108inter 2nd Year CHEMISTRY E

Chemistry II
Paper II
Section A Max M: 60
I Answer all the questions 10 2 =20 M
1. Define mole fraction. Give its units
2. Give the products formed at the platinum electrode when aqueous solution of K
2
SO
4
is electrolyzed.
3. a) How is aluminium useful in the extraction of Chromium and manganese from their oxides?
b) What is the role of graphite rod in the metallurgy of aluminium?
4. Name of the following.
a) most abundant noble gas in atmosphere
b) radio active noble gas
c) noble gas with least boiling point.
d) noble gas forming large number of compounds
e) noble gas not present in atmosphere.
5. What is the molecular shape of I
3
-
ion and what is the type of hybridization in it?
6. a) What is a chealate ligand? Give example
b) How many moles of Agcl is precipitated when 1 mole of Cocl
3
is treated with AgNo
3
solution.
7. a) What are Ambident nucleophiles?
b) What is Racemic mixture?
8. Write the structure and name of the amine produced by Hoffman degradation of Benzamide.
9. Write the Coupling reactions of Benzene diazonium chloride with phenol.
10. Which compound in each of the following with react faster in SN
2
reaction with OH
-

i) CH
3
Br (or) CH
3
I ii) (CH
3
)
3
ccl (or) CH
3
Cl

II Answer any six questions. Each carries four marks 6 4 =24 M
11. a) Write the difference between a conductor and an insulator in terms of band theory.
b) Write the difference between a conductor and a semi conductor in terms of band theory.
12. Define molarity? Calculate the molarity of a solution containing 5 gr of NaoH in 450 ml of solution.
13. Describe the purification of colloidal solutions by the phenomenon of dialysis with a neat diagram.
14. Explain briefly the extraction of aluminium from bauxite.
15. Write the postulates of Wermers theory of coordination compounds and explain with two examples?
16. How are the following prepared and write their uses?
a) Neoprene b) Buna - S
17. Explain the structure of primary, secondary, tertiary and quaternary proteins.
18. What are Cationic and anionic detergents? Give examples for each type.

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Number of Moles of the Component
Total number of Moles of all the Components in the Solution

III Answer any two of the following. Each question carries 8 marks 2 8 =16 M
19. a) What are electro chemical cells? How are they constructed? Explain the working of the different types
of galvanic cells.
b) Determine the values of Kc for the following reaction
Ni
(s)
+2Ag
(eq)
+
Ni
(eq)
2+
+ 2Ag
(s)

(-)
=1.05V
20. How is ammonia manufactured by Habers process? Explain the reactions of ammonia with
a) ZnSo
4
(eq)
b) CuSo
4
(eq)
c) Agcl
(s)

21. How do you distinguish the following pairs of compounds?
(i) propanol and propanone
(ii) Acetophenone and Benzophenone
(iii) phenol and Benzic Acid
(iv) pentan 2 one and pentan 3 one .

Section A
1. Define mole fraction. Give its units.
A. Mole fraction is the ration of number of Moles of one Component to the total number of moles of all the
Components in the Solution.
Mole fraction of a Component

=

2. Give the products formed at the platinum electrode when aqueous solution of K
2
SO
4
is electrolyzed.
A. In aqueous Solution of K
2
So
4
the following reactions occur.
K
2
So
4
2K
+
+ So
4
2-

3. a) How is aluminium useful in the extraction of Chromium and manganese from their oxides?
b) What is the role of graphite rod in the metallurgy of aluminium?
A. Aluminium is a reducing agent because of its electro positive character, in the extraction of chromium and
manganese from their Oxides
Cr
2
O
3
+2Al Al
2
O
3
+2Cr +heat
3Mn
3
O
4
+8A/ 4Al
2
O
3
+9Mn +heat
b) Graphite acts as a reducing agent and reduces Al
2
O
3
to A/
2Al
2
O
3
+3C 4A/ +3Co
2

Graphite acts as a node.

