Chem Board Fiitjee Full

IPE SECOND YEAR
`
KUKTPLLY CENTRE

FIITJEE
INORGANIC CHEMISTRY
VA GROUP ELEMENTS
1. Discuss the structures of the oxides of
2
N
A: Nitrogen forms several oxides
2 2 3 2 2 4 2 5
N O,NO,N O ,NO or N O andN O . The structures of these oxides
are as follows:
* Nitrous oxides ( )
2
N O is a linear molecule with the following resonance structures.

N N O N =N =O
* Nitric oxide ( ) NO is an odd electron molecule containing unpaired electron. It is a resonance hybrid of
the following structures.

N =O N =O N =O

* Dinitrogen trioxide ( )
2 3
N O may have one of the following two structures.

O
O =N N =O
(Symmetric)

N N
O
O
O
(Unsymmetric)

* Nitrogen dioxide ( )
2
NO is an odd electron molecule and paramagnetic in nature in gaseous state due
to the presence of unpaired electron. It is a resonance hybrid of the following structures.

N
O
O
N
O O
N
O O
N
O
O

In the solid state it exist as dimmer
2 4
N O . It is diamagnetic in nature.

N N
O
O
O O
N N
O
O O
O

* Nitrogen Pentoxide ( )
2 5
N O : Its structure is

N N
O
O
O O
O

2. Write an essay on the preparation and structures of any three oxides of Nitrogen.
A: * Nitrous oxide ( )
2
N O : It can be prepared by heating ammonium nitrate.

4 3 2 2
NH NO N O 2H O
D
+
Properties:
a) It is a colourless, neutral gas
b) When inhaled it produces laughing hysteria so it is called laughing gas.
Structure:

N N O N =N =O
* Nitric oxide or Nitrogen oxide ( ) NO : It is prepared by the catalytic oxidation of ammonia.

Catalyst
3 2 2
4NH 5O 4NO 6H O + +

FIITJEE
Properties:
a) It is a colourless, neutral gas.
b) It is an odd electron molecule with paramagnetic character in gaseous state.
c) It is diamagnetic in nature in solid state.
Structure:

N =O N =O N =O

* Nitrogen dioxide( )
2
NO : It is prepared by the thermal decomposition of lead nitrate.
( )
2 2 2
2
2Pb NO 2PbO 4NO O
D
+ +
Properties:
a) It is an odd electron molecule.
b) It is brown coloured gas.
On cooling it converts into solid state. In the solid state it is colourless and diamagnetic. In solid state it
do not contain unpaired electron
Structure:

N
O
O
N
O O
N
O O
N
O
O

In the solid state it exist as dimmer
2 4
N O . It is diamagnetic in nature.

N N
O
O
O O
N N
O
O O
O

3. Write an essay on the structural aspects of the phosphorous series of acids.
A: Phosphorous forms three oxyacids in phosphorous series of acids.
* Orthophosphorous acid
3 3
H PO
* Metaphosphorous acid
2
HPO
* Hypophosphorous acid
3 2
H PO
a) In all oxyacids, phosphorous is involved in
3
sp hybridization and is surrounded by the atoms or groups
tetrahedrally.
b) In all these oxyacids atleast one OH group is in bond with phosphorous.
c) The hydrogen atoms in OH groups are ionizable and are responsible for the acidic nature.
d) The basicity of an oxyacid is equal to the number of OH groups in that acid.
e) The phosphorous series of acids contain P H - bonds and P OH - bonds. The reducing property of
these acids is due to this P H - bonds.
Structures:
* Orthophosphorous acid
3 3
H PO : Its basicity is two. It contains two OH groups and one P H bond.

P
O
H
OH
OH

* Metaphosphorous acid
2
HPO : Its basicity is one. Generally it exists as cyclic compound. The structure
of monomer is HO P O - =
* Hypophosphorous acid
3 2
H PO : Its basicity is one. It contains one OH group and two P H bonds.

P
H
H
OH
OH

FIITJEE
4. Write an essay on the preparation and properties of (a) Hypophosphorous acid (b) Hypophosphoric acid (c)
Metaphosphoric acid
A: (a) Hypophosphorous acid ( )
3 2
H PO :
Preparation: It is prepared in the laboratory by heating white phosphorous with dilute solution of
( )
2
Ba OH
( ) ( )
4 2 2 2 3
2 2
2P 3Ba OH 6H O 3Ba H PO 2PH + + +
From this barium salt
3 2
H PO is obtained.
Properties: It is a mono basic acid. It is very strong reducing agent in basic medium and is oxidized to
3 3
H PO .
(b) Hypophosphoric acid( )
4 2 6
H P O :
Preparation: When phosphorous oxide is exposed to moist air hypophosphoric acid is formed.
Properties: It is a tetra basic acid. Oxidation number of phosphorous in hypophosphoric acid is +4
(c) Metaphosphoric acid ( )
3
HPO :
Preparation: It is prepared by heating orthophosphoric acid at 870 K.

870K
3 3 3 2
H PO HPO H O +
Properties: It gives a glassy transparent solid. So it is called glacial phosphoric acid. It is a monobasic
acid. Its salts are called metaphosphates. Its salts exist as cyclic metaphosphates.
5. Describe Habers process for the preparation of
3
NH . Give a Neat diagram of the plant. Lable it.
A: Ammonia can be manufactured by Habers process. In this method ammonia is manufactured by the direct
reaction between nitrogen and hydrogen.

2 2 3
N 3H 2NH ; H 93.63kJ + D = -
* The above reaction is reversible reaction
* The forward reaction is exothermic reaction.
* When the reactants converts into products the volume decreases, as the number of product molecules
are less than the total number of reactant molecules.
Synthesi s of NH
3
by Habers Process:
or
At ordinary temperature the reaction occurs slowly. Accoridng Le Chateliers principle the following conditions
are more favourable for more yield of ammonia.
(i) Low temperature (ii) High pressure (iii) Catalyst
Ammonia is manufactured at about 725 775 K; using a pressure of 200 to 300 atmospheres. Iron powder
mixed with molybdenum is used as catalyst. Molybdenum acts as promoter to iron catalyst. A mixture of
potassium and aluminium oxides ( )
2 2 3
K OandAl O also act as promoter to the iron catalyst.
Pure and dry
2
N and
2
H mixture in 1 : 3 ratio by volume are made to react at a pressure of 200 to 300
atmospheres. Then it is passed into a catalytic chamber. These gases react at a pressure of 200 to 300
atmosphere. Then it is passed into a catalytic chamber. These gases react in the presence of catalyst at
725-775 K. Ammonia is formed to the extent of about 10%. It is separated from the unreacted
2
N and
2
H
by condensation.
6. Detail the Ostwalds process for the manufacture of
3
HNO . Give balanced equations wherever possible.
A: Ostwalds process for the manufacture of
3
NH : Ammonia mixed with air in 1 : 7 or 1:8 ratio is passed over
hot platinum gauze catalyst. Then ammonia is oxidized to NO.

Pt.gauze
3 2 2
1155K
4NH 5O 4NO 6H O + +
FIITJEE
or
Manufacture of HNO
3
Ostwalds process:
The NO formed in the above reaction is cooled and mixed with oxygen to convert into
2
NO . The
2
NO is
then passed into warm water under pressure in the presence of excess of air to give
3
HNO
2 2
2NO O 2NO +
2 2 2 3
4NO 2H O O 4HNO + +
The acid formed is 61% concentrated. This is further concentrated in three states.
Stage 1: 61%
3
HNO is distilled until 68%
3
HNO is obtained.
Stage 2: 68%
3
HNO is mixed with conc.
2 4
H SO and distilled to get 98% acid.
Stage 3: 98%
3
HNO is cooled in a freezing mixture. Crystals of pure
3
HNO separate out.
7. Describe an industrial method for the preparation of superphosphate of lime. Why is it converted into triple
phosphate of lime?
A: Superphosphate of lime is a mixture of calcium dihydrogen phosphate ( )
2 4
2
Ca H PO

and Gypsum
( )
4 2
CaSO .2H O
It is manufactured by treating the powdered phosphate rock with calculated amount of sulphuric acid.
( ) ( ) ( )
3 4 2 4 2 2 4 4 2
2 2
Ca PO 2H SO 4H O Ca H PO 2 CaSO .2H O + + +

Manufacture of Superphosphate of lime:
The phosphate rock is powdered. It is taken in a cast iron mixer. Calculated amount of sulphuric acid is
added and mixed well. This reaction mixture is dumped in one of the dens
1
D and
2
D through the values
1 2
V andV . The reaction is allowed to take place for about 24 36 hours. The impurities like carbonate and
fluoride are removed in the form of
2
CO and HF gases. The hard mass formed is powdered and sold as
superphosphate of lime.
FIITJEE
The
4
CaSO in the superphosphate of lime is an insoluble waste product and is of no value to the plants. To
avoid this waste product formation, it is converted into triple superphosphate by using phosphoric acids.
( ) ( )
3 4 2 4 2 4
2 2
Ca PO 4H PO 3Ca H PO +
The triple phosphate completely dissolves in water i.e., no waste product formed.
8. What are the similar features of ammonia and phosphine? Write a comparative note on them.
A: Both ammonia and phosphine can be prepared by similar methods. They can be prepared by the hydrolysis
of their binary compounds either with water or dilute acid.
Ex: ( )
3 2 2 3
2
Mg N 6H O 3Mg OH 2NH + + -
( )
3 2 2 3
2
Ca P 6H O 3Ca OH 2PH + + -
Comparative notes on their general properti es:
* Stability of
3
NH is greater than
3
PH because N H bond is stronger than P H bond.
* Both contain one lone pair on central atom, so they can act as Lewis bases. But
3
NH is stronger Lewis
base than
3
PH
* Both can act as reducing agents but
3
NH is weaker reducing agent then
3
PH because of more
stability.
* Both
3
NH and
3
PH are soluble in water but the solubility of
3
NH in water is more than
3
PH .
*
3
NH and
3
PH are volatile and colourless gases but
3
NH is less volatile because it can form inter
molecular hydrogen bonds.
* The hydrogen atoms in
3
NH and
3
PH can be substituted by alkyl group like
3
CH and halogens like
Cl. The ease of substitution decrease from
3
NH to
3
PH
*
3
NH can form salts with any acid forming salts like
4 3
NH Cl.PH can react with very strong acids like
HI.
* Both
3
NH and
3
PH are pyramidal in shape. In
3
NH nitrogen is involved in
3
sp hybridization but in
3
PH the pure p-orbitals participate in bonding. The bond angle in
3
PH (93 36' ) is less than in
( )
3
NH 107
9. In what way the structures of trioxides and pentoxides of
2
N and
4
P differ. Draw their structures and show.
A: Trioxides and Pentoxides of nitrogen and phosphorous are chemically similar but differ in their structures.
The oxides of nitrogen exists as monomers
2 3
N O and
2 5
N O while the oxides of phosphorous
4 6
P O and
4 10
P O exists as dimers. Their structures are given below.
Sl.No. Nitrogentrioxide structure Nitrogen pentoxide structure
1.

O
N N
O
O
asymmetrical form

N N
O
O O
O
O

O
O =N N =O
(Symmetric)

N N
O
O
O O
O

2. Phosphoric trioxide structure Phosphoric pentoxide structure
FIITJEE

P
P
P
P
O O
O
O
O
O
(dotted line does
not represent bond)

P
P
P
P
O O
O
O
O
O
Phosphorous
Oxygen
O
O
O
O
O

10. Write balanced equations for the reactions of
2
H O with
a)
4 6
P O b)
4 10
P O c)
3
PCl d)
5
PCl
A: ( )
4 6 2 3 3
P O 6H O 4H PO Phosphorous acid +
( )
4 10 2 3 4
P O 6H O 4H PO Orthophosphoric acid +
( )
4 10 2 3
little
P O 2H O 4HPO Metaphosphoric acid +
( )
3 2 3 3
PCl 3H O 3HCl H PO Phosphorous acid + +
( )
5 2 3 4
PCl 4H O 5HCl H PO Orthophosphoric acid + +
11. Write a note on the Cyanamide process. Mention any three important uses of
3
NH .
A: Cyanamide process: Ammonia can be manufactured synthetically by cyanamide process. In this method the
calcium is made to react with nitrogen gas in an electric furnace at 1273 1373 K. In this reaction a mixture of
2
CaCl and
2
CaF acts as catalyst. Then a mixture of calcium cyanamide and graphite known as nitrolium is
produced. When super heated steam is passed over calcium cyanamide at 453 K ammonia is produced.

1273 1373K
2 2 2
Graphite
Calcium
Cyanamide
CaCl N CaCN C
-
+ +

453K
2 2 3 3
CaCN 3H O CaCO 2NH + +
Uses of Ammonia:
* Ammonia is used in the manufacture of fertilizers like ammonium sulphate, urea, calcium ammonium
nitrate etc.
* Ammonia is used as refrigerant.
* Ammonia is used in the manufacture of sodium carbonate by Solvay process.
* Ammonia is used in the manufacture of nitric acid and explosives like ammonium nitrate.
12. Discuss the principle underlying the manufacture of
3
HNO
A: Nitric acid can be manufactured by two methods:
* Birkl and and Eyde Method Principl e:
a) An electric arc converts
2
N and
2
O of air into NO.

2 2
N O 2NO +
b) NO is oxidized to
2
NO by air.

2 2
2NO O 2NO +
c)
2
NO is dissolved in water in the presence of oxygen to get
3
HNO

2 2 2 3
4NO 2H O O 4HNO + +
* Ostwalds process-Princi ple
a) Ammonia is oxidized by air when
3
NH and air in 1 : 7 or 1 : 8 ratio passed over platinum gauze
catalyst.
Pt.guaze
3 2 2
1155K
4NH 5O 4NO 6H O + +
FIITJEE
b) NO is then oxidized to
2
NO by air.
2 2
2NO O 2NO +
c)
2
NO is dissolved in water in the presence of oxygen to get
3
HNO
2 2 2 3
4NO 2H O O 4HNO + +
13. What makes the difference between the two following reactions? Phosphate rock treated with
a) Chambers acid b) excess of phosphoric acid write the equation.
A: a) When phosphate rock reacts with chambers acid superphosphate of lime is formed.
( ) ( )
3 4 2 4 2 2 4 4 2
2 2
Ca PO 2H SO 4H O Ca H PO 2CaSO .2H O Heat + + + +
Superphosphate of lime contains insoluble waste product
4
CaSO . So the percentage of phosphorous in
superphosphate of lime become less.
b) To avoid the waste product gypsum in superphosphate of lime the phosphate rock is treated with
phosphoric acid ( )
3 4
H PO . Then triple phosphate of lime or triple superphosphate is formed.
( ) ( )
3 4 3 4 2 4
2 2
Ca PO 4H PO 3Ca H PO +
The triple phosphate completely dissolves in water i.e., no waste product formed.
SAQ
1. What is allotropy? Explain in N and its congeners?
A: If the same element exists in two or more physical states having nearly similar chemical properties but
different physical properties. It is known as allotropy.
Except bismuth all the VA group elements exhibit allotropy.
Solid
2
N exists in and a b forms.
Phosphorous exists in many allotropic forms such as white P, red P, scarlet P, a- black, b - black and violet.
Arsenic exists as metallic or grey arsenic, non-metallic or yellow arsenic, black arsenic.
Antimony exist in three allotropic forms
* crystalline, metallic variety or common variety.
* non-metallic or yellow or a-antimony
* explosive antimony.
2. What is catenation? How does it vary in group 15?
A: Combining capacity of the atoms of same element to form long chains is called catenation. Catenation
capacity depends on bond energy. In the group from top to bottom atomic size increases. So bond length
increases and bond energy decreases, hence catenation capacity decreases. Since nitrogen is smaller atom
it has more catenation power. So it can form
2 2
H N NH - and
3
N H having two and three atoms in a chain
respectively. Phosphorous can form
2 4
P H having two P atoms in the chain. Other elements of VA group
dont exhibit catenation power.
3. Draw the structures of
4 6
P O and
4 10
P O . In what respect do thy resemble each other, what happen when
they react with water?
A:

P
P
P
P
O O
O
O
O
O
(dotted line does
not represent bond)
P
P
P
P
O O
O
O
O
O
Phosphorous
Oxygen
O
O
O
O
O

In both
4 6
P O and
4 10
P O the four phosphorous atoms are arranged in tetrahedral shape. In both
4 6
P O and
4 10
P O six oxygen atoms are acting as bridges between phosphorous atoms forming P O P - - bonds.
In
4 10
P O one oxygen atom is in dative bond with phosphorous atoms.
FIITJEE
When
4 6
P O react with water orthophosphorous acid is formed.
4 10 2 3 4
P O 6H O 4H PO +
4. Write balanced equations for the formation of
3
NCl and
3
PCl . Give their hydrolysis reactions.
A:
3
NCl can be prepared by the action of excess chlorine on ammonia.

3 2 3
NH 3Cl NCl 3HCl + +

3
PCl can be prepared by the direct reaction between phosphorous and chlorine.

4 2 3
P 6Cl 4PCl
D
+
Hydrol ysis:

3
NCl hydrolyses in water forming ammonia and hypochlorous acid

3 2 3
NCl 3H O NH 3HOCl + +

3
PCl hydrolyses in water forming phosphorous acid hydrochloric acid.

3 2 3 3
PCl 3H O H PO 3HCl + +
5. In a compound
5
MX , M is any V group element except Nitrogen why (X) is halogen?
A: Except nitrogen all the VA group elements can form penta halides of the type
5
MX
Ex:
5
PCl ,
5
AsCl ,
5
SbCl ,
5
BiF etc. Nitrogen do not contain d-orbitals, in its valency shell but other VA
group elements contain vacant d-orbitals in their valency shell. So when excited one of the ns electron can go
into the d-orbital.

Ground state electronic configuration
ns
np nd

Excited state electronic configuration
ns
np nd

Since there are five unpaired electrons in the excited state except nitrogen other VA group elements can form
five covalent bonds with halogens. So they can form pentahalides of the type
5
MX . Nitrogen cannot form
pentahalides because of the absence of d-orbitals in its valency shell.
6. Which of the acids of phosphorous does not show monomeric state but cyclic structure? Name any polymer
of the acid.
A: Metaphosphoric acid do not exist as monomer. It exist as cyclic polymer. Ex: Cylcic metaphosphate.

O
P P
O
P
O
O
O O
O
O
O

7. A sample of most ammonia is to be dried. What method do you suggest?
A: Moisture from ammonia can be removed by passing over dry lime or CaO. But it cannot be dried over Conc.
2 4
H SO , fused
2
CaCl or
2 5
P O as they react with ammonia.
8. Write the formula of superphosphate of lime. Why is it converted into triple phosphate?
A: The common formula of superphospate of lime is ( ) ( )
2 4 4 2
2
Ca H PO 2 CaSO .2H O + . It acts as good
fertilizer. The
4
CaSO in its insoluble waste product and its presence has no significance to the plants. To
avoid this waste product
4
CaSO superphosphate is changes into triple phosphate which completely
dissolves in water.
9. How is superphosphate of lime formed? Give an equation. Explain why the product is a hard mass?
A: Superphosphate of lime can be prepared by treating powdered phosphate rock with calculated quantity of
2 4
H SO
( ) ( ) ( )
3 4 2 4 2 2 4 4 2
2 2
Super phosphate of lime
Ca PO 2H SO 4H O Ca H PO 2 CaSO .2H O + + +
The reason for the hardness of the final product obtained in the dens is due to the presence of Gypsum.

FIITJEE
VSAQ
1. Write the composition of phosphate rock.
A: ( )
3 4
2
Ca PO
2. Give any two examples to show negative oxidation state of nitrogen.
A: Ammonia
3
NH 3 - ; Hydrazine
2 4
N H 2 - ; Hydroxyl amine
2
NH OH 1 -
3. Why is NO paramagnetic in nature? When does it become diamagnetic?
A: NO, is an odd electron molecule containing odd number of electrons. The total number of electrons in No
molecule is 15. When all electrons are paired one electron remains unpaired. So NO is paramagnetic. But
when temperature decreases it dimerises and become diamagnetic.
4. How is dinitrogen tetroxide formed? Give equation.
A: When the temperature of
2
NO is decreased it dimerises to convert into dinitrogen tetroxide.

2 2 4
2NO N O
5. How many oxygens surround a phosphorous in phosphorous pentoxide?
A: In phosphorous pentoxide each phosphorous atom is surrounded by four oxygen atoms.
6. Write the equations for the hydrolysis of
3
NCl . How does it differ from hydrolysis of
3
PCl ?
A:
3
NCl hydrolysis in water giving
3
NH and HOCl while
3
PCl hydrolysis in water giving orthophosphorous
acid and HCl.

3 2 3
NCl 3H O NH 3HOCl + +

3 2 3 3
PCl 3H O H PO 3HCl + +
7. What are the orbitals of P that are involved in the formation of
5
PCl ?
A: In the formation of
5
PCl ,
3
sp d hybrid orbitals are involved.
8. What is nitrolim? How is it formed?
A: Nitrolium is a mixture of calcium cyanamide ( )
2
CaCN and graphite. When
2
N is passed over calcium
carbide containing
2
CaCl or
2
CaF as catalyst at 1273 1372 K nitrolim is formed.

1273 1378
2 2 2
Calciumcynamide Grpahite
CaC N CaCN C
-
+ +
9. What drying agent is suitable to dry
3
NH ?
A: Ammonia can be dried by passing over dry lime (CaO) because it does not react with ammonia.
10. What is the function of
2
CaCl in cyanamide process?
A:
2
CaCl acts as catalyst in cynamide process during
2
CaC react with
2
N to form nitrolim.
11. Which oxides of
2
N are neutral oxides?
A: Among the oxides of nitrogen, nitric oxide (NO) and nitrous oxide ( )
2
N O are neutral.
12. Which of the two oxides
2 5
N O and
2 5
P O is better dehydrating agent? Give an example for the same
reaction.
A:
4 10
P O is a strong dehydrating agent than
2 5
N O
Ex: Dehydrating of
3
HNO with
4 10
P O gives
2 5
N O

3 4 10 2 5 3
4HNO P O 2N O 4HPO + +
13. Give reasons for the chemical inactivity of nitrogen at ordinary conditions.
A:
2
N molecule contains triple bond ( ) N N . To break the triple bond large amount of energy
( )
1
945.4kJ mol
-
is required. Due to this high bond dissociation energy nitrogen is apparently inactive
under normal conditions.
14. What is the stability order of VA group hydrides? Explain the gradation in the reducing property of these
hydrides?
FIITJEE
A: The stability order of the hydrides of VA group hydrides is
3 3 3 3 3
NH PH AsH SbH BiH > > > > . As the
stability decrease they dissociate easily and can act as strong reducing agents. So the order of reducing
power of VA group hydrides is
3 3 3 3 3
NH PH AsH SbH BiH < < < < .
15. Why does nitrogen does not form pentahalides?
A: To form pentahalides the ns electron should be excited to nd orbital. In the case of nitrogen there is no d
orbital in its valency shell i.e., second orbit. So nitrogen cannot form pentahalides.
16. Can
5
NCl be prepared by direct union of the elements? Why or why not?
A: No.
5
NCl cannot be prepared by the direct union of elements because nitrogen do not react with chlorine
directly. Further due to the absence of d orbitals in its valency shell nitrogen cannot form
5
NCl
17. Write the structure of
3
HNO
A: The structure of nitric acid is the resonance hybrid of the following structures.

N
O
O
OH
N
O O
OH
Nitric Acid

18.
2 5
P O is strong dehydrating agent. Why is it not used to dry
3
NH ?
A:
2 5
P O is acidic and
3
NH is basic. They bond react to form salt. So
3
NH cannot be dried using
2 5
P O
19. How do you convert
4 3
NH NO into
3
NH give reactions?
A: When ammonium nitrate is heated with a base ammonia gas will be liberated.

4 3 3 3 2
NH NO NaOH NaNO NH H O + + +
When
4 3
NH NO is heated with alkaline solution of Zinc, it is converted into ammonia.

4 3 2 2 3 2
NH NO 4Zn 8NaOH 4Na ZnO 2NH 3H O + + + +
20. How do you prepare hypophosphorus acid in the laboratory?
A: When white phosphorous is boiled with dilute solution of barium hydroxide barium hypophosphite will be
formed.
( ) ( )
4 2 2 2 3
2 2
2P 3Ba OH 6H O 3Ba H PO 2PH + + +
To the barium hypophosphite solution if dil. Sulphuric acid is added hypophosphorous acid will be formed.
( )
2 2 2 4 4 3 2
2
Ba H PO H SO BaSO 2H PO + +

4
BaSO being insoluble can be removed by filtration.
21. How many Valence shell electrons are utilized by each phosphorous atom in
4
P molecule?
A: From the structural representation of
4
P , we can infer that each phosphorous shares three of its valence
electrons with other phosphorous atoms. A lone pair of electrons is seen on each phosphorous.
22. Why is nitrogen is a diatomic gaseous molecule while phosphorous is a tetra atomic solid?
A: Nitrogen atoms are small in size and can approach very close to one another. This facilities the lateral
overlap of the p-orbitals to form p-bonds. In phosphorous only single bonds are formed due to the larger
sizes of phosphorus atoms. Multiple bond formation and through it acquiring octet of electrons is not possible.
Hence
4
P molecules are formed.
23.
3
PH is quite stable in Air. But it catches fire when heated to 150 C . Why?
A:
3
PH frequently contains
2 6
P H (disphosphine) in trace amounts as impurity. This catches fire on heating in
air.
24. Write the names of the compounds formed by the union of
3
PH and
3
AsH separately with HI.
A: The reaction must be similar to the union of
3
NH with HI giving ammonium iodide. Therefore,
3
PH gives
4
PH I (phosphonium iodide) and
3
AsH gives
4
AsH I (Arsonium Iodide)
FIITJEE
25. If pure P-orbitals in As or Sb overlap with the S-orbitals of hydrogens, the bond angle is expected to be 90 ,
why is it 91 .48' in their hydrides?
A: The HMH bond angle in
3
AsH and
3
SbH would be expected to be 90 But due to repulsions between M-H
bonds, the angle increases to 91 .49'
26. Many penta halides of VA group elements are known. NO hydrides of
5
MH exist. Why?
A: To attain the pentavalent state, d-orbitals must be used. Hydrogen is not sufficiently electronegative to make
the d-orbitals effective by contraction.
27. Identify the oxidant and reductant in the given reaction
2 3 2
3HNO HNO 2NO H O + +
A:
2
HNO acts as both the oxidant and reductant.
2
HNO as a reductant changes to
3
HNO .
2
HNO as an
oxidant changes to NO.
28. What is the change in oxidation state of nitrogen in auto oxidation, auto reduction of
2
HNO ?
A:
2 3 2
3HNO HNO 2NO H O + +
In
2
HNO to
3
HNO , the change of oxidation state of nitrogen is from +III to +V. From
2
HNO to NO the
change in oxidation state is from +III to +II
29. What is the difference between tautomeric and resonance structures?
A: In tautomers the skeleton of atoms in the structures differs ( )
2
Ex: HNO . In resonance, the skelton of atoms
does not change (Ex: Benzene)
30. What is nitration mixture?
A: A mixture (1:1) of
3
HNO (Conc.) and Conc.
2 4
H SO is known as nitration mixture. This is used in nitration
reaction.
( )
2 4
H SO
6 6 3 6 5 2 2
60 C
Nitrobenzene
C H HNO Conc. C H NO H O
<
+ +
FIITJEE
VIA GROUP ELEMENTS
1. How is Ozone prepared in the laboratory? Give any three oxidation reactions of
3
O ?
A: Principle: Ozone is prepared by passing silent electric discharge through pure cold and dry oxygen.

( ) ( )
Silent Electric
2 g 3 g
discharge
3O 2O , H 284.5kJ D = +
Siemens and Brodies ozonizers are used to prepare ozone in the Laboratory.

Siemens Ozonizer:
* This ozonizer consists of two coaxial glass tubes sealed at one end.
* The inner sides of the inner tube and the outer sides of the outer tube are coated with tin foils.
* These tin foils are connected to the terminals of a powerful induction coil.
* Cold and dry oxygen is passed through the annular space from one end.
* Oxygen undergoes silent electric discharge partially and 10% Ozone is formed.
* Ozone and oxygen mixture known as ozonized oxygen is collected from the other end.
Oxidising properties of Ozone:
* Ozone oxidizes black lead sulphide (PbS) to white lead sulphate ( )
4
PbSO

3 4 2
PbS 4O PbSO 4O + +
* Hydrogen chloride is oxidized to chlorine by ozone.

3 2 2 2
2HCl O H O Cl O + + +
* Ozone oxidizes moist potassium iodide ( ) KI to iodine ( )
2
I

2 3 2 2
2KI H O O 2KOH O I + + + +
2. How is ozone is prepared in Brodies method? Write any three reduction reactions of
3
O with equations.
A: Preparation of Ozone, Brodies method:
Principle: Ozone is prepared by subjecting cold dry oxygen gas to the silent electric discharge using dilute
sulphuric acid as conducting medium and Cu wires as electrodes.

