Você está na página 1de 105

IPE

SECOND YEAR
KUKATP ALL Y ` CE NTRE

INORGANIC CHEMISTRY
VA GROUP ELEMENTS
1. A: Discuss the structures of the oxides of Nitrogen forms several oxides are as follows:

N2

N 2 O, NO, N 2 O3 , NO2 or N 2 O4 and N 2 O5 . The structures of these oxides


is a linear molecule with the following resonance structures.

Nitrous oxides

( N 2O )

NO

N=N=O
It is a resonance hybrid of

Nitric oxide

( NO ) is an odd electron molecule containing unpaired electron.


N=O N=O N=O

the following structures.

Dinitrogen trioxide

( N 2 O3 )

may have one of the following two structures.

O
O=N N=O

O NN

O (Symmetric)

O (Unsymmetric)

Nitrogen dioxide

( NO2 ) is an odd electron molecule and paramagnetic in nature in gaseous state due
N N O O O O N O O
O N O O N O

to the presence of unpaired electron. It is a resonance hybrid of the following structures.

N O

In the solid state it exist as dimmer

N 2 O 4 . It is diamagnetic in nature.
O O N

O N O

Nitrogen Pentoxide

( N 2O5 ) : Its structure is


O N O O N O O

2. A:

Write an essay on the preparation and structures of any three oxides of Nitrogen.

Nitrous oxide

( N 2O ) : It can be prepared by heating ammonium nitrate.

D NH 4 NO3 N 2O + 2H 2O

Properties: a) It is a colourless, neutral gas b) When inhaled it produces laughing hysteria so it is called laughing gas. Structure:

NO

N=N=O

Nitric oxide or Nitrogen oxide

( NO ) : It is prepared by the catalytic oxidation of ammonia.

Catalyst 4NH3 + 5O2 4NO + 6H 2O

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

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 ( NO 2 ) : It is prepared by the thermal decomposition of lead nitrate.


D 2Pb ( NO 2 )2 2PbO + 4NO2 + O 2

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 O

N O O

N O
O N N O

N O O

In the solid state it exist as dimmer

N 2 O 4 . It is diamagnetic in nature.

O N O
3. A:

O N O

O O

Write an essay on the structural aspects of the phosphorous series of acids. Phosphorous forms three oxyacids in phosphorous series of acids.

* * *
a)

Orthophosphorous acid Metaphosphorous acid Hypophosphorous acid

H3PO3 HPO2 H3PO2


3

In all oxyacids, phosphorous is involved in 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

H3PO3 : Its basicity is two. It contains two OH groups and one P H bond.
O P

* *

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

H H P OH
FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

OH

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

4. A:

Write an essay on the preparation and properties of (a) Hypophosphorous acid (b) Hypophosphoric acid (c) Metaphosphoric acid (a) Hypophosphorous acid

( H3PO2 ) :

Preparation: It is prepared in the laboratory by heating white phosphorous with dilute solution of

Ba ( OH )2

2P4 + 3Ba ( OH )2 + 6H 2O 3Ba ( H 2 PO 2 )2 + 2PH3


From this barium salt

H3PO2 is obtained.

Properties: It is a mono basic acid. It is very strong reducing agent in basic medium and is oxidized to H3PO3 . (b) Hypophosphoric acid ( H 4 P2 O 6 ) : 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

( HPO3 ) :

Preparation: It is prepared by heating orthophosphoric acid at 870 K.


870 K H3PO3 HPO3 + H 2O

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. A: Describe Habers process for the preparation of

NH3 . Give a Neat diagram of the plant. Lable it.

Ammonia can be manufactured by Habers process. In this method ammonia is manufactured by the direct reaction between nitrogen and hydrogen. 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. Synthesis of NH3 by Habers Process:

* * *

N 2 + 3H 2 2NH3 ; DH = -93.63 kJ

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 Pure and dry

( K 2O and Al2O3 )

also act as promoter to the iron catalyst.

N 2 and H 2 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 N 2 and H 2 by condensation. 6. A: Detail the Ostwalds process for the manufacture of Ostwalds process for the manufacture of
Pt. gauze 4NH3 + 5O2 4NO + 6H 2O 1155K
FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

HNO3 . Give balanced equations wherever possible.

NH3 : Ammonia mixed with air in 1 : 7 or 1:8 ratio is passed over

hot platinum gauze catalyst. Then ammonia is oxidized to NO.

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

or Manufacture of HNO3 Ostwalds process:

NO 2 . The NO 2 is then passed into warm water under pressure in the presence of excess of air to give HNO3
The NO formed in the above reaction is cooled and mixed with oxygen to convert into

2NO + O2 2NO 2 4NO2 + 2H 2 O + O 2 4HNO3


The acid formed is 61% concentrated. This is further concentrated in three states. Stage 1: 61% Stage 2: 68% Stage 3: 98% 7. A:

HNO3 is distilled until 68% HNO3 is obtained. HNO3 is mixed with conc. H 2SO 4 and distilled to get 98% acid. HNO3 is cooled in a freezing mixture. Crystals of pure HNO3 separate out.
Ca ( H 2 PO4 ) 2 and Gypsum

Describe an industrial method for the preparation of superphosphate of lime. Why is it converted into triple phosphate of lime? Superphosphate of lime is a mixture of calcium dihydrogen phosphate

( CaSO4 .2H 2O )

It is manufactured by treating the powdered phosphate rock with calculated amount of sulphuric acid.

Ca 3 ( PO4 )2 + 2H 2SO4 + 4H 2O Ca ( H 2 PO 4 )2 + 2 ( CaSO 4 .2H 2O )

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 D1 and D 2 through the values

V1 and V2 . The reaction is allowed to take place for about 24 36 hours. The impurities like carbonate and
fluoride are removed in the form of superphosphate of lime.
FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

CO2 and HF gases. The hard mass formed is powdered and sold as

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

The

CaSO4 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.

Ca 3 ( PO 4 )2 + 4H 2 PO 4 3Ca ( H 2 PO4 )2

8. A:

The triple phosphate completely dissolves in water i.e., no waste product formed. What are the similar features of ammonia and phosphine? Write a comparative note on them. 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:

Ca 3P2 + 6H 2O 3Ca ( OH )2 + 2PH3 -

Mg3 N 2 + 6H 2O 3Mg ( OH )2 +2NH3 -

Comparative notes on their general properties:

* * * * * * * *

Stability of

NH3 is greater than PH3 because N H bond is stronger than P H bond. NH3 is stronger Lewis PH3 NH3 is weaker reducing agent then PH3 because of more

Both contain one lone pair on central atom, so they can act as Lewis bases. But base than

Both can act as reducing agents but stability. Both

NH3 and PH3 are soluble in water but the solubility of NH3 in water is more than PH3 .

NH3 and PH3 are volatile and colourless gases but NH3 is less volatile because it can form inter
molecular hydrogen bonds.

NH3 and PH3 can be substituted by alkyl group like CH3 and halogens like Cl. The ease of substitution decrease from NH 3 to PH 3
The hydrogen atoms in

NH3 can form salts with any acid forming salts like NH 4 Cl.PH3 can react with very strong acids like
HI. Both

NH3 and PH3 are pyramidal in shape. In NH3 nitrogen is involved in sp3 hybridization but in

PH3 the pure p-orbitals participate in bonding. The bond angle in PH3 ( 9336 ' ) is less than in

NH3 (107 )

9. A:

In what way the structures of trioxides and pentoxides of

N 2 and P4 differ. Draw their structures and show.

Trioxides and Pentoxides of nitrogen and phosphorous are chemically similar but differ in their structures. The oxides of nitrogen exists as monomers N 2 O3 and N 2 O5 while the oxides of phosphorous P4 O6 and

P4 O10 exists as dimers. Their structures are given below.


Sl.No. Nitrogentrioxide structure Nitrogen pentoxide structure

O
1.

O N N

O N O
O N O O N

O O N O
O O

O asymmetrical form
O=N N=O O (Symmetric)

2.

Phosphoric trioxide structure

Phosphoric pentoxide structure

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

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

P O O

O O P O O

P (dotted line does not represent bond)


10. Write balanced equations for the reactions of a) A:

O O

P Phosphorous Oxygen

H 2 O with
c)

P4 O6

b)

P4 O10

PCl3

d)

PCl5

P4O6 + 6H 2O 4H3PO3 ( Phosphorous acid ) P4O10 + 6H 2O 4H3PO4 ( Orthophosphoric acid )


P4 O10 + 2H 2 O 4HPO3 ( Metaphosphoric acid )
little

PCl3 + 3H 2O 3HCl + H3PO3 ( Phosphorous acid ) PCl5 + 4H 2O 5HCl + H3PO 4 ( Orthophosphoric acid )
11. Write a note on the Cyanamide process. Mention any three important uses of A:

NH3 .

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 CaCl2 and CaF2 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.
1273-1373 K CaCl2 + N 2 CaCN 2 + Calcium Cyanamide

C
Graphite

453 K CaCN 2 + 3H 2O CaCO3 + 2NH3

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 A: Nitric acid can be manufactured by two methods: * Birkland and Eyde Method Principle: a) An electric arc converts

HNO3

N 2 and O2 of air into NO.

N 2 + O2 2NO
b) NO is oxidized to

NO 2 by air.

2NO + O2 2NO 2
c)

NO 2 is dissolved in water in the presence of oxygen to get HNO3

4NO2 + 2H 2 O + O 2 4HNO3
Ostwalds process-Principle a) Ammonia is oxidized by air when catalyst.
Pt. guaze 4NH3 + 5O2 4NO + 6H 2 O 1155 K

NH3 and air in 1 : 7 or 1 : 8 ratio passed over platinum gauze

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

b) NO is then oxidized to

NO 2 by air.

2NO + O2 2NO 2
c)

NO 2 is dissolved in water in the presence of oxygen to get HNO3

4NO2 + 2H 2 O + O 2 4HNO3
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.

Ca 3 ( PO4 )2 + 2H 2SO4 + 4H 2O Ca ( H 2 PO 4 )2 + 2CaSO 4 .2H 2O + Heat

Superphosphate of lime contains insoluble waste product b)

CaSO4 . So the percentage of phosphorous in

superphosphate of lime become less. To avoid the waste product gypsum in superphosphate of lime the phosphate rock is treated with phosphoric acid

( H3PO4 ) .

Then triple phosphate of lime or triple superphosphate is formed.

Ca 3 ( PO4 )2 + 4H3PO 4 3Ca ( H 2 PO4 )2


The triple phosphate completely dissolves in water i.e., no waste product formed. SAQ

1.
A:

What is allotropy? Explain in N and its congeners?


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

N 2 exists in a and b forms.

Phosphorous exists in many allotropic forms such as white P, red P, scarlet P,

a - black, b - black and violet.

2. A:

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. What is catenation? How does it vary in group 15? 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 H 2 N - NH 2 and N 3 H having two and three atoms in a chain respectively. Phosphorous can form dont exhibit catenation power.

P2 H 4 having two P atoms in the chain. Other elements of VA group

3. A:

Draw the structures of they react with water?

P4 O6 and P4 O10 . In what respect do thy resemble each other, what happen when
O O P O O O P Phosphorous Oxygen O

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

P O O

P (dotted line does not represent bond)


In both

P4 O10
In

P4 O6 and P4 O10 the four phosphorous atoms are arranged in tetrahedral shape. In both P4 O6 and six oxygen atoms are acting as bridges between phosphorous atoms forming P - O - P bonds.

P4 O10 one oxygen atom is in dative bond with phosphorous atoms.

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

When

P4 O6 react with water orthophosphorous acid is formed. NCl3 and PCl3 . Give their hydrolysis reactions.

P4 O10 + 6H 2 O 4H3PO4
4. A: Write balanced equations for the formation of

NCl3 can be prepared by the action of excess chlorine on ammonia. NH3 + 3Cl2 NCl3 + 3HCl PCl3 can be prepared by the direct reaction between phosphorous and chlorine.
D P4 + 6Cl2 4PCl3

Hydrolysis: NCl3 hydrolyses in water forming ammonia and hypochlorous acid

NCl3 + 3H 2 O NH3 + 3HOCl PCl3 hydrolyses in water forming phosphorous acid hydrochloric acid. PCl3 + 3H 2 O H3PO3 + 3HCl
5. A: In a compound

MX5 , M is any V group element except Nitrogen why (X) is halogen? MX5

Except nitrogen all the VA group elements can form penta halides of the type Ex:

PCl5 , AsCl5 , SbCl5 , BiF5 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


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 MX 5 . Nitrogen cannot form 6. A: pentahalides because of the absence of d-orbitals in its valency shell. Which of the acids of phosphorous does not show monomeric state but cyclic structure? Name any polymer of the acid. Metaphosphoric acid do not exist as monomer. It exist as cyclic polymer. Ex: Cylcic metaphosphate.

np

nd

O O O P O
7. A: 8. A:

O P O O O P O

A sample of most ammonia is to be dried. What method do you suggest? Moisture from ammonia can be removed by passing over dry lime or CaO. But it cannot be dried over Conc. H 2SO 4 , fused CaCl2 or P2 O5 as they react with ammonia. Write the formula of superphosphate of lime. Why is it converted into triple phosphate? The common formula of superphospate of lime is fertilizer. The

Ca ( H 2 PO 4 )2 + 2 ( CaSO 4 .2H 2O ) . It acts as good

CaSO4 in its insoluble waste product and its presence has no significance to the plants. To CaSO4 superphosphate is changes into triple phosphate which completely

avoid this waste product 9. A:

dissolves in water. How is superphosphate of lime formed? Give an equation. Explain why the product is a hard mass? Superphosphate of lime can be prepared by treating powdered phosphate rock with calculated quantity of

Ca 3 ( PO4 )2 + 2H 2SO4 + 4H 2 O Ca ( H 2 PO 4 )2 + 2 ( CaSO 4 .2H 2 O )


Super phosphate of lime

H 2SO 4

The reason for the hardness of the final product obtained in the dens is due to the presence of Gypsum.

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

VSAQ

1.
A: 2. A: 3. A:

Write the composition of phosphate rock.

Ca 3 ( PO4 )2

Give any two examples to show negative oxidation state of nitrogen. Ammonia

NH3 - 3 ; Hydrazine N 2 H 4 - 2 ; Hydroxyl amine NH 2 OH - 1

4. A:

Why is NO paramagnetic in nature? When does it become diamagnetic? 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. How is dinitrogen tetroxide formed? Give equation. When the temperature of

NO 2 is decreased it dimerises to convert into dinitrogen tetroxide.

2NO2 N 2O4
5. A: 6. A: How many oxygens surround a phosphorous in phosphorous pentoxide? In phosphorous pentoxide each phosphorous atom is surrounded by four oxygen atoms. Write the equations for the hydrolysis of

NCl3 . How does it differ from hydrolysis of PCl3 ?

NCl3 hydrolysis in water giving NH3 and HOCl while PCl3 hydrolysis in water giving orthophosphorous
acid and HCl.

NCl3 + 3H 2 O NH3 + 3HOCl PCl3 + 3H 2 O H3PO3 + 3HCl


7. A: 8. A: What are the orbitals of P that are involved in the formation of In the formation of

PCl5 ?

PCl5 , sp3d hybrid orbitals are involved.

What is nitrolim? How is it formed? Nitrolium is a mixture of calcium cyanamide carbide containing

( CaCN 2 )

and graphite. When

N 2 is passed over calcium

CaCl2 or CaF2 as catalyst at 1273 1372 K nitrolim is formed.


CaCN 2 + C Calcium cynamide Grpahite

1273-1378 CaC2 + N 2

9. A:

What drying agent is suitable to dry

NH3 ?

Ammonia can be dried by passing over dry lime (CaO) because it does not react with ammonia.

10. What is the function of A:

CaCl2 in cyanamide process?

CaCl2 acts as catalyst in cynamide process during CaC2 react with N 2 to form nitrolim. N 2 are neutral oxides?
Among the oxides of nitrogen, nitric oxide (NO) and nitrous oxide

11. Which oxides of A:

( N 2O )

are neutral.

12. Which of the two oxides reaction. A:

N 2 O5 and P2 O5 is better dehydrating agent? Give an example for the same

P4 O10 is a strong dehydrating agent than N 2 O5


Ex: Dehydrating of

HNO3 with P4 O10 gives N 2 O5

4HNO3 + P4 O10 2N 2 O5 + 4HPO3


13. Give reasons for the chemical inactivity of nitrogen at ordinary conditions. A:
-1

(945.4 kJ 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?

N 2 molecule contains triple bond ( N N ) . To break the triple bond large amount of energy

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

A:

The stability order of the hydrides of VA group hydrides is

NH3 > PH3 > AsH3 > SbH3 > BiH3 . 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 NH 3 < PH 3 < AsH 3 < SbH 3 < BiH 3 . 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 A: No.

NCl5 be prepared by direct union of the elements? Why or why not?

NCl5 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 NCl5 HNO3
OH N O O O
The structure of nitric acid is the resonance hybrid of the following structures.

17. Write the structure of A:

OH N O

Nitric Acid
18. A:

P2 O5 is strong dehydrating agent. Why is it not used to dry NH3 ? P2 O5 is acidic and NH3 is basic. They bond react to form salt. So NH3 cannot be dried using P2 O5 NH 4 NO3 into NH3 give reactions?
When ammonium nitrate is heated with a base ammonia gas will be liberated.

19. How do you convert A:

NH 4 NO3 + NaOH NaNO3 + NH3 + H 2 O


When

NH 4 NO3 is heated with alkaline solution of Zinc, it is converted into ammonia.

NH 4 NO3 + 4Zn + 8NaOH 4Na 2 ZnO 2 + 2NH3 + 3H 2 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.

2P4 + 3Ba ( OH )2 + 6H 2O 3Ba ( H 2 PO 2 )2 + 2PH3 Ba ( H 2 PO 2 )2 + H 2SO 4 BaSO4 + 2H3PO 2

To the barium hypophosphite solution if dil. Sulphuric acid is added hypophosphorous acid will be formed.

BaSO4 being insoluble can be removed by filtration.


21. How many Valence shell electrons are utilized by each phosphorous atom in A: From the structural representation of

P4 molecule?

P4 , 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 P4 molecules are formed. 23. A:

PH3 is quite stable in Air. But it catches fire when heated to 150C . Why? PH3 frequently contains P2 H 6 (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 A: The reaction must be similar to the union of

PH3 and AsH3 separately with HI.

NH3 with HI giving ammonium iodide. Therefore, PH3 gives PH 4 I (phosphonium iodide) and AsH3 gives AsH 4 I (Arsonium Iodide)

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

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?

AsH3 and SbH3 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 MH 5 exist. Why?
A: The HMH bond angle in 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 A:

3HNO 2 HNO3 + 2NO + H 2 O

HNO2 acts as both the oxidant and reductant. HNO2 as a reductant changes to HNO3 . HNO2 as an
oxidant changes to NO.

28. What is the change in oxidation state of nitrogen in auto oxidation, auto reduction of A:

HNO2 ?

3HNO 2 HNO3 + 2NO + H 2 O


In

HNO2 to HNO3 , the change of oxidation state of nitrogen is from +III to +V. From HNO2 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 does not change (Ex: Benzene) 30. What is nitration mixture? A: A mixture (1:1) of reaction.
H 2SO4 C6 H 6 + HNO3 ( Conc.) C6 H5 NO 2 + H 2O < 60C Nitrobenzene

( Ex : HNO2 ) .

