KENDRIYA VIDYALAYA SANGATHAN

RAIPUR REGION

STUDY MATERIAL

(CHEMISTRY)
CLASS XII

2014-15

INDEX
SL.NO

PAGE NO.
Chemistry XII

1.

Solid State

4-10

2.

Solution

11-16

3.

Electrochemistry

17-26

4.

Chemical Kinetics

27-40

5.

Surface chemistry

41-49

6.

Gen Principles & process of isolation

of element

50-57

7.

The p-block elements

58-77

8.

The d&f block element

78-86

9.

Coordination Compounds

87-104

10.

Haloalkanes and Haloarenes

105-115

11.

Alcohols, Phenols and Ethers

116-149

12.

Aldehdes, Ketons and Carboxylic

acids

150-187

13.

Amines

188-211

14.

Biomolecules

212-222

15.

Polymers

223-231

16.

Chemistry in Every Day life

231-246
3

SOLID STATE
KEY CONCEPTS
As we know that matter exists in different physical states under different conditions
of temperature and pressure. For example solid state, liquid , gases , plasma and BEC etc.
Introduction:
1. The state of matter whose m.p. is above room temp is found in solid state. Their constituent
particles are held strongly.
2. Type of solid(Based on arrangement of particle) : 1 : Crystalline 2 :Amorphous
3. Crystalline solids have regular arrangement of constituent particles throughout, melting
point is sharp, anisotropic in nature and give clear cut cleavage.
4. Amorphous solids have no regular arrangement, range of m.p., isotropic in nature. They do
not exhibit cleavage property.
5. Amorphous silica is used in photovoltaic cells(Device for converting light into electricity,
solar panels etc. ).
6. Space lattice is the regular 3D arrangement of constituent particles in the crystalline solid.
7. Smallest repeating unit in a space lattice is called unit cell.
8. There are 4 types of unit cells, 7 crystal systems and 14 bravais lattices.
9. Types of unit cell
No. of atoms per unit cell
i. Simple cubic unit cell
8 x1/8 =1
ii. FCC (Face centered cubic)
8 x 1/8 + 6 x1/2=4
iii. BCC (Body centered cubic)
8 x 1/8 + 1 x1=2
10. Hexagonal close packing and cubic close packing have only 74% of the available space
occupied.
11. Packing efficiency =volume occupied by spheres (Particles)/volume of unit cell x 100
12. For simple cubic unit cell the p.f.=1x4/3 x r3/8 x r3 x 100 =52.4 %
13. The packing efficiency in fcc =4 x 4/3 x r3/16 x 2 1/2 r3 x 100 =74 %
14. The packing efficiency in bcc =2 x 4/3 x r3/64 x 33/2 r3 x 100 =68 %
15. The packing efficiency in hcp =74%
16. Packing efficiency in bcc arrangement in 68% and simple cubic unit cell is 52.4%
17. Unoccupied spaces in solids are called interstitial voids or interstitial sites.
18. Two important interstitial voids are (I). Tetrahedral void and (II). Octahedral void.
19. Radius ratio is the ratio of radius of Cation to the radius of anion.
a. For tetrahedral arrangement(Cordination Number=4), radius ratio=0.225-0.414
For octahedral arrangement(Cordination Number=6), radius ratio=0.414-0.732
20. No. of tetrahedral void=2 x N (N=No. of particles)
21. No. of octahedral void=N
22. Formula of a compound depends upon arrangement of constituent of particles.
23. Density of unit cell
= Z x M/a3 x NA
=density, M=Molar mass, a=side of unit cell, NA=6.022 x 1023
4

24. The relationship between edge length and radius of atom and interatomic or interionic
distance for different types of unit is different as given below
a. Simple cubic unit cell
a=2R
b. f c c
a=4R/
c. b c c
a=4R/ (where R = Radius of sphere)
25. Imperfection is the ir-regularty in the arrangement of constituent particles.
26. Point defect or Atomic defect-> it is the deviation from ideal arrangement of constituent
atom. Point defects are two types (a) Vacancy defect (b) Interstitial defect
27. Vacancy defect lowers the density and
28. Interstitial defect increases the density of crystal.
29. Point defects in the ionic crystal may be classified as:
a. Stoichiometric defect (Ratio of cation and anion is same).
b. Non Stoichiometric defect (Ratio of cation and anion gets disturbed).
c. Impurity defects (due to presence of some impurity ions at the lattice sites)
30. Schottky defect lowers the density of crystal it arises due to missing of equal no. of cations
of anions from lattice sites e.g. NaCl.
31. Frenkel defect is the combination of vacancy and interstitial defects. Cations leave their
actual lattice sites and come to occupy the interstitial spaces. Density remains the same eg.
AgCl, AgBr, ZnS.
32. Non stoichiometric defect
a. Metal excess defect due to anion vacancy.
b. Metal excess defect due to presence of interstitial cation.
c. Metal deficiency due to absence of cation.
SHORT ANSWER QUESTIONS
Q1. What do you mean by paramagnetic substance?
Q2. Which substance exhibit schottky and Frenkel both defects.
Q3. Name a salt which is added to AgCl so as to produce cation vacancies.
Q4. Why Frenkel defects not found in pure Alkali metal halide?
Q5. What is the use of amorphous silica?
Q6. Analysis shows that a metal oxide has the empirical formula M0.98O. Calculate the percentage of
M2+ and M3+ ions in the crystal.
Q9. What is F centre?
Q10. What makes Alkali metal halides sometimes coloured, which are otherwise colourless?
Very Short Answers(1 mark) :
1. How does amorphous silica differ from quartz?
2. Which point defect lowers the density of a crystal?
3. Why glass is called supper cooled liquids?
4. Some of the very old glass objects appear slightly milky instead of being transparent why?
5. What is anisotropy?
6. What is the coordination number of atoms?
a) in fcc structure b) in bcc structure
5

7. How many lattice points are there in one unit cell of a) fcc b) bcc c) simple cubic
8. What are the co-ordination numbers of octahedral voids and tetrahedral voids?
9. Why common salt is sometimes yellow instead of being of being pure white?
Due to the presence of electrons in some lattice sites in place of anions these sites act as F-centers.
These electrons when excited impart color to the crystal.
10. A compound is formed by two elements X and Y. The element Y forms ccp and atoms of X occupy
octahedral voids. What is formula of the compound?
No. of Y atoms be N
No. of octahedral voids N
No. of X atoms be =N
Formula XY

HOTS Very Short Answers:

1. Define F - centers.
2. What type of stoichiometric defect is shown by
a. ZnS
b. AgBr
3. What are the differences between Frenkel and Schottky defect?
4. Define the following terms with suitable examples
o Ferromagnetism
o Paramagnetism
o Ferrimagnetism
o 12-16 and 13-15 compounds
5. In terms of band theory what is the difference
o Between conductor and an insulator
o Between a conductor and a semi-conductor

Short Answers (2 Marks):HOTS

1. Explain how electrical neutrality is maintained in compounds showing Frenkel and Schottky
defect.
In compound showing Frenkel defect, ions just get displaced within the lattice. While in
compounds showing Schottky defect, equal number of anions and Cations are removed from the
lattice. Thus, electrical neutrality is maintained in both cases.
2. Calculate the number of atoms in a cubic unit cell having one atom on each corner and two
atoms on each body diagonal.
8 corner x 1/8 atom per unit cell = 1atom
There are four body diagonals in a cubic unit cell and each has two body centre atoms.
So 4 x 2=8 atoms therefore total number of atoms per unit cell =1+8=9
3. Gold crystallizes in an FCC unit cell. What is the length of a side of the cell(r=0.144nm)
6

r=0.144nm
a=2 x 2r
=2 x 1.414 x 0.144nm
=0.407nm
4. Classify each of the following as either a p-type or n-type semi-conductor.
a) Ge doped with In
b) B doped with Si
(a) Ge is group 14 elements and In is group 13 element. Therefore, an electron deficit hole is
created. Thus semi-conductor is p-type.
(b) Since B is a group 13 element and Si is group 14 element, there will be a free electron, thus it is
n-type semi-conductor.
5. In terms of band theory what is the difference between a conductor, an insulator and a semiconductor?
The energy gap between the valence band and conduction band in an insulator is very large while in
a conductor, the energy gap is very small or there is overlapping between valence band and
conduction band.
6. CaCl2 will introduce impurity defect if added to AgCl crystal. Explain
Two Ag+ ions will be replaced by one Ca2+ ions to maintain electrical neutrality. Thus a hole is
created at the lattice site for due to presence of Ca2+ ion as impurity.
7. The electrical conductivity of a metal decreases with rise in temperature while that of a semiconductor increases. Explain.
In metals with increase of temperature, the kernels start vibrating and thus offer resistance to the
flow of electrons. Hence conductivity decreases. In case of semi-conductors, with increase of
temperature, more electrons can shift from valence band to conduction band. Hence conductivity
increases.
8. What type of substances would make better permanent magnets, ferromagnetic or
ferrimagnetic, why?
Ferromagnetic substances make better permanent magnets. This is because the metal ions of a
ferromagnetic substance are grouped into small regions called domains. Each domain acts as tiny
magnet and get oriented in the direction of magnetic field in which it is placed. This persists even in
the absence of magnetic field.
9. In a crystalline solid, the atoms A and B are arranged as follows:a. Atoms A are arranged in ccp array.
b. Atoms B occupy all the octahedral voids and half of the tetrahedral voids. What is the
formula of the compound?
Let no. of atoms of A be N
No. of octahedral voids = N
No. of tetrahedral voids= 2N
i)
There will be one atom of B in the octahedral void
7

ii)
There will be one atom of B in the tetrahedral void (1/2 x 2N)
Therefore, total 2 atoms of B for each atom of A
Therefore formula of the compound =AB2
10. In compound atoms of element Y forms ccp lattice and those of element X occupy 2/3rd of
tetrahedral voids. What is the formula of the compound?
No. of Y atoms per unit cell in ccp lattice=4
No. of tetrahedral voids= 2 x 4=8
No. of tetrahedral voids occupied by X= 2/3 x 8=16/3
Therefore formula of the compound =X16/3 Y4
=X16 Y12
=X4 Y3
HOTS Short Answer:
1. How many lattice points are there in one unit cell of the following lattices?
o fcc
o bcc
o sc
2. A cubic solid is made of two elements X and Y. Atom Y are at the corners of the cube and X at
the body centers. What is the formula of the compound?
3. Silver forms ccp lattice and X ray studies of its crystal show that the edge length of its unit
cell is 408.6 pm. Calculate the density of silver (Atomic wt= 107.9u).
4. A cubic solid is made up of two elements P and Q. Atoms of the Q are present at the corners
of the cube and atoms of P at the body centre. What is the formula of the compound? What
are the co-ordination number of P and Q.
5. What happens when:o CsCl crystal is heated
o Pressure is applied on NaCl crystal.
Short Answers (3 marks):
1. The density of chromium is 7.2g cm-3. If the unit cell is a cubic with length of 289pm, determine
the type of unit cell (Atomic mass of Cr=52 u and NA = 6.022 x 1023 atoms mol-1).
d= Z x M

a3 x NA
Z=? , a= 289 pm =289x10-10 cm, M=52g mol-1 , d=7.2g cm-3
Z= d x a3 x Na = 7.2(g cm-3) x [289 x 10-10 cm]3 x 6.022 x 1023(atom mol-1)
M
52 g mol-1
2. An element A crystallizes in FCC structure; 200 g of this element has 4.12 x 1024 atoms. If the
density of A is 7.2g cm-3, calculate the edge length of unit cell.
8

3. Niobium crystallizes in bcc structure. If its density is 8.55 cm-3, calculate atomic radius of [At.
Mass of Niobium = 92.9u, NA = 6.022 x 1023 atoms mol-1 ].
4. If radius of octahedral void is r and radius of atom in close packing is R, derive the relationship
between r and R.
5. Non stoichiometric cuprous oxide can be prepared in the laboratory. In this oxide, copper to
oxygen ratio is slightly less than 2:1. Can you account for the fact that the substance is a p=type
semiconductor?
6. The unit cell of an element of atomic mass 50u has edge length 290pm. Calculate its density the
element has bcc structure (NA = 6.02 x 1023 atoms mol-1).
7. Calculate the density of silver which crystallizes in face centered cubic form. The distance
between nearest metal atoms is 287pm (Ag= 107.87g mol-1, NA= 6.022 x 1023).
8. What is the distance between Na+ and Cl-ions in NaCl crystal if its density is 2.165g cm-3. NaCl
crystallizes in fcc lattice.
9. Find the type of cubic lattice having edge length of 400pm, atomic wt. = 60u and density
=6.25g/cc.
HOTS Short Answer:
1. Aluminium crystallizes in cubic closed pack structure. Its metallic radius is 125 pm
o What is the length of the side of the unit cell?
o How many unit cells are there in 100 cm3 of Aluminium.
2. Classify the following as either p-type or n-type semiconductors.
Ge doped with In
B doped with Si
3. Zinc oxide is white but it turns yellow on heating. Explain.
Long Answer(3 Marks):
1. Metal A has face centered cubic lattice. Edge length of lattice cell is 2A0. The density of metal is
2.4g cm-3. How many units cell are present in 200g of metal?
2. A metal crystallizes as face centered cubic lattice with edge length of 450pm. Molar mass of
metal is 50g mol-1. Calculate its density?
3. A compound forms hexagonal close packed structure. What is the total number of voids in 0.5
mol of it? How many of these are tetrahedral voids?
4. Copper Crystallizes into FCC lattice with edge length 3.61 x 10-8 cm. Show that calculated density
is in agreement with measured value of 8.92g/cc.
5. Niobium crystallizes in bcc structure with density 8.55g/cc, Calculate atomic radius using atomic
mass i.e. 93u.
HOTS Long Answer:
1. The compound CuCl has fcc structure like ZnS, its density is 3.4g cm-3. What is the length of the edge
of unit cell?
Hint: d=Z X M /a3 X NA
9

a3=4X99 / 3.4 X 6.022 X 1023

a3=193.4 X 10-24 cm3
a=5.78 X 10-8cm
2. If NaCl is dropped with 10-3 mol% SrCl2. What is the concentration of cation valancies?
3. If the radius of the octahedral void is r and the radius of the atom in the close packing is R. derive
relationship between r and R.
4. The edge length of the unit cell of metal having molecular weight 75g/mol is A 0 which crystallizes
into cubic lattice. If the density is 2g/cm3 then find the radius of metal atom (NA = 6.022 x 1023)
5. The density of KBr is 2.75 gm cm -3 . The length of edge of the unit cell is 654 pm. Predict the type
of cubic lattice..
NA=6.023 x 1023 ; at mass of K=39: Br. = 80
Ans. Calculate value of z= 4 so it has fcc lattice
6. CsCl has bcc arrangement and its unit cell edge lenth is 400 pm . calculate the interionic distance
of CsCl. Ans. 34604 pm
7. The radius of an Iron atom is 1.42 A0 . It has rock salt structure. Calculate density of unit cell. Ans.
5.74 g cm-3
8. What is the distance between Na+ and Cl- in a NaCl crystal if its density is 2.165 gcm-3 NaCl
crystalline in the fcc lattice. Ans.281pm
9. Copper crystalline with fcc unit cell. If the radius of copper atom is 127.8 pm. Calculate the
density of copper metal. At. Mass of Cu=63.55u NA= 6.02 x 1023 Ans. a=22 .r , a3=4.723 x 10-23,
d=8.95/ 5.74 g cm-3
***

10

SOLUTION
KEY CONCEPTS
Solution is the homogeneous mixture of two or more substances in which the components are
uniformly distributed into each other. The substances which make the solution are called components.
Most of the solutions are binary i.e., consists of two components out of which one is solute and other is
solvent. Ternary solution consists of three components
Solubility - Maximum amount of solute that can be dissolved in 100g of solvent at particular temp. to
make saturated solution.
Solid solutions are of 2 types 1. Substitutional solid solution e.g. Brass (Components have almost similar size)
2. Interstitial solid solution e.g. steel (smaller component occupies the interstitial voids)
Expression of concentration of solution
1. Mass percentage= amount of solute present in 100grm solution.
Mass Percentage =
Percentage by volume is expressed as =

( Liquid- liquid solution)

2. Mole fraction it is the ratio of no. of moles of one of the components to the total no. of moles of all
components. It is expressed as x. For two component system made of A and B ,
XA=nA/(nA+nB), XB=nB/(nA+nB) , Sum of all the components is 1 ; XA+XB =1
3. Molarity (M) =
It decreases with increase in temperature as volume of solution increases with temperature.
4. Molality (m) =
No effect of change of temperature on molality as it is mass to mass ratio.
6. Parts per million (ppm) concentration of very dilute solution is expressed in ppm.
Ppm =
Vapor pressure It is defined as the pressure exerted by the vapour of liquid over the liquid in
equilibrium with liquid at particular temperature .vapour pressure of liquid depends upon nature of
liquid and temperature.
Raoults Law
1. For the solution containing non-volatile solute the vapor pressure of the solution is directly
proportional to the mole fraction of solvent at particular temperature
P A XA
PA = P0A.XA
2. For the solution consisting of two miscible and volatile liquids the partial vapor pressure of
each component is directly proportional to its own mole fraction in the solution at particular
temperature.
PA=P0A. XA,
PB=P0B .XB
And total vapor pressure is equal to sum of partial pressure. P total = PA + PB
Ideal solution The solution which obeys Raoults law under all conditions of temperature and
concentration and during the preparation of which there is no change in enthalpy and volume on mixing
the component.
11

Conditions
PA = P0A XA,
PB = P0B.XB
Mix = 0,
mix = 0
This is only possible if A-B interaction is same as A-A and B-B interaction nearly ideal solution are
1. Benzene and Toluene
2. Chlorobenzene and Bromobenzene
Very dilute solutions exhibit ideal behavior to greater extent.
Non-ideal solution
(a) PA P0A.XA
(b) PB P0B.XB
(b)
(d) mix 0
mix 0
For non-ideal solution the A-B interaction is different from A-A and B-B interactions
i. For solution showing positive deviation
PA > P0A, PB> P0B. XB
Mix = positive,
mix=positive (A-B interaction is weaker than A-A and B-B )
E.g. alcohol and water
ii. For the solution showing negative deviation
PA< P0A.XA,
PB<P0B.XB
Mix= negative,
mix = negative
A-B interaction is stronger than A-A and B-B interactions
E.g. Chloroform and acetone, HCl and water
What is Azeotrope? The mixture of liquids at particular composition which has constant boiling point
which behaves like a pure liquid and cannot be separated by simple distillation. Azeotropes are of two
types:
(a) minimum boiling Azeotrope (mixture which shows +ve deviations ) ex. alcohol and water
(b) maximum boiling Azeotrope (which shows ve deviations) ex. acetone and chloroform
Colligative Properties - Properties of ideal solution which depends upon no. of particles of solute but
independent of the nature of particle are called colligative property
Relative lowering in vapour pressure:
(PoA PA )/ PoA = XB
Determination of molar mass of solute
MB=( WA MA PoA)/WA(PoA PA)
Elevator in Boiling Point
TB = Kb. m
Where T B = TB- ToB
Kb = molal elevator constant
M = molality
MB=(Kb1000WB)/TBWA
Depression in Freezing Point:
12

Tf= kf. m
Where Tf = Tf Tf ;m = molality
Kf = molal depression constant
unit = k.kgmol-1
Osmotic Pressure
The hydrostatic pressure which is developed on solution side due movement of solvent particles from
lower concentration to higher concentration through semipermeable membrane denoted as and it is
expressed as
V nRT
n
RT
V
CRT
n = No. of moles; v = volume of solution (L)
R = 0.0821 Latmmol-1; T = temperature in kelvin.
Isotonic solutions have same osmotic pressure and same concentration.
Hypertonic solutions have higher osmotic pressure and hypotonic solutions have lower osmotic
pressure.
0.91% solutions have sodium chloride solution RBC swells up or burst.

13

Q1- What do you mean by Henrys Law? The Henrys Law constant for oxygen dissolved in water is
4.34104atm at 25o C. If the partial pressure of oxygen in air is 0.2 atm, under atmospheric pressure
conditions. Calculate the concentration in moles per Litre of dissolved oxygen in water in equilibrium
with water air at 25o C.
Ans: Partial pressure of the gas is directly proportional to its mole fraction in solution at particular
temperature.
PA XA ; KH = Henrys Law constant
PA = KH XA
KH = 4.34104 atm
pO2 = 0.2 atm
Xo2= pO2 / KH
=0.2 / 4.34104= 4.610-6
If we assume 1L solution = 1L water
n water = 1000/18 = 55.5
XO2 =
nO2 /(nO2+ n H2O ) ~ = nO2 /nH2O
nO2 = 4.6 X 10-6 X 55.5 = 2.55 X 10-4mol
M = 2.55 X 10-4 M
Q.2. What is Vant Hoff factor?
Ans. It is the ratio of normal molecular mass to observed molecular mass .It is denoted as i
i = Theoretical Molar mass / observed molar mass
= Observed no. of particles / Actual no. of particles
= Observed colligative property/Theoretical colligative property
Q.3. What is the Vant Hoff factor in K4[Fe(CN)6] and BaCl2 ?
Ans 5 and 3
Q.4. Why the molecular mass becomes abnormal?
Ans. Due to association or dissociation of solute in given solvent .
Q.5. Define molarity?
Q.6. How molarity is related with percentage and density of solution ?
Ans. M = P x Percentage of density x 10/molar mass
Q.7. What role does the molecular interaction play in the solution of alcohol and water?
Ans. Positive deviation from ideal behavior .
Q.8. What is Vant Hoff factor, how is it related with
a. degree of dissociation
b. degree of association
Ans.a. =i 1/n-1
b. = i -1 / 1/n -1
Q.9. Why NaCl is used to clear snow from roads ?
Ans. It lowers f.p of water
Q10. why the boiling point of solution is higher than pure liquid
Ans. Due to lowering in v.p

14

HOTS
Q1. Out of 1M and 1m aqueous solution which is more concentrated
Ans. 1M as density of water is 1gm/Ml
Q2. Henry law constant for two gases are 21.5 and 49.5 atm ,which gas is more soluble .
Ans. KH is inversely proportional to solubility .
Q.3. Define azeotrope , give an example of maximum boiling azeotrope.
Q.4. Calculate the volume of 75% of H2SO4 by weight (d=1.8 gm/ml) required to prepare 1L of 0.2M
solution
Hint: M1 = P x d x 10 /98
M1 V1 = M2V2
14.5ml
Value based questions:
1. We have many types of water purifiers Zero-B is based on disinfecting properties of iodine. UV
purifier is based on killing of bacteria by UV light. These R.O. Purifiers are being used
(a) What is the full form of R.O. Purifier?
(b) What is the function of Porous membrane ?
(c) Which method of purification is more economical for countries using sea water, flash distillation
or reverse osmosis for getting portable water. Why?
2. Water is used as coolant in vehicles. In cars, ethylene glycol is used as coolant. In cold countries,
water gets frozen so it cannot act as coolant. Ethylene glycol is added to water so that its freezing
point is lower and it does not freeze. At hill station snow fall takes place. Clearing the snow from
the road is essential for smooth running of traffic(a) What is the role of ethylene glycol when added to water?
(b) Why does sprinkling of salt help in clearing snow covered roads in hilly areas? Explain the
phenomenon involved in the process.
(c) How is life of people affected by snow fall?

15

SHORT ANSWERS (2 MARKS)

Q.1. How many grams of KCl should be added to 1kg of water to lower its freezing point to -8.00C (kf =
1.86 K kg /mol)
Ans. Since KCl dissociate in water completely L=2
;m=
m= 8 / 2X1.86 = 2.15mol/kg.
Grams of KCl= 2.15 X 74.5 = 160.2 g.
Q.2. With the help of diagram: show the elevator in boiling point colligative properties?
Q.3. what do you mean by colligative properties, which colligative property is used to determine molar
mass of polymer and why?
Q.4. Define reverse osmosis, write its one use.
Ans. Desalination of water.
Q.5. Why does an azeotropic mixture distills without any change in composition.
Hint: It has same composition of components in liquid and vapour phase.
Q.6. Under what condition Vant Hoffs factor is
a. equal to 1
b. less than 1
c. more than 1
Q.8. Why is it advised to add ethylene glycol to water in a car radiator in hill station?
Hint: Anti- freeze.
Q 9. (a). define the following terms.
3. Mole fraction
4. Ideal solution
(b)15 g of an unknown molecular material is dissolved in 450 g of water. The resulting solution
frrezez at -0.34 0c . What is the molar mass of material? Kf for water= 1.86 K Kg mol-1 .
Ans. 182.35 g/mol
Q 10.(a) explain the following :
1. Henrys law about dissolution of a gas in a liquid.
2. Boling point elevation constant for a solvent
(b) A solution of glycerol (C3H8O3) in water was prepared by dissolving some glycerol in in 500 g of
water. The solution has a boiling point of 100.42 0c . What mass of glycerol was dissolved to make
this solution?
Kb for water = 0.512 k Kg mol-1
(hint:
Tb = KB x WB x 1000
MB x WA
Ans. 37.73 g
Q 11. 2 g of benzoic acid (C6H5COOH) dissolved in 25 g of benzene shows a depression in freezing point
equal to 1.62 K .Kf for benzene is 4.9 K Kg mol-1. What is the percentage association of acid if it
forms dimmer in solution. Ans. 99.2%
Q12. Osmotic pressure of a 0.0103 molar solution of an electrolyte is found to be 0.70 atm at 270c
.Calculate Vant Hoff factor.( R=0.082 L atom mol-1 K-1) Ans. 2.76

16

UNIT-3

ELECTROCHEMISTRY
Concepts:

A cell is of two types:I.

Galvanic Cell
II.
Electrolytic cell.
In Galvanic cell the chemical energy of a spontaneous redox reaction is converted into electrical
work.
In Electrolytic cell electrical energy is used to carry out a non-spontaneous redox reaction.

E0cell = E0cathode-E0anode
The standard potential of the cells are related of standard Gibbs energy.
rG0 = -n FE0cell
The standard potential of the cells is related to equilibrium constant.
rG = -RTlnk
Concentration dependence of the potentials of the electrodes and the cells are given by Nernst
equation.
aA + bB cC + dD

Nernst equation can be written as

Ecell E

o
cell

RT [C ]c [ D]d

ln
nF [ A]a [ B]b

The conductivity, K of an electrolytic solution depends on the concentration of the electrolyte,

nature of solvent and temperature.
Molar Conductivity, m, is defined by K/C where C is the concentration in Mol L -1

k 1000
M

17

the unit of molar conductivity is -1 cm2 mol-1. Conductivity decrease but molar conductivity
increases with decrease in concentration. It increases slowly with decrease in concentration for
strong electrolyte while the increase is very dilute solutions.

Kohlrausch law of independent migration of ions. The law states that limiting conductivity of an
electrolyte can be represented as the sum of the individual contribution to the anion and cation
of the electrolyte.

Faradays laws of Electrolysis

I.

The amount of chemical reaction which occurs at any electrode during electrolysis by
a current is proportional to the quantity of electricity passed through the electrolyte.
II.
The amount of different substances liberated by the same quantity of electricity
passing through the electrolytic solution is proportional to their chemical equivalent
weights.
Batteries and fuel cells are very useful forms of galvanic cells
There are mainly two types of batteries.

Corrosion of metals is an electrochemical phenomenon

In corrosion metal is oxidized by loss of electrons to oxygen and formation of oxides.
Anode (Oxidation): 2Fe(s) 2Fe2+ + 4eCathode (Reduction): O2(g) + 4H+(aq) + 4e- 2H2O

Atmospheric Oxidation:
2Fe2+(aq) + 2H2O(l) + 1/2O2(g) Fe2O3(s) + 4H+(aq)

QUESTION CARRING 1 MARK

1. Name the factor on which emf of a cell depends:Ans. Emf of a cell depends on following factora. Nature of reactants.
b. Concentration of solution in two half cells.
c. Temperature
d. Pressure of gas.
2. What are the units of molar conductivity?
( cm2 ohm-1 mol-1 or Scm2mol-1)
18

3. What is the EMF of the cell when the cell reaction attains equilibrium?
Ans. Zero

4. What is the electrolyte used in a dry cell?

Ans. A paste of NH4Cl, MnO2 and C

8. How is cell constant calculated from conductance values?

Ans. Cell constant= specific conductance/ observed conductance.

9. What flows in the internal circuit of a galvanic cell.

Ans. Ions

10. Define electrochemical series.

Ans. The arrangement of various electrodes in the decreasing or increasing order of their
standard reduction potentials is called electrochemical series.

QUESTIONS CARRYING TWO MARKS

1. Calculate emf of the following cell at 298K
Zn/Zn2+ (10-4 M) || Cu2+ (10-2M)/Cu
Given E0 Zn2+/Zn=-0.76V
E0Cu2+/Cu=+0.34V
Ans. Cell reaction is as follows.
Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)
N=2
T=298K
Ecell=(E0Cu2+/Cu-E0Zn2+/Zn)-0.0591V log[Zn2+(aq)]
[Cu+(aq)]
= 0.34V-(-0.76)-0.02955Vlog10-4
10-2
19

= 1.10V-0.02955V log 10-2

= 1.10V+2 X 0.02955V
= 1.10V + 0.0591 V
= 1.1591V

2. Electrolysis of KBr(aq) gives Br2 at anode but KF(aq) does not give F2. Give reason.
Ans. Oxidation takes place at anode. Now higher the oxidation Potential, easier to
oxidize. Oxidation potential of Br -, H2O, F- are in the following order.
Br- > H2O > FTherefore in aq. Solution of KBr. Br - ions are oxidized to Br2 in preference to H2O.
On the other hand, in aq. Solution of KF, H2O is oxidized in preference to F-. Thus in this
case oxidation of H2O at anode gives O2 and no F2 is produced.

3. Define corrosion. Write chemical formula of rust.

Corrosion is a process of deterioration of metal as a result of its reaction with air and
water, surrounding it. It is due to formulation of sulphides, oxides, carbonates,
hydroxides, etc.
Formula of rust- Fe2O3.XH2O
4. How are standard electrode potentials measured?
5. What is cell constant? How it is determined?
6. Why it is necessary to platinize the electrodes of a conductivity cell before it is used
for conductance measurement?
7. Why mercury cell gives the constant voltage.
8. What is fuel cell, write reaction involved in H2-O2 fuel cell.

QUESTION CARRYING THREE MARKS

1. Write any three differences between potential difference and e.m.f.

E.M.F
POTENTIAL DIFFERENCE
1.It is difference between

1.it is difference of potential

electrode potential of two electrodes

between electrode in a closed

when no current is flowing through

circuit.

circuit.
20

2. it is the maximum voltage obtained

2.it is less than maximum voltage

From a cell.

Obtained from a cell.

3. it is responsible for steady flow of

Current.

3.it is not responsible for steady

Flow of current.

2. for the standard cell

Cu(s)/Cu2+(aq)|| Ag+(aq)/Ag(s)
E0 Cu2+/Cu = +0.34 V
E0 Ag+/Ag =+0.80 V
i. identify the cathode and the anode as the current is drawn from the cell.
ii. Write the reaction taking place at the electrodes.
iii. Calculate the standard cell potential.
Ans. From the cell representation
Ag/Ag+ electrode is cathode and Cu/Cu2+ electrode is anode .
At anode :
Cu(s) Cu2+ ( aq )+2e2Ag+(aq) + 2e 2Ag(s)
E0 cell = E0 cathode E0 anode
= E0 Ag+/Ag E0 Cu2+ /Cu
= +.80 V (+0.34V)
= +0.80V-0.34V
= 0.46V
3. Can we store copper sulphate in (i)Zinc vessel (ii) Silver vessel? Give reasons.
Given E0 Cu2+/Cu = +0.34V, E0Zn2+/Zn= -0.76V) , E0Ag+/Ag = +0.80V

Ans. A metal having lower reduction potential can displace a metal having higher
reduction potential from solution of its salt.of Cu2+(E0Cu2+/C

21

I. Since standard reduction potential of Zn2+(E0Zn2+/Zn = -0.76V) is less than the standard
reduction potentialof Cu2+ (E0Cu2+/Cu=+0.34V), Zn can displace copper from copper
sulphate solution. Thus, CuSo4 solution can be stored in silver vessel.

4. How many grams of chlorine can be produced by the electrolysis of matters NaCl with a
current of 1.02 A for 15 min?
2NaCl(l) 2Na+(l)+2Cl-(l)
2 Cl- Cl2(g) + 2e2 mole 1mol
Q= nf
Q= 2 x 96500 C/mol= 1.93 x 105C

Quantity of electricity used = IT

= 1.02 A X (15 X 60)sec
= 900C
Molar mass of Cl2 = 2 X 35.5 = 71 gmol-1 X 105 C of charge produce chlorine = 71g
1.93 X 105 C of charge produce chlorine = 71gm
900 C of charge produce chlorine 71 X 900
1.93 X 105
= 0.331 gm
5. Define electrode potential. Why absolute value of reduction potential of electrode cannot
be determined?
6. Write the equation showing the effect of concentration on the electrode potential.
7. Derive the relationship between Gibbs free energy change and the cell potential.
8. How Nernst equation can be applied in the calculation of equilibrium constant of any cell
reaction.
9. The cell reaction as written is spontaneous if the overall EMF of the cell is positive.
Comment on this statement.
QUESTIONS CARRYING 5 MARKS

22

1. Explain the term electrolysis. Discuss briefly the electrolysis of (i) molten NaCl (ii) aqueous
sodium chloride solution (iii) molten lead bromide (iv) water.
2. state and explain Faradays laws of electrolysis. What is electrochemical equivalent?
3. What do you understand by electrolytic conduction? what are the factors on which
electrolyte conduction depends.? What is the effect of temperature on electrolytic
conduction?
4. How is electrolytic conductance measured experimentally?
5. Describe normal hydrogen electrode and its applications.
6. Conductivity of 0.00241 M acetic acid is 7.896 x 10-5 s cm-1. Calculate its molar
conductivity if om for acetic acid is 390.5 s cm2 mol-1. What is its dissociation constant ?
7. Three electrolytic cells A,B,C containing solutions of ZnSO4, AgNO3 and CuSO4
respectively are connected in series. A steady current of 1.5 amperes through them until
1.45g of silver deposited at the cathode of cell B. How long did the current flow? What
mass of copper and zinc were deposited?

HOT QUESTIONS
1 Mark questions:1. Why in a concentrated solution, a strong electrolyte shows deviations from Debye-HuckleOnsagar equation?
Ans:- Because interionic forces of attractions are large.

2. What is the use of Platinum foil in the hydrogen electrode?

A: It is used for inflow and outflow of electrons.
3. Corrosion of motor cars is of greater problem in winter when salts are spread on roads to
melt ice and snow. Why?
Ans: Salts provide electrolytic medium which accelerates electrochemical process.

4. Is it safe to stir AgNO3 solution with copper spoon? (E0 Ag+/ Ag = 0.80 Volt; E0 Cu+/ Cu = 0.34
Volt)
Ans: No it is not safe because reacts with AgNO3 Solution ( Emf will be positive.)
5. Why is it necessary to use salt bridge in a galvanic cell?
Ans: To complete inner circuit and to maintain electrical neutrality of the solution.

23

2 mark questions:-

1. Why is Li best reducing agent where as Fluorine is best oxidizing agent ?

0
2. Equilibrium constant is related to Ecell
but not to Ecell. Explain.

3. Why sodium metal is not obtained at cathode when aq NaCl is electrolysed with Pt electrodes
but obtained when molten NaCl is electrolysed ? 2
4. Zn rod weighing 25 g was kept in 100 mL of 1M copper sulphate solution. After
certain time interval, the molarity of Cu2+ was found to be 0.8 M. What is the
molarity of SO4 -2 in the resulting solution and what should be the mass of Zn rod after
cleaning and drying ?
5. Which will have greater molar conductivity and why? Sol A. 1mol KCl dissolved in 200cc of
the solution or Sol B. 1 mol KCl dissolved in 500cc of the solution.

3/ 5 mark questions:1. Which cell is generally used in hearing aids?Name the material of the anode, cathode and
the electrolyte. Write the reactions involved.
2. Iron does not rust even if Zinc coating is broken in agalvanised iron pipe but rusting occurs
much faster if tin coating over iron is broken.Explain.
3. Corrosion is an electrochemical phenomenan, explain.