( ) ( ) 2 g 3 g
3O 68K.Cal. 2O +
* Brodies ozonizer consists of double wall U tube in which dilute
2 4
H SO is placed.
* Copper wires are immersed in dilute
2 4
H SO
* Copper wires are connected to the terminals of powerful induction coil.
* Cold and dry oxygen is passed through annular space between the two walls of U tube.
* Oxygen undergoes silent electric discharge and 15% of oxygen is converted into ozone.

Reducing properties of ozone:
* Ozone reduces hydrogen peroxide to water

2 2 3 2 3
H O O H O 2O + +
* Ozone reduces barium peroxide to barium oxide
FIITJEE

2 3 3
BaO O BaO 2O + +
* Ozone reduces silver oxide to metallic silver

2 3 2
Ag O O 2Ag 2O + +
3. How do you prepare hypo in the laboratory? Giving proper equations detail the reactions of hypo.
A: Crystalline hydrated sodium thiosulphate ( )
2 2 3 2
Na S O .5H O is known as hypo
Laboratory preparation:
In the laboratory hypo is prepared by the following methods.
* By boiling alkaline or neutral sodium sulphite solution with flowers of sulphur.

2 3 excess 2 2 3
Na SO S Na S O +
* By the oxidation of sodium sulphide or sodium polysulphide with air.

Heatin
2 5 2 2 2 3
air
2Na S 3O 2Na S O 6S + +
* By treating sodium sulphide solution with sulphur dioxide.

2 2 2 2 3
2Na S 3SO 2Na S O S + +
Reactions of Hypo:
* Action of heat: On heating hypo undergoes thermal decomposition to give
2 2
H S,SO and S. Hypo
looses all the molecules of water (water by crystallization) when heated to about 488 K.
* Reaction with dilute acids: When hypo reacts with dilute acids like HCl or
2 4
H SO to give
2
SO and S.
2 2 3 2 2
Na S O 2HCl 2NaCl H O SO Sdilute + + + +
* Reaction with
3
AgNO solution: When hypo reacts with
3
AgNO solution, two kinds of reactions may
take place.
a) When dilute hypo is added to
3
AgNO solution, a white precipitate of
2 2 3
Ag S O is formed which readily
changes to a black solid ( )
2
Ag S . The reactions are:
( )
2 2 3 3 3 2 2 3
Na S O 2AgNO 2NaNO Ag S O whiteppt + +
( )
2 2 2 3 2 4 2
H O Ag S O H SO Ag S Black ppt + +
b) When concentrated hypo is added to
3
AgNO solution a white precipitate ( )
2 2 3
Ag S O is obtained first.
The precipitate readily dissolves in excess of sodium thiosulphate due to the formation of complex
compound.
( )
2 2 3 3 2 2 3 3
Na S O 2AgNO Ag S O 2NaNO Whiteppt. + +

( ) ( ) ( )
2 2 3 2 2 3 3 2 3
2
Ag S O 3Na S O 2Na Ag S O Sodiumargentothiosulphate complexcompound +

* Reaction with iodine:
Sodium thiosulphate reacts with iodine to give sodium tetrathionate ( )
2 4 6
Na S O

2 2 3 2 2 4 6
2Na S O I 2NaI Na S O + +
This reaction is used in volumetric analysis to estimate iodine.
* Reaction with exposed photographic film or AgBr:
a) In photography the fixing is done by washing the film with hypo solution.
b) The silver bromide (or the silver halide) on the film reacts with sodium thiosulphate to give a complex
compound.
( )
2 2 3 3 2 3
2
AgBr 2Na S O Na Ag S O NaBr + +

* Reaction with moist Cl
2
: Hypo reacts with moist
2
Cl to give
2 4
Na SO and HCl.
2 2 3 2 2 2 4
Sodiumsulphate
Na S O Cl H O Na SO S 2HCl + + + +
In this reaction hypo is used as antichlor to remove excess of chlorine
FIITJEE
* Reaction with salts: Sodium thiosulphate reacts with ferric chloride, cupric chloride or auric chloride etc.
And converts them into complex thiosulphates.
4. Write the reactions of the following with
3
O .
i)
2 2
C H ii)
2 4
C H iii)
6 6
C H
Give the structures of the products in each case. What happens if these products are treated with
2
Zn/ H O
A: Reactions of O
3
:
* With Acetylene ( )
2 2
C H : Ozone when treated with acetylene, an addition compound called acetylene
ozonide is obtained. This on hydrolysis in presence of zinc, glyoxal is produced.

HC CH +O
3
HC CH
O O
O
Zn
H
2
O
CHO
CHO
+H
2
O
2

(Acetylene ozonide) (Glyoxal)

* With Ethyl ene ( )
2 4
C H : Ozone when treated with ethylene, an addition compound called ethylene
ozonide is obtained. This on hydrolysis in presence of zinc, formaldehyde is produced.

H
2
C CH
2
+O
3
CH

CH
2

O O
O
Zn
H
2
O
2HCHO +H
2
O
2

(Ethylene ozonide)
(Formaldehyde)

* With Benzene ( )
6 6
C H : Ozone on treating with benzene an addition compound called benzene tri
ozonide is obtained, which on hydrolysis gives 3 moles of glyoxal.

+3O
3
O
O
O
O
O
O
O
O
O
Zn
3H
2
O
CHO
3CHO +3H
2
O
2

(Glyoxal)

SAQ
1. What are the bond angles in
2
H O and
2
H S? Why are they different?
A: * 1) In
2
H O oxygen undergoes
3
sp hybridization. Due to the presence of two lone pair of electrons
shape of
2
H O molecule is angular or V-shape with H O H bond angle 104 28'
2) Due to the greater repulsion between lone pair and lone pair of electrons than lone pair and bond pair,
the tetrahedral angle is decreased to 104 28'
* 1) In
2
H S only pure p orbitals of sulphur are involved in bond formation. Hence the bond angle is less
than of 104 28' and it is only 92 30'
2)
2
H S is angular or V-shaped molecule.
2. What are the structures of
2 3
SO andSO ? Explain them in terms of VBT.
A: * Structure of
2
SO :
2
SO is angular molecule. The O S O bond angle is 119 30' . In
2
SO sulphur
atom undergoes
2
sp hybridization in first excited state 3s,
x
3p and
y
3p orbitals undergo
2
sp
hybridization.
z
3p and one d orbital are unhybridised and are used in the formation of p p p- p and
d p p- p bonds.
FIITJEE

S
O
O
S
O
O
( )
x y
p p -
( )
z z
p d -
( )
x y
p p -
( )
z z
p d -
o
1.43A
o
1.43A

* Structure of
3
SO : In gaseous state
3
SO has a planar triangular structure. The O S O bond angle is
120 . In
3
SO sulphur atom undergoes
2
sp hybridization in second excited state. 3s,
x
3p and
y
3p
orbitals underto
2
sp hybridization. One
z
3p and two 3d orbitals are unhybridized state and are used in
the formation of one p p p- p and two d p p- p bonds.

S
O
O
O

3. Give the structures of ( ) ( )
4 6
i SF ii SF . Explain them.
A: Structure of
4
SF :
* The structure of
4
SF is trigonal bipyramidal with one equatorial position occupied by a lone pair.
* Sulphur in
4
SF undergoes
3
sp d hybridization.
* S utilizes four hybrid orbitals for bonding while the fifth orbital accomidates a lone pair of electrons.

F
F
F
F
S

Structure of
6
SF :
* The shape of
6
SF is octahedral or square bipyramidal.
* Sulphur in
6
SF undergoes
3 2
sp d hybridization.
* All hybrid orbitals are used in bonding to form 6 sigma bonds between S and F atoms.

F
F
F
F
F
F
S

VSAQ
1. Write the structure of gaseous sulphur molecule at low temperatures.
A:

O =S

2. What is allotropy? Give the allotropes of oxygen?
A: Existence of an element in two or more physical forms is called as allotropy. Allotropes of oxygen and
2
O
and
3
O .
3. Write the names of the allotropic forms of S.
A: Sulphur exists in many allotropic forms. The important forms are a or rhombic sulphur, b or monoclinic
sulphur, g or monoclinic sulphur, plastic or c sulphur.

FIITJEE
4. At room temperature
2
H O is a liquid while
2
H S is a gas. Explain.
A: At room temperature water exists as liquid because of inter molecular hydrogen bonding. While
2
H S exist as
a gas because of the absence of intermolecular hydrogen bonding.
5. What are the bond angles in
2
H O and
2
H S? Why they differ in their bond angles?
A: Bond angles in
2
H O and
2
H S are 104 36' and 92 30' respectively. In
2
H O molecule oxygen undergoes
3
sp hybridization where as in
2
H S pure p-orbitals are involved in bond formation.
6. What is tailing of mercury? What chemical changes takes place in this process?
A: On passing
3
O , mercury looses it metallic luster and meniscus and it sticks on the glass walls due to
formation of mercurous oxide ( )
2
Hg O . This is known as tailing of mercury. The chemical change takes
place in this process is
3 2 2
2Hg O Hg O O + +
7. Give an example of a reaction which consumes all of the atoms of oxygen in
3
O .
A:
2 3 3
3SO O 3SO +
In this reaction
3
O is completely consumed.
8. What happens when hypo reacts with
3
AgNO ?
A: * When diluted hypo reacts with
3
AgNO solution, it gives a white ppt. of silver thiosulphate which
on hydrolysis gives a black ppt. of silver sulphide.

2 2 3 3 2 2 3 3
dil.hypo Silver thiosulphate
Na S O 2AgNO Ag S O 2NaNO + +

( )
2 2 3 2 2 2 4
Silver sulphide
Black.ppt
Ag S O H O Ag S H SO + +
* When concentrated hypo reacts with
3
AgNO solution, it gives a complex compound.

2 2 3 3 2 2 3 3
Na S O 2AgNO Ag S O 2NaNO + +
( )
2 2 3 2 2 3 3 2 3
2
Sodiumargento thiosulphate
3Na S O Ag S O 2Na Ag S O +

9. How is hypo useful in photography?
A: Hypo is used as fixing agent in photography.
( )
2 2 3 2 2 3
2
Sodiumargento thiosulphate
(Complex compound)
AgBr 2Na S O Na Ag S O NaBr + +

10. Mention two advantages of contact process over other processes.
A: *
2 4
H SO obtained is extremely pure and concentrated.
* The impurities can be tested and the reactants can be recycled.
11. What is the reaction of
3
O with PbS? Give the equation.
A:
3
O oxidizes black PbS to white
4
PbSO

3 4 2
PbS 4O PbSO 4O + +
12. What is antichlor? Give example.
A: The reagent used to remove excess of chlorine in textile industry is called antichlor.

2 2 3 2 2 2 4
Na S O Cl H O Na SO 2HCl S + + + +
In this hypo is used as antichlor agent.
13. Write any two uses of ozone?
A: * As an insecticide and bactericide * In sterilization of water.

FIITJEE
VII GROUP ELEMENTS
1. Describe Whytlaw-Gray method for the preparation of fluorine?
A: * Fluorine is prepared by the electrolysis of fused potassium hydrogen fluoride ( )
2
KHF . The
electrode reactions are:

KHF
2

Fusion
K
+
+H
+
+2F
-

Electrolysis
at cathode
at anode
2H
+
+2e
-
H
2

2F
-
F
2
+2e
-

1
2
3
4
5
8
7
6
9

1. Fused
2
KHF 2. Heating coil 3. Grpahite (anode) 4. Copper diaphragm
5. Fluorspar stopper 6. Fluorine 7. Copper cell (cathode) 8.
2
H
9. Inlet for HF
Manufacture:
* In this method, electrolysis is carried out in an electrically heated copper cell.
* The copper vessel serves as cathode also.
* Anode is made of graphite. The anode is surrounded by a copper diaphragm perforated at the bottom.
* This diaphragm prevents the mixing of
2
H and
2
F which reacts explosively if they come into contact.
*
2
F , liberated at the anode, is passed through the U-tube containing sodium fluoride.
* Hydrogen fluoride vapours accompanying fluorine as impurity, are removed by NaF.
( )
2
NaF HF NaHF +
*
2
H is liberated at the cathode.
* The gaskets used in the cell are coated with Teflon to prevent corrosion of the parts.
2. Write the chemical properties of
2
F with relevant equations?
A: * Reaction with water:

2
F reacts with water and gives ozonized oxygen.

2 2 2
2F 2H O 4HF O ; + +
2 2 3
3F 3H O 6HF O + +
* Reaction with alkalies:
a) When
2
F reacts with cold, dilute NaOH gives sodium fluoride and oxygen difluoride ( )
2
OF .

2 2 2
2NaOH 2F 2NaF OF H O + + +
b) When
2
F reacts with hot, concentrated NaOH gives sodium fluoride and oxygen.

2 2 2
4NaOH 2F 4NaF O 2H O + + +
* Reaction with other halides:
Fluorine oxidizes all other halide ions to the corresponding halogens.

2 2
F 2KCl 2KF Cl + +
* Reaction with inert gases:
Heavier inert gases like Kr and Xe form compounds with fluorine.

2 2
Xe 3F XeF +
* Reaction with KHSO
4
(Potassium hydrogen sulphate):
FIITJEE
Fluorine oxidises potassium hydrogen sulphate to potassiumper sulphate ( )
2 2 8
K S O .

2 4 2 2 8
F 2KHSO K S O 2HF + +
* Reaction with H
2
S:
Fluorine oxidizes
2 6
H StoSF

2 2 6
H S 4F 2HF SF + +
* Reaction with non metals:
Except oxygen and nitrogen, other non-metals directly combine with fluorine and give binary compounds.
2 6
S 3F SF +
* Reaction with metals:
All the metals (including noble metals like Au, Pt, etc.) form metal fluorides.

2 2
Cu F CuF +
3. What is the principle of preparing
2
Cl in the laboratory? Describe Nelsons method for its.
A: Principle:
2
Cl is manufactured by electrolysis of brine solution.
Manufacture:
* Nelson cell consists of U-shaped porous steel vessel lined inside with asbestos.
* It serves as cathode.
* This vessel is suspended in a rectangular iron tank.
* Brine solution (10% NaCl) is taken in the vessel.
* A carbon rod is dipped in the Brine solution which acts as Anode.
* Steam is passed into the cell. On electrolysis, the following reactions take place.

( ) ( ) ( ) aq aq aq
2NaCl 2Na 2Cl
+ -
+
At cathode:
( ) ( )
2 aq 2 g
2H O 2e 2OH H + +
At anode:
( ) ( ) aq 2 g
2Cl Cl 2e +

*
2
Cl gas liberated at anode is collected and is compressed in steel cylinders.
* Sodium ions penetrate through the asbestos paper lining and reach the cathode.
* Here sodium ions combine with OH
-
to form NaOH. In this process,
2
H and NaOH are important
byproducts.
2Na 2OH 2NaOH
+ -
+
4. Write the structures of all the oxyacids of
2
Cl .
A: NAME FORMULA
OXIDATION STATE OF
CHLORINE
BASICITY
Hypochlorous acid HClO +1 1
Chlorous acid
2
HClO +3 1
Chlorine acid
3
HClO +5 1
Perchloric acid
4
HClO +7 1
FIITJEE
Structures of oxyacids of chlorine:
* Hypochlorous acid: HClO

Cl
OH

The chlorine atom in this acid undergoes
3
sp hybridisation. This conjugate base of Hypochlorous acid is
Hypochlorite ion
( )
ClO
-

* Chlorous acid:
2
HClO
Cl
OH
O

3
sp hybridization. The chlorine atom has 2s bonds one p
bond ( ) p d p- p and two lone pairs.
The conjugate base of chlorous acid is chlorite ion
( )
2
ClO
-
which is angular in shape with a bond angle
of 111 .
* Chloric acid:
3
HClO

Cl
OH
O
O
3
sp hybridization. The chlorine atom has 3s bonds, 2p
bonds (both are p d p- p) and one lone pair.
The conjugate base of chloric acid is chlorate ion
( )
3
ClO
-
which is pyramidal in shape with a bond angle
of 106
* Perchlori c acid:
4
HClO

Cl
OH
O
O
O

3
sp hybridization. The chlorine atom has 4s bonds, three p
bonds (all d p p- p) and no lone pairs.
The conjugate base of perchlorine acid is perchlorate ion
( )
4
ClO
-
which is tetrahedral in shape with a
bond angle of 109.5
* The acid strength of different oxyacids of chlorine increases with an increase in the oxidation state of the
chlorine.

2 3 4
HOCl HClO HClO HClO
acid strength increases
< < <
uuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuur

5. How is bleaching power prepared industrially? Give any of its four chemical properties with equations.
A: Industrial preparation of bleaching powder (Baechmanns plant):
* Bachmanns plant consists of a vertical iron tower provided with a hopper at the top and inlets for
chlorine and hot air slightly above the base.
* The tower is fitted with a number of horizontal shelves at regular heights. Each shelf is fitted with a
rotating rake.
* Dry slaked lime is introduced into the tower through the hopper at the top.
* The slaked line moves downwards with the help of the rotating rakes and comes in contact with the
current of chlorine rising upwards.
* This process of moving the reactants in opposite directions is called principle of counter currents.
FIITJEE
* Slaked lime reacts with chlorine and gets converted into bleaching power which is collected in the
container placed at the bottom.
* The hot air drives away unreacted chlorine ( )
2 2 2
2
Ca OH Cl CaOCl H O + +

Chemical properties of bl eaching powder:
* Reaction with water:
With cold water, bleaching powder gives chloride and hypochlorite ion.

2
2
CaOCl Ca Cl ClO
+ - -
+ +
In hot water, it undergoes auto oxidation and gives chloride and chlorate ions.
* (a) Reaction with insufficient amount of dilute acids:
When small amounts of dilute acid is added, bleaching powder liberates oxygen.

2 2 4 2 4 2
2CaOCl H SO CaCl CaSO 2HCl O + + + +
(b) Reaction with excess of dilute acids:
On treating bleaching powder with excess of dilute acid, chlorine is liberated. This liberated chlorine is
known as available chlorine.
2 2 4 4 2 2
CaOCl H SO CaSO H O Cl + + + -
* Effect of a catal yst:
Bleaching powder decomposes to give
2
O in the presence of a catalyst
2
CoCl .

2
CoCl
2 2 2
2CaOCl 2CaCl O + -
* Oxidising property:
Bleaching powder oxidizes lead salts to lead dioxide and ethanol to acetaldehyde.

2
2 2 2
Pb 2CaOCl PbO 2CaCl
+
+ +
( )
2
CaOCl
3 2 3 2
Ethyl alcohol Acetaldehyde
CH CH OH O CH CHO H O + +
6. Write all the chemical properties of bleaching powder. Give equations. How is it useful to man.
A: * On long standing, bleaching powder undergoes auto-oxidation and changes into chloride and
chlorate.
( )
2 2 3
2
6CaOCl 5CaCl Ca ClO +
FIITJEE
* Reaction with water:
With cold water, bleaching powder gives chloride and hypochlorite ion.

2
2
CaOCl Ca Cl ClO
+ - -
+ +
In hot water, it undergoes auto oxidation and gives chloride and chlorate ions.
* Reaction with insufficient amount of dilute acids:
When small amounts of dilute acid is added, bleaching powder liberates oxygen.

2 2 4 2 4 2
2CaOCl H SO CaCl CaSO 2HCl O + + + +
* Reaction with excess of dilute acids:
On treating bleaching powder with excess of dilute acid, chlorine is liberated. This liberated chlorine is
known as available chlorine.
2 2 4 4 2 2
* Effect of a catal yst:
Bleaching powder decomposes to give
2
O in the presence of a catalyst
2
CoCl .

2
CoCl
2 2 2
2CaOCl 2CaCl O + -
* Oxidising property:
Bleaching powder oxidizes lead salts to lead dioxide and ethanol to acetaldehyde.

2
2 2 2
Pb 2CaOCl PbO 2CaCl
+
+ +
( )
2
CaOCl
3 2 3 2
CH CH OH O CH CHO H O + +
Uses
* It is used in the sterilization of water, as bleaching agent, as an oxidizing agent and in the preparation of
chloroform.
SAQ
1. How does
2
F react with (i)
2
H O, (ii) NaOH. Give equations for them.
A: * Reaction with
2
H O:

2
F reacts with water and gives ozonized oxygen.

2 2 2
2F 2H O 4HF O + + ;
2 2 3
3F 3H O 6HF O + +
* Reaction with NaOH:
a) When
2
F reacts with cold, dilute NaOH gives sodium fluoride and oxygen difluoride ( )
2
OF .

2 2 2
2NaOH 2F 2NaF OF H O + + +
b) When
2
F reacts with hot, concentrated NaOH gives sodium fluoride and oxygen.

2 2 2
4NaOH 2F 4NaF O 2H O + + +
2. Give the reaction of
2
Cl with the following:
(i)
2
SO (ii) NaOH (iii) Iron metal
A: * Reaction with
2
SO :

2
Cl when reacts with
2
SO under the influence of sunlight and gives
2 2
SO Cl (sulphuryl chloride).

sunlight
2 2 2 2
SO Cl SO Cl +
* Reaction with NaOH:
a) When chlorine reacts with cold, dilute NaOH gives sodium chloride and sodium hypochlorite
(NaOCl).
2 2
Cl 2NaOH NaCl NaOCl H O + + +
b) When chlorine reacts with hot, concentrated NaOH gives sodium chloride and sodium chlorate.
( )
3
NaClO .
2 3 2
3Cl 6NaOH 5NaCl NaClO 3H O + + +
* Reaction with Iron metal:
Chlorine reacts with iron metal and gives ferric chloride ( )
3
FeCl

2 3
3Cl 2Fe 2FeCl +
FIITJEE
3. What is Available Chlorine? Give chemical equation(s) which determine the same.
A: Available chlorine is the amount of
2
Cl set free when bleaching powder is treated with excess of dilute
2 4
H SO or
2
CO
A good sample of bleaching powder contain about 35-38% available chlorine.

2 2 4 4 2 2

2 2 3 2
CaOCl CO CaCO Cl + + -
VSAQ
1. Why is the E.A. of
2
Cl greater than that of
2
F ?
A: Fluorine has unexpectedly low electron affinity than chlorine. This is due to very small size of the fluorine
atom. As a result, there are strong interelectronic repulsions in the relatively small 2p subshell of fluorine and
thus, the incoming electron does not feel much attraction. Therefore, its electron affinity is less.
2. Write an equation for
2
F reaction with
4
KHSO and tell the nature of the chemical change.
A:
2
F oxidizes potassium hydrogen sulphate to potassium persulphate.

2 4 2 2 8
F 2KHSO K S O 2HF + +
3. Write the balanced equation(s) for the reaction of
2
Cl with
3
NH
A: a) With excess of
2
Cl , nitrogen trichloride ( )
3
NCl and HCl are formed.

3 2 3
NH 3Cl NCl 3HCl + +
b) With excess of
3
NH , ammonium chloride and nitrogen are formed.

3 2 4 2
8NH 3Cl 6NH Cl N + + -
4. 1 mole of
3
NH is mixed with 8 moles of
2
Cl in a reaction vessel. Write the equation for the reaction.
A: Since chlorine is taken in excess amount, 1 mole of Ammonia reacts with 3 moles of chlorine.

3 2 3
NH 3Cl NCl 3HCl + +
5. What is the reaction between bleaching powder and excess of dil.
2 4
H SO ?
A: On treating bleaching powder with excess of dilute
2 4
H SO , chlorine is liberated. This liberated chlorine is
known as available chlorine

2 2 4 4 2 2
6. Give any two uses of bleaching powder.
A: a) It is used in the sterilization of water b) It is used as a bleaching agent for cotton and paper pulp.
7. Give the uses of florine.
A: * It is used in rocket fuels.
* HF is used in etching of glass.
* NaF,
3 6
Na AlF are useful insecticides.
* As a refrigerant (Freon
2 2
CCl F ) and as a plastic ( )
2 4
n
Teflon C F

FIITJEE
TRANSITION ELEMENTS
1. Giving examples explain Werners theory of complex compounds.
OR
Why was Werners theory nessesary? Discuss the theory.
A: Werner explained the mechanism of formation of complexes.
The important postulates of this theory are
* Every complex compound contains a central metal atom (or) ion.
* The central metal shows two types of valences.
a) Primary valency:
* Primary valency is numerically equal to the oxidation state of the metal. These valencies are non
directional and are represented by dotted lines (..)
* Species (or) groups bound by primary valencies undergo complete ionization. These valencies are
identical with the number of ionic bonds. Ex:- In
3
CoCl (
3
Co
+
and 3Cl
-
are present). These are three
primary valencies for Co i.e. three ionic bonds are present.
Ex: Similarly ( )
3 3
6
Co NH Cl

. In this complex the primary valencies of Co are three.
b) Secondary Val ency:
The secondary valencies of metal are directed m space around it in a symmetric order each metal in a
given oxidation state has a characterstic number of secondary valencies.
* The number of secondary valencies is numerically equal to the coordination number of the metal ion in
the complex
* Since the secondary valencies are directional in space a complex has a specific shape.
* Some negative ligands may satisfy both primary and secondary valencies. Such complexes do not
ionize.
* The primary valency of a metal is known as its outer sphere of attraction (or) ionizable valency. The
secondary valencies are known as the inner sphere of attraction (or) coordination sphere or non-
ionizable valency.
i)
3 3
CoCl 6NH :- Since the coordination number (secondary valency) of
3
Co
+
is 6, 6
3
NH groups must
be linked to the central metal ion which do not ionize and 3Cl
-
ions are held by primary valencies.

CO
NH
3

NH
3

NH
3

NH
3

NH
3

NH
3

Cl
-

Cl
-

Cl
-

ii)
3 3
CoCl 5NH :- Since the coordination no. (secondary valency) of
3
Co
+
is 6 to satisfy its coordination
number.
* Ammonia molecules and one Cl
-
ion are linked to central metal ion which are non ionizable. The rest
of the chloride ions i.e. two Cl
-

CO
NH
3

NH
3

NH
3

NH
3

NH
3

Cl
-

Cl
-

Cl
-

iii)
3 3
3
Co
+
is 6 to satisfy its
coordination number, 4 ammonia molecules and two Cl
-
ion are linked to central metal ion which are
non ionizable. The rest of the chloride ions i.e. one Cl
-
FIITJEE

CO
+3
NH
3

NH
3

NH
3

H
3
N
Cl
-

Cl
-

Cl
-

iv)
3 3
3
Co
+
is 6 to satisfy its
coordination number, 3 Ammonia molecules and three Cl
-
ion are linked to central metal ion which are
non ionizable.

CO
+3
NH
3

NH
3

H
3
N
Cl
-

Cl
-

Cl
-

SAQ
1. Define EAN. Calculate the EAN of the following metals in their respective complexes.
i) ( ) ( )
3
2 4
Cu NH OH

ii) ( ) ( )
2 3
6 3
Co H O NO

iii) ( )
4
6
K Fe CN

A: The total number of electrons the central metal in a complex possess after formation of coordination complex
is effective atomic number (EAN) of the metal in that complex.
EAN = [Z(atomic number of metal) No. of electrons lost (oxidation states) + No. of electrons gained
from ligands]
* ( ) ( )
3
2 4
Cu NH OH

EAN 29 2 8 35 = - + =
* ( ) ( )
2 3
6 3
Co H O NO

EAN 27 3 12 36 = - + =
* ( )
4
6
K Fe CN

EAN 26 2 12 36 = - + =
2. What do you understand by the term ligand?
A: Atom, ion or molecule which can donate a pair of electrons to central metal in complex is called ligand.
* Ligands are classified into 3 types based on their charge.
1) Negative ligands:
2 2
4 2 4
X,SO ,CNandC O . The ligands satisfy both primary and secondary valencies
of central metal atom. (where X =halogens)
2) Neutral l igands:
2 3
H O, NH . These ligands satisfy only secondary valency
3) Positive ligand: NO
+

* Based on the number of coordination positions
1) Monodentate ligands: Donate only 1 pair of electrons to central metal.
Ex:
2 2
4 2 4 2 3
X,SO ,CN,S O ,H O,NH
2) Bidentate ligands: Donate 2 pair of electrons to central metal.
Ex: Oxalate ion
( )
2
2 4
C O
-
, Glycinate ion
( )
2 2
NH CH COO
-

3) Pol ydentate ligands: Donate more than 2 pair of electrons (tri, tetra, penta, hexa etc.)
Ex: Diethylenetriamine tridendate,
Triethylenetetramine tetradentate
Another ways of classification of ligands is based on Donor and Acceptor properties of ligands.
1) Ligands with one or more lone pair of electrons. Ex:
2 3
H O,NH
2) Ligands without a lone pair of electrons but with p bonding electrons. Ex:
2 2
C H ,CO,NO
FIITJEE
3. Give the coordination number of the metal in the following compounds.
i) ( )
3 4
4
Cu NH SO

ii) ( )
3 3
6
Co NH Cl

iii) ( ) ( )
4
6
K Fe CN
A: i) ( )
3 4
4
Cu NH SO

in this coordination number of copper is 4, because it is surrounded by
3
4NH
molecules.
ii) ( )
3 3
6
Co NH Cl

in this coordination number of cobalt is 6, because each cobalt is surrounded by 6
3
NH molecules.
iii) ( ) ( )
4
6
K Fe CN in this coordination number of Iron is 6, because central atom Fe is surrounded by 6
cynide groups
VSAQ
1.
4 2
CuSO .5H O has a pale blue colour. While
4 2
ZnSO ,7H O is white. Explain the difference.
A: In
4 2
CuSO .5H O,
2
Cu
+
ion has one unpaired electron in d-orbitals hence it is coloured. It absorbs red
colour radiation and transmits blue colour radiation.
In
4 2
ZnSO ,7H O,
2
Zn
+
ion has completely filled d10 configuration, hence it is colourless.
2. Ferrous salts are more unstable compared to Ferric salts. Explain interms of their configuration.
A: Ferrous salts are unstable, because in
2
Fe
+
, the d-orbitals are partially filled
( )
6 0
3d 4s . Where as
3
Fe
+
ion
has
5
d configuration (Half filled) hence it is stable.
3.
4
CuSO is paramagnetic while
4
ZnSO is diamagnetic explain interms of electronic configuration.
A: In
4
CuSO ,
( )
2 9
Cu 3d
+
ion has unpaired electron so it is paramagnetic in nature. Where as in
4
ZnSO ,
2
Zn
+
ion has no unpaired electron
( )
10
d hence it is diamagnetic.
4. What kind of magnetic property do Fe, Co and Ni show?
A: Fe, Co and Ni exhibits ferromagnetism.
5. Give composition of Nichrome.
A: Nichrome contains 60% Ni, 25% Fe and 15% Cr.
6. What elements are present in Brass? Write its composition.
A: Brass contains Cu and Zn metals. Its composition is 60-80% Cu and 20-40% Zn.
7. What is an alloy? Give the name and composition of an alloy?
A: An intimate mixture having physical properties similar to that of the metal, formed by a metal with other metals
(or) metalloids (or) some times a non-metal, is called as an alloy.
Ex: Brass is alloy which contains 60-80% Cu and 20-40% Zn.
8. Explain EAN with suitable examples.
A: Sum of number of electrons donated by all ligands and those present on central atom or ion in a complex is
called EAN (Effective Atomic Number). General EAN is equal to nearest noble gas configuration for extra
stability of metal complexes.
EAN of ( )( )
3 3 4
5
Co NO NH SO

Pentamminenitro Cobaltate (II) Sulphate.
EAN =27 3 =24 +(6 2 electrons from ligands) =24 +12 =36
EAN of
3
Co
+
=36 which is the atomic number of Krypton (Noble gas). Thus the complex is stable.
FIITJEE
ORGANIC CHEMISTRY

ETHYL CHLORIDE
Q.1) How is Ethyl Chloride obtained from ethyl alcohol by (a) Groves process (b) the action of
3
PCl
and
5
PCl (c) the action of Thionyl chloride
Ans: (a) Groves Process:-
Ethyl alcohol reacts with HCl in presence of anhydrous
2
ZnCl to form ethyl chloride.