In resonance, the skelton of atoms

HNO3 (Conc.) and Conc. H 2SO 4 is known as nitration mixture. This is used in nitration

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

VIA GROUP ELEMENTS


1.
A: How is Ozone prepared in the laboratory? Give any three oxidation reactions of
Silent Electric 3O2( g ) 2O3( g ) , DH = +284.5 kJ disch arg e

O3 ?

Principle: Ozone is prepared by passing silent electric discharge through pure cold and dry oxygen.

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:

* * *
2.
A:

Ozone oxidizes black lead sulphide (PbS) to white lead sulphate

( PbSO4 )

PbS + 4O3 PbSO 4 + 4O2


Hydrogen chloride is oxidized to chlorine by ozone.

2HCl + O3 H 2 O + Cl2 + O2
Ozone oxidizes moist potassium iodide

( KI )

to iodine

( I2 )
O3 with equations.

2KI + H 2 O + O3 2KOH + O2 + I2
How is ozone is prepared in Brodies method? Write any three reduction reactions of 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.

3O2( g ) + 68K.Cal. 2O3( g )

* * * * *

Brodies ozonizer consists of double wall U tube in which dilute Copper wires are immersed in dilute

H 2SO 4 is placed.

H 2SO 4

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

H 2 O 2 + O3 H 2 O + 2O3
Ozone reduces barium peroxide to barium oxide

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

*
3.
A:

BaO 2 + O3 BaO + 2O3


Ozone reduces silver oxide to metallic silver

Ag 2 O + O3 2Ag + 2O 2
How do you prepare hypo in the laboratory? Giving proper equations detail the reactions of hypo. Crystalline hydrated sodium thiosulphate

( Na 2S2O3.5H 2O ) 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.

* *

Na 2SO3 + Sexcess Na 2S2 O3


By the oxidation of sodium sulphide or sodium polysulphide with air.
Heat in 2Na 2S5 + 3O 2 2Na 2S2O3 + 6S air

By treating sodium sulphide solution with sulphur dioxide.

2Na 2S + 3SO2 2Na 2S2 O3 + S


Reactions of Hypo:

* * *
a)

Action of heat: On heating hypo undergoes thermal decomposition to give Reaction with dilute acids: When hypo reacts with dilute acids like HCl or

H 2S,SO2 and S. Hypo H 2SO 4 to give SO2 and S.

looses all the molecules of water (water by crystallization) when heated to about 488 K.

Na 2S2 O3 + 2HCl 2NaCl + H 2 O + SO2 + S dilute


Reaction with take place. When dilute hypo is added to changes to a black solid

AgNO3 solution: When hypo reacts with AgNO3 solution, two kinds of reactions may

( Ag 2S) .

AgNO3 solution, a white precipitate of Ag 2S2 O3 is formed which readily


The reactions are:

Na 2S2O3 + 2AgNO3 2NaNO3 + Ag 2S2 O3 ( white ppt ) H 2O + Ag 2S2O3 H 2SO 4 + Ag 2S ( Black ppt )
b) When concentrated hypo is added to

AgNO3 solution a white precipitate ( Ag 2S2O3 ) is obtained first.

The precipitate readily dissolves in excess of sodium thiosulphate due to the formation of complex compound.

Na 2S2O3 + 2AgNO3 Ag 2S2O3 +2NaNO3 ( White ppt.)

Ag 2S2 O3 + 3Na 2S2 O3 2Na 3 Ag ( S2 O3 )2 ( Sodium argentothiosulphate ) ( complexcompound )

Reaction with iodine: Sodium thiosulphate reacts with iodine to give sodium tetrathionate

( Na 2S4O6 )

2Na 2S2 O3 + I 2 2NaI + Na 2S4 O6

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.

AgBr + 2Na 2S2 O3 Na 3 Ag ( S2 O3 )2 + NaBr

Reaction with moist Cl2: Hypo reacts with moist

Cl2 to give Na 2SO 4 and HCl.

Na 2S2 O3 + Cl2 + H 2 O Na 2SO 4 + S + 2HCl


Sodium sulphate

In this reaction hypo is used as antichlor to remove excess of chlorine


FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

*
4.

Reaction with salts: Sodium thiosulphate reacts with ferric chloride, cupric chloride or auric chloride etc. And converts them into complex thiosulphates.

Write the reactions of the following with i)

O3 .
iii)

C2 H 2

ii)

C2 H 4

C6 H 6 Zn / H 2 O

Give the structures of the products in each case. What happens if these products are treated with A: Reactions of O3:

With Acetylene

( C2 H 2 ) : Ozone when treated with acetylene, an addition compound called acetylene


O CHO CH Zn H2O + H2O2 CHO (Glyoxal)

ozonide is obtained. This on hydrolysis in presence of zinc, glyoxal is produced.

HC

CH + O3

HC

O O (Acetylene ozonide)

With Ethylene

( C2 H 4 ) : Ozone when treated with ethylene, an addition compound called ethylene


O Zn 2HCHO + H2O2 H2O (Formaldehyde)

ozonide is obtained. This on hydrolysis in presence of zinc, formaldehyde is produced.

H2C

CH2 + O3

CH

CH2

O O (Ethylene ozonide)

With Benzene

( C6H6 ) : Ozone on treating with benzene an addition compound called benzene tri
O O O O O O O O O 3CHO + 3H2O2 Zn 3H2O CHO (Glyoxal)

ozonide is obtained, which on hydrolysis gives 3 moles of glyoxal.

+ 3O3

SAQ

1.
A:

What are the bond angles in

H 2 O and H 2S ? Why are they different?

1) In

H 2 O oxygen undergoes sp3 hybridization. Due to the presence of two lone pair of electrons H 2 O molecule is angular or V-shape with H O H bond angle 10428'

shape of

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 10428'

H 2S only pure p orbitals of sulphur are involved in bond formation. Hence the bond angle is less than of 10428' and it is only 9230 ' 2) H 2S is angular or V-shaped molecule.
1) In

2.
A:

What are the structures of

SO2 and SO3 ? Explain them in terms of VBT.

Structure of

SO2 : SO2 is angular molecule. The O S O bond angle is 11930 ' . In SO2 sulphur
sp 2 hybridization in first excited state 3s, 3p x and 3p y orbitals undergo sp 2

atom undergoes hybridization.

3pz and one d orbital are unhybridised and are used in the formation of pp - pp and

dp - pp bonds.

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

(p

) S ( pz - d z ) O O 1.43A
x

- py

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

Structure of

SO3 : In gaseous state SO3 has a planar triangular structure. The O S O bond angle is

120 . In SO3 sulphur atom undergoes sp 2 hybridization in second excited state. 3s, 3p x and 3p y

sp 2 hybridization. One 3pz and two 3d orbitals are unhybridized state and are used in the formation of one pp - pp and two dp - pp bonds. O
orbitals underto

S O
3.
A: Give the structures of Structure of

O
Explain them.

( i ) SF4 ( ii ) SF6 .

SF4 : SF4 is trigonal bipyramidal with one equatorial position occupied by a lone pair.
sp3d hybridization.

* * *

The structure of

Sulphur in SF4 undergoes

S utilizes four hybrid orbitals for bonding while the fifth orbital accomidates a lone pair of electrons.

F
S

F
Structure of

SF6 : SF6 is octahedral or square bipyramidal. SF6 undergoes sp3d 2 hybridization.

* * *

The shape of Sulphur in

All hybrid orbitals are used in bonding to form 6 sigma bonds between S and F atoms.

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

O=S

2.
A:

What is allotropy? Give the allotropes of oxygen? Existence of an element in two or more physical forms is called as allotropy. Allotropes of oxygen and and

O2

O3 .

3.
A:

Write the names of the allotropic forms of S. Sulphur exists in many allotropic forms. The important forms are sulphur, g or monoclinic sulphur, plastic or c sulphur.

a or rhombic sulphur, b or monoclinic

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

4.
A:

At room temperature

H 2 O is a liquid while H 2S is a gas. Explain. H 2S exist as

At room temperature water exists as liquid because of inter molecular hydrogen bonding. While a gas because of the absence of intermolecular hydrogen bonding. What are the bond angles in Bond angles in
3

5.
A:

H 2 O and H 2S ? Why they differ in their bond angles?

H 2 O and H 2S are 10436 ' and 9230 ' respectively. In H 2 O molecule oxygen undergoes

sp hybridization where as in H 2S pure p-orbitals are involved in bond formation.

6.
A:

What is tailing of mercury? What chemical changes takes place in this process? On passing

O3 , mercury looses it metallic luster and meniscus and it sticks on the glass walls due to

formation of mercurous oxide place in this process is

( Hg 2O ) . This is known as tailing of mercury.

The chemical change takes

2Hg + O3 Hg 2 O + O 2 O3 .

7.
A:

Give an example of a reaction which consumes all of the atoms of oxygen in

3SO 2 + O3 3SO3
In this reaction

O3 is completely consumed. AgNO3 ? AgNO3 solution, it gives a white ppt. of silver thiosulphate which

8.
A:

What happens when hypo reacts with

When diluted hypo reacts with

on hydrolysis gives a black ppt. of silver sulphide.

Na 2S2 O3 + 2AgNO3 Ag 2S2 O3 + 2NaNO3


dil. hypo Silver thiosulphate

Ag 2S2O3 + H 2O Ag 2S + H 2SO4
Silver sulphide ( Black.ppt )

When concentrated hypo reacts with

AgNO3 solution, it gives a complex compound.

Na 2S2 O3 + 2AgNO3 Ag 2S2 O3 + 2NaNO3 3Na 2S2 O3 + Ag 2S2 O3 2Na 3 Ag ( S2 O3 )2


Sodium argento thiosulphate

9.
A:

How is hypo useful in photography? Hypo is used as fixing agent in photography.

AgBr + 2Na 2S2 O3 Na 2 Ag ( S2 O3 )2 + NaBr


Sodium argento thiosulphate (Complex compound)

10. Mention two advantages of contact process over other processes. A: * H 2SO 4 obtained is extremely pure and concentrated. * The impurities can be tested and the reactants can be recycled. 11. What is the reaction of O3 with PbS? Give the equation.
A:

O3 oxidizes black PbS to white PbSO 4 PbS + 4O3 PbSO 4 + 4O2

12. What is antichlor? Give example.


A: The reagent used to remove excess of chlorine in textile industry is called antichlor.

Na 2S2 O3 + Cl2 + H 2 O Na 2SO 4 + 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 KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

VII GROUP ELEMENTS


1.
A: Describe Whytlaw-Gray method for the preparation of fluorine?

Fluorine is prepared by the electrolysis of fused potassium hydrogen fluoride electrode reactions are:

( KHF2 ) .

The

at cathode 2H+ + 2eKHF2 Fusion K+ + H+ + 2FElectrolysis at anode 2F-

H2

F2 + 2e-

5 6 7 9 8 4 3 2 1
1. Fused

KHF2

2. Heating coil 6. Fluorine

3. Grpahite (anode) 7. Copper cell (cathode)

4. Copper diaphragm 8.

5. Fluorspar stopper

H2

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.

* * * * *
2.
A:

This diaphragm prevents the mixing of

H 2 and F2 which reacts explosively if they come into contact.

F2 , liberated at the anode, is passed through the U-tube containing sodium fluoride.
Hydrogen fluoride vapours accompanying fluorine as impurity, are removed by NaF.

( NaF + HF NaHF2 )

H 2 is liberated at the cathode.


The gaskets used in the cell are coated with Teflon to prevent corrosion of the parts.

Write the chemical properties of F2 with relevant equations? * Reaction with water:

F2 reacts with water and gives ozonized oxygen.

2F2 + 2H 2 O 4HF + O 2 ; 3F2 + 3H 2 O 6HF + O3


Reaction with alkalies: a) When F2 reacts with cold, dilute NaOH gives sodium fluoride and oxygen difluoride

( OF2 ) .

2NaOH + 2F2 2NaF + OF2 + H 2 O


b) When F2 reacts with hot, concentrated NaOH gives sodium fluoride and oxygen.

* * *

4NaOH + 2F2 4NaF + O2 + 2H 2 O


Reaction with other halides: Fluorine oxidizes all other halide ions to the corresponding halogens.

F2 + 2KCl 2KF + Cl2


Reaction with inert gases: Heavier inert gases like Kr and Xe form compounds with fluorine.

Xe + 3F2 XeF2
Reaction with KHSO4 (Potassium hydrogen sulphate):

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

Fluorine oxidises potassium hydrogen sulphate to potassiumper sulphate

( K 2S2O8 ) .

F2 + 2KHSO4 K 2S2 O8 + 2HF


Reaction with H2S: Fluorine oxidizes

H 2S to SF6

* *

H 2S + 4F2 2HF + SF6


Reaction with non metals: Except oxygen and nitrogen, other non-metals directly combine with fluorine and give binary compounds.

S + 3F2 SF6
Reaction with metals: All the metals (including noble metals like Au, Pt, etc.) form metal fluorides.

Cu + F2 CuF2

3.
A:

What is the principle of preparing Principle:

Cl2 in the laboratory? Describe Nelsons method for its.

Cl2 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.
+ 2NaCl( aq ) 2Na ( aq ) + 2Cl( aq )

At cathode: At anode:

2H 2 O + 2e 2OH( aq ) + H 2( g )

2Cl( aq ) Cl2( g ) + 2e

* * *

Cl2 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 byproducts.

OH - to form NaOH. In this process, H 2 and NaOH are important

2Na + + 2OH - 2NaOH


4.
Write the structures of all the oxyacids of A: NAME

Cl2 .
FORMULA HClO OXIDATION STATE OF CHLORINE +1 +3 +5 +7 BASICITY 1 1 1 1

Hypochlorous acid Chlorous acid Chlorine acid Perchloric acid

HClO2 HClO3 HClO4

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

Structures of oxyacids of chlorine: * Hypochlorous acid: HClO

Cl OH
The chlorine atom in this acid undergoes Hypochlorite ion

( ClO )
-

sp3 hybridisation. This conjugate base of Hypochlorous acid is

Chlorous acid:

HClO2

Cl O
bond

OH
sp3 hybridization. The chlorine atom has 2s bonds one p

The chlorine atom in this acid undergoes

( pp - dp ) and two lone pairs.

The conjugate base of chlorous acid is chlorite ion of

( ClO ) which is angular in shape with a bond angle


2

111 .

Chloric acid:

HClO3

Cl O O OH

The chlorine atom in this acid undergoes bonds (both are

sp3 hybridization. The chlorine atom has 3s bonds, 2p

pp - dp ) and one lone pair.

The conjugate base of chloric acid is chlorate ion of 106

( ClO ) which is pyramidal in shape with a bond angle


3

Perchloric acid:

HClO4

O Cl O O OH
sp3 hybridization. The chlorine atom has 4s bonds, three p
dp - pp ) and no lone pairs.

The chlorine atom in this acid undergoes bonds (all

The conjugate base of perchlorine acid is perchlorate ion

( ClO ) which is tetrahedral in shape with a


4

bond angle of 109.5 The acid strength of different oxyacids of chlorine increases with an increase in the oxidation state of the chlorine.

HOCl < HClO 2 < HClO3 < HClO 4 uuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuur acid strength increases
5.
A: How is bleaching power prepared industrially? Give any of its four chemical properties with equations. 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 KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

* *

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

Ca ( OH )2 + Cl2 CaOCl2 + H 2O

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

CaOCl2 Ca 2+ + 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.

2CaOCl2 + H 2SO 4 CaCl2 + CaSO 4 + 2HCl + O2


(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.

CaOCl2 + H 2SO4 CaSO4 + H 2 O + Cl2 Effect of a catalyst: Bleaching powder decomposes to give
CoCl2 2CaOCl2 2CaCl 2 + O2

O2 in the presence of a catalyst CoCl2 .

Oxidising property: Bleaching powder oxidizes lead salts to lead dioxide and ethanol to acetaldehyde.

Pb +2 + 2CaOCl2 PbO2 + 2CaCl2


CaOCl2 CH3CH 2 OH + ( O ) CH3CHO+ H 2 O Ethyl alcohol Acetaldehyde

6.
A:

Write all the chemical properties of bleaching powder. Give equations. How is it useful to man. * On long standing, bleaching powder undergoes auto-oxidation and changes into chloride and chlorate.

6CaOCl2 5CaCl 2 + Ca ( ClO3 )2

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

Reaction with water: With cold water, bleaching powder gives chloride and hypochlorite ion.

CaOCl2 Ca 2+ + 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.

2CaOCl2 + H 2SO 4 CaCl2 + CaSO 4 + 2HCl + O2


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.

CaOCl2 + H 2SO4 CaSO4 + H 2 O + Cl2 Effect of a catalyst: Bleaching powder decomposes to give
CoCl2 2CaOCl2 2CaCl 2 + O2

O2 in the presence of a catalyst CoCl2 .

Oxidising property: Bleaching powder oxidizes lead salts to lead dioxide and ethanol to acetaldehyde.

Pb +2 + 2CaOCl2 PbO2 + 2CaCl2


CaOCl2 CH3CH 2 OH + ( O ) CH3CHO+ H 2 O Ethyl alcohol Acetaldehyde

Uses * It is used in the sterilization of water, as bleaching agent, as an oxidizing agent and in the preparation of chloroform. SAQ

1.
A:

How does

F2 react with (i) H 2 O , (ii) NaOH. Give equations for them. H 2O :

Reaction with

F2 reacts with water and gives ozonized oxygen.

2F2 + 2H 2 O 4HF + O2 ; 3F2 + 3H 2 O 6HF + O3


Reaction with NaOH: a) When F2 reacts with cold, dilute NaOH gives sodium fluoride and oxygen difluoride

( OF2 ) .

2NaOH + 2F2 2NaF + OF2 + H 2 O


b) When F2 reacts with hot, concentrated NaOH gives sodium fluoride and oxygen.

4NaOH + 2F2 4NaF + O2 + 2H 2 O

2.
A:

Give the reaction of (i)

Cl2 with the following:


(ii) NaOH (iii) Iron metal

SO2
Reaction with

SO2 :

Cl2 when reacts with SO2 under the influence of sunlight and gives SO2 Cl 2 (sulphuryl chloride).
sunlight SO2 + Cl2 SO 2Cl2

Reaction with NaOH: a) When chlorine reacts with cold, dilute NaOH gives sodium chloride and sodium hypochlorite (NaOCl).

Cl2 + 2NaOH NaCl + NaOCl + H 2 O 3Cl2 + 6NaOH 5NaCl + NaClO3 + 3H 2 O

b) When chlorine reacts with hot, concentrated NaOH gives sodium chloride and sodium chlorate.

( NaClO3 ) .

Reaction with Iron metal: Chlorine reacts with iron metal and gives ferric chloride

( FeCl3 )

3Cl2 + 2Fe 2FeCl3


FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

3.
A:

What is Available Chlorine? Give chemical equation(s) which determine the same. Available chlorine is the amount of

Cl2 set free when bleaching powder is treated with excess of dilute

H 2SO 4 or CO2
A good sample of bleaching powder contain about 35-38% available chlorine.

