsule.
Ans. PHBVUC Polyhydroxy butyrate-CO--hydroxy valerated.
Q. 5. Which polymer is used in making electrical goods and why ?
Ans. Bakelite because of its electrical insulator property.
Q. 6. Is (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
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 :

256
Ans. (i) HOCH2 CH2OH and HOOCO COOH

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

(ii) Melamine Formaldehyde
H 2N N NH 2

N N and HCHO
NH 2

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 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.

257
 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.
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.
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
258
Ans: (a) Hexamethylene diamine and adaipic acid.
Q7: Write the Mnomers of Buna-s.
Ans. 1, 3 butadine and styrene
Q8: What are carben fibers ? Give two examples.
Ans: A long thread solid posses high tensile strength. Eg. Terrylen and Nylon.
Q9: What is addition polymerization ?
Ans: A chemical reaction in which monomer unit is repeated to produce a
molecule without
losing of molecule like water or ammonia. Ex. Polythene, Polyvinyl
chloride
Q10: Give one example of each for low density polythene and high density
polthene.
Ans: LDP. Squeze bottle and toys
HDP. Buckets, dustbin, bottles.
02 Marks Questions
Q1. Differentiate between thermo plastic and thermo setting Plastic.
Ans:
Thermo Plastic Polymer Thermo setting Polymer

1. Liner or slightly branched 1. Cross linked or heavy

long change molecules branched molecule
2. Posses intermediate inter 2. This can not be reused
molecular force of attraction. 3. Ex. Bakelite, Urea-Formal
3. Ex. Polythene, Polystyrene dehyde resins
Q2: Give two Polymerisation reactionds for each.
(a) Addition polymers and
(b) Condensation Polymers
Ans: Addition Polymers :-
nCH2=C ( CH2 CH2)n
Condensation Polymers
n H2N(CH2)6 NH2 + n HOOC(CH2) COOH
[NH(CH2)2NHCO(CH2)4CO)]n+nH2O
259
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.
Ans: A synthetic rubber made by chloroprene. It is a synthetic rubbers.
Uses: Conveyor belts in coal mines & gaskets.
Q7: Define Synthetic rubbers. Whether it is homopolymer or co-polymer?
Ans: Any Vuclanised rubbers like polymers. Which is getting stretched to about
twice lengths
and returns to the original shape and size as the external force is released.
Eg. Homopolymers.
Q8: Explain the difference between Buna-N and Buna-S.
Ans: Buna-N:-
1. It is obtained by the copolymerization of 1,3 butadiene and acrylonitrile
in the presence of a Peroxide Catalyst.
2. It is resistant to action of Petrol.
3. It is used in making in oil seals tank lining etc
Buna-S:-
1. It is obtained by the Copolymerisation of buta diene and styrene.
2. It is used for automobile tyres.
Q9: What do you understand by Vulcanised Rubbers?

260
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:-
(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.

261
Q4. Write the name of monomers of Melamine-Formaldehyde.
Ans: Melamine and Formaldehyde.
Q5: What is the monomer of Polyacrylonitrile?
Ans: Acrylonitrile
Q6. Write the polymer of Tetrafluoro ethane.
Ans: Teflon.
Q7: Define Copolymers?
Ans: The polymer is obtained by two or more different monomers.
Q8: Is ( NH CHR CO )n is a homopolymer or a copolymer?
Ans: It is a Copolymer.
Q9: Why should one always use purest monomer in free radical
polymerization?
Ans: The impurities present in monomer may combine with free radical that
slow the rate
of polymerization.
Q10: What is meant by PTEE ? Give its popular name.
Ans: Polytetra fluoroethylene. Teflon.
02 Marks Questions
Q1: Differntiate between addition polymer and condensation polymer.
Ans:
Addition Polymer Condensation Polymer
1. Large no. of unsaturated 1. Large no. of monomers having
monomers combine together to form different functional group with
polymers Eg. Polythene and release of small molecule like water
polystyrene combine to form polymers. Eg.
Nylon and Teflon

Q2: Distinguish between thermoplastic and thermo setting polymers.