2
ZnCl
2 5 2 2 2
C H OH HCl C H Cl H O + +
(b) Action of
3
PCl or
5
PCl on ethyl alcohol: -

3
PCl and
5
PCl react with
2 5
C H OH and form ethyl chloride.

2 5 3 2 5 3 3
3C H OH PCl 3C H Cl H PO + +

2 5 5 2 5 3
C H OH PCl C H Cl HCl POCl + + +
(c) Action of Thionyl Chloride on ethyl Alcohol:-
Thionly chloride reacts with ethyl alcohol to form ethyl chloride.

2 5 2 2 5 2
C H OH SOCl C H Cl SO HCl + + +
Q.2) How is ethyl alcohol prepared from (a) Ethylene (b) Ethane?
Ans: (a) From Ethylene:- Ethylene reacts with HCl in the presence of anhydrous
3
AlCl to give ethyl
chloride.

3
AlCl
2 2 3 2
Anhydrous
H C CH HCl H C CH Cl = = - -
(b) From ethane:- Ethane reacts with chlorine at ordinary temperature in the presence of light to
give ethyl chloride.

h
2 6 2 2 5
400 C
Class Concentration
C H Cl C H Cl HCl
n
+ +
Q.3) What happens when ethyl chloride is treated with (a) Alcoholic KOH (b) Moist silver oxide (c)
Potassium cyanide (d) Silver cyanide
Ans: (a) Alcoholic KOH reacts with ethyl chloride to give ethyl alcohol.

3 2 3 2
CH CH Cl KOH H CCH OH KCl + +
(b) Moist silver oxide reacts with ethyl chloride to give ethyl alcohol.

2 2
Ag O H O 2AgOH +

2 5 2 5
C H Cl AgOH C H OH AgCl + +
(c) Potassium cyanide reacts with ethyl chloride to give ethyl cyanide as the major product.

2 5 2 5
C H Cl KCN C H CN KCl
D
+ +
(d) Silver cyanide reacts with ethyl chloride to give ethyl isocyanide as major product.

2 5 3 2
C H Cl AgCN H C CH NC AgCl
D
+ - - +
Q.4) How does ethyl chloride reacts with (a) potassium or sodium nitrite (b) silver nitrite?
Ans: (a) Ethyl chloride reacts with potassium nitrite to give nitro ethane as major product.

Dimethyl
2 5 2 3 2
formaldehyde
Ethyl nitrite
C H Cl KNO H C H C O N O KCl + - - - = +
(b) Ethyl chloride reacts with silver nitrite ( )
2
AgNO solution to give ethyl nitrite as the major
product.

2 5 2 5 2 2
Nitro ethane
C H Cl AgNO H C NO AgCl + - +

FIITJEE
Q.5) How does ethyl chloride reacts with ammonia? Write the chemical equations.
Ans: Ethyl chloride reacts with alcoholic ammonia under pressure to form a mixture of primary,
secondary, tertiary amines and quaternary ammonium salt.

2 5 3 2 5 2
C H Cl NH C H NH HCl + +
( )
2 5 2 2 5 2 5
2
C H NH C H Cl C H NH HCl + +
( ) ( )
2 5 2 5 2 5
3 3
C H NH C H Cl C H N HCl + +
( ) ( )
2 5 2 5 2 5
3 4
Quaternary ammonium salt
C H N C H Cl C H N Cl
+ -
+
Q.6) Explain Williamsons synthesis with chemical equations.
Ans: Ethyl chloride reacts with sodium ethoxide to form diethyl ether. This is called, Williamsons
synthesis of ether.

2 5 2 5 2 5 2 5
Sodiume ethoxide Diethylether
C H Cl NaOC H C H O C H NaCl + - - +
Q.7) How does ethyl chloride reacts with the following. Explain with chemical equations. (a) Benzene
/
3
AlCl (b) Silver Acetate (c) Mg / Dryether (d) NaBr or KI

+ C2H5Cl
AlCl3
C2H5

Ans: (a) Ethyl chloride reacts benzene in presence of
3
AlCl catalyst to give ethyl benzene.

(b) Ethyl chloride reacts with silver acetate in alcoholic solution to form ethyl acetate.
3 2 5 3 2 5
Ethyl acetate
CH COOAg C H Cl H CCOOC H AgCl + +
(c) Ethyl chloride reacts with magnesium metal in presence of dry ether to give ethyl magnesium
chloride. This is called as Grignards reagent.
Dry ether
2 5 2 5
Ethyl magnesium chloride
C H Cl Mg C H MgCl +
(d) Ethyl chloride reacts with NaBr and KI to give ethyl bromide and ethyl iodide respectively.

2 5 2 5
C H Cl NaBr C H Br NaCl + +

2 5 2 5
C H Cl KI C H I KCl + +
Q.8) Explain the reduction of ethyl chloride and what are the reagents used in this reaction.
Ans: Ethyl chloride is reduced to ethane with (i) Zn / HCl (ii)
4
LiAlH (iii)
2
H /Ni or Pd

4 2
Zn/HCl
2 5 2 6
LiAlH Or H /Ni
C H Cl C H
Q.9) Explain wurtz reaction.
Ans: Ethyl chloride reacts with sodium metal in presence of dryether to form butane. This is called
Wurtz reaction

Dry
5 2 2 5 5 2 2 5
Ether
n butane
H C Cl 2Na Cl C H H C C H 2NaCl
-
- + + - - +
Q.10) What are the used of ethylchloride?
Ans: 1)
2 5
C H Cl is a refrigerant
2) Ethylating agent
3) Preparation of Grignards reagent.
4) It is a local anaesthesia

FIITJEE
CHLORO FORM
Q.1) How is chloro form prepared from (i) ethyl alcohol (ii) Acetone
Ans: Heating ethyl alcohol with bleaching powder and water gives chloro form.
( ) + +
2 2 2
2
CaOCl H O Ca OH Cl
+ +
3 2 2 3
Acetaldehyde
CH CH OH Cl H CCHO 2HCl
+ +
3 2 3
Chloral
H CCHO 3Cl Cl CCHO 3HCl
( ) ( ) + +
3 3
2 2
Chloroform
Calcium formate
2Cl CCHO Ca OH 2CHCl HCOO Ca
With Acetone:
( ) + +
2 2 2
2
CaOCl H O Ca OH Cl
+ +
3 3 2 3 3
Trichloro acetone
H CCOCH 3Cl Cl CCOCH 3HCl
( ) ( ) + +
3 3 3 3
2 2
CalciumAcetate
2Cl CCOCH Ca OH 2CHCl H CCOO Ca
Q.2) How is chloroform prepared from (a) carbon tetra chloride and (b) from chloral hydrate.
Ans: (a) Chloroform is prepared on large scale by the reaction of
4
CCl with iron filings and water.

D
+ +
2
Fe,H O
4 3 3
CCl 2CH HCCl HCl
(b) Chloral hydrate treated with sodium hydroxide to give pure chloroform
( )
( )
D
+ + +
3 3 2 aq 2
Sodium formate
Chloral hydrate
Cl CCH OH NaOH HCCl HCOONa H O
Q.3) Explain oxidation of chloroform in presence of air and light.
Ans: In the presence of air and light, chloroform is slowly oxidised to phosgene a highly poisonous
gas.

( )
+ +
h
3 2 2
Carbonyl chloride
Phosgene
1
HCCl O COCl HCl
2

Anaeshetic chloroform has to be pure. Therefore, chloroform is kept in well stoppered dark
brown or blue bottles by filling them to the brim.
About 1% of ethyl alcohol is also added which is expected to retard the oxidation of chloroform
and also to convert phosgene to harm less ethyl carbonate.
Q.4) How does chloroform reacts with (a)
3
HNO (b) D Ag/ (c) Aq.KOH (d) Acetone
Ans: (a) Chloroform reacts with vapours of
3
HNO to give chloropicrin a poisonous liquid.
+ +
3 2 3 2 2
HCCl HONO CCl NO H O

(b) Chloroform is heated with silver to form acetylene
FIITJEE

D
+ + +
3 3
Acetylene
HCCl 6Ag Cl CH HC CH 6AgCl
(c) Aqueous KOH reacts with chloroform to give formicacid.
( )
-
+ +
2
H O KOH
3 2
3
Potassium formate
Unstable
HCCl 3KOH CH OH HCOOH HCOOK H O
(d) Acetone condense with chloroform in presence of KOH to give chloroetone.

C O
H
3
C
H
3
C
+ HCCl
3
C
H
3
C
H
3
C
OH
CCl
3
Chloretone

Chloretone is a hypnotic drug.
Q.5) Explain (a) Reimer-Tiemann reaction (b) Carbylamine or isocyanide test
Ans: (a) Chloroform reacts with phenol in presence of sodium hydroxide at 65 C to give
orthohydroxybenzaldehyde (Salicylaldehyde)

+ + + +
65 C
6 5 3 2
C H OH CHCl 3NaOH 3NaCl 2H O
OH
C
O
H

(b) Primary amines reacts with chloroform in presence of alcoholic KOH to give phenyl iso
cyanide with offensive odour.
- + + + +
Warm
6 5 2 3 6 5 2
Phenyl isocyanide
C H NH HCCl 3KOH C H NC 3KCl 3H O
Q.6) What are the uses of chloroform?
Ans: (1) Solvent for fats, oils and waxes
(2) Detection of primary amines
(3) Preparation of chloropicrin, chloretone
(4) In the preservation o of anatomical species.

FIITJEE
CHLORO BENZENE
1. Write any two preparations of Chloro Benzene?
Ans: 1) Electrophilic substitution reaction:-
Chlorobenzene is formed by electrophilic substitution when benzene reacts with
2
Cl in presence
of Lewis catalyst Fe or Iron (III) chloride ( )
3
FeCl

+ Cl2
Fe/Dark
Cl
+ HCl

2) Sandmeyers rection:-
Aniline is dissolved in cold aqueous HCl and treated with sodium nitrite to give diazonium salt.

NH2
NaNO2 + HCl
N2Cl
+ HCl
0 to 5
0
C
Benzene dia zonium chloride

Cl
Cu2Cl2
N2Cl
+ N2

This solution is treated with cuprous chloride to give chlorobenzene.
2. Explain electrophilic substitutions reactions of chlorobenzene with
a) Anhydrous
3 2
AlCl /Cl b)
2 4
Conc.H SO c) 1 : 1 reaction
3
Conc.HNO and
2 4
H SO
d) Anhydrous
3 3
AlCl /CH Cl e) Anhydrous - -
3 3
||
O
AlCl /H C C Cl
Ans: a) Chorobenzene reacts with chlorine to give p-dichlorobenzene as major product and O-dichloro
benzene as minor product

Cl
Cl2/Anhydrous AlCl3
Cl
D
Cl
+
Cl
Cl

b) Chlorobenzene reacts with Conc.
2 4
H SO to give chlorobenzene sulphonic acid as major product
and 2-chlorobenzene sulphonic acid as minor product.

Cl
Conc. H2SO4
Cl
D
SO3H
+
Cl
SO3H
4-chloro
benzene
sulphonic acid
2-chloro
benzene
sulphonic acid

c) Chlorobenzene reacts with 1 : 1 ratio
3
HNO and
2 4
H SO to give 1-chloro-4-nitro benzene as
major product and 1-chloro -2- nitro benzene as minor product.

d) Chlorobenzene reacts with
3
CH Cl in presence of Anhydrous
3
AlCl to give 1-chloro-4-methyl
benzene as major product and 1-chloro-2-methylbenzene as minor product.

Cl
Anhydrous AlCl3
Cl
CH3
+
Cl
1-chloro-
4-methyl
benzene
+ CH3Cl
major
1-chloro-
2-methyl
benzene
minor
CH3

e) Chlorobenzene reacts with Acetyl chloride

- -

3
||
O
CH C Cl in presence of Anhydrous
3
AlCl to
give 4-chloro acetophenone as major product and 2-chloro acetophenone as minor product.

Cl
Anhydrous AlCl3
Cl
+
Cl
+ H3CCOCl
major
minor
O = C CH3
C CH3
O

FIITJEE
3. Explain Wurtz-Fitting reaction and Fitting reaction with chlorobenzene.
Ans: a) Chloro benzene reacts with Alkylhalide in presence dry ether and sodium metal to give alkyl benzene.
This is called as Wurtz-Fitting reaction.

R
Dry ether
Cl
+ + 2Na + RX NaX + NaCl

b) Chloro benzene reacts with sodium metal in presence of dry ether to give diphenyl. This is called as
fitting reaction.

Dry ether
Cl
+ + 2Na 2NaCl
Diphenyl
2

4. Write the structure of DDT.

Cl
CCl3 Cl C
H

ALCOHOLS
1. How is ethyl alcohol prepared from
(a) Ethyl halide (b) Ethyl acetate (c) Acetaldehyde (d) Ethylene
(e) Grignards reagent and formaldehyde.
Ans:
a) Ethyl halide on Hydrolysis with aqueous solution of NaOH or AgOH or
2
Ag O in boiling
water forms
2 5
C H OH
+ +
3 2 3 2
H CCH Cl NaOH CH CH OH NaCl

D
+ +
3 2 3 2
H CCH Cl AgOH CH CH OH AgCl
b) From Ethyl Acetate:
Ethyl alcohol is formed by the hydrolysis of ethyl acetate with aqueous alkali.

( )
+ +
3 2 5 3 2 5 aq
H CCOOC H KOH CH COOK C H OH
c) From Acetaldehyde:
Acetaldehyde reduced by
4
LiAlH or
4
NaBH in ether gives Ethyl alcohol

4
4
LiAlH /Ether
3 3 2 or NaBH
H CCHO CH CH OH
d) From ethylene:
Ethylene treated with
2 4
H SO to give ethyl hydrogen sulphate. Then Ethyl hydrogen sulphate
treated with water to give ethyl alcohol.

-
= + -
4
|
75 80 C
2 2 2 4 3 2
SO H
H C CH H SO H C CH
+ +
3 2 2 3 2 2 4
|
4
SO H
H CCH H O H CCH OH H SO
e) Ethyl alcohol is obtained by the action of
3
H CMgX on formaldehyde followed by the hydrolysis.

C = O + H3CMgBr
H
H
C
H
H
OMgBr
CH3
H3C CH2OH + Mg
OH
Br

2. How is ethyl alcohol obtained by fermentation process of molasses.
Ans: Molasses is the mother liquor left behind after the crystallization of sugar from sugarcane juice.
This dark syrupy liquid is diluted with water to have the percentage of sugar in the solution to about 10%.
To the diluted molasses solution
2 4
H SO is added to maintain the pH of the solution at 4. Ammonium
sulphate and ammonium phosphate are added as food for the yeast.
Maltose solution or diluted molasses solutions is cooled to 30 C and fermented with yeast for 24 72
hours.
If the maltose solution is taken:
+ +
Maltose
12 22 2 6 12 6 6 12 6 Enzyme
Maltose Glucose Fructose
C H OH H O C H O C H O
If sucrose solution is taken
+ +
Invertage
12 22 2 6 12 6 6 12 6 Enzyme
Glucose Fructose
C H OH H O C H O C H O
FIITJEE
+
Zymase
6 12 6 2 5 2 Cenzyme
Glucose/Fructose
C H O 2C H OH 2CO
Generally 95% aqueous alcohol is called rectified spirit.
3. How is ethyl alcohol reacts with the following:
a) Hydrogen halide b) Phosphorous halide c) Thionyl chloride
d) Cu /300 C e)
2 2 7 2 4
K Cr O /H SO f)
2
Cl
g)
2
CaOCl h)
2
I /KOH
Ans:
a) Ethyl alcohol reacts with hydrogen halide to form ethyl halide.
The reactivity order is HI >HBr >HCl >HF
HCl reacts with Alcohol in the presence of anhydrous
2
ZnCl catalyst to give ethyl chloride. Conc. HCl +
Anhydrous ZnCl
2
is called as Lucas reagent.
+ +
2
ZnCl
2 5 2 5 2
C H OH HCl C H Cl H O
b) Ethyl Alcohol reacts with PCl
3
or PCl
5
to give ethyl chloride.
+ +
2 5 3 2 5 3 3
3C H OH PCl 3C H Cl H PO
( ) + +
2 5 5 2 5 3
C H OH PCl C H Cl POCl Phosphorous Chloride
c) Thionyl chloride ( )
2
SOCl reacts with ethyl alcohol to give ethyl chloride.
+ + +
2 5 2 2 5 2
C H OH SOCl C H Cl SO 2HCl
d) Dehydrogenation: When ethyl alcohol vapours are passed over freshly reduced copper at 300 C
acetaldehyde is formed.

Cu
2 5 3 2 300 C
||
O
C H OH CH C H H
- - +
e) Oxidation of ethyl alcohol with acidified
4
KMnO or
2 2 7
K Cr O forms Acetic Acid.

+

2 2 7 2 2 7
2 4 2 4
K Cr O K Cr O
3 2 3 3 H SO H SO
CH CH OH CH CHO H CCOOH
f) Action of halogen:
Halogens oxidize ethyl alcohol first to acetaldehyde. Then it undergoes halogenation to form
chloral.
( )
2 2
Cl 3Cl
3 2 3 3
H CCH OH H CCHO Cl CCHO chloral
g) Reaction with Bleaching powder:

2 5
C H OH reacts with
2
CaOCl in water to give chloroform.
( ) + +
2 2 2
2
CaOCl H O Ca OH Cl
[ ] + +
2 2
Cl H O 2HCl O
[ ] + +
3 2 3 2
H CCH OH O H CCHO 2H O
+ +
3 2 3
H CCHO 3Cl CCl CHO 3HCl
( ) ( ) ( ) + +
3 3
2 2
2CCl CHO Ca OH 2CHCl HCOO Ca Calciumformate
h) Iodoform reaction:-
When ethyl alcohol is treated with
2
I solution and KOH solution if forms Yellow crystals of
3
CHI
(Iodoform).

3 2 2 3
||
O
H CCH OH I H C C H 2HI + - - +

3 2 3
Tri iodo acetaldehyde
|| ||
O O
H C C H 3I I C H 3HI - - + - - +

3 3
|| ||
O O
I C C H KOH CHI H C OK - - + + - -
Overall reaction is

2 5 2 3 2
C H OH 4I 6KOH CHI HCOOK 5KI 5H O + + + + +
4. How the maltose is prepared from starch.
Ans: Common sources of starch are wheat, barely, potato etc. The grain is mashed with hot water. It is then
heated with freshly germinated barley (malt) at 50 C for 1 hour. Malt contains the enzyme diastase.
Diastase converts starch into the sugar maltose by hydrolysis.
FIITJEE
( )
Diastase
2 6 10 5 12 22 11
n
Maltose
Starch
n
H O C H O C H O
2
+
5. How is methyl alcohol prepared.
Ans: Water gas is heated at 573-673 K at 200 to 300 atm in presence of
2 3
ZnO Cr O - to give methyl alcohol.

2 3
ZnO Cr O
2 3 200 300 atm
573 673K
CO 2H CH OH
-
-
-
+
6. What is the composition of Azeotropic mixture of
2 5
C H OH with
2
H O.
Ans: A mixture of 95.6% ethyl alcohol and 4.4% water forms constant boiling point mixture, known as Azeotropic
mixture.
7. Explain the reaction of ethyl alcohol with (a) Sodium metal (b) Esterification (c) Grignard
ragent
Ans: (a) Soldium metal reacts with
2 5
C H OH to give sodium ethoxide.

2 5 2 5 2
2C H OH 2Na 2C H ONa H + +
(b) Esterification:- Ethyl alcohol undergoes acid catalysed condensation with a carboxylic acid to form
an ester. The reaction is called Fisher esterification.

2
H O
3 2 5 3 2 5 2
Ethyl acetate
H CCOOH C H OH H C COOC H H O
+ - +

Ethyl alcohol reacts with acid chlorides such as acetyl chloride or acid an hydride such as acetic
anhydride to form the ester such as ethyl acetate.

2 5 3 5 2 3
Ethyl acetate
|| ||
O O
C H OH Cl C CH H C O C CH HCl + - - - - - +
(c) Ethyl alcohol reacts with alkyl magnesium halide to form alkane

C2H5OH + H3CMgI CH4 + Mg
OC2H
I

8. How to identify primary, secondary and tertiary alcohols by using Lucas reagent.
Ans: Lucas reagent is Conc. HCl+Anhydrous
2
ZnCl
Lucas reagent reacts with 3 alcohol to give turbidity within 30 seconds.

2
| |
| |
R R
R R
R C OH HCl R C Cl H O - - + - - +
Lucas reagent reacts with 2 alcohol to give turbidity after 5 minutes.

2
| |
| |
R R
R R
R C OH HCl R C Cl H O - - + - - +
Lucas reagent does not react with 1 alcohols.
9. How is 1 , 2 and 3 alcohols are identified by using Victarmeyers test.
Ans: The alcohol compound is treated with red phosphorous and
2
I , and the product is treated with Silver nitrite
and then with nitrous acid ( )
2 2 4
NaNO H SO + and finally made alkaline.
Primary alcohols give red coloration, Secondary alcohols give blue colouration.
Tertiary alcohols give no reaction.
10. Explain the action of conc.
2 4
H SO on ethyl alcohol at different temperatures.
Ans: (i)
100 110 C
5 2 2 4 2 5 4 2
Ethyl hydrogen sulphate
H C OH H SO C H HSO H O
-
+ +
(ii)
2 4
Conc. H SO
2 5 2 5 5 2 2 5 2 140 C
EthER
C H OH C H OH H C O C H H O
+ - - +
(iii)
2 3
Al O
2 5 2 5 5 2 2 5 2 260 C
C H OH C H OH H C O C H H O
+ - - +
(iv)
2 4
170 C; Conc.H SO
2 5 2 4 2
C H OH C H H O
+

2 3
Al O ,350 C
2 5 2 4 2
C H OH C H H O
+
FIITJEE
PHENOLS
1. How are Phenols prepared form (a) Haloarenes (b) diazonium salts(c) Benzene sulphonic acid (d)
Cumene
Ans: (a) From haloarenes:-
Halobenzene is fused with NaOH at 320 atm and 350 C . It gives sodium Phenoxide and then it
is treated with HCl to give phenol.
ONa
350
o
C, 3220 atm
X
OH
+ NaOH
HCl
+ NaCl

(b) From diazonium salts:
An aromatic primary amine reacts with nitrous acid ( )
2
NaNO HCl + at 0 5 C - to from
diazoinium chloride. Diazonium salts on warming with water or dilute acids hydrolyses to phenol.
N2Cl
NaNO2 + HCl
OH
H2O
+ N2 + HCl
NH2
0 5
o
C warm

(c) From benzene sulphonic acid:-
Benzene is sulphonated with oleum to get benzene sulphonic acid which on heating with molten
NaOH forms sodium phenoxide. Acidification of sodium phenoxide with acid like HCl forms phenol

H2SO4, SO3
O Na
NaO
+ NaCl
NH2 SO3H
HCl
OH

(d) From Cumene:
Phenol is manufactured from the hydrocarbon known as cumene i.e., isopropyl benzene. Cumene
is oxidized in presence of air to cumene hydroperoxide which on treating with dilute acid give
phenol and acetone.

O2
OH
H
+

+ H3C C CH3
CH3
H2O
Cumene
CH H3C H3C C O O H
CH3
O

2. Write the resonance structures of phenol and explain acidic character of phenol.

O H O H O H
O H O H

Ans: When phenol gives H
it gives phenoxide ion. Phenoxide ion is resonance statilised.

O O
O
O O
+ H
+

O

3. Explain the esterification reaction of phenols.
Ans: Phenols react with carboxylic acids and their derivatives like acid chlorides and acid anhydrides to from
esters.

O C R
+ H2O
OH
+ RCOOH
H
+

O

O C R
+ HCl
OH
+ R C - Cl
O
O

4. How is aspirin prepared? Write the equation.
Ans: Introduction of
3
||
O
C CH - - on phenolic oxygen is called acetylation. Salicylic acid on acetylation gives
acetyl salicylic acid or aspirin.
FIITJEE

O C CH3
OH
+ (CH3CO)2O
O
COOH
Salicylic acid
H
+

Acetyl salicylic acid
(Aspirin)
OH

5. Explain the nitration and Halogenation of phenol.
Ans: -OH graph on benzene in phenol is a ring activating and ortho para directing group.
a) Nitration:
Phenol reacts with dilute
3
HNO to give ortho nitrophenol and p-nitrophenol.

OH
dil.HNO3
OH
NO2
P-nitro phenol
+
OH
NO2
O-nitro phenol

With Conc.
3
HNO it gives 2, 4, 6 trinitro phenol known as picric acid.

OH
NO2
NO2
O2N

OH
Conc. H2SO4
OH
SO3H
SO3H

b) Halogenation:
Phenol reacts with
2
Br in presence of
2
CS to give ortho-Bromophenol and para bromo phenol.

OH
Br2/CS2
OH
Br
+
OH
Br
273K

With
2
Br it give 2, 4, 6- tri bromo phenol.

OH
+ 3Br2
OH
Br Br
Br

6. Explain Reimer-tiemann reaction.
Ans: Phenol on treating with chloro form in the presence of NaOH gives
||
O
C H - - group ortho position.

ONa
CHCl3 Aq. NaOH
OH
CHCl2
NaOH
ONa
CHO
H
+

OH
CHO
Salicyladehyde

7. Explain Kolbes reaction:
Ans: Phenol reacts with NaOH to give sodium phenoxide then it is treated with
2
CO and an acid to give 2-
hydroxy benzoic acid.

Phenol
OH ONa
Sodium
phenoxide
(i) CO2
OH
COOH
NaOH
(ii) H
+

major

8. Explain Fries rearrangement?

OH
Acetic anhydride
H3C C
H3C C
O
+
Anhydrous AlCl3
O
O
O C CH3
O
AlCl3
OH
C CH3
O
+
O C CH3
OH
O-hydroxy
acetophenone
P-hydroxy
acetophenone

FIITJEE
9. Explain the reaction of phenol with (a) Zn dust and (b) Chromic acid
Ans: (a) Phenol reacts with Zn to give Benzene

Phenol
OH
+ Zn
+ ZnO
Benzene

(b) Phenol reacts with chromic acid to give benzoquinone.

Chromic Acid
OH
Benzoquinon
[Na2Cr2O7 + H2SO4]
O
O

ETHERS
1. How is diethyl ether prepared from
(i) Ethyl alcohol (ii) ethyl bromide (iii) By Williamsons synthesis
Ans: (i)
(a)From Ethyl alcohol:-
Ethyl alcohol is taken in excess is treated with Conc.
2 4
H SO at 140 C to give diethyl ether.