CaOCl2 + H 2SO4 CaSO4 + H 2 O + Cl2 CaOCl2 + CO 2 CaCO3 + Cl2 VSAQ

1.
A:

Why is the E.A. of

Cl2 greater than that of F2 ?

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. Write an equation for

2.
A:

F2 reaction with KHSO 4 and tell the nature of the chemical change.

F2 oxidizes potassium hydrogen sulphate to potassium persulphate. F2 + 2KHSO4 K 2S2 O8 + 2HF


Write the balanced equation(s) for the reaction of a) With excess of

3.
A:

Cl2 with NH3

Cl2 , nitrogen trichloride ( NCl3 ) and HCl are formed. NH3 , ammonium chloride and nitrogen are formed.

NH3 + 3Cl2 NCl3 + 3HCl


b) With excess of

8NH3 + 3Cl2 6NH 4 Cl + N 2 -

4.
A:

1 mole of

NH3 is mixed with 8 moles of Cl2 in a reaction vessel. Write the equation for the reaction.

Since chlorine is taken in excess amount, 1 mole of Ammonia reacts with 3 moles of chlorine.

NH3 + 3Cl2 NCl3 + 3HCl

5.
A:

What is the reaction between bleaching powder and excess of dil. On treating bleaching powder with excess of dilute known as available chlorine

H 2SO 4 ?

H 2SO 4 , chlorine is liberated. This liberated chlorine is

CaOCl2 + H 2SO4 CaSO4 + H 2 O + Cl2 -

6.
A:

7.
A:

Give any two uses of bleaching powder. a) It is used in the sterilization of water Give the uses of florine. * It is used in rocket fuels. * HF is used in etching of glass.

b) It is used as a bleaching agent for cotton and paper pulp.

* *

NaF,

Na 3 AlF6 are useful insecticides. CCl2 F2 ) and as a plastic Teflon ( C2 F4 )n

As a refrigerant (Freon

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

TRANSITION ELEMENTS
1.
A: Giving examples explain Werners theory of complex compounds. OR Why was Werners theory nessesary? Discuss the theory. 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 Ex: Similarly b) primary valencies for Co i.e. three ionic bonds are present.

CoCl3 ( Co +3 and 3Cl- are present). These are three

Co ( NH3 ) Cl3 . In this complex the primary valencies of Co are three. 6

* * * *

Secondary Valency: 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 nonionizable valency.

i)

CoCl3 6NH3 :- Since the coordination number (secondary valency) of Co +3 is 6, 6 NH3 groups must
be linked to the central metal ion which do not ionize and

3Cl- ions are held by primary valencies.

NH3 NH3 NH3

Cl-

CO

ClNH3 Cl-

NH3
ii)

NH3

CoCl3 5NH 3 :- Since the coordination no. (secondary valency) of Co +3 is 6 to satisfy its coordination
number.

Cl- ion are linked to central metal ion which are non ionizable. The rest of the chloride ions i.e. two Cl ions are held by primary valencies. NH3 NH3 NH3
Ammonia molecules and one

CO Cl
iii)
-

ClNH3 Cl-

NH3

CoCl3 4NH3 :- Since the coordination number (secondary valency) of Co +3 is 6 to satisfy its

Cl- ion are linked to central metal ion which are non ionizable. The rest of the chloride ions i.e. one Cl ions are held by primary valencies.
coordination number, 4 ammonia molecules and two
FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

ClH3N Cliv)

NH3

CO+3 ClNH3

NH3

CoCl3 3NH3 :- Since the coordination number (secondary valency) of Co +3 is 6 to satisfy its
coordination number, 3 Ammonia molecules and three non ionizable.

Cl- ion are linked to central metal ion which are


Cl-

NH3

Cl-

CO+3

NH3

H3N
SAQ

Cl-

1.
A:

Define EAN. Calculate the EAN of the following metals in their respective complexes. i)

Cu ( NH3 ) ( OH )2 4

ii)

Co ( H 2 O )6 ( NO3 ) 3

iii)

K 4 Fe ( CN )6

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]

* * *
2.
A:

Cu ( NH3 ) ( OH )2 EAN = 29 - 2 + 8 = 35 4
Co ( H 2 O )6 ( NO3 ) EAN = 27 - 3 + 12 = 36 3 K 4 Fe ( CN )6 EAN = 26 - 2 + 12 = 36

What do you understand by the term ligand? 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) 2) 3) Negative ligands: Neutral ligands:
2 X,SO2 ,CN and C 2O4 . The ligands satisfy both primary and secondary valencies 4

of central metal atom. (where X = halogens)

H 2 O, NH3 . These ligands satisfy only secondary valency


+

1) 2)

Positive ligand: NO Based on the number of coordination positions Monodentate ligands: Donate only 1 pair of electrons to central metal. Ex:

X,SO2 , CN,S2O2 , H 2O, NH3 4 4


&& ( C O ) , Glycinate ion ( NH CH COO )
2 -2 4 2 2

Bidentate ligands: Donate 2 pair of electrons to central metal. Ex: Oxalate ion

3)

Polydentate 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) 2) Ligands with one or more lone pair of electrons. Ex: Ligands without a lone pair of electrons but with

H 2 O, NH3

p bonding electrons. Ex: C2 H 2 , CO, NO

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

3.

Give the coordination number of the metal in the following compounds. i)

Cu ( NH3 ) SO 4 4
molecules.

ii)

Co ( NH3 ) Cl3 6

iii)

K 4 Fe ( CN )6

A:

i)

Cu ( NH3 ) SO 4 in this coordination number of copper is 4, because it is surrounded by 4NH3 4 Co ( NH3 ) Cl3 in this coordination number of cobalt is 6, because each cobalt is surrounded by 6 6 NH3 molecules. K 4 Fe ( CN )6 in this coordination number of Iron is 6, because central atom Fe is surrounded by 6
cynide groups

ii)

iii) VSAQ

1.
A:

CuSO4 .5H 2 O has a pale blue colour. While ZnSO 4 , 7H 2 O is white. Explain the difference.
In In

CuSO4 .5H 2 O , Cu +2 ion has one unpaired electron in d-orbitals hence it is coloured. It absorbs red ZnSO 4 , 7H 2 O , Zn +2 ion has completely filled d10 configuration, hence it is colourless.

colour radiation and transmits blue colour radiation.

2.
A:

Ferrous salts are more unstable compared to Ferric salts. Explain interms of their configuration. Ferrous salts are unstable, because in has

Fe+2 , the d-orbitals are partially filled 3d 6 4s0 . Where as Fe+3 ion

3.
A:

d5 configuration (Half filled) hence it is stable. CuSO 4 is paramagnetic while ZnSO 4 is diamagnetic explain interms of electronic configuration.
CuSO 4 , Cu +2 3d9 ion has unpaired electron so it is paramagnetic in nature. Where as in ZnSO 4 ,

In

( )

Zn +2 ion has no unpaired electron d10 hence it is diamagnetic.

( )

4.
A:

5.
A:

6.
A:

7.
A:

8.
A:

What kind of magnetic property do Fe, Co and Ni show? Fe, Co and Ni exhibits ferromagnetism. Give composition of Nichrome. Nichrome contains 60% Ni, 25% Fe and 15% Cr. What elements are present in Brass? Write its composition. Brass contains Cu and Zn metals. Its composition is 60-80% Cu and 20-40% Zn. What is an alloy? Give the name and composition of an alloy? 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. Explain EAN with suitable examples. 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.

Co ( NO3 )( NH3 ) SO4 Pentamminenitro Cobaltate (II) Sulphate. 5 EAN = 27 3 = 24 + (6 2 electrons from ligands) = 24 + 12 = 36 +3 EAN of Co = 36 which is the atomic number of Krypton (Noble gas). Thus the complex is stable.
EAN of

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

ORGANIC CHEMISTRY
ETHYL CHLORIDE
Q.1) How is Ethyl Chloride obtained from ethyl alcohol by (a) Groves process (b) the action of PCl 3 and PCl 5 (c) the action of Thionyl chloride

Ans: (a) Groves Process:Ethyl alcohol reacts with HCl in presence of anhydrous ZnCl 2 to form ethyl chloride.
ZnCl 2 C 2 H 5 OH + HCl C 2 H 2 Cl + H2 O

(b) Action of PCl 3 or PCl 5 on ethyl alcohol: PCl 3 and PCl 5 react with C 2 H5 OH and form ethyl chloride. 3C 2 H 5 OH + PCl 3 3C 2 H 5 Cl + H 3 PO 3 C 2 H 5 OH + PCl 5 C 2 H 5 Cl + HCl + POCl 3

(c) Action of Thionyl Chloride on ethyl Alcohol:Thionly chloride reacts with ethyl alcohol to form ethyl chloride.
C 2 H 5 OH + SOCl 2 C 2 H 5 Cl + SO 2 + 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 AlCl 3 to give ethyl chloride.
AlCl 3 H 2 C = CH 2 = HCl H 3 C - CH 2 - Cl Anhydrous

(b) From ethane:- Ethane reacts with chlorine at ordinary temperature in the presence of light to give ethyl chloride.
C 2 H6 +
Class Concentration

Cl 2

hn C 2 H 5 Cl + HCl 400 C

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. Q.3)
CH 3 CH 2 Cl + KOH H 3 CCH 2 OH + KCl

(b) Moist silver oxide reacts with ethyl chloride to give ethyl alcohol. Ag 2 O + H 2 O 2AgOH
C 2 H5 Cl + AgOH C 2 H 5 OH + AgCl

(c) Potassium cyanide reacts with ethyl chloride to give ethyl cyanide as the major product.
D C 2 H5 Cl + KCN C 2 H5 CN + KCl

(d) Silver cyanide reacts with ethyl chloride to give ethyl isocyanide as major product.
D C 2 H 5 Cl + AgCN H 3 C - CH 2 - NC + AgCl

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.
C 2 H 5 Cl + KNO 2 H 3 C - H 2 C - O - N = O + KCl formaldehyde
Ethyl nitrite Dimethyl

(b) Ethyl chloride reacts with silver nitrite ( AgNO 2 ) solution to give ethyl nitrite as the major product.
C 2 H5 Cl + AgNO 2 H5 C 2 - NO 2 + AgCl
Nitro ethane

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

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.
C 2 H 5 Cl + NH 3 C 2 H 5 NH 2 + HCl

C 2 H 5 NH 2 + C 2 H 5 Cl ( C 2 H 5 )2 NH + HCl

( C 2 H5 )3 NH + C 2 H 5Cl ( C 2 H5 )3 N + HCl

( C 2 H5 )3 N + C 2 H 5Cl ( C 2 H5 )4 N + Cl -

Quaternary ammonium salt

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.
C 2 H 5 Cl + NaOC 2 H 5 C 2 H 5 - O - C 2 H 5 + NaCl
Sodiume ethoxide Diethylether

Q.7)

How does ethyl chloride reacts with the following. Explain with chemical equations. (a) Benzene / AlCl 3 (b) Silver Acetate (c) Mg / Dryether (d) NaBr or KI
C2H5

+ C2H5Cl

AlCl3

Ans:

(a) Ethyl chloride reacts benzene in presence of AlCl 3 catalyst to give ethyl benzene. (b) Ethyl chloride reacts with silver acetate in alcoholic solution to form ethyl acetate. CH 3 COOAg + C 2 H 5 Cl H 3 CCOOC 2 H 5 + AgCl
Ethyl acetate

(c) Ethyl chloride reacts with magnesium metal in presence of dry ether to give ethyl magnesium chloride. This is called as Grignards reagent.
C 2 H 5 Cl + Mg
Dry ether

C 2 H 5 MgCl Ethyl magnesium chloride

(d) Ethyl chloride reacts with NaBr and KI to give ethyl bromide and ethyl iodide respectively.
C 2 H 5 Cl + NaBr C 2 H 5 Br + NaCl C 2 H 5 Cl + KI C 2 H 5 I + KCl

Q.8) Ans:

Explain the reduction of ethyl chloride and what are the reagents used in this reaction. Ethyl chloride is reduced to ethane with (i) Zn / HCl (ii) LiAlH 4 (iii) H2 /Ni or Pd
Zn /HCl C 2 H 5 Cl C 2 H6 LiAlH Or H /Ni
4 2

Q.9) Explain wurtz reaction. Ans: Ethyl chloride reacts with sodium metal in presence of dryether to form butane. This is called Wurtz reaction
H5 C 2 - Cl + 2Na + Cl - C 2 H 5 H 5 C 2 - C 2 H 5 + 2NaCl Ether
n - bu tan e Dry

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

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

CHLORO FORM
Q.1) How is chloro form prepared from (i) ethyl alcohol (ii) Acetone
CaOCl 2 + H2 O Ca ( OH )2 + Cl 2
CH 3 CH 2 OH + Cl 2 H 3 CCHO + 2HCl
Acetaldehyde

Ans: Heating ethyl alcohol with bleaching powder and water gives chloro form.

H3 CCHO + 3Cl 2 Cl 3 CCHO + 3HCl


Chloral

2Cl 3 CCHO + Ca ( OH ) 2 2CHCl 3 + ( HCOO )2 Ca


Chloroform Calcium formate

With Acetone:
CaOCl 2 + H2 O Ca ( OH )2 + Cl 2
H 3 CCOCH 3 + 3Cl 2 Cl 3 CCOCH 3 + 3HCl
Trichloro acetone

2Cl 3 CCOCH 3 + Ca ( OH )2 2CHCl 3 + ( H 3 CCOO ) 2 Ca


Calcium Acetate

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 CCl 4 with iron filings and water.
Fe,H 2 O CCl 4 + 2CH 3 HCCl 3 + HCl D

(b) Chloral hydrate treated with sodium hydroxide to give pure chloroform
D Cl 3 CCH ( OH )2 + NaOH( aq ) HCCl 3 + HCOONa + H2 O Chloral hydrate Sodium formate

Q.3)

Explain oxidation of chloroform in presence of air and light. gas.


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

Ans: In the presence of air and light, chloroform is slowly oxidised to phosgene a highly poisonous

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) Ans: How does chloroform reacts with (a) HNO 3 (b) Ag / D (c) Aq.KOH (d) Acetone

(a) Chloroform reacts with vapours of HNO 3 to give chloropicrin a poisonous liquid.
HCCl 3 + HONO 2 CCl 3 NO 2 + H 2 O

(b) Chloroform is heated with silver to form acetylene


FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

D HCCl 3 + 6Ag + Cl 3 CH HC CH + 6AgCl Acetylene

(c) Aqueous KOH reacts with chloroform to give formicacid.


- H2 O KOH HCCl 3 + 3KOH CH ( OH )3 HCOOH HCOOK + H2 O Unstable Potassium formate

(d) Acetone condense with chloroform in presence of KOH to give chloroetone. H3C H3C H3C H3C OH C CCl3

O + HCCl3

Chloretone Chloretone is a hypnotic drug. Q.5) Explain (a) Reimer-Tiemann reaction (b) Carbylamine or isocyanide test orthohydroxybenzaldehyde (Salicylaldehyde) OH O
65 C C 6 H 5 OH + CHCl 3 + 3NaOH

Ans: (a) Chloroform reacts with phenol in presence of sodium hydroxide at 65C to give

H +3NaCl + 2H2 O

(b) Primary amines reacts with chloroform in presence of alcoholic KOH to give phenyl iso cyanide with offensive odour.
Warm C 6 H 5 - NH2 + HCCl 3 + 3KOH C 6 H5 NC + 3KCl + 3H 2 O Phenyl isocyanide

Q.6)

What are the uses of chloroform? (2) Detection of primary amines (3) Preparation of chloropicrin, chloretone (4) In the preservation o of anatomical species.

Ans: (1) Solvent for fats, oils and waxes

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

CHLORO BENZENE
1. Ans: Write any two preparations of Chloro Benzene? 1) Electrophilic substitution reaction:Chlorobenzene is formed by electrophilic substitution when benzene reacts with Cl 2 in presence of Lewis catalyst Fe or Iron (III) chloride ( FeCl 3 )
Cl + Cl2 Fe/Dark + HCl

2)

Sandmeyers rection:Aniline is dissolved in cold aqueous HCl and treated with sodium nitrite to give diazonium salt.
NH2 NaNO2 + HCl 0 to 50C
N2Cl Cu2Cl2

N2Cl + HCl
Cl + N2

Benzene dia zonium chloride

2.

This solution is treated with cuprous chloride to give chlorobenzene. Explain electrophilic substitutions reactions of chlorobenzene with a) Anhydrous AlCl 3 / Cl 2 b) Conc.H 2 SO 4 c) 1 : 1 reaction Conc.HNO 3 and H 2 SO 4 d) Anhydrous AlCl 3 / CH 3 Cl e) Anhydrous AlCl 3 / H 3 C - C - Cl a) Chorobenzene reacts with chlorine to give p-dichlorobenzene as major product and O-dichloro benzene as minor product
Cl Cl2/Anhydrous AlCl3 Cl Cl + Cl Cl
||

Ans:

b) Chlorobenzene reacts with Conc. H 2 SO 4 to give chlorobenzene sulphonic acid as major product and 2-chlorobenzene sulphonic acid as minor product.
Cl Conc. H2SO4 Cl Cl + SO3H 4-chloro benzene sulphonic acid SO3H

2-chloro benzene sulphonic acid

c) Chlorobenzene reacts with 1 : 1 ratio HNO 3 and H 2 SO 4 to give 1-chloro-4-nitro benzene as major product and 1-chloro -2- nitro benzene as minor product. d) Chlorobenzene reacts with CH 3 Cl in presence of Anhydrous AlCl 3 to give 1-chloro-4-methyl benzene as major product and 1-chloro-2-methylbenzene as minor product.
Cl Cl + CH3Cl Anhydrous AlCl3 CH3 major 1-chloro4-methyl benzene + Cl CH3

e)

Chlorobenzene reacts with Acetyl chloride CH 3 - C - Cl in presence of Anhydrous AlCl 3 to

minor 1-chloro2-methyl benzene O

||

give 4-chloro acetophenone as major product and 2-chloro acetophenone as minor product.
Cl + H3CCOCl Anhydrous AlCl3 O = C CH3 major Cl + minor Cl O C CH3

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

3. Ans:

Explain Wurtz-Fitting reaction and Fitting reaction with chlorobenzene. a) Chloro benzene reacts with Alkylhalide in presence dry ether and sodium metal to give alkyl benzene. This is called as Wurtz-Fitting reaction.
Cl R + 2Na + RX Dry ether + NaX + NaCl

b) Chloro benzene reacts with sodium metal in presence of dry ether to give diphenyl. This is called as fitting reaction.
Cl 2 + 2Na Dry ether Diphenyl + 2NaCl

4.

Write the structure of DDT.


H Cl C CCl3

Cl

ALCOHOLS
1. How is ethyl alcohol prepared from (a) Ethyl halide (b) Ethyl acetate (c) Acetaldehyde (e) Grignards reagent and formaldehyde. (d) Ethylene

Ans: a) Ethyl halide on Hydrolysis with aqueous solution of NaOH or AgOH or Ag 2 O in boiling water forms C 2 H 5 OH

H 3 CCH 2 Cl + NaOH CH 3 CH 2 OH + NaCl


D H3 CCH 2 Cl + AgOH CH3 CH2 OH + AgCl

b) From Ethyl Acetate: Ethyl alcohol is formed by the hydrolysis of ethyl acetate with aqueous alkali.