4. Calculate the pH of following cell: Pt, H2/ H2SO4, if its electrode potential is0.03V.
5 . A cell contains two hydrogen electrodes. The negative electrode is in contact with a solution
of 10-5 M H+ ions. The emf of the cell is 0.118 V at 298 K. Calculate the concentration of the H +
ions at the positive electrode.

6. Crude copper containing Fe and Ag as contaminations was subjected to electro refining by

using a current of 175 A for 6.434 min. The mass of anode was found to decrease by 22.260 g,
while that of cathode was increased by 22.011 g. Estimate the % of copper, iron and silver in
crude copper.

7. Zinc electrode is constituted at 298 K by placing Zn rod in 0.1 M aq solution of zinc sulphate
which is 95 % dissociated at this concentration. What will be the
24

0
0.76V
electrode potential of the electrode given that EZn
2
/ Zn

8. At what pH will hydrogen electrode at 298 K show an electrode potential of

-0.118 V, when Hydrogen gas is bubbled at 1 atm pressure? 3

10 Electrolysis of the solution of MnSO4 in aq sulphuric acid is a method for the

preparation of MnO2 as per the chemical reaction
Mn2+ + 2H2O MnO2 + 2H+ + H2
Passing a current of 27 A for 24 hrs gives 1 kg of MnO2. What is the current
efficiency ? What are the reactions occurring at anode and cathode?

Electrochemistry

Q 1.What do you mean by kohlrauchs law: from the following molar

dilution
0m

conductivities at infinite

Ba(OH)2 =457.6 -1 cm2 mol-1

0m Ba Cl2 = 240.6 -1 cm2 mol-1

0m NH4Cl= 129.8 -1 cm2 mol-1

Calculate 0m for NH4OH

Ans. 238.3 -1cm2 mol-1

Q2. Calculate the equilibrium constant for the reaction at 298 K.

Zn + Cd2+

Zn2+ +Cd

If E0 Cd++/Cd =-.403 v
E0 Zn++/Zn= -0.763 v
antilog 12.1827
25

Ans.1.52 x 1012

Q3. Predict the products of electrolyzing of the following

(a) a dil. Solution of H2SO4 with Pt. electrode
(b). An aqueous solution of AgNO3 with silver electrode
(c) An aq. Solution of CuSO4 using platinum electrode.
(d) An aq. Solution of CuSO4 using copper electrode
Q4. Write the electrode reaction of
(a)Dry Cell (b) Lead storage cell (c)Mercury cell (d)Nickel cadmium cell (e)Fuel Cell

26

UNIT-4
CHEMICAL KINETICS
CONCEPT

Rate of chemical reaction- The change in concentration of any reactant or product per unit
time is called rate of reaction.

TYPES OF RATE OF REACTION-

1. Average rate of reaction- The rate of reaction measured over the long time interval is
called average rate of reaction.
Avg rate x/t = -[R]/t = +[P]/t

2. Instantaneous rate of reaction- The rate of reaction measured at a particular instant of

time is called instantaneous rate of reaction.
Instantaneous rate dx/dt= -d[R]/dt= d[P]/dt

FACTORS AFFECTING RATE OF REACTION-

1.
2.
3.
4.
5.
6.

Concentration of reactant
Surface area
Temperature
Nature of reactant
Presence of catalyst
Radiation

RATE CONSTANT (k)- It is equal to the rate of reaction when molecular concentration of
reactant is at unity.

RATE LAW- The rate of reaction is directly proportional to the product of concentration of
reactant and each concentration is raised to some power which may or may not be equal to
stoichiometric coefficient experimentally.

27

For a reaction

aA+bB cC+dD

Rate law = k[A]p[B]q

Where powers P and Q are determined experimentally
MOLECULARITY The total no. of reactants taking part in elementary chemical reaction is
called molecularity.

ORDER OF REACTION- The sum of powers to which the concentrations terms are raised
in a rate law expression is called order of reactions. For above case order = P+Q: orders of
rkn is determined experimentally

HALF-LIFE PERIOD- The time during which the concentration of the reactant is reduced to
half of its initial concentration is called half-life period.

ACTIVATION ENERGY- The minimum extra amount of energy absorbed by reactant

molecules so that their energy becomes equal to the threshold energy is called activation
energy.

Activation energy = Threshold energy kinetic energy

TEMPERATURE COEFFICIENT- The ratio of rate constant at two temperatures having

difference of 100C is called temperature coefficient.

Temperature coefficient = Rate constant at T+100C/Rate constant at T0C

Arhenius Equation-

K= Ae-Ea/RT

28

K-rate constant
A-Arrhenius energy
Ea-Activation energy
R- Rate constant
T-Temperature

Log K = Log A- Ea / ( 2.303RT)

Energy of activation can be evaluated as

log

k2
Ea 1 1

k1 2.303R T1 T2

1 MARKS QUESTION
1. The gas phase decomposition of acetaldehyde

CH3CHO CH4+CO

Follows the first order rate law.

What is the unit of its rate constant?

Ans. sec-1

2. State the order with respect to each reactant and overall reaction.

H2O2 + 3I- + 2H+ 2H2O + I3-

29

Rate = k[H2O2][I-]

Ans. Order of reaction= 1+1= 2

3. Give one example of pseudo first order reaction.

Ans. Hydrolysis of an ester
CH3COOC2H5 + H2O CH3COOH + C2H5OH

4. The conversion of molecules X to Y follows the second order of kinetics. If concentration

of X is increased 3 times, how will it affect the rate of formation of Y.
Ans. Rate = k [X] 2
= k [3X] 2
= 9k [X] 2

The rate of formation will become nine times.

5. The rate law for a reaction is

Rate = K [A] [B] 3/2
Can the reaction be an elementary process? Explain.

Ans. No, an elementary process would have a rate law with orders equal to its molecularities
and therefore must be in integral form.

6. Why rate of reaction does not remain constant throughout?

7. Define specific reaction rate or rate constant.
8. Write the expression for half-life period of zero and first order reaction?

2 MARKS QUESTION
30

1. The rate of a particular reaction quadruples when the temperature changes from 293K to
313K. Calculate activation energy.

Ans. K2/K1 = 4,

T1= 293K

log

T2 = 313K

k2
Ea 1 1

k1 2.303R T1 T2

Log [K2/K1] = Ea[T2-T1]/19.15

Thus on calculating and substituting values we get..

Ea = 52.86 kJ mol-1

2. If the decomposition of nitrogen oxide as

2N2O5> 4NO2 + O2
follows a first order kinetics.
(i)

Calculate the rate constant for a 0.05 M solution if the instantaneous rate is 1.5 x 10 -6
mol/l/s?

Ans. Rate = K [N2O5]

K= Rate
[N2O5]
K=1.5 x 10-6
0.05
K= 3.0 x 10-5
ii) What concentration of N2O6 would give a rate of 2.45 x 10-5 mol L-1s-1
31

Rate = 2.45 x 10-5 mol L-1s-1

[N2O5] = Rate = 2.45 x 10-5
K

3.0 x 10-5

= 0.82 M
3) Write the difference between order and molecularity of reaction.
Ans.

ORDER

MOLECULARITY

It is the sum of the powers of concentration It is the number of reacting speciterms in the rate law expression.

-es undergoing simultaneously

Collision in a reaction.

It is determined experimentally

it is a theoretical concept

Order of reaction need not to be a whole

It is whole no. only

number
Order of reaction can be zero.

It cant be zero or fractional

4) Define Threshold energy and activation energy. How they are related?
Ans. Threshold Energy: It is the minimum amount of energy which the reactant molecules
must possess for the effective collision in forming the products.

Activation Energy: It is the excess energy required by the reactants to undergo chemical
reaction.

Activation energy = Threshold energy Average kinetic energy of molecules.

5(a). Draw a schematic graph showing how the rate of a first order reaction changes in
concentration of reactants.

32

Variation of rate of first order reaction with concentration.

(b). rate of reaction is given by the equation

Rate = k [A] 2[B]
What are the units of rate constant for this reaction?
Ans. Rate = k [A] 2[B]

K = mol L-1s-1
(mol L-1)2(mol-1)
K= mol-2L2s-1

6. List the factors affecting the rate of reaction.

7. Explain with suitable example, how the molecularity of a reaction is different from the order of
a reaction.
8. Define the term rate constant of specific reaction rate.
9. What are Pseudo unimolecular reactions? Explain with the help of a suitable example.
33

10. What is half life period? Derive and expression for half-life period in case of a first order
reaction.

3 marks question

Q1. The rate constant for first order reaction is 60 per s. How much time will it take to reduce
the concentration of the reaction to 1/10 of its initial value.
Ans:t = 2.303 log [R0]
K

[R]

t= 2.303 log [R0]

K

[R0] x 0.1

t = 2.303 log10
60
t = 2.303 = 3.38X 10-2s-1
60
2. The rate of most of reaction double when their temperature is raised from 298k to 308k.
Calculate the activation energy of such a reaction.
Ans:-

log

k2
Ea 1 1

k1 2.303R T1 T2

Ea = 2.303 X 8.314 X 298 X 308 X 0.3010

1000
Ea = 52.89KJ/mol

34

3. A first order reaction takes 69.3 min for 50% completion. Set up on equation for determining
the time needed for 80% completion.
Ans. K=0.693
T1/2
= 0.693/69.3min
= 10-2min-1

T= 2.303log [R0]
K

[R]

T= 2.303/10-2log5

T= 160.9min

4. Following reaction takes place in one step

2NO + O2 2NO2
How will the rate of the reaction of the above reaction change if the volume of reaction vessel is
diminished to 1/3 of its original volume? Will there be any change in the order of reaction with
reduced volume?
Ans. 2NO+ O22NO2

dx/dt = k x [NO]2[O2]1

[Since it is one step]

If the volume of reaction vessel is diminished to 1/3, conc. Of both NO and O 2 will become 3
time, the rate of reaction increased 27 times.
In the order of reaction with the reduced volume.

5. The decomposition of NH3 on platinum surface is a zero order reaction. What are the rate
of production of N2 and H2.
35

If k= 2.5 x 10-4

Ans. 2NH3 N2 + 3H2

-1

d [NH3] = d[N2]

dt

+1

dt

d[H2]
dt

-d[NH3] = rate = k x [NH3]0

dt
= 2.5 X 10-4 molL-1sec-1
d [N2] = - 1 d [NH3]
dt

dt

= 1/2 X2.5X10-4 molL-1sec-1

d[H2] = - 3 d[NH3] = 3/2 X2.5X10-4
2

dt

= 3.75X10-44molL-1sec-1
Rate = - d[NH3] = k X[NH3]0
dt
= 2.5 X 10-4 molL-1sec-1
Rate of production of N2 = 2.5X10-4 molL-1sec-1

6. How is the rapid change in concentration of reactants/products monitored for fast reactions.
7. What are photochemical reactions? Give two examples,
8. What is the effect of temperature on the rate of reaction? Explain giving reasons.
9. During nuclear explosion , one of the products is 90Sr with half life of 28.1 years. If 1 g of
90

Sr was absorbed in the bones of newly born baby instead of calcium, it will remain in the
bones upto 60 years if not lost metabolically.
(i) What precautions should be taken while carrying out nuclear explosion?
(ii) Calculate the value of rate constant k.

36

QUESTIONS CARRYING 5 MARKS

1. What do you understand by order of a reaction? How does rate law differ from law of
mass action? Give two example of each of the reactions of (i) zero order (ii) first order (iii)
second order
2. Derive the equation for the rate constant for a first order reaction. What would be the
units of the first order rate constant if the concentration is expressed in mole per litre and
time in seconds?

37

HOTS

1. The half-life period of two samples are 0.1 and 0.4 seconds. Their initial
Concentrations are 200 and 50 mol L -1 respectively. What is the order of
2. What is the ratio of t3/4 : t1/2 for a first order reaction ?
molecularity reactions (viz. molecularity, 4 and above) are very rare. Why?

reaction?
3. Higher

4. Consider the reaction 2A + B _______> Products

When concentration of B alone was doubled, half life time does not change. When conc. of
A alone is doubled, the rate increases by two times. What is the unit of K and what is the
order of the reaction?

5. For the reaction, the energy of activation is 75KJ / mol. When the energy of activation of a
catalyst is lowered to 20KJ / mol. What is the effect of catalyst on the rate of reaction at 200C.

6. The gas phase decomposition of CH3OCH3 follows first order of kinetics

CH3OCH3 CH4 (g) + H2 (g) + CO (g)
The reaction is carried out at a constant volume of the container at 500 0 C and has t1/2 =14.5min.
Initially only dimethyl ether is present at a pressure of 0.40 atm. What is the total pressure of the
system after 12 min? Assume ideal behavior.
Q 7. See the graph and answer the following question

1). What is the order of rkn

2) what is the value of a and b

? (a)

38

Log [R]

Slope=? (b)

Q 8. 1) what is the order of rkn

2) what is the value of slope and intercept

[R]

Slope= ?

q 9.1). what is the value of slope

log A

39

log[R]

Slope= ?

40

Chapter-5 SURFACE CHEMISTRY

The branch of the Chemistry wich deals with the study of surface phenomena is called
surface Chemistry.
POINTS TO BE REMEMBERED:

1. Adsorption: - The accumulation of molecules species at the surface rather in the bulk of a
solid or liquid is termed adsorption.
2. Desorption:-Removal of adsorbate from the surface of adsorbent is known as Desorption.
3. Sorption:-When adsorption and absorption both takes place simultaneously.
4. Type of adsorption: - On the basis of interaction between adsorption and absorption,
adsorbate are of two types:
(i)Physical adsorption/physisorption: - When weak vander waal interaction involve between
adsorbate and adsorbent.
(ii) Chemical adsorption/chemisortion:-When chemical bonds form between adsorbate and
adsorbent.
5. Adsorption isotherm:-The variation in the amount of gas adsorbed by the adsorbent with
pressure at constant temperature can be expressed by means of a curve termed as adsorption
isotherm.
6. Application of adsorption:(a) Removal of colouring matter from solution using animal charcoal.
(b)Chromatographic analysis is based on adsorption.
7. Freundlich adsorption isotherm:-It is a graph which shows relationship between the
quality of gas adsorbed by unit mass of solid adsorbent and pressure at a particular
temperature.

x/
m

41

Pressure

Log
slope=1/n

X/m

Lo
g
K

Log P
x/m=kp1/n
8 .Factors affecting adsorption:(i)Surface area: - Adsorption increases with increases of surface area of adsorbent.
(ii)Nature of adsorbate:- Easily liquefiable gases are readily adsorbed.
(iii)Temperature:-Low temperature is favorable for physical adsorption and High temperature
for chemisortion.
42

(iv)Pressure: - Pressure increases, adsorption increases.

9. CATALYSIS:- Substances which alter the rate of chemical reaction and themselves remain
chemically and quantitatively unchanged after the reaction are known as catalyst and the
phenomenon is known as catalysis.
10. PROMOTERS AND POISONS
Promoters are substance that enhance the activity of catalyst while poisons decrease the
activity of catalyst.
Fe
N 2 + 3H 2

2NH3 (g)

Mo
Fe =catalyst

Mo= promoter

11. Homogenous catalyst when reactants and catalyst are in same phase.
NO(g)
e.g.

12.

2 SO2 (g)

O 2 (g)

2SO3(g)

Heterogeneous catalyst The catalytic process in which the reactants and catalyst

are in different phase.

Pt
e.g.

SO2 + O2

2SO3 (g)

13. Adsorption theory of Heterogeneous catalysis It explains the mechanism of

heterogeneous catalyst.
The mechanism involves 5 steps:a. Diffusion of reactants to the surface of catalyst.
b. Adsorption of reactant molecules on the surface of catalyst.
c. Chemical reaction on the catalyst surface through formation of an intermediate.
d. Desorption of reaction product from the catalyst surface.
e. Diffusion of reaction product away from the catalyst surface.
14. IMPORTANT FEATURES OF SOLID CATALYST

43

Activity - The activity of a catalyst depend on the strength of chemisorption. Catalytic activity
increases from group 5 to group 11 elements of the periodic table.
Pt
2H2

O2 2H2O

Selectivity The selectivity of a catalyst is its ability to direct a reaction to yield a particular
product.
Ni

CH4 + H2O

1. CO + 3H2

Cu
2.

CO + H2

HCHO

15. SHAPE SELECTIVE CATALYSIS

The catalytic reaction that depends upon the pure substance of the catalyst and the
size of reactant and product molecules is called shape selective catalysis.
e.g.
Zeolites are good shape selective catalyst. ZSM-5 is used in petrochemicals
industry.
16. ENZYME CATALYSIS
Enzymes are protein molecules of high molecular mass which catalyse the biochemical
reaction.
e.g. Inversion of cane sugar by invertase enzyme.
17. Characteristic of enzyme catalysis
a. Enzymes are specific to substrate.
b. Enzymes are highly active under optimum temperature.
c. Enzymes are specific to pH. e.g. Pepsin act in acidic medium
d. Enzymes are inhabited by the presence of certain substance.
Mechanism of enzyme catalysis
1. Binding of enzyme to substrate to form an activated complex.
E + S ES
2. Decomposition of activated complex to form product.
ES E + P
18. Colloid-a colloid is a heterogeneous system in which one substance is
dispersed(dispersed phase)in another substance called dispersion medium and size of
dispersed phase is from 1nm-1000 nm.
19. TYPES OF COLLOIDS
(1) On the basis of nature of interaction between dispersed phase and dispersion medium.
44

(a) Lyophobic colloid-solvent , hating colloid, these colloids can not be prepared by simply
mixing of dispersed phase into dispersion medium.
e.g. metallic sols.
(b) Lyophlic colloid-solvent loving these colloids can be prepared by simply mixing of
dispersion phase into dispersion medium.
e.g. Starch sol.
(2) On the basis of types of particles of the dispersed phase
(a) Multimolecular colloid-on dissolution, a large number of atoms or smaller molecules of a
substance aggregate together to form species having size in colloidal range. The species thus
formed are called Multimolecular colloids.
e.g. Sulphur sol.
(b) Macromolecular colloids: Macromolecules are suitable solvent from solution in which size
of the particles are in range of colloidal range.
e.g. starch sol.
(c) Associated colloids (micelles)-some substances in low concentration behaves as normal
strong electrolyte but at higher concentration exhibit colloidal behavior due to formation of
aggregates. The aggregated particles are called micelles and also known as associated
colloids.
(3) Kraft temperature- Temp. above which formation of micelles takes places.
(4) Critical micelle concentration (CMC) - concentration above which micelle formation
takes place is known as CMC.
(5) PREPERATION OF COLLOIDS
(a) Chemical methods- By double decomposition, oxidation reaction or hydrolysis
OXIDATION
e.g. SO2 +2H2 S

3S (sol)+2H2 O

HYDROLYSIS
e.g. FeCl3 +3H2O Fe (OH) 3+3HCl
(sol)
(b) Bredigs arc method- For preparation of metallic sol. It involves dispersion as well as
condensation.
(c) Peptization- Process of converting a freshly prepared precipitate into colloidal sol. By
shaking it with dispersion medium in the presence of a small amount of suitable electrolyte.
(6)PURIFICATION OF COLLIODAL SOLUTION :45

(a) Dialysis-it is a process of removing a dissolved substance from a colloidal solution by

membrane.
(b)Electro dialysis-when dialysis is carried out with an electric field applied around the
membrane.
(c) Ultra filtration- Use of special filters which are permeable to all ionic substances except
colloidal particles.
(7)PROPERTIES OF COLLOIDAL SOLUTION:(1) They show colligative properties
(2) Brownian movement-zig-zag motion of colloidal particles
(3) Tyndall effect-scattering of light by colloidal particles by which path of beam becomes
clearly visible. This effect is known as tyndall effect.

1. Charge on colloidal particles Colloidal particles which carry on electric charge

and nature of charge is same on all particles.
2. Electrophoresis - Movement of Colloidal particles towards opposite electrode
in presence of external electric field.
3. Coagulation The process of setting of colloidal particles is called
coagulation of the sol.
4. Hardy Sehulze Law Coagulating value of a coagulating ion is directly
proportional to the charge on the ion.
Eg: Na + < Ca ++ < Al 3+ for negatively charged sol.
Cl - < CO 2-3 < PO 3-4 < [Fe (CN) 6 ]4 for positive sol.
5. Emulsion Liquid liquid colloidal system is known as Emulsion.
There are two types of Emulsion.
a) O/W type - Oil dispersed in water. Eg: milk, vanishing cream.
b) W/O type Water dispersed in oil. Eg: Butter & Cream.
6. Emulsifying Agent The substance which stabilizes emulsion.
VERY SHORT ANSWER TYPE QUESTION
(1 marks)

1. What are the physical states of dispersed phase and dispersion medium of
froth?
Ans - Dispersed phase is gas, dispersion medium is liquid.
2. What is the cause of Brownian movement among colloidal particles?
Ans - Due to collision between particles.
3. Arrange the solutions: True solution, colloidal solution, suspension in
decreasing order of their particles size?
Ans Suspension > colloidal > true solution.
4. Give an example of micelles system?
Ans Sodium stearate (C17 H35 COO- Na+)
5. Why is it necessary to remove CO when ammonia is obtained by Habers
process?
Ans- CO acts as poison catalyst for Habers process therefore it will lower the
activity of solution therefore it is necessary to remove when NH3 obtained by
Habers process.
46

6. How is adsorption of a gas related to its critical temperature?

Ans- Higher the critical temperature of the gas. Greater is the ease of
liquefaction.
i.e. greater Vander walls forces of attraction and hence large adsorption will
occur.
7. What is meant by Shape Selective Catalyst?
Ans On the Shape Selective Catalyst, the rate depends upon pore size of the
catalyst and the shape & size of the reactant and products molecules.
8. Of the physiorption & chemisorptions, which type of adsorption has higher
enthalpy of adsorption?
Ans - chemisorptions.
9. Write down the Example of Positive Sol?
Ans Ferric hydro-oxide sol.
10. Write down the Example of Negative Sol?
Ans Arsenic sulphide.
SHORT ANSWER TYPE QUESTION
(2 marks)

1. Differentiate between physical & chemical adsorption?

Ans
Physical adsorption
Chemical adsorption
a) Forces
between
a) Forces between adsorbate
adsorbate & adsorbent
& adsorbent are strong
are week Vander waal
chemical forces.
forces.
b) High heat of Adsorption.
b) Low heat of Adsorption.
2. Differentiate between Lyophobic & Lyophilic colloids?
3. Ans
Lyophilic colloids
Lyophobic colloids
a) These are easily formed by
a) These are easily formed by
direct mixing.
Special method.
b) Particles of colloids are not
b) Particles of colloids are
easily visible even under
easily visible under ultra
ultra microscope.
microscope.
c) These are very stable.
c) These are unstable.
4. Differentiate between multi molecular, macromolecular and associated colloids?
5. Ans:Multi
molecular
Macromolecular
Associated colloids
colloids
colloids
a) They consist of
a) They consist of
a) Behave as colloidal
aggregates
of
large
size
particles
at
atoms
or
molecules.
higher conc.
molecules which
generally
have
diameter
less
than 1nm.
b) They
have
both
b) They are usually
lyophobic character
47

lyophobic

b) They
are
& Lyophilic
hydrophilic.
6. What is difference between Sol. & Gel?
Ans Both are colloidal solutions. Sol has solid as dispersed phase & liquid as
dispersion medium. While Gel has liquid as dispersed phase and solid as
dispersion medium.
7. Action of Soap is due to Emulsification & Micelle formation? Comment.
Ans soaps are sodium & potassium salts of higher fatty acids.
Eg: C17H35COONa oil & Grease in dirt adhere firmly to clothing and is
undisturbed by washing in tap water. Soap acts as an Emulsifying agent and
brings the Greasy dirt into colloidal dispersion the hydrocarbon chain of soap
molecule is soluble in oil or grease. It dissolves in grease and encapsulates. It to
form micelle. The anionic ends of chain protrude from droplets and interact with
water molecules, preventing coalescence of droplets.
SHORT ANSWER TYPE QUESTION
(3 marks)

8. Discuss the effect of pressure & temperature on the adsorption of gases on

solids?
Ans Effect of pressure on adsorption: - At constant temp the extent of
adsorption of gas(x/m) in the solid increases with pressure. A graph between
x/m and the pressure P of a gas at constant temp is called adsorption isotherm.
Freundlich adsorption isotherm i)
At lower range of pressure, (x/m) is directly proportional to the applied
pressure.
X/m p1/n
ii)
At high pressure range, the extent of adsorption of a gas (x/m) is
independent of the applied pressure i.e.

o
X/m p
iii)
At intermediate pressure range, the value of (x/m) is proportional to the
fractional power of pressure i.e.
X/m p1/n
Where 1/n is fraction. Its value may be between 0 and 1
X/m = kp1/n
Log(x/m) = log k + 1/n log p
Effect of temp on Adsorption Adsorption is generally temp. depended.
Mostly adsorption processes are exothermic and hence, adsorption
decreases with increasing temp. However for an endothermic adsorption
process adsorption increases with increase in Temperature.
1. Explain What is observe when
i)
An electrolyte, NaCl is added to hydrate ferric oxide sol.
ii)
Electric current is passed through a colloidal sol.
iii)
When a beam of light is passed through a colloidal sol.
Ans (i) The positively charged colloidal particles of Fe(OH)3 get coagulated
by the positively charged Cl- ions provided by NaCl.
(ii) On passing direct current, colloidal particles move towards the positively
charged electrode where they lose their charge and get coagulated.
48

(iii) Scattering of light by the colloidal particles takes place and the path of
light becomes visible (Tyndall effect).
2. Describes some features of catalysis by Zeolites?
Ans Features of catalysis by Zeolites:I)
Zeolites are hydrated alumino silicates which have a three dimensional
network structure containing water molecules in their pores.
II)
To use them as catalysts, they heated so that water of hydration present
in the pores is lost and the pores become vacant.
III) The size of pores varies from 260 to 740 pm. Thus, only those molecules
can be adsorbed in these pores and catalyzed whose size is small enough
to enter these pores. Hence, they act as molecular sieves or shape
selective catalysts.
An important catalyst used in petroleum industries in zsm-5. It converts
alcohols into petrol by first dehydrating them to form a mixture of hydro
carbons.
Alcohols

Hydro carbons

3. Comment on the statement that colloid is not a substance but state of a

substance?
Ans The given statement is true. This is because the statement may exist as a
colloid under certain conditions and as a crystalloid under certain other
conditions.e.g:NaCl in water behaves as a crystalloid while in benzene, behaves
as a colloid (called associated colloid). It is the size of the particles which
matters i.e. the state in which the substance exist. If the size of the particles lies
in the range 1nm to 1000nm it is in the colloid state.
4. Write short notes on followings:(a)
Tyndall effect
(b)
Brownian Movement
(c)
Hardy Schulze Rule
Ans- (a)Tyndall effect-scattering of light by colloidal particles by which path of
beam becomes clearly visible. this effect is known as tyndall effect
(b) Brownian movement-zig-zag motion of colloidal particles.
(c) Hardy Schulze Law Coagulating value of a coagulating ion is directly
proportional to the charge on the ion.
e.g: Na + < Ca ++ < Al 3+ for negatively changed sol.
Cl - < CO32- < PO43- < [Fe (CN) 6 ]4 for positive sol.
5. Explain the following
(i) Alum is used to purify water.
(ii) Ferric chloride is preferred over potassium chloride to stop bleeding in case
of cut.
(iii) Enthalpy change is always negative for adsorption?

49

CHAPTER : 6
General Principles & Process of Isolation of Elements
Important Points :
1. The chemical substances in the earths crust obtained by mining are called Minerals.
2. Minerals, which act as source for metal, are called Ore. From ore metal can be obtained
economically.
3. The unwanted impurities present in ore are called Gangue.
4. The entire process of extraction of metal from its ore is called Metallurgy.
5. Removal of gangue from ore is called Concentration, Dressing or Benefaction of ore.
6. Concentration by Hydraulic washing is based on the difference in gravities of ore and
gangue particles.
7. Concentration by Magnetic separation is based on differences in magnetic properties of
ore components. If either of ore or gangue is capable of attracted by a magnet field,
then such separation is carried out.
8. Concentration by Froth Flotation Process is based on the facts that sulphide ore is
wetted by oil & gangue particles are wetted by water.
9. Concentration by Leaching is based on the facts that ore is soluble in some suitable
reagent & gangue is insoluble in same reagent. e.g. Bauxite ore contains impurities of
silica, iron oxide & TiO2 .The powdered ore is treated with NaOH which dissolve Al &
impurities remains insoluble in it.
Al2O3 +2NaOH + 3 H2O
2 Na [Al(OH)4].
10. Calcination involves heating of ore in absence of air below melting point of metal. In
this process volatile impurities escapes leaving behind metal oxide.
Fe2O3.xH2O
ZnCO3

Fe2O3 +xH2O
ZnO +CO2

11. Roasting involves heating of ore in presence of air below melting point of metal in
reverberatory furnace. In this process volatile impurities escapes leaving behind metal
oxide and metal sulphide converts to metal oxide.
2 ZnS + 3 O2
2PbS + 3 O2

2ZnO+2SO2
2 PbO +2 SO2

12. Reduction of metal oxide involves heating of metal in presence of suitable reagent
Coke or CO.
13. Reactions taking place at different zones of blast furnace in extraction of iron:(i) Zone of reduction:- Temperature range 250oC-700oC
50

3Fe2O3+CO

2Fe3O4+CO2

Fe3O4+CO

3FeO+ CO2

FeO +CO

Fe+ CO2

(ii) Zone of slag formation:- Temperature range 800oC-1000oC

CaCO3

CaO+CO2

CaO+SiO2

CaSiO3,

SiO2+2C

Si+2CO,

P4O10+10C

4P+10CO,

MnO2+2C

Mn+2CO

(iii) Zone of fusion: - Temperature range 1150oC-1350oC

CO2 + C

2CO

(iv) Zone of fusion: - Temperature range 1450oC-1950oC

C +O2

CO2

14. FLOW SHEET FOR EXTRACTION OF IRON:Iron ore(Magnetite

Fe3O4)(Haematite Fe2O3)

Concentration is done by Gravity separation followed by magnetic separation

Calcination &Roasting i.e. Ore + Air +HeatMoisture,CO2,SO2, As2O3 removed And

FeO oxidized to Fe2O3

Smelting of charge i.e. mixture of ore, coke & CaCO3 takes place in long BLAST
FURNACE. Following reaction take place at different zones:(refer to point 13)

51

Pig iron is obtained, which is remelted and cooled then cast iron is obtained

15. Pig Iron: - It contains Fe 93-95%, Carbon 2.5-5%, and Impurities 3%.
16. Cast Iron: - It contains Fe 99.5-99.8%, Carbon 0.1-0.2% Impurities 0.3%.
17. Spongy iron: - Iron formed in the zone of reduction of blast furnace is called spongy iron. It contains impurities
of C, Mn , Si, etc.

18. FLOW SHEET FOR EXTRACTION OF COPPER:Copper Pyrites CuFeS2

Concentration is done by Froth floatation process

Powdered ore + water +pine oil +air Sulphide ore in the froth

Roasting is presence of air. following reactions take place:S+ O2SO2,

4As+3O22As2O3,

2CuFeS2+O2 Cu2S+2FeS+SO2

Smelting in small blast furnace of a mixture of Roasted ore, coke, and silica.
2FeS + 3O2 2FeO + 2SO2,

FeO + SiO2 FeSiO3(slag)

A mixture of Cu2S, FeS & silica is obtained from blast furnace known as Copper matte

Bessemerisation of copper matte is done in Bessemer converter in presence of air. Following

reactions take place:2FeS + 3O22FeO +2 SO2, FeO + SiO2 FeSiO3 (slag),
2Cu2S + 3O2 2Cu2O+2SO2, 2Cu2O+2Cu2S 6Cu + SO2

52

Melted copper is cooled, and then SO2 is evolved. such copper is known as BLISTER
COPPER(98%Cu+2% impurities)

19. FLOW SHEET FOR EXTRACTION OF ALUMINIUM:Bauxite Al2O3.2H2O

Concentration of ore is done by leaching .Bauxite is treated with NaOH

.Following reaction takes place:Al2O3 +2NaOH + 3 H2O
TiO2 &SiO2 are removed.

2 Na [Al (OH) 4] and impurities of Fe2O3,

Na [Al (OH)4] ,then reacts with CO2 then pure Alumina is obtained.
Na [Al(OH)4] + 2CO2 Al2O3.xH2O + 2NaHCO3

Electrolytic reduction of pure alumina takes place in iron box (cathode) with
cryolite (Na3AlF6) & fluorspar CaF2.Graphide rods act as anode. Following reactions
take place:At cathode:- Al3+ + 3e Al, At Anode:- 2O2- O2 + 4e

By this process 98.8% pure Aluminum is obtained.

20. Vapour phase refining is used for extraction of Nickel (MOND PROCESS) and Zirconium &Titanium (VAN ARKEL
PROCESS).

Monds process : Ni 4CO

[ Ni(CO)4 ]
Ni 4CO

VAN ARKEL PROCESS: Zr 2I 2

ZrI 4
Zr 2I 2

21. Zone refining is used for extraction of Si, Ge, Ga, etc.

53

22. Chromatography method is based on selective distribution of various constituents of a mixture between two
phases, a stationary phase and a moving phase. The stationary phase can be either solid or liquid on solid
support.
22. Column chromatography is based on adsorption phenomenon. This method is useful for those elements,
which are available in small amounts and the impurities are not much different in chemical properties from the
element to be purified.

VERY SHORT ANSWER TYPE QUESTION

(1 marks)
Q.1- What is slag?
A.1- It is easily fusible material, which is formed when gangue still present in roasted ore combines with the flux.
e.g. CaO (flux) + SiO2 (gangue) CaSiO3 (slag)
Q.2- Which is better reducing agent at 983K, carbon or CO?
A.2- CO, (above 983K CO being more stable & does not act as a good reducing agent but carbon does.)
Q.3- At which temperature carbon can be used as a reducing agent for FeO ?
A.3- Above 1123K, carbon can reduce FeO to Fe.
Q.4- What is the role of graphite rods in electrometallurgy of aluminium ?
A.4- Graphite rods act as anode, are attacked by oxygen to form CO2 and so to be replace time to time.
Q.5- What is the role of cryolite in electrometallurgy of aluminium?
A.5- alumina cannot be fused easily because of high melting point. Dissolving of alumina in cryolite furnishes Al3+
ions, which can be electrolyzed easily.
Q.6- What are depressants?
A.6- It is possible to separate two sulphide ore by adjusting proportion of oil to water in froth flotation process by
using a substance known as depressant.
e.g. NaCN is used to separate ZnS and PbS.
Q.7- Copper can be extracted by hydrometallurgy but not Zn. Why?
A.7- The E0 of Zn is lower than that of Cu thus Zn can displace Cu2+ ion from its solution. On other hand side to
displace Zn from Zn2+ ion, we need a more reactive metal than it.

SHORT ANSWER TYPE QUESTION

(2 marks)
Q.1 Describe the method of refining of nickel.
54

A.1- In the Mond Process, Ni is heated in a stream of CO forming a volatile complex, which then decomposes at
higher temperature to give Ni.
At 330-350K: -

Ni + 4CO Ni (CO) 4

At 450-470K

Ni (CO)4 Ni + 4 CO

Q.2- What is Zone Refining? Explain with example.

A.2- Zone refining is a method of obtaining a metal in very pure state. It is based on the principal that impurities
are more soluble in molten state of metal than solidified state.
In this method, a rod of impure metal is moved slowly over circular heater. The portion of
the metal being heated melts & forms the molten zone. As this portion of the rod moves out of heater, it
solidified while the impurities pass into molten zone. The process is repeated to obtain ultrapure metal and end
of rod containing impure metal cutoff.
Q.3 Write the principle of electro-refining.
A.3- In this method of purification impure metal is made Anode and pure metal is made the cathode. On passing
electricity, pure metal is deposited at the cathode while the impurities dissolve in solution as anode mud. E.g.
electro- refining of copper:At Cathode: -

Cu2+ + 2e

At Anode: -

Cu Cu2+ + 2e

Cu

Q.4- Write difference between calcinations and roasting.