- + - - - - +
2 4
Conc. H SO
5 2 2 5 5 2 2 5 2 140 C
H C OH H O C H H C O C H H O
(b)Dehydration of ethyl alcohol to diethylether is also carried out by passing the alcohol vapours at 260 C
over aluminum ( )
2 3
Al O catalyst
- - +
2 3
Al O
2 5 5 2 2 5 2 260 C
2C H OH H C O C H H O
(ii) From ethyl bromide:-
Ethyl bromide reacts with dry silveroxide to from diethyl ether.
+ + - - - +
5 2 2 2 5 5 2 2 5
H C Br Ag O Br C H H C O C H 2AgBr
(iii) Williamsons synthesis:
Ethyl halide reacts with sodium or potassium ethoxide to form diethyl ether.
+ - - +
2 5 2 5 5 2 2 5
C H ONa IC H H C O C H NaI
2. How does ethyl alcohol reacts with (a) Halogen (b) Oxygen (c) Mineral acids (d)
2 4
H SO (e) HI (f) Boiling water (g)
5
PCl (h) - -
3
||
O
H C C Cl (i)
( )
3
2
H CCO O (j)
2 2 7
K Cr O (k)
2 3
Al O /360 C (l) +
3
CO BF
Ans: (a) Halogenation:
Diethyl ether reacts with chlorine or bromine to form halogen substituted ethers.
- - - - - - - -
| |
2
Cl Cl
Cl
3 2 2 3 3 3 Dark
H C CH O CH CH H C CH O CH CH
In the presence of sunlight all hydrogens are displaced.
- - - -
2
Cl
5 2 2 5 5 2 2 5 Sunlight
Perchloro diethyl ether
H C O C H Cl C O C Cl
(b) Oxygen:
Diethyl ether reacts with atmospheric oxygen or ozonised oxygen to form peroxide. The peroxide is highly
explosive.
[ ]
-
- - + - -

5 2 2 5 5 2 2 5
Peroxide
:O:
H C O C H O H C O C H
(c) Formation of oxonium salts:-
Diethyl ether reacts with strong mineral acids such as HCl, HBr and
2 4
H SO stable oxonium slats at low
temperature.

-
- - + - -
e

5 2 2 5 5 2 2 5
H
H C O C H HBr H C O C H .Br
(d) Action of Sulphuric Acid:-
Diethyl ether forms oxonium slats with cold sulphuric acid, it ruptures C-O bond with hot sulphuric acid

( )
D
- - + +
5 2 2 5 2 2 5 2 5 4 4 Conc.
H C O C H H SO C H OH C H HSO
(e) Action of hydrobromic acid or hydro iodic acid
- - + +
2 5 2 5 2 5 2 5
C H O C H HI C H I C H OH
FIITJEE

O C2H5
OH
+ HI
+ C2H5I

(f) Diethyl reacts with Boiling water to give ethyl alcohol.
- - +
2 5 2 5 2 2 5
C H O C H H O 2C H OH
(g) Action of
5
PCl :
Diethyl ether is treated with hot
5
PCl to form ethyl chloride.
- - + +
5 2 2 5 5 2 5 3
H C O C H PCl 2C H Cl POCl
(h) Action of acetyl chloride
Acetyl chloride reacts with diethyl ether in presence of
3
AlCl to form ethyl chloride and ethyl
acetate.
- - + +
3
AlCl
5 2 2 5 3 2 5 3 2 5
Ethyl Acetate
H C O C H H CCOCl C H Cl H CCOOC H
Diethyl ether reacts with acetic anhydride to give ethyl acetate.
( ) - - + - -
2
ZnCl
5 2 2 5 3 3 2 5
2
||
O
H C O C H H CCO O 2H C C OC H
(j) Action of a strong oxidizing agent like
2 2 7
K Cr O :-
Diethyl ether oxidized acetaldehyde and finally acetic acid with strong oxidizing agent.
- -
2 2 7 2 2 7
K Cr O K Cr O
5 2 2 5 3 3 Oxidation Oxidation
H C O C H 2H CCHO 2H CCOOH
(k) Dehydration:- When diethyl ether vapours are passed over alumina at 360 C ethylene is formed

2 3
Al O
5 2 2 5 2 2 2 360 C
H C O C H 2H C CH H O
- - = +
(l) Action of carbon monoxide:-
In the presence of
3
BF at 150 C and 500 atm directly ether reacts with CO to form ethyl propionate.

- - + - - -
3
BF /150 C
5 2 2 5 5 2 2 5 500 atm
Ethyl propionate
||
O
H C O C H CO H C C O C H
3. Explain electrophilic substitutions of alkyl aryl ether.
Ans: Alkoxy group is O, P-directing and ring activating. They give ortho and Para substituted products.

Br2 / CH3COOH
OCH3
Br Anisole
OCH3

Anhydrous AlCl3
OCH3
CH3
+ H3CCl
OCH3
+
OCH3
CH3
P-methoxy
tolene
O-methoxy
tolene

H3CCOCl
OCH3
O = C CH3
OCH3
+
OCH3
C CH3
O

H2SO4/HNO3
OCH3
NO2
OCH3
+
OCH3
NO2

4. Write the uses of diethyl ether.
Ans: (i) It is a refrigerant. A mixture of diethyl ether and dry ice produces - 110 C , very low temperature
(ii) As substituent for petrol after mixing with
2 5
C H OH under the trade name natalite.

FIITJEE
ALDEHYDES & KETONES
Choose the correct answer:
1. How are Aldehydes prepared from the following compounds?
(a) Alcohols (b) Calcium salts of carboxylic acids
(c) Carboxylic acids with mono catalyst (d) From alkenes (Wacker process)
(e) From Alkynes (f) Hydrolysis of Alkylidene chlorides
(g) Acid chlorides
Sol: (a) (i)oxidation of ethyl al cohols:
Oxidation of ethyl alcohol with pyridium dichromate (PDC) or pyridium chlorochromate (PCC) in anhydrous
media like dichloro methane gives acetaldehyde

( )
2 2 2
PDC or PCC
3 2 3 CH Cl H O
H C CH OH H CCHO
-
- -
(ii) By Catalytic dehydrogenation of ethyl alcohol:
When ethyl alcohol vapours are passed over Ag or Cu catalyst at 300 C to give acetaldehyde
Cu or Ag
3 2 3 Air
||
O
CH CH OH H C C H - -
(b) From calcium salts of carboxylic acids:
Acetaldehyde is prepared by heating a mixture of calcium salts of formic acid and acetic acid.
( ) ( )
3 3 3
2 2
Acetaldehyde
Calciumformate CalciumAcetate
HCOO Ca CH COO Ca 2CH CHO 2CaCO
D
+ +
(c) From carboxylic acids:
Acetaldehyde is obtained by passing a mixture of vapours of formic acid and acetic acid over manganous
oxide (MnO) catalyst at 300 C
MnO, 300 C
3 3 2 2
HCOOH H CCOOH H CCHO CO H O
+ + +
(d) From Alkenes (Wacker Process)
Acetaldehyde is obtained by passing ethylene through an acidified aqueous solution of palladium chloride and
cupric chloride.
2
CuCl
2 2 2 2 3
H
H C CH PdCl H O H CCHO Pd 2HCl
+
= + + + +
(e) From Alkynes:- Acetaldehyde is obtained by passing acetylene through an aqueous solution of 40%
Sulphuric acid and 1% mercuric sulphate at 60 C
2 4
4
40%H SO , 60 C
2 2 1%HgSO
|
OH
H C CH H O H C CH tautomerism
- + =
3
H CCHO
(f) From the hydrolysis of alkylidene chlorides:
Heating ethylidene chloride with KOH or NaOH give acetaldehyde
( )
2
2KOH
3 2 3 3 H O 2
Acetaldehyde
H C CHCl H CCH OH H C CHO
-
- -
(g) Reduction of acid chlorides:
Reduction of acetyl chloride with hydrogen in presence of palladium catalyst which is supported on barium
sulphate. This reaction is called Rosenmunds reduction
4
2
Pd BaSO
3 3 H
H CCOCl H CCHO HCl
-
+

FIITJEE
2. How are ketones are prepared by the following compounds.
(a) Oxidation alcohols (b) Catalytic dehydrogenation of
2 5
C H OH
(c) Heating calcium acetate (d) From carboxylic acid
(e) From aalkenes (wacker process) (f) From alkynes
(g) From hydrolysis of alkylidere chlorides (h) From nitriles
Ans:
(a) Oxidation of isopropyl alcohol:-
Isopropyl alcohol on oxidation with pyridum dichromate (PDC) or pyridium chloro chromate (PCC) in
anhydrous media like dichloromethane gives acetone.
PCC
3 3 3 3 Oxidation
Acetone
H CCHOHCH H C CO CH - -
(b) By catalytic dehydrogenation of ethyl alcohol:-
When isopropyl alcohol at 300 C heated in presence of Cu or Ag catalyst to give acetone.
Cu or Ag
3 3 3 3 2 Air
H CCHOHCH H CCOCH H O +
(c) From salts of carboxylic acid salt:
Acetone is prepared by heating calcium acetate.
( )
3 3 3 3
2
H CCOO Ca H CCOCH CaCO
D
+
(d) From carboxylic acids:-
Acetone is obtained by passing the vapours of acetic acid over manganous oxide (MnO) catalyst at 300 C .
MnO, 300 C
3 3 3 2 2
2H CCOOH H CCOCH CO H O
+ +
(e) From alkenes (wacker process)
Propylene is passed through an acidified aqueous solution of palladium chloride ( )
2
PdCl and cupric chloride
( )
2
CuCl
2
CuCl
3 2 2 2 3 3
H
||
O
H C CH CH PdCl H O H C C CH Pd 2HCl
+
- = + + - - + +
(f) From Alkynes:
Acetone is obtained by passing propyne into a solution of 40%
2 4
H SO and 1%
4
HgSO at 60 C
2 4
4
tautomerise 40%H SO
3 2 3 2 3 3 60 c
1%HgSO
| ||
OH O
H CC CH H O H C C CH H C C CH
+ - = - -

(g) Hydrolysis of isopropylidene chloride:-
( )
2
H O 2KOH
3 2 3 3 3 3 3
2
Acetone
||
O
H C CCl CH H C C OH CH H C C CH
-
- - - - - -
(h) From nitriles:-
1-phenol propanone is prepared from propane nitrite and phenyl magnesium halide.

H3C CH2 C N + C6H5MgX
Ether
H3C CH2 C
NMgBr
C6H5
H3O
+

C2H5 C C6H5
O
1-Phenol propanone

FIITJEE
3. How is Benzaldehyde prepared form (a) Methyl benzene (b) Benzene?
(a) (i) Oxidation of methyl Benzene:- (Etard reaction)
Methyl benzene reacts with chromyl chloride followed by hydrolysis.

CH3
+ CrO2Cl2
toluene
CS2
CH(OCrOHCl2) 2
H3O
CHO

(ii) Methyl benzene reacts with
3
CrO in acetic anhydride to give Benzaldehyde.

CH3
+ CrO3 + (H3CCO)2O
273 283 K
CH(OCOCH3) 2
H3O
CHO

(iii) Side chain chlorination followed by hydrolysis

CH3
Cl2/ hn
HCCl2
H2O
CHO
373 K

(iv) Gatterman-Koch reaction:-
Benzene is treated with CO and HCl in the presence of Anhydrous
3
AlCl and
2 2
Cu Cl

CO, HCl
CHO
Anhydrous AlCl3, Cu2Cl2

4. How does acetaldehyde reacts with
(a) HCN (b)
3
NaHSO (c)
3
NH (d)
2
H N OH -
(e)
2 2
H N NH - (f)
2 6 5
H N NHC H - (g)
2 2
||
O
H NNH C NH - - (h) 2, 4-DNP
(i)
5
PCl (j) RMgX (k) ROH (l)
4 4
NaBH or LiAlH
(m) Zn Hg /HCl - (n)
2 2
H N NH /KOH - (o)
2 2 7 2 4
K Cr O /H SO (p)
2
I /NaOH
(q) ( )
2 4
0 C/H SO Polymerisation
Ans:
(a) Action of HCN: Addition of HCN to acetaldehyde gives acetaldehyde cyanohydrin.

C = O + HCN C
CH3
OH
H
CN
H3C
H
Acetaldehyde
cyanohydrin

(b) Action of
3
NaHSO : Addition of sodium bi sulphate to acetaldehyde gives acetaldehyde sodium bisulphite
salt.

C = O + NaHSO3 C
OH
H
SO3
H3C
H
Acetaldehyde
sodium bi sulphate
H3C
Na
+

(c) Action of
3
NH :-

3 3 3 2 3
Acetaldehyde ammonia Ethanalimine
|
OH
H C CHO NH H C CH NH H C CH NH - + - - - =
(d) Action of hydroxylamine:- It gives a acetaldeoxime
FIITJEE

C = O + H2NOH
OH
H
H3C
H
Acetaldoxime
H3C C N
OH
H
H3C C = N OH
- H2O
H

(e) Action of hydrazine: ( )
2 2
H N NH -

C = O + HN2 NH2 C
H3C
NH NH2
H OH
H3C
H
hydrazine
C = N NH2 + H2O
H3C
H
hydrazone

(f) Action of phenylhydrazine:-

C = O + H2N NH C6H5
H3C
H
Phyl hydrazine
C = N NH C6H5
H3C
H
Phenyl hydrazone
- H2O

(g) Action of semi carbazide:-

C = O + H2N NH C NH2
H3C
H
Phyl hydrazine
C = N NHC6H5
H3C
H
- H2O
O
C
H3C
NH NH C NH2
H OH
O
Semi carbozone

(h) With 2,4 DNP

C = O + H2N NH
H3C
H
2,4-dinitro phenyl
hydrazine
C
H3C
NH NH
H OH
NO2
NO2
NO2
NO2
- H2O
C = N - NH
NO2
NO2
H3C
H
2,4-dinitro phenyl
hydrazone

(i) Action of
5
PCl : Acetaldehyde reacts with acetaldehyde to give ethylidene chloride.

H3C C = O + PCl5
H
H3C C Cl + POCl3
H
Cl
Ethylidene chloride

(j) Addition of Grignards reagent: Acetaldehyde reacts with RMgX to give an adduct and after Acid hydrolysis
to give secondary Alcohol

H3C
H
H
+

C = O + RMgX
C
R
OMgX H3C
H
C
R
OH
2
0
Alcohol
H3C
H

(k)
R
H
C = O
C
OH
OR
Acetal
H3C
H
ROH
dry HCl
ROH
H3O
+

R
H
C
OR
OR
+ H2O
Hemi Acetal

(l) Acetaldehyded reduction:
Ni
3 2 3 2
|
H
H C C O H H C CH OH - = + - -
4
4
NaBH
3 3 2 or LiAlH
|
H
H C C O H CCH OH - =
(m) Clemenson reduction:
FIITJEE
H3C
H
CH2 + H2O
C = O
Ethane
H3C
H
Zn Hg
HCl

(n) Wolff-Kishner reduction:

H3C
H
C = O
Ethane
H2N NH2
-H2O
H3C
H
C = N NH2
KOH
Ethylene glycol
H3C CH2 H + N2

(o) Oxidation:
2 2 7
2 4
K Cr O
3 3 H SO
Acetaldehyde Acetic acid
H C CHO H CCOOH -
(p) Iodoform reaction:
3 2 3 2
H CCHO 3I 4NaOH HCOONa HCI 3H O 3NaI + + + + +
(q) Polymerisation of acetaldehyde

3H3CCHO
Paradehyde Hypriotic drug
At room temp.
H2SO4 few drops
O O
O
H3C CH CH - CH3
CH
CH3

4H3CCHO
Metaldehyde
At 0
0
C
H2SO4 few drops
H3C CH O CHCH3
O O
H3C CH O CHCH3
(Solid fuel)

5. How does acetone reacts with
(a) HCN (b)
3
NaHSO (c)
3
NH (d)
2
H N OH -
(e)
2 2
H N NH - (f)
2 6 5
H N NHC H - (g) 2, 4-DNP (h)
5
PCl
(i) RMgX (j) Alcohol addition (k) Chlorination, Bromination
(l)
4 4 2 5
NaBH or LiAlH or Na /C H OH (m) Clemensen reduction
(n) Wolff-Kishner reduction (o)
2 2 7 2 4
K Cr O /H SO
(p)
2
I /NaOH (q) Few drops of
2 4
H SO
(a) Addition of HCN:-

OH
C = O + HCN
H3C
H
C
H3C
H3C CN
Acetaldehyde cyano hydrin

(b) Addition of
3
NaHSO :-
OH
C = O + NaHSO3
H3C
C
H3C
H3C SO3
Acetone sodium bisulphite
H3C
Na
+

(c) Addition of
3
NH
FIITJEE

OH
C = O + NH3
H3C
C
H3C
H3C NH2
Acetone Ammonia
H3C
-H2O
C = NH
H3C
H3C
Propanonimine

(d) Addition of Hydroxyl amine:-

C = O + H2N OH
H3C
C = N OH + H2O
H3C
H3C
Acetoxime
H3C

(e) Addition of Hydrazine

C = O + H2N NH2
H3C
C = N NH2
H3C
H3C
Hydrazone
H3C

(f) Addition of Phenyl hydrazine:-

NH NH
C = O + H2N NH C6H5
H3C
C
H3C
H3C
OH H3C
-H2O
C = N NHC6H5
H3C
H3C
Phenyl hydrazone
C6H5

(g) Addition of semicarbazide:-

C = O + H2NNHCONH2
H3C
C = NHCONH2
H3C
H3C
H3C
-H2O
Semi carbazone

(h) Addition of 2, 4 DNP

C = O + H2N NH
H3C
C = N NH
H3C
H3C
H3C
-H2O
2,4 dinitrophenyl hydrazone
NO2
NO2
NO2
NO2

(i) Addition of
5
PCl

Cl
C = O + PCl5
H3C
C
H3C
H3C
Cl H
Ethylidene chloride
+ POCl3

(j) Addition of Grignard reagent

OMgX
C = O + RMgX
H3C
C
H3C
H3C
R
H3C
H
+
/ H2O
OH
C
H3C
R
3
0
Alcohol
H3C
+ Mg
X
OH

(k) Addition of Alcohol
FIITJEE

OR
C = O
H3C
C
H3C
H3C
OH
H3C
OR
C
R
Acetal
R
ROH
HCl
ROH
H
+
OR
Hemi acetal
(l) Reduction of Acetone

C = O + 2 [H]
H3C
H3C
Na/C2H5OH
H3C CH CH3
OH
2
0
Alcohol

(m) Clemmensen reduction

C = O
H3C
H3C
Zn - Hg
H3C CH2 CH3 +H2O
Propane
HCl

(n) Wolff-Kishner reduction

C = O
H3C
H3C
H2N NH2
H3C CH2 CH3 +N2
Propane
-H2O
C = N NH2
H3C
H3C
KOH /
CH2 OH
CH2 OH

(o) Oxidation:
2 2 7
2 4
K Cr O
3 3 3 H SO
Acetic acid
||
O
H C C CH CH COOH - -
(p) Iodo form reduction:

3 3 2 3 3 2
||
O
H C C CH 3I 4NaOH H CCOONa CHI 3H O 3NaI - - + + + + +
(q) Polymerisation of acetone:

3H3CCOCH3
H2SO4
CH3
CH3
CH3
2, 4, 6 trimethyl benzene
(mesitlylene)

6. Explain the tests for acetaldehyde:-
Ans:
Acetaldehyde responds to Tollens test, Fehlings test and Schiffs base test. But acetone does not respond to
these tests.
(a) Tollens test: - Tollens reagent is Ammonical silver nitrate solution. i.e. ( )
3
2
Ag NH OH

. It gives silver
mirror with acetaldehyde .
( )
3 3 3 4 3 2
2
H CCHO 2 Ag NH OH H CCOONH 2Ag 3NH H O + + + +

Acetaldehyde oxidised to acetic acid
(b) Fehlings test:-
Fehlings solution is the mixture of equal volumes of solution I (
4
CuSO solution) and solution II (
Rochellesalt solution with NaOH (sodium potassium tartreate))
2
3 3 2
H CCHO 2Cu 5OH H CCOO Cu O
+ - -
+ + +
A yellow red ppt
2
Cu O is formed
( )
2 1
Cu Cu
+ +
+3
2
H O
(c) Benedicts solution also gives above test. Benedicts solution is alkaline copper (II) sulphate solution, with
citrate solution.
2
Cu
+
converted to yellow or red
1
2
Cu O
+

FIITJEE
(d) Schiffs base test:-
Schiffs base is p-rosaniline hydrochloride pink aqueous solution decolourised with
2
SO . Acetaldehyde
restores the pink colour of Schiffs base.
7. Explain the tests for Acetone:
Ans:
1. Legal test:- If aqueous solution of acetone is treated with freshly prepared sodium nitroprusside in NaOH
solution wine red solution is formed and on standing to yellow.
2. Indigotest:- When acetone is treated with ortho nitro Benzaldehyde and KOH solution gives blue colour
indigotin.
8. Write the uses of Acetone:-
1) To store acetylene 2) Manufacture of cordite (A smokeless explosive powder)
3) Preparation of plexiglass (unbreakable glass)
4) Manufacture of synthetic rubber
9. What are the uses of acetaldehyde?
A: 1) Antiseptic inhalent in nose troubles
2) In the preparation of paraldehyde (Hypnotic drug)
3) In the preparation of metaldehyde (a solid fuel)
4) Preparations of chloral, rubber, dyes.

10. Explain Aldol condensation.
Ans: In presence of dilute NaOH,
2 3
K CO or HCl acetaldehyde undergoes condensation to form aldol.

OH or H
3 3 2
Aldol
|
OH
2H CCHO H C CH CH CHO
- +
- - -
Aldol on heating gives crotanaldehyde.

2
3 2 3 H O
Crotanaldehyde
|
OH
H C CH CH CHO H C CH CH CHO
D
-
- - - - = -
Acetone gives Ketol

( )
2
3 3 3 2 3 3 3 H O
3
| |
2
|
3
CH
OH
Ba OH
CH
2H CCOCH H C C CH COCH H C C CHCOCH
D
-
- - - - =

11. Explain cannizzaro reaction.
A: Aldehydes that have no a - hydrogen atom under go this reaction involving disproportionation (self oxidation
and reduction) on treating with strong concentrated alkali.
Eg:
1)

C = O
H
Conc. NaOH
formaldehyde
H C OH + H C - OK
H
C = O +
H
H
H
H
O
methanol Potassium formate

2)
FIITJEE

CHO
2
Conc. KOH
CH2OH
+
COOK
Benzaldehyde Benzyl alcohol Sodium benzoate

12. What is the product of the following reaction?

CHO
H2SO4 + HNO3
CHO
273 283K
M Nitro Benzaldehyde

13. Explain cross aldol condensation?
A: If the aldol condensation is between two different Aldehydes or ketones is called crossed aldol condensation.
Eg:
( )
i ) NaOH
3 3 2 3 3 2 ii )
( i ) 2 butenal
ii 2 methyl 2 pentenal
|
3
| |
CH
H H
H C C O H C CH C O H C CH CH CHO H C H C CH C CHO
D
-
- - -
- = + - - = - = - + - - = -

( )
3 3 2
iv pent 2 enal
( iii ) 2 methyl 2 butenal
|
3
CH
H C CH C CHO H C CH CH CHCHO
- -
- - -
+ - = - + - - =

Four products
iii and iv are crossed Aldol products. i and ii are simple or self aldols

FIITJEE
CARBOXYLIC ACIDS

1. How is acetic acid prepared form
(a) 1 alcohol (ethyl alcohol) (b) RMgX (Grignards reagent)
(c) From alkyl cyanide (Alkylnitrites) (d) From
3
CH OH and carbon monoxide
(e) From acetaldehyde (f) Bio chemical oxidation of ethyl alcohol
(g) From alkyl benzene
A: (a) Oxidation of ethyl alcohol:
In presence of
4
KMnO or
2 2 7 2 4
K Cr O /H SO ethyl alcohol gives acetic acid.

4 4
2 2 7 2 4 2 2 7 2 4
KMnO KMnO
3 2 3 3 or K Cr O /H SO or K Cr O /H SO
CH CH OH H C CHO H CCOOH -
(b) From Grignards reagent:
Methyl Magnesium bromide reacts with
2
CO followed by acid hydrolysis to give acetic acid

H3CMgBr + C
H
+
/ H2O
H3C C = O
H3C C OH + Mg
OH
Br
O OMgBr
O
O

(c) Methyl chloride with KCN gives methyl cyanide, then on hydrolysis it gives acetic acid.
3 3
H CCl KCN CH CN KCl + +

CH
3
CN + H
2
O H
3
C C = NH
O
OH
OH
H
3
C C NH
2

H2O
O
H
3
C C OH + NH
3

(d) From methyl alcohol and carbon monoxide:

Cobalt or
3 3 Rhodium, , pressure
H COH CO H CCOOH
D
+
(e) From Acetaldehyde:-
Acetaldehyde is oxidised with air inpresence of manganese acetate commercial quantities of acetic acid are
formed.
2
air Mn
2 3 3
1
O H CCHO H CCOOH
2
+
+
(f) From biochemical oxidation of ethyl alchol:
Dilute ethyl alcohol solution is oxidised in air by the bacteria micoderma aceti to give 6 to 10% of acetic acid
(Vinegar)
3 2 2 3 2
H CCH OH O H CCOOH H O + +
(g) Preparation of Benzoic acid from alkyl benzenes:

CH3
KMnO4, KOH
Heat
COOK
H3O
+

COOH
Toluene

CH2 CH2 CH3
KMnO4, KOH
COOK
H3O
+

COOH

2. How does acetic acid reacts with
(a) active metals (b) Carbonates and bicarbonates (c) NaOH
(d) ethyl alcohol (e)
3 5 2
PCl , PCl SOCl + (f)
3
NH
(g)
2
Red P Cl + (h)
4 10
P O (i) Sodalime
(j) Kolbes electrolysis (k) Calcium acetate (l) Lithium Aluminium hydride
(m) HI / Red P (n) Ni / D
A. (a) Active metals like sodium, potassium reacts with acetic acid to give salt.

3 3 2
Sodiumacetate
2H CCOOH 2Na 2CH COONa H + +
(b) Action of carbonates and bicarbonates:

3 2 3 3 2 2
2H CCOOH Na CO 2H CCOONa CO H O + + +

2 3 3 3 3
Na CO CH COOH H CCOONa NaHCO + +

3 3 3 2 2
NaHCO H CCOOH CH COONa CO H O + + +
(c) Reaction with alkali:

3 3 2
H CCOOH NaOH H CCOONa H O + +
FIITJEE
(d) Action of ethyl alcohol:

3
H O
3 2 5 3 2 5 2
H CCOOH C H OH H CCOOC H H O
+ +
(e) Action of
3 5 2
PCl , PCl , SOCl

3 3 3 3 3
3H CCOOH PCl 3H CCOCl H PO + +

3 5 3 3
H CCOOH PCl H CCOCl HCl POCl + + +

3 5 3 2
H CCOOH SOCl H CCOCl SO HCl + + +
(f) Reaction of
3
NH

3 3 3 4 3 2 2
AmmoniumAcetate Acetamide
||
O
H CCOOH NH H CCOONH H C C NH H O
D
+ - - +
(g) Action of Red P/
2
Cl :

Red P
3 2 2 HCl
|
Cl
H CCOOH Cl CH COOH
-
+ -

Red P
2 2 HCl
|
| |
H
Cl Cl
H C COOH Cl Cl C COOH
-
- + - -

Red P
2 HCl
| |
| |
Cl H
Cl Cl
Cl C COOH Cl Cl C COOH
-
- - + - -
(h) Action of phosphorous pentoxide:

2H3CCOOH
P4O10
-H2O
H3C C
H3C C
O + H2O
O
O
Acetic anhydride

(i) Action of Sodalime:

CaO
3 4 2 3
H CCOONa NaOH CH Na CO + +
(j) Kolbes electrolysis:

3 2 3 3 2 2
At Cathode Anode
2H CCOOK 2H O H C CH 2CO 2KOH H + - + + +
(k) (a) Distillation of Calcium Acetate:
( )
3 3 3 3
2
Acetone
||
O
H CCOO Ca H C C CH CaCO
D
- - +
(b) Mixture of calcium acetate and calcium formate on distillation gives acetaldehyde
( ) ( )
3 3 3
2 2
H CCOO Ca HCOO Ca 2H CCHO 2CaCO + +
(l) Reduction of acetic acid by
4
LiAlH

4
LiAlH
3 3 2
H CCOOH H C CH OH - -
(m) Reduction of Acetate Acid by HI / Red P

HI/Red P
3 3 3
H CCOOH H C CH -

Ni/
3 2 3 3 2
H CCOOH 3H H C CH 2H O
D
+ - +

FIITJEE
ANILINE
1. How are (i)
6 5
C H Cl (ii)
6 5
C H OH converted to aniline?
A. (i) Chloro benzene on heating with ammonia at 200 C under pressure in the presence of
2
Cu O forms
aniline.

2
Cu O
6 5 3 6 5 2 4
C H Cl 2NH C H NH NH Cl + +
(ii) Conversion of
2 5
C H OH to aniline:
Phenol on treating with
3
NH at 300 C under pressure in presence of
2
ZnCl forms aniline.