H3 CCOOC 2 H 5 + KOH( aq ) CH3 COOK + C 2 H5 OH


c) From Acetaldehyde: Acetaldehyde reduced by LiAlH 4 or NaBH 4 in ether gives Ethyl alcohol
LiAlH 4 /Ether H3 CCHO CH3 CH2 OH or NaBH 4

d) From ethylene: Ethylene treated with H 2 SO 4 to give ethyl hydrogen sulphate. Then Ethyl hydrogen sulphate treated with water to give ethyl alcohol.
SO 4 H

H 2 C = CH 2 + H 2 SO 4 H 3 C - CH 2
H 3 C CH 2 + H 2 O H 3 CCH 2 OH + H 2 SO 4
SO 4H
|

75- 80 C

e) Ethyl alcohol is obtained by the action of H 3 CMgX on formaldehyde followed by the hydrolysis.
H H C = O + H3CMgBr H H C OMgBr CH3 H3C CH2OH + Mg OH Br

2. Ans:

How is ethyl alcohol obtained by fermentation process of molasses. 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 H 2 SO 4 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 30C and fermented with yeast for 24 72 hours. If the maltose solution is taken:
Maltose C 12 H 22 OH+ H 2 O C 6 H 12 O 6 + C 6 H 12 O 6 Enzyme Maltose Glu cos e Fructose

If sucrose solution is taken


Invertage C 12 H 22 OH + H 2 O C 6 H 12 O 6 + C 6 H 12 O 6 Enzyme Glu cos e Fructose

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

Glu cos e/Fructose

Zymase C 6 H12 O 6 2C 2 H 5 OH + 2CO 2 Cenzyme

3.

Generally 95% aqueous alcohol is called rectified spirit. How is ethyl alcohol reacts with the following: a) Hydrogen halide b) Phosphorous halide c) Thionyl chloride d) Cu / 300C e) K 2 Cr2 O 7 / H 2 SO 4 f) Cl 2 g) CaOCl 2 h) I 2 / 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 ZnCl 2 catalyst to give ethyl chloride. Conc. HCl + Anhydrous ZnCl2 is called as Lucas reagent.
ZnCl 2 C 2 H 5 OH + HCl C 2 H 5 Cl + H2 O

b) Ethyl Alcohol reacts with PCl3 or PCl5 to give ethyl chloride.

c) Thionyl chloride ( SOCl 2 ) reacts with ethyl alcohol to give ethyl chloride.

C 2 H 5 OH + PCl 5 C 2 H 5 Cl + POCl 3 ( Phosphorous Chloride ) C 2 H 5 OH + SOCl 2 C 2 H5 Cl + SO 2 + 2HCl

3C 2 H5 OH + PCl 3 3C 2 H 5 Cl + H 3 PO 3

d) Dehydrogenation: When ethyl alcohol vapours are passed over freshly reduced copper at 300C acetaldehyde is formed.

C 2 H 5 OH CH 3 - C - H + H2
Cu 300 C

||

e) Oxidation of ethyl alcohol with acidified KMnO 4 or K 2 Cr2 O 7 forms Acetic Acid.
K 2 Cr2 O7 K 2 Cr2 O7 CH 3 CH 2 OH CH 3 CHO H 3 CCOOH + H 2 SO 4 H 2 SO 4

f) Action of halogen: Halogens oxidize ethyl alcohol first to acetaldehyde. Then it undergoes halogenation to form chloral.
Cl 2 3Cl 2 H3 CCH 2 OH H 3 CCHO Cl 3 CCHO ( chloral )

g) Reaction with Bleaching powder: C 2 H 5 OH reacts with CaOCl 2 in water to give chloroform.

CaOCl 2 + H 2 O Ca ( OH )2 + Cl 2

Cl 2 + H2 O 2HCl + [ O ]

H3 CCH 2 OH + [ O ] H3 CCHO + 2H2 O H3 CCHO + 3Cl 2 CCl 3 CHO + 3HCl


2CCl 3 CHO + Ca ( OH )2 2CHCl 3 + ( HCOO )2 Ca ( Calcium formate )

h) Iodoform reaction:When ethyl alcohol is treated with I 2 solution and KOH solution if forms Yellow crystals of CHI 3 (Iodoform).

H3 CCH 2 OH + I 2 H3 C - C - H + 2HI
H3 C - C - H + 3I 2 I 3 - C - H + 3HI
Tri iodo acetaldehyde

||

||

||

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

||

||

C 2 H 5 OH + 4I 2 + 6KOH CHI 3 + HCOOK + 5KI + 5H 2 O


4. Ans: How the maltose is prepared from starch. 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 50C for 1 hour. Malt contains the enzyme diastase. Diastase converts starch into the sugar maltose by hydrolysis.

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

n Diastase H 2 O + ( C 6 H10 O 5 )n C 12 H 22 O 11 2 Maltose Starch


5. Ans: How is methyl alcohol prepared. Water gas is heated at 573-673 K at 200 to 300 atm in presence of ZnO - Cr2 O 3 to give methyl alcohol.
ZnO - Cr2 O 3 CO + 2H2 CH3 OH 200 - 300 atm 573 - 673K

6. Ans: 7. Ans:

What is the composition of Azeotropic mixture of C 2 H 5 OH with H 2 O . A mixture of 95.6% ethyl alcohol and 4.4% water forms constant boiling point mixture, known as Azeotropic mixture. Explain the reaction of ethyl alcohol with (a) Sodium metal (b) Esterification (c) Grignard ragent (a) Soldium metal reacts with C 2 H 5 OH to give sodium ethoxide.

2C 2 H 5 OH + 2Na 2C 2 H 5 ONa + H 2
(b) Esterification:- Ethyl alcohol undergoes acid catalysed condensation with a carboxylic acid to form an ester. The reaction is called Fisher esterification.
2 H3 CCOOH + C 2 H 5 OH H3 C - COOC 2 H 5 + H2 O

H O

Ethyl acetate

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.

C 2 H 5 OH + Cl - C - CH 3 H 5 C 2 - O - C - CH 3 + HCl
Ethyl acetate

||

||

(c)

Ethyl alcohol reacts with alkyl magnesium halide to form alkane OC2H C2H5OH + H3CMgI CH4 + Mg I

8. Ans:

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

R
| |

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

R R
| |

R - C - OH + HCl R - C - Cl + H 2 O
Lucas reagent does not react with 1 alcohols. How is 1, 2 and 3 alcohols are identified by using Victarmeyers test. The alcohol compound is treated with red phosphorous and I 2 , and the product is treated with Silver nitrite and then with nitrous acid ( NaNO 2 + H 2 SO 4 ) and finally made alkaline. Primary alcohols give red coloration, Secondary alcohols give blue colouration. Tertiary alcohols give no reaction. Explain the action of conc. H 2 SO 4 on ethyl alcohol at different temperatures. (i) (ii) (iii) (iv)
100 - 110 C H5 C 2 OH + H2 SO 4 C 2 H5 HSO 4 + H2 O Ethyl hydrogen sulphate

9. Ans:

10. Ans:

C 2 H 5 OH + C 2 H 5 OH H 5 C 2 - O - C 2 H 5 + H 2 O
EthER

Conc. H 2 SO 4 140 C

C 2 H 5 OH + C 2 H 5 OH H 5 C 2 - O - C 2 H 5 + H 2 O
170 C ; Conc.H 2 SO 4 C 2 H 5 OH C 2 H 4 + H 2 O Al 2 O 3 ,350 C C 2 H 5 OH C 2 H 4 + H 2 O

Al 2 O 3 260 C

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

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

(b)

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

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

(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.
CH3 CH3 H 3C CH O2 Cumene H 3C C O O H OH H+ H 2O O + H3C C CH3

2.

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

Ans:

When phenol gives H it gives phenoxide ion. Phenoxide ion is resonance statilised.
O O + H+ O O O O

3. Ans:

Explain the esterification reaction of phenols. Phenols react with carboxylic acids and their derivatives like acid chlorides and acid anhydrides to from esters.
O OH + RCOOH H+ OCR + H2O O OH O + R C - Cl OCR + HCl

4. Ans:

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

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

O COOH OH Salicylic acid H+ O C CH3 OH Acetyl salicylic acid (Aspirin)

+ (CH3CO)2O

5. Ans:

Explain the nitration and Halogenation of phenol. -OH graph on benzene in phenol is a ring activating and ortho para directing group. a) Nitration: Phenol reacts with dilute HNO 3 to give ortho nitrophenol and p-nitrophenol.
OH dil.HNO3 OH OH NO2 +

NO2 O-nitro phenol P-nitro phenol

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


OH O 2N NO2 NO2

OH Conc. H2SO4

OH SO3H SO3H

b)

Halogenation: Phenol reacts with Br2 in presence of CS 2 to give ortho-Bromophenol and para bromo phenol.
OH Br2/CS2 273K OH OH Br + Br

With Br2 it give 2, 4, 6- tri bromo phenol.


OH + 3Br2 Br Br OH Br

6. Ans:

Explain Reimer-tiemann reaction. Phenol on treating with chloro form in the presence of NaOH gives - C - H group ortho position.
OH CHCl3 Aq. NaOH ONa CHCl2 NaOH ONa CHO H+ OH CHO
||

Salicyladehyde

7. Ans:

Explain Kolbes reaction: Phenol reacts with NaOH to give sodium phenoxide then it is treated with CO 2 and an acid to give 2hydroxy benzoic acid.
OH NaOH Phenol Sodium phenoxide ONa (i) CO2 (ii) H+ major OH COOH

8.

Explain Fries rearrangement?


OH + O H 3C C H 3C C O Anhydrous AlCl3

O O C CH3 AlCl3

OH O C CH3 O-hydroxy acetophenone

OH + O C CH3 P-hydroxy acetophenone

O Acetic anhydride

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

9. Ans:

Explain the reaction of phenol with (a) Zn dust and (b) Chromic acid (a) Phenol reacts with Zn to give Benzene
OH + Zn Phenol + ZnO Benzene

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


OH Chromic Acid [Na2Cr2O7 + H2SO4] O Benzoquinon O

ETHERS
1. Ans: How is diethyl ether prepared from (i) Ethyl alcohol (ii) ethyl bromide (iii) By Williamsons synthesis (i) (a)From Ethyl alcohol:Ethyl alcohol is taken in excess is treated with Conc. H 2 SO 4 at 140C to give diethyl ether. (b)Dehydration of ethyl alcohol to diethylether is also carried out by passing the alcohol vapours at 260C
2 3 over aluminum ( Al 2 O 3 ) catalyst 2C 2 H 5 OH H 5 C 2 - O - C 2 H 5 + H 2 O 260 C

Conc. H 2 SO 4 H 5 C 2 - OH + H - O - C 2 H 5 H 5 C 2 - O - C 2 H 5 + H 2 O 140 C Al O

(ii) From ethyl bromide:Ethyl bromide reacts with dry silveroxide to from diethyl ether.

H5 C 2 Br + Ag 2 O + Br - C 2 H5 H5 C 2 - O - C 2 H5 + 2AgBr
(iii) Williamsons synthesis: Ethyl halide reacts with sodium or potassium ethoxide to form diethyl ether.

C 2 H 5 ONa + IC 2 H 5 H 5 C 2 - O - C 2 H 5 + NaI
2. How does ethyl alcohol reacts with (a) Halogen (b) Oxygen (c) Mineral acids (i) (d)

( H3 CCO )2 O
Ans:

H 2 SO 4 (e) HI (f) Boiling water (g) PCl 5


(j) K 2 Cr2 O 7

(h) H 3 C - C - Cl (l) CO + BF3

||

(k) Al 2 O 3 / 360C

(a) Halogenation: Diethyl ether reacts with chlorine or bromine to form halogen substituted ethers.
Cl Cl 2 Dark
|

Cl
|

H 3 C - CH 2 - O - CH 2 - CH 3 H 3 C - CH - O - CH - CH 3
In the presence of sunlight all hydrogens are displaced.
Cl 2 H5 C 2 - O - C 2 H 5 Cl 5 C 2 - O - C 2 Cl 5 Sunlight Perchloro diethyl ether

(b) Oxygen: Diethyl ether reacts with atmospheric oxygen or ozonised oxygen to form peroxide. The peroxide is highly explosive.

H5 C 2 - O - C 2 H 5 + [ O ] H5 C 2 - O - C 2 H5
Peroxide

&& :O:
-

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

(d) Action of Sulphuric Acid:Diethyl ether forms oxonium slats with cold sulphuric acid, it ruptures C-O bond with hot sulphuric acid
D H5 C 2 - O - C 2 H 5 + H 2 SO 4( Conc.) C 2 H5 OH + C 2 H 5 HSO 4

H5 C 2 - O - C 2 H5 + HBr H 5 C 2 - O - C 2 H5 .Br e &&

(e) Action of hydrobromic acid or hydro iodic acid

C 2 H 5 - O - C 2 H 5 + HI C 2 H 5 I + C 2 H 5 OH
FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

O C2H5 + HI

OH + C2H5I

(f) Diethyl reacts with Boiling water to give ethyl alcohol.

C 2 H 5 - O - C 2 H 5 + H 2 O 2C 2 H 5 OH (g) Action of PCl 5 : Diethyl ether is treated with hot PCl 5 to form ethyl chloride. H 5 C 2 - O - C 2 H 5 + PCl 5 2C 2 H 5 Cl + POCl 3
(h) acetate.
AlCl 3 H5 C 2 - O - C 2 H 5 + H 3 CCOCl C 2 H5 Cl + H3 CCOOC 2 H5 Ethyl Acetate

Action of acetyl chloride Acetyl chloride reacts with diethyl ether in presence of AlCl 3 to form ethyl chloride and ethyl

Diethyl ether reacts with acetic anhydride to give ethyl acetate.

H 5 C 2 - O - C 2 H 5 + ( H 3 CCO )2 O 2H 3 C - C - OC 2 H 5
ZnCl 2

||

(j) Action of a strong oxidizing agent like K 2 Cr2 O 7 :Diethyl ether oxidized acetaldehyde and finally acetic acid with strong oxidizing agent.
K 2 Cr2 O7 K 2 Cr2 O7 H5 C 2 - O - C 2 H 5 2H 3 CCHO 2H3 CCOOH Oxidation Oxidation (k) Dehydration:- When diethyl ether vapours are passed over alumina at 360C ethylene is formed Al 2 O 3 H 5 C 2 - O - C 2 H 5 2H 2 C = CH 2 + H 2 O 360 C

(l) Action of carbon monoxide:In the presence of BF3 at 150C and 500 atm directly ether reacts with CO to form ethyl propionate.

H5 C 2 - O - C 2 H 5 + CO H5 C 2 - C - O - C 2 H 5
Ethyl propionate

BF3 /150 C 500 atm

||

3. Ans:

Explain electrophilic substitutions of alkyl aryl ether. Alkoxy group is O, P-directing and ring activating. They give ortho and Para substituted products.
OCH3 Br2 / CH3COOH Anisole Br OCH3

OCH3 + H3CCl Anhydrous AlCl3

OCH3 +

OCH3 CH3

OCH3 H3CCOCl

CH3 O-methoxy P-methoxy tolene tolene OCH3 OCH3 C CH3 + O


O = C CH3 OCH3 NO2

OCH3 H2SO4/HNO3

OCH3 + NO2

4. Ans:

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

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

ALDEHYDES & KETONES


Choose the correct answer: 1. How are Aldehydes prepared from the following compounds? (a) Alcohols (c) Carboxylic acids with mono catalyst (e) From Alkynes (g) Acid chlorides Sol: (a) (i)oxidation of ethyl alcohols: Oxidation of ethyl alcohol with pyridium dichromate (PDC) or pyridium chlorochromate (PCC) in anhydrous media like dichloro methane gives acetaldehyde
( ) H3 C - CH2 - OH H 3 CCHO CH 2 Cl 2 - H 2 O
PDC or PCC Ethyl alcohol Acetaldehyde

(b) Calcium salts of carboxylic acids (d) From alkenes (Wacker process) (f) Hydrolysis of Alkylidene chlorides

(ii) By Catalytic dehydrogenation of ethyl alcohol: When ethyl alcohol vapours are passed over Ag or Cu catalyst at 300C
Cu or Ag CH 3 CH 2 OH H 3 C - C - H Air

to give acetaldehyde

||

(b) From calcium salts of carboxylic acids: Acetaldehyde is prepared by heating a mixture of calcium salts of formic acid and acetic acid.
D ( HCOO )2 Ca+ ( CH 3COO )2 Ca 2CH 3CHO + 2CaCO 3 Calcium formate CalciumAcetate Acetaldehyde

(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 300C
MnO , 300 C HCOOH + H 3 CCOOH H 3 CCHO + CO 2 + H 2 O

(d) From Alkenes (Wacker Process) Acetaldehyde is obtained by passing ethylene through an acidified aqueous solution of palladium chloride and cupric chloride.
CuCl 2 H 2 C = CH 2 + PdCl 2 + H 2 O H 3 CCHO + Pd + 2HCl H+

(e) From Alkynes:- Acetaldehyde is obtained by passing acetylene through an aqueous solution of 40% Sulphuric acid and 1% mercuric sulphate at 60C
40% H 2 SO 4 , 60 C H - C CH + H 2 O H 2 C = CH tautomerism H 3 CCHO 1% HgSO 4

OH

(f) From the hydrolysis of alkylidene chlorides: Heating ethylidene chloride with KOH or NaOH give acetaldehyde
2KOH H3 C - CHCl 2 H 3 CCH ( OH ) 2 H 3 C - CHO - H2 O Acetaldehyde

(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
Pd - BaSO 4 H3 CCOCl H3 CCHO + HCl H2

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

2.

How are ketones are prepared by the following compounds. (a) Oxidation alcohols (c) Heating calcium acetate (d) From carboxylic acid (e) From aalkenes (wacker process) (g) From hydrolysis of alkylidere chlorides (f) From alkynes (h) From nitriles (b) Catalytic dehydrogenation of C 2 H 5 OH

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 H3 CCHOHCH3 H 3 C - CO - CH 3 Oxidation Acetone

(b) By catalytic dehydrogenation of ethyl alcohol:When isopropyl alcohol at 300C heated in presence of Cu or Ag catalyst to give acetone.
Cu or Ag H 3 CCHOHCH 3 H 3 CCOCH 3 + H 2 O Air

(c) From salts of carboxylic acid salt: Acetone is prepared by heating calcium acetate.
D ( H3 CCOO )2 Ca H 3CCOCH3 + CaCO 3

(d) From carboxylic acids:Acetone is obtained by passing the vapours of acetic acid over manganous oxide (MnO) catalyst at 300C .
MnO , 300 C 2H 3 CCOOH H 3 CCOCH 3 + CO 2 + H 2 O

(e) From alkenes (wacker process) Propylene is passed through an acidified aqueous solution of palladium chloride ( PdCl 2 ) and cupric chloride

( CuCl 2 )
H 3 C - CH = CH 2 + PdCl 2 + H 2 O H 3 C - C - CH 3 + Pd + 2HCl
(f) From Alkynes: Acetone is obtained by passing propyne into a solution of 40% H 2 SO 4 and 1% HgSO 4 at 60C
tautomerise 40% H 2 SO 4 H3 CC CH + H2 O H 3 C - C = CH 2 H3 C - C - CH 3 60 c 1% HgSO 4
CuCl 2 H+

||

OH

||

(g) Hydrolysis of isopropylidene chloride:-

H3 C - CCl 2 - CH 3 H3 C - C ( OH )2 - CH 3 H3 C - C - CH3
2KOH - H2 O Acetone

||

(h) From nitriles:1-phenol propanone is prepared from propane nitrite and phenyl magnesium halide.
H3C CH2 C Ether H3C CH2 C NMgBr H3O+ C 6 H5
O

N + C6H5MgX

C 2 H5 C C 6 H5
1-Phenol propanone

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

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 H 3O CHO

(ii) Methyl benzene reacts with CrO 3 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 H 2O 373 K CHO

(iv) Gatterman-Koch reaction:Benzene is treated with CO and HCl in the presence of Anhydrous AlCl 3 and Cu 2 Cl 2
CHO CO, HCl Anhydrous AlCl3, Cu2Cl2

4.