Thermo plastic polymer Thermo setting plastic

1. The inter moliculer forces are 1. The inter molecular force are
262
 intermediate. maximum.
2. there are no cross linkage bond 2. They are cross linkaged.
3. Eg. Polythene and polystyrene 3. Eg. Bakelite

Q3: Distinguish between Homopolymers and Copolymers.

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

Q5: Depict a free radical mechanism of addition polymerization of isoprene.

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

.
R CH2 C=CH CH2
|
CH3

CH3 CH2 -----

and
C=C

R CH2 H

Trans 1, 4 structure
263
 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?
Ans: Nylon 66 means that it is formed by two monomers each containing six
carbon
atoms. While in Nylon 6 means that it is formed by a monomer containing
six carbon
atoms.

Q7: Explain the structural difference between polyacrylats and polyesters

Ans: Polyacrylate-
CH2 = CR
|
COOR
And Polyster

CO
||
O
Q8: What is PHBV ?
Ans: It is a poly hydroxyl butyrate. Co-- hydroxyl Valerate.
It is copolymer of 3- hydroxyl butanoic acid and 3- hydroxyl pentanoic
acid in which
monomer units linked by ester linkage.

264
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.
(b) Neoprene, PVC and Nylon 6.
BRIGHT STUDENT
Very Short Answer Question: 01 Mark
Q1. What does stand for PDI
Ans: Polydispersity Index.
Q2. Write the name of neoprene polymer?
Ans: Chloroprene
Q3: Write the name of reagent use for initating a free radical chain reaction.
Ans: Tertiary Butyle peroxaide.
Q4: What are carbon fiber?
Ans: A long thread solid posses high tensile strength. Eg. Terrylen and Nylon
Q5: A polymer is use for making combs, name the polymer.
Ans : Baklite
Q6: A polymer is used for making paints and lacquers, name it.
Ans: Glyptal.
Q7: Name the monomer of polyvinylchloride.
Ans: Vinylcloride.

265
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
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

266
 pentanoic acid.It is used in speciality packaging , orthopaedic devices.

UNIT -16
CHEMISTRY IN
EVERYDAY LIFE
STUDY MATERIAL

1. Tranquilizers- they are chemicals which are used for treatment of mental
diseases .they act on higher centers of central nervous system. Example
Equanil , Seconal ,luminal or Barbituric acid etc.
2. Antibiotics- Chemical substances which are produced by micro-
organisms(such as moulds and bacteria) and are capable of destroying
other micro organism are called antibiotics .Example penicillin
,Ampiciline.
3. Broad spectrum Antibiotics- Antibiotics which are effective against
several different types of harmful micro-organisms and thus, capable of
curing several infections are called broad spectrum antibiotics Example
chloromycetin, Tetracycline .
4. Antihistamins :- Antihistamins are amines which are used as drugs to
control the allergy effects produced by histamines. Example diphenyl
hydrazine or promethazine .
5. Antipyritics :- Chemical substances which are used to bring down the
body temperature in high fevers are called antipyretic. Example Aspirin,
paracetamole or Analgin etc.
267
6. Disinfectants :- Chemical substances which kill micro organism or stop
their growth but are harmful to human tissue are called disinfectants
.example 1.% solution of phenol (2)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.
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) .
Class 1 preservatives-includes table salts, sugar , vegetable oil.
Class 2 preservativesodium benzoate ,salts of sorbic acids and
propanoic acid.

268
 14. Antioxidants--- Antioxidants are the important class of compounds which
prevent oxidation of food materials.
These compounds retard the action of oxygen on the food and thereby
help in preservation. These act as sacrificial materials i.e. they are more
reactive towards oxygen than the materials they are protecting. Example
(1) Butylated hydroxyl anisole (BHA)
(2) Butylated hydroxyl toluene (BHT)

15. Artificial sweetness sweetness are another type of food additives e.g
ortho sulphobenzimide (saccharin) is marketed as soluble sodium or
calcium salt. It is 300 times sweeter than cane sugar. It is lifesaver for
diabetic patients and is to control intake of calories