A.4- Refer points no 10 &11.
Q.5- Describe the method of refining of Zirconium and Titanium.
A.5- Van Arkel process is used for obtaining ultrapure metal. The impure metal is converted into volatile
compound, which then decomposes electrically to get pure metal.
At 850K: - Zr impure) + 2 I2 ZnI4
At 2075K:-

ZnI4 Zr (pure) + 2 I2

Q.6- Out of C & CO, which is better reducing agent for ZnO?
A.6- Since free energy of formation of CO from C is lower at temperature above 1120K while that of CO2 from
carbon is lower above 1323K than free energy of formation 0f ZnO. However, the free energy of formation of CO 2
from CO is always higher than that of ZnO. Hence, C is better reducing agent of ZnO.
Q.7- The value of f G0 for Cr2O3 is -540kJ/mole & that of Al2O3 is -827kJ/mole. Is the reduction of Cr2O3 possible
with aluminium?
A.7- The desired conversion is
4 Al + 2Cr2O3

2Al2O3 + 4Cr

It is obtained by addition of following two reactions:55

4Al + 3O2 2 Al2O3

2Cr2O3

4Cr + 3O2

f G0=-827kJ/mole
f G0==+ 540 kJ/mole

Therefore, G0 for desired reaction is -827+540=-287, as a result reduction is possible.

Q.8:- Why copper matte is put in silica lined converter?
A.8:- Copper matte consists of Cu2S and FeS. When blast of air is passed through molten matte in silica-lined
converter, FeS present in matte is oxidized to FeO, which combines with silica to form slag.
(i) 2FeS + 3O22FeO +2 SO2,
(III) 2Cu2S + 3O2 2Cu2O+2SO2,

(ii) FeO + SiO2 FeSiO3 (slag),

(IV) 2Cu2O+2Cu2S 6Cu + SO2

Q.9- What is meant by term chromatography?

A.9-Chromato means Colour and graphy means writing because the method was first used for separation of
coloured substance. It is based on selective distribution of various constituents of a mixture between two phases,
a stationary phase and a moving phase. The stationary phase can be either solid or liquid on solid support.
Q.10-Why is reduction of metal oxide easier if metal formed is in liquid state at temperature of reduction.
A.10- The entropy of a substance is higher in liquid state than solid state. In the reduction of metal oxide, the
entropy change will be positive if metal formed is in liquid state. Thus, the value of G0 becomes negative and
reduction occurs easily.

SHORT ANSWER TYPE QUESTION

(3 marks)
Q.1- Explain the following:(i) Zinc but not copper is used for recovery of Ag from the complex [Ag(CN)2]-.
(ii) Partial roasting of sulphide ore is done in the metallurgy of copper.
(iii) Extraction of Cu from pyrites is difficult than that from its oxide ore through reduction.
A.1- (i) Zn is more powerful reducing agent in comparison to copper.Zn is also cheaper than Cu.
(ii) Partial roasting of sulphide ore forms some oxide. This oxide then reacts with remaining sulphide ore to give
copper i.e. self-reduction occurs.
2Cu2S + 3O2 2Cu2O+2SO2,
2Cu2O+2Cu2S 6Cu + SO2 .
(iii) Though carbon is good reducing agent for oxide but it is poor reducing agent for sulphides. The reduction of
metal sulphide does not have large negative value.
Q.2- Name the principle ore of aluminium and describe how Al is extracted from its ore.
56

Q.3- Describe the principles of extraction of Zinc from zinc blende .

A.3- Important ores of Zn:-Zinc blende - ZnS, Calamine- ZnCO3, and Zincite ZnO. ZnS is commercially important
ore of Zn.Various stages involved in the extraction of Zn from ZnS are as following:(i) Concentration of ore:-It is concentrated by Froth flotation process followed by gravity separation process.
(ii) Roasting:- The concentrated ore is roasted in presence of air. Following reactions take place:2ZnS + 3O2

2ZnO + 2SO2

The mass obtained during roasting is porous and is called porous clinker.
(iii) Reduction of ZnO to Zn: - ZnO is made into bricketts with coke and clay and heated ai1163K.Zn formed distills
off and is collected by rapid cooling of zinc vapours.
ZnO + C Zn + CO
***

57

7. p-Block Elements
Points to remember:The general valence shell electronic configuration of p-block elements ns2 np1-6
GROUP 15 ELEMENTS:Group 15 elements ; N, P, As, Sb & Bi
General outer electronic configuration: ns2np3
Physical Properties: Dinitrogen is a diatomic gas while all others are solids.
N & P are non-metals. As & Sb metalloids & Bi is a metals .this is due to decrease in ionization enthalpy &
increase in atomic size .
Electro negativity decreases down the group .
Chemical properties:o Common oxidation states : -3, +3 & +5.
o Due to inert effect, the stability of +5 state decreases down the group & stability of +3 state increases .
o In the case of Nitrogen all Oxidation states from +1 to +4 tend to disproportionate in acid solution , e.g.:3HNO3H2O +2NO
Anamalous behavior of Nitrogen :- due to its small size, high electronegativity, high ionization enthalpy
and absence of d-orbital.
N2 has unique ability to p-p multiple bonds whereas the heavier of this group do not form p p
because there atomic orbitals are so large & diffuse that they cannot have effective overlapping.
Nitrogen exists as diatomic molecule with triple bond between the two atoms whereas other elements
form single bonds in elemental state.
N cannot form d-p due to the non availibility of d-orbitals whereas other elements can.
Trends In Properties:Stability - NH3>PH3>AsH3>SbH3>BiH3
Bond Dissociation Enthalpy- NH3>PH3>AsH3>SbH3>BiH3
Reducing character - NH3>PH3>AsH3>SbH3>BiH3
Basic character- NH3>PH3>AsH3>SbH3>BiH3
Acidic character- N2O3>P2O3>As2O3>Sb2O3>Bi2O3
Boiling points- BiH3>SbH3>NH3>AsH3>PH3
Acidic Character- N2O3<N2O4<N2O5
Dinitrogen:Preparation
Commercial preparation By the liquification& fractional distillation of air.
Laboratory preparation By treating an aqueous solution NH4Cl with sodium nitrate .
NH4Cl +NaNO2N2 + 2H2O + NaCl
Thermal decomposition of ammonium dichromate olsogise N2.
(NH4)2Cr2O7 N2 +4H2O + Cr2O3
Thermal decomposition of Barium or Sodium azide gives very pure N2.
58

PROPERTIES
At high temperature nitrogen combines with metals to form ionic nitride (Mg3N2) & with non-metals ,
covalent nitride.
AMMONIA PREPARATION
In laboratory it is prepared by heating ammonium salt with NaOH or lime.
2NH4Cl + Ca(OH)22NH3+2H2O + CaCl2
In large scale it is manufactured by Haber process
N2+3H2=2NH3
H0= -46.1kJ/mol
Acc.to Lechateliers principle the favourable conditions for the manufacture of NH3 are:Optimum temperature : 700 K
High pressure : 200 atm
Catalytst: Iron Oxides
Promoter : K2O & Al2O3
PROPERTIES
Ammonia is a colorless gas with pungent odour.
Highly soluble in water.
In solids & liquid states it exists as an associated molecule due to hydrogen bonding which accounts for high
melting & boiling points of NH3
Trigonal Pyramidal shape NH3 molecule.
Aqueous solution of ammonia is weakly basic due to the formation of OH-ion .
ZnSO4+ 2NH4OHZn(OH)2+ (NH4)2SO4
Ammonia can form coordinate bonds by donating its lone on nitrogen, ammonia forms complexes.
CuSO4+4NH3[Cu(NH3)4]2SO4
Name

Formula

Oxidation state

Chemical nature

Nitrous oxide or
Laughing gas
Nitric oxide

N2O

+1

Neutral

NO

+2

Neutral

Dinitrogen trioxide

N2O3

+3

Acidic

Dinitrogen tetra oxide

N2O4or NO2

+4

Acidic

Dinitrogenpentaoxide

N2O5

+5

Acidic

NITRIC ACID
PREPARATION:ostwaldsprocees it is based upon catalytic oxidation of ammonia by atmospheric oxidation . The
main steps are

59

Rh Pt guage
4 NH 3 5O2
4 NO 6H 2O

2 NO O2 2 NO2
3NO2 H 2O 2HNO3 NO

PROPERTIES:(i) conc. HNO3 is a strong oxidizing agent & attacks most metals gold & Pt. .
(ii)Cr & Al do not dissolve HNO3 because of the formation of a positive film of oxide on the surface.
(iii) Itoxidisesnon metals like I2 to HNO3, C to CO2 , S to H2so4
(iv) Brown ring test is used to detect NO3-.
PHOSPHOROUS:ALLOTROPIC FORMS: White , red -black &-black .
White phosphorous is more reactive red phosphorous because white P exists as discrete P4molecules .in red P
several P4molecules are linked to formed polymeric chain.
PHOSPHINE
Preparation:It is prepared in laboratory by heating white P with concentrated NaOH solution in an
Inert atmosphere of CO2 [P4+3NaOH+3H2O PH3+3NaH2PO2]
Phosphorous halides
Phosphorous forms two types of halides PX3& PX5 (X=F,I,Br)
Trihalides have pyramidal shape and pentahalides have trigonalbipyramidal structure.
OXOACIDS OF PHOSPHOROUS

The acids in +3 oxidation state disproportionate to higher & lower oxidation.

4H3PO3 3H3PO4+PH3

Acids which contains P-H bond have strong reducing properties.EX:-H3PO2

Are ionisable and cause the basicity.

Hydrogen atom which are attached with oxygen in P-OH form are ionisable

GROUP-16 ELEMENTS (CHALCOGENS)

Grouo 16 Elements:O,S,Se,Te,Po
General electronic configuration:ns2np4
ATOMIC & PHYSICAL PROPERTIES

Ionisation enthalpy decreases from oxygen to polonium.

60

Oxygen atom has less negative electron gain enthalpy than S because of the compact nature of the
oxygen atom.However from the S onwards the value again becomes less negative upto polonium.
Electronegativity gradually decreases from oxygen to polonium,metallic character increases from
oxygen to polonium.
Oxygen & S are non-metals,selenium and telurium are metalloids.Po is a radioactive metal.
Oxygen is a diatomic gas while S,Se&Te are octa atomic solid S8,Se8&Te8 molecules which has
puckered ring structure.

CHEMICAL PROPERTIES

Common oxidation state:- -2,+2,+4 &+6.

Due to inert pair effect,the stability of +6 decreases down the group and stability of +4
increases.

Oxygen exhibits +1 state in O2F2,+2 in OF2.

Anamolous behavior of oxygen-due to its small size,high electronegativity and absence of d-orbitals.
TREND IN PROPERTIES
Acidic character-H2O<H2S<H2Se<H2Te
Thermal stability-H2O>H2S>H2Se>H2Te
Reducing character-H2S<H2Se<H2Te
Boiling point-H2S<H2Se<H2Te<H2O
Reducing property of dioxides-SO2>SeO2>TeO2
Stability of halides-F>Cl>Br>I
HALIDES OF SULPHUR
DI HALIDES:sp3hybridisation but angular structure,SCl2
TETRA HALIDES:SP3hybridisation-see-saw geometry,SF4
HEXA HALIDES:sp3d2,octahedral SF6
DIOXYGEN
2Fe3++SO2+2H2O2Fe2+ + SO42- + 4H+
5SO2+2MnO4- +2H2O5SO42- +4H+ +2Mn2+
SO2 molecule is angular.

OXIDES
A binary compound of oxygen with another element is called oxide. Oxides can be classified on the
basis of nature

61

Acidic Oxides:-Non metallic oxides. Aqueous solutions are acids. Neutralize bases to form
salts.Ex:So2,Co2,N2O5 etc.
Basic Oxides:metallicoxides.Aqueous solutions are alkalis. Neutralize acids to form
salts.Ex:Na2O,K2o,etc.
Amphoteric oxides:-some metallic oxides exhibit a dual behavior. Neutralize bothacids& bases
to form salts.
Ex:-Al2O3,SbO2,SnO,etc..
Neutral non metal oxide CO, N2O, NO

OZONE
PREPARATION
Prepared by subjecting cold, dry oxygen to silent electric discharge.
3O22O3

PROPERTIES
Due to the ease with which it liberates atoms of nascent oxygen, it acts as a powerful
oxidizing agent. For eg:- it oxidisesleadsulphide to lead sulphate and iodide ions to iodine.
PbS+4O3PbSO4+4O2

SULPHUR DIOXIDE
PREPARATION
Burning of S in air
S+O2SO2
Roasting of sulphide minerals
(Iron pyrites)
4FeS2+11022Fe2O3+8SO2
(Zinc blend)2ZnS+3O22ZnO+2SO2

PROPERTIES

Highly soluble in water to form solution of sulphurous acid

SO2+H2OH2SO3
SO2 reacts with Cl2 to form sulphuryl chloride
SO2+Cl2SO2Cl2
It reacts with oxygen to form SO3 in presence of V2O5 catalyst
2SO2+O22SO3

Moist SO2 behaves as a reducing agent. It converts Fe(III) ions to Fe(II) ions&decolourises
acidified potassium permanganate (VII) solution( It is the test for the gas).
SULPHURIC ACID
PREPARATION
It is manufactured by contact process which involves following reactions.
62

S+O2SO2
V2O5

2SO2+O2
2SO3
SO3+H2SO4 H2S2O7
H2S2O7 + H2O 2H2SO4

63

PROPERTIES
1. H2SO4 is a di-basic acid which ionizes as -

H 2 SO4 H 2O H 3O HSO4
HSO4 H 2O H 3O SO42
2. It is a strong dehydrating agent Eg:-charring action of sugar
H 2 SO4
C12 H 22O11
12C 11H 2O

It is a moderately strong oxidizing agent.

Cu+2H2SO4(conc.) CuSO4+SO2+2H2O
C+2H2SO4(conc.)CO2+2SO2+2H2O
GROUP 17 ELEMENTS(HALOGENS)
Group 17 elements: F,Cl,Br,I,At
General electronic configuration:ns2np5
ATOMIC & PHYSICAL PROPERTIES
i.
ii.
iii.
iv.
v.
vi.

Atomic & ionic radii increase from fluorine to iodine.

Ionization enthalpy gradually decreases from fluorine to iodine due to increase in atomic size.
Electron gain enthalpy of fluorine is less than that of chlorine. It is due to small size of fluorine &
repulsion between newly added electron &electrons already present in its small 2p orbital.
Electronegativity decreases from fluorine to iodine. Fluorine is the most electronegative element in the
periodic table.
The colour of halogens is due to absorption of radiations in visible region which results in the excitation of
outer electrons to higher energy level.
Bond dissociation enthalpy of fluorine is smaller than that of chlorine is due to electron-electron repulsion
among the lone pair in fluorine molecules where they are much closer to each other than in case of
chlorine. The trend: Cl-Cl>Br-Br>F-F>I-I.
CHEMICAL PROPERTIES
OXIDATION STATES:-1.However, chlorine, bromine &iodine exhibit +1, +3, +5, +7 oxidation states
also.
Fluorine forms two oxides OF2 and O2F2. These are essentially oxygen fluorides because of the higher
electronegativity of fluorine than oxygen.
Anomalous behavior of fluorine- due to its small size, highest electronegativity, low F-F bond
dissociation enthalpy and absence of d-orbitals.
TRENDS IN PROPERTIES
Oxidizing property F2>Cl2>Br2>I2
Acidic strength- HF<HCl<HBr<HI
Stability & bond dissociation enthalpy- HF>HCl>HBr>HI
Stability of oxides of halogens- I>Cl>Br
Ionic character of halides MF>MCl>MBr>MI
CHLORINE
PREPARATION
1. MnO2 +4HClMnCl2+Cl2+2H2O
2. 4NaCl+MnO2+4H2SO4MnCl2+4 NaHSO4+2H2O+Cl2
3. 2KMnO4+16HCl2KCl+2MnCl2+8H2O+5Cl2
64

4. DEACONS PROCESS
4HCl+O2CuCl22Cl2+2H2O
5. By electrolysis of brine solution. Cl2 is obtained at anode.
PROPERTIES
i.

With cold and dilute Cl2 produces a mixture of chloride and hypochlorite but with hot and
concentrated alkalis it gives chloride and chlorate.

2 NaOH Cl2 NaCl NaOCl H 2O

cold & dil

6 NaOH 3Cl2 5 NaCl NaClO3 3H 2O

hot &conc

ii.

With dry slaked lime it gives bleaching powder.

Ca (OH) 2+Cl2Ca (OCl)Cl+ H2O

iii.

It is a powerful bleaching agent; bleaching action is due to oxidation

Cl2+H2O2HCl+(O)
Colored substance+(O)colorless substance

iv.

Action of concentrated H2SO4 on NaCl giveHCl gas.

NaCl+H2SO4420KNaHSO4+HCl
3:1 ratio of conc. HCl& HNO3 is known as aquaregia& it is used for dissolving noble
metals like Au and Pt.
OXOACIDS OF HALOGENS (SEE TABLE 7.10& FIG.7.8)

Interhalogen compounds
They are prepared by direct combination of halogens.
Ex: ClF, ClF3, BrF5, IF7
They are more reactive than halogens because X-X is weaker than X-X bonds in halogens
(except F-F).
TYPE

STRUCTURE

XX3

Bent T-shaped

XX5

Square pyramidal

XX7

Pentagonal bipyramidal

65

GROUP 18 ELEMENTS
GROUP 18 ELEMENTS: He, Ne, Ar,Kr,Xe&Rn
General electronic configuration:ns2np6
Atomic radii- large as compared to other elements in the period since it corresponds to
Vander Waal radii.
Inert due to complete octet of outermost shell, very high ionization enthalpy & electron
gain enthalpies are almost zero.
The first noble compound prepared by Neil Bartlett was XePtF6&Xenon. O2+PtF6-.led to
the discovery of XePtF6 since first ionization enthalpy of molecular oxygen (1175kJmol-1)
was almost identical with that of xenon (1170kJmol-1).
PROPERTIES

XeF2
Xe+F2
1bar
673 K

873k
XeF4(s)
Xe (g) +2F2 (g)
7 bar
573k
XeF6(s)
Xe (g) +3F2 (g)
6070bar

XeF6+MFM+ [XeF7]XeF2+PF5[XeF]+[PF6]XeF6+2H2OXeO2F2+4HF(partial hydrolysis)

66

SOLVED QUESTIONS
1 MARK QUESTIONS
1. Ammonia has higher boiling point than phosphine. Why?
-AMMONIA FORMS INTERMOLECULAR H-BOND.
2. Why BiH3 the strongest reducing agent amongst all the hydrides of group 15 elements ?
3. Why does PCl3 fume in moisture ?
In the presence of (H2O) , PCl3 undergoes hydrolysis giving fumes of HCl .
PCl3 + 3H2O H3PO3 + 3HCl
4. What Happens when H3PO3is Heated ?
It disproportionate to give orthophosphoric acid and Phosphine .
4H3PO3 3H3PO4 PH3
5. Why H2S is acidic and H2S is neutral ?
The S---H bond is weaker than O---H bond because the size of S atomis bigger than that of O
atom . Hence H2S can dissociate to give H+ Ions in aqueous solution .
6. Name two poisonous gases which can be prepared from chlorine gas ?
Phosgene (COCl2) , tear gas (CCl3NO2)
7. Name the halogen which does not exhibit positive oxidation state .
Flourine being the most electronegative element does not show positive oxidation state .
8. Iodine forms I3- but F2 does not form F3- ions .why?
Due to the presence of vacant D-orbitals , I2 accepts electrons from I-ions to form I3-ions , but
because of d-orbitals F2 does not accept electrons from F-ions to form F3 ions.
9. Draw the structure of peroxosulphuricacid .
10. Phosphorous forms PCl5 but nitrogen cannot form NCl5. Why?
Due to the availability of vacant d-orbital in p.

2 MARK QUESTION (SHORT ANSWER TYPE QUESTION)

1. Why is HF acid stored in wax coated glass bottles?
67

This is because HF does not attack wax but reacts with glass.It dissolves SiO2 present in
glass forming hydrofluorosilicic acid.
SiO2 +6HFH2SiF6+2H2O
2. What is laughing gas? Why is it so called?How is it prepared?
Nitrous oxide (N2O) is called laughing gas, because when inhaled it produced hysterical
laughter. It is prepared by gently heating ammonium nitrate.
NH4NO3N2O+2H2O
3. Give reasons for the following:
(i) Conc.HNO3 turns yellow on exposure to sunlight.
(ii) PCl5 behaves as an ionic species in solid state.
Ans- (i)Conc HNO3 decompose to NO2 which is brown in colour& NO2 dissolves in HNO3 to
it yellow.
(ii)It exists as [PCl4]+[PCl6]- in solid state.
4. What happens when white P is heated with conc.NaOH solution in an atmosphere of
CO2? Give equation.
Phosphorus gas will be formed.
P4+3NaOH+3H2OPH3+3NaH2PO2
5. How is ozone estimated quantitatively?
When ozone reacts with an excess of potassium iodide solution
Buffered with a borate buffer (Ph9.2), Iodide is liberated which can be titrated against a
standard solution of sodium thiosulphate . This is a quantitative method for estimating
O3gas.
6. Are all the five bonds in PCl5 molecule equivalent? Justify your answer.
PCl5 has a trigonalbipyramidal structure and the three equatorial P-Cl bonds are
equivalent, while the two axial bonds are different and longer than equatorial bonds.
7. NO2 is coloured and readily dimerises.Why ?

68

NO2 contains odd number of valence electrons.It behaves as a typical odd molecules .On
dimerization; it is converted to stable N204 molecule with even number of electrons.
8. Write the balanced chemical equation for the reaction of Cl2 with hot and
concentrated NaOH .Is this reaction a dispropotionationreaction? Justify:
3Cl2+6NaOH5NaCl+NaClO3+3H2O
Yes, chlorine from zero oxidation state is changed to -1 and +5 oxidation states.
9. Account for the following.
(i)SF6 is less reactive than SF4
(ii) 0f the noble gases only xenon forms chemical compounds.
Ans-(i)In SF6 there is less repulsion between F atoms than In SF4.
(II)Xe has low ionisation enthalpy & high polarising power due to larger atomic size.
10. With what neutral molecule is ClO-Isoelectronic? Is that molecule a Lewis base?
ClF .Yes, it is Lewis base due to presence of lone pair of electron.

69

3 MARK QUESTIONS
1(i) why is He used in diving apparatus?
(ii)Noble gases have very low boiling points.Why?
(iii)Why is IClmoe reactive than I2?
Ans-(I)It is not soluble in blood even under high pressure.
(ii)Being monoatomic they have weak dispersion forces.
(ii)I-Cl bond is weaker than l-l bond
2. Complete the following equations.
(i)XeF4+H2O
(ii)Ca3P2+H2O
(iii)AgCl(s) +NH3 (aq)
Ans-(i) 6XeF4+12H2O4Xe+2XeO3+24HF+3O2
(ii)Ca2P2+6H2O3Ca (OH) 2+2PH3
(iii)AgCl(s) +2NH3 (aq)[Ag(NH3)2]Cl(aq)
3. (i)How is XeOF4 prepared ?Draw its structure.
(ii)When HCL reacts with finely powdered iron, it forms ferrous chloride and not ferric
chloride .Why?
(i)Partial hydrolysis of XeF6
XeF6+H2OXeOF4+2HF
Structure-square pyramidal. See Fig7.9
(ii) Its reaction with iron produces H2
Fe+2HClFeCl2+H2
Liberation of hydrogen prevents the formation of ferric chloride.
5 MARK QUESTION
1. Account for the following.
70

(i)Noble gas form compounds with F2&O2 only.

(ii)Sulphur shows paramagnetic behavior.
(iii)HF is much less volatile than HCl.
(iv)White phosphorous is kept under water.
(v)Ammonia is a stronger base than phosphine.
Ans-(i)F2&O2 are best oxidizing agents.
(ii)In vapour state sulphur partly exists as S2 molecule which has two unpaired electrons
in the antibonding pi *orbitals like O2 and, hence, exhibitparamagnetism.
(iii)HF is associated with intermolecular H bonding.
(iv) Ignition temperature of white phosphorous is very low (303 K). Therefore on
explosure to air, it spontaneously catches fire forming P4O10. Therefore to protect it from
air, it is kept under water.
(v)Due to the smaller size of N, lone pair of electrons is readily available.
2. When Conc. H2SO4 was added to an unknown salt present in a test tube, a brown gas
(A) was evolved. This gas intensified when copper turnings were added in to test tube.
On cooling gas (A) changed in to a colourless gas (B).
(a)Identify the gases A and B
(b)Write the equations for the reactions involved
The gas A is NO2 whereas B is N2O4.
XNO3 + H2SO4XHSO4 + HNO3
Salt

(conc.)

Cu + 4HNO3 (Conc.) Cu (NO3)2 + 2NO2 + 2H2O

Blue

Brown (A)

2NO2 (on cooling) N2O4

Colourless(B)
3. Arrange the following in the increasing order of the property mentioned.
71

(i)HOCl, HClO2, HClO3, HClO4 (Acidic strength)

(ii)As2O3, ClO2, GeO3, Ga2O3 (Acidity)
(iii)NH3, PH3, AsH3, SbH3 (HEH bond angle)
(iv)HF, HCl, HBr, HI (Acidic strength)
(v)MF, MCl, MBr, MI (ionic character)
Ans(i)Acidic strength:HOCl<HClO2<HCIO3<HCIO4
(ii)Acidity: Ga2O3<GeO2<AsO3<CIO2
(iii)Bond angle: SbH3<AsH3<PH3<NH3
(iv)Acidic strength: HF<HCl<HBr<HI
(v)Ionic character: MI<MBr<MCl<MF
ASSIGNMENTS
Very shot answer type questions:
1) PH3 has lower boiling point than NH3. Explain.
2) Why are halogens coloured.
3) What are chalcogens?
4) Which noble gas is Radioactive?
5) Explain why fluorine always exhibit an oxidation state of - 1 only.
6) Which compound led to the discovery of compounds of noble gas?
7) Name the most electronegative element.
8) Why is OF6 compound not known?
9) Why is N2 not particularly reactive?
10) Ammonia acts as ligand. Explain.
Short answer type questions:
72

1) White Phosphorous is more reactive than red phosphorous. Explain.

2) Why do noble gases have comparatively large atomic sizes?
3) Arrange in decreasing order of Ionic character
M F, M Cl, M Br, M I
4) Phosphinic acid behaves as a monoprotic acid
5) Arrange the following in the order of property indicated:
a)AS2O3, ClO2, GeO2, Ga2O3__Increasing acidity
b) H2O, H2S, H2Se, H2Te__Increasing acid strength.
6) Arrange in decreasing order of bond energy:
F2, Cl2, Br2, I2
7) Complete the following:
i) HNO3 +P4O10

ii) IO-3 + I- + H+
8) Give the chemical reactions in support of following observations:
a) The +5 oxidation state of Bi is less stable than +3 oxidation state.
b) Sulphur exhibits greater tendency for catenation than selenium.
9) How would you account for following?
i)Enthalpy of dissociation of F2 is much less than that of Cl2.
ii)Sulphur in vapour state exhibits paramagnetism.
10) Draw structures of following:
a)Peroxomonosulphuric acid (H2SO5)
b)XeF4
Level III
1. Complete and balance:
73

i) F2 + H2O Cold
ii) BrO-3 + F2 + OH-
iii) Li + N2 (cold)
iv) NH3 + NaOCl
2) Despite lower electron affinity of F2, is stronger oxidising agent than Cl2. Explain.
3) Give reasons:
a) Nitric oxide becomes brown when released in air.
b) PCl5 is ionic in nature in the solid state.
4) Which of the two is more covalent SbCl3 or SbCl5?
5) Addition of Cl2 to Kl solution gives if brown colour but excess at if turns it colourless.
Explain.
Identify hybridization state of central atom and use concept of VSEPR theory .also its
shape (geometry) and draw the structure.
PCl3
PCl5
BrF3
XeF2
XeF4
XeOF4
XeO3
XeF6

sp3
sp3d
sp3d
sp3d
sp3d2
sp3d2
sp3
sp3d3

bp=3
bp=5
bp=3
bp=2
bp=4
bp=5
bp=3
bp=6

lp=1
lp=0
lp=2
lp=3
lp=2
lp=1
lp=1
lp=1

SF4

sp3d

bp=4

lp=1

Pyramidal
Trigonalbipyramid
T- Shape
Linear
Sq Plane
Sq Pyramid
Pyramidal
Distorted
Octahedral
Sea Saw

74

75

76

77

Chapter:-8 The d-and f-Block Elements

POINTS TO BE REMEMBERED:
The elements of periodic table belonging to group 3 to 12 are known as d-Block elements.
The general electronic configuration of these elements is (n -1)d1-10 ns 1-2
d- Block elements are collectively known as Transition Elements because properties of these
elements vary in between s-Block and p-Block elements.
A transition element should have partially filled (n-1) d orbital.
Group 12 elements i.e. Zn, Cd, Hg have completely filled (n-1) d-orbital in atomic & ionic state &
thus these elements are considered as Typical Transition Elements.
All these elements are metals. They are less electropositive than s-block elements & more
electropositive than p-block elements.
The atomic radii decreases from group 3 to 6 (i.e. Sc to Cr) because of increase in effective nuclear
charge gradually.
The atomic radii of group 7,8 9 &10 elements (i.e. Fe,Co,Ni) is almost same because pairing of
electrons take place in (n-1)d orbital causing repulsion i.e. shielding of (n-1)d orbital.
Group 11 &12 elements i.e. Cu & Zn have bigger size due to strong shielding of completely filled (n1)d orbital.
The transition elements show variable oxidation state due to small energy difference between (n1)d &ns orbital as a result both (n-1)d &ns electrons take part in bond formation.
The highest oxidation state of an element is equal to number of unpaired electrons present in (n1)d &ns orbital.
Transition elements have high enthalpy of atomization/ sublimation Because of large number of
unpaired electrons in their atoms, they have stronger interatomic interaction and hence strong
metallic bonding is present between atoms.
Most of transition elements are paramagnetic due to presence of unpaired electrons in
(n-1) d
orbital.
Most of transition elements are used as catalyst. It is due to (i) partially filled (n-1) d orbital (ii)
Variable oxidation state (iii) Ability to change oxidation state frequently.
Most of transition elements form coloured compounds due to presence of unpaired electrons in (n1) d orbital & thus they can undergo d-d transition.
Most of transition elements form complex compounds due to (i) small size (ii) high charge (iii)
presence of vacant d-orbital of suitable energy.
Transition elements have lower value of Reduction Potential due to high ionization potential, high
heat of sublimation & low enthalpy of hydration.
Transition elements form interstitial compounds because size of interstitial voids is similar to size
of non- metals C, N, O, H.
Transition elements form alloys due to similar ionic radii.
The oxides of transition metals in lower oxidation state are BASIC, intermediate oxidation state are
AMPHOTERIC, highest oxidation state are ACIDIC.
LANTHANOIDS:
1. The 14 elements after Lanthanum having atomic number 58 to 71 are collectively known as
Lanthanoids.
2. The general electronic configuration of these elements is [Xe] 4f1-14, 5d0-1 ,6s2 .
3. Most common oxidation state of these elements is +3, but Ce shows +4, Eu +2, because they
acquire stable configuration.
4. The size of Lanthanoids and its trivalent ion decreases from La to Lu due to poor shielding
of 4f electrons. It is known as lanthanoids contraction.
ACTINOIDS:-78

1. The 14 elements after Actinium having atomic number 90 to 113 are collectively known
as Actinoids.
2. The general electronic configuration of these elements is [Rn] 5f1-14, 6d0-1 ,7s2.
3. The size of actinoids and its trivalent ion decreases from Ac to Lw due to poor shielding
of 5f electrons. It is known as actinoids contraction.
4. The elements after U (92) are man made known as transuranic elements.
POTASSIUM DICHROMATE:-Preparation: - It takes place in three steps(i)
(ii)
(iii)

Conversion of chromite ore to sodium chromate.

Conversion of sodium chromate to sodium dichromate.
Conversion of sodium dichromate to potassium dichromate
Following reaction take place:-4 FeCr2O4+ 4 Na2CO3 +7O2
2 Na2CrO4+ 2Fe2O3 +8 CO2
2Na2CrO4 + 2 H+

Na2Cr2O7 + 2 Na+ + H2O

Na2Cr2O7 + 2 KCl

K2Cr2O7 + 2 NaCl

The chromates and dichromates are interconvertible in aqueous solution depending upon Ph of the
solution.
A) In Acedic medium(PH<7)
2CrO42- + 2H+

Cr2O72- +H2O

B) In basic medium (PH >7)

C) 2CrO72- + 2OH-

Cr2O42- +H2O

POTASSIUM PERMANGNATE:-Preparation: -It takes place in two steps:(i)

(ii)

Conversion of pyrolusite ore into potassium magnate

Conversion of potassium magnate to potassium permaganate
Following reactions take place:2 MnO2 + 4 KOH + O2
2 K2MnO4 + 2H2O
3 MnO4 2- +4H+
2 MnO4- +MnO2 +2H2O
QUESTION ANSWERS

(TWO MARK QUESTIONS)

79

Q.1-Explain briefly how +2 oxidation state becomes more and more stable in the first half of the
first row transition elements with increasing atomic number.
A.1-In M2+ ions, 3d-orbitals get occupied gradually as the atomic number increases. Since, the
number of empty d-orbitals decreases, the stability of cations increases from Sc2+ to Mn2+ .Mn2+ is
most stable as all d-orbitals are singly occupied.
Q.2- Explain why transition elements have many irregularities in their electronic configurations?
A.2-In the transition elements, there is a little difference in the energy of (n-1) d-orbitals and nsorbitals. Thus, incoming electron can occupy either of shell. Hence, transition elements exhibit
many irregularities in their electronic configurations.
Q.3-What are different oxidation states exhibited by Lanthanides?
A.3-The common stable oxidation state of lanthanides is +3.However some members also show
oxidation states of +2 & +4.
Q.4-How is the variability in oxidation states of transition metals different from that of the nontransition metals? Illustrate with examples.
A.4-The transition elements use its (n-1)d, ns and np orbital and the successive oxidation states
differ by unity. For example, Mn shows all the oxidation states from +2 to +7. On other hand non
transition elements use its ns, np and nd orbitals and the successive oxidation states differ by two
units e.g. Sn2+, Sn4+ etc.
Q.5- Why do transition elements show variable oxidation states?
A.5- The transition elements show variable oxidation state due to small energy difference between
(n-1) d &ns orbital as a result both (n-1)d &ns electrons take part in bond formation.
Q.6-Why are Mn2+ compounds more stable than Fe2+ compounds towards oxidation to +3 state?
A.6-The electronic configuration of Mn2+ is [Ar] 3d5, i.e. all five d-orbitals are singly occupied. Thus
this is stable electronic configuration and further loss of electron requires high energy .on other
hand side the electronic configuration of Fe2+is [Ar] 3d6, i.e. Loss of one electron requires low
energy.
Q.7-What is meant by disproportionation? Give two examples.
A.7-Those reactions in which same substance undergoes oxidation as well as reduction are called
disproportionation reactions.e.g.
2Cu+

Cu2+ + Cu
2+
3 MnO4 +4 H

2 MnO4- +MnO2 + 2 H2O

Q.8- Which metal in the first series of transition metals exhibits +1 oxidation state most frequently
and why?
A.8- Copper with configuration [Ar] 3d10 4s1 exhibits +1 oxidation state. Copper loses 4s1 electron
easily and achieved a stable configuration 3d10 by forming Cu+.
Q.9- What are inner transition elements?
A.9- The f-block elements in which the last electron accommodated on (n-2) f-subshell are called
inner transition elements. These include atomic numbers 58 to 71 and from 90 to 103.
Q.10- The paramagnetic character in 3d-transition series elements increases upto Mn and then
decreases. Explain why?
A.10- In the 3d-transition series as we move from Sc (21) to Mn (25) the number of unpaired
electrons increases and hence paramagnetic character increases. After Mn, the pairing of electrons
in the d-orbital starts and the number of unpaired electrons decreases and hence, paramagnetic
character decreases.
Q.11- Comment on the statement that elements of the first transition series possess many
properties different from those of heavier transition metal
A.11-The following points justify that the given statement is true:(i) Ionization enthalpies of heavier transition elements are higher than the elements of 3d series.
Consequently, heavier transition elements are less reactive in comparison to 3d-elements.
(ii) Melting points of heavier transition elements are higher than 3d-elements.
80

(iii) Higher oxidation states of heavier transition elements are stable whereas lower oxidation
states are stable in 3d-elements.
Q.12-What are transition elements? Which d-block elements are not regarded as transition
elements and why?
A.12- An element which has partially filled (n-1) d orbital is known as transition elements. Group
12 elements i.e. Zn, Cd, Hg have completely filled (n-1) d-orbital in atomic & ionic state & thus these
elements are not considered as Transition Elements.
Q.13-What are interstitial compounds? Why are such compounds well known for transition metal?
A.13- Compounds of transition metal with relatively smaller non-metals are known as interstitial
compounds. These compounds are well known for transition metals because size of C, N, O, and B
is similar to size of interstitial voids of transition metal
Q.14-For the first row of transition metals the E0 values are:E0 values V
Cr
Mn
Fe
Co
Ni
Cu
M2+/M
-1.18
-0.91
-1.18
-0.44
-0.28
-0.25
+0.34
Explain the irregularity in the above values.
A.14-The E0 ( M2+/M) values are not regular which can be explained from the irregular variation of
ionization energy and sublimation energy of Mn due to half-filled orbitals.
(THREE MARK QUESTIONS)
Q.1- Decide giving reason which one of the following pairs exhibits the property indicated:
(i)Sc3+ or Cr3+ exhibits paramagnetism
(ii)V or Mn exhibits more number of oxidation states
(iii)V4+ or V5+ exhibits colour
A.1- (i) Sc=[Ar] 3d14s2 ;
Sc3+=[Ar] ; it has no unpaired electron so diamagnetic
Cr=[Ar] 3d54s1 ;
Cr3+=[Ar]3d3 ; it has three unpaired electrons paramagnetic
(ii) V=[Ar] 3d34s2
Mn=[Ar] 3d54s2 Thus V exhibit oxidation states of +2, +3, +4, +5
Whereas Mn exhibit oxidation states of +2 to +7.
(iii) V4+=[Ar] 3d1 coloured
V5+=[Ar] colourless
Q.2-(a) Describe the general trends in the following properties of the first series of the transition
elements:(i) Stability of +2-oxidation state
(ii) Formation of oxometal ions
(b) Write steps involved in the preparation of KMnO4 from K2MnO4
A.2- (a) i-The elements of first transition series show decreasing tendency to form divalent cation
as we move left to right in the series. This trend is due to general increase in the first and second
ionization energy. The greater stability of Mn2+ is due to half filled d5 configuration and that of zinc
is due to d10 configuration.
(ii) All metal except Sc from oxide of type MO which are basic. The highest oxidation number in all
oxide, with the group number and is attain in Sc2O3 to Mn2O7. Formation of oxoanions is due to high
electro negativity and small size of oxygen atom.
2-(b) It takes place in two steps:(iii) Conversion of pyrolusite ore into potassium mangnate.
(iv) Conversion of potassium mangnate to potassium permanganate.
Following reactions take place:2 MnO2 + 4 KOH + O2
2 K2MnO4 + 2H2O
2+
3 MnO4 +4H
2 MnO4- +MnO2 +2H2O
Q.3-(a) Write the steps involve in the preparation of K2Cr2O7 from chromite ore.
(b) What is the effect of pH on dichromate ion solution?
A.3-(a):- It takes place in three steps(iv)
(v)

Conversion of chromite ore to sodium chromate.