How does acetaldehyde reacts with (a) HCN (e) H 2 N - NH 2 (i) PCl 5 (m) Zn - Hg / HCl (b) NaHSO 3 (f) H 2 N - NHC 6 H 5 (j) RMgX (n) H 2 N - NH 2 / KOH (c) NH 3 (g) H 2 NNH - C - NH 2 (k) ROH (o) K 2 Cr2 O 7 / H 2 SO 4
||

(d) H 2 N - OH
O

(h) 2, 4-DNP (l) NaBH 4 or LiAlH 4 (p) I 2 / NaOH

(q) 0C / H 2 SO 4 ( Polymerisation ) Ans: (a) Action of HCN: Addition of HCN to acetaldehyde gives acetaldehyde cyanohydrin.
H3C H CH3 C = O + HCN H C OH CN

Acetaldehyde cyanohydrin

(b) Action of NaHSO 3 : Addition of sodium bi sulphate to acetaldehyde gives acetaldehyde sodium bisulphite salt.
H3 C H C = O + NaHSO3 H 3C C H Acetaldehyde sodium bi sulphate SO3 OH Na+

(c) Action of NH 3 :OH

H3 C - CHO + NH3 H3 C - CH- NH2 H 3 C - CH = NH


Acetaldehyde ammonia Ethana lim ine

(d) Action of hydroxylamine:- It gives a acetaldeoxime


FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

OH H3C C = O + H2NOH H H3 C C N H

H OH

- H2O

H3C C = N OH H Acetaldoxime

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


H 3C C = O + HN2 NH2 H hydrazine H 3C H NH NH2 C OH H 3C C = N NH2 + H2O H hydrazone

(f) Action of phenylhydrazine:H 3C C = O + H2N NH C6H5 H Phyl hydrazine - H 2O H 3C C = N NH C6H5 H Phenyl hydrazone

(g) Action of semi carbazide:H 3C H O C = O + H2N NH C NH2 Phyl hydrazine O H 3C H NH NH C NH2 C OH H 3C - H 2O C = N NHC6H5 H Semi carbozone

(h) With 2,4 DNP


NO2 H 3C NO2 NO2 H 3C H NH NH C OH NO2 C = O + H2N NH H 2,4-dinitro phenyl hydrazine - H 2O H 3C H C = N - NH NO2 NO2

2,4-dinitro phenyl hydrazone

(i) Action of PCl 5 : Acetaldehyde reacts with acetaldehyde to give ethylidene chloride.
Cl H3C C = O + PCl5 H H3C C Cl + POCl3 H Ethylidene chloride

(j) Addition of Grignards reagent: Acetaldehyde reacts with RMgX to give an adduct and after Acid hydrolysis to give secondary Alcohol
H3 C C = O + RMgX H H3C H OMgX C R H+ H3 C H OH C R

20 Alcohol

(k)
H3 C H ROH C=O dry HCl R H OR C OH ROH H3O+ R H OR C OR Acetal + H2 O

Hemi Acetal

(l) Acetaldehyded reduction:


Ni H 3 C - C = O + H 2 H 3 C - CH 2 - OH

H
NaBH 4 H 3 C - C = O H 3 CCH 2 OH or LiAlH 4

(m) Clemenson reduction:

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

H3 C H

C=O

Zn Hg HCl

H3 C CH2 + H2O H Ethane

(n) Wolff-Kishner reduction:


H3 C H C=O H2N NH2 -H2O H3 C H C = N NH2 KOH Ethylene glycol H3C CH2 H + N2 Ethane

(o) Oxidation:
K 2 Cr2 O 7 H3 C - CHO H 3 CCOOH H 2 SO 4 Acetaldehyde Acetic acid

(p) Iodoform reaction:

H 3 CCHO + 3I 2 + 4NaOH HCOONa + HCI 3 + 3H 2 O + 3NaI


(q) Polymerisation of acetaldehyde
CH3 At room temp. 3H3CCHO H2SO4 few drops O H3C CH CH O

CH - CH3 O Paradehyde Hypriotic drug


H3C CH O CHCH3 O O H3C CH O CHCH3 Metaldehyde (Solid fuel)

At 00 C 4H3CCHO H2SO4 few drops

5.

How does acetone reacts with (a) HCN (e) H 2 N - NH 2 (i) RMgX (b) NaHSO 3 (f) H 2 N - NHC 6 H 5 (j) Alcohol addition (c) NH 3 (g) 2, 4-DNP (d) H 2 N - OH (h) PCl 5

(k) Chlorination, Bromination (m) Clemensen reduction

(l) NaBH 4 or LiAlH 4 or Na /C 2 H 5 OH (n) Wolff-Kishner reduction (p) I 2 / NaOH (a) Addition of HCN:H3C H3C H3 C C = O + HCN H OH C CN

(o) K 2 Cr2 O 7 / H 2 SO 4 (q) Few drops of H 2 SO 4

Acetaldehyde cyano hydrin

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

Acetone sodium bisulphite

(c) Addition of NH 3

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

H3C H3 C

H3 C C = O + NH3 H3 C

OH C NH2 -H2O

H3C H3C

C = NH

Acetone Ammonia

Propanonimine

(d) Addition of Hydroxyl amine:H3 C H3 C H3C C = O + H2N OH H3C C = N OH + H2O Acetoxime

(e) Addition of Hydrazine


H 3C H 3C H 3C C = O + H2N NH2 H 3C C = N NH2

Hydrazone

(f) Addition of Phenyl hydrazine:H3C H3 C H3 C C = O + H2N NH C6H5 H3 C C OH NH NH C6 H 5 -H2O H3 C H3 C C = N NHC6H5

Phenyl hydrazone

(g) Addition of semicarbazide:H3 C H3C C = O + H2NNHCONH2 -H2O H3 C C = NHCONH2 H3 C Semi carbazone

(h) Addition of 2, 4 DNP


H3 C H3 C NO2 C = O + H2N NH NO2 -H2O H3C C = N NH H3C 2,4 dinitrophenyl hydrazone NO2 NO2

(i) Addition of PCl 5


H 3C H 3C H 3C C = O + PCl5 H C Cl Cl + POCl3

Ethylidene chloride

(j) Addition of Grignard reagent


H 3C H 3C H 3C C = O + RMgX H 3C C R OMgX H+ / H2O H 3C H 3C 30 C R OH + Mg X OH

Alcohol

(k) Addition of Alcohol

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

H3C H3 C C=O

ROH HCl

H3 C H3 C C

OR OH

ROH H+

R R C

OR OR

Hemi acetal

Acetal

(l) Reduction of Acetone


H3 C H3 C C = O + 2 [H] Na/C2H5OH OH H3C CH CH3 20 Alcohol

(m) Clemmensen reduction


H3 C H3 C C=O Zn - Hg HCl H3C CH2 CH3 +H2O Propane

(n) Wolff-Kishner reduction


H3 C H3 C C=O H2N NH2 -H2O H3 C H3 C C = N NH2 KOH / CH2 OH CH2 OH H3C CH2 CH3 +N2 Propane

(o) Oxidation:
K 2 Cr2 O 7 H3 C - C - CH3 CH3 COOH H 2 SO 4 Acetic acid

||

(p) Iodo form reduction:

H3 C - C - CH3 + 3I 2 + 4NaOH H 3 CCOONa + CHI 3 + 3H 2 O + 3NaI


(q) Polymerisation of acetone:
3H3CCOCH3 H2SO4 CH3 CH3 CH3 2, 4, 6 trimethyl benzene (mesitlylene)

||

6.
Ans:

Explain the tests for acetaldehyde:-

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. Ag ( NH 3 )2 OH . It gives silver mirror with acetaldehyde .

H3 CCHO + 2 Ag ( NH 3 )2 OH H3 CCOONH 4 + 2Ag + 3NH3 + H2 O


Acetaldehyde oxidised to acetic acid (b) Fehlings test:Fehlings solution is the mixture of equal volumes of solution I ( CuSO 4 solution) and solution II Rochellesalt solution with NaOH (sodium potassium tartreate)) (

H3 CCHO + 2Cu 2 + + 5OH - H3 CCOO - + Cu 2 O


A yellow red ppt Cu 2 O is formed Cu 2 + Cu +1 + 3 H 2 O (c) Benedicts solution also gives above test. Benedicts solution is alkaline copper (II) sulphate solution, with citrate solution. Cu 2 + converted to yellow or red Cu +1 O 2
FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

(d) Schiffs base test:Schiffs base is p-rosaniline hydrochloride pink aqueous solution decolourised with SO 2 . restores the pink colour of Schiffs base. Acetaldehyde

7.
Ans:

Explain the tests for Acetone:

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.
A:

What are the uses of acetaldehyde? 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, K 2 CO 3 or HCl acetaldehyde undergoes condensation to form aldol.
OH

2H 3 CCHO H 3 C - CH - CH 2 - CHO
Aldol

OH - or H +

Aldol on heating gives crotanaldehyde.


OH
D H 3 C - CH - CH 2 - CHO H 3 C - CH = CH - CHO - H2 O Cro tan aldehyde

Acetone gives Ketol

2H 3 CCOCH 3 H 3 C - C - CH 2 - COCH 3 H 3 C - C = CHCOCH 3


2

Ba ( OH)

OH
| |

CH3
|

CH3

D - H2 O

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

formaldehyde

2)
FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

CHO 2 Benzaldehyde Conc. KOH

CH2OH +

COOK

Benzyl alcohol Sodium benzoate

12. What is the product of the following reaction?


CHO H2SO4 + HNO3 273 283K M Nitro Benzaldehyde CHO

13. Explain cross aldol condensation?


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

( i ) 2 - butenal

( ii ) 2 - methyl - 2 - pentenal

CH 3

+ H 3 C - CH = C - CHO + H 3 C - CH 2 - CH = CHCHO
( iii ) 2 - methyl - 2 - butenal

CH 3

( iv ) pent - 2 - enal

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

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

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 CH 3 OH and carbon monoxide (e) From acetaldehyde (f) Bio chemical oxidation of ethyl alcohol (g) From alkyl benzene (a) Oxidation of ethyl alcohol: In presence of KMnO 4 or K 2 Cr2 O 7 / H 2 SO 4 ethyl alcohol gives acetic acid.
KMnO 4 KMnO 4 CH 3 CH 2 OH H3 C - CHO H3 CCOOH or K 2 Cr2 O7 /H 2 SO 4 or K 2 Cr2 O7 /H 2 SO 4

A:

(b) From Grignards reagent: Methyl Magnesium bromide reacts with CO 2 followed by acid hydrolysis to give acetic acid OMgBr O O OH H+ / H2O H3C C OH + Mg H3CMgBr + C H3 C C = O Br O (c) Methyl chloride with KCN gives methyl cyanide, then on hydrolysis it gives acetic acid.

H 3 CCl + KCN CH 3 CN + KCl


CH3CN + H2O
OH OH O O H2O

H3C C = NH

H3C C NH2

H3C C OH + NH3

(d) From methyl alcohol and carbon monoxide:


Cobalt or H3 COH + CO H3 CCOOH Rhodium , D , pressure

(e) From Acetaldehyde:Acetaldehyde is oxidised with air inpresence of manganese acetate commercial quantities of acetic acid are formed.

1 air Mn 2 + O 2 + H3 CCHO H3 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)

H 3 CCH 2 OH + O 2 H 3 CCOOH + H 2 O
CH3 KMnO4, KOH Heat COOK H3O+

(g) Preparation of Benzoic acid from alkyl benzenes:


COOH

Toluene CH2 CH2 CH3


KMnO4, KOH

COOK H3O+

COOH

2.

How does acetic acid reacts with (a) active metals (b) Carbonates and bicarbonates (d) ethyl alcohol (e) PCl 3 ,PCl 5 + SOCl 2 (f) NH 3 (g) Red P + Cl 2 (h) P4 O 10 (i) Sodalime

(c) NaOH

A.

(j) Kolbes electrolysis (k) Calcium acetate (l) Lithium Aluminium hydride (m) HI / Red P (n) Ni / D (a) Active metals like sodium, potassium reacts with acetic acid to give salt.

2H 3 CCOOH + 2Na 2CH 3 COONa + H 2


Sodium acetate

(b) Action of carbonates and bicarbonates:

2H 3 CCOOH + Na 2 CO 3 2H 3 CCOONa + CO 2 + H 2 O Na 2 CO 3 + CH 3 COOH H 3 CCOONa + NaHCO 3 NaHCO 3 + H 3 CCOOH CH 3 COONa + CO 2 + H 2 O


(c) Reaction with alkali:

H 3 CCOOH + NaOH H 3 CCOONa + H 2 O


FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

(d) Action of ethyl alcohol:


H3 O H3 CCOOH + C 2 H 5 OH H3 CCOOC 2 H5 + H2 O

(e) Action of PCl 3 ,PCl 5 , SOCl 2

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

H3 CCOOH + NH3 H 3 CCOONH 4 H3 C - C - NH 2 + H 2 O


Ammonium Acetate Acetamide

||

(g) Action of Red P/ Cl 2 :


Re d P H 3 CCOOH + Cl 2 CH 2 - COOH - HCl

Cl

H2 C - COOH + Cl 2 Cl - C - COOH
Cl H
| |
Re d P - HCl

Re d P - HCl

| |

Cl

Cl
| |

Cl - C - COOH + Cl 2 Cl - C - COOH
Cl Cl
O

(h) Action of phosphorous pentoxide:


P4O10 -H2O H3C C H3C C
O

2H3CCOOH

O + H2O

Acetic anhydride

(i) Action of Sodalime:


CaO H3 CCOONa + NaOH CH 4 + Na 2 CO 3

(j) Kolbes electrolysis:

2H 3 CCOOK + 2H 2 O H 3 C - CH 3 + 2CO 2 + 2KOH + H2


Anode At Cathode

(k) (a) Distillation of Calcium Acetate:

( H3 CCOO )2 Ca H 3C - C - CH 3 + CaCO 3
D Acetone

||

(b) Mixture of calcium acetate and calcium formate on distillation gives acetaldehyde

( H3 CCOO )2 Ca + ( HCOO )2 Ca 2H3CCHO + 2CaCO 3


LiAlH 4 H3 CCOOH H 3 C - CH 2 - OH

(l) Reduction of acetic acid by LiAlH 4 (m) Reduction of Acetate Acid by HI / Red P
HI/Re d P H 3 CCOOH H 3 C - CH 3

Ni/D H3 CCOOH + 3H2 H 3 C - CH 3 + 2H2 O

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

ANILINE
1.
A. How are (i) C 6 H 5 Cl (ii) C 6 H 5 OH converted to aniline? (i) Chloro benzene on heating with ammonia at 200C under pressure in the presence of Cu 2 O forms aniline.
Cu 2 O C 6 H5 Cl + 2NH 3 C 6 H 5 NH 2 + NH 4 Cl

(ii) Conversion of C 2 H 5 OH to aniline: Phenol on treating with NH 3 at 300C under pressure in presence of ZnCl 2 forms aniline.
ZnCl 2 C 6 H5 OH + NH 3 C 6 H5 - NH2 + H 2 O 300 C

2.
A.

How is nitrobenzene converted to aniline? Zinc and HCl or Sn and HCl, reduces nitrobenzene to aniline.
NO2 + 6[H] NH2 Zn + HCl or Sn + HCl Aniline + 2H2O

3.

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

H3C C H3C C
O

(c) CHCl 3 / KOH /Alcohol (d) NaNO 2 / HCl (e) Br2 / 0 - 5C (f) Cl - C - C 6 H 5 (h) Benzaldehyde / H 2 SO 4
||

(g) Benzene suphonyl chloride (i) H 3 C - C - Cl A. (a)


||

(j) H 2 SO 4
O

Aniline reacts with methyl acetate to give N-acetyl aniline (Acetanilide)


NH2 H N C CH3 + H3COH
O

+ H3C C OCH3

(b)
NH2 +

H3C C H3C C
O

H N C CH3 O + HCl

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 KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

Alcohol C 6 H5 NH 2 + HCCl 3 + 3KOH C 6 H 5 NC + 3KCl + 3H2 O Phenyl isocyanide

(d)

Diazotisation: In this reaction aniline reacts aniline reacts with nitrous acid at 0 - 5C to form diazonium chloride.
NH2 + NaNO2 + 2HCl 0 5 0C N NCl + 2H2O + NaCl

Benzene dia-zonium chloride

(e)

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


NH2 + 3Br2 0 50C Br NH2 Br Br

+ 3 HBr

(f)

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

NH2

CH3COCl or
O

HNC CH3

HNO3

NHCOCH3 hydrolys is NO2

NH2

NO2

H3C C H3C C
O

(g)

Aniline reacts with benzene sulphonyl chloride to give N-phenyl benzene sulphanamide.
NH2 + Cl SO2C6H5 Benzene sulphonyl chloride - HCl H C6H5 N SO2C6H5 N-phenyl Benzene sulphonamide

(h)

Aniline reacts with benzaldehide to give benzalidene aniline.


Conc. H 2 SO 4 C 6 H 5 NH 2 + O = C - C 6 H 5 C 6 H 5 - N = C - C 6 H 5 Benzalidene aniline

(i)

Aniline reacts with acetyl chloride to give acetanilide.


Pyridine C 6 H5 NH2 + Cl - C - CH 3 C 6 H5 - NH - COCH 3 - HCl Ace tan ilide

||

(j)

Aniline when treated with sulphuric acid firstly it gives anilinium hydrogen sulphate. Then it gives zwitter ion
NH2 NH3HSO4 H2SO4 Anilinium hydrogen sulphate SO3H SO3 Zwitterion NH2 NH2

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

4.
A.

What are the uses of aniline? (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.
A.

2 Discuss the mechanism of nucleophilic substitution reactions S 1 and S N . N

Nucleophilic substitution reactions take place in two ways depending on the nature of alkyl halide. These are (i) unimolecular S 1 N

( ) and (ii) bimolecular ( S ) reaction mechanism.