2
ZnCl
6 5 3 6 5 2 2 300 C
C H OH NH C H NH H O
+ - +
2. How is nitrobenzene converted to aniline?
A. Zinc and HCl or Sn and HCl, reduces nitrobenzene to aniline.

NO
2

+ 6[H]
+ 2H
2
O
Zn + HCl
or Sn + HCl
NH
2

Aniline

3. How does aniline react with the following:
(a)
3 3
H COOCH
(b)

H
3
C C
H
3
C C
O
O
O

(c)
3
CHCl /KOH/Alcohol
(d)
2
NaNO /HCl (e)
2
Br /0 5 C - (f)
6 5
||
O
Cl C C H - -
(g) Benzene suphonyl chloride (h) Benzaldehyde /
2 4
H SO
(i)
3
||
O
H C C Cl - - (j)
2 4
H SO
A. (a) Aniline reacts with methyl acetate to give N-acetyl aniline (Acetanilide)

NH
2

+ H
3
C C OCH
3
+ H
3
COH
O
H N C CH
3

O

(b)

NH
2

+ + HCl
H N C CH
3

O
H
3
C C
H
3
C C
O
O
O
Acetic an hydride

(c) Carbylamine reaction: -
Aniline or aprimary amine reacts with chloroform and alcoholic potash to form isocyanide which
possess fouling odour. This is a test to detect a primary amine.
FIITJEE

Alcohol
6 5 2 3 6 5 2
Phenyl isocyanide
C H NH HCCl 3KOH C H NC 3KCl 3H O + + + +
(d) Diazotisation:
In this reaction aniline reacts aniline reacts with nitrous acid at 0 - 5 C to form diazonium chloride.

NH
2

0 5
0
C
+ NaNO
2
+ 2HCl
N
+ 2H
2
O + NaCl
NCl
Benzene
dia-zonium chloride

(e) Aniline reacts with bromine at 0 5 C - to give 2,4,6-tribromo aniline.

NH
2

0 5
0
C
+ 3Br
2

NH
2

+ 3 HBr
Br
Br
Br

(f) Nitration: Aniline is converted to acetanilide then nitration of acetanilide gives p-nitroacetanilide,
after hydrolysis of the compound gives p-nitro aniline.

NH
2

CH
3
COCl
NO
2

NHCOCH
3

NH
2

NO
2

HNC CH
3

or
H
3
C C
H
3
C C
O
O
O
O
HNO
3

hydrolys
is

(g) Aniline reacts with benzene sulphonyl chloride to give N-phenyl benzene sulphanamide.

NH2
+ Cl SO2C6H5
- HCl
C6H5 N SO2C6H5
H
Benzene
sulphonyl chloride
N-phenyl
Benzene sulphonamide

(h) Aniline reacts with benzaldehide to give benzalidene aniline.

2 4
Conc. H SO
6 5 2 6 5 6 5 6 5
Benzalidene aniline
|
H
C H NH O C C H C H N C C H + = - - = -
(i) Aniline reacts with acetyl chloride to give acetanilide.

Pyridine
6 5 2 3 6 5 3 HCl
Acetanilide
||
O
C H NH Cl C CH C H NH COCH
-
+ - - - -
(j) Aniline when treated with sulphuric acid firstly it gives anilinium hydrogen sulphate. Then it gives
zwitter ion

NH2
H2SO4
NH3HSO4
NH2
SO3H
NH2
SO3
Anilinium
hydrogen sulphate
Zwitterion

FIITJEE
4. What are the uses of aniline?
A. (a) In the manufacture of benzene dia zonium chloride (This is for the preparation of several organic
compounds)
(b) In making schifits bases
(c) In the preparation of acetanilide, sulphanilic acid, sulpha drugs and azodyes.
5. Discuss the mechanism of nucleophilic substitution reactions
1
N
S and
2
N
S .
A. Nucleophilic substitution reactions take place in two ways depending on the nature of alkyl halide. These are
(i) unimolecular
( )
1
N
S and (ii) bimolecular
( )
2
N
S reaction mechanism.
(i) Unimolecular reaction
( )
1
N
S : The rate of hydrolysis of alkyl halide depends only on the concentration of
alkyl halide. It does not depend on the concentration of nucleophile
( )
OH
-
. Hence this reaction is called
unimolecular nucelophilic substitution reaction
1
N
S .
Tert. Alkyl halides follow this mechanism.
Rate [tert. Butyl bromide]
Rate =k [tert. Butyl bromide]
Hence the reaction follows first order kinetics.
Mechanism: This mechanism involves two steps.
Step-1: In the first step, C X bond breaks resulting in the formation of carbonium ion.

Slow
3 3
tert. butyl bromide tert. carbonium ion
3
3
|
|
| |
3 3
CH
CH
CH CH
H C C Br H C C Br
- - - +
e

This step is slow step and hence rate determining.
Step 2: In the secondstep, the nucleophile attacks the carbonium ion to give the product, alcohol.

Fast
3 2 3 3
3
3 3
|
| |
| | | |
3 3 3
CH
CH CH
. .
H CH CH CH
H C C H O: H C C O H H C C OH H

- + - - - - - +

ii) bimolecular reaction
( )
2
N
S : The rate of hydrolysis of alkyl halide depends on the concentration of alkyl
halide and also on concentration of nucleophile. Hence this is a second order reaction and biomolecular.
Primary alkyl halides undergoes hydrolysis preferably in this way.
Rate [Primary alkyl halide] [Nucleophile]
Mechanism:
2
N
S reaction mechanism involves only one step. The breaking of C X bond and the making
C OH take place simultaneously.

HO + C Br HO C Br HO C + Br
alcohol
transition state alkyl halide
d
d

FIITJEE
NITROBENZENE
1. How is Nitro benzene prepared?
A. Nitrobenzene is prepared in the laboratory by the nitration of Benzene with the acid mixture of concentrated
nitric acid sulphuric acid at a temperature below 60 C .

+ HNO3
Conc. H2SO4
NO2
> 60
0
C
+ H2O

2. How does Nitrobenzene reacts with
(a) Metal +acid (b) Metal +base (c) Metal +Neutral medium
(d)
4
LiAlH (e) Ni /Pt (f)
2 2
Cl /Br /Fe
(g)
3 2 4
Conc.HNO , Conc. H SO 60 C >
A. (a) Zinc and hydrochloric acid, tin and hydrochloric acid or stannous chloride and HCl reduces nitrobenzene to
aniline.

+ 6 [H]
Zn + HCl
NH2
or SnCl2 / HCl
+ 2H2O
NO2

(b) Alkaline medium:
Nitrobenzene gets reduced with zinc and alcoholic potash to hydrazobenzene.

+ 10 [H]
Zn / KOH
N N
NO2
2
+ 4H2O
H H
Hydrozo benzene

(c) Neutral medium:
Nitrobenzene gets reduced by Zinc and
4
NH Cl solution to phenyl hydroxylamine

+ 4 [H]
Zn /NH4Cl
H N OH
+ 2H2O
NO2
Phenyl hydroxyl amine

(d) With lithium aluminium hydride:
Nitrobenzene is reduced by
4
LiAlH to Azobenzene.

+ 8 [H]
LiAlH4
N N
NO2
2
Azobenzene

(e) Nitrobenzene is reduced catalytically with hydrogen and finely divided Ni or Pt at room temperature to give
aniline

+ 3H2
Ni/Pt
NO2
Aniline
+ 2H2O
NH2

(f) Halogenation :

+ Cl2
Fe
NO2
m-chloro nitro benzene
NO2
Cl

FIITJEE

+ Br2
Fe
NO2
m-bromo nitro benzene
NO2
Br

(g) Nitration above 60 C :

Conc. HNO3 + Conc. H2SO4
NO2
m-dinitro benzene
NO2
> 60
0
C
NO2

3. What are the uses of Nitrobenzene?
A. (a) Preparation of floor polishes
(b) Cheap perfumes preparation coil of mirbane
(c) Oxidising agent
(d) As a solvent, in making dyes

FIITJEE
BIOMOLECULES
Very Short answer Questi ons
1. What are lipids? Give examples.
A. Lipids are carbon compound (oily and greezy) insoluble in water but soluble in organic solvents like
chloroform, ether and benzene. Ex: Fats, Oils, Waxes etc.
2. How are lipids classified?
A. Lipids are classified into simple lipids (homo lipids). Compound lipids (hetero lipids), derived lipids (compound
obtained from simple and compound lipids)
3. What is the alcohol present in neutral lipids? Give its formula.
A. The alcohol present in neutral lipids is glycerol.

-
-
2
2
CH OH
|
CH OH Glycerol
|
CH OH

4. What are waxes? Give one example.
A. Waxes are insect secretions or protective coatings on animal furs and plant leaves.
Ex: Bees wax
5. What are compound lipids? Give one example.
A. Lipids which contain glycerol and other groupings other than fatty acids.
Ex: Lecithin, Cephalin.
6. What are derived lipids? Give one example.
A. Derived lipids are hydrolysis products of simple and compound lipids. Ex: Ergosterol, bile acids.
7. Give two biological function of lipids.
A. 1) Lipids are the energy sources 2) Lipids are the food veserves
8. What is cholesterol?
A. It is a white crystalline substance of molecular formula
27 45
C H OHfound in the tissues of animals,
synthesized by liver.
9. What are hormones and how are they classified?
A. Hormones are molecules of carbon compounds that transfer biological information from one group of cells to
distant tissues or organs. Hormones are classified into 3 groups on the basis of their chemical structures.
They are steroid hormones, protein hormones, amino acid derivatives.
FIITJEE
10. Give the structure of any three hormones?

CH
3
OH
H
H
H
O
,
O H
H H
CH
3
OH
H
,
O
H H
CH
3
H
COCH
3
C H
3

Testosterone Estradiol Progesterone
11. What are plant hormones, give examples.
A. Plant hormones are carbon compounds produced by higher plants. They regulate growth and physiological
functions at a site remote from the place of secretion.
Ex: Auxins, Gibberlines, Cytokinins
12. What are the main functions of sex hormones?
A. Sex hormones are responsible for the development of secondary sexual characteristics such as deep voice,
facial hair, sturdy physical structure in men.
13. What is the structure of insulin and what is its function?
A. Insulin is peptide hormone and has great influence on carbohydrate metabolism.
Structure of Insulin

Leu
Glu
Gln
Gly
Ile
Leu
Val
Glu
Cys
Cys
Thr
Ser
Ile Cys Ser
Asn
Tyr
Gln
Leu
Glu
Tyr
Asn
Cys
Gln
1
2
3
4
5
6
7
8
9
10 11 12
13
14
15
16
17
18
19
20
21
1
2
3
4
5
6
7
8
9
10
11
12
13
14 15 16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
Phe
Val
Asn
HIS
Cys
Gly
Ser
HIS
Leu
Val
Aln
Tyr
Leu
Cys
Val
Cyn
Gly
Glu
Arg
Gly
Phe
Phe
Tyr
Thr
Cys
Pro
Thr
S
S
S S
S
S
A-chain
B-chain

14. Give two examples of steroid hormones.
A. Ex: Androgen, estrogen.
15. Give two examples of protein hormones.
A. Insulin, Thyroxin
FIITJEE
16. What are vitamins? Give one example.
A. Vitamins are low molecular weight compound, their absence in the human body causes deficiency diseases or
disorders.
Ex: Vitamin B-complex
17. How are vitamins classified?
A. Vitamins are classified into two broad groups.
1) Fat soluble vitamins. Ex: Vitamin A, D, E and K
2) Water soluble vitamins. Ex: Vitamin C and B-complex
18. What are water soluble vitamins?
A. Vitamins which are soluble in water are called water soluble. Ex: Vitamin C and B-complex
19. What are fat soluble vitamins?
A. Vitamins which are insoluble in water are called fat soluble vitamins. Ex: Vitamin A, D, E and K
20. *What are the sources for vitamins A, B, C, K?
A. Source of vitamin A Fish oils, liver, rice
Source of vitamin B Cereals, milk, egg
Sources of vitamin C Green leafy vegetables, citrous fruit
Sources of vitamin K Green leafy vegetables, intestinal bacteria
21. *Give the deficiency diseases caused by A, C, D, E, K
Vitamin A Night blind ness, redness in eyes (xeropbthalmia)
Vitamin C Scurvy, delay in wound
Vitamin D Rickets in children
Vitamin E Sterility, neurosis of heart muscles
Vitamin K Blood clotting does not occur
FIITJEE
CHEMISTRY IN EVERYDAY LIFE
1. Define drug. Give two examples.
A. The chemicals of low molecular masses ranging from 100 to 500 U that react with macromolecular targets to
produce a biological response are called drugs.
Ex: Antihistamine, Cardio vascular drug.
2. Define medicine. Give two examples.
A. The drugs that produce biological response therapeutically and that are useful in diagnosis, prevention and
treatment of disease are known as medicines.
Ex: Aspirin, Ibuprofen
3. How do you differentiate between drug and medicine?
A. Drug which produce biological responses and prevent a disease is called a medicine. Drug produces a
biological response by reacting with target. It may or may not prevent a disease.
4. What are Narcotic drugs? Give an example.
A. Narcotic drugs cause depression of central nervous and are strong analgesics.
Ex: Morphine, Codeine
5. What are non-Narcotic drugs? Give an example.
A. The analgesics which have limited use in mild aches, pains like backache and headache.
Ex: - Aspirin, Ibuprofen
6. What are Analgesics? Give two examples.
A. Analgesics reduce or totally abolish pain without causing any damage to consciousness, mental confusion ,
disturbances of nervous system.
Ex: Aspirin, Ibuprofen
7. Define Antipyretics. Give two examples.
A. Drugs used to control fever are called antipyretics.
Ex: Paracetmol, Analgin etc.
8. Define transquilizers. Give two examples.
A. Drugs that cause quieting effect accompanied by relaxation and rest but need not necessarily induce sleep.
Ex: Luminal, Seconal.
9. Define antiseptics. Give example.
A. The chemical compounds that kill or prevent the growth of micro organisms. Ex: Dettol.
10. What are disinfectants?
A. Disinfectants are used for killing or preventing the growth of micro organisms. They are applied to objects like
floors, drainage system etc.
Ex: 1% phenol.
11. Explain antimicrobials. Give examples.
A. Antimicrobials kill or inhibit the growth of organism that cause disease. They increase immunity and
resistance to infection of the body.
Ex:- Lysozyme, Lactic acid.
12. What are antifertility drugs? Give examples.
A. Antifertility drugs are oral contraceptives which are generally steroids.
Ex: Norethindrone, Ethynylestrdiol
FIITJEE
13. Define antibiotics. Give example.
A. It is a substance that is produced wholly or partly by chemical synthesis and in low concentrations inhibits the
growth or destroys micro organisms by interfering in their metabolic process.
Ex:- Penicillin, Chloramphenicol.
14. What are antacids? Give examples.
A. Chemical that remove excess acid in the stomach and maintain the pH to normal level are antacids.
Ex: Omeprazole, Lansoprozole.
15. Define antihistamines. Give examples.
A. Antihistamines prevent the interaction of histamine with receptors of stomach wall theses producing less
amount of acid.
Ex: Dimetane, Sardane.
16. What difference do you find between antacid and antihistamine?
A. Antacid remove acidity in stomach while antihistamine lowers acid content in the stomach indirectly by
preventing the interaction of histamine with receptors of stomach wall.
17. What are food preservatives? Give examples.
A. Chemicals which are used to enhance the appeal and preservation of the food.
Ex: BHT, BHA,
2
SO etc.
18. Why are synthetic food colours not advisable?
A. Generally dyes are used as food colours. They do not have nutritive value, may be harmful for children with
asthma.
Ex: Tetrazine
19. What are artificial sweetening agents? Give examples.
A. Artificial sweetening agents are chemicals used in place of sugar or sucrose. They decrease the calorific
intake and at same time several time sweeter than sucrose.
Ex: Aspartame 100 times sweeter to sugar.
20. What are the advantages with artificial sweetening agents?
A. (1) It decrease the calorific intake, and useful for diabetic patient.
(2) Excreted through urine easily.

FIITJEE
POLYMERS

Q.1) Which of the following polymer is Copolymer? (a) Polythene, (b) Buna S, (c) Nylon 6, 6 and
(d) Polyvinyl Chloride
Ans: (b) Buna S is co-polymer because constituent monomers of it are different (i.e.,) 1, 3-butadiene
and Styrene.
(c) Nylon -6, 6 is copolymer because constituent monomers of it are different (i.e.) hexamethylene
diamine and adipic acid.
Q.2) Give any two examples for semi-synthetic polymers.
Ans: Examples for semi-synthetic polymers are cellulose rayon and cellulose nitrate.
Q.3) Define an elastomer.
Ans: Elastomers: These are the polymers which have rubber like elastic properties. OR
These are the polymers having very weak intermolecular forces of attraction between the polymer
chains. Vulcanished rubber is a very important example of an elastomer.
Q.4) What is cross linking agent used in Vulcanization?
Ans: Sulphur(or) sulphur containing compounds react with rubber molecules to effect cross linking in
vulcanization.
Q.5) Give the complete name for PHBV.
Ans: Poly b-hydroxy butyrate Co - b - hydroxyl valerate is PHBV.
Q.6) Write one difference between the polymers Buns-S and Buna -N.
Ans: Constituent monomers of Buna-S are 1,3-butadiene and Styrene (Vinyl Benzene).
Constituent monomers of Buna-N are 1,3-butadiene and Acrylonitrile(Vinyl Cyanide).
Q.7) What are the most common type of molecular weights used in the case of polymers?
Ans: Following two are most common type of molecular weights used in polymers.
(i) Number average molecular weight
( )
n
M (ii) Weight average molecular weight
( )
w
M
Q.8) What do you meant by polydispersity index?
Ans: The ratio of the weight average
( )
w
M and the number-average
( )
n
M molecular weights of a
polymer is called Polydispersity indes (PDI.

w
n
M
PDI
M
=
Q.9) What is Vulcanization of rubber?
Ans: The process of heating the raw rubber with sulphur (or) sulphur containing compounds at 373-
415K temperature is called Vulcanization of rubber.
FIITJEE
PHYSICAL CHEMISTRY
DILUTE SOLUTIONS
STRAIGHT OBJECTIVE TYPE (SINGLE OPTION CORRECT)

1. Explain with suitable examples the terms Molarity, Molality, Normality and Mole fractions. Which method of
expressing concentration is better than the others? Why?
A: Molarity:
i) The number of moles of solutes present in one litre of solution is known as molarity.
ii) It is denoted by M.
iii) Molarity ( )
( )
( )
No. of moles of solute n
M
Volume of solution in litres v
=
iv) Molarity( )
Weight of solute 1
M
Molecular wt. of solute Volume of solutiion in litres
=
v) Molarity is expressed in moles/litre
Ex: If 40g of NaOH is present in one litre of solution, then it is called 1 M solution or molar solution.
Molality:
i) The number of moles of solute present in 1000 g of solvent is known as molality.
ii) It is denoted by m
iii) Molality ( )
Weight of solute 1
m
Molecular wt. of solute wt. of solvent in kg
=
v) Molality is expressed in moles / kg of solvent.
Ex: If 40 gm of NaOH is present in one kg of solvent, then it is called 1 m solution or molal solution.
Normality:
i) The number of gram equivalents of solute present in one litre of solution is known as normality.
ii) It is denoted by N.
iii) Normality ( )
No. of gram equivalents of solute
N
Volume of solution in lit
=
iv) Normality ( )
Weight of solute 1
N
Equivalent weight of solute Volume of solution in litres
=
v) Normality is expressed in gram equivalents/lit.
Ex: If 53g of anhydrous sodium carbonate is present in one litre of solution, then it is called 1N or normal
solution.
Molefraction:
i) The ratio of number of moles of one component to the total number of moles of all the components of a
solution is known as mole fraction of that component.
ii) It is denoted by x.
iii)
( ) solute
No. of moles of solute
x
No. of moles of solute +No. of moles of solvent
=
iv)
( ) solvent
No. of moles of solvent
x
No. of moles of solute +No. of moles of solvent
=
v) Mole fraction has no units
vi) In a binary solution, the sum of mole fractions of solute and solvent is equal to unity.
vii) Molality is the convenient method for measuring concentration of solutions, because it is independent of
temperature.
2. Calculate the equivalent weights of
2 4 2 3 4
H SO ,Na CO ,KMnO in acid medium and ( )
2
Ba OH .
A: * Equivalent weight of an acid
Molecular weight of the acid
Basicity of the acid
=
Basicity:- Number of replaceable Hydrogen atoms.
Eq. Wt. of
2 4
98
H SO 49
2
= =
* Equivalent weight of a salt
Molecular weight of the salt
Total charge of cation or anion
=

2
2 3 3
Na CO 2Na CO
+ -
+
FIITJEE
Eq. Wt. of ( )
2 3 2 3
106
Na CO 53 molecular weight of Na CO 106
2
= = =
* Equivalent weight of an oxidizing agent
Molecular weight of the substance
Number of electrons involved during oxidation
=
In acid medium,
7
Mn
+
ion in
4
KMnO is reduced to
2
Mn
+
ion
( )
7 2
Mn 5e Mn
+ - +
+
i.e. Eq. Wt. of
4
158
KMnO 31.6
5
= =
* Equivalent weight of base
Molecular weight of base
Acidity of the base
=
Acidity:- Number of replaceable OH
-
ions
( )
2
Ba OH Mol.Wt 171.4 = ; Acidity =2
Eq. Wt. of ( )
2
171.4
Ba OH 85.7
2
= =
3. Define and explain Raoults law. How is it useful in determining the molecular weight of a non-volatile solute?
Or
Define Raoults law for lowering of vapour pressure. How is the law useful in determining the molecular
weight of solvent when a known non-volatile solute is dissolved?
A: Raoults law:
* The relative lowering of vapour pressure of a dilute solution of a non-volatile solute is equal to the mole
fraction of the solute.
* RLVP =mole fraction of solute (x)
* Mathematically, the law is represented as
0 s s
0 s 0
p p n
p n n
-
=
+

Where
0
p is the vapour pressure of pure solvent
s
p is the vapour pressure of solution of a non-volatile solute
s
n is the number of moles of solute
0
n is the number of moles of solvent
And
s 0
a b
n ,n
A B
= =
Where a =weight of solute; A =molecular weight of solute; b =weight of solvent; B =molecular weight of
solvent
Therefore
0 s s
0 s 0
a
p p n
A
a b
p n n
A B
-
= =
+
+

* For dilute solutions, the number of moles of solute ( )
s
n can be neglected in comparision to the number of
moles of solvent ( )
0
n
0 s
0
p p a B
p A b
-
=
Molecular weight of solute ( )
( )
0
0 s
p a B
A
p p b

=
-

4. What are colligative properties? Explain each of them with necessary examples.
* The properties of dilute solutions which depend upon the number of solute particles [molecules (or) ions]
not upon their nature are called colligative properties
* Colligative properties are used to determine the molecular weight of solutes.
* There are four colligative properties.
i) Lowering of vapour pressure ii) Elevation of boiling point
iii) Depression in freezing point iv) Osmotic pressure
i) Lowering of vapour pressure ( P D )
FIITJEE
* The decrease in vapour pressure of pure solvent when a non volatile solute dissolved in it is called lowering
of vapour pressure.
*Ex: Vapour pressure of salt water (solution) is less than vapour pressure of pure water (solvent)
*
( )
0
0 s
p a B
A
p p b

=
-

ii) Elevation of boiling poi nt (
b
T D )
* The increase in the boiling point of a liquid when a non volatile solute dissolved in it is called elevation of
boiling point.
*Ex:- The boiling point of salt water (solution) is greater than the boiling point of pure water (solvent)
* ( )
b
b b
k a 1000
T k m
A b

D = =
where
b
k =molal elevation constant or ebulliscopic constant.
iii) Depression in freezing point (
f
T D )
* The decrease in freezing point of a solvent when a nonvolatile solute dissolved in it is called depression in
freezing point.
* Ex:- The freezing point of slat water (solution) is less than pure water (solvent)
* ( )
f f f
a 1000
T k m k
A b
D = =
Where b =wt. of solvent; a =wt. of solute; B =M.wt. of solvent; A =M.wt. of solute;
f
k =molal depression
constant.
iv) Osmotic pressure( p)
*The process of solvent flowing into the solution when the solvent and the solution are separated by a semi
permeable membrane is called osmosis
* The pressure required to be applied on the solution to prevent osmosis is called osmotic pressure
* CST p =
Where C =concentration of the solution, b =wt. of solvent; S =solution constant; a =wt. of solute
T =temperature in K ; A =M. wt. of solute
5. What is Osmosis? Define Osmotic Pressure? Describe Berkely-Hartley method of determining osmotic
pressure.
A: Osmosis: The process of solvent flowing into the solution when the solvent and the solution are separated by
a semi permeable membrane is called osmosis.
Osmotic pressure: The pressure required to be applied on the solution to prevent osmosis is called osmotic
pressure.
CST p =
Where C =concentration of the solution, S =solution constant; T =temperature in K
Berkel y Hartel y Method
* In this method, the pressure required is applied on solution to just prevent osmosis.
* A porous tube whose both ends are open is taken and copper ferrocyanide is precipitated in the pores of
membrane by electrolytic method.
* The two ends are now closed with two rubber corks.
* Cork thistle funnel is fixed at one cork and a capillary tube is fixed at another cork. This tube is fixed with
outer cylindrical tube made from gun metal. Manometer is fixed on the piston to measure the pressure.
* Outer cylindrical tube is used to measure the pressure.
* Water (or solvent) is added into the porous tube through the funnel
* The space between the inner and outer tubes is filled with the solution
* As osmosis starts, the level of the liquid in the capillary decreases due to flow of water from inner tube into
outer tube.
* Now pressure is applied externally on the piston and the level of liquid in the capillary is brought to initial
position. This applied external pressure is called osmatic pressure.
FIITJEE

1
7
2
3
4
5
6
Berkely Hartley method
1. Solvent reservoir 2. Semipermeable membrane 3. Solution
4. Capillary tube 5. Piston 6. Pressure guage 7. Solvent

SAQ
1. Define molarity, molality.
A: Molarity (M):
* The number of moles of solute present in one litre of solution is called molarity. It is denoted by M.
* Molarity is expressed in moles / lit.
* ( )
( )
Molarity M
Volume of solution lit
=
Molality (m):
* The number of moles of solute in 1000g (1 kg) of solvent is called molality. It is denoted by m.
* Molality is expressed in moles / kg of solvent.
* ( )
( )
Molality m
weight of solvent kg
=
2. What is meant by mole fraction? Explain.
A: Mole fraction: The ratio of number of moles of one component (solute or solvent) to the total number of
moles of all the components present in the solution is called mole fraction of that component (solute or
solvent)
In a binary solution, mole fraction of solute ( )
2
2
1 2
n
n n
c =
+

Mole fraction of solvent ( )
1
1
1 2
n
n n
c =
+

Where
1
n =no. of moles solvent and
2
n =no. of moles of solute

1 2
1 c + c =
3. Derive the equation CRT p =
A: * At constant temperature, the osmotic pressure ( ) p of a dilute solution is directly proportional to the
concentration. C p ; where C =concentration : moles /lit
The volume (V) of a solution is inversely proportional to concentration:
1
V
C

[V is volume of solution in litres containing one mole of the solute]

1
V
\p .(1)
Or
V K p =
K =proportionality constant.
This is similar to Boyles law ( ) PV K =
* The osmotic pressure ( ) p of a solution of constant concentration (C) is directly proportional to the
temperature in the Kelvin scale (T)
T p .(2)
FIITJEE
K T p =
K =proportional constant
This is similar to Charles law. On combining the two equations we get,
1
, T
V
p p
T
S.
V
p =
S =proportionality constant
V ST p =
S is called solution constant
But
1
V
C
=
CST or CRT \p = p =
4. What is meant by an ideal solution?
A: * A solut5ion which obeys Raoults law at all conditions concentration and temperature is called an ideal
solution.
* In all ideal solutions the solute and the solvent molecules have similar structure and polarity, the solute-
solute interactions and the solvent-solvent interactions are the same.
*
mix
H D (Enthalpy change of mixing) is zero and
*
mix
V D (Volume change of mixing) is zero
A few examples of the ideal solutions are:
* Benzene and Toluene
* n-Hexane and n-Heptane
* Carbon tetra chloride and Silicon tetra chloride
* Ethyl bromide and ethyl iodide
* Chloro benzene and bromo benzene
* n-Butyl chloride and n-Butyl bromide etc.
5. How is molar mass related to the elevation in boiling point of a solution? Give the equation.
A: Elevation of boiling point ( )
b
T D
* The increase in the boiling point of a liquid when a non volatile solute dissolved in it is called elevation of
boiling point.
* Ex:- The boiling point of salt water (solution) is greater than the boiling point of pure water (solvent)
* ( )
b b
T K m D =
b
K a 1000
M b

=

Where
b
K is molal elevation constant, a =wt. of solute, W =M.wt. of solvent, M =M.wt. of solute,
f
K =
Molal depression constant
6. Write the equation relating depression in freezing point of a solution and the molar mass of the solute.
Explain the terms.
A: Depression in freezing point ( )
f
T D
* The decrease in freezing point of a solvent when a nonvolatile solute dissolved in it is called depression in
freezing point.
* Ex:- The freezing point of salt water (solution) is less than pure water (solvent)
* ( )
f f
T K m D =
f
a 1000
K
M b
=
Where b =wt. of solvent; a =wt. of solute; W =M.wt. of solvent, M =M.wt. of solute;
f
K =Molal depression
constant.
7. What is Vant Hoffs factor I and how is it related to ' ' a in the case of binary electrolysis.
A: Vant Hoffs Factor: The ratio of experimental values of colligative property and the calculated value of
colligative property is called Vant Hoffs Factor.