Conversion of sodium chromate to sodium dichromate.
81

(vi)

Conversion of sodium dichromate to potassium dichromate

Following reactions take place:-4 FeCr2O4+ 4 Na2CO3 +7O2
2 Na2CrO4+ 2Fe2O3 +8 CO2
+
2Na2CrO4 + 2 H
Na2Cr2O7 + 2 Na+ + H2O
Na2Cr2O7 + 2 KCl
K2Cr2O7 + 2 NaCl
(b) Dichromate ion is orange in acidic solution (pH<7) and turns yellow in basic solution. It is due
to interconversion of dichromate ion to chromate ion. Following reactions take place:2 Cr042- (yellow) +2 H+
Cr2O72- (orange) + H2O
Cr2O72- (orange) +2 OH- 2 Cr042- (yellow) + H2O.
Q.4- (a) What is lanthanide contraction? What effect does it have on the chemistry of the elements,
which follow lanthanoids?
(b) The chemistry of actinoid elements is not so much smooth as that of lanthanoids. Justify these
statements by giving some examples from the oxidation state of these elements.
A.4- (a)The size of Lanthanoids and its trivalent ion decreases from La to Lu. It is known as
lanthanoids contraction.
Cause: - It is due to poor shielding of 4f electrons.
Consequences of lanthanide contraction: - (i) Basic strength of hydroxide decreases from La(OH)3
TO Lu(OH)3. (ii) Because of similar chemical properties lanthanides are difficult to separate.
(b) Lanthanoids show limited number of oxidation states i.e. +2, +3, +4 (out of which +3 is most
common) . This is because of a large energy gap between 4f, 5d and 6s subshell. The dominant
oxidation state of actinides is also +3 but they show a number of other oxidation state also e.g. +4,
+5, and +7. This is due to small energy difference between 5f, 6d and 7s orbitals.
Q.5- Give examples and suggest reasons for the following features of the transition metal
chemistry:
(i) The lowest oxide of transition metal is basic, the highest is amphoteric/acidic.
(ii) A transition metal exhibits highest oxidation state in oxides and fluorides.
(iii) Of the d4 species, Cr2+ is strongly reducing while manganese(III)is strongly oxidizing.
A.5-(i) The oxide of transition metals in lower oxidation states are generally basic while those in
the higher oxidation states are acidic. Acidic character increases with increase in oxidation state is
due to decrease in size of metal ion and increase in charge density.e.g. MnO (basic), Mn 3O4
(amphoteric), Mn2O7 (acidic).
(ii) A transition metal exhibits higher oxidation states in oxides and fluorides because oxygen and
fluorine are the most electronegative elements and thus easily can unpair electrons of metal atom.
(iii) Because oxidizing and reducing property depends on E 0 value. Since E0 value of Cr3+/Cr2+ is
negative while that of Mn3+/Mn2+ is positive, as a result Cr(II) act as reducing agent and Mn(III) is
strong oxidizing.
Q.6-For M 2+/M and M 3+/M2+ systems ,the Eo values for some metals are as follows:
Cr2+/Cr
-0.9V
Cr3+/Cr2+
-0.4V
Mn2+/Mn
-1.2V
Mn3+/Mn2+
+ 1.5V
2+
3+
2+
Fe /Fe
-0.4V
Fe /Fe
+0.8V
Use this data to comment upon :(i)the stability of Fe3+ in acid solution as compared to Cr3+ or Mn3+ and
(ii)the ease with which iron can be oxidized as compared to a similar process for either chromium
or manganese metal.
A.6- (i)Eo for Cr3+/Cr2+ is -0.4V i.e. negative, this means Cr3+ ions in the solution cannot be reduced
to Cr2+ easily i.e. Cr3+ is stable. As Mn3+/Mn2+ is +1.5V i.e positive means Mn3+ can easily reduced to
Mn2+ ions in comparison to Fe3+ ions. Thus relatively stability of these ions is:Mn3+
< Fe3+
< Cr3+
(ii) The oxidation potentials for the given pairs will be +0.9V, +1.2V and 0.4V. Thus, the order of
their getting oxidized will be in the order
Mn>Cr>Fe.
82

Q.7-Account for the following statements:

(i)Cobalt (II) is stable in aqueous solution but in the presence of strong ligands and air, it can be
oxidized to Co (III).
(ii)The d1 configuration is very unstable in ions.
(iii)One among the lanthanides, Ce (III) can be easily oxidized to Ce (IV).
A.7- (i) Strong ligands force cobalt (II) to lose one more electron from 3d-subshell and thereby
induced d2sp3 hybrisation.
(ii) The ion with d1 configuration try to lose the only electron in order to acquire inert gas
configuration.
(iii) The configuration of Ce is [Xe] 4f1, 5d1 ,6s2. There is no much difference between the energy of
4f, 5d and 6s orbitals and thus, Ce can utilize electrons present in these orbitals and hence
oxidation state of +4.
Q.8- Compare the chemistry of actinides with that of the lanthanoids with special reference to:
(i) electronic configuration
(iii) oxidation state
(ii) atomic and ionic sizes and
(iv) chemical reactivity
A.8-

Comparison of Lanthanoids and Actinides

Properties
Electronic
configuratio
n
Atomic/ioni
c sizes

Lanthanoids
[Xe] 4f1-14, 5d0-1 ,6s2

[Rn]

Size decreases from La to Lu,

and size is more than actinides.

Oxidation
states

Common oxidation is +3 where

other oxidation states are +2,
+4.It is due to a large energy gap
between 4f, 5d and 6s subshell

Chemical
reactivity

The earlier member quite

reactive but with increasing
atomic number they behave like
aluminum.
Less tendency to form complex
due to less charge density.

Complex
formation

Actinides
6d0-1 ,7s2.

5f1-14,

Size decreases from Ac to Lw, and

size is smaller than lanthanoids due
to poorer shielding of 5f electrons
Common oxidation is +3 where
other oxidation states are +2, +4,+5
and+7 due to due to small energy
difference between 5f, 6d and 7s
orbitals
The actinides highly reactive
,especially in finely divided.
More tendency to form complex due
to high charge density.

Q.9-(a) What is actinides contraction? What effect does it have on the chemistry of the
elements,
which follow actinides?
(b) Name an important alloy, which contains some of the lanthanide metals. Mention its uses.
A.9- (a) The size of actinoid and its trivalent ion decreases from Ac to Lw. It is known as l actinides
contraction.
Cause: - It is due to poor shielding of 5f electrons.
Consequences of actinides contraction: - (i) Basic strength of hydroxide decreases from Ac(OH)3 To
Lw(OH)3. (ii) Because of similar chemical properties l actinides are difficult to separate.
(b) An important alloy containing lanthanoid metals is mischmetal, which contains 95% lanthanide
metal and 5% Fe along with traces of S, C, Ca and Al. It is used in Mg-based alloy to produce bullets,
shells and lighter flint.
Q.10- Complete following reactions:(i)

MnO4- + H+ + Fe2+

------------+--------------+--------------

83

(ii)

MnO4- + C2O42- + H+

------------+--------------+--------------

(iii) MnO4- + O H- + I-

------------+--------------+--------------

A.10-(i) MnO4- + 8H+ + 5 Fe2+

Mn2+ -

(ii) 2 MnO4- + 5 C2O42- + 16 H+

2 Mn2+ -

+ 10 CO2

(iii) 2 MnO4- + H2O + I-

2MnO2

+ 5 Fe3+

4H2O
+

8H2O

2OH- + IO3-

(FIVE MARK QUESTIONS)

Q.1-Explain giving reasons:
(i) Transition metals and many of their compounds show paramagnetic behaviour.
(ii) The enthalpies of atomisation of the transition metals are high.
(iii) The transition metals generally form coloured compounds.
(iv) Transition metals and their many compounds act as good catalyst.
(v)Transition metals have a strong tendency to form complexes.
A.1- (i)Transition metals and many of their compounds show paramagnetic behaviour due to
presence of unpaired electrons in (n-1) d orbital.
(ii) The enthalpies of atomisation of the transition metals are high Because of large number of
unpaired electrons in their atoms, they have stronger interatomic interaction and hence strong
metallic bonding is present between atoms.
(iii) The transition metals generally form coloured compounds due to presence of unpaired
electrons in (n-1) d orbital & thus they can undergo d-d transition.
(iv) Transition metals and their many compounds act as good catalyst It is due to (i) partially filled
(n-1) d orbital (ii) Variable oxidation state (iii) Ability to change oxidation state frequently.
(v) Transition metals have a strong tendency to form complexes Most of transition elements form
complex compounds due to (i) small size (ii) high charge (iii) presence of vacant d-orbital of
suitable energy.
Q.2- Give reasons for the following:(i) Fe has higher melting point than Cu.
(ii) [Ti (H2O)6]3+ is coloured while [Sc(H20)6] is colourless.
(iii)The 4d and 5d series of transition metals have more frequent metal-metal bonding in
their compound than do the 3d metals.
(iv)Transition metals some time exhibit very low oxidation state such as +1and 0.
(v)Hg is not considered a transition metal.
A.2-(i) This is because Fe (3d6, 4s1) has four unpaired electrons in 3d-subshell. While Cu
(3d10, 4s1) only one unpaired electron in 4s shell. Hence metallic bonding is stronger in Fe than
those in Cu.
(ii) The oxidation state of Ti in [Ti (H2O)6]3+ is +3 and its configuration is [Ar] 3d1 i.e one unpaired
electron and hence it is coloured. Whereas the oxidation state of Sc in [Sc (H2O)6]3+ is +3 and its
configuration is [Ar] 3d0 i.e no unpaired electron and hence it is colourless.
(iii)In the same group of d-block elements, the 4d and 5d transition elements are larger size than
that of 3d elements. Hence, the valence electrons are less tightly held and form metal-metal bond
more frequently.
(iv)+1 oxidation state is shown by elements like Cu because after loss of one electron, it acquire
stable configuration. Zero oxidation state is shown in metal carbonyl, because -electrons donated
by CO are accepted into the empty orbital.
(v)The characteristic properties of transition metal are due to partially filled d-orbitals.Hg has
completely filled d-orbital, as a result it doesnt show properties of transition metals and hence is
not considered as transition metal.
Q.3-(a) write electronic configuration of element having atomic number 101.
(b) Which element show maximum oxidation state in 3d transition series?
84

(c) What is mischmetal?

(d) Explain why Cu+ ion is not stable in aqueous solution?
(e) Name the transition metal which is well known to exhibit +4 oxidation state?
A.3-(a) [Rn] 5f13,6d0, 7s2.
(b) Mn, Which shows +7 oxidation state in KMnO4.
(c) It is an important alloy, which contains 95% lanthanide metal and 5% Fe along with traces of
S, C, Ca and Al. It is used in Mg-based alloy to produce bullets, shells and lighter flint.
(d) Water is a good complexing agent and thus Cu forms complex by losing one more electron
from 3d orbital.
(e)Cerium (Z=58)
Q.4-(a) Write the preparation of potassium dichromate from iron chromite. What happens when
potassium dichromate reacts with (i) Hydrogen sulphide (ii) FeSO4?
(b) Why do Zr and Hf exhibit almost similar properties?
(c)Why is La(OH)3 stronger base than Lu(OH)3.
A.4- (a) Preparation:- It takes place in three steps(i)
Conversion of chromite ore to sodium chromate.
(ii)
Conversion of sodium chromate to sodium dichromate.
(iii) Conversion of sodium dichromate to potassium dichromate
Following reaction takes place:-4 FeCr2O4+ 4 Na2CO3 +7O2
2 Na2CrO4+ 2Fe2O3 +8 CO2
2Na2CrO4 + 2 H+
Na2Cr2O7 + 2 KCl

Na2Cr2O7 + 2 Na+ + H2O

K2Cr2O7 + 2 NaCl

Reactions: - (i) Cr2O7 2- + 8 H+ + 3 H2S 2Cr3+ + 7 H20 + 3S

(ii) Cr2O7 2- + 14 H+ + 6 Fe2+ 2Cr3+ + 7 H20 + 6 Fe3+.
(b) Because both have similar ionic size
(c)Due to lanthanoid contraction size of La3+ is smaller than Lu3+ as a result Lu-O bond will stronger
than La-O bond.
Q.5- Give reasons for the following:(i) Transition metals have high enthalpy of hydration.
(ii) Zn, Cd and Hg are not regarded as transition metal.
(iii) d block elements exhibit a large number of oxidation state than f block elements.
(iv)The second and third members in each group of transition element have similar atomic radii.
(v) K2 [PtCl6] is well known compound whereas the corresponding Ni compound is not known.
A.5-(i) Transition metal ions are smaller and have higher charge, therefore have high enthalpy of
hydration.
(ii) Group 12 elements i.e. Zn, Cd, Hg have completely filled (n-1) d-orbital in atomic & ionic state &
thus these elements are not considered as transition elements.
(iii)The difference in the energy of (n-1) d orbital and ns orbital is very small and thus both subshells are used for bond formation. Whereas in f block elements (n-2)f orbitals lie underneath and
hence are not available for bond formation.
(iv) The second and third members in each group of transition element have similar atomic radii
due to lanthanoid contraction. It arises due to poor shielding of d and f electron.
(v)The oxidation state of Pt in is +4 which is stable for Pt. The +4 oxidation state for Ni is very
difficult to achieve because the sum of first four ionization energies is very high. Hence ,the
corresponding Ni(II) compound is known.
---------------------------------------------------------------

85

86

UNIT 9: CO-ORDINATIONCOMPOUNDS
POINTSTOREMEMBER:
1.
Coordinationcompounds
Coordinationcompounds arecompounds inwhicha centralmetalatomorion islinkedtoa
numberofions orneutralmoleculesby coordinatebonds orwhichcontaincomplexions. ExamplesK4[Fe(CN)6];[Cu(NH3)4]SO4;Ni(CO)4
2.Themain

postulatesofWerners theoryofcoordinationcompounds

i)
Incoordination compounds metals showtwotypesof linkagesorvalencies-Primary
andSecondary.
ii)
Theprimary valenciesare ionisableandaresatisfiedby negative ions.
iii)
The secondary valenciesarenon-ionisableandare satisfiedby neutralmoleculesor negativeions.
The secondary valenceis equaltotheC.Nandisfixedforametal.
iv)
Theions orgroups boundby secondary linkages tothemetalhave characteristic spatial
arrangementscorresponding todifferentcoordinationnos.
3.Differencebetweenadoublesaltandacomplex
Bothdoublesalts as wellas complexes areformedbythecombinationof twoormorestable
compoundsinstoichiometric ratio.However, double salts suchascarnalite,KCl.MgCl2.6H2O,Mohrs salt,
FeSO4.(NH4)2SO4.6H2O,potashalum, KAl(SO4)2.12H2O,etc. dissociateintosimple
ionscompletelywhendissolvedinwater. However,complexions suchas[Fe(CN)6]4of K4[Fe(CN)6],
donotdissociateintoFe2+andCN ions.
IMPOTANT TERMINOLOGY
(i)Coordinationentity: It constitutes the centralmetal ionoratombondedtoa fixednumber of ionsormolecules
representedwithina squarebracket.
(ii)Centralatom/ion:Inacoordinationentity,theatom/iontowhicha fixednumberof ions/groupsare
boundinadefinitegeometrical arrangementaroundit,iscalledthe central atomorion.
iii)Ligands:Theneutralornegativeionsboundtothe centralmetalorioninthe coordinationentity.
Thesedonateapair/sofelectronstothe centralmetal atom/ion. Ligands maybe classifiedasa) Monodentate/Unidentate:Ligandsboundtothe centralmetalatom/ionthrougha singledonoratom. Ex-Cl;H2O;NH3 ; NO2-.
b) Didentate:Ligates throughtwodonoratoms.Ex-C2O4 2-(ox); H2NCH2CH2NH2(en)
c) Polydentate: whichligates throughtwoormoredonoratoms presentinasingleligand. Ex-(EDTA)4d) Chelatingligands: Di-orpolydentateligands that usestwoormoredonoratoms to
bindtoasinglemetaliontoformring-like complexes.(Ox); (edta)
e) Ambidentateligand: Aligand thatcanligatethroughtwodifferentatoms,oneata time.Ex-NO2-;SCNv) Coordinationnumber:Theno.ofliganddonoratoms towhichthemetal isdirectly bondedthroughsigma
bonds only. Itiscommonly4or6.
vi) Counterions:Theionisable groups writtenoutsidethesquarebracket.Ex-K+ in
K4[Fe(CN)6]OR3Cl- in[Co(NH3)6]Cl3
vii) CoordinationPolyhedron:Thespatialarrangementof theligandatoms whichare
directlyattachedtothecentralmetalatom/ion.Theyarecommonly Octahedral, Square-planar orTetrahedral
Oxidationnumber: The chargethatthe centralatomwouldcarryifalltheligands are
removedalongwiththeirpairsofelectrons sharedwiththe centralatom. Itis representedin parenthesis.
viii) Homolepticcomplexes: Complexes inwhichametalisbondedtoonlyone kindof donorgroups.
87

Ex-[Co(NH3)6]3+
ix) Heterolepticcomplexes: Complexes inwhichametalisbondedtomore
thanonekindofdonorgroups.Ex-[Co(NH3)4 Cl2]+
5. NAMING OF MONONUCLEAR COORDINATION COMPOUNDS
* For rules refer to the Page No. 242 , Article 9.3.2 in NCERT Text Book and solve all the solved & unsolved
examples.
6.NAMESOFSOMECOMMONLIGANDS
NEGATIVELIGANDS

CHARGE

NEUTRALLIGANDS

CHARGE

CN-

Cyano

-1

NH3

Ammine

Cl-

Chlorido

-1

H2O

Aqua/aquo

Br-

Bromido

-1

NO

Nitrosyl

F-

Fluoride

-1

CO

Carbonyl

SO42-

Sulphato

-2

PH3

Phosphine

C2O42-

Oxalato

-4

CH2-NH2

(1,2-Ethane
diamine)

CH2NH2
NH2-

Amido

-1

POSITIVELIGANDS

NH2-

Imido

-2

NH2-NH3+

Hydrazinium

+1

ONO-

Nitrito-O

-1

NO+

Nitrosonium

+1

NO2-

Nitrito-N

-1

NO2+

Nitronium

+1

NO3-

Nitrato

-1

SCN-

Thiocyanato

-1

NCS-

Isothiocyanato

-1

CH2(NH2)COO-

Glycinato

-1

-OH

Hydroxo

-1

88

7.ISOMERISMINCOORDINATIONCOMPOUNDS
Twoormore substanceshaving thesamemolecularformulabutdifferentspatialarrangements
arecalledisomersandthe phenomenon is calledisomerism. Coordination compounds show two maintypes
of isomerismA)StructuralIsomerism

B) Stereoisomerism

STRUCTURALISOMERISM:-Itarises duetothedifferenceinstructures of coordination

compounds.Itis furthersubdividedintothe followingtypes1)Ionisationisomerism:Thisformof isomerismarises whenthe counterionina complexsaltis
itselfapotentialligandandcandisplacealigandwhichcanthenbecomethe counterion.Anexampleis
providedbytheionization isomers[Co(NH3)5SO4]Brand [Co(NH3)5Br]SO4.
2)Hydrateorsolvateisomerism:Thisform of isomerismisknownas hydrateisomerism
incasewherewaterisinvolvedas asolvent.Thisis similartoionisationisomerism.Solvate isomers
differbywhetherornotasolventmoleculeisdirectlybondedtothemetal ionor merely
presentasfreesolventmoleculesinthe crystallattice. Anexampleis providedbythe
aquacomplex[Cr(H2O)6]Cl3 (violet)andits solvateisomer[Cr(H2O)5Cl]Cl2.H2O(grey-green).
3)LinkageIsomerism: Linkageisomerismarises inacoordinationcompoundcontaining ambidentateligand.
Asimpleexample is providedbycomplexescontainingthethiocyanateligand,NCS
,whichmaybindthroughthenitrogentogiveMNCSorthroughsulphurtogive MSCN.
4)Coordinationisomerism: Itarisesfromthe interchangeof ligandsbetween cationic andanionic
entitiesof differentmetal ionspresent inacomplex.
Example [Co(NH3)6][Cr(CN)6]&[Cr(NH3)6][Co(CN)6]
STEREOISOMERISM: Stereoisomers havethe samechemicalformulaandchemicalbonds
buttheyhavedifferentspatialarrangement.Theyareof twokinds
A. Geometricalisomerism
B.Opticalisomerism
GEOMETRICALISOMERISM-This typeof isomerism arisesinheterolepticcomplexesdueto different
possible
geometric
arrangementsof
theligands.
Importantexamplesofthis
behaviour
arefoundwithcoordinationnumbers4and6. Inasquareplanarcomplexof formula[MX 2L2]
(XandLareunidentate), thetwoligands Xmay bearrangedadjacenttoeachotherinacisisomer,
oroppositetoeachotherinatrans isomer [MABXL]-WhereA,B,X,LareunidentateTwocis-andonetransisomersarepossible.

89

Anothertypeof geometricalisomerism occursinoctahedralcoordinationentitiesofthe type

[Ma3b3]like[Co(NH3)3(NO2)3].Ifthreedonoratomsofthesameligands occupy adjacent positions
atthecornersofanoctahedralface, wehavethe facial(fac)isomer. Whenthe positions
arearoundthemeridianoftheoctahedron,wegetthemeridional(mer)isomer.

b)OPTICALISOMERISM:Opticalisomers aremirrorimagesthatcannotbe superimposedon oneanother.

Theseare calledas enantiomers.Themoleculesorionsthat cannotbe superimposedare
calledchiral.Thetwoformsare calleddextro(d) andlaevo(l)depending uponthedirectionthey rotatetheplaneof
polarisedlightinapolarimeter(drotates totheright, ltothe left).Opticalisomerismis common
inoctahedralcomplexesinvolvingdidentateligands. Inacoordinationentityofthetype[CoCl2(en)2]2+,onlythecisisomershows opticalactivity

90

TYPES OF HYBRIDISATION
Coordinationnumber

Typeof hybridisation

Acquired geometry

sp3

Tetrahedral

dsp2

Squareplanar

sp3d

Trigonalbipyramidal

sp3d2

Octahedral

d2sp3

Octahedral

8.CRYSTALFIELDTHEORY:
1. Themetal-ligandbondis ionic arising purelyfromelectrostatic interactions between
themetalionandtheligand.
2. Ligands aretreatedas pointcharges ordipolesincaseof anionsandneutral
molecules.
3. Inanisolatedgaseous metalatomorionthe five d-orbitalsaredegenerate.
4. Degeneracy is maintainedifa sphericallysymmetricalfieldof negativecharges
surroundsthemetal /ion.
5. Inacomplexthenegativefieldbecomes asymmetricalandresults insplitting of the

91

d-orbitals.

A)CRYSTALFIELD SPLLITINGINOCTAHEDRALCOORDINATIONENTITIES

1.
Ford4 ions, two possible patternsofelectrondistributionarise:
(i)Ifo<P, the fourthelectronenters oneof theegorbitalsgiving the
configurationt32ge1g.Ligandsforwhicho <Pare knownasweak
fieldligandsandform highspincomplexes.
(ii)Ifo>P,it becomes moreenergeticallyfavourableforthefourthelectrontooccupy at 2g
orbitalwithconfigurationt42ge0g.Ligands whichproducethis effectareknownas strong field
ligandsandformlowspincomplexes.
1.

B)CRYSTALFIELDSPLLITINGINTETRAHEDRALCOORDINATIONENTITIES
Thefoursurrounding ligandsapproachthe centralmetal atom/ionalong theplanes betweenthe
axes.
2. Thet2gorbitalsareraisedinenergy (2/5) t.
3. Thetwoegorbitalsareloweredinenergy(3/5) t
4. The splittingis smallerascomparedtooctahedralfield splitting,
t=(4/9) 0.

92

5. Pairing of electrons is rareandthuscomplexes havegenerallyhighspin

configurations.

BONDINGINMETALCARBONYLS
The metal-carbonbondinmetal carbonyls possess bothand character.TheMC bond
isformedbythedonationof lonepairof electrons onthecarbonylcarbonintoavacantorbital of themetal.
TheMCbond isformedby thedonationof apairof electrons froma filledd orbitalof metal
intothevacantantibonding *orbitalof carbonmonoxide.Themetal toligand bondingcreates a synergic
effectwhichstrengthens thebond betweenCOandthemetal.

SOLVEDQUESTIONS
1MARK QUESTIONS
1. Whatareambidentateligands? Givetwo examples foreach.
ANS.Ambidentateligands areligands thatcanattachthemselvestothe centralmetal atom
throughtwodifferentatoms. Forexample:

(a)
(Thedonoratomis N)

(Thedonoratomisoxygen)

93

(b)
(ThedonoratomisS)

(Thedonoratomis N)

Q2.UsingIUPACnorms writetheformulafor thefollowing:Tetrahydroxozincate(II)

ANS.[Zn(OH)4]2
Q3.UsingIUPACnorms writetheformulafor thefollowing:Hexaamminecobalt(III)
sulphate
ANS.[Co(NH3)6]2 (SO4)3
Q4.UsingIUPACnorms writetheformulafor thefollowing:Pentaamminenitrito-O- cobalt(III)
ANS.[Co(ONO)(NH3)5]2+
Q5.UsingIUPACnorms writethesystematic nameofthefollowing:[Co(NH3)6]Cl3
ANS.Hexaamminecobalt(III)chloride
Q6.UsingIUPACnorms writethesystematic nameofthefollowing:
[Pt(NH3)2Cl(NH2CH3)]Cl
ANS. Diamminechlorido(methylamine)platinum(II)chloride
Q7.UsingIUPACnorms writethesystematic nameofthefollowing:[Co(en)3]3+
ANS.Tris(ethane-1, 2-diammine)cobalt(III)ion
Q8.Drawthestructures ofopticalisomersof: [Cr(C2O4)3]3

ANS .

Q9.Whatis meantbythechelateeffect? Giveanexample.

ANS.Whenaligandattaches tothemetal ion inamannerthat formsaring,thenthemetalligandassociationis foundtobemorestable.

94

2/3MARK QUESTIONS
Q1.Whatis spectrochemicalseries? Explainthedifferencebetweena weakfieldligandanda
strongfieldligand.
ANS.Aspectrochemicalseriesisthearrangementof commonligands intheincreasing orderof theircrystal-field
splitting energy (CFSE) values.

I < Br < S2 < SCN < Cl< N3 < F < OH < C2O42 H2O < NCS H < CN <
NH3< en SO32 < NO2 <phen< CO
Q2.[Cr(NH3)6]3+is paramagnetic while[Ni(CN)4]2is diamagnetic.Explainwhy?
ANS.Cris inthe+3oxidationstatei.e.,d3 configuration.Also, NH3 isa weak fieldligandthat
doesnotcausethepairingoftheelectrons inthe3dorbital.

Cr3+

Therefore,itundergoes d2sp3 hybridizationandtheelectronsinthe3dorbitalsremain unpaired.

Hence, itis paramagnetic innature.
In[Ni(CN)4]2,Niexists inthe+2oxidationstatei.e., d8 configuration.

Ni2+:
CN isastrong fieldligand. It causes thepairing ofthe3dorbitalelectrons. Then,Ni 2+
undergoesdsp2 hybridization.

Q3.Asolutionof [Ni(H2O)6]2+is greenbutasolution of [Ni(CN)4]2is colourless.Explain.

Ans.-In[Ni(H2O)6]2+,
isaweakfieldligand.Therefore,thereareunpairedelectronsin
complex, thedelectronsfromthe lowerenergylevel canbeexcitedtothehigher energy
thepossibilityof ddtransitionis present. Hence, Ni(H2O)6]2+iscoloured.

Ni2+.Inthis
level i.e.,

95

In[Ni(CN)4]2,theelectrons areallpairedas CN- isastrong fieldligand. Therefore, d-d transitionis

notpossiblein[Ni(CN)4]2. Hence, itiscolourless. Astherearenounpaired electrons,it isdiamagnetic.
Q2.Drawalltheisomers(geometricalandoptical)of:
(i)[CoCl2(en)2]+
(ii)[Co(NH3)Cl(en)2]2+
(iii)[Co(NH3)2Cl2(en)]+
ANS.(i)[CoCl2(en)2]+

Intotal,threeisomersarepossible.

96

Trans-isomersareopticallyinactive. Cisisomersareopticallyactive.

(iii)[Co(NH3)2Cl2(en)]+
Q3.Writeallthegeometricalisomersof [Pt(NH3)(Br)(Cl)(py)] andhowmany of thesewill
exhibitopticalisomers?
ANS.[Pt(NH3)(Br)(Cl)(py)

Fromtheaboveisomers, nonewillexhibitopticalisomers. Tetrahedralcomplexesrarely show

opticalisomerization.Theydosoonly inthepresenceof unsymmetricalchelatingagents.
Q4.Whatis meantbystabilityofa coordinationcompoundinsolution? Statethefactors which
governstabilityof complexes.
ANS.Thestabilityof a complexinasolutionreferstothedegreeof associationbetween thetwospecies
involvedinastateof equilibrium. Stabilitycanbeexpressedquantitatively in terms
ofstabilityconstantorformationconstant.

Forthisreaction,thegreaterthevalueof thestabilityconstant, thegreateris theproportionof

ML3 inthesolution.

97

5MARKSQUESTIONS
Q1.(a)Discuss thenatureofbondinginthefollowingcoordinationentities
onthebasisofvalencebondtheory:
(i)[Fe(CN)6]4(ii)[FeF6]3 (iii)[Co(C2O4)3]3(iv)[CoF6]3
ANS.(i)[Fe(CN)6]4Intheabovecoordinationcomplex,ironexistsinthe+II oxidationstate.Fe2+
: Electronic configurationis3d6Orbitalsof Fe2+ion:

As CN is astrongfieldligand,itcausesthepairingof theunpaired3delectrons.Sincethereare sixligands

aroundthe centralmetal ion,themostfeasiblehybridizationisd2sp3.d2sp3hybridizedorbitalsof Fe2+are:

6electronpairsfromCN ionsoccupythesixhybridd2sp3orbitals.Then,

Hence,thegeometryof thecomplexisoctahedralandthe complexis diamagnetic (asthereare

nounpairedelectrons).
(ii)[FeF6]3
Inthiscomplex, theoxidationstateofFeis+3.
OrbitalsofFe+3ion:

Thereare6F ions. Thus,it will undergod2sp3orsp3d2 hybridization.As Fisaweakfield ligand,itdoes

notcausethepairingof theelectronsinthe3dorbital.Hence,themostfeasible hybridizationis sp3d2.sp3d2
hybridizedorbitalsofFeare:

98

Hence,thegeometryof thecomplexisfoundtobeoctahedral.
(iii)[Co(C2O4)3]3
Cobaltexistsinthe+3oxidationstateinthegivencomplex.OrbitalsofCo3+ion:Oxalate is a weakfieldligand.
Therefore, itcannotcausethepairingof the3dorbitalelectrons. As thereare
6ligands, hybridizationhas tobeeithersp 3d2 ord2sp3 hybridization.sp3d2 hybridizationofCo3+:

The6electronpairs fromthe3oxalateions(oxalateanion isabidentateligand) occupythese sp3d2 orbitals.

Hence,thegeometryof thecomplexisfoundtobeoctahedral.
(iv)[CoF6]3Cobaltexistsinthe+3oxidationstate.
Orbitalsof Co3+ion:

Again, fluorideionisa weak fieldligand. It cannotcausethepairingof the3delectrons. As a result,

theCo3+ion will undergosp3d2 hybridization.sp3d2hybridizedorbitalsofCo3+ionare:

Hence,thegeometryof thecomplexisoctahedralandparamagnetic.

99

Q3.WritedowntheIUPACnameforeach of thefollowingcomplexes andindicatethe

oxidationstate,electronic configurationandcoordinationnumber. Also givestereochemistry
andmagnetic momentof thecomplex:
(i)K[Cr(H2O)2(C2O4)2].3H2O(ii)[Co(NH3)5Cl]Cl2ANS.(i)Potassium diaquadioxalatochromate
(III)trihydrate.
Oxidationstateof chromium =3
Coordinationnumber=6

Electronicconfiguration:3d3:t2g3
Shape: octahedral

Stereochemistry:

Magnetic moment,

4BM

(II) [Co( NH3 )5 Cl ]Cl2

IUPAC name: Pentaamminechloridocobalt(III)chloride
OxidationstateofCo=+3
Coordinationnumber=6
Shape: octahedral.