2 N

(i) Unimolecular reaction S 1 : The rate of hydrolysis of alkyl halide depends only on the concentration of N alkyl halide. It does not depend on the concentration of nucleophile unimolecular nucelophilic substitution reaction S 1 . N 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 H 3 C - C - Br H 3 C - C + Br e | |

( )

( OH ) . Hence this reaction is called


-

CH3
|

CH3
|

CH3 tert. butyl bromide

CH3 tert. carbonium ion

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.
CH3
| |
Fast H 3 C - C + H 2 O : H 3 C - C - O - H H 3 C - C - OH + H

..

CH3
| |

CH3
| |

CH3

CH3 H

CH3

ii) bimolecular reaction

( S ) : The rate of hydrolysis of alkyl halide depends on the concentration of alkyl


2 N

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]
2 Mechanism: S N reaction mechanism involves only one step. The breaking of C X bond and the making

C OH take place simultaneously.


d HO d Br

HO +

C Br

HO C alcohol

+ Br

alkyl halide

transition state

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

NITROBENZENE
1.
A. How is Nitro benzene prepared? 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 60C .
NO2 + HNO3 Conc. H2SO4 > 600C + H2O

2.

How does Nitrobenzene reacts with (a) Metal + acid (d) LiAlH 4 (b) Metal + base (e) Ni / Pt (c) Metal + Neutral medium (f) Cl 2 / Br2 / Fe

(g) Conc.HNO 3 , Conc. H 2 SO 4 > 60C A. (a) Zinc and hydrochloric acid, tin and hydrochloric acid or stannous chloride and HCl reduces nitrobenzene to aniline.
NO2 + 6 [H] Zn + HCl or SnCl2 / HCl NH2 + 2H2O

(b) Alkaline medium: Nitrobenzene gets reduced with zinc and alcoholic potash to hydrazobenzene.
NO2 2 + 10 [H] Zn / KOH NN H H Hydrozo benzene + 4H2O

(c) Neutral medium: Nitrobenzene gets reduced by Zinc and NH 4 Cl solution to phenyl hydroxylamine
NO2 + 4 [H] Zn /NH4Cl H N OH + 2H2O Phenyl hydroxyl amine

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


NO2 2 + 8 [H] LiAlH4 NN Azobenzene

(e) Nitrobenzene is reduced catalytically with hydrogen and finely divided Ni or Pt at room temperature to give aniline
NO2 + 3H2 Ni/Pt NH2 + 2H2O Aniline

(f) Halogenation :
NO2 + Cl2 Fe Cl m-chloro nitro benzene NO2

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

NO2 + Br2 Fe

NO2 Br m-bromo nitro benzene

(g) Nitration above 60C :


NO2 NO2 Conc. HNO3 + Conc. H2SO4 > 600 C NO2 m-dinitro benzene

3.
A.

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

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

BIOMOLECULES
Very Short answer Questions

1.
A.

What are lipids? Give examples. 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.
A.

How are lipids classified? Lipids are classified into simple lipids (homo lipids). Compound lipids (hetero lipids), derived lipids (compound obtained from simple and compound lipids)

3.
A.

What is the alcohol present in neutral lipids? Give its formula. The alcohol present in neutral lipids is glycerol.

CH2 - OH | CH - OH | CH2 OH Glycerol

4.
A.

What are waxes? Give one example. Waxes are insect secretions or protective coatings on animal furs and plant leaves. Ex: Bees wax

5.
A.

What are compound lipids? Give one example. Lipids which contain glycerol and other groupings other than fatty acids. Ex: Lecithin, Cephalin.

6.
A.

What are derived lipids? Give one example. Derived lipids are hydrolysis products of simple and compound lipids. Ex: Ergosterol, bile acids. Give two biological function of lipids. 1) Lipids are the energy sources What is cholesterol? It is a white crystalline substance of molecular formula C 27 H 45OH found in the tissues of animals, synthesized by liver. 2) Lipids are the food veserves

7.
A.

8.
A.

9.
A.

What are hormones and how are they classified? 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 KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

10. Give the structure of any three hormones?


CH3 H H O H OH

CH3 H H H

OH
H3C H H

CH3

COCH3

, HO Estradiol

, O Progesterone

Testosterone

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

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

14. Give two examples of steroid hormones.


A. Ex: Androgen, estrogen.

15. Give two examples of protein hormones.


A. Insulin, Thyroxin

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

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 KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

CHEMISTRY IN EVERYDAY LIFE


Very Short answer Questions

1.
A.

Define drug. Give two examples. 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.
A.

Define medicine. Give two examples. 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.
A.

How do you differentiate between drug and medicine? 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.
A.

What are Narcotic drugs? Give an example. Narcotic drugs cause depression of central nervous and are strong analgesics. Ex: Morphine, Codeine

5.
A.

What are non-Narcotic drugs? Give an example. The analgesics which have limited use in mild aches, pains like backache and headache. Ex: - Aspirin, Ibuprofen

6.
A.

What are Analgesics? Give two examples. Analgesics reduce or totally abolish pain without causing any damage to consciousness, mental confusion , disturbances of nervous system. Ex: Aspirin, Ibuprofen

7.
A.

Define Antipyretics. Give two examples. Drugs used to control fever are called antipyretics. Ex: Paracetmol, Analgin etc.

8.
A.

Define transquilizers. Give two examples. Drugs that cause quieting effect accompanied by relaxation and rest but need not necessarily induce sleep. Ex: Luminal, Seconal.

9.
A.

Define antiseptics. Give example. 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. resistance to infection of the body. Ex:- Lysozyme, Lactic acid. They increase immunity and

12. What are antifertility drugs? Give examples.


A. Antifertility drugs are oral contraceptives which are generally steroids. Ex: Norethindrone, Ethynylestrdiol
FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

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, SO 2 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 KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

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. Define an elastomer. 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? 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. 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? (i) Number average molecular weight ( M n ) (ii) Q.8) What do you meant by polydispersity index? Weight average molecular weight ( M w ) Ans: Following two are most common type of molecular weights used in polymers. Ans: Sulphur(or) sulphur containing compounds react with rubber molecules to effect cross linking in Ans: Examples for semi-synthetic polymers are cellulose rayon and cellulose nitrate. Q.3) Ans: Elastomers: These are the polymers which have rubber like elastic properties. OR

Ans: Constituent monomers of Buna-S are 1,3-butadiene and Styrene (Vinyl Benzene).

Ans: The ratio of the weight average ( M w ) and the number-average ( M n ) molecular weights of a polymer is called Polydispersity indes (PDI.
PDI = Mw Mn

Q.9)

What is Vulcanization of rubber? 415K temperature is called Vulcanization of rubber.

Ans: The process of heating the raw rubber with sulphur (or) sulphur containing compounds at 373-

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

PHYSICAL CHEMISTRY

DILUTE SOLUTIONS

STRAIGHT OBJECTIVE TYPE (SINGLE OPTION CORRECT)

1.
A:

Explain with suitable examples the terms Molarity, Molality, Normality and Mole fractions. Which method of expressing concentration is better than the others? Why? 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

(M) =

Volume of solution in litres ( v )


Weight of solute 1 Molecular wt. of solute Volume of solutiion in litres

No. of moles of solute ( n )

iv) Molarity ( M ) =

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

(m) =

Weight of solute 1 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.

No. of gram equivalents of solute Volume of solution in lit Weight of solute 1 iv) Normality ( N ) = Equivalent weight of solute Volume of solution in litres
iii) Normality

( N) =

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.

No. of moles of solute No. of moles of solute + No. of moles of solvent No. of moles of solvent iv) x ( solvent ) = No. of moles of solute + No. of moles of solvent
iii)

x ( solute ) =

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.
A:

Calculate the equivalent weights of

H 2SO 4 , Na 2 CO3 , KMnO4 in acid medium and Ba ( OH )2 .

* Equivalent weight of an acid =


H 2SO 4 = 98 = 49 2

Molecular weight of the acid Basicity of the acid

Basicity:- Number of replaceable Hydrogen atoms. Eq. Wt. of

* Equivalent weight of a salt =


Na 2CO3 2Na + + CO3 2

Molecular weight of the salt Total charge of cation or anion

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

Eq. Wt. of

106 = 53 ( molecular weight of Na 2 CO3 = 106 ) 2 Molecular weight of the substance * Equivalent weight of an oxidizing agent = Number of electrons involved during oxidation Na 2 CO3 =
Mn +7 ion in KMnO 4 is reduced to Mn +2 ion Mn +7 + 5e- Mn +2

In acid medium, i.e. Eq. Wt. of

158 = 31.6 5 Molecular weight of base * Equivalent weight of base = Acidity of the base KMnO4 =

Acidity:- Number of replaceable

Ba ( OH )2 Mol.Wt = 171.4 ; Acidity = 2


Ba ( OH )2 = 171.4 = 85.7 2

OH - ions

Eq. Wt. of

3.

A:

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? 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


Where

p 0 - ps ns = p0 ns + n0

p0 is the vapour pressure of pure solvent

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

a p 0 - ps ns Therefore = = A p0 ns + n0 a + b A B * For dilute solutions, the number of moles of solute ( n s ) can be neglected in comparision to the number of
moles of solvent

( n0 )
p0 a B ( p 0 - ps ) b

p 0 - ps a B = p0 A b
Molecular weight of solute

(A) =

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 ( DP )
Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

* 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) * A=
p0 a B ( p 0 - ps ) b

ii) Elevation of boiling point ( DTb )

* 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) * ( DTb ) = k b m =

k b a 1000 where k b = molal elevation constant or ebulliscopic constant. Ab iii) Depression in freezing point ( DTf ) * 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)

* ( DTf ) = k f m = k f

a 1000 A b

Where b = wt. of solvent; a = wt. of solute; B = M.wt. of solvent; A = M.wt. of solute;

k f = 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

* p = CST

5.
A:

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 What is Osmosis? Define Osmotic Pressure? Describe Berkely-Hartley method of determining osmotic pressure. 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.

p = CST

Where C = concentration of the solution, S = solution constant; T = temperature in K Berkely Hartely 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 KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

5 6 4

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

1.
A:

Define molarity, molality. 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 ) =

No. of moles of solute 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 ) =
2.
A:

No. of moles of solute weight of solvent ( kg )

What is meant by mole fraction? Explain. 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 Mole fraction of solvent

( c2 ) =

n2 n1 + n 2

n1 n1 + n 2 Where n1 = no. of moles solvent and n 2 = no. of moles of solute

( c1 ) =

c1 + c 2 = 1

3.
A:

Derive the equation p = CRT

* At constant temperature, the osmotic pressure ( p ) of a dilute solution is directly proportional to the concentration. p C ; where C = concentration : moles /lit 1 The volume (V) of a solution is inversely proportional to concentration: V C
[V is volume of solution in litres containing one mole of the solute]

\p
Or

1 .(1) V

pV = K

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) p T .(2)


FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

p = K T K = proportional constant
This is similar to Charles law. On combining the two equations we get,

1 ,p T V T p = S. V p
S = proportionality constant

pV = ST

S is called solution constant

1 C \p = CST or p = CRT
But

V=

4.
A:

What is meant by an ideal solution? * 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 solutesolute interactions and the solvent-solvent interactions are the same. * DH mix (Enthalpy change of mixing) is zero and

* DVmix (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. How is molar mass related to the elevation in boiling point of a solution? Give the equation. Elevation of boiling point

5.
A:

* 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) * ( DTb ) = K b m
= K b a 1000 Mb Where K b is molal elevation constant, a = wt. of solute, W = M.wt. of solvent, M = M.wt. of solute, K f =

( DTb )

6.
A:

Molal depression constant Write the equation relating depression in freezing point of a solution and the molar mass of the solute. Explain the terms. Depression in freezing point

* 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) * ( DTf ) = K f m
= Kf a 1000 M b

( DTf )

Where b = wt. of solvent; a = wt. of solute; W = M.wt. of solvent, M = M.wt. of solute;

K f = Molal depression

7.
A:

constant. What is Vant Hoffs factor I and how is it related to ' a ' in the case of binary electrolysis. Vant Hoffs Factor: The ratio of experimental values of colligative property and the calculated value of colligative property is called Vant Hoffs Factor.

\i =

Experimental values of colligative property Calculated value of colligative property

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

\i =

Calculated molar mass of solute Experimental molar mass of solute

For solute dissociation (or) Ionization If a solute on dissociation gives n ions and ' a ' is degree of ionization Total particles = 1 - a + na

1 - a na i=

= 1 + a ( n - 1)

1 + ( n - 1) a

1 i -1 a= n -1 "A n "

For solute associations If n particles of A combines to give

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

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 ) =
2.
A:

No. of moles of solute Wt. of solvent ( kg )

In a binary solution, what is mole fraction? 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.
A:

What is the equivalent weight of a salt? Equivalent weight of a salt

formula weight of the salt total charge on the cation (or) on the anion of the salt

4.
A:

How do you calculate the equivalent weight of an oxidant? 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 H3PO4 ?

5.
A:

Write the relation between the molecular weight and equivalent weight of Equivalent weight of an acid Phosphoric acid

( H3PO4 ) is a tribasic acid

Molecular weight of acid Basicity

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

Equivalent weight of

H3PO4 =

98 = 32.66 3

6.
A:

7.
A:

8.
A:

9.
A:

10.
A:

11.
A:

Define vapour pressure. 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. What prediction can you make for the relation between vapour pressure and temperature? Vapour pressure increases with increase in temperature decreases with decrease in temperature. The increase in vapour pressure with temperature is exponential but not linear. Define boiling point of a liquid in terms of its vapour pressure. The temperature at which the vapour pressure of a liquid becomes equal to the atmospheric pressure is known as boiling point of the liquid. Define osmotic pressure. 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. What is semi-permeable membrane? Give two examples. 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. What is meant by abnormal behaviour of electrolytes in colligative properties? The solutions which are non-ideal show deviation in colligative properties. Some salts under ionization (dissociation) in aqueous solutions

[ Ex : CH3COOH in C6H6 ] .
A:

[ Ex : NaCl in H 2O] where as some substances undergo association

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? The molecular weight is less, due to ionization of solute the no. of particles increases and the molecular weight decreases.

Solved Problems 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

\ Molarity ( M ) =

G 1 . GMW V ( in lit )

4 1 1 = = 0.025 M 40 4 40 \ Molarity of the solution = 0.025 M

2.
A:

Calculate the molarity of 10.6% (W/V)

Na 2 CO3 solution. Na 2 CO3 are dissolved in 100 ml of solution.

10.6% (W/V) solution means 10.6 % of

\ Weight of Na 2 CO3 dissolved = 10.6 g = (G)


Volume of the solution = 100 ml = V (in ml) Gram molecular weight of Na 2 CO3 = 106 g = (GMW) Molarity M = ? = (M) (say) then substitution the data in the formula

M=

G 1000 . we get, ( GMW ) V ( in ml )

10.6 1000 M= =1 106 100 \ Molarity of Na 2 CO3 solution = 1 M

3.
A:

Find the volume of water to be added to 250 ml of 0.05 N Normality of the given solution = 0.05 N = ( N1 ) Initial volume of the solution = 250 ml = ( V1 ml)

Na 2 CO3 solution to make it 0.01 N solution.

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

Required normality after dilution = 0.01 N = ( N 2 ) Final volume of the solution = ? = ( V2 ml) According to the formula

( 250 0.05) = ( V2 0.01)


V2 = 250 0.5 = 1250 ml 0.01

V1 N1 = V2 N 2

\ Volume of water to be added to get 0.01 Na 2 CO3 solution

= ( V2 - V1 ) = (1250 - 250 ) ml = 1000ml

4.
A:

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. Vapour pressure of the pure solvent Weight of solute a = 10 g

( P0 )

= 22.45 mm

\ Number of moles of solute = n s =

10 = 0.083 120

(since molecular weight of solute = M = 120) Weight of the solvent = b = 80 g Molecular weight of the solvent (alcohol) Number of moles of solvent = From Raoults law

( C2H5OH )

= 46.0

n0 =

P0 - Ps ns = P0 n0 + ns

80 = 1.739 46

1-

Ps n s = ( for a dilute solution ) (Q n 0 >> n s ) P0 n 0

P 0.083 \ 1 - s = 22.45 1.739 Ps 0.083 1.656 1= 22.45 1.739 1.739 1.656 \ Ps = 22.45 = 21.378 mm 1.739

5.
A:

The vapour pressure of a solution containing 108.24 g of a non-volatile solute, in 1000g of 17.354 mm Hg. The vapour pressure of Vapour pressure of

H 2 O at 20C is

H 2 O at 20C =17.54 mm Hg. Find the mol. Wt. of the substance.

H 2 O = P0 =17.54 mm Ps = 17.354 mm

Vapour pressure of solution Lowering of vapour pressure

= ( P0 - Ps )

= DP = (17.54 - 17.354 ) = 0.186 mm


Weight of the solute = a g = 108.24 g Weight of H 2 O = ' b ' g = 1000g Mol. Wt. of solute = M = ? Mol. Wt. of H 2 O = W = 18 From Raoults law,

P0 - Ps ns = P0 n0 + ns

a a W M = . (for dilute solution) a + b M b M W


FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

0.186 108.24 18 = 17.54 M 1000 108.24 18 17.54 M= = 183.73 1000 0.186

6.
A:

0.46 g of ethanol dissolved in 1000g of

H 2 O . What is the molality of the ethanol solution?

Given data: Weight of solute = 0.46 gm; Weight of solvent = 1000 gm; Molecular weight of solute = 46 Molality =

(M) =

Weight of solute 1000 molecular weight of solute weight of solvent in grams

0.46 1000 = 0.01 M 46 1000

7.
A:

Calculate the molarity and normality of a dibasic acid solution (mol. Wt. 132) having 33.0 g of the acid in 400 ml. Given data: Weight of solute = 33 gm, Volume of solution = 400 ml; Moleuclar weight of solute = 132;

Moleuclar weight = 66 2 Weight of the solute 1000 Molarity ( M ) = moleuclar weight of the solute volume of the solution in ml 33 1000 = = 0.625 M 132 400 weight of the solute 1000 Normality ( N ) = equivalent weight of the solute volume of solution in ml 33 1000 = = 1.25 N 66 400
Equivalent weight of solute

8.
A:

Calculate the normalities of the following solutions: a) 6.3 g of HNO3 in a litre solution a) Given data: Weight of solute = 6.3 gm

b) 11.2 g of KOH in a litre solution

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

Moleuclar weight = 56 Acidity weight of the solute 1 Normality (N) = equivalent weight of the solute volume of the solution in lit 11.2 1 = = 0.2N 56 1
Equivalent weight of solute

9.
A:

To convert 1 litre of 1.123 N solution of an acid into 1 N solution, how much volume water should be added? Given data:

V1 = 1000 ml, V2 = ? N1 = 1.123 N, N 2 = 1N


For dilution process, the equation is

V1 N1 = V2 N 2 1000 1.123 = V2 1

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

1000 1.123 = 1123 ml 1 Water to be added ( v 2 - v1 ) = 1123 - 1000 = 123 ml V2 =

10. Find the molarity of 3% (W/V) H 2 O2 solution. Weight of the solute 1000 A: Molarity = GMW of the solute vol. of solution ( ml )
3%

H 2 O2 solution means that 3 g of H 2 O2 present in 100 ml of solution.