16. SoapThey are sodium or potassium salts of higher fatty acids like steric
acids, oleic acid and palmitic acid. Soaps are formed by heating fat with
aqueous sodium hydroxide solution the reaction is called saponification.
O

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
Lauryl alcohol Lauryl hydrogen
sulphate Sodium lauryl sulphate

(Anionic detergents)

269
18. Advantage of detergents:
(a) They work well even with hard water.
(b) They are more effective than soaps.
(c) They can work well even with acidic water.
(d) They can work well with woolen garments.
1. Chemotherapy : Treatment of diseases with the help of suitable drugs.

2. Antipyretic : Reduce body temperature. Eg: Aspirin, Analgin.

3. Analgesic : Pain Killer. Eg : Aspirin, Morphin, Heroin, Analgin.

4. Tranquiliser : Decreases anxiety. Eg: Luminal, Seconal.

5. Antibiotic : Cure infections. Eg: Penicilin, Tetracyclin,

Chloroamphenicol.

6. Antimalarial : Eg: Quinine, Chloroquinine.

7. Antifertility Drug : Birth control. Eg: A pill containing estrogen and

progesterone.

8. Preservatives : Chemicals used for preventing spoilage of food materials.

Eg: Sodium Benzoate.

9. Artificial sweetening agent : Eg: Sacharin, Aspartame (methyl ester).

10. Cationic Detergents : Eg: Trimethylstearylammoniumchloride.

270
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.

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?

271
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.

26. Discuss two ways in which drugs prevent attachment of natural

substrate on active site of enzymes.

27. Write one use of followings :

a) Zentac.

b) PCM.

c) Ranitidine.

d) Equanil.

e) Novestrol.

f) Morphin.

g) ChloroamPhenicol.

h) Bithional.

Hints :
5. Analgesics Pain Killer
Classification Narcotic Morphin (to relief post operative pain)
Non Narcotic Aspirin, PCM (to reduce fever , to prevent blood platelets
coagulation)
6. Aspirin act as blood thiner and causes no coagulation.
7. The artificial sweetners are either non metabolized by body or do not
produce carbohydrate like glucose when metabolized.
8. Nonionic detergents
9. Cationic detergents
10. Bithional
12. Zentac Antacid
PCM Antipyretics, Analgesics
Ranitidin Antacids
Equanil Tranquillizer
NonVestrol Antifertility drugs
Morphine Analgesics
ChloroamPhenicol Antibiotics
Bithional Anticeptics
272
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 ?
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.
273
Ans. Triclosan.
Q. 12.Identify the drug :

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 ?

CH3 (CH2)11 CH2 O SO3Na+

Ans. It is a detergent.
Q. 17.Give an example of a drug that is antipyretic as well as analgesic.
Ans. Paracetamol.
Q. 18.Out of morphine, N-Acetyl-para-aminophenol, Diazepam and
tetrahydrocatenol, which can be used as analgesic without causing
addiction ?
Ans. N-Acetyl-para-aminophenol.
Q. 19.Name a sugar substitute which is 160 times as sweet as surcrose.
Ans. Aspartame.
2 MARKS QUESTIONS
Q. 1. When a mixture of salicylic acid, acetic anhydride and acetic acid is
refluxed, what is the product obtained and what is its use in everyday
life ?
Ans. Aspirin used as analgesic.

274
Q. 2. Distinguish between a narrow spectrum and broad spectrum
antibiotic.
Ans. A narrow spectrum antibiotic works against a limited range of microbes
whereas a broad spectrum antibiotic works against a large variety of
microbes.
Q. 3. What is Salvarson ? To which class of drugs does it belong ? For what
distance is it used ?
Ans. Antimicrobial agent.
Used for the treatment of STD called Syphilis.
Q. 4. How does apirin act as an analgesic ?
Ans. It inhibits the synthesis of prostaglandins which stimulates inflammation
of the tissue and cause pain.
Q. 5. What are barbiturates ? To which class of drugs do they belong ?
Ans. 5, 5-derivatives of barbituric acid are called barbiturates. They belong to
the class of tranquilizers. They also act as sleep producing agents.
Eg. Luminal, Veronal.
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.
(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 ?