100

Electronic configuration:d6:t2g6.
Stereochemistry:

MagneticMoment=0

101

LEVEL1
1.Whydotetrahedralcomplexnotshow geometricalisomerism?
2. Why does the colourchangesonheating[Ti(H2O)6]3+.
3. [Fe(H2O)6]3+is strongly paramagnetic whereas [Fe(CN)6]3-is weakly paramagnetic.Explain.
4. Whathappenswhenpotassiumferrocyanidesolutionisaddedtoaferric saltsolution?
LEVEL2
5.Acoordinationcompoundhas aformula(CoCl3.4NH3).Itdoes notliberateNH3butprecipitateschlorideionas
AgCl. GivetheIUPAC nameof thecomplexandwriteits structural formula.
6. Writethe correctformulaforthefollowingco-ordinationcompounds.CrCl3
.6H2O(Violet,with3Chlorideions/Unitformula)CrCl3 .6H2O (Light
greencolourwith2Chlorideions/unitformula)
7. Givetheelectronic configurationof thed-orbitalsof Tiin[Ti(H2O) 6]3+ion inanoctahedralcrystalfield.
8.Co(II)is stableinaqueous solutionbut inthepresenceofstrongligands andair, itcanget oxidizedto
Co(III). (Atomic Numberof cobaltis 27).Explain.
9. Giveachemicaltesttodistinguishbetween[Co(NH3)5Br]SO4 and[Co(NH3)5Br]SO4Br.Name thetypeof
isomerism exhibitedbythese compounds.
10. Whatisthecoordinationentity formedwhenexcess of aqueousKCNis addedtoanaqueous solutionof
coppersulphate? Why is thatnoprecipitateof coppersulphate is obtainedwhenH2S(g)is passedthroughthis
solution?
LEVEL3
11.Aqueous coppersulphatesolution(blueincolour)gives agreenprecipitatewithaqueous potassium
fluoride,a brightgreensolutionwithaqueous potassiumchloride.Explainthese experimentalresults.
12.Ametal complexhaving the compositionCr(NH)4Cl2Brhas beenisolatedintwoforms, A andB.The
form A reactswithAgNO3 solutiontogivea white precipitatereadily solublein diluteaqueous
ammoniawhereas Bgiveapaleyellow precipitate solubleinconcentrated ammoniasolution. Writethe
formulaeof AandBandwritetheirIUPACnames.
13. Explainthefollowing
i.Alloctahedralcomplexesof Ni2+mustbeouterorbitalcomplexes.
ii.NH4+iondoes notform anycomplex.
iii.(SCN)-1ion isinvolvedinlinkage isomerism inco-ordinationcompounds.
14.Ametal ionMn+ havingd4 valenceelectronic configurationcombineswiththreedidentateligandstoform
complexes.Assuming o>PDrawthediagram showingdorbitalsplitting
duringthiscomplexformation.Writetheelectronic configurationof thevalenceelectrons of the metalMn+
ioninterms oft2gandeg.WhattypeofthehybridizationwillMn+ ionhave? Name thetypeof isomerism
exhibitedbythiscomplex.
102

15. Thecoordinationno. of Ni2+ is 4.

NiCl2+KCN(excess)A(acyanocomplex)
A+ConcHCl(excess)B(achlorocomplex)
i)WriteIUPAC nameof AandB
ii) Predictthe magneticnatureof AandB
iii)Writehybridizationof NiinAandB
16. Explainthefollowing
i.Cu(OH)2 is solubleinammoniumhydroxidebutnotinsodium hydroxidesolution.
ii.EDTAisusedtocure leadpoisoning
iii.Bluecoloured solutionof [CoCl4]2-changes topink onreaction withHgCl2.

1 MARK QUESTIONS
Q1. Write the formula for the following coordination compound:
Tetraamineaquachloridocobalt(III) chloride
Q2. Write the IUPAC name of the following coordination compound:
[CoCl2(en)2]Cl
Q3. Why is geometrical isomerism not possible in tetrahedral complexes having two
different types of unidentate ligands coordinated with the central metal ion ?
Q4. Out of the following two coordination entities which is chiral (optically active)?
(a) cis-[CrCl2 (ox)2]3- (b) trans-[CrCl2 (ox)2]3Q5. The spin only magnetic moment of [MnBr4]2- is 5.9 BM. Predict the geometry of
the complex ion?
Q6. [NiCl4]2- is paramagnetic while [Ni(CO)4] is diamagnetic though both are
tetrahedral. Why?

2 MARKS QUESTIONS
Q1. Draw structures of geometrical isomers of [Fe(NH3 )2(CN)4]Q2. Indicate the type of isomerism exhibited by the following complex and draw the
structures for these isomers:
[Co(en)3]Cl3
Q3. Give evidence that [Co(NH3)5 Cl]SO4 and [Co(NH3)5 SO4]Cl are ionization
isomers.
Q4. Calculate the overall complex dissociation equilibrium constant for the
[Cu(NH3)4]2+ ion, given that 4 for this complex is 2.1 1013.
Q5. What is meant by unidentate ligand? Give two examples.
Q6. What is meant by didentate ligand? Give two examples.
Q7. What is meant by ambidentate ligands? Give two examples.
103

Q8. Draw the structures of optical isomers of:

[Cr(C2O4)3]3Q9. Discuss the nature of bonding in metal carbonyls.
Q10. What is meant by the chelate effect? Give an example.
Q11. Draw the structures of:
(i) Ni(CO)4 (ii) Fe(CO)5
3 MARKS QUESTIONS
Q1. Discuss the nature of bonding in the following coordination entities on the
basis of valence bond theory:
(i)[Fe(CN)6]4- (ii) [FeF6]3- (iii) [Co(C2O4)3]3Also predict their magnetic behaviour.
Q2. What is crystal field splitting energy? Draw figure to show the splitting of d
orbitals in an octahedral crystal field. How does the magnitude of o decide the
actual configuration of d orbitals in a coordination entity?
Q3. Discuss briefly giving an example in each case the role of coordination
compounds in:
(i) biological systems (iii) analytical chemistry
(ii) medicinal chemistry .

104

HALOALKANES and HALOARENES

1- Important mechanism
(i)
Nucleophilic substitution
(ii)
Electrophilic substitution
(iii)
Elimination reaction
(iv)
Carbylamine reaction
(v)
Reimer Tiemann reaction
(vi)
Wurtz reaction
(vii) Wurtzfittig reaction
Nucleophillic substitution it involves the replacement of an atom or group by another atom or
group
AB+C
AC+B
It must be remembered that A B and A C both are covalent compounds.
(i) In aliphatic system
R X + OHR OH + XR X + O-C2H5
R-O- C2H5 + X
In general
R X + :B: B-

R B + X-

OH-, RO-, CN-, RCOO-, NO3-, SH-, RS-

Bimolecular Nuclephilic substitution SN2

(i) It takes place in one step.
(ii) Most of the SN2 reaction are second order but some time when Nucleophillic
reagent is present in excess quantity the reaction is of Its order but still
proceeds by SN2
(iii) It is bimolecular
(iv) It leads to inversion of configuration and attack of Nucleophile occur from
direction opposite to the leaving group.
H3C

CH3

Br

HO-

Heat

HO

C2H5 (inversion)
SN1

H + Br C2H5

(i) It takes place in two steps.

(ii) All are Istorder.
(iii) Unimolecular
(iv) It leadsracemisation i:e inversion as well as retantion
105

C2H5C2H5
H

OH-HC

Br

OH

+ Br-

CH3 CH3
The preservation of spatial arrangement of bonds at an asymmetric centre during the chemical
reaction.
Stereochemistry of SN1 reaction
If an alkyl halide is optically active then the product is racemic mixture, Here the attack of
Nucleophiles takes place from the both side [50:50 mix of the two enantiomers.

CH3 CH3
H

Br

+ Br-

C2H5

CH2CH3
OH-

CH3 CH3
H

50%

Mg

OH

C2H5C2H5

HO

50%

106

H2O

RH + Mg (OH) X

R'OH
(i)CO2

RH +

Mg (OR') X

R COOH + Mg (OH) X

R Mg- X

(II)H2O/H

R H + Mg(OH)X

H+/H2O
R

CHO

H+/H2O

R
CH

OH

R2CO R3COH
H+/H2O

H+/H20
HCN
R

R
CN

R2

C=N MgRCHO + Mg(NH2)X

H
H O/H+
C=N MgX R2 C=O+ Mg(NH2)X 2

107

HOH or
R

NaOH/HOH
R' O- Na
Na S HNa
+ -

+ -

+ -

OH,

S R

Reaction is known as hydrolysis

R,

Ethers

Thio Alcohols

R
R

S
S

R
Thio ethers
R'Thio ethers

HNa S H
+
Na-Na
R'S
2SNa2SNa2

RS
2S

[R

]+X- Sulphonium ions

NaCN
Na+N3-

R
R

C N

Alkyl cyanides

N3Azides

R' CC-Na+

R'

C C

Non terminal akyne

OO
C O

O-R'

R'3N
H-

R N-R'3X+
R H

H-

Ester
Quaternary ammonium halide
Hydrocarbons

From LiAlH4

O- N =O
+

R O-N = O + R Alkyl nitrites

From Na O -N=O
AgNO3

R O N = O +R N
(Minor)

(major)

Nitro alkanes

Nitro alkanes

Ag CN
R'Mgx

R N+ CR

Isocyanides

R'

Hydrocarbons

R'Li
R'2CuLi
Moist Ag2O
Dry Ag2O

R'Hydrocarbons

R'

Hydrocarbons

OH
R

R
108

Electrophillic s ubstitution sees in aromatic compound mech.

H

Slow
H

OR
H

fast
E.g. Nitration how Electrophiles produce.
HNO3 + 2H2SO4NO2++ H3O++ 2HSO4-

NO2+
Y+ Cl+

HNO3 + 2H2SO4

[Cl-Cl +FeCl3
SO3[ 2H2SO4

NO2++ H3O++ 2HSO4-

Cl+ + FeCl4-]
SO3+H3O++HSO4Sometime
SO3+H2SO4

CH3+

HSO4 - + HSO3+

[CH3Cl+AlCl3

CH3+ +Cl- + AlCl4- ]

CH3CO+[ CH3COCl+AlCl3 CH3CO+ + AlCl4- ]

Elimination reaction

109

Two groups or atoms attached to two adjacent carbon atom and simultaneous
formation of multiple bonds between these carbon atom.[Reverse of addition]
Two types (i) . Elimination E1
Two step eliminate

E2 One step eliminate

(ii)

- elimination

CC = C

+HX
H

Saytzaffs Rule
(i)
HO-+ H
H

> H

CH2 = CH2 + KBr + H2

Br
Aloc.KOH
CH3 - CH2 CH - CH3 CH3 CH = CH - CH3

Br

81% More highly substituted Alkenes,

More stable

Some important name reaction

1. Haloform reaction
CH3CH2OH + 4I2+ 6 Na OH CHI3 +HCOONa+ 5NaI +5H2O
CH3CHOH CH3+4I2+ 6 Na OH
CHI3 +CH3COONa + 5NaI + 5H2O
CH3COC6H5 + 3I2 + 4NaOH
CHI3 + C6H5COONa +3NaI +3H2O

2. Wurtz reaction
R X + 2Na +Rx ether R R +2 NaX
WurtzFITTIG REACTION
C6H5Br + 2Na + Br + C2H5ether C6H5 C2H5 + 2 NaBr

Diazonium Salt
H3PO2 C6H6
Alcohol C6H6
CuCl/HCl C6H5 Cl

.
Sandmeyerreac

110

C6H5N2+X- CuBr/HBrC6H5 Br
CuCNC6H5CN
HNO2 C6H5NO2
NaNO2/HBF4

N+=NBF4-

Heat
+ BF3 + N2
F
CH3COOH

C6H5OOC CH3

CONCEPTUAL QUESTIONS
Q1. Why haloalkanes are more reactive than haloarenes.
Ans.
In haloarenes, there is partial double bond character b/w carbon and halogen due to +
resonance effect which makes it less reactive.
(ii) In halo benzene, carbon being sp2 hybridisedwhich is smaller in size than sp3 present in
haloalkanes . So C-Cl bond in aryl halides is shorter and stronger.

Q2. Why do haloalkenesunder gonucleophillic substitution whereas haloarenesunder

goelectophillicsubstitution .
Ans. Due to more electro negative nature of halide atom in haloalkanescarbon atom becomes
slightly positive and is easily attacked by nucleophillic reagents.
While in haloarenes due to resonance, carbon atom becomes slightly negative and
attacked by electrophillic reagents.
Q3. When an alkyl halide is treated with ethanolic solution of KCN, the major product is
alkyl cyanide where as if alkyl halide is treated with AgCN,the major product is alkyl
isocyanide.
Ans. KCN is ionic they can attach through C or N but C-C bond is strong than C-N bond. So
alkyl cyanide is the major product but AgCN is covalent so more electronegative N can attach to C
and forms isocyanides.
Q.4. Aryl halides cannot be prepared by the action of sodium halide in the presence H2SO4
.Why?
111

Ans. Due to resonance the carbon- oxygen bond in phenols has partial double bond and it is
stronger than carbon oxygen single bond.
Q5. Why Grignard reagent should be prepared under an hydrous conditions.?
Ans. Grignard reagent react with H2O to form alkanes , therefore they are prepared under
anhydrous condition.
Q6. Why is Sulphuric acid not used during the reaction of alcohols with KI ?
Ans. It is because HI formed will get oxidized to I2 by concentrated Sulphuric acid which is an
oxidizing agent.
Q7. p- dichlorobenzene has highest m.p. than those of ortho and m-isomers.?
Ans. p- dichlorobenzene is symmetrical, fits into crystal lattice more readily and has higher
melting point.
Q8. Although chlorine is an electron- withdrawing group, yet it is ortho and para directing
inelectrophillic aromatic substitution reactions.Why
Ans.Chlorobenzene is resonance hybrid such that there is ve charge atortho and para positions,
electrophillic substitution reaction will take place at orthoand para position due to +R effect. +R
effect is dominating over I effect. .

:Cl:

:Cl : + :Cl:+ :Cl:+ :Cl:+

Q9. The treatment of alkyl chlorides with aqueous KOH lead to the formation of alcohols but
in presence of alcoholic KOH alkenes are major products. Explain?
Ans. In aqueous KOH,OH- is nucleophile which replaces another nucleophile.
R-X +KOH

R-OH +KX

Where as in alcoholic KOH

C2H5OH +KOH

C2H5O- + K+

CH3CH2-Cl + alcoholic KOH

CH2 =CH2 + C2H5OH

(C2H5O-)
Q10.

Explain why vinyl chloride is unreactive in nucleophillic substitution reaction?

Ans. Vinyl chloride is unreactive in nucleophillic substitution reaction because of double bond
character between C=Cl bond which is difficult to break.
112

CH2 = CH Cl

CH2- CH =Cl+

Q11. Arrange the following compounds according to reactivity towards nucleophillic

substitution reaction with reagents mentioned :(i)

Ans-

4- nitro chloro benzene, 2,4 di nitro chlorobemzene, 2,4,6, trinitrochlorobenzene

with CH3ONa

2,4,6, trinitrochlorobenzene> 2,4 dinitrochlorobemzene> 4- nitrochlorobenzene

Q12. Which compound will react faster in SN2 reaction with OH---?
Ans- (a) CH3Br and CH3I
CH3I

(SN2)

will react faster than CH3Br

(b) (CH3)3C-Cl or CH3Cl

(SN2)

CH3Cl will react faster than 30 halide

Q13. Arrange in order of boiling points.
(a) Bromobenzene, Bromoform, chloromethane,Dibromo-methane
(b)1-chloropropane, Isopropyle chloride, 1-Chlorobutane.
Ans. (a) chloromethane<Bromobenzene<Dibromo-methane < , Bromoform
(b) , Isopropyle chloride <1-chloropropane <1-Chlorobutane
(As Branching increases , boiling point decreases)
Q 14. Predict the reactivity in SN1
(a) C6H5CH2Br, C6H5CH (C6H5)Br, C6H5CH(CH3)Br, C6H5C(CH3)( C6H5)Br
Ans. 30 > 20> 10 (SN1)
C6H5C(CH3)(C6H5)Br > C6H5CH(C6H5)Br > C6H5CH(CH3)Br > C6H5CH2Br
(30)

(20)

(20)

(10)

Q15. Which compound undergoes SN1 reaction first ?

113

(a)

Cl

and

Cl
Cl
Cl
(a) Ans. Cl

(b)

Cl

VERY SHORT ANSWER TYPE QUESTION

[1 MARKS]
Q.1. Write the formula & chemical name of DDT?
Q.2. An alkyl halide having molecular formula C4H9Cl is optically active.what is its structure?
Q.3. Why is vinyl chloride less reactive than ethyl chloride?
Q.4. Write the structural isomers of C3H6Cl2 which can exihibitenantiomerism ?
Q.5. Write down the structure of the following compounds;
(a) 1- chloro-4-ethyl cyclohexane
(b)1,4-dibrone but-2-ene
(c) 4-tert,butyl-3-iodoheptane
(d)1-bromo-4-secbutyl-2-methylbenzene
Q.6. Which compound (CH3)3- C-Cl or ; CH3Cl will react faster in sn2reactionwith OH?
Q.7. A hydrocarbon C5H10 does not react with chlorine in dark but it gives a single monobromo
compound in brightsunlight.identify the compound.
Q.8. Out of C6H5CH2Cl & C6H5CH2Cl 6H5 which is more easily hydrolysed with aq. KOH &why ?
Q.9. Chloroform is stored in dark coloured& sealed bottle.why?
Short answer type questions
Q,1. Give the IUPAC names of the following compounds?
114

A)ClCH2C = CCH2Br

b) (CCl3)3CCl

C)CH3CH(Cl)CH(Br)CH3
Q.2. Starting from methyl iodine, how will you prepare :
A) nitromethane

B)methyl nitrite

Q.2. Rearranging the following in order of increasing case of dehydro halogenations

CH3CH2CH2Cl , CH3CHClCH3 , CH3 CHClC(CH3)3
Q.3. Give the uses of (a) CCl4 (b) iodoform
Q.4. Propose the mechanism of the following reaction :
CH3-CH2-Br + CH3O-

CH3-CH2-OCH3 + Br-

Q.5. Which will have a higher boiling point 1-chloropentane or 2-chloro-2-methylbutane?

Q.6.How will you bring the following conversion?
(a) Propene to Propyne
(b) Toluene to Benzyle Alcohol
(c) Aniline to Phenylisocyanide
Q.7.What happens when;
(a) n-butyl chloride is treated with alc.KOH.
(b) ethyl chloride is treated with aq.KOH.
(c) methyl chloride is treated with KCN.
Q.8.Complete the following reaction;
(a)Cl2CH-CH-Cl2+Zn

(b)(CH3)2-CH-CH-CH2-CH3

Ethanol
C2H5ONa

Cl
(c)C6H5ONa+C2H5Cl
***

115

ALCOHOLS PHENOLS AND ETHERS

IUPAC Name

CH3 O CH2 CH2 CH3

1- Methoxypropane

C6H5OCH3

Methoxy benzene
[Anisole]

C6H5O(CH2)6 CH3

1- Phenoxyheptanes

CH3 O CH CH3

2- Methoxy propane

CH3
CH3CH3
OC2H5

2- ethoxy 1, 1- dimethyl cyclohexane

OH
OH

Benzene 1,2 diol

CH3
2,5 Dimethyl phenol
OH
CH3

116

IUPAC names of phenols

117

IUPAC names of some ethers

118

Name reaction
(1) Reimer Tiemann. Reaction [See in haloalkanes]
(2)Transesterification
(3) Williamson synthesis
(4) Kolbe reaction
(5)Friedel craft
Transesterification :
O
O
H+

R C OR + R O H

R C OR + R OH

Williamson synthesis:- Reaction with alkyl halide with sodium alkoxide

or sod. Phenoxidecalled Williamson synthesis.
R X + R1 O Na

R O - R + NaX

H3I + CH3CH2ONa

CH3O.CH2 CH3 + NaI

CH3CH2-O

ONa

CH3CH2 I +

+ NaI

Both simple and mixed ether can be produced.

Depending upon structure and cleavage of unsymmetrical ethers by
halogen acid may occur either by SN2 or SN1 mechanism.
CH3

CH3
373k

e.g. (i) CH3

CH

CH3 + HI

CH3 I + CH3 CH -OH

2

Sn

CH3
(3)CH3C

CH3 + HI (CH3)3 - C I +CH3 - OH

119

CH3

120

LIMITATIONS OF WILLIAMSON SYNTHESIS

CH3
(i)

CH3

O- Na+ + CH3 CH2- Br

CH

CH3
CH3 C O CH2 CH3 +

NaBr
CH3

CH2-H
(ii)

CH3 C Br + Na+ - O-C2H5-

CH3
CH3 C = CH + C2H5OH + NaBr

CH3
CH3
(iii) CH3 CH Br + CH3 CH2 O- - Na+

CH3
CH3 CH = CH2
79%

CH3 CH OCH2 CH3

21%

Kolbe reaction

121

Friedelcraft reaction

DISTINCTION BETWEEN PAIR OF COMPOUNDS

When 10,20, and 30 alcohol treated with lucas reagent [conc. HCl + an hydrous ZnCl2] at room
temp
(i)
(ii)
(iii)

Ifturbidity appears immediately alcohol is 30.

If turbidity appears in five minutes alcohol is20.
10 alcohol does not react with L.R. at room temp.

(II) All those compound like alcohol, aldehyde Ketones which on oxidation giving CH3 - COGroup undergoes iodoform test.
e.g. (i) CH3CH2 OH
(II) CH3 CHO
122

(III) (CH3) CH OH
(IV) CH3 COCH3
(V) C6H5 CO CH3
(VI) CH3 CH- CH2 CH2- CH3
OH
(VII) CH3 C CH2- CH2 CH3

Important mechanism
(i)

Hydration of alkenes
(i)
(ii)
(iii)
(iv)

H2SO4
H+ + HSO4H
H O H + H+
HOH

CH3

C CH2+H O H
CH3

H+

CH3
C+CH2 H
CH3
H2O
CH3 CH3
123

C CH3H2SO4- C CH3
CH3+O HCH3OH
H

+H2SO4

Important reaction
1000C / 373 K

CH3 CH2HSO4
H2SO4
CH3- CH2 OH
OCH2-CH3

413 K

CH3CH2-

124

433 TO 444 K

CH2 = CH2 +
H20

(2) Preparation of phenol from Cumene

(3) Preparation of aspirin and salol

Explain phenol is acidic?

Phenoxide ion is resonance stabilised

125

:-If electron with drawing group are attached into the benzene
ring it enchance acidic character and vice versa.
2,4,6trinitrophenol> 2,4, dinitrophenol> 4-nitrophenol > phenol
Phenol > m- cresol > P cresol > O cresol
m-methoxyphenol> phenol > O methoxy phenol > P methoxy
phenol.
O chloro phenol > O bromophenol> O iodo phenol > O fluoro
phenol
FORMATION OF PICRIC ACID
(I)

+ 3 Br2

Br

OH

Br

Br

2,4,6tribromo phenol (white plot)

126

(I)Phenol gives violet colour with fecl3solution .

PREPARATION OF 10,20,30 ALCOHOLS

HCHO + R Mg x
CH3CHO + R Mg x

Followed by hydrolysis
Followed by hydrolysis

R-CH2OH 10alc
R- CH(CH3)OH
20alc

CH3
CH3

C =0 + CH3 Mg Br

CH3
C- OH 30alc

CH3
CH3
CONCEPTUAL QUESTIONS

Q1) Preparation of ethers by acid dehydration of secondry or 30

alcohols is not a suitable method?
Ans:-The formation of ethers by dehydration of alcohol is a
bimolecular reaction (SN2) group is hindered. as a result
elimination dominates substitution as 30 carbocation is more
stable. Hence in place of others , alkenes are formed.
CH3
127

CH3

C OH conH2S04 CH3

CH3

CH3

C = CH2

Q2) Phenols do not give protonation reactions readily.Why?

Ans:- The lone pair on oxygen of O-H in phenol is being shared
with benzene ring through resonance.Thus,lone pair is not fully
present on oxygen and hence phenols do not undergo
protonatian reactions.
Q3) Ortho- nitrophenol is more acidic than ortho
methoxyphenol ?why?
Ans:- NO2 group is electron with drawing which increases acidic
charcter due to easily ease
REASONING QUESTIONS

Q1. Explain why propanol has higher boiling point than that of
the hydrocarbon, butane?
Ans.The molecules of Butane are held together by weak van der
Waals Forces of attraction while those of propanol are held
together by stronger intermolecular hydrogen bonding.
Q2. Alcohols are comparatively more soluble in water than
hydrocarbons of comparable molecular masses. Explain this fact.
Ans.Alcohols can form hydrogen bonds with water and break the
hydrogen bonds already existing between water molecules
Therefore they are soluble in water. Whereas hydrocarbons cannot
form hydrogen bonds with water and hence are insoluble in water.
128

Q3 . While separating a mixture of ortho and para nitrophenols

by steam distillation, name the isomer which will be steam
volatile. Give reason.
ANS. O-nitrophenol is steam volatile due to intramolecular
hydrogen bonding and hence can be separated by steam distillation
from p-nitrophenol which is not steam volatile because of intermolecular hydrogen bonding.
Q4.Explain why is orthonitrophenol more acidic than
orthomethoxyphenol?

ANS. The nitro-group is an electron-withdrawing group. Thepresence of

this group in the ortho position decreases the electron density in the O-H
bond . As a result, it is easier to lose a proton. Also,the o-nitrophenoxide
ion formed after the loss of protonis stabilized by resonance. Hence,orthonitrophenol is stronger acid.On the other hand, methoxy group is an
electron-releasing group. Thus ,itincreases the electron density in the O-H
bond and hence, the proton cannot be given out easily. Therefor orthonitrophenol is more acidic than ortho- methoxyphenol.
5. Preparation of ethers by acid dehydration of secondary or
tertiary alcohols is not a suitable method. Give reason.
ANS. The formation of ethers by dehydration of alcohol is a
bimolecular reaction SN2
involving the attack of an alcohol molecule on a protonated alcohol
molecule. In the method, the alkyl group should be unhindered. In
case of secondary or tertiary alcohols, the alkyl group is hindered.
As a result, elimination dominates substitution.
Q6. What is meant by hydroboration-oxidation reaction? Illustrate it
with an example .
129

ANS.Diborane (BH3)2 reacts with alkenes to give trialkylboranes as

addition product. This is oxidised to alcohol by hydrogen peroxide in the
presence
of aqueous sodium hydroxide.

Q7. Give the equations of reactions for the preparation of phenol from
cumene.
Ans.

Q8. Write chemical reaction for the preparation of phenol from

chlorobenzene.Ans.Chlorobenzene is fused with NaOH at 623K
and 320 atmospheric pressure. Phenol is obtained by acidification
of sodium phenoxide so produced.

130

Q9. How is aspirin (Acetylsalicylic acid) prepared from salicylic

acid?Ans. Acetylation of salicylic acid produces aspirin.

Q10. Which out of propan-1-ol and propan-2-ol is stronger

acid?Ans.Propan-1-ol is stronger acid than propan-2-ol. The acidic
strength of alcohols is in the order 10>20>30.
Q11. What is denaturation of an alcohol?
Ans.The commercial alcohol is made unfit for drinking by mixing
in it some copper sulphate (to give it a colour) and pyridine (a foul
smelling liquid). It is known as denaturation of alcohol.
Q12. Give IUPAC name of CH3OCH2OCH3
ANS. Dimethoxymethane
Q13. Diethyl ether does not react with sodium. Explain.
ANS. Diethyl ether does not contain any active hydrogen.
2 MARKS QUESTIONS
Q1. Give two reactions that show the acidic nature of phenol.
Compare acidity of phenol with that of ethanol.
ANS. The acidic nature of phenol can be represented by the
following two reactions: (i) Phenol reacts with sodium to give
sodium phenoxide, liberating H2.

131

(ii)

Phenol reacts with sodium hydroxide to give sodium

phenoxide and water as by-products

The acidity of phenol is more than that of ethanol. This is because

after losing a proton, the phenoxide ion undergoes resonance and
gets stabilized whereas ethoxide ion does not.

Q2. How does phenol react with dilute and conc. HNO3 ?
ANS. (i) With dilute nitric acid at low temperature (298 K), phenol
yields a mixture of ortho

132

and para nitrophenols. (ii) With concentrated nitric acid, phenol is

converted to 2,4,6-trinitrophenol. The product is commonly known
as picric acid.

Q3. How does phenol react with Br2 in CS2 and Bromine water?
ANS.(i) When the reaction is carried out in solvents of low
polarity such as CHCl3 or CS2 and at low temperature,
monobromophenols are formed.

(iii) When phenol is treated with bromine water, 2,4,6tribromophenol is formed as white precipitate.

133

Q4. How do you account for the fact that unlike phenol, 2, 4dinitrophenol and 2, 4, 6-trinitrophenol are soluble in aqueous
solution of sodium carbonate?
ANS. 2, 4-Dinitrophenol and 2, 4, 6-trinitrophenol are stronger
acids then carbonic acid (H2CO3) due to the presence of electron
withdrawing NO2 groups. Hence, they react with Na2CO3 to form
their corresponding salts and dissolve in aq. Na2CO3 solution.
Q5.(i) Why is the Dipole moment of methanol higher than that of
phenol? (ii) . Explain why phenols do not undergo substitution of
the OH group likealcohols.
ANS.(i) Due to electron withdrawing effect of phenyl group, the
CO bond in phenol is less polar, whereas in case of methanol the
methyl group has electron releasing effect and hence CO bond in
it is more polar.
(ii) CO bond in phenols has partial double bond character due to
resonance and hence is difficult to cleave.
Q6. Account for the following
a. Boiling point of the C2H5OH is more than that of C2H5Cl
b. The solubility of alcohols in water decreases with increase in
molecular mass.
ANS.a. Because of hydrogen bonding.
b. With increase in molecular mass the non-polar alkyl group
becomes more predominant.
Q7. Answer the following
a. What is the order of reactivity of 10, 20 and 30 alcohols with
sodium metal?
b. How will you account for the solubility of lower alcohols in
water?
ANS: a. 10>20>30.
b. HereOH group is predominant and the alcohol molecules can
form hydrogen bonds with water molecules.
134

Q8. Give reasons:

i)Nitration of phenol gives ortho- and para- products only.
ii)Why do alcohols have higher boiling points than the
haloalkanes of the same molecular mass?
ANS (1) -OH group increases the electron density more at ortho
and para positions through its electron releasing resonance effect.
(2) Alcohols are capable of forming intermolecular H-bonds.
Q9. Account for the following:
i) Phenols has a smaller dipole moment than methanol
ii) Phenols do not give protonation reactions readily.
ANS.(a). In phenol the electron withdrawing inductive effect of
OH group is opposed by electron releasing the resonance effect of
OH.
(b). The lone pair on oxygen of OH in phenol is being shared with
benzene ring through resonance. Thus, lone pair is not fully present
on oxygen and hence phenols do not undergo protonation
reactions.
Q10. Explain the fact that in aryl alkyl ethers
(i) The alkoxy group activates the benzene ring towards
electrophilic substitution and
(ii) It directs the incoming substituents to ortho and para
positions in benzene ring.

ANS. (i)
In aryl alkyl ethers, due to the +R effect of the alkoxy group, the
electron density in the benzene ring increases as shown in the
following resonance structure.

135

Thus, benzene is activated towards electrophilic substitution by the

alkoxy group.
(ii) It can also be observed from the resonance structures that the
electron density increases more at the ortho and para positions
than at the meta position. As a result, the incoming substituents are
directed to the ortho and para positions in the benzene .

3 MARKS QUESTIONS
Q1. How are primary, secondary and tertiary alcohols prepared
from Grignard Reagents?
ANS.

.
The reaction produces a primary alcohol with methanal, a
secondary alcohol with other aldehydes and tertiary alcohol with
ketones.
Q2. Give the equations of oxidation of primary, secondary and
tertiary alcohols by Cu at 573 K.
ANS.
136

Q3. Give equations of the following reactions:

(i) Oxidation of propan-1-ol with alkaline KMnO4 solution.
(ii) Bromine in CS2 with phenol.
(iii) Dilute HNO3 with phenol.
ANS.(i)
(

Q4. Show how will you synthesize:

(i) 1-phenylethanol from a suitable alkene.
(ii) (ii) cyclohexylmethanol using an alkyl halide by an SN2
reaction.
(iii) (iii) pentan-1-ol using a suitable alkyl halide?

137

ANS. (i) By acid-catalyzed hydration of ethylbenzene (styrene), 1phenylethanol can be synthesized.

(ii) When chloromethylcyclohexane is treated with sodium

hydroxide, cyclohexylmethanol is obtained.

(iv) When 1-chloropentane is treated with NaOH, pentan-1ol is produced.

Q5. How are the following conversions carried out?

(i)Propene Propan-2-ol
(ii) Benzyl chloride Benzyl alcohol
(iii) Ethyl magnesium chloride Propan-1-ol.
ANS.(i)If propene is allowed to react with water in the presence of
an acid as a catalyst, then propan-2-ol is obtained.

(ii) If benzyl chloride is treated with NaOH (followed by

acidification) then benzyl alcohol is produced.

138

(iii)When ethyl magnesium chioride is treated with methanol, an

adduct is the produced which gives propan -1-ol on hydrolysis.

Q6. Name the reagents used in the following reactions:

(i) Oxidation of a primary alcohol to carboxylic acid.
(ii) (ii) Oxidation of a primary alcohol to aldehyde.
(iii) Bromination of phenol to 2,4,6-tribromophenol.
ANS. (i) Acidified potassium permanganate
(ii) Pyridiniumchlorochromate (PCC)
(iii) Bromine water
Q7. How is 1-propoxypropane synthesised from propan-1-ol?
Write mechanism of this reaction.
ANS. 1-propoxypropane can be synthesized from propan-1-ol by
dehydration. Propan-1-ol undergoes dehydration in the presence
of protic acids (such as H2SO4, H3PO4) to give 1propoxypropane.
The mechanism of this reaction involves the following three steps:

Step 1: Protonation
139

Step 2: Nucleophilic attack

Step 3: Deprotonation

Q8. Write the equation of the reaction of hydrogen iodide with:

(i)

1-propoxypropane (ii) Methoxybenzene and (iii) Benzyl

ethyl ether
ANS. (i)
(ii)

(iii)

5 MARKS QUESTIONS
Q1. Write equations of the following reactions:
(i) Friedel-Crafts reactionalkylation of anisole.
(ii) Nitration of anisole.
(iii) Bromination of anisole in ethanoic acid medium.
(iv) Friedel-Crafts acetylation of anisole.
140

(v)Reaction of phenol with Zn dust.

ANS.(i)

(ii)

(iii)

(iv)

(v)

141

142

3 MARKS QUESTIONS
Q 1.Alcohols reacts with halogen acids to form haloalkenes but phenol does not form
halobenzene.
Explain
. Ans. The C-O bond in phenol acquires partial double bond character due to resonance and
hence be cleared by X- ions to form halobenzenes. But in alcohols a pure C O bond is
maintained and can be cleared by X ions.
Q 2. Explain why o-nitrophenol is more acidic than o-methoxy phenol?
Ans . Due to R and I effect of NO2 group, e density on O if O H bond decreases and
loss of H+ is easy. I effect In contrast, in o-methoxy phenol due to + R effect, OCH3 increases. e
density on O2 of OH group, and hence loss of H+ is difficult.(both ve charge repel each other)
Q3. Of benzene and phenol, which is more easily nitrated and why?
Ans.Nitration is an electrophilic substitution. The OH group in phenol increases the
electron density at ortho and para position as follows Since phenol has higher electron
density due to electron releasing nature of -OH group , compared to benzene , therefore
nitration is easy in phenol than benzene.
Q4. How will you account for the following? Ethers possess a net dipole moment even if they
are symmetrical in structure?
A. Because of greater electronegativity of o- atom than carbon C O bonds are polar.
C O bond are inclined to each other at an angle of 110 (or more), two dipoles do not cancel out
each other.
Q 6. How do 1, 2 and 3 alcohols differ in terms of their oxidation reaction and
dehydrogenation ?
Ans. (I) Oxidation reaction : (O) (O)
1 alcohol aldehyde carboxylic acid (O) (O)
2 alcohol ketone carboxylic acid (acid with loss of 1 carbon atom) (O)
3 alcohol resistant to oxidation
(II) Hydrogenation reaction : give
1 alcohol aldehyde
2 alcohol ketone
3 alcohol alkene 3 alcohols prefer to undergo dehydration and form alken
Q7. (i)How is diethyl ether prepared from ethyl alcohol?
Ans. Ethyl alcohol is first treated with sodium to form sodium ethoxide
C2H5OH + Na C2H5O Na+ + H2
Sodium ethoxide is then treated with
ethyl halide to form di ethyl ether. SN
C2H5O Na + C2H5X C2H5O C2H5 + NaX (Williamson synthesis)
(II) Complete the reaction:
(a) CH3OCH3 + PCl5 ?
(b) C2H5OCH3 + HCl ? (c) (C2H5)2 O + HCl
A. (a) 2 CH3Cl (b) CH3Cl + C2H5OH (c) C2H5Cl + C2H5OH
Q8. Why are reactions of alcohol/phenol and with acid chloride in the presence of pyridine?
Ans. Because esterification reaction is reversible and presence of base (pyridine) neutralisesHCl
produced during reaction thus promoting forward reaction.
143

LONG ANSWER TYPE QUESTIONS

Q1) How the following conversions can be carried out?
(i) Propene to propan-1-ol
(ii) 1-Bromopropane to 2-bromopropane
(iii) Toluene to benzyl alcohol
(iv) Benzene to 4-bromonitrobenzene
(v) Benzyl alcohol to 2-phenylethanoic acid

144

Q2) How the following conversions can be carried out?