Wt. of solute is = 3 g GMW of H 2 O 2 = 34 g Volume of solution = 100 ml Molarity

3 1000 30 = = 0.88 M 34 100 34

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

CHEMICAL KINETICS, EQUILIBRIUM AND IONIC EQUILIBRIUM


LONG ANSWER TYPE
1.
A. Define rate of chemical reaction and explain the factors that effect the rate of a reaction. 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 c) The temperature of 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: NaCl ( aq ) + AgNO 3( aq ) AgCl + NaNO 3( aq ) Reaction between covalent compounds : b) The concentration of the reactants d) The catalyst in the reaction.

C 2 H5 OH( l ) + CH3 COOH CH 3COOC 2 H5( l ) + H2 O( 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 10C rise of temperature for many reactions. (d) Effect of catalyst: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.

H+

2.
A.

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. 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

V [A ]

2 2

V = K [A ]

Units of rate constant K Zero order reaction

V = K [A ]
FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

V=K

V=

C moles / litre = = moles / litre sec t sec

QV = K
Units of K = moles/litre sec I order reaction

V = K [A ] K=

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

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

3.
A.

Derive the rate equation for a first order reaction? Derive the expression for half life of first order reaction. Let the first order reaction be represented as R P Let the initial concentration be a moles /dm 3 . After time t the concentration of reactant left be

( a - x ) moles /dm 3
The rate -

where x is the amount of A decomposed in time t seconds.

dc dx or at time t is proportional to the concentration of R after time t. dt dt

dx (a - x) dt dx = K (a - x) dt
On integration

dx = Kdt a - x) (

(a - x) =

dx

K.dt

- ln ( a - x ) = Kt + C............... ( 1 ) when t = 0, x = 0 - ln ( a - 0 ) = K(0) + C - ln a = C


Substitution this in equation (1)

- ln ( a - x ) = kt - ln a
Or K t = ln

a (a - x)

1 a K = ln or t a-x K= 2.303 a log t a-x

The above equation is for I order reaction. Half life of I order reaction: When x =

a ; t = t 1/2 2

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

K=

2.303 a log t a-x


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

t 1/2 =

t 1/2 = t 1/2 =

2.303 log 2 log 2 = 0.3010 K 2.303 0.3010 0.693 0.693 = t 1/2 = K K K

4.
A.

What is Le chatliers principle? Explain the same with suitable example? Le chatliers principle : 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:- N 2( g ) + 3H 2( g ) 2NH 3( g ) ; DH = -92.0 kJ


The forward reaction (formation of NH 3 ) is a exothermic reaction. According to the Le chatliers principle low temperatures favour the formation of NH 3 . 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 NH 3 . 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. The reaction is slow at low temperatures so an optimum

5.
A.

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

2SO 2( g ) + O 2( g ) 2SO 3( g ) DH = -189.0 kJ


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 V2 O 5 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 SO 2 is endothermic. So according to Lechatliers principle high temperature favours the formation of sulphur dioxide. Effect of pressure on the reaction :

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

The forward reaction leading to the formation of SO 3 involves decrease in number of molecules (2 molecules of SO 3 ) or decrease in volume. As per Le Chaltiers principle high pressure favours the formation of SO 3 . 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

(Kh )
A.

ionization constant ( K a ) and ionic product ( K w ) of water for sodium acetate solution.

Hydrolysis 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 : NH 4 Cl NH + + Cl 4

NH + React with water as it is strong conjugate acid of weak base NH 3 . 4 NH + + H 2 O NH 4 OH + H + 4


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

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

CH3 COO - + H2 O CH3 COOH + OHAs OH - > H + the pH > 7

CH3 COO - + H2 O CH3 COOH + OH-

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


K[ H
2O

] = Kh =

[CH3COOH] OH-
CH 3 COO -

CH3 COO - H+ ..(1) K a ( of acetic acid ) = [CH3COOH]


K w = H+ OH - ..(2)
H + OH - Kw = [ CH3COOH ] K a CH 3 COO - H +

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

Kh =

[CH3COOH] OH-
CH 3 COO -
Kw Ka

\Kh =

NUMERICAL PROBLEMS
1.
A. The rate constant of a first order reaction is 0.693 sec-1 , what is t 1/2 ?

t 1/2 =

0.698 for I order reaction K

K = 0.693 sec-1
t 1/2 = 0.693 = 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.

r=

d [A ] dt

0.3 - 0.15 0.15 = = 0.065 moles / litre - min 2.3 2.3

3.
A.

The value of K p if the value of K c is 2 10 -3 for H 2( g ) + I 2( g ) 2HI( g ) at 27C .


K p = K c ( RT )
Dn

K p = K c as Dn for the above reaction = 0

K p = 2 10 -3

4.
A.

How many grams of NaOH are present per litre if the pH of NaOH solution is 10 ? pH = 10; POH =4; pH + POH = 14

n = OH - = 10 -4
Normality = Given weight 1000 Equivalent weight Volume in mL

10 -4 =

x 1000 = 40 10 -4 = 4 10 -3 g 40 1000

5.
A.

What is the pH of 0.1 M NaOH?

OH- = 10 -1 POH = - log 10 -1 ; POH = 1


pH = 14 1 = 13

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

6.
A.

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

OH- = 0.05 2 = 0.1 POH = - log 10 -1 = 1 pH = 14 - 1 = 13

7.
A.

Find the pH of 10 -8 M HCl solution. As 10 -8 M HCl is much diluted solution: the concentration of H + in water should be added in the

equilibrium.

H + = 10 -8 + 10 -7 H + = 10 -7 ( 0.1 + 1 ) = 1.1 10 -7

pH = - log 1.1 10 -7 = 7 - log 1.1 = 7 - 0.0414 = 6.95

[Q log 1.1 = 0.0414]

8.
A.

The pH of HCl solution is 5.4. What is the hydrogen ion concentration?

pH = 5.4 log H+ = -5.4 or 6.6 H + = Anti log 6.6 = 3.981 10 -6 M

9.

50 mL of 0.2 N H 2 SO 4 were added to 100mL of 0.2 N HNO 3 . Then the solution is diluted to mL. What is the pH of solution?

300

A.

N=

V1N 1 + V2 N 2 500 0.2 + 100 0.2 = V1 + V2 600

N= =

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

0.2 600 = 0.13 900

pH = - log 0.13 = 1.3 10 -1 = 1 - log 1.3 = 1 - 0.113 = 0.887

10. At a certain temperature the ionic product of H 2 O is 9.55 10 -14 / lit 2 . Then what is the pH of the solution.
A.

H + = OH - = K w = 9.55 10 -14 = 3.21 10 -7

pH = - log 3.21 10 -7

= 7 - log 3.21 = 7 - 0.5051 = 6.5049

11. The K a for 0.2 M CH 3 COOH is 2 10 -5 . What is the pH? (Assume CH 3 COOH as a strong acid)
A. As we assume it to be strong acid,

H + = 0.2M = 2 10 -1
FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

pH = 1 log2 = 1 0.3010 = 0.6990

12. Find the pH of 0.5 M NH 4 OH solution. K b for NH 4 OH is 2 10 -5 . (Assume NH 4 OH as strong base)


A.

OH- = 0.5M

POH = - log 0.5 = 5 10 -1 = 1 - log 5 = 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.

N = H+ =

Given wt. 1000 3.65 1000 = 0.4 = Eq.wt. V in mL 36.5 250

pH = - log H+ = - log 0.4 = 4 10 -1 = 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
CH 3 COOH = 4.8
A.

pH = pKa + log

[salt ] [acid]

[salt ] = 1 mole / lit ; [acetic] = 0.1 mole / lit


pH = 4.8 + log 0.1 = 4.8 + log 10 -1 pH = 4.8 + 1 = 5.8 1

15. 20 mL of 0.2 M CH 3 COOH and 20 mL of 0.4 M sodium acetate were mixed together to form a buffer. What
is the pH if pKa of CH 3 COOH is 4.8 A.

pH = pKa + log

[salt ] [acid]

20 0.4 40 = 4.8 + log 2 = 4.8 + 0.3010 = 5.1 pH = 4.8 + log 20 0.2 40

16. Find the hydrolysis constant of 0.1 M sodium acetate Ka of CH 3 COOH = 2 10 -5


A.

Kh =

Kw Ka

K w = 1 10 -14 =

1 2 10
-5

10 -14 ; K a = 2 10 5

= 0.5 10 -9 or 5 10 -10

17. What is the pH of a buffer formed by mixing 20 mL of 0.1 M NH 4 Cl and 2 mL of 0.1 M NH 3 ? pKb for
NH 4 OH = 4.8
A.

POH = pK b + log

[salt ] [ base ]

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

20 0.1 40 = 4.8 + log 1 = 4.8 = pK b + log 20 0.1 40

pH = 14 - 4.8 = 9.2

18. The hydrolysis constant for NH 4 Cl solution is 0.5 10 -9 . Then what is the dissociation constant of the
base? A.

Kh =

Kw 1 10 -14 0.5 10 -9 = Kb Kb

Kb =

1 10 -14 0.5 10
-9

1 5 10
-10

10 -14 = 0.2 10 -4

19. The dissociation constant of NH 4 OH and CH 3 COOH are 2 10 -5 and 1.8 10 -5 respectively. Find the
hydrolysis constant of ammonium acetate. A.

Kh =

Kw 1 10 -14 1 10 -14 = = = 0.2 10 -4 = 2 10 -5 K a K b 2 10 -5 1.8 10 -5 3.6 10 -10

20. 50 mL of 1 M CH 3 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 CH 3 COOH = 4.8)

A.

50 0.5 [salt ] = 4.8 log 100 = 4.8 log 1 = 4.8 pH = pKa + log 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.

H + = 50 1 - 50 0.1 = 50 - 5 = 45 = 0.45 = 4.5 10 -1 100 100

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; H + = 10 -5

H + = c.a

10 -5 = 0.005 a
= 10 -5 5 10
-3

: 0.2 10 -2 or 0.2%

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

AB A + + B K sp = S S = S 2

S = K sp = 10 -10 = 10 -5 moles / lit

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

24. The solubility of A 2 B = 2 10 -3 moles / lit. What is solubility product?


A.

K sp = ( 2S ) S = 4S 2
= 4 2 10 -3

= 8 10 -9

SHORT ANSWER TYPE


1.
A. Define and explain the terms with suitable examples order and molecularity of a reaction. Order: The order of the reaction is sum of the powers of the concentration terms in the rate equation of the reaction. Ex: 1. N 2 O 5( g ) N 2 O 4( g ) +

1 O 2 2( g )

rate = K [ N 2 O 5 ] Hence I order.


2. 2N 2 O( g ) 2N 2( g ) + O 2( g )

rate = K [ N 2 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+

CH 3 COOC 2 H 5 + H 2 O CH 3 COOH + C 2 H 5 OH
As water is taken in excess it will be an example of pseudo unimolecular reaction.

2.
A.

Describe any two methods for the determination of order of reaction. The methods used for the determination of the order of reaction include: (1) integral equation method or trial and error method (3) Vant Hoff differential method (2) half-time 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 ) ; k = I order k =

[ R ]0 - [R ]t
t

[R ]0 2.303 a 2.303 log or log t a-x t [ R ]t

(2) Half-time ( t 1/2 ) 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 ( t 1/2 ) is inversely proportional to a and n is the order of the reaction.

( n -1) where a is the initial concentration of the reactant

t 1/2

1 a
n -1

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

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.

t 1/2 t 1/2

n -1 a = a

3.
A.

What are the main postulates of simple collision theory of reaction state? (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.
A.

What are equilibrium processes? chemical processes.

Explain with examples equilibrium physical processes and equilibrium

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 physical 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.

a - su lphur b - sulphur
Equilibrium chemical 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: CaCO 3( s ) CaO( s ) + CO 2( g )

5.
A.

What is meant by dynamic equilibrium? Explain with suitable example. 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 KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

Ex: CaCO 3( s ) CaO( s ) + CO 2( g )

6.
A.

Give the characteristics of chemical equilibrium. (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.
A.

Explain K c and K p and derive the relation between them?

K c : Equilibrium constant taking the molar concentration of different substance in a reaction.

K p : The equilibrium constant taking the partial pressures of the reacting substances which are in gaseous
state.

Ex: aA + bB cC + dD

[ C ]c .[D ]d Kc = [A ]a [B]b

Kp =

c d PC PD a b PA PB

Derivation of relation between K p and K c From ideal gas equation: PV = nRT ; P =

n RT V

n = concentration V
c d PC PD

P = CRT .(1)

Kp =

a b PA PB

.(2)

Substituting the value of P in equation 2 we get,

[ CRT ]c [ DRT ]d ; K = [ C ]c [D ]d .RT ( c+d )-( a+ b) Kp = p [ART ]a [ BRT ]b [A ]a [ B]b


K p = K c ( RT )
Dn

[ C ]c [D ]d ; QKc = [A ]a [ B]b

8.
A.

Explain the concepts of Bronsted acids and Bronsted bases. Illustrate the same with example. Bronsted Acid: A substance which loses or donate a proton is called an acid. Ex: HCl, H 3 PO 4 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 KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

HCl + H2 O H3 O + + Cl Water accepts a proton from the HCl hence acts as a base.

NH3 + H2 O NH+ + Cl 4
When ammonia is dissolved in water, NH 3 accepts a proton from water. Water acts as acid. In the above two examples H 3O + and NH + are Bronsted acids. Cl - and OH - are Bronsted bases. 4

9.
A.

What are conjugate acids an conjugate bases? Give 4 examples. 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.

HCl + H2 O H3 O + + Cl HCl and Cl - are the conjugate pair, H 2 O and H 3O + are the conjugate pairs in the above example.

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

( H2 O )

has its conjugate acid

( H3O + )
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 + , BF3 , SnCl 4 Lewis base:- A substance that can donate a lone pair of electrons to form a coordinate covalent bond with the acceptor. Ex: H 2 O , NH 3 , lignads in complex compounds. Acid-Base reaction: An acid base reaction should involve formation of coordinate covalent bond
F H | | F - B N - H F - B + : N- H | | | | F F H H F
|

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 ( K a ) 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 Initial Conc C

+ H + X -

After time ( t ) C ( 1 - a )

Ca

Ca

If a is the degree of dissociation


FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

H + X - Ca.Ca Ca 2 Ka = = Ka = C (1 - a) (1 - a) [HX ]
Where K a is dissociation constant for weak acid HX For bases; K b =

Ca 2 (1 - 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.

1 pH = - log 10 H + = log 10 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: CH 3 COOH + CH 3COONa ; NH 4 OH + NH 4 Cl

VERY SHORT ANSWER TYPE


1.
A. Define rate of reaction. Rate of reaction is defined as change in the molar concentration of reactants or products per unit time. What is rate law? 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.

2.
A.

3.
A.

Define order of a reaction. The order of a reaction is the sum of the powers of the concentration terms in the rate equation of the reaction.

4.
A.

Name two first order reactions you know? 1. H 2 O 2( aq ) H 2 O( l ) + What is half life? 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.

1 1 1 O 2( g ) ; rate = K [ H2 O 2 ] 2. N 2 O 5( g ) N 2 O 4( g ) + O 2( g ) ; rate = K [ N 2 O 5 ] 2 2

5.
A.

6.
A.

What is zero order reaction? Reactions in which the rate of reaction is independent of the concentration of the reacting substances is called zero order reactions.

7.
A.

Give the integrated form of the rate equilibrium for first order reaction.

K=

[ R ]0 2.303 a 2.303 log = log t t (a - x) [ R ]t

8.
A.

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

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

9.
A.

State law of mass action. 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 K p and K c .


A.

K p = K c ( RT )

Dn

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


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. NH 3

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:

H + ,BF3

14. Define ionic product of water.


A. The ionic product of water, K w 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.

( 1) CH 3COOH + CH 3COONa - acid buffer

( 2 ) NH 4 OH + NH 4 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.

Cl - + H 2 O HCl + OH HCl being strong electrolyte undergo complete ionization. Hence Cl - do not undergo hydrolysis.

19. Is the pH of aqueous solution of NH 4 Cl greater or smaller than 7? Why?


A.

NH 4 Cl NH + + Cl 4 NH + being strong undergo hydrolysis and the solution is acidic. 4 NH + + H 2 O NH 4 OH + H + 4


Hence pH is less than 7.

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

20. (a) For the hydrolysis of ammonium acetate, write the relation between K h ,K a ,K b and K w .
(b) What is solubility product of salt? A. (a) Ammonium acetate ( CH 3COONH 4 ) is 9 salt of weak acid and weak base. K h =

Kw K a .K b

(b) CH 3 COONH 4 CH 3 COO - + NH + 4


CH3 COO - = NH + 4
K sp = S S = S 2
Very Short answer Questions

1.
A.

Define rate of reaction. Rate of reaction is defined as change in the molar concentration of reactants or products per unit time. What is rate law? 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.

2.
A.

3.
A.

Define order of a reaction. The order of a reaction is the sum of the powers of the concentration terms in the rate equation of the reaction.

4.
A.

Name two first order reactions you know? 1. H 2 O 2( aq ) H 2 O( l ) + What is half life? 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.

1 1 1 O 2( g ) ; rate = K [ H2 O 2 ] 2. N 2 O 5( g ) N 2 O 4( g ) + O 2( g ) ; rate = K [ N 2 O 5 ] 2 2

5.
A.

6.
A.

What is zero order reaction? Reactions in which the rate of reaction is independent of the concentration of the reacting substances is called zero order reactions.

7.
A.

Give the integrated form of the rate equilibrium for first order reaction.

K=

[ R ]0 2.303 a 2.303 log = log t t (a - x) [ R ]t

8.
A.

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

9.
A.

State law of mass action. 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 K p and K c .


A.

K p = K c ( RT )

Dn

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

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


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. NH 3

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:

H ,BF3

14. Define ionic product of water.


A. The ionic product of water, K w 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.

( 1) CH 3COOH + CH 3COONa - acid buffer

( 2 ) NH 4 OH + NH 4 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?
Cl - + H 2 O HCl + OH HCl being strong electrolyte undergo complete ionization. Hence Cl - do not undergo hydrolysis.

19. Is the pH of aqueous solution of NH 4 Cl greater or smaller than 7? Why?


A.

NH 4 Cl NH + + Cl 4 NH + being strong undergo hydrolysis and the solution is acidic. 4 NH + + H 2 O NH 4 OH + H + 4


Hence pH is less than 7.

20. (a) For the hydrolysis of ammonium acetate, write the relation between K h ,K a ,K b and K w .
(b) What is solubility product of salt? A. (a) Ammonium acetate ( CH 3COONH 4 ) is 9 salt of weak acid and weak base. K h =

Kw K a .K b

(b) CH 3 COONH 4 CH 3 COO - + NH + 4


CH3 COO - = NH + 4
K sp = S S = S 2

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

SOLID STATE
1.
A: Write short notes on the following giving suitable examples. a) Schottky defect b) Frenkel defect 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
-

BBA+

A+
B
-

BA+ BA+

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+

A+ B-

BA

A+ B-

BA+ B-

Interstitial site

2.
A:

This defect occurs mainly in 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 What do you know about amorphous substances? Discuss. * 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

A+

B-

A+

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

3.
A:

Amorphous solids can be moulded or blown into articles of different shapes. Amorphous solids are used in domestic constructions and appliances like photovoltaic cells. How many types of semi conductors are known? Explain the influence of doping on the conductivity of crystalline solids. A) Semiconductors: The solids whose conductivity is in order of These are two types:

* *

10-6 to 104 ohm-1cm-1 are known as semiconductors.