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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.
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.
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
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 18. What type of drug is Phenacetin?
19. How are synthetic detergents better than soaps?
20. What is tincture of Iodine?

FOR BELOW AVERAGE STUDENTS

A1. The branch of science which deals with the treatment of diseases
using suitable chemicals is known as chemotherapy.
A2. They are chemicals which are used for treatment of mental diseases.
Example
Equanil.
A3. Antioxidants are the compounds which prevent oxidation of food
materials.
Examples, BHA (Butylated hydroxy anisol) and BHT( Butylated
hydroxy
toluene.
A4. Class I- preservatives Table salt, sugar and vegetable oil.
Class II preservatives Sodium benzoate
A5. (a) Simple antibiotics- Penciline, Ampiciline
(b) Broad spectrum antibiotics Chloromycetin.
A6. Bithional is added to soaps to impart them antiseptic properties. Such
soaps are used to reduce odor due to bacterial action on skin surface.
A7. Morphine or heroin.
A8. They are chemicals which kill or prevent the growth of microorganisms.
They are applied to living tissues. Example- 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.
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.

277
FOR AVERAGE
01 Mark Questions

1. What are main constituents of Dettol?

2. What are food preservatives?
3. Name the sweetening agent used in the preparation of sweet for a diabetic
patient.
4. Why do soaps not work in hard water?
5. If water contains dissolve calcium hydrogen carbonate, out of soaps and
synthetic detergents which one will you use for cleansing cloths?
6. Why should not medicine be taken without consulting doctors?
7. Name two narcotics which are used as analgesics?
8. What is an antipyretics ? Give an example.
9. What are antagonists and agonists ?
10. Pick out the odd amongst the following compounds on the basis of there
medicinal properties.
Luminal, Seconal, Phenacetin, Equanil.
FOR ABOVE AVERAGE
01 Mark Questions

1. Write the chemical formula of

(i) Sodium stearate (ii) Sodium palmitate
2. Write chemical equation of soaponification.
3. What is biodegradable detergents?
4. Write chemical formula of (i) Sodium dodecyl benzene sulphonate and
(ii) Sodium lauryl sulphate.
5. What are pathogens ?
6. What is the chemical formula of cataionic detergents ?
FOR BELOW AVERAGE
02 Mark Questions

1. Mention one important use of each of the following

(i) Equanil (ii) sucralose
2. Name a broad spectrum antibiotics and state two diseases for which it is
prescribed.
3. State the function along with one example each of (i) Antihistamines (ii)
Antioxidents.
4. Describe the following with an example.
(i) Antimicrobials (ii) Analgesics
5. Name the medicines used for the treatment of the following diseases (i)
Tuberculosis (ii) Typhoid
6. Describe the following with example.
(i) Preservatives (ii) Biodegradable detergents
7. Describe the following with giving examples
(i) Edible colours (ii) Antifertility drugs
278
8. Define the followings and give one examples.
(i) Antipyrites (ii) Antibiotics
9. Give one important use of each of the following :
(i) Bithional (ii) Chloramphenicol (iii) Streptomycine
(iv) Paracetamol
FOR AVERAGE
02 Mark Questions
1. Why do we require artificial sweetening agents?
2. Which process is involved in holding the drugs to the active site of
enzymes?
3. What are different types of synthetic detergents ? Explain with sutable
Examples.
4. How are synthetic detergents better than soap?
5. Describe the cleansing action of detergents.

FOR ABOVE AVERAGE

02 Mark Questions
1. What are biodegradable and non biodegradable detergents?
2. Explain the following terms with suitable examples.
(a) Cationic detergents (b) anionic detergents.
3. Why are detergents usually preferred to soap for washing cloths?
4. Why biodegradable detergents are more prefer now a days.
5. Define the following terms with suitable examples.
(i) Antacids (ii) Antihistamines (iii) Antibiotics
(iv) Antifertility drugs (v) Foodpreservatives.

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