I
I
I

4. Name of the following.
a) most abundant noble gas in atmosphere
b) radio active noble gas
c) noble gas with least boiling point.
d) noble gas forming large number of compounds
e) noble gas not present in atmosphere.
A. a) Argon b) Radon c) Helium d) Xenon e) Radon

5. What is the molecular shape of I
3
-
ion and what is the type of hybridization in it?
A.

I
3
-
is linear
Central Iodine atom in Sp
3
d hybridization

6. a) What is a chealate ligand? Give example
b) How many moles of Agcl is precipitated when 1 mole of Cocl
3
3
solution.
A. a) Chelate lig: - A ligand which can form ring type complex is called chelate ligand.
Ethylendiamine H
2
N CH
2
CH
2
NH
2
is a chelate ligand.
It can from ring type of complex.
b) Three Moles of Agcl is precipitated when 1 Mole of Cocl
3
3
Solution.

7. a) What are Ambident nucleophiles?
b) What is Racemic mixture?
A. a) Ambident nucleophiles: Groups like Cyanides and nitrites which possess two nucleophilic centres are
called Ambident nucleophiles.
b) Racemic mixture: A mixture containing two enantiomers in equal proportion will have zero Optical
rotation, as the Rotation due to one isomer will be exactly Cancelled by the Rotation due to the other isomer,
Such Mixture is known as Racemic mixture.

8. Write the structure and name of the amine produced by Hoffmann degradation of benzamide
A. Benzamide is C
6
H
5
CoNH
2
which contains seven carbon atoms. On Hoffmann degradation it gives an
aromatic primary amine containing six carbon atoms only.


9. Write the Coupling reactions of Benzene diazonium chloride with phenol
A. Diazonium Salts react with aromatic amines and phenol to give azo compounds having the general formula.
Ar N =N Ar! The reaction is known as Coupling reaction. The Coupling of benzene diazonium chloride
with phenols is carried out in Mild alkaline solution and with amines in weakly acidic Medium.
Coupling with Phenol: -

10. Which compound in each of the following with react faster in SN
2
reaction with
-
OH
i) CH
3
Br (or) CH
3
I ii) (CH
3
)
3
ccl (or) CH
3
Cl
A. (i) CH
3
I will react faster than CH
3
Br in SN
2
reaction with
OH because iodine is a better leaving group

because of its larger Size.
(ii) Of the two compounds CH
3
Cl and (CH
3
)
3
ccl, the former i.e,
CH
3
Cl will react faster in SN
2
reaction with
OH because there are only three small hydrogen atoms on carbon,

(CH
3
)
3
ccl is a tertiary alkyl halide. It is least reactive under SN
2
conditions because the bulky groups hinder The
approaching nucleophiles.

Section B

11. a) Write the difference between a conductor and an insulator in terms of band theory.
b) Write the difference between a conductor and a semi conductor in terms of band theory.
(a). Difference between a conductor and an insulator in terms of band theory: In a Metal the outer Orbitals
of very large number of atoms overlap to form a very large number of Molecular Orbitals that are delocalised
over the Metal. As a result a large number of energy levels are crowded together into bands. The highest
occupied energy band is called the valence band while the lowest unoccupied energy band is called
conduction band. The energy difference separating the valence band and conduction band is called band gap
or energy gap.
Conduction band
Empty band
Forbidden Zone
(Large energy gap)
filled band
Valance Band
Insulator
(b)
Overlapping
bands
Partially filled
band
Metal
(b)
E
n
e
r
g
y