(i) Ethanol to propanenitrile
(ii) Aniline to chlorobenzene
(iii) 2-Chlorobutane to 3, 4-dimethylhexane
(iv) 2-Methyl-1-propene to 2-chloro-2-methylpropane
(v) Ethyl chloride to propanoic acid

145

Q3) How the following conversions can be carried out?

(i) But-1-ene to n-butyliodide
(ii)2-Chloropropane to 1-propanol
(iii) Isopropyl alcohol to iodoform
(iv) Chlorobenzene to p-nitrophenol
(v) 2-Bromopropane to 1-bromopropane

146

147

Q4) How the following conversions can be carried out?

(i) Chloro ethane to butane
(ii)Benzene to diphenyl
(iii) tert-Butyl bromide to isobutyl bromide
(iv) Aniline to phenylisocyanide

148

***

149

ALDEHYDES, KETONES AND CARBOXYLIC ACIDS

Addition to C=O bonds
The structure of the carbonyl group in aldehydes and Ketones is
, not entirely adequately represented by >C=O, nor by the
alternative >C+-O-. The real structure or resonance hybrid lies
somewhere between the following structure:

>C=O

>C+=O-

For Mechanism
>C=O + H+

OH

slow
reaction

C+ -OH:A-

C
slow

A
O-

Second Mechanism
>C = O + :A-

SLOW

OH
H+

>C

REACTION

>C

Fast

Reactivity of aldehyde and Ketones is as

HCHO>RCHO>RCOR>RCOOR>RCONH2.

POINTS TO REMEMBER
:-Lower members are soluble in water because they can form Hbond with water.
:-Higher members are insoluble in water due to large size of their
hydrophobic group.
:-Aldehydes are prepared by150

a. Dehydrogenation of primary alcohols

b. Controlled oxidation of primary alcohols.
c. Controlled and selective reduction of acyl halides
Aromatic aldehydes can be prepared bya. Oxidation of toluene with chromyl chloride or CrO3 in the
presence of acetic anhydride
b. Formylation of arenes with carbon monoxide and Hydrochloric
acid in the
presence of anhydrous aluminiumchloride / Cuprous chloride
c. Hydrolysis of benzal chloride
Ketones are prepared bya. oxidation of secondary alcohols
b. Hydration of alkenes
c. Reaction acyl chlorides with dialkylcadmium
d. By friedel crafts reaction
Carboxylic acids are prepared by
a. oxidation of primary alcohols, aldehydes and alkenes
b. hydrolysis of nitriles
c. Treatment of grignard reagent with carbondioxide.

NAME

REACTIONS

.
ROSENMUND REDUCTION:

The catalytic hydrogenation of acid chlorides allows the formation of aldehydes.

Mechanism of the Rosenmund Reduction
Side products :

1.ROSENMUND REDUCTION:
151

O
H2/Pd-BaSO4
-C-Cl +

-CHO

Benzoyl chloride

Benzaldehyde

2. STEPHEN REACTION
RCN +SnCl2 +HCl
ETARD REACTION

H3O
RCHO 3.

RCH=NH

CH3

CHO
CrO2Cl2
CCl4

CHYYYYYYUUUUUUUIIIOTVBBNTTTTEW
H
3
CHO
H
OR

CCCC

CLEMMENSEN REDUCTION
>C=O
HCl
RY

Zn-Hg
>CH2 + H2O
Alkanes E

WOLFF- KISHNER REDUCTIONGRTGDSS

S
152

>C=O
-H2OHeat

NH2NH2
>C=NNH2KOH/ethylene glycol>CH2 + N2

ALDOL CONDENSATION
Aldehydes and ketones having at least one -hydrogen condense in the
presence of dilute alkali as catalyst to form -hydroxyalddilehydes (aldol) or
-hydroxy ketones (ketol).
NaOH
2CH3-CHO CH3-CH-CH2-CHO
CH3-CH=CH-CHO
ethanal
-H2O
But-2-enal
OH (Aldol)
C CH3CH3
FBa(OH)2 Heat
2CH3-CO -CH3CH3-C-CH2-CO-CH3CH3-C=CH-CO-CH3
Propanone
-H2O
4-Metylpent-3-en2-one
OH (Ketal)
CROSS- ALDOL CONDENSATION
When aldol condensation is carried out between two different aldehydes and
/ or ketones,a mixture of self and cross-aldol products are obtained.
CH3CHO 1NaOHCH3CH=CH-CHO + CH3CH2CH=C-CHO
+ 2 But-2-en-1-al
CH3-CH2-CHO
CH3
2-Methylpent-2-ena
CH3-CH=C-CHO +
CH3CH2-CH=CHCHO
CH3
2 -Methylbut-2-enal

Pent-2-enal

CANNIZARO REACTION
Aldehydes which do not have an -hydrogen atom, undergo self oxidation
and reduction (dispropotionation) reaction on treatment with concentrated
alkali,to yield carboxylioc acid salt and an alcohol respectively.
H-CHO + H-CHO + Conc.KOH
CH3OH
+ HCOOK
Formaldehyde
153

Methanol
Pot. Formate
-CHO + NaOH (con.)
C6H5COONa
BenzaldehydeBenzyl alcohol

C6H5CH2OH +

Sodium benzoate

CARBOXYLIC ACID
1. HELL-VOLHARD-ZELINSKY REACTION (HVZ)
i X2/ Red phosphorus
RCH2-COOH

ii H2O

R-CH-COOH

X
X=Cl,Br
halocarboxylic acids

2. ESTERIFICATION
RCOOH + ROH
Carboxylic acid alcohol

H+

RCOOR +H2O
Ester

3. DECARBOXYLATION:
NaOH and CaO /
RCOONa
MECHANISMS
.
1.
CH3CH2OH

R-H +Na2CO3

Con H2SO4
CH2 = CH2 + H2O
443 K

154

Mechanism:
(i) H2SO4

H+ + HSO4+

(ii) CH3CH2 O H + H+

CH3 CH2 O+ H

H
(iii)

(iv)
(v)

CH3CH2 O+ H + H+CH3 CH2+ + H2O

|
H
+
CH3 CH2
CH2 = CH2 + H+
H+ + HSO4-

H2SO4

Con H2SO4
2 2CH3 CH2 OH

CH3 CH2 O CH2 CH3 + H2O

413 K

Mechanism:i) H2SO4
+
ii) CH3 CH2 OH +H+

H+ + HSO-4 CH3 CH2 O H

|
H

(iii) CH3CH2 O+ H

CH3 CH2+ + H2O

H
iv) CH3 CH2 O H + CH3 CH2+ CH3 CH2 O+ H
CH2CH3

v) CH3CH2 O+ H

CH3CH2 O CH2CH3 + H+

CH2CH3

155

NOMENCLATURE
Refer NCERT Text Book Exercise part

DISTINGUISH
Q1:-Distinguish between the following:(a)Phenol and alcohol
(b)Benzaldehyde and Propanal
(c)Acetic acid and formic acid
(d)Benzophenone and acetophenone
(e)Ethanal and propanal
(f)Propanol and ethanol
(g)Pentanone-2-one Pentanone-3-one
(h) 20 Alcohol and 30alcohol
(i)1,2,3 amine
(j)Benzoic acid and benzene
(k)Phenol and benzoic acid
(l)Aniline and ethyl amine
(m)Aniline and nitrobenzene
(n)Benzaldehyde and acetophenone
(o)Methanol and benzaldehyde
(p)Chloro benzene and benzyl chloride

ANSWERS
156

(a)

Phenol
It gives FeCl3 test
(voiletcolour)

(b) BenzaldehydePropanal
It gives tollen'sIt also give tollen's
reagent test
It doesn't give fehling
solution test

Alcohol
It doesn't give this test

It gives fehling solution

test

(c)

Acetic acid
It doesn't gives tollen's reagent
It doesn't givefehling's test

(d)

BenzophenoneAcetophenone
It doesn't give iodoform test

It gives iodoform test

EthanalPropanal
It gives iodoform test

It doesn't gives iodoform

(f)

Propanol
It doesn't give iodoform test

Ethanol
It gives iodoform test

(g)

pentanone-2
It gives iodoform test

pentanone-3
It doesn't gives iodoform

(e)

Formic acid
It gives tollen's test
It gives fehling test

test

test
(h)
2 alcohol
CH3CH3
CH-OH
CH3C-OH
CH3CH3

3 alcohol

HCl+ZnCl2 HCl +ZnCl2

It takes 5 minutes
seconds

(i)

turbility is formed within no

10 amine by Hinsbergtest :Hinsbergreaent

157

C2H5NH2+C6H5SO2Cl C6H5NH-SO2-C6H5
(benzenesulphonyl chloride)
soluble in alkali
2 amine
C2H5-NH+C6H5SO2Cl C2H5-N-SO2C6H5
C2H5 C2H5
Insoluble in KOH
3 amine
C2H5-N-C2H5+C6H5SO2ClX (No reaction)
C2H5
(J)
Benzoic acid
add NaHCO3
Effervescence obtained(CO2)
(k)

Phenol
It gives voiletcolour with FeCl3 test
with FeCl3
It doesn't give effervescenes of
CO2
is added

Benzene
no effervescence
obtained
Benzoic acid
It doesn't give voiletcolour

Effervescence of CO2
evolve when NaHCO3

(l)

Aniline
It gives azo-dye test
(orange dye)

Ethyl amine
It doesn't give azo-dye

(m)

Aniline
It gives azo-dye test

Nitrobenzene
It doesn't

(n)

BenzaldehydeAcetophenone
It gives tollen's test

It doesn't

It doesn't give iodoform test

It gives iodoform test

MethanalBenzaldehyde
It gives fehling solution test

It doesn't

(o)

(p)

Chloro benzene
Benzyl choride
Does not give test with aquKOH
of AgCl)
followed by treatment with AgNO3

give test (white precipitate

158

CONCEPTUAL QUESTIONS
Q1)
Although phenoxide ion has more no. of resonating structures
than carboxylate ion , even though carboxylic acid is a stronger acid
why ?
Ans:-The phenoxide ion has non equivalent resonance structures in which
ve charge is at less electronegative C atom and +ve charge as at more
electronegative O-atom.
In carboxylate ion ve charge is delocalized on two electronegative Oatoms hence resonance is more effective and a stronger acid.
O-

O
R

R
O-

C
O

Q.2
Why Corboxylic acid have higher boiling point than alcohols
as alcohol forms strongest inter molecular hydrogen bonding?
Ans.As Corboxylic acid forms a dimer due to which their surface area
increses and forms strong intermolecular H-bonding
It having more boiling point than alcohols.
Q.3 There are two-NH2 group in semicarbazide .However only one
is involved in formation of semicarbazones. Why?
Ans.

O
NH2- C NH NH2

Due to resonance one NH2 group undergoes or involved in resonance and

hence cant participate in the formation of semicarbazone.

N H2 = C NH NH2
159

OLong pair of NH2 group is not involved in resonance and is available

for nucleophillic attack
Q.4 Why does solubility decreases with increasing molecular mass
in carboxytic acid?
Ans. Because of increase in alkyl chain length which is hydrophobic in
nature.
Hence solubility decreases.
Q.5 Why are aldehydes are more reactive than ketones when
undergo nucleophillic addition reaction?
Ans (a) + I effect:- The alkyl group in Ketones due to their e-releasing
character decrease the +ve charge on C-Atom and thus reduce its
reactivity.
(b)
Steric hinderance:- Due to steric hinderance in ketones they are
less reactive.
H
R
C=O
C=O
R
R
Q.6 Why PCC cannot oxidise methanol to methanoic acid and while
KMNO4 can?
Ans.This is because PCC is a mild oxidising agent and can oxide
methanol to methanal only.
While KMNO4 being strong oxidising agent oxidises it to methanoic acid.
Q.7 During preparation of esters from a carboxylic acid and an
alcohol in the presence of acid catalyst water or ester formed should
be removed as soon as it is formed.

160

Ans.The formation of esters from a carboxylic acid and an alcohol in the

presence of acidcatelyst in a reversible reaction.
R COOH + ROH

H2SO4

R COOR + H2O

To shift the equilibrium in forward direction, the water or ester formed

should be removed as fast as it is formed.
Q.8 Why HCOOH does not give HVZ reaction while CH3COOH
does?
Ans.CH3COOH contains -hydrogens and hence give HVZ reaction but
HCOOH does not contain -hydrogen and hence does not give HVZ
reaction.
Q.9 Suggest a reason for the large difference in the boling point of
butanol and butanal although they have same solubility in water.
Ans. Because Butanol has strong intermolacular H-bonding while butanal
has weak dipole-dipole interaction.
However both of them form H-bonds with water and hence are soluble.
Q.10 Would you expect benzaldehyde to be more reactive or less
reactive in nuderophillic addition reaction than propanol. Explain.
Ans. C-atom of Carbonyl group of benzaldehyde is less electrophilic than
C-atom of Carbonyl group in propanol.
Polarity of Carbonyl group is in bonzaldehyde reduced due to resonance
making it less reactive in nucleophillic addition reactions.
O=CH

OCH
+

161

Q.11 Why does methanal not give aldol condensation while ethanol
gives?
Ans.This is because only those compounds which have -hydrogen atoms
can undergo aldol reaction ethanol pessess -hydrogen and undergoes
aldol condensation Methanal has no alpha hydrogen atoms hence does not
undergo aldol condensation.
Q.12

Why does methanal undergo cannizaros reaction?

Ans.because it does not possesses -hydrogen atom.

Q.13

Which acid is stronger and why?

F3C-C6H4COOH and CH3C6H4COOH

Ans.CF3- has strong (-I)effectWhereas, CH3- has strong (+I)effect
Due to greater stability of F3CC6H4COO ion over CH3-C6H4COO ion
CF3 C6H4COOH is much stronger acis than CH3-C6H4COOH.
Q.14 Explain why O-hydroxybenzaldehyde is a liquid at room
temperature while p- hydroxybenzaldehyde is a high melting solid.
Ans. Due to intramolecular H-bonding in O-hydroxybenzaldehyde exists
as discrete molecule whereas due to intermolecular H-bonding phydroxybenzaldehyde exist as associated molecules.
To break this intermolecular H-bonds a large amount of energy is needed.
Consequently P-isomer has a much higher m.p. and b.p. than that of Oisomer.As a result O-hydroxybenzaldehyde is liquid.
Q.15
Why is the boiling point of an acid anhydride higher than the
acid from which it is derived?
Ans.Acid anhydrides are bigger in size than corresponding acids have
more surface area more van der Waals. Force of attraction hence have
higher boiling point.
162

Q.16 Why do Carboxylic acids not give the characteristic reactions

of a carbonyl group?
Ans. Due to resonance, It doesnt give the characteristics reactions of
carbonyl group. It does not have free
C=O group
Q.17
Cyclohexanone forms cyanohydrin in good yield but
2,2,6trimethylecyclo-hexanone does not. Why?
Ans.In 2,2,6trimethylcyclohexaunone there is strearichinderance of 3
methyl groups, It does not form cynohydrin in good yield.
Q.18

Why is carboxyl group in benzoic acid meta directing?

Ans. In benzoic acid the Carboxyl group is meta directing because it is

electron-withdrawing
There is +ve charge on ortho acid para positions
Electrophillic substitution takes place at meta-position.
Q.19 Treatment of Benzaldehyde with HCN gives a mixture of two
isomers which cannot be separated even by careful fractional
distillation. Explain why?
Ans.It is because we get two optical isomers which have same physical
properties
Cannot be Separated by Fractional distillation.
O
C6H5 C H + HCN

C6H5 C CN
H

CN

CN

H C OH

OH C - H
163

C6H5
d(+)

C6H5
l(-)

Q.20
Sodium Bisulphite is used for the purification of aldehydes
and Ketones. Explain.
Ans.Aldehydes and Ketones form addition compounds with NaHSO3
whereas impurities do not.
On hydrolysis we get pure aldehydes and Ketones back.
O
CH3 C H + NaHSO3

OH
CH3 CH SO3Na
H2O
O
CH3 - C - H + NaHSO3
(PURE)

Q.21 Why pH of reaction should be carefully controlled while

preparing ammonia derivatives of carbonyl compound?
Ans. In strongly acidic medium ammonia derivatives being basic will
react with acids and will not react with carbonyl compound. In basic
medium, OH- will attack carbonyl group.
pH of a reaction should be carefully controlled.
Q.22

Why formic acid is stronger acid than acetic acid?

Ans. Due to +I effect, CH3- group in acetic acid increases e- density on

carbon atom which makes it.Weak acid.
While in formic acid no such pushing group is present, hence is more
stronger acid than acetic acid.

164

Q.23
Why is oxidation of alcohals to get aldehydes carried out
under controlled conditions?
Ans.It is because aldehydes get further oxidised to acids, oxidation of
alcohals to aldehydes needs to be controlled.

Q.24
Why the oxidation of toluene to benzaldehyde with CrO3 is
carried out in the presence of acetic anhydride.
Ans. If acetic anhydride is not used we will get benzoic acid.
Acetic anhydride used to prevent oxidation of benzaldehyde to
benzoic acid.
Q.25 Melting point of an acid with even no. of carbon atoms is
higher than those of its neighbour with odd no. of carbon atoms.
Ans.They fit into crystal lattice more readily than odd ones that is why
they have higher lattice energy and higher melting point.
Q.26
Why do aldehydes have lower boiling point than
corresponding alcohals?
Ans.alcohals have lower boiling point as they are not associated with
intermolecular whereas alcohals are associated with intermoleculer Hbonding
Aldehydes have lower B.p.
Q.27

Why do aldehydes behave like polar compounds?

Ans. Due to presence ofC=O group whoch is polar

Q.28
Most aromatic acids are solids while acetic acid and others of
this series are liquids. Explain why?
Ans. Aromatic acids have higher molecular weight,

165

More van-der waals force of attracrtion as compared to aliphalic

acidsThey are solids.
Q.29 ethers possess a dipole moment ever if the alkyl radicals in the
molecule are identical. Why?
Ans. It is because ethers are bent molecles, dipole do not get cancelled.
O
R

Q.30
Why does acyl chorides have lower boling point than
corresponding acids?
Ans. Acyl chlorides are not associated with intermolecular H-bonding
They have lower boiling point.
Q.31

Why ethers are stored in coloured bottles?

Ans. They are stored in coloured bottles. In presence of sunlight they react
with oxygen to form peroxides which may cause explosion.
Q.32 Why formaldehyde cannot be prepared by Rosenmunds
reduction?
Ans. Because the formyl chloride thus formed is unstable at room
temperature.
Cannot be prepared by Rosenmund reduction.
Q1. An organic compound (A) {C8H16O2} was hydrolysed with

dilute sulphuric acid to give a carboxylic acid (B)and an alcohol

(C). Oxidation of (C)with chromic acid produced (B).(C) on
dehyration gives but-1-ene .Identity A,B,C
H2SO4
Ans-: CH3CH2CH2COOCH2CH2CH2CH3 +H2O
(A) Butyl Butanoate
CH3CH2CH2COOH
166

(B)
+
CH3CH2CH2CH2OH
(C)
CH3CH2CH2 CH2OH

K2Cr2O7

CH3CH2CH2COOH

(c)

(B)

CH3CH2CH2 CH2OH

Conc.
H2SO4

CH3CH2CH = CH2 (bute 1-ene)

Q2 -: An organic compound with the molecular formula C9H10O

forms 2,4 DNP derivative reduces tollens reagent and undergoes
cannizaro reaction . on vigorous oxidation ,it gives 1,2
benzenecarboxylic acid . identify the compound .
Ans:-

H
C=O

NO2

CH2CH3

+ NH2 - NH

NO2

(2,4, DNP)
NO2
CH = N - NH

NO2

CH2CH3
167

CHO

COOH
CH2CH3

Hot KMnO4

COOH

KOH

Q3. An organic compound (A) with molecular formula C8H8O

forms an orange-red precipitate with 2,4 DNP reagent and gives
yellow precipitate on heating with iodine in the presence of
sodium hydroxide. It neither reduces tollens or fehlings
reagent , nor does it decolourise bromine water or baeyers
reagents .On drastic oxidation with chromic acid .it gives a
carboxylic acid (B) having molecular formula C7H6O2. Identify
the compounds (A) and (B).
COCH3

NO2
+ NH2 - NH

NO2

(A)
CH3
C = N

NO2

NH

NO2

(2,4,DPN derivative)
COOH

COCH3
H2CrO4

(B)

(A)

COONa
NaOH
I2

+ CHI3

168

Q4. Two moles of organic compound A on treatment with a

strong base gives two compounds B and C. Compound B on
dehydration with cu gives A while acidification of C yields
carboxylic acid D having molecular formula of CH2O2 .Identify
the compoundsA,B,C,D
Ans:- 2HCHO Conc.

HCOOK + CH3OH

KOH

(A)

(C)

CH3OH Cu
573 K

(B)

HCOOK +HCL
(c)

(B)

HCHO
(A)
HCOOH +KCL
(D)

Q5. An aliphatic compound Awith a molecular formula of

C3H6O reacts with phenylhydrazine to give compound B .
Reaction ofA with I2 in alkalene medium on warming gives a
yellow precipitate C. Identify the component A,B,C
Ans:- CH3COCH3 + C6H5 NH NH2
o

(A)

CH3C CH3 + 3I2 + NaOH

(A)

CH3C=N HN C6H5
CH3 (B)

CHI3
(Iodoform)
(c)
169

Q6 .A compoundA with molecular formula C5H10O gave a

positive 2,4 DNP test but a negative tollens reagents test . It
was oxidised to carboboxylic acidB with molecular formula
C3H602when treated with alkalines KMnO4 under vigrous
condition . sodium salt of B gave hydrocarbon C on
kolbeeletrolysis reduction . Identify A,B,C and D.
KMnO4
Ans:- CH3 CH2 C CH2 CH3
CH3CH2COOH
KOH
O
(A)
(B)
NO2
CH3 CH2 C = O + NH2 NH
NO2
CH2
CH3
CH3 CH2 C = N- NH
CH2
CH3
2CH3CH2COONa electrolysis CH3CH2CH2CH3
Sodium propanoate
(c) + 2CO2

NO2
NO2

Q7 An organic compound A has the molecular formula

C5H10O .It does not reduce fehlings solution but forms a
bisulphite compound .It also gives positive Iodoform test. What
are possible structure of A ?Explain your reasoning.

170

Ans-: it does not reduce fehlings solution but forms bisulpphite

compound so it is a ketone therefore it gives positive iodoform
test therefore it is methyl ketone .
The possible structure are-:

CH3 C CH2 CH2CH3 And CH3 C CH

CH3
CH3
Q8.
An organic compound A which has charactersticodour ,
on treatment with NaOH forms two compounds B and C.
Compound B has the molecular formula C7H8O which on
oxidation gives back compound A. Compound C is the
sodium salt of an acid which when heated with soda lime yields
an aromatic hydrocarbon D. Deduce A,B,C,D
Ans.
CHO

CH2OH
+

NaOH
(A)
CH2OH

COONa

(B)

(C)
CHO

OXIDATION
(B)
171

COONa
+ Na2CO3

Na(OH) ,CaO

Q9. An organic compound A is resistant to oxidation forms

an oxidation forms a compound 'B(C3H80) on reduction
.B'reacts with HBr to form a bromide C which on treatment
withalkoholic KOH forms an alkene D (C3H6). Deduce A,B,C,D.
Ans:- CH3 C CH3

LiAlH4

CH3CH CH3

OH

(A) (B)
CH3-CH CH3 + HBr

CH3CH CH3

OH

Br

(B)

(C)

CH3-CH CH3alc KOH

Br

CH3 - CH =CH2 + KBr

(D)

Q10. Eherial solution of an organic compound 'A when

heated with magnesium gave 'B on treatment with ethanal
followed by acid hydrolysis gave 2-propanol .Identify the
compound 'A . What is 'B' known as?
Ans:-

CH3 Br + Mg

CH3MgBr

Dry ether

172

(a)

(b)

CH3CHO + CH3MgBr

CH3 CH CH3
OH + Mg (OH)Br

Q11.

Identify A,B,C,D

A + CH3MgBr

CH3CH2 CH CH3
H2O

OH
alc

CONC. H2SO4

DC B
KOH

Br2

ANS.
A = CH3CH2CHO
B = CH3CH = CH CH3
C = CH3 CH CH CH3
Br

Br

D = CH3 C =C CH3
Q12. Primary alkyl halide C4H9Br (A) reacted with alcoholic
KOH to give compound (B) is reacted with HBr to give (C) which
is an isomer of (A). When (A) is reacted with sodium metal it
gives compound (D) C8H18 that was different from the
compound formed when n-butyl bromide is reacted with
sodium . Give the formula of (A) and write equations.
Ans:- CH3 CH CH2Br + alc. KOHCH3 C = CH2
CH3 (A)

CH3

CH3 (B)
173

CH3 - C = CH2 +HBr

CH3 C CH3

CH3 (B)

Br (c)

C is the isomer of A

CH3
CH3 - CH CH2Br +2Na+ CH2Br CH CH3
CH3

CH3 CH CH2 CH2 CH CH3

CH3 CH3
(C8H18)

Q13 . An organic compound 'A having molecular formula C4H8

on treatment with dil.H2SO4 gives 'B .Bon treatment with conc.
HCL and anhydrous ZnCl2gives C and on treatment with
sodiumethoxide gives back A.Identify A,B,C.
Ans:- CH3CH = CH CH3 + H20
(A)

H2SO4

(B)
CH3 CH CH2 CH3

OH
CH3 CH CH2 CH3

HCL CH3 CH CH2 CH3

ZNCl2

Cl (c)
C2H5OH-KOH
CH3 CH = CH CH3 (A)
174

Q14.An aromatic compound A on treatment with aqueous

ammonia and heating forms compound B which on heating with
Br2 and KOH forms a compound C of molecular formula C6H7N
.Identify A,B,C .
Ans:- COOH

CONH2
NH3

NH2
KOH
Br2

(Benzoic acid)

(Benzamide)

(Aniline)

Q15 . Two isomeric compound A and B having molecular formula

C15H11N , both lose N2 on treatment with HNO2 and gives
compound C and D. C is resistant to oxidation but immediately
responds to oxidation to lucas reagent after 5 minutes and gives
a positive Iodoform test. Identify A and B .
Ans:- CH3 CH CH2 CH3 + HNO2
NH2 (B)

CH3 CH CH2 CH3

OH (D) + N2

CH3

CH3

CH3 C CH3 + HNO2

NH2

CH3 C CH3
OH (c) + N2

CH2CH3 C2H5
CH3 C CH3
OH

CONC. HCL

Anhy Zncl2

CH3 C CH3
Cl

(30)

But D respond to lucas reagent in 5 minutes.

175

..

CH3 CH CH2 CH3 +Hcl

CH3 CH CH2 CH3

OH (D)

Cl

CH3 CH(OH) CH2 CH3 + I2 + NaOH CHI3 + CH3 CH2COONa

Q16. An organic compound A having molecular formula

C2H5O2N reacts with HNO2 and gives C2H4O3N2. On reduction A
gives a compound B with molecular formula C2H7N.C on
treatment with HNO2 gives C which givespositiveidoform test .
Identify A,B,C.
Ans:- CH3CH2NO2 + HNO2

CH3 CH NO2

(A)

N-OH
(B)

CH3 CH2NO2 + SN/HCL CH3 CH2NH2

HNO2
CH3CH2OH
(C) I2/NaOH
CHI3 (IODOFORM)

Q17. An organic compound A having molecular formula C3H5N

on reduction gave another compound B. The compound B on
treatment with HNO2 gave propyl alcohol . B on warming with
CHCl3 and alcohalic caustic potash give the offensive smelling C
.Identify A,B,C
Ans:- C2H5CN + 2H2
(A)

HNO2

CH3CH2CH2NH2CH3CH2CH2OH
(B)

CH3CH2CH2NH2 + CHCl3 + 3KOH

(B)

CH3CH2CH2NC

(C)
176

Q18 .Iodomethane reacts with KCN to form a major product A

.CompoundA on reduction in presence of LiAlH4 forms a higher
amine 'B. Compound B on treatment with CuCl2 forms a blue
colur complex C . Identify A,B,C
reduction

Ans .M

CH3I + KCN

CH3 CN

CH3CH2NH2 (B)
CuCl2

[Cu(CH3CH2NH2)4]Cl2
Bluecomplex

Q19. An aliphatic compound A with molecular formula C2H3Cl

on treatment with AgCN gives two isomeric compounds of
unequal amount with the molecular formula C3H3N .The minor of
these two products on complete reduction with H2 in the
presence of Ni gives a compound B with molecular formula
C3H9N.Identify the compounds.
Ans:- CH2 = CH Cl + AgCN

CH2 = CH CN + CH2 =CH N- C

(A) (MINOR)

(MAJOR)

Ni

CH2 =CH C = N CH3 CH2 CH2 NH2

H2

Q20. A compound X having molecular formula C3H7NO

reacts with Br2 in presence of KOH to give another compound Y.
the compound Y reacts with HNO2 to form ethanolN2 gas.
Identify X,Y,
Ans:- CH3CH2CONH2 + Br2 + 4 KOH
(X)

CH3CH2NH2
(Y)
177

HN02
CH3CH2OH + N2 (g)

Q21. A compound A of molecular formula C3H7O2N reaction

with Fe and conc, HCl gives a compound B OF molecular
formula C3H9N. Compound B on treatment with NaNO2 and HCl
gives another compound C of molecular formula C3H8o.The
compound Cgives effervescences with Na on oxidation with
CrO3.The compound C gives a saturated aldehyde containing
three carbon atom deduce A,B,C.

Ans:- CH3CH2CH2NO2 CH3CH2CH2NH2 (B)

NaN02/HCL
CH3CH2CH2OH (C)
Na
CH3CH2CH2ONa
Sodium propoxide
CH3CH2CH2OH

oxidation

CH3CH2CHO

CrO3

(C)
Q22. A Chloro compound A on reduction with Zn Cu and
alcohol gives the hydro carbon (B) with five carbon
atom.WhenA is dissolved in ether and treated with sodium
2,2,5,5 tetramethylhexhane is formed structure of A and B?
Ans. CH3
178

CH3 C CH2 Cl + 2Na (ether )

CH3 (A)

CH3

CH3

CH3 C CH2 - CH2 C CH3

Zn- CU

CH3

CH3

CH3
CH3 C CH3 (B)
CH3

IDENTIFY A,B,C
Q1. CH3COOH

A
NaOBr

NH3

Fe/HCl

Q2. C6H5NO2
Q3. C6H5NO2

Fe/HCl

Q4. CH3CH2Br

KCN

CuCN

H2O/H+

Q6.CH3CH2I

NaNO2

NaNO2/HCl

H2O/H

NaNO2

Q5. C6H5N+2Cl-

HCl

Q8. C6H5N2+Cl-NaNO2/Cu

OH

B
Partial hydrolysis

Q7. C6H5NH2 +(CH3C02)2O

HNO2

B
-

C
C

NH3

NaCN

C6H5OH

LiAlH4

C+

C
Br2+NaOH

A
A

HBF4
NaOH

HNO2

Red P/I2

179

Q9. A
Q10. A
C6H5N2+ClQ11. A

Br2
Dil HNO3

D (CH3I)

Sn/HCl

NaNO2 + HCl

Br2

KOH

HNO2

C2H5NH2
CH3I

Q12. A

AgCN

Sn/HCl

CH3

H + /H2O

LiAlH4

Q13. CH3 CN
Q14. R2CO
Q15.

CH3 CH2- N H

A
NH2

LI/H2

B
B

CH2Br
CN

LiAlH4

Q16. NO2
NaNO2/HCl

B
O0C

CuCl

Q17. NO2
H2SO4/SO3

Fe/HCl

373K

ANSWERS
180

1.A= CH3CONH2

, B = CH3NH2 , C = CH3OH

2.A = C6H5NH2 , B =C6H5N2+Cl- , C =

N =N-

3.A = CH3CH2CN , B =CH3CH2-CH2NH2 , C = CH3CH2CH2OH

4.A= C6H5NH2, B= C6H5N2+Cl-, C= CH3CH2CH2OH
5.A = C6H5CN , B = C6H5COOH , C= C6H5CONH2
6.A= CH3CH2CN, B = CH3CH2CONH2 , C = CH2CH2NH2
7.A ) NHCOCH3
+ CH3COOH
8. C6H5NO2 = A
9. A = CH3CONH2 , B = CH3NH2 , C = CH3OH
10.A) OH

, B) OH , C) OH

NO2NH2

11.A= CH3CH2COONH4 , B= CH3CH2CONH2 , C=

CH3CH2NH2

12.A = CH3Cl , B = CH3NC , C= CH3-CH2-NH-CH3

181

13.A = CH3COOH , B = CH3CH2OH

14.A = R C = NH , B = R CH NH2
R

15) CH2CN

CH2CH2NH2

(A)

(B)

16)A= NO2

Cl

N2+Cl-

16)

17) A =

NO2

B=

NH2

SO3H
SO3H

1 MARK QUESTIONS
Q1 Suggest a reason for the large difference in the boiling points of
butanol and butanal, although they have same solubility in water
182

. A. The b.p. of butanol is higher than that of butanal because butanol has
strong intermolecular H-bonding while butanal has weak dipole-dipole
interaction. However both of them form H-bonds with water and hence are
soluble.
Q 2.What type of aldehydes undergo Cannizaroreaction ?
A.Aromatic and aliphatic aldehydes which do not contain - hydrogens.
Q 3.
Out of acetophenone and benzophenone, which gives
iodoformtest ? Write the reaction involved. (The compound should have
CH3CO-group to show the iodoform test.)
A. Acetophenone (C6H5COCH3) contains the grouping (CH3CO attached to
carbon) and hence given iodoform test while benzophenone does not contain
this group and hence does not give iodoform test.
C6H5COCH3 + 3 I2 + 4 NaOHCHI3 + C6H5COONa + 3 NaI + 3
H2O
AcetophenaneIodoform
I2/NaOH
C6H5COC6H5No reaction
Q4. Give Fehling solution test for identification of aldehyde gp (only
equations). Name thealdehyde which does not give Fehlings soln. test.
A. R CHO 2 Cu2+ + 5 OHRCOO + Cu2O + 3 H2O
Benzaldehyde does not give Fehling soln. test. (Aromatic aldehydes do not
give this test.)
Q5.
What makes acetic acid a stronger acid than phenol ?
A. Greater resonance stabilization of acetate ion over phenoxide ion.
Q.6
Why HCOOH does not give HVZ (Hell VolhardZelinsky) reaction
but CH3COOH does?
A. CH3COOH contains - hydrogens and hence give HVZ reaction but
HCOOH does not contain -hydrogen and hence does not give HVZ reaction
Q7. During preparation of esters from a carboxylic acid and an alcohol
in the presence of an acid catalyst, water or the ester formed should be
removed as soon as it is formed.
A. The formation of esters from a carboxylic acid and an alcohol in the
presence of acidcatalyst in a reversible reaction.

RCOOH

ROH

H2SO4

RCOOR + H2O
183

Carboxylic acid
alcohol
Ester
To shift the equilibrium in the forward direction, the water or ester
formed should be removed as fast as it is formed
Q 8.Arrange the following compounds in increasing order of their acid strength.
Benzoic acid, 4-Nitrobenzoic acid, 3, 4-dinitrobenzoic acid, 4-methoxy benzoic
acid.
A. 4-methoxybenzoic acid < benzoic acid < 4-nitrobenzoic acid <4, dinitrobenzoic
acid.

Q9.

How is tert-butyl alcohol obtained from acetone? A.

2 / 3 MARKS QUESTIONS
1. Arrange the following compounds in increasing order of their boiling
points.
CH3CHO, CH3CH2OH, CH3OCH3, CH3CH2CH3.
A. The molecular masses of all these compounds are comparable :
CH3CHO (44), CH3CH2OH (46), CH3COCH3 (46), CH3CH2CH3 (44).
Thus the overall increasing order of boiling points is :
CH3CH2CH3 < CH3OCH3< CH3CHO < CH3CH2OH
2.
Which acid of each pair shown here would you expect to be
stronger?
CH3CO2H or FCH2CO2H

184

Thus due to lesser electron density in the O H bond and greater stability
of
FCH2COO ion over CH3COO ion FCH2COOH is a stronger acid than
CH3COOH.
3.