Experimental values of colligative property
i
Calculated value of colligative property
\ =
FIITJEE

Calculated molar mass of solute
i
Experimental molar mass of solute
\ =
For solute dissociation (or) Ionization
If a solute on dissociation gives n ions and ' ' a is degree of ionization
1 n -a a
Total particles 1 n = -a + a ( ) 1 n 1 = + a -

( ) 1 n 1
i
1
+ - a
=

i 1
n 1
-
a =
-

For solute associ ations
If n particles of A combines to give
n
"A "

n
nA A
If ' ' a is degree of dissociation
1
n
a
-a =
Total particles =1
n
a
-a+

1
1 1
n

= + - a

1
1 1
n
i
1

+ - a

=

i 1
1
1
n
-
a =
-

VSAQ
1. Define molality.
A: The number of moles of solute present in 1000g (1kg) of solvent is known as molality. It is denoted by m.
( )
( )
Molality m
Wt. of solvent kg
=
2. In a binary solution, what is mole fraction?
A: Mole fraction is the ratio of number of moles of one component to the total number of moles of all components
in binary solution.
Ex: Mole fraction of solute
number of moles of solute
total no. of moles in solution
=
3. What is the equivalent weight of a salt?
A: Equivalent weight of a salt
formula weight of the salt
total charge on the cation (or) on the anion of the salt
=
4. How do you calculate the equivalent weight of an oxidant?
A: Equivalent weight of an oxidant calculated by dividing the molecular weight of oxidant by number of electrons
involved in the reaction.
Equivalent weight of oxidant =
formula weight of oxidant
electrons gained by the oxidant
=
5. Write the relation between the molecular weight and equivalent weight of
3 4
H PO ?
A: Equivalent weight of an acid
Molecular weight of acid
Basicity
=
Phosphoric acid ( )
3 4
H PO is a tribasic acid
FIITJEE
Equivalent weight of
3 4
H PO =
98
3
=32.66
6. Define vapour pressure.
A: Vapour Pressure: The pressure exerted by the vapour molecules on the surface of the liquid, when both the
liquid and the vapour are in equilibrium with each other at a given temperature is called vapour pressure of the
liquid.
7. What prediction can you make for the relation between vapour pressure and temperature?
A: Vapour pressure increases with increase in temperature decreases with decrease in temperature. The
increase in vapour pressure with temperature is exponential but not linear.
8. Define boiling point of a liquid in terms of its vapour pressure.
A: The temperature at which the vapour pressure of a liquid becomes equal to the atmospheric pressure is
known as boiling point of the liquid.
9. Define osmotic pressure.
A: The minimum pressure which should be applied on the solution, so as to prevent the migration of solvent
molecules into the solution through a semi-permeable membrane is called osmotic pressure.
10. What is semi-permeable membrane? Give two examples.
A: Semi-permeable membranes are the porous membranes which allow only the solvent molecules to pass
through them.
Ex: Cellophane, parachment paper and animal protein membrane.
11. What is meant by abnormal behaviour of electrolytes in colligative properties?
A: The solutions which are non-ideal show deviation in colligative properties. Some salts under ionization
(dissociation) in aqueous solutions [ ]
2
Ex: NaCl inH O where as some substances undergo association
[ ]
3 6 6
Ex:CH COOHinC H . The behavior is known as abnormal behaviour of electrolytes.
12. Will the molecular weight determined for an ionizing solute be greater or lesser than that calculated by
elevation of boiling point method?
A: The molecular weight is less, due to ionization of solute the no. of particles increases and the molecular
weight decreases.

Solved Probl ems
1. 4.0 of NaOH are dissolved in 4 lit. of the solution. Find the molarity of the solution.
A: Volume of solution =4 litres =(v)
Weight of NaOH dissolved =4.0 g =(G)
Gram molecular weight (GMW) of NaOH =40 g
( )
( )
G 1
Molarity M .
GMW V inlit
\ =

4 1 1
0.025M
40 4 40
= =
\Molarity of the solution =0.025 M
2. Calculate the molarity of 10.6% (W/V)
2 3
Na CO solution.
A: 10.6% (W/V) solution means 10.6 % of
2 3
Na CO are dissolved in 100 ml of solution.
\ Weight of
2 3
Na CO dissolved =10.6 g =(G)
Volume of the solution =100 ml =V (in ml)
Gram molecular weight of
2 3
Na CO =106 g =(GMW)
Molarity M =? =(M) (say) then substitution the data in the formula

( ) ( )
G 1000
M .
GMW V inml
= we get,

10.6 1000
M 1
106 100

= =

\ Molarity of
2 3
Na CO solution =1 M
3. Find the volume of water to be added to 250 ml of 0.05 N
2 3
Na CO solution to make it 0.01 N solution.
A: Normality of the given solution =0.05 N =(
1
N )
Initial volume of the solution =250 ml =(
1
V ml)
FIITJEE
Required normality after dilution =0.01 N =(
2
N )
Final volume of the solution =? =(
2
V ml)
According to the formula
1 1 2 2
V N V N =
( ) ( )
2
250 0.05 V 0.01 =

2
250 0.5
V 1250ml
0.01
= =
\ Volume of water to be added to get 0.01
2 3
Na CO solution
( ) ( )
2 1
V V 1250 250 ml 1000ml = - = - =
4. Calculate the vapour pressure of a solution containing 10g of a non volatile solute in 80 g of ethanol at K.
Given the molecular weight of the solute as 120; the vapour pressure of alchol is 22.45 mm of Hg at 298 K.
A: Vapour pressure of the pure solvent ( )
0
P =22.45 mm
Weight of solute a =10 g
\ Number of moles of solute =
s
10
n 0.083
120
= =
(since molecular weight of solute =M =120)
Weight of the solvent =b =80 g
Molecular weight of the solvent (alcohol) ( )
2 5
C H OH =46.0
Number of moles of solvent =
0
80
n 1.739
46
= =
From Raoults law
0 s s
0 0 s
P P n
P n n
-
=
+

( ) ( )
s s
0 s
0 0
P n
1 for a dilute solution n n
P n
- = >> Q

s
P 0.083
1
22.45 1.739

\ - =

s
P 0.083 1.656
1
22.45 1.739 1.739

- =

s
1.656
P 22.45 21.378mm
1.739
\ = =
5. The vapour pressure of a solution containing 108.24 g of a non-volatile solute, in 1000g of
2
H O at 20 C is
17.354 mm Hg. The vapour pressure of
2
H O at 20 C =17.54 mm Hg. Find the mol. Wt. of the substance.
A: Vapour pressure of
2
H O =
0
P =17.54 mm
Vapour pressure of solution
s
P =17.354 mm
Lowering of vapour pressure ( )
0 s
P P = -
( ) P 17.54 17.354 0.186mm = D = - =
Weight of the solute =a g =108.24 g
Weight of
2
H O 'b' g 1000g = =
Mol. Wt. of solute =M =?
Mol. Wt. of
2
H O =W =18
From Raoults law,
0 s s
0 0 s
P P n
P n n
-
=
+

a
a W M
.
a b M b
M W

=

+

(for dilute solution)
FIITJEE

0.186 108.24 18
17.54 M 1000
=

108.24 18 17.54
M 183.73
1000 0.186

= =

6. 0.46 g of ethanol dissolved in 1000g of
2
H O. What is the molality of the ethanol solution?
A: Given data:
Weight of solute =0.46 gm; Weight of solvent =1000 gm; Molecular weight of solute =46
Molality ( )
Weight of solute 1000
M
molecular weight of solute weight of solvent in grams
=
=
0.46 1000
0.01M
46 1000
=
7. Calculate the molarity and normality of a dibasic acid solution (mol. Wt. 132) having 33.0 g of the acid in 400
ml.
A: Given data:
Weight of solute =33 gm, Volume of solution =400 ml; Moleuclar weight of solute =132;
Equivalent weight of solute
Moleuclar weight
66
2
= =
Molarity ( )
Weight of the solute 1000
M
moleuclar weight of the solute volume of the solution in ml
=

33 1000
0.625M
132 400
= =
Normality ( )
weight of the solute 1000
N
equivalent weight of the solute volume of solution in ml
=

33 1000
1.25N
66 400
= =
8. Calculate the normalities of the following solutions:
a) 6.3 g of
3
HNO in a litre solution b) 11.2 g of KOH in a litre solution
A: a) Given data:
Weight of solute =6.3 gm
Equivalent weight of solute =
Moleuclar weight
63
Basicity
=
Normality (N)
Equivalnet weight of the solute volume of the solution in lit
=

6.3 1
0.1N
63 1
= =
b) Given data:
Weight of solute =11.2 gm
Equivalent weight of solute
Moleuclar weight
56
Acidity
= =
Normality (N) =
weight of the solute 1
equivalent weight of the solute volume of the solution in lit

11.2 1
0.2N
56 1
= =
9. To convert 1 litre of 1.123 N solution of an acid into 1 N solution, how much volume water should be added?
A: Given data:

1 2
V 1000ml, V ? = =

1 2
N 1.123N, N 1N = =
For dilution process, the equation is
1 1 2 2 2
V N V N 1000 1.123 V 1 = =
FIITJEE

2
1000 1.123
V 1123ml
1
= =
Water to be added ( )
2 1
v v 1123 1000 123ml - = - =
10. Find the molarity of 3% (W/V)
2 2
H O solution.
A: Molarity
( )
GMW of the solute vol.of solution ml
=
3 %
2 2
H O solution means that 3 g of
2 2
H O present in 100 ml of solution.
Wt. of solute is =3 g
GMW of
2 2
H O =34 g
Volume of solution =100 ml
Molarity
3 1000 30
0.88M
34 100 34
= = =
FIITJEE
CHEMICAL KINETICS, EQUILIBRIUM AND IONIC EQUILIBRIUM
LONG ANSWER TYPE
1. Define rate of chemical reaction and explain the factors that effect the rate of a reaction.
A. The rate of a reaction at any instant is directly proportional to the product of the concentration of the reactants
taking part in the reaction at that instant.
Factors that affect reaction rate are
a) The chemical nature of the reactants b) The concentration of the reactants
c) The temperature of the reaction d) The catalyst in the reaction.
(a) The chemical nature of the reactants:
The reaction taking place between the ionic compounds is faster than the reaction taking place between the
covalent compounds. Reactions taking place between covalent compounds involve breaking and formation of
bonds, hence the reactions are slow.
Reaction between ionic compound:
( ) ( ) ( ) aq 3 aq 3 aq
NaCl AgNO AgCl NaNO + +
Reaction between covalent compounds : -

( ) ( ) ( )
H
2 5 3 3 2 2 5
C H OH CH COOH CH COOC H H O
+
+ +
l l l

(b) Effect of concentration of reactants:
The rate of a reaction depends on the concentration of the reactants at any given temperature. Greater the
concentration of the reactants, greater is the rate
(c) Effect of temperature:-
The rate of reaction generally increases with increase in the temperature of the reaction. The specific rate of
a reaction is approximately doubled for every 10 C rise of temperature for many reactions.
(d) Effect of catal yst:-
Catalyst increases the rate of reaction by changing the path of the reaction. The reaction takes place through
a different path of lower activation energy.
2. What is meant by rate law? Write the rate laws of elementary reactions of I and II order reactions. Deduce
the units for the rate constant (K) of zero and first order reactions.
A. The equation that describes mathematically the dependence of the rate of a reaction on the concentration
terms of the reactants is known as the rate equation or rate law.
I order reaction
A Pr oducts
[ ] V A

Or [ ] V K A

= (where K is specific reaction rate or rate constant)
II order reaction
2A Pr oducts
[ ]
2
V A
[ ]
2
V K A =
Units of rate constant K
Zero order reaction
[ ] V K A =
FIITJEE
V K =

C moles /litre
V moles /litre sec
t sec
= = =
Q V = K
Units of K =moles/litre sec
I order reaction
[ ]
1
V K A =

[ ]
V moles/litre sec
K
A moles /litre
= =

1
K sec
-
=
Units for rate constant of I order reaction =
1
sec
-

3. Derive the rate equation for a first order reaction? Derive the expression for half life of first order reaction.
A. Let the first order reaction be represented as R P
Let the initial concentration be a
3
moles /dm . After time t the concentration of reactant left be
( )
3
a x moles /dm - where x is the amount of A decomposed in time t seconds.
The rate
dc
dt
- or
dx
dt
at time t is proportional to the concentration of R after time t.
( )
dx
a x
dt
-
( )
dx
K a x
dt
= -
( )
dx
Kdt
a x
=
-

On integration

( )
dx
K.dt
a x
=
-

( ) ( ) ln a x Kt C............... 1 - - = + when t =0, x =0
( ) ln a 0 K(0) C - - = + lna C - =
Substitution this in equation (1)
( ) ln a x kt lna - - = -
Or
( )
t
a
K ln
a x
=
-

1 a
K ln
t a x
=
-
or

2.303 a
K log
t a x
=
-

The above equation is for I order reaction.
Half life of I order reaction:
When
1/2
a
x ; t t
2
= =
FIITJEE

2.303 a
K log
t a x
=
-

( )
1/2
2.303 a
t log
K a a /2
=
-
2.303 a
log
K a /2
=

1/2
2.303
t log2
K
= log2 0.3010 =

1/2
2.303 0.3010 0.693
t
K K
= =
1/2
0.693
t
K
=
4. What is Le chatliers principle? Explain the same with suitable example?
A. Le chatliers principl e :
If a chemical reaction at equilibrium is subjected to a change in temperature, pressure or concentration (of the
reactants/products) the equilibrium shifts in the direction in which this change is reduced or nullified.
Ex:-
( ) ( ) ( ) 2 g 2 g 3 g
N 3H 2NH ; H 92.0 kJ + D = -

The forward reaction (formation of
3
NH ) is a exothermic reaction. According to the Le chatliers principle low
temperatures favour the formation of
3
NH . The reaction is slow at low temperatures so an optimum
temperature of 725-775 K is used.
Catalyst : Fe Mo + promoter.
The number of molecules of ammonia (2) is less (hence less volume) compared to the reactants (4).
According to Le chatliers principle high pressure favours the formation of
3
NH . Hence 200 atmospheres
pressure is used
The backward reaction is endothermic and has more number of molecules (or volume). So according to Le
chatliers principle high temperature and low pressure favours the backward reaction.

5. Explain Le chaltliers principle and apply the same to the equilibrium:
( ) ( ) ( ) 2 g 2 g 3 g
2SO O 2SO +

A. Le chatliers principl e :
If a chemical reaction at equilibrium is subjected to a change in temperature, pressure or concentration (of the
reactants/products) the equilibrium shifts in the direction in which this change is reduced or nullified.
( ) ( ) ( ) 2 g 2 g 3 g
2SO O 2SO H 189.0 kJ + D = -

Effective of temperature on forward reaction :
The forward reaction leading to the formation of sulphur trioxide is exothermic reaction. So according to
Lechatliers principle low temperature favours the forward reaction. But at low temperature the reaction is
very slow. Therefore, the optimum temperature of 673 K is used and a catalyst
2 5
V O or platinised asbestos
is used to speed up the reaction.
Effect of temperature on backward reaction :
As forward reaction is exothermic, backward reaction formation of
2
SO is endothermic. So according to
Lechatliers principle high temperature favours the formation of sulphur dioxide.
Effect of pressure on the reaction :
FIITJEE
The forward reaction leading to the formation of
3
SO involves decrease in number of molecules (2 molecules
of
3
SO ) or decrease in volume. As per Le Chaltiers principle high pressure favours the formation of
3
SO .
But at high pressure, the towers used get corroded. Therefore optimum conditions are used.
The backward reaction which has more number of molecules is favoured at low pressure.
6. Explain the term hydrolysis of salts with suitable examples. Give the relation between hydrolysis constant
( )
h
K ionization constant ( )
a
K and ionic product ( )
w
K of water for sodium acetate solution.
A. Hydrol ysis of Salt:
It is the phenomenon in which the anion or cation or both of salt react with water producing excess or both of
salt react with water producing excess of OH
-
ions or H
+
ions or both in aqueous solution.
Ex : -
(1) Salt of strong acid and weak base.
In water :
4 4
NH Cl NH Cl
+ -
+

4
NH
+
React with water as it is strong conjugate acid of weak base
3
NH .

4 2 4
NH H O NH OH H
+ +
+ +
As the solution has more H
+
concentration the solution is acidic having pH <7
(2) Salt of Weak acid and Strong base

3
CH COONa
In water
3 3
CH COONa CH COO Na
- +
+
Acetate ions are strong conjugate base of weak acid acetic acid, hence undergo hydrolysis to give a basic
solution.
3 2 3
CH COO H O CH COOH OH
- -
+ +

As OH H
- +

>

the pH >7
3 2 3
CH COO H O CH COOH OH
- -
+ +

[ ]
[ ]
3
3 2
CH COOH OH
K
CH COO H O
-
-

=

[ ]
[ ]
2
3
h H O
3
CH COOH OH
K K
CH COO
-
-

= =

( )
[ ]
3
a
3
CH COO H
K of acetic acid
CH COOH
- +

= ..(1)
w
K H OH
+ -

=

..(2)
[ ]
w
3
a
3
H OH
K
CH COOH
K
CH COO H
+ -
- +

=

FIITJEE
[ ]
3
h
3
CH COOH OH
K
CH COO
-
-

=

w
h
a
K
K
K
\ =

NUMERIC L PROBLEMS
1. The rate constant of a first order reaction is 0.693
1
sec
-
, what is
1/2
t ?
A.
1/2
0.698
t
K
= for I order reaction

1
K 0.693 sec
-
=

1/2
0.693
t 1 sec
0.693
= =

2. The initial concentration of A is 0.3 moles / lit. The concentration after 2.3 minutes is 0.15 moles / litres. What
is the value of rate constant.
A.
[ ] d A
0.3 0.15 0.15
r 0.065 moles /litre min
dt 2.3 2.3
-
= = = = -
3. The value of
p
K if the value of
c
K is
3
2 10
-
for
( ) ( ) ( ) 2 g 2 g g
H I 2HI +

at 27 C .
A. ( )
n
p c
K K RT
D
=

p c
K K = as n D for the above reaction =0

3
p
K 2 10
-
=
4. How many grams of NaOH are present per litre if the pH of NaOH solution is 10 ?
A. pH =10;
OH
P =4;
OH
pH P 14 + =

4
n OH 10
- -

= =

Given weight 1000
Normality
Equivalent weight Volume in mL
=

4 4 3
x 1000
10 40 10 4 10 g
40 1000
- - -
= = =
5. What is the pH of 0.1 M NaOH?
A.
1
OH 10
- -

=

1
OH
P log 10
-

= -

;
OH
P 1 =
pH =14 1 =13

FIITJEE
6. Find the pH of 0.05 ( )
2
Ba OH aqueous solution.
A. Each ( )
2
Ba OH molecules gives 2OH
-
ions.
OH 0.05 2 0.1
-

= =

1
OH
P log 10 1
-

= - =

pH 14 1 13 = - =
7. Find the pH of
8
10 M
-
HCl solution.
A. As
8
10 M
-
HCl is much diluted solution: the concentration of H
+

in water should be added in the
equilibrium.

8 7
H 10 10
+ - -

= +

( )
7 7
H 10 0.1 1 1.1 10
+ - -

= + =

7
pH log1.1 10 7 log1.1 7 0.0414 6.95
-
= - = - = - = [ ] log1.1 0.0414 = Q
8. The pH of HCl solution is 5.4. What is the hydrogen ion concentration?
A. pH 5.4 =
log H 5.4
+

= -

or 6.6

6
H Anti log 6.6 3.981 10 M
+ -

= =

9. 50 mL of 0.2 N
2 4
H SO were added to 100mL of 0.2 N
3
HNO . Then the solution is diluted to 300
mL. What is the pH of solution?
A.
1 1 2 2
1 2
V N V N
N
V V
+
=
+
500 0.2 100 0.2
600
+
=

100 20
N 0.2
600
+
= = ; 0.2 600 900 = x

0.2 600
0.13
900
= =

1
pH log0.13 1.3 10 1 log1.3
-
= - = = - 1 0.113 0.887 = - =
10. At a certain temperature the ionic product of
2
H O is
14 2
9.55 10 /lit
-
. Then what is the pH of the solution.
A.
14 7
w
H OH K 9.55 10 3.21 10
+ - - -

= = = =

( )
7
pH log 3.21 10
-
= -
7 log3.21 7 0.5051 6.5049 = - = - =
11. The
a
K for 0.2 M
3
CH COOH is
5
2 10
-
. What is the pH? (Assume
3
CH COOHas a strong acid)
A. As we assume it to be strong acid,

1
H 0.2M 2 10
+ -

= =

FIITJEE
pH =1 log2 =1 0.3010 =0.6990
12. Find the pH of 0.5 M
4
NH OH solution.
b
K for
4
NH OH is
5
2 10
-
. (Assume
4
NH OH as strong base)
A. OH 0.5M
-

=

POH log0.5 = -
1
5 10 1 log5 1 0.6990 0.3010
-
= = - = - =
pH 14 0.3010 13.6990 = - =
13. What is the pH of HCl solution containing 3.65 g in 250 mL?
A.
Given wt. 1000 3.65 1000
N H
Eq.wt. V in mL 36.5 250
+

= = =

=0.4

1
pH log H log0.4 4 10
+ -

= - = - =

1 log 4 1 0.6021 0.497 = - = - =
14. A litre of buffer solution contains 0.1 moles of acetic acid and 1 mole of sodium acetate. Find its pH of pKa of
3
CH COOH 4.8 =
A.
[ ]
[ ]
salt
pH pKa log
acid
= +
[ ] salt 1 mole /lit = ; [ ] acetic 0.1 mole /lit =

1
0.1
pH 4.8 log 4.8 log10
1
-
= + = + pH 4.8 1 5.8 = + =
15. 20 mL of 0.2 M
3
CH COOH and 20 mL of 0.4 M sodium acetate were mixed together to form a buffer. What
is the pH if pKa of
3
CH COOH is 4.8
A.
[ ]
[ ]
salt
pH pKa log
acid
= +

20 0.4
40
pH 4.8 log
20 0.2
40

= +

4.8 log2 4.8 0.3010 5.1 = + = + =
16. Find the hydrolysis constant of 0.1 M sodium acetate Ka of
5
3
CH COOH 2 10
-
=
A.
w
h
a
K
K
K
=

14 14 5
w a
5
1
K 1 10 10 ; K 2 10
2 10
- -
-
= = =

9 10
0.5 10 or 5 10
- -
=
17. What is the pH of a buffer formed by mixing 20 mL of 0.1 M
4
NH Cl and 2 mL of 0.1 M
3
NH ? pKb for
4
NH OH 4.8 =
A.
[ ]
[ ]
b
salt
POH pK log
base
= +
FIITJEE

b
20 0.1
40
pK log
20 0.1
40

= +

4.8 log1 4.8 = + =
pH 14 4.8 9.2 = - =
18. The hydrolysis constant for
4
NH Cl solution is
9
0.5 10
-
. Then what is the dissociation constant of the
base?
A.
w
h
b
K
K
K
=
14
9
b
1 10
0.5 10
K
-
-

=

14
14 4
b
9 10
1 10 1
K 10 0.2 10
0.5 10 5 10
-
- -
- -
= = =

19. The dissociation constant of
4
NH OH and
3
CH COOH are
5
2 10
-
and
5
1.8 10
-
respectively. Find the
hydrolysis constant of ammonium acetate.
A.
w
h
a b
K
K
K K
=
14 14
4 5
5 5 10
1 10 1 10
0.2 10 2 10
2 10 1.8 10 3.6 10
- -
- -
- - -

= = = =

20. 50 mL of 1 M
3
CH COOH solution when added to 50 mL of 0.5 M NaOH gives a solution with pH value of X.
Find the value of X (pKa of
3
CH COOH =4.8)
A. pH =
[ ]
[ ]
50 0.5
salt
100
pKa log 4.8 log 4.8 log1 4.8
50 0.5 acid
100

+ = = =

21. What is the pH of a solution formed by mixing 50 mL of 1 M HCl and 50 mL of 0.1 M NaOH?
A.
1
50 1 50 0.1 45
H 50 5 0.45 4.5 10
100 100
+ -
-

= = - = = =

pH 1 log 4.5 1 0.658 0.34 = - = - =
22. The 0.005 M monobasic acid has pH of 5. What is the degree of dissociate?
A. pH =5;
5
H 10
+ -

=

H c.
+

= a

5
10 0.005
-
= a

5
2
3
10
: 0.2 10 or 0.2%
5 10
-
-
-
=

23. The solubility product of salt
10 2
AB 10 moles /lit.
-
= What is the solubility?
A. AB A B
+ -
+

2
sp
K S S S = =

10 5
sp
S K 10 10 moles /lit
- -
= = =
FIITJEE
24. The solubility of
3
2
A B 2 10 moles /lit.
-
= What is solubility product?
A. ( )
2
2
sp
K 2S S 4S = =

( )
3
3 9
4 2 10 8 10
- -
= =
SHORT NSWER TYPE
1. Define and explain the terms with suitable examples order and molecularity of a reaction.
A. Order: The order of the reaction is sum of the powers of the concentration terms in the rate equation of the
reaction.
Ex: 1.
( ) ( ) ( )
2 2 5 g 4 g 2 g
1
N O N O O
2
+
[ ]
2 5
rate K N O = Hence I order.
2.
( ) ( ) ( )
2 g 2 g 2 g
2N O 2N O +
[ ]
2
2
rate K N O = Hence II order reaction.
Molecularity : The number of atoms or ions taking part in the rate determining step is called molecularity of
the reaction.
Ex: Pseudo Unimolecular reaction.

H
3 2 5 2 3 2 5
CH COOC H H O CH COOH C H OH
+
+ +
As water is taken in excess it will be an example of pseudo unimolecular reaction.
2. Describe any two methods for the determination of order of reaction.
A. The methods used for the determination of the order of reaction include:
(1) integral equation method or trial and error method (2) half-time method
(3) Vant Hoff differential method (4) Ostwalds isolation method.
(1) Trial and Error Method or Integral form of rate equation method.
The concentration of the reactant or reactants (a) initially when time is 0 and the concentration of the reactant
after time t (a x) are measured by suitable analytical methods and substituted in different rate equations of
different orders. The order of the reaction will be the one which gives constant k values.
Zero order ( ) Z R P - ;
[ ] [ ]
0 t
R R
k
t
-
=
I order
[ ]
[ ]
0
t
R
2.303 a 2.303
k log or log
t a x t R
=
-

(2) Half-time (
1/2
t ) method:
The time required for the initial concentration (a) of the reactant to become half of its value (a/2) during the
process of the reaction is called half time of the reaction.
The half time (
1/2
t ) is inversely proportional to
( ) n 1
a
-
where a is the initial concentration of the reactant
and n is the order of the reaction.
1/2
n 1
1
t
a
-

FIITJEE
Therefore for a given reaction two half-time values with initial concentration a and a are determined
experimentally and the order is established in the equation.
n 1
1/2
1/2
t
a
t a
-

=

3. What are the main postulates of simple collision theory of reaction state?
A. (1) Molecules have to collide with each other for the reaction to occur.
(2) All collisions do not lead to the formation of the products.
(3) The colliding molecules have to possess minimum energy to form products. This minimum energy is
called Threshold energy.
(4) The energy of the molecules at STP is less than this threshold energy.
(5) The difference between the threshold energy and the energy of molecules in the normal state is called
activation energy.
Activation energy =Threshold energy Energy of normal molecules.
(6) The molecules possessing the threshold energy are called activated molecules.
(7) Collisions taking places between activated molecules are activated collisions and these collisions lead to
the formation of products.
(8) The fraction of activated collisions among the total collisions is very much less.
4. What are equilibrium processes? Explain with examples equilibrium physical processes and equilibrium
chemical processes.
A. Any process whether physical or chemical that takes place in the forward as well as in the reverse (opposite)
direction under the same conditions is generally referred as reversible process.
Equilibrium physi cal process:
Equilibrium between any two phases of the same substance provided both the phases occurs at the given set
of conditions and no phase disappears in the process is called physical equilibrium.
Solid
liquid (melting or fusion)

Solid
vapour (sublimation)
Equilibrium between 2 allotropic forms of the same substance will be examples of physical equilibrium.
sulphur sulphur a - b -

Equilibrium chemi cal process :
A reaction is considered reversible, if the reaction mixture contains the reactants as well as the products and if
both forward and backward reactions are taking place under experimental conditions.
Ex:
( ) ( ) ( ) 3 s s 2 g
CaCO CaO CO
D
+

5. What is meant by dynamic equilibrium? Explain with suitable example.
A. The forward and the reverse reaction of a reversible reactions have to take place with equal rates
simultaneously at the equilibrium state also. Then the equilibrium is called dynamic equilibrium.
At equilibrium state the reaction does not stop. Both the forward and backward reactions continuously take
place. The equilibrium concentrations of the reactants and the products remain unchanged with time provided
the reaction conditions are not altered. The physical properties such as colour, density, pressure etc do not
change.
FIITJEE
Ex:
( ) ( ) ( ) 3 s s 2 g
CaCO CaO CO
D
+

6. Give the characteristics of chemical equilibrium.
A. (1) Both forward and reverse reactions continue to take place.
(2) The rate of forward reaction is equal to the rate of backward reaction
(3) The properties such as pressure, concentration, density, colour etc remain unchanged with time.
(4) Addition of a catalyst to the reaction does not alter the position of the equilibrium. It only speeds up the
attainment of the equilibrium
(5) The same chemical equilibrium can be reached by carrying out the reaction starting with reactants or by
carrying out the reaction staring with products.
(6) Change in pressure or concentration of the reactants or the products may change the position of
equilibrium.
7. Explain
c
K and
p
K and derive the relation between them?
A.
c
K : Equilibrium constant taking the molar concentration of different substance in a reaction.

p
K : The equilibrium constant taking the partial pressures of the reacting substances which are in gaseous
state.
Ex: aA bB cC dD + +

[ ] [ ]
[ ] [ ]
c d
c
a b
C . D
K
A B
= ;
c d
C D
p
a b
A B
P P
K
P P
=
Derivation of relation between
p
K and
c
K
From ideal gas equation: PV nRT = ;
n
P RT
V
=
Q
n
concentration
V
=
P CRT = .(1)

c d
C D
p
a b
A B
P P
K
P P
= .(2)
Substituting the value of P in equation 2 we get,

[ ] [ ]
[ ] [ ]
c d
p
a b
CRT DRT
K
ART BRT
= ;
[ ] [ ]
[ ] [ ]
( ) ( )
c d
c d a b
p
a b
C D
K .RT
A B
+ - +
=
( )
n
p c
K K RT
D
= ;
[ ] [ ]
[ ] [ ]
c d
c
a b
C D
K
A B
= Q
8. Explain the concepts of Bronsted acids and Bronsted bases. Illustrate the same with example.
A. Bronsted Acid: A substance which loses or donate a proton is called an acid.
Ex: HCl,
3 4
H PO etc.
Bronsted base: A substance which has a tendency to gain a proton or accepts is a proton called a base.
In an acid base reaction proton transfer takes place. This process of transfer of proton from an acid to a base
is referred as neutralization.
FIITJEE
2 3
HCl H O H O Cl
+ -
+ +

Water accepts a proton from the HCl hence acts as a base.
3 2 4
NH H O NH Cl
+ -
+ +

When ammonia is dissolved in water,
3
NH accepts a proton from water. Water acts as acid. In the above
two examples
3
H O
+
and
4
NH
+
are Bronsted acids. Cl
-
and OH
-
are Bronsted bases.
9. What are conjugate acids an conjugate bases? Give 4 examples.
A. In all acid-base reactions at equilibrium (according to Bronsted Lowry theory) two acids and two bases are
involved. An acid is converted to a corresponding base and vice versa. Such a related pair of an acid and a
base which differ by a single proton is said to be conjugate pair.