In conductors the valence band is only partially filled. Electrons may easily excited from
lower energy level to higher energy level by supplying a very small amount of energy, when a voltage is
applied to a metal crystal, electrons are excited to the unoccupied orbitals in the same band and more
towards the positive terminal. Thus, a material with partly filled energy band is a conductor.
In the of insulations, the highest occupied band is completely filled, the energy gap between
the fully filled balance band and the vacant conduction band is very large and it is not possible to excite the
electrons to the conduction band. So they become insulators.
(b) Difference between a conductor and a semi conductor in terms of band theory: In a metal the outer
orbitals of very large number of atoms overlap to form a very large number of molecular orbitrals that are
delocalized over the metal. As a result a large number of energy levels are crowded together into bands. The
highest occupied energy band is called the valence band while the lowest unoccupied energy band is called
conduction band. The energy difference separating the valence band and conduction band is called band gap
or energy gap.
In conductors the valence band is only partially filled. So electrons may easily excited from
lower energy level to higher energy level by supplying a very small amount of energy, when a voltage is
applied to a metal crystal, electrons are excited to the unoccupied orbitals in the same band and move
towards the positive terminal. Thus, a material with partly filled energy band is a conductor.
In the case of semiconductors, the forbidden band i.e, the energy gap between valence
band and conduction band is little. The thermal energy available at room temperature is enough to excite
some electrons from the highest occupied band to the next permitted energy band.
So conductivity occurs but their conductivity is in between the conductors and insulators.

Moles of Solute
Volume of solution in litre
5g
40 g mol
-1

Moles of Solute
Volume of solution in litre
0.125Mol 1000ML L
-1

450ML
12. Define molarity? Calculate the molarity of a solution containing 5 gr of NaoH in 450 ml of solution.
A. Molarity: - Molarity (M) is defined as number of Moles of the Solute dissolved in one litre (or one cubic
decimeter) solution.

Molarity (M) =

Solution: -
Moles of NaoH = = 0.125Mol

Volume of the solution in litres =450Ml/1000mL L
-1

Using equation M =

Molarity = =0.278M
=0.278 Mol L
-1

=0.278 Mol dm
-3

13. Describe the purification of colloidal solutions by the phenomenon of dialysis with a neat diagram.
A.

Dialysis is a process of removing a dissolved substance from a colloidal solution
using a suitable membrane. The apparatus used for this purpose is called dialyses. A bag of suitable membrane
containing the colloidal solution is suspended in a vessel containing a continous flow of water. The bag made
with animal membrane, or parchment paper or cellophane sheet. Allow the molecules or ions to diffuse
through it into the water and pure colloidal solution is left behind in the bag.

14. Explain briefly the extraction of aluminium from bauxite.
A. 1) Bauxite is digested with hot conc. NaoH at 523K, Al
2
O
3
dissolves impurities are filtered off.
Al
2
O
3
+2NaoH +3H
2
O (1) 2Na [Al (OH)
4
] aq
The aluminate is alkaline in nature and is neutralized by passing CO2 gas. Al
2
O
3
is precipitated
2Na [Al (OH)
4
] (aq) +Co
2
(g) Al
2
O
3
XH
2
O + 2NaoHCo
3

1470K
The sodium Silicate remains in the solution and the insoluble hydrated alumina is filtered, dried and
heated to give pure Al
2
O
3

Al
2
O
3
XH
2
O Al
2
O
3
(S) +H
2
O (g)
(2) The purified Al
2
O
3
is mixed with Na
3
AlF
6
or CaF
2
which lower the melting point of the mix and also
increases conductivity. The fused matrix is electrolyzed.
Steel vessel with lining of carbon acts as cathode and graphite anode is used. The overall
reaction mat be
2Al
2
O +3C 4Al +3CO
2

Reactions: - At cathode Al
3
+(melt) +3e
-
Al
At anode (cs) +O
2-
(melt) Co (g) +2e
-

(cs) +2O
2-
(melt) Co
2
(g) +4e
-

Flow Diagram: -
Bauxite Al
2
O
3
2H
2
O

digested with hot Conc. NaoH

Al
2
O
3
dissolves impurities eliminated

Na [Al (OH)
4
]

Co2 bubbled

Al (OH)
3
ppt

Pure alumina

Electrolysis of alumina mixed with molten cryolite or CaF
2
at 1200K using carbon
. lining of cell cathode carbon rods anode.