Which acid is stronger and why?

F3C C6H4 COO H,
CH3 C6H4 COOH
A.
CF3 has a strong( I) effect.
CH3 has a weak (+ I) effect.
It stabilises the carboxylate ion
Itstabilises the carboxylate ion
by dispersing the ve charge.
by intensifying the ve charge.
Therefore due to greater stability of F3C C6H4 COO (p) ion over
CH3 C6H4COO (p) ion, F3C C6H4 COOH is a much stronger
acid than CH3 C6H4 COOH.

4.

Arrange the following compounds in increasing order of their

reactivity towards HCN. Explain it with proper reasoning.
Acetaldehyde, Acetone, Di-tert-butyl ketone, Methyl tert-butyl ketone.
ANS. Addition of HCN to the carboxyl compounds is a nucleophilic addition
reaction.
The reactivity towards HCN addition decreases as the + I effect of the alkyl
groups increases and/or the steric hindrance to the nucleophilic attack by
CN at the carboxyl carbon increases. Thus the reactivity decreases in the
order.

+ I effect increases
Steric hindrance increases
Reactivity towards HCN addition decreases
In other words, reactivity increases in the reverse order, i. e.
Ditert-butyl Ketone <tert-Butyl methyl Ketone < Acetone < Acetaldehyde
185

5.
Explain why o-hydroxybenzaldehyde is a liquid at room temperature
while p-hydroxybenzaldehyde is a high melting solid.
ANS.
Due to interamolecular H-bonding ortho-hydroxybenzaldehyde exists as
discrete molecule whereas due to intermolecular H-bonding, phydroxybenzaldehyde exists as associated molecules. To break these
intermolecular H-bonds, a large amount of energy is needed.
Consequently, p-hydroxybenzaldehyde has a much higher m.p. and b.p.
than that of o-hydroxybenzaldehyde. As a result, o-hydroxybenzaldehyde
is a liquid at room temperaturewhile p-hydroxybenzaldehyde is a high
melting solid.

5 MARKS QUESTIONS
1.

Arrange the following compounds in order ot their property as

indicatedi) Acetaldehyde,Acetone, di-tert-butyl ketone, Methyl tert-butyl
ketonereactivity towards HCN
- di-tert-butyl ketone < Methyl tert-butyl ketone <Acetone
<Acetaldehyde
-aldehydes are more reactive towards nucleophilic addition across the
>C=O due to steric and electronic reasons.
-Sterically the presence of two relatively large substituents inketones
hinders the approach of nucleophile to carbonyl carbon than in
aldehydes having only one such substituent.
Electronically , the presence of two alkyl groups reduces the
electrophilicity of the carbonyl carbon in ketones.

ii ) CH3CH2CHBrCOOH,CH3CHBrCH2COOH, (CH3) 2CHCOOH,

CH3CH2CH2COOH acid strength
-(CH3)2CHCOOH<CH3CH2CH2COOH<CH3CHBrCH2COOH< CH3CH2CHBrCOOH
-Electron withdrawing groups like Br increases the acidity of carboxylic aids by
stabilizing the conjugate base through delocalisation of negative charge by negative

186

inductive effect. The closer the electron withdrawing group to the COOH group,
greater is the stabilising effect.
-Electron donating groups decrease the acidity by destabilizing the conjugate
base.greater the number of CH3 groups, greater the destabilizing effect and lower
the acidity.
iii)
Benzoic acid, 4-Nitrobenzoic acid, 3,4-Dinitrobenzoic acid, 4Methoxybenzoic acid ( acid strength)
4- Methoxybenzoic acid< Benzoic acid <4-Nitrobenzoic acid < 3,4Dinitrobenzoic acid
- Benzoic acid is a stronger acid than aliphatic carboxylic acid due to
stabilization of the conjugate base due to resonance.
- Presence of electron withdrawing group-NO2 on the phenyl ring of
aromatic carboxylic acid increases their acidity while electron donating
groups-OCH3 decreases their acidity.
***

187

UNIT 13:
AMINES
IUPAC NOMENCLATURE
For practice refer Page No. 383 and Exercise Question Page No. 400 of NCERT Text Book.
NAMEREACTIONS
1.Gabrielphthalimidesynthesis

2.Hoffmannbromamidedegradationreaction

Alkanamide

Alkyl amine

3.Carbylaminereaction (Isocyanide Test for Primary Amine

4.HinsbergTest: (to distinguish 1o,2o and 3o amines)

Benzenesulphonylchloride(C6H5SO2Cl),whichisalsoknownasHinsbergsreagent, reacts with
primary andsecondaryamines toformsulphonamides.
(a)Thereactionof benzenesulphonylchloridewithprimary amine yieldsNethylbenzenesulphonylamide.

188

Thehydrogenattachedtonitrogeninsulphonamideisstronglyacidicduetothepresenceof strong
electronwithdrawing sulphonylgroup.Hence,itis solubleinalkali.
(b)Inthereactionwithsecondaryamine,N,N-diethylbenzenesulphonamideisformed.

SinceN,N-diethylbenzenesulphonamidedoesnotcontainanyhydrogenatomattachedto
nitrogenatom,itisnotacidic andhenceinsoluble inalkali.
(c) Tertiary aminesdonot react with benzenesulphonylchloride.
5.SandmeyerReaction
TheCl,BrandCNnucleophilescaneasilybeintroducedinthebenzeneringofdiazoniumsalts inthepresenceof
Cu(I)ion.

6.GattermanReaction

189

7.Couplingreactions

DISTINCTIONBETWEENPAIRSOFCOMPOUNDS
Giveonechemicaltesttodistinguishbetweenthe followingpairsof compounds.

(i)
Methylamineanddimethylamine
(ii)
Secondaryandtertiaryamines
(iii) Ethylamineandaniline
(iv)
Anilineand benzylamine
(v)
Anilineand N-methylaniline.
ANS.
(i)
Methylamineanddimethylaminecanbedistinguishedbythecarbylaminetest.
Carbylaminetest:Aliphaticandaromaticprimaryaminesonheatingwithchloroform
andethanolicpotassium hydroxideformfoul-smellingisocyanidesorcarbylamines.
Methylamine(beinganaliphaticprimaryamine)givesapositivecarbylaminetest,but
dimethylaminedoesnot.

(ii)Secondaryandtertiaryaminescanbedistinguishedbyallowingthemtoreactwith
Hinsbergsreagent(benzenesulphonylchloride,
C6H5SO2Cl).Secondary
amines
react
withHinsbergsreagenttoformaproductthatisinsoluble inanalkali.Forexample,N, Ndiethylamine
reacts
with
Hinsbergs
reagent
to
form
N,
Ndiethylbenzenesulphonamide, which isinsoluble in an alkali. Tertiary amines, however, donot
react withHinsbergsreagent.
(iii) Ethylamine andaniline canbe distinguished using the azo-dye test. A
dyeis
obtainedwhenaromaticaminesreactwithHNO2
(NaNO2
+dil.HCl)at0-5C,followed
byareactionwiththealkalinesolutionof2-naphthol.The
dye
isusuallyyellow,red,or
orangeincolour.Aliphaticamines
giveabriskeffervescence
due(totheevolutionofN2gas)under
similar conditions.
(iv)Anilineandbenzylaminecanbedistinguishedbytheirreactionswiththehelpof nitrous acid, which
is prepared in situ from a mineral acid and sodium nitrite.
Benzylaminereactswithnitrousacidtoformunstablediazoniumsalt,whichinturn
givesalcohol
withtheevolutionofnitrogengas.
190

Onthe other hand, aniline reactswithHNO2 ata low temperature toformstable diazoniumsalt.
Thus,nitrogengasisnotevolved.
(v) Aniline andN-methylanilinecan be distinguished using the Carbylaminetest.
Primaryamines,onheatingwithchloroformandethanolicpotassiumhydroxide,form
foulsmellingisocyanidesorcarbylamines.Aniline,beinganaromaticprimaryamine,
givespositivecarbylaminetest. However,N-methylaniline,beingasecondaryamine doesnot.
REASONINGQUESTIONS
Q1. Accountforthefollowing:
(i)pKbof anilineis morethanthatofmethylamine.
(ii)Ethylamineis solubleinwaterwhereas anilineis not.
(iii)

Methylamineinwaterreactswithferric chloridetoprecipitatehydratedferric oxide.

(iv) Althoughaminogroupisoandpdirectinginaromatic
electrophilicsubstitutionreactions,anilineonnitrationgives asubstantialamountof mnitroaniline.
(v) Anilinedoes notundergoFriedel-Craftsreaction.
(vi)Diazoniumsaltsof aromatic amines aremorestablethanthoseofaliphatic amines.
(vii)Gabrielphthalimidesynthesis is preferredforsynthesising primary amines.

NS. (i) pKbofanilineismorethanthat ofmethylamine:

Aniline undergoes resonance and as a result, the electrons on the N-atom are delocalized over the
benzene ring. Therefore, theelectrons on the N-atom areless availabletodonate.
Ontheotherhand,incaseofmethylamine(duetothe+Ieffectofmethylgroup),the electron densityon the
N-atom isincreased. As aresult, aniline
islessbasicthan methylamine. Thus,pKb
ofanilineismorethanthat ofmethylamine.
(ii) Ethylamineissolubleinwaterwhereasanilineisnot:
EthylaminewhenaddedtowaterformsintermolecularHbondswithwater.Hence,it
issoluble inwater.
ButanilinedoesnotundergoHbondingwithwatertoaverylargeextentduetothe
presenceofalargehydrophobicC6H5group. Hence, anilineisinsolubleinwater.
(iii) Methylamine inwater reactswithferric chloride toprecipitate hydrated ferric
oxide:
Duetothe+Ieffect
ofCH3 group,methylamine
ismorebasicthan
water.
Therefore,in

+
water,methylamineproducesOH ions byacceptingH ions fromwater.

191

Ferricchloride(FeCl3)dissociatesinwatertoform Fe3+andClions.
Then,OHionreacts withFe3+ionto formaprecipitateofhydratedferricoxide.

(iv) Although amino group is o,p directing in aromatic electrophilic substitution

reactions,anilineonnitrationgivesasubstantialamount ofm-nitroaniline:
Nitrationiscarriedoutinanacidicmedium.Inanacidicmedium,aniline isprotonated to
giveaniliniumion(whichismeta-directing).
Forthis reason,anilineonnitrationgivesasubstantialamount ofm-nitroaniline.
(v)AnilinedoesnotundergoFriedel-Craftsreaction:
AFriedel-CraftsreactioniscarriedoutinthepresenceofAlCl 3.ButAlCl3
nature,whileanilineisastrongbase.Thus,anilinereactswithAlCl 3
toformasalt(as
inthefollowingequation).

isacidicin
shown

DuetothepositivechargeontheN-atom,electrophilicsubstitutioninthebenzenering isdeactivated.
Hence,anilinedoesnotundergotheFriedel-Crafts reaction.
(vi) Diazoniumsaltsofaromaticaminesaremorestablethanthoseofaliphaticamines:
Thediazoniumionundergoesresonanceasshownbelow:

Thisresonanceaccountsforthestabilityofthediazoniumion.Hence,diazoniumsalts
ofaromaticaminesaremorestablethanthoseofaliphaticamines.
(vii) Gabriel phthalimidesynthesisispreferredfor synthesisingprimaryamines:
Gabrielphthalimidesynthesisresultsintheformationof1amineonly.2or3amines arenotformed
inthissynthesis.Thus,apure1aminecanbeobtained.Therefore,
Gabriel phthalimidesynthesisispreferred forsynthesizingprimaryamines.
Q2.Why cannotaromaticprimary amines be preparedbyGabriel phthalimidesynthesis?

ANS.Gabrielphthalimidesynthesisisusedforthepreparationofaliphaticprimary
amines.Itinvolvesnucleophilicsubstitution(SN2)ofalkylhalidesbytheanionformed
bythephthalimide.
Butarylhalidesdonotundergonucleophilicsubstitutionwiththeanionformedbythe
phthalimide.
Hence,aromaticprimaryaminescannot beprepared bythisprocess.
Q3.Giveplausibleexplanationforeachof thefollowing:
(i)
Whyareaminesless acidicthanalcoholsof comparablemolecularmasses?
(ii)
Whydoprimaryamineshavehigherboilingpoint thantertiaryamines?
(iii)Whyarealiphaticaminesstrongerbasesthanaromaticamines?
192

ANS. (i) Aminesundergoprotonationtogiveamideion.

Similarly, alcohol losesaprotontogivealkoxide ion.

Inanamideion,thenegativechargeisontheN-atomwhereasinalkoxideion,the negative chargeis on the

O-atom.
Since
Ois
more
electronegative
than
N,
O
can
accommodatethenegativechargemoreeasilythanN.Asaresult,theamideionisless
stablethanthealkoxideion.Hence,aminesarelessacidicthanalcoholsofcomparable molecularmasses.
(ii)Inamoleculeoftertiaryamine,therearenoHatomswhereasinprimaryamines,
twohydrogenatomsarepresent.DuetothepresenceofHatoms,primaryamines
undergoextensiveintermolecularHbonding.

Asa result, extra energy isrequired toseparate the moleculesof primary amines.
Hence,primaryamineshavehigherboilingpointsthantertiaryamines.
(iii)DuetotheReffectofthebenzenering,theelectronsontheN-atomareless
availableincaseofaromaticamines.Therefore,theelectronsontheN-atominaromatic aminescannotbe
donatedeasily.Thisexplainswhyaliphaticaminesarestrongerbases thanaromaticamines.

193

1MARKQUESTIONSSOLVEDQUESTIONS
Q1.GivetheIUPACnameofthecompoundandclassifyintoprimary,secondaryor tertiaryamines.
1-Methylethanamine(10amine)
Q2.GivetheIUPACnameofthecompoundandclassifyintoprimary,secondaryor tertiaryamines.
Propan-1-amine(10 amine)
Q3.GivetheIUPACnameofthecompoundandclassifyintoprimary,secondaryor tertiaryamines.
NMethyl-2-methylethanamine(20 amine)
Q4.GivetheIUPACnameofthecompoundandclassifyintoprimary,secondaryor tertiaryamines.
2-Methylpropan-2-amine(10amine)
Q5.GivetheIUPACnameofthecompoundandclassifyintoprimary,secondaryor tertiaryamines.
NMethylbenzamineorN-methylaniline(20 amine)
Q6.Writeshortnoteson diazotization
Aromaticprimaryaminesreactwithnitrousacid(preparedinsitufromNaNO 2 anda mineralacid
suchasHCl)atlow temperatures (273-278K) to formdiazoniumsalts. This
conversionofaromaticprimaryaminesintodiazoniumsaltsisknownasdiazotization. For example, on
treatment with NaNO2and HClat 273278 K, aniline produces benzenediazoniumchloride,
withNaCland H2Oasby-products.

Q7.Writeshortnotesonammonolysis
Whenan alkyl or benzyl halide is allowed to react with an ethanolicsolution of
replacedbyan
ammonia,itundergoesnucleophilicsubstitutionreactioninwhichthehalogenatomis
amino(NH2)group.Thisprocessofcleavageofthecarbon-halogen bondisknownasammonolysis.

Whenthissubstitutedammoniumsaltistreatedwithastrongbasesuchassodium hydroxide,
amineisobtained.

194

Thoughprimary
amineisproducedasthe
major
product,
thisprocessproducesa
mixtureofprimary,secondaryandtertiaryamines,andalsoaquaternaryammonium salt

Q8.Writeshortnotesonacetylation.
Acetylation (or ethanoylation)is the process of introducing anacetyl group into a molecule.
Aliphaticandaromaticprimaryandsecondaryaminesundergoacetylation
reactionbynucleophilicsubstitutionwhentreatedwithacidchlorides,anhydridesor
esters.ThisreactioninvolvesthereplacementofthehydrogenatomofNH 2
or>NH
groupbytheacetylgroup,whichinturnleadstotheproductionofamides.Toshiftthe
equilibriumtotherighthandside,theHClformedduringthereactionisremovedas
soonasitisformed.Thisreactioniscarriedoutinthe presenceofabase(suchas pyridine) whichisstronger
thantheamine.
pyridine
C2 H5NH2+CH3COCl--------- C2H5NHCOCH3+HCl
Q9.Whyareamines basic incharacter?
ANS.Likeammonia,thenitrogenatominaminesRNH2 istrivalentandbearsan
pairofelectrons.ThusitactslikeaLewisbaseanddonatesthepairofelectronstoelectronspecieswhichfurtherincreases dueto+Ieffectof alkylradical.

unshared
deficient

Q10. Arrangethefollowingindecreasingorderof theirbasicstrength:

C6H5NH2,C2H5 NH2,(C2H5)2NH,NH3
Thedecreasingorderof basicstrengthoftheaboveaminesandammonia
followsthefollowingorder:
(C2H5)2NH>C2H5 NH2>NH3 >C6H5NH2
SOLVEDEXAMPLES(2Marks)
Q1.Write chemicalequations forthe followingreactions: (i)
Reactionof ethanolicNH3 withC2H5Cl.
(ii)Ammonolysis of benzylchlorideandreactionof aminesoformed withtwo
molesofCH3Cl

195

ANS.

Q2.Write chemicalequations forthe followingconversions: (i)CH3

CH2 ClintoCH3CH2 CH2 NH2

(ii)C6H5CH5Cl intoC6H5 CH2 CH2 NH2

Q3.Writestructures andIUPAC names of

(i)theamidewhichgives propanamine byHoffmannbromamidereaction.

(ii)theamineproducedbytheHoffmanndegradationofbenzamide.
ANS.(i)Propanaminecontainsthreecarbons.Hence,theamidemoleculemustcontain
fourcarbonatoms.StructureandIUPACnameofthestartingamidewithfourcarbon atoms
aregivenbelow:
(Butanamide)
(ii)Benzamideisanaromaticamidecontainingsevencarbonatoms.Hence,theamineformed
frombenzamideis aromatic primary amine containing sixcarbonatoms.

(Anilineorbenzenamine)
Q4.Howwill youconvert4-nitrotolueneto2-bromobenzoicacid?

196

ANS.

Q5.Writethereactionsof(i)aromatic and(ii)aliphatic primary amines withnitrous acid.

ANS.(i)Aromaticaminesreactwithnitrousacid(preparedinsitufromNaNO2
anda
mineralacidsuchasHCl)at273278Ktoformstablearomaticdiazoniumsaltsi.e., NaCland H2O.

(ii)Aliphaticprimaryaminesreactwithnitrousacid(preparedinsitufromNaNO2
amineralacidsuchasHCl)toformunstablealiphaticdiazoniumsalts,whichfurther
producealcoholandHClwiththeevolutionof N2 gas.

and

Q6.How willyouconvert:

197

(i)Ethanoic acidintomethanamine

(ii)Hexanenitrileinto1-aminopentane
ANS.(i)

(ii)

Q7.How willyouconvert:
(i)Methanol toethanoic acid
(ii)Ethanamineintomethanamine

ANS. (i)

(ii)

198

Q8.How willyouconvert
(i)Ethanoic acidintopropanoic acid
(ii)Methanamine intoethanamine

ANS. (i)

(ii)

Q9.How willyouconvert
(i)Nitromethane intodimethylamine
(ii)Propanoic acidintoethanoic acid?

(i)

199

(ii)

Q10. An aromatic compound A on treatment with aqueous ammonia and heating forms
compoundBwhichonheatingwithBr2
andKOHformsacompoundCofmolecularformula
C6H7N.Writethestructures andIUPACnamesofcompounds A, BandC.

ANS.ItisgiventhatcompoundChavingthemolecularformula,C6H7Nisformedby
heatingcompoundBwithBr2
andKOH.ThisisaHoffmannbromamidedegradation
reaction.Therefore,compoundBisanamideandcompoundCisanamine.Theonly
aminehavingthemolecularformula,C6H7N
isaniline,(C6H5NH2).Thegivenreactions
canbeexplainedwiththehelpof thefollowingequations:

3MARKSQUESTIONS
Q1. Arrangethe following:

(i)

Indecreasingorder ofthepKbvalues:
C2H5 NH2,C6H5NHCH3,(C2H5)2 NHandC6H5NH2

200

(ii)Inincreasingorderofbasic strength:
C6H5NH2,C6H5N(CH3)2 ,(C2H5)2 NHandCH3NH2
(iii)Inincreasing orderof basic strength: Aniline, pnitroanilineandp-toluidine

ANS.(i) Theorderofincreasingbasicityof thegivencompoundsisas follows: C6H5NH2

<C6H5NHCH3<C2H5NH2 <(C2H5)2NH
Weknowthatthehigherthebasicstrength, the loweristhepKb values.
C6H5NH2>C6H5NHCH3>C2H5NH2 >(C2H5)2NH
(ii)Theincreasingorderof thebasicstrengthsofthegivencompoundsisasfollows:
C6H5NH2 <C6H5N(CH3)2<CH3NH2<(C2H5)2NH
(iii) Theincreasingorder of thebasicstrengthsofthegivencompoundsis:
p-Nitroaniline<Aniline<p-Toluidine
Q2. Arrangethefollowing
(i) Indecreasingorder ofbasicstrengthingasphase:
C2H5NH2,(C2H5)2NH,(C2H5)3NandNH3
(ii)Inincreasingorderofboilingpoint:
C2H5OH,(CH3)2NH,C2H5NH2
(iii) Inincreasingorder ofsolubilityinwater:
C6H5NH2,(C2H5)2NH,C2H5NH2.
ANS.(i)Thegivencompoundscanbearrangedinthedecreasingorderoftheirbasic
strengthsinthegasphaseas follows:
(C2H5)3N> (C2H5)2NH>C2H5NH2 >NH3
(ii)Thegivencompoundscanbearrangedintheincreasingorderoftheirboilingpoints as follows:
(CH3)2NH<C2H5NH2 <C2H5OH
(iii)ThemoreextensivetheHbonding,thehigheristhesolubility.C 2H5NH2
containstwoH-atoms
whereas
(C2H5)2NHcontainsonlyoneH-atom.Thus,C2H5NH2
undergoes
moreextensiveHbondingthan(C2H5)2NH.Hence,thesolubilityinwaterofC2H5NH2ismorethanthat
of(C2H5)2NH.
Q3.Accomplishthefollowingconversions:
(i) Nitrobenzeneto benzoicacid (ii)
Benzeneto m-bromophenol(iii)
Benzoicacid toaniline
ANS.(i)

201

(ii)

(iii)

Q4.Accomplishthefollowingconversions: (
i)
Anilineto2,4,6-tribromofluorobenzene
ii)
Benzyl chlorideto2-phenylethanamine
iii)
Chlorobenzenetop-chloroaniline
202

ANS. (i)

(ii)

(iii)

203

Q5.Accomplishthefollowingconversions:
(i) Anilinetop-bromoaniline
(ii) Benzamidetotoluene
(iii) Anilinetobenzyl alcohol.
ANS. (i)

(ii)

(iii)

204

5MARKS QUESTIONS
Q1.GivethestructuresofA, B andC inthefollowingreactions:
(i)
(ii)

(iii)

(iv)
(v)
ANS. (i)

(ii)

(iii)

205

(iv)

(v)

Q2.Completethefollowingreactions:
(i)
(ii)
(iii)
(iv)
(v)
ANS. (i)

(ii)

206

(iii)

(iv)

(v)

Assignments
Level1
1. WriteIUPACName ofC6H5N(CH3)3Br?
2. Whichreactionisused forpreparationofpurealiphatic&aralkylprimaryamine ?
3. Name onereagentused fortheseparationofprimary,secondary&tertiaryamine?
4. What aminesalts areusedfordetermingtheirmolecularmasses?
5. Whatisthedirective influence ofaminogroupinarylamines?
6. Whyarebenzene diazoniumsaltssoluble inwater?
7. Whichismorebasic:CH3NH2 & (CH3)3N?
8. Whichismoreacidic,aniline orammonia?
9. WritetheIUPACname ofC6H5NHCH3 ?
10.Mentiontwousesofsulphanilicacid?

Level2
1. Whatforarequaternaryammoniumsaltswidelyused?
2. Whatproductisformedwhenaniline isfirstdiazotizedandthentreatedwith
Phenolinalkaline medium?
3. Howisphenylhydrazineprepared fromaniline?
4. WhatistheIUPACname ofatertiaryaminecontainingone methyl,one ethyl
Andone n-propylgroup?
5. Explainwhysilverchloride issoluble inaqueoussolutionofmethylamine?
6. WritetheIUPACname ofC6H5N(CH3)3Br?
7. Primaryamineshavehigherboilingpointsthentertiaryamineswhy?

8. Whyisitnecessarytomaintainthetemperaturebetween273K&278Kduring diazotization?
9. Arrangethefollowinginorderofdecreasingbasic strength:
Ethylamine,Ammonia,Triethylamine?
10.Whyaniline is acetylatedfirsttoprepare monobromoderivative?

LEVEL 3
1. Arrangethefollowingindecreasingorderoftheirbasicstrength.
C6H5NH2,C2H5NH2, (C2H5)2NH,NH3
2. Writechemicalequationfortheconversion
CH3-CH2-ClintoCH3 CH2-CH3-NH2
3.Writethe equationinvolvedinCarbylamines reactions?
4. Howwillyoudistinguishthefollowingpairs?
(i)MethanamineandN-methylmethaneamine
(ii)Anilineandethylamine
5.Writechemicalsectionsinvolvedin followingnamereactions.
(i) HoffmannBromoamidereaction.
(ii)Diazotisationreaction.

1 MARK QUESTIONS
Q1. Arrange the following in decreasing order of their basic strength:
C6H5NH2, C2H5NH2, (C2H5)2NH, NH3
Q2. Arrange the following in decreasing order of the pKbvalues:
C2H5NH2, C6H5NHCH3, (C2H5)2NH and C6H5NH2
Q3. pKbof aniline is more than that of methylamine. Why?

Q4. Ethylamine is soluble in water whereas aniline is not. Give reason.

Q5. Methylamine in water reacts with ferric chloride to precipitate hydrated ferric oxide. Why?
Q6. Although amino group is o and p directing in aromatic electrophilic substitution reactions, aniline on
nitration gives a substantial amount of
m-nitroaniline. Give reason.
Q7. Aniline does not undergo Friedel-Crafts reaction. Why?
Q8. Diazonium salts of aromatic amines are more stable than those of aliphatic amines. Why?
Q9. Gabriel phthalimide synthesis is preferred for synthesising primary amines. Give reason
Q10. Why cannot aromatic primary amines be prepared by Gabriel phthalimide synthesis?
Q11. Why do primary amines have higher boiling point than tertiary amines?
Q12. Why are aliphatic amines stronger bases than aromatic amines?
Q13. Direct nitration of aniline is not carried out. Give reason.
Q14. The presence of base is needed in the ammonolysis of alkyl halides. Why?

2 MARKS QUESTIONS
Q1. Write structures and IUPAC names of
(i) the amide which gives propanamine by Hoffmann bromamide reaction.
(ii) the amine produced by the Hoffmann degradation of benzamide.
Q2. Give one chemical test to distinguish between the following pairs of compounds.
(i) Methylamine and dimethylamine (ii) Ethylamine and aniline
Q3. Write short notes on the following:
(i) Carbylaminereaction (ii) Diazotisation
Q4. Explain the following with the help of an example.
(i) Hofmanns bromamidereaction (ii) Coupling reaction
Q5. Explain the following with the help of an example.
(i) Ammonolysis (ii) Gabriel phthalimide synthesis
Q6. How can you convert an amide into an amine having one carbon less than the starting compound? Name
the reaction.
Q7. Give a chemical test to distinguish between:
(a) C6H5NH2& CH3NH2
(b) CH3NHCH3& (CH3)3N
Q8. Give the IUPAC names of:
(a) (CH3)2CHNH2

(b) (CH3CH2)2NCH3
Q9. Write the structures of:
(a) 3-Bromobenzenamine
(b) 3-Chlorobutanamide

3 MARKS QUESTIONS
Q1. How will you convert
(i) Benzene into aniline (ii) Benzene into N, N-dimethylaniline
(iii) Aniline to Sulphanilic acid
Q2. An aromatic compound A on treatment with aqueous ammonia and heatingforms compound B which
on heating with Br2 and KOH forms a compound Cof molecular formula C6H7N. Write the structures and
IUPAC names of compounds A, B and C.

Q3. How will you carry out the following conversions (Write Chemical equations and reaction conditions):
(a) Aniline to Phenol
(b)Acetamide to Ethylamine
(c) Aniline to p-nitroaniline

Bio molecule
1.Carbohydrates- These are polyhydroxy aldehydes or ketones or the compounds which produce
these on hydrolysis.
2. Classification(i) Monosaccharides Those carbohydrates which cannot be hydrolysed into further simpler
carbohydrates. e.g. glucose ,fructose, galactose etc.
(ii)Disaccharides: Those carbohydrates which produces two monosaccharides on hydrolysis. Eg;
Sucrose, maltose and lactose
(iii) Oligosaccharides- Those carbohydrates which give two to ten monosaccharides on hydrolysis .
(iv) Polysaccharides- Those carbohydrates which on hydrolysis give large number of
monosaccharides hydrolysis.eg starch, cellulose, glycogen.
3. Sugar- Carbohydrates which are sweet in taste
(i)Reducing Sugars- Those which reduce Fehlings or Tollens reagent due to availability of free
aldehydic groups, eg , glucose, fructose , galactose
(ii)Non Reducing Sugars- Those which do not reduce Fehlings or Tollens reagent. They do not have
free aldehydic group ,e.g., sucrose
4. Glucose- It is a monosaccharides with molecular formula C6H12O6
5. Preparation
(i)From Sucrose
C12H22O11 + H2O -------> C6H12O6 + C6H12O6 ( Only from sucrose)
(ii)From Starch
(C6H10O5)n + nH2O -------> C12H22011 + H20 ------> 2C6H12O6
6.Structure
(i)Fischer structure
(+) Glucose has `D configuration as shown

CHO
H
HO

OH
H

OH

OH
CH2OH

`D means OH group on first chiral `C from the bottom is on right hand and + means it is dextro
rotator, i.e, it rotates plane polarized light towards right.
Objections against Open chain structure of Glucose
The open chain structure was unable to explain the following reactions.
(a) It does not give the 2, 4-DNP test, Schiffs Test and does not form the hydrogensulphide product with
NaHSO3 .
(b) The pentacetate of glucose does not react with NH2OH, indicating the absence of free aldehydic group.
(iii) Glucose exist in 2 different crystalline forms and forms. These are called anomers. They differ in
optical rotation, they also differ in melting point.
After which a close chain(cyclic) structure of glucose was proposed by Haworth.
* Anomers are isomers which have a different configuration at C-1
7. Glycosidic Linkage: The linkage between two monosaccharide units through oxygen is called the
glycosidic linkage.
8. Proteins: These are macro molecules made up of amino acids joined by amide linkage ( -(-CONH-)- is here
called as peptide linkage). These are required for growth and development of the body.
9. Amino Acids: These contain an amino (-NH2) and an acidic (-COOH) group and are therefore amphoteric in
nature. In solution they exist in the form of zwitter ion(a dipolar ion).
10. Classification
Fibrous Protein
(i) Polypeptide chains run parallel or anti-parallel
and held together by hydrogen and disulphide
bonds.
(ii) Generally insoluble in water. e.g. Keratin,
collagen,myosin,fibroin.

Globular Protein
(i) Chains of Polypeptide coil around to give a
spherical shape.

(ii) Usually soluble in water. e.g., insulin,

thyroglobin,albumin, haemoglobin and fibrinogen
gets converted into fibrous protein fibroin on
clotting of blood.
11. Structure And Shape of Protein(Ref. page No-416 NCERT book)
Primary Structure

Secondary Structure

Tertiary Structure

Quaternary Structure

The specific sequence of

amino acids in the
polypeptide chain.
Change in amino acids
sequence changes the
protein completly. They
have covalent bonds.

It is the shape in which the

long polypeptide chain can
exist. It is of two types : helix and - pleated. These
structures arise due to
regular folding of the
backbone of the polypeptide
chain due to H-bonding
between the C=o and NHgroups of the peptide bond.

Represents overall
folding of the
polypeptide chain. It
gives rise to the fibrous
or globular molecular
shapes. Forces stabilizing
the 2o and 3o structures
are hydrogen bonds,
disulphide linkages, van
der waals and
electrostatic forces of
attraction.

Protein can be composed

of two or more
polypeptide chains called
sub units. The spatial
arrangement of these
sub units with respect to
each other is quaternary
structure of the protein.

12.Native State of Protein: The parental state or the natural state in which the protein is found.
13. Denaturaion of Protein: Destruction of the native state of protein is denaturation. It can be brought by
physical and chemical methods. The 2o and 3o structures are destroyed, only 1o structure is retained.
Enzymes: These are biocatalyst and generally globular proteins e.g., invertase,zymase,phenyl,
alaninehydroxylase, urease etc.
Main Characteristics of Enzyme:
1.It speed up the biological reaction upto million times.
2.It is highly specific and work on lock and key theory.
3.It is highly sensitive to pH and temperature.
14. Vitamins: They are organic compounds required in the diet in small amounts to perform specific
biological functions for maintenance of optimum growth and health of the organism. They are classified as
follows
(i) Fat Soluble Vitamins: Vitamin A,D,E and K. They are stored in liver and adipose tissues.
(ii) Water Soluble Vitamins: B group vitamins and vitamin C. They need to supplied regularly in diet as they
are excreted in urine and cannot be stored(except vitamin B12) in our body.
Their deficiency causes diseases.(Ref table in page no-418of NCERT book)
Biotin (Vit H) is however neither fat nor water soluble. Its deficiency leads to loss of hair.
15. Nucleic Acids: These are biomolecules which are long chain polymers of nucleotides. They are of two
types:
(i) Deoxyribonucleic acid (DNA)
(ii) Ribonucleic acid (RNA)

They are responsible for protein synthesis and transfer of genetic characteristics to offsprings.
16. Composition of Nucleic Acid:
They are made up of pentose sugar(-D-2-deoxyribose in DNA and -D-ribose in RNA), phosphoric acid and a
nitrogen containing heterocyclic compound(base).
DNA- Bases present are Adenine(A), Thymine(T),Guanine(G) and Cytosine(C).
RNA- contains Adenine(A), Guanine(G), Cytosine(C) and Uracil(U).
19.DNA : has a double helical structure with AT and GC linked together through 2 and 3 hydrogen bonds
respectively. It is responsible for transfer of genetic characteristics.
20. RNA: is of three types- messenger RNA(m-RNA), ribosomal RNA(r-RNA) and transfer RNA (t-RNA). RNA
helps in protein synthesis.
21. Biological Functions of Nuclei Acid: DNA is chemical basis of hereditary and have the coded message for
proteins to be synthesized in the cell. RNA carry out the protein synthesis in the cell.
22.DNA fingerprinting: A sequence of bases on DNA is unique for a person and can not be altered by any
known treatment. It is therefore very much useful in identification of criminals, paternity of individuals.

Questions (1 Mark)
Q1 Which functional groups are present in monosaccharides?
Ans - OH and CHO or OH and >CO
Q2 Name an aldopentose, aldohexose and ketohexose.
Ans Ribose, glucose and fructose respectively.
Q3 What is animal starch?
Ans Glycogen.
Q4 Which types of bonds are present in a protein molecule?
Ans Peptide bonds, hydrogen bonds, sulphide bonds, ionic bonds etc.
Q5 Which one of -helix and -helix is more stable and why?
Ans -helix is right handed and is more stable due to intermolecular H bonding
between first and fourth amino acid.

Q6 The sequence of bases in one strand of DNA is TACGGACA. What is the sequence of
bases of complementary strand of DNA.
Ans ATGCCTGT.
Q7 Name the vitamin whose deficiency causes rickets?
Ans Vitamin D.
Q8 Classify the bases present in DNA.
Ans Purine derivatives:Adenine and guanine.
Pyrimidine derivatives: Cytocine and Thymine
Q9 Give an example of
(a)water soluble (b)fat soluble is
Ans (a)Vitamin C (b)Vitamin D.
Q10. Differentiate Nucleotides and nucleoside.
Nucleotides: Pentose sugar + N- containing base+ Phosphate
Nucleosides: Pentose sugar + N- containing base only

Q11 Name a protein which is insoluble in water.

Ans Veratin.