2 3
HCl H O H O Cl
+ -
+ +

HCl and Cl
-
are the conjugate pair,
2
H O and
3
H O
+
are the conjugate pairs in the above example.
Cl
-
is the conjugate base of HCl and
3
H O
+
is the conjugate acid of
2
H O. Every protonic acid (HCl in the
above example) has its conjugate base (Cl
-
) and every bronsted base ( )
2
H O has its conjugate acid
( ) 3
H O
+

10. Explain with suitable examples Lewis acid-base theory?
A. Lewis-acid: A substance than can accept an electron pair to form a coordinate covalent bond with donor.
Ex: H
+
,
3
BF ,
4
SnCl
Lewis base:- A substance that can donate a lone pair of electrons to form a coordinate covalent bond with the
acceptor.
Ex:
2
H O,
3
NH , lignads in complex compounds.
Acid-Base reaction:
An acid base reaction should involve formation of coordinate covalent bond

| | | |
| | | |
F H F H
F F H H
F B : N H F B N H

- + - - -

11. What is degree of ionization in respect of weak acids and weak bases? Derive relation between the degree of
ionization ( ) a and the ionization constant ( )
a
K
A. All acids and all bases do not ionize to the same extent. Extent of ionization depends on the polarity of HX
(Acid) or BOH(base). If the extent of the ionization of substance is large it is called strong acid or strong base.
If the extent of ionization of the substance is less, the compound is called weak acid or base.
Extent of ionization large Strong
Extent of ionization less Weak
The extent of ionization is represented by a

( ) ( )
HX H X
Initial Conc C
After time t C 1 C C
+ -
+
- -
- a a a

If a is the degree of dissociation
FIITJEE

[ ] ( )
a
H X
C .C
K
HX C 1
+ -

a a

= =
- a

( )
2
a
C
K
1
a
=
- a

Where
a
K is dissociation constant for weak acid HX
For bases;
( )
2
b
C
K
1
a
=
- a

12. Define pH. What is a buffer solution? How are buffer solutions prepared?
A. The negative value of the logarithm to the base 10 of the hydrogen ion concentration.

10 10
1
pH log H log
H
+
+

= - =

A buffer solution is that solution which resists any change in its pH value on dilution or addition of small
amount of strong acid or strong alkali.
Buffer solutions are prepared generally, by mixing equal or different volumes of equimolar solution of a weak
base and its salt.
Ex:
3 3
CH COOH CH COONa + ;
4 4
NH OH NH Cl +

VERY SHORT NSWER TYPE
1. Define rate of reaction.
A. Rate of reaction is defined as change in the molar concentration of reactants or products per unit time.
2. What is rate law?
3. Define order of a reaction.
A. The order of a reaction is the sum of the powers of the concentration terms in the rate equation of the
reaction.
4. Name two first order reactions you know?
A. 1.
( ) ( ) ( )
[ ]
1
2 2 2 2 2 aq 2 g
1
H O H O O ; rate K H O
2
+ =
l
2.
( ) ( ) ( )
[ ]
2 2 2 5 5 g 4 g 2 g
1
N O N O O ; rate K N O
2
+ =
5. What is half life?
A. The time required for the initial concentration (a) of the reactant to become half of its value (a/2) during the
progress of the reaction.
6. What is zero order reaction?
A. Reactions in which the rate of reaction is independent of the concentration of the reacting substances is called
zero order reactions.
7. Give the integrated form of the rate equilibrium for first order reaction.
A.
( )
[ ]
[ ]
0
t
R
2.303 a 2.303
K log log
t a x t R
= =
-

8. What is activation energy?
A. The difference between the threshold energy and the energy of the molecules in the normal state is called
activation energy.

FIITJEE
9. State law of mass action.
A. The rate of a reaction at any instant is directly proportional to the product of the concentrations (active
masses) of the reactants taking part in the reaction at that instant.
10. Write the relation between
p
K and
c
K .
A. ( )
n
p c
K K RT
D
=
11. What is the effect of pressure on
( ) ( ) ( ) 2 g 2 g 3 g
N 3H 2NH +

?
A. When pressure is increased on the reaction at equilibrium, favours the reaction in the direction in which the
volume or number of molecules decreases. When pressure is decreased on the reaction, it favours the
reaction towards reactants (in the direction in which the volume or number of molecules increases) When
pressure is increased it favours forward reaction.
12. What is Bronsted base? Give one example.
A. A chemical substance that has a tendency to gain a proton from donor, i.e., proton acceptor.
Ex.
3
NH
13. What is Lewis acid? Give one example.
A. A substance that can accept an electron pair to form a coordinate covalent bond with the donor. Ex:
3
H , BF
+

14. Define ionic product of water.
A. The ionic product of water,
w
K at a given temperature, is defined as the product of the concentration of H
+

and OH
-
in water or in aqueous solution.
15. What is a buffer solution?
A. A solution which resists any change in its pH value on dilution or on addition of a small amount of strong acid
or strong alkali.
16. Give one example each for acid and base buffer solution.
A. ( )
3 3
1 CH COOH CH COONa acid buffer + - ( )
4 4
2 NH OH NH Cl basic buffer + -
17. Explain hydrolysis of a salt?
A. It is the phenomenon in which the anion or cation or both of a salt react with water producing excess of OH
-

ions or H
+
ion or both in aqueous solution.
18. Which ions are released in the hydrolysis of Cl
-
ions with water?
A.
2
Cl H O HCl OH
- -
+ +
HCl being strong electrolyte undergo complete ionization. Hence Cl
-
do not undergo hydrolysis.
19. Is the pH of aqueous solution of
4
NH Cl greater or smaller than 7? Why?
A.
4 4
NH Cl NH Cl
+ -
+

4
NH
+
being strong undergo hydrolysis and the solution is acidic.

4 2 4
NH H O NH OH H
+ +
+ +
Hence pH is less than 7.
FIITJEE
20. (a) For the hydrolysis of ammonium acetate, write the relation between
h a b w
K , K , K and K .
(b) What is solubility product of salt?
A. (a) Ammonium acetate ( )
3 4
CH COONH is 9 salt of weak acid and weak base.
w
h
a b
K
K
K .K
=
(b)
3 4 3 4
CH COONH CH COO NH
- +
+

3 4
CH COO NH
- +

=

2
sp
K S S S = =


1. Define rate of reaction.
A. Rate of reaction is defined as change in the molar concentration of reactants or products per unit time.
2. What is rate law?
3. Define order of a reaction.
A. The order of a reaction is the sum of the powers of the concentration terms in the rate equation of the
reaction.
4. Name two first order reactions you know?
A. 1.
( ) ( ) ( )
[ ]
1
2 2 2 2 2 aq 2 g
1
H O H O O ; rate K H O
2
+ =
l
2.
( ) ( ) ( )
[ ]
2 2 2 5 5 g 4 g 2 g
1
N O N O O ; rate K N O
2
+ =
5. What is half life?
A. The time required for the initial concentration (a) of the reactant to become half of its value (a/2) during the
progress of the reaction.
6. What is zero order reaction?
A. Reactions in which the rate of reaction is independent of the concentration of the reacting substances is called
zero order reactions.
7. Give the integrated form of the rate equilibrium for first order reaction.
A.
( )
[ ]
[ ]
0
t
R
2.303 a 2.303
K log log
t a x t R
= =
-

8. What is activation energy?
A. The difference between the threshold energy and the energy of the molecules in the normal state is called
activation energy.
9. State law of mass action.
A. The rate of a reaction at any instant is directly proportional to the product of the concentrations (active
masses) of the reactants taking part in the reaction at that instant.
10. Write the relation between
p
K and
c
K .
A. ( )
n
p c
K K RT
D
=

FIITJEE
11. What is the effect of pressure on
( ) ( ) ( ) 2 g 2 g 3 g
N 3H 2NH +

?
A. When pressure is increased on the reaction at equilibrium, favours the reaction in the direction in which the
volume or number of molecules decreases. When pressure is decreased on the reaction, it favours the
reaction towards reactants (in the direction in which the volume or number of molecules increases) When
pressure is increased it favours forward reaction.
12. What is Bronsted base? Give one example.
A. A chemical substance that has a tendency to gain a proton from donor, i.e., proton acceptor.
Ex.
3
NH
13. What is Lewis acid? Give one example.
A. A substance that can accept an electron pair to form a coordinate covalent bond with the donor. Ex:
3
H , BF
+

14. Define ionic product of water.
A. The ionic product of water,
w
K at a given temperature, is defined as the product of the concentration of H
+

and OH
-
in water or in aqueous solution.
15. What is a buffer solution?
A. A solution which resists any change in its pH value on dilution or on addition of a small amount of strong acid
or strong alkali.
16. Give one example each for acid and base buffer solution.
A. ( )
3 3
1 CH COOH CH COONa acid buffer + - ( )
4 4
2 NH OH NH Cl basic buffer + -
17. Explain hydrolysis of a salt?
A. It is the phenomenon in which the anion or cation or both of a salt react with water producing excess of OH
-

ions or H
+
ion or both in aqueous solution.
18. Which ions are released in the hydrolysis of Cl
-
ions with water?

2
Cl H O HCl OH
- -
+ +
HCl being strong electrolyte undergo complete ionization. Hence Cl
-
do not undergo hydrolysis.
19. Is the pH of aqueous solution of
4
NH Cl greater or smaller than 7? Why?
A.
4 4
NH Cl NH Cl
+ -
+

4
NH
+
being strong undergo hydrolysis and the solution is acidic.

4 2 4
NH H O NH OH H
+ +
+ +
Hence pH is less than 7.
20. (a) For the hydrolysis of ammonium acetate, write the relation between
h a b w
K , K , K and K .
(b) What is solubility product of salt?
A. (a) Ammonium acetate ( )
3 4
CH COONH is 9 salt of weak acid and weak base.
w
h
a b
K
K
K .K
=
(b)
3 4 3 4
CH COONH CH COO NH
- +
+

3 4
CH COO NH
- +

=

2
sp
K S S S = =

FIITJEE
SOLID STATE
1. Write short notes on the following giving suitable examples.
a) Schottky defect b) Frenkel defect
A: a) Schottky defect :
* Schottky defect is a point defect.
* This defect arises when an atom or an ion is missing from its normal site in the lattice.
* Ionic crystals maintain electrical neutrality. Hence no. of vacancies at cation sites are equal to no. of
vacancies at the anion sites.
Ex: AB is ionic compound

A
+
B
-
A
+
B
-
B
-
B
-
A
+
A
+
B
-
A
+
B
-
B
-
A
+
A
+
Cation Vacancy
Anion Vacancy

* This defect occurs mainly in
(a) Highly ionic compound where the cationic and anionic sizes are similar
(b) Compounds with high coordination numbers.
* The density of the crystal may be decreased or may become unpredictable.
Ex: NaCl, CsCl
b) Frenkel defect:
* Frenkel defect is point defect.
* This defect arises when an atom or ion is missing from its normal site and occupies interstitial space in
lattice.
* In ionic crystals, usually cation escapes from its site and occupies the space among anions because of
small size.
Ex: AB is ionic compound.

A
+
B
-
A
+
B
-
B
-
B
-
A
+
A
+
B
-
A
+
B
-
Interstitial site
A
+

a) Ionic compound where the large difference exists in sizes between the cation and anion
b) Compounds with low coordination numbers.
* The density of the crystal is not changes.
Ex: AgCl, AgI, ZnS
2. What do you know about amorphous substances? Discuss.
A: * Amorphous solids are those substances that do not have sharp melting points but they melt over a
range of temperature.
Ex: Glass
* In amorphous solids, the arrangement of component particles are in random manner.
* Amorphous solids do not have long range orders or crystal, they have short range orders like in liquids.
* Any given material can be converted into amorphous solids or glassy by sudden cooling (quenching) a
melt or freezing vapour of that substance.
Molten crystalline solid
quenching
amorphous solids
Ex: Quartz is melted and quenched then it turns into amorphous solid.
* The melting of amorphous solids when slowly cooled (annealed) changes as crystalline solids at a
definite temperature.
Molten amorphous
annealing
crystalline solid
* Amorphous solids can be moulded or blown into articles of different shapes.
* Amorphous solids are used in domestic constructions and appliances like photovoltaic cells.
3. How many types of semi conductors are known? Explain the influence of doping on the conductivity of
crystalline solids.
A: A) Semi conductors:
The solids whose conductivity is in order of
6
10
-
to
4
10
1 1
ohm cm
- -
are known as semiconductors.
These are two types:
FIITJEE
(i) Intrinsic semi conductors:
Pure substances whose conductivity increases with rise in temperature are called as intrinsic
semiconductors. Conductivity of these substances is due to thermal electrons and holes in the lattice of
semiconductors.
These are insulators at room temperature.
Ex: Pure Si or Ge
(ii) Extrinsic or impurity semiconductors
Extrinsic semiconductors are those in which conductivity depends on the concentration of electron donor
or acceptor i.e. impurity.
Addition of impurity to the semiconductors is called as doping and the added substance is called as
dopant. Based on impurity these are of two types.
(a) n-type semiconductors:
When Si or Ge is doped with VA or 15 th group elements (P, As, Sb or Bi) is known as n-type
semiconductors. n standing for negative means that negatively charged electrons are responsible for
electrical conductivity.
(b) p-type semiconductors:
When Si or Ge is doped with IIIA or 13 th group elements (B, Al, Ga or In) is known as p-type
semiconductors.
p stands for positive means that positively charged holes (electron vacancy) are responsible for
electrical conductivity.
(B) When crystalline solids (insulators) are doped with suitable element, they conduct electricity even at
ordinary temperatures
4. What do you mean by imperfection in solids? Write an essay on crystal defects.
A: Imperfection in solids: The term imperfection (or) defect generally denotes departure from regularity in the
arrangement of the constituent particles (atoms or ions or molecules) in crystal. The defect may appear at a
point, along a line or over a surface.
Following are the main defects in crystals:
Schottky defect:
* Schottky defect is a point defect.
* This defect arises when an atom or an ion is missing from its normal site in the lattice.
* Ionic crystals maintain electrical neutrality. Hence no. of vacancies at cation sites are equal to no. of
vacancies at the anion sites.
Ex: AB is ionic compound

A
+
B
-
A
+
B
-
B
-
B
-
A
+
A
+
B
-
A
+
B
-
B
-
A
+
A
+
Cation Vacancy
Anion Vacancy

(a) Highly ionic compound where the cationic and anionic sizes are similar
(b) Compounds with high coordination numbers.
* The density of the crystal may be decreased or may become unpredictable.
Ex: NaCl, CsCl
Frenkel defect:
* Frenkel defect is point defect.
* This defect arises when an atom or ion is missing from its normal site and occupies interstitial space in
lattice.
* In ionic crystals, usually cation escapes from its site and occupies the space among anions because of
small size.
Ex: AB is ionic compound.

A
+
B
-
A
+
B
-
B
-
B
-
A
+
A
+
B
-
A
+
B
-
Interstitial site
A
+

a) Ionic compound where the large difference exists in sizes between the cation and anion
b) Compounds with low coordination numbers.
* The density of the crystal is not changes.
Ex: AgCl, AgI, ZnS
FIITJEE
5. Derive Braggs equation.
Or
Derive Braggs equation for X-rays of wavelength ( ) l and a diffraction angle ( ) q for an nth order reflection.

First layer
Second layer
Third layer
d q q
q
q
A
B
C D
1st ray
2nd ray

A: 1st ray is diffracted from point A in the plane (I layer). 2nd ray is diffracted from point B in the plane (II
layer). The second X-ray wave traveled more distance than the first X-ray.
The extra distance traveled by second X-ray =CB +BD
If the two waves are in constructive interference they exist in same phase i.e., the path difference is integral
multiple of the wave length.
CB BD n , heren 1,2,3,... \ + = l =
From the figure, in
CB CB
ABC, sin
AB d
D q = =
CB dsin \ = q
In
BD BD
ABD, sin
AB d
D q = =
BD dsin \ = q
CB BD dsin dsin 2dsin + = q+ q = q
n 2dsin \ l = q
This is known as Braggs equation.
Here n is known as order of diffraction.
n =1, is called as first order diffraction; n =2 is called as second order diffraction,
n =3 is called as third order diffraction.
6. Draw the differences between Schottky and Frenkel defects.
A:
Schottky defect Frenkel defect
i)
Schottky defect is due to absence of ions in
the lattice sites
i)
Frenkel defect is due to missing of an ion from
lattice site and occupying in the interstitial space
ii)
This defect arises in the compounds of high
coordination number
ii)
This defect arises in the compounds of low
coordination number
iii)
This defect arises in the compounds where the
cation and anion sizes are similar
iii)
This defect arises in the compound where
cation size is small and anion size is large
iv)
Due to this defect density of crystal decreases
Ex: NaCl, CsCl
iv)
Due to this defect density of crystal does not
changes:
Ex: AgCl, AgI

SAQ
1. Giving suitable examples, explain the following terms.
a) Paramagnetic substances b) Feromagnetic substances
c) Piezo electric effect
A: a) Paramagneti c substances:
* The substances which are attracted into the applied magnetic field are called as paramagnetic
substances.
* Paramagnetism is due to the presence of unpaired electrons in atoms, ions or molecules.
Ex:
2
O ,NO,Na atoms.
* They lose their magnetism when the applied magnetic fields are removed.

FIITJEE
b) Ferro magnetic substances:
* The substances which shows permanent magnetism even after the applied magnetic field is removed.
* Ferro magnetism is due to presence of domains of magnetism.
Ex: Fe, Co, Ni
* A spontaneous alignment of magnetic moments in the same direction gives rise to ferromagnetism.

c) Piezo el ectri c effect :
The electrons in the insulators are closely bound to the individual atoms or ions. They do not migrate
under an applied field. But dipoles are created by shift in charges resulting in polarization. If these
dipoles may align themselves in an ordered manner such that there is a net dipolement in the crystal,
such crystals are deformed when mechanical stress or if an electric field is applied. The ions or atoms
are displaced in this process, and hence electricity is produced. This is known as piezo electricity or
pressure electricity.
Ex: Quarts, Lead Zirconate etc.
2. Write the differences between crystalline and amorphous solids.
A:
Crystalline solids Amorphous solids
i)
They have definite and regular geometrical
shape
i)
They do not have any definite geometrical
shape
ii) They have sharp melting point ii) The do not have sharp melting point
iii) They are rigid and incompressible iii)
They are not very rigid and compressibility is
very less
iv) They have long range orders of crystals iv) They have short range orders
v) X-rays are diffracted v) X-rays diffraction bands are not given

VSAQ
1. What is metallic bond?
A: The force that binds a metal ion to the mobile electrons within its sphere of influence is known as metallic
bond
2. What is intrinsic region and extrinsic region?
A: Intrinsic region:
The temperature zone where the conductivity depends on the thermal electrons and the holes in the lattice of
the semiconductor is called as intrinsic region.
Extrinsic region:
At low temperatures the conductivity is mainly determined by the concentrations of the electron donors and
the acceptors. This region is known as extrinsic region.
3. What are antiferromagnetic substances? Give an example.
A: If the alignment of magnetic moments is in opposite directions with the equal number, the net magnetic
moment is zero. Such substances are termed as antiferromagnetic substances.
Ex:
2 3
V O ,NiO
4. What are Ferrimagnetic substance? Give an example.
A: When unequal number of magnetic moments are aligned in opposite directions, the net magnetic moment is
not zero. Such substances are called as ferromagnetic substance.
Ex:
3 4
Fe O
5. How the purity of the metal can be estimated?
A: Purity of the metal can be estimated by a measurement of the resistance of the metal, as resistance ratio
300K
4.2K
r
r
.
6. What will be the magnitude of the vapour pressure of these ionic crystals?
A: At ordinary temperatures the vapour pressure is very low. Therefore, the heats of vapourization are very high.
Examples of ionic crystals: NaCl, MgO,
2
CaCl ,
3
KNO ,
2 4
Na SO ,
3
CaCO
FIITJEE
7. Which group and period of the periodic table does polonium occupy?
A: VIA group or 16th group of the long form of the periodic table and 6th period.
8. Do amorphous solids have unit cells in them?
A: Recent investigations report that the amorphous solids contains minute crystals but for all purposes
apparently they do not have unit cells or crystalline structures.
9. The diffracted X-rays from copper sulphate crystal are allowed to fall on a photographic plate. What happens
to the photographic plate?
A: The photographic plate gets alternate bright and dark patched that result from the constructive and destructive
interference of the diffracted rays.
10. Calculated contributions of lattice points in body centered cubic lattice arrangement.
A: Contributions from 8 corners =
1
8
8
=1 atom
Contributions from body centered point =1 atom
Total contribution per unit cell =2 atoms or points.
11. A metal crystallizers into two cubic phases, f.c.c. and b.c.c. whose unit cell lengths are 3.6
0
A and 2.7
0
A ,
respectively. Calculate the ratio of densities of f.c.c. and b.c.c.
A: Density ( )
3
1
Zand r r
a

3
1 1 2
3
2 2 1
Z a
Z a
r
=
r

Here in f.c.c. density =
1
r In b.c.c. density =
2
r
Total number of atoms ( )
1
Z 4 = Total number of atoms ( )
2
Z 2 =
Length of the unit cell ( )
1 0
a 3.6A = Length of the unit cell ( )
2 0
a 2.7A =
By substitution the values

( )
( )
3
1
3
2
2.7
4 27
2 32
3.6
r
= =
r
\ The ratio of densities of f.c.c. and b.c.c. is
27
32

FIITJEE
ELECTROCHEMISTRY
VERY SHORT ANSWER TYPE
1. What is electrolysis? Illustrate.
A. The decomposition of a chemical substance in the molten or in the solution state into its constituent elements
under influence of an applied EMF.
Ex: When molten potassium chloride is electrolysed potassium is obtained at cathode and
2
Cl at anode.
2. What products are obtained in the electrolysis of fused KCl and aqueous KCl between platinum electrodes.
A. Fused KCl: 2KCl 2K 2Cl
+ -
+
At cathode (reduction ): 2K 2e 2K
+ -
+
At anode (oxidation):
2
2Cl Cl 2e
- -
+
Aqueous KCl:
2KCl 2K 2Cl
+ -
+ ;
2
2H O 2H 2OH
+ -
+

2
2H 2e H
+ -
+ -; 2K 2OH 2KOH
+ -
+
At Anode: (oxidation)

2
2Cl Cl 2e
- -
+
3. State Faradays First Law.
A. The mass of substance liberated or deposited or dissolved or underwent electrode reaction at an electrode
during the electrolysis of an electrolyte is directly proportional to the quantity of electricity passing through the
electrolyte.
4. Write the cell reaction for a : Ni|Ni ||Cu |Cu
++ ++
, b:
2
1
Cu|Cu || Cl |Cl
2
+ -

A. At LHS electrode oxidation half reaction
( )
2
aq
Ni Ni 2e
+ -
+

At RHS electrode reduction half reaction
aq
Cu 2e Cu
++ -
+

Cell Reaction
( )
2
aq
Ni Cu Ni Cu
++ +
+ +

5. Calculate the E of ( ) Cu 0.1M |Cu
++
electrode and ( )
2
1
Cl 0.1M | Cl , Pt
2
-
electrode
A.
o
Cu /Cu
E 0.33V
++
= ;
2
o
1
Cl /Cl
2
E 1.36V
-
= +
( )
2
o
cell 1
Cu /Cu
Cl /Cl
2
E E E 1.36 0.33 1.03V
++
-
= - = - + =
6. Write the equation for specific conductance.
A. Specific conductance K C
a
=
l
where C =conductance,
a
l
=cell constant
( ) ( )
1
1 1 1 1 1
2
ohm cm
units ohm cm cgs ohm m SI Sm
cm
-
- - - - -
= = = =

FIITJEE
7. Give the equation for equivalent conductance.
A. Equivalent conductance ( )
Specific conductance 1000 k 1000
Normality N

L = =
Where k =specific conductance , N =Normality
( )
1 3
1 2 1
2
ohm cm 1000 cm
Units ohm cm equiv in CGS
cm equiv
-
- -

= =

( )
1 2 1 2 1
ohm m equiv SI Sm equiv
- - -
= =
8. What is fuel cell?
A. A fuel cell is a galvanic cell in which the chemical energy of fuel-oxidant system (combustion of fuel) is
converted directly into electrical energy.
SHORT NSWER TYPE
1. State Faradays Laws of electrolysis.
A. Faradays Fi rst Law:
The mass of substance liberated or deposited or dissolved or underwent electrode reaction at an electrode
during the electrolysis of an electrolyte is directly proportional to the quantity of electricity passing through the
electrolyte.
m q or m eq =
q C t =
Where q =quantity of electricity in coulombs, C =current in amperes, t =time (in seconds)
e =electrochemical equivalent of the metal deposited.
Faradays Second Law:
If same quantity of electricity is passed through different electrolytic cells connected in series containing
different electrolytic solutions the masses of different species deposited or liberated or dissolved at the
electrodes are directly proportional to the chemical equivalents of the substance.
1 1
2 2
m E
m E
=
Where
1 2
m and m are masses of the substances deposited at electrodes.
1 2
E and E are chemical equivalents of the substances which are deposited at electrode.
2. What are galvanic cells? Give two examples.
A. Galvanic cells are the electrochemical cells. Electrochemical cell is a device which make use of spontaneous
redox reaction for the generation of electrical energy. In this device chemical energy is transformed into
electrical energy. Daniel cell is an exmple.
The spontaneous oxidation reduction reaction in the Daniel cell is
(1)
( ) ( ) ( ) ( ) s 4 aq 4 aq s
Zn CuSO ZnSO Cu + +
Representation of the cell:
( ) ( ) aq aq
Zn|Zn ||Cu |Cu
++ ++

(2)
( ) ( ) ( ) ( ) s 4 aq 4 aq s
Ni PdSO NiSO Pb + +

( ) ( ) aq aq
Ni|Ni ||Pb |Pb
++ ++

FIITJEE
3. What is single electrode potential and write the Nernst equation.
A. A metal rod dipped in aqueous solution of its salt or a gaseous non-metal in contact with solution containing
its anion in the form of salt, function as single electrode.
The value of this potential depends on the chemical identity of the metal or nonmetal. The concentration of
the concerned ion in aqueous solution and temperature.
Nernst equation for single electrode potential.
(1) Cation or metal ion electrodes:

0.059
E E logC
n
= + where n is number of electrons transferred in the electrode reaction
(2) For anion electrodes:

0.059
E E logC
n
= -
4. What is equivalent conductance?
A. The conductance of a volume of a solution containing one gram equivalent of the electrolyte placed between
two parallel electrodes separated by unit length of 1 m or 1 cm is called equivalent conductance ( ) L .
Equivalent conductance ( )
Normality N

L = =
Where k =specific conductance , N =Normality
( )
1 3
1 2 1
2
ohm cm 1000 cm
Units ohm cm equiv in CGS
cm equiv
-
- -

= =

( )
1 2 1 2 1
ohm m equiv SI Sm equiv
- - -
= =

5. What is Kohlrausch law?
A. The law states that the equivalent conductance ( )
a
L at infinite dilution of an electrolyte is equal to the
algebraic sum total of the equivalent conductances or mobilities of the cation
( ) 0
+
l and the anion
( ) 0
-
l of the
electrolyte at infinite dilution ( )
0 0 0
ions
+ -
L = l + l
The equivalent conductance of the ions at infinite dilution
( ) 0 0
,
+ -
l l are known as ionic conductance at infinite
dilution. These are proportional to ionic mobilities
( )
u , u
+ -

0 0
u
+ +
l ;
0 0
u
- -
l
or

0 0
k u
+ +
l = ;
0 0
k u
- -
l =
Where k is proportionality constant. Its value is found to be 96,500 Faradays.