NH
3

NH
3

NH
3

Cl
Cl
Cl
Cocl
3
. 6NH
3

Ex: - 1
H
3
N
Pure aluminium Metal

Electrolytic cell for the extraction of auminium

15. Write the postulates of Wermers theory of coordination compounds and explain with two examples?
A. Werner proposed two types of valencies to explain the formation and the structure of these complex
compounds.
(i) The primary valence: - This corresponds to the oxidation state of the central transition metal ion in the
complex compounds. This primary valence is satisfied by a negative ion only in the complex compound.
(ii) Secondary valence: - This is equal to the number of chemical groups bound to central metal ion. The no. of
secondary valencies is called co ordination number of the metal.
(iii) These secondary valencies are directed in space which determines the shape of the complex.

CO
Co ordination no: 6
Structure: Octahedral.
The ligand NH
3
satisfies only
secondary valency.
NH
3

Cl
NH
3

NH
3

NH
3

Cl
Cl
Cocl
3
. 5NH
3

Ex: - 2
Ex: - 3
Cl
-

NH
3

NH
3

NH
3

Cl
-

H
3
N
H
3
N
Cocl
3
. 4NH
3

CO
Co ordination no: 6
One Cl
-
ion satisfies both
primary and secondary
valencies.
CO
+3

Co ordination no: 6
Two Cl
-
ion satisfies both
valencies.
Ex: - 4
Cl
-

Cl
-

Cl
-

NH
3

Polymerisation
Polychloroprene or Neoprene Chloroprene

In Werners representation, dotted lines represent primary Valency whereas thick lines
represent secondary valency. some negative ligands, depending upon the complex, may satisfy both primary
and secondary valencies, such ligands do not ionize.
iv) Primary valencies are ionisable valencies, secondayy valencies are non ionisable valencies.

16. How are the following prepared and write their uses?
a) Neoprene b) Buna - S
A. Synthetic rubber is any vulcanisable rubber like polymer which is capable of getting stretched to twice its
length. It returns to its original shape and size when the stretching force is removed.
a) Neoprene: - Neoprene is formed by the free radical polymerization of chloroprene.

2 2
1
c
n C CH
CH CH

2
2
cl
n
CH
CH C CH

l

Uses: - Neoprene is used in the manufacture of Conveyer belts gaskets and hosepipes.
(b) Buna S: - Buna S is obtained by the copolymerization of 1, 3 Butadiene and styrene.
nCH
2
=CH CH =CH
2
+NC
6
H
5
CH =CH
2
(CH
2
CH =CH CH
2
CH
2
CH) Buna S
Uses: - Buna S is used in making automobile tyres and footwear.

17. Explain the structure of primary, secondary, tertiary and quaternary proteins.
A. The structure and shape of proteins can be studied at four different levels, i.e. primary, secondary, tertiary
and quarternary.
(i) Primary structure of Proteins: - Proteins may have one or more polypeptide chains. Each polypeptide in a
protein has amino acids linked with each other in a specific sequence. It is this sequence of amino acids that is
said to be the primary structure. The primary structure represents the constitution of the protein.
CO
+3

Co ordination no: 6
Three Cl
-
ion satisfies both
valencies.
(ii) Secondary structure of proteins: - The secondary structure of proteins refers to the shape in which a long
poly peptide chain can exist. These chains are found to exist in two different types of structure (1) at helix and
(2) [ pleated sheet structure. These structure arise due to the regular folding of the back bone of the
polypeptide chain due to hydrogen bonding between C =0 and NH groups of the peptide bond.
(iii) Tertiary structure of proteins: - The tertiary structure of proteins represents over all folding of the
polypeptide chains i.e. further folding of the secondary structure. It gives rise to two major molecular shapes
viz. fibrous (thread like) and globular.
(iv) Quarternary structure of proteins: - Some of the proteins are composed of two or more polypeptide chains
referred to as sub units. The special arrangement of these sub units with respect to each other is known as
quarternary structure.