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

(i)

4.
A:

Intrinsic semiconductors: 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 What do you mean by imperfection in solids? Write an essay on crystal defects. 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
-

BBA+

A+
B
-

BA B+

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 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+

A+

A+
B-

BA B-

A+
B-

BA+ B-

Interstitial site

This defect occurs mainly in 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 KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

A+

A+

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

5.

Derive Braggs equation. Or Derive Braggs equation for X-rays of wavelength


2nd ray 1st ray

(l)

and a diffraction angle

( q)

for an nth order reflection.

First layer Second layer Third layer


A:

C q q D B

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 = nl, here n = 1, 2,3,... CB CB From the figure, in DABC, sin q = = AB d \ CB = d sin q BD BD In DABD, sin q = = AB d \ BD = d sin q CB + BD = d sin q + d sin q = 2d sin q \ nl = 2d sin 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. Draw the differences between Schottky and Frenkel defects. Schottky defect i) ii) iii) iv) Schottky defect is due to absence of ions in the lattice sites This defect arises in the compounds of high coordination number This defect arises in the compounds where the cation and anion sizes are similar Due to this defect density of crystal decreases Ex: NaCl, CsCl i) ii) iii) iv) Frenkel defect Frenkel defect is due to missing of an ion from lattice site and occupying in the interstitial space This defect arises in the compounds of low coordination number This defect arises in the compound where cation size is small and anion size is large Due to this defect density of crystal does not changes: Ex: AgCl, AgI

6.
A:

SAQ

1.
A:

Giving suitable examples, explain the following terms. a) Paramagnetic substances b) Feromagnetic substances c) Piezo electric effect a) Paramagnetic 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:

O2 , NO, Na atoms.

They lose their magnetism when the applied magnetic fields are removed.

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

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)

2.
A:

Piezo electric 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. Write the differences between crystalline and amorphous solids. Crystalline solids i) ii) iii) iv) v) They have definite and regular geometrical shape They have sharp melting point They are rigid and incompressible They have long range orders of crystals X-rays are diffracted i) ii) iii) iv) v) Amorphous solids They do not have any definite geometrical shape The do not have sharp melting point They are not very rigid and compressibility is very less They have short range orders 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:

V2 O3 , NiO

4.
A:

What are Ferrimagnetic substance? Give an example. 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:

Fe3O 4

5.
A:

How the purity of the metal can be estimated? Purity of the metal can be estimated by a measurement of the resistance of the metal, as resistance ratio

r300K . r4.2K

6.
A:

What will be the magnitude of the vapour pressure of these ionic crystals? At ordinary temperatures the vapour pressure is very low. Therefore, the heats of vapourization are very high. Examples of ionic crystals: NaCl, MgO,

CaCl2 , KNO3 , Na 2SO 4 , CaCO3

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

7.
A:

8.
A:

9.
A:

10.
A:

Which group and period of the periodic table does polonium occupy? VIA group or 16th group of the long form of the periodic table and 6th period. Do amorphous solids have unit cells in them? Recent investigations report that the amorphous solids contains minute crystals but for all purposes apparently they do not have unit cells or crystalline structures. The diffracted X-rays from copper sulphate crystal are allowed to fall on a photographic plate. What happens to the photographic plate? The photographic plate gets alternate bright and dark patched that result from the constructive and destructive interference of the diffracted rays. Calculated contributions of lattice points in body centered cubic lattice arrangement. Contributions from 8 corners =

1 8 =1 atom 8

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 A 0 and 2.7 A 0 ,
respectively. Calculate the ratio of densities of f.c.c. and b.c.c. A: Density

( r ) Z and r

1 a3

r1 Z1 a 3 = 2 3 r 2 Z 2 a1

Here in f.c.c. density = Total number of atoms

r1 In b.c.c. density = r2

( Z1 ) = 4 Length of the unit cell ( a1 ) = 3.6 A 0


By substitution the values

( Z2 ) = 2 Length of the unit cell ( a 2 ) = 2.7 A 0


Total number of atoms

r1 ( 2.7 ) = 27 4 = r2 ( 3.6 )3 2 32
3

\ The ratio of densities of f.c.c. and b.c.c. is

27 32

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

ELECTROCHEMISTRY VERY SHORT ANSWER TYPE


1.
A. What is electrolysis? Illustrate. 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 Cl 2 at anode.

2.
A.

What products are obtained in the electrolysis of fused KCl and aqueous KCl between platinum electrodes. Fused KCl: 2KCl 2K + + 2Cl At cathode (reduction ): 2K + + 2e - 2K At anode (oxidation): 2Cl - Cl 2 + 2e Aqueous KCl:

2KCl 2K + + 2Cl - ;
2H + + 2e - H 2 - ;
At Anode: (oxidation)

2H 2 O 2H + + 2OH -

2K + + 2OH- 2KOH

2Cl - Cl 2 + 2e -

3.
A.

State Faradays First 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.

4.
A.

Write the cell reaction for a : Ni|Ni ++ ||Cu ++ |Cu , b: Cu|Cu + || Cl 2 |Cl -

1 2

+2 At LHS electrode oxidation half reaction Ni Ni ( aq ) + 2e ++ At RHS electrode reduction half reaction Cu aq + 2e - Cu
++ Cell Reaction Ni + Cu( aq ) Ni +2 + Cu

5.
A.

Calculate the E of Cu ++ ( 0.1M )|Cu electrode and Cl - ( 0.1M )| Cl 2 ,Pt electrode

1 2

Eo ++ /Cu = 0.33V ; Eo 1 Cu
2

Cl 2 /Cl -

= +1.36V

E cell = E 1
2

Cl 2 /Cl

- Eo ++ /Cu = 1.36 - ( +0.33 ) = 1.03V Cu

6.
A.

Write the equation for specific conductance. Specific conductance K = C

l l where C = conductance, = cell constant a a

units =

ohm -1 cm cm 2

= ohm -1 cm -1 ( cgs ) = ohm -1m -1 ( SI ) = Sm -1

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

7.
A.

Give the equation for equivalent conductance. Equivalent conductance ( L ) =

Specific conductance 1000 k 1000 = Normality N

Where k = specific conductance , N = Normality

Units =

ohm -1 cm 1000 cm 3 cm equiv


2

= ohm -1 cm 2 equiv -1 ( in CGS )

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

8.
A.

What is 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.

SHORT ANSWER TYPE


1.
A. State Faradays Laws of electrolysis. Faradays First 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 = Ct
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.

m 1 E1 = m 2 E2
Where m 1 and m 2 are masses of the substances deposited at electrodes.

E1 and E 2 are chemical equivalents of the substances which are deposited at electrode.

2.
A.

What are galvanic cells? Give two examples. 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) Zn ( s ) + CuSO 4( aq ) ZnSO 4( aq ) + Cu( s )
++ ++ Representation of the cell: Zn|Zn ( aq ) ||Cu( aq ) |Cu

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


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

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

3.
A.

What is single electrode potential and write the Nernst equation. 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:

E = E +

0.059 log C where n is number of electrons transferred in the electrode reaction n 0.059 log C n

(2) For anion electrodes:

E = E -

4.
A.

What is equivalent conductance? 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 ( L ) =

Specific conductance 1000 k 1000 = Normality N

Where k = specific conductance , N = Normality

Units =

ohm -1 cm 1000 cm 3 cm equiv


2

= ohm -1 cm 2 equiv -1 ( in CGS )

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

5.
A.

What is Kohlrausch law? The law states that the equivalent conductance

( La )

at infinite dilution of an electrolyte is equal to the

+ algebraic sum total of the equivalent conductances or mobilities of the cation l 0

( ) and the anion ( l0- ) of the

+ electrolyte at infinite dilution L 0 = l 0 + l 0 ( ions )

( dilution. These are proportional to ionic mobilities ( u + ,u - )


+ + l 0 u0 ; l 0 u0

+ The equivalent conductance of the ions at infinite dilution l 0 , l 0

) are known as ionic conductance at infinite

or
+ + l 0 = k u0 ; l 0 = k u0

Where k is proportionality constant. Its value is found to be 96,500 Faradays.


+ u0 = + l0 lor u 0 = 0 F F

6.
A.

What is lead accumulator? 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 KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

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 PbO 2 as cathode. The charged cell is represented simply as Pb|H 2 SO 4 |PbO 2 . At LHS electrode:

Pb Pb +2 + 2e - ( oxidation )

Pb+2 + SO -2 PbSO 4 4
At RHS electrode:

PbO 2 + 2H2 O Pb+4 + 4OH-

Pb+4 + 2e - Pb +2
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.
A.

What is a fuel cell? 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.
A.

What is corrosion? 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.

M M + n + ne Corrosion can be defined in electrochemical terms as anodic dissolution of the metal.

9.
A.

What is passivity? 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 KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

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.

NUMERICALS
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 0.14807 W-1m -1 . Calculate the cell constant. A.

l a l a

R=S

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

1 1 1 l = where = cell constant l R S a a C = k 1 l or C = k l a a

1 l = 0.14807 702 a

l = 0.14807 702 = 103.9 m -1 a

2.
A.

The specific conductance of 0.1 N KCl is 0.14870 W-1m -1 . Calculate equivalent conductance. Equivalent conductance ( L ) = If k is given in ohm -1m -1 L =

Specific conductance 1000 k 1000 = (if k is given ohm -1 cm -1 ) N N k 0.14870 = = 1.487 ohm -1m 2 eq -1 N 0.1

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.

Eo ++ /Cu = 0.33V Cu
o EAg ++ /Ag = 0.8V

++ + Cell is Cu|Cu( aq ) |Ag ( aq ) |Ag


o o E = EAg - ENi = 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 Zn +2 ions?

A.

E = E +

0.059 0.059 log Zn +2 = -0.77 + log [ 0.01] = -0.77 - 0.05 = -0.82V . n 2

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

THERMODYNAMICS VERY SHORT ANSWER TYPE


1.
A. Explain system and surroundings. 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.
A.

Name three intensive properties. Density, surface tension, viscocity. Name three extensive properties. Mass, volume, internal energy Explain enthalpy. Enthalpy is the amount of heat exchanged by a system with its surroundings at constant pressure and temperature.

3.
A.

4.
A.

5.
A.

What is heat capacity? Explain. Heat capacity (C) of a substance is defined as the amount of heat required to raise its temperature through one degree.

6.
A.

What is thermochemical equation? Give one example. The chemical equation in which heat change accompanying a reaction is also numerically specified with proper sign by DH or DE 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.

C( graphite )+ O 2( g ) CO 2( g ) ; DH = -393.5 kJ

7.
A.

State Hesss law? 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.
A.

What is Gibbs energy? The thermodynamic function which involves both enthalpy (H) and entropy(S) functions.

DG = DH - TS

9.
A.

What is Gibbs equation?

DG = DH - TDS
Where G is Gibbs energy or Gibbs function, H is Enthalpy, S is entropy

SHORT ANSWER TYPE


1.
A. State first law of thermodynamics or state and explain I law of thermodynamics. 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

DE = Q - W or Q = DE + W
For infinitesimally small changes q = dE + W

DE change in internal energy


Q heat content of the system W work done by the system

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

2.
A.

Give the mathematical formulation of I law of thermodynamics. Let a system in state A, has internal energy EA 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 EB The increase in internal energy DE of the system is given by the equation DE = EB - EA If W is the workdone by the system in the process the net gain of energy

( Q - W ) must

be equal to

DEa from first law. The increase in the internal energy of the system therefore is

DE = ( EB - EA ) = Q - W or Q = DE + W
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.
A.

State second law of thermodynamics. 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.
A.

What is entropy? 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 DS between any two states is given

q by the equation DS = rev T


q rev = Heat absorbed by the system isothermally and reversibly at T during the state change.

5.
A.

State third law of thermodynamics. The entropy of a pure and perfectly crystalline substance is zero at the absolute zero temperature ( -273C ) . 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.
TC 0

ST =

.dT

Entropy(S) of a substance at any temperature is calculated if the temperature dependence of C P is known in evaluating the absolute value of entropy of any substance.

6.
A.

State and explain the significance of second law. 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 KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

(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.
A.

Explain the terms entropy. Gibbs energy. 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 DS between any two states is given

q by the equation DS = rev T


q rev = 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:

DG = DH - TDS

Where G is Gibbs energy or Gibbs function, H is Enthalpy, S is entropy.

8.
A.

What are the criteria for the spontaneous nature of a chemical reaction? Give examples. 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

( DS = positive ) .
DS total = DS system + DS surrounding > 0
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.
A.

State and explain enthalpy and internal energy terms of substance. 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 during a chemical change can be experimentally and directly determined.

( DH )

DH = Hproducts - Hreactants
Reaction in which DH value is negative are called exothermic reactions and those which have DH 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 DH and DE related for a gaseous equilibrium reaction?


CaCO 3( s ) CaO( s ) + CO 2( g )
A.

What is

( DH - DE )

for

DH = DE + PDV or DH = DE + DnRT

DH is change in enthalpy, DE is change in internal energy


FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

CaCO 3( s ) CaO( s ) + CO 2( g )
Dn = Gaseous products Gaseous reactants = 1 DH - DE = DnRT or DH = DE + RT

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.

DH f = - ve for exothermic compounds

DH f = + ve 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:
Strongacid

HCl ( aq ) + NaOH( aq ) NaCl ( aq ) + H 2 O( l ) ;


Strong base

DH = -57.3 kJ DH = -51.46 kJ

Strongacid

HCl ( aq ) + NH 4 OH( aq ) NH 4 Cl ( aq ) + H 2 O( l ) ;
Strong base

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: CO 2 is obtained from graphite and oxygen in two different path ways. I path : C( graphite ) + O 2( g ) CO 2( g ) ; DH = -393.5 kJ II path: C( graphite ) + O 2( g ) CO( g ) ; DH = -110.5 kJ 2

1 CO + O 2( g ) CO 2( g ) ; DH = -283.02 2
Total DH = - -110.5 + ( -283.02 ) = -393.52 kJ The two DH values are same.

14. What are C p and C v ?


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 C v gives the measure of the change of internal energy (E) of a system with temperature.

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

H Cp = T p
FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

SURFACE CHEMISTRY VERY SHORT ANSWER TYPE


1.
A. What is adsorption? Concentration or accumulation of a substance on the surface of a solid or a liquid is known as adsorption. What is absorption? The process of concentration of molecules of gas or liquid on the surface of the solid and throughout the solid is called absorption.

2.
A.

3.
A.

Give the mathematical equation relating the pressure (P) and the extent of adsorption (x/m) of gas on a metal.

x P 1/n m x = KP 1/n at constant temperature m


Where x is amount of gas adsorbed, m is mass of adsorbent, P is adsorption equilibrium pressure K and n are adsorption constants.

4.
A.

What is physisorption? 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 H 2 or O 2 on charcoal.

5.
A.

What is the chemisorption? 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: H 2 gas passed over Ni surface

6.
A.

What is catalyst? The substance which increases rate of a reaction to which it is added without itself undergoing chemical change is called catalyst.

7.
A.

What is negative catalyst? A catalyst which decreases the rate of reaction is called negative catalyst. What is homogenous catalysis? Give example. If the catalyst and the reactants are in the same phase it is called homogeneous catalysis. Ex: 2SO 2( g ) + O 2( g ) 2SO 3( g ) The reactants and the catalyst are in same phase.
NO( g )

8.
A.

9.
A.

What is heterogeneous catalysis? If the catalyst and the reactants are in different phase it is called heterogeneous catalysis. Ex: 2SO 2( g ) + O 2( g ) 2SO 3( g )
Pt( s )

10. What are the catalyst used in the reactions?


N 2( g ) + 3H2( g ) 2NH 3( g ) and 2SO 2( g ) + O 2( g ) 2SO 3( g )
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 KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

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 KMnO 4 in acidic medium. The Mn +2 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 KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

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 ANSWER TYPE


1.
A. What is adsorption? Explain with two examples. 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 CO 2 , SO 2 , Cl 2 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.
A.

What is absorption? Explain with two examples? 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.
A.

What is physical adsorption? Give example. 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 H 2 or O 2 on charcoal.

4.
A.

What is chemical adsorption? Give example. 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). chemisorption. It is a strong force and irreversible. Ex: Adsorption on Ni metal surface, H 2 molecules are held by valence forces on the surface. The adsorption is called chemical adsorption or

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

5.

Write any forces differences between physical and chemical adsorption. A. (1) Property Nature of adsorption Physical adsorption Held by Physical forces or van der Waals forces hence weak (2) Reversibility process (3) Temperature adsorption pronounced (4) Effect of change in Decreases with rise in temperature at is which more Low temperature (below the boiling point of the adsorbate gas) High temperature (generally of adsorption Reversible and occurs rapidly Held Chemical adsorption by chemical bond

formation, hence strong Irreversible and occurs slowly

above the boiling point of the adsorbate gas Increases temperature with rise in

temperature

6.
A.

Give the factors that effect adsorption of gases on metals. 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 increases with increase m

in surface area of adsorbent. Gases like H 2 ,N 2 ,CO,NH 3 , SO 2 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. SO 2 ,NH 3 ,HCl,CO 2 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.
A.

What is colloidal solution? Give example. 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

1mm - 1m . It is heterogeneous binary system. (1 millimicon = 10 -9 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. (1) (2) (3) (4) Property Particle size External appearance Nature of system Tyndall effect True solution Colloidal solution

< 1mm
Very clear Homogeneous Not shown

1mm - 1m
Generally clear or opaque. Heterogeneous Shown

FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

9.
A.

What are lyophilic colloids and lyophobic colloids? 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 Catalyst

CO + 3H2 CH 4 + H2 O CO + H2 HCHO
Cu Catalyst

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 catalysis: In both the reactants and catalyst are present in same phase then it is called homogeneous catalysis.
FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

Ex:

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

NO

( ) 2CO ( g ) + O 2( g ) 2CO 2( g )
g

NO

Heterogeneous catalysis: If the reactant and catalyst are present in different phases it is called heterogeneous catalysis.
( s) 2SO 2( g ) + O 2( g ) 2SO 3( g )
Pt

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) 2KMnO 4 + 5H 2 C 2 O 4 + 3H 2 SO 4 2MnSO 4 + K 2 SO 4 + 8H 2 O + 10CO 2

MnSO 4 formed acts as autocatalyst.


(2) 2AsH 3 2As + 3H 2 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 HardySchulze 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.

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

K + < Ba +2 < Al +3

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.

Wwish you all the bestW


FIITJEE KUKATPALLY CENTRE: # 22-97, Plot No.1, Opp. Patel Kunta Huda Park, Vijaynagar Colony, Hyderabad - 500 072. Ph.: 040-64601123

Regd. Off.: 29A, ICES House, Kalu Sarai, Sarvapriya Vihar, New Delhi - 110 016. Ph: 011 - 2651 5949, 2656 9493, Fax: 2651 3942

Você também pode gostar