0 0
0 0
u or u
F F
+ -
+ -
l l
= =
6. What is lead accumulator?
A. In a battery or storage battery or secondary cell chemical changes occur during the charging of the cell with
current. These changes are reversed during discharging.
FIITJEE
Acid storage cell or lead accumulator is an example of reversible storage cell.
It consists of two lead electrodes, sponge lead anode, lead coated with
2
PbO as cathode. The charged cell
is represented simply as
2 4 2
Pb|H SO |PbO .
At LHS el ectrode:
( )
2
Pb Pb 2e oxidation
+ -
+

2 2
4 4
Pb SO PbSO
+ -
+

At RHS electrode:

4
2 2
PbO 2H O Pb 4OH
+ -
+ +

4 2
Pb 2e Pb
+ - +
+

Both the electrodes are reversible. During passing of electricity (using a charger), the accumulator is
charged. During the use of accumulator, reverse reactions of the above occur and the accumulator is
discharged.
7. What is a fuel cell?
A. Fuel Cell :
A fuel cell is a galvanic cell in which the chemical energy of fuel-oxidant system (combustion of fuel) is
converted directly into electrical energy.
In fuel cell, the fuel is oxidised at the anode. The fuel cell has two electrodes and an electrolyte. Fuel cell has
two electrodes and an electrolyte. Fuel cell are liquid fuel cells and Gaseous fuel cells.
Liquid fuel cells use methanol, ethanol, hydrazine, formaldehyde as fules. Gaseous fuel cells use Hydrogen,
alkanes, carbon monoxide as fules.
Oxygen, air, hydrogen peroxide, nitric acid are some oxidants used in fuel cells. The electrodes used are Pt,
porous PVC or PTFE (Teflon) coated with Ag to produce conducting surface.
8. What is corrosion?
A. The natural tendency of conversion of a metal into its mineral compound form on interaction with the
environment is known as corrosion.
The process of conversion may be chemical or electrochemical in nature. The electrochemical corrosion is
considered as the anodic dissolution of the metal undergoing corrosion. In anodic dissolution, the metal
getting corroded undergoes oxidation to the metal ion.

n
M M ne
+ -
+
Corrosion can be defined in electrochemical terms as anodic dissolution of the metal.
9. What is passivity?
A. A state of non-reactivity reached with time of action after an initial state of reactivity is passivity. Passivity of
the metal can be classified into
(1) Chemical passivity (2) Mechanical passivity (3) Electrochemical passivity
Passivity is explained on the basis of the formation of an invisible metal oxide layer on the metal. The oxide
layer is so thin that it is not visible to the naked eye. Its presence can be proved only through chemical
reactions.
10. What are electrolytes? Distinguish between electronic conductors (metallic) and electrolyte.
A. The substance which undergo dissociation to oppositively charged ions when electricity is passed through
them are called electrolytes. Ex: NaCl
FIITJEE
Electronic conductors: The conductivity of them is due to movement of electrons. Ex: Metals
Increase in temperature increase the conductivity of electrolytes while decreases in electronic conductors.
Electrolytes conduct due to movement of ions while in electronic conductors it is due to movement of
electrons.
NUMERIC LS
1. The resistance of 0.1 N KCl solution is found to be 702 W when measured in a conductivity cell. The specific
conductance of 0.1 N KCl is
1 1
0.14807 m
- -
W . Calculate the cell constant.
A. R
a
l

R S
a
=
l

Here R =702 W; k =
1 1
0.14807 m
- -
W

1 1 1
R S
a
=
l
where
a
l
=cell constant

1
C k or C k
a
a
= =
l
l

1
0.14807
702 a
= =
l

1
0.14807 702 103.9 m
a
-
= =
l

2. The specific conductance of 0.1 N KCl is
1 1
0.14870 m
- -
W . Calculate equivalent conductance.
A. Equivalent conductance ( )
N N

L = = (if k is given
1 1
ohm cm
- -
)
If k is given in
1 1 1 2 1
k 0.14870
ohm m 1.487 ohm m eq
N 0.1
- - - -
L = = =
3. The electrode potentials of Cu |Cu
++
and Ag |Ag
++
electrode are +0.33 V and +0.8 V respectively. What
is the emf of the cell constructed from the electrodes.
A.
o
Cu /Cu
E 0.33V
++
=

o
Ag /Ag
E 0.8V
++
=
Cell is
( ) ( ) aq aq
Cu|Cu |Ag |Ag
++ +

( )
o o
Ag Ni
E E E 0.8 0.33 0.8 0.33 0.47 = - = - + = - =
4. The E value of Zn |Zn
++
electrode is 0.77V - . What is the E value of electrode containing 0.01 M
2
Zn
+

ions?
A. [ ]
2
0.059 0.059
E E log Zn 0.77 log 0.01 0.77 0.05 0.82V
n 2
+

= + = - + = - - = -

.
FIITJEE
THERMODYNAMICS
1. Explain system and surroundings.
A. System: System is that part of the universe which is under observation within a definite boundary.
Surrounding: Surrounding is that part of the universe other than the system. The surrounding and the
system are separated by the boundary which may be real or imaginary
2. Name three intensive properties.
A. Density, surface tension, viscocity.
3. Name three extensive properties.
A. Mass, volume, internal energy
4. Explain enthalpy.
A. Enthalpy is the amount of heat exchanged by a system with its surroundings at constant pressure and
temperature.
5. What is heat capacity? Explain.
A. Heat capacity (C) of a substance is defined as the amount of heat required to raise its temperature through
one degree.
6. What is thermochemical equation? Give one example.
A. The chemical equation in which heat change accompanying a reaction is also numerically specified with
proper sign by H D or E D by the side of the equation are known as thermochemical equation. In these
equations, the physical states of the reactants and the products are mentioned in brackets.
( ) ( ) ( ) graphite 2 g 2 g
C O CO
+
; H 393.5 kJ D = -
7. State Hesss law?
A. The total heat change in a reaction is the same whether the chemical reaction takes place in one single step
or in several steps.
8. What is Gibbs energy?
A. The thermodynamic function which involves both enthalpy (H) and entropy(S) functions.
G H TS D = D -
9. What is Gibbs equation?
A. G H T S D = D - D
Where G is Gibbs energy or Gibbs function, H is Enthalpy, S is entropy
SHORT NSWER TYPE
1. State first law of thermodynamics or state and explain I law of thermodynamics.
A. The law is known as law of conservation of energy. The law states that the energy in a process may be
transformed from one form into the other but is neither created nor destroyed.
Mathematical formula of I law
E Q W D = - or Q E W = D +
For infinitesimally small changes q dE W = +
E D change in internal energy
Q heat content of the system
W work done by the system

FIITJEE
2. Give the mathematical formulation of I law of thermodynamics.
A. Let a system in state A, has internal energy
A
E absorb from the surroundings a certain amount of heat ( ) q Q
and undergo a change in its state to B. Let the internal energy of B, be
B
E
The increase in internal energy E D of the system is given by the equation
B A
E E E D = -
If W is the workdone by the system in the process the net gain of energy ( ) Q W - must be equal to
a
E D from first law. The increase in the internal energy of the system therefore is
( )
B A
E E E Q W D = - = - or Q E W = D +
For infinitesimally small changes q dE W = +
As per IUPAC conventions; heat absorbed by a system is given +sign, heat given out by a system is given -
sign. Work done by a system is given -sign and work done on a system is given +sign.
3. State second law of thermodynamics.
A. II law of thermodynamics is stated in different forms:
(1) All spontaneous process are thermodynamically irreversible and entropy of the system increases
in all spontaneous process.
(2) Heat cannot be converted into work completely without causing some permanent changes in the
system involved or in the surroundings.
(3) Heat cannot flow from a colder body to a hotter body on its own.
4. What is entropy?
A. Entropy is taken as a measure of disorder of molecules or randomness of a system. The greater the disorder
of molecules in a system, the higher is the entropy. The entropy change S D between any two states is given
by the equation
rev
q
S
T
D =

rev
q = Heat absorbed by the system isothermally and reversibly at T during the state change.
5. State third law of thermodynamics.
A. The entropy of a pure and perfectly crystalline substance is zero at the absolute zero temperature ( ) 273 C - .
This is known as the third law of thermodynamics. Some times it is referred to as Nernst heat theorem.
III law of thermodynamics imposes a limitation on the value of entropy.
T
p
T
0
C
S .dT
T
=

Entropy(S) of a substance at any temperature is calculated if the temperature dependence of
P
C is known in
evaluating the absolute value of entropy of any substance.
6. State and explain the significance of second law.
A. II law of thermodynamics is stated in different forms:
(1) All spontaneous process are thermodynamically irreversible and entropy of the system increases
in all spontaneous process.
(2) Heat cannot be converted into work completely without causing some permanent changes in the
system involved or in the surroundings.
(3) Heat cannot flow from a colder body to a hotter body on its own.
The II law of thermodynamics deals with the draw backs like
FIITJEE
(1) Whether a process (or transformation) occurs in the specified direction on its own or not without
the intervention of any external agency.
(2) If a transformation or a process occurs, what fraction of one form of energy is converted into
another form of energy in this transformation or process.
7. Explain the terms entropy. Gibbs energy.
A. Entropy is taken as a measure of disorder of molecules or randomness of a system. The greater the disorder
of molecules in a system, the higher is the entropy. The entropy change S D between any two states is given
by the equation
rev
q
S
T
D =

rev
q = Heat absorbed by the system isothermally and reversibly at T during the state change.
Gibbs Energy
The thermodynamic function which involves both enthalpy (H) and entropy(S) functions.
G H TS = -
Gibbs Equation: G H T S D = D - D
Where G is Gibbs energy or Gibbs function, H is Enthalpy, S is entropy.
8. What are the criteria for the spontaneous nature of a chemical reaction? Give examples.
A. All natural process are spontaneous. When the disorderness increases the process will be spontaneous. A
process is said to be spontaneous if it occurs on its own without the intervention of any external agency.
Entropy increases in all spontaneous process. Entropy is thus taken as a measure of disorder of molecules or
randomness of a system. For a spontaneous process in an isolated system the entropy change is positive
( ) S positive D = .

total system surrounding
S S S 0 D = D + D >
Ex: Crystalline solid state is the state with lowest entropy and the gaseous or vapour state is the state with
highest entropy. In liquid state the entropy lies between the values for solids and the gaseous state.
9. State and explain enthalpy and internal energy terms of substance.
A. Enthalpy is the amount of heat exchanged by a system with its surroundings at constant pressure and
temperature.
The absolute value of H cannot be determined directly by experiment. But the change in enthalpy ( ) H D
during a chemical change can be experimentally and directly determined.
products reactants
H H H

D = -

Reaction in which H D value is negative are called exothermic reactions and those which have H D positive
are endothermic reactions.
Internal energy:
The energy stored in the substances at constant temperature and pressure is called the internal energy and is
denoted by E.
The value of E depends on state conditions.
10. How are H D and E D related for a gaseous equilibrium reaction? What is ( ) H E D - D for
( ) ( ) ( ) 3 s s 2 g
CaCO CaO CO +
A. H E P V D = D + D or H E nRT D = D + D
H D is change in enthalpy, E D is change in internal energy
FIITJEE

( ) ( ) ( ) 3 s s 2 g
CaCO CaO CO +
n D =Gaseous products Gaseous reactants =1
H E nRT D - D = D or H E RT D = D +
11. Define and explain heat of formation of a compound.
A. The amount of heat evolved or absorbed during the formation of one mole of the compound at constant
temperature from the constituent elements in the standard state.
Compound which liberate heat in their formation reaction from the constituent elements are called exothermic
compounds. Compounds which absorb heat in the formation from the constituent elements are called
endothermic compounds.
f
H ve D = - for exothermic compounds ,
f
H ve D = + for endothermic compounds.
12. What is heat of neutralization? Explain.
A. Heat evolved when one gram equivalent of an acid is neutralized completely with one gram equivalent of an
alkali, at constant temperature.
Neutralization process is always exothermic. But the amount of heat liberated depends on the fact whether
the acid or base or both are strong or weak.
Ex:
( ) ( ) ( ) ( )
2 aq aq aq
Strongacid Strong base
HCl NaOH NaCl H O ; H 57.3 kJ + + D = -
l

( ) ( ) ( ) ( )
4 4 2 aq aq aq
Strongacid Strong base
HCl NH OH NH Cl H O ; H 51.46 kJ + + D = -
l

13. State Hesss law of constant heat summation and explain it with an example.
A. The total heat change in a reaction is the same whether the chemical reaction takes place in one single step
or in several steps.
Ex:
2
CO is obtained from graphite and oxygen in two different path ways.
I path :
( ) ( ) ( ) graphite 2 g 2 g
C O CO + ; H 393.5 kJ D = -
II path:
( ) ( ) ( ) graphite 2 g g
1
C O CO
2
+ ; H 110.5 kJ D = -

( ) ( ) 2 g 2 g
1
CO O CO
2
+ ; H 283.02 D = -
Total ( ) ( )
H 110.5 283.02 393.52 kJ D = - - + - = -
The two H D values are same.
14. What are
p
C and
v
C ?
A. Heat capacity (C) of a substance is defined as the amount of heat required to raise its temperature through
one degree.
Heat capacity at constant volume
v
C gives the measure of the change of internal energy (E) of a system with
temperature.
v
v
E
C
T

=

Heat capacity at constant pressure
p
C gives the measure of change of enthalpy (H) of a system with
temperature.
p
p
H
C
T

=

FIITJEE
SURFACE CHEMISTRY
1. What is adsorption?
A. Concentration or accumulation of a substance on the surface of a solid or a liquid is known as adsorption.
2. What is absorption?
A. The process of concentration of molecules of gas or liquid on the surface of the solid and throughout the solid
is called absorption.
3. Give the mathematical equation relating the pressure (P) and the extent of adsorption (x/m) of gas on a metal.
A.
1/n
x
P
m

1/n
x
KP
m
= at constant temperature
Where x is amount of gas adsorbed, m is mass of adsorbent, P is adsorption equilibrium pressure K and n are
adsorption constants.
4. What is physisorption?
A. If the molecules of the adsorbate are held on the surface of adsorbent with physical forces or van der Waals
forces, the process is called physisoaption or physical adsorption.
Ex: Adsorption of
2
H or
2
O on charcoal.
5. What is the chemisorption?
A. If the molecules of the adsorbate are held on the surface of adsorbent with chemical forces, the process is
called chemisorption or chemical adsorption.
Ex:
2
H gas passed over Ni surface
6. What is catalyst?
A. The substance which increases rate of a reaction to which it is added without itself undergoing chemical
change is called catalyst.
7. What is negative catalyst?
A. A catalyst which decreases the rate of reaction is called negative catalyst.
8. What is homogenous catalysis? Give example.
A. If the catalyst and the reactants are in the same phase it is called homogeneous catalysis.
Ex:
( ) ( )
( )
( )
g
NO
2 g 2 g 3 g
2SO O 2SO +
The reactants and the catalyst are in same phase.

9. What is heterogeneous catalysis?
A. If the catalyst and the reactants are in different phase it is called heterogeneous catalysis.
Ex:
( ) ( )
( )
( )
s
Pt
2 g 2 g 3 g
2SO O 2SO +
10. What are the catalyst used in the reactions?
( ) ( ) ( ) 2 g 2 g 3 g
N 3H 2NH + and
( ) ( ) ( ) 2 g 2 g 3 g
2SO O 2SO +
A. The catalyst used in the formation of ammonia is Fe.
The catalyst used in the formation of sulphur trioxide is NO or Pt.

FIITJEE
11. What is auto catalysis? Give two examples.
A. If the product of the reaction acts as a catalyst, for the reaction itself, the process is called autocatalysis.
Ex: Oxidation of oxalic acid by
4
KMnO in acidic medium. The
2
Mn
+
ion formed in the reaction is acting as
catalyst.
12. What is lyophilic colloid? Give example.
A. The colloidal solution in which the dispersed phase has great affinity with the dispersion medium is called
lyophilic collidal solution.
Ex: Starch solution.
13. What is lyophobic colloid? Give example.
A. The colloidal solution in which dispersed phase has not much affinity with the dispersion medium is called
lyophobic colloid.
Ex: Gold solution
14. What is emulsion? Give example.
A. Colloidal solution in which both the dispersed phase and dispersion medium are liquids is called emulsion.
Ex: Milk fat in water emulsion; cold cream water in fat
15. What is micelle?
A. A colloidal sized particle formed in water by the association of simple molecules each having a hydrophobic
end and hydrophobic end.
Ex: Higher concentration of soap solution.
16. What is gold solution?
A. It is an aqua solution or hydro solution. It is colloidal suspension of gold particles in water.
Dispersed phase: Gold particles (solid)
Dispersion medium: Water (liquid)
17. What is milk?
A. This is liquid in liquid type of colloid. Liquid fat is dispersed in water.
Dispersed Phase: Liquid fat ; Dispersion medium: Water
18. What is emulsifying agent?
A. The third substance added in small amounts to an emulsion to keep the emulsion stable is emulsifier or
emulsifying agent.
19. What is cloud?
A. It is an aerosol. Water (drops) disperses in air and forms the colloidal solution.
Dispersed phase: Water drops (liquid)
Dispersion medium: Air (gas)
20. What is smoke?
A. This is an aerosol. It is formed by the dispersion of carbon particles in air.
Dispersion phase: Carbon particles (solid)
Dispersion medium: Air (gas)
21. What is tyndall effect?
A. When light passes through a solution we will be able to see the path of light as a luminous beam. This is
called tyndall effect.

FIITJEE
22. What is gold number?
A. The minimum mass in milligrams of a dry lyophilic solution which is required to be added to 10 mL of standard
gold to just prevent its coagulation by addition of 1 mL of 10% NaCl solution or red gold solution to become
blue gold solution.
23. What is protective colloid?
A. A lyophobic solution can be protected from coagulation by adding electrolyte, which is lyophilic colloid. This
lyophilic solution added is called protective colloid.
24. What is Brownian movement?
A. The zigzag movement of colloidal particles in colloidal solution is called Brownian movement.
25. What is coagulation?
A. Precipitation of lyophobic colloids on addition of electrolytes is called coagulation of flocculation.
SHORT NSWER TYPE
1. What is adsorption? Explain with two examples.
A. Accumulation or concentration of a substance on the surface of a solid or a liquid is known as adsorption.
The molecules of gases or liquid or the solutes in solutions get adhered to the surface of solids. When the
solids are kept in contact with them for sufficiently long time.
(Adsorption occurs more effectively if the surface of the solid is clean and free from the surface impurities)
Ex. 1: Activated charcoal adsorbs gases like
2
CO ,
2
SO ,
2
Cl etc.
Ex. 2: Pt or Ni metal kept in contact with a gas - Hydrogenation of oils
In the process of adsorption, two substances are involved one is solid or liquid on which adsorption occurs.
The second is the gas or liquid or solute from a solution which gets adsorbed on the surface. These two
substances are called adsorbent and adsorbate.
2. What is absorption? Explain with two examples?
A. The process of concentration of molecules of gas or liquid on the surface of the solid and throughout the solid
is called absorption.
In absorption the molecules of a gas, liquid or a solute present in a solution are not only present on the
surface but also pass through the surface of the solid/liquid into the bulk of the solid or liquid. The substance
that passes into the bulk of the solid or liquid is uniformly distributed. Absorption is a bulk phenomenon.
Ex: 1. If a chalk piece dipped into a solution of coloured ink and kept for some time, the chalk piece absorbs
the coloured substance.
2. A sponge placed in water absorbs water into it.
3. What is physical adsorption? Give example.
A. Physical adsorption is also called as physisorption. If the forces responsible for the adsorption of adsorbate
molecules on the surface of the adsorbed are physical forces or van der Waals forces, the adsorption is
referred as physical adsorption or physisorption. It is a weak force and is reversible.
Ex: Adsorption of
2
H or
2
O on charcoal.
4. What is chemical adsorption? Give example.
A. Chemical adsorption is also called as chemisorption (or) activated adsorption.
If the forces that are responsible for the adsorption of adsorbate molecules on the surface of the adsorbent
are chemical forces (i.e. chemical bond formation). The adsorption is called chemical adsorption or
chemisorption. It is a strong force and irreversible.
Ex: Adsorption on Ni metal surface,
2
H molecules are held by valence forces on the surface.
FIITJEE
5. Write any forces differences between physical and chemical adsorption.
A. Property Physi cal adsorption Chemical adsorption
(1) Nature of adsorption Held by Physical forces or van der
Waals forces hence weak
Held by chemical bond
formation, hence strong
(2) Reversibility of adsorption
process
Reversible and occurs rapidly Irreversible and occurs slowly
(3) Temperature at which
adsorption is more
pronounced
Low temperature (below the boiling
point of the adsorbate gas)
High temperature (generally
above the boiling point of the
adsorbate gas
(4) Effect of change in
temperature
Decreases with rise in temperature Increases with rise in
temperature
6. Give the factors that effect adsorption of gases on metals.
A. The extent of adsorption of gases depend on the following factors.
(1) Surface area of adsorbent
The extent of adsorption is directly proportional to the surface area. Greater the surface area, greater is the
extent of adsorption. The amount of gas adsorbed by unit mass of the adsorbent
x
m
increases with increase
in surface area of adsorbent. Gases like
2 2 3 2
H , N , CO, NH , SO are adsorbed on the surface of finely
divided transition metals such as Ni, Co, Pt and Pd.
(2) Nature of adsorbate (gas)
Easily liquefiable gases are generally adsorbed to great extent.
2 3 2
SO , NH , HCl, CO are easily liquefied.
Hence they are easily adsorbed.
(3) Pressure of the adsorbate (gas)
In case of physisorption the gas forms monolayer at low pressure and multilayer at high pressure. Increase in
pressure leads to increase in extent of adsorption.
(4) Temperature
Physisorption takes place at low temperature while chemisorption takes place at high temperature.
7. What is colloidal solution? Give example.
A. Colloidal solution contains two phases dispersed phase and dispersion medium. The continuous medium of
the colloidal solution in which disperse phase particles are dispersed is dispersion medium.
Colloidal solution is a binary system in which the particle size of the dispersed phase (solute) is of the order
1m 1 m - m . It is heterogeneous binary system. (1 millimicon =
9
10
-
m)
Colloidal solutions are classified into lyophilic solutions and lyophobic solutions.
Lyophilic solution - Ex: Starch solution
Lyophobic solution Ex: Gold solution
8. Give any four differences between true solution and colloidal solutions.
A. Property True solution Colloidal solution
(1) Particle size 1m < m 1m 1 m - m
(2) External appearance Very clear Generally clear or opaque.
(3) Nature of system Homogeneous Heterogeneous
(4) Tyndall effect Not shown Shown
FIITJEE
9. What are lyophilic colloids and lyophobic colloids?
A. The colloidal solution in which the dispersed phase has great affinity with the dispersion medium is called
lyophilic collidal solution.
The colloidal solution in which dispersed phase has not much affinity with the dispersion medium is called
lyophobic colloid.
10. What is emulsion? Give two examples.
A. Colloidal solution in which both the dispersed phase and dispersion medium are liquids is called emulsion.
Ex: Milk fat in water emulsion; cold cream water in fat
Both milk and cold cream are liquid in liquid type of colloid. Liquid fat is dispersed in water.
Dispersed Phase: Liquid fat
Dispersion medium: Water
Gold solution:
It is an aqua solution or hydro solution. It is colloidal suspension of gold particles in water.
Dispersed phase: Gold particles (solid)
Dispersion medium: Water (liquid)
11. How are emulsions classified? Give examples.
A. Emulsions are classified into two classes. They are (1) Oil in water (2) water in oil
(1) Oil in water (o/w) type solutions:-
In this type of emulsion the dispersed phase is oil (immiscible liquid) and the dispersion medium is water.
Ex: Milk, Vanishing cream
(2) Water in oil (w/o) type emulsion:- In this type of emulsion the dispersed phase is water and the
dispersion medium is oil (immiscible liquid)
Ex: Stiff greases: Water in lubrication oils ; Cold liver oil: Water in cod liver oil
12. Explain the cleaning action of soap.
A. Clothes which are to be washed contain greeze or fat adhered to cloth called dirt.
In cleaning process dirt forms an emulsion with water which is used for cleaning. This emulsion is not stable,
it is stabilized by converting the dirt into micelle by the soap. Soap dissolves in water and gives Na
+
and
stearate ions containing hydrophobic end (alkyl group end). This is the tail part of anion. The stearate ion
also contain hydrophilic end
( )
COO
-
. This is called head part of anion. The tail part dissolves the dirt and
forms micelle and this micelle is removed by water in the cleaning process.
13. What is catalyst? Give two examples.
A. A catalyst is the substance that increase the rate of a chemical reaction to which it is added without itself
being consumed in the reaction.

Ni
2 4 2
Catalyst
CO 3H CH H O + +

Cu
2
Catalyst
CO H HCHO +
14. How is catalysis classified? Give examples.
A. Catalysis is classified into two types based on the physical state (phase) of the catalyst and the reactant.
They are homogeneous and heterogeneous catalyst.
Homogeneous catal ysis: In both the reactants and catalyst are present in same phase then it is called
homogeneous catalysis.
FIITJEE
Ex:
( ) ( )
( )
( )
g
NO
2 g 2 g 3 g
2SO O 2SO +

( ) ( )
( )
( )
g
NO
g 2 g 2 g
2CO O 2CO +
Heterogeneous catal ysi s: If the reactant and catalyst are present in different phases it is called
heterogeneous catalysis.

( ) ( )
( )
( )
s
Pt
2 g 2 g 3 g
2SO O 2SO +

15. What is autocatalysis? Give two examples.
A. In a reaction if one of the intermediate product formed itself functions as catalyst it is called autocatalysis.
Ex: (1)
4 2 2 4 2 4 4 2 4 2 2
2KMnO 5H C O 3H SO 2MnSO K SO 8H O 10CO + + + + +

4
MnSO formed acts as autocatalyst.
(2)
3 2
2AsH 2As 3H +
As formed functions as autocatalyst.
16. What is tyndall effect? Explain.
A. It is an optical property. When light enters a colloidal solution, it is scattered by the large sized colloidal
particles. When light passes through a solution we will be able to see the path of the light as luminous beam.
This is called tyndal effect. This luminescent path can be viewed through a microscope placed at right angles
to the direction of the path of the light. The bright come of light is tyndall cone. Tyndall effect is observed
when
(1) The diameter of dispersed particles is not much smaller than the wavelength of light used and
(2) The refractive indices of the dispersed phase and dispersion medium differ greatly in magnitude.
17. What is coagulation? Write about Hardy-Schulze law.
A. The phenomenon of colloidal substance loosing charge and coming down as a precipitate on addition of an
electrolyte is called coagulation or flocculation.
The effectiveness of an ion or electrolyte in causing coagulation is dependent on the sign of the charge and
magnitude of charge. This fact is explained by Hardy and Schulze. Hence the law or rule is known as Hardy-
Schulze rule.
Hardy Schulze Law
The ion with charge opposite to the charge of the colloid particle is effective in coagulating the colloid.
Greater the charge of the ion greater is the coagulating ability of the ion.
Positive colloids are coagulated by negative ions or anions of the salt added.

2 3
4 4
Cl SO PO
- - -
< <
Negative colloide are coagulated by positive ions or cations of the salt added.

2 3
K Ba Al
+ + +
< <
18. What is Brownian movement?
A. Robert Brown observed that pollen grains when suspended in a liquid and absorbed under microscope show
random motion of pollen grains. This type of motion is known as Brownian movement. All colloidal particles
in colloidal solution exhibit this type of motion. The motion becomes less vigorous as the size of the particle
increases and also with the viscocity of the dispersion medium but increases with rise in temperature.

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IPE SECOND YEAR

it gives phenoxide ion. Phenoxide ion is resonance statilised.

liquid (melting or fusion)

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