SAI Type Questions

Q1 Name the constituents of starch and what is the difference between them.
Ans Amylose: A linear polymer of -glucose, water soluble
Amylopectin: Branched polymer of -glucose. water insoluble.
Q2 Differentiate DNA and RNA
DNA

RNA

1.Bases:A, T, C, G

1.Bases A, U, C, G

2.Double helix

2.Single helix

3.Replication

3.Protein Synthesis

4. 2-deoxyRibose

4.Ribose Sugar

Q2 What are anomers?

Ans Monosaccharides which differs in configuration at C-1,.e.g, -glucose and glucose.
Q3 Where does the water present in the egg go after boiling the egg?
Ans On boiling during denaturation process water gets adsorbed/absorbed in the
denatured proteins.
Q4 Write two main functions of carbohydrates in plants.
Ans (i)structural material (ii)reserved food material.
Q5 What do you understand by glycosidic linkage?
Ans During condensation of two monosaccharides, a water molecule given out and two
monosaccharides get linked together by an oxide or ethereal linkage (O) called as
glycosidic linkage.
Q6 What are essential and non essential amino acid? Give two examples of each type.
Ans Essential amino acids are those which are not produced in our body and required
to be supplied from outside e.g.,valine, leucine.
Non-essential amino acids are those which are produced by our body. e.g.glycine and
alanine.
Q7 How do you explain the amphoteric behavior of amino acids?
Ans Amino acids have both carboxylic acid as well as basic amino group, therefore they
are amphoteric in nature.
Q9 Define (a)Enzymes (b)Antibody

Ans (a)Enzymes they are biological catalyst which catalyse biochemical reactions.e.g.,
C12H22011 + H20

----------> C6H1206 + C6H1206

sucrose

glucose

fructose

This reaction is catalysed by the enzyme invertases.

(b)Antibody they are chemical substances which destroy antigens that cause infections.
e.g., vaccination for typhoid produces antibodies in our body to prevent typhoid.

SA II Type Questions
Q3 Give reactions with support cyclic structure of glucose.
Ans (a)Glucose does not give 2,4-DNP test, Schiff`s test and sodium hydrogen suphide
test.
(b)The pentaacetate of glucose does not react with NH2OH indicating absence of free
CHO group.
(c)Glucose exists in two crystalline form and .
Q4 Define with example
(a)Isoelectric point (b)Mutarotation (c)Transcription
Ans (a)Isoelectric point the pH at which there is no net migration of any ion towards
electrode. e.g,amino acids have isoelectric point at pH = 5.5-6.3
(b)Mutarotation - it is spontaneous change in optical rotation when an optically active
substance is dissolved in water.e.g, -glucose when dissolved in water changes its optical
rotation from 111o to 52.5 o.
(c)Transcription it is process by which mRNA is generated from DNA.e.g,if DNA has
base sequence ATACA then mRNA has base sequence TATCGT.

Q5 What happens when glucose reacts with

(a)HI
Ans

(b) HNO3

(c)Br2 water

(a)
(b)
(c)

C6H1206 + HI ------> n-hexane C6H14

C6H1206 + HNO3 -------> saccharic acid
C6H1206 +Br2 water --------> gluconic acid

Q6 Differentiate primary , secondary and tertiary structure of protein.

Ans -In primary structure specific sequence of amino acid are present joined by
covalent bonds.
-secondary structure is responsible for the shape of a protein. -helix and -pleated in
which polypeptide chains have peptide bonds.
-tertiary structure represents overall folding of polypeptide chain and give rise to the
fibrous or globular molecular shape.
Q7. Discuss the specificity and mechanism of enzyme action.
Ans. In case of enzymatic reaction the enzyme is so built that it binds to the substrate in a
specific manner. Enzymatic reaction involves following steps (Lock and Key Model)Step (i): Binding of substrate(S) to enzyme (E) to form complex
E + S [ES] (Enzyme substrate complex)
Step (ii): Product formation in complex
[ES] EP (Enzyme product complex)
Step (iii): Dissociation of enzyme product complex, leaving enzyme unchanged
EP E + P
The specificity of enzyme is due to presence of some specific regions called active site on
their surface.
Q10. Glucose or Sucrose are soluble in water but cyclohexane and benzene are insoluble in
water. Explain.
Ans. Glucose contains five-OH groups and Sucrose contains eight-OH groups, because of this
they form intermolecular hydrogen bonding, so they are soluble in water. But benzene and
cyclohexane does not contain OH groups, hence does not form intermolecular hydrogen
bonding, so they are not soluble in water.

HOTS Questions

VSA (1 Mark)

Q1. How many atoms are present in the ring of pyranose structure of glucose?
Ans. 5 Carbon atoms and one Oxygen atom.

Q2. Write the formula of Zwitter ion for Glycine.

Ans.
R-CH-COO-

CH2-COO-

NH3+

NH3+

General Formula

Zwitter ion of glycine

Q3. Which proteins possess -Helix structure?

Ans. Keratin and myosin possess -Helix structure.

Q4. What is the native state of protein?

Ans. The energetically most stable shape of the protein at normal pH and temperature is
called native state.

Q5. Fresh tomatoes are a better source of Vitamin C that which have been stored for some
time. Explain.
Ans. Vitamin C is destroyed on prolonged exposure to air due to its oxidation.
Q6. Why are carbohydrates generally active?

Ans. It is due to the presence of Chiral Carbon atoms in their molecules.

Q7. What type of linkages hold together monomers in DNA?

Ans. Monomers in DNA are linked by phosphate linkages.
Q8. Why is cellulose not digested in human body?
Ans. It is due to the fact that human beings do not have enzymeto digest cellulose.
Q9. Name the enzyme that is used to dissolve blood clots?
Ans. Streptokinase.
Q10. Name two diseases caused due to deficiency of enzymes.
Ans. Albinism and phenyl keto urea.

SA Type I (2 Marks)

Q1. Give reasons for the following(i) On electrolysis in acidic solution amino acids migrate towards cathode, while in alkaline
solution these migrate towards anode.
(ii) The monoamino monocarboxylic acids have two pKa values.
Ans. (i) In acidic solution, the carboxylate anion accept a proton and gets converted into
carboxylic group resulting in the formation of positive ion.

H3N+ CHCOO- +

|
R
(Zwitter ion)

H3N-CHCOOH
|

(acid)

R
(Positive ion)

In presence of a base the N+H3 ion changes to NH2 group by losing a proton and this gives a
negative ion.

H3N+CHCOO-

OH

base

R
(Zwitter ion)

H2NCHCOO|

+H2O

R
(Negative ion)

This means that in acidic medium, the amino acid migrates towards the cathode while in
alkaline solution it migrates towards anode on electrolysis.
(ii) In aqueous solution, monoamino monocarboxylic amino acid behave like salt at isoelectric
point. At a pH lower than isoelectric point (i.e. in acidic medium) it shows one pKa value
which corresponds to structure

O
||
RCHCO|
+

NH3

and at a pH higher than isoelectric point, it shows a pKa value which corresponds to another,

O
||
-

RCHCO
|
NH2

Q2. Which forces are responsible for the stability of -helix? Why is it named as 3.613 helix?
Ans. Hydorgen bonds between N-H and C=O groups of peptide bonds give stability to the
structure.
It is known as 3.613 helix, since each turn of helix has approximately 3.6 amino acid residue
and a 13 member ring is formed by hydrogen bonding.

SA(II)
3 Marks
Q6. Draw simple Fishcher projections of D and L- glucose. Are these enantiomers?

CHO

CHO

OH

HO

HO

OH

OH

OH

HO

HO

CH2OH
D-Glucose

H
CH2OH
L-Glucose

Yes these two fischer projections are called enatiomers.

Value based Question

1.Vitamines are required in small amounts in our diet but their deficiency causes many diseases. Most of the
vitamins can not be synthesised in our body, so these are essential for our good health.
A. Name a vitamin whose deficiency causes pernicious anemia. Which metal atom is present in it?
B . Deficiency of which vitamins cause rickets (bone deformation) in children and is needed for adsorption of
calcium by body? Give its chemical name.

POLYMERS

1. Polymer:
It is a very large molecule having molecular mass 103 - 107 g mol-1. They are formed by

joining together repeating structural units.

2. Classification of Polymers:

(a) Based On Source:

(i) Natural:

Found in plants and animals, e.g. Proteins, cellulose, natural rubber, silk,

wool.

(ii) Synthetic:

Man-made e.g. Nylon, polyster, neoprene, Bakelite, Teflon, PVC,

polystyrene.

(b) Based On Structure:

(i) Linear Polymers:

this consist of long and straight chain repeating units e.g.

Polythene (HDPE), PVC, nylon, polyester.

(ii) Branched Polymers:

This contain linear chains having some branches e.g.

amylopectin, glycogen etc.

(iii) Cross Linked Polymers:

Strong covalent bonds are present between various

linear polymer chains. E.g. Bakelite, urea- formaldehyde polymer, melamine, formaldehyde

polymer etc.

(c) Based On Mode Of Polymerization:

(i) Addition Polymers:

These are formed by the repeated addition of monomer

molecules possessing multiple bonds, e.g., polythene, polypropene, polystyrene, PMMA

(polymethyl metha crylate)

These are formed by the repeated condensation

(ii) Condensation Polymers:

reaction of different bifunctional or trifunctional monomers, with the elimination of small

molecules like water,HCL,NH3, alcohol etc. e.g. Bakelite,nylon,polyster,urea- formaldehyde

resin.

(d) Based On Molecular Forces:

(i) Elastomers:

Forces of interaction between polymer chains is weakest, e.g. natural

rubber, neoprene, vulcanized rubber.

(ii) Fibers:

Strong hydrogen bonds are present between the polymer chains. They have

high tensile strength e.g., nylon.polyster, silk, wool, orlon, rayon etc.

(iii) Thermoplastics:

They are linear/slightly branched chains molecules capable of

repeated softening on heating and hardening on cooling,e.g., polythene,PVC, polystrene,

polypropene.

(iv) Thermosetting Plastics:

They are cross-linked or heavy branched molecules,

which on heating undergo extensive cross-linkages and become infusible, e.g., bakelite,urea

formaldehyde resin.

(e) Based On Growth Of Polymerization:

Depending upon the mechanism of

Polymerization, polymers are classified as

(i) Addition Polymers Or Chain Growth Polymers:

They follow mostly free radical mechanism.

(ii) Condensation Polymers or Step Growth Polymers

because they are

formed in gradual steps.

Polymer

(i) Polyethene

Monomer
Ethene

(ii) Polytetra
Tetrafluoroethene
Fluroethene(Teflon)
(iii) Polyarcylonitrile Acrylonitrile
(iv) Terylene or
Glycol + Terephthalic
Decron
Acid

(v) Nylon-6,6

Hexamethylenediamine +
Adipic acid

(vi) Nylon-6
(vii) Novolac

Caprolactum
Phenol + Formaldehyde

(viii) Phenol
Formaldehyde resin
(ix) Melamine
polymers
(x) Buna-S
Copolymer
(xi) Natural rubber
(xii) Neoprene
(xiii) Buma-N

Formaldehyde + Phenol
Melamine + Formaldehyde

Uses
Insulation of wires, toys,
manufacture of dustbins etc.
Oil seal and Gasket and non
Stick kitchen wares
Substitute for wool
Ropes, safety belts,
tyre -cord , sails of boats,
saree and dress material
Stocking, socks, ropes,
Parachutes, fabrics,
bristles of tooth brush
Tyre-cords, Ropes, fabrics
Used for binding glue, laminated
wooden planks
Combs, switches boards etc

Manufacture of unbreakable
crockery
1,3-Butadiene + Styrene
Auto tyres, floor, foot-wear
components
2-methyl-1,3-butadiene
Used for tyres
2-chloro-1,3-butadiene
Conveyor belts, gasket , hoses
1,3-butadiene + acrylonitrile Resistance to action of petrol.
Make oil seals, tank linings etc.
(xiv) (PHBV) poly- 3-hydroxybutanoic acid +
Packaging orthopedic devices
hydroxybutyrateco- 3-hydroxypantanoic acid
- hydroxyl valerate
(biodegradable)
(xv) Nylon-2-nylon-6 Glycine + aminocaproic acid It is biodegradable step growth

Polymer
Note : For formation of polymer from monomer see pages 425 to 435 of NCERT book

VSA

(1 marks)

1.Name a natural elastomer.

Ans . Natural rubber.
2. Name of monomer of Nylon 6.
Ans. Caprolactam
3. Write the monomer units of Bakelite.
Ans. Phenol and formaldehyde.
4. Define a copolymer.
Ans. The polymers made by addition polymerisation from two different
monomers are termed as copolymers, e.g., Buna-S, Buna-N, etc.
5. Write one use of PVC.
Ans: In manufacture of rain coats & vinyl flooring.
6. Define Polymer.
Ans: Polymer is defined as very large molecules having
molecular mass (103-107u). These are also referred
to as macromolecules,
7. Give an example of thermoplastics.
Ans: Thermoplastics are polythene, polystyrene, polyvinyl chloride etc.
8. Name the monomers of terylene?
Ans: Ethylene glycol and teryphthalic acid.
SA-1

(2 marks)

1. Arrange the following polymers in increasing order of their intermolecular

forces.
(i) Nylon 6,6, Buna-S, Polythene.
(ii) Nylon 6, Neoprene, Polyvinyl chloride.
Ans. (i) Buna-S< Polythene<Nylon 6,6

(ii)Neoprene < Polyvinyl chloride< Nylon 6.

2. Classify the following as addition and condensation polymers: Terylene,
Bakelite,
Polyvinyl chloride, Polythene.
Ans. (i) addition polymers :Polyvinyl chloride, Polythene.
(ii) condensation polymers: Terylene , Bakelite.
3. What is a biodegradable polymer ? Give an example of a biodegradable
aliphatic polyester.
Ans. Polymers which disintegrate by themselves over a period of time due to
environmental degradation by bacteria,etc.are called biodegradable
polymers. e.g. PHBV
4.What is meant by PTFE ?Give its popular name.
Ans.Polytetrafluoroethylene.it is called Teflon.
5.Write chemical name of (Ziegler-Natta catalyst).
Ans: Triethylaluminium and titanium tetrachloride
6.Write down the two differences between thermoplastic and thermosetting
plastic and examples.
Ans: Thermoplastic are the linear or slightly branched long chain molecules
capable of repeatedly softening on heating and hardening on cooling.
These polymers possess intermolecular forces of attraction
intermediate between elastomers and fibres. Some common
thermoplastics are polythene, polystyrene, polyvinyls, etc.
Thermosetting plastic polymers are cross linked or heavily branched
molecules,
which on heating undergo extensive cross linking in moulds and
again become infusible. These cannot be reused. Some common
examples are bakelite, urea-formaldelyde resins, etc.

7. Distinguish between the terms homopolymer and copolymer and give an

example of each.
Ans: the addition polymers formed by the polymerisation of a
single monomeric species are known as homopolymers, e.g.,
polythene.
The polymers made by addition polymerisation from two different
monomers are termed as copolymers, e.g., Buna-S, Buna-N, etc.
8. How will you differentiate between LDP and HDP?
Ans: Low density polythene: It is obtained by the polymerisation
of ethene under high pressure of 1000 to 2000 atmospheres
at a temperature of 350 K to 570 K in the presence of traces
of dioxygen or a peroxide initiator (catalyst).
Low density polythene is chemically inert and tough but flexible
and a poor conductor of electricity.e.g., squeeze bottles, toys and flexible
pipes.
High density polythene: It is formed when addition
polymerisation of ethene takes place in a hydrocarbon solvent
in the presence of a catalyst Ziegler-Natta catalyst at a temperature
of 333 K to 343 K and under a pressure of 6-7 atmospheres.
HDP consists of linear molecules and has a high density due to close packing.
It is
more tougher and harder. It is used for manufacturing buckets, dustbins,
bottles, pipes, etc.
SA-II (3 marks)
1. Write the names of monomers of the following polymers:
(i) Nylon 6,6 (ii) Neoprene(iii) Buna N
Ans. (i) hexamethylenediamine and adipic acid.
(ii)

chloroprene.

(iii) 1, 3 butadiene and acrylonitrile.

2. Write the monomers of the following polymers:

(i) Buna-N (ii) Teflon(iii) Neoprene.
Ans.(i) 1, 3 butadiene and acrylonitrile (ii) tetrafluoroethene (iii)
chloroprene.
3. What is the function of sulphur in vulcanisation of rubber?
Ans: Sulphur introduces sulphur bridges.So it is become more tensile
strength,elasticity and resistance to abrasion etc.
4. Write Commercially Importants of following Polymers
(1) Polypropene (2) Polystyrene (3) Glyptal
Ans: (1) Manufacture of ropes, toys, pipes, fibres, etc.
(2)As insulator, wrapping material, manufacture of toys, radio and television
cabinets.
(3) Manufacture of paints and lacquers.
HOTS QUESTIONS
VSA (1mark)
1.What is the main constituent of bubble gum?
Ans - Styrene - butadiene copolymer (SBR).
2.What is a plasticizer?
Ans; The substances which are added to increase the softness of hard
polymers.
3.Give the name of polymer which is used for making non- stick utensils.
Ans: Teflon(CF2=CF2)
4.What is the % of sulphur using during in vulcanization of rubber ?
Ans: 3% to 5%
SA-I(2 marks)
1.Discuss the two main purpose of vulcanization of rubber.
Ans: (i)It makes the rubber hard.

(ii)It is more elastic.

(iii)It has more wear and tear resistance.
2.Explain the term Thermosetting polymers and give one example.
Ans: Thermosetting polymers:These polymers are cross linked or heavily
branched molecules,
which on heating undergo extensive cross linking in moulds and
again become infusible. These cannot be reused. Some common
examples are bakelite, urea-formaldelyde resins, etc.
3. Why should one always use purest monomer in free radical
polymerisation?
Ans: Impurities of other substances if present,may inhibit or hinder the
chain propagation.
4.How is dacron obtained from ethylene glycol and terephthalic acid?
Ans: It is the condensation product of ethylene glycol and terephthalic acid
Carried out at 420 to 460K in the presence of catalyst mixture of zinc
acetate and antimony trioxide.
SA-II(3 marks)
1.What does the following polymers stand for ?
(i)PVC (ii) PAN
Ans: (i) Polyvinylchloride
(ii) Polyacrylonitrile
2. Why is Bakelite a thermosetting polymer?
Ans: It is a cross-linked polymer. On heating it sets permanently into a solid.It
can not be remoulded by heating again.
3.(i) Give an example of a synthetic rubber.
(ii) Mention main advantage of synthetic rubber.
(iii)Arrange the polymers in the increasing order of tensile strength,
Nylon-6, Buna-S,Polythene.
Ans: (i) synthetic rubber is Buna-S
(ii) It is used for making oil seals, tank linings.
(iii) Buna-S<Polythene< Nylon-6

Value Based Question:

Synthetic polymers find their application in almost all spheres of life because of their
resistance to wear and tear, chemicals and temperature. But there is one major problem
associated with them is their resistance to biodegradability over a period of time. It has
created a serious problem of waste management . If over use of plastic continues , soon
the entire civilization might got buried under it.
(a)Is it advisable to continue with the overuse of plastic due to their immense usefulness
in daily life? Explain
(b)Enlist some values from above passage.
Ans(a)Though it is impossible to discontinue with the synthetic polymer, but their
overuse can be minimized. We should opt for those polymers which are biodegradable. If
we do not control this things at the right time the life become miserable for us. To
minimize the use of plastic is meant for the betterment of mankind and nature.
(b)Concern the mankind awareness towards hazards of overuse of plastic. Health,
consciousness and good citizenship are some of the values evident from the above
passage.

Unit-16

CHEMISTRY IN EVERYDAY LIFE

POINTS TO BE REMEMBERED

1. DRUGS Drugs are chemical of low molecular masses, which interact with macromolecular targets and
produce a biological response.
2. CHEMOTHERAPY- The use of chemicals for therapeutic effect is called chemotherapy.
3. CLASSIFICATION OF DRUGS
(a)
ON THE BASIS OF PHARMACOLOGICAL EFFECT-drugs for a particular type of problem as analgesics-----for
pain relieving.
(b)
ON THE BASIS OF DRUG ACTION-Action of drug on a particular biochemical process.
(c)
ON THE BASIS OF CHEMICAL ACTION-Drugs having similar structure .eg-sulpha drugs.
(d)
ON THE BASIS OF MOLECULAR TARGETS- Drugs interacting with biomolecules as lipids, proteins.
4. ENZYMES AS DRUG TARGETS
(i)
CATALYTIC ACTION OF EN ZYMES(a)
Enzymes have active sites which hold the substrate molecule .it can be attracted by reacting molecules.
(b)
Substrate is bonded to active sites through hydrogen bonds, ionic bonds, Vander Waal or dipole dipole
interactions.
(ii)
DRUG- ENZYME INTERACTIONS(a)Drug complete with natural substrate for their attachments on the active sites of enzymes .They are called
competitive inhibitors.
(b)Some drugs binds to a different site of the enzyme called allosteric sites which changes the shape of active
sites.
5. ANTAGONISTS- The drugs that bind to the receptor site and inhibit its natural function.
6. AGONISTS-Drugs mimic the natural messenger by switching on the receptor.
7. ANTACIDS-These are compounds which neutralize excess acid of stomach.eg-Aluminium hydroxide,
Magnesium hydroxide.
8. ANTI HISTAMINES-The drugs which interfare with the natural action of histamines and prevent the allergic
reaction. eg- rantidine,tegarnet, avil.
9. TRANQULIZERS-The class of chemical compounds used for the treatment of stress,mild or even severe
mental diseases. Eg-idardil, iproniagid, luminal, second equaqnil .
10. ANALGESICS-They reduce pain without causing impairment of consciousness, mental confusion or some
other disturbance of the nervous system.
Eg - aspirin, seridon , phenacetin.
11. ANTIMICROBIALS-They tend to prevent/destroy or inhibit the pathogenic action of microbes as bacteria
,virus ,fungi etc .They are classified as
(i)ANTIBIOTICS-Those are the chemicals substances which are produced by micro-organisms.
Eg- Pencillin , ofloxacin .

NARROW SPECTRUM ANTI-BIOTICS-These are effective mainly against gram positive or gram negative bacteria.
Eg- Penicillin , streptomycin.
BROAD SPECTRUM ANTI-BIOTICS-They kill or inhibit a wide range of micro-organisms.
eg- chloramphenicol , tetracydine .
(ii)ANTISEPTICS OR DISINFECTANT-These are which either kill/inhibit the growth of micro-organisms
Antiseptics are applied to the living tissuses such as wounds, cuts, ulcers etc. eg-furacine,chloroxylenol &
terpinol(dettol) .Disinfectant are applied to inanimate objects such as floors , drainage , system.
Eg- 0.2% solution of phenol is an antiseptic while 1% solution is an disinfectant.

12. ANTIFERTILITY DRUGS- These is the chemical substances used to control the pregnancy. They are also called
oral contraceptives or birth control pills.
Eg-Mifepristone, norethindrone.
13. ARTIFICIAL SWEETNING AGENTS-These are the chemical compounds which give sweetening effect to the
food without adding calorie.
They are good for diabatic people eg- aspartame, saccharin, alitame , sucrolose.
14. FOOD PRESERVATIVES- They prevents spoilage of food to microbial growth.eg-salt, sugar, and sodium
benzoate.
15. CLEANSING AGENTS(i) SOAPS- They is sodium or potassium salts of long chain fatty acids.They are obtained by the soapnification
reaction, when fatty acids are heated with aqueous sodium hydroxide.
They do not work well in hard water.
(iii) TOILETS SOAP-That are prepared by using better grade of fatty acids and excess of alkali needs to be
removed .colour & perfumes are added to make them attractive.
(iv) MEDICATED SOAPS- Substances of medicinal value are added.eg- Buthional , dettol.
16. SYNTHETIC DETERGENTS-They are cleaning agents having properties of soaps, but actually contain no soap
.They can used in both soft and hard water .They are(i)ANIONIC DETERGENTS-They are sodium salts of sulphonated long chain alcohols or hydrocarbons.egsodium lauryl sulphonate . They are effective in acidic solution.
CH3 (CH2) CH2OH CH3 (CH2)10CH2OSO3H
(laurylalchol)
CH3 (CH2)10CH2SO3-Na+
(Sodium lauryl sulphonate)
(ii)CATIONIC DETERGENTS- They are quarternary ammonium salts of amines with acetates , chlorides, or
bromides.They are expensive used tolimited extent.eg- cytyltrimethylammoniumbromide

(iii)NON-IONIC DETERGENTS- They does not contain any ions. Some liquid dishwashing detergents which are
of non-ionic type .
17. BIODEGREDABLE DETERGENTS- The detergents which are linear and can be attacked by micro-organisms are
biodegradable.
Eg -sodium 4-(1-dodecyl) benzene \ sulphonate.
18. NON-BIODEGREDABLE DETERGENTS- The detergents which are branched and cannot be decomposed by microorganisms are called non-biodegdradable.eg-sodium 4-(1,3,5,7 tetramethyloctl)-benzene sulphonate .It creates
water pollution.

VERY SHORT ANSWER TYPE QUESTION

(1 marks)

Q-1 Define the term chemotherapy?

Ans.- Treatment of diseases using chemicals is called chemotherapy.
Q-2 why do we require artificial sweetening agents?
Ans.- To reduce calorie intake.
Q-3 what are main constiuent of Dettol?
Ans.- Choloroxylenol & Terpinol .
Q-4 what type drug phenaticinis?
Ans.- It is antipyretics.
Q-5 Name the drug that are used to control allergy?
Ans.- Antihistamines.
Q-6Why is the use of aspartame limited to cold food and drinks?
Ans.- It is unstable at cooking temperature and decompose.
Q-7What is tranquilizers? Give an example?
Ans.- They is the drug used in stress, mild severe mental disease.
Q-8 what type of drug chloramphenicol?
Ans.- It is broad spectrum antibiotic.
Q-9Why is bithional is added to the toilet soap?

Ans.-It acts as an antiseptic.

Q-10 what are food preservatives?
Ans- The substances which prevent spoilage of food due to microbial growth. eg- sodium benzonate.

SHORT ANSWER TYPE QUESTION

(2 marks)
Q-1 Mention one important use of the following(i) Equanil

(ii)Sucrolose

Ans- (i) Equanil- It is a tranquilizer.

(ii) Sucrolose-It is an artificial sweetener.
Q-2 Define the following and give one example(i)Antipyretics

(ii) Antibiotics

Ans- (i) Antipyretics- Those drugs which reduce the temperature of feveral body are called Antipyretics.
Eg - Paracetamol
(ii) Antibiotics-The drugs which prevent the growth of other micro-organisms. Eg- Pencillin.
Q-3 what are tincture of iodine?
Ans- 2-3% iodine solution of alcohol water is called tincture of Iodine. It is a powerful antiseptics and is applied on
wounds.
Q- 4 What is artificial sweetening agent? Give two examples?
Ans- The substances which give sweetening to food but dont add calorie to our body .
Eg- Saccharin, alitame.
Q-5 How is synthetic detergents better than soaps?
Ans- (i) Detergents can be used in hard water but soaps cannot be used.
(ii) Detergents have a stronger cleansing action than soaps.
Q-6 what are sulpha drugs? Give two examples?
Ans- A group of drugs which are derivatives of sulphanilamide and are used in place of antibiotics is called sulpha
drugs.
Eg- Sulphadizine, Sulphanilamide.

Q-7 what forces are involved in holding the active sites of the enzymes?
Ans- The forces are involved in holding the active sites of the enzymes are hydrogen bonding , ionic bonding ,
dipole-dipole attractions or Vander waals force of attractions.
Q-8 Describe the following giving an example in each
case- (i) Edible colours
(ii) Antifertility drugs
(i)

Edible colours- They are used for dying food.

Eg- saffron is used to colour rice.

(ii)
Antifertility drugs- Those drugs which control the birth of the child are called antifertility drugs.
Q-9 Give two examples of organic compounds used as antiseptics?
Ans- Phenol (0.2%), iodoform

SHORT ANSWER TYPE QUESTION

(3 marks)
Q-1 what are Biodegredable and non-biodegdredable detergents? Give one example of each.
Ans- Detergents having straight hydrocarbon chain and are easily decomposed by micro-organisms are called
Biodegredable detergents.The detergents having branched hydrocarbon chain and are not easily decomposed by
micro-organisms are called Non-Biodegredable detergents.
Q-2 what are barbiturates? To which class of drugs do they belong? Give two examples.
Ans- Derivatives of barbituric acid are called barbiturates.They are tranquilizers. They also act as hypnotics. egluminal , seconal.
Q-3 what is the use of
(i) Benadryl (ii) sodium benzoate (iii) Progesterone
Ans- (i) Antihistamines
(ii) Preservatives
(iii) Antifertility drug
Q-4 Identify the type of drug(i) Ofloxacin (ii) Aspirin (iii) Cimetidine
Ans- (i) Antibiotic (ii) Analgesics & Antipyretics
(iii) Antihistamines & antacid

Q-5 Describe the following with suitable example(i) Disinfectant (ii) Analgesics
(iii) Broad spectrum antibiotics
(i) Disinfectant- chemicals used to kill the micro-organisms can applied on non living articles.
(ii) Analgesics- They are the drugs which are used to relieve pain. eg Aspirin , Ibuprofen.
(iii) Broad spectrum antibiotics- They kill the wide range of gram positive and gram negative bacteria. EgChloramphenicol , ofloxacin.

Chapter-5

Surface Chemistry

Q1.Gelatine is generally added to ice creams. Why?

Ice cream is an emulsion of milk or cream in water (o/w type). Gelatine is generally added to
act as emulsifiers to form the stable emulsion.

Q2. Why is chemisorption called activated absorption?

For a chemisorption to take place ,reactants should acquire
minimum energy of activation.

Q3. Why is desorption necessary in catalytic reaction?

Desorption is necessary in catalytic reaction to maintain the flow of reaction.

Q4. In chemical reaction can a product formed act as catalyst? If so

give example.
Yes, Example: hydrolysis of ester. Ester hydrolysis is catalysed by acid. In the course of the
reaction carboxylic acid is produced which catalyses the reaction.

Q5. What is colloidion solution?

Colloidion solution is the solution which is used to impregnate the filter paper to make it an
ultra filter.

Q6. Give conditions for Tyndall effect to take place?

The refractive indices of dispersion medium & dispersed phase should not be same. The
wavelength of the light should not be too low.

Q7 Why is the ester hydrolysis slow in the beginning & becomes faster after
The ester hydrolysis slow in the beginning & becomes faster after sometime
because the carboxylic acid produced acts as the catalyst.

Q8. What are the reasons for charge on sol particles?

Frictional electrification
Electron capture
Preferential adsorption of ions from solutions
Dissociation of surface molecules

sometime?

Q9. Why colloidal medicines are more effective?

Colloidal medicines have large surface area for the reaction. Hence colloidal medicines are
more effective.

Q10.Give the factors governing colour of colloidal solution?

Wavelength of light scattered, the manner in which light is received by observer, particles
size.

Q11. Why are Lyophylic colloids self stabilized?

Due to the force of attraction between dispersion medium & dispersed phase.

Q12. State one application ZSM-5.

Used for the conversion of alcohol to gasoline.

Q13. Explain the role of catalyst in a chemical reaction.

It lowers the activation energy & hence increases the rate of the reaction.

Q14. Adsorption is always exothermic. Why?

During adsorption, the bonding takes place between adsorbate &
adsorbent and there is a decrease in surface area & decrease in entropy.

Q15. Define weeping of gels. Give the other name of weeping?

When gels are allowed to stand for a long time they give out small quantity of trapped liquid
which accumulates on its surface. This action of gels is called as weeping, other name is
syneresis.

Q16. What is Thixotrophy?

Conversion of sol to gel is called thixotrophy.

Q17. Why is FeCl3 preferred over KCl for a cut leading to bleeding?
Fecl3 has more positive charge and causes coagulation of blood
quickly.

Q18. Why is silica gel used as dehumidifier?

Silica gel adsorpes moisture on its surface quickly.

Q19. Give the kinetics of adsorption of gases on metal surfaces.

Adsorption of gases on metal surfaces follows zero order kinetics.

Q20.

G is negative for adsorption process. Why?

Adsorption is exothermic & decrease in entropy occurs in adsorption.

Q21. Give the significance of Brownian movement.

It gives stirring effect to the colloid. Hence colloidal particles do not aggregate. The colloid
becomes stable.

Q22. What happens when blood charcoal is shaken with conc. Kcl
in one case and its dilute KCl solution in other case?
In conc. KCl positive adsorption occurs & in dilute Kcl negative adsorption occurs.

Q23.Give the principle used in gas masks?

Competing adsorption

Q24. Gold sol appears red , purple & also golden in colur Why?
Colour of the gold sol changes with its particle size.Its colour is red
& becomes puple when size increases & finally becomes golden.

Q25. Give the sign of H & S when Br2 gas gets adsorbed on charcoal.
negative & S = positive

Q26. What is Argyrol?

Colloid of Ag with proteine(mild silver protein)
Antiseptic & used for treating gonoria (a disease)

Q27. What happens when NaCl is added to ferrichydroxide sol?

When NaCl is added to ferrichydroxide sol coagulation occurs.

H =

Q28.Differentiate dilute soap solution & concentrated soap solution.

Dilute soap solution behaves like a true solution & concentrated soap solution behaves like a
colloid.

Q29. Comment: Colloid is not a substance but it is a state of a substance.

The nature of the sub whether colloid or crystalloid depends upon the particle size.When the
size of the solute particles lies between 1000 10000 pm , it behaves as a colloid & whenit is
less than this value it behaves as a crystalloid. Thus Colloid is not a substance but it is a state
of a substance which depeds upon the particle size.

Q30. What happens when Fe(OH)3 is added to Gold sol?Why?

The Gold sol is negatively charged, Fe(OH)3 is positively charged
& so coagulation occurs.Color of Gold sol changes from red to blue. Gold sol changes from
red to blue due to the change in the particle size.

(AS THIS CHAPTER HAS NO NUMERICALS HOTS MAY INCLUDE THE QUESTIONS OF THE ABOVE
TYPE)

Chapter-8

d and f block Elements

1. Silver atom has completely filled d orbitals in its ground state. How can you say that it
is a transition element?
Ans: It forms AgF2 a dark brown crystalline solid

2. Transition elements exhibit their highest oxidation state in their oxides not in
Flourides.Why?
Ans: Because oxygen can form covalent multiple bonds.

3. Explain why, Zn (II) salts are white while Mn (VII) are deep purple in colour?
Ans: due to charge transfer between O2- ion to Mn7+

4. KMnO4 is used in acidic medium quite frequently than in its aqueous or alkali for
oxidizing purpose. Why?
Ans: In acidic medium MnO4- involves the addition of 5e- or Eo = +1.52v

5.Inspite of low enthalpy of atomiza

6.Give reasons:
i) Zr and Hf have identical sizes
ii) In the titration of FeSO4 with KMnO4 in the acidic medium dil.H2SO4 is used instead
of dil HCl
Ans: i) Due to lanthanoid contraction
ii) dil.HCl is reducing agent and liberates chlorine on reacting with KMnO4 soln.
7.Calculate the spin only magnetic moment of Iron present in the following compound.
Fe(H20)5NO 2+

Ans: 5.92 BM

8. K2 PtCl6 is a well known compound whereas the corresponding Ni compound is not

known. State the reason for it.
Ans: The oxidation state of Pt in K2 PtCl6 is +4, which is a stable oxidation state for Pt. The
same oxidation state Ni is very difficult because of (I.E1 + I.E 2+ I.E 3+I.E 4)

9. Among the ionic species Sc 3+ ,Ce 4+ and Eu2+ Which one is a good oxidizing agent?
Ans: Ce 4+ is a good reducing agent because it can readily change to the most stable
oxidation state by gaining one electron. Others cannot do so.

10. Why are Fe 3+ and Cu 2+ prominent in their aqueous solutions?

Ans: Because of high hydration enthalpies.

11. There is a dip in the melting point curve at Mn, though the preceding element also has
similar electronic configuration. Why?
Ans: Due to 3d 5 half filled configuration which are tightly held by more effective nuclear
charge of Mn

12. CrO3 is an acid anhydride. Explain.

Ans: It dissolves in water to give chromic acid.
CrO3 + H2O

H2 CrO4

13. Though both Cr 2+ and Mn 3+ have d4 configuration, yet Cr2+ is reducing and Mn3+ is
oxidizing. Explain Why?

Ans: Because of the stable half filled configuration of t2g sets Cr3+

*********