18. What are Cationic and anionic detergents? Give examples for each type.
A. (i) Cationic detergents: - cationic detergents are quarternary ammonium salts of amines with acetates,
chlorides or bromides as anions. Cationic part possesses a long hydrocarbon chain and a positive charge on
nitrogen atom.
Ex: - CH
3
(CH
2
)
15
-N
+
(CH
3
)
3
Br
Cetyl trimethyl ammonium bromide is a popular cationic detergent. It is used in hair conditioners.
(ii) Anionic detergents: - Anionic detergents are Sodium salts of sulphonated long chain alcohols or
hydrocarbons. In these detergents, the anionic part of the molecule is involved in the cleasing action. Sodium
salts of alkyl benzene sulphonates are an important class of anionic detergents.
Ex: - Sodium dudecyl benzene sulphonate.
CH
3
(CH
2
)
11
SO
3
-
Na
+

Section C
19. a) What are electro chemical cells? How are they constructed? Explain the working of the different types
of galvanic cells.
b) Determine the values of Kc for the following reaction
Ni
(s)
+2Ag
(eq)
+
Ni
(eq)
2+
+ 2Ag
(s)

(-)
=1.05V
A. a) The device in which chemical energy is converted into electrical energy is called galvanic cell or electro
chemical cell or voltaic cell.
In galvanic cell, a redox reaction is carried out in an indirect manner and the decrease in free
energy during the chemical process is made to appear as electrical energy. The indirect redox reaction is such
that reduction and oxidation processes are carried out in separate vessels. The working of different types of
galvanic cells can be understand by considering the Zn CUSO
4
reaction as the basis of the cell reaction.
A zinc strip is dipped in zinc sulphate solution and a copper strip is dipped in copper sulphate
solution taken in separate beakers,. The two metallic strips which act as electrodes are connected by the
conducting wire through a volt meter. The two solutions are joined by a U tube known as salt bridge which
contain some electrolyte such as Kcl, KNO
3
or NH
4
Cl. Along with gelatin or agar agar to convert it into semi
solid paste.
(i) Zinc undergoes oxidation to form zinc ions.
Zn(s) Zn
2+
(aq) +2e
-
(oxidation)
(ii) The electrons liberated during oxidation are passed through the connecting wire to copper strip
(iii) Copper ions move towards copper strip, pick up electrons and get reduced to copper atoms which are
deposited on the copper strip.
At the zinc strip oxidation of zinc atoms takes place and becomes a source of electrons
acquiring negative charge. It acts as anode, since oxidation occurs at it. At the copper strip reduction of copper
ions takes place and acquires positive charge. It acts as cathode since reduction takes place.
The flow of electrons from zinc strip to copper strip produce electric current through the
outer circuit from copper to zinc strip which is indicated by the deflection in voltmeter.
b) E
cell
(-)
=
2.303 R1
nP
log Kc
Given E
cell
(-)
=1.05V; R =8.314J;
I
=298K; n =2; F =96500

1.05 =
2.3030 8.314 298
2 96500
log Kc
=0.0295 log K
eq
or K
eq
=Anti log
1.05
0.0295

=3.411 1035
19 (a)

20. How is ammonia manufactured by Habers process? Explain the reactions of ammonia with
a) ZnSo
4
(eq)
b) CuSo
4
(eq)
c) Agcl
(s)

Ans. On a large scale, ammonia is manufactured by Habers process.
N
2
(g) +3H
2
(g) 2NH
3
(g); F H =-46.1. KJmol
-1

The optimum conditions for production of ammonia are a pressure of about 2000 10
5
pa and
a temperature of 700K. Iron oxide is the catalyst with small amounts of K
2
O and Al
2
O
3
.

Compressed mixture of N
2
and H
2
in the volume ratio is heated to 700K at a
pressure of 200 atm and passed over finely divided iron oxide mixed with small amounts of K
2
O and Al
2
O
3
.
Ammonia formed is liquified and unreacted mixture of N
2
and H
2
again pumped into catalytic chamber.
(a)With ZnSO
4
, Zinc hydroxide precipitate is formed,
ZnSO
4
(aq) +2 NH
4
OH (aq) Zn (OH)
2
(s) +(NH
4
)
2
SO
4(aq)


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108inter 2nd Year CHEMISTRY E

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Chemistry II

OH because iodine is a better leaving group

OH because there are only three small hydrogen atoms on carbon,

=298K; n =2; F =96500

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